Studies in Surface Science and Catalysis 135

ZEOLITES AND MESOPOROUS MATERIALS

AT THE DAWN OF THE 21 STCENTURY
This Page Intentionally Left Blank
Studies in Surface Science and Catalysis
Advisory Editors: B. Delmon and J.T. Yates

Vol. 135

ZEOLITES AND M E S O P O R O U S
M A T E R I A L S AT THE DAWN
OF THE 21 sTC E N T U R Y
Proceedings of the 13t" International Zeolite Conference,
Montpellier, France, 8-13 July 2001

Edited by

A. Galarneau, F. Di Renzo and F. Fajula

Ecole Nationale Superieure de Chimie de Montpellier,
8 Rue de I'Ecole Normale, 34296 Montpellier Cedex 5, France

J. Vedrine
University of Liverpool, Leverhuime Centre for Innovative Catalysis,
P.O. Box 147, Liverpool L69 3BX, U.K.

2001
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Preface

The International Zeolite Conference is one of the pillars on which the identity of the
zeolite community stands, at the same level of the definitions of zeolite structures provided
by the Structure Commission of the International Zeolite Association, the dedicated journal
which was Zeolites and is now Microporous and Mesoporous Materials, and the meetings of
several national and regional zeolite associations.

The 13th International Zeolite Conference has been held in Montpellier, France, from
July 8 to 13, 2001, organized by the French Zeolite Group on behalf of the IZA. It has been
preceded by a School on the Industrial Applications of Zeolites, held in Poitiers, and followed
by a Field Trip in the natural zeolite localities of Massif Central.

These proceedings are the expression of the oral and poster communications which
have been presented during the Conference. They are subdivided into 32 thematic sessions
going from the genesis of materials to their applications through their characterization. The
paper volume contains the full texts of the 5 plenary and 6 keynote lectures and informative
summaries of 150 oral and 540 poster presentations. It is intented to provide the participants
a complete guide to the scientific programme. In order to gather all the communications in a
handy document, the full texts of oral and poster presentations are available in a CD-ROM.
These contributions have been selected among the 903 submissions received from a
total of 57 countries! The evaluation was possible through the timely and efficient refereeing
by the members of the International Advisory Board. The editors would like to namely
acknowledge the dedication of the members of the Paper Selection Committee: Alberto
Alberti, Giuseppe Bellussi, Colin Cundy, Jean-Pierre Gilson, Annick Goursot, Philip
Llewellyn, Johann Martens, Jo~l Patarin, Cl6ment Sanchez, Alain Tuel and Herman van
Bekkum.

With the 13th IZC, zeolite science enters the new millennium with a vitality and an
audience never reached before. Besides the fields of zeolite science always represented at
IZCs (synthesis, characterization, catalysis .... ), some subjects strengthen their position
(mesoporous materials, theory and modelling), new areas emerge (advanced materials,
environmental and life sciences) and older ones regain interest (natural zeolites). The
understanding and development of the unique properties of porous materials relies on a
unique blend of multidisciplinary knowledge: material science, with the implication of organic
and colloid chemistry, to prepare micro- and mesoporous materials, surface and adsorption
science sustained by theory and modelling to understand the peculiar behavior of molecules in
confined systems, special branches of catalysis, physics, chemical engineering and life science
to design novel applications. The gathering of these elements is at the basis of a fruitful and
evolutionary zeolite science, as it is hopefully reflected by these proceedings.

Before concluding, the editors address a special and grateful acknowledgement to all
the staff of the "Laboratoire de Mat6riaux Catalytiques et Catalyse en Chimie Organique"
from Montpellier for their outstanding involvement all along the Conference organization.
vi

700

600 Papers published in IZC proceedings

-~ 500

~4oo
Im

300
g~

200

100

0
Year 67 70 73 77 80 83 86 89 92 94 96 98 2001

~... .- v -o, f f o

The vitality of zeolite community is witnessed by the trend of the contributions to

International Zeolite Conferences.

Montpellier, April 12, 2001

Anne Galarneau Francois Fajula

Francesco Di Renzo Jacques V6drine

 vii

ORGANIZING COMMITTEE

General Chairman
Francois Fajula Ecole Nationale Sul~rieure de Chimie de Montpellier, France

Scientific Chairman
Jacques Vedrine University of Liverpool, UK

Secretary
Francesco Di Renzo Ecole Nationale Sup6rieure de Chimie de Montpellier,~France

Treasurer
Pascale Massiani Universit6 Pierre et Marie Curie, Paris, France

Pre-Conference School
Michel Guisnet Universit6 de Poitiers, France
Jean-Pierre Gilson Universit6 de Caen, France

Field Trip Subcommittee

Philippe Rocher Service Gtologique Rtgional Auvergne, Clermont-Ferrand, France
Alain Tuel Institut de Recherche sur la Catalyse, Villeurbanne, France

Finance
Jean-Pierre Gilson Universit~ de Caen, France

Publications
Anne Galarneau Ecole Nationale Suptrieure de Chimie de Montpellier, France

Liaison to the IZA Council

Giuseppe Bellussi EniTecnologie, San Donato Milanese, Italy

INTERNATIONAL ADVISORY BOARD

Belgium
Janos B.Nagy Faeultts N. D. de la Paix, Namur
Peter Jacobs Katholieke Universiteit Leuven, Hevedee
Johan Martens Katholieke Universiteit Leuven, Hevedee
Bulgaria
Christo Minchev Bulgarian Academy of Sciences, Sofia
Canada
Serge Kaliaguine Universit6 Laval, Quebec, Sainte Foy
China
Da-Dong Li SINOPEC R/PP, Beijing
Zhongmin Liu Dalian Institute of Chemical Physics, Dalian
viii

Ruren Xu Jilin University, Changchun

Croatia
Boris Subotic Ruder Boskovic Institute, Zagreb
Cuba
Gerardo Rodriguez
-Fuentes Universidad de la Habana, Facultad de Fisica, La Habana
Czech Republic
Blanka Wichterlova J. Heyrovsky Institute of Physical Chemistry, Praha
France
G~rard Ferey Institut Lavoisier, Versailles
Jacques Fraissard Universit6 Pierre et Marie Curie, Paris
Annick Goursot Ecole Nationale Sup6rieure de Chimie de Montpellier
Philippe Llewellyn Universit6 de Provence, Marseille
Alain M6thivier Institut Fran~ais du P6trole, Rueil-Malmaison
Joel Patarin Ecole Nationale Sup6rieure de Chimie de Mulhouse
Cl6ment Sanchez Universit6 Pierre et Marie Curie, Paris
Jacques Tellier TFE, Groupement de Recherches de Laeq, Lacq
Georgia
George Tsitsiehvili Georgian Academy of Sciences, Tbilisi
Germany
Peter Behrens Institut far Anorganische Chemie, Hannover
Thomas Bein Ludwig-Maximilians Universitat, Munchen
Wolfgang Hoelderich RWTH-Aachen, Aachen
Hellmut Karge Fritz-Haber Inst. Max Plank Gesellschaft, Berlin
Jorg Karger Leipzig Fakultat for Physik und Geowissenschaften, Leipzig
Johannes Lercher Technische Universitat MOnchen
Ferdi Sch0th Max Planck Institut ft~ Kohlenforshung, Muelheim
Klaus Unger Johannes Gutemberg Universitat, Mainz
Jens Weitl~mp Universitat Stuttgart
Hungary
Herman Beyer Hungarian Academy of Sciences, Budapest
Denes Kallo Hungarian Academy of Sciences, Budapest
Imre Kiricsi Jozsef Attila University, Szeged
India
Paul Ratnasamy National Chemical Laboratory, Pune
Italy
Alberto Alberti Universit~ di Perugia
Giuseppe Bellussi EniTecnologie SpA, San Donato Milanese
Paolo Ciambelli Universith di Salerno, Fisciano
Carmine Colella Universith di Napoli Federico II, Napoli
Bite Fubini Universith di Torino
Adriano Zecchina Universith di Torino
Japan
Mazakazu Anpo Osaka Prefecture University, Osaka
Tomoyuki Inui Daido Hoxan, Inc., Sakai, Osaka
Mazakazu Iwamoto Tokyo Institute of Technology, Yokohama
 Yoshio Ono Tokyo Institute of Technology, Yokohama
Takashi Tatsumi Yokohama National University, Yokohama
Osamu Terasaki Tohoku University, Sendai
Tatsuki Yashima Tokyo Institute of Technology, Yokohama
Korea
Hakze Chon Korea Advanced Institute of Science and Technology, Taejon
Ryong Ryoo Korea Advanced Institute of Science and Technology, Taejon
Norway
Michael Stocker SINTEF, Oslo
New Zealand
Neil Milestone Industrial Research Ltd, Lower Hutt
The Netherlands
Koos Jansen Delft University of Technology, Delft
Thomas Maschmeyer Waterman Institute, Delft
Herman van Bekkum Delft Unniversity of Technology, Delft
Rutger van Santen Eindhoven University of Technology, Eindhoven
Poland
Miroslaw Derewinski Polish Academy of Sciences, Cracow
Mafia Ziolek A. Mickiewicz University, Poznan
Romania
Emil Radu Russu ICERP SA, Ploiesti
Russia
Irina Ivanova Moscow State University, Moscow
Leonid Kustov Russian Academy of Sciences, Moscow
South Africa
Ciryl O'Connor University of Capetown, Rondebosch
Spain
Avelino Corma Universidad Politecnica de Valencia
Joaquim Perez-
Pariente Instituto de Catalisis y Petroleoquimica CSIC, Madrid
Switzerland
Thomas Armbruster Universitat Bern
Lynne Mc Cusker ETH Zarich
Attain Pfenninger CU Chemie Uetikon AG, Uetikon
Taiwan
Kuei-Jtmg Chao National Tsing Hua University, Hsinchu
United Kingdom
Michael Anderson UMIST Chemistry Department, Manchester
Richard Catlow Royal Institution of Great Britain, London
Eric Coker BP Amoco Chemicals, Sunbury on Thames
Colin Cundy UMIST Chemistry Department, Manchester
Eric Derouane University of Liverpool
USA
John Armor Air Products & Chemicals Inc., PA - Allentown
Kenneth Balkus Jr. University of Texas at Dallas, TX- Richardson
David Bish Los Alamos National Laboratory, NM - Los Alamos
Anthony Cheetham University of California, CA- Santa Barbara
Brad Chmelka University of California, CA- Santa Barbara
Mark Davis California Institute of Technology, CA - Pasadena
Juan Garces Dow Chemical Company, MI - Midland
Charles Kresge Dow Chemical Company, MI - Midland
Fred Mumpton SUNY - College at Brockport, NY - Brockport
Alexandra Navrotsky University of California at Davis, CA - Davis
Michael O'Keeffe Arizona State University, AZ - Tempe
Thomas Pinnavaia Michigan State University, MI - East Lansing
Galen Stucky University of California, CA- Santa Barbara
Rose-Marie Szostak Georgia Institute of Technology, GA - Atlanta
Robert Thompson Worcester Polytechnic Institute, MA - Worcester
Michael Treaty NEC Research Institute, NJ- Princeton
David Vaughan Pennsylvania State University, PA- University Park
Stephen Wilson UOP, Inc., IL - Des Plaines
Stacey Zones Chevron Research & Tech. Co., CA- Richmond

IZA COUNCIL

President
Jens Weitkamp Universitat Stuttgart, Germany

Vice-President
Cyril T. O'Connor University of Capetown, Rondebosch, South Africa

Secretary
Koos Jansen Delft University of Technology, Delft, The Netherlands

Treasurer
Rose-Marie Szostak Georgia Institute of Technology, GA - Atlanta, USA

Members
Giuseppe Bellussi EniTecnologie, San Donato Milanese, Italy
Hakze Chon Korea Advanced Institute of Science and Technology, Taejon, Korea
Tomoyuku Inui Daido Hoxan, Inc., Sakai, Osaka, Japan
Hellmut G. Karge Fritz-Haber Inst. Max Plank Gesellschaft, Berlin, Germany
Johannes Lercher Technische Universitat M0nchen, Germany
Johan A. Martens Katholieke Universiteit Leuven, Heverlee, Belgium
Lynne Me Cusker ETH Z0rich, Switzerland
Michael St0cker SINTEF, Oslo, Norway
Michael Treaty NEC Research Institute, NJ - Princeton, USA
Ruren Xu Jilin University, Changchun, China
Tatsuaki Yashima Tokyo Institute of Technology, Tokyo, Japan
 Support and Sponsoring
(As of April 17, 2001)
The Organizing Committee wishes to thank various institutions and companies for their
financial support to IZC 13. Their contribution allowed a reduced registration fee for students
and a bursary programme.

Institutions
Minist&e de la Recherche
CNRS
R6gion Languedoc-Roussillon
District de Montpellier
Conseil G6n~ral de l'H&ault
Universit~ Montpellier II
Ecole Nationale Sup6rieure de Chimie de Montpellier
St Nikon Foundation

Partners

ExxonMobil
TotalFinaElf
UOP
Institut Franqais du P6trole

Sponsors and Friends

Air Liquide
DSM Research
Dow Chemicals
EniTecnologie
Grace Davison
Haldor Topsoe
Procatalyse
Rhodia
xii

,,
List and schedule of sessions
Sessions ,, , ,
Oral ,,
Poster
01- Mineralogy of natural zeolites ...................................... Tuesday am Tuesday pm
02- Zeolite nucleation and growth ....................................... Monday pm Monday pm
03- New methods of zeolite synthesis ................................ Thursday pm Thursday pm
04- Isomorphous substitutions ............................................ Friday am Thursday pm
05- Synthesis of new materials ............................................ Tuesday pm Tuesday pm
06- Fundamentals of micelle templating .............................. Monday am Monday pm
07- New mesoporous molecular sieves ................................ Tuesday am Tuesday pm
08- Syntheses with non-ionic surfactants ............................ Friday pm Wednesday pm
09- Crystal structure determination ..................................... Wednesday am Wednesday pm
10- Host-guest chemistry .................................................... Monday am Monday pm
11- Post-synthesis modification ......................................... Monday pm Monday pm
12- In-situ spectroscopy and catalysis ............................... Monday am Monday pm
13- Frameworks and acid sites ............................................. Friday pm Thursday pm
14- Frameworks, cations, clusters ....................................... Friday am Thursday pm
15- Modelling and theoretical studies A .............................. Tuesday am Tuesday pm
16- Modelling and theoretical studies B .............................. Tuesday pm Tuesday pm
17- Principles of adsorption ................................................ Monday am Monday pm
18- Adsorption and separation processes ........................... Monday pm Monday pm
19- Diffusion: fundamental approach .................................. Tuesday pm Tuesday pm
20- Zeolite membranes and films ......................................... Wednesday am Wednesday pm
21- Nanoeomposite fundamentals and applications ............ Wednesday am Wednesday pm
22- Advanced materials ........................................................ Thursday pm Thursday pm
23- Micro- and mesoporous materials in fine
chemistry ............................................................................. Monday pm Monday pm
24- New routes to hydrocarbon activation .......................... Tuesday am Tuesday pm
25- Conversion of aromatics ................................................ Tuesday pm Tuesday pm
26- Catalysis for oil refining ................................................ Wednesday am Wednesday pm
27- Selective oxidation and sulfur resistance ....................... Thursday pm Thursday pm
28- Confinement and physical chemistry for catalysis ....... Friday am Wednesday pm
29- New approaches to catalyst preparation ...................... Friday pm Wednesday pm
30- Environmental catalysis ................................................. Friday am Wednesday pm
31- Environment-friendly applications of zeolites...: .......... Friday pm Thursday pm
32- Zeolite minerals and health sciences .............................. Thursday pm Thursday pm
 xiii

Frequently a s k e d questions:

- When do I have to present my oral communication?

Look in the authors index section the code S-O-x corresponding to your communication(s)
where S is the session number, 0 meaning oral and x the position of the communication, then
refer to the previous page. Oral communications start in the morning at l Oh (except on
Monday (l 0h30)) and in the afternoon at 16h30 and last 30 min each including 10 min
discussion.

- When do I have to present my poster communication?

Look in the authors index section the code S-P-x corresponding to your communication(s)
where S is the session number, P meaning poster, then refer to the previous page. Poster
communications are from 14h to 16h each day except on friday.
Posters of the day session should be hanged during the morning coffee break (lOh-lOh30).

Further details on the programme are provided in the following pages.

 CONFERENCE PROGRAMME

- -

13:OO Lunch Lunch Lunch Lunch Lunch

13:30
A
14:OO Poster1 Poster I1 Poster III Poster N 29-0- 08-0- 31-0- 13-0-
01 01 01 01
14:30 Sessions Exhibition Sessions Exhibition Sessions Exhibition Sessions Exhibition 29-0- 084- 31-0- 13-0-
02 02 02 02
15:OO 02 12 01 16 08 26 03 22 29-0- 084- 31-0- 13-0-
06 17 05 19 09 28 04 27 03 03 03 03
1930 10 18 07 24 20 29 13 31 29-0- 08-0 31-0- 1343
11 23 15 25 21 30 14 32 0 4 0 4 0 4 0 4
16:OO Coffee Break/Exhibition Coffee BreakExhibition Coffee BreakExhibition Conciudiig Remarks

16:30 23-K- 02-0- 11-0- 18-0 25-0- 19-K- 16-0- 05-0- 16.30 Departure forthe 27-0- 03-K- 22-0- 32-0
01 01 01 01 01 01 01 01 evening outing at 01 01 01 01
17:OO 23-0- 02-0- ll-0- 18-0- 25-0- 19-0- 16-0- 05-0- 27-0- 03-0- 22-0- 32-0- 17:OO Departure to
02 02 02 02 02 02 02 02- 02 02 02 02 FIELD TRIP
17:30 23-0- 02-0- 11-0- 18-0 25-0- 19-0 16-0- 05-0- "MANADE Saint Gabriel" 27-0- 03-0- 22-0- 32-0-
03 03 03 03 03 03 03 03 03 03 03 03
18:OO 23-0- 02-0- ll-0- 18-0- 25-0- 19-0 16-0 05-0- 27-0- 03-0- 22-0- 32-0-
0 4 0 4 0 4 0 4 0 4 0 4 0 4 0 4 0 4 0 4 0 4 0 4
18:30 23-0- 02-0- ll-0- 18-0- 25-0- 19-0- 16-0 05-0- 27-0- 03-0- 22-0- 32-0-
05 05 05 05 05 05 05 05. , 05 05 05 05
2 1:00 CONCERT 20:OO CONFERENCE
DINER

NB: Keynotes (S-K-01) (grey) will begin 10 min before the start of oral sessions
This Page Intentionally Left Blank
 xvii

SCIENTIFIC PROGRAMME AND CONTENT OF PROCEEDINGS

Plenaries
PL-1- Monday 9h - Ordered mesoporous materials - State of art and prospects
F. Schiith

PL-2- Tuesday 8h30 - Clinoptilolite-heulandite: applications and basic research

T. Armbruster 13

PL-3- Wednesday 8h30 - Evolution of extra-large pore materials

M.E. Davis 29

PL-4- Thursday 8h30 - Evolution of refining and petrochemicals. What is the place
of zeolites?
C. Marcilly 37

PL-5- Friday 8h30 - Is electron microscope an efficient magnifying glass for micro-
and meso- porous materials?
O. Terasaki and T. Oshuna 61

Note: The conference has been divided into 32 sessions. Each communication has a
code S-M-x with S being the number of the Session, M = K (keynote), O (oral), P
(poster) and x the number of the communication.

Keynotes
23-K-01- Monday 16h20- Delaminated zeolites as active catalysts for processing
large molecules
A. Corma and V. Forn~s 73

01-K-01- Tuesday 9h50 - Pentasil zeolites from Antartica: from mineralogy to

zeolite science and technology
A. Alberti, G. Cruciani, E. Galli, S. Merlino, 1~ Millmi, S. Quartieri, G. Vezzalini
and S. Zanardi 83

19-K-01- Tuesday 16h20 - Use of 1H NMR imaging to study the diffusion and co-
diffusion of gaseous hydrocarbons in HZSM-5 catalysts
P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L. Bonardet, J.-M. Dereppe
and J. Fraissard 93

21-K-01- Wednesday 9h50 - Zeolite-based nanocomposites: synthesis,

characterization and catalytic applications
B. K Romanovsky 103

03-K-0 I- Thursday 16h20 - Application of combinatorial tools to the discovery and

commercialization of microporous solids: facts and fiction
J. Holmgren, D. Bem, M. Bricker, 1L Gillepsie, G. Lewis, D. Akporiaye, I. Dahl,
A. Karlsson, A#..Plassen and R. Wendelbo 113
 xviii

30-K-01- Friday 9h50 - The local structures o f transition metal oxides incorporated
in zeolites and their unique photocatalytic properties
M. Anpo and S. Higashimoto 123

Note: In the b o o k are only the summaries o f the communications. The text o f the full
papers o f oral and poster c o m m u n i c a t i o n s are in the C D - R O M .

, Programme o f o r a l s e s s i o n s (a~. lOh30-12h30 and pm 16h30-19h) S u m m a r y pages

Monday am
12- In-situ spectroscopy and catalysis .......................................................... 133
06- F u n d a m e n t a l s o f micelle templating ........................................................ 134
10- H o s t - g u e s t chemistry ............................................................................... 135
17- PrinciPles o f a d s o r p t i 0 n ................. ... ....... .. ........................ .... . ..... ..,,.,: ..... 137
Monday p m
23- Micro- and m e s o p o r o u s materials in fine chemistry ............................... 138
02- Zeolite nucleation and growth ................................................................. 140
11- Post-synthesis modification .................................................................... 141
18- Adsorptio n and separation processes .................................... ..:... .... ... .... .. 143
Tuesday am
24- N e w routes to hydrocarbon activation .................................................... 145
01- M i n e r a l o g y o f natural zeolites ................................................................ 146
15- M o d e l l i n g and theoretical studies A ........................................................ 148
07- N e w m e s o p o r 0 u s molecular sieves .......................................................... 150
Tuesday pm
25- Conversion o f aromatics .......................................................................... 151
19- Diffusion: fundamental approach ............................................................. 153
16- M o d e l l i n g and theoretical studies B ......................................................... 155
05- Synthesis .of n e w materials ............. ..:...:... ....... ...................................... 156
Wednesday am
26- Catalysis for oil refining .......................................................................... 158
21- N a n o c o m p o s i t e fundamentals and applications ...................................... 160
20- Zeolite m e m b r a n e s and films ................................................................... 161
09- Crystal structure determination ............................................................... 163
Thursday pm
27- Selective oxidation and sulfur resistance .................................................. 165
03- N e w m e t h o d s o f zeolite synthesis ........................................................... 166
22- A d v a n c e d materials .................................................................................. 168
32- Zeolite minerals and health sciences ........................................................ 170
Friday am
30- E n v i r o n m e n t a l catalysis ........................................................................... 171
28- C o n f i n e m e n t and physical chemistry for catalysis ................................. 173
04- I s o m o r p h o u s substitutions ...................................................................... 175
14- F r a m e w o r k s , cations , clusters ....... ::. ...... :..::...,.,,:. .................. :. ........ :.:;::.. 176
Friday pm
29- N e w a p p r o a c h e s to catalyst preparation ................................................ 178
08- Syntheses with non-ionic surfactants ...................................................... 179
31- Environment-friendly applications o f zeolites ........................................ 181
13- F r a m e w o r k s and acid sites ....................................................................... 182
 xix

Posters should be hanged during the morning coffee break (1 Oh- 10h30).

Programme o f poster sessions (14h00-16h30) , Summary pages

Monday
02- Zeolite nucleation and growth ................................................................. 185
06- Fundamentals o f micelle templating ........................................................ 198
10- Host-guest chemistry ............................................................................... 206
11- Post-synthesis modification .................................................................... 208
12- In-situ spectroscopy and catalysis .......................................................... 217
17- Principles o f adsorption ........................................................................... 222
18- Adsorption and separation processes ...................................................... 226
23- Micro- and mesoporous materials in fine chemistry ............................... 230
Tuesday
01- Mineralogy o f natural zeolites ................................................................ 240
05- Synthesis o f new materials ...................................................................... 244
07- N e w mesoporous molecular sieves .......................................................... 249
15- Modelling and theoretical studies A ........................................................ 256
16- Modelling and theoretical studies B ......................................................... 264
19- Diffusion: fundamental approach ............................................................ 269
24- N e w routes to hydrocarbon activation .................................................... 271
25- Conversion o f aromatics .......................................................................... 280
Wednesday
08- Syntheses with non-ionic surfactants ...................................................... 284
09- Crystal structure determination ............................................................... 288
20- Zeolite membranes and films ................................................................... 291
21- Nanocomposite fundamentals and applications ...................................... 296
26- Catalysis for oil refining .......................................................................... 301
28- Confinement and physical chemistry for catalysis ................................. 307
29- New approaches to catalyst preparation ................................................ 311
30- Environmental catalysis ........................................................................... 320
Thursday
03- N e w methods o f zeolite synthesis ........................................................... 330
04- Isomorphous substitutions ...................................................................... 335
13- Frameworks and acid sites ....................................................................... 340
14- Frameworks, cations, clusters .................................................................. 347
22- Advanced materials .................................................................................. 359
27- Selective oxidation and sulfur resistance .................................................. 365
31- Environment-friendly applications o f zeolites ........................................ 369
32- Zeolite minerals and health sciences ........................................................ 373

AUTHOR INDEX 377

SUBJECT I N D E X 399
This Page Intentionally Left Blank
 xxi

F u l l p a p e r s (Texts included in the CD-ROM)

O1 - M i n e r a l o g y of Natural Zeolite

0 1 - O - 0 2 - Natural zeolites mineralization in the Oligocene-Miocene volcano-

sedimentary succession of Central Sardinia (Italy)
P. CappellettL G. Cerri, M. de Gennaro, A. Langella, S. Naitza, G. Padalino, M.
Palomba and R. Rizzo 147

01-O-03 - C a t i o n location and its influence on the stability of clinoptilolite

M.N. Johnson, G. Sankar, C.R.A. Catlow,. D. O'Connor, P. Barnes and D.Price 147

0 1 - O - 0 4 - The structure of Li-phillipsite

A.F. Gualtieri 147

01-O-05 - Ion-exchange features of intermediate-silica sedimentary phillipsite

C. Colella, E. Torracca, A. Colella, B. de Gennaro and D. Caputo
and M. de Gennaro 148

0 l - P - 0 6 - Zeolites in impact craters

M. V. Naumov 240

0 l - P - 0 7 - AI ordering in a dachiardite framework

M. Kato and K. Itabashi 240

0 l-P-08 - Chemical composition and ion-exchange properties of a natrolite from

Zahedan Region, Iran
A.R. Sardashti, H. Kazemian and M. Akramzadeh Ardakani 240

0 l-P-09 - Physical, chemical and structural characterization of the volcanic tuff

from the Maramures area, Romania
R. Pode, G. Burtica, S. Herman, A. Iovi and 1. Calb 241

0 l-P-10 - Heulandite group zeolites from the Paleogene fresh water lake
Blateshnitza Graben, Southwest Bulgaria
Z. Milakovska, E. Djourova and R. Tzankarska 241

0 l-P-11 - Isodimorphism of templates in zeolites. New crystal chemistry of

analcime and its analogues
V. V. Bakakin 241

0 l-P-12 - Evaluation of clinoptilolite tuffs from Russia as ion exchangers using

NH4 ions
1. V. Komarova, N.K. Galkina, V.A. Nikashina, B.G. Anfilov
and K.I. Sheptovetzkaya 242
xxii

0 l-P-13 - Mineralogy, chemistry and ion-exchange properties of the zeolitized

tufts from the Sheinovets caldera, E Rhodopes (South Bulgaria)
R. Ivanova, Y. Yanev, Tz. lliev, E. Koleva, T. Popova and N. Popov 242

0 l-P- 14 - Synthesis of titanium, niobium, and tantalum silicalite- 1 by microwave

heating of the mixed oxide xerogel precursors
W.S. Ahn, K.Y. Kim, M.H. Kim and Y.S. Uh 242

0 l-P-15 - Different silver states stabilized in natural clinoptilolites

N. Bogdanchikova, B. Concepcion Rosabal, V. Petranovskii, M. Avalos-Borja and
G. Rodriguez-Fuentes 243

0 l-P-16 - Physical-chemical and adsorptive properties of Armenia natural zeolites

F. Grigoryan, A. Hambartsumyan, tl. Haroyan and A. Karapetyan 243

0 l-P-17 - The sorption equilibria in natural zeolite-aqueous solutions systems

J. Perik, M. Trgo and S. Cerjan-Stefanovik 243

02 - Z e o l i t e N u c l e a t i o n a n d G r o w t h

02-0-01 - Small angle X-ray scattering on TPA-Silicalite-1 precursors in clear

solutions: influence of silica source and cations
C.J.Y. Houssin, B.L. Mojet, C.E.A. Kirschhock, V. Buschmann, P.A. Jacobs, J.A.
Martens and R.A. van Santen 140

02-0-02 - Nucleation processes in zeolite synthesis revealed through the use of

different temperature-time profiles
C.S. Cundy, J.O. Forrest and R.J. Plaisted 140

02-0-03 - High yield synthesis of colloidal crystals of faujasite zeolites

Qinghua Li, D. Creaser and J. Sterte 140

02-0-04 - Colloid chemical properties of silicalite-1 nanoslabs

S. Kremer, C. Kirschhock, P. Rouxhet, PA. Jacobs and J.A. Martens 141

02-0-05 - Atomic force microscopy (AFM) used to relate surface topography

growth mechanisms in SSZ-42
M. W. Anderson, N. Hanif J.R. Agger, C.-Y. Chen and S.I. Zones 141

02-P-06 - Epitaxial overgrowth of MAZ onto EMT type zeolite crystals

A.M. Goossens, V. Buschmann and J.A. Martens 185

02-P-07 - The transformation of zeolite A and X into nitrate cancrinite under low
temperature hydrothermal reaction conditions
J. C. Buhl and C. Taake 185
 xxiii

02-P-08 - Comparison of crystal linear growth rates for silicalite-1 in thermal and
microwave syntheses
C.S. Cundy and J. O. Forrest 185

02-P-09 - Effect of initial hydrogel milling on Na-ZSM-5 synthesis

C. Falamaki, M. Edrissi and M. Sohrabi 186

0 2 - P - 1 0 - Synthesis and characterization of zeolite Z S M - 2 5

S.B. Hong, W.C. Paik, W.M. Lee, S.P. Kwon, C.-H. Shin, I.-S. Nam and B.-H. Ha 186

02-P-11 - A study on the crystallization of a lamellar aluminophosphate APO-M

to a three-dimensional aluminophosphate APO-CJ3
K. Wang, J. Yu, Y. Song, Y. Zou and R. Xu 186

0 2 - P - 1 2 - S y n t h e s i s o f nanosized offretite crystals

J. Hedlund and E. Kurpan 187

02-P-13 - Silicon oxide plays a driving role in the synthesis of microporous

SAPO- 11
Z-Q. Liu and R. Xu 187

0 2 - P - 1 4 - S y n t h e s i s o f nanocrystal zeolite Y and its host effect

H. Yang, R. L i, B. Fan and K. Xie 187

02-P-15 - Tailoring crystal size and morphology of zeolite ZSM-5

Ming Liu and S. Xiang 188

02-P-16 - Modeling of silicalite crystallization from clear solution

K.A. Car&son, J. Warzywoda and A. Sacco, Jr. 188

02-P- 17 - Interaction/synergistic effect of Mg 2+ and Ba 2+ on the size and

morphology of the zeolite L crystals
S. Ferchiche, J. Warzywoda and A. Sacco, Jr. 188

0 2 - P - 1 8 - In-situ NMR study of mechanisms of zeolite A formation

M. SmaihL S. Kallus and J.D.F. Ramsay 189

02-P-19 - E f f e c t s o f synthesis parameters on zeolite L crystallization

Y.S. Ko, S.H. Chang and W.S. Ahn 189

0 2 - P - 2 0 - Some aspects of NU-86 zeolite crystallization

S. V. Dudarev, A. V. Toktarev, G. V. Echevsky, C.L. Kibby and D.J. O'Rear 189

0 2 - P - 2 1 - S y n t h e s i s o f zeolite Sr, K-ZK-5

P.C. Russell S.L. Stuhler. A.L. Kouli, J. Warzywoda and A. Sacco, Jr. 190
xxiv

02-P-22 - Evidence for in-situ directing agent modification in zeolite syntheses

J.C. Vartuli, G.J. Kennedy, B.A. Yoon and A. Malek 190

02-P-23 - The influence of different silica sources on the crystallization kinetics

of zeolite Beta
W. Schmidt, A. E Toktarev, E Schath, K.G. lone and K. Unger 190

02-P-24 - Population balance: a powerful tool for the study of critical processes of
zeolite crystallization
B. Subotic, T. Antonid and J. Bronik 191

02-P-25 - Synthesis of TMA-SOD from a novel type layered silicate by solid state
transformation
Y. KiyozumL F. MizukamL Y. Akiyama, T. lkeda and T. Nishide 191

02-P-26 - Direct conversion of bulk-materials into MFI zeolites by a bulk-

material dissolution technique
S. Shimizu and H. Hamada 191

02-P-27 - Synthesis of a new microporous silicate using DABCO-based structure-

directing agent
Y. Kubota, J. Pldvert, T. Honda, P. Wagner, M.E. Davis, T. Okubo, Ya. Goto,
Y. Fukushima and Y. Sugi 192

02-P-28 - Heteroepitaxial connection of zeolites with different pore structures

T. Wakihara, J. Pldvert, S. Nair, M. Tsapatsis, S. Yamakita, Y. Ogawa,
H. Komiyama, M. Yoshimura, M.E. Davis and T. Okubo 192

02-P-29 - Study of zeolite A crystallization from clear solution by hydrothermal

synthesis and population balance simulation
J. Bronic, P. Frontera, E Testa, B. Subotic, R. Aiello and J. B.Nagy 192

02-P-30 - Synthesis of zeolite SSZ-35 using N-methyl hexahydrojulolidinium salt

as a new family of structure-directing agents (SDAs)
Y Kurata, T.-A. Hanaoka and H Hamada 193

02-P-31 - The Fitting equation for zeolite crystallization with seeds

V. Toktarev and S. V. Dudarev 193

02-P-32 - Influence of the thermal treatment of the aluminosilicate gel precursor

on the zeolite nucleation
C. Kosanovi~, B. SubotiO and D. Kralj" 193

02-P-33 - Efficient co-templating roles of amines and amides admixed with

alkylammonium salts for the stabilisation of new A1PO4-n topologies
C. Borges, M.F. Ribeiro, C. Henriques, M.T. Duarte, J.P. Lourenqo
and Z. Gabelica 194
 XXV

02-P-34 - Static synthesis of zeolite M C M - 2 2

Y.-M. Wang, X.- T. Shu and M.- Y. He 194

02-P-35 - Synthesis of pure silica Beta by the conventional hydrothermal method

W Guo, J. Yao, Y. Luo and Qi. Li 194

02-P-36 - Hydrothermal transformation of a layered silicate, Na-magadiite, into

mordenite zeolite
T. Selvam and W Schwieger 195

02-P-37 - In-situ diagnostic of zeolite crystal growth by real time ultrasound

monitoring
R. Herrmann, W Grill T.J. Kim, O. Scharf R. Schertlen, M. Schmachtl, W
Schwieger, C. Stenzel, H. Toufar and Y. Venot 195

02-P-38 - Effect of ageing on the decomposition of tetra-alkylammonium ions as

studied by microwave heating
A. Arafat, H. van Bekkum, Th. Maschmeyer and J. C. Jansen 195

02-P-39 - Synthesis of siliceous mordenite from system free of amine

X. Qi, X. Liu and Z Wang 196

02-P-40 - High-resolution solid state MAS NMR studies on the role of promoter
(phosphate) in the nucleation and crystallization of Silicalite -1 (Si-MFI)
P.R. Rajamohanan, P. Mukherjee, S. Ganapathy and R. Kumar 196

02-P-41 - The influence of concentration on the structure-directing effects of

diethylenetriamine in the synthesis of porosils
P. Behrens, V.J. Hufnagel and A.M. Schneider 196

0 2 - P - 4 2 - Synthesis of high-silica MWW zeolite

L.M. Vtjurina, S.S. Khvoshchev and I. V. Karetina 197

03- New Methods of Zeolite Synthesis

03-0-02- Mesoporous zeolites

CJ.H. Jacobsen, J. Hou~,vicka, A. Carlsson and I. Schmidt 167

03-0-03 - Synthesis of novel zeolites SSZ-53 and SSZ-55 using organic

templating agents derived from nitriles
S.A. Elomari and S.I. Zones 167

03-0-04 - Synthesis of IFR-type zeolites optimized for spectroscopic study

B.S. Duersch and L. W. Beck 167
xxvi

03-0-05 - Competitive role of sodium and potassium cations during hydrothermal

zeolite crystallization from Na20-K20-A1203-SiO2-H20 gels
A.F. Ojo, F.R. Fitch, M. Balow and M.-L. Lau 168

03-P-06 - Zeolitization of a spanish bentonite in seawater medium. Effect of

alkaline concentration and time
R. Ruiz, C. Blanco, C. Pesquera and E Gonz61ez 330

03-P-07 - Silicalite-1 spheres prepared from preformed resin-silicate composites

L. Tosheva and J. Sterte 330.

03-P-08 - The synthesis of offretite single crystals using pyrocatechol as complex

agent
E Gao, G. Zhu, Xiaotian Li, S. Qiu, B. Wei, C. Shao and O. Terasaki 330

03-P-09 - Synthesis of FER type zeolite in presence of tetrahydrofuran

G.-Q Guo, Y-J. Sun and Y.-C. Long 331

03-P- 10 - Utilization of dry-gel conversion method for the synthesis of

gallosilicate zeolites Beta, ZSM-5 and ZSM- 12
R. Bandyopadhyay, Y. Kubota, S. i Nakata and Y. Sugi 331

03-P-11 - A novel method for the synthesis of cancrinite type zeolites

C.F. Linares, S. Madriz, M.R. Goldwasser and C. Urbina de Navarro 331

03-P-12 - High-throughput strategies for the hydrothermal synthesis of zeolites

and related materials
N. Stock, N. Hilbrandt, K. Choi and T. Bein 332

03-P-13 - Static zeolite MCM-22 synthesis using two-level factorial design

J. Warzywoda, S. Dumrul, S. Bazzana and A. Sacco, Jr. 332

03-P-14 - Influence of nano-particle agglomeration on the catalytic properties of

MFI zeolite
S. Inagaki, I. Matsunaga, E. Kikuchi and M. Matsukata 332

03-P-15 - Rapid and mass production of porous materials using a continuous

microwave equipment
D.S. Kim, J.M. Kim, J.-S. Chang and S.-E. Park 333

03-P- 16 - Hydrothermal synthesis of vanadium-containing microporous

aluminophosphates via the design of experiments approach
L. Frunza, P. Van Der Voort, E.F. Vansant, R.A. Schoonheyd and B.M.
Weckhuysen 333
 xxvii

03-P-17 - Synthesis of a thin Silicalite-1 membrane, through sintering, for use in a

membrane reactor
E.E. McLeary, A. W. Hoogesteger, R.D. Sanderson and J.C. Jansen 333

03-P-18 - Mixed alkali templating in the Si/A1 = 3 and 10 systems: a combi-

natorial study
G.J Lewis, D.E. Akporiaye, D.S. Bem, C. Bratu,.I.M. Dahl, A. Karlsson, R.C.
Murray, R.L. Patton, M. Plassen and R. Wendelbo 334

03-P-19 -Factors affecting composition and morphology of mordenite

F. Hamidi, M. Pamba, A. Bengueddach, F. Di Renzo and F. Fajula 334

04- Isomorphous Substitutions

04-0-01 - Direct synthesis of Cu(I)-MFI zeolite in the presence of Cu(II)

methylamino complexes as mineralizing and reducing agents
S. Valange, F. Di Renzo, E. Garrone, F. Geobaldo, B. Onida and Z. Gabelica 175

04-0-02 - Preparation and catalytic properties of a novel type of zeolites with

basic properties
S. Ernst, M. Hartmann and S. Sauerbeck 175

04-0-03 - Preparation and characterization of iron-substituted zeolites

G. Giordano, A. Katovic, A. Fonseca and J. B.Nagy 175

04-0-04 - Influence of the nature of T atoms on the morphology and crystal size
of KZ-2 and ZSM-22 zeolites isomorphously substituted with AI or Fe
M. DerewihskL M. Kasture, J. Krydciak and M. Stachurska 176

04-0-05 - Synthesis and characterisation of novel large-pore vanadosilicates AM-

13 and AM-14
P. Brand6o, A. Philippou, N. Hanif, J. Rocha and M. Anderson 176

04-P-06 - Uniform distribution of nickel during the synthesis of Si-ZSM-5

through solid-state transformation
M. Salou, Y. Kiyozumi, E Mizukami, S. Niwa, M. lmamura and M. Haneda 335

04-P-07-Synthesis, characterization and catalytic activity of FeBEA and FeMFI

zeolite obtained by xerogel wetness impregnation
O.A. Anunziata, L.B. Pierella, E.J. Lede and F.G. Requejo 335

04-P-08 - A novel method for the synthesis of chromium aluminosilicate with

BEA structure
X.-H. Tang, L.-R. Pan, J.-Z. Wang and H. -X. Li 335
xxviii

04-P-09 - Pure SAPO, CoAPSO and ZnAPSO ATO-like molecular sieves through
optimized synthesis procedures
A. Azzouz, N. Bflba, M. Attou, A. Zvolinschi and S. Asaftei 336

04-P-10 - Relation between amount of the niobium ammonium complex in the

reaction mixture and the crystal size of an Nb- MFI zeolite
H. Munhoz Jr., S. Rodrigues," P.K. Kiyohara and W. Sano 336

04-P-11 - Spectroscopy of the formation of microporous transition-metal ion

containing aluminophosphates under hydrothermal conditions
B.M. Weckhuysen, D. Baetens and R.A. Schoonheydt 336

04-P-12 - Co-templated synthesis of CrAPO-5 with various organic acids

J. Kornatowski, G. Zadrozna, J.A. Lercher and M. Rozwadowski 337

04-P-13 - How to increase the amount of framework Co 2+ in microporous

crystalline aluminophosphates?
W. Fan, R.A. Schoonheydt and B.M. Weckhuysen 337

0 4 - P - 1 4 - Preparation of zinc containing zeolite catalysts

A. Katovic, E. Szymkowiak, G. Giordano, S. Kowalak, A. Fonseca and J. B.Nagy 337

04-P-15 - Synthesis of Zn and Fe substituted mordenite using citric acid as

complexing agent
M. Dong, J.-G. Wang and Y.-H. Sun 338

04-P-16 - ET(Zr)S-4 molecular sieve' kinetic and morphological characterization

D. Vuono, P. De Luca, A. Fonseca, J. B.Nagy and A. Nastro 338

0 4 - P - 1 7 - Influence of alcali cations on the incorporation of iron into MFI

structure in fluoride media
F. Testa, F. Crea, R. Aiello, K. L6zdr, P. Fejes, P. Lentz and J. B.Nagy 338

04-P-18 - Synthesis and characterization of Co-containing zeolites of MFI

structure
E. Nigro, F. Testa, R. Aiello, P. Lentz, A. Fonseca, A. Oszko, P. Fejes, A.
Kukovecz, I. Kiricsi and J. B.Nagy 339

05 - Synthesis of New Materials

05-0-01 - SOMS: Sandia Octahedral Molecular Sieves. A new class of ion

exchangers selective for the removal of Sr 2÷ from waste streams
T.M. Nenoff M. Nyman, A. Tripathi, J.B. Parise, W.T.A. •Harrison
and RS. Maxwell 156
 xxix

05-0-02 - Hydrothermal synthesis of various titanium phosphates in the presence

of organic amine templates
Yunling Liu, Y. Fu, J. Chen, Y. Zou and W. Pang 157

05-0-03 - On the role of azamacrocycles and metal cations in the syntheses of

metalloaluminophosphates STA-6,-7 a n d - 8
R. Garcia, E.F. Philp, A.M.Z Slawin, P.A. Wright and P.A. Cox 157

05-0-04 - Chiral transference and molecular recognition in novel Co(en)3Cla-

templated zinc phosphates
J. Yu, Yu Wang, Z Shi and R. Xu 157

05-0-05 - Very open microporous materials: from concept to reality

A.K. Cheetham, H. Fjellvgtg, T.E. Gier, K.O. Kongshaug, K.P. Lillerud and G.D.
Stucky 158

05-P-06 - Synthesis and structures of GIS, ABW and GME beryllophosphate

molecular sieves from amine solutions
H. Zhang, M. Chen, Z. Shi, Y. Zhou, Xin Xu and D. Zhao 244

05-P-07 - Microporous gallosilicate TNU materials and their implications for the
synthesis of low-silica molecular sieves
W.C. P a i l M.A. Camblor and S.B. Hong 244

05-P-08 - Synthesis and characterization of novel nickel phosphates from non-

aqueous systems
Yunling Liu, L. Zhang, P. Zhang, Y. Zou and W. Pang 244

05-P-09- Synthesis, characterization and properties of an anionic

aluminophosphate molecular sieve with Br6nsted acidity
W. Yan, J. Yu, R. Xu, Y. Han, K. Sugiyama and O. Terasaki 245

05-P-10 - Synthesis and characterization of an open-framework aluminophosphate

[AIP206(OH)2][H30] containing propeller-like chiral motifs
W Fan, J. gu, Z Shi and R. Xu 245

05-P-11 - Synthesis and characterization of an aluminum-substituted manganese

phosphate with GIS topology
H.-M. Yuan, Y.-S. Jiang, W. Chen, J.-S. Chen and R. Xu 245

05-P-12 - Synthesis and characterisation of novel microporous framework cerium

and europium silicates
D. Ananias, P. Ferreira, A. Ferreira, J. Rocha, J.P. Rainho, C.M. Morals
and L.D. Carlos 246
xxx

05-P-13 - Novel microporous framework stannosilicates

Z. Lin and J. Rocha 246

05-P- 14 - Magadiite intercalated M C M - 2 2

M. MunsignattL A.J.S. Mascarenhas, A.L.S. Marques and H. O. Pastore 246

05-P-15 - Synthesis of aluminum phosphite microporous materials

N. Li and S. Xiang 247

0 5 - P - 1 6 - Synthesis, characterization and structural aspects of novel microporous

indium
L.M. King, J. Gisselquist, S.C. Koster, D.S. Bem, R.W. Broach, S.G. Song
and R.L. Bedard 247

05-P-17 - Synthesis and characterization of the silicoaluminophosphate SAPO-47

L. Xu, Z. Liu, P. Tian, Y. Wei, C. Sun and ShL Li 247

05-P-18 - Synthesis, characterization and catalysis of SAPO-56 and MAPSO-56

molecular sieves
P Tian, Z. Liu, L. Xu and C. Sun 248

05-P-19 - Synthesis and structural characterization of a novel microporous zeolitic

type aluminium phosphate
C. Sassoye, S. Girard, C. Mellot-Draznieks, T. Loiseau, C. Hugeunard, F.
Taulelle and G. Fdrey 248

05-P-20 - Hydrothermal synthesis and crystal structures of two novel open

frameworks: (enH2)3[Co3W4P4028] and (dapH2)3[Co3WnP4028]
B. Yah, Y. Xu, N.K. Goh and L.S. Chia 248

06- Fundamentals of Micelle Templating

06-0-01 - The effect of stoichiometry and synthesis conditions on the properties

of mesoporous M41S family silicates
W.J. Roth and J. C. Vartuli 134

06-0,02 - What are circular crystals?

F. Marlow 134

06-0-03 - Hierarchically mesostructured zeolitic materials with the MFI structure

D. Trong On, P. Reinert, L. Bonneviot and S. Kaliaguine 135

06-0-04 - Pore size engineering of MCM-48: The use of different additives as

expanders
M. Mathieu, E. Van Bavel, P Van Der Voort and E.E Vansant 135
 xxxi

06-P-05 - X-ray diffraction analysis of ordered mesoporous silica

M. Ookawa, Y. Yogoro, T. Yamaguchi and K. Kawamura 198

06-P-06 - Active MCM-48 supported catalysts: different strategies to increase the

structural and chemical stability
P. Van Der Voort, M. Mathieu and E.F. Vansant 198

06-P-07 - Strong acidic and high temperature hydrothermally stable mesoporous

aluminosilicates with well-ordered hexagonal structure
Zo. Zhang, Y. Han, R. Wang, S. Qiu, D. Zhao and F.-S. Xiao 198

06-P-08 - Studies on the synthesis of A I - l V I C M - 4 1 mesoporous materials

G.A. Eimer, L.B. Pierella and O.A. Anunziata 199

06-P-09 - Controlled synthesis of microporous and mesoporous silica-based

molecular sieves in the presence of dodecyldimethylbenzylammonium chloride
Z Y. Yuan, W. Zhou, L.M. Peng, J.-Z Wang and H.X. Li 199

06-P-10 - Formation of double-mesopore silica and its transformation into

MCM-41
X.-Z. Wang, T. Dou, Y.-Z. Xiao and BI Zhong 199

06-P-11 - The synthesis and hydrothermal stability of directly usable hexagonal

mesoporous silica by efficient primary amine template extraction in acidified
water
K. Cassiers, P. Van Der Voort and E.F. Vansant 200

06-P-12 - Synthesis and characterization of highly ordered chromium-substituted

MCM-48 materials with tailored pore sizes
C. Pak and G.L. Haller 200

06-P-13 - Preparation and characterisation of mesoporous silica spheres

R. Van Grieken, D.P. Serrano, C. Martos and A.M. Melgares 200

06-P-14 - Rapid synthesis of high quality MCM-41 silica via ultrasound

irradiation
X.-H. Tang, Yanquing Wang, W Huang, S. Liu, O. Palchik, E. Sominski, Y.
Koltypin and A. Gedanken 201

06-P-15 - Synthesis of mesoporous aluminosilicate FSM-materials derived from

synthetic and natural Saponite
T. Linssen, M. Barroudi, P. Cool and E.F. Vansant 201

06-P-16 - 129Xe NMR and adsorption studies of Si-MCM-48 and A1-MCM-48

G. Oye, M.-A. Springuel-Huet, J. Fraissard, M. StOcker and J. Sjoblom 201
xxxii

06-P-17 - 27A1.NMR studies on A1-MCM-41 molecular sieves synthesized with

different Si/AI ratios and different aluminum sources
W. BOhlmann and D. Michel 202

06-P-18 - Control of formation of mesoporous SBA-3 and SBA-1 through organic

additives
S. Che and T. Tatsumi 202

06-P-19 - The influence of A1, La or Ce in the thermal and hydrothermal

properties of MCM-41 mesoporous solids
R.A.A. Melo and E.A. Urquieta-Gonzdlez 202

06-P-20- Controlling the assembly of silica mesoporous materials by varying the

decrease in pH
J. Rathous~, J. Cejka, P.J. Kooyman, M. Slabovd and A. Zukal 203

06-P-21 - Characterisation of MCM-41 aged for different periods

H. Al-Megren, T.-C Xiao, A.P.E. York, J. Sloan, S. Al-Khowaiter, S.-E Ji and
ML.H. Green 203

06-P-22 - Synthesis and characterization of silica and aluminosilica-surfactant

nanocomposites
E. Popovici, A. Visan, D. Filip, G. Burtica and R. Pode 203

06-P-23 - Improved thermal stability of mesoporous alumina support of catalysts

for the isomerization of light paraffins
V. Gonzdlez-Peha, C. Mdrquez-Alvarez, E. Sastre and J. Pdrez-Pariente 204

06-P-24 - Synthesis of mesoporous molecular sieves MCM-48 under several

reaction conditions
S. Rodrigues da Rocha and L. Domiciano Fernandes 204

06-P-25 - Parallel synthesis of mesostructured materials

P. Behrens and C. Tintemann 204

06-P-26 - Mesostructural transformation in the presence of fluoride anions

Q-H. Xia, K. Hidajat and S. Kawi 205

06-P-27 - Swelled Micelle-Templated Silicas (MTS): structure control and

hydrophobic properties
D. Desplantier-Giscard, A. Galarneau, F. Di Renzo and F. Fajula 205

06-P-28 - Synthesis of pure and iron-containing mesoporous silica. Effect of

washing and removal of template on the porous structure
L. Pasqua, E Testa, R. Aiello, E Di Renzo and E Fajula 205
 xxxiii

07 - N e w M e s o p o r o u s M o l e c u l a r Sieves

07-0-01 - Ordered mesoporous carbon molecular sieves by templated synthesis:

the structural varieties
R. Ryoo, S.H. Joo, S. Jun, T. Tsubakiyama and O. Terasaki 150

07-0-02 - One-pot synthesis of phenyl functionalized porous silicates with

hexagonal and cubic symmetries
V. Goletto, M. Impdror and F. Babonneau 150

07-0-03 - State and redox behavior of iron in MCM-41

G. Pdl-Borb~ly, A. Szegedi, K. L6zdr and H.K. Beyer 150

07-0-04 - A comparative study of Cu interaction with niobium- and aluminum-

containing MCM-41 molecular sieves
M. Ziolek, I. Sobczak, I. Nowak, P. Decyk and J. Stoch 151

07-0-05 - A novel synthesis strategy leading to the formation of stable transition-

metal-oxide mesostructures
X.S. Zhao, J. Drennan and G.Q. Lu 151

07-P-06 - Vanadosilicate: Cubic mesoporous molecular sieve

M. Chatterjee, T. lwasaki, Y. Onodera, H. Hayashi, T. Ebina and T. Nagase 249

07-P-07 - Synthesis and characterization of mesoporous Cu-silica spheres via a

novel co-assemble route
P. Zhang, N. Bai, X. Meng and W. Pang 249

07-P-08 - Synthesis and characterization of mesostructured alumina prepared in

the presence of dodecylphosphate
L. Sicard, B. Lebeau, C. Marichal, J. Patarin and F. Kolenda 249

07-P-09 - Synthesis and characterizations of mesoporous zirconia-based oxide

composites
J. Zha, D. Wu, Y.-H. Sun," Zh. Zhang, H. Zhang and D. Zhao 250

07-P-10 - Preparation and catalytic property of FeL/Y composite by a new

method
B. Fan, W. Fan and R. L i 250

07-P-11 - Mesoporous zirconia: an anionic surfactant inorganic composite,

precursor of a tridimensional porous material.
G. Pacheco and J.J. Fripiat 250

07-P-12 - Synthesis of micelle templated TiO2 mesophases by a sol-gel approach:

effect of the surfactant removal
D.P. Serrano, G. Calleja, R. Sanz and P. Pizarro 251
xxxiv

07-P-13 - Preparation and characterization of iron oxide nanoparticles in the

channels of MCM-41
C.M. Yang and K.J. Chao 251

07-P-14 - The evaluation of iron chromophore concentrations from iron

containing MCM-41
C. Nenu, R. Ganea, R Bfrjega, Gr. Pop and M. Pitu 251

07-P-15 - Synthesis and characterization of the mesoporous material of single

crystal particles
B. Lee, J. N. Kondo, D. Lu and K. i Domen 252

07-P-16 - Stabilization of uniformly sized and dispersed copper particles in new

Cu-Zn-A1 mesoporous catalysts
S. Valange, J. Barrault, A. Derouault and Z. Gabelica 252

07-P-17 - A direct synthesis route to the mesoporous silicate SBA-2 bearing thiol
groups
I. Diaz, F. Mohino, J. Pdrez-Pariente, E. Sastre, P.A. Wright and W. Zhou 252

07-P-18 - Template synthesis and characterisation of nanoporous alumina with

narrow pore size distribution from inorganic salts
H. Y. Zhu, P. Cool G. Q. (Max) Lu and E. F Vansant 253

07-P-19 - Preparation and characterization of copper oxide modified MCM-41

molecular sieves
C. Minchev, R. KOhn, T. Tsoncheva, M. Dimitrov and M. Fr6ba 253

07-P-20 - Crystalline, mesoporous NiO-ZrO2-based solid oxide fuel cell catalysts

P. Ratnasamy, D. Srinivas, H.S. SonL A.J. Chandwadkar, H.S. Potdar,
C.S. Gopinath and B.S. Rao 253

07-P-21 - Application of the AASBU method to the prediction of inorganic

structures built exclusively of sodalite cages
S. Girard, P. PullumbL C. Mellot-Draznieks and G. F~rey 254

07-P-22 - Novel synthesis of nanoporous carbons using colloidal templates

S.B. Yoon, 1.S. Shin and J.-S. Yu 254

07-P-23 - Synthesis and characterization of mesoporous cerium silicate analogues

of MCM-41 type molecular sieves
S. Laha, P. Mukherjee and R. Kumar 254
 XXXV

07-P-24 - Synthesis of mesoporous materials using filtrate of alkali treatment of

MFI zeolite
M. Ogura, E. Kikuchi and M. Matsukata 255

08- Syntheses with Non-Ionic surfactants

08-0-01 - Mesoporous MSU-X silica tuned for filtration and chromatography

applications
C. Boissibre, A. Larbot and E. Prouzet 179

08-0-02 - Highly ordered mesoporous silicas synthesis using deca(oxyethylene)

oleylether as surfactant: variation of the weight percentage of surfactant and
incorporation of transition metal cations
G. Herrier and B.-L. Su 180

08-0-03 - Silica walls of calcined mesostructured SBA-15 materials templated by

triblock copolymers
M. Imp&or and A. Davidson 180

08-0-04 - Template / AISBA-15 interaction: double resonance N M R study and

consequences on structural properties
J.-B. d'Espinose de la Caillerie, Y. Yue and A. Gdd~on 180

08-P-05 - The double-step synthesis of MSU-X silica: decoupling the assembly

mechanism
E. Prouzet, C. BoissiOre, N. Hovnanian and A. Larbot 284

08-P-06 - Steam - stable aluminosilicate MSU-S mesostructures assembled from

zeolite seeds
Yu Liu, W. Zhang and T.J. Pinnavaia 284

08-P-07 - A study on the mesoporous silica structures templated by triblock

copolymers
C.-P. Kao, H.-P. Lin, M.-C. Chao, H.-S. Sheu and C.-Y. Mou 284

08-P-08 - Study of methyl modified MSU-X silicas

Y. Gong, Z Li, S. Wan, D. Wu, Y.-H. Sun, F. Deng, Q. Luo and }1. Yue 285

08-P-09 - Study of mesoporous materials with ultra high surface area prepared
from alternate surfactants and silicate sources
J. F. P~rez-Ardvalo, J.M. Dominguez, E. Terrds, A. Rojas-Herndndez and M. Miki 285

08-P-10 - Synthesis and catalytic properties of SO3H-mesoporous materials from

gels containing non-ionic surfactants
1. Diaz, F. Mohino, E. Sastre and J. Pdrez-Pariente 285
xxxvi

08-P-11 - Secondary hydrolysis process to synthesize highly ordered mesoporous

silica from nonionic surfactant with long hydrophilic chain
J. Fan, C. Yu and D. Zhao 286

08-P-12 - Mesostructure design using mixture of nonionic amphiphilicblock

copolymers
J.M. Kim, S.-E. Park and G.D. Stucky 286

08-P-13 - Stability of mesoporous material SBA-15 and its benefit in catalytic

performance
C. Nie, L. Huang, D. Zhao and Q. Li 286

08-P-14 - Comparative study of the wall properties in highly-ordered silicate and

aluminosilicate mesostructured materials of the MCM-41 and SBA-15 types
L.A. Solovyov, V.B. Fenelonov, A. Yu. Derevyankin, A.N. Shmakov, E. Haddad, A.
Gedeon, S.D. Kirik and V.N. Romannikov 287

09-Crystal Structure Determination

09-O-01 - Localisation of K + ions in (Na,K)-LSX and K-LSX zeolites by Rietveld

analysis and 39KNMR spectroscopy. A new cationic site in the orthorhombic
dehydrated K-LSX at room temperature
J.L. Paillaud, P. Caullet, L. Delmotte, J.C. Mougenel, S. Kayiran and B. Lledos 163

09-0-02 - NMR crystallography of A1PO4-CJ2

F. Taulelle and C. Huguenard 163

09-0-03 - FOS-5, a novel zeotype with 3D interconnected 12- ring channels

T. Conradsson, X. Zou and M.S. Dadachov 164

09-0-04 - Neutron diffraction study of protons in four lanthanum exchanged X

and LSX zeolites
D.H. Olson, B.H. Toby and B.A. Reisner 164

09-0-05 - Optimized synthesis and structural properties of lithosilicate RUB-29

So-Hyun Park, J.B. Parise and H. Gies 164

09-P-06 - Crystal structure of a cadmium sorption complex of dehydrated fully

Cd(II)-exchanged zeolite X
E. E Choi, S.H. Lee, Y.W. Han, E Kim and K. Serf 288

09-P-07 -The structure of a copper molybdate and its relation to other natural and
synthetic porous materials based on transition metal polyhedra
L. A. Palacio, A. Echavarria, A. Simon and C. Saldarriaga 288
 xxxvii

09-P-08 - A 3-D open-framework nickel aluminophosphate [NiA1P2Os][C2N2H9]:

assembly of 1-D AIP2083 chains through [NiOsN] octahedra
B. Wei, Jihong Yu, Guangshan Zhu, F. Gao, Y. Li, R. Wang, Bo Gao, Xian. Xu, S.
Qiu and O. Terasaki 288

09-P-09 - Structural modifications induced by high pressure in scolecite and

heulandite: in-situ synchrotron X-ray powder diffraction study
G. Vezzalini, S. Quartieri, A. Sani and D. Levy 289

09-P- 10 - Preparation, characterization, and crystal structures of fully indium-

exchanged zeolite X
N.H. Heo, S. W. Jung, S.W. Park J.S. Noh, W.T. Lim, M. Park and K. Serf 289

09-P-11 - Structural investigation by powder X-ray diffraction and solid state

nuclear magnetic resonance of A1PO4-SOD
M. Roux, C. Marichal, d.L. Paillaud, L. Vidal, C. Fernandez, C. Baerlocher
and J.M. Chezeau 289

09-P-12 - Layered germanates with 9-membered rings

X. Zou, T. Conradsson and M.S. Dadachov 290

09-P-13 - Dehydration dynamics of mordenite by in-situ time resolved syn-

chrotron powder diffraction study: a comparison with electrostatic site energy
calculations.
A. Martucci, M. Sacerdoti and G. Cruciani 290

09-P-14 - Study of water vapor adsorption in the organically-lined channels of

A1MepO-13 using X-ray powder diffraction
K. Maeda, L.B. McCusker and C. Baerlocher 290

10- Host-Guest Chemistry

10-O-01 - Investigation of indium loaded zeolites and additionally promoted

catalysts for selective catalytic reduction of NO× by methane
F.-W. Schatze, H. Berndt, M. Richter, B. L~icke, C. Schmidt, T. Sowade
and W. Granert 135

10-0-02 - Ion exchange of alkali metals and control of acidic/basic properties of

MCM-22 and MCM-36
J.-O. Barth, R. Schenkel, J. Kornatowski and J.A. Lercher 136

10-0-03 - Insertion compounds of metal halides with porosils: "Structured Gases"

P. Behrens, M. Hard, G. Wirnsberger, A. Popitsch and B. Pillep 136
xxxviii

10-0-04 - Site selective adsorption and catalytic properties of iron in FER and
BEA zeolites
Z Sobalik, J.E. Sponer, Z. Tvarfi~,kovd, A. Vondrovd, S. Kuriyavar
and B. Wichterlovd 136

10-P-05 - Non-acidic zinc zeolite systems: preparation methods, formation

processes and catalytic properties in dehydrogenation of methanol
N. Ya. Usachev, E.P. Belanova, A. V. Kazakov, V.P. Kalinin, A.S. Fomin, 1.M.
Krukovsky, G. V. Antoshin and O.K. Atal 'yah 206

10-P-06 - Incorporation of Ga ions into Y zeolites by reductive solid-state ion

exchange
R.M. MihdlyL H.K. Beyer and M. Keindl 206

10-P-07 - Heavy metal exchanged zeolites as precursors for high temperature

stable phases
W. Schmidt and C. Weidenthaler 206

10-P-08 - Preparation and characterization of H-ZSM-5 exchanged with cobalt by

solid state ion exchange
M. Mhamdi, S. Khaddar-Zine, A. Ghorbel, Y. Ben Taarit and C. Naccache 207

10-P-09 - Cyclic chemical vapour deposition of TEOS on ZSM-5: effect of

deposition temperature on shape selective performance
H. Manstein, K.P. Moller and C.T. O'Connor 207

11 - Post-synthesis Modification

11-O-01 - Gold-based mono- and bimetallic nanoparticles on HY zeolites

G. Riahi, D. Guillemot, M. Polisset-Thfoin, D. Bonnin and J. Fraissard 141

11-O-02 - Unravelled from the back: kinetics of alkoxysilane CVD on zeolites

and evidence for pore mouth plugging determined from model conversion over
stepwise silanised samples
H.P. ROger, H. Mantein, W. BOhringer, K.P. MOller and C.T. O'Connor 142

11-O-03-Templating role of F towards D4R units : study of the transformation of

the fluorogallophosphate Mu-3 into Mu-2
A. Matijasic, P. Reinert, L. Josien, A. Simon and J. Patarin 142

11-O-04 - Modification of the Si/Ti ratio in ETS-10

G. Koermer, A. Thangaraj and S. Kuznicki 142

11-O-05 - Binuclear oxo-Fe species in Fe/ZSM-5 catalyst prepared by chemical

vapour deposition
P Marturano, L. Drozdovd, A. Kogelbauer and R. Prins 143
 xxxix

1 l-P-06 - Dealumination of zeolite KL

E.E. Knyazeva, V.V. Yuschenko, F. Fajula and I.I. Ivanova 208

1 l-P-07 - Formation of acidic hydroxyl groups during preparation of Pt/KL

catalysts as studied by ~H MAS NMR
T. Sato, S.-I. 1to, K. Kunimori and S. Hayashi 208

1 l-P-08 - Synthesis and characterization of mesopore Y Zeolite

B. Ma, W.F. Sun, Z.L. Sun and L.R. Chen 208
1 l-P-09 - Controlling the pore size of Hi3 zeolite by improved chemical vapor
deposition of (CH3)3Si-O-Si(CH3)3
Y. Chun, X. Ye, Q.H. Xu and A.-Z. Yan 209

1 l-P- 10 - Influence of pH of the solution on realumination of BEA zeolite

Y. OumL R. Mizuno, K. Azuma, S. Sumiya, S. Nawata, T. Fukushima, T. Uozumi
and T. Sano 209

1 l-P-11 - Formation of carbon-intercalated molybdenum sulfides

J.-S. Chen, Y. Wang, Y. Guo, Y. Zou and W. Xu 209

1 l-P- 12 - Characterization of partly-detemplated GaPO4-LTA

S.-F. Yu, C.-Y. Xi, H.-M. Yuan and J.-S. Chen 210

1 l-P-13 - Another study on the microwave heating of zeolite - without special

loading materials
J. Dong, L. Xie, X. Jing, H. Xu, F. Wu and J. Hao 210

1 I-P-14 - Microwave plasma treatment as an effective technique for activation of

zeolite catalysts
I.I. Lishchiner, O. V. Malova and E.G. Krasheninnikov 210

1 l-P-15 - Synthesis and characterization of microporous titanium-silicate

materials
S. Mintova, B. Stein, J.M. Reder and T. Bein 211

1 l-P-16 - From borosilicate to gallo- and aluminosilicate zeolites: new methods

for lattice substitution via post-synthetic treatment
C.Y. Chen and S. 1. Zones 211

1 l-P-17 - Studies on the structure of zeolite Y modified by radio-frequency

fluorocarbon plasma treatment
S. Yamazaki, T. Nishimura, K. Furukawa, H. Ijiri and K. Tsutsumi 211

11-P-18 - Dual-temperature reagent-less ion-exchange separations on zeolites

V.D. Timofeevskaja, O.T. Gavlina, V.A. Ivanov and El. Gorshkov 212
1 l-P-19 - Rare earth exchange in small pore zeolites and its effect on their
hydrothermal stability
G. Cao, M.J. Shah and W.A. Wachter 212

1 l-P-20 - Modification of mordenite and natural clinoptilolite by copper: role of

drying temperature
I. Rodriguez-lznaga, V. Petranovskii, G. Rodriguez-Fuentes, N. Bogdanchikova
and 3/1. Avalos 212

1 l-P-21 - Study on the acidity of modified HY zeolites prepared by combination

of chemical dealumination and hydrothermal treatment
M. Han, L.-P Zhou, X.-W. Li and L.-Q. She 213

11-P-22 - Modification of Beta-zeolite by dealumination and realumination

J. Y. Zhang, L-P. Zhou and X. W. Li 213

11-P-23 - Ultrastable zeolites Y (USY) modified with phosphorus and boron

A. V. Abramova, Ye. V. Slivinsky, L. Ye. Kitaev, A.A. Kubasov, H. Lechert,
W.D. Basler, V. V. Yushchenk and Z M. Matieva 213

11-P-24 - Structural properties and sieving effects of surface modified ZSM-5

S. Zheng, tl. Heydenrych, H.P. ROger, A. Jentys and J.A. Lercher 214

11-P-25 - The use of binary adsorption studies to investigate the effect of

hydrothermal treatment on zeolites Rho and Mordenite
L.H. Callanan, C.T. O'Connor and E. van Steen 214

11-P-26 - Acid sites in thermal transformations of Ca-rich clinoptilolite

G.P. Valueva, I.S. Afanassiev, E.A. Paukshtis, Y.V. Seryotkin, N.K. Moroz
and A.A. Budneva 214

11-P-27 - The effect of calcination on the isomorphously substituted microporous

materials using ozone
D. Mehn, A. Kukovecz, I. Kiricsi, F. Testa, E. Nigro, R. Aiello, G. Daelen,
P. Lentz, A. Fonseca and J. B.Nagy 215

11-P-28 - Alumination of siliceous zeolites

A. Omegna, M. Haouas, G. Pirngruber and R. Prins 215

11-P-29 - New hydrophobic Ti-Beta catalyst obtained by silylation and its

catalytic performance for olefin epoxidation.
A. Corma, M.E. D6mine, J.A. Gaona, M.T. Navarro, F. Rey and S. Valencia. 215

1 l-P-30 - MFI zeolite with uniform mesopores created by alkali treatment

M. Ogura, E. Kikuchi and M. Matsukata 216
 xli

12 - In-situ Spectroscopy and Catalysis

12-0-01 - 2D correlation IR spectroscopy of xylene isomerisation on H-MFI

zeolite
F. Thibault-Starzyk, A. Vimont and J.-P. Gilson 133

12-O-02 - Structure/reactivity correlation in Fe/ZSM5 for deNOx applications. In-

situ XAFS characterization and catalysis
A.A. Battiston, J.H. Bitter and D.C. Koningsberger 133

12-0-03 - Interaction of diazines with faujasites studied by IR spectroscopy,

temperature-programmed desorption, and molecular modeling methods
J. DObler, E. Geidel, B. Hunger, K.H.L. Nulens and R.A. Schoonheydt 133

12-0-04 - DRIFT study of dinitrogen and dihydrogen adsorption on Li- and Na-
forms of LSX zeolite
V.B. Kazansky, A.I. Serykh, E. Tichomirova, V. Yu Borovkov and M. Bulow 134

12-P-05 - Study of relationship between mordenite acidity and structure with

calcination temperature
Z. Zhu, Q. Chen and We. Chen 217

12-P-06 - Infrared observation of the stable carbenium ions formed by adsorption

of olefins on zeolite Y at low temperatures
S. Yang, J.N. Kondo and K. Domen 217

12-P-07 - Characterization of aluminosilicate zeolites by UV-Raman spectroscopy

Y. Yu, G. Xiong, C. Li and F.-S. Xiao 217

12-P-08 - Adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on sodium-

ion exchanged faujasites with different Si/A1 ratios
1.A. Beta, H. BOhlig, J. DObler, H. Jobic, E. Geidel and B. Hunger 218

12-P-09 - DRIFT and FTIR spectra of N2 and C2H4adsorbed on CuNaY

G. Habner and E. Roduner 218

12-P-10 - Raman study of the building units in the zeolite structure

P.P.H.J.M. Knops-Gerrits, X.-Y. Li, N.-T. Yu and P.A. Jacobs 218

12-P-11 - Positron annihilation study in MCM-41

1t. Y. Zhang, Y.J. He, Y.B. Chen, H.Y. Wang and T. Horiuchi 219

12-P-12 - N M R studies on the pyrrole adsorption over Na +, Li + exchanged

zeolites of type FAU
M. Sdlnchez-S6nchez and T. Blasco 219
xlii

12-P-13 - Variable-temperature FTIR study of the equilibrium between C-bonded

and O-bonded carbon monoxide in H-ZSM-5
G. Turnes Palomino, M. Peharroya Mentruit, A.A. Tsyganenko,
E. Escalona Platero and C. Otero Aredn 219

12-P-14 - Role of the various acid sites in MOR on o-xylene conversion: An in-
situ I.R. approach
O. Marie, F. Thibault-Starzyk, P. Massiani and J.C. Lavalley 220

12-P-15 - FTIR- Studies on adsorption and decomposition of NO on in-situ

synthesized ZSM-5/cordierite catalysts
N. Guan, X. Shan, X. Zeng, S. Xiang, A. Trunschke and M. Baerns 220

12-P-16 - Acid sites in dealuminated mordenite

V.L. Zholobenko and G.P. Mitchell 220

12-P-17 - Infrared study of iron-exchanged Y zeolite and its HDS activity

M Nagai, O. Uchino and S. Omi 221

13 - F r a m e w o r k s and Acid Sites

13-0-01 - Where are the acid sites in zeolites? A novel NMR approach to
measure B/A1 ordering around structure directing agents
H. Koller, M. Kalwei, C. Fild, R.F. Lobo, MA. Camblor, L.A. Villaescusa
and L. van W~illen 182

1 3 - 0 - 0 2 - The effect of the nature of heteroatoms (A1, Fe, B) on their distribution

in the ZSM-5 structure
J. D~degek, M. Tudor and J. (~ejka 182

13-0-03 - Toward the quantification of aluminum in zeolites using high-

resolution solid-state NMR
C. Fernandez, A.-A. Quoineaud, V. Montouillout, S. Gautier and S. Lacombe 183

13-0-04 - Acidity of ITQ-2 zeolite as studied by FT-IR spectroscopy of adsorbed

molecules in comparison with that of MCM-22
B. Onida, F. Geobaldo, L. Borello and E. Garrone 183

13-P-05 - In-situ FTIR studies of the acidity of H3PWl2040 and its porous salts.
Interaction with H20, NH3 and pyridine
N. Essayem, A. Holmqvist, G. Sapaly, J.C. V~drine and Y. Ben Tdarit 340

13-P-06 - Dynamics of p-nitroaniline in the micropore of zeolite ZSM-5 studied

by solid-state N M R
S. Hayashi and Y. Komori 340
 xliii

13-P-07 - The use of microcalorimetry to study the effects of post-synthesis

treatments on the modification of the acidity of several HY-type zeolites
A. Auroux and M.L. Occelli 340

13-P-08 - ESR investigations of the catalytic properties of Lewis acid sites in H-

mordenite
T.M. Leu and E. Roduner 341

13-P-09 - External surface acidity of modified zeolites: ESR via adsorption of

stable nitroxyl radicals and IR spectroscopy
A.B. Ayupov, G.V. Echevsky, E.A. Paukshtis, D.J. O'Rear and C.L. Kibby 341

13-P-10 - Very strong acid site in HZSM-5 formed during the template removal
step; its control, structure and catalytic activity
A. Kohara, N. Katada and M. Niwa 341

13-P-11- Correlation between liB NMR isotropic chemical shifts and structural
parameters in borates and boro-silicates
J. Pl~vert, F. Di Renzo and F. Fajula 342

13-P-12 - Investigation of the paramagnetic effect of oxygen in the Z3Na MAS

NMR and 23Na MQMAS NMR spectra of LiNaX
R.J. Accardi, M. Kalwei and R.F. Lobo 342

13-P-13 - Characterization of acidic sites in HY and LaY zeolites by laser-

induced fluorescence of adsorbed quinoline
A. Lassoued, J. Thoret, P. Batamack, A. Gdddon and J. Fraissard 342

13-P- 14 - Dynamic behaviour of acetonitrile molecules adsorbed in ALPO4-5 and

SAPO-5 studied by solid NMR method
S. lshimaru, M. lchikawa, K. Gotoh and R. lkeda 343

13-P-15 - Determination of the Si/A1 ratio of faujasite-type zeolites

C.H. Rascher, J.-C. Buhl and W. Lutz 343

13-P-16 - Theoretical investigation of the chemical shift anisotropy of toluene

adsorbed on zeolite X
A. Simperler, A. Philippou, D.-P. Luigi, R.G. Bell and M. W. Anderson 343

13-P-17 - Acid properties of dexydroxylated ferrierites studied by IR

spectroscopy
J. Datka, B. Gil and K. G6ra-Marek 344

13-P-18 - Aluminium species in activated zeolites: solid-state NMR spectroscopy

of the active sites
B.H. Wouters, T.-H. Chen and P.J. Grobet 344
xliv

13-P-19 - Aluminium distribution in high silica pentasil ring zeolites

B. Wichterlovd, J. Dgdedek, Z Sobalik and J. Cejka 344

13-P-20 - Effects of hydration on A1PO4-14 and AIPO4-18 structures: 31p MAS

and 27A1 3Q-MAS NMR study
C. V. Satyanarayana, R. Gupta, K. Damodaran, S. Sivasanker and S. Ganapathy 345

13-P-21 - Comparative study of the acidity of the structurally related faujasite

type zeolites: FAU, EMT and ZSM-20
H. Kosslick, R. Fricke, H. Miessner, D.L. Hoang and W. Storeck 345

13-P-22 - The effect of flexible lattice aluminum in zeolites during the nitration of
aromatics
M. Haouas, A. Kogelbauer and R. Prins 345

13-P-23 - Characterization of acidic sites in zeolites by heteronuclear double

resonance solid state NMR
S.B. Waghmode, A. Abraham, S. Sivasanker, J.P. Amoureux and S. Ganapathy 346

13-P-24 - Measurement of MQMAS heteronuclear correlation spectra in

microporous aluminophosphates
C. Fernandez and M. Pruski 346

13-P-25 - FTIR studies of the interaction of aromatic and branched aliphatic

compounds with internal, external and extraframework sites of MFI-type zeolite
materials
7". Armaroli, A. Guti~rrez Alejandre, M. Bevilacqua, M. Trombetta, F. Milella,
J. Ramirez and G. Busca 346

14- Frameworks, Cations, Clusters

14-0-01 - Imaging the mesopores in zeolite Y using three-dimensional

transmission electron microscopy
A.H. Janssen, A.J. Koster and K.P. de Jong 176

14-O-02 - 170 NMR studies of the structure and basic properties of zeolites
D. Freude, T. Loeser and U. Pingel 177

14-0-03 - Theoretical interpretation of UV-VIS spectra of Cu- and Ag-species in

zeolites: structure vs. transition energies.
P. Nachtigall, M. Davidov6, M. Silhan and D. Nachtigallovd 177

14-0-04 - Silver ions and quantum-sized silver sulfide clusters in zeolite A

D. Brtihwiler, C. Leiggener and G. Calzaferri 177
 xlv

14-O-05 - Elucidating the nature and reactivity of cobalt ions in CoAPOs. A

combined FTIR and EPR study of NO and NO2 adsorbed at 77 K and 298 K
E. Gianotti, M.C. PaganinL G. Martra, E. Giamello, S. Coluccia and L. Marchese 178

14-P-06 - Relaxation processes of Na ion in dehydrated Nal2-A zeolite

T. Ohgushi and K. Ishimaru 347

14-P-07 - Adsorption of DTBN at monovalent cations in zeolite y as studied by

electron spin resonance spectroscopy
M. Gutjahr, W. BOhlmann, R. BOttcher and A. POppl 347

14-P-08 - Nature of the active sites of Mo-containing zeolites. XANES studies at

Mo K and LIH-edges
F.G. Requejo, E.J. Lede, L.B. Pierella and O.A. Anunziata 347

14-P-09 - EPR studies on nitrogen monoxide in zeolites

H. Yahiro, N.P. Benetis, A. Lund and M. Shiotani 348

14-P-10 - Evidence of partially broken bridging hydroxyls in molecular sieves

from IH MAS spin echo NMR spectroscopy
T.-H. Chen, B.H. Wouters and P.J. Grobet 348

14-P-11 - Structure change of molecular sieve SAPO-37 at high temperature

studied by 27A1 MQ MAS NMR
T.-H. Chen, B. Wouters and P. Grobet 348

14-P-12 - Effects of molecular confinement on structure and catalytic behaviour

of metal phthalocyanine complexes encapsulated in zeolite-Y
S. Seelan, D. Srinivas, M.S. Agashe, N.E. Jacob and S. Sivasanker 349

14-P-13 - Investigations on isomorphous substitution and catalytically active

centres in MeAPO-31 (Me = Mn, Co, Zn, Ti)
N. Novak Tusar, A. Ristic, A. Ghanbari-Siahkali, J. Dwyer, G. Mali, I. Arcon
and V. Kaucic 349

14-P-14 - A comparative study of Ti 4+ sites in titanium silicalite (TS-1)

synthetized by different methods
N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, M.V. CagnolL S.G. Marchetti
and A.A. Yeramian 349

14-P-15 - Behaviour of Fe(III) ions in Y zeolites in the presence of Cu(II) and

Ag(I) ions: an ESR study
A.L. Kustov, E.E. Knyazeva, E.A. Zhilinskaya, A. Aboukais and B. V. Romanovsky 350

14-P-16 - FT-Raman spectroscopic studies of host-guest interactions in zeolites

Y. Huang, J.H. Leech and R.R. Poissant 350
xlvi

14-P-17 - High-temperature MAS NMR investigation of the mobility of cations

and guest compounds in zeolites X and Y
M. Hunger, A. Buchholz and U Schenk 350

14-P-18 - Generation of long-lived electron-hole pairs through sorption of

biphenyl into acidic ZSM-5 zeolites
I. Gener, A. Moissette, H. Vezin, J. Patarin and C. Br~mard 351

14-P-19 - Defects study in microporous materials by HRSEM, HRTEM and

diffraction techniques
G. Gonzalez, Z Lopez and R. Reichelt 351

14-P-20 - The effect of the framework structure on the chemical properties of the
vanadium oxide species incorporated within zeolites and their photocatalytic
reactivity
S. Higashimoto, M. Matsuoka, M. Che and M. Anpo 351

14-P-21 -Characterization of aluminium and iron sites in MCM-22

J. (;ejka, J. D~dedek, J. Kotrla, M. Tudor, N. Zilkovct and S. Ernst 352

14-P-22 - Valency and coordination states of iron in FeAPO-11. An in-situ

M6ssbauer study
K. L6z6r, N. Zilkov6 and J. Cejka 352

14-P-23 - C o m p a r a t i v e properties of modified HEMT and HY zeolites from the

FTIR study of CO adsorption: effect of the dealumination and amorphous debris
on the Br6nsted acidity
O. Cairon and T. Chevreau 352

14-P-24 - Raman spectroscopic study of 2,2'-bip;cridine sorbed into ZSM5

A. Moissette, C. Br~mard, 1. Gener and N. Louchart 353

14-P-25 - Fractals of silica aggregates

Z. Li, D. Wu, Y.-H. Sun, J. Wang, Yi Liu and B. Dong 353

14-P-26 - Structure of Mo species incorporated into SBA-1 and SBA-3 studied by

XAFS and UV-VIS spectroscopies
H. Yoshitake, S.H. Lim, S. Che and T. Tatsumi 353

14-P-27 - Quantification of electric-field gradients in the supercage of Y zeolites

by comparing the chemical shifts of 131Xe (I = 3/2) and 129Xe (I = 1/2)
Y. Millot, P.P. Man, M.-A. Springuel-Huet and J. Fraissard 354

14-P-28 - Iron species present in Fe/ZSM-5 catalysts prepared by ion exchange in

aqueous medium or in the solid state
M.S. Batista, M.A.M. Torres, E. Baggio-Saitovich and E.A. Urquieta-Gonz6lez 354
 xlvii

14-P-29 - Laser ablation mass spectrometry : a technique for observing zeolite

occluded molecules
S. Jeong, K.J. Fisher, G.D. Willett and R.F. Howe 354

14-P-30 - Characterisation of TS-1 active sites by adsorption of organic probes

C. Flego, A. Carati and M.G. Clerici 355

14-P-31 - NIR FT-Raman spectroscopy on molecular sieves

E. LOftier and M. Bergmann 355

14-P-32 - Characterization of Zn and Fe substituted mordenite by XAFS

M. Dong, J.-G. Wang and Y.-H. Sun 355

14-P-33 - Identification of vanadium species in VAPO and VAPSO

aluminophosphate by UV resonance raman spectroscopy
Jia. Yu, Z. Liu, Q. )(in and C. Li 356

14-P-34 - On the interaction of H20 with TS-1: a spectroscopic and ab-initio

study
A. Damin, G. Ricchiardi, S. Bordiga, F. Bonino, A. Zecchina, F. Ricci, G. Span6,
F. Villain, and C. Lamberti 356

14-P-35 - Spectroscopic study of the nature of vanadyl groups: influence of the

support (SiO z and All3 and SiB zeolites).
S. Dzwigaj, M. Matsuoka, M. Anpo and M. Che 356

14-P-36 - Characterization ofNi, Pt zeolite catalysts by TEM and EDX

M.H. Jord6o and D. Cardoso 357

14-P-37 - NMR and ESR investigations of alkali metal particles in NaY zeolite
F. Rachdi and L.C. de M~norvat 357

14-P-38 - Topochemical changes in large MFI-type crystals upon thermal

treatment in oxidizing and non-oxidizing atmosphere
O. Pachtov6, B. Bernaue, J.-A. Dalmon, S. Miachon, I. Jirka, A. Zik6nov6
and M. Kodi(ik 357

14-P-39 - Structure of Fe(III) sites in iron substituted aluminophosphates: a

computational and X-ray spectroscopic investigation
C. Zenonos, A. Beale, G. Sankar, D.W. Lewis, J.M. Thomas and C.R.A. Catlow 358

14-P-40 - Possible formation of Cu+2(CO)2(H20)n complexes in a ZSM-5 zeolit.e

prepared by direct synthesis: evidence for the occurrence of Cu+-Cu + pairs?
F. Geobaldo, B. Onida, M. Rocchia, S. Valange, Z Gabelica and E. Garrone 358
xlviii

15 - Modelling and Theoretical Studies A

15-0-01 - Proton jumps in dehydrated acidic zeolite catalysts. Rate predictions

based on ab-initio calculations
M. Sierka and J. Sauer 148

15-0-02 - Ab-initio simulation of dynamical processes in zeolites

L. Benco, T. Demuth, J.Hafner, F. Hutschka and 14. Toulhoat 148

15-0-03 - A theoretical study of the methylation of toluene by methanol over acid

mordenite
A. Vos, X. Rozanska, R. Schoonheydt, R. van Santen, F. Hutschka and J. Hafner 149

15-0-04 - Coverage effects on adsorption of water in faujasite: An ab-initio

cluster and embedded cluster study
J. Limtrakul, S. Nokbin, P. Chuichay, P. Khongpracha, S. Jungsuttiwong
and T.N. Truong 149

15-0-05 - The Beckmann rearrangement catalyzed by silicalite: a spectroscopic and

computational study
G.A. Fois, G. Ricchiardi, S. Bordiga, C. Busco, L. Dalloro, G. Span6
and A. Zecchina 149

15-P-06 - A reactivity index study to choose the best template for zeolite
synthesis
A. Chatterjee and T. lwasaki 256

15-P-07 - Effects of ion-exchanged alkali metal cations on the photolysis of alkyl

ketones included within ZSM-5 zeolite cavities: A study of ab-initio molecular
orbital calculations
H. Yamashita, S. Takada, M. Nishimura, H. Bessho and M. Anpo 256

15-P-08 - Encapsulated guest atoms within the basic beta cage of sodalitic zeolite.
A theoretical ab-initio study
N. U. Zhanpeisov and M. Anpo 256

15-P-09 - n-Hexane aromatization over Pt-alkaline zeolites: ab-initio calculations

on the influence of the exchanged cations and zeolite type (L, 13 and Y) on
electronic properties of Pt
S.B. Waghmode, P. Bharathi, R. Vetrivel and S. Sivasanker 257

15-P-10 - A theoretical study of adsorption of carbon monoxide on Ag-ZSM-5

zeolite
S. Jungsuttiwong, P. Khongpracha, T.N. Truong and J. Limtrakul 257

15-P-11 - A theoretical/spectroscopic study of the coordination of transition metal

ions in zeolites
A. Delabie, M.H. Groothaert, R.A. Schoonheydt and K. Pierloot 257
 xlix

15-P-12 - Ab-initio study of the adsorption and reactions of hydrocarbons in

mordenite
T. Demuth, L. Benco, J. Hafner, H. Toulhoat and F. Hutschka 258

15-P- 13 - Properties of C u 2+ and Cu + cations in MFI framework: DFT and IR

studies
E. Broclawik, J. Datka, B. Gil and P. Kozyra 258

15-P-14 - Nonempirical (ab-initio) and semiempirical calculations of the

elementary fragments of zeolites. Permeability of rings zeolite fragments
A.V. Gabdrakipov, L.D. Volkova, N.A. Zakarina and V.Z Gabdrakipov 258

15-P-15 - Modelling light alkane transformation over HZSM-5 zeolite

X. Wang, F. Lemos and F.R. Ribeiro 259

15-P-16 - Activity-acidity relationship in Y zeolite: an experimental and quantum-

chemical study
X. Wang, M.A.N.D.A. Lemos, F. Lemos, C. Costa and F.R. Ribeiro 259

15-P-17 - DFT study of structure changes in hydrated A1PO4-n: The case of

A1PO4-34
G. Poulet, A. Tuel and P. Sautet 259

15-P-18 - A mechanistic exploration of alkene epoxidation mediated by H202

within porous titanosilicate catalysts
C.M. Barker, N. Kaltsoyannis and C.R.A. Catlow 260

15-P-19 - Transition-state shape-selectivity insights from a Fukui function overlap

method
L.A. Clark and R. Q. Snurr 260

15-P-20 - A DFT study of the isomerization reactions of aromatics catalyzed by

acidic zeolites
X. Rozanska, R.A. van Santen, F. Hutschka and J. Hafner 260

15-P-21 - Ab-initio investigation of non-framework aluminum species in zeolites

D. Lopes Bhering, C.J.A. Mota and A. Ramirez-Solis 261

15-P-22 - A DFT study of the cracking reaction of thiophene activated by zeotype

catalysts: role of the basic Lewis site
X. Rozanska, R.A. van Santen and F. Hutschka 261

15-P-23 - Modelling transition metal cations in zeolites: how do they interact with
the framework?
D. Berthomieu, A. Goursot, J-M. Ducdr~, G. Delahay, B. Coq and A. Martinez 261
15-P-24 - Theoretical prediction of IR spectra of guest molecules in zeolites: the
stretching frequency of CO adsorbed at various cationic sites in ZSM-5
T.A. Wesolowski, A. Goursot and J. Weber 262

15-P-25 - Development of a tight-binding treatment for zeolites

M. Elstner, A. Goursot, Z. Hajnal, T. Heine and J. Weber 262

15-P- 26 - 1-D growth of selenium wires in silicalite-1 zeolite

C. Bichara and R.J.-M. Pellenq 262

15-P-27 - Cumulative coordinates for approximations of atomic multipole

moments in cationic forms of aluminosilicates
A. V. Larin and D.P. Vercauteren 263

15-P-28 - Computer simulations of water in zeolites

C. Bussaia, R. Haberlandt, S. Hannongbuai and S. Jost 263

16 - Modelling and Theoretical Studies B

16-0-01 Simulating shape selectivity in alkane hydroconversion by zeolites

M. Schenk, T.L.M. Maesen and B. Smit 155

16-O-02 - Molecular dynamics of the faujasite (111) surface

B. Slater and C.R.A. Catlow 155

16-0-03 - Adsorption of xylene isomers and water in faujasites.

A molecular simulation study
S. Buttefey, A. Boutin and A.H. Fuchs 155

16-0-04 - Reaction dynamics in acidic zeolites: room temperature tunneling

effects
J. T. Fermann and S.M. Auerbach 156

16-0-05 - Molecular modeling of multicomponent diffusion in zeolites and

zeolite membranes
M.J. Sanborn, A. Gupta, L.A. Clark and R.Q. Snurr 156

16-P-06 - Location of triethylmethylammonium ions in MFI by combining

molecular modeling and X-ray diffraction
R. Millini 264

16-P-07 - A hypothetical zeolite structure MCR16: topological design and

template choice
B. Li, P. Sun, Q. Jin and D. Ding 264
16-P-08 - Computational analysis of the shape-selective isopropylation of
biphenyl over large pore zeolites
J. Joffre, D. Mravee and P. Moreau 264

16-P-09 - De novo simulation and spectroscopic study of iron speciation in

ZSM-5 and CIT-5
P.-PH.J.M. Knops-Gerrits and W.A. Goddard III 265

16-P-10 - Exact statistical mechanical treatment of a lattice model of hydrocarbon

adsorption on zeolites
G. Manos, L.J. Dunne, Z Du and M.F. Chaplin 265

16-P-11 - Computational studies of the structure of Na- and H-Mordenite

A.E. Gray, A. 0 'Brien and D. W. Lewis 265

16-P-12 - Monte Carlo simulation of isobutane in silicalite

D. Paschek and R. Krishna 266

16-P- 13 - Characterisation of hypothetical zeolite frameworks

M.D. Foster, R.G. Bell and J. Klinowski 266

16-P-14 - Cation mobility and the sorption of chloroform in zeolite NaY: a

molecular dynamics study
N.A. Ramsahye and R.G. Bell 266

16-P- 15 - Computational studies of the calcination of fluorinated gallophosphates:

exploration of their template-free calcined forms
S. Girard, J.D. Gale, C. Mellot-Draznieks and G. Fdrey 267

16-P-16 - Molecular simulation studies on the effectiveness of template type on

TS- 1 crystal morphology
tl. Zhou, H. He and Z Jing 267

16-P-17 - A molecular dynamic approach on the selective conformational change

of ethylene glycol in sodalite cage
M. Sato 267

16-P-18 - The mutual influence of dynamic processes acting in different time

scales
S. Fritzsche, R. Haberlandt, A. Schfiring and M. Wolfsberg 268

16-P-19 - Lattice-dynamical calculations for zeolites of natrolite group

S. V. Goryainov and M.B. Smirnov 268

16-P-20 - Kinetic modelling of the dynamic interaction between NO and N20

over Cu-ZSM5
R. Pirone, P. Ciambelli, A. Di Benedetto, B. Palella and G. Russo 268
lii

17- Principles of Adsorption

17-0-01 - Liquid-solid and solid-solid phase transitions of oxygen in a single

cylindrical pore
K. Morishige and Y. Ogisu 137

17-0-02 - Structural study of benzene, tetrachloroethene and trichloroethene

sorbed phases in silicalite-1
N. Floquet, J.P Coulomb, G. Weber, O. Bertrand and J.P Bellat 137

17-0-03 - Molecular ordering of the adsorbed phase within the microporous

model aluminophosphate A1PO4-11 at cryogenic temperatures
N. Dufau, N. Floquet, J-P. Coulomb, P.L. Llewellyn and J. Rouquerol 137

17-0-04 - - Adsorption properties of a supercritical fluid on mesoporous

molecular sieves under high pressure
Ya. Goto, N. Setoyama, Y. Fukushima, T. Okubo, Yu. Goto, Y. lmada, Y. Kubota
and Y. Sugi 138

17-P-05 - Confinement in model host materials: experimental study of quasi-(1 d)

systems.
J.P. Coulomb, N. Floquet, C. Martin, Y. Grillet and J. Patarin 222

17-P-06 - Studies on desorption behavior of organics on siliceous ferrierite

B. Qian, Y. Zeng and Y.-C. Long 222

17-P-07 - Investigation of hydrocarbon adsorption on large and extra-large pore

zeolites
C. Y. Chen and S.I. Zones 222

17-P-08 - Different chemisorption methods applied to zeolite supported

Pt-catalysts
J.C. Groen, J. P~rez-Ramirez and L.A.A. Peffer 223

17-P-09 - Structure vs. adsorption properties of 5A zeolites

H. Paoli, T. Bataille, B. Rebours, A. M~thivier and H. Jobic 223

17-P-10 - Hydrogen adsorption in lithium exchanged Na A zeolites

S. Kayiran, F. Darkrim and A. Gicquel 223

17-P- 11 - Macroscopic and microscopic investigations of the interaction of a

chloroalkene on a MFI zeolite
V. Francois, S. Maure, F. Bouvier, G. Weber, O. Bertrand, J.P. Bellat
and C. Paulin 224

17-P-12 - Sorption and pore condensation behavior of pure fluids in mesoporous

MCM-48 silica, MCM-41 silica and controlled pore glass
M. Thommes, R. KOhn and M. FrOba 224
 liii

17-P-13 - Pore size analysis with H20 adsorption measurement of organically

modified MCM-41 type materials
N. Igarashi, K. Nakai, K. Hashimoto and T. Tatsumi 224

17-P-14 - Adsorption of carbon dioxide by X zeolites exchanged with Z n 2+ and

Cu2+: isosteric heat and adsorption isotherms
A. Khelifa, Z. Derriche and A. Bengueddach 225

17-P-15 - A combination of high resolution manometry, gravimetry and

microcalorimetry to study the co-adsorption of Ar/N2 mixtures on 5A and 13X
zeolites
S. Moret, F. Rouquerol, J. Rouquerol and P.L. Llewellyn 225

17-P-16 - Gas adsorption microcalorimetry on zeolites under supercritical

conditions up to 15 bars
T. Poyet, F. Rouquerol, J. Rouquerol and P.L. Llewellyn 225

18- Adsorption and Separation Process

18-0-01 - An experimental adsorbent screening study for CO2 removal from flue
gas
P.J.E. Harlick, H. Halsall-Whitney and F. Handan Tezel 143

18-0-02 - Amino acids in BEA type channels

C. Buttersack and A. Perlberg 143

18-O-03 - Kinetic separation of binary mixtures of carbon dioxide and C2

hydrocarbons on modified LTA-type zeolites
C.J. Guo, D. Shen and M. Btilow 144

18-0-04 - A novel adsorbent for the separation of propane/propene mixtures

W. Zhu, F. Kapteijn and J. A. Moulijn 144

18-0-05 - Iodide removal using zeolite-based reactive adsorption

S. Kulprathipanja and B. Spehlmann 144

18-P-06 - Evaluation of mesoporous silicas as stationary phases for high

performance liquid chromatography (HPLC)
L. Sierra, B. Lopez, A. Ramirez and J.-L. Guth 226

18-P-07 - Adsorption of N-nitrosamines by zeolites in solutions

Ying Wang, J.H. Zhu, D. Yan, W. Y. Huang and L.L. Ma 226

18-P-08 -An adsorption-desorption process for separation of C8 aromatics

G.-Q. Guo and Y.-C. Long 226
liv

18-P-09 - Preparation of Na-A zeolite capillary columns by in-situ synthesis

D. Kou, Z. Li, J. Wu, Ming Liu and S. Xiang 227

18-P-10 - Adsorption of C02, S02 and NH3 on zeolitic materials synthesized from
fly ash
S. Herndndez, R. Juan, X. Querol, N. Moreno, P. Ferrer and J.M. Andrds 227

18-P-11 - Dibenzothiophene adsorption over zeolites with faujasite structure

J.L. Sotelo, M.A. Uguina, M.D. Romero, J.M. G6mez, V.I. Agueda and M.A. Ortiz 227

18-P-12 - Pressure swing adsorption of ethyl acetate on silica MCM-41

S. Namba, D. Yomoda, J. Aoyagi, K. Minagawa, T. Kugita and J. Izumi 228

18-P-13 - P occlusion in LTA: an approach for enhancing N2 adsorption

properties
L. Johnson and M. Miller 228

18-P-14 - Sulfur guard bed material from local bentonite deposits

S. Mikhail and T. Zaki 228

18-P- 15 - Simulation for removal of binary solvent vapor by adsorption onto high
silica zeolite.
K. Chihara, T. Saito, H. Suzuki, H. Yamaguchi and Y. Takeuchi 229

1 9 - Diffusion: Fundamental Approach

19-0-02 - Studies of adsorption, diffusion and molecular simulation of cyclic

hydrocarbons in MFI zeolites
L. Song, Z L. Sun and L. V. C Rees 153

19-0-03 - The effect of silanisation on the intracrystalline diffusivity of ZSM-5

W.L. Duncan and K. P. MOller 154

19-0-04 - Interference microscopy as a tool of choice for investigating the role of

crystal morphology in diffusion studies
O. Geier, S. Vasenkov, E. Lehmann, J. Kgirger, R.A. Rakoczy and J. Weitkamp 154

19-0-05 - Estimation of the interphase thickness and permeability in polymer-

zeolite mixed matrix membranes
A. Erdem-~enatalar, M. Tather and ~.B. Tantekin-Ersolmaz 154

19-P-06 - Modeling of sulfur dioxide breakthrough curves from ternary wet

mixtures on MOR type zeolite
M. Mello, M. EiO, S. Ho&var and U. Lavrendid-Stangar 269
 lv

19-P-07 - The diffusion and sorption dynamics of acetylene in zeolites

Gy. Onyesty6k, J. Valyonand and L. K C. Rees 269

19-P-08 -Transient uptake measurements using an oscillating microbalance: effect

of acid leaching on the diffusivity of n-hexane in Pt/H-Mordenite
S. van Donk, A. Broersma, O.L.J. Gijzeman, J.H. Bitter and K.P. de Jong 269

19-P-09 - Use of 129XeNMR spectroscopy to study gaseous hydrocarbon

diffusion in a fixed bed of HZSM-5 zeolite
M.-A. Springuel-Huet, P N'Gokoli-Kekele, C. Mignot, J.-L. Bonardet
and J. Fraissard 270

19-P-10 - Adsorption and diffusion of alkanes and their mixtures in silicalite

studied with positron emission profiling technique
A. O. Koriabkina, D. Schuring, A.M. de Jong and R.A. van Santen 270

2 0 - Zeolite Membranes and Films

20-0-01 - Polyamines as strong covalent linkers for the assembly of mono and
double layers of zeolite crystals on glass
K. Ha, Y.S. Chun, A. Kulak, Y.S. Park, Y. -J. Lee and K.B. Yoon 161
20-0-02 - The use of seeds in the synthesis of mono-and bi-layered zeolite
membranes
L. Gora, G. Clet, J.C. Jansen and Th. Maschmeyer 162

20-0-03 - Growth of oriented mordenite membranes on porous (x-AI203 supports

G. Li, X. Lin, E. Kikuchi and M. Matsukata 162

20-0-04 - Depth-sensitive structural study of silicalite-1 films with grazing

incidence X-ray diffraction
S. Mintova, T.H. Metzger and T. Bein 162

20-0-05 - Regeneration of supercritical carbon dioxide by alumina supported MFI

zeolite and mesoporous silica membranes
K.J. Chao, C.H. Kao, Y.W. Chiu, X.R. Lin and C.S. Tan 163

20-P-06 - Dehydrogenation of ethylbenzene to styrene using ZSM-5 type zeolite

membranes as reactors
X.-F. Zhang, Y.-S. Li, J.-Q. Wang, H.-O. Liu and C.-H. Liu 291

20-P-07 - Preparation of high-permeance ZSM-5 tubular membranes by varying-

temperature synthesis
Y.-S. Li, Xio. Zhang, J.-G. Wang and S. Guo 291
lvi

20-P-08 - Synthesis of FAU type films on steel supports using a seeding method
Z Wang, J. Hedlund and J. Sterte 291

20-P-09 - Structured zeolite ZSM-5 coatings on ceramic packing materials

O. Ohrman, U Nordgren, J. Hedlund, D. Creaser and J. Sterte 292

20-P-10 - Effects of synthesis parameters on intra-pore zeolite formation in

zeolite A membranes
M. Lassinantti, J. Hedlund and J. Sterte 292

20-P-11 Pure-silica zeolite low-k dielectric thin films by spin-on process

Zhen. Wang, H. Wang, A. Mitra, L. Huang and Yu. Yan 292

20-P-12 - Preparation of silicalite-1 and beta zeolite/ceramic composite

membranes and removal of trace phenol and benzene from water through them
Xiansen Li and S. Xiang 293

20-P-13 - Factors affecting film thickness in the preparation of supported

ZSM-5 zeolite
E.I. Basaldella, A. Kikot, J.E Bengoa andJ. C. Tara 293

20-P-14 - Growing zeolite films onto gold surfaces

E I. Basaldella, A. Kikot, J.O. Zerbino and J.C. Tara 293

20-P- 15 - Diffusivities of zeolite coatings

M. Tather, ~.B. Tantekin-Ersolmaz andA. Erdem-~enatalar 294

20-P-16 - Crystal growth mechanism of LTA and FAU and densification process
of zeolite film by seed growth
I. Kumakiri, Y. Sasaki, W. Shimidzu, T. Yamagushi. and S.-I. Nakao 294

20-P-17 - In-situ synthesis of ZSM-5 on aluminum surfaces

F. Scheffler and W. Schwieger 294

20-P- 18 - Conceptual process design of an all zeolite membrane reactor for the
hydroisomerization of CflC6
E.E. McLeary, R.D. Sanderson, C. Luteijn, E.J.W. Buijsse, L. Gora,
Th. Maschmeyer and J. C. Jansen 295

21 - N a n o c o m p o s i t e Fundamentals and Applications

21-O-02 - Methods of synthesis for the encapsulation of dye molecules in

molecular sieves
M. Wark, M. Ganschow, Y. Rohlfing, G. Schulz-Ekloff and D. Wohrle 160
 lvii

21-O-03 -MCM-41 silica monoliths and diluted magnetic semiconductors: a

promising union for fabricating nanosized quantum wires
F. Brieler, M. Brehm, L. Chen, P.J. Klar, W. Heimbrodt and M. FrOba 160

21-O-04 - Potential microlasers based on AIPO4-5/DCM composites

O. Weifl, F. Schuth, L. Benmohammadi and F. Laeri 161

21-O-05 - Light-emitting BN, Si, and SiC nanoparticles encapsulated in molecular

sieves
Xiaotian Li, C. Shao, F. Gao, S. Qiu, F.-S. Xiao and O. Terasaki 161

2 l-P-06 - Fabrication of hollow fibers and spheres composed of zeolites by layer-

by-layer adsorption method
E Tang, Y.-J. Wang, X.-D. Wang, W.-L. Yang and Z. Gao 296

2 l-P-07 - The zeolitisation of diatoms to create hierarchical pore structures

S.M. Holmes, R.J. Plaisted, P. Crow, P. Foran, C.S. Cundy and M. W Anderson 296

2 l-P-08 - Generating the narrowest single-walled carbon nanotubes in the

channels of A1PO4-5 single crystals
G.D. Li, Z.K. Tang, N. Wang, K.H. Wong and J.S. Chen 296

21-P-09 - Zeolite- an effective nucleating agent of NazHPO4" 12H20

J. Dong, X. Jing and Yu. Zhang 297

2 l-P-10 - Synthesis and characterization of SnO2 nano particles in zeolite hosts

Yi. Zhang, Xu. Wang and Xi. Wang. 297

2 l-P-11 - Encapsulation of Mn(bipy)2 into the zeolite Y prepared via different

routes
B. Fan, W Cheng and R. Li 297

2 l-P-12 - Preparation of zeolite Beta/polystyrene beads and the corresponding

hollow spheres
V. Valtchev and S. Sferdjella 298

2 l-P-13 - Synthesis, characterization and catalysis of manganese(II) complexes

encapsulated in NaX and NaY zeolites
J.M. Silva, R. Ferreira, C. Freire, B. de Castro and J. L. Figueiredo 298

2 l-P-14 - Guest-host interactions in systems containing liquid crystals confined to

molecular sieves
S. Frunza, L. Frunza, A. SchOnhals, H.-L. Zubowa, H. Kosslick and R. Fricke 298

2 l-P-15 - Zeolite Beta ordered macroporous structures with improved mechanical

strength and controlled mesoporosity
V. Valtchev, S. Sferdjella and H. Kessler 299
lviii

2 l-P- 16 - Synthesis of zeolites with organic lattice

K. Yamamoto, Y. Takahashi and T. Tatsumi 299

2 l-P-17 - Crystallization mechanism of A1MePO-I3

Y. Qi, G. Wang and Z. Liu 299

2 l-P-18 - Crystal structure and magnetic properties of rubidium clusters in zeolite

LTA
T. Ikeda and T. Kodaira 300

22 - Advanced Materials

22-0-01 - The effect of the location of framework negative charge on the ordering
of templates in zeolite IFR
R.E. Morris and L.A. Villaescusa 168

22-0-02 - A new family of microporous vanadium phosphates and related

compounds with organic coordination
S. Feng, Z. ShL L. Zhang, H. Zhao, D. Zhang and Z Dai 168

22-0-03 - Catalytic properties of novel nickel(II) phosphate with nanoporous

structure
J.-S. Chang, D.S. Kim, S.-E. Park, P.M. Forster, A.K. Cheetham and G. Ferey 169

22-0-04 - Characterization of corrosion-resistant zeolite coatings on A1 alloys

H. Wang, Zhen. Wang, X. Cheng, A. Mitra, L. Huang and Y. Yan 169

22-0-05 - Template synthesis and catalysis of bimetallic platinum-rhodium and -

palladium nanowires in mesoporous materials
A. Fukuoka, Y. Sakamoto, S. Inagaki, iV. Sugimoto, Y. Fukushima and M.
Ichikawa 169

22-P-06 - Tailored generation of titanium oxide species within porous

Si-MCM-41
P. Prochnow, G. Schulz-Ekloff M. Wark, J.K. Thomas, A. Zukal
and J. Rathousky 359

22-P-07 - Optical switching with photochromic dye molecules encapsulated in the

pores of molecular sieves by in-situ synthesis
C. Schomburg, D. WOhrle, G. Schulz-Ekloff and M. Wark 359

22-P-08 - Formation of carbon nanotubes on various molecular sieves supported

metal oxides
A. M Zhang, Q H. Xu, J.J. Zhao and J.M. Cao 359
 lix

22-P-09- Encapsulation of Tb[(C1BOEP)4P](acac) in Si-MCM-41 by the method

of ship-in-bottle and its luminescent properties at 77 K
Q Xu, Z. Zhao, L. LL G. Liu, 11. Ding, J. Yu and R. Xu 360

22-P-10 - A new adsorbent with magnetic properties based on natural

clinoptilolite
V. Pode, V. Georgescu, V. Dalea, R. Pode and E. Popovici 360

22-P-11 - Preparation of microcalorimetric gas sensors with CoAPO-5

S. Mintova, J. Visser and T. Bein 360

22-P-12 - Study of cation-exchange properties of an organozeolite

V.A. Nikashina, E.M. Kats, 1. V. Komarova, N.K. Galkina and K.1. Sheptovetskaja 361

22-P-13 - Advanced electrode materials based on mesoporous aluminum-

stabilized anatase
A. Attia, S.H. Elder, R. Jir6sek, L. Kavan, P. Krtil, J. Rathousk~ and A. Zukal 361

22-P-14 - Dye-zeolite assemblies for optical sensing applications

J.L. Meinershagen and T. Bein 361

22-P-15 - A new sorbent based on clinoptilolite-containing tuff modified by

polyethylene
1.N. Meshkova, V.A. Nikashina, T.M. Ushakova, V.G. Grinev, N. Yu. Kovaleva,
A.A. Zaborskii, T.A. Ladygina and L.A. Novokshonova 362

22-P-16 - Molecular sieves from pillaring of some romanian bentonite

E. Popovici, 1. Bedelean, D. Pop, G. Singurel, D. Macocinschi and H. Bedelean 362

22-P-17 - Electronic states and arrangements of AgI and CuI clusters incorporated
into zeolite LTA
T. Kodaira and T. Ikeda 362

22-P-18 - PbI2 nanoclusters in zeolite LTL: host-guest chemistry and optical

properties
G. Telbiz, O. Shvets, V. Vozny and M. Brodyn 363

22-P-19 - Application of the molecular sieves as matrices for the pigments

S. Kowalak, A. Jankowska, N. Pietrzak and M. Str6zyk 363
22-P-20 - Laser dye doped mesoporous silica fibers: host-guest interaction and
fluorescence properties 363
G. Telbiz, O. Shvets, S. Boron, V. Vozny, M. Brodyn and G. Stucky

22-P-21 - Spectroscopic properties of dye-loaded mesoporous silicas of the

structural type MCM-41
B. Onida, B. Bonelli, M. Lucco-Borlera, L. Flora, C. Otero Aredn and E. Garrone 364
lx

23 - M i c r o - a n d M e s o p o r o u s M a t e r i a l s in F i n e C h e m i s t r y

23-0-02 - Pd-zeolites as catalysts for the Heck reaction: a screening of reaction

parameters affecting catalyst heterogeneity
M. Dams, D.E. De Vos, L. Drij'koningen and P.A. Jacobs 138

23-0-03 - Beckmann rearrangement of cyclohexanone oxime over mesoporous

MCM-41 and MCM-48 type materials
R. Glaser, 11. Kath and J. Weitkamp 139

23-0-04 - Knoevenagel condensation between ethylcyanoacetate and

benzaldehyde over base catalysts immobilized on mesoporous materials
Y. Choi, K.-S. Kim, J.-H. Kim and G. Seo 139

23-0-05 - One-step synthesis of MIBK from acetone over Pt/X catalysts

L. V. Mattos, F.B. Noronha andJ.L.F. Monteiro 139
2 3 - P - 0 6 - Selective hydroxyethylation of furfuryl alcohol with aqueous
acetaldehyde in the presence of H-form zeolites
A. Finiels, W. Balmer and C. Moreau 230

23-P-07 - Selective synthesis of monooctylamines by ammonia alkylation with

octanol using NaY, ZSM-5, SAPO-5, SAPO-1 l, SAPO-31, SAPO-34
S. Amokrane, R. Rebai, S. Lebaili, D. Nibou and G. Marcon 230

23-P-08 - Conversion of monoethanolamine in other organic nitrogen compounds

on H-mordenite and H-clinoptilolite
G. Torosyan, S. Sargsyan and A. Grigoryan 230

23-P-09 - The influence of ammonia adsorption on Y Zeolite and natural

clinoptilolite activity in ethanol transformation
L. Akhalbedashvili, A. Mskhiladze and Sh. Sidamonidze 231

23-P-10 - Enantioselective synthesis and separation of terminal epoxides and diols

using a catalytic membrane system containing chiral Co(III) salen
S.-D. Choi and G.-J. Kim 231

23-P-11 - Asymmetric trimethylsilylcyanation of benzaldehyde catalyzed by

chiral Yi(IV) salen complexes immobilized on MCM-41
J.-H. Kim and G.-J. Kim 231

23-P-12 - Mechanistic study of aniline methylation over acidic and basic zeolites Y
1.1. lvanova, E.B. Pomakhina, A.1. Rebrov, Yu.G. Kolyagin, M. Hunger
and J. Weitkamp 232

23-P-13 - Heterogeneous base catalysis" characterization of zeolites and mixed

oxides using nitromethane as a NMR probe molecule and activity in the Michael
condensation of nitromethane and cyclohex-2-en-l-one
E. Lima, L.-C. de Mdnorval, M. Laspdras, J.-F. Eckhard, D. Tichit, P. Graffin and
F. Fajula 232
 lxi

23-P-14 - Synthesis of ot-pinene derivatives using redox-mesoporous molecular

sieves
Y.-W. Suh, T.-M. Son, N.-K. Kim, W.-S. Ahn and H.-K. Rhee 232

23-P-15 - Ring opening reactions of methyloxirane over DZSM-5 and

DA1MCM-41 molecular sieves - A mechanistic study
A. Fdsi, I. Pdlink6, ,4. GOmOry and I. Kiricsi 233

23-P-16 - Hydrodechlorination of 1,2,4-trichlorobenzene on Ni/A1-MCM-41

catalysts
Y. Cesteros, P. Salagre, F. Medina, J.E. Sueiras and G.L. Haller 233

23-P-17 - Adsorption of cytochrome c onto ordered mesoporous silicates

J. Deere, E. Magner, J.G. Wall and B.K. Hodnett 233

23-P-18 - Vapor phase Beckmann rearrangement of cyclohexanone oxime over

tantalum pillared magadiite
S.J. Kim, M.H. Kim, Y. Ko, G. Seo and Y.S. Uh 234

23-P-19 - Hydration of a-pinene over heteropolyacids encaged.in USY zeolites

J. Vital, A.M. Ramos, I.F. Silva, J.E. Castanheiro, M.N. Blanco, C. Caceres, P.
Vasquez, L. Pizzio and H. Thomas 234

23-P-20 - Selective adsorption of trans unsaturated fatty acid compounds in MFI

type zeolites
S. Paulussen, M. Goddeeris and P.A. Jacobs 234

23-P-21 - Novel delaminated zeolites are more active acid catalysts than
conventional zeolites and mesoporous AI/MCM-41 for the synthesis of fine
chemicals
M.J. Climent, A. Corma, V. Fornds, H. Garcia, S. Iborra, J. Miralles
and I. Rodriguez 235

23-P-22 - The design of zeolites catalysts for the synthesis of orange blossom and
apple fragrances
M.J. Climent, A. Corma and A. Velty 235

23-P-23 - Catalytic in-situ infrared spectroscopic study of n-butyraldehyde aldol

condensation
U. Rymsa, M. Hunger and J. Weitkamp 235

23-P-24- Oxyhalogenation of aromatic compounds in presence of KC1 or KBr

and H202 over zeolites.
N. Narender, P. Srinivasu, S.J. Kulkarni and K. V. Raghava~ 236
lxii

23-P-25 - Synthesis and characterization of mesoporous Pt-MCM-41 and its

application in enantioselective hydrogenation of 1-phenyl-1,2-propanedione
E. Toukoniitty, B. Sevcikovdt, N. Kumar, P. Mdiki-Arvela, T. Salmi, J. Vdiyrynen,
T. Ollonqvist, E. Laine, P.J. Kooyman and D. Yu. Murzin 236

23-P-26 - Isomerization of p-eugenol on palladium-containing zeolites

Ts.M. Ramishvili, M.K. Charkviani and L.D. Kashia 236

23-P-27 - The use of MCM-22 as catalyst for the Beckmann-rearrangement of

cyclohexanone oxime to e-caprolactam
G. Dahlhoff U. Barsnick, W. Eickelberg and W.F. HOlderich 237

23-P-28 - Nickel supported on zirconium doped mesoporous silica as catalysts for

the gas phase hydrogenation of acetonitrile
P. Braos-Garcia, L. Diaz, P. Maireles-Torres, E. Rodriguez-Castell6n
and A. Jim6nez-L6pez 237

23-P-29 - Synthesis of fine chemicals intermediates over basic zeolites

C.O. Veloso, A.C. Pinto, E.N. Santos and J.L.F. Monteiro 237

23-P-30 - Selective chlorination of diphenylmethane over zeolite K-L

A.P. Singh and S.M. Kale 238

23-P-31 - Butylation of phenol on medium pore A1PO4 -11, -31 and -41
structures: effect of silicon incorporation
C. V. Satyanarayana, U. Sridevi and B.S. Rao 238

23-P-32 - The catalytic synthesis of the glycidol from the glycerol carbonate in
presence of zeolite A
J. W. Yoo and Z. Mouloungui 238

23-P-33 - Transfer hydrogenation of unsaturated ketones catalyzed by Al-iso-

propoxide dispersed on MCM-41
J. Wahlen, D.E. De Vos, M. De bruyn, PJ. Grobet and PA. Jacobs 239

2 4 - N e w R o u t e s to H y d r o c a r b o n Activation

24-0-01 - Dehydroisomerization of n-butane to isobutene over Pd modified

silicoaluminophosphate molecular sieves
Y. Wei, G. Wang, Z. Liu, C. Sun and L. Xu 145

24-0-02 - Conversion of methane over Ag-Y in the presence of ethene

T. Baba, H. Sawada, Y. Abe and Y. Ono 145

24-0-03 - Peculiarities in the hydroconversion of n-hexadecane over bifunctional

catalysts
L. Perrotin, A. Finiels, F. Fajula and T. Cholley 145
 lxiii

24-0-04 - HI3 catalyzed heterogeneous aziridination of olefins

B. Chanda, R. Vyas, A. V. Bedekar, B.B. Kasture and V.N. Joshi 146

24-0-05 - MCM-41 as support for metallocene catalysts - ethylene

polymerization
C.A. Henriques, M.F.V. Marques, S. Valange, Z Gabelica and J.L.F. Monteiro 146

24-P-06 - Study of coke and deactivation over H-Beta zeolite

Z Zhu, T. Ruan, Q. Chen, W. Chen and D. Kong 271

24-P-07- Photoionization of N-alkylphenothiazines in transition-metal-ion

modified mesoporous silica SBA-15 molecular sieves
Z. Luan and L. Kevan 271

24-P-08 - Potential use of AIMCM-41 for activation of metallocene catalyst

T. Sano, T. Niimi, T. Miyazaki, S. Tsubaki, Y. Oumi and T. Uozumi 271

24-P-09 - Activation of butanes with olefins carbenium cations over zeolite

catalysts
S.E. Dolinsky and V.A. Plakhotnik 272

24-P-10 - Immobilization and mobilization of surface species during

transformation of ethylene over HZSM-5 catalysts
Ziktinovgt, M. Ko~iHk, M. Derewihski, P. Sarv, J. Dubsk~, P. Hudec
and A. SmieJkovd 272

24-P-11 - Zeolite-L as support of Fe microcystals for the Fischer-Tropsch

synthesis
M.V. Cagnoli, N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, A.A. Yeramian
and S. G. Marchetti 272

24-P-12 - Nb- and Ti-containing silica-based mesoporous molecular sieves as

catalysts for photocatalytic oxidation of methane
J. Xin, X. Chen, J. Suo, Xia. Zhang, L. Yan and Shuben Li 273

24-P-13 - Catalytic properties of micelle templated microporous and mesoporous

materials for the conversion of low-density polyethylene
J. Aguado, D.P. Serrano, R. Van Grieken, J.M. Escola and E. Garagorri 273

24-P-14 - Epoxidation of propylene in fixed bed reactor using supported titanium

silicalite catalyst
X.S. Wang, Gang Li, H.S. Yan and X. W. Guo 273

24-P-15 - Acetylene and alkene oligomerization on ETS-10 having induced

Bronsted acidity
A. Zecchina, C. Paz& C. Otero Aredn, G. Turnes Palomino, F.X. Llabr& i
Xamena and S. Bordiga 274
lxiv

24-P-16 - Isomerization of n-butane over small crystals of H-Beta and Pt-H-Beta

zeolite catalysts
N. Kumar, M. Vaini, V. Nieminen, R. Byggningsbacka, L.-E. Lindfors, T. Salmi,
D. Yu. Murzin and E. Laine 274

24-P-17 - Ethylene oligomerization with nickel-containing NaX zeolite

M.O. de Souza, F.M.T. Mendes, R.F. de Souza, J.H. Z. dos Santos, L. Caumo, V.
Conz, F. Majolo and L. V. Barbosa 274

24-P-18 - Studies of the methanol to hydrocarbons reaction using isotopic

labeling: mounting evidence for a hydrocarbon pool mechanism
S. Kolboe 275

24-P-19 - Formation and reactivity of alkoxy species through the reaction of

alkylhalides with metal-exchanged zeolites
R.J. CorrOa and C.J.A. Mota 275

24-P-20 The use of ITQ-7 as catalyst for alkylation of isobutane with 2-butene
-

A. Corma, M.J. Diaz-Cabaftas, C. Martinez and S. Valencia 275

24-P-21 Butene isomerization over ferrierite and SUZ-4 zeolite

-

V.L. Zholobenko and C.L.T. Stevens 276

24-P-22 - Volatile products of the conversion of cyclohexene over AI-MCM-41

M. Rozwadowski, M. Lezanska, J. Wloch, K. Erdmann, G. Zadrozna
and J. Kornatowski 276

24-P-23 - C u - Y zeolite catalysts for methanol and ethanol steam reforming

M. Laniecki 276

24-P-24 - Hexenes obtaining on the nickel - ion exchanged zeolites

M.K. Munshieva 277

24-P-25 - Catalytic sites of mesoporous silica in degradation of polyethylene

A. Satsuma, T. Ebigase, Y. Inaki, H. Yoshida, S. Kobayashi, Md.A. Uddin, E
Sakata, and T. Hattori 277

24-P-26 - The nature of medium acidity in [CuO/ZnO/ZrO2]SAPO-34 hybrid

catalyst for CO2 hydrogenation: the study of the interactions between metal
oxides and acid sites in zeolite
S.-K. Ihm, S.-W. Back, Y.-K. Park and K.-C. Park 277

24-P-27 - Reaction pathways for the aromatization of cyclohexane and

cyclohexene on Zn/H-ZSM-5 zeolites
A. Urdgt, G. Telbiz and I. Sgmdulescu 278
 lxv

24-P-28 - Coke species and coking mechanism of SAPO-34 in MTO process

Y. Qi, G. Wang, Z. Liu, L. Xu, X. Gao and W. Cui 278

24-P-29 - Pt-2,2'bipyridine complex encapsulated in Y zeolite - catalysts for

ethylene selective dimerization
R. Zavoianu and E. Angelescu 278

24-P-30 - Aromatics formation from C4-C4- technical fraction over zinc- and
zinc/copper-containing ZSM-5 zeolites
N. Bilba, Gh. Iofcea, 1. Asafiei, D.M. Padurariu and C.C. Pavel 279

24-P-31 - Aromatization of mixed-C4 hydrocarbons over the HZSM-5 catalysts

modified by Zn and Ni cations
L. Wei, J.Z. Gui, H.S. Ding, X.T. Zhang, H.Y. Li, L. Song, Z.L. Sun and L. V.C. Rees 279

25 - C o n v e r s i o n of A r o m a t i c s

25-0-01 - Shape-selective methylation of 4-methybiphenyl into 4,4'-

dimethybiphenyl over modified ZSM-5 catalysts
J.-P. Shen, L. Sun and C. Song 151

25-0-02 - Facile Friedel-Craft's alkylation of phenol with 4-hydroxybutan-2-one

over 13 and Y zeolites to produce raspberry ketone
K.K. Cheralathan, 1.S. Kumar, B. Arabindoo, M. Palanichamy and V. Murugesan 152

25-0-03 - Selective alkylation of naphthalene to 2,6-dimethylnaphthalene

catalyzed by MTW zeolite
G. Pazzuconi, G. Terzoni, C.Perego and G. Bellussi 152

25-0-04 - Transalkylation reaction of phenol with trimethylbenzenes over Y and

EMT zeolites
V. Hulea, 1. Fechete, P. Caullet, H. Kessler, T. Hulea, C. Chelaru, C. Guimon
and E. Dumitriu 152

25-0-05 - Benzene alkylation with alkanes over modified MFI catalysts

A. V. Smirnov, E. V. Mazin, O.A. Ponomoreva, E.E. Knyazeva, S.N. Nesterenko
and 1.1. Ivanova 153

25-P-06 - Isopropylation of napthalene over large pore zeolites

R.K. Ahedi, S. Tawada, Y. Kubota and Y. Sugi 280

25-P-07 - Shape-selective tert-butylation of biphenyl over HM, HY and HI3

zeolites in the liquid phase
D. Mravec, J. Horniakovd, M. Krdlik, M. Hronec, J. Joffre and P. Moreau 280
lxvi

25-P-08 - 1-Acetyl-2-methoxynaphthalene isomerization over zeolites. Effect of

pore structure.
V. Moreau, E. Fromentin, P. Magnoux and M. Guisnet 280

25-P-09 - Alkylation of phenol with propylene over solid acid catalysts

B. Wang, C. W. Lee, T.-X. Cai and S.-E. Park 281

25-P-10 - Transalkylation of trimethylbenzene with toluene over large pore

zeolites
J. Cejka, A. Krejdi and J Hanika 281

25-P-11 - Physicochemical characterization and catalytic activity of A1-HMS for

N-methylation of aniline
JM. Campelo, A. Garcia, D. Luna, J.M Marinas, A.A. Romero
and J.J. Toledano 281

25-P-12 - Catalytic activity of secondary aluminated mesoporous molecular sieve

A1MCM-41 in the Friedel-Crafis reaction of bulky aromatic compounds
H. Hamdan, A.B. Kim and M.N. Mohd Muhid 282

25-P-13 - Naphthalene alkylation with methanol employing solid catalysts

J. Aguilar-P, A. Corma, J.A. de los Reyes, L. Noreha, G. Muhoz, J.M. Sanchez,
A. Torales and I. Herndndez 282

25-P-14 - Alkylation of biphenyl and naphthalene with propene. Is zeolite Beta a

shape-selective catalyst?
D.M. Roberge and W.F. Holderich 282

25-P-15 - Alkylation of benzene by propane with participation of space divided

centres
S.I. Abasov, R.R. Zarbaliyev, G.G. Abbasova, D.B. Tagiyev and M.I. Rustamov 283

25-P-16 - Alkylation of isopropylnaphthalene over heteropoly acid catalysts

supported on mesoporous materials
M-W. Kim, W.-G. Kim, J.-H. Kim, Y. Sugi and G. Seo 283

25-P-17 - Highly selective isopropylation of xylenes catalyzed by zeolite Beta

C.R. Patra, S. Kartikeyan and R. Kumar 283

26 - Catalysis for Oil Refining

26-0-01 - The isomerization selectivity in FCC process

L.-J. Yan, M-Y. He, J. Fu and J. Long 158

26-0-02 - Design of zeolite catalyst for paraffin isomerisation

J. Hou~vidka, C.J.H. Jacobsen and I. Schmidt 158

26-0-03 - Cyclohexane ring opening on metal-zeolite catalysts

T.V. Vasina, O.V. Masloboishchikova, E.G. Khelkovskaya-Sergeeva, L.M. Kustov
and P. Zeuthen 159
 lxvii

26-0-04 Selective ring opening of naphthenic molecules

-

M. Daage, G.B. Mc Vicker, M.S. Touvelle, C. W. Hudson, D.P. Klein, B.R. Cook,
J.G. Chen, S. Hantzer, D.E.W. Vaughan and E.S. Ellis 159

26-0-05 - Reforming of FCC heavy gasoline and LCO with novel borosilicate
zeolite catalysts
C. Y. Chen and S.I. Zones 159

26-P-06 - Hydroisomerization of n-decane in the presence of sulfur. Effect of

metal-acid balance and metal location
L.B. Galperin, S.A. Bradley and T.M. Mezza 301

26-P-07 - Hydrodesulfurization of benzothiophene over noble metals supported

on mesoporous silica MCM-41
M. Sugioka, A. Seino, T. Aizawa, J.K.A. Dapaah, Y. Uemichi and S. Namba 301

26-P-08 - Catalytic functionalities of USY zeolite supported hydrotreating

catalysts
K.S. Rawat, M.S. Rana and G. Murali Dhar 301

26-P-09 - Highly active, selective and stable ferrierite-based catalysts for the
skeletal isomerization of n-C5-C7
C.P. Nicolaides, J. Makkonen and M. Tiitta 302

26-P-10 - Producing synthetic steamcracker feed from cycloalkanes (or

aromatics) on various zeolite catalysts
A. Raichle, H. Scharl, Y. Traa and J. Weitkamp 302

26-P-11 - n-Heptane hydroconversion and methylcyclohexane cracking as model

reactions to investigate the pore topology of Nu-88 zeolite.
S. Lacombe, A. Patrigeon and E. Benazzi 302

26-P-12 - New Mo and NiMo hydrodesulfurization catalysts supported on AI-

MCM-41. Effect of the support Si/A1 molar ratio
T. Klimova, M. Calder6n and J. Ramirez 303

26-P-13 - Hydrogenation and ring opening of mono- and diaromatics for Diesel
upgrading on Pt/Beta catalysts
M.A. Arribas, J.J. Mahiques and A. Martinez 303

26-P-14 - Hydro denitrogenation activity of N i O - MoO3 catalysts supported on

various mesoporous alumino silicates
K. Shanthi, N.R. Sasi Rekha, R. Moheswari and T. Sivakumar 303

26-P-15 - Model hydrocracking catalysts combining NiMo sulfide and large-pore

zeolite: effect of the zeolite nature on the location of NiMo sulfide in relation with
catalytic properties
J. Leglise, D. Cornet, M. Badlala, C Potvin and J.-M. Manoli 304
Ixviii

26-P-16 - Effect of zeolite acidity characteristics on the deactivation behavior of

bifunctional large-pore zeolite catalysts during cyclopentane hydroconversion
S. Gopal and P G. Smirniotis 304

26-P-17 - Characterization and catalytic activities of MCM-41 supported WS2

hydrotreating catalysts
T. Chiranjeevi, P. Kumar, M.S. Rana, G. Murali Dhar and T.S.R. Prasada Rao 304

26-P-18 - Isomerization and hydrocracking of n-heptane and n-decane over

bifunctional mesoporous molecular sieves
C. Bischof and M. Hartmann 305

26-P-19 - Isomerization of cyclohexane, n-hexane and their mixtures on zeolite

catalyst
A. Holl6, J. Hancs6k and D. Kall6 305

26-P-20 - Application of adsorption Dubinin-Radushkevich equation for study of

n-pentane and m-xylene conversion catalysts microporous structure
S.B. Agayeva, B.A. Dadashev, S.I. Abasov and D.B. Tagiyev 305

26-P-21 - Hydroisomerization of n-hexadecane over Pt/A1-MCM-41 catalysts:

two different A1 incorporation methods
K.-C. Park and S.-K. Ihm 306

26-P-22 - Zr-containing hexagonal mesoporous silicas as supports for

hydrotreating catalysts
N.G. Kostova, A.A. Spojakina, L.A. Petrov, O. Solcova and K. Jiratova 306

26-P-23 - New catalysts for isomerization of long-chain n-paraffins

M.I. Levinbuk, L.M. Kustov, T.V. Vasina, O.V. Masloboishchikova, M.L. Pavlov,
I.E. Gorbatkina and V.A. Khavkin 306

27 - Selective Oxidation and Sulfur Resistance

27-0-01 - Singular catalytic properties of Ti-MWW in the selective oxidation of

alkenes
P. Wu, T. Komatsu, T. Yashima and T. Tatsumi 165

27-0-02 - Epoxidation of propylene over T S - 1 containing trace aluminum

X. Guo, Xi. Wang, Min Liu, Gang Li, Yo. Chen and J. Xiu 165

27-0-03 - One step benzene oxidation to phenol using N20 over acid zeolites
G. Juttu and R.F. Lobo 165
27-0-04 - Dual pathways for benzene hydrogenation on Pt/mordenites:
implication for sulfur tolerance
L. Simon, J.G. van Ommen, A. Jentys and J.A. Lercher 166
 lxix

27-0-05 - Sulfur resistance of PtPd catalysts: preparation, characterization and

catalytic testing
K. Thomas, C. Binet, T. Chevreau, D. Cornet and J.-P. Gilson 166

27-P-06 - Microporous metallosilicates for the oxidation of hydrocarbons:

preparation, characterization and catalytic activity
U. Arnold, R.S. da Cruz, D. Mandelli and U. Schuchardt 365

27-P-07 - High catalytic activity of Fe(III)-substituted aluminophosphate

molecular sieves (FeAPO) in oxidation of aromatic compounds
X. Meng, Y. Yu, L. Zhao, J. Sun, K. Lin, M. Yang, D. Jiang, S. Qiu, and F.-S. Xiao 365

27-P-08 - Selective oxidation of propyl alcohols over zeolites modified with

cations of the transition metals
A.M. Aliyev, D.B. Tagiyev, S.M. Medzhidova, S.S. Fatullayeva, A.R. Kuliyev,
T.N. Shakhtakhtinsky, G.A. Ali-zade and K.1. Matiyev 365

27-P-09 - Niobium leaching from the catalysts applied in the sulfoxidation of

thioethers with hydrogen peroxide
M. Ziolek, A. Lewandowska, M. Renn, 1. Nowak, P. Decyk and J. Kujawa 366

27-P-10 - Biomimetic oxygen transfer by Co and Cu complexes immobilized in

porous matrices
K. Hernadi, I. P6link6, E. BOngyik and I. Kiricsi 366

27-P-11 Titanium molecular sieves convert hydrogen peroxide into 102

-

F.M. van Laar, D.E. De Vos, P. Grobet, J.-M. Aubry, L. Fiermans and P.A. Jacobs 366

27-P-12 - Propane oxidation on Cu/ZSM-5 catalyst: the effect of copper and

aluminum content in the reducibility and in the activity of Cu active species
M.S. Batista and E.A. Urquieta-Gonz6lez 367

27-P- 13 - Oxidizing conversion of isobutanol on zeolites

S. Zulfugarova 367

27-P-14 - Photocatalytic production of H202 over heterogenized quinone in

zeolite
J.S. Hwang, C.W. Lee, H.S. Chai and S.-E. Park 367

27-P-15 - Liquid-phase oxidation of cyclohexane in the presence of chromium

and iron ETS-10 materials
A. Valente, P. Brand, o, Z. Lin, F. Gonqa!ves, 1. Portugal M. W. Anderson
and J. Rocha 368

27-P- 16 - Effect of oxygen concentration on catalyst deactivation rate in vapor

phase Beckmann rearrangement over acid catalysts
T. Takahashi and T. Kai 368
lxx

27-P-17 - On the role of the titanium active site in the phenol/anisole

hydroxylation over titanium substituted crystalline silicates
U WilkenhOner, D.W. Gammon and E. van Steen 368

2 8 - Confinement and Physical Chemistry for Catalysis

28-O-01 - Reactivity enhancement by molecular traffic control - a consequence

of released single-file constraints
P. Brgiuer and J. Kcirger 173

28-0-02 - Aromatization of n-hexane over ZnNi/HZSM-5 catalyst induced by

microwave irradiation
J.Z Gui, H.S. Ding, N.N. Liu, Y.R. Gao, Z.L. Cheng, X.T. Zhang, B. Ma, L. Song,
Z.L. Sun and L. V.C. Rees 173

28-0-03 - Artificial photosynthesis using zeolites

N. Castagnola and P.K. Dutta 174

28-0-04 - Synthesis of macrocycles using molecular sieve catalysts

3/1. Radha Kishan, N. Srinivas, S.J. Kulkarni, M. Ramakrishna Prasad,
G. Kamalakar and K. V. Raghavan. 174

28-0-05 - Effect of single-file diffusion on the hydroisomerization of 2,2-

dimethylbutane on platinum loaded H-mordenite
F.J.M.M. de Gauw, J. van Grondelle and R.A. van Santen 174

28-P-06 - Use of coke-selectivated H-ZSM-5 in xylene isomerization

E Bauer and A. Freyer 307

28-P-07 - Photocatalytic reactions on chromium containing mesoporous

molecular sieves under visible light irradiation: decomposition of NO and partial
oxidation of propane
H. Yamashita, K. Yoshizawa, M. Ariyuki, S. Higashimoto and M. Anpo 307

28-P-08 - Enhancing the shape selectivity ofnanocrystalline HZSM-5 zeolite v/a

comprehensive modifications
H.C. Guo, X S. Wang and G.R. Wang 307

28-P-09 - Nature of shape-selective catalysis in the ethylation and the

isopropylation of biphenyl over H-mordenites
Y. SugL S. Tawada, T. Sugimura, Y. lmada, Y. Kubota, T. Hanaoka
and T. Matsuzaki 308

28-P-10 - Adsorption of selected amino acids from aqueous solutions on

mesoporous molecular sieves
S. Ernst, M. Hartmann and S. Munsch 308
 lxxi

28-P-11 - Influence of OH groups of Beta zeolites on the synthesis of MTBE

F. Collignon and G. Poncelet 308

28-P-12 - About a possibilities of effectiveness increasing of porous catalyst

granules with controlled activity profile
V. V. Andreev 309

28-P-13 - Effects of channel structures of wide pore zeolites on m-cresol

transformation
F. L6pez, L. Gonzdtlez, J.C. Herndmdez, A. Uzc6tegui, F.E. Imbert and G.
Giannetto 309

28-P-14 - A study on the use of zeolite Beta as solid acid catalyst in liquid and gas
phase esterification reactions. The influence of the hydrophobicity of the catalyst
M.J. Verhoef R.M Koster, E. Poels, A. Bliek, J.A. Peters and H. van Bekkum 309

28-P-15 - The influence of pore geometry on the alkylation of phenol with

methanol over zeolites
G. Moon, K.P. MOller, W. BOhringer and C.T. O'Connor 310

28-P-16 - Diffusion analysis of cumene cracking over ZSM5 using a jetloop

reactor
P. Schwan and K.P. MOller 310

2 9 - New Approaches to Catalyst Preparation

29-0-01 - The catalytic performance of zeolite ERS-10

C. Perego, M. Margot& L. Carluccio, L. Zanibelli and G. Bellussi 178

29-0-02 - Towards total hydrophobisation of MCM-41 type silica surface

T. Martin, A. Galarneau, D. Brunel, V. lzard, V. Hulea, A.C. Blanc, S. Abramson,
F. Di Renzo and F. Fajula 178

29-0-03 - Novel Lewis-acid catalysts (NLACs): their properties, characterisation

and use in catalysis
M.H. Valkenberg, C. deCastro and W.F. Hoelderich 179

29-0-04 - A controlled dispersion of A13+ onto a silica mesoporous material. A

comparative study with A13+ mcorporation.
•
O. Collart, A. Galarneau, F. Di Renzo, F. Fajula, P. Van Der Voort and E. F.
Vansant 179

29-P-05 - Catalytic properties of MFI zincosilicates

S. Kowalac, E. Szymkowiak, 1. Lehmann and G. Giordano 311
lxxii

29-P-06 - Acidity characterization of dealuminated H-ZSM-5 zeolites by

isopropanol dehydration
C.S. Triantafillidis, V.A. Tsiatouras, A.G. Vlessidis and N.P. Evmiridis 311

29-P-07 - Acidic ZrO2/SO4 2" in mesoporous materials

Y. Sun, L. Zhu, H. Lu, D. Jiang and F.-S. Xiao 311

29-P-08- HMS catalysts containing transition metals or transition metal

complexes
Z. Fu, Du. Yin , W. Zhao, Y. Chen, Do. Yin, J. Guo, C. Xiong and Luxi Zhang 312

29-P-09 -Synthesis of hydrophobic mesoporous molecular sieves by surface

modification
K.-K. Kang and H.-K. Rhee 312

29-P-10 - Guanidine catalysts supported on silica and micelle templated silicas:

new basic catalysts for organic chemistry
D.J. Macquarrie, D. Brunel, G. Renardand A. C. Blanc 312

29-P-11 - Texture of dealuminated mordenite catalysts modified with cerium and

catalytic properties in the isopropylation of biphenyl
M. Krdlik, J. Horniakova, D. Mravec, V. Jorik, M. Michvocik and P. Moreau 313

29-P-12 - Partially crystalline zeolitic material as novel solid acid catalysts

Ming Liu, Z. Li, S. Lou, Q Wang and S. Xiang 313

29-P-13 - Novel mesoporous carbon as a catalyst support for Pt and Pd for liquid
phase hydrogenation reactions
W.S. Ahn, K.1. Min, Y.M. Chung, H.-K. Rhee, S.H. Joo and R. Ryoo 313

29-P-14 - Investigation of catalytic activity of framework and extraframework

cobalt and manganese in MeAPO-34 prepared from fluoride medium
A. Ristik, G. Avgouropoulos, T. Ioannides and V. Kaudid 314

29-P-15 - Preparation and characterization of bimetallic Pt-Zn catalysts supported

on zeolite NaX
J. Silvestre-Albero, F. Coloma, A. Sepfilveda-Escribano and F. Rodriguez-
Reinoso 314

29-P-16 - Surface modification of the uncalcined acid'made mesoporous silica

materials in a one-step procedure
H.-P. Lin, Y.-H. Liu, C.-P. Kao, S.-B. Liu and C.-Y. Mou 314

29-P-17 - Zirconia nanoparticles in ordered mesoporous material SBA-15

J. Sauer, S. Kaskel, M. Janicke and F. Schath 315
 lxxiii

29-P-18 - Preparation using ozone treatment, characterization and application of

isomorphously substituted Ti-, V- and Zr-MCM-41 catalysts
D. Mdhn, J. Haldsz, E. Meretei, Z. K6nya, A. Fonseca, J. B.Nagy and 1. Kiricsi 315

29-P-19 - Preparation and catalytic evaluation of [Ga]MCM-58 and of MCM-58-

type catalysts with different aluminum contents
S. Ernst, M. Hartmann, T. Hecht and A. Weber 315

29-P-20- IR study on the reaction path of methanol decomposition over basic

zeolites
M. Rep, J.G. van Ommen, L. Lefferts and J.A. Lercher 316

29-P-21 - Synthesis and characterization of highly ordered mono- and bimetallic

substituted MCM-41 molecular sieves and their catalytic properties in selective
oxidation of hydrocarbons
V. Pdrvulescu, C. D~tscalescu and B.L. Su 316

29-P-22 - On the direct synthesis of noble metal cluster containing MCM-41

using surfactant stabilised metal nanoparticles
A.B.J. Arnold, J.P.M. Niederer, W.F. Hoelderich, B. Spliethof B. Tesche, M.
Reetz and H. Boenneman 316

29-P-23 - Microporous zincophosphates as solid base catalysts

L.A. Garcia-Serrano, T. Blasco, J. Pdrez-Pariente and E. Sastre 317

29-P-24 - Zirconium containing AI-MCM-41- synthesis, characterisation and

catalytic performance in 1-hexene isomerisation
I. Eswaramoorthi, V. Sundaramurthy and N. Lingappan 317

29-P-25 - Iron containing zeolites and mesoporous silica as sulfuric acid catalyst
A. Wingen, W. Schmidt, F. Schiith, A.C. Wie, C.N. Liao and K.J. Chao 317

29-P-26 - Deep-bed dealumination of ZSM-5 zeolites: changes in structure and

catalytic activity
P. Hudec, A. Smiegkovdl, Z Zidek, L. Sabo and B. Liptdkovd 318

29-P-27 - Fabrication of honeycomb structures with powder MCM-48 silica

Y.-S. Ahn, M.-H. Han, S. Jun and R. Ryoo 318

29-P-28 - Acidic hybrid catalysts prepared by grafting large-pore silica M41S

materials
B. Lindlar, M. Lachinger, M. Haouas, A. Kogelbauer and R. Prins 318

29-P-29 - Preparation of tungsten carbide supported on (A1-)FSM-16 and its

catalytic activity
M. Nagai, K. Kunieda, S. Izuhal and S. Omi 319
lxxiv

29-P-30 - Ti-MCM-48 with different titanium loading: synthesis, spectroscopic

characterization and catalytic activity
V. Dellarocca, M.L. Pe~a, F. Rey, A. Corma, S. Coluccia and L. Marchese 319

29-P-31 - Comparison of 3-aminopropylsilane linked to MCM-41 and HMS type

silicas synthesised under biphasic and monophasic conditions
D.J. Macquarrie, M. Rocchia, B. Onida, E. Garrone, P. Lentz, J. B.Nagy,
D. Brunel, A.C. Blanc and F. Fajula 319

30- Environmental Catalysis

30-0-02 - Characterization and performance of ex-framework FeZSM-5 in

catalytic N20 decomposition
J. Pdrez-Ramirez, G. Mul, F. Kapteijn, 1. W.C.E. Arends, A. Ribera
and J.A. Moulo'n 172

30-O-03 - Effect of carbon number in hydrocarbon reductant on the selective

catalytic reduction of NO over cation-exchanged MFI zeolites
A. ShichL Y. Kawamura, A. Satsuma and T. Hattori 172

30-0-04 - The temperature-dependent storage of NOx on metal-containing

zeolites under dry and wet conditions
R. Fricke, M. Richter, E. Schreier, R. Eckelt and H. Kosslick 172

30-0-05 - Catalytic destruction of chlorinated VOCs.- Influence of characteristics

of Pt/HFAU catalysts on the destruction of dichloromethane
L. Pinard, J. Tsou, P. Magnoux and M. Guisnet 173

30-P-06 - Effect of the reductant nature on the catalytic removal of N20 on a Fe-
zeolite-Beta catalyst
G. Delahay, M. Mauvezin, B. Coq and S. Kieger 320

30-P-07 - Degradation of N-nitrosamines on zeolites

J.H. Zhu, B. Shen, Y. Xu, J. Xue, L.L. Ma and Q.H. Xu 320

30-P-08 - ZrO2/NaY: a new material for removal of N-nitrosamines pollution

J.H. Zhu, J.R. Xia, Ying Wang, G. Xie, J. Xue and Y. Chun 320

30-P-09 -Total oxidation of n-pentane, cyclohexane and their mixtures on the

Cu-containing ZSM-5 zeolites
M.A. Botavina, IV. V. Nekrasov and S.L. Kiperman 321

30-P-10 - Modified natural zeolite in catalytic clearing of exhaust and ejected

gases from nitric and carbon oxides
L. Akhalbedashvili and Sh. Sidamonidze 321
 lxxv

30-P-11 - Selective catalytic reduction of N20 with light alkanes over different
Fe-zeolite catalysts
S. Kameoka, S. Tanaka, K. Kita, T. Nobukawa, S. Ito, T. Miyadera
and K. Kunimori 321

30-P-12 - Selective catalytic reduction of NOx by NH3 over Mn supported

MCM-41 mesoporous materials
E.E. Iojoiu, P. Onu, S. Schmitzer and W. Weisweiler 322

30-P-13 - Transition metal exchanged-MCM-22 catalysts for N20 decomposition

A.J.S. Mascarenhas, H.M.C. Andrade and H.O. Pastore 322

30-P-14 - The NO and N20 selective catalytic reduction on copper and iron
containing ZSM-5 catalysts: a comparative study
G. Fierro, G. Ferraris, M. Inversi, M. Lo Jacono and G. Moretti 322

30-P-15 - A comparison of different preparation methods of indium-modified

zeolites as catalysts for the selective reduction of NO
C. Schmidt, T. Sowade, F.-W. Schutze, 14. Berndt and W. Granert 323

30-P- 16 - Local structures of Ag+/ZSM-5 catalysts and their photocatalytic

reactivity for the decomposition of N20 into N2 and 02
M. Matsuoka, W.-S. Ju and M. Anpo 323

30-P-17 - One stage catalytic cracking of plastic waste on zeolitic catalysts

K. Gobin, D. Koumantaropoulos and G. Manos 323

30-P-18 - Analysis of the deep catalytic oxidation of binary CVOCs mixtures over
H-ZSM-5 zeolite
R. L6pez-Fonseca, J.I. Guti&rez-Ortiz, A. Aranzabal and J.R. Gonz6lez-Velasco 324

30-P-19 - Solid state MAS NMR studies of zeolites and alumina reacted with
chlorofluorocarbons (CC12F2, CHC1F2)
I. Hannus, Z K6nya, P. Lentz, J. B.Nagy and I. Kiricsi 324

30-P-20 - Zeolite-containing photocatalysts for treatment of waste-water from

petroleum refineries
A.K. Aboul-Gheit and S.M. Ahmed 324

30-P-21 . Autoreduction of C u 2+ species in Cu-ZSM-5 catalysts studied by diffuse

reflectance spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry
and elemental analysis
G. Moretti, G. Ferrarbx and P. Galli 325

30-P-22 - Performance of bi-and tri-metallic mordenite catalysts for the lean SCR
of NOx by methane
F. Bustamante, P. A vil and C. Montes de Correa 325
lxxvi

30-P-23 - Total oxidation of volatile organic compounds - catalytic oxidation of

toluene over CuY zeolites
A.P. Antunes, J.M. Silva, M.F. Ribeiro, F.R. Ribeiro, P. Magnoux and M. Guisnet 325

30-P-24 - Study on relationship between the local structures of Ti-HMS

mesoporous molecular sieves and their photocatalytic reactivity for the
decomposition of NO into N2 and 02
J. Zhang, B. He, M. Matsuoka, H. Yamashita and M. Anpo 326

30-P-25 - Influence of synergistic effects on the selective catalytic reduction of

NO× with CnHm over zeolites
S.N. Orlik and V. L. Struzhko 326

30-P-26 - Catalytic properties of Fe-Co double layered hydroxides synthesised

with Beta zeolite for toluene oxidation
J. Carpentier, S. Siffert, J.F. Lamonier and A. Aboukags 326

30-P-27 - Selective catalytic reduction of NO over Fe z e o l i t e s - catalytic and in-

s i t u - DRIFTS studies
F. Heinrich, E. LOftier and W. Grunert 327

30-P-28 - Selective catalytic reduction of NO by methane over AgNaZSM-5

catalysts in the excess of oxygen
C. Shi, M. Cheng, Z Qu, X. Yang and X. Bao 327

30-P-29 - ZSM-5/Raney Fe composite used as DeNO× catalyst

B. Zong, W. Wang, L. Lu and X. T. Shu 327

30-P-30 - Reduction of nitric oxide by hydrocarbons on Ni-ion exchanged zeolites

B.I. Mosqueda-Jim~nez, M. Brandmair, A. Jentys, K. Seshan and J.A. Lercher 328

30-P-31 -NOx Reactivity on microporous MeAPOs. Spectroscopic and catalytic

studies
A. Frache, M. Cadoni, S. Coluccia, L. Marchese, B. Palella, R. Pirone and P.
Ciambelli 328

30-P-32 - Adsorption characteristics on zeolite catalysts for hydrocarbon removal

under cold-start engine condition
H.K. Seo, J. W. Oh and S.J. Choung 328

30-P-33 - In-situ synthesized ZSM-5 on cordierite substrate and NO

decomposition on the monolithic catalysts
N. Guan, X. Shan, X. Zeng, S. Liu, S. Xiang, U. Illgen and M. Baerns 329

30-P-34 - Selective reduction of NO to N2 in the presence of oxygen

T. Furusawa, K. Seshan, S.E. Maisuls, J.A. Lercher, L. Lefferts and K. Aika 329
 lxxvii

30-P-35 - Catalytic behaviour of Co-exchanged ferrierite for lean NOx-SCR with

methane
D. Sannino, M. Concetta Gaudino and P. Ciambelli 329

31 - E n v i r o n m e n t - F r i e n d l y Applications of Zeolites

31-O-01 - Influence of Jordanian chabazite-phillipsite tuff on nutrient

concentration and yield of strawberry
K.M. Ibrahim, A.M. Ghrir and 14.N. Khoury 181

31-O-02 - Improvements in yield and quality of crops with NASA zeoponic

fertilizer delivery systems: turf, flowers, vegetables and grain
R.D. Andrews and S.B. Kimi 181

31-O-03 - Fe/MFI as a new heterogeneous Fenton-type catalyst in the treatment

of wastewater from agroindustrial processes
G. Centi, S. Perathoner and G. Romeo 181

31-O-04 - Investigation of the storage properties of zeolites and impregnated

silica for thermochemical storage of heat
J. Jcinchen, ,4. Grimm and H. Stach 182

3 l-P-05 - Application of sorbing composites on natural zeolite basis for heavy

metals contaminated territories rehabilitation
W. Sobolev, V. llyin, F. Bobonich and S. Bdrdny 369

3 l-P-06 - Investigation of lead removal from wastewater by Iranian natural

zeolites using 2~2pb as a radiotracer
H. Kazemian, P. Rajec, F. Macasek and J. O. Kufacakova 369

3 l-P-07 - Purification of the waste liquid hydrocarbons using cation-exchanged

forms of clinoptilolite
M.Kh. Annagiyev, S.G. Aliyeva and T. M.Kuliyev 369

3 l-P-08 - The use of transcarpathian zeolites for concentrating trace contaminants

in water
V. O. Vasylechko, L. O. Lebedynets, G. V. Gryshchouk, Yu.B. Kuz 'ma,
L.O. Vasylechko and V.P. Zakordonskiy 370

3 l-P-09 - Ammonia removal from drinking water using clinoptilolite

and Lewatit S 100
H.M. Abd El-Hady, A. Grtinwald, K. Vlckova and J. Zeithammerova 370

3 l-P-10 - Pilot plant of ammonium removal from nitrogen industry waste waters
by an Ukrainian clinoptilolite
Yu.I. Tarasevich and V.E. Polyakov 370
lxxviii

3 l-P-11- Croatian clinoptilolite and montmorillonite-rich tufts for ammonium

removal
M. Rozic and S. Cerjan-Stefanovic 371

3 l-P-12 - Ammonia removal from water by ion exchange using South African
and Zambian zeolite samples, and its application in aquaculture
M. Mwale and H. Kaiser 371

3 l-P- 13 - Permanent storage of chromium in hardened FAU-type zeolite/cement

pastes
C. Colella, D. Caputo and B. de Gennaro 371

3 l-P-14 - Phosphorus removal from wastewater in upgraded activated sludge

system with natural zeolite addition
J. Hrenovic, Y. Orhan, H. BiiyfikgfingOr and D. Tibljad 372

3 l - P - 1 5 - Application of natural zeolites to purify polluted river water

M. Okamoto and E. Sakamoto 372

3 l-P-16 - Elimination of ammonium in seawater by zeolitic products

J.M. Lopez-Alcalgl andJ.L. Lopez-Ruiz 372

32 - Zeolite Minerals and Health Sciences

32-0-01 - Biomedical applications of zeolites

K. Pavelic, B. Subotic and M. Colic 170

32-0-02 - Zeolites and other porous materials in the toxicity of inhaled mineral
dusts
I. Fenoglio, L. Prandi, M. Tomatis and B. Fubini 170

32-0-03 - Study of the reaction of a Ca-clinoptilolite and human bile

R. Sim6n Carballo, G. Rodriguez-Fuentes, C. Urbina and A. Fleitas 170

32-0-04 - In vitro adsorption of zearalenone by octadecyldimethylbenzyl

ammonium-exchanged clinoptilolite-heulandite tuff and bentonite
A. Dakovic, M. Tomasevic-Canovic, V. Dondur, D. Stojsic and G. Rottinghaus 171

32-0-05 - Zeolites in sexual confusion: slow release of pheromones

J. Muftoz-Pallares, E. Primo, J: Primo and A. Corma 171

32-P-06 - Effects of dietary inclusion of natural zeolite on broiler performance

and carcass characteristics
E. Christaki, P. Florou-Paneri, A. Tserveni-Gousi, A. Yannakopoulos
and P. Fortomaris 373
 lxxix

32-P-07 - Interaction studies between aspirin and purified natural clinoptilolite

A. Rivera, L.M. Rodriguez-Albelo, G. Rodriguez-Fuentes and E. Altshuler 373

32-P-08 - Channel model for the theoretical study of aspirin adsorption on

clinoptilolite: water influence
A. Lam and A. Rivera 373

32-P-09 - In vitro and in vivo effect of natural clinoptilolite on malignant tumors

M. Poljak Blazi, M. Katic, M. Kralj, N. Zarkovic, T. Marotti, B. Bosnjak,
V. Sverko, T. Balog and K. Pavelic 374

32-P-10 - Effects of natural clinoptilolite-rich tuff and sodium bicarbonate on

milk yield, milk composition and blood profile in Holstein cows
A. Nikkhah, A.R. Safamehr and M. Moradi - Shahrbabak 374

32-P-11 - Effect of natural clinoptillolite-rich tuff on the performance of Varamini

male lambs
A. Nikkhah, A. Babapoor and M. Moradi- Shahrbabak 374

32-P-12 - Clinoptilolite and the possibilities for its application in medicine

N. Izmirova, B. Aleksiev, E. Djourova, P. Blagoeva, Z Gendjev, Tz. Mircheva,
D. Pressiyanov, L. Minev, T. Bozhkova, P. Uzunov, 1. Tomova, M. Baeva,
A. Boyanova, T. Todorov and R. Petrova 375
This Page Intentionally Left Blank
Studies in Surface Sbience and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved.

Ordered Mesoporous Materials - State of the Art and

Prospects

F. Schtith

MPI ftir Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mtilheim, Germany

Research in ordered mesoporous oxides has increased dramatically in intensity

over the last years. Developments not foreseen at the time when MCM-41 and
FSM-16 were discovered have taken place, and in some cases applications of
these materials are on the horizon. This paper will cover the discoveries which
have expanded the scope of research in this field and try to give an outlook where
new developments could take place.

1. I N T R O D U C T I O N

When one searches for the key words (MCM-41 or FSM-16 or SBA-15 or ordered
mesoporous oxides or ordered mesoporous materials) in the Web of Science,
almost 1500 hits were
450 reported in F e b r u a r y 2001,
w 400 and this set of key words
c
.o 350 i i does not even give hits for
(g
o 300 II all relevant publications,
,Q
= 250 II since in the early
12.
~ 2oo i l l publications these materials
'- 150 I I I I were called "mesoporous
E 100 - I I I I molecular sieves". Research
= 50 = l i l l E increased dramatically in
__111111 the recent years: About half
of the 1500 publications
result from 1999 or 2000.
year One might have expected
t h a t after an initial phase
Fig. 1: Development of publications on ordered on the synthesis and
mesoporous oxides since 1990.
characterization of such
materials, by now the
applications would have moved into the center of attention. However, this proved
to be the case to a limited extent only. The synthesis and characterization had to
offer so m a n y new aspects, that this still seems to be the most active area of
research.
In the following the major achievements - seen from a personal perspective - of
the last years in the field shall be highlighted, but it is not intended to give a
comprehensive review. It will then be attempted to give a projection where the
research on ordered mesoporous materials might move in the future.

2. S T R U C T U R E S

After initially FSM-16 [1] and MCM-41 [2] as the hexagonal members and MCM-
48 [3] as the cubic Ia3d member of the ordered mesoporous materials had been
synthesized, a wide range of other structures became available quite rapidly,
most of which had pure surfactant liquid crystal counterparts. Some, however,
were unique structures only known for silica-surfactant composites.
For the hexagonally ordered mesoporous silicas the route leading to the
formation of SBA-15 [4] is the most exciting novel development after the
discovery of the initial pathways. Before this discovery pore sizes of ordered
mesoporous silica were limited to approximately 10 nm, as reported already in
the initial papers, wall thickness was always found to be around 1 nm. The use of
the triblockcopolymers of the Pluronics type expanded the accessible range
dramatically. Substantially higher pore sizes and a wall thickness up to 6 nm
could be achieved. The blockpolymer template can easily be removed by
extraction or calcination, and the resulting material has a very good stability
against water. After this initial publication, many other researchers used SBA-15
instead of MCM-41 type materials for further investigations.
A serious problem in analyzing the structures of ordered mesoporous materials
is, however, the fact that typically X-ray diffraction patterns are obtained which
have only few reflections. Thus, often only space groups can be assigned, but no
full structure solution is possible. So far, most structural models are just that, i.e.
models, and they still have to be confirmed by either X-ray or electron
crystallography. The 2-dimensionally ordered MCM-41 and the cubic MCM-48
have until recently probably been the two examples which were structurally well
characterized by XRD and TEM [5,6]. One of the most notable developments,
from the structure characterization point of view as well as with respect to the
structure of the materials itself, was the structure solution of SBA-1, SBA-6, and
SBA-16 with a novel electron crystallographic technique [7].
This technique uses the fact that the TEM image contains information both on
the phase and the amplitude of the structure factors. To obtain the 3-D image of
the structure, different 2-D projections of the structure are recorded with TEM.
Fourier analysis of the images taken along different directions collectively
provide information on the 3-D structure in reciprocal space. This data set can be
backtransformed which eventually gives the 3-D real space structure. The
technique allowed to gain surprisingly detailed insight into the structure of three
different ordered mesoporous silicas. Both SBA-1 and SBA-6 have interesting
bimodal pore size distributions. Both structures consist of a packing of differently
sized A- and B-cages, the difference between the two being the dimensions of
pores and walls. The pores ]n SBA-6 have sizes of 2 nm and 3.3 x 4.1 nm, resp., in
 SBA-1 pore sizes are determined to be
0.2 nm and 1.5 x 2.2 nm, resp. The
smaller pore size of the SBA-1 is not
fully ascertained as yet, since sorption
analysis suggests a somewhat bigger
size for this type of pores. For SBA-16
a bcc packing of cavities with a
diameter of 9.5 nm is determined, in
which the cavities are connected by
pores of 2.3 nm along the [111]
directions. These bimodal size
distributions of structural pores
observed for SBA-1 and SBA-6 are
unique for ordered mesoporous
materials. The pore size distribution of
SBA-15 is probably also bimodal, in
which the bigger, hexagonally ordered
structural pores determined by the
surfactant are connected by micropores
through the silica walls [8]. However,
these micropores do not seem to be
well ordered and are rather the result
Fig. 2: a) Typical TEM of calcined of the fact, that part of the
KSW-2 (pH 4.0) and the corresponding triblockcopolymer surfactant
ED pattern indexed as hk0 projection. penetrates the silica.
b) Typical TEM and the corresponding Another very remarkable structure
ED pattern of as-synthesized KSW-2 was recently reported by the group of
(pH 6.0). c) Another TEM of the as- Kuroda [9]. So far all structures with
synthesized KSW-2 (pH 6.0). Arrows one dimensional pore systems were
imply the observed place of the bending either hexagonally packed or
of silicate sheets derived from disordered. Kuroda succeeded in
kanemite, from ref. [9]. synthesizing a square packing of pores
(Fig. 2) in an orthorhombic structure
which are most probably formed following the folded sheet mechanism originally
proposed for FSM-16. Formation of the material - called KSW-2 - is possible by
strict pH control during the transformation of the kanemite-surfactant
composite.

3. C O M P O S I T I O N S

The first ordered mesoporous materials reported were silicas or

aluminumsilicates. The majority of all published investigations is still based on
such compositions. In addition, many different elements, recently listed in a
comprehensive review [10], have been introduced into the framework of ordered
mesoporous oxides, just as in zeolitic frameworks. Such compositions could
become important in catalytic applications, similar to the progress made in
zeolite chemistry, where, for instance, TS-1 was a major advance in oxidation
chemistry over zeolites. Conceptually, however, the synthesis of fully non-
siliceous frameworks was the bigger step. The possibility to extend the approach
had been predicted very early [5], and the first partial success was achieved in
1994, when several different non-siliceous materials were introduced [11].
However, all those materials were not stable upon template removal. The first
stable compositions were synthesized in 1995 and 1996 as TiO2 [12] and ZrPxOy
[13]. From then on many other materials were obtained, not only in a
mesostructured, but also in a mesoporous form. Most of these, however, where
rather disordered, and the highest degree of order is still observed in the titania
and zirconia based materials. Non-siliceous mesoporous materials are reviewed
in a recent review [14].
The majority of the hitherto reported
non-siliceous mesoporous materials
are hexagonally ordered or totally
disordered. We recently reported a
zirconium-based cubic mesostructure
[15], which at that time could not be
stabilized to result in a mesoporous
material. Using the phosphate route
developed previously for the
stabilization of the hexagonal phase
[13] we now also succeeded in
obtaining a mesoporous cubic
zirconium oxo phosphate (Fig. 3) [16].
Other non-hexagonal structures were
prepared by the route to non-siliceous
materials analogous to the synthesis of
SBA-15 described by the Stucky group
[17]. Other than for SBA-15, the
synthesis is carried out in alcohol
instead of aqueous solution. The
pathway is remarkable, because it
allows the synthesis of various
different framework compositions and
probably has the highest flexibility
with respect to structure, pore sizes
and composition of all preparations
known so far. Amongst others, it is
suitable for the preparation of a well
ordered mesoporous cubic titania, as
Fig.4: TEM of an SBA-15 sample demonstrated by XRD, sorption and
loaded with 28wt.% of Y203. The TEM.
coating of the walls is visible as the
high contrast.
An alternative pathway to obtain essentially non-siliceous compositions was
reported recently. This route relies on the fact, that some oxides spread under
suitable conditions on silica. If a mesoporous silica is thus coated with a different
oxide, a material with essentially the surface area of silica, but the surface
functionality of the spreaded oxide results. This has been demonstrated for rare
earth oxides [ 18], a TEM image of which is shown in fig. 4.
More surprising than these non-silica oxides, however, was the discovery of non-
oxidic compositions: Already relatively early it was shown that noble metals
could be mesostructured and even
obtained in mesoporous form using the
true liquid crystal templating
mechanism [19]. Later on, similar
structures were obtained via a
"nanocasting" route with SBA-15 as a
mold and a volatile Pd-precursor [20].
After dissolution of the SBA-15
mesostructured Pd-particles were left.
Another highly innovative
development with respect to
framework composition were the
materials containing carbon or even
consisting of pure carbon. Silicas with
partly carbonaceous walls were
pioneered by the groups of Inagaki
[21], Stein [22] and Ozin [23]. The
synthetic feature which allows
introduction of the alkyl group as an
integral part of the wall structure is
the use of silicon precursors of the
general type RO3Si-R-SiOR3 in which
the alkoxy units are hydrolized and
provide the linkage to other units, but
the bridging alkyl is not attacked
during mesostructure formation and
remains in the material. Even more
fascinating is the synthesis of purely
carbonaceous ordered mesoporous
materials. However, here the pathway
is totally different. The "nanocasting"
mentioned already above has in fact
been pioneered for this class of
Fig. 5: TEM image of an ordered materials, called CMK-1 [24]. A silica
mesoporous carbon CMK-1 obtained with a 3-dimensional pores system (the
from ,,nanocasting" in a MCM-48 micropores connecting the linear pores
mold (top). SEM image of particles of in SBA-15 also provide for
CMK-1 (bottom), from ref. [24]
threedimensionality in this respect) is impregnated with a suitable carbon
precursor, for instance sucrose/H2SO4. The carbon precursor is pyrolized in the
pore system and then the silica framework is removed by leaching with NaOH or
HF. The remaining mesoporous carbon structure has remarkable textural
features due to the low density of carbon, such as a surface area exceeding 1500
m2/g and specific pore volumes far above 1 ml/g. In addition, the mesopore
structure as well as the morphology of the particles on a micrometer scale are
surprisingly perfect (Fig. 5).

4. M A C R O S T R U C T U R E S

The products resulting from the early syntheses of mesoporous silica were
typically finely divided powders with no well defined morphology. Soon, however,
monoliths became available from the true liquid crystal templating route [25] and
from 1996 on a wide variety of different shapes, including spheres, fibers, thin
films, and many other more complex morphologies were reported, some of which
were designed by the process conditions, such as emulsion templating or spin
casting, some of which formed spontaneously by a self-organization process.
These various morphologies are covered in a recent review [26] and shall not be
discussed extensively here.
However, one type of morphologies has
very remarkable structural properties.
These are the fibers and small particles
formed spontaneously in the acidic
quiescent system introduced by Huo et al.
[27]. At the time of the discovery of these
fibers the internal architecture was not
clear, although there were indications
that the channels would run parallel to
the fiber axis [27]. However, recently in
an elegant series of observations, the
group of Marlow clarified the internal
structure of the fibers [28,29]: The fibers
have a circular internal structure, with
the channels of the hexagonal
mesostructure whirling around the fiber
Fig. 6: TEM image of the fiber center axis (Fig. 6). The smaller particles with
of an ordered mesoporous fiber circular or distorted circular symmetry
taken perpendicular to the fiber axis reported in several publications probably
on a microtomed sample, from ref. have a very similiar internal structure,
[28]. which is, however, formed presumably
from a slightly different kind of seed. This kind of internal organization raises
several highly interesting questions, for instance concerning the mechanism of
formation of such structures. Even more fascinating seems to be the fact that
these ordered mesostructured fibers are a novel type for the organization of solid
matter. The objects are neither crystals (no translation periodicity) nor
quasicrystals, but objects with a rotational type of symmetry, called circulites
[30]. This leads to an altered reciprocal space, where the fibers are not
represented as points, as a crystal would, but rather as complex ring structures.
The altered reciprocal space structure is not just a mathematical construct, but
has, for instance, consequences for the diffraction behavior of the fibers.

5. A P P L I C A T I O N S

First obvious applications of ordered mesoporous materials were seen in

catalysis, where a need for zeolite-like materials with bigger pore sizes was
identified to process heavier residues more efficiently. However, since the acidity
of ordered mesoporous materials does so far not substantially exceed that of
amorphous aluminumsilicates, the high expectations could not be met.
If one asks critically, where the advantages of ordered mesoporous materials over
more conventional supports lie, enthusiams will most probably be dampened. For
catalysis, one of the major points is the high surface area of MCM-41, FSM-16,
SBA-15 and all related materials, which can be exploited for depositing metals,
incorporating metals in the walls, or grafting species to the walls. However, this
high surface area is achieved on the expense of a relatively high susceptibility to
hydrothermal degradation and a rather expensive synthesis. Silicas with
approximately half the surface area of ordered mesoporous silica are accessible
by much cheaper and simpler routes. This is not quite the same for non-siliceous
compositions, but here no major efforts seem to have been directed towards their
investigation in catalytic applications, yet. A second beneficial feature of ordered
mesoporous oxides in catalysis could be the sharp pore size distribution which is
reminiscent of zeolites and thus suggests applications in shape selective
reactions. However, the pore sizes realized in ordered mesoporous materials are
so big, that simple molecules will not be processed shape selectively. Large
molecules, on the other hand, are typically so flexible, that the discrimination
between differently sized molecules will not be as effective as, for instance, for
differently substituted benzene derivatives in zeolites.
Therefore, only few publications have appeared, where a clear advantage of
ordered mesoporous materials in catalytic applications has been demonstrated
which would justify their more expensive and complicated synthesis. In addition,
often a good benchmark, such as a high surface area precipitated silica was
lacking for comparison, so that the relevance of published data are difficult to
judge.
Therefore only three examples for the use of surfactant templated mesoporous
oxides in catalytic applications shall be highlighted here. More encompassing
reviews on their catalytic properties can be found in two review articles [31,32]
The first study elegantly used the combination of a suitable acid site strength
and the influence of the regular mesopore system for the preparation of acetals
from aldehydes [33]. MCM-41 was found to be superior to zeolites and amorphous
 aluminumsilicates, if bulky reagents exceeding the size of the zeolite pores shall
be converted. The regular mesopore size of the MCM-41 type materials allows the
whole pore system to be used even with bulky reagents or products, while zeolitic
pores and part of the smaller pores of the amorphous aluminumsilicate are
inaccessible and the catalysts are thus less active. It can be envisaged, t h a t other
reactions in fine chemistry would benefit from the use of ordered mesoporous
materials as well. However, in fine chemistry catalysts are often not tuned to the
process, but rather a standard catalyst off the shelf is used. Ordered mesoporous
silicas and substituted silicas will have to compete with such s t a n d a r d catalysts.
The second example where ordered mesoporous materials were clearly superior
to conventional catalysts is a very old process, the oxidation of sulfur dioxide [34].
Nowadays, part of the sulfuric acid is 10( ....... 4--.
produced from the sulfur dioxide 90 / "'.~quilibriumconversion
released during roasting of sulfidic E 8o V4-111 MCM-41"""
ores. Since the smelters tend to use = 70 /SyFeS:l
0 9e

oxygen instead of air in modern "~ 60 ~ . .""

processes, the resulting gas is very ~ 50 ~ "~'.
sulfur rich and can not be processed u~ 40
over the conventional vanadium c7 3o v 16os
based catalysts. Iron oxide on r 20
surfactant templated silica was found lO
to be a suitable, stable catalyst for o . . . . . . . .
this reaction and clearly 6oo 700 8oo 9oo looo
Temperature [K]
advantageous compared to a
commercial iron-on-silica catalyst, Fig. 7:SO2 conversion vs. temperature
Fig. 7. Also iron oxide deposited on a over v a n a d i u m reference catalyst (V4-
conventional silica was substantially 111), Fe/MCM-41, and commercial iron
less active. The process is ready for catalyst (V1605), from ref [34].
commercialization and a commercial
plant would probably use a catalyst based on an adapted mesoporous silica.
In the last example the mesostructure has been used essentially as a support for
the iron, which is the active component. Another quite spectacular example was
published recently, where a single site polyolefin catalyst was anchored in the
pore system of ordered mesoporous fibers, and the pore system itself was used as
a "nanoextruder" [35]. The resulting polymer consists of crystalline fibers with a
diameter of 30 to 50 n m and a very high molecular weight of 6.200.000 Dalton.
However, since the real structure of the fibers is circular (see above) the
nanoextrusion process claimed is difficult to envisage. The results of the authors
are indeed very remarkable, but they seem to have not been confirmed so far.
Outside of catalysis, other application fields seem to be quite promising. Feng et
al. [36] modified the internal surface of MCM-41 with mercaptopropyl groups.
The resulting materials had excellent binding behavior for heavy metals which
was far superior to commercial adsorbents [37]. Such modified mesoporous silicas
could find applications for water remediation.
 Still relatively unexplored, but potentially a large application field of ordered
mesoporous materials is optics and electronics. Marlow et al. succeeded in the
synthesis of ordered mesoporous silica fibers doped with a rhodamin laser dye
[38]. Upon laser irradiation the waveguide effect reported earlier [27] led to
amplification by stimulated emission along the fiber axis. The light emitted from
the ends of the fibers was spectrally narrowed and highly directional. The effect
observed can be described as a mirrorless lasing which can be useful in the
construction of optical circuits.
A first step in this direction was taken by Yang et al. who produced a prototype
optical circuit with waveguides and mirrorless lasers by soft lithography [39].
The decisive step to realize the waveguide on a support was the use of an ordered
mesoporous silica thin film. For waveguiding to occur, the waveguide needs to
have a higher refractive index t h a n the surrounding. This is a problem, if the
silica waveguide is placed on glass or even on silicon, because there the refractive
index of the support is similar or even higher t h a n t h a t of the mesostructure.
However, a mesoporous silica has, due to the high porosity, a very low refractive
index of only 1.15. This allowed confinement of the light in the structure placed
on this support and enabled the construction of the optical circuit board.
The low refractive index also corresponds to another highly attractive feature of
ordered mesoporous materials, i.e. a low dielectric constant. The search for low k
dielectrics is very intense in m a n y laboratories in the world, since the
semiconductor industry is targeting for dielectric films with k substantially below
2.5. First reports on the dielectric constant of ordered mesoporous silica films by
Zhao et al. [40] gave values between 1.45 and 2.1, depending on the exact nature
of the film. In a subsequent more extensive study these data were essentially
confirmed [41]. Recently the group of Brinker has introduced several highly
innovative methods for structuring mesoporous silica thin films, for instance by
incorporating a photoacid generator which upon UV-exposure leads to generation
of the acid which catalyzes silica condensation. Thus, using masks during UV
exposure, thin films of mesoporous silica can be patterned [42]. Also "printing"
techniques have been developed by this group to prepare micropatterned
structures of ordered mesoporous silica [43]. Due to the easy processability and
the variety of different pathways available to prepare [44] and structure films of
ordered mesoporous silica, the optical and dielectric properties could indeed lead
to their use in technical devices in the electronics industry.

6. P R O S P E C T S

A predicition of future developments is very difficult in any field, but especially

so in a fast moving field such as ordered mesoporous materials. Such prospects
can only be of a very general nature, partly due to the fact t h a t for any specific
interesting idea we would be already working on the realization!
The work published so f a r - and one should realize t h a t ten years ago this field of
research did not even exist! - suggests, t h a t there are virtually no limitations
with respect to the structures and compositions, which can be synthesized as
10

more or less mesostructured compounds. With respect to the compositions, the

successful synthesis of metals and mesostructured carbon by the "nanocasting"
process suggests a very general pathway to produce ordered mesoporous
materials. One will certainly try to load the mesoporous silica templates with
various other precursors and then remove the silica structure. If the material
which shall be casted is not stable against the conditions used for silica removal
(HF or NaOH), one could go one step further and first cast a carbon structure
from a silica mold and then, after silica removal, use the carbon negative as a
new mold to cast the desired material. The carbon structure can then be
removed, for instance, by calcination. It is no great risk to predict exciting
developments in this area.
With respect to applications, there will certainly be more and more investigations
where ordered mesoporous materials are used as catalysts or catalyst supports.
However, the more skeptical note of the section on catalysis shall be repeated
here: In many cases, much cheaper and simpler alternatives exist, and the
properties of ordered mesoporous materials are not so much superior to justify
the higher effort of their synthesis. On a longer time scale, non-siliceous
compositions will probably be used more frequently in catalysis. If one analyzes
the catalytic processes implemented today, the majority is not based on silica as
catalyst or support, and the single most important area of aluminumsilicates,
acid catalysis by zeolites, seems to be less attractive for ordered mesoporous
aluminumsilicates, unless a crystallization of the walls to zeolitic structures or
the assembly of such materials from colloidal zeolites to enhance the acid
strenght becomes possible.
Good opportunities, however, lie in applications outside of catalysis. There are
already very promising initial results, such as the adsorbents for heavy metals or
the low dielectric constant applications. The big advantage for applications in
optics and electronics is the high compatibility of ordered mesoporous silica with
the existing technology, since the chemistry is almost perfectly adapted for use
with silicon, which is covered by a thin silica layer anyway. Also the methods
available for processing, such as spin-coating or dip-coating are well established
techniques, and thus relatively small adaption problems are foreseen, although
they should certainly not be underestimated. First commercial applications will
possibly emerge rather in these fields than in catalysis, but many factors
influence decisions to go commercial with a product, so that the future will show,
whether and where ordered mesoporous solids will find their first practical uses.

7. A C K N O W L E D G E M E N T S

Research of my group in this field was continuously supported by the FCI and
grants from the EU and the DFG which are gratefully acknowledged.
 11

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Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 13

Clinoptilolite-heulandite: applications and basic research

Thomas Armbruster

Laboratorium fur chemische und mineralogische Kristallographie, Universitat Bern,

Freiestr. 3, CH-3012 Bern, Switzerland

Structural peculiarities of clinoptilolite and heulandite are reviewed. Special attention is

given to partial Si, A1 ordering within the tetrahedral framework structure. There is strong
evidence that the Si, A1 ordering pattern depends on the size, charge, and placing of the
original extraframework cations. Even if exchanged to homoionic forms clinoptilolite and
heulandite may display different properties depending on the degree and type of Si, A1
ordering. In some cation-exchanged heulandites symmetry lowering from the topological
symmetry C2/m to Cm or C1 has been observed due to partial Si, A1 ordering and low
symmetry site preference of extraframework cations. Major applications of clinoptilolite are
reviewed. In the field of pollution abatement not only the natural product but also surface
modified clinoptilolites gain importance.

1. INTRODUCTION

Clinoptilolite with the simplified formula (Na,K)6Si30A16072 "nH20 is the most common
natural zeolite found mainly in sedimentary rocks of volcanic origin. Such deposits aroused
strong commercial interest because clinoptilolite tuffs are often rather pure and can be mined
with simple techniques. Approximately 25 years ago ca. 300,000 tons of zeolitic tuff were
mined per year [1]. In 1997 ca. 3.6 Mio tons of natural zeolites (mainly clinoptilolite and
chabazite) were worldwide produced [2], ca. 2/3 alone were stoped in China. Demand for
natural zeolites has increased rapidly over the past decade, particularly in agricultural
applications. Growth rates as high as 10% per year are forecasted [2].
A typical zeolite mining company in the USA, Canada, and Europe has less than 50
employees and produces in open pits 20,000 to 50,000 tons per year. Characteristic
clinoptilolite rocks consist of 60-90% clinoptilolite with the remaining being mainly feldspars,
clays, glass, and quartz. Depending on quality and specification the prize ranges between 50
and 300 US$ per ton. In North America and Europe a large portion of the production goes into
the area of animal hygiene including cat litter and other animal bedding products. The rest is
divided among applications in animal feed, fertilizer, environmental absorption, and building
materials. Zeolitic building material includes dimension stones, pozzolanic cements and
concrete, and lightweight aggregates.
Some of the pioneering zeolite research has been carried out on heulandite with the
simplified formula Ca4A18Si28072 9nH20 because large crystals of this species are available in
limited quantities from cavities and vugs in volcanic rocks, e.g. in the Deccan Trap basalts of
Western India [3]. Already in 1934 Tiselius [4] studied the temperature, pressure, and
concentration dependence of the anisotropic H20 diffusion in heulandite single-crystals. Other
14

recent pioneering studies like atomic force microscopy (AFM) and application of heulandites
as electrodes will be discussed below.

1.1. Mineralogical nomenclature

Zeolite minerals species shall not be distinguished solely on the basis of the framework
Si/A1 ratio. An exception is made in the case of heulandite and clinoptilolite; heulandite is
defined as the zeolite mineral series having the distinctive framework topology of heulandite
(HEU) and the ratio Si/A1 < 4.0. Clinoptilolite is defined as the series with the same
framework topology and Si/A1 > 4.0. The exception is based on entrenched usage of the names
heulandite and clinoptilolite, and their convenience for recognizing an important chemical
feature [5]. Note that in older studies thermal stability has been used to distinguish
clinoptilolite from heulandite. This is a derivative property as an aid to identification, and it is
not appropriate as the basis for definition.
Individual species in a zeolite mineral series with varying extraframework cations are
named by attaching to the series name a suffix indicating the chemical symbol for the
extraframework element that is most abundant in atomic properties, e.g. heulandite-Ca,
heulandite-Na, clinoptilolite-K, clinoptilolite-Ca etc. [5].

2. CRYSTAL STRUCTURE

The structural topology of the tetrahedral HEU framework [6] is well understood and
possesses C2/m space group symmetry with oblate channels confined by ten-membered (7.5 x
3.1 A) and eight-membered tetrahedral rings (4.6 x 3.6 A) parallel to the c-axis. Additional
eight-membered ring channels (4.7 x 2.8/~) running parallel to [100] and [102] cross-link the
former channels within (010), giving rise to a two-dimensional channel system parallel to
(010) responsible for a layer-like structure (Fig. 1).

Fig. 1. Columnar model of the two-

dimensional channel arrangement parallel
to (010) in HEU frameworks. The dark
gray columns parallel to [001] represent
eight- and ten-membered ring channels.
These channels are cross-linked by the
light gray eight-membered ring channels
running parallel to [100] and [102].
 15

There is still doubt about the true symmetry of clinoptilolite and heulandite. Ventriglia [7]
determined heulandite to be piezoelectric but none of the subsequent studies on natural
samples could confirm this low symmetry (either space group Cm or C1). The possible reason
for acentricity is partial Si, A1 ordering within the various tetrahedral sites which is difficult to
resolve by analytical or structural techniques. Thus C2/m is the maximum symmetry which
may be lowered to C2, Cm, C1, and C1. In addition, multiple polymorphs, distinguished by
different distributions of partially Si, A1 ordered tetrahedra, exist in each space group. In a
review of C2/m heulandites and clinoptilolites it was found that: (i) in all cases the tetrahedron
T2 had the highest A1 concentration but below 50%, (ii) the tetrahedron with the second
richest A1 occupation (below 25% A1) could either be T1, T3, T4, or T5 depending on the
sample [8]. In analogy to alkali feldspars it can be postulated that each clinoptilolite or
heulandite may be structurally different, even if a constant Si/A1 ratio is maintained. This
problem is not only of academic interest but has also strong influence on cation diffusion,
cation exchange, gas sorption, and catalytic properties, etc.

2.1. Examples of inconsistent properties

Gunter et al. [9] used three different natural HEU samples of the following composition, H-
I: Ca3.6Ko.8A18.sSi27.4072 926.1 H20, H-II: Ca2.1Mg0.3Na2.sK0.3A18.0Si28.2072 925.5 H20, and H-
III: Ca3.7Nal.3K0.1A18.9Si27.1072 921.4 H20 to study Pb 2+ exchange. The crystals were crushed
to 100-500 Ixm and stirred for 4 weeks in 2 M solution of NaC1 at 100~ to obtain standard
conditions (Na-exchanged varieties). After this time only sample H-III was completely Na-
exchanged whereas samples H-I and H-II stilled revealed significant concentrations of the
original extraframework cations in the core of the crystals. In a second step Na-exchanged
crystals were treated in a similar way for 3 weeks in 2 M solution of lead acetate to obtain
pbE+-exchanged varieties. However, only sample H-III completely exchanged. In particular,
sample H-I with a tetrahedral framework composition almost identical to sample H-In
revealed only Pb 2+ exchange in a very narrow seam on the rim and around cracks. The reason
for this different exchange behavior was not understood [9].
Tarasevich et al. [10] performed K § and Pb 2§ exchange experiments on Na-exchanged
forms of two different natural clinoptilolite samples and noted different selectivity for these
samples although the difference in the SIO2/A1203 ratio was insignificant and the cation
exchange capacities were virtually the same. It should be noted that the selectivity was only
different on a quantitative scale. The characteristic exchange sequence of low-field strength
zeolites [11, 12] remained uninfluenced. Tarasevich et al. [10] speculated that some specific
features of the clinoptilolite structure are responsible for the difference in selectivity. One of
their sample formed in nature as Ca-rich variety whereas the other as clinoptilolite-Na. It was
suggested [10] that an originally Ca2§ clinoptilolite crystallizes for effective charge
balance with a different Si, A1 distribution compared to a Na+-rich clinoptilolite with similar
Si/A1 ratio. Thus even in its Na-exchanged form both clinoptilolites have a 'memory' in the
sense that the originally Ca 2+ rich sample has a stronger selectivity for Pb 2+ (of similar charge
and size) than the originally Na + rich sample which is more selective for K +. This memory
effect is imprinted by the Si, A1 distribution.

Additional exchange isotherms Pb 2§ (solution) ~ 2Na + (clinoptilolite) were recorded [13,

14] under comparable conditions as in [10]. However, a maximum exchange level of ca. 80%
[13, 14] is in contrast to ca. 95% for two different samples [10]. Such discrepancies in the
exchange behavior were discussed by Langella et al. [ 14] concluding that the cation exchange
16

selectivity of clinoptilolite is markedly dependent on its original cationic composition, as not

all the cationic sites in the structure can be made available for exchange. The pronounced
differences in the exchange isotherms (Fig. 2), reported by various research groups [10, 13-
16], are mainly due to assumption of different cation exchange capacities (CEC) for
clinoptilolite. The CEC values are either experimentally determined by different methods or
calculated from the chemical composition of clinoptilolite [13, 17]. In most cases, a so-called
Na-exchanged clinoptilolite is not completely Na-exchanged but still preserves additional
extraframework cations [13, 16]. Furthermore, surface analytical investigations on cation-
exchanged heulandite have demonstrated that metal accumulation on the crystal surface due to
adsorption of soluble and surface precipitation of insoluble hydrolysis products must be
considered [ 18].

2.2. The memory effect in HEU frameworks

Support for the hypothesis of imprinted Si, A1 distributions during crystal growth
depending on the environment and conditions [10] comes from three different approaches: (i)
study of growth texture of natural crystals [19], (ii) structure modeling applying lattice energy
minimization techniques to HEU frameworks with Na and Ca as extraframework cations [20-
23], and (iii) synthesis of HEU frameworks prepared from aluminosilicate gels at 180~ in the
presence of alkali hydroxides [24].

1.0
.....__..... .... - . . . . . . . . . . "='---.---==.---- __ .

0.8 /f ""'"
iS ........................

/ ..7..I
~ o.6ti; ./" ~ /

II/ /

0.2

0 . 0 ~
0.0 0.2 0.4 0.6 0.8 1.0
Xpb (solution)

Fig. 2. Experimentally determined exchange isotherms for Pb 2§ ---, 2 Na § in different natural

clinoptilolites at 20 - 25~ and at 0.1 total solution normality: intermediate and long dashed
curves [ 10], dotted curve [13], solid curve [14]. The discrepancies of the curves are explained
by differences in CEC, extraframework cation distribution, and partial Si, A1 ordering.
 17

Akizuki et al. [19], using optical and X-ray techniques, found within one macroscopic
'single crystal' of heulandite domains of triclinic and monoclinic symmetry. The symmetry is
different from growth sector to growth sector. The two-dimensional atomic arrangement
exposed on a growth-step surface of a tetrahedral (Si, A1) framework differs on each surface.
Depending on whether an extraframework cation is adsorbed on the surface, A13§ (for charge
balance) o r Si 4+ will be incorporated into the adjacent tetrahedron. Thus the degree of partial
Si, A1 ordering is different from growth sector to growth sector depending on its
crystallographic orientation and type of extraframework occupant [19]. In other words, each
crystal is composed of various polymorphs intergrown in a twin-like relationship.
Channon et al. [20] and Ruiz-Salvador et al. [21-23] calculated the minimum energy Si, A1
arrangement for H20-free clinoptilolite-Na, heulandite-Ca, and solid solution members and
determined different A1 site preferences depending on type and placing of extraframework
cations. Characteristic of such models is that for each bulk composition there are always
several possible extraframework cation distributions leading to different Si, A1 arrangements.
Although these calculations were performed for anhydrous species, at least a corresponding
difference in A1 preference may be expected during crystal growth in a natural hydrous
system.
Zhao et al. [24] noticed during HEU framework synthesis that for a given aluminosilicate-
gel composition the Si/A1 ratio in the zeolite framework strongly depended on the applied
alkali hydroxide. Na and K produced HEU zeolites with an Si/A1 ratio significantly higher
than the one in the starting gel, the opposite was found for Li, whereas clinoptilolite-Rb had a
composition close to the gel. These results may be interpreted that depending on the alkali
cation, a different crystal growth mechanism operates. Thus during crystallization different
growth surfaces are exposed leading to a different distribution of A1 tetrahedra [ 19].

2.3. Low symmetry HEU frameworks

There is also direct experimental evidence for low symmetry HEU frameworks. In a series
of exchange experiments (K, NH4, Rb, Cs, Cd, and various alkylammonium ions) using as
starting material the same Na-exchanged heulandite from Nasik (India) with the original
c o m p o s i t i o n Nao.96Ko.09Ca3.54A18.625i27.51072 9 nH20, different space groups (C2/m, Cm, and
C1) were analyzed for the exchanged products [25-28]. The differences in symmetry were
also reflected in different patterns of Si, A1 ordering. There are two explanation for this
observation: (i) The large single-crystals (up to 0.5 mm in maximum dimension) from Nasik
were structurally inhomogeneous [19], (ii) the crystals were all triclinic, space group C1, and
the observed space group depended on whether the exchanged cations occupied a position on
a special position of local 2/m, or m, or 1 symmetry enhancing the symmetry information of
the Si, A1 distribution in the framework. The difference of partial Si, A1 ordering alone
(deviating from C2/m symmetry) is not sufficiently pronounced to be resolved from an X-ray
single-crystal experiment. Notice that not necessarily the 'true' Si, A1 distribution will be
resolved in such a diffraction experiment but only the contribution from the Si, A1
arrangement that is in resonance with the 'signals' from the extraframework occupant.
Probably a combination of both inhomogeneity and low symmetry enhancement is the reason
for the observation of different space groups. Yang and Armbruster [25] studied the structure
of two Cs-exchanged crystals both had C1 symmetry but one crystal displayed a more
pronounced Si, A1 ordering pattern than the other one. This example suggests an
18

inhomogeneous starting material [19]. For all hitherto analyzed triclinic HEU frameworks the
deviation of the tx and ~ angles from 90 ~ was below 0.5 ~ [19, 25, 28, 29].

2.4. Consequences for further research

The above observations and discussions indicate that HEU frameworks behave differently
compared to most synthetic zeolites with disordered or partly disordered Si, A1 distribution.
Even for a given Si/A1 ratio the exact exchange behavior of a HEU framework can not be
predicted based on the existing knowledge. One of the reasons is the low topological
symmetry (C2/m) of the HEU framework compared to the cubic frameworks of e.g. LTA or
FAU. In low symmetry structures the distribution of Si and A1, or the existence of numerous
polymorphs, plays a much more important role than in a high symmetry framework. In
summary, we have to accept the conclusion [14] that for any 'sophisticated' practical
application of natural clinoptilolites specific studies on representative samples from the
deposit that is being examined for its exploitation potential have to be carried out.
Even exact knowledge of the exchange behavior of well defined synthetic HEU
frameworks [24] would not circumvent this problem. For a natural sample we never know its
original formation condition and extraframework composition. It could well be that
subsequent penetrating fluids in the deposit altered the original composition.
The positive aspect of the structural complexity of HEU frameworks is that it offers the
chance to learn more about tailor-made design of synthetic tetrahedral framework structures
with only partly ordered Si, A1 distribution.

2.5. The Si, AI distribution in 'activated' clinoptilolite

For most catalytic applications 'activated' zeolites are required. There are two standard
routes how this activation can be achieved. Fairly well understood is ion-exchange to
clinoptilolite-NH4 with subsequent release of H20 and NH3 upon heat treatment above 843 K
leading to anhydrous clinoptilolite-H with BrCnsted centers [e.g. 30, 31]. Upon
dehydroxylation at higher temperature the concentration of BrCnsted sites (acidic hydroxyl
groups) decreases and Lewis sites are formed. Heat treatment of clinoptilolite-NH4 above 673
K leads also to partial dealumination of the framework and migration of A1 to extraframework
sites [32, 33].
The second mechanism is based on acid treatment of the 'raw' zeolite [e.g. 34]. It was
hitherto believed that the extraframework cations are replaced by H30 + and the tetrahedral
framework is altered by loss of A1. According to Sychev et al. [34] 27A1 and 29Si NMR spectra
of acid treated clinoptilolite-Na indicated that tetrahedral fragments consisting of SiO4
tetrahedra connected to two A104 tetrahedra are attacked, decreasing (for 2M HC1) the A1
concentration from originally 5.9 to 4.1 pfu. Misaelides et al. [35] leached natural heulandites
for 48 h with HC1 solution of varying concentration (0.001 to 2 M) and noticed for samples
treated with 1 and 2 M HC1 partial surface amorphization and decreasing A1 concentrations
from the interior to the rim. The rim approached characteristics of amorphous silica gel [35-
37]. Yamamoto et al. [38] imaged by atomic force microscopy the (010) surface of heulandite
leached with 0.2 N H2SO4 and found pits caused by layer-to-layer dissolution. Heulandite-Na
exposed for 15 weeks at 423 K to 0.5 M REEC13 solution (pH 2.8) led to surface erosion and
almost complete extraction of Na also in the center of heulandite crystals [39]. The loss of A1
in the center of the crystals was low. Subsequent X-ray single-crystal structure analysis [39]
indicated partial rearrangement of framework A1 to hydrated extraframework A1, where A1
 19

preferred octahedral coordination. Thus not only H30 § but also A13§ appeared as
extraframework cations.
In other words acid leaching of heulandite causes (i) A1 and extraframework cation
depletion on the surface leading to an amorphous silica layer and (ii) depletion of
extraframework cations in the core of the crystals where the HEU framework is still intact. In
extreme cases all extraframework cations are lost and for charge balance two different
exchange mechanisms operate:

Na8A18Si28072 + 8 H30+ ----~[H30+]8A18Si28072 + 8 Na § (1)

Na8A18Si28072 + 2 Si 4+ ~ [A13+]2A16Si30072 + 8 Na + (2)

These data indicate that the structural state of acid leached heulandite or clinoptilolite is
only poorly defined. The acidity of the solution, the time and temperature of leaching, crystal
size, original crystal structure and composition have a strong influence on the leached
structure. Variation of any of these parameters may cause variations in the structural state and
in the associated catalytic behavior of the leached material.

3. RECENT P I O N E E R I N G STUDIES

3.1. Atomic force microscopy (AFM)

Selective catalytic reactions occur also by molecular recognition on the external surface of
zeolite crystals and therefore surface-structural information is vital for understanding catalytic
mechanisms [40]. Large natural crystals of heulandite are available from various deposits and
for this reason some of the pioneering AFM imaging of zeolite surfaces has been performed
on these minerals [41-45]. 'Molecular resolution' was obtained for the heulandite (010) face
that is densely packed without giving access to the two-dimensional channel system. This face
was selected because it is prominent in natural crystals and (010) is also a perfect cleavage
plane. In contrast, the resolution of the (100) surface, characterized by channel mouths of the
eight-membered ring channels, was considerably poorer. Channel in- or outlets could not be
resolved but appeared as undifferentiated grooves. Yamamoto et al. [45] argued that the lower
resolution is caused by the tip-sample interactions on corrugated surfaces due to the channel
mouths. In addition, it must be considered that faces like (100) are always decorated by traces
of the perfect (010) cleavage and have therefore a rough surface. Corresponding low-
resolution results were obtained for channel mouths in natural stilbite and mordenite.
However, the ordered pore structure characterized by 12-membered tings could be imaged on
the (001) face of a synthetic mordenite after scrapping off amorphous coatings [46].
Crystal growth induced steps (n x 9/~) on the heulandite (010) surface are either one or
multiple tetrahedral layers thick [45]. Similar features have previously been observed on (010)
cleavage plates [42]. In addition, growth spirals [44] and etch pits [38] on heulandite (010)
faces were imaged.
Adsorption of pyridine bases is generally applied to test the surface acid properties of
zeolites. Adsorbed pyridine base molecules interact with the surface acid site and the strength
of the interaction can be monitored by spectroscopic methods. Komiyama et al. [47] obtained
in situ molecular AFM images of well ordered arrays of pyridine and I]-picoline on the (010)
20

surfaces of heulandite and stilbite and examined their orientation by semi-empirical molecular
orbital calculations.

3.2. Clinoptilolite- heulandite electrodes for analytical application

A carbon paste electrode modified with Cu2+-doped clinoptilolite powder has been
evaluated as an amperometric sensor for non-electroactive NH4 + in flow injection analyses
[48]. The conductivity of heulandite single crystals parallel to [ 100] has been studied under
isothermal conditions as a function of the H20 content, small polar organic molecule
concentration, and charge compensating cations. Results indicate that heulandite electrodes
will be applicable for analytical purposes in aqueous solution [49].

4. APPLICATION

4.1. Ion exchange and adsorption

Clinoptilolite and heulandite are low field strength zeolites for which the cation specivities
Cs + > R b + >NH4 + > K + > N a + > L i + >I-V, andBa 2+ > S r 2+ > C a 2+ > M g 2+ are predicted[ll,
12]. Corresponding theoretical estimates yielded Ba 2+ > Pb 2+ > Cd 2+ > Zn 2+ > Cu 2+ [16] but
experiments revealed Pb 2+ -~ Ba 2+ >> Cu 2+ , Zn 2+ , Cd 2+ . Using clinoptilolite-Na as reference
N H 4 + > P b 2+ > Na + > C d 2+ > C u 2 + _= Z n 2+ [ 14] and P b 2+ > N H 4 + > C u 2+ ___-C d 2+ > Z n 2+ ~ C o 2+ >
Ni 2+ > Hg 2+ [15] has been determined.
Charge-balancing cations present on the surface of very fine-grained clinoptilolite can be
replaced by high-molecular-weight quaternary amines [50], such as hexadecyl-
trimethylammonium (HDTMA) whereas the intemal zeolite cavities remain accessible for
small cations. Surfactant modified zeolites (SMZ) absorb CrO42-, benzene, and
perchloroethylene (PCE) suggesting that a stable HDTMA bilayer (Fig. 3) formed on the
external surface of the zeolite. Nonpolar organic solutes are sorbed by the organic phase
whereas anions (CrO42) are retained on the outward pointing positively charged headgroups
of the surfactant bilayer [50]. Various types of surfactants on clinoptilolite were applied to
extract benzene, toluene, and xylenes from petrochemical spills [51]. HDTMA modified
clinoptilolite exhibits enhanced sorption of U 6+ [52, 53].

Fig. 3. Sketchy drawing of

HDTMA forming a bilayer (tail
to tail) on the surface of
clinoptilolite [50]. Nonpolar
organic molecules (PCE)
partition into the bilayer, anions
(CrO42) exchange with the
counterions of the suffactant,
cations (Pb 2+) bind to the zeolite
surface.
 21

~i-MnO2 precipitated on the clinoptilolite surface was successfully applied for removal of
Mn 3§ from surface and deep-well water [54, 55] and for the treatment of paint-shop effluents
[56].

4.1.1. Pollution abatement

Pilot studies of NH4+ removal from municipal wastewater by using clinoptilolite-containing
tuff were reported from various countries. After exchange and subsequent regeneration of the
zeolite with NaC1/KC1 solutions ammonia was stripped from the solution and an ammonium-
phosphate fertilizer was produced. The Tahoe-Truckee Sanitation Agency, California, treated
between 1978 and 1993 8.107 m 3 wastewater applying a clinoptilolite tuff for ammonia
exchange. The system was designed to accommodate a flow rate of 26,100 m3/day of
wastewater and to extract 19.5 mg NH4/liter (507 kg) from a feedwater containing ca 25
mg/liter [57]. Ca-saturated clinoptilolite is used for ammonia removal from NASA's advanced
life support wastewater system [58] to establish long term human presence in space. Natural
zeolites are also produced for Pb 2§ and Cd 2§ removal from wastewater [e.g. 59, 60] and many
other environmental application [61 ].
Low-cost surfactant-modified zeolites (SMZ) have been prepared in multi-ton quantities for
use as subsurface permeable barriers to ground-water contaminant migration [50]. Most other
studies on SMZ comprise small-scale laboratory experiments [e.g. 62, 63].

4.1.2. The 1986 Chernobyl disaster

In the USA and Great Britain phillipsite-, clinoptilolite-, and chabazite-rich tufts are
routinely applied for the decontamination of radioactive wastewater to remove Cs and Sr
radioisotopes [e.g. 64]. However, these are small-scale operations compared to the extensive
use of natural zeolites at Chernobyl.
During the Chernobyl disaster thirty to forty times the radioactivity of the atomic bombs
dropped on Hiroshima and Nagasaki were released. The main radioactive isotopes from the
Chernobyl accident were ~37Cs, 134Cs, 9~ and 89Sr. The details of zeolite applications at
Chernobyl remain rather obscure because of a secrecy problem still remaining after
disintegration of the former Soviet Union. About 500,000 tons of zeolite rocks, mainly
containing clinoptilolite, were processed at various deposits in Ukraine, Georgia, and Russia
specifically for use at Chernobyl [65]. The majority of the zeolites was used for the
construction of protective barriers and for agricultural applications in polluted areas.
Decontamination of potable water of the Dnieper fiver by using a combination of dust-like
clinoptilolite and aluminum sulfate followed by filtration through clinoptilolite layers led to a
drastic decrease of radioactivity [66, 67]. In addition, filters of clinoptilolite tufts were
suggested to extract radionucleides from the drainage water of the encapsulated Chernobyl
nuclear power plant. Filtration reduced 137Cs by 95% and 90Sr by 50-60%. After one year the
filters carrying a radioactivity of 10.5 Ci/kg were exchanged and buffed [66].
To reduce Cs radionucleides in cow milk in Bulgaria 10% clinoptilolite was added to the
cow feed resulting in 30% Cs reduction in the milk [68]. For Cs decontamination of children
chocolate and biscuits were prepared containing 2-30 wt.% pure and powdery clinoptilolite
[68]. In Western Europe clinoptilolite was tested to reduce radionucleide levels in soil [69],
plants [70], sheep [71], broiler chicken [72], and fruit juice [73].

4.1.3. Agronomic and horticultural applications

The purpose of zeolite application in this field is slow-release fertilization or a combination
of ion-exchange and mineral dissolution reactions. Mainly K- or NH4-saturated clinoptilolites
22

are used [74]. The term zeoponics can be applied to the cultivation of plants in any artificial
soil in which zeolite minerals constitute an important component, e.g. in microgravity
environments or lunar outposts [75]. The first zeoponic space vegetables grown from seeds
were tiny radish roots produced on MIR OS in 1990 [76].

4.1.4. Animal hygiene and bedding products

Application of clinoptilolite in this area is favorable because of its high NI-I4+ exchange
capacity and surface absorption of odors (e.g. ethylene, aldehydes, mercaptans, ketones, H2S).
Cat litter is sold in small bags yielding a profitable prize of ca. 800 US$ per ton [77].
Clinoptilolite occupies only a small niche in this market. The majority of cat litter is produced
from clays. The annual volume of cat litter worldwide consumed equals about the annual
production of natural zeolites.

4.1.5. Nutrition and health

The physiological effects of clinoptilolite appear to be related to their high cation-exchange
capacity, which affects tissue uptake and utilization of NH4+, Pb 2+, Cd 2+, Cu 2+, Cs +, and other
cations in animals [78]. Clinoptilolite appears to be stable in the gastrointestinal tract and
reduces ammonia toxicity in pigs and sheep. In ruminants clinoptilolite alters rumen
fermentation, thereby modifying volatile fatty acid production by rumen microbes and
changing milk and body fat content. Pigs, chickens, and turkeys are protected from
mycotoxins in contaminated grains. The aflatoxin concentration in milk is reduced if cows are
fed aflatoxin-contaminated feeds. The details of this protection mechanism is not yet
understood but adsorption on the zeolite-surface may play an important role. In general,
addition of 1 to 5 wt.% clinoptilolite to the diet of animals has been shown to improve growth
and feed utilization and to reduce the incidence and severity of diarrhea in pigs, cattle, sheep,
and chickens. Ag-exchanged clinoptilolite eliminates the microorganisms E. coli and S.
faecalis from water after 2 h of contact time [79]. Clinoptilolite application is not restricted to
animals but an anti-diarrheic drug (ENTEREX) has also been developed for humans [80].
Preliminary studies have been performed to test the potential use of clinoptilolite as a matrix
for slow drug release [81, 82].

4.1.6. Gas separation

The gas adsorption characteristic of clinoptilolite strongly depends on the extraframework
cations [83]. Nitrogen uptake, relative to methane, increases significantly away from the either
pure Ca- or K-exchanged form. It is suggested that a specific K-Ca distribution within the
structural channels may act as hydration controlled nano-valve [84] permitting diffusion of N2
but repelling CH4. Partly exchanged clinoptilolites applied for N2 and 02 separation from air
yielded increasing separation rates for the sequence K > Rb > Na > Cs > Li [85]. There are
several patents describing separation of CI-I4 from N2, hydrocarbons from CO2 and N2, 02
enrichment in air, and SO2 separation from air.

4.2. Catalysis
As examples, xylene isomerization, toluene hydrodemethylation, n-butene isomerization,
dehydration of methanol to demethyl ether, hydration of acetylene to acetaldehyde [31],
catalytic reduction of NO [86] have been described to be successful if applying different
varieties of treated clinoptilolite (cation exchanged or 'activated'). For a rough estimate about
the importance of clinoptilolite for catalytic applications a search in the Chemical Abstracts
 23

was performed (clinoptilolite and catalysis) leading to 413 hits between 1966 and 1999 (1-32
papers per year). Due to the low number of publications per year the histogram (Fig. 4) reveals
a fairly coarse structure but a maximum in the early eighties and a minimum in the early
nineties with a subsequent increase to recent times is recognized. If the statistical clinoptilolite
data are normalized to the total number of papers dealing with zeolite and catalysis (31,034
hits) the maximum in the early eighties (ca. 3 % of the papers on zeolite catalysis) becomes
even more prominent (Fig. 4). A closer look at research subjects in the statistical peak area
does not indicate any specific invention that could be responsible for the increased scientific
activity at this time. However, during increased activity (early eighties) more than 70% of the
listed papers were written in Russian. In contrast, in 1998 ca. 60% were written in English
(20% in Russian) but ca. 40% of the research institutions still belonged to countries of the
former Soviet Union. The shallow minimum in the early nineties is characterized by a
decreased publication activity in the former Soviet Union.
Thus the statistical pattern is governed by the political development in Eastern Europe.
During the cold war East European countries had no excess to the major producers of
synthetic zeolites thus they developed technologies to use their abundant natural deposits for
catalytic applications. The disintegration of the Soviet Union, accompanied by a political and
economic crisis, led to a decrease of research activity in this field. The slight recovery of this
trend in recent time is associated with an increased number of English papers written by East
Europeans (lift of the iron curtain). One may extrapolate that in the future natural zeolites will
become less important for catalytic applications.

Fig. 4. Histogram of papers listed in the Chemical Abstracts dealing with clinoptilolite and
catalysis. The inlet displays a histogram of papers on zeolite and catalysis. This histogram is
used to normalize the clinoptilolite and catalysis histogram. Notice the maximum in the early
eighties caused by an increased research activity in the former Soviet Union.
24

5. OUTLOOK

The highest profits for clinoptilolite seem to be achieved in the field of cat litter, animal
bedding, and odor absorbents. With increasing environmental conscious applications in
pollution abatement gain importance, in particular, if large amounts of ion exchanger or
absorber are needed. The versatility of surface modified clinoptilolite is not fully explored yet.
As the recent example of U 6§ sorption [52,53] on the surfactant indicates, many other
applications seem possible where the advantages of the porous bulk structure are combined
with specific properties of well-chosen surfactants.
Most of the basic research work concentrated on ion exchange behavior studied in form of
exchange isotherms. Nevertheless kinetic aspects are equally important [9, 87, 88] and there is
a lack of knowledge, in particular for structurally and chemically well-defined clinoptilolites.
Structure modeling has to be expanded to hydrous systems [89] to provide better
understanding of H20 interactions with extraframework cations and the inner cavity or
channel surface. HEU frameworks are interesting research subjects because of the only partly
ordered Si, A1 distribution, the low symmetry of the framework, and the different types of
channel systems. In this respect understanding of structure and properties of clinoptilolite
provides a key for zeolites in general.

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Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 29

Evolution of extra-large pore materials

Mark E. Davis

Chemical Engineering, California Institute of Technology, Pasadena, CA 91125

The history of extra-large pore, crystalline materials is briefly reviewed.

Relationships between extra-large pore molecular sieves and ordered mesoporous
solids are outlined and the difficulties in creating crystalline, mesoporous
materials discussed. The possible importance of three-membered rings in the
preparation of extra-large pore microporous and/or mesoporous structures is
described. The dichotomy between the high cost of production of extra-large pore
materials via large, organic structure-directing agents and the low cost of the
inorganic solid for typical commercial applications is enumerated and a new
synthetic strategy provided to circumvent this problem.

Keywords: extra-large pore materials, ordered mesoporous materials,

zincosilicates, three-membered rings, large organic structure-directing agents

1. Introduction
It has been slightly over a decade since the first publication on the
existence of an extra-large pore molecular sieve; namely VPI-5 [1]. We
suggested at that time the use of the term extra-large pore to describe crystalline
materials having pores comprised of greater than 12 tetrahedral atoms (> 12 MR)
[2]. This area of scientific endeavor has grown substantially in the past ten years
and was certainly one of the factors contributing to the discovery of the ordered,
mesoporous materials [3,4]. Here, I will review the brief history of extra-large
pore materials, discuss the search for new extra-large pore materials, describe the
relationships between extra-large pore materials and ordered, mesoporous
materials and end by outlining a new strategy for the preparation of extra-large
pore materials.

2. History of extra-large pore materials

Richard Barrer and his collaborators were the first to publish (in 1969) on
the idea of extra-large pore, crystalline materials [5]. Barrer and Villiger
presented a series of hypothetical structures related to zeolites L, cancrinite,
offretite and gmelinite that had 24 MR pores with free diameters of approximately
30

15 * [5]. Some of these networks consist of known, local atomic arrangements

that do not violate crystal chemistry constraints, e.g., bond lengths and angles.
The following passage is taken directly from the Barrer and Villiger paper:
"Structures of the kind illustrated in Fig. 8 and Table 4, column 5, if they can be
synthesized, may be of special significance. Both in respect of accessibility of
intracrystalline pores and of total porosity (-- 0.6 of crystal volume) they would be
well above any crystal hitherto known." Clearly, Barrer and Villiger set the stage
for what was to come. However, what is surprising is that it took over a decade
before significant discussions of extra-large pore materials appeared in the
literature. In 1984, Smith and Dytrych described nets with channels of unlimited
diameter and in particular a series of nets denoted 81 (n) [6]. Nets 81 and 81 (1)
later turned out to be the topologies of A1PO4-5 and VPI-5, respectively [1].
Smith and Dytrych realized the significance of this net: "The 81 (n) series of nets
is particularly rigid, and might prove useful in engineering design." Additionally,
they suggested that large organic species, including chains and helices, should be
considered as structure directing agents to prepare extra-large pore materials, e.g.,
81(n) where n > 1. It is clear that Smith and Dytrych also anticipated the
synthesis of extra-large pore, phosphate-based materials since they discussed the
existence of the large channels (15 * ) in the phosphate-based mineral cacoxenite
[7].
In the mid-1980's we began a program with the specific goal of
synthesizing extra-large pore materials. Using the aforementioned literature as
models, we initiated the exploration using large organic structure directing agents
(including low generation dendrimers) with both silica and phosphate-based
chemistries. In 1986, we prepared the material now denoted as VPI-5. It is not
surprising that extra-large pore materials can be phosphate-based because of the
existence of cacoxenite. VPI-5 was an unusual extra-large pore molecular sieve
since it did not require a large organic structure directing agent for synthesis [8].
After the discovery of VPI-5, numerous phosphate-based, extra-large pore
materials were prepared, e.g., see Table 1 of ref. 9, [10], etc. All of these
materials require an organic component as part of the synthesis mixture (as does
VPI-5 when preparing highly stable, good quality crystals). However, only VPI-5
does not contain organic components filling the pore space in the as-synthesized
form.
As expected, silica-based extra-large pore materials have also been
prepared, i.e., UTD-1 [11] and CIT-5 [12]. UTD-1 requires an organometallic
structure directing agent while CIT-5 uses more traditional quaternary ammonium
compounds. Thus, the preparations of UTD-1 and CIT-5 follow the reasoning
outlined by Smith and Dytrych with regard to the organic phase. The phosphate-
based, extra-large pore materials are not consistent with the idea of using large
organics since they tend to contain a high volume fraction of smaller organics
(that is, they do not structure direct) or none at all (VPI-5).
 31

Since the phosphate-based, extra-large pore materials do not reveal

stability that is likely sufficient for many commercial applications, I will limit my
discussions below to silica-based materials. As I have discussed elsewhere, the
lack of stability in phosphate-based materials may not be due to the presence of
extra-large rings, but rather to the nature of the structural units [9]. With silica-
based, extra-large pore materials, it appears that bulky structure directing agents
will be required for their preparation. I will make this assumption in further
discussions below.

3. From extra-large pore crystalline materials to ordered, mesoporous

materials
The announcement of VPI-5 proved that extra-large pore molecular sieves
could exist. This report encouraged significant further work. In addition to
stimulating research on crystalline materials, VPI-5 played an interesting role in
the discovery of the ordered, mesoporous materials. The paper by Kresge et al. in
1992 [3] opened the way for the vast amount of effort that has now been
performed on ordered, mesoporous materials. The Kresge et al. report clearly
showed the ordering that could occur in these types of materials and some of their
properties. They also suggested how these materials may be formed. The solid
with hexagonal symmetry was identified early on and several groups suggested
that it may be one of the members of the 8 l(n) series for which VPI-5 is 81(1).
However, we clearly showed that these types of materials are not crystalline, but
more like amorphous oxides since dehydrated samples had Raman bands
indicative of planar 3 MR stretching vibrations [ 13]. Crystalline frameworks with
3 MR do not reveal these vibrations [14] as only 3 MR at the surface of
amorphous oxides reveal planar 3 MR vibrations [15]. Thus, it was absolutely
clear from our results that the ordered, mesoporous materials were not crystalline
frameworks [13]. Knowing this, it is expected that the mesoporous materials can
be formed from any element combination making amorphous solids (including
organic-inorganic materials [16]). Thus, it is not surprising that the ordered,
mesoporous materials can be prepared to contain numerous element combinations
and ones not available to crystalline solids.
Since many properties of crystalline oxides, e.g., acidity, hydrothermal
stability, etc., are the essential features exploited in commercial applications of
these oxides, it is not unexpected that the ordered, mesoporous materials have not
yet found much commerical use. The large void volumes, pore sizes and surface
areas of the ordered, mesoporous materials provide advantages over microporous
solids in certain areas of application but issues such as stability remain. Thus, if
crystalline, extra-large pore solids could be prepared in the pore size and void
volume ranges of the mesoporous materials, they would be immediately
commercialized. The question remains as to why crystalline materials of this size
range have not been synthesized. Navrotsky et al. have shown that pure silica,
ordered, mesoporous silicas are energetically very close to pure silica, crystalline
32

molecular sieves [17]. For example, pure silica FAU has an enthalpy of 13.6 +
0.7 kJ/mol relative to quartz while MCM-41 has a value of 14.5 + 0.5 kJ/mol.
Since the thermal energy at 373 K is 3.1 kJ/mol, these two structures are well
within the available thermal energy of one another. Also, I predicted that if the
materials were to be synthesized from aqueous solutions, they would have void
fractions of approximately 0.8 or below [9]. There are ordered, mesoporous
materials that conform to this limit. Thus, one is left to ponder why crystalline
mesoporous materials have not yet been synthesized.
The ordered, mesoporous materials can be prepared by many synthetic
routes. This is not surprising since the lack of crystallinity does not place as many
demands on the assembly process as with zeolites. By following the assembly
process with in situ NMR, we were able to show that the high temperature
construction of MCM-41 involved the formation of organic aggregates that
subsequently ordered silica to form the final composite [18]. At other conditions,
the assembly process can be different and involve layered phases [ 19]. Since it is
now established that layered materials can be transformed into crystalline solids,
e.g., MCM-22 [20], FER [21], VPI-5 [22], ERB-1 [23], the lack of crystalline
mesoporous materials is not likely due to the inability to form layered
intermediates.
A possible reason for the lack of a crystalline mesoporous material could
be related to the nature of the building units used for assembly. In 1989, Brunner
and Meier [24] published a correlation between the framework density, FD
(number of tetrahedral atoms per nm3), and the minimum ring size in the structure
(MINR). For structures where the smallest ring for certain T-atoms is variable,
the MINR value would have a + associated with it, e.g., MINR = 4+ for structures
with some T-atoms in 4 MR whereas for others it is larger. I articulated some of
the implications of this correlation at the time of the Brunner-Meier publication
[25]. Of importance, I mentioned the possible synthesis of MINR = 3 or 3+
structures using elements other than beryllium because of its toxicity. If the
Brunner-Meier correlation is correct, then the highest void volume, crystalline
silica likely already exists. Since 3 MR are not synthetically feasible with
crystalline silicas, a MINR = 4 framework will contain the highest void volume.
From the Brunner-Meier correlation, the FAU topology is near the maximum void
volume for MINR = 4 structures. To achieve the higher void volumes like those
of the mesoporous materials, MINR = 3 or 3+ structures may need to be prepared.
Berylosilicate chemistry does promote the formation of 3 MR as evidenced by a
number of berylosilicate minerals, e.g., lovdarite, phenakite, euclase, and a
synthetic analogue of lovdarite does exist [26]. However, the use of beryllium
renders berylosilicates to be commercially unacceptable because of toxicity
issues. Thus, in 1989, we began a program to prepare MINR = 3 or 3+ materials
using zincosilicate chemistry since there are many zincosilicate analogues to 3
MR-containing berylosilicates. Listed below are the new zincosilicates prepared
in our group.
 33

Table 1. New Zincosilicates

Material Structure Si/Zn Pore Size M I N R = 3+ Re f.

VPI-7 VSV (FD= 17.1) 3.5 9 MR yes 27

VPI-8 VET (FD=19.8) > 20 12 MR no 28

VPI-9 VNI (FD= 16.7) 4 8 MR yes 29

VPI- 10 no code (FD= 15.3) 3.5 9 MR yes 30

Zn-ANA ANA (FD= 18.6) 4 8 MR no 31

Zn-SOD SOD (FD= 17.2) 6 6 MR no 32

CIT-2 no code (FD=15.8) 4 9 MR yes 33

CIT-6 *BEA (FD=15.0) > 15 12 MR no 34

Additionally, Rohrig and Gies [35] have synthesized a zincosilicate denoted

RUB-17 (RSN, FD = 16.8, MINR = 3+). Zinc is a relatively inexpensive, non-
toxic element and as shown above, can be used to prepare MINR = 3+ materials.
Additionally, there is a MINR = 3 zincosilicate mineral giving precedence for the
existence of MINR = 3 micro and/or mesoporous, crystalline solids. Thus, the
use of silica-based frameworks containing zinc could in principle lead to
commercially viable extra-large pore materials that may be near the porosity of
the ordered, mesoporous materials.

4. A new strategy for synthesizing extra-large pore materials

It is clear that crystalline, extra-large pore materials would be of
significant commercial interest. The problem is their preparation and ultimately
control of their properties. Based on the known extra-large pore materials, silica-
based systems would be preferred over phosphate-based ones when dealing with
issues such as stability and acidity. Another critical item is cost. For numerous
applications, e.g., cracking and other refinery processes, the materials cannot be
expensive. If one assumes that large organic moieties will be necessary for the
preparation of extra-large pore, silica-based materials, the costs of the organic
components are not compatible with the ultimate application of the porous solid.
Thus, this issue must also be resolved.
In some cases, the organic can be extracted from the molecular sieve. For
pure-silica *BEA, Jones et al. [36] were able to extract the tetraethylammonium
fluoride that was used as the structure directing agent (SDA). In that case, a small
organic was used to prepare a 12 MR material. In some aspects, this situation is
34

like that of the small organics used to prepare some of the extra-large pore,
phosphate-base materials. The major difference of course is the stability of the
inorganic portion; *BEA has very good stability while the phosphate materials do
not. In principle, the small organics could organize and pack into ordered
arrangements to yield large void spaces upon their removal. However, in
practice, this type of organization has yielded only non-crystalline mesoporous
materials (organics can also be extracted from mesoporous materials [13]). Thus,
if a single large, bulky organic is necessary to structure direct extra-large pore,
crystalline materials and the cost of the final product is somewhat limited, then
how does one achieve the goal of producing such a material? In Fig. 1 a
schematic of a new concept for the synthesis of extra-large pore materials is
shown and illustrates how the previously posed question may be answered.

component A +
component B
ble
extra-large f
pore z ~ l i t e / /

~~~) + [component A +
component B]
bulky component C (SDA)

extra-large ~ [or precursors to]

pore zeolite ~

disassemble ~ ~ . ynthesis,
component C, ~ ( component )~_...-~
e.g., at low pH ~ e.g., at high pH
extra-large
pore zeolite
Figure 1. New Concept for Extra-Large Pore Zeolite Synthesis [37]

The idea is to combine two or more components into a large, bulky organic
structure directing agent. The assembly can be via the formation of covalent
bonds and/or through non-covalent interactions. The assembled SDA must
remain stable to synthesis conditions, e.g., high pH with zeolites, in order to
structure direct an extra-large pore material. Upon formation of the organic-
inorganic composite, the organic component now is disassembled at conditions
that are not sufficient to harm the inorganic structure. The key to this concept is
that the organics formed from the disassembly of the SDA can be re-assembled to
make again the SDA. Thus, a large, bulky SDA is used to prepare the inorganic
 35

structure and the components of the SDA are recycled in order to make the cost of
the synthesis low. Numerous strategies can be employed with this idea. The
concept is not unlike what happens in the assembly of the ordered, mesoporous
phases. However, for the synthesis of extra-large pore crystalline materials, the
assembly most likely will involve a small number of molecules (likely 2 or 3) to
form the SDA and covalent linkages may also be exploited.

5. Summary
The areas of extra-large pore, crystalline solids and non-crystalline,
ordered mesoporous materials both continue to flourish. By investigating further
the fundamental rules involved in their syntheses, it may be possible to make new
solids with the advantageous properties of both existing classes of materials.
Some of the issues of concern when performing such syntheses have been
outlined here and several new suggestions for research provided.

REFERENCES
[ 1] M.E. Davis, C. Saldarriaga, C. Montes, J. Garces and C. Crowder, Nature,
331 (1988) 698.
[2] M.E. Davis, P.E. Hathaway and C. Montes, Zeolites, 9 (1989) 436.
[3] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli and J.S. Beck,
Nature, 359 (1992) 710.
[4] T. Yanagisawa, T. Shimizu, K. Kuroda and C. Kato, Bull. Chem. Soc.
Jpn., 63 (1990) 988.
[5] R.M. Barrer and H. Villiger, Z. Kristallogr., 128 (1969) 352.
[6] J.V. Smith and W.J. Dytrych, Nature, 309 (1984) 607.
[7] P.B. Moore and J. Shen, Nature, 306 (1983) 356.
[8] M.E. Davis, C. Montes and J.M. Garces, ACS Syrup. Ser., 398 (1989) 291.
[9] M.E. Davis, Chem. Eur. J., 3 (1997) 1745.
[10] G.Y. Yang and S.C. Sevov, J. Am. Chem. Soc., 121 (1999) 8389.
[11 ] C.C. Freyhardt, M. Tsapatsis, R.F. Lobo, K.J. Balkus Jr. and M.E. Davis,
Nature, 381 (1996) 295.
[12] M. Yoshikawa, P. Wagner, M. Lovallo, K. Tsuji, T. Takewaki, C.Y. Chen,
L.W. Beck, C. Jones, M. Tsapatsis, S.I. Zones and M.E. Davis, J. Phys.
Chem. B, 102 (1998) 7139.
[13] C.Y. Chen, H.X. Li and M. E. Davis, Microporous Mater., 2 (1993) 17.
[14] M.J. Annen and M. E. Davis, Microporous Mater., 1 (1993) 57.
[15] C.J. Brinker, R.J. Kirkpatrick, D.R. Tallant, B.C. Bunker and B. Montez,
J. Non-Cryst. Solids, 99 (1988) 418.
[16] S. Inagaki, S. Guan, Y. Fukushima, T. Ohsuna and O. Terasaki, J. Am.
Chem. Soc., 121 (1999) 9611.
[17] A. Navrotsky, I. Petrovic, Y. Hu, C.Y. Chen and M.E. Davis, Microporous
Mater., 4 (1995) 95.
36

[181 C.Y. Chen, S.L. Burkett, H.X. Li and M.E. Davis, Microporous Mater., 2
(1993) 27.
[19] A. Firouzi, D. Kumar, L.M. Bull, T. Besier, P. Sieger, Q. Huo, S.A.
Walker, J.A. Zasadzinski, C. Glinka, J. Nicol, D. Margolese, G.D. Stuckey
and B.F. Chmelka, Science, 267 (1995) 1138.
[20] M.E. Leonowicz, J.A. Lawton, S.K. Lawton and M.K. Rubin, Science, 264
(1994) 1910.
[21] L. Schreyeck, P. Caullet, J.C. Mougenel, J.C. Guth and B. Marler, J.
Chem. Soc. Chem. Commun., (1995) 2187.
[22] M.E. Davis, C. Montes, P.E. Hathaway and J. M. Garces, Stud. Sur. Sci.
Catal., 49 (1989) 199.
[23] R. Millini, G. Perego, W.D. Parker Jr., G. Bellussi and L. Carlussio,
Microporous Mater, 4 (1995) 221.
[24] G.O. Brunner and W.M. Meier, Nature, 337 (1989) 146.
[25] M.E. Davis, Nature, 337 (1989) 117.
[261 S. Ueda, M. Koizumi, Ch. Baerlocher, L.B. McCusker and W.M. Meier,
7th IZC, Tokyo, Poster Paper 3C-3 (1986).
[271 M. Annen, M.E. Davis, J.B. Higgins and J.L. Schlenker, J. Chem. Soc.
Chem. Commun. , (1991) 1175.
[28] C.C. Freyhardt, R.F. Lobo, S. Khodabandeh, J.E. Lewis Jr., M. Tsapatsis,
M. Yoshikawa, M. Camblor, M. Pan, M.H. Helmkamp, S.I. Zones and
M.E. Davis, J. Am. Chem. Soc., 118 (1996) 7299.
[29] L.B. McCusker, R.W. Grosse-Kunstleve, Ch. Baerlocher, M. Yoshikawa
and M.E. Davis, Microporous Mater., 6 (1996) 295.
[30] R.W. Grosse-Kunstleve, Ph.D. Thesis, Swiss Federal Institute of
Technology, ZUrich (1996).
[311 M. Annen, Ph.D. Thesis, Virginia Polytechnic Institute, Blacksburg, VA
(1992).
[321 M.A. Camblor, R.F. Lobo, H. Koller and M.E. Davis, Chem. Mater. 6
(1994) 2193.
[33] P. Wagner, unpublished.
[34] T. Takewaki, L.W. Beck and M.E. Davis, J. Phys. Chem. B., 103 (1999)
2674.
[35] C. Rohrig and H. Gies, Angew. Chem. Int. Ed. Engl., 34 (1995) 63.
[36] C.W. Jones, K. Tsuji and M.E. Davis, Nature, 393 (1998) 52.
[37] M.E. Davis and S.I. Zones, U.S. Pat. Appl. (2000).
Studies in SurfaceScienceand Catalysis135
A. Galarneau,F. Di Renzo,F. Fajulaand J. Vedrine(Editors)
9 2001 ElsevierScienceB.V.All rightsreserved. 37

E v o l u t i o n o f R e f i n i n g and P e t r o c h e m i c a l s . W h a t is the place o f zeolites

Christian Marcilly

Institut Franqais du P6trole, Division Cin6tique et Catalyse, 1 et 4 Avenue de Bois Pr6au,

92852 Rueil Malmaison, France.

Introduction

Refining and petrochemicals are the industries where zeolites are by far the most
frequently used for adsorption and catalysis. The earliest application goes back to the end of
the fifties, after the discovery by the company Linde of the synthesis of the A-type zeolite (1)
capable of separating normal and branched paraffins. The second, and certainly the most
significant event was the introduction of X and Y-type zeolites in catalytic cracking at the
beginning of the sixties, which generated some deep technological changes in the process and
substantial gains in gasoline yield. The first use of shape selectivity properties for zeolites
dates back to 1968 with selective hydrocracking on erionite for normal paraffins of gasoline
cuts. Over the last 40 years, zeolites were introduced first in refining, and then in
petrochemicals, and now hold what may be considered a key position.
The future of zeolites in refining and petrochemicals is obviously for a large part, directly
related to the evolution of these two sectors, and we will be looking at their development in
the first part of this paper. In the second part, we will discuss the place occupied by zeolites
among catalysts and adsorbents used in refining and petrochemicals, and will briefly discuss
some possible potential application for the future.

1. REFINING AND PETROCHEMICALS: EVOLUTION AND CHALLENGES IN

THE 21st CENTURY
Obviously it is not possible to discuss the long term prospects of these two domains of the
petroleum sector seriously without referring to that of the petroleum resources that supply
them.

1.1. The future of petroleum resources

At the end of 99, world proven reserves were estimated at some 145 Gigatons (Gt) (2).
These proven reserves will be depleted in about 40 years at the present rate of consumption
(3.4 Gt/year) (2) and in 29 years if the growth in world consumption is 2 % a year.
The ultimate reserves are extremely difficult to assess, as there are many unknowns. The
figures given, which depend on the nature of the reserves considered and the degree of
specialists' optimism, vary considerably. For instance, the liquid hydrocarbon reserves
(conventional and non-conventional crude and gas-associated liquids) are estimated at 370 Gt
i.e. 2,700 Gb by the IEA (International Energy Agency) and at 645 Gt i.e. 4,700 Gb by the
DOE/EIA (Energy Informatibn Agency) (3).
Depending on which hypothesis is adopted at the outset, the world production in liquid
hydrocarbons is expected to reach a maximum in about 2015-2035. Depending on the growth
38

scenarios, ultimate reserves of 370 Gt should cover 60 to 100 years requirements (4, 5) and
those of 645 Gt over 150 years. So the liquid hydrocarbon reserves are still substantial but
their mobilization will demand significant efforts of research to make them usable (2).
Sometime in the middle of the 21 st century, we will be turning to natural gas as the principal
source of energy, coal and new renewable energies should remain at a modest level (6).
Although the present petroleum resources are quite sufficient to satisfy the requirements
of the first half of the 21 st century, their many and varied locations do pose a problem. The
major part (66.5 %) of the 145 Gt of proven petroleum reserves is to be found in a
geographical zone (The Middle East) where the political climate is unsettled, and on which
the world will be depending more and more in the coming decades. Moreover, most
consumer zones are far from producing zones, which means a intensive transportation
activity between the two.

1.2. The demand in refined and petrochemical products

1.2.1. The development of requirements from 1970 to the end of the 2 0 th century
Over the last thirty years, refining and petrochemicals have known an unsettled time with
two oil crises (causing an economic downturn on a world wide scale), the Gulf war and an
awakening of awareness regarding the degradation of our environment.
Table 1 (2, 7) shows the development of the world petroleum consumption structure
between 1970 and 2000. The following landmarks stand out :
9 The heavy fuels sector dropped rapidly, from 30 % in 1970 to 13 % in 2000 (a sharp and
massive drop in the demand of electric power stations). This decrease should continue but
at a slower rate.
9 By contrast, the part of light products increased during this period; especially that of
middle distillates (jet fuels and gas oils) which increased from 27 to about 35 % between
1970 and 2000 and is likely to continue to grow, mainly due to the increased number of
diesel engines among the European automotive population, whereas the proportion of
gasoline has remained fairly steady since 1970.

Table 1"
Evolution of the structure of the demand in petroleum throughout the world (market economy
countries) between 1970 and 2000.
1970 1980 1990 2000
106 t o n s % 106 t o n s % 106 t o n s * % 106 t o n s %
Gasolines 492 25.4 626 26.6 750 26.8 876 26.2
Middle distill. 530 27.4 721 30.6 950 33.9 1163 34.8
Heavy fuels 608 31.4 645 27.4 500 17.9 426 12.8
Others 307 15.8 363 15.4 600 21.4 875 26.2
Total 1937 100 2355 100 2800 100 3340 100
Middle distillates: jet fuels, heating oil, diesel-oil.
Others: refinery gas, LPGs, naphtas, solvents, lubricants, wax, bitumen, petroleum coke ...
* Approximate values

At the end of 1999, the world refining capacities were a little below 4.1Gt, with a low
growth rate of about 10 % over 10 years (3.74 Gt in 1989).
 39

In petrochemicals, the demand in olefins stagnated between 1978 and 1982 and then
picked up and has grown fairly steadily since then, a little over 5 % a year on average,
increasing from 65 Mt to126 Mt approximately between 1983 and 1997 (8). This annual
growth can be broken down as 5.3 % for ethylene, 6 % for propylene, 15 % for isobutene and
2.2 % for butadiene (9).
At the same time aromatics were on the increase, with an average growth of slightly under
5 % between 1983 and 1997, increasing from 30 Mt to some 57 Mt (8). During this period,
benzene and especially PX, had the strongest growth, especially in South-East Asia. In 1997,
world production of benzene represented a little less than half of the production of
monoaromatics (27 Mt) (10).
In the past 30 years, in order to handle changes in both the quantity and quality of demand,
European refining has become more complex (table 2 ), stepping up conversion capacity
(FCC in particular) and installing new hydrotreatment (reduction of sulphur content in fuels),
hydrocracking and gasoline production units (11). The trend is even more strongly marked in
the Asia-Pacific region due to the fast development of certain countries in the zone (South
Korea for instance). Figures were noticeably high in 1999 compared with 1989, and this was
also due in large part to the fact that China has recently been taken into account (China has
over one third of the FCC units in the Asia-Pacific region). In North America, hydrogenating
processes (HDT and hydrocracking (HDC)) continue to progress, whereas the others
(cracking and special processes) appear to be stagnating. On a global scale, world refining
capacities showed a downturn in the eighties due to the petroleum crises of 1970 and the
resulting economic slump. Refining capacities picked up again in the nineties under the
stimulus of the reduction in the price of gasoline and the economic expansion of South-East
Asia, among other things.

Table 2 (12-16):
Development in the structure of world refining capacities between 1979 and 1999 and for the
main geographical zones in Mt/year (the zones that did not have a market economy in 1979
and 1989 are not included in these two periods but are integrated in 99 : Former Soviet Union,
China, North Korea, several Eastern European countries etc.).
1979 1989 1999
N. W. Asia World N. W. Asia World N. W. Asia World
Amer. Eur. Pacific Amer. Eur. Pacific Amer. Eur. Pacific
HDT 437 346 214 9 523 311 240 1290 577 404 374 1835
FCC. 260 49 30 400 304 88 51 531 298 106 125 688
HDC 46 6 1 9 72 15 14 130 84 34 35 201
Atm. 997 998 520 3210 870 832 500 2840 923 723 982 4077
Dist.
HDT : Hydrotreatments, FCC : Fluid catalytic cracking, HDC : Hydrocracking, Atm. Dist.:
crude in atmospheric distillation.

1.2.2. Development forecast in market demand for products in the year 2010.
Without any major changes in the general trend of demand, the policies applied regarding
energy and crude prices should mean that annual petroleum consumption will increase from
3.3-3.4 Gt/year to over 5 Gt/year in 2020. In the coming decades, refining and petrochemicals
will probably be operating in a restrictive context marked, among other things, by the
following political-economic requirements :
40

9 The Environment : more respect for the environment will be demanded, limiting the
release of pollutant gases (NOx, SO• volatile organic compounds), or discharge of
contaminating liquids and solids, as much as possible.
9 Consumption : master consumption of petroleum products in order to limit gases with
greenhouse effect (CO2 in particular), which will also help to preserve non-renewable
resources.
9 Growth : promote the development of developing and newly developed countries as much
as possible, controlling pollution and consumption. Maintain minimum sustainable growth
making it possible to absorb the technological mutations imposed by progress (policy of
full employment).

1.2.2.1. Quantitative demand

It is interesting to assess what world refining will look like in the year 2010, considering
both a developed geographical zone and one being developed. Table 3 (2) shows the
development between 1990 and 2000 and that forecast between 2000 and 2010 in the demand
for various petroleum products (especially gasoline, middle distillates and heavy fuels) in
Europe (East + West), in the Asia-Pacific region (excluding Japan) and world wide. The
global consumption of petroleum products increases only very moderately in Europe (the
same applies to the United States) but more significantly on a global scale due to the
substantial contribution of developing countries, in particular Asia. As shown on Table 3, the
least developed part of the Asia-Pacific region has caught up with Europe by 2000 and will be
well ahead of it in 2010. The forecast for 2010 for global demand in petroleum products
reaches the 1999 figure for global refining capacity (4.1 Gt approx.) which should therefore
increase moderately in the coming years.

Table 3:
Expected development of the demand for various petroleum products in Mt/year, in the
European Union (EU), Asia-Pacific and the world between 1990 and 2010) (2)
Europe* Asia-Pacific ** World
Years 1990 2000 2010 1990 2000 2010 1990 2000 2010
Gasoline 138 153 168 114 183 253 746 876 1047
Middle distill. 235 303 342 174 312 451 950 1163 1472
Heavy fuels 90 77 60 82 104 132 504 426 456
Others 134 183 207 93 227 291 600 875 1046
Total 597 716 961 463 826 1127 2800 3340 4021
* Western + Eastern Europe (countries of former Soviet Union excluded) (Eastern Europe
10-15 % of Western Europe)
** Asia-Pacific except Japan
Others: refinery gas, LPGs, naphthas, solvents, lubricants, wax, bitumen, petroleum coke ...

Regarding petrochemicals, the demand in olefins and aromatics is, and will remain steady.
Between 1995 and 2005 the demand for olefins is expected to grow at a rate of over 4 % on
average, and that for aromatics by 3.6 % (8). Among the olefins, demand will typically be in
the region of 4 to 5% for ethylene, 5 to 6 % for propylene, 6 % for isobutene and 3.3 % for
butadiene (9, 17).
 41

Forecasts up to 2003-2005 for the global demand in aromatics shows a growth of all
monoaromatics, but it will vary considerably according to the compound considered and
according to information source (10): it is in the range of 3.5 to 4.5 % a year for benzene (10,
17), from 5 to 8 % for PX approximately and significantly lower for the other aromatics (2,
10). What stands out, is the lack of balance between the growth in demand for benzene and
xylene. The overall demand for petrochemicals should reach about 250 Mt in 2005 (8).

1.2.2.2. Changes in product quality

Specifications regarding product quality have been getting increasingly stringent since the
seventies, and this trend is most probably going to continue during the coming decade. The
known or estimated development of specifications for the principal petroleum products
between 1996 and 2010 is shown in Table 4 (2).

Table 4:
Evolution of specifications for three major petroleum products between 1996
and 2005 - 2010 (2)
Europe Average
Califomia (4)
Specifications 1996-99 2000 2005 (project) 2010 (z)
.... (possibility)
Gasoline
S (ppm) 500 150 50 < 10 18-20
Benzene (% vol.) 5 1 <1 ? _<1 0.4-0.6
Arom. (% vol.) 42 35 _<35 23
Olefins (% vol.) 18 14 h 18 ? < 10 3.5-4.0
Oxygen (% vol.) 2.7 2.7 < 2.7 ? < 2.7 2.0-2.2
RON/MON 95/85 95/85 ? 95/85 ?
Diesel fuel
Density max. 0,860 0,845 0,840 h 0,845 ? 0.82-0,84 0.842
S (ppm) 500 350 50 _< 10 140
Cetane number 49 51 51 ~ 53 ? > 55 53.8
Cetane index 46 46 48 h 50 ? > 52 ?
Dist. 95% vol. 370 360 340 b. 360 ? < 340 ?
Polyarom. (% mass) 11 3 ~ 11 ? <2 ?
Total Aromatics < 15
Domestic fuel
S (% masse) 0,2 0,2 0,2 0,1 (3)
Heavy FO
S (% masse) 2 2 1 (l)

(l) probable maximum value for 2003.

(2) extreme values considered for fuels by automobile manufacturers (World-wide fuel
charter, April 2000).
(3) specification coming into force in 2008 but already taken into consideration in the
choice of new HDS units to be built for 2005.
(4) ref. 18.
42

The gasoline pool is obtained by blending gasolines from various origins (Table 5):
Straight run, Reforming, FCC, coking, hydrocracking, isomerization, alkylation,
polymerization and additives (butane, ethers). Table 5 gives the average percentages of these
various components in a gasoline pool for the United States in the nineties (2, 19-24) and in a
western European pool and indicates the main characteristics of each.

Table 5:
Components of the gasoline pool: typical contents and characteristics

Source U S A % W.Eur. S(ppm) Arom. Benz. Olef. RON MON RVP

(19-24) % (2) vol% vol% vol% (kPa)
Distill. 3.8 7.5 100-200 2-4 1-2 < 1 65-80 60-75 70-80
Reform. 34.0 40 0 60-75 3-5 < 1 100 89 30-35
FCC 36.0 27 500-2000 25-35 0.7-1.5 40-50 93 80 40-50
Pyrolyse - 0 - 0 2. ~ 4.103 5-60 2-35" 20-35 82-96 74-85 70-80
Hydrocr 2 - 0 0 2-5 3 < 0.5 85 80 70-80
Isom. 4.5 10 0 < 0.5 < 0.5 < 0.5 85-88 82-85 70-80
Alkyl. 13 9 0 < 0.5 <0.5 < 1 94 92 40-45
Polym. - 0 -~ 0 0-150 < 0.5 < 0.5 > 95 95 82 60-70
Butanes 5 5.5 0 0 0 - 95 92 **
MTBE 1.7 1.0 0 0 0 - 113-117 95-101 55
* benzene -- low values in the case of low T pyrolysis (VB or Coking) and very high in the
case of Steam cracking.
** 1% nC4 --)+ 50 kPa

Most of these gasoline sources present various problems regarding changes in

specifications:
9 Gasolines from steam cracking have a high content of S, benzene and other aromatics.
9 FCC gasoline has a high content of S and olefins, with a somewhat poor octane number
(MON for example).
9 Reforming gasoline is highly aromatic. The increased hydrogen production sought for the
refinery will lead to an increase in the content of aromatic compounds, for which an outlet
has to be found in petrochemicals. In all cases, the benzene content must be lowered
9 Hydrocracking gasoline has inadequate octane. Rich in naphthenic structures, it provides
an excellent reforming feed, but in this case adds to the production of aromatics which are
likely to be excessive for the market.
The diesel fuel pool is also a mixture of basic products from various different origins
(Table 6) (2, 21):
 43

Table 6:
Components of the diesel pool" typical contents and characteristics (2, 21)
Source W. Eur% S (ppm) Arom. (vol%) Cetane Cloud Point
GO Str. run 70-90 * 3 &20.103 20-40 42-54 -10 &+5
GO pyrolysis <5* > 20.103 30 ~ 60 28 ~ 45 -4 ~ - 8
LCO FCC < 10 * 14.103 60-85 18-27 -10
GO HDC < 10 * < 20 8 > 60 < - 15
GO Oligom. - 0 < 1 0 < 50 < -48
Fischer-Tropsch 0 < 1 0 > 75 -9
*" after suitable HDT of sulphur-rich diesel fuels

The sources of gas oil that raise problems are, in order of importance :
9 FCC gas oil (LCO (Light Cycle Oil)) : it has a high S content and low cetane number and
may be hydrotreated after blending (-~ 30 % for example) with straight run gas oil, but it is
difficult to improve the cetane of the LCO (+ 6 to 15 points only depending on conditions)
(20,25);
9 steam cracking diesel fuels 9 these have a very high content of aromatics especially
dealkylated polyaromatics.

The typical aromatics content of most diesel fuels is more in the 30-35 % range, and
although there are no particular specifications for the total aromatics content, this content is
bound to drop due to the foreseeable evolution of S and specific gravity specifications which
will limit integration of LCOs and pyrolysis gas oils in the gas oil pool (26).
Pollutant emissions from automobile vehicles, whether running on gasoline or diesel fuel,
do not depend much on the composition of the corresponding fuels. However, for new models
of both categories of vehicle, the reduction of pollutant emissions will need technologies (lean
bum engine, NOx traps, etc) which demand fuels with a very low sulphur content. Therefore,
it is to be expected that the specifications will become even more stringent in the coming
years meaning further constraints for refiners in forming the fuel pools (2).
As regards petrochemicals, the general quality-related trend of the main products
researched, olefins and aromatics, tends towards greater purity.

1.3. Changes in refining schemes (27)

Present tendencies and those in the coming decades regarding changes in refining
requirements for catalyst processes, operate within a context marked by 4 key constraints :
9 The almost total disappearance in the demand for heavy fuel oil with a high sulphur
content (except for maritime heavy fuels) and the loss of the corresponding outlets for
heavy residues.
9 The need to have clean processes producing clean products to reduce polluting gaseous,
liquid and solid discharge.
44

An active concern about the risk of global warming (problem of. CO2).
The maintenance of a policy for cutting costs at all levels in order to adapt to a constantly
changing technical-economic world, and survive.

This being so, refining processes will be called on to evolve. As there are many processes,
we will only be looking at them briefly and classifying them in three major categories:
processes : those that reduce the molecular weight of the feed (conversion), those that mostly
modify the structure of the molecules without changing their size, while eliminating certain
impurities (improved quality), and finally those that increase the average molecular weight of
the feed (synthesis).

1.3.1. Conversion

1.3.1.1. Standard conversion

The two major processes concerned here are catalytic cracking and hydrocracking which
convert vacuum distillate type feeds (cracking can also absorb part of the atmospheric residue
(AR)). In spite of the average or even inferior quality of the gasoline that it produces and the
poor quality of some of its by-products (LCO and residue), catalytic cracking is an
unavoidable and economic conversion tool in refining and its capacity on a world-wide scale
is going to continue to grow.

1.3.1.2. Deep conversion

The drop in demand for heavy fuel oil which is expected to continue in the coming years
and the continuous growth in the demand for white (light) products, should promote the
increase in capacities for the conversion of residues and more specifically vacuum resid (VR).
However, due to the high investment costs required, the present low yield of this conversion,
and the existence of alternative solutions (exporting of residues, sourcing with lighter crudes
with a low sulphur content, reorganising existing units etc.), refiners have adopted a "wait and
see" attitude and will continue to do so for the next few years. This development of refining
should be looked at as a medium, or rather a long term (5 to 15 years) solution. So catalytic
conversion tools can be expected to take the lion's share, thermal processes (coking and
thermal cracking) which are much less selective being kept for highly contaminated residues
(28).
The hydrotreatments required for deep conversion demand additional hydrogen to make up
that supplied traditionally by the refinery reformer. The new source of hydrogen may by
supplied by a gas steam-reforming unit, but more often by partial oxidation of the ultimate
residue as it makes it possible to totally convert the residue into synthesis gas.

1.3.2. Petroleum cut quality improvement

Between 1990 and 1999, the global capacity of hydrotreatment had already increased by
more than 40 % and is expected to continue to grow in the coming years. Certain cuts that
escaped hydrodesulphurization in the past will have to undergo this treatment in the future
(certain kerosenes and straight run gas oils or FCC gasolines).
 45

In order to satisfy the octane requirements for gasoline, C5-C6 isomerization units will
become more common, whereas reforming will continue to grow but a little more slowly.
Today, reforming is unavoidable as a provider of hydrogen and a high octane number
gasoline, and the very low pressure operation also allows significant progress for these two
objectives but produces more aromatics. The latter should be introduced in limited quantities
in gasoline, and petrochemicals should absorb at least part of the excess production.
Concerning the improved quality of gas oils and lube oils, of which a steadily increasing
proportion will be provided by hydrocracking, it will be necessary to build units for the
controlled hydroisomerization of long paraffins contained in these cuts in order to improve
the cold resistance while minimizing losses through cracking.

1.3.3. Synthesis processes

The processes concerned are more particularly : aliphatic alkylation, olefin
oligomerizations and etherifications (28).
The gasoline obtained by isobutane-olefins alkylation is an ideal component for the
gasoline pool through its substantial contribution to the octane number and the absence of
aromatics and olefins. The technologies used go back a long way and are technically well
mastered, but the liquid catalysts used pose some problems : human risk regarding
hydrofluoric acid, large quantities of waste ("red oils") that have to be retreated for the
sulphuric acid. These problems somewhat slow down development which would otherwise be
rapid.
Oligomerizations make it possible to produce high octane number gasolines, but their
strong olefinicity demands saturation by hydrogen. These processes will probably only have a
limited growth in the future. The production of gas oil by oligomerization will remain
marginal as the cetanes obtained barely exceed a value of 50.
Etherifications are proven processes which do not raise any specific problems and should
spread rapidly unless the banishing of ethers from gasolines decided in California spreads to
the rest of the United States and then the world.

1.3.4. Refining scenarios for 2010

Figure 1 (29) shows a typical refining scheme for 2010 and the rest of the decade. Every
refinery would not be able to house all the installations presented, as the corresponding
investments would be too heavy. However, overall, the refineries in the same oil corporation
should correspond more or less to this scenario. It includes deep conversion units with a POX
for residues for refinery hydrogen production, hydrotreatments on all the distillation cuts and
the LCO of the catalytic cracker and specific additional units for quality improvement :
isomerization of light paraffins, aliphatic alkylation and etherification.
46

Figure 1 :
Refining scenario for 2010 (29)

1.4. New deals for refining and heavy petrochemicals

1.4.1. For the refiner

1.4.1.1. Refining, hydrogen and self-consumption

The expected evolution for refining (deeper hydrodesulphuration, better product quality
and finally, in the long run, deep conversion) means a significant growth in the hydrogen
requirements of the refinery (28, 29). Compared with the simple refinery (hydroskimming) of
the seventies and eighties, the hydrogen demand of the whole refinery in 2010 and the decade
shown in Figure 1 could be multiplied by a factor in the order of 5.
The production of hydrogen would be one of the principal reasons for the increase in self-
consumption. This increase would be very limited to start with in classic refineries that will
gradually be acquiring the equipment to comply with the new specifications imposed, without
going so far as to install a resid hydroconversion or a POX unit. It is thus expected that the
increase will only be from 6 to 7 % of the crude treated in the European Union between 1996
and 2010 thanks to the savings made at the same time by the refiners (11), especially through
the use of co-generation on a much larger scale. But as shown on Table 7 (2), it could become
significant for a complete refinery corresponding to the scenario on Figure 1.
 47

Table 7:
Evolution of investments, self-consumption and of the hydrogen demand for an average
refinery

Type of refinery Investments (G$) Self-consumption H2 consumption (3)

(% wt of crude)
Simple 0.5 - 4 tx
Classical conversion 1 - 1.5 (l) -6 2 c t - 3tx
Deep conversion (2) 2.5 -~ 10 5c~
(~): according to product quality
(2): including specific units devoted to improving quality
(3): the figures given are not absolute, as the hydrogen consumption, and therefore of tx,
will depend on operating conditions (nature of the treated crude, S content of the
products, etc.)

The production of hydrogen by steam-reforming of methane or by partial oxidation of

heavy residues (POX) inevitably leads to an increase in self-consumption and additional
emissions of CO2.

1.4.1.2. Refining and sulphur

Gaseous sulphur emissions coming from the refineries and their products, represent a risk
for the environment (smoke and acid rain) and a health hazard. Also gas emissions containing
sulphur from the combustion of fossil fuels inhibit the catalysts of exhaust systems and there
is every reason to think that the level of 50 ppm fixed for 2005 for gasoline and gas oil may
well only be a step towards levels closer to zero (2, 30).
Regulations regarding the sulphur contents of petroleum products and sulphur emissions
from the refinery, mean that most of the sulphur is now recovered in Claus and Claus tail gas
units in the refinery in the form of elemental sulphur.
Figure 2 shows the changes between 1996 and 2005 in the distribution of sulphur leaving
an average sized refinery treating 8.1 Mt/year of a crude with 1.13 % S (i.e. 91,506 t of S).
Part of the sulphur leaving the refinery is distributed among the products and gaseous
emissions of the refinery, the rest is collected in the form of elemental sulphur. Between 1996
and 2005, the part of the sulphur in the gaseous emissions drops significantly, but it is mainly
that present in the refining products that is reduced (from 51 to 37 %), leading to a substantial
increase in elemental sulphur production (from 41 to 57 %) (31).
 48

Figure 2 9
Evolution of the distribution of sulphur leaving a refinery between 1996 and 2005 (31)

Refining is now a major sulphur (S) producer, and will become even more so. For instance,
a large refinery, such as that of Shell at Rotterdam which treats some 20 Mt crude a year,
already produces between 250,000 and 300,000 tons of S per year (32).
The production of S worldwide (inclusive of all forms) in 1998 was about 62 Mt, with 40.5
Mt in the form of elemental sulphur (32) produced mainly by refineries (approximately 1/3)
(33) and natural gas. This figure is expected to increase to 68.5 Mt in 2003 and then 74.5 Mt
in 2008, with 47.8 and 53.1 Mt respectively of elemental S, the proportion of S recovered
from fossil hydrocarbon sources increasing steadily. At the present time the zones with the
highest S production (inclusive of all forms) are North America which comes far ahead of
Asia and Europe (32).
The main outlet for S is sulphuric acid (90 % approx.) with the two main outlets for
utilization being fertilizers (approximately 60 % of S) and chemicals (textiles, solvents,
paints, detergents etc.) (31, 34). However, certain outlets (SO4H2,CS2) are expected to have a
lower demand by the year 2008 (35).
For several years, the offer of sulphur has already exceeded the demand, which has led to
significant lowering of prices (34, 36, 37). Over about fifteen years, the price of sulphur has
therefore dropped from a value of over 100 $/t to much lower values fluctuating between 45
and 65 $/t. The coming decades are likely to be marked by an even greater production excess
(32, 36, 37). Initially a valuable industrial product, sulphur has become a by-product, which
has already made some traditional production sources unprofitable and forced them to cease
activities. It is fast on the way to becoming a waste if new outlets are not discovered (37).

1.4.1.3. Refining and CO2

In addition to the limitation of traditional atmospheric pollutants such as the sulphur and
nitrogen oxides and hydrocarbons, we now have to consider the reduction of greenhouse
gases, in particular CO2.
 49

1.4.1.3.1. CO2 in the atmosphere and the world climate

Carbon dioxide is said to be the main culprit in global warming. Although the heating
power attributed to it is considerably less than that of other pollutants (about 30 times less
than CH4 and 200 times less than N20), the significant CO2 contents in the atmosphere mean
that this gas is the principal contributor to the greenhouse effect (about 55 % in 1990) (38).
The coinciding of industrial development of human society and the increase in the CO2
content in the atmosphere explains why the latter is considered as being mainly due to human
activities. Since 1860, the year in which the second industrial revolution started (the time
when electricity and petroleum were discovered), the average concentration in CO2 in the
atmosphere has increased from 288 ppm to 315ppm in 1957 and 368 ppm in 2000, meaning
an increase of almost 30 % in 140 years (39). Experts predict that this tendency will continue
reaching a possible figure of 600 ppm in 2050.
The awareness of the risk presented by CO2 for the future of the climate began well before
1990, and in spite of a lack of knowledge and perspective making it difficult to grasp the true
validity and full impact, ecologists and many scientists called for preventive measures to be
taken urgently (40). The Kyoto Protocol, adopted on 10 November, 1997 within the
framework of the master convention of the United Nations on the climate change, and
appealing to industrialized countries to reduce their greenhouse gas emissions by an average
of 5 % by 2010 compared with 1990, could not be respected, because for one thing the time-
line was too short to allow effective technologies to be developed and diffused (41), and for
another thing, there is reason to doubt the motivation of a certain number of countries
implicated.. However, even although the summit of The Hague in November 2000 did not end
in the hoped for decisions being taken, in the coming years, we can expect CO2 emissions to
be increasingly taken into account at all levels of human activity.

1.4.1.3.2. The role of human activities in the total CO2 emissions world-wide:
Out of the 28 Gt of CO2 released every year into the atmosphere by human activities, some
21.5 do in fact come from fossil fuels and the rest, i.e. 6.5 Gt are due mostly to deforestation
(34, 42, 43). The figure of 28 Gt does indeed appear low compared with the 770 Gt/year of
natural CO2 emissions (i.e. 96.5 % of the total emissions) (43), and from this view point
industrial activities (industries, electric power stations) and those related to transport would
only be responsible for 2.2 % of global emissions and petroleum only for 1.3 % (44, 45). But
unlike natural emissions which are part of a natural carbon cycle and are offset over one year
by the same volume of CO2 that is absorbed or transformed, these 28 Gt would be considered
as an excess volume of emissions, not offset in the yearly cycle (this still has to be
ascertained). It is generally accepted that a minimum of 120 years would be necessary to
return to the initial situation of 1860 if CO2 were to be brought back to its level at that time
(39).
Table 8 (43) which shows the emissions of CO2 world wide according to type of human
activity, shows that transport is responsible for a little less than 20 % of these emissions. But
emissions due to transport are essentially a phenomenon of developed countries. For instance
in the United States, transport contributes 32 % of CO2 emissions, three quarters being due to
road transport (46).
50

Table 8"
Annual emissions of CO2 due to human activities (1996) (*)
Activity % of 28 Gt % of total emissions
, (800Gt)
Electric power stations 25 0.875
Residential and tertiary 23 0.805
Industry 19 0.665
Transport 18 0.63
Private vehicles 5,5 0.19
Trucks 6 0.21
Planes 3 0.1
Ships 1,5 0.05
Other 2 0.07
Burnin/~ of the biomass 15 0.525
(*): These CO2 emissions differ significantly from one geographical region to another.

1.4.1.3.3. Refining and CO2 : need to adopt a rational approach (47-49)

The impact of measures taken regarding CO2 should not only be considered in terms of
emissions from motors but must be the result of an overall assessment from the time the crude
enters the refinery up to the end use of finished products. Such an assessment would
inevitably point to the necessity to find compromises :
9 A first and short term compromise should be found between the reduction of the sulphur
and the increase in refinery self consumption. Low sulphur content fuels, the production
of which is responsible for an increase in CO2 emissions, is only necessary for vehicles
fitted with new technologies. Is it really necessary to supply an automobile population
with these fuels as early as 2005 when the major part of the population will not yet be
fitted with the new technologies? (50)
9 A second compromise between the other specifications which will be set for fuels in 2005
and the increase in self-consumption has also to be found. Some of these specifications
are effectively interdependent and this interdependence must be taken into account when
selecting them. For instance, in the future why would it be necessary to keep the aromatics
content below 35% in gasoline if the almost complete elimination of sulphur enables total
elimination of harmful hydrocarbons discharged in exhaust gas (50)7 A similar question
can be asked regarding the lowering of the T95 in diesel fuel which aims at limiting the
formations of polyaromatics and soot in exhaust gas, when eventually diesel vehicles will
be fitted with particle filters (50).
 51

Balancing the production of finished refinery products is also a kind of compromise and a
less well known way of minimizing CO2 emissions : the example given below shows that
adopting a position outside the large domain of acceptable variations for ratios between
the production of gasoline and gas oil, has a negative impact on energy consumption and
therefore on refinery CO2 emissions. Actually, these emissions, although significantly
lower than those of vehicles running on gasoline and diesel fuel (approximately 7 to 8
times less) (47) are far from negligible.
Extreme operating limits of a refinery, the principal conversion tool of which is the
FCC, correspond to middle distillates/light distillates (light distillates - gasolines)
(MD/LD) ratio which are roughly equal to 1 and 2. Between these two values, the refinery
modifies the gas oil/gasoline ratio of its fuel production by playing on the nature of the
crude supply and the cut points of the products, but globally, CO2 emissions remain more
or less constant.
The MD/LD ratio equal to 2 corresponds to a proportion of diesel engines of the
automobile population of about 25 %. At the present time, a country such as France has
already, in the year 2000, a 33 % proportion of diesel engines (MD/LD ratio of 2.3
approx.) and should reach 37 % in about 2005. By contrast, the American situation
corresponds to an unbalanced market in the other direction, with an MD/LD ratio that is
well below 1 (about 0.6). It is therefore interesting to find out what happens to the CO2
emissions on either side of the previous operating range.
Figure 3 (48) shows that any significant imbalance between the gas oil and gasoline
productions lying either on the "all gas oil" side or on the "all gasoline" side of the
"optimum equilibrium" range generates a rapid increase in the emissions of CO2 emissions
in the refinery.
If France had to produce its own diesel gas oil, it would have to carry out some large
scale installation work in hydrocracking units, or even hydroconversion of residues, which
would lead to a sharp increase in global CO2 emissions. Other European countries also
encourage the sale of cars running on diesel fuel, and from this point of view, a country
such as Spain is at present European leader with 49% licensing of new public vehicles
running on diesel against 39 for France and 25 for the European average. By contrast,
excess emission of CO2 corresponding to the American situation is due mainly to the need
to produce gasoline by a deeper conversion of the crude (including by hydrocracking of the
FCC LCO) which means an increase in refinery self-consumption. At the present time,
excess emission of CO2 is partially avoided in France, through an intense import-export
activity. In order to ensure a balance between offer and demand, France imports gas oil and
exports its excess gasoline, but manages to generate less pollution than the United States
where the opposite is the case. This situation is obviously precarious and can be disrupted
by any change in the energy policy of one of the actors.
The most rational approach would therefore consist in reducing the rate of the
production of diesel engines in France and in Spain and increasing that in the United
States.
52

Figure 3"
Impact of a change in the ratio between middle distillates and light distillates on
refinery self-consumption (middle distillates = jet fuel + diesel oil +FOD;
light distillates = gasolines). (48)

Refinery self-consumption
(or C O 2 emissions)
S )ain

(a.u.) "*.,_
USA

l
+
I
Europe
J a p a n (EU)
Prance
I /
:: :: Optimum i :
l
i

: : equilibrium zone :
: : : ,
i i
i

I .... I I I i i I > MDILD ratio

0 0.65 1 2 2.35 2.5 3
Gasoline max GO max

1.4.1.4. A stronger interaction between refining and petrochemicals in the future (5 l)

Faced with the complexity of the demands and increasingly stringent constraints, the two
industries, refining and petrochemicals, will gradually have to tighten the bonds which had
become somewhat slack over the last two decades. They will have to strengthen their
exchange of products and make the most of all opportunities of complementarity in order to
adapt to the new economic context. The following points can be given as examples :
9 Evolution of steam cracking feeds. Less availability of light naphthas, more and more
frequently used by refining for reformulated gasoline, will oblige petrochemicals to look
towards lighter feeds (petroleum gas, C3-C4 cuts from refineries with the olefins
eliminated as well as gas condensates which could become significant feeds in the future)
or towards heavier petroleum cuts with higher aromatic contents.
9 Recovery of light olefins for the petrochemical industry from a certain number of refinery
effluents : refinery ethylene gas, propylene from the FCC LPGs
9 Recovery of effluents rich in hydrogen for the refinery and of isobutene and isopentenes
from the steam-cracking C4 and C5 cuts respectively, for the production of ethers if these
are not prohibited in gasolines.
9 Recovery of aromatics extracted from gasolines. By the year 2005, there will be a surplus
of aromatics on the European market. The problem is that the European and world markets
for aromatics are small compared with the corresponding gasoline markets. (Figure 4 )
(18). Thus the 1998 European market of aromatics is 13 Mt which breaks down into 6.5 Mt
of B, 2 of T, 2.5 of X (mixture) and 2 of isomers (OX+PX) (18). The 1998 European
market (East + West) for gasoline was about 168 Mt and the world market of 975 Mt (2).
Every % of benzene in world gasoline represents about 1.5 times the European benzene
production i.e. -~ 9.7 Mr. It should be possible for the European petrochemical sector to
 53

absorb the surplus of benzene and of the other aromatics created by the enforcement of the
2000 specifications ( 1 % and 42 % in gasoline respectively) (18). This sector at present
produces some 13-14 Mt of aromatics. However the limit of 35 % for aromatics in gasoline
expected for 2005 will probably mean a further excess of over 10 Mt on the market if all
the aromatics were to be extracted. (18) Such a quantity of aromatics could not be absorbed
by the market and would cause prices to collapse (18). In such a situation, only the
refineries that are large enough with a good enough performance could allow themselves to
produce low cost aromatics. The others would have to find other solutions.
9 Use by the refining sector of processes initially developed by petrochemicals such as
steam-reforming of natural gas, partial oxidation of residues, Fischer-Tropsch synthesis
etc.

Figure 4 (18):
1998 markets of aromatics in Asia, North America and Europe compared with
corresponding markets and world markets of gasoline

1.4.2. For catalyst manufacturers and holders of process licenses (2, 52-54)
Refining and heavy petrochemical industries can, on average, be considered mature
industries (2, 51) where the differences between catalysts and/or the technologies of various
competitors decrease. Thus, catalyst manufacturers and license holders attach increasing
importance to factors of cost and productivity in order to remain competitive and survive (52,
54

53). In difficult economic context, this leads to turbulent times when associations and
company mergers proliferate, all the actors seeking to strengthen their positions regarding
innovation, productivity and commercial activities. In the coming decades, for the catalyst
manufacturers, and for process license holders, the purpose will be first and foremost to
remain competitive regarding the performance of commercialised products and their costs.
The need for technical or technological innovation, whether small or big, to improve products
or introduce new ones, remains a fundamental requirement, and from this view point, the
rapidity at which innovations can be produced becomes of major importance. New method are
still appearing (increasingly sophisticated techniques for characterisation, combinatorial
chemistry, molecular modelisation, rapid information access and analysis) which will make it
possible to speed up the rate at which innovations occur in the near future. But innovation is
not the only lever for success. Other levers are in fact increasingly important for keeping
ahead of the competition :
9 Cost reduction (improved productivity);
9 Proposal for complete sets of processes and catalyst systems;
9 Improvement of the number and quality of services associated with the catalyst and/or the
process (integrated set of services for sale, technical assistance, treatment of used catalysts
or recovery of worn catalysts etc.).

2. C A T A L Y S T S IN THE REFINING AND PETROCHEMICALS

INDUSTRY. IMPLICATIONS AND OPPORTUNITIES FOR ZEOLITES

2.1. Catalysts: World market

In 1999, the world market for catalysts (including precious metals) reached 9 G$ with 24
% for refining, 23 % polymers, 24 % chemicals and 29 % environment. Table 9 gives the
refining catalyst market in tons and $ by application for 1999 and 2005 (2).

Table 9
1999 2005
Processes 103 tons % G$) 103 tons % G$)
Cracking 495 77 0.7 560 73.6 0.83
Hydrotreatments 100 15.5 0.72 135 17.7 0.96
Hydrocracking 7 1.1 0.10 9 1.2 0.12
Reforming 6 0.9 0.12 7 0.9 0.15
Others - 35 5.5 0.56 -~50" 6.6 0.64
Total solids - 640-650 100 2.2 -760 100 2.7
Alkylation .3100' - 0.85 3700* - . 1
~<Others >r catalysts for H2 production, polymerization, isomerization, etherification.,
Claus, lubes etc...
* approximate values.

En 1999, North America accounted for about 30 to 40 % of the market in $ depending on

the sources of information (2, 55, 56) and Western Europe for 20 %. In 2005, their respective
shares will be about 35-38 % and 19 % of this market.
 55

Regarding petrochemicals, the world market of catalysts represented 2.16 G$ and 630 Mt
in 1999 and will probably account for 2.53 G$ and 735 Mt in 2005 (2).

2.2. Zeolites: applications and general trends of development

2.2.1. Zeolites: main fields of application and markets (2, 57, 58)
The world zeolite market has developed strongly over the last decades and at present
represents some 1.6 Mt per year (58), with about 290,000 t/year for natural zeolites
(approximately l 8 %) used in ionic exchange and adsorption.
Applications of synthetic zeolites concern three major fields of activity amounting to some
1.3 Mt : detergents (A-type zeolites), adsorbents and desiccators (A and X-type zeolites
mainly) and finally catalysis (especially Y-type zeolite). In 1998, the world market for these
synthetic zeolites was approximately 1.6 G$, of which catalysis represented a little over 50
%) (2). As shown on Table 10 which gives these fields of activity according to major
geographical regions, the share of catalysis in tons is much less and only represents a little
over 12 %:

Table 10: Consumption of synthetic zeolites in thousands of tons (1998)

N. Amer. W. Eur. E. Eur. Japan Other TOTAL

Detergents 275 505 55 85 130 1050
Catalysts 80 25 15"- 10 30 160
Adsorb/Desic 43 27 5.5 6.5 18 100
Total 398 557 75.5 101.5 178 1310

The expected evolution over 5 years (up to the year 2003) is on average a moderate global
growth in the order of 1 to 1.5 % per year approximately for catalysis, from 1 to 2 % for
adsorbents and desiccators and, for detergents, a slight decrease on average (-~1-2 % per year)
in the major developed countries (lower quantities of zeolite in detergents).
Out of the 1.3 Mt of synthetic zeolites produced annually, the A-type zeolite, with 1.1Mt,
is by far the most commonly used (58). Its principal field of application is in the detergent
industry, where certain modern detergents contain up to 40 % weight.
About 100,000 tons per year of synthetic zeolites go to the adsorption sector (58-60) :
desiccation and purifying standard applications (insulating windows mostly, refrigeration,
treatment of natural and industrial gas, purification of olefins, desiccation of alcohols) and
separations (n-paraffins, xylenes, PSA/VSA systems for the production of oxygen or
hydrogen etc.). Among the zeolites used, the A-type zeolite is in a large majority (58) for
desiccation and separations in particular, followed by X-type zeolite for the elimination of
traces of polar impurities, and to a lesser degree, by various zeolites with high silicon contents
such as mordenite and ZSM-5 for desiccation of acid gases or the elimination of volatile
organic compounds.
Regarding catalysis, almost all the zeolites used in the world are used in refining and
petrochemicals. In refining, the principal applications are cracking (FCC), hydrocracking,
isomerization of C5-C6 cuts and dewaxing or isodewaxing. In petrochemicals, the principal
use is in aromatic transformation (alkylations, isomerization, disproportionation/
transalkylation) which, in 1999 represented 8.4 % and 6 % respectively of the financial
volume and tonnage of petrochemical catalysts, i.e about 2 % of the financial volume of
56

world catalysts. The Y-type zeolite present in the FCC catalysts alone accounts for almost 95
% of the world consumption.
Speciality zeolites, which account for only a few % of the world consumption of zeolites in
catalysis, are mainly Y-type zeolites modified for hydrocracking and ZSM-5 zeolite as FCC
additive. The production of other zeolites remains marginal.
In all, out of 126 known zeolitic structures, only about a dozen are used in industrial or
pre-industrial applications (2, 61, 62); these are the following"
9 A : (detergents, desiccation and separation) ;
9 F A U : X (desiccation, purification, separation) and Y (separation, catalysis) ;
9 M O R : (adsorption and catalysis) ;
9 LTL : KL-type zeolite (catalysis: aromatization) ;
9 MFI : Silicalite and ZSM-5 (adsorption and catalysis) ;
9 B E A : Beta-type zeolite (catalysis: cumene) ;
9 MTW : zeolite MCM-22 (catalysis: ethylbenzene, probably cumene ?) ;
9 CHA 9SAPO-34 (methanol to olefins or MTO process- demonstration unit );
9 F E R : Ferrierite (skeletal isomerization of n-butenes- demonstration unit) ;
9 AEL and/or TON : SAPO-11 and possibly ZSM-22 (improvement of pour point for
petroleum cuts by straight long paraffin isomerization) ;
9 Structures not revealed (for aromatic Cs isomerization) : one is certain (IFP) and the
second is possible (UOP).

2.2.2. Openings f o r z e o l i t e s in r e f i n i n g a n d p e t r o c h e m i c a l s
Zeolites have been present in refining since the beginning of the sixties (FAU cracking)
and in petrochemicals of first generation intermediaries since the seventies ( transformation of
aromatics on MOR). The success of zeolites in second generation intermediary chemistry and
fine chemicals (63-73) are on the whole, more recent (63-70, 72, 73) and benefit from the
zeolitic materials developed mostly for the first two industries. Significant improvements of
these materials are still possible, and new applications using new materials or not yet used so
far, will be emerging in the coming decades. However, it is very likely that from this point of
view, fine chemicals will be more profitable than the mature industries like refining and
petrochemicals for at least two reasons: (i) the variety of reactions is greater and the catalysts
far from optimized (ii) the products have an added value that is greater and may make the
high cost of certain zeolitic material acceptable. However, the quantities of products involved
in the fine chemicals sector are small, and the volumes of zeolitic materials used will still be
minor compared with those of refining.
Considering the specifications imposed relating to petroleum products in general and fuels
in particular, the refining industry and that of petrochemicals has, and will always have a need
for more active catalysts and even more for more selective catalysts. On the latter point,
zeolites will continue to hold a strong position to offer innovative solutions. The opportunity
concerning the progress that they can provide must be sought first of all in existing processes
or new processes aiming at producing the following hydrocarbons :

9 Light olefins from C3 to C5 as raw materials for petrochemicals or for the production of
clean, good quality fuels.
9 Highly branched paraffins from C5 to C12 for the gasoline pool or longer and slightly
branched paraffins for the kerosene and gas oil pools.
 57

Specific molecules as first and/or second generation intermediaries in petrochemicals:

alkylmonoaromatics in particular. From this point of view, the development of processes
of inter-transformation of these aromatics can certainly be expected.

More precisely, the following few opportunities for zeolites can be mentioned :

9 FCC : although it is not likely that the Y-type zeolite will be replaced as principal active
agent, there may be room for additives enabling selective production of light olefins
ranging from propylene to pentenes as long as these additives are competitive with the
ZSM-5 regarding costs, activity and stability.
9 Hydrocracking (HDC) : the main factor for progress here would be to find a zeolitic
catalyst dedicated to the production middle distillates, associating both the activity and the
stability of zeolites and the selectivity of amorphous catalysts.
9 Aliphatic alkylation : the best zeolite found to date is the Beta-type zeolite, which does not
contribute any octane gain compared with existing processes. A three-dimensional zeolite,
more open than the Beta and at least as active, would be needed for this application.
9 Isomerization of paraffins : in the domain of middle paraffins from 7 to 9 carbons of the
gasoline fraction, there is a need for a catalyst making it possible to achieve a thorough
isomerization selectively (2 branches or more) while minimizing the cracking. However
this is a difficult challenge for a bifunctional acid catalyst.
9 Dewaxing (gas oils, HDC residues, lube oils) : recent innovations in this domain
(dewaxing by hydroisomerization) represent a significant breakthrough compared with
classic processes by hydrocracking (on MFI structure). Progress is still possible in
particular to further limit loss through cracking of isomerized products at high conversion.
9 Hydrodecyclization of polyaromatics of middle distillate cuts (LCO in particular) remains
a significant challenge. The difficulty which acid catalysis comes up against is that the
cycle opening is generally slower than the consecutive cracking of open products.
9 Transformation of aromatics : nearly all catalysts used are zeolitic. New zeolites can still
provide gains in selectivity and stability. Also, the alkylation of aromatics other than
benzene is of interest (ethyltoluene, isopropylbenzene, disopropylbenzene,
paraethyltoluene, alkylnaphtalenes et dialkylnaphtalenes etc.).
9 Hydrotreatments : several studies have made it possible to detect some interesting
potential among certain metal sulphides dispersed in the zeolites to desulphurize and
denitrogenate certain refractory heteroatomic molecules (certain alkyldibenzothiphenes
for example). One of the difficulties that has to be solved is to avoid excessive cracking of
the hydrocarbons to be purified.
9 In the field of adsorption/separation, significant progress can be expected with the
optimization of materials that are already known (crystalline defects, Si/A1 ratios, nature
and position of cations, external surface properties, crystal size etc.) and the discovery of
new materials.
58

Zeolitic membranes. In spite of many studies carried out since the eighties, the penetration
of zeolitic membranes in industry has been very slow and has still not been integrated in
refining and petrochemicals activities. These do however, represent an important
application potential in the long term in the domain of molecular separation for certain
catalytic separations. Considerable progress remains to be made regarding manufacture of
these membranes (74).

Conclusion
The global demand for petroleum products and therefore the capacities of refining and
petrochemicals will continue to grow for many years to come. Refining and petrochemicals
are mature industries that are constantly changing. For the last three decades, refining
schemes have indeed evolved considerably. They continue to change to adapt to numerous
constraints which are not likely to decrease in the foreseeable future, and which are due to the
need to limit consumption of petroleum products (in particular CO2-related issues), to have
greater respect for the Environment and minimize refining costs.
In this context, zeolites have an important role to play. The contribution of zeolitic
catalysts to refining and petrochemicals is already substantial. We can hope for further
achievements in the future through improvements to existing catalysts and the development of
new catalysts, as the association of the properties of acidity and shape selectivity offered by
zeolites is unique. These achievements could occur in a wide variety of domains, affecting not
only the major processes of hydrorefining and conversion, but also smaller capacity, more
specialized processes. But the development of any new process always comes up against the
unavoidable need to be profitable and competitive, which is often a difficult obstacle to
overcome in mature industries like refining and petrochemicals.

Acknowledgement
I would like to extend my gratitude to a number of people at IFP for their help in providing
technical and economical information: M. Baraqu6, O. Clause, L. Cuiec, G. Fournier, L.
Kerdraon, J. Larue, A. Methivier,, X. Montagne, I. Prevost, and more particularly to J.B.
Sigault. Additionnally, I would like to thank Mrs E. Ubrich for its precious assistance in
library information searches.

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Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 61

Is Electron Microscope an Efficient Magnifying Glass for Micro- and

Meso-porous Materials ?

Osamu TERASAKI a'b'* and Tetsu OHSUNA ~

a: Deptartment of Physics and CIR, Tohoku University, Sendai 980-8578, Japan_

b: CREST, JST, Tohoku University, Sendai 980-8578, Japan
c: Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
* Corresponding Author: terasaki@msp.phys.tohoku.ac.jp

Using electron microscopy(EM), we can solve three dimensional structures of micro-

and meso-porous materials through newly developed methods based on electron
crystallography. The underlying principle among diffraction, image and Fourier
transformation for the methods, and a resolution of the method are discussed in terms of
structure details we are interested in. An example of structure analysis for SBA-6 shows
power of the methods, and future tasks will be discussed at the Conference.

1. INTRODUCTION
1-1. Microscope and Resolution
The optical microscope is an instrument that uses lenses to produce enlarged images
of small objects especially too small to be seen by the naked eye In an optical
microscope, the spatial distribution of absorption or reflectance of light is enlarged. It
is seldom, as far as we know, an optical microscope is used to obtain diffraction
information except a conoscope. Big effort was paid to improve the resolution of
optical microscope to observe smaller objects. However, the resolution of perfect
lens(theoretical), Rth, is given from Rayleigh criteria as

Rth =1.22 X/ct, (eq. 1)

where ct and X are angular aperture size and wavelength. Necessary resolution comes
from what kind of structural information we are interested in. The resolution of optical
microscope is far below to resolve structure in atomic scale, as X is 3000-8000A for
visible light and a is order of 1 (most of text books used semi-angle, or/2). Although
the wavelengths of characteristic X-ray for ka radiation of 3d-transition metals are
suitable range of 1.5-2.5 A for atomic resolution, we can not make a reasonable lens.
62

Electron has charge, and we can make an electromagnetic lens through the Lorentz
force and hence an electron microscope(EM). Applying the de Broglie relation, the
wavelength of electrons is determined by
(A) = h/~/(2meV) -- ~/{150/V(volts)}, (eq. 2 )
where h, m, e and V are Planck's constant, electron mass, electron charge and
accelerating voltage, respectively. ~, is 0.037 A at 100 kV and looks small enough to
resolve structure in atomic scale if we can keep o~ to be order of 1. Is the resolution of
electron microscope enough to resolve structures in atomic scale? In case of
electromagnetic lens, lens is not perfect with different kinds of aberrations. From
geometrical optics, a point source will be imaged as not a point but a disk by a lens
with spherical aberration. Disk diameter of confusion, R~ph,is given by Cs(ct/2) 3, where
C, is a spherical aberration constant of the lens. Taking the effect of the aberration into
account, the resolution R can be expressed as
R = ~/{(Rth2+ R~ph2)} (eq. 3)
as Rth and P~phare independent event each other. R takes minimum value
R~in = 0.9 (X3/4Cs1/4) (eq. 4 )
at optimum angular aperture size
t~opt - 1.54 (L/Cs)TM (eq. 5 )
In other words, an effective value of t~ in eq. 1 for the electromagnetic lens is
essentially given by a spherical aberration as 1.54(2qC~)TM, and is order of 10 -3. The
attainable resolution is given by 0.9 (X3/4CsTM)and is 1.8 - 2.5 A range for most of 200
and 300 kV EMs. However, it is very hard to reach the resolution mentioned above for
a case of zeolites(microporous materials), because they are so electron beam sensitive
that we can not irradiate enough number of electrons onto them for taking HREM
images. Therefore HREM is not enough to resolve atomic arrangement for zeolites[ 1-
3].
Diffraction study is another and principal approach for structural study. It is well
known that X-ray diffraction(XRD) can give average structural information with very
high resolution and XRD has been used to solve structure of zeolites in atomic scale
and also to show long range order in mesoporous materials. Using EM, however, we
are able to observe both electron diffraction(ED) patterns and images. ED is free from
the aberration effect and provides like XRD structural information with much higher
spatial resolution than HREM images, and we can obtain ED data with much smaller
 63

number of electrons. Electrons are scattered through the interaction with the
electrostatic potential formed by the electrons and nucleus of the constituent atoms.
The scattering power of atoms for electrons is called as the atomic scattering factor and
is approximately 104 times as large as that for X-rays. This suggests that compared to
X-ray scattering, smaller scatterers can provide sufficient structural information and
thus much smaller objects(ca. 10-8 times) can be studied with electrons. It is to be
noted here that we could choose a proper small crystalline area in image mode and
obtain single crystal diffraction information only from the same area, and that EM is
very powerful for micro- and meso-porous materials as they are mostly synthesized as
panicles of c a . 1 lam in size.
In this paper, we will give general background of electron crystallography to solve
micro- and mesoporous structures and show EM is unique and powerful technique by a
few examples. At the Conference, other relateds will be also discussed.

1-2. Diffraction, Image and Fourier Transform

Figure 1 shows a schematic drawing, which gives length scale of our interests.
Crystal is a three-dimensional (3-d) periodic array of unit cells, each of which contains a
same arrangement of atoms. Therefore to solve atomic arrangement, that is, to
determine distribution of scattering density, V(r), in a unit cell is a central problem for

Resolution of
Electron Mkroseopy
I
I' I

Wave length of Wave length Wave length

light of X-ray of eleclron

V
lOOA 2 A, lit 0.1.~
t + I I I d (X)
v
Structures of Framework Atomic Coordinates
Mesoporous Strueture of Atomic coordinates are
Diameters of Zeolites obtained by statistical
Pore & Cage are Bond di st~ces, treatment from many
20-500 A T-O = 1.6 A rdlecti ons up to large
scattering vectors.
T- (O) -T= 3 A

Fig. 1 Schematic Length Scale

64

structure analysis. V(r) can be obtained from analysis of crystal structure factor(CSF),
F(h), for h (h,k,1) reflection, which are Fourier coefficient of V(r) as
F(h) = ~ V(r) exp 2hi h r d r = [ F(h) [ exp{ i 0(h)}, (eq. 6)
where 0(h) is phase of CSF. CSF is complex in general.
A position r in the unit cell can be given by fractional coordinates with lattice vectors a,
b, c, as
r = xa+yb+zc. (eq. 7)
Reciprocal vector h is given by a set of (h,k,l) and reciprocal lattice vectors, a*, b*, c*,
h=ha*+kb*+lc* . (eq. 8)
Once, 3-d data set ofF(h) is obtained then structure V(r) can be determined by an
inverse Fourier transform straightforwardly as
V(r) = ~ F(h) exp(- 2rcir h) dh . (eq. 9)
Diffraction intensity I(h) for h reflection is given by
I(h) = F(h)* F(h) = [I F(h) I ]2 (eq. 10)
and looses phase information. Therefore we can obtain only absolute value, moduli,
I F(h) I from diffraction intensity. For a centrosymmetric crystal, we can make F(h)
real, that is phases of F(h) are either 0(+) or ~(-)by taking an origin at inversion centre
for eq. 7. Hereafter, we will treat only centrosymmetric crystals for simplicity. In
order to show an importance of the
phases of CSFs for obtaining correct ceelxl ~.
, "~_~.f f

structure V(r), one dimensional

model system is shown schematicaly
in Fig. 2. Two structures among a i[ 0=0 ] "? -t
number of possible ones, (a) and (b),
give exactly the same diffraction cod3xl /-\ f \ ,/~x
/ v \./ \
$=0 ~=g
intensities, only difference between
the two is phases 0(h) in F(h), that is,
(a) cos[x] + cos[2x], cos[3x] (b) cos[x]- cos[2x]- cos[3x]
phases of g, 2g, 3g reflections are +,
4

+, + for case of (a) and + , - , - for , _(a)

9 (b
2

case of (b). r

O
After determining space group,
-I

two major approaches to solve the -Z

Fig. 2 Importance of phases in CSFs is shown

schematically for one dimensional case.
 65

Fig. 3 Flow chart of Structure Solution

structure by tackling phase problem are schematically shown in Fig. 3.

(1) Through ED patterns: Attempts to find phases have been based on a trial-and-error
process. CSFs were calculated for a trial structure and compared with intensity I(h)
under the measure of agreement, so called reliability index Reac-Patterson function
method or heavy-atom method helped greatly to reduce number of trial structures by
giving information of interatomic vectors of main scatterers or of heavy-atom positions.
Direct method opened new fields for the process in estimate of the phases ab initio from
66

the magnitudes of the structure factors. In order to apply this method, intensities for
many independent reflections must be measured.
(2) Through HREM images: HREM images carry phase information, and in this case we
can determine phases uniquely without pre-assumed structure models. Now, let us think
by Figs..2 and 3 a relation between diffraction and image, and information limit for
phases by EM image. Electrons are incident to a crystal as a plane wave. We will take
the direction of incident electrons to be z-axis. The role of the objective lens is to
transfer Fourier transform of wave field at the exit of the sample for a set o f g
reflections with CSFs of F(g) as shown in Fig. 2, i.e., Franhoufer diffraction, to the back
focal plane of the lens. The lens further (inverse) Fourier transforms the diffraction to
image at the image plane. ED patterns and EM images are observed as an intensity
distribution in reciprocal space and real space, respectively. From this procedure, it is
obvious EM images carry phase information of CSFs, but the information of CSFs
within a range given by Ctopt (eq. 5) is transferred (see Fig. 3).

2. Mesoporous materials:
The local structure variations in mesoporous materials are common and produce a
small number of reflections and large peak widths in powder XRD patterns, even
though the materials show nice crystal morphology. This situation can be shown by an
example for MCM-48 in Figure 4. Two structural characteristics of the meoporous
materials are clearly observed in the powder XRD pattern(Fig. 4a), where (i) disorder
on the atomic scale (short-range) can be seen as diffuse intensity at medium range of
scattering angles and (ii) distinct order on the mesoscopic scale (long-range) can be seen

Fig. 4 Powder XRD pattern and SEM imageof MCM-48.

 67

as a few sharp diffraction peaks at small scattering angles. SEM image of MCM-48(Fig.
4b) clearly shows nice crystal morphology which is commensurate with point symmetry
ofm-3m.
By noticing 3-d mesoporous material as crystalline, we have developed a new method
for solving the structures with meso-scale ordering without assuming any structural
models based on section 1-2. The resolution for the structure is primarily limited by
the quality of the HREM images, which depends on the long-range meso-scale ordering
and the treatment of the EM image processing. Further progress may give better

Fig. 5 HREM images of SBA-6 and corresponding Fourier diffractograms

68

resolution, but no change in conclusions will be necessary about structure because the
validity of a solution does not depend on the resolution[4,5].
Figure 5 shows a set of HREM images of SBA-6 together with Fourier diffractograms.
From image we can choose thin
areas which are free from
dynamical scattering and the
Fourier diffractograms from thin
regions are also shown in Fig. 5.
From observations in extinction
conditions from the diffractograms
and in point group symmetry from
SEM image, the space group of
SBA-6 was uniquely determined
to be Pm-3n. Basic structure of
SBA-6 can be obtained only from
two HREM images of [100] and
[110] incidences. The images of
[ 111 ] and [210] incidences
Fig. 6 Structure solution of SBA-6. Pm-3n.
improved fine details of structures
of cages and tunnels between
them[5]. The cages are arranged in A3B type, where the A-cage is the larger with a
diameter of 85 ,/~ at (1/2,0,1/4), (1/2,0,3/4), (0,1/4,1/2), (0,3/4,1/2), (1/4,1/2,0) and
(3/4,1/2,0), and the B-cage is the smaller with a diameter of 73 fit at (0,0,0) and
(1/2,1/2,1/2). A B-cage is surrounded by 12 A-cages that are connected through
openings of 20/k, while the openings between A-cages are about 33 x 41 A.
The materials synthesized in the spaces of mesoporous throw us new challenging
problems to solve their structures by EM, and it will be discussed at the conference.

3. Zeolites:
Now we can measure ED intensities easily by using CCD camera or imaging plate
as they have larger dynamic range and better linearity of output to input electrons than
photographic film. Applying "Direct method" to collected ED intensities of 326
independent reflections from 11 zone axes, we could solve unknown structure of
 69

zeolite SFE(SSZ-48) from very small crystal[6]. As zeolites have low density,
kinematical treatment in diffraction is a good approximation for analysis of ED
intensity distribution, if specimens are thinner than a few hundreds A. This is not so
difficult conditions for zeolites if we can obtain as a single(pure) phase, Therefore this
method is very powerful.

Fig. 7 HREM images of ETS- 10

70

Once a high quality HREM image is obtained, we can build important structural
units and geometrical relations between them by making plastic bond-models. A clear
example is shown here for ETS-10, which contains many different types of defects. It
was confirmed from ED patterns and HREM images that ETS-10 has 4-fold symmetry
in projection along z-axis and that the projected structures along x- and y-axes are
identical. An HREM image(Fig.7a) gives important pore arrangement and the
framework connectivity, and hints to build a primary structure unit(Fig.8 a). Fig. 7b
shows surface structure suggesting that a rod is a secondary building and is growth unit
in ETS-10(Fig. 8b). An ideal structure was determined from the observations as shown
in Fig.8c[7,8,9]. This analysis requires deep knowledge of both structure and EM.

Fig. 8 Schematic drawings of framework structure of ETS-10

Recently we have developed a new powerful method for obtaining structure

solutions of zeolites by combining HREM images and ED intensity data[ 10]. This will
open up new field for the structure analysis of zeolites, however, we should continue
to develop the method of solving structures further in order to make E M better
magnifier towards atomic resolution.

4. Acknowledgments
The authors greatfully acknowledge CREST, JST for financial support. We thank P.
Wagner, A. Carlsson, Y. Sakamoto, M. Kaneda, Z. Liu, K. Hiraga and T.
Tsubakiyama for their contributions.
 71

References and Notes

[1] O. Terasaki. Molecular Sieves, Science and Technology. Vol. 2, pp71-112., Eds by
H.G. Karge & J. Weitkamp, Springer-Verlag, Berlin, 1999.
[2] O. Terasaki & T. Ohsuna. Catlysis Today 23(1995), 201-218.
[3] O.Terasaki, T.Ohsuna, N.Ohnishi & K.Hiraga. Current Opinion in Solid State & Materials
Science 2(1997), 94-100.
[4] A.Carlsson, M. Kaneda, Y. Sakamoto, O. Terasaki, R. Ryoo & H. Joo J. Electron
Microscopy. 48 (1999), 795-798.
[5] Y. Sakamoto, M. Kaneda, O. Terasaki, D.Y. Zhao, J.M. Kim, G. Stucky, H.J. Shin &
R. Ryoo. Nature 408 (2000), 449-453.
[6] P. Wagner, O. Terasaki, S. Ritsch, S.I. Zones, M.E. Davis and K. Hiraga. J. Phys.
Chem. B103 (1999), 8245-8250.
[7] M.W. Anderson, O. Terasaki, T. Ohsuna, P. Phillppou, SP MacKay. A. Ferrelra, J.
Rocha & S. Lidin: Nature 367(1994), 347-351.
[8] T. Ohsuna, O. Terasaki, D. Watanabe, M.W. Anderson & S. Lidin: Studies in
Surface Science and Catalysis, Vol 84, 1994, 413-420.
[9] M.W. Anderson, O. Terasaki, T. Ohsuna, P.J.O Malley, P. Phillppou, SP. MacKay.
A. Ferrelra, J. Rocha & S. Lidin: Phil. Mag 71(1995), 813-841.
[ 10] T. Ohsuna et al., in preparation
This Page Intentionally Left Blank
 Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 73

Delaminated zeolites as active catalysts for processing large molecules

A. Corma* and V. Forn6s

Instituto de Tecnologfa Qufmica, UPV-CSIC, Universidad Polit6cnica de Valencia, Avda. de

los Naranjos s/n. 46022 Valencia, Spain

Zeolite nanolayers have been obtained by delaminating the lamellar precursors of four
zeolites. These materials present very high well structured extemal surface areas larger than
600 mZ.gl. Catalytic active sites can be introduced during the synthesis or by post-synthesis
treatments, yielding active and selective catalysts for processing large size molecules of
interest in oil refining and for the production of fine chemicals.

1. INTRODUCTION

Zeolites have shown great utility as catalysts in the field of oil refining, petrochemistry
and in the synthesis of chemicals and fine chemicals (1-3). In some cases shape selectivity
effects are highly desired when using zeolites, while in others the main objective is to replace
liquid acids using instead the environmentally more friendly solid acids. In this second case,
there is a continuous interest to find molecular sieves with large and ultra-large pores that can
convert bulky reactant molecules. If this could be achieved, the impact of zeolites would be
even more important in processes such as fluid catalytic cracking (FCC), hydrocracking,
hydrotreating, and in the production of chemicals and fine chemicals. Up to now, zeolites with
14 member ring (MR) pores are the ones with the largest pore synthesised (4,5). However, in
these structures the pores are unidirectional and offer little advantage with respect to the tri-
directional 12 MR Y and Beta zeolite for processing large molecules (6). Recently,
mesoporous molecular sieves with different topologies have been synthesised (7-9). They
show no short range order and the catalytic behaviour is closer to that of an amorphous silica-
alumina with a narrow pore size distribution, than to a zeolite. There is then incentive to
develop zeolitic materials that while keeping the short range crystallinity of zeolites, can have
the accessibility of silica-alumina towards very large reactant molecules. One possibility along
this direction is to synthesise small zeolite crystals (nanocrystalline zeolites) (10) that show a
high ratio of external to internal surface, with enhanced possibilities to adsorb large reactant
molecules on the external surface of the crystallites. While we have seen that this, can be an
interesting approach in some cases (11), we have recently explored another direction (12,13)
which involves the preparation of lamellar zeolites whose structure is subsequently
delaminated, making accessible through the external surface all the potential active sites. The
main difference between these type of materials and the mesoporous molecular sieves of the
74

MCM-41 type is that in the nanocrystalline and delaminated zeolites there is short-range order
and consequently the active sites are of zeolitic nature.

2. DELAMINATED Z E O L I T E STRUCTURES

Up to now, we have delaminated four different lamellar zeolitic precursors which have
generated the materials named as ITQ-2, ITQ-6, ITQ-18 and ITQ-20 (12,13). The first one,
ITQ-2, was obtained by delaminating a MWW zeolite precursor (14) while ITQ-6 and ITQ-20
were prepared by delaminating laminar precursor of ferrierite (15) and MCM-4"7 (16,17),
respectively, while the structure of ITQ-18 is still unknown to us. The artist view of the
structure of the two first material is presented in Figure 1.

Fig. 1. Artistic view of the structure oflTQ-2 and ITQ-6 delaminated zeolites.

As a general procedure, the lamellar precursors of zeolites are swelled, at the adequate
pH, using an alkyl ammonium bromide, or even an amine or an alcohol can also be used, to
separate the layers. After this the swelled material can be delaminated by means of
ultrasound, freezdrying, or by vigorous stirring. The "in situ" delaminated material can form
an slurry or a paste with a matrix component and a binder, and the final product can be spry
dried or extruded, respectively. If desired, the pure delaminated materials can be recovered by
centrifugation. Activation is carried out by extracting the organics in liquid phase, or by
decomposing them by calcination in air at 500~ It has to be noticed that these materials are
stable upon calcinations at 700~
As one can expect, the X-Ray diffractogram of delaminated zeolites, show a small
number of peaks, which are due to the reflections along the two main dimensions of the layers,
while those due to the regular ordering of layers one above the other have disappeared owing
to the delamination. More specifically (Fig. 2), in the case of ITQ-2 the XRD does not show
the 001 and 002 peaks at 20=3-7 ~ while in the case of ITQ-6 the hOe reflections have
practically disappeared.
 75

, , , , , , , , , . . . . . . . . .

0 10 20 30 40 0 10 20 30 40
20 20

Fig. 2. XR diffractograms of MWW and ferrierite (a,a'), their precursors (b,b'), and the
delaminated ITQ-2 and ITQ-6 (c,c').

140 ' 9 ]-] 140 I 9ITQ6

9FER
120 9
12MR
cavities
!/ 120

g 100 - 100'

[ [ 10MR
D 80' pores &&
k ,"
k ." i
10MR 9 9
~ 60. pores == ==

<
40- 40'

;.-'.."
0 0
1E-06 0.00001 0.0001 0.001 0.01 0.1 0.000001 0.00001 0.0001 0.001 0.01 0.1

P/Po (logarithmic scale) PIPo (logarithmic scale)

Fig. 3. Argon isotherms of MWW and ferrierite (a,a'), their precursors (b,b'), and the
delaminated ITQ-2 and ITQ-6 (c,c').
76

While the IR and 29SiMAS NMR spectra are consistent with the delaminated structure
of ITQ-2 and ITQ-6, the Argon isotherms represented as a function of log P/P are highly
informative on the changes in topologies experienced during delamination (Fig. 3). It can be
seen there that ITQ-2 does not show the adsorption corresponding the large 12 MR cavities
characteristics of the MWW structure, while preserves that of the intralayer 10 MR circular
channels. Meanwhile, in the case of ITQ-6, the adsorption at the 10 MR pores of ferrierite has
practically disappeared.
It appears then that during the delamination of lamellar zeolitic precursors we have
produced disordered individual sheets of crystalline zeolitic material that may be forming a
"house of cards" type of structure, leaving mesopores in between them and allowing
accessibility of reactants to the external active sites. This gives to delaminated zeolites
extremely large external surface areas (Table 1) that are highly desirable for many catalytic
processes. Notice that the area remains stable at high calcinations temperatures and even after
steaming at 650~

Table 1
Surface area determined by N2 adsorption after calcination at 550~ for 3 hours.
Material SBET(m2g"l) SEXT(m2g"1)
MWW 452 97
ITQ-2 841 776
Ferrierite 278 53
ITQ-6 620 575

The resultant delaminated materials, when are prepared in a silica-alumina form, show
strong Brtinsted acidity of the zeolitic type, which are much stronger than those of MCM-41
and accessible to large molecules, as indicated by the adsorption of 2,6-di-tert-butylpyridine.

3. CATALYTIC P R O P E R T I E S
3.1. Oil refining and petrochemistry
The accessibility to acid sites of large oil molecules is shown by comparing the relative
rates of MWW and ferrierite with respect to the corresponding ITQ-2 and ITQ-6 for cracking
diisopropyl- and triisopropyl-benzene, and vacuum gasoil (Table 2). The results clearly show,
that despite the fact that the delaminated zeolites have a lower number of total acid sites, as
measured by pyridine adsorption, due to some dealumination occurring during the preparation,
their activity is much higher, owing to a better accessibility of the reactants to the acid sites.
 77

Table 2
Cracking activity of non delaminated and delaminated zeolitic materials
Kinetic rate constants (s "l)
Material Diisopropyl- Triisopropyl- Vacuum Acidity a
Benzene Benzene Gasoil
MWW 0.10 -- 0.025 24
ITQ-2 0.18 -- 0.050 15
Ferrierite -- 0.03 -- 19
ITQ-6 -- 0.14 -- 9
a Brrnsted acidity measured by pyridine, after desorbing at 523 K and 10 -2 Tor.

One may reasonably think that these materials are probably too costly and probably not
enough stable to be commercially used in FCC units, but they may have a possibility as a
component of hydrocracking catalysts. In this case, it would be highly desirable to have a
material which could combine the good selectivity for diesel of amorphous silica-alumina,
with the high activity of zeolites. It appears then, that delaminated zeolites could accomplishes
these two objectives. Thus, we present here (Fig. 4) the results obtained during mild
hydrocracking of vacuum gasoil on NiMo/ITQ-2, NiMo/USY, NiMo/ASA, NiMo/7-A1203, all
catalysts containing 12 wt% MoO3 and 3 wt% NiO.

Fig. 4. Hydrocracking (HC) conversions obtained for the different catalysts as a function of
the reaction temperature. Reaction conditions: 3.0 MPa. 2 h l WHSV and 1000 H2 (stp)/feed
ratio: ( 9 ) NiMo/ITQ-2. (m) NiMo/USY. (A) NiMo/ASA. ( v ) NiMo/),-A1203.

Figure 4 presents hydrocracking conversion at 3.0 MPa, 2 h -1 ~rHSV, 1000 H2 (stp)

feed ratio, and different reaction temperatures. It can be seen there that NiMo/ITQ-2 shows the
highest activity, closely followed by NiMo/USY, and in any case the activity of the former is
much higher than that of NiMo/SiO2-A1203. The product selectivity at 50-55% of HC
conversion is compared in Figure 5. As expected, NiMo/ITQ-2 presents a selectivity
78

behaviour which is intermediate between NiMo/SiO2-A1203 and NiMo/USY. In this way,

NiMo/ITQ-2 it produces more diesel and less gases than NiMo/USY, showing promise as a
hydrocracking catalyst, since it combines the high activity typical of zeolite-based catalysts
with the good selectivity of amorphous catalysts.

Fig. 5. Selectivity to the different hydrocracked fractions obtained at ca. 55% hydrocracking
conversion over NiMo-containing catalysts: (m) NiMo/ASA. ~ )NiMo/USY. (Fq)NiMo/
ITQ-2. Gases: C~-C4. Naphtha: C5-195~ Middle distillates: 195-360~

3.2. Delaminated zeolites for fine chemicals

There are cases in where the production of fine chemicals involves the use of large
reactant molecules or the formation of bulky products. In both cases, zeolites show limitations
either for the reactants to penetrate into the pores, or for products to diffuse outside of the
pores. In this case one can certainly decrease the crystallite size of the zeolite or even to use
mesoporous materials to favour diffusivity. However, will show some cases in where there is a
clear benefit of using delaminated zeolites over the other two types of materials.
There is an important number of acetals that are used as fragrances. The synthesis of
acetals is generally carried out by reacting aldehydes with alcohols. These are reactions which
involve mild acid sites as catalysts. Here, we present firstly the synthesis of acetals from
aldehydes of different molecular sizes on three catalysts, i.e. Beta zeolites with different
crystallite sizes, mesoporous MCM-41, and the delaminated ITQ-2 material. The results
presented in Table 3 clearly show that for small size acetals that can penetrate inside the
micropores of Beta, this is the most active catalyst owing to its larger amount of acid sites, and
also to concentration effects within the micropores that can favour bimolecular reactions.
However, when the size of the aldehyde increases, the activity of Beta zeolite, even within
crystallite sizes as small as 60 nm, is strongly diminished and is lower than that of MCM-41
and ITQ-2. In this case, the activity of the delaminated zeolite is clearly superior to either Beta
of MCM-41 as a result of combining high accessibility to reactants with acid sites of zeolitic
nature.
More specifically, the synthesis of 2-methyl-2-naphthyl-4-methyl-l,3-dioxolane which
has an orange blossom fragrance, was obtained by reacting 2-acetonaphthanone with 1,2-
propanediol at 419K in a batch reactor.
 79

Table 3
Synthesis of acetals on different zeolitic materials

R1 R2
R20CH 3
' II Rn---- H - , I O C H 3 1 CH3(CH2)4 H (Eq. 1)
2 Ph CH 3
Rl u CH-C,, Solid Catalysts H Ph
H 3 Ph
1-3 la-3a
Initial rates and conversion for the acetalization of aldehydes 1, 2 and 3 with trimethyl
orthoformate ~TMOF) over different acid catal~,sts b.

Catalysts 1 2 3
ro(h'l) Conversion a ro(h-1) Conversion a ro(h-1) Conversion a

Beta (~0.06) 200 78 120 65 48 15

(Si/Al=l 8)
Beta(~0.86) 177 75 67 43 10 6
(Si/Al=18)
Beta (t~ 0.1 ) 450 90 108 40 48 27
(Si/A1-50)
MCM-22 (Si/A1= 50) 150 40 55 23 50 25
ITQ-2 (Si/AI= 50) 420 95 330 85 210 75
MCM-41 ~Si/A1 =40) 210 80 180 70 180 71
a)lh reaction time. b) Reaction conditions: aldehyde (2.5 mmol), TMOF (12.7 mmol), catalyst
(30 mg) in 25 ml CC14 at 78~

Table 4
Synthesis of Blossom oranged. Reaction conditions: 7.4% wt/wt of catalyst respect to 2-
acetonaphthanone, 419 K, volume ratio: toluene/2-acetonaphthanone = 26.6.

Yield of Blossom oranged

Reaction Time
Catalyst Si/A1 lh 3h
ITQ-2 50 32 80
MCM-22 50 5 12
HI32a 15 4 5
H~3 b 15 24 45
MCM-41 15 9 24

a Commercial sample, b Nanocrystalline zeolite

80

The reaction was carried out using Beta, Beta nanocrystalline, MCM-41, and ITQ-2 as
catalysts. The results presented in Table 4 show that ITQ-2 is more active than the
nanocrystalline Beta, despite the fact that the number of acid sites is much smaller in the
former, and much more active than MCM-41. The selectivity to the desired product on ITQ-2
is practically 100%.
The synthesis of lactames has interest for the production of chemicals and fine
chemicals. In the case of more bulky lactames derived from cyclodedecanone-oxime and
cyclooctanone-oxime, they are used for producing nylon-12 and for the preparation of the
precursor of azacycloalkanediphosphonic derivates which have pharmaceutical interest for the
treatment of Ca 2+ metabolism disorders, respectively.
In this case, the conversion of cyclododecanone and cyclooctanone oxime were done
by the Beckman rearrangement in liquid phase, in a batch reactor at 403 and 433 K,
respectively, with a catalyst to oxime ratio of 1:2 wt.wt ~, and chlorobenzene and sulfolane as
solvent, respectively. The results reported in Table 5 show a higher activity for the
delaminated ITQ-2 sample. Moreover, adsorbed products are easier to be removed from the
surface of the delaminated material, as indicated by the smaller amount of organic left on the
solid after reaction which was in the case of cyclododecanone-oxime, 2, 3 and 5 wt% for
ITQ-2, MCM-41 and Beta, respectively. By optimising temperature and solvent, conversions
higher than 95% with selectivities to the lactames > 98% can be obtained with ITQ-2.

Table 5
Synthesis of the lactames of cyclooctanone and cyclododecanone oxime at 430~ and 90
minutes reaction time on various catalyst with a Si/AI ratio of 50.

Conversion (%)
Catalyst Cyclododecanone oxime Cyclooctanone oxime
ITQ-2 98 82
MCM-41 67 60
Beta (0.1 lam) 32 26

3.3. Delaminated zeolites as catalysts supports

Improving the quality of the Light Cycle Oil (LCO) produced in the FCC unit can be a
necessary task to meet future diesel specifications. In order to improve the quality of LCO,
polyaromatics should be hydrogenated and sulfur reduced. Owing to its high sulfur content, a
dual-stage hydrogenation process has to be used where the feed is first hydrotreated to reduce
the sulfur content, and then hydrogenated using a noble metal catalyst in the second reactor. A
hydrotreated LCO which contained 400 ppm sulfur, and 68% aromatics with the distribution
between mono, di and tri + aromatics given in Figure 6, was hydrogenated using Pt on different
supports, i.e. amorphous silica-alumina, USY zeolite and ITQ-2. Acid supports were used here
to increase the thioresistance of the catalysts. The results (Fig. 6) show that Pt/ITQ-2 gives the
highest aromatics reduction, being mainly the tri +- and di-aromatics the ones reduced.
 81

Fig. 6. Total aromatics content and aromatics distribution obtained in the hydrogenation of a
hydrated LCO (HT-LCO) over the different Pt supported catalysts. Reaction temperature:
300~ The values corresponding to the HT-LCO feed are also included for comparison. ( D )
Mono-aromatics. (El) Di-aromatics. ( I ) Tri §

The ferrierite delaminated ITQ-6 material has been successfully used as a support for
enzymes (18). More specifically, ~-galactosidase from Aspergillus Oryzae, and penicillin
Gacylase have been electrostatically and covalently immobilised on ITQ-6, resulting with
enzyme catalysts highly active and stable. The advantage of delaminated zeolites as enzyme
support is derived from the well structured external surface in where the silanol groups are
regularly distributed. This allows a multipoint attachment between the enzyme and the
supports, perhaps involving the most reactive groups of the protein surface.

4. CONCLUSION

A new type of materials has been developed by delaminating the lamellar precursors of
some zeolites. These materials show external surface areas > 600 m2.g"1 from where active
sites can be accessible to very large molecules. If on one hand delamination eliminates
geometrical shape selective properties of zeolites, it allows on the other hand to dispose of
catalysts with the good reactant accessibility of mesoporous materials, but with the stability
and active sites characteristics of zeolites. The very large and well structured external surface
area can be specially suited for supporting different catalytic functions, which include, among
others, metals, transition metal complexes and enzymes.

5. R E F E R E N C E S

1. A. Corma, Chem. Rev., 95 (1995) 559.

2. I.E. Maxwell and W.H.J. Stork, Stud. Surf. Sci. Catal., 58 (1991) 571.
3. R.A. Sheldon and H. van Bekkum (eds.), Fine Chemicals Through Heterogeneous
Catalysis., Wiley-VCH, Weinheim (2001).
4. K.J. Balkus, Jr., A.G. Gabrielov and N. Saudler, Mater. Res. Soc. Symp. Proc., 368 (1995)
359.
5. P. Wagner, M. Yoshikawa, M. Lovallo, K. Tsuji, M. Taptsis and M.E. Davis, Chem.
Commun. (1997) 2179.
82

J. Martinez-Triguero, M.J. Diaz-Cabafias, M.A. Camblor, V. Fom6s, Th.L.M. Maesen and

A. Corma, J. Catal., 182 (1999) 463.
J.S. Beck, J.C. Vartulli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.W.
Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgings and J.L. Schlenker, J.
Am. Chem. Soc., 114 (1992) 10834.
A. Monnier, F. Schilth, Q. Huo, D. Kumar, D. Margolese, R. S. Maxwell, G. D. Stucky,
M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke and B. F. Chmelka, Science, 261
(1993) 1299.
. A. Corma, Chem. Rev., 97 (1997) 2373.
10. B.J. Schoeman, J. Sterte and J.E. Otterstedt, Zeolites, 14 (1994) 110.
11. M.A. Camblor, A. Corma, A. Martinez, V. Martinez-Soria and S. Valencia, J. Catal., 179
(1998) 537.
12. A. Corma, V. Fom6s, S.B. Pergher, Th.L.M. Maesen and J.G. Buglass, Nature, 396 (1998)
353.
13. A. Corma, U. Diaz, M. Domine and V. Fom6s, Angew. Chem. Int. Ed., 39 (2000) 1499;
and J. Am. Chem. Soc., 122 (2000) 2804.
14. S.L. Lawton, A.S. Fung, G.J. Kennedy, L.B. Alemany, C.D. Chang, G.H. Hatzikos, D.N.
Lissy, M.K. Rubin, H.J.C. Timken, S. Stenemagel and D.E. Woessner, J. Phys. Chem.,
100 (1996) 3788.
15. L. Schreyeck, P.H. Caullet, J.C. Mougenel, J.L. Guth and B. Marler, Chem. Commun.
(1995)2187.
16. E.W. Valyocsik, US Patent N ~ 5 068 096 (1991).
17. A. Burton, R.J. Accardi, R.F. Lobo, M. Falcioni and M.W. Deem, Chem. Mater., 12
(2000) 2936.
18. A. Corma, V. Fom6s, J.L. Jordh, F. Rey, R. Fem6.ndez-Lafuente, J.M. Guis6.n and C.
Mateo, Chem. Commun. (2001) in press.
Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 83

Pentasil zeolites from Antarctica" from mineralogy to zeolite science and

technology

A. Alberti a, G. Cruciani a, E.Galli b, S. Merlino c, R. Millini d, S. Quartieri e, G.Vezzalini b, S.

Zanardi a

aDipartimento di Scienze della Terra, Universith di Ferrara, Italy.

bDipartimento di Scienze della Terra. Universith di Modena e Reggio Emilia, Italy.

CDipartimento di Scienze della Terra, Universit/l di Pisa, Italy.

dEniTecnologie S.p.A., S. Donato Milanese, Italy.

eDipartimento di Scienze della Terra, Universit/l di Messina, Italy.

SUMMARY

In the course of a systematic investigation of zeolites from Northern Victoria Land,

Antarctica, a large number of zeolitic species was identified in the Jurassic Ferrar Dolerites
of Mt. Adamson. Noteworthy was the presence of three new zeolites: gottardiite, the natural
counterpart of the synthetic NU-87, terranovaite, and mutinaite, the analogue of ZSM-5, as
well as the two very rare zeolites tschernichite, the counterpart of zeolite beta, and boggsite.
The chemical and crystallographic properties of these natural materials were compared with
those of their synthetic analogues. The tetragonal and monoclinic polymorphic phases,
intergrown in the beta zeolite, were isolated and structurally refined in tschernichite crystals,
which differ by crystal size, morphology and chemistry. The occurrence of these natural
zeolites demonstrates that the chemical existence field of their synthetic counterparts is
larger than that argued up to now, and that their synthesis can be obtained in the absence of
an organic template.

1. INTRODUCTION

It is well known that zeolites containing a high proportion of five-membered rings of

tetrahedra in their framework are widely used in heterogeneous catalysis; these include
synthetic ZSM-5, ZSM-11, beta, theta-1, NU-87, the synthetic analogues of natural
mordenite and ferrierite and the natural zeolite heulandite.
During an investigation of zeolites from Northern Victoria Land, Antarctica, numerous
zeolitic species, among which the pentasils are predominant, were found in the Jurassic
Ferrar Dolerites of Mt. Adamson: heulandite, stellerite, stilbite, mordenite, erionite, levyne,
84

cowlesite, phillipsite, chabazite, epistilbite, ferrierite, analcime and, particularly interesting,

the rare zeolites boggsite and tschernichite, the natural counterpart of zeolite beta [1].
Noteworthy is the presence of three new pentasil zeolites: gottardiite [2], the natural
counterpart of NU-87, terranovaite [3] and mutinaite [4], the natural counterpart of ZSM-5.
Very striking is the occurrence at Mt. Adamson of so many natural analogues of
important synthetic zeolites and of two minerals (boggsite and terranovaite) still lacking
their synthetic counterpart.
The aim of this contribution is to highlight the impact that the study of mineral zeolites
can have on zeolite knowledge. In particular:
a) natural zeolites usually occur in crystals which are large enough for single-crystal X-ray
diffraction studies; these investigations allow structural information to be obtained
which is far more detailed and accurate than that gathered by powder diffraction data or
other experimental techniques;
b) the counterparts of synthetic zeolites found up to now in nature usually have
significantly different Si/A1 ratios and extraframework contents. This shows that the
chemical existence field of these topologies is wider than that up to now deduced from
the compositions of the synthesised phases; it should also be borne in mind the extent to
which chemical characteristics can influence the technological properties of the
materials, and how much detailed structural information is essential for their
comprehension.
Below we describe the crystal-chemistry of the new and rarest zeolites from Mt.
Adamson, with a particular emphasis on the most recent results conceming the structural
features of the tschernichite-type mineral and a comparison with its synthetic analogue beta.

2. GOTTARDIITE

The first of the new natural zeolites found at Mt. Adamson was gottardiite [2]. The
crystals occur as thin lamellae, pseudo-hexagonal in shape or elongated along the a axis. The
crystals, transparent and colorless, rarely occur in isolation; more frequently they form
aggregates of a few individual crystals. The chemistry of gottardiite (unit cell content:
Na2.sK0.zMg3.1Ca4.9Al18.8Sil17.zOzvz'93H20) is characterized by a high magnesium content
and a very high Si/A1 ratio (6.2) compared with other natural zeolites. Gottardiite shows a
high thermal stability and very high re-hydration capacity; the mineral quickly and
completely regains its weight loss at temperatures of up to 800~ whereas at 1100~ its
rehydration capacity becomes zero, probably due to the framework destruction occurring in
this temperature range [2]. Its fast and complete rehydration suggests that no T-O-T bridge
breaking occurs during dehydration [5].
The mineral is orthorhombic (a=13.698(2), b=25.213(3), c-22.660(2) A), with
topological symmetry Fmmm and real symmetry Cmca [6]. In the Fmmm symmetry there
are five non-symmetry-related sites on inversion centers. In this topological symmetry two
oxygen atoms lie on two of these 1, causing energetically unfavourable T-O-T angles of
180 ~ In the Cmca sp.gr, these two inversion centers disappear, while the other three remain.
This situation is common to all zeolites where, in the topological symmetry, framework
oxygens lie on centers of symmetry [7].
 85

The topology of gottardiite, which has not been found in other natural zeolites, is the
same as that of synthetic zeolite NU-87 [8]. This is more evident if we describe the NU-87
unit cell not on the basis of the conventional monoclinic unit cell P21/c (a = 14.324 A, b =
22.376 A, c= 25.092 A, 13=151.52~ ), but in the pseudo-orthorhombic unit cell C l l 2 / / b (a =
13.663 A, b = 25.092 A, c = 22.376 A, ~/=90.37~ ).
The framework of gottardiite can be described by the interconnection of the
polyhedral subunits 5262, 5462 and 54. 5262 and 5462 units have also been found in other
zeolites, whereas the unit 54 has been found here for the first time in zeolites. By
interconnecting the 5462 and 54 units, a chain is generated which develops along the b axis.
These chains are connected to form an impermeable sheet parallel to the ab plane. Each
sheet is bonded to other parallel sheets through 4-rings of tetrahedra.
The crystal structure is characterized by a two-dimensional channel system. Straight
10-ring channels run parallel to a, whereas 12-ring channels develop along b. These 12-ring
channels are interrupted every 25 A (the value of parameter b) by the 4-ring between the
sheets, and are connected to the 10-ring parallel to the a axis by a 10-ring window.
Therefore these 12-ring channels are not straight, but "snake" in the b direction.

3. TERRANOVAITE

The second new natural zeolite found at Mt. Adamson was terranovaite [3]. This
mineral is very rare and frequently occurs in globular masses, sometimes in tabular,
transparent, bluish crystals, closely associated with heulandite, from which it is barely
distinguishable. Yerranovaite [(Na4.zK0.2Mg0.2Ca3.7)tot=8.3(Al12.3Si67.7)tot=80.0O160">29H20]is
rich in sodium and calcium and has quite a high Si/A1 ratio (about 5.5).
Its topological symmetry, hitherto unknown in either natural or synthetic materials, is
orthorhombic, space group C m c m (a = 9.747(1), b = 23.880(2), c=20.068(2)A). However, the
presence of a framework oxygen on an inversion center, with an unfavorable T-O-T angle of
180 ~ and the strong anisotropy of some framework oxygen atoms, indicate that the real
symmetry is probably described by the acentric sp.gr. C2cm.
The framework of terranovaite (Fig. 1), characterized by a pentasil chain, can be
described by the interconnection of the polyhedral subunits 4264, 4254 and 5462. The 4264
unit has been found in laumontite and boggsite; the 4254 unit has been found in brewsterite,
heulandite group zeolites and in synthetic SSZ-23 and SSZ-33; the 5462 unit has been found
in gottardiite, boggsite and in synthetic EU-1. The net of terranovaite projected onto the bc
plane (Fig. 1) is equivalent to that of many other pentasil zeolites (ferrierite, boggsite, ZSM-
5, ZSM-11, theta-1), while the net projected onto the ab plane is equivalent to that of A1PO4-
41 [9].
A two-dimensional channel system parallel to the (010) plane is present in the
terranovaite framework. Straight ten-membered ring channels run along [100] and [001];
the former is about circular in section (5.5 x 5.1 A), while the latter is strongly elliptic (7.0 x
4.3 A) (Fig. 1). These channels are connected through a 10-ring window.
86

Fig. 1. Perspective projection of terranovaite framework along [ 100].

4. M U T I N A I T E

The third new natural zeolite found in the Ferrar Dolerites of Mt. Adamson is
mutinaite [4], the natural counterpart of synthetic ZSM-5. The mineral [(Naz.76K0.11Mg0.21
Ca3.78)(All 1.20Si84.91)O192"60H20] occurs as subspherical aggregates of tiny radiating lath-like
fibers or as aggregates of transparent tiny tabular crystals, with good (001) cleavage. This
zeolite, very rich in calcium, has a Si/A1 ratio equal to 7.6, the highest found in natural
zeolites; however, it is far lower than that of ZSM-5, where this ratio is always greater than
12. Moreover, mutinaite is characterized by a very high thermal stability and a high re-
hydration capacity. The mineral quickly regains more than 95% of its weight loss at
temperatures up to 900~ [4].
The single-crystal structure refinement of mutinaite [ 10] was performed on a micro-
crystal of 0.03x0.03x0.015mm 3, collecting the data at the beamline ID 11 of the synchrotron
radiation source of the European Synchrotron Radiation Facility (ESRF) of Grenoble. The
mineral resulted orthorhombic with space group Pnma (a--20.201(2), b-19.991(2),
c=13.469(2)A, V=5439 A3). This symmetry is consistent with the high aluminum
percentage, and with the content and distribution of the extra-framework species. The
structural refinement of mutinaite revealed the absence of order in the Si,AI distribution in
the framework; this result is consistent with the conclusions of Toby et al. [ 11 ], who report
the absence of highly occupied Br6nsted sites in the high-alumina ZSM-5.
When mutinaite is compared with synthetic ZSM-5 phases (with Pnma symmetry)
loaded with different molecules, we observe that the mean T-O-T angle is similar: 154 ~ in
mutinaite, 155 ~ in TPA-ZSM-5 [12], and 154 ~ in PDCB (p-diclorobenzene-ZSM-5), PNAN
(p-nitroaniline-ZSM-5) and NAPH (naphthalene-ZSM-5) [13]. On the contrary, many of the
 87

single T-O-T angles of mutinaite strongly differ from the corresponding angles in the
synthetic phases (by up to 19~ for T1-O1-T2 of mutinaite with respect to NAPH). These
differences mainly affect the shape of the straight ring channel: in mutinaite it is strongly
elliptical and, above all, the directions of minimum and maximum elongation are
interchanged with respect to those of the synthetic phases.

5. BOGGSITE

Boggsite was first described by Howard et al. [14]. This pentasil zeolite occurs in
close association with tschernichite in Eocene basalts near Goble, Columbia County
(Oregon), and was found for the second time at Mt. Adamson. Boggsite topology [ 15] was
hitherto unknown in either natural or synthetic materials. The framework (topological and
real symmetry Imma, a=20.25(2), b=23.82(1), c=12.78(1)A) can be described by the
interconnection of the polyhedral subunits 4254, 4264, 5462 (found also in terranovaite), 5262
(present with 5462 in gottardiite) and 4262. A straight 12-membered ring channel runs along
[100], and a straight 10-ring channel develops in the [010] direction. These channels are
connected by a 10-ring window [ 15].
The chemical analyses of boggsite from Goble and Mt.Adamson indicate a constant
value of the Si/A1 ratio (about 4.3), which is a usual value for the already known pentasil
zeolites, but rather low when compared with that of the other pentasil zeolites from Mt.
Adamson. Ca is always the most abundant extraframework cation, whereas Na is rather
variable and can reach a content nearly equal to that of Ca. Minor quantities of K and Mg
are present.

6. T S C H E R N I C H I T E

Tschernichite was structurally defined as the natural counterpart of synthetic zeolite

beta [ 16]. At Mr. Adamson the mineral occurs either as large, steep tetragonal dipyramids
terminating in a basal pinacoid, or as radiating hemispherical groups of small crystals. Large
and small drusy crystals were also reported from Goble tschernichite [17]. Microprobe
chemical analyses [1] of large and small tschernichite crystals clearly show that large
crystals are richer in A1 than the small ones (Si/A1 ratios 2.66 and 3.94, respectively), as
applies also to tschernichite from Goble [17]. Due to the paucity of materials it was not
possible to determine the thermal behaviour of tschemichite from Mt. Adamson, but a study
on tschernichite from Goble [18] showed that its ammonium form is thermally stable to a
temperature as high as 900~
It is known that synthetic zeolite beta can be regarded as a close intergrowth of two
distinct, but related, structures [ 19] which can be described as consisting of (001) tetragonal
layer-like building units [20]. According to the OD theory, these two structures represent the
two maximum degree of order (MDO) topologies.
The X-ray powder diffraction pattern of the large crystals of tschernichite-type
mineral from Antarctica shows significant discrepancies, mainly in the low 0 region, with
respect to those of Goble tschernichite [17] and beta zeolite [19]. These discrepancies,
together with the different Si/A1 ratios between large and small crystals of tschernichite,
88

Fig. 2. Projection along [110] of the monoclinic polytype of tschernichite.

suggest that a different ratio of the two polytypes may be present in the crystals of this
mineral, depending on their dimensions.
We have recently used single crystal X-ray diffraction to study the structure of the
two different morphologies of tschemichite from Antarctica, in order to verify if they are
characterized by different structural features. Intensity data were collected on a fragment of
a large crystal and on a small crystal, using an automatic four-circle Nonius KappaCCD
diffractometer equipped with a CCD detector (radiation MoKot).
A data collection performed on a large crystal indicated a monoclinic unit cell with
a=17.983(3)A, b=17.966(2)A, c=14.625(2)A, [3=114.31(1) ~ V=4306.1A 3 and sp.gr. C2/c. A
similar investigation on a small single crystal indicated a tetragonal unit cell with
a=12.622(1)A, c=26.674(3)A, V=4249.6A 3 and sp.gr. P4122. The structure refinements of
both samples were carried out starting from the DLS atomic coordinates of Higgins et al.
[21]. Extraframework sites were located using Fo and AF Fourier maps.
The diffraction patterns of both tetragonal- and monoclinic-dominant crystals have in
common a set of sharp reflections, with h (and k) = 3n, which are related to the superposition
structure. Due to layer stacking disorder, reflections with h (and k) = 3n + 1 show
continuous streaks elongated in the c* direction. A detailed structural analysis of each
polytype requires a 3-dimensional analysis of the diffuse peaks and an accurate intensity
measurement, which can be obtained with an area-detector based diffractometer. For the two
tschernichite crystals, the real symmetry was checked with the help of synthetic precession
images constructed from the collected flames.
 89

Figures 2 and 3 report the projection along [110] and [ 100] of the two polytype structures.
The main results of the structure refinements are the following: a) regular T-O distances and
partial Si/A1 ordering in both frameworks; b) identification of two Ca sites in the monoclinic
structure; c) identification of two Ca sites in comparable positions in the tetragonal structure,
but with lower occupancy; d) a further cation site probably occupied by Mg in tetragonal-
dominant crystals; e) the presence of many other extraframework sites characterized by low
electron densities and large distances from the framework oxygens.

Fig. 3. Projection along [ 100] of the tetragonal polytype of tschemichite

90

7. CONCLUSIONS

The discovery at Mt. Adamson of so many new and rare high-silica pentasil zeolites,
most of which being natural counterparts of synthetic phases largely used in many
technological applications, is of great interest as:
a) it implies that organic templates, used as directing agents, may not be essential for their
synthesis;
b) the finding of the natural zeolites discussed above, with a Si/A1 ratio lower than that of
the corresponding synthetic phases, suggests that the range of chemical composition
required for the crystallization of their structural type is greater than that believed up to
now;
c) gottardiite, mutinaite and the ammonium form of tschernichite from Goble are stables to
temperatures as high as 900~ We can argue that also terranovaite and boggsite are
characterized by a similar, very high thermal stability,
d) terranovaite and boggsite are interesting additions to the pentasil family, and the
synthesis of their analogues should be of great interest to all those who work in the field
of microporous materials.
All the above described zeolites from Mt. Adamson are characterized by the dispersion
of the extraframework ions over a large number of sites; they are usually characterized by
weak electronic density and large distances from the framework oxygens which prevent
(with the exception of tschernichite) an unambiguous site assignment of cations and water
molecules. These features, together with the crystal growth structures of tschernichite, could
suggest that these minerals grew very quickly, possibly during a rapid environment cooling,
and that they could be metastable at room conditions. The defining of the genetic conditions
of these phases, which are potentially useful as molecular sieves and catalysts, is the aim of
our future research work.
In conclusion, we believe that the results of this research well demonstrate how much
natural materials can contribute to the knowledge of microporous materials. To stress this
point again, we remind the reader of the recent occurrence of two natural zeolites analogous
to previously synthesized phases, and two others lacking their synthetic counterparts: a)
gaultite [22], a framework silicate unique in nature with zinc in tetrahedral sites, chemically
and structurally analogous to VPI-7; b) pahasapaite [23], a berylloposphate with the same
topology as the synthetic aluminosilicate RHO; c) maricopaite [24], an interrupted
framework aluminosilicate with lead as dominant extraframework cation, forming
Pba(O,OH)4 clusters; and d) tsch[]rnerite [25], characterized by a super-cage with 96
tetrahedra and 50 faces and by CuZ+12(OH)24-bearing clusters.

ACKNOWLEDGEMENTS

Italian PNRA, CNR and MURST ("Transformations, reactions, ordering in minerals" COFIN
1999) are acknowledged for financial support.

REFERENCES

[1] E. Galli, S. Quartieri, G. Vezzalini and A. Alberti, Eur. J. Mineral., 7 (1995) 1029.
 91

[2] E. Oalli, S. Quartieri, G. Vezzalini and A. Alberti, Eur. J. Mineral., 8 (1996) 687.
[3] E. Galli, S. Quartieri, G. Vezzalini, A. Alberti and M. Franzini, Amer. Mineral., 82
(1997a) 423.
[4] E. Galli, G. Vezzalini, S. Quartieri, A. Alberti and M. Franzini, Zeolites, 19 (1997b) 318.
[5] A. Alberti and G. Vezzalini, in: Proceeding of the Sixth International Zeolite
Conference, D. Olson and A. Bisio (eds.),Butterworth & Co., Guildford, UK, (1984) 834.
[6] A. Alberti, G.Vezzalini, E. Galli and S. Quartieri, Eur. J. Mineral., 8 (1996) 69.
[7] A. Alberti, in: New developments in zeolite science and technology. Y. Murakami, A.
Iijima and J.W. Ward (eds.), Proc. 7 th Int. Zeolite Conf. Kodansha, Tokio, (1986) 437.
[8] M.D. Shannon, J.L. Casci, P.A. Cox and S.J. Andrews, Nature, 353 (1991) 417.
[9] R.M. Kirchner and J.M. Bennett, Zeolites, 14 (1994) 523.
[ 10] G. Vezzalini, S. Quartieri, E. Galli, A. Alberti, G. Cruciani and ,4,. Kvick, Zeolites, 19
(1997) 323.
[11] B. Toby, S. Purnell, R. Hu, A. Peters and D.H. Olson, in: Proceeding of the 12th
International Zeolite Conference. Treacy, B.K. Marcus, M.E. Bisher and J.B. Higgins (eds.),
Materials Research Society, (1999), 2413.
[12] H. Van Koningsveld, H. van Bekkum and J.C. Jansen, Acta Cryst., B43 (1987) 127.
[13] H. Van Koningsveld, and J.H. Koegler, Microporous Materials, 9 (1997) 71.
[14] D.G. Howard, R.W. Tschernich, J.V. Smith and G.L. Klein, Amer. Mineral., 75 (1990)
1200.
[15] J.J. Pluth and J.V. Smith, Amer. Mineral., 75 (1990) 501.
[16] J.V. Smith, J.J. Pluth, R.C. Boggs and D.G. Howard, J. Chem. Soc., Chem. Commun.,
(1991) 363.
[17] R.C. Boggs, D.G. Howard, J.V. Smith and G.L. Klein, Amer. Mineral., 78 (1993) 822.
[18] R. Szostak, K.P. Lillerud and M. St6cker, J. Catal., 148 (1994) 91.
[19] J.M. Newsam, M.M.J. Treaty, W.T. Koetsier and C.B. De Gruyter, Proc. Roy. Soc.
London, A420 (1988) 375.
[20] B. Marler, R. B6hme and H. Gies, in: Proceeding of the 9th International Zeolite
Conference, Montreal 1992, R. von Ballmoos, J.B. Higgins and M.M.J. Treacy eds,
Butterworth-Heinemann, (1993) 425.
[21] J.B. Higgins, R.B. LaPierre, J.L. Schlenker, A.C. Rohrman, J.D. Wood, G.T. Kerr and
W.J. Rohrbaugh, Zeolites, 8 (1988) 446.
[22] T.S. Ercit and J. Van Velthuizen, Canad. Mineral., 32 (1994) 855.
[23] R.C. Rouse, D.R. Peacor and S. Merlino, Amer. Mineral., 74 (1989) 1195.
[24] R.C. Rouse and D.R. Peacor, Amer. Mineral., 79 (1994) 175.
[25] H. Effenberger, G. Giester, W. Krause and H.J. Bernhardt, Amer. Mineral., 83 (1998)
607.
This Page Intentionally Left Blank
 Studies in Surface Science and Catalysis 135
A. Galameau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 93

Use of 1H NMR imaging to study the diffusion and co-diffusion of gaseous

hydrocarbons in H ~ M - 5 catalysts"

P. N'Gokoli-Kekele, M.-A. Springuel-Huet**, J.-L. Bonardet, J.-M. Dereppe, J. Fraissard

aLaboratoire S.I.E.N.-Chimie des Surfaces, ESA-CNRS 7069, Universit6 P. et M. Curie, 4 place

Jussieu, 75252 PARIS Cedex 05, France
bLaboratoire de Chimie-Physique et Cristallographie, Universit6 Catholique de Louvain-la-
Neuve, 1348 Louvain-la-Neuve, Belgium

I H N1V[R imaging has been used to study the diffusion of pure hydrocarbons (benzene, n-
hexane,) during their adsorption in or desorption from a fixed bed of zeolite crystallites. This
technique is used to visualize the progression of the diffusing molecules in the zeolite bed and to
determine their intracrystallite diffusion coefficients. In the case of competitive adsorption, it
gives the time dependence of the distribution of the two coadsorbed gases.

I. INTRODUCTION

NMR imaging (MR/) techniques were developed in the 70s mainly in the medical and
biological fields, using essentially the ~H nucleus but also 3He, 19F ,31p, and more recently
hyperpolarized 129Xenuclei, etc.
The fact that this technique is non-invasive and non-radiative, coupled with the development
of more and more powerful equipment and increasingly sophisticated numerical treatment of
images, has tended to generalize magnetic resonance imaging in the medical field. However,
medicine is not the only field of application of MR/, and the 90s saw considerable progress in
this technique for the study of porous media. MR/has been successfully used to study solvent
penetration and the dynamics of water in polymers [1,2], the structure and dynamics of polymer
gels [3], the segregation of grains in blends [4], the permeation resistance of cement [5], pore size
distribution mapping [6] as well as the drying kinetics of gels [7]. It can be also used in
microporous systems to investigate the diffusion and molecular mobility of water in 4A zeolites
[8] or hydrocarbon diffusion in deactivated Y zeolites [9].
We present here an application of this technique to the study of the diffusion of pure or mixed
hydrocarbons (benzene, n-hexane) in a fixed bed of HZSM-5 zeolite during their adsorption at
room temperature. In particular, we show for the first time that it is possible to visualize the

*The oral presentation in the form of a keynotespeech will also mentionthe studyof diffusion by xenon NMR
l~ublishedin this Proceedings
to whom correspondenceshouldbe adressed. E-mail: mas@ccr.iussicu.~
94

distribution of several gases adsorbed competitively, even if certain results are still essentially
qualitative.

2 PRINCIPLE OF THE TECHNIQUE

Figure 1 illustrates the principle of the technique. Magnetically equivalent spins in a

homogeneous magnetic field B0 (Figure l-a) will give a single signal at a resonance frequency
COo,the intensity of which depends only on their number and is independent of their distribution
within the sample. However, if a field gradient, g, is superimposed on B0 in the z direction
(Figure l-b), the effective field applied to the spins is of the form Bz = B0 + g z; the resonance
frequency and the signal intensity depend then on the position and the density, respectively, of
the spins at each point z of the sample. More generally, the application of pulsed field gradients
during the NMR pulse sequence used for the detection of the resonance signal leads to
concentration profiles of resonating spins in the direction(s) of the gradient(s). It is therefore
possible to obtain images in one, two or three dimensions. It should be noted that the signal
detected depends on the spin density p at each point of the sample but also, depending on the
pulse sequence used, on relaxation. For example, in our studies we have used two sequences.
In the sequence shown in Figure 2-a, the field
(a) 13o (b) 13o + gz gradient is applied during the n/2 pulse and
throughout the signal acquisition time, which
makes it possible to avoid the problem of spin
relaxation and to obtain the real spin
--+------4 ......... ~-P Z --~-- t .... ~ Z concentration profile. In spin echo detection the
Zl 7,2 Z3 Zl Z2 Z3
i i
intensity of the signal depends on relaxation.
Acq uisition Acq uisition Figure 2-b details, in that case, the periods
during which the gradient is applied depending
on the pulses used. This sequence can be useful
when there is a distribution of the spin
relaxation times T2 in the sample, as we have
too t~l o~ tt~3 shown in a study of Y zeolite deactivation
during catalytic cracking [9]
Fig. 1. Prizlciple of 1D NMR Imaging

I. EXPERIMENTAL SECTION

HZSM-5 zeolite consisting of crystallites, assumed to be spherical, of average radius R = 20

ktrn, was used in the form of a powder or compressed (at 103 bar) into cylindrical pellets 7 mm in
diameter and between 5 and 15 mm long, either pure or with a binder (amorphous silica-alumina,
SBET ~ 700 m 2 g-l, mean pore diameter 5 nm). Samples placed in the cell (Figure 3) were held
under vacuum (10 -5 mbar) at 673 K overnight before the adsorption of gaseous hydrocarbon(s) at
constant pressure at 293 K.
 95

Fig. 2. Schematic representation of the 1D Imaging NMR sequence: a)Direct acquisition;

b) Spin echo acquisition.

At time t - 0 the sample is put into contact with

the supply of liquid hydrocarbon (n-hexane or
benzene) in equilibrium with the gas and is
then placed quickly in the magnet. The liquid
phase is either pure or consists of a mixture
such that the two partial pressures of the gases
are equal to 60 mbar (assuming that the
mixture obeys Raoult's law). To distinguish the
hydrocarbons when they are mixed, one is
perhydro and the other perdeutero.
The proton 1D NMR images, which represent
the concentration profiles of the hydrocarbons
along the NMR tube axis are recorded as a
function of time with a MSL 300 Bruker
spectrometer. They are obtained by applying a
magnetic field gradient (Gz ~ 4 T m l) along
the direction of the NMR tube axis during
which a ~/2 r.f. pulse (RF) is applied and signal
acquisition (AQ) is performed (Figure l-a).
The length of the sample is small enough (5-15
mm) to permit the application of the excitation
pulse during the magnetic gradient.

Fig. 3. Schematic representation of the cell

containing the sample.
96

3. RESULTS AND DISCUSSION

3.1 Diffusion of pure gases

The diffusion equations are given by the hydrocarbon mass balance in macropores (eq. 1) and
in micropores (eq. 2) [ 10, 11]"

t~c c92c 3(1 ~Dintra( tgq]

I~inter'~-t -- Dintereinter ~0z2- -13inter s R ~ r=R (1)

cOq ( t 9 2 q , 2 cOq/
cgt = Dint r~ ~ T r 2 "- 7--~r )
(2)

where c and q are the hydrocarbon concentrations in macropores and micropores, respectively; z
(linear) and r (radial) coordinates in the bed (from the bottom) and in the crystallite (from the
centre); Dinter and Din~ the inter and intracrystallite diffusion coefficients and einter the
macroporosity of the sample.
These experiments were conducted at pressures where the intercrystaUite diffusion is very
rapid with respect to the intracrystallite diffusion. One can verify these conditions from the
rectangular concentration profile of the images. In this case only equation 2 is used, with the
following boundary conditions:

q(r, t=0) = 0; q(r=R, t) = qoo[1 - exp(-kt)]; aq(r = 0, t) = 0

tgr

where k is the transfer constant of molecules to the external surface of the crystallites, and qoo the
hydrocarbon concentration in each crystallite at equilibrium adsorption; then we can use the
solution of the diffusion equation (3), obtained by Cranck [ 12],

Mt _ 1- ~ e x p ( - k t )
[1- cot + )-',
exp (3)
Moo kR 2 D intra ~ D intra X2Dintra n = I n 2 (n 2/i;2 - kR 2 / Dintra)

where Mt is the total amount of adsorbed gas at time t (given by the integral of the NMR image
signal) and Moo the corresponding value at equilibrium state.
It should be pointed out first of all that the hydrocarbon concentration in the gas phase and in
the macropores is always negligible compared to that in the micropores (even right at the
beginning of adsorption). Consequently, the signal observed is due essentially to adsorption in
the micropores.
 97

3.1. L Benzene
At the very beginning of adsorption, (0 < t < 0.1 h) the 1D images of benzene adsorbing in the
powder HZSM-5 bed show a strong concentration gradient decreasing towards the bottom of the
sample (Figure 4a). When t > 0.2 h rectangular profiles are obtained for the loose as well as for
the compressed powder (Figure 4b) proving that after this time, under these experimental
conditions (high pressure of the gas phase) the benzene concentration is the same in any part of
the bed and that the diffusion of hydrocarbon is then controlled by the micropores, as discussed
by Heink et al. [13]. This allows the determination of Dm~. The results appear to contradict those
obtained by NMR of the xenon probe, which demonstrate the influence of intercrystallite
diffusion, but in this latter case, the relative benzene pressure is lower a part of the zeolite free
volume is already occupied by xenon.. Since compressing the powder increases the density of the
sample, the NMR signal is better defined for the compressed sample. The signal intensity
increases with the adsorption time. The total amount, M(t), of benzene adsorbed in the sample is
directly proportional to the integral of the NMR profiles. The experimental kinetic curves of M(t)
= fit) are simulated using equation 3. The simulation gives a Dmt~ value of about 1x 10-14 m 2 s"l
whatever the form, powder or pellet, of the sample. This value agrees well with that obtained by
129Xe NMR [14].

a) b)
Time (h)

~ 16.00
............. 9.00
...... 4.25
Time (h) ............ 2.25
.......... 1.67
15.3 ........... 1.42
2.4 ",--------- 1.17
~~ 0.4
0.2
-',-------- 0.83
/.- . . . . \_ 0.58
0.25
9 i. . . . '7. 9 9
z=e z=O z=e z=0
r--

gas flow gas flow

Fig. 4. 1D-NMR profiles of adsorbed benzene: a) on powder ; b) on pellet

When the sample is the powder zeolite mixed with silica-alumina (60% weight of zeolite,
length 25 mm), the benzene concentration profiles (Figure 5-a) present an adsorption front which
lasts more than 30 min. On one hand, the intercrystallite diffusion rate is decreased by the
presence of the mesoporous silica-alumina, on the other hand benzene also adsorbs on the silica-
alumina. In the case of a compressed mixed sample (length 12 mm) the profiles are rectangular as
98

of the first spectrum (Figure 5-b). The difference between the two cases is mainly due to the
decrease in the macroporosity and the length of the sample. These results show that mass
transport in industrial catalysts depends greatly on the binder, the dimensions and the
compression of the sample.
a) ~ Time (h) b) ~ Time (h)
t" A .,~___~
_ 1/'_" --'--'~-~k 12.00
- - ~ / ~ \ ~ - - s.oo
----J/ X~--- 5.40 11~
=:=~// \~ 4.00
060

;!;;
. . . . .

-J/~,,_--~-~~-- 0.30
0.25
-~//-~ ~~,~- 0.20 -----~/~\~, 0.25
_J/ ~ ~-- o.15
~ 0.08
z=~ z=0 z=e z=0
gas flow gas flow

Fig. 5.1D-NMR profiles in a mixture (zeolite/silica-alumina binder) during benzene adsorption:

a) powder ; b) pellet
3.1.2. n-Hexane
In the case of n-hexane adsorption on a powder
sample, the concentration profiles (Figure 6)
become perfectly rectangular after only t = 0.03
h. The value obtained for Dm~ (~10 -13 m 2 s -l) is
of the same order of magnitude as that reported
Time (h) in the literature using other techniques (zero
length column, frequency response, etc.) [ 13].
17.80
----37 3.2. Diffusion of gas mixtures
__--- l:~l
__. 0.11
i 0.04
Different types of experiments were performed
z=~ z=O with n-hexane and benzene. Here we report the
gas flow results concerning" i) their competitive
Fig. 6.1D-NMR profiles of n-hexane adsorbed adsorption, ii) variation of the distribution of a
pre-adsorbed hydrocarbon during the
in HZSM5 zeolite in powder form. adsorption of a second one.
 99

3.2.L Competitive adsorption.

When the adsorption of n-hexane proceeds from a gas phase mixture of n-hexane C6H14and
benzene C6D6 both at the same partial pressure, 60 mbar, the intensity of the profiles first
decreases from the top to the bottom of the bed (Figure 7-a). Such a profile, which indicates a
strong hexane concentration gradient in the sample, persists up to a time of 0.13 h, whereas the
adsorption of pure hexane leads very rapidly to rectangular profiles (Figure 6). Several reasons
can be proposed to explain this evolution: intercrystallite diffusion slowed, surface barrier lower
for n-hexane than for benzene; etc. At intermediate time, there is a slight excess of n-hexane in
the bottom of the bed before a homogeneous distribution all over the bed is reached at
equilibrium. Whatever the reason, n-hexane adsorbs in the first layers before its pressure becomes
equal throughout the bed. The benzene molecules, whose intracrystallite diffusion is much slower
than that of n-hexane, progress along the bed and adsorb then on the subsequent layers whose
crystallites are free of any adsorbate. As time increases, benzene also adsorbs on the first layers,
displacing n-hexane towards the bottom where n-hexane displaces in turn the benzene molecules
to finally obtain a distribution governed by thermodynamics. This scenario is confirmed by the
evolution of the benzene concentration along the bed, recorded during an identical experiment in
which benzene C6H6 and n-hexane C6D14 were used (Figure 7-b). These profiles clearly show that
benzene first adsorbs preferentially in the bottom layers before displacing the n-hexane adsorbed
in the top layers and finally the equilibrium is reached over the entire sample.

a)
Time (h) ne (h)

~ 8.70
5.88
4.58
~ 5.08
4.33
2.53
0.83
~ _ ~ 1.02
0.47 0.57
0.22 0.32
0.13 0.25
~.---__--- 0.12 0.08
0.07 0.02
Z=s z=O z= s z=O
Ip
gas flow gas flow

Fig. 7. 1D-NMR profiles ofn-hexane a) and benzene b) during their competitive adsorption in
HZSM-5 zeolite.
100

The intermediate states of the systems are the result of competing kinetic and thermodynamic
effects, the diffusion of n-hexane being faster than that of benzene while the latter is more
strongly adsorbed inside the crystallite.

3.2.2. Distribution of pre-adsorbate during the adsorption of another gas.

Figure 8-a shows the evolution of the distribution of n-hexane C6Hn4 pre-adsorbed at 2 mbar
during the adsorption of benzene C6D6 at its saturation vapour pressure. At time t = 0, the
concentration profile of pre-adsorbed n-hexane is rectangular. Immediately upon contact with
benzene, hexane is seen to be desorbed but preferentially from the upper layers, as is shown in
Figure 8-b. However, a practically rectangular concentration profile is obtained rapidly, in about
0.2 h. It should be noted that the amount of hexane desorbed between the beginning of the
experiment and the attainment of a new equilibrium is about 40%.
Figure 9-a corresponds to the case of benzene C6I-I6 being pre-adsorbed at equilibrium at 6.4
mbar and n-hexane C6Dl4 adsorbing at its saturation pressure.

a) b)

140
~" 120
me (h) ~ 100
80
0 ~ 60

3.90 20
9.00 0 I i
!
9 [
9 0.17 0.3 0.47 0.72
z =~ z=0 z/~
gas flow
Fig. 8. a) 1D-NMR profiles of pre-adsorbed C6H14 during C6D6 adsorption, b) Signal intensity
versus time for different values of z/g in the bed of the catalyst: II (t - 0 h), [2 (t = 0.02 h),
x (t =0.13 h), A(t = 0 . 3 0 h ) , o (t = 1.16h), r (t= 3.90 h ) , * (t= 9.00 h)
Time increases from the top to the bottom in figure 8a.

We initially observe a rectangular profile corresponding to a uniform distribution of benzene. The

total signal area decreases slowly with time. The decrease of the benzene concentration between
the beginning and the end of the experiment is about 25 %. But its distribution in the sample is
particularly inhomogeneous, as is shown in Figure 9-b. The intensity decreases at the top and
increases markedly at the bottom of the bed, showing that the n-hexane adsorbs first in the upper
 101

layers, "pushing" the benzene towards the bottom of the tube. The local partial pressure of
benzene and, in parallel, its concentration in the bottom of the bed increase.

b~
i o e (h)

-----~~A~,,, "--~---- 0.02 60 T

-~-~~A~"-- gl 50
,-':,.
- 0.09
~4o

,Vo 20
.=
-~--'-~ ~ ~ ' - ~
- -'-~~~~'~~----~
"~----- 1.51
4.77
tot
0 I I I ~
- .-7 i. . .! .~"7 - - - - 1 6 0 6 0.16 0.33 0.5 0.8 0.9

Z=s Z=0 z/~

Fig. 9. a) 1D-NMR profiles of pre-adsorbed C6H6 during C6DI4 adsorption, b) Signal intensity
versus time for different values of z/s in the bed of the catalyst. A (t = 0 h), O (t = 0.02 h),
II (t = 0. 09 h), [] (t= 0.17 h), O ( t = 0 . 3 1 h ) , x ( t = l . 0 3 h ) , A(t=l.51h), r
9 (t = 16.06 h)
Time increases from the top to the bottom in figure 9a.

As the "wave" of n-hexane reaches the bottom, this latter gas adsorbs on the lower layers; the
two partial pressures become uniform along the sample, and the benzene molecules can adsorb
again in the upper layers until the thermodynamic equilibrium is obtained. The distribution of
adsorbed gases is first determined by kinetics and then the system is governed by
thermodynamics.
The difference in the extent of displacement of one gas by another in the two experiments
confirms, if this were necessary, the greater affinity of HZSM-5 zeolite for benzene.

4. CONCLUSION

The application of ~H 1D-MR/ for the study of hydrocarbon diffusion gives two types of
information. First, the variation with time of the surface area of the full signal (amount adsorbed
as a function of time) during adsorption makes it possible to determine transport coefficients by
simulation of the kinetic curves. For example, the intracrystallite diffusion coefficients of hexane
and benzene in HZSM-5 determined by this technique are 10"13 and 10"14 m 2 s"i, respectively, in
good agreement with data in the literature. Second, the shape of the instantaneous concentration
102

profiles reflects the variation of the local adsorbate concentration, and reveals a competition
between kinetic and thermodynamic effects.
In the case of competitive adsorption of several gases, this technique appears to be the only
one capable of visualizing the relative distribution of each of the gases in the adsorbate and its
variation with time.

REFERENCES

1. S. Blackband and P. Mansfield, J. Phys. C: Solid State Phys., 19 (1986) L49.

2. N. Tanaka, S. Matsukawa, H. Kurosu and I. Ando, Polymer, 39 (20) (1998) 4703.
3. I. Ando, H. Kurosu, S. Matsukawa, A. Yamasaki, A. Hotta and N. Tanaka, Wileys Polym.
Networks Group Rev., Ser. I (1998) 331. J. Wiley & Sons, Ltd. Publ.
4. P. Porion, N. Sommier and P. Evesque, Europhysics-Letters, 50 (3) (2000) 319.
5. G. Papavassiliou, M. Milia, M. Fardis, R. Rumme, E. Laganas, A. Sepe, R. Blinc, M.M.
Pintar J. Am. Ceram. Soc., 76 (1993) 2109.
6. J.H. Strange, J.B.W. Webber and S.D. Schmidt, Magnetic Res. Imaging, 7-8 (1996) 803.
7. I. Koptyug, V.B. Fenelonov, MY. Khitrina, R.Z. Sagdeev and V.N. Parmon, J. Phys. Chem.,
B, 102 (1998) 3090.
8. M.R. Halse, Magnetic Res. Imaging, 7-8 (1996) 745.
9. J.-L.Bonardet, T. Domeniconi, P. N'Gokoli-Kekele, M.-A. Springuel-Huet and J. Fraissard,
Langmuir, 15 (1999) 5836.
10. E. Ruckenstein, A.S. Vaidyanathan and G.R. Youngquist, Chem. Eng. Sci., 26 (1971) 147.
11 L.K. Lee, AIChE. J. 24 (1978) 531
12. J. Cranck, The Mathematics of Diffusion, Clarendon Press, U. K. Oxford, 1956.
13. W. Heink, J. K~ger and H. Pfeifer, Chem. Eng. Sci., 33 (1978) 1019.
14. P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L.Bonardet and J. Fraissard, Proceedings 13th
International Zeolite Conference, in press. Elsevier Publ. 2001.
Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 103

Zeolite-based nanocomposites: synthesis, characterization and catalytic

applications
B.V.Romanovsky

Chemistry Department, Moscow State University, Leninskiye Gory, Moscow, 117234,

Russia

The oxidative in-situ degradation of mono and polynuclear complexes of transition

metals within the Y zeolite supercages has been employed to produce an array of oxide
nanoclusters encapsulated in the intercrystalline voids of the matrix. The resulting
materials were characterized by using a number of experimental techniques. The
nanocomposites display extraordinary high activities in oxidation of CO and MeOH.

1. INTRODUCTION

Nanocomposites in which one of constituent phases has at least one dimension smaller
than 100 nm have recently attracted much attention as perspective functional materials of
broad spectrum of applications. The growing interest to these novel systems is quite
understandable since the bulk behavior of materials can be dramatically altered by
controlling their cluster nanostructures, and this control can lead to greatly improved
performance. Besides, the characteristics of nanomaterials could be purposely tuned not
only by the variation of the chemical composition of the clusters but also by variation of
their size and size distribution.
One of the major difficulties in creating the nanosystems lies in the great excess of the
surface free energy and as a result in their thermodynamic instability that causes an
irreversible aggregation of nanoclusters into larger particles under kinetically favorable
conditions. This urged the development of such a research branch as the creation of
composite materials in which the nanosized particles are encapsulated in the internal voids
of the microporous solids where the cluster size and their interaction to form large
aggregates are strongly limited by the steric hindrance
Zeolites and zeolite-like materials with their well-organized and regular systems of pores
and cavities represent almost ideal matrices to host nanosized particles. The high thermal
and chemical stability of zeolite-like matrices would afford the nanocomposites which
could operate in a broad range of temperatures and in various media.
The zeolite cavities can be considered as peculiar reaction nanovessels where the
chemical processes carried out inside them and their products are affected by the confines
in which they are being performed. This main principle was proven in mid-70's when the
first synthesis of neutral phthalocyanine complexes encapsulated in Y zeolites via
intracrystalline assembling was performed at Moscow State University [1,2]. Once formed
within the bottle-shaped supercages of Y zeolite, the resulting electroneutral complexes
cannon leave them because of spacial restrictions. Later, this new type of inclusion
compounds was termed as "ship-in-a-bottle" systems [3].
104

The general strategy for preparing the zeolite-included composites is also based on the
ability of restrictive void spaces of the zeolite to control growth of size-confined phases.
The in-situ thermal or redox treatments of inorganic or organometallic precursors
preloaded into the matrix internal voids yield the metal or oxide particles hosted inside the
supercages. The major problems deal usually with the choice of appropriate precursors.
Apart from meeting the obvoius geometric criteria, the optimal precursor should also
display the substantial solubility in a selected solvent and be stable toward solvolysis or
have a substantial vapor pressure and evaporate without essential dissociation or
association. The in-situ transformation of the precursor molecules into oxide clusters
should be performed under the mildest possible conditions. Otherwise, the elevated
temperatures can cause the migration of primarily formed species to the outer surface of a
matrix and their aggregation.
The present paper reported below is a brief review of our recent advances in the
synthesis and investigation of the zeolite-incorporated oxides of some transition metals.

2. PREPARATION OF ZEOLITE-INCORPORATED METAL OXIDES

2.1 Preeursor loading

There exist two routes to load the zeolite matrix with metal-containing precursors. First
one is the ion exchange of Na for complex cations. In an alternative way, the zeolite is
loaded with neutral precursor molecules by utilizing the incipient wetness impregnation
technique. Of course, the size requirements for precursor species and the matrix openings
are evident to be the key factor in both cases. However, the impregnation technique has
some advantages over ion exchange. In fact, the methods for preparing various homo and
heterometallic, mono and polynuclear complexes or cluster compounds have been well
developed so that the most of requirements to size, shape and solubility of a precursor can
be satisfied. This factor becomes crucial when bimetallic oxide clusters should be prepared.
Loading the zeolite matrix with discrete precursor molecules containing different metals
affords incorporated products with much more predictable and controllable properties than
those made via the ion exchange procedure In this respect, the variations of ionic forms of
precursors are substantially restricted not to mention some specific limitations imposed on
the ion exchange technique.
In the present work, we applied a variety of both monometallic and bimetallic complexes
to load the zeolite matrix with a precursor. They are listed in Table 1.

Table 1
Transition metal complexes used as precursors
Monometallic complexes Bimetallic complexes
(l.t4-O)L4Cu4C16*, CuPc, NiPc, CoPc,
Fe3(CO)12, Fe(acac)3, Ru(acac)3, Zn3(acac)6, Co2Ni2(acac)4(MeO)4(AcO)2,
Ni3(acac)6, Ag2(FAcO)2**, Cu2(FAcO)4, CuNi2(OH)(EtCOO)3(OCH(Me)N(Me)2)2,
NiE(FAcO)4, [RuE(AC)4]C1, Fe4(CO)I3(Et4N)2,
FesC(CO)I4(Et4N)2, Fe6C(CO)I6(Et4N)2, ReMoOffMeO)7
[Fe30(AcO)6(HEO)a]AcO,
[RuaO(AcO)6(H20)3]C104,
 105

*L = N,N-diethylnicotinamide, **FAcO = CFH2COO- - monofluoracetate anion

Of particular interest are two polynuclear precursors: (kt4-O)L4Cu4C16 and
ReMoO2(OMe)7 complexes. The first adamantan-like complex has been shown by Davis et
al. [4,5] to loose its diethylnicotinamide ligands on contacting the complex in methylene
chloride with dry NaY so that only N-free bare (kt4-O)Cu4C16 units enter the zeolite pores.
We obtained the similar result with ReMo oxomethoxide complex: after loading it into
NaY zeolite since no traces of organic ligands as determined by elemental analysis were
found in the sample. So that in this particular case, simple loading the NaY zeolite with
these ReMo oxomethoxide complexes results in the ReMo oxide species molecularly
dispersed in the matrix bulk. No additional treatment of the metal-loaded zeolite are
required to obtain nanomaterial. On the other hand, this very important finding means that
the polynuclear core species residing within the zeolite supercages are stabilized by the
host framework that plays the role of a peculiar macroligand.
Special attention should be paid to the selection of an appropriate solvent. Apart from an
obvious requirement of good solubility, the complex precursor used must not dissociate in
a selected solvent, e.g., in water. Otherwise, the impregnation may give not only the neutral
precursor molecules loaded but also the ion-exchanged species unless the special
precautions are taken. As a result, after removing solvent the zeolite cages will contain
three types of particles, i.e., precursor molecules, precursor cations and some amount of Na
compound. In this case, the outcome of subsequent thermal treatment of the material
becomes rather uncontrollable. We faced this situation using the aqueous solution of
copper (II) monofluoracetate (see Table 1) to impregnate NaY zeolite. In fact, the starting
solid Cu(II) monofluoracetate consists of dimer Cu2(CFH2COO)2 molecules. However, on
dissolving in water it gives the monomer species which in turn dissociate into Cu(II) and
fluoracetate ions. After impregnation, the resulting sample exhibited some amounts of
isolated Cu(II) ions as was evidenced by the characteristic signal of these paramagnetic
centers in ESR spectra. This signal remains unchanged even after the treatment of the
sample at 400~ in air while the DTA-TG data indicate complete oxidation of the
precursor organic part by 250~ [6].

2.2 Transformation of zeolite-loaded precursors into oxide species

With the exception of two very specific cases mentioned above, subsequent in-situ
oxidation of loaded precursors is required to convert them into oxide species. It should be
kept in mind that by varying the nature of precursor ligands lower oxidation temperatures
and therefore better dispersion and lover degree of aggregation can be obtained. As a rule,
this procedure can be performed by simple calcination of the material in dry air or oxygen
flow at 200-450~ depending on the precursor nature. Oxidation of the loaded precursor to
corresponding oxide phase is easily monitored both qualitatively and quantitatively by the
DTA-TG technique. In some cases, the GLC analysis of effluent gases can be utilized to
control the oxidation of precursors.
Another important factor of the oxidation step which must be well controlled during this
procedure are eventual losses of the metal precursor compound due to its high volatility. If
the rate of oxidation is inadequate, the loaded precursor can sublimate before its oxidation
occurs. For example, we found that up to 50% of Zn acetylacetonate as determined by
106

elemental analysis could be lost when the sample with this loaded precursor is heated in a
gas flow at about 400~ for 4 hr.

3. C H A R A C T E R I Z A T I O N OF Z E O L I T E - I N C O R P O R A T E D METAL OXIDES
Various experimental techniques were employed to characterize the prepared samples.
Often, several methods are required to be applied simultaneously to control the consecutive
stages of preparation protocol.
N__2-BET measurements. These measurements were performed with selected oxidized
samples in order to ascertain whether blocking of matrix channels by forming oxide phase
takes place. This can be judged on comparing the surface area of starting NaY zeolite with
that of the sample after its high-temperature treatment. In fact, a few samples showed about
two-fold decrease in surface area which indicates the formation of large particles of oxide
phase out of the matrix bulk.
X-ray diffraction. Appearance of diffraction peaks consistent with an individual non-
zeolitic phase shows unambiguously the formation of oxide particles much more than
nanosized [7]. Though the lack of such peaks does not mean the contrary.
IR and UV-VIS spectroscopies. The use of IR method enables one to control the loading
of precursors and their further transformation into the oxide moiety. At the metal loading as
low as a few wt % (metal basis), the IR bands characteristic of metal oxides are too weak to
judge on their formation. As to electron absorption spectra, this technique was successfully
applied in [8] not only to identify the metal sulfide and solenoid nanoclusters encapsulated
in zeolites but also to estimate their mean sizes basing on the blue-shift of absorption-edge
in respect to bulk material. Unfortunately, this technique in studying the supported metal
oxides turned out to be ineffective mainly because of too broad bands obtained for the
samples subjected these investigation.
Temperature-programmed reduction by H2. The H2-TPR experiments provide very
important information concerning the distribution of metal oxide moiety between the bulk
of zeolite support and its external surface. This distinction can be made basing on the
positions of peaks in H2-TPR profiles obtained for a sample after the oxidation of loaded
precursors and for the corresponding free oxide taken as a standard. For example,
NiO/NaY sample gives two H2-TPR peaks centered at 410 and 575~ while bulk NiO
exhibits only one reduction maximum at 390~ This result suggests that the high-
temperature peak on the first H2-TPR profile could be ascribed to the reduction of intemal
NiO species while the low-temperature maximum is very probable to arise from outer
nickel oxide. In addition, the measurements of hydrogen uptake in H2-TPR experiments
could be used to reveal the valent state of a transition metal present as oxide phase. In the
case of Re system, the nominal content of metal was 3.7 wt % with corresponds to 0.74
mmole O/g as Re207 or 0.63 mmole O/g as ReO3. whereas the total amount of H2-TPR
consumed between 100 and 1000~ was estimated as 0.72 mmole/g.
Measurements of magnetic susceptibility. The zeolite-included oxide clusters obtained
from their metallocomplex precursors may in their turn play the role precursor in preparing
the materials including nanoscale metal particles. In a few cases of ferromagnetic metals,
the measurements of magnetic susceptibility of reduced samples make it possible to
establish the distribution of reduced metal between the surface and the bulk of support.
Even though the precursor species are at the very beginning evenly distributed, the high-
temperature reduction results inevitably in the formation of large metal particles on the
 107

external surface of support. Experimental data on the measurements of magnetic

susceptibility for a set of Ni containing sample are given in Table 2. On considering these
data, it should to be taken into account that the experiments were performed in an
apparatus allowing to determine the metal particles sized more than 2 nm, smaller particles
are magnetically silent.
Given that two-nanometer sized metal particles cannot reside within the zeolite
supercages, we measured only the magnetic moiety of reduced nickel on the outer surface
of zeolite matrix. It is seen from these results that the share of metal nickel present as small
particles less than 2 nm in size decreases dramatically on diminishing the amount of metal
loaded. Of course, these estimates correspond also the concentrations of oxide precursors
initially hosted in the supercages but only their bottom limit, and the real content of oxide
component present as the cage-hosted nanoclusters may be substantially higher.

Table 2.
Metal contents determined by elemental analysis and by magnetic measurements for
nickel-containing samples reduced by H2 at 400~
Total nickel, wt % (EA) External nickel, wt % (MM) Internal nickel, %
1.89 0.60 68

1.68 0.91 45

0.81 0.69 15

ESR method. This technique can reveal the changes in coordination and valent state of
the paramagnetic ions which may occur during the different treatments of the zeolite with
loaded precursor. Also, ESR spectroscopy make it possible to discover any interaction
between the paramagnetic centers of different nature when they present simultaneously in a
catalyst [9].
Elemental analysis and XPS technique. Joint use of these methods give the important
information about the distribution of in-situ formed species between the bulk and the outer
surface of zeolite matrix [ 10

4. CATALYSIS BY Z E O L I T E - I N C O R P O R A T E D METAL OXIDES

Two model reactions were applied to characterize the catalytic behavior of the zeolite-
incorporated metal oxides: carbon monoxide oxidation and methanol conversion. As is
clear from what follows, the catalytic activity turned out to be the most sensitive properties
toward the minor changes in a catalysts "biography". Therefore, some disagreements may
rise on comparing the activity of supposedly similar samples with the same composition
but of different preparation history.

4.1 Carbon monoxide oxidation.

This reaction was studied using the zeolite-incorporated CuO catalysts; the samples were
prepared employing tetranuclear (I.t4-O)L4Cu4C16 complex as a precursor [7,11]. For
comparison, the activity of bulk CuO with surface area of 8.6 m2/g was also evaluated. The
108

process was carried out in a gradientless reactor with the stoichiometric CO+O2 mixture at
450~ and atmospheric pressure. The results are summarized in Table 3.

Table 3.
Oxidation of CO over the zeolite-incorporated and bulk CuO
Cu content, wt % 2.72 7.52 80
Reaction rate, mole/s.g 7.5x 10"2 18.4• 10.2 1.94x 10-2
TOF, molecule/s per atom 1.78x 102 1.55• 102 -~ 3• 10 2**
* Pure CuO, ** Evaluated basing on the surface concentration of c.a. 1015 atoms Cu/cm 2
As seen, the reaction rates calculated per unit mass of catalyst for the zeolite-based
samples are substantially higher than that for the bulk copper oxide regardless many times
smaller content of the active phase. Any doubt, the extraordinary high dispersion of CuO
explains this difference. In contrast, the TOF values seem to be of the same order of
magnitude if one takes into account very approximate evaluation for the surface
concentration of Cu atoms. On the other hand, some diminishing in the TOF values on
increasing the metal loading suggests that the oxide particles agglomerate probably in
neighboring supercages which effect cannot be revealed by any other way.
These conclusions are fully supported by the results in which the oxygen storage
capacities (OSC) was measured for the samples. The values of OSC were determined by
titration of the samples at 450~ with consequent pulses of CO which were introduced into
the dry nitrogen flow passing through the sample bed in a quartz reactor till the formation
of CO2 ceases. The results obtained in this series of determinations are given in Table 4.

Table 4.
Oxygen storage capacities of zeolite-incorporated CuO
Cu content, wt % 2.72 7.52

OSC, mmol O/g 0.40 1.04

Atomic Cu/O ratio 1.05 1.14

The ratio of copper and reactive oxygen contents which were determined by two
independent ways is very close to CuO stoichiometry. This indicates near molecular
dispersion of copper oxide moiety incorporated with in the zeolite matrix.

4.2. Methanol oxidation

The reaction was carried out in a fixed-bed quartz reactor at 90-400~ The reaction
products were analyzed by a GLC technique. Carbon dioxide and formaldehyde were found
to be the only products of methanol oxidation; in no case the formation of CO was
detected. In parallel to oxidation, the dehydration of methyl alcohol also occurs, dimethyl
ether (DME) being a product.
Fig.1 shows the results obtained with the Fe containing sample prepared using
hexacarbonyl triiron (see Table 1) as a precursor. Similarly to the case of CO oxidation,
TOF values for methanol oxidation are noticeably dependent of the total metal loading.
This also could be due to the intracrystalline agglomeration of iron oxide nanoparticles that
 109

decreases the efficiency of Fe active centers because of the changes of their mean
coordination to oxygen atoms. An alternative explanation for these findings would be
suggested such as influence of diffusion limitations inside the matrix micropores. In fact, a
non-linear dependence of the measured reaction rates on active component concentrations
is to be expected, provided the diffusion limitations would play a significant role (see $2
histogram series in Fig.l). However, this effect seems to be little possible since the
difference in the measured values of reaction rates for CO and MeOH oxidation amounts to
two order of magnitude which makes the Thiele modulus to vary ten times. This latter
excludes the diffusion effects from consideration.
On the other hand, the results of catalytic measurements could discover the effect of
steric non-compatibility of precursor molecules and matrix pore openings that makes it
impossible to load the matrix with a precursor compound. In Table 5, the total conversions
of MeOH are compared for a set of iron-containing samples with about 1 wt % Fe prepared
by utilizing the iron carbonyl complexes of various nuclearity - from 3 to 6 (see Table 1).
In contrast to four-nuclear Cu and ReMo complexes that can readily loose their labile
ligands before entering the zeolite channels as mentioned in the previous section,
polynuclear Fe cluster compounds are too rigid and cannot penetrate the matrix pores
unless the molecular size allows this.

Table 5.
Total methanol conversion over zeolite-incorporated Fe oxide
Sample NaY Fe3/NaY Fea/NaY Fes/NaY Fe6/NaY

Methanol conversion, % 11.7 54.1 2.6 2.2 2.9

NaY starting material, Fe3, Fe4, Fe5 and Fe6 - samples obtained from tri, tetra, penta
-

and hexanuclear iron carbonyl complexes, respectively; reaction temperature - 400~

As seen from these data, the loading of parent NaY zeolite with iron oxide via trinuclear
Fe carbonyl as a precursor increases greatly the total rate of methanol conversion because
of the appearance of oxidative active centers. In contrast, the use of carbonyl complexes of
four and more nuclearity resulted in a dramatic drop of MeOH conversion even in
comparison to the starting material. It should be noted that all Fe-containing samples have
the same amount of iron oxide (about 1 wt %, metal basis), and such an effect can be
explained only on assuming the formation of multilayer oxide deposits that cover the outer
zeolite surface including its pore mouths. This assumption was verified by measuring the
surface area for this set of samples that decreases from about 700 m2/g for NaY down to a
few tens m2/g for three last samples in Table 5.
It should be added that these findings seem to be significant in one more respect. They
allow to make some conclusions, though indirect, concerning the behavior of complex
molecules other than iron ones as precursors upon reaction with microporous
matrices like NaY material. In fact, the large complexes such as
CuNi2(OH)(EtCOO)3(OCH(Me)N(Me)2)2 and C02Ni2(acac)a(MeO)n(AcO)2 are evident to
be impossible to penetrate the Y zeolite channels of 0.7 nm in diameter. Nevertheless, the
impregnation of NaY zeolite with acetonitrile solutions of these complexes yielded about
1% loading (metal basis) with a negligible decrease in the surface area. Even though there
were no analytical measurements for organic residues in the samples prepared by such a
110

route, these multiligand polynuclear complexes could be expected to behave in a very

similar way that analogous ReMoO2(OMe)7 and (kta-O)LaCu4C16 complexes do. As
depicted previously, on contacting with parent NaY material, namely they loose their
organic ligands stabilizing the polynuclear metal core and change them for an inorganic
environment on residing within the supercages. Of course, this conclusion can by no means
be generalized so that every particular case of a metallocomplex with polynuclear core as a
potential precursor to be loaded into a micropore matrix required the special investigation.
It would be of interest to compare the zeolite-based oxide catalysts prepared by loading
the parent material with polynuclear metallocomplex precursors with those obtained via
traditional impregnation with a metal salt. In Table 6, the experimental results on methanol
oxidation we obtained for a series of Co and Ni containing samples are summarized.
Although the samples (except for the first one) contains the same amounts of loaded metal
oxide, the efficiency of those obtained via polynuclear precursors differs dramatically from
that for the conventional zeolite-supported NiO. These data are well consistent with the
results found for CO oxidation that was carried out over the analogous set of catalysts.

Table 6.
Methanol conversion over the zeolite-incorporated Co and Ni oxides

Catalyst Co2Ni2/NaY Co4/NaY Ni4/NaY Ni/NaY

Metal, wt % 0.5 1 1 1
Temperature, ~ 250 250 250 350
Reaction time, min 82 122 163 80 120 142 84 131 242 60 120
Conversion,% 85 83 88 91 93 94 73 79 72 5 4
Selectivity b, %
carbon dioxide 99 98 99 98 99 97 98 99 97 3 4
dimethylester 1 2 tr. 2 1 3 2 1 3 97 96

Note: Co2Ni2/NaY, Co4/NaY and Ni4/NaY samples were obtained via four-nuclear
complexes (see Table 1), Ni/NaY sample was prepared by the impregnation of parent
NaY material with aqueous solution of Ni nitrate
Lastly, the comparison of activities determined for monometallic and bimetallic oxide
catalysts can provide an important information on whether two oxide components are
independent active entities or they can interact with each other. This was illustrated by
Fig.2 where the TOF values for monometallic Ru (S 1series) and Fe ($3 series) samples and
bimetallic RuFe ($2 series) samples are depicted. It should be noted that in the mixed RuFe
samples ruthenium and iron concentrations are close to their content in corresponding
monometallic analogs. As seen, the activity of Fe-containing samples is significantly
smaller than that of Ru-containing catalysts. From this result, the activities of mixed RuFe
samples would be expected to be similar to those for Ru catalyst set provided the additive
effect is operative. However, it is not the case, and the activity of ruthenium centers
becomes inhibited in the presence of iron species. Such non-additive effect could be due to
the chemical interaction of oxides which occurs within the nanosized internal voids of
zeolite matrix and is enhanced by severe spatial restrictions. Similar effects we have
observed [9] for Fe-containing Y zeolite. Upon loading this zeolite with Cu(II) acetate
 111

complex, the Fe(III) centers becomes fully ESR silent because of interaction of neighboring
paramagnetic atoms.
The examination of zeolites modified with transition metals as catalysts of methanol
conversion have revealed the close connection of redox and acid-base functions of these
catalytic systems. In fact, methyl alcohol can react by two pathways that are supposed to be
rather independent. The acid centers of zeolites are commonly believed to be responsible
for dehydration of methanol to dimethyl ether while the oxidative sites account for the
formation

Fig. 1. Activity in MeOH

oxidation of Y zeolite-
included iron(Ill) oxide:
1-0.18 wt% Fe; 2-0.39
wt% Fe; 3-0.76 wt%Fe.
S 1 - TOF values, a.u.
$2 - activity per unit
mass

Fig.2. Activity in MeOH

oxidation of Y zeolite-
included ruthenium (S 1),
rutheniun-iron ($2) and
iron ($3) oxides per unit
mass of metal as the
function of Ru (1-4),
RuFe (5,6) and Fe (7-9)
loading

of formaldehyde and carbon oxides. In this connection, we have investigated more closely
the simultaneous occurrence of both reactions using the zeolite-incorporated oxide
catalysts [12]. The catalysts was obtained by oxidative degradation of Cu, Ni and Co
phthalocyanine molecules (see Table 1) that were previously "ship-in-bottled" into NaY
zeolite. Methanol conversion was performed in air or in nitrogen flow. Below 250-280~
the yields of dimethyl ether in air were found to be noticeably higher than in nitrogen.
These somewhat unexpected results were explained by assuming the dual-site mechanism
112

of methanol dehydration. It was suggested that the transition state includes both basic and
acid sites that further gives DME. Besides, the basic center can react with MeOH molecule
yielding carbenoid-like surface intermediate. These intermediates are more or less stable in
an inert media and thereby break the well-organized structure of dual sites which make it
impossible to form the transition state of dehydration pathway. On the contrary, the
carbenoid species are readily oxidized in air and this restores the active sites accounted for
methanol dehydration.

4. CONCLUSIONS

Faujasite-type zeolites with the bottle-shaped supercages are the most suitable matrices
that provide good opportunities for preparation of the nanocomposite materials using mono
and polynuclear metal complexes with organic ligands as precursors. The spatially-
hindered in-situ oxidation of these precursors preloaded into the cages yields the highly
ordered systems of oxide nanoclusters. The migration of these clusters is strongly retarded
within the matrix micropores so that their aggregation to form large particles on the outer
surface is little probable. The highly dispersed oxides incorporated into the zeolite
intracrystalline voids exhibits good catalytic performance in carbon monoxide and
methanol oxidation.

ACKNOWLEDGEMENT

This work was financially supported by Grant 99-03-3298 and Grant 00-15-97346 from
the Russian Foundation for Basic Research.

REFERENCES

1. Romanovsky B.V., Zakharov V.Yu., Borisenkova S.A., USSR Patent, No.552752, 1975.
2. Zakharov V.Yu., Romanovsky B.V., Bull. Mosc. State Univ., Ser 2, 18 (1977) 142.
3. Herron N., Stucky G.D., Tolman C.A., Inorg. Chim. Acta, 100 (1985) 135.
4. Abdel-Fattah T.M., Davies G., In: Multifunctional Mesoporous Inorganic Solids
(C.A.C.Sequeira and M.J.Hudson, Eds.,), Kluwet Acad. Publ., 1993, p. 121.
5. Davies G., Giessen B.C., Shao L., Mater. Lett., 9 (1990) 231
6. Boltalin A.I., Knyazeva E.E., Zhilinskaya E.A., Aboukais A., Russian J. Phys. Chem.,
75 (2001) 231.
7. Abdel-Fattah T.M., Davies G., Romanovsky B.V., Shakhnovskaya O.L., Larin A.M.,
Jansen S.A., Palmieri M.J., Catal. Today, 89 (1996) 1121.
8. Tolkachev N.N., Stacheev A.Yu., Kustov L.M. Abstr. Internat. Boreskov Memorial
Conf., 2nd, "Catalysis on the Eve of XXI Century", Novosibirsk, 1997, p.256.
9. Boltalin A.I., Knyazeva E.E., Zhilinskaya E.A., Aboukais A., Bull Mosc. State Univ.,
Ser 2, Chem., 41 (2000) 293.
10.Romanovsky B.V., Gabrielov A.G., Mendeleev Commun., 1 (1991) 14.
11.Berdanova E.I., Larin A.M., Shakhnovskaya O.L., Romanovsky B.V., Bull. of Russian
Acad. Sci., Ser.2, Chem., (1997) 1761.
12.Kustov A.L., Moskovskaya I.F.,Romanovsky B.V., Zhilinskaya E.A., Aboukais A.,
Recent Reports at the lntern. Congr. on Catal., 12th, Granada, 2000.
Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 113

Application of Combinatorial Tools to the Discovery and

Commercialization of Microporous Solids: Facts and Fiction

Jennifer Holmgren, a David Bem, a Maureen Bricker, a Ralph Gillespie, a Gregory Lewis, a
Duncan Akporiaye, b Ivar Dahl, b Arne Karlsson, b Martin Plassen, b Rune Wendelbo b

a UOP LLC, 25 East Algonquin Rd., Des Plaines, Illinois, 60017, USA

b SINTEF, P.O. Box 124, Blindern, 0314 Oslo, Norway

During the past three years, combinatorial tools and methods have received increasing
amounts of attention as potentially enabling methodologies for the chemical industry. We
have developed a combinatorial multiautoclave, which can be used to explore hydrothermal
space efficiently and effectively. Our recent results illustrate the applicability of this
capability to both the discovery and scale-up of microporous solids.

1. INTRODUCTION

The chemical industry faces an extremely competitive business climate. In addition,

innovation in this industry has slowed as catalyst and process technology has matured. 1
Despite the maturity of the catalyst industry, there is a continuing and growing need for
improvements in catalyst performance, to increase the efficiency of industrial processes and
reduce their environmental impact. Such increases cannot be obtained through incremental
improvements using existing development methodologies. In order for the chemical industry
to maintain a competitive advantage, a breakthrough in catalyst R&D methodologies is
greatly needed.

The pharmaceutical industry faced similar circumstances in the 1980s as the high cost
of drug discovery became incompatible with downward pressure on drug prices. In that case,
combinatorial chemistry, with high throughput screening and integrated informatics, provided
a breakthrough methodology for the pharmaceutical industry to increase its innovation
ability.

We believe that the successful application of combinatorial methods to the chemical

industry could have similar benefits: 1) an increase in the rate of catalyst innovation and 2) a
decrease in commercialization cycle times. Because of this belief, UOP and SINTEF have
developed their End-to-End T M combinatorial catalyst discovery system. This system includes
the ability to perform all the critical catalyst processing operations combinatorially (Figure 1).
We have validated each of these steps using commercially relevant catalyst examples. In
addition, we have utilized the entire system to prepare and test catalysts for catalytic
applications.
114

Figure 1. Unit operations in our End-to-End SMcombinatorial catalyst

discovery system.

An essential element of extending combinatorial methods to catalysis is the ability to

synthesize libraries of inorganic materials. 2'3'4'5 Workers at SINTEF were the first to report
the successful development and implementation of a combinatorial hydrothermal synthesis
cell. This cell lies at the heart of our library preparation system. 2 Other workers have also
reported methods to synthesize libraries of materials from hydrothermal reaction. 3'4

The successful implementation of a miniaturized hydrothermal synthesis

multiautoclave requires dealing with a number of technical hurdles:

9 Demanding experimental conditions related to high pressure and high temperature

9 Chemically aggressive conditions such as high pH and HF
9 High sensitivity to preparative procedures
9 Complex heterogeneous systems including gel formation and phase separation
9 Labour intensive work-up procedures, and
9 Complex characterization

Our multiautoclave addresses the problems of parallel syntheses, parallel work-up and
rapid screening and offeres a new tool for efficiently charting a variety of chemistries. Using
this multiautoclave as its foundation, we have created an integrated, fully automated
hydrothermal synthesis system, which includes the following fully integrated capabilities:

9 Statistical experimental design with chemical constraints

9 Reagent transfer
9 Data logging of all relevant process conditions
9 Parallel work-up and isolation
9 Automated X-ray and SEM analysis
 115

We have successfully utilized our integrated system to synthesize and characterize

zeolites, A1POs, microporous oxides and other relevant inorganic oxides. We find that
although we are working with microliters of reagents, that the results in this multiautoclave
are scalable to the laboratory scale (125 ml). In terms of applicability, we have utilized this
system for the discovery, optimization, and the scale-up of new materials. We will present
four examples throughout this paper to demonstrate this capability.

2. EXPERIMENTAL

To illustrate the experimental procedures used, details regarding the experimental

work for a Zn-Cu-V-O example are presented here. The compositional variables, reagents,
and digestion parameters used for the Zn-Cu-V-O combinatorial experiment are given in
Table 1. The aqueous reagents were delivered to a multiautoclave via a robotic pipetter with
concurrent agitation of the reaction mixtures. After sufficient homogenization, the
multiautoclaves were sealed and digested at the appropriate conditions. After the digestion,
the samples were washed, pulverized, isolated and mounted for powder X-ray analysis. The
recovery process was completed using parallel methods. X-ray diffraction data were collected
on a Bruker AXS D8 powder diffractometer. The diffractograms were then analyzed using
automated data handling methods.

Table 1
Variables and Their Values in the Vanadate Combinatorial Experiment
Variable Multiplicity Values
Zn-Cu Mixture 5 ZnxCUl_x, x = 0, 0.25, 0.5, 0.75, 1.0
(Zn + Cu)/V Ratio 2 (Znx + Cul.x)/V = 1or 2; x as above
OH-/V 4 0, 0.33, 0.67, 1.0
H20/V 1 200
Replicate Standards 8 Zn:V:OH:H20=2:l :0.33:200
Temperature 3 100 ~ 150 ~ 200 ~
Time 2 38hr, 168hr
Reagents Zn(NO3)2*25 H20, Cu(NO3)2*25 H20, H20,
NaOH*5 H20, and Na3VO4*60 H20
Total Experiments 288

3. RESULTS AND DISCUSSION

In a conventional investigation, one often will prepare a homogenous reaction mixture,

split the reaction mixture among several autoclaves, and digest these autoclaves for a variety
of temperatures and times. Essentially, the conventional experiment explores digestion
conditions for a specific synthesis gel. A combinatorial or multiautoclave experiment, on the
other hand, is designed to study a variation of compositions across the multiautoclave
assembly. The digestion study can be performed by preparing a series of multiautoclaves
with a set of gel compositions and digesting each multiautoclave at a different condition. By
using a specific multiautoclave assembly to explore gel composition space and a series of
multiautoclaves to study digestion conditions, composition space can be mapped very
efficiently.
116

K20 K20
0.0 1.0
Original Design ~176
o.y'\og
02/ . \o8 _" Combinatorial Design__ 0 .u~v ~ u.i8: 0 ~, " .8.7
~ \o~
04/ , \o~ o.~:',,\ .* ,,, \06
~ .\o~ 0~/,., ~ ..'~o~
~ ~o~ ~ V;,~4
~ 9 \o~ 0~--~- ~ : \0.3
~ , 9 \o~ 0 ~ - , ; , , . \0.2
~ , \Ol
~.o / . . . . . ," \ o.o 1.0# - v v v v v - ~" v ; ~ . ~"
TEA20 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Na20 TEA20 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0"0Na20

Figure 2. Exploration of the xTEA20: yNa20: zK20: A1203:10 SiO2:150 H20

(x+y+z=3) system. The first phase diagram illustrates the experiments done
in the conventional design of experiments (DOE); the second shows the
experiments performed using the combinatorial approach.

3.1 Combinatorial Investigation of Al-Si-O Systems

Figure 2 shows two phase diagrams. These represent the exploratory investigation of
a zeolitic synthesis space at a 10:1 SIO2/A1203. In this experiment, the impact of varying the
K20:Na20:(TEA)20 ratio was examined. The original experiment, done using conventional
methods, explored 10 compositions while the combinatorial experiment explored 100
compositions. In order to validate that the multiautoclave effectively mimics the laboratory
scale, the combinatorial experiment also included the 10 original gel compositions. In all
cases, the laboratory results were reproduced. In addition, because oxide synthesis and
crystallization is intrinsically an inhomogeneous process, to ensure reproducibility on the
scale of the combinatorial experiment, replicates were used within and between the
multiautoclaves. In all cases the experimental results were consistent with expectations.

In this example, the work done to explore the original 10 compositions required
approximately one man-month of labor during an elapsed time of six months. The
combinatorial experiment, on the other hand, was done over a one-week period utilizing only
two days of labor. In addition to the tremendous increase in productivity demonstrated here,
the experiment also illustrates that the combinatorial approach can more effectively cover the
entire reaction space. Because these synthesis systems are inherently discontinuous, a broader
exploration will likely result in increased knowledge and a decreased probability of missing a
critical result.

The previous example illustrates the use of combinatorial methods to explore novel
reaction space. This next example will illustrate the use of combinatorial methods to focus on
the details and reexamine a "known" system: mixed alkali structure direction in the Si/A1 = 3
and 10 systems. The experiment consisted of 15 high symmetry alkali combinations of Li §
Na +, K § and Cs § including four 1-way interactions, six 2-way interactions, four 3-way
interactions, and a 4-way interaction. This design is shown in Figure 3. Including replicated
reactions run for quality control, 960 reactions were run. This work is described in depth in
the paper presented by Lewis at this conference. 6
 117

Na

Li
9 Single
9 4-way interaction
9 3-way interaction
+ 2-way interaction

K Cs
mmm Temp
125~ 150~

Figure 3. Experimental design for alkali template combinations investigated displayed on

a tetrahedral quaternary phase diagram, along with reaction stoichiometries and
process conditions. The high-symmetry points selected to cover the
experimental space include the four individual templates (o), the six 2-way
combinations (+), the four 3-way combinations (A), and the one 4-way
combination (m), yielding 15 unique alkali template combinations.

This study mapped out the compositions and conditions leading to the major pure
products, including BEA, ANA, MER, LTL, and pollucite (ANA-Cs). An assumption in this
experiment, that TEA + would do little structure direction at Si/A1 = 3, proved valid as BEA
was only observed at Si/A1 = 10. Pollucite, the Cs analog of analcime (ANA-Cs), was the
only other major pure product observed at Si/AI = 10, forming at the higher hydroxide levels
of OH-/(Si+A1) = 0.55 and 0.64, while BEA formed at 0.45 and 0.55. Cs + was the strongest
structure director among the alkali at Si/A1 = 10; BEA did not form if the Cs level exceeded
0.67 Cs/A1. The low ratio materials LTL and ANA were also observed on several occasions
at Si/A1 = 10, but only at the highest hydroxide level of OH/(Si+A1) = 0.64. Presumably the
hydroxide concentration was high enough to dissolve sufficient silica to allow the lower ratio
materials to form. Such a study can be easily done in a month's time using combinatorial
methods and illustrates the value of the combinatorial tool in mapping compositional space.
In addition, this experiment illustrates the difficulty in designing the experiment such that the
key interactions of the variables can be understood in a minimum number of experiments.

3.2 Combinatorial Investigation of the Zn-Cu-V-O System

The use of the multiautoclave assembly is not limited to the exploration of zeolitic
synthesis gels. A study was carried out in the Cu-Zn-V-O system, a system that we had
previously examined as part of an effort to prepare novel metal oxides. This study resulted in
an increase in fundamental knowledge of a well-known system due to the increased density of
the information collected using combinatorial methods. The conventional study yielded the
material Zn3V2OT(OH)2*2H20, the structure of which was solved by ab initio methods on
powder x-ray diffraction data. 7 The hexagonal structure consists of LDH- or brucite-like Zn
oxyhydroxide layers separated by pyrovanadate groups. Since a similar monoclinic structure
was known for the Cu analog, the mineral volborthite s, we explored the Zn-Cu mixed metal
system. This study resulted in a new structure that was prepared at high temperature having
118

the stoichiometry CuZnVO4OH. 9 The LDH-like Zn and Cu layers are buckled in this structure
giving rise to a more dense structure containing orthovanadate groups and 5-coordinate Cu
and Zn between the layers.

The structural evolution of the reaction composition given by Zn : Cu : V : H20 of 1.5

: 0.5 : 1 : 200 in temperature and time is shown in Figure 4. The crystallinity of the
Zn3V207(OH)2*2H20 phase increases with time at 100 ~ and 150 ~ while conversion to
the CuZnVOaOH-type structure is observed at 200 ~ An examination of the replicate
composition as the Zn is systematically replaced by Cu, is shown in Figure 5. The figure
clearly shows the hexagonal pattern associated with the Zn-rich compositions converting to an
intermediate species when equal amounts of Zn and Cu are present. Further addition of Cu
yields the more complicated monoclinic pattern associated with volborthite,
Cu3V207(OH)2*2H20. These three structures were the dominant products in the 100 ~ and
150 ~ chemistry.

1250'

j/k A200oc,

~ ; i :,i li' i
: ;jr ~ t.j ~ , il i .:, ~1 ! ~ 150~ 7d

2~o_ i !./ \ :~ ! ! ]/I i ^ IA150~ 2d

~ ,
I i "~- i' I'' t I I' ! 100~ 2d
0 ' ' ' I ' I

5 10 15 20 25 30 35
2-Theta(*)

Figure 4. The structural evolution of the reaction composition given by 1.5 Zn: 0.5
Cu: 1.0 V: 200 H20 in temperature and time.
There were several other interesting products observed at 100 ~ and 150 ~ over the
course of this study. The layered intermediate Cu2(OH)3NO3 was observed in a number of
preparations that usually included the higher levels of NaOH. Zn-containing analogs were
also observed. These products were observed only after 38 hr; by 168 hr they were always
converted to volborthite or one of the similar Zn-containing phases. The Cu2(OH)3NO3
structure has a similar LDH or brucite-like structure observed in the layers of volborthite and
Zn3V207(OH)2*2H20. ]~ This intermediate had never been observed in the original
conventional study, probably due to the fact that acetates rather than nitrates had been
employed. It is not apparent whether these hydroxynitrates are precursors or just less stable
competing phases.
 119

Another material in this category had an unidentified x-ray diffraction pattern and was
the major product in 11 of the reactions, often forming along with volborthite. A single
formulation, Cu : V : O H : H20 of 1 : 1 : 0.33 : 200 digested at 150 ~ for 168 hr gave a
pure material. This formulation was scaled up in a 125 ml autoclave. A comparison of the
diffraction patterns from the combinatorial experiment and the scale-up show excellent
agreement. Further characterization by elemental, thermal analysis and SEM showed this
material to be a new copper vanadium oxyhydroxide with the empirical formula
CUllVa(OH)8017 and a needle-like morphology.
1500

Monoclinic Cu3V207(OH)2 0

1000
t.o 0.5
r--

c-
1
e--

500 -

1.5

=2
0

5 lO 15 20 2~ 3o 35
2-Theta(*)

Figure 5. Impact of systematically replacing the Zn by Cu [(Znx Cu2_x)/V=2,

OH-/V=0.33]. Phase transition from hexagonal to monoclinic observed
with increased Cu incorporation.

These data illustrate the value of combinatorial methods to elucidate fine details of the
synthetic chemistry. We believe this is one of the key features of using a combinatorial
experiment - the ability to carefully define the phase space of interest and develop a deep
understanding of the chemistry. In addition, even in a well-studied system like this one, new
materials were uncovered that had been missed in the previous conventional work.

3.3 Combinatorial Investigation of M-AI-P-O Systems

As a final example, the preparation and characterization of a series of
metalloaluminophosphates was performed by screening a diverse mixture of gels based on
variation of the chemistry of the inorganic and organic components. This involved the
introduction of cobalt, magnesium or silicon into gels formed using cyclohexylamine,
cyclopentylamine, N-methylcyclohexylamine and 4-methylcyclohexylamine as the organic
structure directing agents. A total of 200 gel mixtures were prepared, including a series of
120

selected replicates and controls to probe the reproducibility of the experimental procedures
across the parallel format. Crystallization of the gels was carried out for 24 h at 200 ~
followed by parallel filtering and washing stages. A set of eight identical gel compositions all
generating a major AFI phase, randomly distributed within and between plates, confirmed the
level of reproducibility achievable across the parallel format, even at this miniaturized scale.

Figure 6. Distribution of the AFI (dark) and CHA phases obtained in the A1PO-
syntheses. Labelling defined as follows: CH = cyclohexylamine,
CP = cylcopentylamine, NCH = N-methylcyclohexylamine,
MCH = 4-methylcyclohexylamine. The inorganic composition is defined
according to: A = aluminophosphate, AX = metalloaluminophosphate
composition (e.g. ASi = SAPO).

Within the compositions studied, two of the major known phases identified were the
AFI and CHA topologies. A correlation of these two phases as a function of synthetic
parameters has been analyzed, and is summarized in Figure 6. Under the conditions presented
here, many of the products were, not surprisingly, dominated by the presence of the AFI
phase. However, in the presence of cyclohexylamine and cyclopentylamine pure CHA phases
were obtained. To our knowledge, the formation of a pure SAPO-34 in the presence of
cyclopentylamine has not been reported previously. This example again serves to illustrate
the value of using combinatorial methods to fully characterize well-known systems. New
information and knowledge can be collected even when exploring well-known/characterized
systems.

3.4 Combinatorial Chemistry as a Scale-up Tool

Materials manufacturing can also benefit from combinatorial methods. Libraries to
optimize recipes and process conditions can be studied using many of the methods and assays
developed for materials discovery. The ability to correlate the synthesis variables with
materials properties is valuable in determining manufacturing specifications for a given
 121

material and ensuring the robustness of its synthesis. These tools and the resulting
information will decrease the cost of manufacturing development and speed delivery of new
materials to market.

We have demonstrated the applicability of combinatorial methods to accelerate the

scale-up and commercialization of new materials. In a recent example, we worked on the
scale-up of a novel zirconium silicate. ~2'~3 These proprietary materials have demonstrated
excellent selectivity for ammonium cations and as such could be important ion exchange
materials in medical applications. 14 To accelerate commercialization of these new materials,
we used combinatorial methods to determine the most robust composition region for their
synthesis. A relevant subset of the 144 distinct compositions that were prepared is shown in
Figure 7. In this work, the impact of gel composition on the formation of two distinct
zirconium silicate phases was studied: "Product 1" and "Product 2." In this particular case,
"Product 1" was the desired product. In the experiment, the Na, Zr, water and seed levels
were varied. The initial laboratory scale work was performed in the left upper quadrant: high
water, low Na, low Zr, no seed. Note that in this region small changes in any of the
parameters results in formation of "Product 2" and amorphous material. The combi
experiment uncovered a more robust region: the right, lower quadrant. In this region, the
desired product could be synthesized over a wide range of Na, Zr, and water levels. This
region is more robust: formation of "Product 1" is relatively insensitive to synthesis
conditions. Such a robust recipe can be transferred more quickly to manufacturing. This
optimization work was done in a two-week period and resulted in a significant reduction of
the commercialization timeline for this product.

Low Na High Na Low Na H i g h Na Low Na H i g h Na

iI /
1 1 I 1 1 [ 1 1 I / 9
9 9 9 9 9 9 9 9 9 9 9 i 9 m m j 9 Low Zr
II ..
II .~
..~ 9 m 9 9 Am 9 9 9 9 9 9 I,~ m 9 lm 9 High Zr
ii
II ]
IN J
IN ,j
I I .
Iml
9 9 9 9 9 9 IroN 9 mm-A
9 9 9 9 9 9 9 9 9 9 9 IroN 9 mm 9- 9 Low Zr
ImI ._.
Iml
o m 9 9 9 9 9 9 9 9 9 9 9 9 9 mm"mm 9 High Zr
.d
I I '.k
t t ..

No Seed Seed 2 Seed 1

Identified
Product #1" 9 Robust Region
Product #2: Wk for Product 1
Amorphous: l

Figure 7. Combinatorial optimization study of a zirconium silicate synthesis. This

data was used to accelerate the scale-up and commercialization of a new
material.
122

4. S U M M A R Y

We have successfully applied combinatorial synthesis methods to 1) discover and 2)

scale-up inorganic oxides. We find that the tighter control of reaction conditions, coupled
with the ability to systematically vary gel composition, enables a broader exploration and
results in an increase in the fundamental understanding of the space being studied. The
suggestion that combinatorial methods are a degeneration of the scientific process to a
"monkey approach" is inconsistent with our experience. In fact, we find that combinatorial
chemistry presents a greater challenge in experimental design and can be used equally well
for the gathering of fundamental information as for the discovery of new materials.
Furthermore, the fully computer controlled system with online monitoring of every step in the
process ensures quality control and reproducibility. Unfortunately, it is difficult to distinguish
between truth and fiction at such an early stage in the implementation of combinatorial tools
to heterogeneous catalyst processes. In the next few years, we will learn the value and
limitations of the combinatorial tool through exposure and use of this new methodology. Our
experience to date, however, does suggest that the possibilities for the application of
combinatorial tools in the chemical industry are exciting. We look forward to the challenges
and opportunities that this will present.

REFERENCES

1. W. Rothwell, C. Shearer and G. Taylor, Chemtech, 1995, 25 (6), 6.

2. D. E. Akporiaye, I. M. Dahl, A. Karlsson and R. Wendelbo, Angew. Chem., Int. Ed.,
1998, 37 (5), 609.
3. K. Choi, D. Gardner, N. Hilbrandt and T. Bein, Angew. Chem., Int. Ed., 1999, 38 (19),
2891.
4. J. Klein, C. W. Lehmann, H-W. Schmidt and W. F. Maier, Angew. Chem., Int. Ed., 1998,
37 (24), 3369.
5. E. Danielson, M. Devenney, D. Giaquinta, J. Golden, R. Haushalter, E. McFarland, D.
Poojary, C. Reaves, W. Weinberg and D. Xu, Science, 279 (6), 837, 1998.
6. G. J. Lewis, D. E. Akporiaye, D. S. Bem, C. Bratu, I. M. Dahl, A. Karlsson, R. C.
Murray, R. L. Patton, M. Plassen and R. Wendelbo, 13th IZC, July, 2001, in press.
7. R. Broach and G. Lewis, unpublished results, 1992. The structure has been published by
Whittingham; Zavalij P. Y., Zhang F., Whittingham M. S.; Acta Crystallog., C53,
1738- 1739, 1997.
8. M. Lafontaine, A. Le Bail and G. Ferey, 3". Solid State Chem., 85, 220-227, 1990.
9. R. Broach and G. Lewis, unpublished results, 1993. The structure was solved from single
crystal data.
10. A. Wells, Structural Inorganic Chemistry, FitCh Ed., Oxford University Press, New York,
1986, p. 650.
11. D. Akporiaye, Microporous and Mesoporous Materials, ZMPC 2000, Sendai, Japan,
August 2000, in print.
12. D. Bem, J. Sherman, A. Napolitano, A. Leon-Escamilla, G. Lewis and R. Bedard, US
Patent 5,888,472, 1997.
13. D. Bem, R. Bedard, R. Broach, A. Leon-Escamilla, J. Guisselquist and J. Pluth, Mater.
Res. Soc. Symp. Proc., 1999, 549 (Advanced Catalytic Materials- 1998), 73-78.
14. J. Sherman, D. Bern, G. Lewis, US Patent 6,099,737, 2000.
Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 123

The Local Structures of Transition Metal Oxides Incorporated in Zeolites

and their Unique Photocatalytic Properties
Masakazu Anpo* and Shinya Higashimoto

Dept. of Applied Chemistry, Graduate School of Engineering,Osaka Prefecture University

Gakuen-cho, Sakai, Osaka 599-8531, Japan. e-mail: anpo@ok.chem.osakafu-u.ac.jp

Zeolite catalysts incorporated or encapsulated with transition metal cations such as

Mo 6§ V 5+, or Ti 4§ into the frameworks or cavities of various microporous and mesoporous
molecular sieves were synthesized by a hydrothermal synthesis method. A combination of
various spectroscopic techniques and analyses of the photocatalytic reaction products has
revealed that these transition metal cations constitute highly dispersed tetrahedrally
coordinated oxide species which enable the zeolite catalysts to act as efficient and effective
photocatalysts for the various reactions such as the decomposition of NOx into N2 and 02 and
the reduction of CO2 with H20 into CH3OH and C H 4 . Investigations on the photochemical
reactivities of these oxide species with reactant molecules such as NO• hydrocarbonds, CO2
and H20 showed that the charge transfer excited triplet state of the oxides, i.e., (Mo 5+ -O-)*,
(V 4+- O')*, and (Ti 3+ - O-)*, plays a significant role in the photocatalytic reactions. Thus, the
present results have clearly demonstrated the unique and high photocatalytic reactivities of
various microporous and mesoporous zeolitic materials incorporated with Mo, V, or Ti oxide
species as well as the close relationship between the local structures of these transition metal
oxide species and their photocatalytic reactivities.

1. INTRODUCTION

It is hopefully expected that mankind will strive for the recovery and preservation of a
better greener environment with the establishment of environmentally-friendly, clean, safe,
and sustainable technologies for the 21 st Century. However, up until now, environmental
pollution and destruction on a global scale as well as the lack of sufficient clean energy
supplies have drawn much attention and concern to the vital need for ecologically clean
chemical technology, materials, and chemical processes, the most important challenge facing
chemical scientists today.
Although we are moving in a positive direction in the development of such clean and
safe chemical systems using photofunctional materials such as titanium oxide photocatalysts,
we have yet to gain a complete understanding of the reaction mechanisms for the design of
highly efficient and selective photo-induced reaction systems.
In recent years, increasing attention has been focused on studies concerning the
production of new zeolite materials such as microporous and mesoporous molecular sieves
due to their very unique and interesting physicochemical properties such as a pore structure of
a molecular scale, the capacity for ion-exchange, a strong surface acidity and a unique
124

with transition metal oxide species, such as M o, V, or Ti-oxides, are of special interest due to
their high and unique catalytic and photocatalytic properties [1,2]. Thus, it is very
important to obtain detailed information on the effect of the zeolite framework structure on
the chemical function of these metal oxide species as well as on the relationship between the
local structures of these oxide species and their photocatalytic reactivities.
The present study deals with the characterization of the active sites of various
hydrothermally synthesized zeolite materials which include the Mo, V, or Ti-oxide species
within their frameworks and cavities, and their photocatalytic reactivities including the
detection of the intermediate species. Variousmolecular spectroscopic methods such as in-
situ photoluminescence, ESR, XAFS (XANES and FT-EXAFS), were employed along with
analyses of the reaction products to clarify the reaction mechanisms at the molecular level.

2. EXPERIMENTAL

The M o-MCM-41 mesoporous molecular sieves (0.5, 1.0, 2.0, 4.0 M o wt%) were
synthesized using tetraethylorthosilicate (TEOS) and (NH4)6Mo7024"4H20 as the starting
materials and cetyl trimethylammonium bromide (CTMABr) as the template, in accordance
with previous literature [3]. Vanadium silicalites (VS-1 and VS-2; 0.2 wt% as V) were
prepared by hydrothermal synthesis using tetraethylorthosilicate (TEOS), VOSO4 and VCI3
as the starting materials, and tetrapropylammonium hydroxide (TPAOH), and
tetrabutylammonium hydroxide (TBAOH) as a structure directing agent, respectively, under
conditions reported in previous literature [4,5]. The V-HMS mesoporous molecular sieve
(0.2 wt% as V) was synthesized using tetraethylorthosilicate (TEOS) and VOSO4 and
dodecylamine (DDA) as the structure directing agent under conditions reported in previous
literature [3]. The V/SiO2 catalyst (0.2 wt% as V) was prepared by an impregnation
method of SiO2 with an aqueous solution of NH4VO3. After the products were recovered
by filtration, washed with distilled water several times and dried at 373 K for 12 h,
calcination of the samples were carried out under a dry flow of air at 773 K for 8 h. TS-1
and TS-2 (Si/Ti -- 85), Ti-MCM-41 (Si/Ti - 100) and Ti-MCM-48 (Sifri -- 80) were
hydrothermally synthesized according to procedures previously reported [6,7].-. Ti/FSM-16
and Ti/Vycor glass were prepared by a chemical vapor deposition method (CVD) of the Ti-
oxides onto FSM-16 or Vycor glass, respectively, through a facile reaction of TiCh with the
surface OH groups of these supports in the gas phase at 453-473 K, followed by treatment
with water vapor to replace the chlorine atoms with the OH groups [8,9]. A TiO2
powdered catalyst, JRC-TIO-4 (anatase 92 %, rutile 8 %), supplied by the Catalysis Society
of Japan, was used.
Prior to spectroscopic measurements and photocatalytic reactions, the catalysts were
degassed at 773 K for 2 h and calcined in 02 (> 20 Torr) at 773 K for 2 h, then degassed at
473 K for 2 h. The photoluminescence and lifetimes were measured at 77 K with a
Shimadzu RF-501 spectrofluorophotometer and an apparatus for lifetime measurements,
respectively. The ESR spectra were recorded with a JEOL-2X spectrometer (X band) at 77
K. XAFS (XANES and EXAFS) spectra were obtained at the BL-10B facility of the High
Energy Acceleration Research Organization (KEK) in Tsukuba. The XAFS spectra of the
 125

dehydrated samples were recorded at the M o K-edge, Ti, and V K-edge absorption in the
transmittance and fluorescence mode at 293 K, respectively. The EXAFS data were
examined by an analysis program by Rigaku EXAFS (REX). The photocatalytic reactions
of NO in the absence and presence of the CO molecules were carried out at 298 K with a high
pressure mercury lamp through an UV cut filter (/l > 270 nm). The products were
analyzed by online gaschromatography.

3. RESULTS AND DISCUSSION

3.1. Molybdenum Oxide Catalysts

Results of the XRD patterns and the BET surface area of the Mo-MCM-41 catalysts
indicated that they have a hexagonal lattice having mesopores larger than 2 0 A and that they
possess a high BET surface area (-- 1000 m2/g) as compared with amorphous silica (300 m2/g),
so that they can be considered effective photocatalysts [3].
From analyses of the XAFS (XANES and EXAFS) spectra, it was found that M o-
M CM-41 in the lower loadings of the M o-oxides (1.0 M o wt%) include highly dispersed
tetrahedrally coordinated M o-oxide species, having two shorter M o-O bonds and two longer
ones, while the M o-MCM-41 in higher loading amounts of Mo-oxides (4.0 M o wt%),
tetrahedrally coordinated M o-oxides (M oO42")n with an additional M o-O-M o bond could be
observed [ 10].
M o-M CM-41 (1.0 M o wt%) exhibits a photoluminescence spectrum at around 400-600
nm upon excitation at around 295 nm (defined as X), which coincides with the
photoluminescence spectrum of the tetrahedrally coordinated M o-oxides highly dispersed on
SiO2, as shown in Fig, 1 [11]. The excitation and emission spectra are attributed to the
following charge transfer processes on the M o-O moieties of the tetrahedral molybdate ions
(MOO42), involving an electron transfer from the 0 2- to M o 6+ ions and a reverse radiative
decay from the charge transfer excited triplet state [2,11 ].

hv hv'
[ M 0 6+- O 2" ] [ M o s+ - O" ] W [ M 0 6+ -- 0 2- ]
absorption photoluminescence

The width and the wavelength at the maximum intensity of the emission band do not
change upon varyingthe excitation wavelength, indicating that there is only one emitting site
with a photoluminescence lifetime of 2.25 ms at 77 K. These results indicate that the M o-
oxides showing absorption in the region of 295 nm form a tetrahedral coordination in a highly
dispersed state.
On the other hand, as shown in Fig, 2, there are at least two luminescent species (the
absorption spectrum can be deconvoluted into two components having wavelength regions of
X and Y in Fig. 3 at 295 and 310 ran, respectively) on Mo-MCM-41 (4.0 Mo wt%) [12].
The increase in M o content, from 1.0 to 4.0 M o wt%, leads to the formation of not only the
emitted X site with a photoluminescence lifetime of 2.25 ms but also another emitting site (in
the region of Y) probably induced by M o-M o interactions via the oxygen ions (M o-O-M o),
which cause a more efficient radiationless energy leading to a decrease in the
126

photoluminescence lifetime (0.91 ms). Taking into account the XAFS data, only the
isolated tetrahedrally coordinated M o-oxides are formed in lower M o loadings, while two
types of tetrahedrally coordinated M o-oxides at highly dispersed levels and (M 0042-) n are
formed in higher Mo loadings, as shown in Fig. 3.

A a't
(a)
(A) (e)
) (el 5

.z, J 9b(Y) . (b)

(/)
E:

._c (c)
m
.> (x (c)

2,1,.,.
~ff. )

Ar I, .~~
200 300 400 500 600 200 300 400 500 600
Wavelength / nm Wavelength / nm
Fig. 1. Effect of the addition of NO on Fig. 2. Effect of the addition of NO on
the photoluminescence spectrum and the the photoluminescence spectrum and the
excitation spectrum of Mo-MCM-41 with excitation spectrum of Mo-MCM-41 with
loading amount of 1.0 Mo wt%. a Si/Mo ratio of 40. Pressure of added
Pressure of added NO : (A, a) 0; (b) NO : (A, a) 0; (b) 0.6; (C, c) 4 Torr; (d)
0.07; (C, c) 0.4 Torr; (d) excess; (e) excess; (e) degassed after (d). Spectrum
degassed after (d). (A) can be deconvoluted into (X) and (Y).

(a) H ,.r~A (b) O .O Q o /H

1.74A~kk / 3.1~9A~ //
Sl ~, .//Mo /
\Z ";" \o d9o/
Fig. 3. Proposed local structures of the isolated (a) as well as oligomeric
Mo-oxide sites (b) in the Mo-MCM-41 catalyst.

3.1.1. Photocatalytic Decomposition Reaction of NO by the Coexistence of Additive

Gasses on the Mo-MCM-41 Catalysts and their Photocatalytic Reactivity
The photocatalytic decomposition reactions of NO in the absence and presence of
various kind of additive gases such as CO, propane, ethane, methane, and propylene were
performed on M o-MCM-41 under UV-irradiation (X > 270 nm). No products could be
detected under dark conditions nor did the silicious M CM-41 or bulk M 003 exhibit any
photocatalytic reactivities. However, UV-irradiation of Mo-MCM-41 in the presence of
NO led to the evolution of N2 as well as N20 and NO2. It was found that the efficiency of
 127

the photocatalytic decomposition

reactions of NO strongly
depended on the kind of additives
used. The order of the reactivity
for the photocatalytic
decomposition reactions is as
follows: CO > propane > ethane
> propylene -- methane. In
line with these results, further
investigations showed that the
photocatalytic decomposition
reactions of NO exhibited high
efficiency by the coexistence of
propane and CO.
The photocatalytic
decomposition of NO into N2 and
CO2 on M o-M CM-41 was found
Fig, 4. Reaction time profiles of the photocatalytic
to proceed effectively and decomposition reaction of NO by the coexistence of
efficiently by the coexistence of CO on M o-M CM-41 (1.0 M o wt%). Yields of CO2
CO. As shown in Fig, 4, UV-
(A), N2 (11), N20 ( O ) ; conversion of NO (C)).
irradiation (A > 270 nm) of M o-
MCM-41 in the presence of a Amount of added NO or CO: 180 /z mol-g-catl
mixture of NO and CO led to the formation of N2 and CO2 with a good linearity against the
UV-irradiation time as well as a good stoichiometry, while the turnover frequency exceeded
unity after irradiation for 2h. These results clearly indicate that the reaction proceeds
photocatalytically. Also, atter UV-irradiation for 3 h, NO conversion and selectivity for the
formation of N2 reached close to 100 %, leading to the formation of small amounts of N20
during this reaction in the gas phase [ 13,14].
UV-irradiation of Mo-MCM-41 in the presence of CO alone and its subsequent
evacuation at 293 K led to an efficient quenching of the photoluminescence, which suggests
..

that the charge transfer excited triplet state of the [M 05+ - O-]* complex reacts with CO,
leading to the formation of M o4+ ions as well as CO2, which exhibits no ESR signals due to
the M 05+ ions [ 13-16]. Exposure of the NO molecules into the photo-formed M o4+ ions led
to the formation of N20 under dark conditions. In fact, after subsequent evacuation, the
photoluminescence intensity recovered, but not to its original photoluminescence intensity
due to the formation of carbonyl species such as [M 04+ - CO] which decompose only upon
heating at temperatures above 373 K [ 17]. In fact, the exposure of NO and N20 onto M o4+
ions under dark conditions led to the formation of N20 and N2, respectively. From these
results, the photocatalytic decomposition reaction mechanism of NO by the coexistence of
the CO reaction can be proposed, as shown in Scheme 1. After the subsequent evacuation
of the catalyst, the photoluminescence intensity recovered accompanied by the oxidation of
Mo 4+ to Mo 6+ ions. In-situ photoluminescence and ESR measurements demonstrated that
this reaction proceeds in a redox cycle between alternating M 06+ and M o4+ ions, i.e., it was
128

found that the photo-formed M o4+ ions, through a reaction of the charge transfer excited
triplet state with CO, are oxidized to the original M 06+ ions in the presence of NO or N20,
leading to the formation of N2.

(MOs+- O')*
S xtetrahedral!y
cited triplet state of t h e ~ ~,.,
hl ~I/ h V coordinated
Mtor_oxides
) ated
L,u
~ C O 2

(M06+= OZ-) N2 [ t - - ' - CO (M04+)

ff etrahedrallycoordinated t
Mo-oxides) CO2
~~---- (M~4+)
NO

~ ~ . . (M06+," ~ ' x NO

Scheme 1. Catalytic cycles for the photocatalytic decomposition of

NO in the coexistence of CO.

3.1.2. Relationship between the Local Structures of Mo-oxides and their

Photocatalytic Reactivities for the Decomposition of NO by the Coexistence of CO
Photoluminescence and
XAFS investigations of M o-
MCM-41 were performed and
the results revealed that the
absorption in the X and Y
regions are attributed to
tetrahedrally coordinated Mo-
oxides at a highly dispersed
level and (M 0042-) n,
respectively. Figure 5 shows
the parallel relationship
between the yields of N2
formation for the
decomposition of NO on Mo-
MCM-41 (0.5-4.0 M o wt%) Fig, 5. Relationships between the yields of N2
by the coexistence of CO and formation for the photocatalytic decomposition
the relative intensity of the reactions of NO by the coexistence of CO, and the
absorption spectra observed in relative intensity of the absorption in the total region of
the total region (X and Y) of the (X and Y) of M o-M CM-41 (0.5, 1.0, 2.0, and 4.0 M o
catalyst. The intensities of the wt%). Added NO or CO: 180 tt mol-e-cat. -I
 129

absorption spectra of two types of tetrahedral M o-oxides in the total region of X and Y were
found to have a good relationship with the yields of N2 for the photocatalytic decomposition
of NO in the presence of CO [13]. These results indicate that in the presence of CO, two
types of tetrahedral M o-oxides at a highly dispersed level as well as (M 0042) n work as the
active sites.

3.2. Titanium Oxide Catalysts

The development of efficient photocatalytic systems which are able to decompose NO
directly into N2 and O2 or to reduce CO2 with H20 into chemically valuable compounds such
as CH3OH or CH4 are among the most described yet and challenging goals in the research of
enviromentally-friendly catalysts. From this point of View, much attention has been
focused on the useful application ofTi-oxide photocatalysts, mainly as TiO2 semiconductors,
TiO2 thin films, and isolated tetrahedrally coordinated Ti-oxides [1,2]. Recently, we have
reported that highly dispersed tetrahedrally coordinated Ti-oxides, when compared with bulk
TiO2 powder, exhibit high and unique photocatalytic reactivity for the NO decomposition
reaction as well as the reduction of CO2 with H20 [1,8,9]. It can be seen that understanding
the relationship between the local structure of the Ti-oxides and their photocatalytic
reactivity, especially their selectivity among various types of Ti-oxide catalysts is of special
importance.
In-situ characterizations of Ti-oxides included within various types of zeolites or
anchored on support surfaces by means of UV-Vis, ESR, photoluminescence and XAFS
(XANES and EXAFS) investigations provided important insights into their local structure
and their photocatalytic reactivity for the
decomposition of NO into N2 and 02 as well 100 , ~
as the reduction of CO2 with H20 into .~ Ileal,."
CH3OH and CH4. It was found that Ti- c 8 0 " o12~
o
oxides prepared within zeolites or on ~ oa-
support surfaces exhibit quite different and ~ 60 o.~"rl ~ o 2 -
high photocatalytic reactivity as compared o oa-" ~ /Oa"
0 2-
to bulk powdered TiO2 and also that the high z 6 - ~ [i
reactivity of the charge transfer excited o 4 0 " II 02-
triplet state of the tetrahedrally coordinated ~i-
Ti-oxides, (Ti 3+ - O-)*, plays a significant _~ 20 -
role in the unique and high photocatalytic 0~
reactivity of these catalysts. I t I I
XAFS (XANES and EXAFS) 03.5 4 4.5 5 5.5 6 6.5
investigations of these Ti-oxide catalysts at Coordination Number
the T i K-edge were carried out and the
results revealed the Ti-oxides to have a Fig, 6. Relationship between the
coordination number of the Ti-oxides and the
tetrahedral coordination within the Ti-oxide
catalysts, while the Ti-oxides have an selectivity for N2 formation in the
octahedral coordination in the case of the photocatalytic decomposition of NO into N2
and 02 on various titanium oxide catalysts.
bulk TiO2 photocatalyst. Figure 6 shows
130

the relationship between the coordination number of the Ti-oxides and the selectivity for N 2
formation in the photocatalytic decomposition reaction of NO on various Ti-oxide
photocatalysts. The clear dependence of the N2 selectivity on the coordination number of
the Ti-oxides can be observed, i. e., the lower the coordination number of Ti-oxides, the higher
the N2 selectivity [1]. From these results, it can be proposed that a highly efficient and
selective photocatalytic decomposition of NO into N2 and 02 can be achieved using Ti-
containing zeolites as a photocatalyst which involves highly dispersed tetrahedrally
coordinated T i-oxides as the active species. The reactivity of such a charge transfer excited
state was also found to strongly depend on the differences in the molecular environment of
the T i-oxides such as the rigidity or flexibility of the zeolite framework and the local
structures of the TiO 4 unit, i. e., Ti(OSi)4, Ti(OH)(OSi)3 or Ti(OH)2(OSi)2 [ 1,18,19].

3.3. Vanadium Zeolite Catalysts

Zeolites having V-oxides in their frameworks have been the focus of much attention for
their interesting and distinctive physico-chemical properties as well as photocatalytic
reactivities. So far, several types of vanadium silicalite catalysts in which vanadium ions are
incorporated into the zeolite framework have been developed, however, the true chemical
nature and reactivities of these vanadium silicalites are yet little known.. The results of XAFS
(XANES and EXAFS), ESR, photoluminescence and FT-IR measurements of such V-
silicalites (VS-1 and VS-2), V-HMS, and V/SiO2 have shown that they include highly
dispersed tetrahedrally coordinated V-oxides having one oxygen in the shorter V-O distance
and three oxygen atoms in the longer V-O distance within the zeolitic framework or on the
silica surface. These V-oxide catalysts exhibited a phosphorescence spectrum attributed to
the radiative decay from the charge transfer excited triplet state [ 1,2,20].
Table 1 shows a comparison of the chemical properties of the VO4 unit of the various
types of V-oxide catalysts. The values of the vibrational transition energy between the (0 ---~

Table 1. Comparison of the various physical and chemical parameters of the V-

oxide species formed within the zeolite frameworks and SiO 2 surface.

Photocatalysts VS-I VS-2 V-HMS WSiO 2

,

Coordination tetrahedral tetrahedral tetrahedral tetrahedral

V=O bond length, (A) 1.68 1.66 1.63 1.62

,.

V-O bond length, (A) 1.78 1.77 1.77 1.78

V=O vibrational energy,

(cm-1) 960 980 1010 1035

Lifetime of the excited

state, (ms) 5.8 6.9 7.6 8.4

O=V-O bond angle, ( 4~) 4~1 ___ 4~2 < 4~3 <__ 4~4
 131

0) and (0 ~ 1) transition bands calculated from the second-derivative phosphorescence spectra

of VS-1, VS-2, V-HMS, V/SiO2 were found to be about 960, 980, 1010 and 1035 cm -~,
respectively, and they are attributed to the vibrational transition having a V=O vanadyl bond,
showing that they correspond with the decrease in the V=O bond distance from 1.68/~ to
1.62 ~. Moreover, the phosphorescence lifetimes ofVS-1, VS-2, V-HMS and V/SiO2 were
found to be about 5.8, 6.9, 7.6 and 8.4 ms at 77 K, respectively. The increase in the lifetime
from 5.8 to 8.4 ms can be interpreted in terms of an increase in the distortion of the VO4
unitand a decrease in the V=O bond length [20,21 ]. These results indicate that the VO4 unit
incorporated within the V-silicalites has a Td-like
symmetrical structure and exhibits a smaller O:V-O-(Si, H) 0 a-
bond angle than that of V-HM S or V/SiO2 on the basis of %*
the VSEPR (valence shell electron pair repulsion) theory, as
/ O t:=="~~ O
shown in Fig. 7 [21]. It is well known that V-silicalites
have a rigid zeolite framework structure while V-HM S has si \
a greatly flexible structure. Taking these results into O Si
consideration, the zeolitic rigid framework structure of V-
silicalites causes a more significant and pronounced effect
I
Si
on the chemical properties of the VO4 unit than the flexible Fig. 7. Structure of V-
framework structure ofV-HMS, which is similar to V/SiO2. oxide species.
Furthermore, the dynamic quenching of the
phosphorescence by adding reactant molecules showed that the charge transfer excited trip let
state of these tetrahedrally coordinated V-oxides plays a significant role in the photocatalytic
decomposition reaction of NO.

4. C O N C L U S I O N S

Unique and efficient photocatalytic systems incorporating transition metal oxides (M o,

Ti, V) have been designed using the cavities and frameworks of zeolites and mesoporous
molecular sieves. The present results have demonstrated the unique ph~csicochemical
properties of the local structure of such anchored metal oxides, which were theresult of the
rigidity or flexibility of the zeolite framework, as well as their photocatalytic reactivities.
These well-defined photocatalysts can be considered one of the most promising candidates
for use in the environmentally-friendly reaction systems.

REFERENCES
1. M. Anpo (eds.), in Photofunctional Zeolites, NOVA Publishers Inc. (2000).
2. M. Anpo and M. Che, Adv. Catal., 44 (1999) 119, and references therein.
3. W. Zhang, J. Wang, P. T. Tanev, and T. J. Pinnavaia, J. Chem. Soc., Chem. Commun.,
(1996) 979.
4. H.P. Rao, P. R. Ramaswamy, V. P. Ratnasamy, J. Catal., 137 (1992) 225.
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(1996) 895.
132

7. S.G. Zhang, Y. Fujii, H. Yamashita, K. Koyano, T. Tatsumi, and M. Anpo, Chem.

Lett., (1997) 659.
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89 (1985) 5017.
9. K. Ikeue, H. Yamashita, M. Anpo, Chem. Lett., (1999) 1135.
10. S. Higashimoto, R. Tsumura, M. Matsuoka, H. Yamashita, M. Che, M. Anpo, submitted
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12. S. Higashimoto, R. Tsumura, S. G. Zhang, M. Matsuoka, H. Yamashita, C. Louis,
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14. R. Subbotina, B. N. Shelimov, V. B. Kazansky, A. A. Lisachenko, M. Che, and S.
Coluccia, J. Catal., 184 (1999) 390.
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Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 133

SUMMARIES of O R A L P R E S E N T A T I O N S

12 - In-Situ Spectroscopy and Catalysis (Mondayam)

12-O-01 - 2D correlation IR spectroscopy of xylene isomerisation on H-MFI

zeolite
F. Thibault-Starzyk*, A. Vimont and J.-P. Gilson
Laboratoire Catalyse & Spectrochimie, CNRS ISMRA, Caen, fts@ismra.fr, France

New data treatment methods such as 2D correlation infrared spectroscopy (2D-COS) lead to
significant improvements for in situ studies. We report here the application of 2D-COS to the
in situ infrared study of orthoxylene isomerisation in H-MFI zeolite in working conditions.
This led to improve the quantitative monitoring of xylene isomers in the micropores of the
solid and to the detection of ffaces of coke in the catalyst. A correlation was found between
coke and the perturbation of specific hydroxy groups in the solid.

12-O-02 - Structure/reactivity correlation in Fe/ZSM5 for deNOx

applications. In-situ XAFS characterization and catalysis
A.A. Battiston, J.H. Bitter, D.C. Koningsberger
Department of Inorganic Chemistry and Catalysis, Utrecht University, The Netherlands

In-situ XAFS spectroscopy performed at 350 ~ shows that in Fe/ZSM5 synthesized through
the FeCI3 sublimation technique (Si/AI - !7) Fe is predominantly present in the form of
binuclear oxo/hydroxo-complexes. During reaction with i-C4Hl0 a clear reduction in the
oxidation state of the iron is detected, accompanied by changes in only one of the three Fe-O
shells. This confirms the presence of a specially reactive oxygen and demonstrates the
possibility of XAFS of studying the local environment around iron in Fe/ZSM5 under
experimentally realistic conditions (in-situ, at 350~

12-O-03 - Interaction of diazines with faujasites studied by IR spectroscopy,

temperature-programmed desorption, and molecular modeling methods
J. D6bler (a), E. Geidel (a), B. Hunger (b), K.H.L. Nulens (c) and R.A. Schoonheydt (c)
a Institut fiir Physikalische Chemie, Universitgit Hamburg, doebler@chemie.uni-hamburg.de,
Germany, b Wilhelm-Ostwald-Institut, Universitgit Leipzig, Germany, c Centrum voor
Oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Belgium

The adsorption behavior of diazines in X and Y zeolites has been studied by infrared
spectroscopy (IR), temperature-programmed desorption (TPD), and simulation techniques.
The studies showed that the interaction is determined by a donation of electron density from
the nitrogen atoms of the probe molecules to the Lewis-acidic cations. The individual nature
of the adsorption strongly depends on the Si/A1 ratio of the zeolites, the kind of extra-
framework cation, and the positions of heteroatoms in the probe molecules.
 134

1 2 - O - 0 4 - D R I F T study of dinitrogen and dihydrogen adsorption on Li- and

Na- forms of LSX zeolite
V.B. Kazansky(a), A.I. Serykh(a), E. Tichomirova(a), V.Yu. Borovkov(a) and M. Bulow(b)
a Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia,
vbk@ioc.ac.ru, b BOC GASES, Technical Center, Murray Hill NJ, USA
Adsorption of H2 at 77 K on Li-LSX zeolite with DRIFT control of perturbation of adsorbed
molecules has discriminated three different types of adsorption sites. Two of them were
ascribed to H2 adsorption on Li + ions localized in supercages of the zeolite framework at Sm
and SIII' sites, while the latter one most likely belongs to H2 adsorption on Li + ions at SII sites.
Adsorption of N2 by Li + ions at SIII and SIII' sites is the strongest resulting in a decrease of
intensity of the corresponding DRIFT bands from adsorbed H2. N2 dsorption by Li + at Su sites
is very much weaker.

0 6 - Fundamentals of Miceile Templating (Monday am)

06-O-01 - The effect of stoichiometry and synthesis conditions on the

properties of mesoporous M41S family silicates
W.J. Roth and J.C. Vartuli
ExxonMobil Research and Engineering, Annandale, USA wieslaw_j roth@email.mobil.com,
james c vartuli@email.mobil.com
Basic quantitative relationships and trends governing the formation of the M41S mesoporous
molecular sieves MCM-41 and MCM-48 are presented. The syntheses with
hydroxide/surfactant molar ratio close to unity afforded high quality MCM-41 and proved
particularly suitable for quantifying the effects of synthesis mixture composition and
synthesis conditions upon the nature and properties of the mesoporous products. Increasing
temperature and duration of crystallization resulted in unit cell expansion and a more robust
silica framework. Syntheses with silica to surfactant molar ratio equal to 5:1 and higher gave
MCM-41 while MCM-48 was observed at lower (3.5:1) ratios.

0 6 - 0 - 0 2 - What are circular crystals?

F. Marlow
MPI fiir Kohlenforschung, 45470 Miilheim/Ruhr, marlow@mpi-muelheim.mpg.de, Germany
Translational symmetry is usually considered a pre-requisite for a perfect long range
organization of matter. This is realized for crystals in all three dimensions. However, we have
found materials architecture with perfect long range three dimensional order and no
translational symmetry. The first example are mesostructured silica fibers consisting of
channels wound around the fiber axis, thereby forming an array with hexagonal short range
order. The whole structure is controlled by a singularity which is the fiber axis. In reciprocal
space, the fibers are represented by a system of rings instead of a reciprocal lattice known for
crystals. A physical consequence of this are unusual X-ray diffraction properties. Because of
the new reciprocal space representation the circular architecture has to be regarded as a
qualitatively new form of solid state organization.
 135

0 6 - 0 - 0 3 - Hierarchically mesostructured zeolitic materials with the MFI

structure
D. Trong On a, P. Reinert b, L. Bonneviot b and S. Kaliaguine a
aDepartment of Chemical Engineering, Laval University, Ste Foy, Quebec, Canada
blnstitut de Recherche sur la Catalyse, CNRS UPR-5401, Villeurbanne, France
A new approach for the synthesis of mesostructured zeolitic materials (namely UL-TS-1 and
UL-ZSM-5) is reported. The materials were obtained in the solid state by heating TPAOH-
impregnated mesoporous materials for several days. Various techniques including XRD, N2
adsorption, UV-visible, FTIR, TEM and 29Si MAS NMR were used to monitor the physico-
chemical properties of these materials as a function of crystallization time. The increase in the
percentage of crystallinity is correlated with the corresponding variations in micropore and
mesopore volumes, BET and BJH surface areas. The results indicate that the mesopore walls
consist of zeolite nanocrystals. Depending on crystallization time, a range of materials from
totally amorphous up to 80% crystalline is observed, while some of mesopores are preserved.

0 6 - 0 - 0 4 - Pore size engineering of M C M - 4 8 : the use of different additives

as expanders
M. Mathieu, E. Van Bavel, P. Van Der Voort and E.F. Vansant
Dept. of Chemistry- Laboratory of Adsorption and Catalysis, University of Antwerp (U.LA.),
Wilrijk, Belgium, mariska.mathieu@ua.ac.be
For the first time the pore size engineering of mesoporous MCM-48 materials using several
additives during the synthesis is discussed. It was shown that dimethyltetradecyl amine
(DMTDA) is a convenient expander, resulting in a MCM-48 structure with a pore size
enlargement from 1.7 nm to 2.4 nm pore radius. Also a wide range of dimethylalkyl amines,
with varying chain length were applied as swelling agents. Hereby, the influence of the chain
length and the effect of the molar ratio of amine/surfactant on the crystallinity and pore size of
the MCM-48 were studied. Other additives, such as ethanol and decane, were also found to be
suitable for the synthesis of large pore MCM-48.

10 - Host-Guest Chemistry (Monday am)

10-O-01 - Investigation of indium loaded zeolites and additionally promoted

catalysts for selective catalytic reduction of NOx by methane
F.-W. Schtitze a, H. Berndt a, M. Richter a, B. Lticke a, C. Schmidt b, T. Sowade b and
W. Grtinert b
Institut[ar Angewandte Chemie Berlin-Adlershof (ACA), Berlin, Germany," schuetze@aca-
berlin.de Lehrstuhl fur Technische Chemie, Ruhr-Universitdt-Bochum, Bochum, Germany
The nature of active sites of In zeolites and their function and behavior in the SCR of NO•
with methane has been investigated. In zeolite structures (mordenite, ZSM-5) were prepared
by various methods. The catalysts were additionally promoted by oxidic components, above
all CeOx, to improve their activity as well as to stabilize their performance in the presence of
water vapor. The obtained composite materials showed promising activity under reaction
conditions. The promoting effect of the oxidic components will be discussed shortly.
136

10-O-02 - Ion exchange of alkali metals and control of acidic/basic

properties of MCM-22 and MCM-36
J.-O. Barth, R. Schenkel, J. Kornatowski and J.A. Lercher
Technische Universitdt Mfmchen, Lehrstuhl Il fi~r Technische Chemie, Munich, Germany
jan-olaf barth@ch, tum. de

MCM-22 (Si/AI = 12) and MCM-36 pillared with SiO2 (Si/AI = 29) were modified by ion
exchange of alkali cations. A critical point was the pH of the solution, which should be
adjusted to about 9 and 4, respectively. At pH 9 the pillared mesoporous structure of MCM-
36 was destroyed as indicated by nearly amorphous XRD patterns and severely reduced BET
surface areas. The degree of exchange decreased from Na to Cs (except the lowest value for
Li). In spite of this, the basic character in both series increased from Li to Cs as demonstrated
by IR spectra of adsorbed pyridine and TPD of ammonia.

10-O-03 - Insertion compounds of metal halides with porosils: "Structured

Gases"
P. Behrens (a), M. Hartl (a), G. Wirnsberger (b), A. Popitsch (b) and B. Pillep (c)
a) Institut fiir Anorganische Chemie, Universitat Hannover, Hannover, Germany,"
Peter.Behrens@ mbox.acb.uni-hannover.de; b) Institut ffir Physikalische und Theoretische
Chemie, Technische Universitdt Graz, Austria; c) Patent- und Rechtsanwaltskanzlei Kador &
Partner, Mfinchen, Germany

Insertion compounds of porosils with mercury(II) halides HgX2 (X: C1, Br, I) and with
gold(Ill) chloride were synthesized and characterized by a variety of analytical techniques.
Due to the electroneutral character of the pure SiO2 framework of the porosil hosts, host-guest
interactions are restricted to weak forces of the van der Waals-type. The compounds contain
isolated HgX2 molecules or Au2C16 dimer molecules, respectively. These molecules have
properties that are very similar to the corresponding molecules in the gaseous state.

10-O-04 - Site selective adsorption and catalytic properties of iron in FER

and BEA zeolites
Z. Sobalik, J.E. ~;poner, Z. Tvarfl~kov/t, A. Vondrov~i, S. Kuriyavar and B. Wichterlovfi
J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic- Sobalik@l'h-inst.cas.cz

FTIR spectroscopy, interaction with oxygen, NO, N20, catalytic oxidation of NO to NO2, and
reduction of NOx with propane have been used to characterise Fe cations in FER and BEA
zeolites. Three cationic positions for Fe ions in dehydrated samples of Fe-FER, and one in Fe-
BEA have been identified. A complex nature of the reversible interaction of the Fe(II) cations
in FER and BEA with 02, NO, N20 has been described. The experimental study is
complemented with a simple theorical investigation of Fe(II) and Fe(III) coordination over the
most populated 13 site.
 137

17 - Principles of Adsorption (Monday am)

17-O-01 - Liquid-solid and solid-solid phase transitions of oxygen in a single

cylindrical pore
K. Morishige and Y. Ogisu
Department o f Chemistry, Okayama University of Science, Okayama,
morishi@chem, ous. ac.jp, Japan

To study the liquid-solid and solid-solid phase transitions of a confined 02, we performed X-
ray diffraction measurements of O2 confined inside the cylindrical pores of six kinds of
regular mesoporous adsorbents (MCM-41 and SBA-15) with different pore radii as a function
of temperature. Hysteresis effects between the y-to-J3 and [3-to-)' solid-solid phase transitions
are considerably larger than those between freezing and melting and the depression of the [3-
to-), transition point is slightly smaller than that of the melting point.

17-O-02 - Structural study of benzene, tetrachloroethene and trichloro-

ethene sorbed phases in silicalite-1
N. Floquet a, J.P. Coulomb a, G. Weber b, O. Bertrand b and J.P. Bellat b
aC.R.M. C 2 - CNRS, Campus de Luminy, Case 901, 13288 Marseille Cedex 9- France
bL.R.R.S. - CNRS, Universit6 de Bourgogne, B.P. 400, 21011 Do'on Cedex - France

From our detailed neutron diffraction investigation of the structural properties of C2HCI3,
C2C14 and C6D6 sorbed phases in Silicalite-I, we deduce that the steps observed in their
adsorption isotherms are not signatures of phase transitions but are correlated to the different
stages observed during the Silicalite-I loading. For C6D6 such a loading is a three stages
process (the C6D6 molecules fill successively, the intersections, the straight and the sinusoidal
channels). Concerning C2C14, it is a two stage process (the C2C14 molecules fill the
intersections and after indifferently the straight channels and the sinusoidal channels). Usual
sorption is observed for C2HC13 which fills all parts of the Silicalite-I porosity indifferently.

17-O-03 - Molecular ordering of the adsorbed phase within the

microporous model aluminophosphate AIPO4-11 at cryogenic temperatures
N. Dufau*, N. Floquet**, J-P. Coulomb**, P.L. Llewellyn* and J. Rouquerol*
* Groupe MADIREL, C.T.M. du C.N.R.S., 26 rue du 141 ~meR.I.A. 13003 Marseille (France)
** C.R.M. C2., Campus de Luminy, Case 901, 13288 Marseille cedex 9 (France)

The present paper highlights the influence of molecular sized micropores on the ordering of
the adsorbed phase within AIPO4-11. A range of simple probe molecules was used including:
Ar, Kr, CH4, O2, N2 and CO. Their adsorption properties were studied by adsorption
microcalorimetry at 77 K and 87 K as well as by neutron scattering measurements in the
temperature range from 20 to 100 K.
138

1 7 - O - 0 4 - Adsorption properties o f a supercritical fluid on mesoporous

molecular sieves under high pressure
Ya. Goto a, N. Setoyama b, Y. Fukushima b, T. Okubo c, Yu. Goto c, Y. Imada c, Y. Kubota c and
Y. Sugi c
a) Japan Chemical Innovation Institute, el O60@mosk.tytlabs.co.jp, Japan, b) Toyota Central
R&D Labs. Inc., 41-1 Yokomichi,Nagakute, Aichi, Japan; c) Faculty of Engineering, Gifu
University, Gifu, Japan

High pressure argon adsorption isotherms were measured up to 10 MPa on mesoporous

molecular sieves with various pore sizes at 303 K. The adsorption properties of argon onto
mesopores were energetically analyzed by Langmuir theory. The calculated adsorption energy
decreased monotonically with increase of pore diameter even in mesopore range, caused by
an enhancement of molecule-surface interaction due to the curvature of pore wall.

2 3 - M i c r o - and Mesoporous Materials in Fine Chemistry (Mondaypm)

23-K-01 - Delaminated zeolites as active catalysts for processing large

molecules
A. Corma* and V. Forn6s
Instituto de Tecnologia Quimica, UP V-CSIC, Universidad Polit~cnica de Valencia, Valencia,
Spain - acorma@itq, upv. es

Zeolite nanolayers have been obtained by delaminating the lamellar precursors of four
zeolites. These materials present very high well structured external surface areas larger than
600 m2.g~. Catalytic active sites can be introduced during the synthesis or by post-synthesis
treatments, yielding active and selective catalysts for processing large size molecules of
interest in oil refining and for the production of fine chemicals.

23-0-02 - Pd-zeolites as catalysts for the Heck reaction: a screening o f

reaction parameters affecting catalyst heterogeneity
M. Dams, D.E. De Vos, L. Drijkoningen and P.A. Jacobs*
Centre for Surface Chemistry and Catalysis, K.U.Leuven, Heverlee, Belgium -
pierre.jacobs@agr, kuleuven, ac. be

Heck reactions were performed with 4-bromoacetophenone and n-butyl acrylate, yielding the
trans-substituted acrylate ester with high selectivity. Pd-mordenite was used as catalyst. The
heterogeneous nature of the catalysis largely depends on the solvent used and on the base.
With tributylamine as the base and in toluene, the Pd(0)-mordenite catalyzed Heck olefination
is truly heterogeneous. The heterogeneous catalyst is less air-sensitive than typical
homogeneous palladium catalysts that contain phosphine ligands.
 139

2 3 - 0 - 0 3 - B e c k m a n n rearrangement of cyclohexanone oxime over meso-

porous M C M - 4 1 - and M C M - 4 8 - t y p e materials
R. GRiser, H. Kath and J. Weitkamp*
Institute of Chemical Technology, University of Stuttgart, Stuttgart, Germany-
jens. weitkamp@po, uni-stuttgart.de

The Beckmann rearrangement of cyclohexanone oxime in the gas phase has been investigated
over siliceous MCM-41- and MCM-48-type materials. At 275~ complete conversion occurs
for several hours with selectivities for ~-caprolactam up to 65 %, until the catalysts deactivate
rapidly. The deactivation of the mesoporous catalysts is considerably reduced as compared to
that obtained over an amorphous silica gel. MCM-48 exhibits the highest catalyst lifetime
which, for MCM-41-type materials, is longer with larger pore diameter. With an aluminum-
containing H-MCM-41 catalyst an increased ~-caprolactam selectivity is achieved.

23-0-04- K n o e v e n a g e l condensation between ethylcyanoacetate and

benzaldehyde over base catalysts immobilized on m e s o p o r o u s materials
Youngyun Choi, Keun-Sik Kim, Jong-Ho Kim and Gon Seo
Department of Chemical Technology and The Research Institute for Catalysis,
Chonnam National University, Gwangju, Korea

Three different organic bases, imidazole (IM), triazole (TZ) and hydrogenated 1,8-diaza-
bicyclo(5.4.0) undecene-7 (DBU) were immobilized on mesoporous materials. Immobilized
state of organic bases and their catalytic activities in Knoevenagel condensation between
ethylcyanoacetate and benzaldehyde was studied. Organic bases immobilized mainly on
mesopore still retained their catalytic activities with an inevitable loss due to immobilization.
Imidazole catalyst immobilized on KIT-1 disordered mesoporous material with three-
dimensional channels showed a sufficient activity for multi-repeated use.

2 3 - 0 - 0 5 - One-step synthesis of M I B K from acetone over Pt/X catalysts

L.V. Mattos (a), F.B. Noronha (b) and J.L.F. Monteiro (a)
a NUCAT/PEQ/COPPE/UFRJ, monteiro@peq.coppe.ufrj.br, Brazil," b Instituto Nacional de
Tecnologia (INT), bellot@int, gov. br, Brazil

The synthesis of MIBK was studied over Pt supported on NaX and CsX zeolites. The activity
increased as both the temperature and the Hz/Ac ratio were increased. Temperature had also a
beneficial effect on the selectivity to MIBK but the H2/Ac ratio had an opposite effect.
Activities and selectivities were always higher for Pt/NaX than for Pt/CsX. For Pt/NaX,
increasing the reduction temperature increased the activity but decreased the selectivity to
MIBK. Both catalysts were quite stable and selectivities to MIBK of 70 % were obtained over
P t ~ a X at 613 K and Hz/Ac = 0.5. The absence of both strong acidic and strong basic sites
and a proper balance between metallic and basic sites are responsible for behavior observed.
140

0 2 - Zeolite Nucleation and Growth (Monday pm)

02-O-01 - Small angle X-ray scattering on TPA-Silicalite-I precursors in

clear solutions: influence of silica source and cations
C.J.Y. Houssin a, B.L. Mojet a, C.E.A. Kirschhock b, V. Buschmann c, P.A. Jacobs b, J.A.
Martens b and R.A. van Santen a
a Schuit Institute of Catalysis, Eindhoven, The Netherlands - c.].y.houssin@tue.nl; b K. U.
Leuven, Leuven, Belgium; c Darmstadt University of Technology, Darmstadt, Germany
The formation and growth of crystal nuclei of TPA-Silicalite-1 (aluminium free ZSM-5) from
clear solutions using TEOS and silicic acid as silica sources were studied with small angle X-
ray scattering (SAXS). Information was obtained on the size and shape of nanoscopic
precursor particles of silicalite-1. The SAXS data can be interpreted assuming the presence of
tablets of 4•215 nm up to 8•215 nm depending on the synthesis conditions. Starting
solutions have been studied varying the silica source and the cations content (sodium,
potassium and TPA). Although the nanoparticles differ in size, their shape is very similar and
these data strenghten our confidence that TPA-Silicalite-1 formation is rather nanoblocks
based aggregation mechanism than growth via monomer addition.

0 2 - 0 - 0 2 - Nucleation processes in zeolite synthesis revealed through the use of

different temperature-time profiles
C.S. Cundy, J.O. Forrest and R.J. Plaisted
Centre for Microporous Materials, UMIST, colin,cundy@umist.ac, uk, UK
A comparison between thermal and microwave syntheses of colloidal silicalite-1 has provided
a clear demonstration of the separate contributions of room-temperature ageing, heating rate
and synthesis temperature to the nucleation process. At ageing times up to about 50 days, the
product crystal size obtainable from a single synthesis composition is sensitive to reaction
temperature and heating rate. After this time, ageing-generated proto-nuclei are so numerous
that the normal self-nucleation of the reaction mixture is suppressed and the product crystal
size is independent of reaction conditions. There is a limit to the number of crystals which can
be nucleated and this is an intrinsic property of the system.

0 2 - 0 - 0 3 - High yield synthesis of colloidal crystals of faujasite zeolites

Qinghua Li, D. Creaser and J. Sterte
Division of Chemical Technology, Lule~t University of Technology, decr@km.luth.se
A method for the preparation of colloidal zeolite Y in high yields is presented. Sodium was
added to a colloidal zeolite Y synthesis mixture at varying times during the synthesis to
increase the Na20/A1203 ratio to levels that normally favour the crystallization of zeolite A. A
two-stage varying-temperature synthesis method was used to determine the nucleation period
of colloidal zeolite Y. It was found that if sodium was gradually added after nucleation,
instead of the formation of zeolite A, pure colloidal zeolite Y with a size of less than 120 nm
and a more than six-fold increase in yield was obtained. The effect of the amount and the rate
of Sodium addition during the crystallization on the formation of colloidal zeolite Y were also
investigated.
 141

0 2 - 0 - 0 4 - Colloid chemical properties of silicalite-I nanoslabs

S. Kremer (a), C. Kirschhock (a), P. Rouxhet (b), P.A. Jacobs (a) and J.A. Martens (a)
Centrum voor Oppervlaktechemie en Katalyse, K.U. Leuven, Belgium
johan, martens@agr, kule uven. ac. be.
(b) Unitd de Chimie des Interfaces, Universitd Catholique de Louvain, Belgium

Aggregation of Silicalite-1 nanoslabs in concentrated suspensions was studied. Nanoslabs

have negative zeta potential and contain occluded and externally adsorbed TPA. At room
temperature, the nanoslabs form physical aggregates, which dissociate upon dilution. The
formation of these reversible aggregates accelerates Silicalite-1 synthesis upon heating. The
influence on crystallisation of dilution with water or TPAOH solution and of salt addition
may be explained by changes of the nanoslab mobility and of the nanoslab-nanoslab
interfaces. The externally adsorbed TPA controls the formation of ordered chemical bonds
between nanoslabs in contact and the subsequent crystal formation.

0 2 - 0 - 0 5 - A t o m i c force microscopy (AFM) used to relate surface topo-

graphy growth m e c h a n i s m s in SSZ-42
M.W. Anderson (a), N. Hanif (a), J.R. Agger (a), C.-Y. Chen (b) and S.I. Zones (b)
a UMIST Centre for Microporous Materials, Manchester, m.anderson@umist.ac.uk, United
Kingdom," b Chevron Research & Technology Co., Richmond, CA, USA

This work details the atomic force microscopy of three faces of the microporous material
SSZ-42. Interesting surface features have been observed on each face that are distinct and
related to the structure of SSZ-42. These have been used to determine the crystal growth
mechanism of SSZ-42. This study supports a layer growth mechanism whereby growth of
crystals occurs at terrace sites and edges from nutrient in the solution and elucidate the
templating mechanism.

11 - Post-Synthesis Modification (Monday pm)

11-O-01 - Gold-based mono- and bimetallic nanoparticles on H Y zeolites

G. Riahi, D. Guillemot, M. Polisset-Thfoin, D. Bonnin and J. Fraissard
Laboratoire SIEN, Universitd Paris VI, Paris, polisset@ccr./ussieu.fr, France
fax: 01.44.27.55.36

Stable nanoparticles of monometallic gold, or bimetallic Pd-Au and Pt-Au systems supported
on Y-zeolite are obtained by an original method, in which the metallic precursors and the
support play an important part in the formation and the stability of the particles. This method
involves exchange of complexed cations with counter-ions of an acidified zeolite and their
thermal reduction by the ligand (ethylenediamine) under inert gas flow. This preparation leads
to nanometric mixed bimetallic particles. The particles have good stability at high temperature
(500~ in dihydrogen or dioxygen.
142

11-O-02 - Unravelled from the back: kinetics of alkoxysilane CVD on

zeolites and evidence for pore mouth plugging determined from model
conversion over stepwise silanised samples
H.P. ROger (a,b), H. Mantein (a), W. B6hringer (a), K.P. M611er (a) and C.T. O'Connor (a)
(a) Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town,
South Africa - wboe@chemeng.uct.ac.za; (b) present address: Sad-Chemie AG, Division
Catalysts, R&D, Bruckm~ihl, Germany

Chemical vapor deposition (CVD) of tetraethoxysilane on HZSM5 was performed stepwise

under well-controlled, mild conditions. Several test reactions were performed over the series
of modified samples. Under mild conditions, CVD follows first order kinetics with respect to
uncovered external sites on the zeolite crystals. The external surface is homogeneous with
regard to both CVD and catalytic activity. Reactions, which are controlled by strong internal
mass transfer restrictions, do respond in a way, which indicates that CVD causes pore mouth
plugging rather than pore mouth narrowing.

11-O-03 - Templating role of F towards D4R units: study of the

transformation of the fluorogallophosphate Mu-3 into Mu-2
A. Matijasic, P. Reinert, L. Josien, A. Simon and J. Patarin
Laboratoire de Mat~riaux Min~raux, UPRES-A 7016, ENSCMu, UHA, 3, rue Alfred Werner,
68093 Mulhouse Cedex, France, j.patarin@univ-mulhouse.fr

After a brief review on the templating role of F in the synthesis of molecular sieves, this
study focuses on the transformation of Mu-3 into Mu-2, two fluorinated gallophosphates with
1D and 3D arrangement of fluorinated D4R units respectively. Depending on the water
content and on the temperature, Mu-2 or another gallophosphate free of D4R units
crystallizes. The transformation is studied by XRD analysis and NMR spectroscopy. The
different results obtained show clearly that this transformation does not occur via a complete
dissolution. Based on the 19F NMR spectra, the presence of a fluorinated D4R unit, in the
solution, cannot be excluded.

1 1 - O - 0 4 - Modification of the Si/Ti ratio in E T S - 1 0

G. Koermer, A. Thangaraj and S. Kuznicki
Engelhard Corporation, Iselin, NJ 08830, USA, gerald, koermer@engelhard, corn

ETS-10 is a thermally stable titanosilicate molecular sieve with potential for application in
catalysis and adsorption. The as-synthesized Si/Ti ratio is 5. Methods for modification of the
Si/Ti of ETS-10 are described. The resulting materials are characterized by elemental
analysis, XRD, NMR, IR and raman techniques. These modified sieves show catalytic activity
for oxidation of organic substrates with peroxide.
 143

11-O-05 - Binuclear oxo-Fe species in Fe/ZSM-5 catalyst prepared by

chemical vapour deposition
P. Marturano a, L. Drozdovfi a, A. Kogelbauer b and R. Prins a
aLab. Tech. Chem., ETH-Z~irich, CH-8092 Ziirich, Switzerland (prins@tech. chem. ethz. ch)
bDept. Chem. Eng. and Chem. Tech., Imperial College, London SW7 2BY, UK

The existence of the binuclear oxo-iron species postulated in the literature for Fe/ZSM-5 was
proved using EXFAS spectroscopy. The structural parameters obtained allowed to propose a
model structure which closely resembles that of the active species of the methane
monooxygenase enzyme ([Fe(~t-O)zFe] 2+ or [Fe(~t-O)(~t-OH)Fe]+). Magnetic susceptibility
measurements (SQUID) further supported this conclusion, as they revealed the expected
antiferromagnetic coupling between the Fe 3+ ions of the dimer. The electronic spectra also
showed features attributable to such dimeric species. The hydrolysis occurring during the
washing of the zeolite, after sublimation, was concluded to be the key step of the preparation.

1 8 - Adsorption and Separation Process (Mondaypm)

18-O-01 - An experimental adsorbent screening study for CO2 removal

from flue gas
P.J.E. Harlick, H. Halsall-Whitney and F. Handan Tezel*
Department of Chemical Engineering, University of Ottawa, Ottawa, Ontario, Canada-
tezel@eng, uottawa, ca

The selection of a suitable zeolite adsorbent for C02 removal from flue gas (mixture of C02
and N2) has been carried out. The limiting heats of adsorption, Henry's Law constants for CO2
and N2, CO2 pure component adsorption isotherms and expected working capacity curves for
Pressure Swing Adsorption (PSA) separation application were determined. The results show
that the most promising adsorbent characteristics are a near linear CO2 isotherm and a low
SIO2/A1203 ratio with a cation in the zeolite structure that has strong electrostatic interaction.

18-O-02 - Amino acids in BEA type channels

C. Buttersack (a) and A. Perlberg (b)
a Institutfiir Technologie der Kohlenhydrate e. V., Braunschweig, Germany
christoph, buttersack@nordzucker.de, b. Max-Planck-Institut Dynamik komplexer
technischer Systeme, Magdeburg, perlberg@mpi-magdeburg.mp2.dG Germany

Adsorption isotherms of amino acids in BEA type zeolites (SiO2/A1203 = 25 ...300, ionic
form: H +, Na +, K +, Ca ++) have been analyzed. Phenylalanine, leucine, isolecine, methionine,
and arginine were found to form dimers in the zeolite pores (SiOz/A1203 = 25, H +, Na + ). In
case of higher content of silicium the dimerization was less pronounced. The adsorption was
rather selective, depending on the pH and ionic form. Sorbate-zeolite interaction was
essentially interpreted in terms of hydrophobic forces.
144

18-O-03 - Kinetic separation of binary mixtures of carbon dioxide and C2

hydrocarbons on modified LTA-type zeolites
C.J. Guo, D. Shen and M. Btilow
The BOC Gases Technology, Murray Hill, NJ 07974, USA; martin.bulow@us.gtc.boc.com
A solution is offered to separate mixtures of carbon dioxide and C2-C4 hydrocarbons by enhancing
equilibrium sorption selectivity via kinetic selectivity to achieve high overall separation efficiency.
Basic Na-LTA type zeolite is modified gradually by ion exchange, K+ vs. Na+, to alter the effective
cross-section of entrances to micropores of zeolite crystals. This leads to favorable differences
between sorption uptake rates for carbon dioxide'and C2 hydrocarbons, viz., ethane, ethylene and
acetylene. A challenging separation becomes practically viable by utilizing processes of pressure
swing adsorption, PSA.

18-O-04 - A novel adsorbent for the separation of propane/propene

mixtures
w. Zhu, F. Kapteijn and J.A. Moulijn
Section Industrial Catalysis, DelfiChemTech, Delft University of Technology, Julianalaan 136,
2628 BL Delft, w.zhu@tnv~:tudelft.nl, The Netherlands

The adsorption of light hydrocarbons, such as ethane, ethene, propane, propene, and
unsaturated linear C4 molecules, on the all-silica DD3R has been investigated using the
tapered element oscillating microbalance, TEOM. Single component adsorption isotherms are
reported at temperatures in the range from 303 to 473 K. Only minor differences exist
between the adsorption of ethane and ethene. Transient adsorption experiments reveal that the
eight-ring windows of the all-silica DD3R are accessible to propene, trans-but-2-ene, and
buta-l,3-diene molecules, while they exclude propane, cis-but-2-ene, and but-l-ene
molecules. The high shape selectivity for propene suggests that the all-silica DD3R might be
effective as an adsorbent for the separation of propene and propane mixtures.

1 8 - O - 0 5 - Iodide removal using zeolite-based reactive adsorption

S. Kulprathipanja and B. Spehlmann
UOP LLC, 50 East Algonquin Road, Des Plaines, IL 60017-5017, USA

UOP has developed Ag exchanged high silica to alumina ratio zeolite-Y adsorbents (e.g. Ag
exchanged LZ-210) for the removal of both organic and inorganic iodide compounds from
commercial acetic acid feed streams (1). Experimentally, good results were obtained with Ag
exchanged LZ-210 having framework silica to alumina molar ratios of about 10-12.
Specifically, laboratory breakthrough experiments demonstrated that Ag-LZ-210 removed
methyl iodide, hexyl iodide, and hydrogen iodide from acetic acid having initially several
hundred parts per million (ppm) by weight of total iodine to a level of 1 part per billion (ppb)
in the effluent.
 145

2 4 - New Routes to H y d r o c a r b o n Activation (Tuesday am)

24-O-01 - D e h y d r o i s o m e r i z a t i o n of n-butane to isobutene over Pd modified

s i l i c o a l u m i n o p h o s p h a t e molecular sieves
Y. Wei, G. Wang, Z. Liu, C. Sun and L. Xu
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian, zml@dicp.ac.cn, China

Several aluminophosphate molecular sieves with AEL topology structure were synthesized
and modified by Pd for direct transformation reaction of n-butane to isobutene. The effect of
pore geometry of the molecular sieves was studied. Pd modified 10-member ring SAPO-11
and metal-substituted A1PO-11 and SAPO-11 showed high selectivity towards isobutene. The
incorporation of metal into the molecular sieves had effect on the product distribution.
Catalytic properties and the result of chemical adsorption of monoxide predicted the
interaction between the transition metal for substitution and the supported palladium.

2 4 - 0 - 0 2 - Conversion of methane over A g - Y in the presence of ethene

T. Baba, H. Sawada, Y. Abe and Y. Ono
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo
Institute of Technology, Ookayama, Meguro-ku, Tokyo, Japan.

Ag-Y catalyzed the conversion of CH4 into higher hydrocarbons in the presence of C2H4. The
conversions of CH4 and C2H4 were 6.3 % and 16.8 %, respectively at 673 K. Products were
C2 - C5 hydrocarbons. The main product was C2H6, while the other hydrocarbon was mainly
C3H6, which accounted for 28.8 mol% of the products. Both acidic proton and silver cations
are essential for the activation of CH4 to from C3H6 by the reaction of CH4 with C2H4. H-
ZSM-5 loaded with various cations such as Ag + also catalyzed the conversion of CH4 in the
presence of C2H4. H-ZSM-5 loaded with Ag + showed the highest catalytic activity. The
conversion of CH4 was 13.2% at 673 K, while C2H4 conversion was 86.3 %. Aromatics were
mainly formed and the product composition was 30.3 mol%.

2 4 - 0 - 0 3 - Peculiarities in the hydroconversion of n - h e x a d e c a n e over

bifunctional catalysts
L. Perrotin a, A. Finiels a, F. Fajula a and T.Cholley b
a UMR 5618, ENSCMontpellier- CNRS, Montpellier, France," b TotalFinaElf Feluy, Belgique

A kinetic study of n-hexadecane hydroconversion has been carried out over bifunctional
catalysts prepared from EMT and FAU zeolites, MCM-41-type molecular sieves and
amorphous silica alumina. A unique influence of hydrogen partial pressure characterized by a
sharp optimum of activity at intermediate pressures has been revealed. A reaction model
including the conventional bifunctional mechanism and the generation of active sites by
hydrogen spillover is proposed to describe the experimental results.
146

2 4 - 0 - 0 4 - HI3 catalyzed heterogeneous aziridination of olefins

B. Chanda a , R. Vyas a, A.V. Bedekar a, B.B. Kasture b and V.N. Joshi b
~Division of Organic Chemistry. Technology bCatalysis Division, NCL Pune, India.
bhanu@dalton, ncl. res. in; bhanu.c'handa@yahoo, com

A non-metal catalyzed synthesis of aziridines using HI3 zeolite under heterogeneous

conditions was developed. The methodology gives aziridines in good yields and obviates the
drawbacks of metal catalyzed aziridinations. Even the less reactive olefins like cinnamates
underwent this reaction at ambient temperatures. Aliphatic, alicyclic and aromatic olefins all
undergo the transformation. An interesting feature of the conversion of olefins is the selective
formation of trans isomer. Under metal catalyzed homogenous conditions the same substrates
give cis/trans mixtures. It has been speculated that the reaction takes place inside the pore of
the cavity of the zeolite which is large enough for the aziridine molecule to fit into. In order to
demonstrate this, molecular modelling studies were carried out on both the isomers using
PCMODEL software.

24-0-05 - MCM-41 as support for metailocene catalysts - ethylene

polymerization
C.A. Henriques a, M.F.V. Marques b, S. Valange c, Z. Gabelica d and J.L.F. Monteiro e
alnstituto de Quimica/UERJ, RJ, Brasil," blnstituto de Macromoldculas Prof. Eloisa
Mano/UFRJ, RJ, Brasil; c ESIP, Poitiers, France," dENSCMu, GSEC; Mulhouse, France,"
eNUCA T - COPPE/UFRJ, monteiro@peq, coppe, ufrj. br, RJ, Brasil

Al-containing (A1MCM) and all-silica (SiMCM) MCM-41 were evaluated as supports for
Cp2ZrCI2 as a catalyst for C2H4 polymerization. While SiMCM without pre-treatment with
metallocene/methylaluminoxane (MAO) did not fix the metallocene in a catalytically active
form, as also observed for a commercial silica sample, Cp2ZrC12 supported on MAO-free
A1MCM yielded polymers with narrow polydispersity and the highest molecular weight of the
series, although with a low activity. All the MAO pre-treated supports originated catalysts
that exhibited activities comparable to those of homogeneous zirconocenes.

01 - Mineralogy of Natural Zeolite (Tuesday am)

OI-K-OI - Pentasil zeolites from Antarctica: from mineralogy to zeolite

science and technology
A. Alberti a, G. Cruciani a, E. Galli b, S. Merlino c, R. Millini d, S. Quartieri ~, G.Vezzaliniband S.
Zanardi a
~Universitit di Ferrara, Italy, alb@dns.unife.it; bUniversit~t di Modena e Reggio Emilia,
Italy." CUniversit~t di Pisa, Italy. dEniTecnologie S.p.A., S. Donato Milanese, Italy.
eUniversit~l di Messina, Italy
This paper deals with chemical and crystallographic properties of new and very rare zeolites
found at Mt. Adamson (Northern Victoria Land, Antarctica). These are gottardiite, mutinaite
and tschernichite, the natural counterparts of synthetic NU-87, ZSM-5 and beta, respectively,
and terranovaite and boggsite, whose frameworks are unknown among synthetic materials.
Mineral properties are compared with those of the synthetic analogues.
 147

01-O-02- Natural zeolites mineralization in the Oligocene-Miocene

volcano-sedimentary succession of Central Sardinia (Italy)
P. Cappellettia, G. Cerria, M. de ~ a , A. LangeUab, S. Naitzac, G. PadalinoC,M. Palomba~and R, Rizzoc
aDipartimento di Scienze della Terra, Universith di Napoli Federico II, Napoli, Italy
bFacolt~t di Scienze, Universith del Sannio, Benevento, Italy
CDipartimento di Geoingegneria e Tecnologie Ambientali, Universit~ di Cagliari, Cagliari, Italy
dCentro Studi Geominerari e Mineralurgici del CNR, Universit~t di Cagliari, Cagliari, Italy
Investigations performed on the Cenozoic volcano-sedimentary sequence of Central Sardinia
recognized widespread secondary mineralization processes, differently affecting the volcanic
and sedimentary units cropping out in the region. Mineralogical studies evidence zeolite mineral
association consisting of clinoptilolite and mordenite, locally attaining economic con-
centrations. Chemical composition of mordenite and clinoptilolite is strongly correlated with the
rhyodacitic glassy precursor. Secondary mineralization process which affected the volcaniclastic
and epiclastic deposits, enables to identify the most interesting areas, as far as zeolite grade is
concerned. Up to now, available data are not sufficient for an exhaustive definition of the
complex and articulated minerogenetic processes which originated the zeolitization.

01-O-03 - Cation location and its influence on the stability of clinoptilolite

*M.N. Johnson, *G. Sankar, *C.R.A. Catlow, **D. O'Connor, **P. Barnes and +D. Price.
*Royal Institution of Great Britain, London, UK. matt@ri.ar **Birkbeck College,
Crystallography Dept., London, +University College London, Geology Dept., London, UK
Clinoptilolite is used as a medium for storage of low grade nuclear waste. Here we present
data collected on the Energy Dispersive X-ray Diffraction (EDXRD) station 16.4 at
Daresbury Synchrotron Radiation Source, UK, that clearly identifies the effects of various ion
exchanged cations upon the structural stability of clinoptilolite. This data is the beginning of a
much larger project that potentially will increase the sorption capabilities and storage
potential of clinoptilolite for safer storage of nuclear waste.

0 1 - O - 0 4 - The structure of Li-phillipsite

A.F. Gualtieri
Dipartimento di Scienze della Terra, Universitgt di Modena e Reggio Emilia, Italy,
alex@unimo.it

This work describes the results of the Rietveld structure refinement of a Li-exchanged natural
phillipsite in the frame of a long term project on the crystal chemistry and properties of
exchanged phillipsites. A natural phillipsite from Vallerano (Rome, Italy) with a Si/(Si+A1)
ratio of 0.63 was exchanged with Li + and its structure was refined with the Rietveld method
using conventional powder diffraction data. The structure has K + and water in site I and Na +
and Ca ++ in site II. Li + was refined in site II' with a population of 100% and a tetrahedral
coordination with 2 framework oxygens and 2 water molecules at an average distance of
1.961 A. The assignment of the Li + position was possible by considering the short cation-
anion distances.
148

01-O-05 - Ion-exchange features of intermediate-silica sedimentary

phillipsite
C. Colella l, E. Torracca 2, A. Colella 3, B. de Gennaro I I). Caputo I and M. de Gennaro 3
I Universit~ Federico II, Napoli, Italy," 2Universith Roma 3, Roma, Italy," 3Universit~ Federico
II, Napoli, Italy
Equilibrium ion-exchange data for intermediate-silica Na-exchanged phillipsite at 25~ in
the presence of cation pairs Na/X, where X is Ba, Co, NH4, K or Ca, were collected and the
relevant thermodynamic parameters were computed. Phillipsite was found very selective for
Ba, K and NH4, unselective for Co, whereas only about 50% Na could be readily replaced by
Ca. This behaviour was interpreted in terms of phillipsite's structural features. On the basis of
the present and the previous data concerning other cations, possible applications of alkali-
trachytic phillipsite-rich rocks could be envisaged in the treatment of wastewaters containing
Ba, Cs, Pb and/or NH4, especially if the waters are lacking K as an interfering cation.

1 5 - Modelling and Theoritical Studies A (Tuesday am)

15-O-01 - Proton jumps in dehydrated acidic zeolite catalysts. Rate

predictions based on ab-initio calculations
M. Sierka and J. Sauer*
Humboldt-Universitat zu Berlin, Institut fiir Chemie, Berlin, Germany
On-site proton jumps between neighboring oxygen atoms of the A104 tetrahedron in proton
forms of CHA, FAU, and MFI zeolites are studied. Comparison is made with inter-site jumps
to neighboring Si-O-Si bridges. In H-MFI the barrier for leaving the AIO4 tetrahedron is 132
kJ/mol. The barriers for on-site jumps are between 52 and 106 kJ. While in all three zeolites
both low and high barriers exist, different structural features of the three frameworks suggest
that the proton mobility is generally lower in chabazite and faujasite than in ZSM-5, in
agreement with NMR results. The calculations of the energy barriers employ the QM-Pot
method. At room temperature the calculated rates vary over a broad range of 10-6 to 105 s"~.
Proton tunneling effects appear to be negligible above room temperature.

1 5 - O - 0 2 - A b - i n i t i o simulation of dynamical processes in zeolites

L. Benco (a), T. Demuth (a), J. Hafner (a), F. Hutschka (b) and H. Toulhoat (c)
alnstitut fuer Materialphysik and Center for Comput. Mater. Science, Wien, Austria,
lubomir.benco@univie.ac.at, bTotal Raffinage Distribution, Centre Europden de Recherche et
Technique, Harfleur, France, Clnstitut Frangais du Pdtrole, Rueil-Malmaison Cedex, France
Ab-initio density-functional molecular dynamics is used to characterize dynamical processes
in zeolites. Simulations performed on the structure of gmelinite show that the proton transfer
between the O-sites is a spontaneous process enabled in both Na-free and Na-zeolite by just
one water molecule adsorbed to the acid site. A proton attack of the acid zeolite at the
hydrocarbon molecule is investigated at increased temperature of 700 K. In the protonated
molecule a series of proton jumps are observed indicating their high mobility.
 149

15-O-03 - A theoretical study of the methylation of toluene by methanol

over acid mordenite
A. Vos (a), X. Rozanska (b), R. Schoonheydt (a), R. van Santen (b), F. Hutschka (c) and J. Hafner
(d)
a Centrum voor Oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Belgium
b Schuit Institute of Catalysis, Eindhoven University of Technology, The Netherlands
c TotalFina, Centre Europden de Recherche et Technique, Harfleur, France
d Institutfiir Materialphysik, Universitcit Wien, Austria

A theoretical study of the alkylation of toluene by methanol catalysed over acid mordenite is
presented. Cluster DFT as well as periodic structure DFT calculations have been performed to
obtain full reaction energy diagrams of the elementary reaction steps leading to the formation
of the three xylene isomers. The use of periodic structure calculations allows to take into
account the framework electrostatic contributions and steric constraints that are important in
zeolite catalysis.

1 5 - O - 0 4 - Coverage effects on adsorption of water in faujasite: an ab-initio

cluster and embedded cluster study
J. Limtrakul, S. Nokbin, P. Chuichay, P. Khongpracha, S. Jungsuttiwong and T. N. Truong
Laboratory for Computational & Applied Chemistry, Chemistry Department, Kasetsart
University, Bangkok 10900, Thailand, e-mail."fscijrl@ku.ac.th

The influence of high coverages of adsorbing molecules on zeolites has been investigated by
means of both the density functional theory quantum cluster and the embedded cluster
methods. For cluster models, equilibrium structures determined for the adsorbing molecules
successively added from one to four molecules per acid site. While [H3SiOAI
(OH)zSiH3]/[H20] and [H3SiOAI(OH)2SiH3]/[H20]2 are a hydrogen-bonded complex, cluster
of [H3SiOAI(OH)2SiH3]/[H20]4 they contain both types of ion-pair and neutral complexes. It
is shown that for the zeolite/(H20)3 complex, a complete proton transfer, ZO(H30+)(H20)2,
can be observed when the zeolite lattice potential is taken in to account.

15-O-05- The Beckmann rearrangement catalyzed by silicalite: a

spectroscopic and computational study
G.A. Fois a, G. Ricchiardi a, S. Bordiga a, C. Busco a, L. Dalloro b, G. Span6 b and A. Zecchina b
a Dipartimento di Chimica IFM, Via P. Giuria 7, 1-10125 Torino, Italy,
Ricchiardi@ch.unito. it; b EniChem S.p.A., Centro Ricerche Novara, "Istituto Guido Donegani

The rearrangement of cyclohexanone oxime to caprolactam over zeolites with MFI and FAU
structure is investigated by means of spectroscopical (IR) and computational methods.
Hydrogen bond interactions, proton transfer and rearrangement are detected. The thermal
reaction mechanism and that catalyzed by H + are studied with QM methods of B3LYP/6-
31 +G(d,p) quality. The same reaction path in presence of HC1 and silanol is studied in order
to model acids of different strength. The H+-catalyzed mechanism is found to be a multi-step
mechanism in which proton transfer from N to O in the oxime is the rate determining step.
With weaker acids, a single-step mechanism is found.
150

0 7 - New Mesoporous Molecular Sieves (Tuesdayam)

07-O-01 - Ordered mesoporous carbon molecular sieves by templated

synthesis" the structural varieties
R. Ryoo (a)*, S.H. Joo (a), S. Jun (a), T. Tsubakiyama (b) and O. Terasaki (b,c)
a Korea Advanced Institute of Science and Technology, Taejon, Korea,
rryoo@mail.kaist.ac.kr, b Department of Physics and CIR, Tohoku University, Sendai, Japan
c CREST, JST Corporation, Tohoku University, Sendai 980-8578, Japan

Ordered mesoporous carbons (OMC) of various structures, designated as CMK-1-5, have

been synthesized by carbonization of sucrose, furfuryl alcohol or other carbon sources inside
silica or aluminosilicate mesopores that are interconnected into three-dimensional networks
such as in MCM-48, SBA-1 and SBA-15. The mesoporous carbon molecular sieves, obtained
after template removal, show TEM images and XRD patterns characteristic of the ordered
arrangement of uniform mesopores. The OMC, which are opening up a new area of the
nanoporous materials, exhibit high BET specific surface areas, excellent thermal stability in
inert atmospheres and strong resistance to attack by acids and bases.

0 7 - 0 - 0 2 - One-pot synthesis of phenyl functionalized porous silicates with

hexagonal and cubic symmetries
V. Goletto (a), M. Imp6ror (b) and F. Babonneau (a)
a Chirnie de la Mati~re Condensde, UPMC, Paris; b Universitd Paris-Sud, Orsay, France

Phenyl functionalized silicates with cubic Pm3n and 2D p6m symmetries have been prepared
by direct reaction of a mixture of phenyltriethoxysilane and tetraethoxysilane with an aqueous
solution of cetyltrimethylammonium bromide, under acidic or basic conditions. Their
structural characterization by XRD using synchrotron radiation, multinuclear MAS-NMR
(including 2-dimensional 1H homonuclear correlation) and N2 adsorption-desorption
isotherms will be reported in order to better describe the localization of the phenyl groups in
the silicate framework.

0 7 - 0 - 0 3 - State and redox behavior of iron in MCM-41

G. P~l-Borb61ya, A. Szegedi a, K. L~zfirb and H.K. Beyer a
a Institute of Chemistry, Chemical Research Center, Hungary, borbely@cric.chemres.hu
b Institute of Isotope and Surface Chemistry, Chemical Research Center, Hungary

Mesoporous Fe-MCM41 samples with different framework iron contents were synthesized
and characterized by TPR, in situ FTIR and M6ssbauer spectroscopy after thermal
pretreatments in high vacuum (autoreduction) and treatments in reductive (CO) and oxidative
(O2/He) atmospheres. Changes in the coordination and oxidation state of iron in Fe-MCM41
subjected to successive redox treatments were detected by both spectroscopic methods. At
higher temperatures (720 K) all iron proved to be reversibly involved in Fe(III)~--~Fe(II) redox
cycles. The results are interpreted in terms of structural features of iron species
isomorphically incorporated into MCM41. A reaction mechanism involving the formation of
framework oxygen vacancies during reduction and restoration of the structure upon
reoxidation is proposed for the redox process.
 151

0 7 - 0 - 0 4 - A comparative study of Cu interaction with niobium- and

aluminium-containing MCM-41 molecular sieves
M. Ziolek a, I. Sobczak a, I. Nowak a, P. Decyk a and J. Stoch b
aA m. University, Poznan, Poland, ziolek@amu.edu.pl, b Institute of Catalysis and Surface
Chemistry, Polish Academy of Sciences, Cracow, Poland
The interaction between Cu and Nb in the mesoporous molecular sieves of MCM-41 type has
been studied. The results were compared with those found for copper containing alumino-
silica sieves (A1MCM-41). Cu cations in NbMCM-41 matrix are slightly reduced during
heating at 723 K under a low vacuum and deeply (<+1) under a high vacuum, whereas, in
A1MCM-41 copper is partially reduced to Cu + under a high vacuum. The results of the
reaction between copper and the extra framework niobium species are discussed. The strong
interaction of copper species with niobium, introduced into the framework of the molecular
sieves, determines the catalytic properties of the materials.

07-0-05 - A novel synthesis strategy leading to the formation of stable

transition-metal-oxide mesostructures
X.S. Zhao (a), J. Drennan (b) and G.Q. Lu (a)
a Nanomaterials Center and Department of Chemical Engineering, b Center for Microscopy
and Microanalysis, The University of Queensland, xiusongz@cheque.uq.edu.au, Australia.
This paper describes a new synthesis strategy of preparing thermally stable mesostructured
transition metal oxides, namely, two-step synthesis (TSS). Basically, the synthesis course
involves two steps: (1) formation of a mesostructured transition metal oxide solid mediated by
surfactant in a basic aqueous solution; and (2) treatment of the solid product in an acidic
organic solvent containing the respective precursor from which the solid product was
produced. The final material synthesized according to such a method is thermally stable and
structurally mesoporous with high surface area and uniform pores arranged disorderedly.

25 - Conversion of Aromatics (Tuesday pm)

25-O-01 - Shape-selective methylation of 4-methybiphenyl into 4,4'-

dimethybiphenyl over modified ZSM-5 catalysts
J.-P. Shen, L. Sun and C. Song
Clean Fuels and Catalysis Program, The Energy Institute, and Department of Energy & Geo-
Environmental Engineering, The Pennsylvania State University, USA, csong@psu.edu
A linear polycyclic compound, 4,4'-dimethylbiphenyl (4,4'-DMBP), is an intermediate for
making monomer of some advanced polymer materials, but the selective synthesis of 4,4'-
DMBP is difficult. In this work, modifications were made on a ZSM-5 zeolite for selective
methylation of 4-methybiphenyl (4-MBP) to form 4,4'-DMBP. The use of binder, deposition
of basic oxide such as calcium oxide over zeolite internal and external surface can effectively
improve the product selectivity. An isomorphous substitution of ZSM-5 framework AI with
Fe by a post-synthetic treatment, coupled with modification of external and internal surface
by P or Ca leads to high-performance catalyst with stable activity and superior selectivity for
synthesis of 4,4'-DMBP by 4-MBP methylation.
152

25-0-02 - Facile Friedei-Craft's alkylation of phenol with 4-hydroxybutan-

2-one over 13 and Y zeolites to produce raspberry ketone
K.K. Cheralathan, I.S. Kumar, B. Arabindoo, M. Palanichamy and V. Murugesan*
Department of Chemistry, Anna University, Chennai, India- v murugu@hotmail.com

Friedel-Craft's alkylation of phenol with 4-hydroxybutan-2-one was investigated over HI3,

HY and Zn 2+ and Fe 3+ ion exchanged [3 and Y zeolites. The expected para-alkylated product
raspberry ketone [4-(4-hydroxyphenyl)butan-2-one] was obtained regioselectively over HI3
(SIO2/A1203=10) catalyst in 77% yield. The para product is formed not only by direct
alkylation but also by the facile rearrangement of O-alkylated product. HY and cation
exchanged catalysts yielded O-alkylated, para-alkylated and small amount of ortho-alkylated
products.

2 5 - 0 - 0 3 - Selective alkylation of naphthalene to 2,6-dimethylnaphthalene

catalyzed by M T W zeolite
G. Pazzuconi a, G. Terzoni b, C. Perego a and G. Bellussi a
a EniTecnologie S.p.A., San Donato Milanese, gpazzuconi@enitecnologie.eni.it, Italy
b EniChem S.p.A., San Donato Milanese, Italy

The methylation of naphthalene and methylnaphthalene with zeolitic catalysts was studied.
The main purpose was to achieve a selective synthesis of 2,6-dimethylnaphthalene (2,6-dmn).
The alkylation of naphthalene with methanol didn't give interesting results. Best performances
were obtained with 1,2,4-trimethylbenzene as solvent/reagent, together with methanol. In
such chemical system, among several medium and large pore zeolites, MTW stands out for
both activity and selectivity to 2,6-dmn. As transalkylation is the main reaction, this behavior
can be explained if a restricted transition state shape selectivity takes place.

2 5 - 0 - 0 4 - Transalkylation reaction of phenol with trimethylbenzenes over Y

and EMT zeolites
V. Hulea (a), I. Fechete (a), P. Caullet (c), H. Kessler (c), T. Hulea (a), C. Chelaru (b), C.
Guimon (d) and E. Dumitriu (a)
a Iasi Technical University, Iasi, vhulea@ch.tuiasi.ro~ Romania; b Institute of
Macromolecular Chemistry, Iasi, Romania; c Ecole Nationale Sup~rieure de Chimie de
Mulhouse, France ; d Laboratoire de Physico-Chimie MoHculaire, Pau, France

The catalytic properties of dealuminated Y and EMT-type zeolites for the vapor phase
transalkylation reaction of phenol with the trimethylbenzenes were investigated. The
influence of the reaction temperature, the degree of dealumination and the concentration of
acid sites, and the nature of the TMB isomer, were taken into account. High catalytic
performances (activity and selectivity to cresols) and good resistance to coking of the
dealuminated zeolites were observed.
 153

2 5 - 0 - 0 5 - Benzene alkylation with alkanes over modified MFI catalysts

A.V. Smirnov, E.V. Mazin, O.A. Ponomoreva, E.E. Knyazeva, S.N. Nesterenko and I.I.
Ivanova*
Chemistry Department, Moscow State University, iiivanova@phys.chem.msu.ru
Benzene alkylation with ethane, propane and i-butane has been studied on acidic H-MFI
zeolite with SIO2/A1203 ratio of 104; mixed (H-MFI + Pt/CeO2) catalytic systems and Pt/H-
MFI bifunctional catalysts with Pt content of 0.3 %. In some of the experiments, hydride-
forming metals (M) were added to the catalytic systems to ensure H2 removal from the
reaction zone. The conversion of alkanes and the selectivity to the products of direct addition
was found to increase in the following order of catalytic systems: H-MFI < (H-MFI +
Pt/CeO2) < Pt/H-MFI < (Pt/H-MFI + M). The reactivity of alkanes increased in the following
order of reactants: C2H6 < C3H8 < C4HI0; while their alkylating ability was found to increase
in the reverse order.

1 9 - Diffusion: Fundamentals Approach (Tuesdaypm)

19-K-01 - Use of ~H N M R imaging to study the diffusion and co-diffusion of

gaseous hydrocarbons in H Z S M - 5 catalysts
P. N'Gokoli-Kekele (a), M.-A. Springuel-Huet (a), J.-L. Bonardet (a), J.-M. Dereppe (b) and
J. Fraissard (a)
~Laboratoire S.I.E.N, Universit6 P. et M. Curie, Paris, bonardet@ccr.jussieu.fr, France
6Laboratoire de Chimie-Physique et Cristallographie, Universit6 Catholique de Louvain-la-
Neuve, Belgium
IH NMR imaging has been used to study the diffusion of pure hydrocarbons (benzene, n-
hexane,) during their adsorption in or desorption from a fixed bed of zeolite crystallites. This
technique is used to visualize the progression of the diffusing molecules in the zeolite bed and
to determine their intracrystallite diffusion coefficients. In the case of competitive adsorption,
it gives the time dependence of the distribution of the two coadsorbed gases.

19-O-02 - Studies of adsorption, diffusion and molecular simulation of

cyclic hydrocarbons in MFI zeolites
L. Song (a), Z.L. Sun (b) and L.V.C. Rees (a,*)
a Chemistry Department, University of Edinburgh, West Mains Road, Edinburgh EH93JJ, UK,
Lovat.Rees@ed.ac.uk; b Applied Chemistry Department, Fushun Petroleum Institute, Fushun,
Liaoning, 113001, P.R. China

The adsorption and diffusion of C6-C8 aromatics and alkylcyclohexanes in MFI zeolites have
been investigated systematically using a gravimetric balance and the frequency-response (FR)
technique respectively. The packing arrangements patterns of these sorbate molecules in
silicalite-1 at different loadings were also simulated using the Solid_Docking software
package in InsightII, which combined MD, MC and EM techniques, developed by MSI. The
configurations derived from the calculations are shown in detail.
 154

19-O-03 - The effect of silanisation on the intraerystalline diffusivity of

ZSM-5
W.L. Duncan and K.P. M611er
University of Cape Town, South Africa warwick@chemeng.uct.ac.za
Deposition of silane on a zeolite's external surface is a well-established method of increasing
its shape selective properties by increasing diffusion resistances. In this work, the
intracrystalline diffusivities of both parent and silanised ZSM-5 samples are measured by the
zero length column technique. It is found that the apparent intracrystalline diffusivity does
decrease in the modified samples. This change'is either the result of a surface barrier caused
by pore mouth narrowing or an increase in intracrystalline tortuosity as a result of pore
blockage. It was attempted to clarify the dominant mechanism by considering various
mathematical models.

19-O-04 - Interference microscopy as a tool of choice for investigating the

role of crystal morphology in diffusion studies
O. Geier l, S. Vasenkov l, E. Lehmannl, j. K/~rgerl, R.A. Rakoczy 2 and J. Weitkamp 2
t Universitcit Leipzig, kaerger@physik, uni-leipzig.de; 2Universitgit Stuttgart, Germany
Interference microscopy is applied to carry out investigations of the influence of the regular
intergrowth effects commonly observed in large silicalite crystals on adsorption/desorption of
adsorbate molecules. The intracrystaline concentration profiles measured by the interference
microscopy during adsorption of isobutane are compared with those simulated using the
Monte Carlo method. The comparison of the simulated and the measured profiles allows to
rule out the uptake of isobutane from gas phase into silicalite crystals directly through the
internal interfaces separating the intergrowth sections of the crystals.

1 9 - O - 0 5 - Estimation of the interphase thickness and permeability in

polymer-zeolite mixed matrix membranes
A. Erdem-$enatalar, M. Tather and ~.B. Tantekin-Ersolmaz
Istanbul Technical University, Maslak, Istanbul, (aerdem@itu.edu.tr), Turkey
A method for determining the effect of particle size on the effective permeability values of
zeolite-polymer mixed matrix membranes has been developed in this study. The model
presented is a modified form of the effective medium theory, including the permeability and
thickness of an additional phase, the interphase, which is assumed to surround the zeolite
particles in the polymer environment. The interphase thickness and permeability values were
determined by taking into consideration the assumptions that in case the size of the zeolite
particles is held constant, the interphase thickness should be equal for different gases and in
case the zeolite particle size is varied, the interphase permeability should remain constant for
the same gas. The model seems to fit the experimental permeability data for O2, N2 and CO2
in the silicalite-PDMS mixed matrix membranes well.
 155

1 6 - Modelling and Theoritical Studies B (Tuesday pm)

16-O-01 Simulating shape selectivity in alkane hydroconversion by zeolites

M. Schenk a, T.L.M. Maesen b and B. Smit a
aDepartment of Chemical Engineering, Universiteit van Amsterdam, Nieuwe Achtergracht
166, 1018 WVAmsterdam, The Netherlands
bChevron Research and Technology Company, Richmond, CA, USA

Using configurational-bias Monte Carlo simulations we quantify how molecular sieves shape
selectively modify the free energy of formation of adsorbed hydrocarbons. This allows for a
basic thermodynamic analysis to explain the differences in alkane hydroconversion between
MFI- and MEL-type molecular sieves, and regularities in the alkane yields of TON-type
molecular sieves.

16-O-02- Molecular dynamics of the faujasite (111) surface

B. Slater and C.R.A. Catlow
Davy-Faraday Research Laboratory, The Royal Institution of Great Britain,
ben@ri.ac.uk, United Kingdom

We report classical molecular dynamics results for the most stable faujasite surface, which
dominates in the crystalline morphology. The changes that occur at external apertures (which
provide access to the crystal interior/exterior for select molecules) at ambient temperatures are
interpreted in the context of recent calculations on the adsorption of benzene at this surface.

16-O-03 - Adsorption of xylene isomers and water in faujasites. A molecular

simulation study
S. Buttefey, A. Boutin and A.H. Fuchs
Laboratoire de Chimie Physique, Orsay, France, fuchs@lcp.u-psud /k

Grand canonical ensemble Monte Carlo simulations of the adsorption properties of several
model faujasite zeolites were performed using the statistical bias method. The results enable a
better understanding of the effect of cation exchange in the selective adsorption of binary
mixtures of para and meta xylene isomers. We predict that adding a small amount of water
molecules could enhance the adsorption selectivity in favour of p-xylene.
156

16-O-04 - Reaction dynamics in acidic zeolites: room t e m p e r a t u r e tunneling

effects
J.T. Fermann and S.M. Auerbach
University of Massachussets, Amherst, MA 01003 (fermann@chem. umass, edu)

We present recommendations for accurately and efficiently calculating transition state

parameters for proton transfer reactions in zeolites. DFT with the B3LYP functional gives
accurate structures and vibrational frequencies. MP2 energies in larger basis sets are
augmented with MP4 energies in more limited basis sets to yield accurate classical barrier
heights. Even after correcting for the effect of long range interactions, our barrier heights are
significantly larger than those reported in the experimental literature. By evaluating proton
transfer rate coefficients using semiclassical transition state theory, we attribute the
discrepancy to neglect of tunneling in the interpretation of experimental data.

16-O-05 - M o l e c u l a r modeling of m u l t i c o m p o n e n t diffusion in zeolites and

zeolite m e m b r a n e s
M.J. Sanborn, A. Gupta, L.A. Clark and R.Q. Snurr
Department of Chemical Engineering, Northwestern University, Evanston, IL 60208 USA

Molecular dynamics (MD) simulations have been used to simulate non-equilibrium binary
diffusion in zeolites. Highly anisotropic diffusion in boggsite provides evidence in support of
"molecular traffic control." For mixtures in faujasite, Fickian, or transport, diffusivities have
been obtained from equilibrium MD through appropriate correlation functions and used in
macroscopic models to predict fluxes through zeolite membranes under co- and counter-
diffusion conditions. For some systems, MD cannot access the relevant time scales for
diffusion, and more appropriate simulation techniques are being developed.

0 5 - Synthesis of N e w Materials (Tuesdaypm)

05-O-01 - SOMS: Sandia octahedral molecular sieves. A new class of ion

e x c h a n g e r s selective for the removal of Sr 2+ from waste streams
T.M. Nenoff a, M. Nyman a, A. Tripathi b, J.B. Parise b,c, W.T.A. Harrison d and R.S. Maxwell e
a Sandia National Labs, Alb., NM 87185-0755, USA, tmnenof@sandia.gov
b Dept. ofGeosciences, CDept. of Chemistry; SUNY-.Stony Brook, NY 11790, USA
d Dept. of Chemistry, University ofAberdeen, UK; e LLNL, Livermore, CA 94551, USA

We report on a new class of Sandia Octahedral Molecular Sieves (SOMS). The niobate-based
sieves have a Na/MmV/Nb (M = Ti, Zr) oxide framework, with variable MlV:Nb (1:50-1:4)
ratios, exchangeable Na cations and H20 in open channels. Synchrotron X-ray, NMR, thermal
and elemental analyses were combined to solve the structure of SOMS-I" Na16Ti3.2Nb12.8044.8
(OH)3.2o8H20. SOMS have extreme selectivity for divalent cations. The ion-exchanged SOMS
undergo direct thermal conversion to perovskite-type phases, indicating a promising new
method for removal and immobilization of radioactive Sr-90 and industrial RCRA metals.
 157

0 5 - 0 - 0 2 - Hydrothermal synthesis of various titanium phosphates in the

presence of organic amine templates
Yunling Liu, Yunlong Fu, Jiesheng Chen, Yongcun Zou and Wenqin Pang*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, P R. China. E-mail. wqpang@mail.jlu.edu.cn

By varying the amine used as a structure-directing agent, the reaction temperature and the
composition of the reaction mixture, a number of titanium phosphates (TiPO4-Cn, n=l-13)
with a new structure have been obtained. The products were characterized by means of X-ray
diffraction, scanning electron microscopy, IR spectroscopy, inductively coupled plasma
characterization, thermogravimetric and differential thermal analyses and single crystal
structure characterization. Structural characterization indicates that TiPO4-Cn crystals are
invariably composed of octahedral TiO6 and tetrahedral PO4 units.

0 5 - 0 - 0 3 - On the role of azamacrocycles and metal cations in the syntheses

of metalloaluminophosphates STA-6, -7 and - 8
R. Garcia, a E.F. Philp, a A.M.Z. Slawin, a P.A. Wright a'* and P.A. Cox b
aSchool of Chemistry, The University of St. Andrews, UK, paw2@st-andrews.ac.uk
b Centrefor Molecular Design, University of Portsmouth,, Hants, UK

The azaoxamacrocycle 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (K22) and the aza-

macrocycle 1,4,8,11-tetramethyl-l,4,8,11-tetraaza-cyclotetradecane (tmtact) act as structure
directing agents in the hydrothermal crystallisation of metalloaluminophosphates (MAPO's).
K22 templates a CoAPO (STA-8) with the MSO framework topology. The crystalline
products using tmtact depend strongly on the metal cations added. Nickel and rhodium may
be incorporated, complexed by the macrocycle, within STA-6 and STA-7.

05-O-04 - Chiral transference and molecular recognition in novel

Co(en)3Cl3-templated zinc phosphates
Jihong Yu, Yu Wang, Zhan Shi and Ruren Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, rrxu@mail.jlu.edu.cn, People's Republic of China
Two novel zinc phosphates, [ZngP6024C1][Co(en)3]'2H20 (I) with 3-dimensional open-
framework structure and [Zn6PsO32Hs]'2[Co(en)3] (II) with 2-dimensional layered structure,
have been hydrothermally prepared using a racemic Co(en)3C13 complex as the template and
structurally determined by single-crystal X-ray diffraction. This work gives a nice example of
how recognition phenomena between an organometallic chiral guest and an inorganic host
framework or network can lead to crystallization of structures that retain the chiral character
of the guest.
158

0 5 - 0 - 0 5 - Very open microporous materials: from concept to reality

A.K. Cheetham(c), H. Fjellvfig(a), T.E. Gier(b), K.O. Kongshaug(a), K.P. Lillerud(a*) and G.
D. Stucky(b)
a Chemistry, University ofOslo, P.O Box 1033 Blindern, N-0315 Oslo, Norway
bDepartment of Chemistry, University of California, Santa Barbara, CA 93106, USA
cMaterials Research Laboratory, University of California, Santa Barbara, CA 93106, USA

Two new zeolite topologies named, OsloSantaBarbara-1 and -2 are presented. These
structures are base on 3-ring architectures. OSB-1 is the first example of a zeolite topology
constructed from 3-rings only, The 14-ring channels are chiral and formed by a double helix
chain out of 3-rings. The OSB-2 structure possess the most open, non interrupted, frame-work
ever, FDsi OSB-2 = 12.7. OSB-1 has the same low FDsi as FAU.

26 - Catalysis for Oil Refining (Wednesday am)

26-O-01 - The isomerization selectivity in F C C process

L.-J. Yan, M.-Y. He, J. Fu and J. Long
Research Institute of Petroleum Processing, hemingyuan@ripp-sinopec.com, P R China

The chain mechanism of n-hexane cracking has been studied. A parameter "cracking chain
length" (CCL) has been proposed and used to correlate with bi-molecular reactions and
isomerization selectivity. The effects of zeolite structure on the mechanism of n-hexane
cracking and CCL have been studied. Catalyst design is based on the understanding of the
chain mechanism of the cracking reactions and the correlation between CCL and zeolite
properties. A new series of catalysts GOR has been developed and commercially applied in a
number of FCC units.

2 6 - 0 - 0 2 - Design of zeolite catalyst for paraffin isomerisation

J. Hou~vi6ka, C.J.H. Jacobsen and I. Schmidt
Haldor Topsoe A/S, Lyngby, Denmark

Mesoporous zeolites are novel materials. They consist of large, single crystals, each with an
2
internal mesopore system with specific surface areas above 100 m / g . These mesoporous
zeolites are more active isomerisation catalysts than ordinary zeolites of a similar
composition, this being ascribed to lower diffusion limitations, particularly in the case of
longer paraffins and narrow pore zeolites. The higher activity is achieved by the large number
of active sites in the pore mouths which are easily accessible via the mesopores. External OH-
groups are too weak acids to be active in isomerisation. This conclusion is reached as the
selectivity pattern remains unchanged despite the very large external surface area.
 159

2 6 - 0 - 0 3 - Cyciohexane ring opening on metal-zeolite catalysts

T.V. Vasina (a), O.V. Masloboishchikova (a), E.G. Khelkovskaya-Sergeeva (a), L.M.
Kustov(a) and P. Zeuthen (b)
(a) N.D.Zelinsky Institute of Organic Chemistry, Moscow, Russia- LMK@IOC.AC.RU
(b) Haldor Topsoe A/S, Lyngby, Denmark

Various zeolite catalysts (H-ZSM-5, H-MOR, H-Beta, La-FAU) modified with noble metals
(Pt, Pd, Rh, Ru) were tested in ring opening of cyclohexane. Methylcyclopentane, gas
products (CI-C4), n-hexane, and isohexanes were shown to be the main reaction products. The
highest ring opening selectivity was found for Pt/H-ZSM-5, Rh/H-ZSM-5, and Pt/H-Beta
catalysts. The metals reveal the following order of ring-opening activity: Pt ~ Rh > Pd >> Ru
~ Ni. Acidity was found to be important for achieving reasonable activity in ring opening of
cyclohexane and simultaneous isomerization into methylcyclopentane and isohexanes.

2 6 - 0 - 0 4 - Selective ring opening of naphthenic molecules

M. Daage, G.B. Mc Vicker, M.S. Touvelle, C.W. Hudson, D.P. Klein, B.R. Cook, J.G. Chen,
S. Hantzer, D.E.W. Vaughan and E.S. Ellis
ExxonMobil Research and Engineering, USA

Selective Ring Opening (SRO) requires that only one C-C bond internal to each naphthene
ring is broken thereby preventing molecular weight reduction. Alkylcylopentanes (RC5) SRO
can be readily achieved by hydrogenolysis on noble metal catalysts. Under similar conditions,
alkylcyclohexanes (RC6) SRO is very slow and requires the addition of a controlled
isomerization, i.e. a non-branching ring contraction. Non-branching ring contraction can be
achieved using mesoporous crystalline materials, such as high Si/AI ratio faujasitic zeolites.
We found that high activity hydrogenolysis catalysts, such as Ir, coupled with a mesoporous
high Si/AI faujasite such as ECR-32 outperform conventional bifunctional catalysts for the
selective conversion of naphthenes to acyclic paraffins.

26-0-05 - Reforming of FCC heavy gasoline and LCO with novel

borosilicate zeolite catalysts
C.Y. Chen and S.I. Zones
Chevron Research and Technology Co., Richmond, CA, USA, cych@chevron.com

In this paper we report the application of novel borosilicate zeolites in reforming of FCC
heavy gasoline and light cycle oil (LCO). In this new technology, the borosilicate zeolite
catalysts show breakthroughs in activity, selectivity, sulfur-tolerance and stability in terms of
reforming these feedstocks which are unusually heavy and contaminated for conventional
reforming processes. This new technology demonstrates the value of combining advanced
catalytic materials with novel engineering processes to meet the demand for making advances
in product-generating technologies.
160

21 - Nanocomposite Fundamentals and Applications (Wednesday am)

21-K-01 - Zeolite-based nanocomposites: synthesis, characterization and

catalytic applications
B.V. Romanovsky
Chemistry Department, Moscow State University, bvromanovsky@phys.chem.msu.ru, Russia
The oxidative in-situ degradation of mono and polynuclear complexes of transition metals
within the Y zeolite supercages has been employed to produce an array of oxide nanoclusters
encapsulated in the intercrystalline voids of the matrix. The resulting materials were
characterized by using a number of experimental techniques. The nanocomposites synthesized
by such a way display extraordinary high activities in the model reactions of CO and MeOH
oxidation.

2 1 - O - 0 2 - Methods of synthesis for the encapsulation of dye molecules in

molecular sieves
M. Wark (a), M. Ganschow (a), Y. Rohlfing (b), G. Schulz-Ekloff (a) and D. W6hrle (b)
a Institute of Applied and Physical Chemistry, University of Bremen, Germany,
mwark@chemie, uni-bremen,de
b Institute of Organic and Macromolecular Chemistry, University of Bremen, Germany

Several methods for the stable encapsulation of various dyes in different molecular sieve hosts
were successfully developed. The dye molecules are monomerically included in the void
structure of the molecular sieves. The high variability in the anchoring method togethe r with
the possibility to tune the morphologies of the molecular sieves will be of importance
regarding the potential applications of these composites in optical micrometer-sized devices.

2 1 - O - 0 3 - M C M - 4 1 silica monoliths and diluted magnetic semiconductors" a

promising union for fabricating nanosized quantum wires
F. Brieler(a), M. Brehm (a), L. Chen (c), P.J. Klar(c)*, W. Heimbrodt(c) and M. Fr6ba(a,b)*
(a) Institute of Inorganic and Applied Chemistry, University of Hamburg, Hamburg, Germany
(b) Institute of Inorganic Chemistry, University of Erlangen-Nuremberg, Erlangen, Germany
Fr~176 (c) Department of Physics and Materials Science
Centre, Philipps University of Marburg, Marburg, Germany

Here we report on the first synthesis and characterization of nanostructured Cd~.• • within
the mesoporous system of MCM-41 silica. Several characterization techniques (e.g. TEM,
XRD, nitrogen physisorption, x-ray absorption and PLE spectroscopy have been applied to
show the preservation of the pore structure as well as to investigate the structure and physical
properties of the included diluted magnetic semiconducting guest species. The obtained
results reveal a coating of the inner surface of the mesoporous silica matrix by CdS which is
almost statistically doped with magnetic localised Mn 2§ ions.
 161

2 1 - O - 0 4 - Potential microlasers based on AIPO4-5/DCM composites

O. WeiBa, F. Schtith a, L. Benmohammadi b and F. Laeri b
aMax-Planck-Institut fi2r Kohlenforschung, 45470 Miilheim,
schueth@mpi-muelheim, mpg.de, Germany,
bDarmstadt University of Technology, 64289 Darmstadt,, Germany
Via in situ inclusion perfect hexagonal grown A1PO4-5 crystals were loaded with the laser dye
DCM. The highest dye concentration is located in the middle of the crystals decreasing to the
ends, showing that the dye is icluded in the early times of crystals growth. As DCM exceeds
the pore diameter of A1PO4-5 (7,3 A) mesopores are induced during incorporation.
Spectroscopic investigations proved the alignment of the dye molecules within the one-
dimensional channel system of the AFI structure. Data from literature show that DCM
undergoes trans-cis photoisomerization. As spectra of DCM in A1PO4-5 indicate the presence
of another absorbing species it is suggsted that a mixture of trans and cis DCM is present in
the pores.

21-O-05 - Light-emitting BN, Si, and SiC nanoparticles encapsulated in

molecular sieves
Xiaotian Li (a), C. Shao (a), F. Gao (a), S. Qiu (a*), F.-S. Xiao (a) and O. Terasaki (b)
a Department of Chemistry and Key Laboratory of Inorganic Synthesis and Preparative
Chemistry, Jilin University, Changchun 130023, sqiu@mail.jlu.edu.cn, China
b Department of Physics, Graduate School of Science, Tohoku University, Sendai 980-77,
Japan
Nanoparticles of Si, BN, and SiC encapsulated in zeolites, such as ZSM-5, L, APO-5, and
MCM-41, have been successfully prepared and strong visible photoluminescence (PL) have
been observed at room temperature. Analysis of the PL spectra leads us to proposing that the
transformation from indirect-gap semiconductor materials to quasi-direct-gap ones by
encapsulation in the channels of zeolites is the possible origins of the strong PL.

2 0 - Zeolite Membranes and Films (Wednesday am)

20-O-01 - Polyamines as strong covalent linkers for the assembly of mono

and double layers of zeolite crystals on glass
K. Ha, Y.S. Chun, A. Kulak, Y.S. Park, Y.-J. Lee, and K.B. Yoon*
Center for Microcrystal Assembly, Department of Chemistry, Sogang University, Seoul 121-
742, KOREA
Introduction of polyamines led to a remarkable increase in the strength of the binding between
the zeolite crystals and glass compared to those made by direct covalent linkages between the
surface-bound AP, EP, CP, and hydroxyl groups. Such a result is proposed to arise from the
ability of the large polyamine linkers to position in such a way between the two uneven
surfaces, that results in the large increase in the number of covalent linkage between the
multiple amine groups and the surface-bound EP or CP groups. Such a remarkable increase in
the binding between zeolite crystals and glass substrates allowed us successful assembly of
double layers of zeolite crystals.
162

2 0 - 0 - 0 2 - The use of seeds in the synthesis of mono-and bi-layered zeolite

membranes
L. Gora a, G. Clet b, J.C. Jansen a and Th. Maschmeyer a*
aLaboratory for Applied Organic Chemistry and Catalysis, DelfiChemTech, Delft University
of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
bLaboratoire de Catalyse et Spectrochimie, ISMRa, University of Caen 6, Bd du Mardchal
Juin 14032 Caen (cedex)- France
*tel..'+31 15 278 8826, fax.:+31 15 278 4289, e-mail: T.h.Maschmeyer@tnw.tudelft.nl

Supported zeolite Y, silicalite-1, A and a composite of silicalite-1 on A can be synthesised in

a membrane configuration in a reproducible manner. Synthesis techniques using seeds were
applied in the membrane preparation. The double layer type membrane has great potential in
the bifunctional operation in one integrated unit.

2 0 - 0 - 0 3 - Growth of oriented mordenite membranes on porous ct-AI203

supports
G. Li, X. Lin, E. Kikuchi and M. Matsukata*
Department of Applied Chemistry, Waseda University, mmatsu@mn.waseda.ac.jp, Tokyo,
Japan.

A highly oriented mordenite membrane with c-axis of crystals perpendicular to the support
surface was successfully prepared on a porous c~-alumina support. Seeding was essential to
form a compact layer of mordenite. Based on the XRD and SEM results, it was concluded that
"evolutionary selection" mechanism significantly contributes to the formation of a sharply
oriented mordenite layer. Pervaporation results for separation of a water/iso-propanol (10:90,
w/w) mixture showed highly preferential permeation (a=3615) of water through the oriented
mordenite membrane.

2 0 - 0 - 0 4 - Depth-sensitive structural study of silicalite-1 films with grazing

incidence X-ray diffraction
S. Mintova(a), T.H. Metzger(b) and T. Bein(a)
aDepartment of Chemistry, University of Munich, Butenandtstr. 11, 81377 Munich, Germany,
svetlana, mintova@cup, uni-muenchen, de
bEuropean Synchrotron Radiation Facility, ESRF, BP 220, Grenoble, France,
metzger@esrffr

The change of crystal orientation within different MFI zeolite film structures was followed
with the depth-sensitive grazing incidence diffraction technique. The measurements of the
adsorbed and grown zeolite films at different incident and exit angles reflect the distribution
of the crystal orientation along the film thickness. With increasing zeolite film thickness most
of the crystals change their b-axes orientation from parallel to perpendicular to the sample's
surface.
 163

20-0-05- Regeneration of supercritical carbon dioxide by alumina

supported MFI zeolite and mesoporous silica membranes
K.J. Chao *l, C.H. Kao I, Y.W. Chiu 2, X.R. Lin 2 and C.S. Tan .2
Departments of Chemistry I and Chemical Engineering 2, National Tsinghua University,
Hsinchu 300, Taiwan
e-mail." kjchao@mx, nthu. edu. tw

The regeneration of supercritical carbon dioxide from a mixture containing caffeine by

microporous MFI zeolite and mesoporous silica membranes supported on alumina was
studied. The experimental data show that a caffeine rejection higher than 90% or 70% and a
permeation flux of supercritical carbon dioxide more than 0.05 or 0.07 mol/mZ/s could be
obtained at 10.5 MPa.

0 9 - Crystal Structure Determination (Wednesday am)

09-O-01 - Localisation of K + ions in (Na,K)-LSX and K-LSX zeolites by

Rietveld analysis and 39K N M R spectroscopy. A new cationic site in the
orthorhombic dehydrated K-LSX at room temperature
J.L. Paillaud (a), P. Caullet (a), L. Delmotte (a), J.C. Mougenel (a), S. Kayiran (a) and B.
Lledos (b)
a Ecole Nationale Sup~rieure de Chimie de Mulhouse, JL.Paillaud@univ-mulhouse.fr,
France; b Air Liquide, Jouy-en-Josas, France
A LSX zeolite sample was studied under its as-made form and its fully exchanged potassium
form. Upon dehydration, a lowering of the symmetry is observable at room temperature. This
phenomenon was confirmed by MAS NMR spectroscopy. The structure reveals for the first
time a simultaneous occupancy of sites I and I' by potassium cations. This is due to a shift of
site I from the centre of the D6R unit. 39Kwide line NMR spectroscopy confirms the Rietveld
analysis, especially the absence of K + ions on site I in the as-made Na72,Kz4-LSXsample.

0 9 - 0 - 0 2 - N M R crystallography of AIPO4-CJ2
F. Taulelle and C. Huguenard
RMN et Chimie du Solide, UMR 7510 ULP-Bruker-CNRS, Universit6 Louis Pasteur, 4 rue
Blaise Pascal, 67070 Strasbourg Cedex, France. e-mail. taulelle@chimie.u-strasbg.fr

AIPO4-CJ2 is an aluminophosphate with an open framework structure. This compound has

been studied by in-situ NMR to follow its crystallogenesis. It has also been characterized
recently by different types of high resolution solid state NMR methods. F-P and F-A1 MAS
HETCOR have been used to prove the disordered nature of units building the solid, those with
a fluorine in bridging position and those with hydroxide at the same bridging positions.
A1PO4-CJ2 is considered here to illustrate its crystallographic structure determination by solid
state NMR of the powder. The main steps of NMR crystallography are described in this
contribution: topological analysis, space group and metric determination.
164

0 9 - 0 - 0 3 - FOS-5, a novel zeotype with 3D interconnected 12- ring channels

T. Conradsson, Xiaodong Zou and M.S. Dadachov
Structural Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden
An organically templated microporous germanium dioxide, FOS-5, with a novel zeotype
topology, [Ge32064]has been synthesised under hydrothermal conditions and characterised by
single-crystal X-ray diffraction and thermogravimetric analysis. The compound crystallizes in
the centred tetragonal space group I41/amd with a - 26.017(3), c = 27.218(3) A, V = 18421(4)
A 3 and Z=8. The structure is stable up to 723K, sufficiently high for the complete removal of
the organic guest molecules. Single-crystal diffraction data have been collected and the crystal
structures were successfully solved and refined for both the as-synthesised and the
detemplated forms. The compound has a three-dimensional framework structure, built up by
GeO4 vertex connected tetrahedra to form intersecting 12-membered ring channels along all
the three crystallographic axes. The free diameters of the channel apertures are 5.8 by 6.0 A
along both the [100] and the [010] directions and 6.4 A along the [001] direction. Fluorine
ions inserted in the [Ge8Ol6] double 4-rings are charge compensated by protonated
trimethylamine cations encapsulated in the large channels.

09-0-04- Neutron diffraction study of protons in four lanthanum

exchanged X and LSX zeolites
D.H. Olson a, B.H. Toby b and B.A. Reisner b
a) University of Pennsylvania, Philadelphia, dholson@seas,upenn, edu," b) NIST,
Gaithersburg, USA
The positions of protons and other extra-framework species in HLaLSX dehydrated at 200
and 400~ HLaNaLSX dehydrated at 515~ and LaX dehydrated at 200~ have been
determined by neutron powder diffraction. Four hydrogen sites have been found, three
framework and one nonframework a La-hydroxyl proton. The results are compared to IR
spectroscopic assignments. Protons have been located in the supercage bonded to the O1 and
02 oxygen atoms. For one material, HLaLSX dehydrated at 400~ protons were also found
bonded to 03 oxygen atoms.

0 9 - 0 - 0 5 - Optimized synthesis and structural properties of lithosilicate

RUB-29
S.H. Park ~ J.B. Parise ~ and H. Gies #
~ of Geosciences, +Chemistry Dpt, State University of New York at Stony Brook, USA,
# Institutf~r Geologie, Mineralogie, Geophysik, Ruhr-Universitdt-Bochum, Germany

The structure of a new member of the lithosilicate family, RUB-29

(Cs14Li24[LilsSi72Olv2]e 14H20), was determined using NMR spectroscopy, synchrotron single
crystal and neutron powder diffraction (NPD). The material contains Si- and Li-centered
tetrahedra segregated into alternating layer-like building units, producing a framework
containing a three dimensional system of channels bounded by 8- and 10-membered rings.
Lithium cations play an important role in the framework and in pore systems, and are
responsible for structurally and physico-chemically unique properties of the material.
 165

2 7 - Selective Oxidation and Sulfur Resistance (Thursday pm)

27-O-01 - Singular catalytic properties of Ti-MWW in the selective oxidation of

alkenes
P. Wu a, T. Komatsub, T. Yashimab and T. Tatsumi a
~Division of Materials Science & Chemical Engineering, Faculty of Engineering, Yokohama
National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama240-8501, Japan
bDepartment of Chemistry, Tokyo Institute of Technology, 2-12-10okayama, Meguro-ku, Tokyo
152-8551, Japan
Ti-MWW has been hydrothermally synthesized in the presence of boric acid and with piperidine as
a structure-directing agent. Acid treatment of the as-synthesized samples is necessary for removing
the extrafi'amework Ti species. Ti-MWW nearly flee of anatase species with Si/Ti ratio as low as 40
is prepared. Ti-MWW effectively catalyzes the oxidation of linear alkenes with H202, and also
shows a significant activity for the sterically demanding reactions such as oxidation of cyclohexene
with tert-butyl peroxide. Ti-MWW exhibits a singularity, never observed on the other titanosilicate,
that it selectively epoxidize the trans isomer in the oxidation of geometric mixture of cis/trans
alkenes.

2 7 - 0 - 0 2 - Epoxidation of propylene over TS-1 containing trace a l u m i n u m

Xinwen Guo, Xiangsheng Wang, Min Liu, Gang Li, Yongying Chen and Jinghai Xiu
State Key Laboratory,Dalian University of Technology, guoxw@dlut.edu.cn, Dalian, China
Titanium silicalite (TS-1) containing trace aluminum was successfully synthesized using
TPABr as the template and silicon sol as silicon source in a 100L stainless steel autoclave.
The synthesized TS-1 exhibits high activity and low selectivity for propylene oxide (PO) in
the epoxidation of propylene with dilute H202. The selectivity of PO can reach about 90 %
through adjusting the pH value of the reaction mixture. But, extra amount of basic substance
will make the utilization and the conversion of H202 decrease. The utilization of H202
increases after acid treatment for the low Si/Ti ratio TS-1, but the utilization of HzO2does not
change for the high Si/Ti ratio TS-1 in the epoxidation of propylene. Experimental results of
thermal-stability show that the as-synthesized TS-1 calcined between 540~ and 900~
exhibits high activity and thermal stability.

2 7 - 0 - 0 3 - One step benzene oxidation to phenol using N20 over acid zeolites
G. Juttu and R.F. Lobo
Department of Chemical Engineering, University of Delaware, lobo@che.udel.edu, Newark
DE, USA
We have investigated the gas phase partial oxidation of benzene to phenol over zeolite H-
MCM-22 using as the oxidant. H-MCM-22 is active (15% benzene conversion at 603 K) and
nearly 100% selective for the partial oxidation of benzene to phenol. We have also
investigated the reaction in an in-situ IR cell. Both benzene and phenol interact strongly with
the Bronsted acid site whereas does not interact strongly with the zeolite. We find the
presence of Bronsted acidity is critical for the reaction and we found no correlation of the
activity with the iron content, as reported previously by others.
166

2 7 - 0 - 0 4 - Dual pathways for benzene hydrogenation on Pt/mordenites:

implication for sulfur tolerance
L. Simon a'b, J.G. van Ommen b, A. Jentys a and J.A. Lercher a
a Technische Universitgit Miinchen, Garching, lercher@ch.tum.de, Germany
bFaculty of Chemical Technology, University ofTwente, Enschede, The Netherlands
The catalytic testing of Pt supported MOR with various Na+/H + ratio shows that benzene
hydrogenation occurs via two pathways (i) on metal sites and (ii) on Bronsted acid sites with
hydrogen spilt over from the close metal surface. In the presence of sulfur the metal surface is
poisoned and the catalytic activity remains on Bronsted acid sites. Due to a subtle balance
between a high Bronsted acid site concentration that deactivates the catalysts by coking and
metal sulfur poisoning and a low Bronsted acid site concentration, i.e., a low benzene
conversion on the acid sites, Pt supported on partially exchanged MOR showed a higher rate
of benzene conversion and a higher sulfur resistance than on all other catalysts.

27-0-05 - Sulfur resistance of PtPd catalysts: preparation, characterization

and catalytic testing
K. Thomas, C. Binet, T. Chevreau, D. Cornet and J.-P. Gilson
Laboratoire de Catalyse et Spectrochimie, ISMRA, Caen, France (gilson@ismra.fr)
Pt, Pd and PtPd metallic precursors are deposited on amorphous silica aluminas and
dealuminated FAU zeolites. The catalytic activity is measured in the hydrogenation of toluene
in the absence or presence of sulfur (200 ppm). In the absence of sulfur, alloying Pt with Pd
decreases the hydrogenation activity. In general, catalysts made from ammoniated precursors
are the most active with one remarkable exception. In the presence of sulfur, thioresistance is
a function of reaction temperature, i.e. sulfur coverage of the metallic phase. Pd increases
substantially the sulfur resistance. The effect of support acidity on thioresistance is observed
only at high sulfur coverage.

03 - New Methods of Zeolite Synthesis (Thursday pro)

03-K-01 - Application of combinatorial tools to the discovery and

commercialization of microporous solids: facts and fiction
J. Holm~ren a, D. Bern a, M. Bricker a, R. Gillespie a, G. Lewis a, D. Akporiaye b, I. Dahl b, A.
Karlsson ~ M. Plassen b and R.Wendelbo b
UOP LLC, jsholmgr@uop.com, Des Plaines, IL, USA; b SINTEF, Norway
During the past three years, combinatorial tools and methods have received increasing
amounts of attention as potentially enabling methodologies for the chemical industry. We
have developed an integrated End-to-End TM combinatorial catalyst discovery system, which
allows us to perform all the critical catalyst processing operations combinatorially. A critical
component of this system is a combinatorial multiautoclave assembly, which can be used to
explore hydrothermal space efficiently and effectively. Our recent results illustrate the
applicability of this capability to both the discovery and scale-up of microporous solids. The
expected impact of these combinatorial tools in new product commercialization and the
chemical industry will be discussed.
 167

03-0-02 - Mesoporous zeolites

C.J.H. Jacobsen, J. Hou~vicka, A. Carlsson and I. Schmidt*
Haldor Topsoe A/S, Nymollevej 55, DK-2800 Lyngby, Denmark

Mesoporous zeolite crystals have already been shown to exhibit promising properties in
catalytic processes, here, it is shown how mesoporous ZSM-5 crystals can be synthesized by a
variation of the Confined Space Synthesis method. It is discussed how the synthesis
conditions influence the morphology of the zeolites.High nucleation rates favour formation of
nanosized zeolites whereas low nucleation rates favour formation of mesoporous zeolites. In
this way, it is possible to obtain either large (1-10 ~tm) or small (100-500 nm) mesoporous
zeolite crystals. The structure and morphology of the mesoporous zeolite crystals are
illustrated by transmission and scanning electron microscopy. Mesoporous zeolites have high
mesopore volumes (0.8-1.2 ml/g) and high mesopore surface areas (100-200 mZ/g). The
advantages of mesoporous zeolite crystals as heterogeneous catalysts are discussed.

03-0-03 - Synthesis of novel zeolites SSZ-53 and SSZ-55 using organic

templating agents derived from nitriles
S.A. Elomari and S.I. Zones
Chevron Research & Tech. Co., elom@chevron.com, Richmond 94802 CA, USA

In our quest for finding novel high silica zeolites using amine-based structure-directing agents
(SDA) in our synthetic schemes, here we report a new class of SDA derived from
carbonitriles. This class of SDA was designed in an attempt to overcome making cage-like
zeolitic products commonly produced by using polycyclic rigid SDA or making other known
zeolites such as MFI and MTW usually produced by using freely rotating SDA. The use of
this class of SDA in zeolite synthesis did not only avoid making such materials, but has led,
among others, to new high silica large pore zeolites SSZ-53 and SSZ-55. In our presentation
we will describe these new SDA and their zeolitic products.

03-0-04 - Synthesis of IFR-type zeolites optimized for spectroscopic study

B.S. Duersch and L.W. Beck*
The University of Michigan, Department of Chemistry
930 N. University Ave., Ann Arbor, MI 48109-105.5 USA, * lbeck@umich.edu

The synthesis of highly ordered boron and aluminum containing materials of structure-type
IFR is presented. The IFR-type zeolite materials synthesized by this method have
exceptionally uniform particle size and crystal morphology. These materials exhibit improved
resolution by NMR characterization including the partial resolution of crystallographic T-sites
in these acidic frameworks. The preferred synthesis conditions are more concentrated than
previously reported and require much less SDA (ammonium cation). This synthesis procedure
is both flexible and reliable yielding large uniform single crystals. The high-resolution of the
NMR spectra indicate an unusual degree of short-range crystalline order for these materials.
168

03-0-05 - Competitive role of sodium and potassium cations during

hydrothermal zeolite crystallization from Na20-K20-AI203-SiO2-H20 gels
A.F. Ojo (a), F.R. Fitch (a), M. Btilow (a) and M.-L. Lau (b)
a BOC Gases Technology, adeola.~o@us.gtc.boc.com, Fax No. 908-771-6488, USA.
b Schering-Plough Research Institute, USA

Zeolites A, F, Q, X and sodalite were synthesized hydrothermally from NazO-K20-A1203-SiOz-

H20 gels. The crystallization processes were monitored as a function of the fraction of sodium
cations in the sodium-potassium cation gel system. Pure phases were obtained in three distinct
alkali composition ranges: zeolite A was.crystallized at Na20/(Na20+K20) - 0.9 to 1.0, zeolite
X at NazO/(NazO+K20) - 0.7 to 0.8, and zeolite F at NazO/(NazO+K20) < 0.5. The structure-
directing roles of these alkali cations, the phase evolution of products, as well as size and
morphology of the crystals are discussed.

2 2 - Advanced Materials (Thursday pro)

22-O-01 - The effect of the location of framework negative charge on the

ordering of templates in zeolite IFR
R.E. Morris and L.A. Villaescusa
School of Chemistry, University of St. Andrews, Purdie Building, St. Andrews, Scotland KY16
9ST; reml @st-and.ac.uk
The non-centrosymmetric ordering of benzylquinuclidinium structure directing agents inside
the centrosymmetric IFR framework has been shown by single crystal X-ray diffraction and
second harmonic generation measurements. The reasons behind this effect and the
requirements of the zeolite structural architecture needed to show this ordering are discussed.

22-0-02 - A new family of microporous vanadium phosphates and related

compounds with organic coordination
Shouhua Feng*, Zhan Shi, Lirong Zhang, Hui Zhao, Dong Zhang and Zhiming Dai
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, People's Republic of China, shfeng@mail.jlu.edu.cn
A new family of microporous vanadium phosphates and related compounds with organic
coordination were hydrothermally crystallized and their crystal structures were characterized
by single crystal X-ray diffraction. Structural diversity of these open inorganic-organic hybrid
materials derives from considerable variables for both inorganic and organic parts from the
point of view of syntheses and structures. Current study in this field showed great challenges
not only in crystal chemistry of microporous materials but also in biological properties such
as helical array and ligand exchange.
 169

2 2 - 0 - 0 3 - Catalytic properties of novel nickel(ll) phosphate with nano-

porous structure
J.-S. Chang, D.S. Kim, S.-E. Park, P.M. Forster, A.K. Cheetham b and G. Fereyc
aCatalysis Center for Molecular Engineering, Korea Research Institute of Chemical
Technology, Taejon, Korea," bMaterials Research Laboratory, University of California, Santa
Barbara, USA," Clnstitut Lavoisier, UMR CNRS 173, Universitd de Versailles Saint Quentin,
Versailles, France

Ni (II) phosphate, VSB-1, develops a unidimensional pore system which is delineated by 24

NiO6 and PO4 polyedra and the free diameter of the channel is estimated to be 8.8 A. It
becomes microporous on calcination in air at 350~ For cyclodimerization of 1,3-butadiene,
VSB-1 itself shows excellent selectivity for ethylbenzene. Reduced Ni-VSB-1 yields good
selectivity for hydrogenation of 1,3-butadiene to butenes and Pd-containing VSB-1 exhibit
good catalyst performance for direct production of H202 from H2 and O2.

2 2 - 0 - 0 4 - Characterization of corrosion-resistant zeolite coatings on A!

alloys
Huanting Wang, Zhengbao Wang, Xiaoliang Cheng, Anupam Mitra, Limin Huang, and
Yushan Yan
Department of Chemical and Environmental Engineering, University of California, Riverside,
CA 92521, USA, yushan, yan@ucr.edu.

Zeolite films have been developed for corrosion-resistant coatings on Al-alloys and other
metals. In present work, thermal and thermal shock stability, and mechanical properties
(cutting, impact, bending and abrasion) of ZSM-5 coatings on A1 alloys were investigated.
The results show that the coatings have good thermal/thermal-shock stability, adhesion and
wear-resistance, and are flexible to some extent. Therefore, zeolite coating is a potential
candidate for corrosion protection of A1 alloys and other metals.

2 2 - 0 - 0 5 - Template synthesis and catalysis of bimetallic platinum-rhodium

a n d - p a l l a d i u m nanowires in mesoporous materials
A. Fukuoka (a), Y. Sakamoto (a), S. Inagaki (b), N. Sugimoto (b), Y. Fukushima (b), and M.
Ichikawa (a)
a Hokkaido University, fukuoka@cat.hokudai.ac.jp, Sapporo, Japan; b Toyota Central R&D
Labs., Inc., Aichi, Japan

Template synthesis of transition metal nanowires in mesoporous materials is presented. Pt,

Rh, Pt-Rh, and Pt-Pd nanowires are synthesized in HMM-1 and FSM-16 by the
photoreduction method. The bimetallic nanowires in HMM-1 are alloy crystallite with a
necklace-like structure. The Pt-Pd wire/HMM-1 shows higher magnetic susceptibility at low
temperature than the Pt wire. In butane hydrogenolysis, Pt-Rh wire/FSM-16 shows high
selectivity to isobutane.
170

32 - Zeolite m i n e r a l s and H e a l t h Sciences (Thursday pm)

3 2 - O - 0 1 - B i o m e d i c a l a p p l i c a t i o n s of zeolites
*K. Pavelic 1, B. Subotic I and M. Colic 2
IRudjer Boskovic Institute, Zagreb, Croatia," 2Molecutec Corporation., Goleta, USA -
pavelic@rudjer, irb. hr

Natural and synthetic zeolites as well as other mesoporous and microporous solids are used in
many industrial and household applications. However, it is less known that in recent years
these exciting materials are increasingly being used in biomedical applications. In this review
different current and possible future biomedical applications, together with our own research
results obtained from studies of such materials, are critically described. Current needs for
synthesis and characterization of novel mesoporous and microporous materials which would
be better suited for biomedical applications are also described.

3 2 - 0 - 0 2 - Zeolites and other p o r o u s materials in the toxicity o f inhaled

m i n e r a l dusts
I. Fenoglio, L. Prandi, M. Tomatis and B. Fubini*
Dipartimento di Chimica IFM, Universitb di Torino, Torino, Italy-fubini@ch.unito.it

Some porous materials, typically fibrous erionite, are toxic per se. Others may be used as
"model solids" to mimic real pathogenic minerals. It has been hypothesized that erionite
catalyses free radical generation which damage DNA. Erionite released OH" only when
incubated with ferric iron. Iron mobility in asbestos has been studied by means of cyclic
voltammetry. Ferrosilicalite and one Fe-Y zeolite were "model solids" for iron mobility.
Porosils have been employed in the study of silica cytotoxicity. Cell growth inhibition
correlates with the outer surface, measured from particle morphology, but not with the BET
surface, suggesting particle-cell contact as a primary step in cell growth inhibition. MCM-41
with spin active labels, in contact with cells, acted as a sensor of phagocytosis, the active
nitroxide being quenched by cell generated oxidant.

3 2 - 0 - 0 3 - S t u d y of the reaction of a Ca-clinoptilolite and h u m a n bile

R. Sim6n Carballo (a), G. Rodriguez-Fuentes (b), C. Urbina (c) and A. Fleitas (a)
a Instituto Nacional de Angiologia y Cirugia Vascular, experim@infomed.sld.cu, Cuba
b Instituto de Materiales y Reactivos, Univ. La Habana, zeolitas@lae.ff.oc.uh.cu, Cuba
c Universidad Central de, curbina@electra.ciens.ucv, re, Venezuela

The calcium exchanged form of the purified natural clinoptilolite (NZ) from the Tasajeras
deposit, Cuba, is the active ingredient of a drug designed to reduce total blood cholesterol and
prevent atherosclerosis. The study of the Ca2+-NZ - human bile reaction has revealed that it
occurs through the adsorption of three major human bile compounds: bile acids,
phospholipids and bilirubin. The adsorption of phospholipids on the external surface of the
clinoptilolite crystals produces a phospholipids-zeolite interface with anionic activity that
allows the adsorption of bile acids.
 171

3 2 - 0 - 0 4 - In vitro adsorption of zearalenone by oetadecyldimethylbenzyl

ammonium-exchanged clinoptilolite-heulandite tuff and bentonite
A. Dakovic(a), M. Tomasevic-Canovic(a),V. Dondur(b), D. Stojsic(c) and G. Rottinghaus (d)
a ITNMS, cl.dakovic@itnms.ac.yu, Belgrade, Yugoslavia," b Faculty of Physical Chemistry,
Belgrade, Yugoslavia; c VMA Institute for Hygiene, Belgrade, Yugoslavia; d College
Veterinary Medicine, University of Missouri, Columbia, USA

Chemical modification of zeolitic tuff and bentonite with octadecyldimethylbenzyl ammonim

ion (ODMBA) increased adsorption of zearalenone (ZEN) as the levels of ODMBA
increased. The organozeolite required 10X less ODMBA than the organobentonite for
maximum ZEN adsorption (100%). In addition, changing the pH from 3 to 9 had little effect
on adsorption of ZEN on organozeolites.

3 2 - 0 - 0 5 - Zeolites in sexual confusion" slow release of pheromones

J. Mufioz-Pallares, E. Primo, J. Primo and A. Corma
Instituto de Tecnolog[a Quimica (C.S.I. C-UP. V), Valencia. Spain

Semiochemicals can be adsorbed in zeolites and their diffusion-desorption rate can be

controlled by modifying the physicochemical and structural parameters of zeolites. By
matching the nature of the semiochemical, its functional groups, and the framework, extra-
framework composition and pore topology of the zeolite, it is possible to design dispensers
that allow to achieve the adequate air concentration of the pheromone (the most important
group of semiochemical) within times long enough to be used for insect sexual confusion for
the preservation of crops.

3 0 - Environmental Catalysis (Friday am)

30-K-01 - The local structures of transition metal oxides incorporated in

zeolites and their unique photocatalytic properties
M. Anpo* and S. Higashimoto
Dept. Appl. Chem., Osaka Prefecture University, anpo@ok.chem.osakafu-u.ac.jp, Japan

Various microporous and mesoporous zeolite catalysts incorporated or encapsulated with

transition metal cations such as M o 6§ V 5+, or Ti 4+ into their frameworks or cavities were
synthesized by a hydrothermal synthesis method. In-situ spectroscopic techniques and
analyses of the photocatalytic reaction products have revealed that these transition metal
cations constitute highly dispersed tetrahedrally coordinated oxide species which enable the
zeolites to act as efficient and effective photocatalysts for the various reactions such as the
decomposition of NOx into N2 and 02 and the reduction of CO2 with H20 into CH3OH and
CH4. The charge transfer excited triplet state of these oxides, i.e., (Mo 5+- O')*, (V 4+ - O')*, and
(Ti 3§ O')*, was found to play a significant role in the unique and efficient photocatalytic
reactions on various zeolitic materials incorporated with Mo, V, or Ti oxide species.
172

3 0 - 0 - 0 2 - Characterization and performance of ex-framework FeZSM-5 in

catalytic N 2 0 decomposition
J. P6rez-Ramirez a'*, G. Mul a, F. Kapteijn a, I.W.C.E. Arends b, A. Ribera b and J.A. Moulijn a
a Industrial Catalysis, b Laboratory for Organic Chemistry and Catalysis, Delft University of
Technology, j.perezramirez@tnw.tudelfi.nl, The Netherlands

Catalytic N20 decomposition was investigated over FeZSM-5 prepared by a novel ex-
framework method. This method comprises the introduction of Fe in the MFI framework,
followed by calcination and steam treatment to extract the iron to extra-framework positions.
The ex-framework method induces superior activity for direct N20 decomposition, compared
to FeZSM-5 catalysts prepared by solid and aqueous ion-exchange methods. The
extraordinary catalytic performance of ex-FeZSM-5 is attributed to the highly dispersed state
of the Fe in the zeolite matrix and the Fe(III)/Fe(II) redox behaviour of a significant fraction
of the iron centers in the catalyst.

3 0 - 0 - 0 3 - Effect of carbon number in hydrocarbon reductant on the

selective catalytic reduction of NO over cation-exchanged MFI zeolites
A. Shichi, Y. Kawamura, A. Satsuma and T. Hattori
Applied Chemistry, Nagoya University, hattori@apchem.nagoya-u.ac.jp, Nagoya, Japan
In order to examine the possibility of using higher hydrocarbon as a reductant for the selective
catalytic reduction of NO, the effect of carbon number in n-alkane was investigated over Cu-,
Ag- and Co-MFI zeolites. On all the catalysts, NO conversion showed a volcano-type
correlation to the carbon number in n-alkane, although the carbon number at maximum NO
conversion varied with the exchanged cation species and the presence of water vapor. The NO
conversion increased with increasing carbon number, while the deactivation by carbonaceous
deposition and/or strongly adsorbed species became significant. The catalyst deactivation
could be suppressed by the presence of water vapor and by periodic SCR reaction operation.

3 0 - 0 - 0 4 - The temperature-dependent storage of NOx on metal-containing

zeolites under dry and wet conditions
R. Fricke, M. Richter, E. Schreier, R. Eckelt and H. Kosslick
Institute of Applied Chemistry (ACA), Berlin, Germany-fricke@aca-berlin.de
The development of new catalysts for the storage and reduction of NOx from lean-burn
engines is a challenge to meet the demands of the Euro IV norm in 2005. The new catalyst
systems should also be able to adsorb NO• already at comparable low temperature and desorb
it at high temperature. Cu and Ba exchanged zeolites of various types (Y, MOR, MFI, L,
CHA) and their ability to adsorb NOx isothermally from a dry feed and to desorb it under
temperature-programmed conditions (55-600~ are described. Their NOx adsorption
/desorption properties under wet conditions are compared. Furthermore, a zeolite material
modified by manganese oxide is developed which is able to adsorb NOx from a wet feed
already at temperatures as low as 120 ~ and desorb it above 350~
 173

3 0 - 0 - 0 5 - Catalytic destruction of chlorinated VOCs. Influence of

characteristics of Pt/HFAU catalysts on the destruction of dichloromethane
L. Pinard, J. Tsou, P. Magnoux and M. Guisnet
Laboratoire de Catalyse en Chimie Organique, UMR CNRS 6503, patrick.magnoux@univ-
poitiers fr, France
Catalytic oxidation of dichloromethane (1000 ppm, 4% steam) was investigated over a series
of Pt/HFAU catalysts differing by their Pt content (from 0 to 1.0wt%) and their framework
Si/A1 ratio (5, 17, 47 and 100). The higher the reaction temperature, the faster the CH2C12
oxidation. For a given zeolite support, the rate of CH2C12 transformation is independent of the
platinum content. On the other hand, the CH2C12 oxidation into CO2 appears as a bifunctional
mechanism: the oxidation rate increases firstly with the Pt content (or nPt) then remains
constant above a certain value of nPt. The support plays also an active role for this oxidation:
the higher the zeolite acidity, the faster the CH2C12 oxidation. Furthermore, Lewis acid sites
seem to intervene in a positive way for CH2C12 transformation.

2 8 - Confinement and Physical Chemistry for Catalysis (Friday am)

28-O-01 - Reactivity enhancement by molecular traffic control- a

consequence of released single-file constraints
P. Br~uer and J. K~irger
Universitcit Leipzig, Abteilung Grenzfldchenphysik, Linndstrasse 5, D-04103 Leipzig,
kaerger@physik, uni-leipzig, de, Germany
Reactivity enhancement by molecular traffic control has been postulated to occur as a
consequence of the reduced mutual transport inhibition if reactant and product molecules are
able to use different pathways. Representing the catalyst as a network of intersecting single-
file systems, the concept of molecular traffic control is investigated quantitatively. Differences
in the accommodation probability of the reactant and product molecules in the individual
single-file systems are in fact found to lead to the predicted output enhancement of product
molecules. This gain in reactivity is correlated with the establishment of concentration
gradients which counteract transport inhibition by single-file confinement.

2 8 - 0 - 0 2 - Aromatization of n-hexane over Z n N i / H Z S M - 5 catalyst induced

by microwave irradiation
J.Z. Gui (a), H.S. Ding (a), N.N. Liu (a), Y.R.Gao (a), Z.L. Cheng (a), X.T. Zhang (a), B. Ma
(a), L. Song (a,b), Z.L. Sun (a,*) and L.V.C. Rees (b)
a Dept. of Appl. Chem., Fushun Petroleum Institute, Fushun, P . R . China,
zlsun@mail.fsptt.ln.cn, b Dept. of Chem., The University of Edinburgh, Edinburgh, UK
The aromatization of n-hexane over a ZnNi/HZSM-5 catalyst has been investigated using two
different heating methods; microwave irradiation heating and conventional heating. The
characteristics of the ZnNi/HZSM-5 catalysts prepared under the two heating methods
respectively have also been studied using XRD, BET and TGA techniques. The influence of
the microwave on the properties and the catalytic performance of the catalysts were given in
details. The reaction mechanisms were also discussed.
174

2 8 - 0 - 0 3 Artificial photosynthesis using zeolites

N. Castagnola and P.K. Dutta
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210,
Dutta. l @osu. edu

The goal of this study is to assemble a chemical architecture that can split water into hydrogen
and oxygen using sunlight. Zeolites provide opportunities for novel spatial arrangement of
molecules. The photochemical process begins with electron transfer from sensitizers to
acceptor molecules in the zeolite. We find that the short-circuiting back electron transfer
process is significantly slower in the zeolite and the intrazeolitic packing of the acceptor
molecules also leads to long-lived charge separation and the charge-separated species can be
chemically exploited by suitable catalysts. The challenge is to incorporate all these elements
of the system into a single architecture and we are examining zeolite membranes for this
purpose.

2 8 - 0 - 0 4 - Synthesis of macrocycles using molecular sieve catalysts

M. Radha Kishan, N. Srinivas, S.J. Kulkarni*, M. Ramakrishna Prasad, G. Kamalakar and
K.V. Raghavan.
Catalysis Group, Indian Institute of Chemical technology, Hyderabad, India

For the first time we report the synthesis of macrocycles like calixpyrrole, cyclotriveratrylene
(CTV), cyclotetraveratrylene (CTTV), porphyrine etc over molecular sieve as a catalyst.
Calixpyrroles are synthesized from pyrrole and a ketone like acetone over MCM-41 under
reflux conditions using suitable solvent. In case of MCM-41 cyclic calixpyrroles were
obtained. On the other hand due to shape selectivity in case of Y zeolite linear di-, tri- and
tetra- polypyrroles were obtained and cyclic tetramers were not observed. The mechanism of
the synthesis of calixpyrrole is either by the dimerization of dimer with simultaneous
cyclization to cyclic tetramer or cyclization of linear tetramer via recoil phenomenon.

2 8 - 0 - 0 5 - Effect of single-file diffusion on the hydroisomerization of

2,2-dimethylbutane on platinum loaded H-mordenite
F.J.M.M. de Gauw, J. van Grondelle and R.A. van Santen
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven
University of Technology, Eindhoven, The Netherlands - F.J.M.M.de. Gauw@tue.nl

The effect of single-file diffusion limitation on the rate of an irreversible first order catalytic
reaction was studied both theoretically and experimentally. A rate equation was derived using
a relation between the effective diffusion constant and the concentration of adsorbed
molecules under single-file conditions which is valid on the time scale of catalytic reactions.
The hydroisomerization of 2,2-dimethylbutane on platinum loaded large crystallites of H-
Mordenite was used as a test reaction to verify the theoretical results.
 175

0 4 - Isomorphous Substitutions (Friday am)

0 4 - O - 0 1 - Direct synthesis of C u ( I ) - M F I zeolite in the presence o f C u ( I I )

methylamino complexes as mineralizing and reducing agents
S. Valangea, b, F. Di Renzo c, E. Garroned, F. Geobaldo~, B. Onida d and Z. Gabelica a
a ENSCMu, GSEC, 3 Rue A. Werner, F-68093, Mulhouse, France, b Present address 9
LACCO, UMR CNRS 6503, ESIP, 40 Av. du Recteur Pineau, F-86022 Poitiers, France,
sabine.valange@univ-poitiers.fr, ~ ENSCM, 8 rue de l'Ecole Normale, F-34053 Montpellier,
France, a Politecnico di Torino, Corso Duca degli Abruzzi 24, 1-10129 Torino, Italy

We report for the first time the direct synthesis of a Cu bearing MFI zeolite using amino
complexes as mineralizing agents and give experimental evidence of an in-situ reduction of
Cu(II) to Cu(I) by methylamine. Cu(I) ions alone never integrate the Al-free MFI framework,
while they are partly incorporated in the A1-MFI crystals. Investigation of the nature of the
Cu(I) ions in this particular (Cu,A1)-ZSM-5 by UV-vis and FTIR shows that the Cu(I) species
are strongly anchored to the MFI framework and are particularly stable and resistant to
elution. The kinetics of the Cu(I) incorporation is discussed on the basis of the particular
structural model proposed for (Cu,A1)-ZSM-5

0 4 - 0 - 0 2 - Preparation and catalytic properties o f a n o v e l t y p e o f zeolites

with basic properties
S. Ernst, M. Hartmann and S. Sauerbeck
Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany,
sernst@rhrk, uni-kl, de

Novel basic zeolite catalysts are obtained by ammonia treatment of crystalline, microporous
aluminosilicates at temperatures from 700~ to 900~ The resulting materials are active
catalysts in the Knoevenagel condensation of benzaldehyde with malononitrile, presumably
due to the presence of nitrogen-containing species bound to the crystalline framework. As
active sites of the new materials both, terminal -NH2 and bridging -NH-groups can principally
be envisaged. A decrease in catalytic activity is observed upon extended exposure to moisture
due to hydrolysis of the Si-NH2 groups. The initial catalytic activity, however, can easily be
restored by a new ammonia treatment.

04-0-03 - Preparation and characterization of iron-substituted zeolites

G. Giordano (a), A. Katovic(a), A. Fonseca (b) and J. B.Nagy (b)
(a) Universitdt della Calabria, RENDE (CS), Italy
(b) Laboratoire de RMN, FacultOs Universitaires Notre-Dame de la Paix, NAMUR, Belgium

Iron is introduced into the framework of three different zeolite-types: MFI, MTW and TON
by direct hydrothermal synthesis from alkaline reaction mixtures containing iron complexes
(oxalate or phosphate). The synthesis conditions for each zeolite-type and the results on the
characterization of the samples by XRD, AAS, thermal analysis, SEM and 29Si-, 13C- and 3~p_
NMR spectroscopy are discussed.
176

0 4 - 0 - 0 4 - Influence of the nature of T atoms on the m o r p h o l o g y and crystal

size of KZ-2 and ZSM-22 zeolites isomorphously substituted with Al or Fe
M. Derewifiski*, M. Kasture a, J. Kry~ciak and M. Stachurska
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, 30-239 Cracow,
Niezapominajek Str. 8, Poland, e-mail." ncderewi@cyf-kr, edu.pl
on leave from National Chemical Laboratory, Pune, India
Syntheses of KZ-2 and ZSM-22 zeolites isomorphously substituted with iron or aluminium
were carried out for a wide range of the Si/T ratio (T=A1, Fe). Effect of the gel composition
on size and morphology of the crystals formed was studied. It has been shown that using
diethylamine as a template it is possible to synthesize iron containing KZ-2 zeolites with the
similar crystals (in size and morphology) independently of Si/Fe ratio in gel. No such effect
was observed when the syntheses were carried out in the presence of aluminium in the gel.
The results point to an important role of the nature of T cations in the process of the zeolite
crystal growth.

0 4 - 0 - 0 5 - Synthesis and characterisation of novel large-pore vanadosilicates

A M - 1 3 and A M - 1 4
P. Brand~o a'b, A. Philippou a, N. Hanif% J. Rocha b and M. Anderson a
aDepartment of Chemistry, UMIST, PO Box 88, Manchester M60 1QD, UK
bDepartment of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal, Rocha@dq.ua.pt
The novel large-pore vanadosilicates AM-13 and AM-14 (Aveiro-Manchester, structure
number 13 and 14) containing stoichiometric amounts of vanadium (Si/V - 10 and 4,
respectively), have been synthesised. Characterisation techniques such as bulk chemical
analysis (ICP), powder X-ray diffraction (XRD), scanning (SEM) and transmission (TEM)
electron microscopy, and N2, n-hexane, benzene, tripropylamine and perfluorbutylamine
adsorption measurements were used for the structural studies. The acid-base and redox
properties of these materials were assessed by the conversion of isopropanol and ethanol
oxidation, respectively. Both materials exhibit high selectivity to acetaldehyde indicating that
these two novel vanadosilicates are promising redox catalysts.

1 4 - F r a m e w o r k s , Cations, Clusters (Friday am)

14-O-01 - Imaging the mesopores in zeolite Y using three-dimensional

transmission electron microscopy
A.H. Janssen (a), A.J. Koster (b) and K.P. de Jong (a)
a Department of Inorganic Chemistry and Catalysis, Utrecht, The Netherlands
k.p.dejong@chem.uu.nl; b Department of Molecular Cell Biology, Utrecht, The Netherlands
A 3D-TEM study on a series of Y zeolites reveals the mesopores (generated by steaming
and/or acid leaching) with great clarity. Both the diameters and shapes of the visualised pores
correspond very well with nitrogen physisorption measurements of the entire sample. Also
amorphous alumina in the mesopores and on the external surface can be visualised, which is
in agreement with results obtained by XPS on these samples. From these results a more
detailed model for the formation of mesopores in zeolite Y is proposed.
 177

14-O-02 - 170 NMR studies of the structure and basic properties of zeolites
D. Freude, T. Loeser and U. Pingel
Universitgit Leipzig, Abteilung Grenzfli~chenphysik,freude@uni-leipzig.de

DOR and MQMAS NMR techniques were applied in the high field of 17.6 T to the study of
several oxygen-17 enriched zeolites with the ratio Si/AI = 1. The tendency that the isotropic
chemical shift of the 170 NMR decreases with increasing bond angle (or s-character of the
oxygen hybrid orbital) was confirmed by this study. A quite linear correlation exists for the
oxygen sites in the zeolites A and LSX, if the data are limited to the sodium form of the
hydrated zeolites. Ion exchange of the hydrated zeolites (Li-, Na-, K-, Rb-, Cs- and T1 forms)
generates strong chemical shift effects. The increase of the basicity of the oxygen framework
of the zeolite LSX is reflected by a downfield shift of ca. 10 ppm going from the lithium to
the cesium form. The substitution of sodium by thallium in the zeolite A causes a shift of
34 ppm for the 03 signal.

1 4 - O - 0 3 - Theoretical interpretation of UV-VIS spectra of Cu- and Ag-

species in zeolites" structure v s . transition energies
P. Nachtigall, M. Davidovfi, M. Silhan and D. Nachtigallovd
J. Heyrovskfi Institute of Physical Chemistry, Academy of Sciences of the Czech Republic and
Center for Complex Molecular Systems and Biomolecules, DolejJkova 3, 182 23 Prague 8,
Czech Republic

The :,nteraction of Ag and Cu ions with MFI and ferrierite was studied with the combined
quantam mechanics / interatomic potential function (QM-Pot) technique. The structure and
coordination of Ag and Cu ions, Cu 2+ reduction, and photoluminescence spectra were
investigated. The experimental data are analyzed in light of the results of the QM-pot
compatational study. A consistent interpretation at the atomic scale level is offered and the
implications for the catalytic activity of these systems are discussed.

14-O-04 - Silver ions and quantum-sized silver sulfide clusters in zeolite A

D. Brahwiler, C. Leiggener and G. Calzaferri*
Department of Chemistry and Biochemistry, University of Bern, Switzerland
*gion. calzaferri@iac, unibe, ch

UV/vis spectroscopic studies of Ag+xNal2_xA, Ag+xCa2+_0.5xA and Ag~.5ZK-4 in

conjunction with molecular orbital calculations lead to the result that 4-ring coordinated Ag §
is responsible for the deep yellow color observed in silver loaded zeolite A activated at room
temperature. Electronic transitions can be interpreted as charge transfer from zeolite oxygen
lone pair to Ag +. The reaction of H2S with activated Ag+-loaded zeolite A leads to the
formation of quantum-sized, luminescent silver sulfide clusters inside the zeolite cavities. The
cluster size can be varied by adjusting silver loading.
178

14-O-05 - Elucidating the nature and reactivity of cobalt ions in CoAPOs. A

combined FTIR and EPR study of NO and NO2 adsorbed at 77K and 298K
E. Gianotti a, M.C. Paganini a, G. Martra a, E. Giamello a, S. Coluccia a and L. Marchese b
aDip. di Chimica IFM, Universith di Torino, Italy;bDip, di Scienze e Tecnologie Avanzate,
Universit~t del Piemonte Orientale "A. Avogadro ", Alessandria, Italy- marchese@ch.unito.it

A combined FTIR and EPR study, using NO and NO2 as molecular probes of the nature and
reactivity of cobalt ions in microporous cobalt-aluminophosphates with chabasite-related
structure (CoAPO-18 and CoAPO-34) has been performed both at 298 K and 77 K. CoAPOs
materials were prepared by following a facile route during which the cobalt ions were directly
inserted in the synthesis gels.

2 9 - New Approaches to Catalyst Preparation (Friday pro)

29-O-01 - The catalytic performance of zeolite ERS-10
C. Perego, M. Margotti, L. Carluccio, L. Zanibelli and G. Bellussi
EniTecnologie S.p.A., Via Maritano 26, 20097 San Donato Milanese (MI) Italy

Zeolite ERS-10 has been characterised as acid catalyst for ethylbenzene(EB) dispro-
portionation and benzene alkylation. In the disproportionation of EB, ERS-10 shows some
similarity with ZSM-12. In the alkylation of benzene with propylene a peculiar behaviour is
related to the by-production of diisopropylbenzenes (DIPBs). Like ZSM-5 and ZSM-12, the
preferred isomer produced by ERS-10 is the para. A Spaciousness Index (SI) = 5.3 and the
preferred formation ofp-DIPB seem to indicate that the effective pore-width of ERS-10 is in
the intermediate range between large and medium pore zeolites.

2 9 - 0 - 0 2 Towards total hydrophobisation of MCM-41 type silica surface

T. Martin, A. Galameau, D. Brunel, V. Izard, V. Hulea, A.C. Blanc, S. Abramson, F. Di Renzo
and F. Fajula
Laboratoire des Matdriaux Catalytiques et Catalyse en Chimie Organique- UMR-5618-CNRS
-ENSCM, MONTPELLIER - France. brunel@cit, enscm.fr

Refinement of the procedure for MCM-41 surface functionalisation was studied with various
octylsilanes in order to obtain a maximum surface coverage. Two different types of surface
modification using different grafting agents were performed on MTS samples. MTS samples
possessing three different pore sizes were functionalised by hydrolysis and polymerisation of
pre-adsorbed monolayer of octylsilanes on MTS surface or by chlorine substitution from
chlorooctylsilane with nucleophilic assistance. The effect of various experimental parameters
on the hydrophobicity and the grafted chain loading was analysed.
 179

2 9 - 0 - 0 3 - Novel Lewis-acid catalysts (NLACs): their properties, charac-

terisation and use in catalysis
M.H. Valkenberg, C. deCastro and W.F. Hoelderich*
Department of Chemical Technology and Heterogeneous Catalysis, University of Technology
RWTH Aachen, Aachen, Germany

Different methods for the preparation of Novel Lewis-Acid Catalysts (NLACs) consisting of
ionic liquids immobilised on mesoporous support materials are presented. The focus will be
placed on materials bound to the carrier via the organic cation of the ionic liquid, either by
grafting or by the preparation of organically modified HMS. After addition of
aluminium(III)chloride the materials were used as catalysts e.g. in Friedel-Crafts alkylations,
in which they displayed high activities and selectivities.

2 9 - 0 - 0 4 - A controlled dispersion of A! 3+ onto a silica m e s o p o r o u s material.

A comparative study with A! 3§ incorporation
O. Collart (a), A. Galarneau (b), F. Di Renzo (b), F. Fajula (b), P. Van Der Voort (a) and E.F.
Vansant (a)
a Laboratory of Adsorption en Catalysis, Department of Chemistry, U.I.A., Universiteitsplein
1, Wilrijk, Belgium - oliviercollart@ua.ac.be," b Laboratoire de Matdriaux Catalytiques et
Catalyse en Chimie Organique, ENSCM, Montpellier, France

A pure silica MCM-48 is activated by a controlled dispersion of A1 onto the substrate surface
performed by anchoring of the Al(acac)3 complex onto the surface silanols. A calcination
step removes the organic ligands. The characteristics of the final structure are evaluated by
comparison with A1 incorporated MCM-48. The type and concentration of Lewis/Bronsted
acid sites is investigated by the adsorption of NH3 and CDBCN.

0 8 - Syntheses with Non-Ionic Surfactants (Friday pm)

08-O-01 - M e s o p o r o u s M S U - X silica tuned for filtration and chromato-

graphy applications
C. Boissi6re, A. Larbot and E. Prouzet*
Institut EuropOen des Membranes, L.M.P.M. (CNRS UMR 5635) C.N.R.S., 1919 Route de
Mendes, F-34293 Montpellier cedex 5, FRANCE. e-mail ."prouzet@iemm.univ-montp2.fr
Mesoporous MSU-X silica was synthesized with a two-step pathway, that allowed us to get a
high control degree on both the final material shape and the porous size distribution. These
materials were developed and tested for separating applications, including HPLC
chromatography and ultrafiltration membranes. Both applications show that the specific
structure of the Micellar Templated Structures exhibits a new behavior in the separation
applications, compared with other materials. They are explained by the combined effect of the
silica nature and the specific cylindar pore shape.
180

0 8 - 0 - 0 2 - Highly ordered mesoporous silicas synthesis using deca-

(oxyethylene) oleylether as surfactant: variation of the weight percentage of
surfactant and incorporation of transition metal cations
G. Herrier and B.-L. Su
Laboratoire de Chimie des Mat&iaux Inorganiques, Universitd de Namur, Belgium

The synthesis of highly ordered mesoporous silicas using nonionic Cls-lEO10 surfactant has
been made by varying the surfactant weight percentages and by incorporation of transition
metal ions in the gel. First, the variation of the micellar solution composition leads to
reorganization of the phase diagram of micelles and the formation of highly organized
hexagonal CMI-3 materials. Second, the role of transition metal cations added during the gel
reparation, and the formation mechanism of hexagonally ordered CMI-4 silicas are discussed.

0 8 - 0 - 0 3 - Silica walls of calcined mesostructured SBA-15 materials

templated by triblock copolymers
M. Imp6ror a and A. Davidson b
aLaboratoire de Physique des Solides, UMR 8502-CNRS, e-mail: imperor@lps.u-psud.fr
6Laboratoire de R~activit~ de Surface, UMR 7609-CNRS, e-mail." davidson@ccr.jussieu.fr

Silica-based SBA-15 materials, synthetised using triblock copolymers as templates, have a 2-

dimensional hexagonal symmetry. PEO chains are deeply occluded within silica walls of
SBA-15 and therefore the density of these walls, after calcination and elimination of PEO
chains, may not be uniform. Hydrothermal treatment of SBA-15 can be used to increase their
main mesopore diameter and decrease their wall thickness. Unique informations provided by
modelling of XRD data complemented by TEM and N2 sorption show that calcined SBA-15
solids cannot be considered as ideal arrays of mesopores imbedded in a uniform silica matrix.
The silica walls structure is complex as mesopores appear to be surrounded by a microporous
corona of silica. We will also describe how this corona is affected by hydrothermal treatment.

0 8 - 0 - 0 4 - Template / AISBA-15 interaction: double resonance N M R study

and consequences on structural properties
J.-B. d'Espinose de la Caillerie(a), Y. Yue(b) and A. G6d6on(b)
a Laboratoire de Physique Quantique, Ecole Sup&ieure de Physique et de Chimie
Industrielles de la Ville de Paris, Jean-Baptiste.Despinose@espci.fr,, France
b Laboratoire de Chimie des Surfaces, Universit~ Pierre et Marie Curie, France

Mesoporous Al-incorporated SBA-15 have been obtained by direct synthesis. The surfactant-
aluminosilicate interaction during synthesis was studied by double resonance NMR
(HETCOR and TRAPDOR) and confronted with the structural properties of the materials
obtained after calcination. It is concluded that the microporosity of SBA-15 originates in the
partial hydrolysis of the TEOS precursor itself rather than incomplete PEO - silicate phase
separation.
 181

31 - Environment-friendly Applications of Zeolites (Friday pm)

31-O-01 - Influence of Jordanian chabazite-phillipsite tuff on nutrient

concentration and yield of strawberry
K.M. Ibrahim (a), A.M. Ghrir (b) and H.N. Khoury (b)
a Dep. of Earth & Env. Sciences, Hashemite University, Zarqa, Jordan, ibrahim@hu.edu.jo
b Department of Geology, University of Jordan, Amman, Jordan
Chabazite-phillipsite tuff was successfully used as a soil conditioner for planting strawberry
under greenhouse conditions for the first time in Jordan. The zeolitic tuff-soil mixture with
(2:5) ratio has improved the yield and the height of the plant and has decreased the death
percent, the maximum increase in the total yield of the strawberry reaches up to 71.5%. The
average gain of the plant height is about 19% and the plant death has decreased to an average
of 68%. The results show increase in the nutrient contents except for Mn and Na. The average
N gain in the young mature leaves is 39%, whereas in the old leaves is 15.18%.

31-O-02 - Improvements in yield and quality of crops with NASA zeoponic

fertilizer delivery systems" turf, flowers, vegetables and grain
R.D. Andrews (a) and S.B. Kimi (b)
a ZeoponiX, Inc., rich@zeoponix.com, USA
b Malaysian Agricultural Research and Development Institute, kimi@mardi.my, Malaysia
Zeoponic plant growth media and fertility systems developed by NASA and industry consist
of (a) plant nutrient ion exchanged natural/synthetic zeolites and (b) synthetic apatite, a
phosphorus and trace element fertilizer constituent. Combined, these materials produce
superior plant performance in a wide range of commercially important crops, in floriculture,
vegetable horticulture, specialty sports turf and important food grains, notably rice. Quality
improvements include better germination, higher yields, lower fertilizer requirements,
reduced environmental nutrient losses, and better aesthetics in such crops as flowers and
sports turf.

3 1 - O - 0 3 - Fe/MFI as a new heterogeneous Fenton-type catalyst in the

treatment of wastewater from agroindustrial processes
G. Centi, S. Perathoner and G. Romeo
Dip. Chimica Ind. ed Ing. dei Materiali, Univ. Messina, perathon@www.unime.it, Italy
A critical issue for a sustainable use of water regards the development of new technologies for
the treatment of wastewater from agroindustrial processes. The use of Fe/MFI as a Fenton-
type heterogeneous catalyst in the wet H202 oxidation of p-cumaric acid, a model compound
representative of the phytotoxic phenols present in wastewater from agroindustrial processes,
is reported. Aspects analyzed were the effectiveness of the catalyst in comparison with iron
salts in solution, the efficiency in the use of H202, the effect of pH, and the behavior of
Fe/MFI samples, prepared either by ion exchange or chemical vapour deposition, in relation
to activity, by-products and iron leaching. An outline of a possible process flow-sheet is also
presented.
182

31-O-04 - Investigation of the storage properties of zeolites and

impregnated silica for t h e r m o c h e m i c a l storage of heat
J. J~inchen (a), A. Grimm (a) and H. Stach (b)
a FHTW Berlin, University of Applied Sciences, Berlin, internet@bib.fia-berlin.de, Germany
b ZeoSys GmbH, Berlin-Adlershof Germany
The sorption equilibrium of water in modified zeolites of different types and in silica gels
impregnated with hydrophilic salts as well as the texture of the modified silica gels were
investigated by thermogravimetry, differential scanning calorimetry, measurements of the
isotherms and electron microscopy, respectively. Whereas the modified mesoporous silica
materials show a high thermochemical storage capacity because of the high uptake of water
the zeolites reveal a better temperature lift since the adsorption equilibrium of the zeolites is
shifted toward considerable lower partial pressure. A stepwise hydratation of the salts
confined in the pores of the silica gel is correlated with a stepwise curse of the isotherms.

1 3 - F r a m e w o r k s and Acid Sites (Fridaypm)

13-O-01 - W h e r e are the acid sites in zeolites? A novel N M R approach to

measure B/Ai ordering around structure directing agents
H. Koller a, M. Kalwei a, C. Fild a, R.F. Lobo b, M.A. Camblor c, L.A. Villaescusa d, L. van
W011ene
a lnstitut far Physikalische Chemie and Sonderforschungsbereich 458, University of Munster,
Manster, Germany," b Univ. of Delaware, USA," c lndustrias Quimicas del Ebro Poligono de
Malpica, Zaragoza, Spain," d Univ. of St. Andrews, Scotland; e MPI fur FestkOrperforschung,
Stuttgart, Germany
The orientation of quaternary ammonium compounds towards the BO4/2-and AIO4/2-groups
in a series of as-made zeolites have been determined by 23C{ZH}-IIB REDOR, 13C{1H}-27A1
REAPDOR, and ~H-27A1 REAPDOR solid state NMR. The distribution of acid sites is not
random, and a local charge-ordering around monoquaternary structure directing agents
(SDAs) is discerned. No such charge ordering was observed for diquaternary SDAs. These
methods provide a versatile tool to locate acid sites around the SDA.

13-O-02 - The effect of the nature of heteroatoms (AI, Fe, B) on their

distribution in the ZSM-5 structure
J. D~de6ek, M. Tudor and J. 12ejka
Academy of Sciences of the Czech Republic, Czech Republic," dedecek@]h-inst.cas.cz
The effect of the type of isomorphously substituted atoms (AI, Fe, B) on the number of
isolated heteroatoms, their pairs and on the distribution of these pairs in the framework of
ZSM-5 structure was investigated using UV-Vis spectroscopy of Co 2+ ions. It was found that
the distribution of heteroatoms in the framework of ZSM-5 is not random and depends on the
type and concentration of heteroatoms. The number of pairs of boron is significantly lower
compared to the number of A1 and Fe pairs for similar concentrations of heteroatoms. All A1,
Fe and B pairs are present in three different rings forming, thus, three different sites for
divalent cations.
 183

1 3 - O - 0 3 - Toward the quantification of aluminum in zeolites using high-

resolution solid-state NMR
C. Fernandez (a), A.-A. Quoineaud (a), V. Montouillout (a), S. Gautier (b) and S. Lacombe
(b).
a Laboratoire de Catalyse et Spectrochimie, CNRS UMR 6506, ISMRA/Universit~ de Caen,
France, b Institut Frangais du Pdtrole, Rueil-Malmaison, France
Christian. Fernandez@ismra.fr
The recent introduction of multiple-quantum NMR (MQMAS), a new high-resolution NMR
method facilitates the interpretation of the 27A1NMR spectra of zeolites and thus allows a fast
and correct identification of the various aluminum sites. Moreover, this technique yields new
information about the structural distortions around the aluminum atoms. The information
given by simulation of both MAS and MQMAS leads to the correct quantification of the
different sites present in the sample.

13-O-04 - Acidity of ITQ-2 zeolite as studied by FT-IR spectroscopy of

adsorbed molecules in comparison with that of MCM-22
B. Onida, F. Geobaldo, L. Borello and E. Garrone
Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Turin,
Italy, onida@athena.polito, it

ITQ-2, a novel zeolitic structure prepared by swelling and delaminating a MWW precursor,
has been studied by IR spectroscopy. The same precursor yields, when calcined, the zeolite
MCM-22. Bronsted acidity has been measured as the propensity either to engage in H-bonds
or to transfer the proton to unsaturated hydrocarbons. Comparison with MCM-22 shows that
dealumination accompanies the process of delamination, but no appreciable change in
residual Bronsted acidity takes place. Reaction of propene with Bronsted sites to branched
oligomers occurs mainly on the external surface. Oligomers show no tendency to evolve to
allylic cationic species, in contrast with MCM-22.
This Page Intentionally Left Blank
Studies in Surface Science and Catalysis 135
A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 185

S U M M A R I E S of P O S T E R P R E S E N T A T I O N S

02 - Zeolite Nucleation and Growth (Monday)

02-P-06 - Epitaxial overgrowth of M A Z onto EMT type zeolite crystals

A.M. Goossens (a), V. Buschmann (b) and J.A. Martens (a)
a Centrum voor Oppervlaktechemie en Katalyse, KU Leuven, Belgium
johan, martens@agr, kuleuven, ac. be, b FB Materialwissenschaft, TU Darmstadt, Germany.
The possibility of growing epitaxial zeolite films on micrometer-sized, structurally different
zeolite support crystals was explored with the aim to develop polyfunctional zeolite materials
with spatially separated adsorptive and/or catalytic functions. Support crystals of one zeolite
type were added to a hydrogel for crystallization of a second zeolite type. Tuning of the
crystallization conditions led to the formation of a MAZ-on-EMT overgrowth material
consisting of an oriented, continuous film of MAZ crystallites completely covering the
surface of the EMT support crystals. The epitaxial relations between the two phases were
established using HRTEM and SAED.

0 2 - P - 0 7 - The transformation of Zeolite A and X into nitrate cancrinite

under low temperature hydrothermal reaction conditions
J.C. Buhl and C. Taake
Institut far Mineralogie, Universitdt Hannover, J'Buhl@mineral~176
Germany
Investigations on the hydrothermal crystallisation of nitrate enclathrated cancrinite were
performed using the alkaline transformation of zeolites A and X at a temperature of 353 K in
2-molar and 16-molar NaOH-solutions. The conversion of the zeolites was followed in the
early stage of the reactions for times up to 48 hours by XRD and IR- spectroscopy. A fast and
total transformation of zeolite X into cancrinite could be stated in most of the experiments,
independent of the alkalinity. In contrast the conversion of zeolite A under low alkaline
conditions was slower and accompanied by a sodalite-cancrinite cocrystallisation as well as
the formation of an intermediate phase between both structure types. The results indicate a
more kinetically controlled reaction mechanism for zeolite A transformation.

02-P-08 - Comparison of crystal linear growth rates for silicalite-I in thermal

and microwave syntheses
C.S. Cundy and J.O. Forrest
Centre for Microporous Materials, UMIST, colin.cundy@umist.ac.uk, UK
A series of crystal growth experiments has been carded out on reaction mixtures seeded with 43
nm nanocrystals of silicalite-1. For a fixed synthesis composition of 3.1Na20 : 60SIO2 :
6.0TPABr : 5560H20 : 240EtOH, product crystal size was controlled in the range 71-98 nm by
varying the quantity of seed crystals added to the synthesis batch. In a comparison between
conventional and microwave heating at 100 ~ no significant difference in nucleation or growth
behaviour was found between the two methods. Crystal linear growth rates (0.5 A1/At) were the
same for all experiments (0.025 + 0.002 ~m h l) and agreed well with published values. Under
these experimental conditions, the growing crystals experience the same reaction environment,
regardless of the heating method.
186

02-P-09 - Effect of initial hydrogel milling on N a - Z S M - 5 synthesis

C. Falamaki (a), M. Edrissi (b) and M. Sohrabi (b)
a Materials and Energy Research Center, P.O. Box 14155-4777, MERC88@DCI.Iran.Com.,
Tehran, Iran
b Chemical Engineering Department, Amirkabir University of Technology, Tehran, Iran

The effect of milling the initial hydrogel on the synthesis of Na-ZSM-5 using 1,6-hexanediol
as structure directing agent has been investigated. In both static and dynamic systems, milling
results in a significant increase in the crystal average size and crystal size distribution
broadness. Increasing milling time interestingly increases the induction time while the total
reaction time decreases with respect to no gel pretreatment. Increasing milling periods
simultaneously shift the nucleation curve towards the end of the crystallization process,
suppressing it. Milling also increases largely the crystal growth rate; so that increasing the
milling time from 24 to 32 h increases the growth rate from 2.71 to 17.07 ~tm h ~. An
explanation for the observed results is given.

02-P-10 - Synthesis and c h a r a c t e r i z a t i o n of zeolite Z S M - 2 5

S.B. Hong *a, W.C. Paik a, W.M. Lee a, S.P. Kwon b, C.-H. Shin b, I.-S. Namr and B.-H. Ha d
aChemical Engineering and Technology, Taejon National University of Technology, Korea
bChemical Engineering, Chungbuk National University, Korea," CChemical Engineering,
Pohang University of Science and Technology (POSTECH), Korea," aChemical Engineering,
Hanyang University, Korea

The synthesis and characterization of the intermediate-silica zeolite ZSM-25 in the presence
of sodium and tetraethylammonium cations is described. The overall characterization results
of this study suggest that ZSM-25 is probably an 8-ring or constrained 10-ring pore material
containing 4-rings as the smallest structural unit. However, the proton form of ZSM-25 was
found to have a poor thermal stability, revealing a serious drawback in its applications as a
shape-selective catalyst for acid-catalyzed hydrocarbon conversions.

02-P-11 - A study on the crystallization of a lamellar a l u m i n o p h o s p h a t e

A P O - M to a t h r e e - d i m e n s i o n a l a l u m i n o p h o s p h a t e A P O - C J 3
K. Wang, J. Yu, Y. Song, Y. Zou and R. Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry,
Jilin University, Changchun 130023, rrxu@mail.jlu.edu.cn, People's Republic of China.

An intermediate phase [A12P208][C2H9NO].xH20, denoted APO-M, is crystallized during the

formation of three-dimensional open-framework [AlzP2Os][OCH2CH2NH3] (APO-CJ3) in the
gel with a molar composition of 2.0 AI('PrO)3:2.8 H3PO4:12.0 ethanolamine: 180 H20. XRD
analysis indicates that it has a lamellar structure. It is thermally stable up to 200 ~ The phase
transformation from APO-M to APO-CJ3 is investigated by XRD, SEM, ICP, 27A1 and 31p
MAS NMR techniques.
 187

02-P-12 - Synthesis of nanosized offretite crystals

J. Hedlund and E. Kurpan
Division of Chemical Technology, Luleh University of Technology, johe@km.luth.se, Sweden

Colloidal offretite crystals with a maximum size of up to 250 nm were prepared by

hydrothermal synthesis at 100~ The system is unusual in the sense that colloidal crystals
form from a gel and that the yield sometimes is very high. The effects of the duration of
hydrothermal treatment and the composition of the synthesis mixture on the product were
investigated using XRD, DLS and SEM. Some syntheses resulted in mixtures of offretite and
amorphous material or colloidal sodalite, whereas others resulted in a pure and colloidal
offretite product.

02-P-13 - Silicon oxide plays a driving role in the synthesis of microporous

SAPO-II
Z.-Q. Liu and R. Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, rrxu@mail.jlu.e.du.cn, P. R. China.

This paper deals with the kinetic study on the synthesis of microporous SAPO-11. It is found
that the addition of SiO2 to the starting gel makes the crystallization rate of SAPO-11 fast.
The quantitative relationship between the crystallization rate and the amount of SiOz in the
starting gel was expressed. Moreover, the relationship between the activation enthalpy in the
crystallization of SAPO-11 and SIO2/A1203 in starting gel indicates that a larger SIO2/A1203
decreases the crystallization activation enthalpy, demonstrating that the silicon oxide plays the
driving role in the synthesis of SAPO-11.

02-P-14 - Synthesis of nanocrystal zeolite Y and its host effect

H. Yang, R. Li*, B. Fan and K. Xie
Institute of Special Chemicals, Shanxi Key Lab of Coal Science and Technology, Taiyuan
University of Technology, Taiyuan 030024, China

Well-crystallized nanometer-sized zeolite Y of particle size less than 70nm (denoted as nano-
Y) has been successfully synthesized by a two-step-way and characterized by XRD, TEM,
TG-DTA. Its performances as host for metal complex in zeolites have also been studied. The
UV-vis spectra, XRD patterns and TG-DTA curves show that [Fe (phen) 3] 2+ has been formed
in the supercage of zeolite Y, and higher complex concentration can be obtained in the
samples by using nano-Y as host via the 'flexible-ligand' method. [Fe (phen) 3] 2+/nano-Y
exhibited higher activities for the liquid phase oxidation of cyclohexane with aqueous H202
than [Fe (phen) 3] 2+/y due to the higher surface area and shorter diffusion pathways.
188

02-P-15- Tailoring crystal size and morphology of zeolite ZSM-5

Ming Liu and S. Xiang*
Department of Chemistry, Nankai University, Tianjin 300071, shxiang@public.tpt.tj.cn, P. R.
China

Highly crystalline zeolite ZSM-5 with various Si/A1 ratios and two distinct crystal
morphology, lath shape and ball shape which appeared as euhedralite or spherulite, with
crystal size ranging from 3.7-100/~n and 1.0-62 /.tm were prepared from Na + and K +
containing aluminosilicate gels. Approaches for tailoring crystal size and morphology such as
seeding, cation effect control, oxyanion addition, aging the precursor gel and lowering
alkalinity during the intermediate stage were found applicable. The method of combining
aging and lowering alkalinity was proved to be useful for preparing lath-shape euhedralite
from a broad range of crystal size.

02-P-16 - Modeling of silicalite crystallization from clear solution

K.A. Carlsson, J. Warzywoda and A. Sacco, Jr.
Center for Advanced Microgravity Materials Processing, Chemical Engineering Department,
Northeastern University, Boston, MA 02115, USA, asacco@coe.neu.edu.

A mathematical model of Silicalite crystallization from "clear solution" was developed and
solved numerically. Crystallization was considered to be solution-mediated, and to involve
three categories of silica species and three steps: activation, nucleation, and crystal growth.
Nucleation was represented by a condensation reaction between the hydroxyl groups present
on the surface of 10 nm amorphous silica particles and the soluble silica species, producing
activated complexes, which transform to crystalline nuclei. Both nucleation and crystal
growth were considered to be reaction controlled. The model simulated well the in situ
experimental data. This suggests that the hypothesized nucleation mechanism can be used to
qualitatively describe the nucleation event during clear solution Silicalite crystallization.

02-P-17 - Interaction/synergistic effect of Mg 2+ and Ba 2+ on the size and

morphology of the zeolite L crystals
S. Ferchiche, J. Warzywoda and A. Sacco, Jr.
Center for Advanced Microgravity Materials Processing, Chemical Engineering Department,
Northeastern University, Boston, MA 02115, USA, asacco@coe.neu.edu.

The effect of Mg 2§ and Ba2§ added separately and added together on the purity, morphology,
and size of the products of zeolite L was investigated. All products were 100% pure zeolite L.
The results of a 22 factorial experiment (two factors: gel Mg 2§ and Ba 2§ content) showed a
two-factor interaction: the average crystal length depended on the concentration of both
cations in the gel, and decreased with the increasing gel cation content. A synergistic effect
was observed: the crystals formed with both cations were smaller and their morphology
improved from poorly to well formed cylinders compared to crystals obtained by combining
products grown using Mg 2§ and Ba2§ added separately at the corresponding concentrations.
 189

02-P-I 8 - In-Situ N M R study of mechanisms of zeolite A formation

M. Smaihi, S. Kallus and J.D.F. Ramsay
LMPM UMR 5635 CNRS-ENSCM-UM2, 1919 route de Mende, 34293 Montpellier Cedex 5,
France. smaihi @lmpm. cnrs-mop,fr

In-situ liquid-state NMR has been used to follow the first steps of zeolite A synthesis. 27A1
and lac NMR has been used to study the species that occur in solution and the role of
tetramethylammonium hydroxide as structure directing agent (SDA). 27AI NMR results
indicate that several aluminosilicate species are formed immediately during the first stage of
the synthesis reaction. Furthermore, lac NMR results indicate that short-range intermolecular
interactions between the SDA and these species occur just after the mixing of silicate and
aluminate solutions. These results suggest that small oligomeric species are created which
form a cage around the SDA and further A1/Si substitutions occur at the edge of these species.

02-P-19- Effects of synthesis parameters on zeolite L crystallization

Y.S. Ko, S.H.Chang and W.S. Ahn +
School of Chemical Science and Engineering, Inha University, Inchon, Korea 402-751 ,
w has ahn@ inha. ac. kr

Zeolite L was prepared from a substrate having the molar composition of 5.4K20-5.5Na20-
A1203-30SiO2-500H20 at temperatures of 373-443K. The influence of synthesis parameters
such as starting raw materials, reaction temperature, gel aging, stirring, seeding, heating rate
and mixing sequence on the crystallization rate and particle size distribution was investigated.
Crystallization rate was promoted by introducing gel aging, seeding, stirring and rapid heating
rate. The crystal size could be decreased significantly by stirring the gel during the synthesis
or subjecting the substrate mixture to an aging treatment at room temperature.

02-P-20- Some aspects of NU-86 zeolite crystallization

S.V. Dudarev a, A.V. Toktarev a, G.V. Echevsky a, C.L. Kibby b and D.J. O'Rear b.
~Boreskov Institute of Catalysis, Ak. Lavrentieva Av. 5, Novosibirsk, 630090, Russia.
bChevron Research and Technology Company, 100 Chevron Way, Richmond, CA 94802,
USA.

Crystallization of wide-pore NU-86 zeolite was investigated using different templates and
silica sources, different chemical compositions of the reaction gels, and with or without
seeding. It was found that NU-86 zeolite forms best from thick and seeded reaction gels based
on Cab-O-Sil fumed silica. Seeding with NU-88 zeolite leads to formation of a pure NU-86
zeolitic phase. Other concurrent zeolitic phases are ZSM-23, mordenite, ZSM-12, and
analcime. We found a higher optimum alkalinity for the reaction gel and a lower optimum
stirring rate than those reported in the literature.
190

02-P-21 - S y n t h e s i s of zeolite S r , K - Z K - 5
P.C. Russell, S.L. Stuhler, A.L. Kouli, J. Warzywoda and A. Sacco, Jr.
Center for Advanced Microgravity Materials Processing, Chemical Engineering Department,
Northeastern University, Boston, MA 02115, USA, asacco@coe.neu.edu.

Zeolite Sr,K-ZK-5 (KFI) with purity >95% was grown statically in Teflon-lined autoclaves at
100-150 ~ Reaction composition diagrams showed that Sr,K-ZK-5 crystallizes as a nearly
pure phase in a narrow composition range in which the variations of A1203, SiO2, and K20
must be held to less than 10 tool%. Four impurity phases were identified: zeolites L (LTL), T
(ERI), W (MER), and chabazite-type (CHA). Crystallization curves showed that the time to
obtain a fully crystalline Sr,K-ZK-5 increased from ~80 to ~100 h with the gel SiO2 content
increasing from 75.5 to 77 mol% and from ~80 to ~280 h with the synthesis temperature
decreasing from 150 to 100 ~ Attempts to obtain pure Sr,K-ZK-5 by seeding, aging, the use
of different sources of Si and A1, and the use of stainless steel autoclaves were not successful.

0 2 - P - 2 2 - E v i d e n c e for in-situ directing agent modification in zeolite

syntheses
J.C. Vartuli, G.J. Kennedy, B.A. Yoon and A. Malek
ExxonMobil Research and Engineering, Corporate Strategic Research, Annandale, NJ 08801-
3059, USA, J C Vartuli@email.mobil.com

ZSM-22 (TON) can be produced from potassium based 1,6 hexamethylenediamine synthesis
mixture, while, ZSM-34 (an OFF/ERI intergrowth) is synthesized from the same synthesis
mixture with the addition of sodium. NMR analyses of the as-synthesized zeolite samples
indicated the presence of a carbonyl species in all of the ZSM-34 samples, but not in any of
the preparations that produced ZSM-22. The carbonyl species was present only after the
synthesis mixture was heated above ambient temperature. Molecular modeling studies
calculated a favorable fit of the carbamic species within the pore system of the Erionite
suggesting a reason for the formation of the OFF/ERI intergrowth.

0 2 - P - 2 3 - T h e influence of different silica sources on the crystallization

kinetics of zeolite beta
W. Schmidt (a), A.V. Toktarev (b), F. SchtRh (a), K.G. Ione (b) and K. Unger (c)
a MPIfiir Kohlenforschung, Mtilheim, w~ Germany
b Institute of Catalysis, Academy of Sciences of Russia, Novosibirsk, Russia
c Institutf~r Anorganische Chemie, Johannes Gutenberg- Universitcit, Mainz, Germany

Zeolite beta was synthesized with different silicon sources. The dissolution of the silicon
sources and the reaction temperature obviously determined the crystallization rate of the
zeolite. Silica sol reacted rapidly at 110, 140, and 170~ while fumed silica and TEOS only
reacted readily at 170~ The aluminum content in the reaction gel determined the termination
of the crystal growth, after all aluminum was consumed, the crystal growth stopped. The
acidic properties of the obtained materials were very similar, but a significant influence of the
silicon source on the particle size of the resulting zeolite was observed.
 191

02-P-24 - Population balance: a powerful tool for the study of critical

processes of zeolite crystallization
B. Subotic, T. Antonid and J. Bronid
Rudjer Boskovic Institute, P.O.Box 180, Bijenicka c. 54, HR-10 001 Zagreb, Croatia
subotic@rudjer, irb.hr

A new insight in the population balance of zeolite crystallization is given, by introduction of

new functions of nucleation and crystal growth as well as the correction of the crystal growth
curves by introduction of the heating function of the reaction mixture. The modified
population balance is used for the analysis of the critical processes (nucleation and crystal
growth of zeolite) during crystallization of zeolites A, X and ZSM-5.

02-P-25- Synthesis of TMA-SOD from a novel type layered silicate by solid

state transformation
9 .a 9 .a
Y. Klyozuml , F. Mlzukaml , Y. Akiyama b, T. Ikeda c and T. Nishide d
aNational Institute of Materials and Chemical Research, I-I Higashi, Tsukuba 305-8565 Japan,
kiyozumi@nimc,go.jp
bAmersham Pharmacia Biotech, 3-25-1 Hyakuninchou, Shinjuku-ku, Tokyo 169-0073 Japan,
CNational Institute for Research in Inorganic Materials, Tsukuba, Ibaraki 305-0044 Japan,
dNihon University, Dep. of Materials Chemistry and Engineering, Koriyama 963-8642 Japan,

TMA-SOD was synthesized from a novel type of layered silicate (HLS) by solid state
transformation. HLS was easily converted to the TMA-SOD by mixing it with NaAIO2 and
heating at 70 - 150~ for 3 - 24h even without addition of HzO as the solvent. NaAIO2 is
inserted into the HLS layers, that is, the-Si(OSi)3 (Q3) sheets, and accelerates the cleavage of
the sheets into certain building units which subsequently form SOD structure. It was found
that the obtained TMA-SOD becomes dark blue under X-ray irradiation indicating TMA + and
Na43+ cluster are occluded within the SOD cage.

02-P-26- Direct conversion of bulk-materials into MFI Zeolites by a bulk-

material dissolution technique
S. Shimizu (a)(b) and H. Hamada (e)
a Joint Research Center for Harmonized Molecular Materials,
Japan Chemical Innovation Institute, si-simiz@kubota.co.jp, Japan
b Advanced Technology Laboratory, Kubota Corporation, si-simiz@kubota.co.jp, Japan
c National Institute of Materials and Chemical Research, hamada@nimc.go.jp, Japan

By using a novel synthetic technique named DBMD, we succeeded in converting glass bulk
materials by replacing the glassy part to MFI zeolite crystals from the surface to the inside. A
thoroughly converted zeolitic tube and partially converted zeolitic fibers and fabric were
prepared with this technique. Seed crystals accelerated crystallization and improved both
coverage and uniformity of the crystals.
192

0 2 - P - 2 7 - Synthesis of a new microporous silicate using DABCO-based

structure-directing agent
Y. Kubota a, J. Pl~vert b, T. Honda a, P. Wagner c, M.E. Davis c, T. Okubo b, Y. Goto d, Y.
Fukushima e and Y. Sugi a
aGifu University, Gifu 501-1193, Japan, kubota@apchem, gifu-u.ac.jp, sugi@apchem, gifu-u, ac.jp
bThe University of Tokyo, Tokyo 113-8656, Japan
CCalifornia Institute of Technology, Pasadena, CA 91125, U S. A.
dJapan Chemical Innovation Institute, 12-3-5 Kandajimbocho Chiyoda, Tokyo 101-0051, Japan
eToyota Central R&D Labs., Inc., Nagakute, Aichi 480-1192, Japan

A new zeolitic phase (GUS-1) is synthesized by hydrothermal method from all-silica

synthesis mixture using 1,1'-butylenedi(4-aza-l-azonia-2,5-dimethylbicyclo[2.2.2]octane)as
SDA. Results of the synthesis and structure-determination are described. The behavior of the
SDA during synthesis is also discussed.

02-P-28 - Heteroepitaxial connection of zeolites with different pore

structures
T. Wakihara a, J. P16vert a, S. Nair b, M. Tsapatsis b, S. Yamakita a, Y. Ogawa a, H. Komiyama a,
M. Yoshimura c, M.E. Davis a and T. Okubo a'c
a. The University of Tokyo, wakihara@chemsys.t.u-tokyo.ac.jp, Japan. b. University of
Massachusetts, Amherst, US.A c. Tokyo Institute of Technology, Yokohama, Japan d.
California Institute of Technology, Pasadena, U.S.A e. PRESTO, JST, Japan
Some zeolite structures are composed of repeated sequences of layer stacking. By controlling
the sequences, novel structures can be constructed. In this paper, ABC 6-member ring zeolites
are grown on millimeter-sized sodalite single crystals. Cancrinite with one-dimensional
channels and chabazite with three-dimensional intersections are selected as the overgrown
species. As a result, the first in-plane and out-of plane oriented cancrinite films are obtained.
In the case of chabazite, the textured planes with axis symmetry on sodalite substrates are
formed.

02-P-29 - Study of zeolite A crystallization from clear solution by

hydrothermal synthesis and population balance simulation
J. Bronic a, P. Frontera b, F. Testa b, B. Subotic a, R. Aiello b and J. B.Nagy c
a) Ruder Boskovic Institute, Zagreb, josip.bronic@irb.hr, Croatia; b) University of Calabria,
Rende, Italia; c) Facultes UniversitairesNotre-Dame de la Paix, Namur, Belgium
The influence of real time temperature increase from ambient to synthesis temperature
precursor ageing, and crystallization temperature, was studied on crystallization of zeolite A
from the clear solution under static conditions. Phase composition, crystal size, mass and
morphology were followed using various experimental techniques such as XRD, SEM, LLS,
and NMR. Simulation of the nucleation and crystal growth processes was made adopting
population balance model for synthesis from clear solution. Correlation of the measured and
simulated (calculated) data gives very good agreement.
 193

02-P-30 - Synthesis of zeolite SSZ-35 using N-methyl hexahydrojulolidinium

salt as a new family of structure-directing agents (SDAs)
Y. Kurataa , T.-A. Hanaoka b and H. Hamada b
Japan Chemical Innovation Institute (JCII), Tsukuba, Ibaraki 305-8565, Japan
b National Institute of Materials and Chemical Research, Tsukuba Ibaraki 305-8565, Japan

Three isomers of N-methyl hexahydrojuladinium salts were successful in preparing molecular

sieves for the first time. When they were used as structure-directing agents (SDAs), they gave
rise to the synthesis of three molecular sieves, SSZ-35, SSZ-31 and RUB-13. The stereo-
configurations of these organics are supposed to be an extremely important factor.

02-P-31 - The fitting equation for zeolite crystallization with seeds

A.V. Toktarev and S.V. Dudarev
Boreskov Institute of Catalysis, Ak. Lavrentiev Av. 5, Novosibirsk, 630090, Russia.

The simple two-parametric equation for fitting the crystallization curve of zeolite in the
presence of seeds is proposed. The equation is genetically related with Avrami-Erofeev
equation and has the following expression, x = 1- exp[-k• Applicability of the
proposed equation was verified by examples on ZSM-5 and NaA crystallization with MFI and
LTA type seeds, respectively.

02-P-32 - Influence of the thermal treatment of the aluminosilicate gel

precursor on the zeolite nucleation
C. Kosanovi6, B. Suboti6 and D. Kralj
Ruder BogkoviO Institute, Bij'enidka 54, 10000 Zagreb, Croatia
cleo@rudjer, irb. hr

Solid phase (X-ray amorphous aluminosilicate) separated from the hydrogel having the batch
composition 3.23 Na20'A1203'l.93 SIO2"128 H20, was calcined at different temperatures
(100-800~ for l h and then transformed into zeolite A by heating in a 2M NaOH solution at
80~ Analysis of both precursors and products (zeolite A) has shown that the calcination of
the precusor lowers the concentration of nuclei in the gel matrix and hence influences the
particulate properties of the zeolite obtained during the hydrothermal treatment of the
precursors
194

02-P-33 - Efficient co-templating roles of amines and amides a d m i x e d with

a l k y l a m m o n i u m salts for the stabilisation of new A I P O 4 - n topologies
C. Borges(a), M.F. Ribeiro(a), C. Henriques(a), M.T. Duarte(a), J.P. Louren~o(b) and Z.
Gabelica(c)
a Instituto Superior TOcnico, Lisboa, Portugal; e-mail.'filipa.ribeiro@ ist.utl.pt b
Universidade do Algarve, 8000 Faro, Portugal CGSEC, ENSCMu, Univ. de Haute Alsace,
Mulhouse, France
Two different aluminophosphate structures were synthesised in aqueous media using as main
template methylamine (MA), directly added, ,or generated in situ from methylformamide
(MF). Both involve novel A1PO4-n topologies that undergo structural transformations upon
template removal, yielding above 350~ microporous thermostable materials with interesting
properties. Tetraalkylammonium (TEA) cations were used optionally as co-templates along
with MA. Only non protonated MA was found incorporated into the pore volume. TEA
appeared to stabilise one of the phases during nucleation and/or growth processes.

02-P-34 - Static synthesis of zeolite M C M - 2 2

Y.-M. Wang, X.-T. Shu 2and M.-Y. He
Research Institute of Petroleum Processing, China Petrochemical Corporation,
wangym@public.eat.cn.net, P. R. China

Zeolite MCM-22 has been synthesized as a pure phase and with good crystallinity under static
conditions by using either two-step method or a seeding method. In the two-step method an
initial crystallization step at a much higher temperature (at least higher than 443K) makes it
possible to statically synthesize a high-quality MCM-22, which considerably reduces the time
for crystallization and the consumption of the organic template. And in this method the silica
sources with lower surface areas (less than 500 mZ/g) can yield zeolite MCM-22. Also the
directing-gel prepared at a higher temperature similarly has the desired effect on the static
synthesis of MCM-22, and the aging step can be left out in this method.

02-P-35 - Synthesis of pure silica Beta by the conventional h y d r o t h e r m a l

method
W. Guo, J. Yao, Y. Luo and Qi. Li*
Department of Chemistry, Fudan University, Shanghai 200433, P. R. China
qzli@fudan.edu.cn

Pure silica Beta has been crystallized from alkali-free hydrogel containing tetraethyl-
ammonium hydroxide and fumed silica at 413 K by the conventional hydrothermal synthesis
method. Characterization has been done by XRD, IR, SEM, solid-state NMR, thermal
analysis and N2 adsorption. The results show that a highly crystalline pure silica Beta is
formed. 29Si MAS NMR reveals that the pure silica Beta has a small number of Q3 sites
originating from structural defects and almost half of Q3 sites are silanol groups. Thermal
analysis shows that pure silica Beta possesses nonequivalent Q3 sites that are siloxy groups
counterbalanced by TEA + cations.
 195

02-P-36- Hydrothermal transformation of a layered silicate, Na-magadiite,

into mordenite zeolite
T. Selvam and W. Schwieger*
Institute of Technical Chemistry I, University of Erlangen, D-91058 Erlangen, Germany
wilhelm, schwieger@rzmail, uni-erlangen, de

Hydrothermal transformation of a layered silicate, Na-magadiite, into a commercially impor-

tant mordenite zeolite is achieved, at 175 ~ using tetraethylammonium hydroxide as the
intercalating and/or structure directing agent. Samples were characterized by XRD, IR, SEM,
DTA and N2 adsorption measurements. The results indicate that the mordenite samples
obtained by this new route are highly crystalline, more uniform and smaller in size (0.1-0.2
~tm).

02-P-37 - In-situ diagnostic of zeolite crystal growth by real time ultrasound

monitoring
R. Herrmann(b)*, W. Grill(c), T.J. Kim(c), O. Scharf(b), R. Schertlen(d), M. Schmachtl(c),
W. Schwieger(b), C. Stenzel(a), H. Toufar(e) and Y. Venot(d)
a Astrium GmbH, b University Erlangen, c University Leipzig, d University Karlsruhe,
e Tricat Zeolites GmbH- Technical Chemistry 1, University Erlangen, Egerlandstr. 3, D-
91058 Erlangen, Germany - e-mail. ralph.herrmann@rzmail, uni-erlangen.de
The aim of the present work is the detection of characteristic changes in synthesis gels of
different zeolites by the measurement of variations of the attenuation and the sound velocity
of ultrasonic waves traveling in the reaction fluids. For the zeolites A and X characteristic
changes of the measured ultrasound signals correlating with the processes of gel formation
and zeolite crystallization were observed. It could be shown, that the used ultrasound
monitoring is capable to demonstrate aging effects of the mixtures and to observe the onset of
fast crystal growth, which was verified by ex-situ XRD analysis. The real-time in-situ US-
diagnostic is a new promising tool for zeolite crystallization and it is also feasible under
microwave heating conditions.

02-P-38- Effect of ageing on the decomposition of tetra-alkylammonium

ions as studied by microwave
2
heatin~2 TM

A. Ararat l, H. van Bekkum, T. Maschmeyer and J.C. Jansen 2.

1- Chemistry Department, Faculty of Science, Helwan University, Ain Helwan, Cairo, Egypt.
2- Laboratory of Applied Organic Chemistry and Catalysis, Delft University of Technology,
Delft, The Netherlands.

Extremely fast decomposition of tetraalkylammonium salts in freshly prepared aqueous

alkaline solutions was observed upon immediate heating of the solutions, whereas no
decomposition was observed in aged solutions. This is of importance when zeolite synthesis
under fast heating conditions such as microwaves is performed. The decomposition reaction is
initially first order in the hydroxide concentration and comes to completion due to OH-
consumption. The results are discussed in terms of the formation of water-clathrate-like
structures around the alkylammonium groups upon ageing of the starting solutions.
196

02-P-39 - Synthesis of siliceous mordenite from system free of amine

X. Qi, x. Liu and Zhan Wang
Research Institute of Beijing Yanshan Petrochemical Corporation, 102500,
liu_xyOOl@sohu.com, China

The stability phase domain to give mordenite in the absence amine but with fluoride was
investigated. As compared with the system without fluoride, the domain producing mordenite
is broadened and the area leading to quartz is reduced. ZSM-5 and ferrierite are no longer
formed. The action of fluoride anion to favor the crystallization of mordenite is clearly shown.
When F/SiO2 ratio is above 0.10, the SIO2/A1203 ratio of product increases with the F/SiO2
ratio and quartz is no longer formed. The results clearly show the strong action of fluoride
anion in directing the system towards the formation of siliceous mordenite.

02-P-40 - High-resolution solid state MAS NMR studies on the role of

promoter (phosphate) in the nucleation and crystallization of Silicalite-1
(Si-MFI)
P.R Rajamohanan a, P. Mukherjee b, and S. Ganapathy a and R. Kumar b
aPhysical Chemistry Division, National Chemical Laboratory, Pune - 411 008, India
bCatalysis Division, National Chemical Laboratory, Pune - 411 008, India

With the help of multinuclear solid state NMR experiments, the promoter (phosphate)
induced acceleration of zeolite formation is proved unambiguously. It is proposed that the
hydration spheres of the silicate units formed by the hydrolysis of the tetraethyl ortho silicate
(TEOS) will be modified as part of the water molecules will be taken away by the promoter.
This will speed up the process of the association of Ql, Q2, and Q3 units to form more Q4
units in the gel, leading to the formation of secondary building units at a faster rate. The
promoter can also enhance the assembling of the SBU's in the similar way.

02-P-41 - The influence of concentration on the structure-directing effects

of diethylenetriamine in the synthesis of porosils
P. Behrens, V.J. Hufnagel and A.M. Schneider
Institut fiir Anorganische Chemie, Universitcit Hannover, Callinstrafle 9, D-30167 Hannover,
Germany," E-mail. Peter.Behrens@ mbox.acb.uni_hannover.de

Various parameters are known to influence the kinetically controlled synthesis of silica-rich
zeolites and related compounds such as porosils. In syntheses where diethylenetriamine is
acting as a structure-directing agent (SDA), different porosil structures can crystallize:
nonasil, ZSM-48, silicalite-1 and an unknown structure. The type of porosil obtained is found
to depend upon the concentration of the SDA, i.e. upon the compositional ratio between
diethylenetriamine and water in the synthesis gel. The results can be rationalized on the basis
of the structural arrangements of the diethylenetriamine molecules in the porosil formed.
These arrangements are influenced by the competition between intramolecular hydrogen
bonds within individual diethylenetriamine molecules, by the ability to form intermolecular
hydrogen bonds between the molecules of the SDA and by the solvation of these molecules by water.
 197

02-P-42- Synthesis of high-silica MWW zeolite

L.M. Vtjurina, S.S. Khvoshchev and I.V. Karetina
Coming Scientific Center in St.Petersburg, vtjurinaLM@corning.com, Russia

The synthesis and characterization of pure and highly crystalline MWW are reported. Using
silica sole as SiO2 source allows to obtain the MWW crystals with SIO2/A1203 = 80 at the
static synthesis conditions without preliminary aging. Adsorption data for Ar at 77 K and
C6H6 at ambient temperature on MWW with SiOJA1203 -- 80 are given. Thermostability of
MWW increases with increasing SIO2/A1203 ratio. Adsorption of NO on MWW zeolites is
considerably influenced by the nature of cations.
198

06 - Fundamentals of Micelle Templating (Monday)

06-P-05 - X-ray diffraction analysis of ordered mesoporous silica
M. Ookawa (a), Y. Yogoro (a), T. Yamaguchi (a) and K. Kawamura (b)
a Department of Applied Chemistry, Ehime University, Matsuyama, ookawa@en3.ehime-
u.ac.jp, Japan," b Department of Earth and Planetary Sciences, Tokyo Institute of Technology,
Japan
The analysis of wall structure of MCM-41 prepared under acidic or basic condition was
attempted by X-ray diffraction (XRD) using Mo Kc~. The profiles of XRD in the wide angle
region for MCM-41 were similar regardless preparation methods. The significant difference
was shown in profiles of XRD and interference function of silica glass and MCM-41.
Correlation function suggests that pore wall of MCM-41 prepared under acidic condition have
a structure of narrow Si-O-Si angle compared with MCM-41 prepared under basic condition
or silica glass.

0 6 - P - 0 6 - Active MCM-48 supported catalysts" different strategies to

increase the structural and chemical stability
P. Van Der Voort, M. Mathieu and E.F. Vansant
University of Antwerpen (U.I.A.), Dept. of Chemistry, pascal, vandervoort@ua.ac.be, Belgium
Several strategies have been developed and compared to increase the mechanical and
hydrothermal stability of pure silica MCM-48. A thickening of the walls, using SiCI4 and
water, results in a wall thickening of 50% and strongly improves the mechanical stability of
the samples. A partial hydrophobization with an amphiphilic silane, such as dimethyl-
dichlorosilane, has extremely beneficial effects on the thermal, mechanical and hydrothermal
stability of the samples and strongly reduces the leaching of the active centers. Both wall
thickening and hydrophobization can be combined into one simple post-synthesis treatment.
Such treatments will be necessary to allow a practical (industrial) use of the MCM-48 support
as catalysts support or adsorbent.

06-P-07 - Strong acidic and high temperature hydrothermally stable

mesoporous aluminosilicates with well-ordered hexagonal structure
Zo. Zhang (a), Y. Han (a), R. Wang (a), S. Qiu (a), D. Zhao (b) and F.-S. Xiao (a*)
a Dept. of Chem., Jilin Univ., Changchun 130023,fsxiao@mail.jlu.edu.cn, China.
b Dept. of Chem., Fudan Univ., Shanghai 200433, China.
Strong acidic and high temperature hydrothermally stable mesoporous aluminosilicates with
well-ordered hexagonal structure (MAS-5) have been successfully synthesized from assembly
of pre-formed aluminosilicate precursors with cetyltrimethylammonium bromide (CTAB)
surfactant. The MAS-5 shows extraordinary stability both in boiling water (over 300 h) and
in steam (800~ for 2 h). Temperature programmed desorption of NH3 shows that acidic
strength of MAS-5 is much higher than that of MCM-41.
 199

06-P-08 - Studies on the synthesis of A I - M C M - 4 1 m e s o p o r o u s materials

G.A. Eimer, L.B. Pierella and O.A. Anunziata
CITeQ(Centro de lnvestigaci6n y Tecnologia Quimica), Facultad C6rdoba. Universidad
Tecnol6gica Nacional. CC36 (5016) C6rdoba. Argentina. Tel-FAX.'54-351-4690585
email :oanunziata@scdt.frc, utn. edu.ar
The novel synthesis method of AI-MCM-41, using tetraethoxysilane (TEOS) and sodium
aluminate (NaA102) as Si and A1 sources, was studied. Dodecyltrimethyl ammonium bromide
was employed as template and the initial gel was hydrothermally treated at 100~ The
influence of reaction conditions such as surfactant/Si molar ratio and synthesis time have been
evaluated. The samples showed well-defined X-ray diffraction patterns indicating a highly
ordered structure of pore arrays. MCM framework was characterized by infrared analysis and
a tentative assignment of bands was performed. Both XRD and FT-IR studies could be
correlated and an optimal characterization of material could be reached.

06-P-09 - Controlled synthesis of microporous and m e s o p o r o u s silica-based

molecular sieves in the presence of d o d e c y l d i m e t h y l b e n z y l a m m o n i u m
chloride
Z.Y. Yuan (a), W. Zhou (b), L.M. Peng (a), J.-Z. Wang (c) and H.X. Li (c)
a Be~'ing Laboratory of Electron Microscoscopy, Chinese Academy of Sciences, Beijing
zyyuan@blem.ac.cn, P.R. China, b School of Chemistry, University of St. Andrews, St.
Andrews, UK, c Department of Chemistry, Nankai University, Tianjin, P.R. China
Microporous silicas with pore size of 12.2 A were prepared by either S+XI + or S+I pathways
at room temperature using dodecyldimethylbenzylammonium chloride (DDBAC) surfactant.
The pore size of the synthesized materials could be tuned from microporous to mesoporous
range by the crystalline temperature or using mixed surfactants of DDBAC and cetyl-
pyridinium chloride. The pore structure can transfer from disordered tubular array to ordered
hexagonal phase by the increase of the molar ratio of CPC1 to DDBAC.

06-P-10 - F o r m a t i o n of d o u b l e - m e s o p o r e silica and its transformatoin into

MCM-41
X.-Z. Wanga,T. Doua,y.-z. Xiao a and B. Zhong b
~Institute of Special Chemicals, Taiyuan University of Technology. Taiyuan 030024 China
bState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, the Chinese Academy
of Sciences. Taiyuan 030001 China

The influence of alkali/silica molar ratio in the synthesis of mesoporous molecular sieve
materials was studied in a simple synthesis system containing tetraethylorthosilicate, water,
alkali and the cetyltrimethylammonium bromide at room temperature. The resulting silicate
materials were characterized by XRD, 29Si MAS NMR, TEM and N2 adsorption-desorption
isotherms. The results suggest that the formation of different surfactant-silicate aggregation
array morphology not only relies on an interaction between silicate ions and the surfactant,
but also on a proportion of the silicate species to surfactant.
200

06-P-11 - The synthesis and hydrothermal stability of directly usable

hexagonal mesoporous silica by efficient primary amine template extraction
in acidified water
K. Cassiers, P. Van Der Voort and E.F. Vansant
Dept. of Chemistry- Laboratory of Adsorption and Catalysis, University of Antwerp (U.I.A.),
Universiteitsplein 1, B-2610 Wilrij'k, Belgium, e-mail: kristofcassiers@ua.ac.be

High quality HMS was repeatedly and reproducibly prepared by a novel extraction procedure
to remove the primary amine template using acidified water. This very efficient extraction
(100%) does not affect the physical properties of the resulting mesostructure. Compared to the
ethanol-extracted HMS, no subsequent calcination step is required to remove the surface
ethoxy groups produced during the ethanol extraction. Moreover, the recovered surfactant can
be easily re-used in a fresh synthesis. Furthermore, an improved hydrothermal stability was
observed after using the acidified water extraction procedure.

06-P-12 - Synthesis and characterization of highly ordered chromium-

substituted MCM-48 materials with tailored pore sizes
C. Pak and G.L. Hailer
Department of Chemical Engineering, Yale University,
P.O. Box 208286, New Haven, CT 06520-8286, USA
Cr-substituted MCM-48 materials have been prepared by a direct hydrothermal procedure
using mixtures of cationic alkyltrimethylammonium surfactant with different alkyl chain
length and neutral surfactants. At least eight X-ray diffraction peaks corresponding to the
cubic Ia3d structure and high surface areas were observed for all the samples, which indicates
that the Cr containing materials have a highly ordered MCM-48 structure. Average pore size
of Cr-MCM-48 samples was increased from 3.2 to 3.9 nm with increasing alkyl chain from 14
to 18 carbons. It is suggested from an intense pre-edge peak in the XANES that the Cr in the
MCM-48 structure has tetrahedral coordination. -

06-P-13 - Preparation and characterization of mesoporous silica spheres

R. Van Grieken, D.P. Serrano, C. Martos and A.M. Melgares
ESCET. Universidad Rey Juan Carlos, c/Tulipdn s/n, 28933 M6stoles, Madrid, Spain.
e-mail: r. vangrieken@escet, urjc. es
The effect of different variables in the preparation of mesoporous silica spheres has been
investigated through a two-phase method that requires tetrabutoxy silane as silica source,
cetyltrimethylammonium chloride as surfactant, and water as solvent. The materials
synthesized show regular pores with sizes around 2.0 nm, BET surface areas larger than
1000 m2/g and a narrow spherical particle size distribution. These textural properties are
achieved through the surfactant removal by a mild calcination procedure, otherwise the
porous structure is partially destroyed. The size of the silica spheres so obtained can be
controlled in the range 300-700 pm through different variables, mainly by varying the
stirring speed of the two-phase solution.
 201

0 6 - P - 1 4 - Rapid synthesis of high quality MCM-41 silica via ultrasound

irradiation
X.-H. Tang (a,b), Ya. Wang (a), W. Huang (a,b), S. Liu (a,b), O. Palchik (a), E. Sominski (a),
Y. Koltypin (a) and A. Gedanken (a)
a Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900,
gedanken@mail.biu.ac, il, Israel
b College of Chemistry, Nankai University, Tianjin 300071, P. R. China

High quality MCM-41 silica has been sonochemically synthesized in a relatively short time
and characterized by XRD, TEM, 29Si MAS NMR, nitrogen sorption and hydrothermal
treatment. It reveals that ultrasound promotes the condensation of surface silanol groups
among micelles and accelerates the formation of MCM-41 framework. The as-synthesized
MCM-41 silica, whose pore size shows a very narrow distribution, possesses a thicker wall
and enhanced thermal stability as compared to those prepared with conventional methods.

0 6 - P - 1 5 - Synthesis of mesoporous aluminosilicate FSM-materials derived

from synthetic and natural Saponite.
T. Linssen (a), M. Barroudi (a), P. Cool (a) and E.F. Vansant (a)
a Laboratory of Adsorption and Catalysis, Univ. of Antwerp (U.I.A), linssen@uia.ua.ac.be

A new successful synthesis route for the preparation of FSM-16 is developed using leached
Saponite, in combination with cetyltrimethyl ammoniumbromide [CI6Ha3N+(CH3)3Br or
CTMA+Br ] as structure directing agent. Acid treatment of the clays allows the formation of
mesoporous aluminosilicate hexagonal structures (M41S family) with high porosity (max. 0.6
cc/g), high specific surface area (max. 900 cc/g), high pore wall thickness, a narrow pore size
distribution and uniform pore size distributions. Using natural clays as silica source is of great
interest in an economical and ecological way while the aluminium present in the clay and
finally in the mesoporous structure is an additional advantage looking to acid catalysis.

06-P-16 - 129Xe NMR and adsorption studies of Si-MCM-48 and Al-MCM-

48
G. Oye (a), M.-A. Springuel-Huet (b), J. Fraissard (b), M. St/3cker (c) and J. Sj~blom (d)
a Department of Chemistry, University of Durham,, Durham, UK
b Laboratoire Chimie des Surfaces, ESA 7069, Universitd P. et M. Curie, Paris, France
c SINTEF Applied Chemistry, Blindern, Oslo, Norway
d Statoil A/S R&D Centre, Rotvoll, Trondheim, Norway

Si-MCM-48 and A1-MCM-48 materials have been investigated by means of 129Xe NMR
spectroscopy and gas adsorption measurements. The chemical shift of adsorbed Xe in these
samples is found to be in the same range as for MCM-41 materials. Furthermore, A1-MCM-48
shows a higher chemical shift and a broader line width compared to Si-MCM-48. This might
be due to specific Xe-AI interactions or to interactions of Xe with a more irregular surface.
202

06-P-17 - 27Al-NMR studies on A I - M C M - 4 1 molecular sieves synthesized

with different Si/A! ratios and different a l u m i n u m sources
W. BOhlmann and D. Michel
University of Leipzig, Faculty of Physics and Geosciences, LinnOstr. 5, D-04103 Leipzig,
Germany, e-mail. bohlmann@physik uni-leipzig, de

AI-MCM-41 molecular sieves in there sodium and hydrogen form with different Si/A1 ratios
(16...256) were synthesized using aluminum sulfate and aluminum triisopropylate as source.
In all experiments the pH value was held at about 10 during the synthesis procedure. The
products in the as-synthesized form and after calcination were characterized by means of
XRD diffraction, nitrogen adsorption-desorption, and two different techniques of the solid-
state 27A1 MAS NMR spectroscopy. Applying the cross-polarization (CP) magic angle
spinning (MAS) spectroscopy makes it possible to determine the local environments of the
aluminum species and to distinguish better between framework and non-framework
aluminum.

06-P-18 - Control of formation of m e s o p o r o u s SBA-3 and SBA-1 through

organic additives
S. Che and T. Tatsumi
Division of Materials & chemical Engineering, Faculty of Engineering, Yokohama National
University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
The synthesis and kinetics of formation of SBA-1 mesoporous molecular sieve was greatly
affected by the addition of trimethylbenzene (TMB) isomers. The synthesis of SBA-1 was
performed at 0~ using tetraethyl orthosilicate (TEOS) as the silicon source and
cetyltriethylammonium bromide (CTEABr) as the template under acidic conditions. XRD
shows that a well ordered hexagonal p6mm SBA-3 mesophase rapidly forms and then
transforms to cubic Pm3n SBA-1 mesophase with proper TMB/CTEABr molar ratios. The
presence of 1,2,3-TMB was the most favored to form p6mm hexagonal mesophase, and 1,2,4-
TMB showed an intermediate behavior.

06-P-19 - The influence of AI, La or Ce in the thermal and h y d r o t h e r m a l

properties of M C M - 4 1 m e s o p o r o u s solids
R.A.A. Melo and E.A. Urquieta-Gonzfilez*
Dep. Chem. Eng., C. Postal 676, S~o Carlos-SP, Brazil. e-mail." urquieta@power.ufscar.br
The thermal (at 1153 K) and hydrothermal stability (at 933 K) of Si-, AI-, La- and Ce-MCM-
41 were studied. The solids were synthesized at 373 K. XRD data indicated that Si-MCM-41
presented the more resolved XRD pattern, therefore the most ordered porous structure. XRD
and N2 sorption showed that the thermal treatment leads to a structure degradation with La-
MCM41 showing the higher stability and Ce-MCM-41 suffering a total structure collapse. In
the hydrothermal treatment, Ce-MCM-41 maintained above of 80% of its SBETarea and 55%
of its primary mesoporous volume. In those thermally conditions La-MCM-41and A1-MCM-
41 were more stable than Si-MCM-41. The intensity of the band at 960 cm l in the FT-IR
spectra can be well related with the order of porous array in the prepared MCM-41 solids.
 203

06-P-20- Controlling the assembly of silica mesoporous materials by

varying the decrease in pH
J. Rathousk~, (a), J. t2ejka (a), P.J. Kooyman (b), M. Slabovfi (a) and A. Zukal (a)
a J. Heyrovskfi Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolej~kova 3, 182 23 Prague 8, Czech Republic, e-mail.'jiri.rathous~@/h-inst.cas.cz
b National Centre for High Resolution Electron Microscopy, Delft University of Technology,
Delft, The Netherlands, e-mail." p.j.kooyman@tnw.tudelfi.nl

The synthesis of mesoporous silicas was performed from an isotropic reaction mixture using
cationic surfactant as a structure directing agent. The decrease in pH, which causes the
formation of solid particles, was achieved by hydrolysis of methyl acetate. The procedure
enabled to obtain not only siliceous MCM-41 but also a less well-ordered hexagonal silica
with extraordinary large surface area and silica with bimodal mesoporous structure containing
the MCM-41 mesopore system and a system of mesopores with a mean diameter of 14 nm.

06-P-21 - Characterization of MCM-41 aged for different periods

H. A1-Megren a ,T.-C. Xiao a, A.P.E York a, J. Sloan a, S. AI-Khowaiter b, S.-F. Ji a and M.L.H.
Green a*
Wolfson Catalysis Centre, Inorganic Chemistry Laboratory, Oxford University, South Parks
Road, Oxford, UK, OX1 3QR, email: malcolm.green@chem.ox.ac.uk
bPetroleum and Petrochemicals Research Institute, King Abdulaziz City for Science and
Technology, P. O. Box 6086, Riyadh 11442, Saudi Arabia.
A series of MCM-41 samples have been synthesised with varying aging times and
characterized using XRD, TEM, N2-adsorption, Laser Raman and IR spectroscopy. The aging
time effects the structure, crystallinity and adsorption properties of the MCM-41 molecular
sieves. In our preparations, the sample aged for 7 d had the highest crystallinity, while an
aging time over 7 d gives rise to irregular morphology of the MCM-41 particles, and a lower
crystallinity. Calcination not only removes the template inside the molecular sieve, but also
causes the sample to restructure and improves the crystallinity.

06-P-22 - Synthesis and characterization of silica and aluminosilica-

surfactant nanocomposites
E. Popovici a, A. Visan b, D. FilipC,G. Burtica d and R. Pode ~
"Al.I. Cuza" University of lasi, Romania, eveline@uaic.ro b ICERP Ploiesti, Romania
c"p.Poni" Institute of Macromolecular Chemistry, Iasi, Romania
d "Politehnica" University of Timisoara, Romania

Silica and aluminosilica-surfactant nanocomposite materials were prepared in the presence of

[C18H37(CH3)3N]+ cations. The crystallinity, surface area, pore diameter distribution, thermal
stability and the proportion of organic phase of these materials have been investigated in
correlation with SiO2/R, AlzO3/R, SIO2/A1203 molar ratios of reaction mixture. It was found a
specific interaction between organic cations and aluminum atoms of oxidic framework
204

06-P-23 - Improved thermal stability of mesoporous alumina support of

catalysts for the isomerization of light paraffins
V. Gonz~ilez-Pefia, C. M~irquez-Alvarez, E. Sastre and J. P~rez-Pariente
Instituto de Catdtlisis y Petroleoquimica (CSIC), Madrid, Spain. jperez@icp.csic.es

Mesoporous alumina samples have been synthesized using poly(ethylene oxide)-based

nonionic surfactants. The effect that the addition of n-alkylamines to the synthesis gel has on
the texture and thermal stability of mesoporous aluminas is studied. Textural and structural
characterization using nitrogen adsorption, powder X-ray diffraction, 27A1nuclear magnetic
resonance and Fourier Transform infrared spectroscopy, as well as catalytic n-hexane
hydroisomerization tests are performed.

06-P-24 - Synthesis of mesoporous molecular sieves M C M - 4 8 under several

reaction conditions
S. Rodrigues da Rocha and L. Domiciano Fernandes
Universidade Federal Rural do Rio de Janeiro, e-mail. lindoval@ufrrj.br

Samples of MCM-48 mesoporous molecular sieves were synthesized by changing reaction

conditions. Synthesis temperature was varied in the 373-423K range and crystallization time
was 24-192 hours. Synthesis gel presented a molar composition of 1.0 SIO2:0.25 Na20:0.2-
1.0 CTABr:60-400 H20. It was observed that highly ordered MCM-48 samples were obtained
at 373K for 72 hours, from a gel presenting CTABr/SiO2 ratio of 0.55 and intermediate
dilution. Samples recovered under this synthesis conditions had surface area greater than 1000
mVg, pore volumes of 0.8 cmVg and narrow pore size distribution. It was showed that
MCM-48 was an intermediate phase between hexagonal and lamellar and that the transition to
lamellar could be prevented by pH adjustment or NaCI addition.

06-P-25 - Parallel synthesis of mesostructured materials

P. Behrens and C. Tintemann
Institut fiir Anorganische Chemic, Universitat Hannover, Callinstrafle 9, Hannover,
Germany," Peter.Behrens@ mbox.acb, uni-hannover.de

The formation of mesostructured materials of the M41S family and of related materials is a
very complex field. Synthesis field diagrams (SFDs), which list the conditions of formation of
different structural topologies as a function of the concentrations of the surfactant and silica
precursors, reveal interesting details about the synthesis process. For the construction of an
SFD, it is necessary to perform 120 to 150 synthesis experiments. The time necessary to
construct an SFD for a certain set of reaction conditions (temperature, reaction time, basicity
of the solution) can be reduced drastically by using the approach of parallel synthesis. Here
we present an autoclave array allowing the parallel synthesis of 24 samples and our results
obtained with this invention.
 205

06-P-26 - Mesostructural transformation in the presence of fluoride anions

Q.-H. Xia, K. Hidajat and S. Kawi*
Department of Chemical and Environmental Engineering, National University of Singapore,
Singapore, Republic of Singapore - chekawis@nus, edu.sg
Most mesoporous M41s materials are hydrothermally synthesized at temperatures below 150~
In some cases, there is a dependence of mesostructural transformation on time, temperature and
compositions. When the temperature is over 150~ the formation of zeolites like ZSM-5 can take
place. MCM-41 with enhanced hydrothermal stability can also be synthesized in fluoride medium.
Here we report the factors influencing mesostructural transformation in fluoride medium. The
appearance of lamellar and zeolite phases like ZSM-5 can be prevented through the molar
compositions of precursor, and MCM-41 can be formed at temperatures as high as 170~ With
the molar composition of 1.0 SIO2:0.54 NaOH: 0.50 CTMABr: 0.34 HF: 100 H20, the sequence
of structural transformations does not undergo through the formation of lamellar and zeolites. We
have also found that the mesostructure with type H2 hysteresis loop also possesses good
hydrothermal stability.

0 6 - P - 2 7 - Swelled micelle-templated silicas (MTS): structure control and

hydrophobic properties
D. Desplantier-Giscard, A. Galameau, F. Di Renzo and F. Fajula
Laboratoire de Mat~riaux Catalytiques et Catalyse en Chimie Organique, UMR 5618 CNRS-
ENSCM, Montpellier. France- galarne@cit.enscm.fr
The synthesis of swelled-MTS with cylindrical mesopores is highly dependent on the nature
of the swelling agent: aromatics allow to preserve the cylindrical geometry of pores, aliphatics
change pore geometry to a system of interconnected spheres. This is due to the different sites
of solubilization of the organics in CTAB micelles. For polarizable molecules, like aromatics,
there are two sites of solubilization: near the micellar interface (interaction with ammonium
head group) and in the micellar core. Aliphatic molecules are directly dissolved in the center
of the micelles. Purely silliceous and aluminosilicates MTS with regular cylindrical pores up
to 150 A were obtained. Uncalcined swelled MTS present an original property: they are
hydrophobic and this will extend the applications of MTS as adsorbents.

06-P-28 - Synthesis of pure and iron-containing mesoporous silica. Effect of

washing and removal of template on the porous structure
L. Pasqua a, F. Testa a, R. Aiello a, F. Di Renzob and F. Fajula b
"Dip. Ingegneria Chimica e dei Materiali, Universit~t della Calabria, Rende, Italy-
f.testa@unical.it- bUMR 5618 CNRS, ENSCM, Montpellier, France.
Synthesis of pure and iron-containing mesoporous silicas are carried out from CTMA
mixtures containing different salts and hydrochloric acid. Ferric salts decrease the pH of the
synthesis batch, except when complexed by fluoride ions. Samples obtained from neutral
batches in the presence of fluoride are stable when washed and calcined. For syntheses at
acidic pH and low temperature, a low degree of silica condensation is responsible for thin
unstable silica walls. When surfactant molecules are extracted by washing or calcination, the
porosity shrinks and disordered microporous solids are formed from ordered mesophases with
40 A micelles.
206

10 - Host-Guest Chemistry (Monday)

10-P-05- Non-acidic zinc zeolite systems: preparation methods, formation

processes and catalytic properties in dehydrogenation of methanol
N.Y. Usachev*, E.P. Belanova, A.V. Kazakov, V.P. Kalinin, A.S. Fomin, I.M. Krukovsky,
G.V. Antoshin and O.K. Atal'yan; N.D. Zelinsky Institute of Organic Chemistry, RAS, 47
Leninsky Prosp., Moscow, Russia 117334, * FAX. (7095) 135-5328, e-mail: ny@ioc.ac.ru
New methods of micro heterogeneous super loaded ZnO/FAU systems synthesis were
developed which allow to control oxide phases state. Their formation and properties were
studied by TG-DTA, XRD and IR spectroscopy. High ZnO dispersion, which is provided by a
decomposition of Zn salts on ion exchanged FAU, is favorable for catalytic conversion of
CH3OH to water-free CH20 over these systems. Suggested methods can be used for a
preparation of systems containing oxide phases of one or several transition metals which, due
to their unusual properties, may find various applications in adsorption and catalysis.

10-P-06 - Incorporation of Ga ions into Y zeolites by reductive solid-state

ion exchange
R.M. Mih~lyi, H.K. Beyer and M. Keindl
Institute of Chemistry, Chemical Research Center, Hungary, rosmag@cric.chemres.hu
The incorporation of cationic Ga species into Y zeolites by reductive solid-state ion exchange
and the oxidation state of introduced Ga were studied by IR spectroscopy and TPR. In mix-
tures of NH4Na-Y (Si/A1 = 2.5) with Ga203 thermally treated in a static H2 atmosphere,
RSSIE and dehydroxylation, both consuming Br6nsted acid sites, were found to proceed
simultaneously. The incomplete incorporation of cationic Ga was accompanied by release of
part of the framework A1. In contrast, partially dealuminated Y zeolite (13.2) obtained by
solid-state dealumination with (NH4)2[SiF6] could be completely exchanged by RSSIE, i.e. no
de-hydroxylation occured due to higher thermal stability of the Br6nsted sites. Though reduc-
tion was found to be an indispensable step in the ion-exchange process in static H2, primarily
formed Ga + ions seem to react immediately with the reaction product water to GaO + and H2.

10-P-07- Heavy metal exchanged zeolites as precursors for high

temperature stable phases
W. Schmidt and C. Weidenthaler
MPI fi~r Kohlenforschung, Mfilheim, wolfgang.schmidt@mpi-muelheim.mpg.de, Germany
Dense heavy metal containing phases were synthesized by the calcination of ion exchanged
zeolites. The phases formed and their properties were dependent on various parameters such
as ion exchange conditions, calcination conditions and composition of the zeolites. The type
of exchanged cation determined the structures that were formed during the calcination.
Generally, thermodynamically stable phases were formed at high temperature and sufficiently
long calcination but by kinetic control metastable intermediates could be obtained as well.
The control of these parameters enabled the synthesis of high temperature stable materials
with well defined properties, which can be used as refractive materials and for catalysis or
sensor technology.
 207

10-P-08- Preparation and characterization of H-ZSM-5 exchanged with

cobalt by solid state ion exchange
M. Mhamdi l., S. Khaddar-Zinel'2, A. Ghorbel l, Y. Ben Taarit 3 and C. Naccache 3
ILaboratoire de Chimie des Matdriaux et Catalyse, Facultd des Sciences de Tunisi Tunisia.
2Institut Prdparatoire aux Etudes d'ingdnieur de Nabeul, El Merazka, Nabeul, Tunisia.
3Institut de Recherches sur la Catalyse Villeurbanne - France.

Physico-chemical and catalytic properties of Co-ZSM-5 zeolites prepared by solid state

exchange with different Co/A1 ratios and exchange temperatures were compared. The
catalysts were characterized by XRD, Nz-BET, FTIR, UV-Vis and TPD of ammonia. Solid-
state ion exchange generated new Lewis acid sites and one proton was exchanged per Co 2+
species. UV-Visible spectra indicate the presence of some minor cobalt oxides, not detected
by XRD. Catalyst using Co/AI ratio equal to 1 and issued from exchange temperature equal to
500~ show high activity and selectivity towards acetonitrile by ammoxidation of ethylene.

10-P-09 - Cyclic chemical vapour deposition of TEOS on ZSM-5: effect of

deposition temperature on shape selective performance
H. Manstein, K.P. M~ller and C.T. O'Connor
Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town,
South Africa - Heiko@chemeng. uct.ac.za

H-ZSM-5 catalyst was modified with tetraethoxysilane using a cyclic chemical vapour
deposition technique between 50~ and 400~ External activity was eliminated and the
shape-selective performance of the catalyst could be improved to 90% para-isomer for all
temperatures studied. Elevated deposition temperatures led to faster changes in the product
distribution of xylenes but also to a more rapid decrease in the conversion of toluene which
reduced the yield to the para-isomer. It was shown that modification at low temperatures
resulted in the best improvements of the catalyst for the disproportionation of toluene.
208

11 - Post-synthesis Modification (Monday)

I I - P - 0 6 - Dealumination of zeolite KL
E.E. Knyazeva l, V.V. Yuschenko l, F. Fajula 2 and I.I. Ivanova l
1Laboratory of Kinetics and Catalysis, Department of Chemistry, Moscow State University,
Moscow, Russia, e-mail: Illvanova@chem.phys.msu.ru
2Laboratoire de Mat6riaux Catalytiques et Catalyse en Chimie Organique, UMR 5618,
Montpellier, France, e-mail:fajula@cit.enscm.fr

Zeolite KL has been dealuminated by combining hydrothermal, ion exchange and acid attack
treatments. The dealumination process is govemed by the removal of potassium ions from cationic
sites located inside the cancrinite cages which exert a long-range inductive stabilization of the
framework. Deep bed calcination of the partly exchanged samples promotes migration of these cations
towards exchangeable sites. Further steam dealumination and acid attack allow to produce highly
crystalline materials, with a global Si/AI ratio close to 10 and featuring strong acid sites 9

1 l - P - 0 7 - Formation of acidic hydroxyl groups during preparation of Pt/KL

catalysts as studied by tH M A S N M R
T. Sato (a), S.-I. Ito (a), K. Kunimori (a) and S. Hayashi (b)
a Institute of Materials Science, University of Tsukuba, Tsukuba, Japan
b National Institute of Materials and Chemical Research, hayashi@nimc.go.jp, Japan

Acidic hydroxyl groups in Pt/KL zeolite prepared by the ion exchange method have been
characterized quantitatively by IH MAS NMR. After the ion exchange by [Pt(NH3)4] 2+, the
calcination process produces acidic hydroxyl groups. NH4 + ions produced by decomposition
of [Pt(NH3)4] 2§ are considered to be the origin 9 The H2 reduction process also produces the
9
acidic hydroxyl groups by the reaction Pt 2 + + H2 ---> Pt 0 + 2H + . This9 indicates
9 9
that after the
calcination P(+ ions are dominant species. ~H chemical shift depends on the concentrations of
Pt and the acidic hydroxyl groups and also on the Pt state. The stronger acidity is originated in
the following order of Pt 2§ > H § > K §

II-P-08 - Synthesis and characterization of mesopore Y zeolite

B. Ma a,b, W.F. Sun c, Z.L. Sun b and L.R. Chen a
aLanzhou Institute of Chemical Physics, The Chinese Academy of Sciences, Lanzhou, P. R.
China," bFushun Petroleum Institute, Fushun, P R China
CFushun Research Institute of Petroleum and Petrochemicals, Fushun, P R China

In this presentation, the HY zeolite with a lot of secondary pores (the diameters of the
secondary pores are larger than 2 nm), unblocked channels and low acid site density has been
prepared by steaming and acid leaching treatment of HY zeolite. The steaming and acid
leaching treatment conditions were examined in details, and the optimal treatment conditions
were determined. This kind of HY zeolite, so called mesopore HY zeolite, showed higher
activity than HY zeolite in hydrocracking larger molecules 9
 209

1 l-P-09 - Controlling the pore size of HI~ zeolite by improved chemical

vapor deposition of (CH3)aSi-O-Si(CHa)a
Y. Chun a*, X. Ye b, Q.H. Xu a and A.-Z. Yan a
Department of Chemistry, Nanjing University, Nanjing 210093, China,"ychun@nju.edu.cn
bDepartment of French, Nanjing University, Nanjing 210093, China
The pore size of large-pore zeolite HB is controlled by an improved chemical vapor deposition
(CVD). In this method, ammonia or tripropylamine was used to protect the acidic sites in
zeolite before deposition of (CH3)3Si-O-Si(CH3)3, differently from the conventional CVD.
The pore volume of zeolite HI3 was reduced and the pore size was narrowed upon this
modification. The results from IR spectra and catalytic decomposition of isopropanol
demonstrated that the modified samples showed stronger acidity than that prepared from
conventional CVD. In the transformation of trimethylbenzenes (TMB), conversion of 1,3,5-
TMB was suppressed while conversion of 1,2,3-TMB was almost unaffected on the improved
CVD samples; the selectivity of 1,2,4-TMB on these samples was increased in the alkylation
reaction of m-xylene with methanol.

I I - P - 1 0 - I n f l u e n c e of pH of the solution on r e a l u m i n a t i o n of B E A
zeolite
Y. Oumi (a), R. Mizuno (a), K. Azuma (a), S. Sumiya (a), S. Nawata (b),
T. Fukushima (b), T. Uozumi (a) and T. Sano (b)
a School of Materials Science, Japan Advanced Institute of Science and Technology,
Tatsunokuchi, Ishikawa 923-1292, t-sano@jaist.ac.jp, Japan.
b Tosoh Corporation, Shin-nanyo, Yamaguchi 746-8501, Japan.
The influence of pH value in the solution on the realumination process of BEA zeolite was
investigated by mean of nitrogen adsorption, XRD, 27A1 MAS NMR and FT-IR. It was found
that non-framework aluminum species (octahedrally coordinated aluminums) in the solution
are easily reinserted into the framework of dealuminated BEA zeolite by controlling the pH
value o( the solution below 7. The cumene cracking activity of the realuminated BEA zeolite
at pH 5.1 was comparable to that of the parent BEA zeolite. The influence of aluminum
species in the solution on the realumination process was also investigated using various
aluminum compounds.

I I - P - I I - Formation of carbon-intercalated molybdenum sulfides

J.-S. Chen,* Y. Wang, Y. Guo, Y. Zou and W. Xu
Key Laboratory of Inorganic Synthesis and Preparative Chemistry Jilin University.
chemcj@mail.jlu.edu.cn, Changchun, P R. China

Molybdenum sulfide compounds (MoS2-C) with intercalated carbonaceous matter have been
obtained by pyrolysis of a surfactant-containing mesolamellar molybdenum sulfide in a
nitrogen flow at various temperatures. The samples contain about 22 wt% of carbon, and the
interlayer distance for the MoS2-C compounds is about 9.8 A. The solid obtained by treatment
at 973 K exhibits considerable N2 adsorption capacity. The electrical conductivity for the
MoS2-C materials is higher than that of the pristine MoS2 at low measurement temperatures,
and it strongly depends on the pyrolysis temperature. It is believed that the carbon intercalated
between the MoSa sheets plays a role in the conductivity enhancement.
210

1 I - P - 1 2 - Characterization of partly-detemplated GaPO4-LTA

S.-F. Yu, C.-Y. Xi, H.-M. Yuan and J.-S. Chen*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
chemcj@mail.jlu, edu. cn, Changchun, P. R. China

Gallophosphate GaPO4-LTA crystals were heated under vacuum and in a nitrogen

atmosphere, respectively. It has been found that the resulting materials are partly-detemplated
and retain the LTA framework structure even in moist atmosphere. The thermally-treated
GaPO4-LTA compounds exhibit considerable adsorption capacities for water and nitrogen but
the adsorption behavior depends on the pyrolysis conditions. In contrast to the channels of
AFI in which the generation of carbon nanotubes has been realized, the a-cages of GaPO4-
LTA have a space large enough for the formation of fullerene-like materials that might exist
in the carbonaceous matter of the partly-detemplated GaPO4-LTA compound.

l l - P - 1 3 - Another study on the microwave heating of zeolite without special

loading materials
J. Dong (a), L. Xie(a), X. Jing(a), H. Xu (a), F. Wu (b) and J. Hao (c)
a Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024,
Shanxi, P.R.China* email: jxdong @ public ty.sx.cn; b Department of Chemical Engineering,
Beijing Institute of Technology, Beijing 100081, P.R.China; c Department of Information
Engineering, Taiyuan University of Technology, Taiyuan 030024, PR. China
The heating and phase-transformation of zeolites caused by microwave irradiation at
2450MHz without special loading materials are examined. It is found that zeolite X was
heated to 1473K about 90 seconds at power output of 400W. It is verified that the center of
microwave absorption is not water or surface hydroxyl groups, not silica in zeolites, but
electron bearing AIO4 tetraedra. The ability of zeolites to absorb microwave energy depends
on zeolitic framework structure, exchangeable cations, Si/AI molar ratio, as well as adsorbed
compounds in zeolite.

II-P-14 - Microwave plasma treatment as an effective technique for

activation of zeolite catalysts
I.I. Lishchiner (a), O.V. Malova (a) and E.G. Krasheninnikov (b)
(a) Institute of Organic Chemistry RAS, zaporozhsky@hotmail.com
(b) Russian Research Center "Kurchatov Institute" Moscow, Russia
An afterglow microwave plasma with stabilized pulse power was applied to the activation of
zeolite catalysts for isobutane alkylation with butenes. It was found that the pretreatment of
zeolite catalysts in a microwave plasma discharge affected their properties. The catalysts
exhibited higher activity, stability in operation, and selectivity (the fraction of
trimethylpentanes in the alkylate increased). The properties of catalysts after plasma
activation depend on the treatment conditions such as plasma "temperature" and non-
equilibrium character and depend only slightly on the initial activity of catalysts, which is
primarily controlled by the catalyst preparation conditions.
 211

1 I - P - 1 5 - Synthesis and characterization of microporous titanium-silicate

materials
S. Mintova, B. Stein, J.M. Reder and T. Bein*
Department of Chemistry, University of Munich, Butenandtstr. 11-13 (E), 813 77 Munich,
Germany, svetlana, mintova@cup, uni-muenchen, de

The synthetic counterparts of the minerals zorite and pharmacosiderite were hydrothermally
synthesized in SiQ-TiOz-MzO-(TMA)20-water systems using atypical precursor gel
compositions which result in different crystal morphologies. Nanocrystalline pharmaco-
siderite with individual particles of <100 nm were prepared using an organic template.
Micrometer sized ETS-4 with a flattened cuboid morphology was also synthesized. The ion-
exchange of Na + and K + for NH4+, Sr2+ and Mg 2+ was performed. The as-synthesized and the
ion-exchanged samples were characterized by XRD, SEM, as well as IR, UV-vis and Raman
spectroscopies.

1 I-P-16 - From borosilicate to gallo- and aluminosilicate zeolites:

new methods for lattice substitution via post-synthetic treatment
C.Y. Chen and S.I. Zones
Chevron Research and Technology Co., Richmond, CA 94802, USA, cych@chevron.com

In this paper we report new methods for the lattice substitution of heteroatoms in large and
extra-large pore borosilicate zeolites via post-synthetic treatment to prepare catalytically more
active zeolites. Ga-SSZ-33, A1-SSZ-33 and AI-UTD-1 prepared from B-SSZ-33 and B-UTD-
1, respectively, are discussed as examples. The materials are characterized with various
physicochemical techniques and catalytic reactions. In particular, the advance of these
methods is demonstrated by the exceptionally high activity of the resulting A1-SSZ-33 for
acid-catalyzed hydrocarbon conversions.

I I - P - 1 7 - Studies on the structure of zeolite Y modified by radio-frequency

fluorocarbon plasma treatment
S. Yamazaki a, T. Nishimura a, K. Furukawa b, H. Ijiri c and K. Tsutsumi d
a Shizuoka Institute of Science and Technology, Shizuoka, Japan, yamazaki@ms.sist.ac.jp
b Adv. Sci. and Tech. Center for Cooperative Research, Kyushu University, Fukuoka, Japan
c Interdisciplinary Graduate School of Eng. Sci., Kyushu University, Fukuoka Japan
d Toyohashi University of Technology, Toyohashi, Japan

H-type zeolites Y with silica/alumina ratios of 5.6 and 29 were modified by a radio frequency
CF4 plasma treatment. On the basis of the weight loss due to the elimination of carbon and
fluorine atoms observed by TG/DTA-MASS spectroscopy, functional groups existing on the
surface were stable up to 700K. The amount of component elimination in high aluminum
content zeolite Y was larger than that in low aluminum content, which suggests that the
functional groups were introduced near aluminum site in the framework.
212

I I-P-18 - Dual-temperature reagent-less ion-exchange separations on

zeolites
V.D. Timofeevskaja, O.T. Gavlina, V.A. Ivanov and V.I. Gorshkov
Department of Chemistry, M. V. Lomonosov Moscow State University,
Moscow 119899, Russia
E-mail." ivanov@physch, chem. msu.su

Dual-temperature ion-exchange purification of concentrated solutions of alkali metal salts

from divalent and monovalent ion admixtures on a number of natural and artificial zeolites
without auxiliary reagents consumption is studied. Two types of dual-temperature techniques
- the temperature-swing mode of separation and the parametric pumping - are used.

I I - P - 1 9 - Rare earth exchange in small pore zeolites and its effect on their
hydrothermal stability
G. Cao, M.J. Shah and W.A. Wachter
ExxonMobil Research and Engineering Company, gcao@erenj.com, USA

While zeolites with 8-ring pore openings have been the target of numerous studies of ion-
exchange because of their relevance to water softening and radioactivity management, study
of their rare earth ion-exchange properties in the context of catalysis has been scarce. We
report here solution and solid-state rare earth exchange reaction in ZK-5 and chabazite, the
kinetics and thermodynamics of the solution exchange, and the effect of exchange on the
hydrothermal stability of the zeolites. While the solid-state exchange method results in loss of
crystallinity, the solution exchange method is effective, but the exchange rate is slow even at
elevated temperatures. The exchange isotherms show that selectivity for rare earth cation is
low with both zeolites. Rare earth exchange is found to improve the hydrothermal stability of
both zeolites, for which a speculative explanation is forwarded.

1 l-P-20 - Modification of mordenite and natural clinoptilolite by copper:

role of drying temperature
I. Rodriguez-Iznaga (a, b), V. Petranovskii (r G. Rodriguez-Fuentes (b), N. Bogdanchikova (c)
and M. Avalos (c)
a Higher Mining-Metallurgical Institute ofMoa, Las Coloradas, 83329 Moa, Holguin, Cuba
b Zeolites Engineering Laboratory, Institute of Materials and Reagents (IMRE), Faculty of
Physics, University of Havana, 10400 Havana, Cuba
c Centro de Ciencias de la Materia Condensada, UNAM, Ensenada, Mexico, vitalii@ccmc.unam.mx

The influence of pre-reduction heating treatment in air on the reducibility of copper supported
on clinoptilolite and mordenite was investigated. After dehydration the process of Cu-mordenite
reduction is hindered and the formation of copper particles is suppressed. This result could be
used for the stabilization of Cu inside the zeolite pores and the prevention of copper agglomeration
on the external surface, which could lead to improved catalysts for de-NOx processes.
 213

II-P-21 - Study on the acidity of modified H Y zeolites prepared by combi-

nation of chemical dealumination and h y d r o t h e r m a l treatment
M. Han, L.-P. Zhou, X.-W. Li and L.-Q. She*
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871,
liqin@chemms, chem.pku, edu. cn, China
Acidity of modified HY zeolites prepared by combination of chemical dealumination and
hydrothermal treatment have been characterized by IR, MAS NMR and n-butylamine
titration. The results showed that by increasing the level of dealumination, the total amount of
acid sites decreased while the strongest acid sites (H0 < -8.2) increased. The strength
population profile of acid sites revealed that only the aluminum atoms associated with the
stronger acid sites (-8.2 < H0 < -5.6) were extracted from the framework during the
dealumination steps. These results were correlated with the population of Si(nA1) groupings
obtained from the spectra of 29Si MAS NMR. The acidity changes at each step of preparation
procedure are discussed.

11-P-22 - Modification of Beta-zeolite by dealumination and realumination

J.Y. Zhang, L.-P. Zhou and X.-W. Li
Department of Chemistry, Peking University, Beijing 100871, China
xwli@chemms, chem.pku, edu. cn

The dealumination and realumination of low sodium [3-zeolite have been studied by IR
spectroscopy and powder X-Ray diffraction. The calcination-dealuminated HI3 was easily
realuminated by direct treatment with aluminate sodium solution. After transformation into
protonic HI3, the framework Bronsted sites (IR band at 3610 cm ~) were restored and the
acidity was the same as in the original HI3. The realumination of acid dealuminated HI3 was
difficult, but could be achieved with aluminate sodium solution by hydrothermal treatment in
autoclave. This incorporation of A1 into zeolite framework increased the number of acid sites,
in particular that of weak acid sites which in comparison with parent HI3.

11-P-23 - Ultrastable zeolites Y (USY) modified with p h o s p h o r u s and boron

A.V. Abramova a, Y.V. Slivinsky a, L.Y. Kitaev b, A.A. Kubasov b, H. Lechert c, W.D. Basler c,
V.V. Yushchenko b and Z.M. Matieva a
a A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences,
Leninsky prospect, 29, 117912, Moscow, B-71, Russia, e-mail." tips@ips.ac.ru
b Moscow 34. V. Lomonosov State University, Moscow, Russia
r Institute of Physical Chemistry, University of Hamburg, Hamburg, Germany

USY zeolite has been modified by an acid treatment with H3PO4 and H3BO3. The properties
of the modified samples have been investigated by various methods. After loading with
platinum the catalytic properties with respect to n-hexane isomerisation have been studied.
The modification changes significantly the adsorption properties. The modified catalysts are
more active in n-hexane isomerization than USY.
214

11-P-24 - Structural properties and sieving effects of surface modified

ZSM-5
S. Zheng l, H. Heydenrych l, H.P. R~ger 2, A. Jentys I and J.A. Lercher l
l TU-Mfmchen, Institute f Chemical Technology, Garching, Germany,
http.'//www, chemie, tu-muenchen, de/tc2/ ; 2Sud-Chemie A G, Bruckmuehl-Heufeld, Germany

Chemical liquid deposition of tetra-ethoxysilane was used to modify the external surface and
pore mouth region of HZSM-5 with different crystal sizes. After modification, a decrease in
the overall concentration of silanol and bridging hydroxide groups was observed.
Modification led to only minor changes in the micropore volume of HZSM-5 and in the
diffusivities of toluene and p-xylene, while the diffusivity of o-xylene was substantially
suppressed and the p-selectivity in the disproportionation of toluene was significantly
increased. A more significant modification effect could be achieved with a single cycle
silanization of large HZSM-5 crystals compared to a three-cycle silanization of small crystals.

11-P-25 - The use of binary adsorption studies to investigate the effect of

h y d r o t h e r m a l treatment on zeolites Rho and M o r d e n i t e
L.H. Callanan (a), C.T. O'Connor (b) and E. van Steen (b)
a Lehrstuhl II fur Technische Chemic, Tech. Uni. M~nchen, linda.callanan@ch.tum.de,
Germany," b Catalysis Research Unit, Dept. of Chem. Eng., University of Cape Town, South
Africa

Adsorption studies of methanol, water and ammonia, and binary mixtures of these
compounds, have been used to explain the difference in the change in reaction behaviour of
zeolites Rho and mordenite in the methanol amination reaction after hydrothermal treatment.
It is found that the changes in the total adsorption capacities were related to the changing pore
volumes and to the presence of extra-framework aluminium within the pores of the catalysts.
The changes in the reaction performance of the catalysts for the methanol amination reaction
were also correlated to the changes in acidity, structure and adsorption capacity of the
catalysts.

11-P-26 - Acid sites in thermal transformations of Ca-rich clinoptilolite

G.P. Valueva a, I.S. Afanassiev b, E.A. Paukshtis c, Y.V. Seryotkin a, N.K. Moroz b and A.A.
Budneva ~
~Institute of Mineralogy and Petrography, Acad. Koptyug ave. 3, 630090, Novosibirsk, Russia
bInstitute of Inorganic Chemistry, Lavrentyev ave, 3, 630090, Novosibirsk, Russia
CInstitute of Catalysis, Lavrentyev ave, 5, 630090, Novosibirsk, Russia

Five cycles of heating (450 ~ exerted over a Ca-rich clinoptilolite from basalt,
resulted in the distortion of structure and its stabilization. The symmetry was lowered from
monoclinic to triclinic, positions of extraframework cations and H20 molecules were retained.
These changes conform with the formation of framework (bridging) OH groups, detected by IR-
and NMR-spectroscopy. The most drastic changes occurred during the first heating, exhibited as
deficiency of rehydration and the most extensive OH group formation. During further cycles OH
groups changed their positions and the deficiency of rehydration stabilized.
 215

11-P-27- The effect of calcination on the isomorphously substituted micro-

porous materials using ozone
D. Mehn a, A. Kukovecz a, I. Kiricsi a, F. Testa b, E. Nigro b, R. Aiello b, G. Daelen c, P. Lentz c, A.
Fonseca c and J. B.Nagy c
aApplied Chemistry Department, University of Szeged, H-6720 Szeged, Hungary
bOip. di Ingegneria Chimica e dei Materiali, Univ. della Calabria, 1-87030 Rende (CS) Italy
r de RMN, Facult6s Universitaires Notre-Dame de la Paix, 61 Rue de Bruxelles,
5000 Namur, Belgium

The templating organic molecules or ions have been eliminated by using an oxygen or an
ozone treatment. The mild conditions used for the latter preserve quasi intact the various
tetrahedral framework elements in B-, Co-, Co, A1-ZSM-5 and in Ga-MCM-22 zeolites.

11-P-28- Aiumination of siliceous zeolites

A. Omegna, M. Haouas, G. Pirngruber and R. Prins
Lab. Tech. Chem., ETH-Z~irich, CH-8092 Ziirich, Switzerland (prins@tech. chem. ethz. ch)
The post-synthesis incorporation of aluminium into the lattice of pure siliceous zeolite-~ was
attempted using aluminium isopropoxide as aluminating agent in a non-aqueous environment.
The XRD structural analysis of the Al-grafted materials showed an increase in the unit cell
parameters which was associated with the insertion of aluminium into the framework.
Quantitative multinuclear NMR investigation showed that the amount of framework
aluminium incorporated into the zeolite lattice was related to the concentration of defect sites
in the parent Si-[3 zeolite. This indicated that the alumination proceeds through a mechanism
which involves the reaction between AI(OPr)3 and silanol groups at defect sites. Calcination
after alumination led to the completion of the process, whereby octahedral-coordinated
aluminium, (partially) attached to the framework, was transformed into tetrahedral-
coordinated framework aluminium.

11-P-29- New hydrophobic Ti-Beta catalyst obtained by silylation and its

catalytic performance for olefin epoxidation
A. Corma, M.E. D6mine, J.A. Gaona, M.T. Navarro, F. Rey* and S. Valencia.
Instituto de Tecnologia Quimica (UP V-CSIC), Valencia, Spain. frey@itq, upv. es.

Silylated Ti-Beta materials show a superior selectivity for epoxidation reactions than
analogous fluoride synthesized Ti-Beta. This enhanced yield to the desired epoxide was
attributed to the synergetic effect of the basic amine adsorbed on the Ti sites and the presence
of silyl groups anchored on the silanol and/or titanol groups of the precursor Ti-Beta catalyst
which prevents the oxirane ring opening reaction.
216

I I - P - 3 0 - M F I zeolite with u n i f o r m m e s o p o r e s created by alkali t r e a t m e n t

M. Ogura, E. Kikuchi and M. Matsukata
Department of Applied Chemistry, Waseda University, mmatsu@mn.waseda.ac.jp, Japan.

Mesopores were created in MFI zeolite by alkali treatment technique without deterioration of
zeolitic microporous structure. The size of formed mesopore is ca. 4 nm and more uniform
than that of MCM-41. Mesopores are formed along a boundary of MFI crystallite twinning,
which shows a weak quality against alkalinity, apart from the microporous structures. This
unique structure causes superiority in acid catalysis because of the combination of its strong
acidity originated by ZSM-5 with newly created mesoporosity.
 217

12 - In-situ Spectroscopy and Catalysis (Monday)

1 2 - P - 0 5 - Study of relationship between mordenite acidity and structure

with calcination temperature
Z. Zhu, Q. Chen and W. Chen
Shanghai Research Institute of Petrochemical Technology, China, zhuzhirong@yahoo.com
The nonstructural aluminum, removed from H-MOR framework during calcination, is located
within zeolite pores in octahedral and pentacoordinated aluminum oxides, and does not affect
the acidity of Br0nsted acid sites remaining in the framework. Although H-MOR dealu-
mination amounts to about 60% of the previous framework aluminum during calcination at
1123 K, its crystallinity is still over 70%, with its adsorption capacity decreasing to 56% of
the previous. In addition to framework dealumination, the dehydroxylation of H-MOR frame-
work is another important factor resulting in both decrease of Br6nsted acid sites and increase
of Lewis acid sites during calcination at a temperature higher than 923 K.

12-P-06 - Infrared observation of the stable carbenium ions formed by

adsorption of olefins on zeolite Y at low temperatures
S. Yang, J.N. Kondo and K. Domen
Chemical Resources Laboratory, TITech, Yokohama, Japan. E-mail.
kdomen@res, titech, ac.jp.
The formation of alkenyl carbenium ions, characterized by an IR band at ca. 1510 cm "1, was
successfully observed by adsorption of 1-methylcyclopentene, methylenecyclopentane and 1-
methylcyclopentanol on zeolite Y. At temperatures as low as 150 K, the carbenium ions were
formed soon after introducing the olefins. The characteristic band at ca. 1510 cm 1 increases
in intensity with the elevation of temperature and is stable up to 373 K. For MCPOH, the
characteristic band appears at temperatures above 245 K after its dehydration. The formed
species were assigned to be dimerized alkenyl carbenium ions by calibrating the acid sites of
HY using 1-butene at 235 K. UV-vis spectroscopic studies confirm the formation of
momoenylic and dienylic carbenium ions, with bands at 323 and 400 nm, respectively.

12-P-07 - Characterization of aluminosilicate zeolites by UV-Raman spectroscopy

Y. Yu (a), G. Xiong (b), C. Li (b), and F.-S. Xiao (a*)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry & Department of
Chemistry, Jilin University, Changchun 130023, fsxiao@mail.jlu.edu.cn, China.
b State Key Laboratory of Catalysis, Dalian Institute of Chemistry Physics, Chinese Academy
of Sciences, P. O. Box 11 O, Dalian 116023, China.
A series of aluminosilicate zeolites are characterized by UV Raman spectroscopy for the first
time. UV-Raman spectra of various zeolites give strong and clear bands with high resolution,
while conventional Raman spectra of these zeolites are difficult to obtain because of a strong
background fluorescence. A summary of these UV Raman spectra over various
aluminosilicate zeolites suggests that the bands at 470-530, 370-430, 290-410, and 220-280
cm l are assigned to the bending modes of 4-, 5-, 6-, and 8-membered rings of aluminosilicate
zeolites, respectively.
218

12-P-08 - Adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on

sodium-ion exchanged faujasites with different Si/A! ratios
I.A. Beta (a), H. BOhlig (a), J. D6bler (b), H. Jobic (c), E. Geidel (b) and B. Hunger (a)
a Wilhelm-Ostwald-Institutfiir Physikalische und Theoretische Chemie, Universitgit Leipzig,
D-04103 Leipzig, Germany, ~@sonne.tachemie.uni-leipzig.de
b Institutf~r Physikalische Chemic, Universitcit Hamburg, D-20146 Hamburg, Germany
c CNRS, Institut de Recherches sur la Catalyse, F-69626 Villeurbanne Cedex, France

The adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on sodium-ion exchanged

faujasites with different Si/A1 ratios was studied by combining temperature-programmed
desorpt!on (TPD), inelastic neutron scattering (INS), Fourier transform infrared spectroscopy
(FTIR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), quantum
mechanical computations and Monte-Carlo simulations.

12-P-09- DRIFT and FTIR spectra of N2 and C2H4 adsorbed on CuNaY

G. H~ibner and E. Roduner
Universit~t Stuttgart, Germany e.roduner@ipc, uni-stuttgart, de

DRIFT and FTIR spectra of N2 and C2H4 adsorbed on vacuum dehydrated CuNaY were
measured. Due to the anisotropic environment the symmetry of these probe molecules is
broken and both the N2 stretching mode and the al modes of CzH4 are active. N2 interacts with
sites like Na + and Cu(I) as shown by absorption bands at 2335 cm l and 2299 cm -1,
respectively. At higher loadings an interaction with acidic OH groups takes place, as
confirmed by the simultaneous decrease of the OH band at 3645 cm ! and the growth of a
shoulder around 2327 cm "l. The spectra of C2H4 show two strongly redshifted band pairs of
the al modes at 1545 cm l and 1535 cm i and at 1278 cm ~ and 1264 cm "l, respectively,
proving the existence of two different Cu(I) sites. The interaction of C2H4 with Cu(l) sites is
confirmed by coadsorption of N2 which cannot displace C2H4 from their adsorption sites.

12-P-10 - Raman study of the building units in the zeolite structure

P.P.H.J.M. Knops-Gerrits (a)*, X.-Y. Li (b), N.-T. Yu(b) and P.A. Jacobs(c)
(a)Ddpartement de Chimie, Universitd Catholique de Louvain (UCL), Belgium (b)
Chemistry Department, HKUST, Hong-Kong; (c) COK, KU Leuven, Belgium, *
Corresponding Author. Tdl ." (32)10-47 29 39 Fax : 47 23 30; ppkg@chim.ucl.ac.be

In the development of zeolite science, infrared spectroscopy has been one of the major
tools for structure and reactivity characterization. However, the field of zeolite Raman
spectroscopy is gaining importance. The Raman effect is an intrinsically weak
phenomenon, and Raman spectra of zeolites are often obscured by a broad fluo-
rescence. Just like IR spectroscopy, Raman can detect small, X-ray amorphous zeolite
particles. Therefore, Raman spectroscopy has been used to examine zeolite synthesis
mixtures with ex-situ methods (with separation of solid and liquid) and in-situ
methods. In this work we give an overview of the zeolite framework vibrations, zeolite
synthesis, adsorption on zeolites and metal substitution and ion exchange in zeolites.
 219

12-P-11 - Positron annihilation study in M C M - 4 1

H.Y. Zhang !'2, Y.J. He Z'2, Y.B. Chen l, H.Y. Wang 1'2 and T. Horiuchi 3
1 . . . . . .
Department of Physws, Tslnghua Umverstty, Betjing 100084, P. R. China
2
Key laboratory for Quantum Informatton and Measurements, MOE, P. R. China," 3National
Industrial Research Institute of Nagoya, Hirate-cho, Kita-ku, Nagoya 462-8510, Japan

Positron annihilation lifetime spectra of MCM-41 and zeolite Y were measured in vacuum
and air. For MCM-41 a very long positron lifetime component could be observed not only in
vacuum, but also in air, while for zeolite Y it can only be observed in vacuum with a weak
intensity. These peculiar positron annihilation characteristics were explained by air quenching
mechanism of o-Ps annihilation in MCM-41. For comparison, positron annihilation lifetime
spectra of MCM-41 were also measured in different O2 and N2 level. The results show that
oxygen is more effective in quenching than nitrogen because of its spin unpaired electron.

12-P-12 - N M R studies on the pyrrole adsorption over Na +, Li +

exchanged zeolites of type FAU
M. Sfinchez-Sfinchez and T. Blasco*
Instituto de Tecnologia Quimica (UPV-CSIC), Universidad Polit6cnica, Avda. de los
Naranjos s/n, 46022-Valencia, Spain. E-mail: tblasco@itq.upv.es

Multinuclear solid state nuclear magnetic resonance (NMR) has been applied to study the
interaction of pyrrole with extra framework compensating cations in zeolites LiNaY and
LiNaX. Upon adsorption over zeolite LiNaY, Na + and Li + cations migrate towards accessible
positions in the supercage to interact with one molecule of pyrrole. The adsorption over
zeolite LiNaX decreases the mobility of SIII' Na + cations, while pyrrole molecules do not
interact with Li + cations. At lower loading, pyrrole adsorbs over more basic sites, which are
associated with Na + cations in zeolite LiNaY.

12-P-13 - V a r i a b l e - t e m p e r a t u r e F T I R study of the equilibrium between C-

bonded and O - b o n d e d carbon m o n o x i d e in H - Z S M - 5
G. Turnes Palomino (a), M. Pefiarroya Mentruit (a), A.A. Tsyganenko (b), E. Escalona Platero
(a) and C. Otero Arefin (a)
a Dpto. de Qu[mica, UIB, 07071 Palma de Mallorca, Spain
b Institute of Physics, St. Petersburg State University, 198904 St. Petersburg, Russia

Infrared spectroscopic studies have shown that adsorbed carbon monoxide interacts with
Bronsted acid Si(OH)A1 groups of the zeolite H-ZSM-5 forming hydrogen-bonded H'"CO
and H'"OC species, which are characterized by C-O stretching IR absorption bands at 2175
and 2112 cm l , respectively. By means of variable-temperature FTIR spectroscopy, these C-
bonded and O-bonded adducts were found to be in a temperature dependent equilibrium
which can be described as ZH-..CO-~---- ZH."OC, where Z stands for the zeolite framework.
The corresponding enthalpy change was found to be AH~ = 4.2 kJ mol 1, as derived from a
van't Hoff analysis of the intensity of the corresponding IR absorption bands as a function of
temperature.
220

12-P-14 - Role of the various acid sites in M O R on o-xylene conversion: an

in-situ I.R a p p r o a c h
O. Marie (a), F. Thibault-Starzyk* (a), P. Massiani (b) and J.C. Lavalley (a)
a Laboratoire Catalyse & Spectrochimie, CNRS ISMRA, Caen, fis@ismra.fr, France b
Laboratoire de R~activit~ de Surface, CNRS-UPMC, Paris, France

Two different bridged OH are distinguished in MOR (in side pockets or main channels). The
activity of these two different acid sites was studied by in situ IR spectroscopy of working
catalysts. Progressive Na + / H + exchange was used to prepare the various samples. Acid
strength in the main channels is not influenced by the presence of Na + in the side pockets. In
xylene isomerisation, OH groups in the side pockets strongly influence initial selectivity for
disproportionation and final coke amount, although we show that they do not directly
participate in the reactions.

12-P-15 - F T I R - Studies on adsorption and d e c o m p o s i t i o n of N O on

in-situ synthesized ZSM-5/cordierite catalysts
N. Guan *a, X. Shan a, X. Zeng a, S. Xiang a, A. Trunschke b and M. Baerns b
Department of Chemistry, Nankai University, 300071 Tianjin PR. China
blnstitute of Applied Chemistry, Rudower Chaussee 5, Berlin-Adlershof , D-12489
Berlin, Germany

The adsorption of NO on in-situ synthesized CuZSM-5/cordierite monolithic catalysts of

different Si/A1 ratios was studied by diffuse reflectance FTIR spectroscopy at different NO
partial pressures from 500 ppm to 2000 ppm and temperatures from 298 K to 773 K. At room
temperature, Cu mostly exists in oxidized Cu 2+ form. A lot of N20 species were observed on
the surface even at room temperature. A band at 2133 cm l is attributed to NO+-Oiattice and
only related to the number of lattice A1 in the zeolite. There may exist a copper-zeolite-
substrate interaction on such as synthesized monolithic catalysts.

1 2 - P - 1 6 - Acid sites in dealuminated mordenite

V.L. Zholobenko and G.P. Mitchell
Keele University, Staffordshire, UK (fax:44 1782 584352; e-mail: chalO@keele.ac.uk)

TGA, TPD-MS and FTIR characterisation of acid sites in dealuminated mordenite has been
carried out for quantitative determination of the number of Bronsted acid sites and their
accessibility using ammonia, pyridine, mono- and diamines as probe molecules. The uniform
decrease in intensity of the HF and LF OH bands of the bridging hydroxyls observed in the
dealuminated materials can be explained by the similar degree of dealumination in the 8- and
12-ring channels of the zeolite structure or by its partial reconstruction during the sample
activation. Our data suggest that mild dealumination of the mordenite framework provides
more uniform conditions for transport and adsorption in the 8- and 12-ring channels,
representing the first step towards formation of the three-dimensional dealuminated mordenite
catalysts.
 221

12-P-17- Infrared study of iron-exchanged Y Zeolite and its HDS activity

M. Nagai, O. Uchino and S. Omi
Graduate School of Bio-applications and Systems Engineering, Tokyo University of
Agriculture and Technology, Nakamachi, Koganei, Tokyo, Japan.

The acid sites of iron-exchanged Y zeolite were studied using NH3-TPD and diffuse
reflectance FTIR spectroscopy. The Bronsted acids of three iron-exchanged Y zeolites were
correlated with the activity for dibenzothiophene HDS at 240 and 280~ and 10.1 MPa. The
FTIR data on NH3 and NO adsorption showed that Fe 2§ ions on the zeolites was correlated
with their activities during dibenzothiophene HDS.
222

1 7 - Principles of Adsorption (Monday)

17-P-05 - Confinement in model host materials: experimental study of

quasi-(1D) systems
J.P. Coulomb a, N. Floquet a, C. Martin b, Y. Grillet c and J. Patarin d
aC.R.M.C2 - CNRS, Campus de Luminy, Marseill, France; bL.P.I.I.M. - URA 773, Campus
de St. J6rome, Marseille, France," cC. T.M.- C.N.R.S, Marseille, France, aLab. des Mat6riaux
Min6raux, Universit6 de Haute Alsace, Mulhouse, France.

We present a summary of our most recent experimental results concerning the properties of
confined quasi-(1D) molecular systems both at the macroscopic scale (thermodynamic) and
microscopic scale (structure and dynamic). In the mesoscopic size regime (2 < O MCM-4~< 4
nm) the confined matter undergoes phase transitions as bulk matter. But the transition
temperatures are strongly displaced towards the low temperature side. In the microscopic size
regime (0 AIPO4-5--< 1 nm) the intrinsic phase transitions of confined matter vanish.

17-P-06 - Studies on desorption behavior of organics on siliceous ferrierite

B. Qian, Y. Zeng and Y.-C. Long*
Department of Chemistry, Fudan University, Shanghai 200433, P. R. of China
yclong@)Cudan.edu.cn. FAX." (+86)-21-5653-3195

TG/DTG/DTA was employed to determined the Aw value, affinity index, for comparing the
interaction between the perfect Si-O framework of siliceous ferrierite and the adsorbed
organic compounds with various functional groups, such as alkyl-amines, alkyl-alcohols and
n-alkanes. The relation between Av values and interaction strength (AH0 is discussed as well.

17-P-07 - Investigation of hydrocarbon adsorption on large and extra-large

pore zeolites
C.Y. Chen and S.I. Zones
Chevron Research and Technology Co., Richmond, CA 94802, USA, cych@chevron.com

Large and extra-large pore zeolites with one-dimensional channel systems (SSZ-24, SSZ-31,
SSZ-42, SSZ-48, CIT-5, UTD-1 and VPI-5) are investigated with hydrocarbon adsorption
using a series of adsorbates with varying molecule sizes. Valuable input from adsorption for
the determination of zeolite structures is demonstrated with zeolite SSZ-42 that contains an
undulating, one-dimensional 12-MR channel system. The adsorptive properties of two newer
zeolites with unknown structures, SSZ-53 and SSZ-55, are discussed. The observed
adsorptive characteristics provide useful information for the structure characterization of
novel zeolites.
 223

17-P-08- Different chemisorption methods applied to zeolite supported

Pt-catalysts
J.C. Groen (a), J. P6rez-Ramirez (b) and L.A.A. Peffer (a)
a Applied Catalyst Characterization, b Industrial Catalysis,
Delft University of Technology, j. c.groen@tnw, tudelft, nl, The Netherlands.

Chemisorption measurements of hydrogen and carbon monoxide on zeolite supported Pt-

catalysts have been studied by the static volumetric adsorption method and the dynamic pulse
adsorption method. Zeolites with different pore size and Si/A1 ratio have been investigated
and compared to traditional supports such as A1203 and SiO2. Both methods show an
excellent agreement for determination of the metal dispersion for low and highly-dispersed
Pt-catalysts, using CO and H2. Weak gas-metal-support interactions did not influence the
results achieved. Application of the extrapolation procedure in the static volumetric
adsorption method is strongly discouraged.

17-P-09 - Structure vs. adsorption properties of 5A zeolites

H. Paoli (a), T. Bataille (), B. Rebours ta), A. M~thivier (a) and H. Jobic (b)
alnstitut Franqais du P6trole, herve.paoli@ifp.fr, Rueil-Malmaison, France
bInstitut de Recherches sur la Catalyse, CNRS, Villeurbanne, France
To correlate the adsorption and diffusion properties to the cation distribution in the structure
of CaNaA zeolites, temperature programmed desorption, anomalous X-ray powder diffraction
and quasi elastic neutron scattering experiments were performed. It is shown that water
adsorption and diffusion behaviour differs with the calcium content. Fourier maps obtained
from anomalous diffraction experiments near the Ca K-edge allow to identify the calcium
crystallographic sites unambiguously.

17-P-10- Hydrogen adsorption in lithium exchanged Na A zeolites

S. Kayiran, F. Darkrim* and A. Gicquel
Laboratoire d'Ing~nierie des Mat~riaux et des Hautes Pressions, LIMHP CNRS UPR n~
99 Av. J. B. Cldment 93430 Villetaneuse, France, farida.darkrim@limhp.univ-parisl 3.fi"

The present work is devoted to the analysis of the influence on gas adsorption of the crystal
structure modifications by ionic exchanges of the dehydrated Li A zeolite. We studied the
hydrogen adsorption under pressure up to 1 MPa and at room temperature on the NaA zeolite
and on its fully and partially lithium exchanged forms. The Na A zeolite is prepared by
hydrothermal method, and its ionic exchange in different level by lithium is obtained by
successive contacts. The structural characterisations have been evaluated by Scanning
Electronic Microscopy (SEM), X Ray Diffraction (XRD), Nuclear Magnetic Resonance
(NMR), Atomic Absorption and helium density measurements. We noted that there was no
loss of crystallinity after ionic exchange in the zeolites. The hydrogen adsorption capacity
varied with the increase of the cation exchange rates. Hydrogen adsorption is due to sterical
effects and gas-solid molecular interactions which are intimately linked to the adsorbent
structure modifications and the chemical nature of cations containing zeolite.
224

17-P-I 1 - M a c r o s c o p i c and microscopic investigations of the interaction of a

chloroalkene on a MFI zeolite
v. Frangois, S. Maure, F. Bouvier, G. Weber, O. Bertrand, J.P. Bellat and C. Paulin
Laboratoire de Recherches sur la R6activit~ des Solides, Do'on, France
Guy. weber@u-bourgogne,fr
Gravimetric, microcalorimetric, in-situ XRD and in-situ FTIR spectroscopic studies of the
interaction of trichloroethene and tetrachloroethene on high siliceous zeolites were carried out
to look further into knowledge of adsorption processes of large admolecules in the
microporous network of MFI adsorbents. Trichloroethene gives classical type I isotherms
whereas tetrachloroethene gives stepped isotherms at 298 K. Furthermore, structural changes
of the adsorbent were observed for the adsorption of either trichloroethene or
tetrachloroethene. A comparative analysis of macroscopic and microscopic data is proposed
and correlations are established between thermodynamic and structural data.

17-P-12 - Sorption and pore condensation behavior of pure fluids in

mesoporous M C M - 4 8 silica, M C M - 4 1 silica and controlled pore glass
M. Thommes l, R. K6hn 2 and M. Fr6ba 2'3
I Quantachrome GmbH, Rudolf-Diesel-Strafle 12, 85235 Odelzhausen, Germany
2 Inst. oflnorg. Chem., University of Hamburg, Hamburg, Germany
3 Inst. oflnorg. Chem., University ofErlangen-Nuremberg, Erlangen, Germany
A systematic study of the sorption and pore condensation behavior of nitrogen, argon and
krypton in various silica materials (MCM-48, MCM-41 and Controlled Pore Glass (CPG)) at
87 and 77 K is presented. A detailed characterization with respect to surface area, pore
volume and pore size distribution together with a comparison of sorption hysteresis in MCM-
48 and MCM-41 silica materials of nearly equal pore size has been performed. In addition we
focus on the sorption and phase behavior of argon and krypton below the bulk triple-point
temperature.

17-P-13 - Pore size analysis with H 2 0 adsorption measurement of

organically modified M C M - 4 1 type materials
N. Igarashi (a), K. Nakai (b), K. Hashimoto (a) and T. Tatsumi (c)
aThe University of Tokyo, Tokyo, Japan; bBel Japan, Inc., Osaka, Japan
Cyokohama National University, Yokohama, Japan, ttatsumi@ynu, ac.jp.
Hexagonally structured mesoporous molecular sieves (MCM-41) containing organic groups
have been synthesized under various conditions and were used to test the applicability of the
Kelvin equation to water adsorption. It was shown that the pore size estimation, assuming the
Kelvin equation corrected for the statistical film thickness of H20, is in quite good agreement
with that obtained with N2 adsorption for the relatively hydrophilic samples when the
appropriate value of the radius of curvature of the meniscus was used. The correction of
contact angle of curvature of the meniscus was necessary for the hydrophobic materials in
order to match the pore sizes estimated on the basis of H20 adsorption to those obtained by
N2 adsorption.
 225

1 7 - P - 1 4 - Adsorption of carbon dioxide b y X zeolites exchanged with Z n 2+

and Cu 2+" isosteric heat and adsorption isotherms
A. Khelifa (a), Z. Derriche (b) and A. Bengueddach (c)
a Laboratoire S.T.E.V.A., B. P. 1001, R. P., Mostaganem, Telefax." +213 45 21 10 18, Alg6rie.
b Laboratoire ale physico-chimie ales mat~riaux, U. S. T. Oran, Alg6rie.
c Laboratoire de chimie des mat6riaux, Universit~ d'Oran, Alg~rie.
Adsorption of C02, at intervals of 30 K between 303 and 363 K, has been carried out on M2+X
zeolites (Mz+=zn 2+ or Cu 2+) exchanged at different degrees. Analysis of the isosteric heat
reveals a character energetically heterogeneous only for NaX and Zn(x)X exchanged at higher
degree and at low coverages. Several models have been used to describe the experimental
isotherms. The best fit of adsorption isotherm data is obtained with the Sips model, while the
adsorbed phase would be localised on adsorptive centres and is subject to minor adsorbate-
adsorbate interactions. These interactions have repulsive character.

1 7 - P - 1 5 - A combination of high resolution manometry, gravimetry and

microcalorimetry to study the co-adsorption of Ar/N2 mixtures on 5A and
13X zeolites
S. Moret, F. Rouquerol, J. Rouquerol and P.L. Llewellyn
MADIREL, CNRS/University of Provence, Marseille cedex 3, France.
The adsorption of three argon/nitrogen binary mixtures at 310 K and up to 0.6 bar are
presented. A continuous, quasi-equilibrium flow technique of adsorptive introduction was
used to allow high-resolution isotherms to be obtained. These are compared to differential
enthalpies of adsorption determined using adsorption microcalorimetry.

1 7 - P - 1 6 - Gas adsorption microcalorimetry on zeolites under supercritical

conditions up to 15 bars
T. Poyet, F. Rouquerol, J. Rouquerol and P.L. Llewellyn
MADIREL, CNRS/University of Provence, 26 rue du 141 ~meRIA, 13331 Marseille cedex 3,
France.
The adsorption of nitrogen on silicalite, DAY and NaX at 310 K was carried out up to a
pressure of 15 bars. Combined manometric and microcalorimetric measurements were carried
out under high-resolution conditions. The isotherms show a marked deviation from Henry's
law behaviour.
226

18- Adsorption and Separation Process (Monday)

18-P-06 - Evaluation of mesoporous silicas as stationary phases for high

performance liquid chromatography (HPLC)
L. Sierra (a), B. Lopez (a), A. Ramirez (a) and J.-L. Guth (b)
a Departamento de Quimica, Universidad de Antioquia, Medellin,
lsierra@catios.udea.edu.co, Colombia; b Laboratoire de Matdriaux Min~raux UPRES-A
7016, Universitd de Haute Alsace, Mulhouse Cedex, France.
Four mesoporous silicas, formed of isometric particles with 2.8 nm and 5.6 nm pores, were
prepared by varying the synthesis conditions (silica source, surfactant, pH and temperature).
A part of each sample was silylated with C8 chains. The silanol and silyl groups contents
were estimated by 29Si NMR. Good separations have been obtained on mixtures of aromatic
molecules by normal-phase HPLC with the four materials. In reversed-phase HPLC the
results exhibit differences in function of the pore filling by the silyl groups.

18-P-07 - Adsorption of N-nitrosamines by zeolites in solutions

Ying Wang, J.H. Zhu*, D. Yan, W.Y. Huang and L.L. Ma
Department of Chemistry, Nanjing University, Nanjing 210093, China

Zeolite could selectively adsorb N-nitrosamines in the solution of methylene chloride or

water, and the equilibrium data were fitted to Freundlich-type isotherms. Textural and acid-
basic properties of zeolite determined their adsorption capacity. The extraordinary adsorption
properties of NaA zeolite for N-nitrosamines is inferred that the adsorbates inert the channel
with the group-N=N-O. Larger amount of N-nitrosamines was adsorbed on ZSM-5 zeolite in
water instead in methylene chloride, due to the hydrophobicity of the zeolite. Application of
zeolite to remove N-nitrosamines from beer seems successful. Up to 100% of the worst
carcinogenic compounds could thus be removed with 1.4 g/L of zeolite which was proven to
be better adsorbent than silica or alumina. On Na[3 zeolite and MCM-41 mesoporous material
N-nitrosodimethylamine decomposed above 573 K and the liberated NOx could be detected
even at 773 K during the TPSR process, indicating the strong adsorption of N-nitrosamines on
molecular sieves that makes zeolite become the functional materials for environmental
protection.

18-P-08 -An adsorption-desorption process for separation of C8 aromatics

G.-Q. Guo (a, b) and Y.-C. Long (b*)
a Research Institute ofBeijing Yanshan Petrochemical Corporation, SINOPEC, Beijing
102500, P.R. China, guoqing_guo@263.net
b Department of Chemistry, Fudan University, Shanghai 200433, P.R. China
An adsorption-desorption process has been developed through the study of static equilibria of
C8 aromatics in liquid phase. The binder-free adsorbent used is high silica MFI type zeolite,
which possesses high hydrophobicity. Six organic compounds as desorbents matched with the
adsorbent were screened. The competitive adsorption curves of multi-component feed were
also investigated.
 227

18-P-09 - Preparation of Na-A zeolite capillary columns by in-situ synthesis

D. Kou, Z. Li, J. Wu, Ming Liu and S. Xiang*
Department of chemistry, Nan Kai University, Tianjin, P.R. China- shxiang@public.tpt.tj.cn

The traditional zeolite PLOT column has lots of shortcomings, which considerably restrict the
further development of zeolite in practical utilization. In this paper, a new kind of NaA zeolite
GC column has been prepared and characterized by in-situ synthesis technique. The form
process and mechanism in capillary column have also been discussed. On the basis, gas-solid
and gas-liquid capillary columns have been prepared, which both show good separation of
various organic compounds and extensively broaden the range of the utilization of zeolite in
GC. Furthermore, the zeolite large bore column has also been prepared and the test result is
very good. Consequently, the possibility to replace packed column in a great deal of regular
analysis has been pursued.

18-P-10 - Adsorption of CO2, SO2 and NH3 on zeolitic materials synthesized

from fly ash
S. Hernfindez (a), R.Juan (a), X. Querol (b), N. Moreno (b), P. Ferrer (a) and J.M. Andr6s (a).
a Instituto de Carboquimica (CSIC), rjuan@carbon.icb.csic.es, Spain.
b Instituto de Ciencias de la Tierra ((Jaume Almera))(CSIC), xquerol@paleo.ij'a.csic.es, Spain

Zeolites synthesized from fly ash were selected for determining the adsorption capacity of
CO2, SO2 and NH3 and the surface area. The results showed a low retention capacities for
Sodalite, Analcime, NAP1, F Linde and KM (3.2-9.3 mg CO2/g, 1.1-3.9 mg SO2/g and 0.5-4.8
mg NH3/g) that could be explained for the low Sco2 measured in the working conditions (23-
47 m2/g). High retention capacities were found for Herschelite and Zeolite A by the same
technique (30.3-73.5 mg CO2/g, 9.3-21.7 mg SO2/g and 8:1-110.7 mg NH3/g). The results
suggest a certain relationship between surface area and adsorption capacities.

18-P-II - Dibenzothiophene adsorption over zeolites with faujasite

structure
J.L. Sotelo, M.A. Uguina, M.D. Romero, J.M. G6mez, V.I. Agueda and M.A. Ortiz.
Chemical Engineering Department. Faculty of Chemistry. Complutense University of Madrid,
Madrid, Spain. chedpt@eucmax.sim, ucm. es

Adsorption of dibenzothiophene (DBT) over FAU zeolites exchanged with alkali cations has
been studied. Cristallinity (by XRD and IR), exchange level (XRF) and basic properties (CO2
TPD) of different adsorbents used have been determined. The influence of Si/A1 molar ratio
and type of cation exchanged in the zeolite as well as the presence of toluene in feedstock
mixture on DBT adsorption capacity and selectivity of adsorbent has been also determined.
Thermogravimetric analysis showed a stronger DBT adsorption over X zeolites.
 228

18-P-12 - Pressure swing adsorption of ethyl acetate on silica MCM-41

S. Namba (a), D. Yomoda (a), J. Aoyagi (a), K. Minagawa (a), T. Kugita (a) and J. Izumi (b)
a Teikyo University of Science & Technology, Yamanashi, namba@ntu.ac.jp, Japan.
b Nagasaki R & D Center, Mitsubishi Heavy Industries, Ltd., Nagasaki, Japan.

Fundamental studies on removal/recovery of ethyl acetate vapor from industrial waste effluent
gas by pressure swing adsorption (PSA) on silica MCM-41 were made. From effects of
pretreatment temperatures (673-1073 K) and trimethylsilylation it is found that ethyl acetate
molecules are irreversibly adsorbed on surface -OH groups on silica MCM-41 through
hydrogen bonding at a low adsorption/desorption temperature of 303 K. With increasing
adsorption temperature from 303 to 373 K the amount of irreversible adsorption decreased to
almost nil. Therefore a combination of PSA and temperature swing adsorption operation is
desirable for remove/recovery of ethyl acetate vapor. The reversible adsorption capacity
becomes 250 mg g~ by the combination.

18-P-13 - P occlusion in LTA: an approach for enhancing N2 adsorption

properties
L. Johnson and M. Miller
Air Products & Chemicals, Inc., Allentown, PA, USA, johnsolm@apci.com

Ca ion exchange treatments and thermal activation of ZK-21 with different P and A1 contents
prepared the materials for adsorption studies. The activated CaZK-21 materials contain both
occluded P and framework substituted P. The relative amounts of occluded P and framework
P change with the starting composition of the ZK-21 and the post synthetic treatment. The N2
Henry's Law constant (KH N2) at 23 ~ and the Henry's law N2 selectivity (KHN2/KHO2) at 23
~ increase with increasing amounts of occluded P in the CaZK-21 materials and are
independent of Ca content, indicating the occluded P is enhancing the effectiveness of the
available Ca for N2 adsorption. CaZK-21 with 5.1 occluded P/unit cell achieves the same KH
N2 at 23 ~ as CaLTA, even though the CaLTA contains 50% more Ca cations.

18-P-14 - Sulfur guard bed material from local bentonite deposits

S. Mikhail and T. Zaki
Egyptian Petroleum Research Institute - Nasr City- Cairo - Fax No." O0 202 2747433-Egypt.

The new preceding step in the catalytic hydrotreating process is the application of a guard bed
adsorbent in the refinery, to get a product containing least amount of sulfur, which is
necessary for making an acceptable feed for steam refining process. This work deals with the
study of the preparation of sulfur guard bed from locally cheapest material. Guard bed is
prepared by loading the more efficient adsorbent bentonite clay with high capacity nickel for
the removing of trace sulfur. The nickel was anchored in the silicate layered clay structure via
new technique "electroless technique" to assure the realization of a fine dispersion and a
maximum homogeneous distribution of the active nickel metal on the clay surface area. The
structure of the original clay and the prepared guard bed has been studied physically and
chemically by applying different techniques: x-ray analyses, thermal analyses, acidity and
pore size distribution.
 229

18-P-15- Simulation for removal of binary solvent vapor by adsorption

onto high silica zeolite
K. Chihara, T. Saito, H. Suzuki, H. Yamaguchi and Y. Takeuchi
Dept. of Ind. Chem, Meij'i University, 1-1-1 Higasi-Mita, Tama-ku, Kawasaki, Japan

Adsorption of some organic solvent vapours onto HSZ were studied. Binary adsorption
equilibriums except azeotropic mixture-HSZ systems could be correlated by Markham-
Benton equation for the whole concentration range, and the break times could be estimated
well by using the Extended-MTZ-Method. For azeotropic mixture-HSZ systems, the
equilibriums and the break times could be correlated and estimated only for a part of the all
concentration range. Then, two azeotropic points appeared in the adsorption equilibriums for
IPA-TCE -Y-type system. For this binary systems adsorption equilibrium data could be
expressed by proposed equation, similar to liquid-vapour azeotropic equilibrium equation.
Breakthrough curve could be simulated using the Stop&Go method in the whole range for
azeotropic mixture systems as well as for zeotropic systems.
230

23 - Micro- and Mesoporous Materials in Fine Chemistry (Monday)

23-P-06- Selective hydroxyethylation of furfuryl alcohol with aqueous

acetaldehyde in the presence of H-form zeolites
A. Finiels, W. Balmer and C. Moreau
UMR 5618 ENSCM-CNRS, E. N. S. C. Montpellier, France- cmoreau@cit.enscm.fr

Hydroxyethylation of furfuryl alcohol with aqueous acetaldehyde was performed at 318 K in

the presence of FAU, MOR and MFI zeolites in their protonic form. Besides the
hydroxyethylation reaction, two other parallel reactions may compete, i.e. oligomerisation of
acetaldehyde and resinification of furfuryl alcohol. The former reaction is easily controlled
over a MFI catalyst with a Si/A1 ratio of 25 but the latter is not, and linear furanic polymers,
capable of deactivating the catalyst, were often formed. A selectivity of about 55 % in the
carbinol intermediate was initially achieved in the presence of the MFI (25) catalyst for a
furfuryl alcohol conversion up to 65 %. However, after optimization of the kinetic parameters,
the selectivity is increased to 95 %, but to the detriment of furfuryl alcohol conversion.

2 3 - P - 0 7 - Selective synthesis of monooctylamines by ammonia alkylation

with octanol using NaY, ZSM-5, SAPO-5, SAPO-II, SAPO-31, SAPO-34
S. Amokrane (a), R. Rebai (a), S. Lebaili (b), D. Nibou (b) and G. Marcon (c)
a Institut de Chimie Industrielle, fax ." 022132247182, Alger, Algerie
b Institut de Gdnie Mdcanique, fax ." 022132247182, Alger, Algerie.
c L TPCM/INPG/CNRS, gmarcon@ltpcm, inpg.fr, St. Martin d'HOres, France.

This work deals with the synthesis of monooctylamines by ammonia alkylation with octanol-I
in gaseous phase using various catalysts. These microporous materials were prepared by the
hydrothermal method. Y-faujasite and ZSM-5 supports were exchanged by lead and uranyl
ions at different concentrations in order to increase their surface acidity necessary for reaction
mechanism. The obtained results show that the use of these catalysts results in the formation
of primary amines. Monooctylamines selectivities of 90 % were obtained in the present work.
It was observed that when SAPO-34 is used, the trioctylamine isomer could be formed in the
external surface of the catalyst.

23-P-08- Conversion of monoethanolamine in other organic nitrogen

compounds on H-mordenite and H-clinoptilolite
G. Torosyan, S. Sargsyan and A.Grigoryan
State Engineering University of Armenia, Yerevan, Armenia, hau@dolphin.am.

The synthesis of ethyleneimine from monoethanolamine over H-mordenite and H-clinop-

tilolite has been studied. The natural zeolites of Armenia were used as support. The proposal
method synthesis has advantages over the Wenkler ethyleneimine synthesis: no using of
acidic corrosion equipment and disposal of waste water containing sulfuric acid. It has been
formed piperazine and its derivatives as by-products. The last nitrogen compounds are formed
generally with monoethanolamine excess in reaction conditions. In this case, for these
compounds formation has been proposed three pathways. It was investigated the adsorption of
amine substrate when using zeolites too.
 231

23-P-09 - The influence of ammonia adsorption on Y Zeolite and natural

clinoptilolite activity in ethanol transformation
L. Akhalbedashvili (a), A. Mskhiladze (b) and S. Sidamonidze (a)
a Tbilisi State University, 380028, 3 Ave. Chavchavadze, e-mail." aklali@yahoo.com., Tbilisi,
Georgia," b Sukhumi State University, Jikia, 12, Tbilisi, Georgia
The effect of NH3 adsorption on catalytic activity and selectivity of cation-exchanged Y
zeolite and natural clinoptilolite (deposit of Georgia) in ethanol transformation was
investigated. The ODH of alcohol is accompanied by dehydration to ethylene and diethylether
and deep oxidation to CO2. NH3 blocks the acidic active centers of dehydration of Y zeolites
and promotes the oxidative activity of samples with transition metal cations. The influence of
the ion nature for the catalytic transformation of ethanol was shown by a considerable
increase of carbon dioxide formation after NH3 adsorption. The cation associated has been
destroyed under NH3 influence, and NH3 formed with cations coordinated-unsaturated
complexes.

2 3 - P - 1 0 - Enantioselective synthesis and separation of terminal epoxides

and diols using a catalytic membrane system containing chiral Co(III) salen
S.-D. Choi and G.-J. Kim
College of Engineering, Inha University, Inchon, Korea, kimg/@inha.ac.kr
The importance to use optically pure isomers as pharmaceuticals, food additives, agro-
chemicals, (etc) is becoming more and more evident. The classical resolution still accounts for
a large part of chiral production, however the asymmetric synthesis and the use of chiral
separation system one becoming increasingly popular. The enantioseletive hydrolytic
resolution of racemic epoxides was performed in the ZSM-5/MCM-41 membrane system
containing chiral salen complexes. The chiral salen complexes immobilized on the membrane
showed a very high enantioselectivity in the hydrolysis of epichlorohydrine, epoxybutane,
styrene oxide and 1,2-epoxyhexane.

23-P-11 - Asymmetric trimethylsilylcyanation of benzaldehyde catalyzed by

chiral Ti(IV) salen complexes immobilized on MCM-41
J.-H. Kim and G.-J. Kim
Department of Chemical Engineering, College of Engineering, Inha University,
Inchon 402-751, KOREA, kimg]@inha.ac.kr
The efficiency of new unsymmetrical chiral salen ligands was examined in the asymmetric
trimethylsilylcyanation of benzaldehyde. A very high level of enantioselectivity was
attainable over chiral Ti(IV) salen complexes prepared from salicylaldehyde and 3,5-Di-tert-
butylsalicylaldehyde derivative as compared to the conventional salen catalyst. Enantiomeric
excess of the corresponding reaction product was generally more than 70% over unsymmetric
chiral salen catalysts. The chiral Titanium(IV) salen complexes immobilized on a mesoporous
MCM-41 by multi grafting method showed a relatively high enantioselectivity for the
addition of trimethylsilyl cyanide to the benzaldehyde.
232

23-P-12 - Mechanistic study of aniline methylation over acidic and basic zeolites Y
I.I. Ivanova (a), E.B. Pomakhina (a), A.I. Rebrov (b), Y.G. Kolyagin (a), M. Hunger (c) and
J. Weitkamp (c)
a Moscow State University, Moscow 119899, e-mail. iiivanova@phys.chem.msu.ru
b Institute of Petrochemical Synthesis, RAS, Leninsky pr. 29, 117012 Moscow, Russia
c Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany

13C MAS NMR has been performed in-situ under batch conditions to investigate the mechanism
of aniline alkylation with methanol on acidic H-Y and basic CsNa-Y impregnated with cesium
hydroxide. On acidic zeolite H-Y, methanol reacts with zeolitic hydroxyl groups to give surface
methoxy groups which, in turn, play a role as alkylating species in aniline methylation. On the
basic zeolite Y, methanol is converted into formaldehyde, which is responsible for the N-
alkylation. Both on acidic and basic zeolites, N-methylaniline is the primary alkylation product.
Toluidines and N-methyltoluidines are formed only on the acidic zeolite at elevated temperatures
after complete conversion of methanol into N-methylaniline.

23-P-13 - Heterogeneous base catalysis: characterization of zeolites and

mixed oxides using nitromethane as a N M R probe molecule and activity in
the Michai~i condensation of nitromethane and cyclohex-2-en-l-one
E. Lima, L.-C. de Mtnorval, M. Lasptras, J.-F. Eckhard, D. Tichit, P. Graffin and F. Fajula
Ecole Nationale Sup6rieure de Chimie de Montpellier, lasperas@cit.enscm.fr

The use of nitromethane as a probe of basicity of zeolites (NaX, CsX, CsX 9Cs) and mixed
oxides, Mg(AI)O, is discussed. Various species (physisorbed nitromethane, aci-anion
nitromethane, and methazonate salt analogue) formed upon nitromethane adsorption were
characterized by 13C MAS NMR spectroscopy. Heterogeneous base catalysis of the Michael
addition of nitromethane on cyclohex-2-en-l-one was also studied. Low rates were obtained
for catalysts showing only nitromethane physisorption. Formation of aci-anion nitromethane
was observed for solids of medium efficiency; correlation of the chemical shift with the initial
rate was established. Finally, the decrease of Lewis acidity and concomitant increase of
basicity led to methazonate formation and to the more efficient catalysts.

23-P-14 - Synthesis of ot-pinene derivatives using redox-mesoporous

molecular sieves
Y.-W. Suh (a), T.-M. Son (a), N.-K. Kim (b), W.-S. Ahn (b) and H.-K. Rhee* (a)
a School of Chemical Engineering and Institute of Chemical Processes, Seoul National
University, Kwanak-ku, Seoul 151-742, hkrhee@snu.ac.kr, Kore a
b School of Chemical Science and Engineering, Inha University, Inchon 402-751, Korea

Ti-HMS catalyst was successfully used as a bifunctional catalyst for the one-step conversion
of a-pinene to campholenic aldehyde.
 233

23-P-15 - Ring opening reactions of methyloxirane over D Z S M - 5 and

D A I M C M - 4 1 molecular sieves - A mechanistic study
A. Ffisi (a), I. Pfilink6 (b), A. G6m6ry (a) and I. Kiricsi (c)
a Chemical Research Center of the HAS, P.O. Box 17, Budapest, H-1525 Hungary
b Department of Organic Chemistry, c Department of Applied and Environmental Chemistry,
University of Szeged, D6m t6r 8, Szeged, H-6720 Hungary, palinko@chem.u-szeged.hu

The ring opening reactions of methyloxirane (single C-O scission and dimerization were the
main transformation channels) on DZSM-5 and DA1MCM-41 aluminosilicates were studied
in a pulse microreactor at 363 K. Deuterium distribution in the products was monitored. For
deuterium exchange to occur during ring opening at least one Bronsted site is necessary. For
the formation of deuterium-exchanged dioxolane derivatives two neighbouring Bronsted-
Lewis site pairs, while for the formation of deuterium-exchanged dioxane derivatives the
interplay of a Bronsted-Lewis acid pair and a Lewis-Lewis acid pair seem to be the most
advantageous.

2 3 - P - 1 6 - Hydrodechiorination of 1,2,4-trichlorobenzene on Ni/AI-MCM-41

catalysts
Y. Cesteros (a), P. Salagre (a), F. Medina (b), J.E. Sueiras (b) and G.L. Hailer (c)
a Facultat de Quimica. Universitat Rovira i Virgili, Tarragona, cesteros@quimica.urv.es,
Spain.
b Escola d'Enginyeria Quimica. Universitat Rovira i Virgili, Tarragona, Spain..
c Department of Chemical Engineering. Yale University, USA.

Several Ni/A1-MCM-41 catalysts were prepared by the incipient wetness method followed by
calcination and reduction. These catalysts are highly active (100%) and selective (100%)
towards benzene in the hydrodechlorination of 1,2,4-trichlorobenzene in the gas phase at mild
conditions of work: 1 atm pressure and reaction temperatures between 473-523K. This
catalytic behaviour has been correlated with the structural characteristics of the catalysts.

23-P-17 - Adsorption of cytochrome c onto ordered m e s o p o r o u s silicates

J. Deere, E. Magner, J.G. Wall and B.K. Hodnett.
Department of Chemical and Environmental Sciences, Materials and Surface Science Institute,
University of Limerick, Limerick, Kieran.Hodnett@ul.ie, Ireland.

Adsorption and desorption characteristics of the protein cytochrome c onto ordered meso-
porous silicates are detailed. The amount of adsorption is related to the characteristics of the
mesopore diameter with most adsorption associated with materials having pore diameters in
excess of the size of cytochrome c. Adsorbed protein did not desorb with repeated washing in
buffer but polyethylene glycol and/or ammonium sulphate in buffer caused considerable
desorption.
234

23-P-18 - Vapor phase Beckmann rearrangement of cyclohexanone oxime

over tantalum pillared magadiite
S.J. Kim (a), M.H. Kim (a), Y. Ko (a), G. Seo (b) and Y.S. Uh (a)
a KIST, P.O. Box 131, Cheongryang, Seoul 130-650, uhvoun~kistmail.kist.re.kr, Korea
b Chonnam National University, Kwang/u 500-757, Korea

Vapor phase Beckmann rearrangement of cyclohexanone oxime to e-caprolactam has been

carried out using tantalum-pillared magadiites (Ta-magadiites) with different surface areas as
catalysts. The Ta-magadiite catalysts of relatively large surface areas showed high catalytic
activities, due to a large number of active sites. For the Ta-magadiite catalyst of the largest
surface area, the oxime conversion reached 99.1% with 97.5 % of lactam selectivity. FT-IR
and NH3-TPD results demonstrated that the new hydroxyl groups and a large amount of acidic
sites generated by Ta pillaring into the magadiite interlayer were responsible for the high
catalytic performance of Ta-magadiite catalyst.

23-P-19 - Hydration of cz-pinene over heteropolyacids encaged in USY

zeolites
J. Vital a*, A.M. Ramos a, I.F. Silva a, J.E. Castanheiro a, M.N. Blanco b, C. Caceres b, P.
Vasquez b, L. Pizzio b and H. Thomas b
CQFB, Faculdade de Ci~ncias e Tecnologia, Universidade Nova de Lisboa, 2825-114
CAPARICA, Portugal. E-mail."jmv@dq.fct, unl.pt
b Conicet, UNLP, Cindeca 47, n ~257, 1900 La Plata, Argentina

The catalytic performance of dodecamolibdophosphoric acid (PMol2) encaged in the

supercages of zeolite USY or silica supported, was compared concerning the hydration of ot-
pinene in aqueous acetone at 50 ~ C. A selectivity value of 75%, towards cz-terpineol, was
achieved with the encaged PMol2, at total conversion. Selectivity values obtained with the
encaged catalyst are similar to those obtained with the free PMol2, but higher than those
obtained with the silica supported HPA.

23-P-20 - Selective adsorption of t r a n s unsaturated fatty acid compounds in

MFI type zeolites
S. Paulussen, M. Goddeeris and P.A. Jacobs
Katholieke Universiteit Leuven, Centrum voor Oppervlaktechemie en Katalyse,
Kasteelpark Arenberg 23, B-3001 Heverlee, Belgium (pierre.jacobs@agr.kuleuven.ac.be)

A zeolite structure that selectively adsorbs trans unsaturated fatty acid compounds in the
presence of their cis unsaturated counterparts is selected among several topologies using a
liquid phase chromatographic study of the adsorption of oleic and elaidic acid methylester.
The functioning of the present adsorbent is based on the restricted adsorption of the curved cis
unsaturated compounds in the pores of highly siliceous MFI type zeolites while the straight
trans isomers experience significantly less limitations. The present selectivity is retained
when the complexity of the substrate molecules is gradually increased from methylesters to
triacylglycerols.
 235

23-P-21 - Novel delaminated zeolites are more active acid catalysts than
conventional zeolites and mesoporous AI/MCM-41 for the synthesis of fine
chemicals
M.J. Climent, A. Corma,* V. Forn6s, H. Garcia, S. Iborra, J. Miralles and I. Rodriguez
ITQ-CSIC-UPC, Universidad Polit6cnica de Valencia, Valencia, Spain. Fax 34 96 3877807.

ITQ-2 zeolite prepared by delamination of MCM-22 precursor, is formed by disordered

individual sheets of crystalline zeolitic layers in where the Bronsted acid sites are of zeolitic
nature and the vast majority of them accessible to large molecules. The delaminated zeolite
combines the acid characteristic of microporous zeolites with accessibility of the sites of
mesoporous A1/MCM-41 and amorphous silica-alumina. The superior catalytic performance
of delaminated zeolites compared to conventional zeolites and A1/MCM-41 is examplified for
reactions involving large reactant molecules, namely: the preparation of dimethyl acetals, the
Beckmann rearrangement of bulky cycloalkanone oximes and hydroxylation of aromatics.

23-P-22 - The design of zeolites catalysts for the synthesis of orange blossom
and apple fragrances
M.J. Climent, A. Corma and A. Velty
Instituto de Tecnologia Quimica (UP v-csIc). Universidad Polit6cnica de Valencia. Avenida
de los Naranjos s/n, 46022, Valencia, Spain.

The synthesis of propylene glycol acetal of methylnaphthyl ketone and ethylene glycol acetal
of ethyl acetoacetate, which are flavouring materials with orange blossom and apple scent
respectively, have been obtained successfully in presence of different zeolites. It has been
found that a higher concentration of acid sites in the catalyst does not guarantee a better
catalytic performance and for acetalization reaction the hydrophobic properties of catalyst are
as important as the concentration of active sites. This work presents the crucial role that the
control of the textural and adsorption properties play in optimizing a zeolite catalyst for the
production of these two fragrances.

23-P-23 - Catalytic in-situ infrared spectroscopic study of n-butyraldehyde

aldol condensation
U. Rymsa, M. Hunger and J. Weitkamp
Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany

Aldol condensation of n-butyraldehyde on cesium-exchanged zeolites X and Y, mesoporous

MCM-41 and silica gel impregnated with cesium salt yield initially 2-ethylhexenal with 100
% selectivity at a high conversion. The active catalysts suffer from fast deactivation, which is
probably caused by a Tishchenko side reaction leading to the formation of butyric acid. A
carboxylate ion strongly adsorbed on the catalyst surface is detected by in-situ infrared
spectroscopy. It probably poisons the active sites and furthermore blocks the pores of micro-
and mesoporous catalysts. Carboxylate formation cannot be suppressed by carrying out the
reaction in hydrogen or by adding water to the feed. However, complete catalyst regeneration
can be achieved by heating in nitrogen at around 350 to 400 ~
236

2 3 - P - 2 4 - Oxyhalogenation of aromatic compounds in presence of KCI or

KBr and H202 over zeolites
N. Narender, P. Srinivasu, S.J. Kulkarni and K.V. Raghavan
Catalysis Group, Indian Institute of Chemical Technology, Hyderabad, India
The oxychlorination and oxybromination reactions of aromatic compounds were carried out
over modified Y and ZSM-5 zeolites in presence of KC1 or KBr and H202. The process is
facile and ecofriendly and the catalyst can be reused. In the oxychlorination of phenol, the
yields of para chloro- and ortho chloro phenol were 63.0% and 22.0% at 85% conversion,
over CeZSM-5(30) catalyst. CeZSM-5 is a better catalyst for oxychlorination compare to
HZSM-5 and modified Y zeolites. In the oxybromination of aniline the yields of para bromo-
and ortho bromo aniline were 76.0% and 15.0% respectively at 91.0% conversion over
HZSM-5 catalyst in presence of KBr and H202. The performance of HZSM-5 was better than
HY and SIO2/A1203 and in absence of H202 or catalyst the conversion was less. The work
using titanium zeolite or other redox system and oxidant is in progress

2 3 - P - 2 5 - Synthesis and characterization of mesoporous Pt-MCM-41 and

its application in enantioselective hydrogenation of l-phenyl-l,2-propa-
nedione
E. Toukoniitty a, B. Sevcikovfi a, N. Kumar a, P. M~iki-Arvelaa, T. Salmi a, J. V~,yrynenb, T.
Ollonqvist b, E. Laine c, P.J. Kooyman ~ and D.Y. Murzin a
~ of Industrial Chemistry,/[bo Akademi, Turku, Finland," bDe])artment of Applied
Physics; CDepartment of Physics, University of Turku, Turku, Finland, "National Centre for
HREM, Delft University of Technology, Delft, The Netherlands
Pt-MCM-41 with three different Pt contents was synthesized, characterized and tested in
enantioselective hydrogenation of 1-phenyl-l,2-propanedione. The maximum enantiomeric
excess (ee) of (R)-l-hydroxy-l-phenylpropanone was 44% with the 15 wt.% Pt-MCM-41
modified with (-)-cinchonidine (compared to 54% obtained with 5 wt.% Pt/A1203). The
highest ee obtained with 15 wt.% Pt-MCM-41 was due to the slightly larger Pt particles.
Further optimization of the reaction conditions is a very important task in order to utilize
mesoporous materials in enantioselective hydrogenation.

23-P-26- Isomerization of p-eugenol on palladium-containing zeolites

Ts.M. Ramishvili, M.K. Charkviani and L.D. Kashia
P.G. Melikishvili Institute of Physical and Organic Chemistry, Georgian Academy of
Sciences, Tbilisi, Georgia - dmk 20@hotmail.com
The Y, 13 and M zeolites with SIO2/A1203 ratios of 3.9, 24 and 32, respectively, produced via
recrystallization from the natural clinoptiolite in palladium form ( 0 . 6 2 - 6.16% Pd) at 413-
458K in He, H2 and air atmosphere isomerize p-eugenol basically into trans-isoeugenol with
70-93% selectivity; dihydroeugenol is also produced in the H2 atmosphere. The Pd-forms M
and 13 are most active in the He atmosphere. Induction period at the beginning of the reaction
observed in the helium atmosphere at temperature over 425 K is reduced in the air atmosphere
and with 2-6% Pd content in the catalyst the condensation and oxidation reactions are rather
intensive.
 237

23-P-27 - T h e use of M C M - 2 2 as catalyst for the B e c k m a n n - r e a r r a n g e m e n t

of c y c l o h e x a n o n e oxime to s-caprolactam
G. Dahlhoff, U. Barsnick, W. Eickelberg and W.F. H61derich
Heterogeneous Catalysis, RWTH, Aachen, hoelderich@rwth-aachen.de, Germany
A variety of catalysts have been applied to the Beckmann-rearrangement of cyclohexanone
oxime to s-caprolactam. Experiments with MFI structures yielded good results showing the
importance of weak acidic sites, a large outer surface and pore structure accessible only
through 10MR channels. Recent reports recommended the MCM-22 catalyst with its large
outer surface and special structure for the use in the Beckmann-rearrangement. In the present
study the synthesis and brief characterisation of MCM-22 was carried out followed by the
first in depth analysis of its applicability for the Beckmann rearrangement of cyclohexanone
oxime to s-caprolactam. The performance of the material was compared to one of the
established catalysts - the [B]-MFI - showing several drawbacks like lower yields.

23-P-28 - Nickel supported on zirconium doped m e s o p o r o u s silica as

catalysts for the gas phase hydrogenation of acetonitrile
P. Braos-Garcia, L. Diaz, P. Maireles-Torres, E. Rodriguez-Castelldn and A. Jim~nez-L6pez
Departamento de Quimica Inorgdnica, Cristalografia y Mineralogia, Facultad de Ciencias,
Universidad de Mdlaga, Campus de Teatinos, 29071 M~ilaga (Spain)

Gas-phase hydrogenation of acetonitrile has been studied by using catalysts based on nickel
supported on zirconium doped mesoporous silica. All catalysts are active in this catalytic
reaction, but the activity decreases with the time, being more stable when increasing the
nickel loading. After catalytic reaction, all catalysts contain nitrogen and carbon, being their
percentages higher for shorter times of deactivation. Nevertheless, the activity and selectivity
patterns are totally recovered after treatment with H2 at high temperature, which indicates that
these nitrogen and carbon species can be totally removed from the surface of catalysts by
hydrogenation.

23-P-29 - Synthesis of fine chemicals intermediates over basic zeolites

C.O. Veloso a, A.C. Pinto b, E.N. Santos c and J.L.F. Monteiro a
~NUCAT/COPPE, Universiclade Federal do Rio de Janeiro, monteiro@peq.coppe.ufrj.br
6IQ, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil
ClCEx, Universidade Federal de Minas Gerais, Minas Gerais, Brazil
X zeolites exchanged with cesium and impregnated with cesium species were active as
catalysts for the Knoevenagel reaction between the aldehyde obtained by the hydro-
formylation of limonene and ethyl acetoacetate. The product distribution observed has shown
that other reactions were occurring, such as decarboxilation and aldol condensation reactions
that also led to products of potential commercial interest. The best results were obtained for
the sample with 14 cesium atoms impregnated per unit cell, at 403 K and ethyl acetoacetate /
menthene molar ratio of 5. In such a condition, yields of products of interest as intermediates
for fine chemicals production were as high as 90% after 4 h of reaction.
238

23-P-30 - Selective chlorination of diphenylmethane over zeolite K-L

A.P. Singh* and S.M. Kale
Catalysis Division, National Chemical Laboratory, Pune-411 008, India, Fax No. +91-20-
5893761, Email." apsingh@cata.ncl.res.in

The liquid phase chlorination of diphenylmethane (DPM) to 4,4'-dichlorodiphenyl-methane

(4,4'-DCDPM) is investigated over a number of zeolite catalysts using sulfuryl chloride as the
chlorinating agent under mild reaction conditions. Zeolite K-L is found to be highly active
and selective in the formation of 4,4'-DCDPM. The conventional Lewis acid catalyst AIC13 is
not at all selective in this reaction. The conversion of DPM increases with time over all the
catalysts. The reaction is very fast with zeolite K-L and gives almost 68 wt.% conversion after
5 min of reaction time. Also the yields of DCDPM increase with reaction time with an
obvious decrease in the yields of monochlorodiphenylmethanes (MCDPM).

23-P-31 - Butylation of phenol on medium pore A I P O 4 - 1 1 , - 3 1 and-41

structures" effect of silicon incorporation
C.V. Satyanarayana, U. Sridevi and B.S. Rao
Catalysis Division, National Chemical Laboratory, Pune, satya@cata.ncl.res.in, India.

Butylation of phenol with tert-butylalcohol (TBA) is reported on medium pore alumino-

phosphates AIPO4-11, -31 and -41. Their activity is compared with their silicon substituted
versions SAPO-11, -31 and -41. AIPO4 frameworks without silicon substitution were found to
be active. Terminal hydroxyls in A1PO4's are active for butylation of phenol. It was found that
a temperature as moderate as 140~ is sufficient for considerable butylation of phenol.
However, selectivities of the industrially important 4-TBP and 2,4-DTBP are enhanced at
higher temperatures. An equimolar feed concentration of phenol and TBA is optimum to yield
4-TBP and 2,4-DTBP selectively and also a lower space velocity of about lhr ~ favours this
reaction.

23-P-32 - The catalytic synthesis of the glycidol from the glycerol carbonate
in presence of zeolite A
J.W. Yoo and Z. Mouloungui*
Ecole Nationale Sup~rieure des Ing~nieurs en Arts Chimiques Et Technologiques-Laboratoire
de Chimie Agroindustrielle- UMR 1010-INRA-INPT/ENSIACET zmouloungui@ensct_fr
A study on the direct synthesis of the glycidol from the glycerol carbonate was carried out in
presence of the zeolite A as a catalyst and the glycerol as an initiator. The cationic/anionic
ring opening-dimerization of glycerol carbonate and cyclization of the dimer to the glycidol
and the carbon dioxide as gas form is proposed in the multi-phase reaction system
(liquid/solid/gas). This system overcomes the difficulty of mass transfer in the meso-porous
zeolite A. The yield for glycidol reached 86 % with the zeolite A and the glycerol.
 239

23-P-33 - Transfer hydrogenation of unsaturated ketones catalyzed by AI-

isopropoxide dispersed on MCM-41
J. Wahlen, D.E. De Vos*, M. De Bruyn, P.J. Grobet and P.A. Jacobs
Centre for Surface Chemistry and Catalysis, K. U. Leuven, Belgium.
dirk. devos@agr, kuleuven, ac. be

Aluminium alkoxides were anchored in the pores of siliceous MCM-41 type materials. The
resulting catalysts were used in the hydrogen transfer reduction of c~,13-unsaturated ketones to
the corresponding allylic alcohols. The most active material is obtained by exposure of MCM-
41 to a toluene solution of AI(OPr~)3. With benzalacetone as a model substrate, optimum
reaction conditions are cyclopentanol (hydride donor), toluene (solvent), and addition of 5A
molecular sieve (water trapping).
240

01 - Mineralogy of Natural Zeolite (Tuesday)

0 1 - P - 0 6 - Zeolites in impact craters

M.V. Naumov
Karpinsky All-Russia Geological Research Institute (VSEGEI), mvn@mail, wplus.net

Zeolites are common post-impact minerals in three giant impact craters: Popigai (mordenite,
stilbite, chabazite, and heulandite), Kara (analcime with minor chabazite, laumontite, stilbite,
and mordenite), and Puchezh-Katunki (heulandite, chabazite, analcime, stilbite, laumontite,
with minor erionite, philippsite, and clinoptilolite). Zeolites occur mainly as fissure-filling and
vugs. In the central uplift area, zeolites exhibit a vertical zonation due to the thermal gradients
existing during impact-induced hydrothermal circulation whereas in the annular depression
the differentiation of zeolites is caused by inhomogeneity of substrate. Zeolite formation by
itself and specific features (e.g., enrichment in silica) of zeolites in impact craters are provided
by the occurrence of large amounts of shock-disordered silicate matter there.

0 1 - P - 0 7 - A! ordering in a dachiardite framework

M. Kato(a) and K. Itabashi(b)
(a) Research Centerfor Chemometrics, Toyohashi University of Technology, Toyohashi 441-
8580, Japan
(b) Nanyo Research Laboratory, Tosoh Corporation, Shinnanyo 746-8501, Japan
AI ordering in a dachiardite framework was examined based on the structural data and 29Si
MAS NMR spectra. Obtained ordered distribution model of dachiardite contains four AI
atoms per unit cell, and its space group was P2/m instead of the conventional C2/m. A1 atoms
are located on T3 and T4 sites which construct 4 rings. Because AI content in a mined sample
is larger than four, small amount of Si atoms should be substituted by AI atoms and some
extent of AI atoms move to another site in order to satisfy the Loewenstein's rule. Simulated
NMR spectrum based on this substitution was in excellent agreement with the observed ones.

OI-P-08 - Chemical composition and ion-exchange properties of a natrolite

from Zahedan region, Iran
A.R. Sardashti a, H. Kazemian b and M. Akramzadeh Ardakani a
~Dep. of chem. fac. of sci. Sistan & Baloochestan university, Zahedan, Iran
bjaber Ibn Hayan Research Labs., AEOI, North Amir Abad Ave. Tehran 14374, Iran,
e-mail" hkazemian@w~176

This paper reports on the ion-exchange behavior of a natural zeolite from Zahedan region of
Iran towards various heavy metal cations. The distribution coefficients (Kd ,ml/g), equilibrium
constant (Ka) and Gibbs free energy AG~ ~) were calculated from the isotherms data at
at 298K and 323K as the thermodynamic parameters. The pre-purified material was natrolite
rich-ore with some calcite as impurity. The ion-exchange experiments of the zeolite were
performed in order to investigate its ability for removing the considered cations from
industrial wastewater streams. The natrolite mineral exhibited the selectivity sequence:
Ag+>>pb+2> Cd+2>Cu +2 > Zn +2 but was not promising from a pratical point of view.
 241

0 1 - P - 0 9 - Physical, chemical and structural characterization of the volcanic

tuff from the Maramures area, Romania
R. Pode (a), G. Burtica (a), S. Herman (a), A. Iovi (a) and I. Calb (b)
a University "Politehnica" of Timisoara, Romania, Email: tcapm@rectorat.utt.ro
b Cemacom SA, 4700 Zalau, Romania, Fax ." +40 60 661003

The present work pursued the physical, chemical and structural characterisation of the
volcanic tuff that comes from the northern part of Romania (Barsana, Maramures County).
The X-ray studies pointed out the presence of clinoptilolite as the main mineralogical phase
(about 68%). The thermal analysis allowed evaluating the limiting temperature for the thermal
stability, which agreed with literature reports for zeolites with SIO2/A1203 ratio of around
5.12, as it also resulted from our experiments. The acid treatment allowed elaborating an
integrated technology for the use of volcanic tuff as an adsorbent material. Moreover, the
resulting acid solution could be used in wastewater treatment.

01-P-10 - Heulandite group zeolites from the Paleogene flesh water lake
Blateshnitza Graben, Southwest Bulgaria
Z. Milakovska (a), E. Djourova (b) and R. Tzankarska (a)
a Geological Institute, Bulg. Academy of Sciences, Sofia, zlatkam@geology.bas.bg, Bulgaria
b Faculty of Geology and Geography, Sofia University, djourova@gea, uni-sofia.bg, Bulgaria

The Blateshnitza Graben is a continental fresh water lake basin filled with polymictic
conglomerates, breccia-conglomerates and strongly subordinated sandstones. In the lowest
volcaniclastic bed (---29 m depth), found in the upper part of the Zemen bore core (central part
of the graben), heulandite group zeolites and probably ferrierite were identified by optical
microscopy, SEM, XRD and DTA. Judging from the thermal stability, the main zeolite is
heulandite, but the chemical data suggest that it should be considered as clinoptilolite. The
features of the geological position and the environment of deposition suggest a zeolite genesis
in an open hydrologic system.

01-P-11 - Isodimorphism of templates in zeolites. New crystal chemistry of

analcime and its analogues
V.V. Bakakin
Institute of Inorganic Chemistry, Russian Academy of Sciences, 630090, Novosibirsk, Russia

A mechanism and reasons of an isomorphism of zeolite templates with numerically varying

atoms are considered. The additional extraframework sites in the ANA type structures are
separated and used. A simple graph of template nets is proposed and new algorithms of
structural formulas are given. The notion of "template units" (TU) is brought forward. A set of
TU that are involved in the formation of ANA compounds is determined. Examples of the
actual combinations of these TU are given along with a summary of the corrected formulas and
typical illustrations. A new interpretation of experimental data is given for 15 compounds and
isomorphous series. Practically all inconsistencies in published data are eliminated.
242

01-P-12- Evaluation of clinoptilolite tuffs from Russia as ion exchangers

using NH4 ions
I.V. Komarova, N.K. Galkina, V.A. Nikashina, B.G. Anfilov and K.I. Sheptovetzkaya
Vernadsky Institute of Geochemistry and Analytical Chemistry Russian Academy of Sciences
(RAS), Kosygin str., 19, Moscow ,fax (095) 938 2054) e-mail elkor@geokhi.msk.su Russia
This investigation resulted in the creation of the database of the equilibrium and kinetic
characteristics of the zeolite tuffs using dynamic breakthrough curve. The computer-
controlled system was developed in order to obtain experimental breakthrough curves, to
carry out their mathematical treatment and to calculate necessary characteristics. The
effective equilibrium and kinetic coefficients of some Russian clinoptilolite-containing tuffs
from different deposits for the sorption of ammonium-ions were evaluated using this method,
the data base was created. The chemical composition, the content of clinoptilolite in tuffs and
total cation-exchange capacity of tuffs have been also included in the data base.

01-P-13 - Mineralogy, chemistry and ion-exchange properties of the

zeolitized tufts from the Sheinovets caldera, E Rhodopes (South Bulgaria)
R. Ivanova (a), Y. Yanev (a), Tz. Iliev (a), E. Koleva (a), T. Popova (b) and N. Popov (c)
(a)Geological Institute, Acad G. Bonchev St., 1113 Sofia, Bulgaria, yotzo@geology.bas.bg
fo)Niproruda AD, 205 Stamboliiski Blvd., 1309 Sofia, Bulgaria
(c)Institute of Cryobiology and Lyophilization, 65 Cherni Vrah Blvd., 1407 Sofia, Bulgaria

Zeolitized tuffs from the Eastern Rhodopes Paleogene volcanic area have been studied. Na-
mordenite and Ca-clinoptilolite are the main products of the acid glass alteration. Erionite,
analcime and stilbite are also identified. Opal and adularia are most abundant at the base of
tuff succession. Zeolite content increases upward; mordenite is prevailing in the middle and
clinoptilolite in the topmost levels of the studied section. Compared with flesh perlite
zeolitized tuffs are depleted in Na20, Y, Rb, Ba and Mn and enriched in CaO and Sr. C.E.C.
coefficient ranges from 60.66 to 94.53 meq/100g. Low-temperature hydrothermal solutions,
heated by the initially hot pyroclastic material are the inferred cause of the zeolite formation.

01-P-14 - Synthesis of titanium, niobium, and tantalum silicalite-1 by

microwave heating of the mixed oxide xerogei precursors
W.S. Ahn *a, K.Y. Kim a, M.H. Kim b and Y.S. Uh b
aSchool of Chemical Science and Engineering, Inha University, Inchon, Korea 402-751
whasahn@inha, ac. kr
bMaterials Science and Technology Division, Korea Institute of Science and Technology,
P. O. Box 131, Cheongryang, Seoul, Korea 130-650

Titanium (TS-1), niobium (NbS-1), and tantalum silicalite-1 (TaS-1) with MFI structure were
synthesized by microwave heating of the TPAOH impregnated xerogels which were prepared
by sol-gel process. Highly crystalline products were obtained in 30 min to 2 h with yields
over 90%. The metallosilicates showed high catalytic performances in Beckmann
rearrangement of cyclohexanone oxime to caprolactam.
 243

01-P-15 - Different silver states stabilized in natural clinoptilolites

N. Bogdanchikova (a), B. Concepcion Rosabal (b), V. Petranovskii (a), M. Avalos-Borja (a) and
G. Rodriguez-Fuentes (b)
a Centro de Ciencias de la Materia Condensada, UNAM, Ensenada, Mexico, nina@ccmc.unam.mx
b Universidad de La Habana, La Habana, Cuba, gerardo@lae.ffoc.uh.cu

A set of samples prepared by introducing Ag into natural clinoptilolite were studied. Ag +

cations, Agn and Agnm+ neutral and positively charged clusters, subcolloidal and large Ag
particles were found in the prepared samples. It was revealed that variation of reduction
temperature from 293 to 873 K allows to vary their contribution. All samples show a
significant microbicide action against Escherichia coli strain bacteria and tumed out to be
stable in air for more than 3 months. The natural clinoptilolite samples with Ag clusters and
particles of different sizes is expected to be active in processes where a slow release of Ag +
cation with olygodynamic properties is necessary.

01-P-16 - Physical-chemical and adsorptive properties of A r m e n i a natural

zeolites
F. Grigoryan, A. Hambartsumyan, H. Haroyan and A. Karapetyan
State Engineering University of Armenia, Yerevan, e-mail." chemdep@seua.am

The present research is devoted to the study of the physical-chemical properties of natural
zeolites from Armenia. The adsorption of H2, O2, Ar, N2, CO2, SO2 on natural mordenite from
Shirak deposit as well as the adsorption of Ar, N2, 802 and Xe on Shirak mordenite treated
by hydrochloric acid have been studied by volumetric method. The kinetics of O2, Ar and N2
adsorption on natural mordenite have been studied. The isosteric heats of adsorption for H2,
O2, Ar, N2, CH4, CO2, SO2, Xe have been measured by chromatographic method. The portion
of quadropole interaction has been determined.

01-P-17 - The sorption equilibria in natural z e o l i t e - aqueous solutions

systems
J. Peri6 a, M. Trgo a and S. Cerjan-Stefanovi6 b
~Faculty of Chemical Technology, jperic@ktf-split, hr, mtrgo@ktf-split, hr~ Split, Croatia
bFaculty of Chemical Engineering and Technology, Zagreb, Croatia

Equilibrium properties of the hydrolysis and ion exchange process have been examined for
natural and pre-treated zeolite-clinoptilolite by measuring the concentration of exchangeable
N a+, K +, Ca2 + and Mg 2 + ions
. . .
with .
time in the liquid phase. The analysis of the relation of
concentrations of ionic species leaving the zeolite and those entering the zeolite structure (H+,
Zn2+) has found to be a non-stoichiometric process.The established non-stoichiometry of the
overall mass transfer process through the outer and inner surface of zeolite particles is due to
the strength of the bond of exchangeable ions in the structure, as a phenomenon of sorption.
The sorption takes place on characteristic locations on the zeolite particle surface, which has
been confirmed by SEM images and EDX analysis.
244

0 5 - Synthesis of New Materials (Tuesday)

05-P-06 - Synthesis and structures of GIS, A B W and G M E beryllo-

phosphate molecular sieves from amine solutions
H. Zhang (a), M. Chen(b), Z. Shi (c), Y. Zhou (a), Xin Xu (a) and D. Zhao (a)*
a Department of Chemistry; b Analysis and Measurement Center, Fudan University,
Shanghai, 200433," c Department of Chemistry, Jilin University, Changchun, 130023, P. R.
China. * dyzhao@_fudan,edu. cn.
Several pure phase beryllophosphate molecular sieves with the topology similar to the
gmelinite, gismondine and ABW frameworks have been successfully synthesized with the
concentrated amines such as triethylene tetramine, piperazine, and pyridine as the structure-
directing agents. BePO4-GME is the first example of an open framework with the gmelinite
topology in the phosphate system.

05-P-07 - Microporous gallosilicate TNU materials and their implications

for the synthesis of low-silica molecular sieves
W.C. Paik a, M.A. Camblor b and S.B. Hong *a
aDepartment of Chemical Technology, Taejon National University of Technology, Taejon
305-719, Korea; blndustrias Quimicas del Ebro, 50057 Zaragoza, Spain
Hydrothermal syntheses of a series of gallosilicate molecular sieves, denoted TNU-n (Taejon
National University Number n, where n = 1-7) are presented. The introduction of Ga into
silicate frameworks was found to be a viable route to the discovery of novel low-silica zeolite
structures. Among the materials prepared here, TNU-3 and TNU-4 with the NAT topology are
characterized as members of a family of materials in which the two end members have
random and non-random distributions of Si and Ga atoms over the available T-sites in the
framework, respectively.

05-P-08 - Synthesis and characterization of novel nickel phosphates from

non-aqueous systems
Yunling Liu, L. Zhang, P. Zhang, Y. Zou and W. Pang*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, P R. China. E-mail. wqpang@mail.jlu.edu.cn

Three novel organically templated nickel phosphates, NiPO4-n (n=l-3) have been prepared
under solvothermal conditions using ethylenediamine as a structure directing agent. It is
found that the use of solvothermal techniques and the involvement of fluoride ions are very
essential to the outcome of the novel nickel phosphates. The products were characterized by
powder X-ray diffraction, IR spectroscopy, SEM, TGA-DTA, ICP and elemental analysis and
single crystal structure characterization. NiPO4-2 is a layered compound with 12-ring layers,
NiPO4-3 is a new fluorinated nickel phosphate with a chain structure.
 245

05-P-09 - Synthesis, characterization and properties of an anionic alumino-

phosphate molecular sieve with BrSnsted acidity
W. Yan(a), J. Yu(a), R. Xu(a)*, Y. Han(a), K. Sugiyama(b) and O. Terasaki(c)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, rrxu@mail.jlu.edu.cn, People's Republic of China
b Department of Earth and Planetary Science, University of Tokyo, Tokyo113-0033, Japan
c CREST, Japan Science and Technology Corporation, Tohoku University, Sendai, Japan

An anionic aluminophosphate molecular sieve [AlzPI3052][(CH2)6N4H3] (denoted A1PO-

CJB 1) with Br6nsted acidity upon removal of the template has been solvothermally prepared.
It is constructed from alternation of Al-centered polyhedra (A104 and AIOs) and P-centered
PO4 tetrahedra via vertex oxygens to form a negatively charged open-framework. The
adsorption, ion-exchange and acidity properties are further characterized.

05-P-10 - Synthesis and characterization of an open-framework alumino-

phosphate [AIP206(OH)2][H30] containing propeller-like chiral motifs
W. Yan, J. Yu, Z. Shi and R. Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, rrxu@mail./lu.edu.cn, People's Republic of China

A new open-framework aluminophosphate [A1P206(OH)2][H30] (denoted A1PO-CJ4)

containing propeller-like chiral motifs with both A and A configurations has been prepared at
the presence of 2-aminopyridine in a solvent of 2-BuOH. Single-crystal structural analysis
gives that it crystallizes in the triclinic space group P-l, with a=7.1127(2)A, b=8.6729(2)A,
c=9.220(3)A, a=65.108(2)~176176 and Z=3. A1PO-CJ4 is further
characterized by X-ray powder diffraction, ICP, TG, and NMR analyses.

05-P-II - Synthesis and characterization of an aluminum-substituted

manganese phosphate with GIS topology
H.-M. Yuan, Y.-S. Jiang, W. Chen, J.-S. Chen* and R. Xu
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
chemcj@mail.jlu, edu. cn, Changchun, P. R. China

An aluminum-substituted manganese phosphate (A1MnPO-GIS) containing tetrahedrally-

coordinated Mn 2§ ions has been synthesized by using ethylene glycol as the predominant
solvent and ethanolamine as the structure-directing agent under a solvothermal condition. It
has been revealed that the material is analogousz§ to. zeolite glsmondine." The successful
synthesis of A1MnPO-GIS suggests that the Mn -dominant aluminum-manganese phosphates
with a different zeolite structure can be obtained by variation of template and reaction
conditions.
246

05-P-12 - Synthesis and characterisation of novel microporous framework

cerium and europium silicates
D. Ananias (a), P. Ferreira (a), A. Ferreira (a), J. Rocha (a), J.P. Rainho (a,b), C.M. Morais (a)
and L.D. Carlos (b)
a Department of Chemistry, University of Aveiro, 3810 Aveiro, Portugal
b Department of Physics, University of Aveiro, 3810 Aveiro, Portugal

The synthesis, structural characterization and luminescence spectroscopy studies of AV-5

and AV-9 (Aveiro microporous solids no. 5 and 9), the first examples of microporous
framework cerium(III) and europium(III) silicates (Na4KzX2Si16038"10H20, X = Eu, Ce) are
reported. Both materials display interesting photoluminescence properties and present
potential for applications in optoelectronics. This work illustrates the possibility of combining
in a given framework silicate microporosity and optical activity.

05-P-13 - Novel microporous framework stannosilicates

Z. Lin and J. Rocha
Department of Chemistry, University of Aveiro, 3810 Aveiro, rocha@dq.ua.pt, Portugal

Reactions in the R20 - S n O 2 - S i O 2 - H 2 0 (R = Na, K) system have been studied under mild
hydrothermal conditions (170 - 230 ~ Synthesis variables such as time, temperature and the
HzO/Sn, Si/Sn, K/Sn, K/Na and OH/Sn ratios have been investigated. Two novel
microporous framework stannosilicates, AV-6 and AV-7, have been prepared. These
materials possess corner-sharing [SnO6] octahedra and [SiO4] tetrahedra forming three-
dimensional frameworks, with no Sn-O-Sn-O chains, stable up to ca. 700 and 450 ~
respectively. After calcination of AV-6 and AV-7 for 5 hours at 900 and 1000 ~
respectively, a new phase (AV-11) forms. At higher temperature, AV-11 converts to a
wadeite type structure. The materials have been characterized by SEM, powder XRD, 298i and
l l9Sn MAS NMR and TGA.

0 5 - P - 1 4 - Magadiite intercalated MCM-22

M. Munsignatti, A.J.S. Mascarenhas, A.L.S. Marques and H.O. Pastore*
Grupo de Peneiras Moleculares Micro- e Mesoporosas, Instituto de Quimica, Universidade
Estadual de Campinas, CP 6154, CEP 13083-970, Campinas, SP, Brasil. E-mail adress:
lolly@iqm, unicamp, br

MCM-22 precursor samples were prepared with magadiite. The layered assembly was
intercalated with CTABr/TPAOH, sonicated, Soxhlet extracted and calcined. The material
was characterized by XRD, pore analysis, SEM, FTIR, elemental analysis and DTG. The
samples obtained appear to be the result of magadiite layers intercalated at least partially,
between MCM-22 layers.
 247

05-P-15- Synthesis of aluminum phosphite microporous materials

N. Li and S. Xiang*
Department of Chemistry, Nankai University, Tianjin 300071, P R. China
E-mail." shxiang@public, lpt. tj. cn
A series of aluminum phosphite and phosphite-phosphate molecular sieves were synthesized
by using P (III) (phosphorous acid) partly or completely replaced P (V) (phosphoric acid) as
the source of phosphorus materials. DPA (di-n-propylamine), TEA (triethylamine) and CHA
(cyclohexylamine) were used as the template respectively. SEM photographs showed the
shapes of these crystalline inorganic solid. It was very interesting that a kind of aluminum
phosphite NKX-4 can be synthesized with or without template.

0 5 - P - 1 6 - Synthesis, characterization and structural aspects of novel

microporous indium
L.M. King, J. Gisselquist, S.C. Koster, D.S. Bern, R.W. Broach, S.G. Song and R.L. Bedard
UOP-LLC, 25 East Algonquin Road, Des Plaines, Illinois

This paper reports the synthesis and characterization of a new family of indium silicate
microporous materials, designated InSi-n. The InSi-n phases have been synthesized with 11
novel framework topologies and contain In/Si ratios of 0.25-1. Most InSi-n phases are stable
to calcination to at least 500 ~ and show adsorption behavior that is zeolitic in character. Ion
exchange behavior similar to zeolites has also been observed in InSi-n materials. Preliminary
structural details include a crystal structure determination of a new topology with 8-ring
channels and HREM evidence for large pores in members of the InSi-n family.

05-P-17 - Synthesis and characterization of the silicoaluminophosphate

SAPO-47
L. Xu, Z. Liu, P. Tian, Y. Wei, C. Sun and Shinian Li
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, P. O. Box 110, Dalian 116023, zml@dicp.ac.cn,
China

Synthesis of a novel small-pore SAPO-47 molecular sieve was described. The effects of the
templates and silica concentration in the synthesis gel on the crystallinity and phase purity of
SAPO-47 were studied. The results show that pure SAPO-47 could be obtained in a wide
range of SIO2/A1203 using sec-butylamine, methylbutylamine or iso-butylamine as templating
agent. It is evident that the strength and the amount of the acid sites are related closely to the
silicon content and distribution in the framework. SAPO-47 molecular sieve catalyst with
expected acidity could be obtained by controlling the SIO2/A1203 in the initial gel.
248

05-P-18 - Synthesis, characterization and catalysis of SAPO-56 and

MAPSO-56 molecular sieves
P. Tian, Z. Liu, L. Xu and C. Sun
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian, zml@ms.dicp,ac.cn, China

Using N,N,N',N'-tetramethyl-l,6-hexandiammine as organic template, SAPO-56 and its

metal-containing silicoaluminophosphates (M=Co, Mn and Zr) were synthesized hydro-
thermally. The synthesis phase diagram and crystallization kinetics of SAPO-56 were
obtained. The synthesis regulation of pure MAPSO-56 molecular sieves was also
investigated. The samples were characterized by XRD, SEM, TG-DTA and MAS NMR.
SAPO-56 and MAPSO-56 were studied with respect to their catalytic behaviors in the
methanol-to-olefins conversion and the oxidation of alkane, respectively.

05-P-19 - Synthesis and structural characterization of a novel microporous

zeolitic type aluminium phosphate
C. Sassoyea, S. Girard a, C. Mellot-Draznieks a, T. Loiseau a, C. Hugeunard b, F.Taulelle b and G.
F6reya
alnstitut Lavoisier (IREM), UMR CNRS 8637, Universit6 de Versailles, 45, avenue des Etats-
Unis, Versailles, France - loiseau@chimie.uvsq.fr; bRMN et Chimie du Solide, UMR ULP-
Brtiker-CNRS 7510, Universit6 Louis Pasteur, Strasbourg, France

This contribution deals with the hydrothermal synthesis and the structure characterization of a
new microporous aluminium phosphate AI4(PO4)4(OH), NC4HI0, labelled MIL-34. The open-
framework is built up from interconnected tunnels bounded by 8-membered rings. The
cyclobutylamine molecules which are used as structure-directing agent are found at the
intersection of the 8-ring channels.

05-P-20 - Hydrothermai synthesis and crystal structures of two novel open

frameworks: (enH2)3[Co3W4P402s] and (dapH2)3[Co3W4P402s]
B. Yan*, Y. Xu, N.K. Goh and L.S. Chia
Natural Science, Nanyang Technological University, Singapore -yanbangbo@hotmail.com

Two novel microporous cobalt tungsten(VI) phosphates, (enH2)3[Co3W4P4028] 1 and

(dapH2)3[Co3W4P402s] 2, were hydrothermally synthesized and characterized by
thermogravimetry, elemental analysis, IR spectroscopy and single-crystal X-ray diffraction.
The structure of solid 1 comprises corner sharing PO4, CoO4 tetrahedra and WO6, CoO6
octahedra linked through bridging oxygen atoms. The pore system contains 7- and 8-
membered rings. The structure of solid 2 has the same topology as structure 1.
 249

07 - N e w M e s o p o r o u s Molecular Sieves (Tuesday)

07-P-06 - Vanadosilicate: cubic m e s o p o r o u s molecular sieve

M. Chatterjee, T. Iwasaki, Y. Onodera, H. Hayashi, T. Ebina and T. Nagase
Inorganic Materials Section, Tohoku National Industrial Research Institute, Nigatake 4-2-1,
Miyagino-ku, Sendai 983-8551, Japan

Mesoporous vanadosilicate molecular sieves with MCM-48 structure and atomic Si/V ratio
30-200 have been synthesized using vanadyl sulphate as the source of vanadium. The product
was characterized using X-ray diffraction (XRD), N2 adsorption analysis, transmision electron
microscopy (TEM), electron spin resonance (ESR), Fourier-transform Infrared (FTIR),
Diffuse reflectance UV-visible spectroscopy (UV-vis) and 5~V solid state NMR. A noticeable
decrease in unit cell parameters and main pore diameter was observed. Thus, a strong
interaction between vanadium and mesoporous wall can be suggested.

07-P-07 - Synthesis and characterization of m e s o p o r o u s Cu-silica spheres

via a novel c o - a s s e m b l e route
P. Zhang, N. Bai, X. Meng and W. Pang*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry,
Jilin University, Changchun, 130023, P R. China Email." wqpang@mail./lu.edu.cn
Transparent mm-sized mesoporous Cu-silica spheres have been synthesized successfully
through the introduction of Cu(II)-APTMOS complex into the reaction mixture. The products
are characterized by powder XRD, N2 adsorption, TEM, SEM, ESR, and ICP techniques. The
pore structure of Cu-silica spheres is disordered. The Cu II ions in Cu-silica spheres are in
typical six-coordinated environment and cannot be exchanged by other metal ions. The
primary experimental results show that the mesoporous Cu-silica spheres exhibit high
catalytic activities in the hydroxylation of phenol under the presentation of H202

07-P-08- Synthesis and characterization of m e s o s t r u c t u r e d alumina

prepared in the presence of d o d e c y l p h o s p h a t e
L. Sicard a, B. Lebeau a, C. Marichal a, J. Patarin a and F. Kolenda b
a Laboratoire de Matdriaux Mindraux, Ecole Nationale Supdrieure de Chimie de Mulhouse,
B.Lebeau@univ-mulhouse fr, France.
b Institut Frangais du Pdtrole, Vernaison, France.

The present study focuses on the mechanisms of formation of two dodecylphosphate (DDP)
mesostructured alumina synthesized at pH = 5 and 8 respectively. For the material
synthesized under acidic conditions, NMR experiments seem to indicate the presence of AI-
O-P bonds. The material would be of aluminophosphate type rather than a pure alumina. The
sample synthesized under basic conditions contains large amounts of sodium. In this case, the
interactions between the surfactant S and the alumina framework I are weak and the
mechanism of formation would be of SM+I ~ type, where M is the counterion (Na+).
250

07-P-09 - Synthesis and characterizations of mesoporous zirconia-based

oxide composites
J. Zhaoa; D. Wua; Y.-H. Suna*; Zh. Zhangb; H. Zhang b and D. Zhao b
a Institute of Coal Chemistry, C.A.S., SKLCC@public.ty.sx.cn, P R. China
b Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China
The thermal stability of mesoporous zirconia with tetragonal wall was greatly improved via
incorporation with SiO2 and A1203. FT-IR and NMR indicated that there were chemical
interactions between SiO2 (A1203) with zirconia, which strengthened tetragonal framework,
thereby improving the thermal stability of crystalline mesoporous zirconia.

0 7 - P - 1 0 - Preparation and catalytic property of FeL/Y composite by a new

method
B. Fan, W. Fan and R. Li*
Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P.R.
China. E-mail: rfli~tvut, edu. cn

A new method, viz. the recrystallization of MCM-41 impregnated metal complex in the
synthesis system of zeolite Y, has been developed to immobilize the guest complex in zeolite
host. In this way, a series of FeL/Y composites (with L=phenanthroline (phen), 8-quinolinol
(Qx), salicylic acid (SA)) have been prepared. The as-prepared materials are characterized by
XRD, FTIR, UV-vis, TG-DTA and ICP techniques. Furthermore, their catalytic properties in
the reaction of cyclohexane oxidation were also investigated. It was shown that this method
made it possible to immobilize different metal complexes, including the cationic, the anionic
and the neutral. In addition, the content of metal complex can be controlled by varying its
amount impregnated on MCM-41.

07-P-II - Mesoporous zirconia" an anionic surfactant inorganic composite,

precursor of a tridimensional porous material
G. Pacheco and J.J. Fripiat
Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin,
Milwaukee, P.O.Box 413, Milwaukee, WI, USA.

Mesoporous zirconias obtained by hydrolyzing zirconium isopropoxide at low pH (.3) in

presence of alkyl straight-chain surfactant are disordered composite materials that develop
high surface areas and mesoporosity. They differ essentially from mesoporous materials
obtained by templating since their surface area and porosity are available in the presence of
the surfactant. Another building mechanism, accounting for this difference is suggested.
 251

07-P-12 - Synthesis of micelle templated TiO2 mesophases by a sol-gel

approach: effect of the surfactant removal
D.P. Serrano, G. Calleja, R. Sanz and P. Pizarro
ESCET, Universidad Rey Juan Carlos. C~ Tulip~n s/n , 28933 M6stoles, Madrid, Spain.
e-mail: dserrano@escet, urjc. es

Mesoporous TiO2 has been synthesized in the presence of a non-ionic surfactant by N~ ~

assembly, using a Ti alkoxide as Ti source. The porous structure partially collapses upon
calcination. However, this fact can be avoided by extraction of the surfactant with boiling
acid/ethanol mixtures. Thus, TiO2 samples with surfaces areas up to 470 m2/g and pore sizes
in the range 2-6 nm have been obtained. DR UV-Vis spectra of the as-synthesized samples
show the presence of Ti species with both tetrahedral and octahedral coordinations, which
resemble that of anatase powder.

0 7 - P - 1 3 - Preparation and characterization of iron oxide nanoparticles in

the channels of MCM-41
C.M. Yang and K.J. Chao
Department of Chemistry, National Tsinghua University, Hsinchu 300, Taiwan
e-mail." kjchao@mx, nthu. edu. tw

Ferrocene was incorporated into the templating micelles of synthetic siliceous MCM-41, and
found to affect the morphology and structure of MCM-41. Ferrocene was oxidized to
tetrahedrally coordinated oxide isolatedly grafted on the pore wall after calcination at 600~
in oxygen, and transformed to oxide nanoparticles in MCM-41 by further heating at 800~
under vacuum, characterized by TEM, in-situ XAS and EPR measurements.

07-P-14 - The evaluation of iron chromophore concentrations from iron

containing MCM-41
C. Nenu, R. Ganea, R Birjega, Gr. Pop and M. Pitu
ZECASIN S.A., Spl. Independentei 202, Bucharest, zecasin@com.pcnet.ro, Romania

This study aims to provide a fast method to evaluate the iron incorporation degree in the walls
of iron-containing mesoporous materials. Both Fe-MCM-41 systems and Fe+AI-MCM-41
systems were prepared with C~6TMABr as surfactant, in hydrothermal conditions. The colour
of the iron containing MCM-41 samples is determined just by coloured chromophores and,
taking into account that the intratetrahedral FeO4 is not, it can be established a connection
between colour, respectively luminescence (L), and the concentration of iron chromophores,
in fact the extraframework species. An incorporation degree of iron into MCM-41 walls and
additionally, an extraframework iron percent would be evaluated by this method.
252

07-P-15 - Synthesis and characterization of the mesoporous material of

single crystal particles
B. Lee (a), J.N. Kondo (a), D. Lu (b) and K. Domen (a, b)
a Chemical Resources Laboratory, Tokyo Institute of Technology, kdomen@res.titech.ac.jp,
Japan
b Core Research for Evolutional Science and Technology, JST, Japan

Mesoporous structure was constructed in single crystal particles of niobium and tantalum
mixed oxide 9 TEM and electron diffraction indicated single crystal phase with the mean pore
size of 10 nm. The crystallized mesoporous material showed mechanical and hydrothermal
stability.

07-P-16 - Stabilization of uniformly sized and dispersed copper particles in

new Cu-Zn-A! mesoporous catalysts
S. Valangea, b, J. Barrault b, A. Derouault b and Z. Gabelica a
ENSCMu, GSEC, 3, Rue A. Werner, F-68093, Mulhouse, Z.Gabelica@univ-mulhouse.fr,
France
bLACCO, UMR CNRS 6503, ESIP, 40, Av. du Recteur Pineau, F-86022 Poitiers, France

A series of binary Cu-A1 and ternary Cu-Zn-A1 surfactant assisted mesoporous precursors
prepared through direct synthesis yielded after calcination and reduction, both Cu ~ and Cu20
clusters of variable size, well dispersed on the mesoporous alumina substrate. These materials
proved particularly selective in the hydrogenation of the carbonyl group of cinnamaldehyde,
due to the presence of a large number of nanometer sized Cu20 particles that stay uniformly
dispersed and in strong interaction with the A1 mesoporous walls. In the ternary Cu-Zn-A1
mesoporous systems, ZnO exerts a major influence on the catalytic performance of such
catalysts. Experimental evidence of a CuzO/ZnO synergetic interaction is given.

07-P-17 - A direct synthesis route to the mesoporous silicate SBA-2 bearing

thiol groups 9 a*
I. Diaz a, F. Mohino a, J. P6rez-Panente , E. Sastre a, P.A. Wright b and W. Zhou b
Instituto de Catdlisis y Petroleoquimica (CSIC), Cantoblanco, 28049 Madrid, Spain.
b School of Chemistry, The University of St. Andrews, Fife KY16 9ST, Scotland, U.K.

The mesoporous silicate SBA-2 has been prepared in the presence of mercapto-
propyltriethoxysilane (MPTES) and gemini surfactants in basic medium. The thiol-containing
units are incorporated quantitatively and at a loading of 10%MPTES a high degree of
structural order is retained, as shown by XRD and TEM. Attempts to remove the templates by
extraction were successful, and it is possible to oxidize thiol to sulfonic acid groups. The
oxidized material containing -SO3H groups has been tested in the esterification of fatty
acids.the esterification of glycerol with oleic acid. Factors affecting the catalytic performance
of these materials are discussed.
 253

07-P-18- Template synthesis and characterization of nanoporous alumina

with narrow pore size distribution from inorganic salts
H.Y. Zhul, p. Cool 2, G.Q. Lu I and E.F. Vansant 2
i Department of Chemical Engineering, The University of Queensland, Australia,
hyzhu@cheque, uq. edu. au
2 Laboratory of Adsorption and Catalysis, University of Antwerp (UIA), Belgium
A polyethylene oxide (PEO) surfactant and an aqueous solution of inorganic aluminum salt
were used to prepare activated aluminas with narrow pore size distributions (PSD). The
condensation of the aluminum hydrolysate species around the micelles of the surfactant was
induced by urea. Mesoporous structure of alumina formed as the surfactant was removed. It is
also found that the function of the PEO surfactant depends on synthesis route. Highly porous
alumina was obtained by another process, from the same PEO surfactant and an inorganic salt
of aluminium. The proposed synthesis approach is of importance to the preparation of
activated alumina with various pore structures in industrial practice.

0 7 - P - 1 9 - Preparation and characterization of copper oxide modified

MCM-41 molecular sieves
C. Minchev a, R. K~hn b, T. Tsoncheva a, M. Dimitrov a and M. FrOba b'c
aInstitute of Organic Chemistry, BAS, 1113 Sofia, Bulgaria
bInstitute of Inorganic and Applied Chemistry, University of Hamburg, Germany
cInstitute of Inorganic Chemistry, University of Erlangen-Nuremberg, Germany

Using three different preparation methods copper oxide modified MCM-41 silica and A1-
MCM-41 materials were obtained and characterized by various techniques (nitrogen
physisorption, XRD and TPR-TGA) and methanol decomposition as a catalytic test reaction.
At certain conditions of impregnation and drying at room temperature and under vacuum it
was possible to form highly dispersed CuO nanoparticles incorporated almost exclusively
within the mesoporous host structure. These particles could be reduced with H2 at
considerably lower temperatures than the bulk CuO.

0 7 - P - 2 0 - Crystalline, m e s o p o r o u s N i O - Z r O 2 - b a s e d solid oxide fuel cell catalysts

P. Ratnasamy,* D. Srinivas, H.S. Soni, A.J. Chandwadkar, H.S. Potdar, C.S. Gopinath and
B.S. Rao
National Chemical Laboratory, Pune 411 008, India, prs@ems.ncl.res.in

Nickel-supported, yttria-stabilized zirconia, alumina-yttria-stabilized zirconia and ceria-

stabilized zirconia samples were prepared as fuel cell anode catalysts by three different
methods. The structural, textural and electronic properties of the materials were investigated
by XRD, N2 adsorption, chemisorption, XPS, DRS and EPR techniques. These materials have
cubic fluorite structure stable upto 973K and high specific surface area and average mesopore
size. Cerium promotes the reduction of Ni 2* ions. Samples prepared by hydrothermal
synthesis in the presence of structure-directing templates, like quaternary ammonium ions
have a high surface concentration of nickel, high catalytic activity and a slower deactivation
in the steam reforming of n-decane.
254

07-P-21 - Application of the A A S B U method to the prediction of inorganic

structures built exclusively of sodalite cages
S. Girard (a), P. Pullumbi (b), C. Mellot-Draznieks (a) and G. F6rey (a)
a Institut Lavoisier (IREM), Universit6 de Versailles, France, girard@chimie.uvsq.fr,
mellot@chimie, uvsq.fr
b Air Liquide, Centre de Recherche Claude-Delorme, Jouy-en-Josas, France.

The AASBU computational method is used here with the aim of producing a library of
inorganic zeolitic structures based on sodalite cages exclusively. The calculations are based
on a combination of a simulated annealing procedure and "cost function" minimizations that
enforce connections between individual sodalite cages. The assumptions for each simulation
run are the space group and the number of sodalite cages per unit-cell. The simulations
successfully generated the known SOD or LTA frameworks as well as hypothetical
frameworks. Lattice energy calculations of these hypothetical frameworks in their pure
silicate form, SiO2, suggest that they have stabilities similar to existing zeolites.

07-P-22 - Novel synthesis of nanoporous carbons using colloidal templates

S.B. Yoon, I.S. Shin and J.-S. Yu*
Department of Chemistry, Hannam University, Taejon, 306-791, Chungnam, Korea
jsyu@mail.hannam.ac.kr; fax: 82-42-629-7446

Ordered porous carbons were synthesized by replication of colloidal templates made from 30
- 100 nm diameter silica spheres and removal of the silica templates using aqueous HF. To
create the templates, the monodisperse particles were pressed into pellets and then sintered
slightly at their points of contact. The silica template were filled with carbon precursor
solution of divinylbenzene (DVB) and a free radical initiator, azobisisobutyronitrile (AIBN).
Polymerization and carbonization of the precursor solution and subsequent dissolution of the
silica templates leave a polycrystalline network of carbon with interconnected uniform pores.
The degree of order of the silica template is faithfully reproduced in the carbon replicas.

07-P-23 - Synthesis and characterization of mesoporous cerium silicate

analogues of M C M - 4 1 type molecular sieves
S. Laha, P. Mukherjee and R. Kumar
Catalysis Division, National Chemical Laboratory, Pune 411 008, INDIA
(Fax. +91-20-5893761/5893355; E-mail: rajiv@cata.ncl.res.in)

Cerium-containing MCM-41 mesoporous materials were synthesized using different methods.

X-ray diffraction pattem, N2 adsorption and different spectroscopic analyses of the samples
reveal that organized mesoporous MCM-41 materials were prepared. The presence of Ce is
confirmed by EDX analysis. High BET surface area (494-1415 m2gl ) and typical XRD
pattern of MCM-41 type hexagonal structure of these materials indicate the presence of
hexagonal mesopores in the samples. The presence of a strong absorption centered at ca. 290
nm and an absence of ca. 400 nm absorption in the UV-Vis spectra, indicate the presence of
tetra coordinated cerium in the Ce-MCM-41 samples.
 255

07-P-24 - Synthesis of m e s o p o r o u s materials using filtrate of alkali

t r e a t m e n t of M F I zeolite
M. Ogura, E. Kikuchi and M. Matsukata
Department of Applied Chemistry, Waseda University, mmatsu@mn.waseda.ac.jp,
Japan.

Synthesis of M41S mesoporous materials was attempted using MFI type zeolite as
sources of silica and aluminum, that is, dissolution of MFI zeolite in an alkaline solution
and successive precipitation of dissolved aluminosilicate species with a surfactant,
cethyltrimethylammonium bromide (CTAB). Pure phase of M41S was obtained when
the filtrate of alkali-treated slurry was mixed with CTAB and crystallized at 293K. The
M41S materials obtained in this method showed a catalytic activity originated from
Br~nsted acid site of the parent MFI zeolite. This method enables us to obtain a new
type of mesoporous materials, which have both characteristics of zeolitic and meso-
porous materials: a strong Bronsted acidity and mesopores with a uniform size.
256

1 5 - Modelling and Theoritical Studies A (Tuesday)

15-P-06 - A reactivity index study to choose the best template for zeolite
synthesis
A. Chatterjee and T. Iwasaki
Inorganic Materials Section, Tohoku National Industrial Research Institute, 4-2-1 Nigatake,
Miyagino-ku, Sendai 983-8551, JAPAN. Email: chatt@tniri.go.jp, Fax.'81-22-236-6839
The activity of different representative templating molecules along with zeolite framework is
investigated using a range of reactivity indexes using density functional theory (DFT). From
the values of local softness and the charge on the hydrogen atom of the bridging hydroxyl,
resulted from the presence of aluminum in the framework, it is observed that the acidities of
the aluminum containing zeolite type model systems, are dependent on several characteristics
which are of importance within the framework of hard and soft acids and bases (HSAB)
principle. We investigated the local softness of the interacting templates, to compare their
affinity with the zeolite framework cluster models. A priori rule is formulated to choose the
best template for a particular zeolite (e.g. ZSM-5) synthesis.

15-P-07- Effects of ion-exchanged alkali metal cations On the photolysis of

alkyl ketones included within ZSM-5 zeolite cavities: A study of ab-initio
molecular orbital calculations
H. Yamashita*, S. Takada, M. Nishimura, H. Bessho and M. Anpo*
Osaka Prefecture University, yamashita@chem, osakafu-u.ac.ip, Japan
Effects of ion-exchanged alkali metal cations on the adsorption and the photolysis (Norrish
type I and type II reactions) of 2-pentanone included within the alkali metal cation-exchanged
ZSM-5 zeolite have been investigated by experimental and theoretical approaches. The yields
of the photolysis decreased and the ratio of the type I/ type II reactions increased,
respectively, by changing the ion-exchanged cations from Cs + to Li +. The observed IR spectra
of the adsorbed ketones and the ab initio molecular orbital calculations of this host-guest
system indicate that the type I and type II reactions proceed from the staggered and eclipsed
conformations of 2-pentanone, respectively, and that the smaller cation has the stronger
electrostatic interaction between ketone and promotes the type I reaction of ketone efficiently.

15-P-08 - Encapsulated guest atoms within the basic beta cage of sodalitic
zeolite. A theoretical ab-initio study
N.U. Zhanpeisov and M. Anpo
Department of Applied Chemistry, Osaka Prefecture University, 1-I Gakuen-cho, Osaka 599-
8531, Japan, nurbost,n@ok. chem. osakafu-u.ac.jp

Ab-initio quantum chemical calculations at the HF/3-21G* level of theory were applied to
consider the nature of the active sites of sodalite [3-cage of the LTA type zeolite and faujasite
structures. Especially, the nature of sodium, potassium and silicon atoms encapsulated within
the sodalitic [3-cage, and their structural and molecular parameters have been described. We
have shown that up to four sodium and four potassium atoms as well as five silicon atoms
could be encapsulated within the sodalite 13-cage. The unique properties of these nano-size
materials relate directly to the encapsulated guest atom containing fragments stabilized within
the sodalite [3-cage of the LTA type zeolite or faujasite structures.
 257

15-P-09- n-Hexane aromatization over Pt-alkaline zeolites: ab-initio

calculations on the influence of the exchanged cations and zeolite type (L, 13
and Y) on electronic properties of Pt
S.B. Waghmode, P. Bharathi, R. Vetrivel and S. Sivasanker*
Catalysis Division, National Chemical Laboratory, Pune 411 008, lndia; siva@cata.ncl.res.in

Zeolites L, 13 and Y exchanged with different ions (H, Li, Na, K, Cs and Ba) and loaded with
0.6 wt% Pt have been tested for n-hexane aromatization activity. Activity of the catalysts
depends on the exchanged ion and on the zeolite support. Ab-initio calculations (restricted
Hartree-Fock) made, using representative cluster models of the three zeolites and a Pt5 cluster,
to determine the average charge of Pt supported on different ion-exchanged zeolites reveal an
increase in the electronic charge on Pt with the basicity of the exchanged ion. Relationship
between the average charge on Pt and benzene yields over the catalysts is reported.

15-P-10- A theoretical study of adsorption of carbon monoxide on Ag-

ZSM-5 zeolite
S. Jungsuttiwong, P. Khongpracha, T.N. Truong, and J. Limtrakul
Laboratory for Computational & Applied Chemistry, Chemistry Department, Kasetsart
University, Bangkok 10900, Thailand," e-mail: fscijrl@ku.ac.th

Calculated results obtained from the embedded cluster method at B3LYP/6-31G(d,p) yielded
a metal-oxygen distance of 2.300 (2.30+0.03) A for the Ag+-ZSM-5; the value in the
parenthesis is taken from the experimental results. The Madelung potential, represented by
sets of point charges surrounding the quantum cluster causes metal-oxygen distances to be
elongated by 0.05-0.07 A which make all predicted results agree very well with the
observations. The calculated high frequency of C-O stretching in the Ag+-ZSM-5 complex is
on account of the larger Ag+-C bond (2.07.3,) as compared to the Cu+-C bond (1.85 A). This
large distance can to some extent prevent the contribution of the 7t-back bonding in silver
carbonyl complexes.

15-P-I 1 - A theoretical~spectroscopic study of the coordination of transition

metal ions in zeolites
A. Delabie (a), M.H. Groothaert (b), R.A. Schoonheydt (b) and K. Pierloot (a)
a Laboratory of Quantum Chemistry, University of Leuven, Celestijnenlaan 200 F, B-3001
Heverlee-Leuven, Belgium," b Center for Surface Chemistry and Catalysis, University of
Leuven, K. Mercierlaan 92, B-3001 Heverlee-Leuven, Belgium.

Knowledge about the coordination of transition metal ions in zeolites is important for the
understanding of the catalytic properties of these materials. ESR and DRS have provided
9 2+ . . . . . .
spectroscopic signatures for Cu in different zeohtes. In this work, high-level theoretical
calculations (DFT, CASPT2) are used for the assignment of the spectroscopic signals to
specific coordination modes. The general features of the Cu2+-zeolite interaction are
summarized in three rules, which are then illustrated by the siting of Cu 2+ in mordenite.
258

1 5 - P - 1 2 - Ab-initio study of the adsorption and reactions of hydrocarbons

in mordenite
T. Demuth(a), L. Benco(a), J. Hafner(a), H. Toulhoat(b), and F. Hutschka(c)
alnstitut fi~r Materialphysik, Universiti~t Wien, Sensengasse 8/12, 1090
Wien,Austria, Thomas.Demuth@univie.ac.at blnstitut Franfais du Pdtrole, F-92852 Rueil-
Malmaison, France CTotalFina Raffinage Marketing, B.P. 27, F-76700 Harfleur, France
We have studied the interaction of n-alkanes, n-alkenes, and benzene with acid mordenite
using density functional theory. The adsorption strength is correlated to the local structural
distortion of the zeolite framework, especially of the acid site. Only for strong adsorption, the
molecule is slightly deformed as in the case of benzene adsorption. The analysis of the
differential indicates pronounced polarization effects on both the acid site and the adsorbed
molecule. The H/D exchange reaction of benzene has been analyzed by calculating the
reaction energy diagram.

15-P-13 - Properties of Cu 2+ and Cu + cations in MFI framework: DFT and

IR studies
E. Broclawik a, J. Datka b, B. Gil b and P. Kozyra b
alnstitute of Catalysis, Polish Academy of Sciences, brociawi@chemia.uj.edu.pl, ul.
Niezapominajek 8, 30-239 Cracow, Poland
bFaculty of Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Cracow, Poland
In this paper we present quantum chemical calculations for the extended model of ZSM-5
framework based on seven T sites in two fused 5T rings cut off the MFI structure. This
model is large enough to be a good host for Cu 2+ and Cu + and for adsorbed NO molecule 9
Coordination of the copper cation depends strongly on its oxidation state. Divalent copper
prefers planar square coordination in the centre of 6T ring while Cu + forms three bonds with
framework oxygens in a five-ring. NO molecule is strongly bonded by both Cu 2+ and Cu + but
it becomes significantly activated only after sorption on Cu +. Combined calculations and IR
data confirm migration of copper after oxidation/reduction and NO adsorption. Cu+ZSM-5
activates NO very strong and is very active in deNOx.

15-P-14 - Nonempirical (ab-initio) and semiempirical calculations of the

elementary fragments of zeolites. Permeability of ring zeolite fragments
A.V. Gabdrakipov, L.D. Volkova, N.A. Zakarina and V.Z. Gabdrakipov*
Institute of Organic Catalysis and Electrochemistry, Ministry of education and Science.
Kunaev Street 142, Almaty, 480100, Kazakhstan.
With the purpose of determining the permeability of rings S6R in zeolites, calculations at the
Hartree-Fock (ab-initio) and semiempirical PM3 levels have been performed for models
9 , + 9 + + . . . . .

including H , L1 , N a , Rb ions and H, He, Ar, Kr atoms. The semlempmcal calculations

9 . + + 9

were achieved for models with H and Na ions and H20, NH3, CH4, C2H6, C3H8 molecules.
The geometry of a fragment of zeolite, i.e. a cubic octahedron Si24036(OH)24, was optimized
with PM3. Then the fragment Si6018 was extracted and the free valency oxygen atoms in
S6R were saturated with hydrogen atoms 9The ab-initio calculations have shown the presence
of a potential hole at the center of the fragment S6R. Barrier values have been evaluated in
the case of atoms He, Ar, Kr (ab-initio) and simple molecules (PM3).
 259

15-P-15 - Modelling light alkane transformation over HZSM-5 zeolite

x. Wang a' b, F. Lemos a, and F. Ram6a Ribeiro a
aCentro de Engenharia Biol6gica e Quimica, Departamento de Engenharia Quimica, Instituto
Superior T6cnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. blnstitute of Industrial
Catalyst, Dalian University of Technology, 158 Zhongshan Road, 116012 Dalian, China.

Light alkane conversion over HZSM-5 zeolite occurs usually by a protolytic monomolecular
mechanism. In the present study we will analyse a set of experimental results obtained for the
transformation of light alkanes over HZSM-5, at various temperatures (350 ~ - 500 ~ and
compare these results with quantum chemical calculations for these transformations over
model acid sites. It was concluded that similar transition states were formed for the cracking
of C-C bonds in different alkanes, always with relatively high activation energies.

1 5 - P - 1 6 - Activity-acidity relationship in Y zeolite: an experimental and

quantum-chemical study
X. Wang a' b, M.A.N.D.A. Lemos a, F. Lemos a, C. Costa a, and F. Ram6a Ribeiro a
~Centro de Engenharia Biol6gica e Quimica, Departamento de Engenharia Quimica, Instituto
Superior T6cnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal.
blnstitute of Industrial Catalyst, Dalian University of Technology, 158 Zhongshan Road,
116012 Dalian, China.

The aim of the present paper is to show that there is a clear relation between the catalytic
activity and the acidity for acid catalysis using Y zeolites and that this relationship has
theoretical support through quantum chemical calculations on model acid sites. The study
presented is centred on the transformation of ethene and propene over acidic Y and USY
zeolites.

15-P-17 - DFT study of structure changes in hydrated AIPO4-n : the case of

AlPO4-34
G. Poulet, A. Tuel and P. Sautet
Institut de Recherches sur la Catalyse, gpoulet@catalyse.univ-lyonl.fr, France.

The structural relaxation of calcined A1PO4-34 and the geometry distortion of the compound
upon adsorption of water have been studied by DFT plane-wave calculations on periodic
models. A good correlation was found between experimental and optimized structures for
both the dehydrated and fully hydrated compounds. In the latter, the 3D-channel system is
filled with water molecules, some of them being coordinated to framework aluminum, and
forming a strong H-bond network. Energetic and geometric calculations reveal that one
specific non-framework water molecule is less strongly bonded and can reversibly desorb at
room temperature, in agreement with the existence of a partially hydrated phase observed
experimentally by X-ray diffraction.
260

15-P-18 - A mechanistic exploration of alkene epoxidation mediated by H202

within porous titanosilicate catalysts
C.M. Barker(a), N. Kaltsoyannis(b) and C.R.A. Catlow(a)
aThe Royal Institution of Great Britain, London, UK, richard@ri.ac.uk.
bUniversity College London, UK.

Density Functional Theory has been employed to examine the geometry, coordination,
stability, energetics of formation and oxygen-donating mechanism of Ti-peroxo complexes in
peroxide doped Ti substituted molecular sieve epoxidation catalysts. Through a combination
of DFT calculations and Ti EXAFS of a tert-butyl hydroperoxide exposed surface grafted
Ti?MCM41 catalyst we have determined that the active species in titanosilicate catalysts are
6 coordinate. Furthermore, we propose that both Ti(q2-OOR) and five membered ring Ti(TI2-
OOR) complexes are energetically stable and are likely to be present in peroxide/Ti
substituted molecular sieve systems.

15-P-19 - Transition-state shape-selectivity insights from a Fukui function

overlap method
L.A. Clark a and R.Q. Snurr
Department of Chemical Engineering and Center for Catalysis and Surface Science,
Northwestern University Evanston, IL 60208 ~email."louie@fiesta.cqe.northwestern.edu

The theory and implementation of a novel computational method capable of looking at large
transition-state shape-selective systems is outlined. It is then applied to the alkylation reaction
of toluene in the gas phase as well as in zeolites MFI, MOR and BEA. Alkylating agents from
the series methyl, ethyl, iso-propyl and tert-butyl are employed to investigate the size and
shape effects of the confinement.

15-P-20 - A DFT study of the isomerization reactions of aromatics catalyzed

by acidic zeolites
X. Rozanska, R.A. van Santen, F. Hutschka a and J. Hafner b
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven
University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
aTotalFinaElf, Centre Europ6en de Recherche et Technique, D6partement Chimie des
Proc6d6s, B.P. 27, 76700 Harfleur, France
blnstitut fiir Materialphysik, Universitdt Wien, Sensengasse 8, A-1090 Wien, Austria

A DFT study of the isomerization reactions of toluene catalyzed by acidic zeolite is reported.
Monomolecular isomerization reactions have been considered and analyzed. The different
reaction pathways have been discussed in detail. The uses of periodical structure calculations
as well as small cluster approach method calculations allow to analyze the effect of zeolite
electrostatic contributions and steric constraints on reactivity.
 261

15-P-21 - Ab-initio investigation of non-framework aluminum species in

zeolites
D. Lopes Bhering a, C.J.A. Mota a and A. Ramirez-Solis b
~Instituto de Quimica, Universidade Federal do Rio de Janeiro, Rio de Janeiro, 21949-900,
Rio de Janeiro, Brazil. (cmota@iq. ufrj. br)
6Faculdad de Ciencias, Universidad Aut6noma del Estado de Morelos, Cuernavaca, Morelos,
6221 O, MOxico

Structure and chemical shifts of non-framework aluminum (NFA) were studied by ab-initio
methods. A T6 cluster (T=Si, A1) was used to simulate the zeolite structure. The NFA are
preferentially coordinated to the oxygen atoms of the framework AIO4. For 3- and 4-
coordinated species, the predicted "A1 NMR results show downfield chemical shifts (70-
95ppm) related to the experimentally observed ones (0-60ppm). This suggests that some of
the species do not exist or that they may be coordinated with water. For 5-coordinated NFA
the calculated chemical shifts was between the octahedral and tetrahedral value (45-55 ppm).

15-P-22 - A DFT study of the cracking reaction of thiophene activated by

zeotype catalysts: role of the basic Lewis site
X. Rozanska, R.A. van Santen and F. Hutschka a
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven
University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
~TotalFinaElf, Centre Europ~en de Recherche et Technique, D6partement Chimie des
Proc~d6s, B.P. 27, 76700 Harfleur, France

A DFT study of the cracking reaction of thiophene catalyzed by zeolite is reported. The use of
different zeotype catalysts (viz. acidic, metal-exchanged and methoxy) has been shown to
successfully induce this reaction. It appears that the thiophene cracking reaction is catalyzed
by a basic Lewis site and that acid Bronsted site has only a limited influence on the reaction.

15-P-23 - Modelling transition metal cations in zeolites: how do they

interact with the framework?
D. Berthomieu a, A. Goursot a, J-M. Duc6r6 a, G. Delahay a, B. Coq a and A. Martinez b
~LMCCCO UMR-CNRS 5618, ENSCM, 8, rue de l'Ecole Normale, 34296 Montpellier
Cedex 5- France- bertho@critl.univ-montp2.fr
blnstituto de Investigaciones in Materiales, Circuito Exterior s/n, C. U. Apdo.
Postal 70-360, C. P. 04510, Mdxico, D.F. Mdxico

Density Functional Theory has been used to study model clusters of zeolites Y and 13
containing Fe(II), Co(II) and Cu(II) TM cations. The calculations yield a charge of around + 1
on TM whatever are their coordination, the size of the cluster and the A1 distribution. This
result is obtained only with TM and most probably comes from a charge transfer from the
zeolite to TM. We show that the TM-zeolite system behaves as a supermolecule and that the
zeolite is able to keep or release electrons when reactive molecules are incoming.
262

15-P-24 - Theoretical prediction of IR spectra of guest molecules in

zeolites: the stretching frequency of CO adsorbed at various cationic sites
in Z S M - 5
T.A. Wesolowski (a), A. Goursot (b) and J. Weber (a)
(a) Department of Physical Chemistry, University of Geneva, 30 quai Ernest Ansermet, 1211
Genbve 4, Switzerland
(a) UMR 5618 CNRS, Ecole de Chimie, 8 rue de l'Ecole Normale, 34296, Montpellier, C~dex
5, France

The influence of the microscopic environment of the cationic site in ZSM-5 as well as the
long-range effects on the CO stretching frequency and on its binding energy has been studied
using a DFT-based methodology. Our results show that the choice of the A1 site does not
affect significantly the calculated shifts whereas the binding energies display more variations.
The calculated frequency shifts agree with experiment within few cm l.

15-P-25 - D e v e l o p m e n t of a tight-binding treatment for zeolites

M. Elstner a, A. Goursot b, Z. Hajnal c, T. Heine d and J. Weber d
Department of Molecular Biophysics, D-69120 Heidelberg; b UMR 5618, Ecole de Chimie, 8
rue de l'Ecole Normale, F-34296 Montpellier,'~University of Paderborn, Department of
Theoretical Physics, D-33098 Paderborn, d University of Geneva, Department of Physical
Chemistry, CH-1211 Geneva 4," thomas.heine@chiphy.unige.ch

Density-Functional based Tight-Binding (DFTB) calculations of two types of zeolites (MAZ,

BEA) are presented. For these systems, a unit-cell was fully optimized using periodic
boundary conditions in the G point approximation and these results are compared with cluster
approximations, where unit-cell dangling bonds are saturated with H. For mazzite, a small
cluster model including the two crystallographic sites are also compared with full Density-
Functional theory (DFT) results. The method shows good agreement with experimental X-ray
data and DFT values. It is extended to treat zeolites containing aluminum.

15-P- 26 - 1-D growth of selenium wires in silicalite-1 zeolite

C. Bichara a and R.J.-M. Pellenq b
a CRMC2- CNRS, Campus de Luminy, Case 913, 13288, Marseille, xtof@crmc2.univ-mrs./k.
b CRMD - CNRS et Universit6 d'OrHans, 1bis rue de la F6rollerie, OrHans, 45071.

A computer simulation of the adsorption of Selenium in silicalite is presented. The Se-Se

interactions are calculated in a quantum mechanical tight-binding approach. The Se-silicalite
interactions are assumed to be of Van der Waals type. The adsorption/desorption isotherms
are characteristic of a mechanism where adsorbate-adsorbate interactions are much larger than
the adsorbate/matrix interactions: they exhibit a large hysteresis loop which tends to disappear
as temperature increases. At sufficiently low temperature, the adsorption branch shows some
sub-steps which magnitude and position depend on the simulation box size. These sub-steps
are followed by brutal jumps corresponding to filling of the remaining porosity. All these
features are rather uncommon for adsorption in a microporous system.
 263

1 5 - P - 2 7 - Cumulative coordinates for approximations of atomic multipole

moments in cationic forms of aluminosilicates
A.V. Larin (a) and D.P. Vercauteren (b)
a Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, B-234,
119899, Russia; b Laboratoire de Physico-Chimie Informatique, Facultds Universitaires
Notre Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium

Atomic multipole moments (MMs) are calculated for three LiABW, NaNAT, and BaEDI
aluminosilicates with the periodic Hartree-Fock CRYSTAL95 code. The positions of the
cations with and without included water molecules were optimised. Approximate functions
for the MMs which can be used for further calculations of the electrostatic potential in an
arbitrary zeolite are proposed in terms of the charges and geometry of their neighbour
atoms.

15-P-28- Computer simulations of water in zeolites

C. Bussaia b, R. Haberlandt a, S. Hannongbuai b and S. Jost a
a,b University Leipzig, Institutefor Theoretical Physics, Leipzig, Germany, b Department of
Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, Thailand

The topic of water in zeolites is viewed from different points. On the one hand, Hatree-Fock
and MP2 quantum chemical calculations have been performed to investigated water-silicalite
interaction as well as the energy barrier and water orientations during diffusion in the
silicalite. The results indicate how water molecules move and turn during movement through
the center of the silicalite pore. The energy barriers for water molecules to enter the pore and
to diffuse from one channel to the other have been examined. The water molecules enter and
leave the pores preferably by pointing its d~pole vector towards the center of the cavity. On
the other hand we present molecular dynamics simulations with a well established empirical
water model in the chabazite. Both water molecule and zeolite lattice are modelled flexible.
The diffusion and the configuration of the water molecules inside the zeolite are examined.
264

16- Modelling and Theoriticai Studies B (Tuesday)

16-P-06- Location of triethylmethylammonium ions in MFI by combining

molecular modeling and X-ray diffraction
R. Millini
EniTecnologie S.p.A, 20097 San Donato Milanese (MI-Italy) - rmillini@enitecnologie.eni.it

A Quench Dynamics protocol (a combination of high temperature Molecular Dynamics and

Energy Minimization techniques) is used for predicting the location of triethylmethyl-
ammonium (TEMA) cations in zeolite MFI.' Rietveld refinement of the high-resolution
synchrotron X-ray diffraction data confirms these predictions. The TEMA cations are located
at the channels intersections in two different conformations with two ethyl groups located in
the linear channel.

16-P-07 - A hypothetical zeolite structure MCRI6: topological design and

template choice
B. Li (a), P. Sun (b), Q. Jin (a) and D. Ding (a)
a Department of Physics; Nankai University, Tianjin 300071, dingdt@nankai.edu.cn, China
b The State Key Laboratory of Functional Polymer Materials for Adsorption and Separation,
Institute of Polymer Chemistry," Nankai University, Tianjin, China

The topological structure of a novel zeolite, named MCR16, with cylindrical channels
spanning 16-membered rings, is constructed by means of the sigma transformation of the
known zeolite mordenite. The consistent molecular mechanics force field is employed, and
the minimized energy structure is obtained. The calculated heat of formation of MCR16 is
comparable to that of mordenite. Six organic molecules that might be used as template in
synthesizing this novel structure are discussed based on the calculations of the non-bonding
interaction energies between the organic molecules and MCR16 frameworks.

16-P-08 - Computational analysis of the shape-selective isopropylation o!

biphenyl over large pore zeolites
J. Joffre (a), D. Mravec (b) and P. Moreau (a)
a Ecole Nationale Sup&ieure de Chimie de Montpellier, joffre@cit, enscm.fr, France.
b Organic Technology, Slovak University of Technology, Bratislava, Slovak Republic.
Computational analysis of molecular dimensions and diffusion energies of the various mono-
and di-isopropylbiphenyl isomers has been performed, using molecular mechanics and
quantum mechanics methods. The 4,4'-diisopropylbiphenyl has the lowest kinetic diameter
and diffusion energy, which is in agreement with the experimental results regarding the high
para-selectivity observed in the isopropylation reaction of biphenyl over H-mordenites. The
above calculations in the biphenyl series show that modelling analysis appears to be useful to
understand the experimental results, and confirms other computational results in the field of the
shape-selective alkylation of naphthalene.
 265

16-P-09 - De novo simulation and spectroscopic study of iron speciation in

ZSM-5 and CIT-5
P.-P.H.J.M. Knops-Gerrits l* and W.A. Goddard III2
t CMAT, D@artement de Chimie, Univ. Cath. de Louvain, Belgium, ppkg@chim.ucl.ac.be
: MSC, Beckman Institute (139-74), California Inst. of Technology, USA
wag@wag, caltech, edu

The introduction of iron in the lattice of zeolite topologies such as MFI and CFI is performed
via direct synthesis and post-synthetic modification. Dinuclear iron clusters in appropriate
zeolites realize oxidation of methane into methanol at room temperature after NzO activation.
Both mono and dinuclear iron coordination and lattice coordination is treated with theory and
experiment. In FeCIT-5 and Fe-ZSM5 are made by "over-exchange" via sublimation of iron
salts in Al-zeolites. When extra-framework iron oxides are made in zeolites, the extra-
framework iron oxide clusters can be anchored to zeolites.

1 6 - P - 1 0 - Exact statistical mechanical treatment of a lattice model of

hydrocarbon adsorption on zeolites
G. Manos (a), L.J. Dunne (b,c), Z. Du (c) and M.F Chaplin (c)
Department of Chemical Engineering, University College London, Torrington Place,
~.manos@ucl.ac.uk, London, WCIE 7JE, UK
School of Chemistry, University of Sussex, Brighton, UK.
c School of Applied Science, South Bank University, London SE10AA, UK.

In this paper, we present an exact calculation of the statistical mechanics of a lattice model of
hydrocarbon adsorption in the quasi one-dimensional pores of zeolites, based on a matrix
method that utilises the Constant Pressure partition. The model is tested on benzene
adsorption, where it reproduces experimentally observed steps in isotherms. The model has
been extended also to linear alkanes where it reproduces very accurately experimental
adsorption isotherms as well as Monte-Carlo simulation results of ethane.

16-P-I 1 - Computational studies of the structure of Na- and H-Mordenite

A.E. Gray, A. O'Brien and D.W. Lewis
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University
College London, U.K., aileen.gray@ucl.ac.uk, d.w.lewis@ucl.ac.uk

A combined Monte Carlo and energy minimisation method has been developed to model
zeolitic materials with low and medium Si/A1 and with a variety of extra-framework species.
We present results for Na- and H-Mordenites with Si/A1 of 5 and 11. The A1 and cation
distributions obtained are in reasonably good agreement with experimental studies.
Furthermore, our calculated vibrational spectra are in excellent agreement with experiment,
which has allowed us to re-interpret the de-convolution and assignment of the various acid
sites.
266

16-P-12 - M o n t e Carlo simulation of isobutane in silicalite

D. Paschek and R. Krishna
University of Amsterdam, paschek@its, chem. uva.nl, The Netherlands

Recent experimental work on transport diffusion of alkanes in zeolite Silicalite [B. Millot et
al., J. Phys. Chem. B, 103 (1999) 1096; B. Millot et al., Micropor. Mesopor. Mater., 38 (2000)
85] indicates a possible change of the diffusion mechanism of branched components when
approaching higher loadings. Therefore, we report kinetic Monte Carlo (KMC) simulations of
diffusion of isobutane adsorbed in Silicalite. By using configurational-biased Monte Carlo
(CBMC) simulations we get evidence for the presence of repulsive interactions between
molecules adsorbed at adjacent intersection and straight channel sites. Our KMC simulations
reveal that even weak repulsive interactions have a rather strong influence on the diffusivities
at higher loadings and therefore could serve as a possible explanation for the experimentally
observed behavior.

16-P-13 - Characterisation of hypothetical zeolite f r a m e w o r k s

M.D. Foster (a), R.G. Bell (a) and J. Klinowski (b)
a DFRL, Royal Institution of GB, London, UK, martinf@ri.ac.uk, rob@ri.ac.uk.
b Dept. of Chemistry, Univ. Cambridge, UK

A series of hypothetical zeolite structures has been evaluated on the basis of calculated lattice
energies and structural properties. The structures were those generated by Delgado and co-
workers, using recent advances in tiling theory. Over 900 structures are currently under
evaluation, from which results are presented of the 157 uninodal structures based on a quasi-
simple tiling unit, which include all 18 presently known uninodal zeolite structures. Treating
each structure as a silica polymorph, we have calculated relative lattice energies, framework
densities and coordination sequences. An automated procedure uses these quantities and
correlations between them, to make an initial selection of likely candidate zeolite structures.

16-P-14 - Cation mobility and the sorption of chloroform in zeolite NaY: a

molecular d y n a m i c s study
N.A. Ramsahye and R.G. Bell
DFRL, Royal Institution of Great Britain, London, UK;rob@ri.ac.uk

Molecular dynamics simulations at temperatures of 270 K, 330 K and 390 K have been
carried out in order to address the question of cation migration upon chloroform sorption in
zeolite NaY. The results show that the cations located in different sites exhibit different types
of mobility. These may be summarised as follows: 1. SII cations migrate towards the centre of
the supercage upon sorption, due to interactions with the polar sorbate molecules. 2. SI'
cations migrate from the sodalite cage into the supercage to fill vacant SII sites. 3. The SI
cations are able to migrate across double six rings and sodalite cages in order to fill another
vacant SI' site. SI' cations can also migrate to fill another vacant SI' site.
 267

1 6 - P - 1 5 - Computational studies of the calcination of fluorinated gallo-

phosphates" exploration of their template-free calcined forms
S. Girard (a), J.D. Gale (b), C. Mellot-Draznieks (a) and G. F6rey (a)
Institut Lavoisier (IREM), Universitd de Versailles, France, girard@chimie.uvsq.fr,
mellot@chimie, uvsq.fr
b Department of Chemistry, Imperial College of Science Technology and Medecine, UK.

The stability of four fluorinated templated gallophosphates upon calcination is anticipated

using lattice energy minimizations and appropriate interatomic potentials, starting from their
as-synthesized structures. A careful analysis of the frameworks and energetics of the four
predicted calcined structures helped us to consider their viability. Three of them have zeotype
frameworks and their lattice energies suggest the stability of their as-synthesized forms upon
calcination. One of the latter compounds corresponds to its experimentally calcined structure,
thus validating the calculations. The last predicted calcined compound shows unrealistic
structural feature suggesting the high unstability of its as-synthesized form upon calcination.

16-P-16 - Molecular simulation studies on the effectiveness of template type

on TS-I crystal morphology
H. Zhou, H. He and Z. Jing
Research Institute of Petroleum Processing, China Petrochemical Corporation, P.O. Box
914, Beijing 100083, zhouhans@btamail.net.cn, China.

Molecular simulation approaches were used to investigate the effectiveness of template type
on TS-1 crystal morphology. Calculations indicated that docking of hexane diamine on
surfaces of TS-1 crystal strongly changes crystal size and morphology. It is also found that
hexane diamine can pack together with TPA in TS-1 structure to play an important template
effect. Simulation results consistent well with experimental results.

16-P-17- A molecular dynamic approach on the selective conformationai

change of ethylene glycol in sodalite cage
M. Sato
Department of Chemistry, Gunma University. Kiryu, Gunma376, Japan

In order to investigate the conformational stability of ethylene glycol molecule in the sodalite
cage, a molecular dynamic simulation is performed on the force field MM+ as well as semi-
empirical PM3. As the result, the gauche(+) conformer is confirmed to be more stable than the
gauche(-) one in the sodalite cage.
268

1 6 - P - 1 8 - T h e mutual influence of dynamic processes acting in different

time scales
S. Fritzsche a, R. Haberlandt a, A. Schfiring a and M. Wolfsberg b
a University Leipzig, Institute for Theoretical Physics, Leipzig, Germany," b Institute for
Surface and Interface Science, University of California, Irvine, USA.

Diffusion and relaxation processes of different nonspherical guest molecules in zeolites are
examined by MD simulations with rigid and flexible lattice and molecules. Interrelations
between such processes are studied by different tools, e.g. correlation functions. The results
show that there exsist cases where a strong mutual influence can be found and others in which
there is only small influence.

1 6 - P - 1 9 - Lattice-dynamical calculations for zeolites of natrolite group

S.V. Goryainov (a) and M.B. Smirnov (b)
a Institute of Mineralogy and Petrography, Novosibirsk-90, Russia, svg@uiggm.nsc.ru
b Institute for Silicate Chemistry, St. Petersburg-155, Russia, mike@isc.nw.ru

Lattice-dynamical calculations for unit cells of natrolite and edingtonite were performed. It
was shown that strongest Raman bands of natrolite at 534 cm z and edingtonite at 530 cm 1 are
related to breathing modes of 4-membered rings. Assignment of vibrational spectra of used
zeolites, presented here for symmetric modes of natrolite, may provide a base for
interpretation of vibrations in other zeolites. Calculated natrolite crystal structure exhibits
instability at about 5.5 GPa, which corresponds to amorphization observed at pressure range
of 4-7 GPa.

16-P-20 - Kinetic modelling of the dynamic interaction between NO and

N20 over Cu-ZSM5
R. Pirone a, P. Ciambelli b, A. Di Benedetto a, B. Palella c and G. Russo a
~lstituto di Ricerche sulla Combustione, CNR, Napoli, Italy- pirone@irc.na.cnr.it;
bDipartimento di Ingegneria Chimica e Alimentare, Universit~ di Salerno, Fisciano, Italy,"
~Dipartimento di Ingegneria Chimica, Universit~ di Napoli "Federico II", Napoli, Italy.

Spontaneous and isothermal oscillations of N20 decomposition rate have been observed in
Cu-ZSM5. In the presence of NO, oscillations desappear and the overall reaction rate
significantly increases. A kinetic model has been developed to describe this phenomenom
proposing a redox mechanism which describes the interaction between NO and N20 over Cu-
ZSM5.
 269

1 9 - Diffusion: Fundamental Approach (Tuesday)

19-P-06 - Modeling of sulfur dioxide breakthrough curves from ternary wet

mixtures on MOR type zeolite
M. Mello a, M. Eid a, S. Ho(,evarb and U. Lavren6i~-Stangarb
aDepartment of Chemical Engineering, University of New Brunswick, P.O. Box 4400,
Fredericton, N.B., Canada E3B 5A3 (meic@unb.ca); bNational Institute of Chemistry,
Laboratory of Catalysis and Reaction Engineering, Hajdrihova 19, 61115 Ljublj'ana, Slovenia
The adsorption of SO2 from temary mixtures with water and CO2 on high silica MOR zeolite
was investigated using the breakthrough curve method. The breakthrough model was based on
axially dispersed plug flow through the column, and mixture equilibrium was described by
Langmuir 1 extended model. The solution was obtained by finite element collocation method
using the commercial software gPROMS. Infra-red spectroscopic measurements gave further
evidence that water was more strongly adsorbed than SO2, thus displacing it and causing roll-
up effect.

19-P-07- The diffusion and sorption dynamics of acetylene in zeolites

G. Onyestydk (a), J. Valyon (a) and L.V.C. Rees (b)
a Institute of Chemistry, Chemical Research Center, Hungarian Academy of Sciences
valyon@cric, chemres, hu, Hungary
b Department of Chemistry, University of Edinburgh, Edinburgh, United Kingdom

Species formed from acetylene (Ay) adsorbed in zeolite Y, mordenite, beta and ZSM-5 have
been studied by IR spectroscopy. The dynamics of Ay physisorption has been characterized
by the frequency response method (FR). The rate of micropore diffusion governed the
transport in Na-mordenite, while sorption was the rate limiting process step for all the H-
zeolites. The equilibrium constants (Ka) of Ay sorption have been determined applying the
Langmuir rate equation to describe the pressure dependence of the sorption time constants.
The n-octane hydroconversion activity of Pt/H-zeolites was found to increase linearly with the
Ka of Ay sorption on the H-zeolites.

19-P-08 -Transient uptake measurements using an oscillating micro-

balance: effect of acid leaching on the diffusivity of n-hexane in Pt/H-
mordenite
S. van Donk, A. Broersma, O.L.J. Gijzeman, J.H. Bitter and K.P. de Jong*
Department of Inorganic Chemistry and Catalysis, Debye Institute, Utrecht University,
The Netherlands; *Corresponding author, e-mail: K.P.deJong@chem.uu.nl
Measurements performed in a tapered element oscillating microbalance (TEOM) reveal that
diffusivities can be derived from uptake data monitored under full reaction conditions. In this
way the effect of acid leaching on the diffusional behaviour of n-hexane in Pt/H-Mordenite is
investigated. It is shown that acid leaching largely enhances the n-hexane uptake rate, but
does not result in a net increase in the intracrystalline steady state diffusivity. It is concluded
that the accelerated uptake after acid leaching merely arises from the shorter intracrystalline
diffusion path resulting from the mesoporous structure.
270

19-P-09 - Use of 129Xe N M R spectroscopy to study gaseous hydrocarbon

diffusion in a fixed bed of HZSM-5 zeolite
M.-A. Springuel-Huet, P. N'Gokoli-Kekele, C. Mignot, J.-L. Bonardet and J. Fraissard
Laboratoire SIEN-Chimie des Surfaces, Universitd P. et M. Curie, Paris, mas@ccr:/ussieu.:fr,
France

The diffusion of gaseous benzene and paraxylene during their adsorption in a fixed bed of
HZSM-5 zeolite crystallite has been studied by 129Xe NMR of adsorbed xenon used as a
probe. The equations of diffusion in the macropores and micropores have been analytically
solved, giving the hydrocarbon concentration profiles against time in both types of pores and
allowing the simulation of the 129Xe NMR spectra. The comparison of simulated and
experimental spectra leads to the value of the intracrystallite diffusion coefficients which are
in good agreement with the literature.

19-P-10 - Adsorption and diffusion of alkanes and their mixtures in

silicalite studied with positron emission profiling technique
A.O. Koriabkina, D. Schuring, A.M. de Jong and R.A. van Santen
Schuit Institute of Catalysis, Technical University of Eindhoven, a.koryabkina@TUE.NL, The
Netherlands

With the TEX-PEP technique experiments on the diffusion and adsorption of mixture of n-
hexane/2-methylpentane in large silicalite-1 crystals have been performed. By modeling the
experimental tracer exchange curves values of intracrystalline diffusion coefficient and
adsorption constant were obtained. Slight preference for the adsorption of n-hexane was
found. Diffusivity of n-hexane sharply decreases with increasing fraction of its isomer, since
the last one occupies channel intersections thus blocking zeolite network.
 271

2 4 - N e w Routes to H y d r o c a r b o n Activation (Tuesday)

24-P-06 - Study of coke and deactivation over H-Beta zeolite

Z. Zhu, T. Ruan, Q. Chen, W. Chen and D. Kong
Shanghai Research Institute of Petrochemical Technology- China, zhuzhirong@yahoo.com

The nature of coke over H-Beta strongly relates to different types of reactions. The coking
rate, in line with the deactivating rate during three reactions, increases in the following order:
toluene disproportionation, n-heptane cracking, benzene alkylation. With the increase of H-
Beta Si/A1 ratio, the decrease of the coking rate becomes slower, because the effect of the acid
site decrease on coking is compensated by the increase of the space available for coking from
the secondary pores. But the decrease of deactivating rate keeps constant. The coking rate
over H-Beta is higher than that over H-MOR. The deactivation rate of H-Beta is much lower
than that of H-MOR since its three-dimensional interlining system without supercage is not as
easy to be blocked as pseudo-unidimensional channels of H-MOR.

2 4 - P - 0 7 - Photoionization of N - a l k y i p h e n o t h i a z i n e s in transition-metal-ion
modified m e s o p o r o u s silica S B A - 1 5 molecular sieves
Z. Luana, b and L. Kevan a
aDepartment of Chemistry, University of Houston, Houston, Texas 77204-5641
E-mail. KEVAN@ UH.EDU
bphilip Morris, P.O. Box 26583, Richmond, VA 23261-6583

N-Alkylphenothiazines with variable alkyl chain lengths have been incorporated into meso-
porous silica SBA-15 containing framework titanium or vanadium. Photoionization at room
temperature forms stable alkylphenothiazine cation radicals (PCn +) which are monitored by
electron spin resonance. The results reveal that the photoyield and stability of PCn + increase
with increasing titanium and vanadium content suggesting that these ions serve as effective
electron acceptors. The overall photoyield and stability of PCn + also increase with increasing
alkyl chain length of the alkylphenothiazines.

24-P-08 - Potential use of A I M C M - 4 1 for activation of metallocene catalyst

T. Sano, T. Niimi, T. Miyazaki, S. Tsubaki, Y. Oumi and T. Uozumi
School of Materials Science, Japan Advanced Institute of Science and Technology,
Tatsunokuchi, Ishikawa 923-1292, Japan 9E-mail " t-sano@iaist.ac.jp

Polymerizations of ethylene and propylene were conducted with racethylene(bisindenyl)-

zirconium dichloride(rac-Et(Ind)2ZrClz) with triisobutylaluminium(Al(i-C4H9)3) using
A1MCM-41 evacuated at various temperatures. A linear relationship between the polymer
yield and the number of Lewis acid sites on the A1MCM-41 was observed. Lewis acid sites on
the A1MCM-41 are able to activate effectively the metallocene compound, resulting in the
formation of active species for olefin polymerization.
272

24-P-09 - Activation of butanes with olefins' carbenium cations over zeolite

catalysts
S.E. Dolinsky(a) and V.A. Plakhotnik (b)
a New Catalytic Technologies Ltd., dolser@cacr.ioc.ac.ru, Moscow, Russia
b Institute of Organic chemistry RAS, Moscow, Russia
Most publications concerning alkylate manufacturing (as component of blended gasoline)
from light hydrocarbons assume application of "new types" of zeolites - BETA, MCM, EMT.
However "old types" of zeolites have not yet completely discovered their potential. We
developed modified technique for producing bi-functional zeolite X based catalysts with
superacid centers of narrow acidity distribution (various analytical data to prove this fact are
given). Besides, such zeolites are employed for the alkylation of n-butane and ethylene
yielding isobutane/butylenes. Catalyst lifetime and content of isooctanes in alkylate increase
significantly (up to 5 times and up to 95 % respectively).

24-P-10 - Immobilization and mobilization of surface species during

transformation of ethylene over H Z S M - 5 catalysts
A. Zikdnovd (a), M. Ko6ifik (a), M. Derewifiski (b), P. Sarv (c), J. Dubsk)~ (a), P. Hudec(d)
and A. Smie~kovfi (d)
a* J. Heyrovs~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolejgkova 3, 182 23 Prague 8, kocirik@l'h-inst.cas.cz, Czech Republic,
b* Institute of Catalysis and Surface Chemistry,, Niezapominajek l, 30-239 Cracow, Poland,
c*Institute of Chemical Physics and Biophysics, Estonian Acad. of Sciences Tallin, Estonia
d* Slovak University of Technology, Radlinsk~ho 9, SK 81237 Bratislava, Slovak Republic

Amount of ethylene immobilized in HZSM-5 catalysts was estimated from sorption and
reaction dynamics as a function of reactor temperature. Space accessible in loaded crystals
was measured using water sorption at 298 K.

24-P-11 - Zeolite-L as support of Fe microcrystals for the F i s c h e r - T r o p s c h

synthesis
M.V. Cagnoli, N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, A.A. Yeramian and S.G. Marchetti
CINDECA, Fac. Cs. Exactas, Fac. Ingenieria, UN.L.P., CIC, CONICET.,
mavic@quimica, unlp. edu. ar
Calle 47 N ~ 257 (1900) La Plata, Argentina.

Zeolite-L in potassic form (Fe/ZLK) was used as support of iron species to be used as catalyst
in the Fischer-Tropsch reaction. The oxide precursor was reduced using two different
programmes. Thermal programme reduction (TPR), X-Ray Diffraction (XRD), Specific
Surface area (BET), "In-situ" M6ssbauer Spectroscopy (MS) between room temperature and
15K, H2 chemisorption and Volumetric Oxidation (VO) were used to characterize the solids.
Using a slow reduction treatment, it was possible to maintain a high quantity of Fe ~
microcrystals inside the pore structure, leading to a higher activity to low molecular weight
paraffin.
 273

24-P-12 - Nb- and Ti-containing silica-based mesoporous molecular sieves

as catalysts for photocatalytic oxidation of methane
J. Xin a, X. Chen b, J. Suo a, Xia. Zhang a, L. Yan a and Shuben Li a
aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences, Lanzhou,, jssuo@ns.lzb.ac, cn, China
bCollege of Chemistry and Chemical Engineering, Guangxi University, Nanning, China
Nb- and Ti-containing silica-based mesoporous molecular sieves were used as catalysts for
photocatalytic oxidation of methane. It is found that methanol was formed at 323 K and water
pre-adsorbed samples exhibited higher catalytic activity than their pure metal oxides. By
comparison with Nb-MCM-41, Ti-MCM-41 gave better methane conversion and methanol
yield although traces of formaldehyde were observed over Nb-MCM-41 catalyst.
Interestingly, OH radical was detected by the in-situ ESR spectroscopy using DMPO as
trapper.

24-P-13 - Catalytic properties of micelle templated microporous and

mesoporous materials for the conversion of low-density polYbethylene
J. Aguado a, D.P. Serrano a, R. Van Grieken a, J.M. Escola a and E. Garagorri
aSuperior School of Exp. Sciences and Technology (ESCET), Rey Juan Carlos University,
c~ Tulip{m s/n, 28933, M6stoles, Madrid, Spain, e-mail: d.serrano@escet.urjc.es
bChemical Engineering Department, Complutense University, Av. Complutense s/n, 28040,
Madrid, Spain
Both microporous and mesoporous micelle templated aluminosilicates have shown high
catalytic activity for the LDPE craking. A1-SBA-15 materials have been used for the first time
as higly effective catalyts for the conversion of polyolefins. The most active catalyts,
according to their TOF values, were those with the highest Si/A1 atomic ratios (Si/AI> 150),
which has been assigned mainly to a lower deactivation kinetic. For all the samples
investigated, the main products were liquid hydrocarbons within the range C5-C 14 (-70%).

2 4 - P - 1 4 - Epoxidation of propylene in fixed bed reactor using supported

titanium silicalite catalyst
X.S. Wang, Gang Li, H.S. Yan and X.W. Guo
State Key Laboratory, Dalian University, Dalian, P. R. China (Fax." +86-411-3689065)

Two molding methods were adopted to prepare the titanium silicalite catalyst used in a fixed
bed reactor. One is the traditional extruding method in which strip TS-1 catalyst is obtained.
The other is a new kind of molding method in which lamina TS-1 catalyst is made by
spraying the powdery TS-1 on a small inert ball. The lamina TS-1 catalyst exhibits better
performance in propylene epoxidation than the strip TS-1 catalyst.
274

2 4 - P - 1 5 - Acetylene and alkene oligomerization on ETS-10 having induced

Bronsted acidity
A. Zecchina a, C. Paz~ a, C. Otero Arefinb; G. Turnes Palominob; F.X. Llabr6s i Xamena b and S.
Bordiga a
aDipartimento di Chirnica I.F.M., Univ. di Torino, Torino, Italy," b Departamento de
Quimica, Univ. de las Islas Baleares, Palma de Mallorca, Spain

H-ETS-10, prepared by careful thermolysis of ammonium-exchanged ETS-10, was found to

have significant Bronsted acidity as revealed by its ability to protonate adsorbed pyridine.
Interaction of methyl-acetylene with the Bronsted acid sites of H-ETS-10 results in
protonation, followed by formation of oligomeric species with carbocationic character. The
n-delocalization of the positive charge of oligomers results in a characteristic spectroscopic
response both in the IR and UV-Vis. Similarly, propylene was also found to undergo
oligomerization on H-ETS-10.

24-P-16 - Isomerization of n-butane over small crystals of H-Beta and Pt-H-

Beta zeolite catalysts
N. Kumar l, M. Vainio l, V. Nieminen I, R. Byggningsbacka l, L.-E. Lindfors I, T. Salmi I, D.Y.
Murzin I and E. Laine 2
1Laboratory of Industrial Chemistry, Process Chemistry Group,/[bo Akademi University,
Biskopsgatan 8, FIN-20500 Abo, Finland, Fax." 358 2 2154479
2Department of Physics, University of Turku, 20014 Turku, Finland

Beta zeolites with average crystal sizes of 2 pm and 0.6 pm were synthesized and
characterized using different techniques. The Pt-H-Beta and H-Beta catalysts were prepared
using 0.6 ~tm crystals of Beta zeolite. The catalytic activities of the synthesized catalysts were
investigated in the isomerization of n-butane to iso-butane. The influence of reaction
temperature, catalyst pretreatment and carrier gas was investigated for the conversion of n-
butane and selectivity to iso-butane. The Pt-H-Beta catalyst in presence of hydrogen as a
carrier gas led to higher conversion of n-butane and selectivity to iso-butane than nitrogen.

24-P-17 - Ethylene oligomerization with nickel-containing NaX zeolite

M.O. de Souza, F.M.T. Mendes, R.F. de Souza, J.H.Z. dos Santos, L. Caumo, V. Conz, F.
Majolo and L.V. Barbosa.
Universidade Federal do Rio Grande do Sul- Instituto de Qufmica- Av. Bento Gongalves,
9500- 91501-970 Porto Alegre, Brazil-e-mail." Mich@if.ufr~s.br FAX" (51) 3191499

Nickel complex-containing zeolite materials Ni(MeCN)6(BF4)2/NaX and Ni(acac)2 have been

prepared and characterized by X Ray photoelectron spectroscopy (XPS). These materials are
catalytically active for ethylene dimerization and 1-butene isomerization. The supported
systems show higher selectivity towards 1-butene formation compared with the homogeneous
system. These features were attributed to a new nickel species formed in the supported
systems.
 275

2 4 - P - 1 8 - Studies of the methanol to hydrocarbons reaction using isotopic

labelling. Mounting evidence for a hydrocarbon pool mechanism
S. Kolboe
Department of Chemistry, University of Oslo, P.O. Box 1033, N0315 Oslo, Norway.

Recent data, published and unpublished, provide strong evidence that the common views on
the reaction mechanism of the MTH reaction are not tenable. The data rather point to ethene
and propene formation from an adsorbate hydrocarbon pool, probably of aromatic nature.
There are strong indications that the catalytic cycle is based on arenes that are continually
methylated by methanol/dimethyl ether, and dealkylations leading to ethene, propene and
most likely also isobutene via molecular rearrangements. Penta- and hexamethylbenzene
appear prone to undergo this reaction. However, there is also clear evidence that higher
alkenes, if present in substantial amount, may take part in the "classical" homologation
system.

24-P-19- Formation and reactivity of alkoxy species through the reaction of

alkylhalides with metal-exchanged zeolites
R.J. Corr~a and C.J.A. Mota
Instituto de Quimica, Universidade Federal do Rio de Janeiro, Cidade Universit6ria CT Blco
A, Ilha do Fund6o, Rio de Janeiro, 21949-900, Brazil. (cmota@iq.ufrj.br)

The formation of alkoxy species on metal exchanged zeolites was observed upon exposure to
5 Torr of butylchlorides at ambient temperature. The reaction was followed by infrared
spectroscopy and the reactivity of the alkoxy species toward proton elimination was also
monitored.

24-P-20 - The use of ITQ-7 as catalyst for alkylation of isobutane with 2-

butene
A. Corma, M.J. Diaz-Cabafias, C. Martinez and S. Valencia
Instituto de Tecnologia Quimica, UP V-CSIC, acorma@itq, upv. es, Spain.

The catalytic behavior of an AI-ITQ-7 zeolite, with a three-dimensional system of large pore
channels, has been evaluated for the liquid phase alkylation of isobutane with 2-butene, and
compared to that of a Beta zeolite. In absence of deactivation (TOS=I min), zeolite ITQ-7
gives a higher proportion of C5-C7/C5+, obtained by cracking of C8 and specially of the bulky
C9+. However, the main differences are observed in the distribution of the trimethylpentane
(TMP) isomers. Although zeolite ITQ-7 is more selective to TMP in the C8 fraction than
Beta, the most abundant isomers are 2,3,3- and 2,3,4-TMP instead of the primary 2,2,3-TMP
or the thermodynamically favored 2,2,4-TMP. This is a clear shape selectivity effect, due to
the smaller pore size of ITQ-7 as compared to Beta, and the fact that 2,3,3- and 2,3,4-TMP are
the isomers with less restricted transition states and smaller diffusion problems.
276

2 4 - P - 2 1 - Butene isomerisation over ferrierite and SUZ-4 zeolite

V.L. Zholobenko and C.L.T. Stevens
Keele University, Staffordshire, UK (fax.'44 1782 584352," e-mail. chalO@keele.ac.uk)
Medium pore zeolites have been evaluated as catalysts for n-butene isomerisation using a
conventional continuous flow microreactor and a diffuse reflectance IR cell-reactor. The role
of acid sites in ferrierite and SUZ-4 zeolite in this reaction and the mechanism of their
deactivation have been investigated employing high temperature in-situ diffuse reflectance
FTIR and on-line analysis of the products. The catalytic data show that both medium pore
ferrierite and SUZ-4 zeolites are effective isomerisation catalysts providing high yield and
selectivity towards isobutene. Further work, however, is required to optimise catalytic
performance and hydrothermal stability of SUZ-4 zeolite. Enhanced selectivity and yield of
isobutene obtained on the medium pore zeolites originate from the restricted transition state
shape selectivity effects and a lowered concentration of the 'working' active sites, which favour
the monomolecular reaction mechanism.

24-P-22 - Volatile products of the conversion of cyclohexene over A I - M C M - 4 1

M. Rozwadowski a, M. Lezanska a, J. Wloch a, K. Erdmann a, G. Zadrozna b and J.
Kornatowski b
aFaculty of Chemistry, N. Copernicus Univ., Torun, Poland, mrozwad@chem uni. torun.pl
bLehrstuhl H fiir Technische Chemic, Technische Universitcit Mfinchen, Garching, Germany
The analysis of volatile products of the conversion of cyclohexene over A1-MCM-41 with
various AI contents has revealed that the reaction runs mainly according to two mechanisms
known as cyclohexene skeletal isomerization (CSI) and cyclohexene hydrogen transfer (HT).
The results show which of the two schemes predominates, depending on the reaction
temperature and the AI content of the catalyst. The processes of CSI and HT are
accompanied by cracking and alkylation, which are proved by the presence of products with
1 to 9 carbon atoms even though the C6 compounds strongly prevail in all cases. Composition
of the volatile products of the conversion depends on both concentration and strength of
Br~nsted and Lewis acid centres.

2 4 - P - 2 3 - C u - Y zeolite catalysts for methanol and ethanol steam reforming

M. Laniecki
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznah, Poland.
Email: laniecki@main.amu.edu.pl
Cu-Y zeolites were used as catalysts for the methanol and ethanol steam reforming for
hydrogen generation. The effect of copper loading and the way of catalyst preparation on the
structure and catalytic performance were examined. XRD, thermogravimetry, TPR, FTIR
with adsorbed pyridine and hydrogen chemisorption were used to characterize Cu containing
zeolites. The best catalytic performance was found for impregnated samples and CH3OH
reforming. Catalysts acidity leads many undesirable reactions.
 277

24-P-24 - Hexenes obtaining on the n i c k e l - ion exchanged zeolites

M.K. Munshieva
Institute of Inorganic and Physical Chemistry, Azerbao'an Academy of Sciences, 370143,
Baku, Azerbao'an Republic, 29 H.Javid Avenue, E-mail." chem@dcacs.ab.az

The dimerization of propylene in liquid phase over nickel-ion exchanged zeolites with various
structures modified by treatment with A1Et2CI is studied. The mechanism of propylene
dimerization on these catalysts is similar to the mechanism of olefin dimerization on Ziegler-
Natta catalytic systems. The different catalytic behaviours of the studied zeolites are
connected with their crystalline structure. The X-ray investigation of the crystalline structure
of zeolites after the repeated treatment with A1Et2C1 demonstrates its preservation.

24-P-25 - Catalytic sites of mesoporous silica in degradation of polyethylene

A. Satsuma a, T. Ebigase a, Y. Inaki a, H. Yoshida a, S. Kobayashib, M.A. Uddin b, Y. Sakata b,
and T. Hattori a
aDepartment of A~plied Chemistry, Nagoya University, satsuma@apchem, nagoya-u, ac.jp,
Nagoya, Japan. Department of Applied Chemistry, Okayama University, Okayama, Japan

Catalytic sites of mesoporous silica catalysts in degradation of polyethylene were investigated

using characterizations by adsorption of NH3 and isohexane cracking. Siliceous materials
gave a high liquid yield close to that of non-catalytic run, and degradation rate was enhanced
by incorporation of aluminum. Mesoporous silica containing impurity level of aluminum
exhibited as high activity as H-MFI and SIO2-A1203 with similar A1 content. The initial rate of
degradation depended on the aluminum content and structure of mesoporous silica catalysts.
FSM-16 exhibited exceptionally higher activity, which may be due to the presence of radical
type catalytic sites on FSM-16.

24-P-26 - The nature of medium acidity in [CuO/ZnO/ZrO2]SAPO-34

hybrid catalyst for CO2 hydrogenation: study of the interactions between
metal oxides and acid sites in zeolite
S.-K. Ihm, S.-W. Baek, Y.-K. Park and K.-C. Park
Dept. of Chem. Eng., KAI ST, Taejon, skihm@mail.kaist.ac.~ ~, South Korea.

Direct synthesis of hydrocarbons through carbon dioxide hydrogenation was investigated over
hybrid catalysts composed of methanol synthesis catalysts (CuO/ZnO/ZrO2) and zeolites
(HZSM-5, SAPO-34). New peak around 350~ due to the medium acidity appeared during
the NH3-TPD of hybrid catalyst, and the areas of these new peaks were well correlated with
the hydrocarbon yields in CO2 hydrogenation. The appearance of the new NH3-TPD peak was
ascribed to the interaction between CuO/ZnO/ZrO2 and SAPO-34, which leads to the mutual
changes in acidity of zeolite and reducibility of metal oxides.
278

24-P-27 - Reaction pathways for the aromatization of c y c l o h e x a n e and

cyclohexene on Z n / H - Z S M - 5 zeolites
A. Urd~ a, G. Tel'biz b and I. S~ndulescu a
a University of Bucharest, Faculty of Chemistry, Department of Chemical Technology and
Catalysis, P.O. Box 12-241, Bucharest, Romania; a_urda@chim.upb.ro
b Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine,
Nauki Prospect 31, 252038, Kyev, Ukraine

Aromatizations of cyclohexane and cyclohexene were studied on Zn/ZSM-5 catalysts with

different zinc concentrations, at different residence times, with or without added gas (nitrogen
or hydrogen). The results suggest that the first steps, at low Zn concentration, are the cracking
of the feed molecule into unsaturated fragments and oligomerization. These are followed by a
hydrogen transfer reaction, leading to aromatic compounds. Only at high zinc concentrations
the direct dehydrogenation of the feed seems to play an important role.

24-P-28 - Coke species and coking m e c h a n i s m of S A P O - 3 4 in M T O process

Y. Qi, G. Wang, Z. Liu, L. Xu, X. Gao and W. Cui
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023, China, zml@dicp.ac.cn

The coking behavior of SAPO-34 in MTO process was investigated. The primary coking
dynamics, the characteristics of coke species and the effects of coke deposition on catalyst
performance were studied. It was found that the coke species differed with reaction
temperature. The coke consists of both aromatics and oligomers at lower reaction
temperature, while mainly of aromatics at higher reaction temperature. It is suggested that the
coking mechanism at different reaction temperatures goes through different routes, i.e.
through oligomerization at lower temperature while through aromatization at higher
temperature.

24-P-29 - Pt-2,2'bipyridine complex encapsulated in Y zeolite - catalysts for

ethylene selective dimerization
R. Zavoianu and E. Angelescu
University of Bucharest, Dept. of Chemical Technology and Catalysis, bd. Regina Elisabeta
no. 4-12, Bucharest-70346, Romania, fax. 04013159249, email: e_angelescu@chim, upb.rp

This paper presents results concerning the synthesis of Pt(2,2'-bipyridine)C12 (K)

encapsulated in Y zeolite and its activity in C2H4 selective dimerization to linear butenes.
Diffuse reflectance UV-VIS spectroscopy and FTIR are used to investigate the state of the
complex encapsulation. The influence of the reaction parameters on C2H4 selective
dimerization to linear butenes is studied, we concluded that Pt(2,2'-bipyridine)C12
encapsulated in Y zeolite is a selective catalyst for ethylene dimerization to linear butenes at
low temperatures (80 - 150~ and a reactant flow rate corresponding toWHSV 2h z .
 279

24-P-30 - A r o m a t i c s formation from C 4 - C 4 = technical fraction over zinc-

and z i n c / c o p p e r - c o n t a i n i n g Z S M - 5 zeolites
N. Bilba (a), G. Iofcea (b), I. Asaftei (a), D.M. Padurariu (b) and C.C. Pavel (a)
a "AI.I. Cuza" University of Iasi, Faculty of Chemistry, nbilba@ch.tuiasi.ro, Romania
b S.C. "CAROM" S.A. Onesti, 5450 Onesti, Romania

The catalytic and product distribution over HZSM-5, Zn-HZSM-5 and Zn-CuHZSM-5 during
C4 - C4= (from catalytic cracking) conversion, have been studied. Product distributions at 123
K indicated that Zn-ZSM-5 and ZnCuZSM-5 exhibited higher aromatization activities
compared with higher oligomerization activity of HZSM-5. Meanwhile, the time on stream
increases from 24 h on HZSM-5 to 60 h on bifunctional catalysts and the resulting gases
contain hydrogen only when metallic catalysts are used. Copper presence in ZnCu-HZSM-5
allows to work at 793 K without loosing Zn and obtaining a raw material composed only of n-
and/-butane.

24-P-31 - A r o m a t i z a t i o n of mixed-C4 h y d r o c a r b o n s over H Z S M - 5 catalysts

modified by Zn and Ni cations
L. Wei (a), J.Z. Gui (a), H.S. Ding (a), X.T. Zhang (a), H.Y. Li (a), L. Song (a,b), Z.L. Sun
(a,*) and L.V.C. Rees (b)
a Dept. of Appl. Chem., Fushun Petroleum Institute, Fushun, Liaoning, P. R. China,
zlsun@mail.fsptt.ln.cn; b Dept. of Chem., The University of Edinburgh, Edinburgh

The aromatization of mixed-C4 hydrocarbons, prevalent by-products derived from petroleum

refining processes, over HZSM-5 catalysts modified by both Zn and Ni cations via different
impregnating methods has been systematically studied in two different sizes of reactors at
various temperatures and space velocities of the feeds. The reaction mechanisms were
discussed according to the liquid and gas product distributions. The acidity of the catalysts
were also characterized using the frequency response (FR).
280

25 - Conversion of Aromatics (Tuesday)

25-P-06 - Isopropylation of naphthalene over large pore zeolites

R.K. Ahedi, S. Tawada, Y. Kubota and Y. Sugi*
Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501-1193 (JAPAN).
Email: sugi@apchem.gifu-u.ac.jp; Fax. 81-58-293-2597

[A1]-SSZ-31 was active in isopropylation of naphthalene, however, the selectivity was lower
as compared to mordenite. Large pore zeolites viz. ZSM-12, CIT-5, SSZ-31, CIT-5 and HY
were compared. CIT-5 and HY were very active, but, less selective. ZSM-12 and SSZ-31
showed better selectivity for 2,6-DIPN than CIT-5 and HY. Mordenite was the best catalyst.

25-P-07 - Shape-selective tert-butylation of biphenyl over H M , H Y and HI3

zeolites in the liquid phase
D. Mravec(a), J. Homiakovd(a), M. Krdlik(a), M. Hronec(a), J. Joffre(b) and P. Moreau (b)
a, Slovak University of Technology, Bratislava, mravec@chtf.stuba.sk, Slovak Republic
b, Ecole Nationale Sup6rieure de Chimie, Montpellier, France

The alkylation of biphenyl with tert-butanol has been carried out over different zeolites under
liquid phase conditions. HM (17.5) and HY (15) zeolites have been found to be the most
active, with a maximum biphenyl conversion near 60 %. Dealuminated mordenite HM (17.5)
leads to very high selectivities to 4-(tert-butyl)biphenyl (99%) and 4,4'-di(tert-butyl)biphenyl
(96%). Selectivity to linear 4-TBB and 4,4'-DTBB depends on diffusional possibilities of
relatively voluminous mono tert-butyl- and di (tert-butyl)biphenyl isomers from the zeolite
pores. The most suitable temperature has been found to be 160 ~ An increase of the
temperature leads to a significant decrease of selectivities to the desired products, as a result
of secondary reactions.

2 5 - P - 0 8 - 1-Acetyl-2-methoxynaphthalene isomerization over zeolites. Effect

of pore structure.
V. Moreau, E. Fromentin, P. Magnoux and M. Guisnet
LCCO, UMR6503, University of Poitiers, patrick'rnagn~176 France.
Isomerization of 1-acetyl-2-methoxynaphthalene was investigated over HFAU, HBEA and
HMFI zeolites (batch reactor, T=120~ Due to its pore size, HMFI was inactive for
isomerization while HFAU is about 3 times more active than HBEA. This can be attributed to
the easier desorption of the isomers from the HFAU pores. However, the selectivity of 2-
acetyl-6-methoxynaphthalene (the desired isomer) is favoured over HBEA. Analysis of the
compounds retained in the zeolite pores show that the reaction occurs inside the micropores of
the zeolites. Indeed, the desired isomer was found to be retained in the pores of HMFI
showing that even for this zeolite, isomerization occurs in its micropores and that the
desorption of the reaction products appears to be the limiting step.
 281

25-P-09 - Alkylation of phenol with propylene over solid acid catalysts

B. Wang*, C.W. Lee, T.-X. Cai* and S.-E. Park ~
Catalysis Center for Molecular Engineering, KRICT, P. O. Box 107, Yusung, Taejon
305-600, KOREA
*School of Chemical Engineering, Dalian University of Technology,, P. R. China

The alkylation of phenol with propylene over several solid acid catalysts such as HZSM-5
with different silica to alumina ratios, H-Beta, H-USY and 7-A1203 has been studied. It has
been found that zeolite structure has great influence on product distribution. Apart from shape
selectivity taking effect in phenol alkylation with propylene over HZSM-5 zeolites, acidic
properties (i.e. acid strength and acid density) also influence product distribution. It has been
found that H-ZSM-5 exchanged with different alkali metal ions, such as Na + and Cs + could
apparently enhance the selectivity for para-iso-propylphenol due to the change of acidic
properties. The acidic properties of the zeolites were characterized by NH3-TPD.

2 5 - P - 1 0 - Transalkylation of trimethylbenzene with toluene over large pore

zeolites
J. (~ejka (a), A. KrejU (a) and J. Hanika (b)
a J. Heyrovst9) Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic, cejka@l'h-inst.cas.cz
b Department of Organic Technology, Institute of Chemical Technology, Technick6 5,
CZ-166 28 Prague 6, Czech Republic

The role of the channel geometry and architecture of large pore zeolites FAU, BEA and MOR
on the activity, selectivity and time-on-stream stability in trimethylbenzene transalkylation
with toluene to xylenes was investigated. It was found that the reaction mechanism is strongly
controlled by the transport of reactant trimethylbenzenes and tetramethylbenzenes formed
during the reaction. The highest yield to xylenes and long-term stability of conversion was
achieved with zeolite BEA.

25-P-11 - Physicochemical characterization and catalytic activity of

AI-HMS for N-methylation of aniline
J.M. Campelo, A. Garcia, D. Luna, J.M. Marinas, A.A. Romero and J.J. Toledano.
Departamento de Quimica Org(mica, Facultad de Ciencias, Universidad de C6rdoba,
Campus Universitario de Rabanales, Edificio C3, qolcapej@uco.es, Spain

AI-HMS mesoporous molecular sieves with Si/AI ratio in the range 10-40 were synthesized
by using dodecylamine as template. They were characterized by XRD, N2 adsorption, MAS
NMR, and DRIFT, and their acid properties were determined by pyridine (PY) adsorption.
Aniline methylation was a pseudo-first-order process with respect to aniline concentration.
Alkylation is a sequential reaction process, in which methylation of aniline produces N-
methylaniline (NMA), then N,N-dimethylaniline (NNDMA) and subsequently N,N-
dimethyltoluidines (NNDMT, p- > o-). N-methylation products (NMA+NNDMA) were
predominant with a selectivity over 97 mol% at 573 K.
282

25-P-12 - Catalytic activity of secondary aluminated mesoporous molecular

sieve AIMCM-41 in the Friedel-Crafts reaction of bulky aromatic
compounds
H. Hamdan (a), A.B. Kim (b) and M.N. Mohd Muhid (b)
albnu Sina Institute for Fundamental Science, hali@kimia.fs.utm.my
bFaculty of Science, Universiti Teknologi Malaysia, UTM 81310, Johor, Malaysia

Secondary aluminated MCM-41 (A1MCM-4 l(sec)) with Si/A1 ratio of 1.75 was synthesized.
Characterization indicates that secondary alumination incorporates aluminium into the
framework without affecting the long range order of the mesopores and structural stability of
the framework. Friedel-Crafts alkylation of 2,4-di-t-butylphenol with cinnamyl alcohol
catalyzed by the A1MCM-41 (sec) catalyst gave a high conversion. 29Si MAS NMR shows a
different distribution of aluminium in the framework of MCM-41 by secondary synthesis as
compared to direct synthesis. A1MCM-41 (sec) possesses Lewis and Br6nsted acidity and is a
more efficient catalyst for reaction of large compounds.

25-P-13 - Naphthalene alkylation with methanol employing solid catalysts

J. Aguilar-P, A. Corma a, J.A. de los Reyes b, L. Norefia, G. Mufioz, J.M. Sanchez, A. Torales
and I. Hemdndez.
Area de Qu/mica Aplicada, UAM-A. Av. San pablo 180, CP 02200, Mdxico, D.F.
a Instituto de Tecnologia Quimica, UP V-CSIC, Av. de los Naranjos s/n 46022, Val. Spain.
b UAM-L Av. Michoacan y la Purisima, CP 09340, Mdxico, D.F.

The relation between the structure of the catalyst and the reaction activity and selectivity was
studied with MCM-22, MCM-41, HY, Beta and BZR5 catalysts. High selectivity in 13-
methylnaphthalene (2-MN) was obtained using MCM-41 catalyst. For the MCM-22 catalyst,
the presence of 10 member ring (MR) channels and windows present severe constraint for the
diffusion of naphthalene into the channels, therefore, the reaction possibly takes place at the
external surface of this material. The order of activity is as follows: MCM-22 > Beta > HY >
MCM-41 >BZR5.

25-P-14- Aikylation of biphenyl and naphthalene with propene. Is zeolite

beta a shape-selective catalyst?
D.M. Roberge and W.F. H61derich
Department of Chemical Technology and Heterogeneous Catalysis, R WTH-Aachen,
Worringerweg 1, D-52074 Aachen, Germany, Hoelderich@rwth-aachen.de.

An acid treated zeolite beta with a 6 M HNO3 acid solution is a shape-selective catalyst for
the alkylation of biphenyl with propene. This is however not the case for the alkylation of
naphthalene. The reaction is highly mass transfer limited and the selectivity mechanism is
attributed to a product selectivity. The major effect of the acid treatment is to deactivate the
external surface area so that the intrinsic micropore properties can come out. Contrary to
zeolite mordenite, the acid treatment does not reduce deactivation and the formation of highly
aromatic coke remains important at high temperatures.
 283

25-P-15- Aikylation of benzene by propane with participation of space

divided centres
S.I. Abasov, R.R. Zarbaliyev, G.G. Abbasova, D.B. Tagiyev and M.I. Rustamov
Institute of Petrochemical Processes, Academy of Sciences of Azerbaijan
30 N.Rafiyev st., Baku-370025, Azerbaijan Republic
Fax." (9412) (90-35-20); E-mail. anipcp@dcacs.ab.az,ipcp@baku-az.net

The benzene alkylation by propane has been investigated using a zeolite-containing catalyst.
The isopropylbenzene formation is shown to begin at 180-350~ over HY and Pt, Re/A1203
admixed catalysts. The temperature increase leads to C3H6(250~ and other alkylbenzenes
(300~ formation. The by-products may be reduced by the selective poisoning of Br6nsted
acidic centres by ammonium. From the considerations on the reaction, the probable
mechanism of benzene dehydroalkylation by propane has been proposed.

25-P-16 - Alkylation of isopropylnaphthalene over heteropoly acid catalysts

supported on mesoporous materials
M.-W. Kim a, W.-G. Kim a, J.-H. Kim a, Y. Sugi b and G. Seo a
~Department of Chemical Technology & The Research Institute for Catalysis, Chonam
National University, Gwang/u 500- 75 7, Korea
bDepartment of Chemical, Faculty of Engineering, Gifu University, Gifu 501-1193, Japan

The isopropylation of 2-isopropylnaphthalene was studied over heteropoly acid catalyst

supported on mesoporous material. The physico-chemical state of loaded heteropoly acid was
investigated using XRD, nitrogen adsorption measurement and FT-IR techniques. Heteropoly
acid was highly dispersed on the wall of mesoporous material, and retained its Bronsted
acidity. The conversion and the selectivity for [3, 13 -diisopropylnaphthalene were very high
over the mesoporous material with a large loading amount of heteropoly acid. The treatment
of heteropoly acid was helpful for the improvement of the acidity of mesoporous material.

25-P-17 - Highly selective isopropylation of xylenes catalyzed by zeolite Beta

C.R. Patra, S. Kartikeyan and R. Kumar
Catalysis Division, National Chemical Laboratory, Pune 411 008, INDIA
raj iv@cata.nc 1.res. i n)

The isopropylation of xylenes to form corresponding dimethyl cumene(s) was carried out with
isopropanol over large pore high silica zeolite H-beta as catalyst under continuous vapor
phase fixed bed down flow glass reactor system at atmospheric pressure and moderate
temperatures (413K to 453K). Zeolite H-Beta exhibited quite high activity, selectivity and
stability. The effect of reaction temperature, space velocity, substrate to alkylating agent
molar ratio and time-on-stream on conversion and selectivity was studied. As high as 90-99 %
selectivity for dimethylcumene(s) was obtained in relatively lower reaction temperature range
of 413-433 K at quite high xylene conversion (80-90% of theoretical value).
284

08- Syntheses with Non-Ionic surfactants (Wednesday)

08-P-05 - The double-step synthesis of MSU-X silica: decoupling the

assembly mechanism
E. Prouzet*, C. Boissi&e, N. Hovnanian and A. Larbot.
Institut Europden des Membranes, L.M.P.M. (CNRS UMR 5635) Universitd Montpellier II,
CC 047, F-34095, Montpellier, cedex 5, FRANCE. e-mail : prouzet@cit.enscm.fr

In a new double-step synthesis of MSU-X type silicas, which was reported previously, a first
step allows the preparation of a colorless stable and homogeneous aqueous solution where
both nonionic surfactants and silica oligomers are mixed. Dynamic light scattering (DLS),
small angle X-ray scattering (SAXS) and 29Si NMR analyzes revealed that this first step
allows the assembly of surfactants and silica oligomers in specific micellar hybrid objects that
are described.

0 8 - P - 0 6 - S t e a m - stable aluminosilicate MSU-S mesostructures assembled

from zeolite seeds
Yu Liu, W. Zhang and T.J. Pinnavaia
Department of Chemistry, Michigan State University, Pinnavai@cem.msu.edu
The hydrothermal stability and acidity of aluminosilicate mesostructures can be improved
substantially through the surfactant - directed assembly of protozeolitic aluminosilicate
nanoclusters that normally nucleate (seed) the formation of microporous zeolites. Our results
indicate that zeolite type Y, Beta, and ZSM-5 seeds are particularly effective at forming steam
stable aluminosilicate mesostructures, which we generally denoted as MSU-S.

0 8 - P - 0 7 - A Study on the mesoporous silica structures templated by triblock

copolymers
C.-P. Kao(a), H.-P. Lin(b), M.-C. Chao(a), H.-S. Sheu(c) and C.-Y. Mou(a)*
a National Taiwan University, Taipei, c~ymou@ms.cc.ntu.edu.tw, Taiwan
b Institute of Atomic and Molecular Sciences Academia Sinica, Taipei, Taiwan
c Synchrotron Radiation Research Center, Hsinchu, Taiwan

The well-ordered mesostructures SBA-15 or SBA-16 could fast grow from the chemical
composites of triblock copolymers (EOnPOmEOn)-TEOS-HC1-H20. At the desired
TEOS/EOz0PO70EO20 ratio, an organic surfactant-silica macrosphere of about 1 cm was
successfully obtained, and the organic-inorganic mesostructural macrospheres have the
particularly elastic property. Post-hydrothermal treatments at high temperature promoted the
increase of the unit cell and pores.
 285

08-P-08 - Study of methyl modified M S U - X silicas

Y. Gonga, Z. Lia, S. Wanga, D. WUa, Y.-H. Suna, F. Dengb, Q. Luob and Y. Yueb
a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese
Academy of Sciences(CAS), Taiyuan China
bState Key Laboratory of Magnetic Resonance and Atomic Molecular Physics, Wuhan
Institute of Physics and Mathematics, CAS, China
Methyl-modified MSU-1 mesostructures were prepared by one-pot strategy. The
microstructure and the interfacial characteristic were measured with N2 sorption, IR,
29SiNMR, SEM, TEM, TGA and SAXS. The results showed that methyl groups have been
incorporated into MSU-X silica framework and the surface and texture properties of the
resultant materials varied with the amount of incorporated methyl groups.

08-P-09 - Study of mesoporous materials with ultra high surface area

prepared from alternate surfactants and silicate sources
J.F. P4rez-Ar~valo a'b, J.M. Dominguez c, E. Terr6s c, A. Rojas-Hem~indez b and M. Miki d
a UNAM,, FES-Cuautitl6n, b UAM-I, c1MP, aCIMAE M6xico.jmdoming@imp.mx
A comparison study on the synthesis of mesoporous materials from Triton X-100/Na-
metasilicate and CTAB/TEOS was performed and their textural and structural parameters
were characterized by XRD, N2 adorption and TEM. The CTAB/TEOS solids presented high
surface mesopore areas, exceeding 1100 m2/g, while the Triton X-100/Na-metasilicate
presented areas from 1200 up to 1467 m2/g. The analysis of the textural data indicated that
upon calcination pore sintering occurs in the Triton/Na-metasilicate solids, while it does not
occurs in the CTAB/TEOS system. This is probably due to the different packing effective
factor of the surfactant molecules.

08-P-10 - Synthesis and catalytic properties of SO3H-mesoporous materials

from gels containing non-ionic surfactants
I. Diaz, F. Mohino, E. Sastre and J. P6rez-Pariente
Instituto de Cat6lisis y Petroleoquimica, C.S.1.C., esastre@icp, csic. es, Madrid, Spain

A variety of mesoporous silicates containing mercaptopropyl groups have been prepared by

direct synthesis from gels containing non-ionic surfactants. By adjusting properly several
synthesis parameters, thiol-containing SBA-15 have been obtained from gels containing
Pluronic 123, whereas a stable material probably related with SBA-12 has been synthesized
from Brij 76. These materials possess large surface areas and pore sizes of 3.2 and 1.8 nm,
respectively and have been structural characterized by transmission electron microscopy. The
oxidation of the thiol groups with hydrogen peroxide leads to sulfonic acid groups which have
been shown to catalyze the esterification of glycerol with oleic acid. Factors affecting the
catalytic performance of these materials are discussed.
286

08-P-I1 - Secondary hydrolysis process to synthesize highly ordered

mesoporous silica from nonionic surfactant with long hydrophilic chain
J. Fan, C. Yu and D. Zhao*
Department of Chemistry, Fudan University, Shanghai 200433, P. R. China
dyzhao@)Cudan,edu. cn

In this paper, we have demonstrated a simple secondary hydrolysis process to synthesize a

highly ordered hexagonal mesoporous silica structure by using nonionic oligomeric surfactant
with long hydrophilic chain. This process involves an adsorption step of extra silica source
and secondary hydrolysis process and can result in large improvement on the ordering and
hydrothermal stability for the mesoporous silica materials.

08-P-12 - Mesostructure design using mixture of nonionic amphiphilic

block copolymers
9 a
J.M. K l m , S.-E. Park a and G.D. Stucky b
a Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical
Technology (KRICT), P.O. Box 107, Yusong, Taejon 305-600, Korea;
separk@pado, krict, re. kr
b
Department of Chemistry, University of California, Santa Barbara, CA 93106, USA

Formation of mesoporous silica materials has been studied using mixtures of amphiphilic
diblock copolymers (CnH2,+I(OCH2CH2)xOH, C,EOx, n = 12 - 18 and x = 2 - 100) as the
structure directing agents and sodium silicate as the silica source. Results obtained from X-ray
diffraction patterns and transmission electron microscopy indicate that silica/polymer
mesostructures are transformed from lamella to 2-d hexagonal (P6mm), 3-d hexagonal
(P6y'mmc), cubic Pm3m and cubic Im3m, as the size (x) of hydrophilic head group increases.
Optimum ratios between the hydrophilic EO groups and hydrophobic tail groups are
investigated in order to obtain highly ordered mesoporous silica materials.

08-P-13 - Stability of mesoporous material SBA-15 and its benefit in

catalytic performance
C. Nie, L. Huang, D. Zhao and Q. Li*
Dep. Chem., Fudan University, Shanghai 200433, P. R. China qzli@)Cudan.edu.cn

The stability of mesoporous material SBA-15 and A1-SBA-15 was investigated under
steaming treatment (100 % H20) at 800 ~ for different time. A1-SBA-15 catalyst has been
prepared via post-synthesis procedure. The results show that the mesostructure of SBA-15
and A1-SBA-15 can be retained at 800 ~ steaming for 8 h, while MCM-41 totally loses its
mesostructure under the same condition just for 2 h. Moreover, A1-SBA-15 still has cracking
activity of n-hexadecane and Pt/A1-SBA-15 has hydroisomerization activity of n-dodecane to
some extent even after steaming treatment at 800 ~ for 8 h. Meanwhile, A1-MCM-41and
Pt/A1-MCM-41 catalysts totally lose their activity under the same treatment condition just for
2h.
 287

08-P-14 - Comparative study of the wall properties in highly-

ordered silicate and aluminosilicate mesostructured materials of the
MCM-41 and SBA-15 types
L.A. Solovyov (a), V.B. Fenelonov (b), A.Y. Derevyankin (b), A.N. Shmakov (b),
E. Haddad (c), A. Gedeon (c), S.D. Kirik (a) and V.N. Romannikov (b).
a Institute of Chemistry and Chemical Engineering, kirik@icct.krsk, infotel.ru.
b Boreskov Institute of Catalysis: rvn@catalysis.nsk.su
c Universit6 P. et M. Curie ag@ccr.jussieu.fr.

X-ray diffraction structural modeling based on a continuous electron density

representation and textural analyses by the combined XRD-adsorption method were
applied for to quantify distinctions in the wall structure of the MCM-41 and SBA-15
types of mesostructured materials.
288

09-Crystal Structure Determination (Wednesday)

09-P-06 - Crystal structure of a cadmium sorption complex of dehydrated

fully Cd(II)-exchanged zeolite X
E.Y. Choi a, S.H. Lee a, Y.W. Han b, Y. Kim a and K. Seff c
aDepartment of Chemistry, Pusan National University, Pusan, Korea, ykim@hyowon.pusan.ac.kr
bDepartment of Science Education, Pusan National University of Education, Pusan, Korea
CDepartment of Chemistry, Universityof Hawaii, 2545 The Mall, Honolulu, Hawaii 96822, U. S. A.

A single crystal of fully dehydrated Cd2+-exchanged zeolite X, Cd46SiI00A1920384, was exposed at

o
320 C to 0.005 Torr of Cd vapor for 9 d. The resultant crystal, Cd68SiI00A1920384 (a = 24.953(6)
A), was studied by single-crystal XRD techniques in the cubic space group Fd-3 m at 21(1) ~ In
this structure, Cd species are found at seven sites. Twenty-eight Cd 2+ are found at sites I', II', and
II with occupancies of eight, six, and fourteen. Thirty-six Cd + are found at sites I, I', and II with
occupancies of six, eighteen, and twelve. The eight Cd 2+ at I' associate with four Cd ~ atoms (II') to
form four bent Cd2+-Cd~ 2+ clusters per unit cell in the sodalite cavities.

09-P-07 - The structure of a copper molybdate and its relation to other

natural and synthetic porous materials based on transition metal polyhedra
L.A. Palacio (a), A. Echavarria (a), A. Simon (b) and C. Saldarriaga (a)*
(a)Department of Chemical Engineering, University of Antioquia
A.A. 1226, Medellin, Colombia (csm@udea.edu.co)
(b)Laboratoire de Materiaux Mineraux, UPRES-A-7016, C.N.R.S., 3 rue Alfred Werner
68093 Mulhouse Cedex, France

A new non-stoichiometric copper molybdate of ideal composition (NH4OH)3/2(CuMoO4)2 was

synthesized hydro thermally and its crystal structure was solved from powder data. The
material shows the hexagonal parameters a=6.0775(3) and c=21.601(1) A in the space group
R-3m. The green powder exhibits the same building units observed in the mineral Volborthite
and the layered structure of other materials based on transition metal polyhedra.

0 9 - P - 0 8 - A 3-D Open-framework nickel aluminophosphate

[NiAIP2Os][C2N2H9]" assembly of I-D AIP2Os a" chains through [NiOsN]
octahedra
B. Wei a, J. Yu a, G. Zhu a, F. Gao a, Y. Li a, R. Wang a, B. Gao a, Xian. Xua,S. Qiu a* and O.
Terasaki b
aKey Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of
Chemistry, Jilin University, Changchun 130023, P. R. China,e-mail." sqiu@mail.jlu.edu.cn;
bCREST; Department of Physics, Tohoku University, Sendai 980-8578, Japan

A 3-D Open-framework [NiA1P208][C2NzH9] (NiAPO-1) was synthesized successfully in a

solvothermal system. Its structure was solved by CCD single crystal X-ray diffractometer,
with Monoclinic, space group P21/c (No. 14), a=8.542(2) A, b=15.564(3) A, c=7.627(1) A,
and [3=110.60(1) ~ V=949.1(3)A 3, Z=4, assemblied by 1-D A1P2083- and 1-D [Ni-O-Ni]
chains. It was characterized by powder X-ray diffraction, thermogravimetric/differential
thermal analysis, ICP, element analysis, 27A1, 31p MAS NMR and magnetic measurement.
 289

09-P-09- Structural modifications induced by high pressure in scolecite and

heulandite: in-situ synchrotron X-ray powder diffraction study
G. Vezzalini a, S. Quartieri b, A. Sani c and D. Levy d
~Dipartimento di Scienze della Terra, Universitg~ di Modena, Italy, giovanna@unimo, it
bDipartimento di Scienze della Terra, Universit~t di Messina, Italy
~INFMand European Synchrotron Radiation Facility, Grenoble Cedex, France
dDipartimento di Scienze Mineralogiche e Petrologiche, Universitdt di Torino, Italy
We present an in-situ synchrotron X-ray powder diffraction study on the
compressibility and the pressure-induced structural modifications in scolecite and
heulandite. The cell parameter refinements were carried out up to 7.5 GPa and 6 GPa
for scolecite and heulandite, respectively. The HP-induced deformations of both
zeolites can be interpreted on the basis of the mechanisms observed during the
dehydration processes of the two minerals. Heulandite amorphization process is
reversible and occurs at a lower pressure.

09-P-10- Preparation, characterization, and crystal structures of fully

indium-exchanged zeolite X
N.H. Heo, a S.W. Jung, a S.W. Park, a J.S. Noh, a W.T. Lim, b M. Park a and K. Seff c
aDqpartment of Industrial _Chemistry, Kyungpook National University, Taegu 702-701,
t~htieo~kvungpook, ac. kr, Korea
~ Accelerator Laboratory Pohang Institute of Industrial Science & Technology, P. O.
Box 12S. Pohang 790-600, wtlimJ'~g)ostec~h.ac.kr, K6rea
CDepartment of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822-2275,
kseff@gold.chem.hawaii.edu, U. S. A.
o

In-X has been prepared by solvent-free redox ion-exchange of T1-X with In metal at 350 C.
EPXMA showed the product to be an indium aluminosilicate (ca. 47 wt% In) free of T1.
Single crystal X-ray diffraction and XPS experiments showed that In-X contained indiums in
various oxidation states. In+ and In2+ ions are found at a variety of 3-fold axis and supercage
sites, and In5n+ clusters are seen at the centers of some sodalite cavities. Exposure to the
atmosphere, washing with H20, and redehydration caused only a small change in
+ 7+
composition, from (In+)v8(In57+)2-X to (In)74 5(In5 )2 5-X, with a change of space group from
Fd3 to Fd3m.

09-P-11 - Structural investigation by powder X-ray diffraction and solid

state nuclear magnetic resonance of AIPO4-SOD
M. Roux a, C. Marichal a, J.L. Paillaud a, L. Vidal a, C. Femandez b, C. Baerlocher c and J.M.
Chezeau a
a Laboratoire de Matdriaux Min6raux, ENSCMu,, m.roux@univ-mulhouse.fr, France.
b Laboratoire de Catalyse et Spectrochimie, ISMRA, 14050 Caen, France.
c Laboratoriumfiir Kristallographie, ETH, CH-8092 Z~rich, Switzerland

The crystalline structure of A1PO4-SOD, an aluminophosphate, was investigated by high

resolution powder X-ray diffraction and various solid state nuclear magnetic resonance
(NMR) techniques. In particular, 31p homonuclear correlation and 27A1/31P 3QHETCOR NMR
experiments allowed the complete assignment of 3~p and 27A1 resonances to the corresponding
crystallographic sites. All results from the different NMR techniques are compared with the
refined structure resulting from a Rietveld analysis on powder synchrotron data.
290

09-P-12 - Layered germanates with 9-membered rings

X. Zou, T. Conradsson and M.S. Dadachov
Structural Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden

Two germanates, (NH4)4[(GeO2)3(GeOI.sF3)2]'0.67H20 and (C2N2HI0)2[(GeO2)3(BO2.5)2],

were prepared by hydrothermal synthesis. The framework layers are formed by 3- and 9-
membered rings in both compounds and the structure topology within the layers is very
similar. The 3-membered rings in both compounds are built by three GeO4 tetrahedra. These
3-rings are connected by pairs of GeO3F3 octahedra in (NH4)4[(GeO2)3(GeO1.sF3)2]'0.67H20
and by pairs of BOa tetrahedra in (C2N2Hlo)2[(GeO2)3(BO2.5)2] in such a way that 9-membered
rings are formed. The framework layers are interrupted by ammonium cations and water
molecules in the former compound and protonated ethylenediamine in the latter compound.
The 2D frameworks of the germanate and the borogermanate are compared with other related
structures.

0 9 - P - 1 3 - Dehydration dynamics of mordenite by in-situ time resolved

synchrotron powder diffraction study: a comparison with electrostatic site
energy calculations.
A. Martucci, M. Sacerdoti and G. Cruciani
Dipartimento di Scienze della Terra, Sezione di Mineralogia, Universith di Ferrara, Corso
Ercole I d'Este, 32, 1-44100 Ferrara, Italy; e-mail: mrs@dns.unife.it

The structural transformation of a natural mordenite by in-situ heating to 830~ was studied,
using Rietveld structure analysis. At 830~ mordenite maintains the space group Cmcm and
behaves as a non-collapsible framework, featuring only a slight cell volume contraction
(-1.9%) related to the water release. The removal of water molecules was accompanied by a
migration of the cation sites near the framework oxygens. The extra-framework cation
positions in dehydrated mordenite were also simulated by electrostatic energy calculations.

09-P-14 - Study of water vapor adsorption in the organically-lined channels

of AIMepO-[3 using X-ray powder diffraction
K. Maeda (a,b), L.B. McCusker (a) and C. Baerlocher (a)
Laboratory of Crystallography, ETH-Zurich, Zurich, Switzerland
bNational Institute of Advanced Industrial Science and Technology (National Institute of
Materials and Chemical Research), Tsukuba, maeda@nimc.go.jp, Japan

The structural changes in the framework of the aluminomethylphosphonate A1MepO-13 upon

water vapor sorption and the location of the sorbed water molecules have been investigated
using X-ray powder diffraction techniques. Only small differences between the framework
structures of the degassed and the water-sorbed sample were found. However, the latter did
contain additional water positions in the channels. The differences between the water sorption
behavior of the two polymorphs of A1MepO (-cz and-13) are discussed.
 291

20 - Zeolite Membranes and Films (Wednesday)

2 0 - p - 0 6 - Dehydrogenation of ethylbenzene to styrene using ZSM-5 type

zeolite membranes as reactors
X.-F. Zhang, Y.-S. Li, J.-Q. Wang, H.-O. Liu and C.-H. Liu
Institute of Adsorption and Inorganic Membrane, Dalian University of Technology,
158 Zhongshan Road, Dalian 116012, zhangxiongfu@263.net, China.

Factors on dehydrogenation of ethylbenzene to styrene in ZSM-5 type zeolite membrane

reactors were studied. About 18% conversion of ethylbenzene increase in the Fe-ZSM-5
membrane reactor can be obtained over the fixed-bed reactor. This result is better than that
obtained in the other membrane reactors. The bigger is the permeability and permselectivity
of ZSM-5 membranes, the higher is the conversion of ethylbenzene. The order of membrane
stability for ethylbenzene dehydrogenation is silicalite-1 > Fe-ZSM-5 > Fe/ZSM-5 > ZSM-5.

2 0 - P - 0 7 - Preparation of high-permeance ZSM-5 tubular membranes by

varying-temperature synthesis
Y.-S Li, Xio. Zhang, J.-G. Wang and S. Guo
Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, Dalian,
116012, China, Liyongsheng@hotmail.com

In this work, high-permeances ZSM-5 zeolite membranes were synthesized on porous a-alumina
tubes by a varying-temperature in-situ hydrothermal treatment using n-butylamine(NBA) as a
template. The membranes were characterized by XRD, SEM and single-gas permeation
measurements. The highest H2 permeance is up to 2.3x 106mol/m2.s.Pa, the highest ideal
selectivities are 201 for H2/n-C4Hl0, 13 for n-C4Hlo/i-C4Hlo, at 293 K. Few non-zeolite pores
formed in the membrane when the sol was renewed during the varying-temperature process,
so that the membrane had high ideal selectivity of n-C4Hlo/i-C4Hlo above 473 K. The
separation properties of the membranes were largely determined by synthesis procedure.

20-P-08 - Synthesis of FAU type films on steel supports using a seeding

method
Z. Wang, J. Hedlund and J. Sterte
Division of Chemical Technology, Lulegt University of Technology, johe@km.luth.se, Sweden

FAU type films were synthesized on polished steel supports using a seeding method. The
feasibility of the method was demonstrated for a wide variety of steel types. After 12 h of
synthesis the film was continuous with a thickness of about 2 gm. A prolonged synthesis time
in one single step resulted in significant attachment of sediments on the film surface for some
preparations. Several identical 12 h synthesis steps were therefore used to increase the
thickness of the films by approximately 2 ~tm with each additional synthesis step.
Morphology and film thickness was independent of steel type. All films were continuous and
crack free prior to calcination.
292

20-P-09 - Structured zeolite ZSM-5 coatings on ceramic packing materials

O. Ohrman, U. Nordgren, J. Hedlund, D. Creaser and J. Sterte
Luledt University of Technology, Sweden. Email."jost@km.luth.se

Homogeneous coatings of zeolite ZSM-5 were prepared by the seed film method on porous
ceramic foams and on alumina spheres. The zeolite was predominately present in the form of
a film on the support surface rather than as aggregated crystals on the surface. The results
from gas adsorption and SEM analysis indicated that the entire surface of the foams was
successfully covered with a 450 nm film. A 500 nm film was formed on the external surface
and also in pores close to the external surface of the spheres. Zeolite was not formed on the
internal surface of the alumina spheres. Aluminum leaching from the foams was observed but
did not seem to have any detrimental effects on the substrates.

20-P-10 - Effects of synthesis parameters on intra-pore zeolite formation in

zeolite A membranes
M. Lassinantti, J. Hedlund and J. Sterte
Division of Chemical Technology, Lule~t University of Technology, johe@km.luth.se, Sweden

Na-A films were synthesized on porous substrates using a seeding technique. Effects of
synthesis temperature, synthesis duration and gel composition on the morphology of the films
were evaluated. Higher synthesis temperature resulted in relatively more growth of zeolite
into the porous support compared to the film growth on top of the support. By using a multi-
step synthesis procedure at low temperature, thicker films with less growth into the support
could be prepared.

20-P-II Pure-silica zeolite Iow-k dielectric thin films by spin-on process

Zhengbao Wang, H. Wang, A. Mitra, L. Huang and Y. Yan*
Department of Chemical and Environmental Engineering, University of California,
Riverside, CA 92521, USA; yushan,yan@ucr.edu.

Spin-on silicalite thin films were prepared from silicalite nanocrystals. Spin-on silicalite films
with high porosity have a dielectric constant (k) of 1.8-2.2. A secondary growth of
nanocrystals was carried out on spin-on films under microwave treatment. It was found that a
secondary growth of nanocrystals by microwave treatment could increase the mechanical
strength and control the inter-particle pore size and porosity of spin-on silicalite films.
Microwave-treated spin-on films have a k value of 2.2-2.4. The effect of moisture on k value
was also studied. The silylation of silicalite films with chlorotrimethylsilane was conducted to
eliminate the effect of moisture on the dielectric constant. It was revealed that stable k values
were obtained after silylation.
 293

20-P-12 - Preparation of silicalite-I and beta zeolite/ceramic composite

membranes and removal of trace phenol and benzene from water through
them
Xiansen Li and S. Xiang*
Department of Chemistry, Nankai University, Tianjin, shxiang@public.tpt.tj.cn, P. R. China

The in-situ syntheses of silicalite-1 and beta zeolite membranes on the ceramic filter
substrates were performed. The physico-chemical properties of the zeolite composite
membranes were characterized by XRD, SEM and UV. The removal of phenol and benzene
from water through the zeolite composite membranes was studied. It was found that silicalite-
1 and beta membranes possessed good separation ability for PhOH/H20 and C6H6/H20 and
that beta membrane was better than that of silicalite-1 for PhOH/HzO. The average rejection
rates of beta and silicalite-1 membranes for PhOH/H20 were 69.9% and 51.5% respectively.
The separation capacity of silicalite-1 zeolite membrane for PhOH/H20 and C6H6/H20
increased after twice synthesis and steam treatment

20-P-13 - Factors affecting film thickness in the preparation of supported

ZSM-5 zeolite
E.I. Basaldella, A. Kikot, J.F. Bengoa and J.C. Tara
Centro de Investigaci6n y Desarrollo en Procesos Cataliticos (CINDECA), Universidad
Nacional de La Plata, CONICET, CIC, 47 N~ (1900) La Plata, Argentina.

The growth of hydrogel based ZSM-5 zeolite films on cordierite monoliths was studied varying
some specific synthesis parameters. More diluted gels decrease the simultaneous production of
loose crystals without altering the characteristics of the film formed, while a temperature decrease
leads to similarly thick films, though made up of smaller crystals. As films of about the size of a
crystal were obtained by increasing acid addition, it would be possible to control film thickness by
changing the acidity of the medium. Besides, stirring proved to be essential to obtain uniform
coating.

20-P-14 - Growing zeolite films onto gold surfaces

E.I. Basaldella a, A. Kikota, J.O. Zerbino b and J.C. Taraa
aCentro de Investigaci6n y Desarrollo en Procesos Cataliticos (CINDECA), Universidad
Nacional de La Plata, CONICET, CIC, 47 N~ (1900)La Plata-Argentina.
blnstituto de Investigaciones Fisicoquimicas Te6ricas y Aplicadas (INIFTA), Universidad
Nacional de La Plata, CIC, C. C. 16, Suc. 4, (1900) La Plata- Argentina

Silicalite layers were hydrothermally synthesized on gold surfaces by the in-situ

crystallization method, using hydrazine and oxigenated water as additives. In this way, it is
possible to alter the gold-zeolite electrostatic interaction by changing the electric charge of the
metal surface. The effects on the layer growth process related with this change are discussed.
Besides, it is proved that metal roughness improves the zeolite layer adherence.
294

20-P-15 - Diffusivities of zeolite coatings

M. Tather, ~;.B. Tantekin-Ersolmaz and A. Erdem-$enatalar
Department of Chemical Engineering, Istanbul Technical University, Maslak, 80626 Istanbul,
(aerdem@itu. edu. tr), Turkey
A method was proposed for the determination of the diffusivities of zeolite coatings. The
simulation of the operation of a thermogravimetric analyzer by modeling studies together with
experimental TGA measurements allows the estimation of the diffusion coefficient whenever
relatively thick zeolite coatings, for which mass transfer resistances exist, are available. The
diffusion coefficient of the zeolite 4A-water pair obtained by using the method developed was
quite close to the value measured by using the PFG NMR method. This deduction could be made
by taking into account the results obtained for a consolidated 4A powder sample and a coating
prepared by repeated syntheses. Relatively higher apparent diffusivities were obtained for the
relatively thicker zeolite 4A coatings prepared by using the direct heating method, which leads to
the formation of coatings with more open structures.

20-P-16 - Crystal growth mechanism of LTA and FAU and densification

process of zeolite film by seed growth
I. Kumakiri a* , Y. Sasaki,b W. Shimidzu,b T. Yamagushi a and S.-I. Nakao a
aDepartment of Chemical @stem Engineering, The University of Tokyo, 7-3-1, Hongo,
Bunkyo-ku, Tokyo, 113-8656, Japan, bResearch and Development Laboratory, Japan Fine
Ceramics Centre, 2-4-1, Mutsuno, Atsuta-ku, Nagoya, 456-8587, Japan

Zeolite NaA and FAU crystals were grown under the same hydrothermal condition using the
same composition of clear solution. The only difference was the type of seed crystal used.
This result suggested that the crystal growth did not occur by the attachment of nano-crystals.
Zeolite films/membranes were prepared by the growth of seeded crystals. Based on the SEM
and TEM observations and single gas permeation measurements, densification model of
film/membrane is presented.

20-P-I 7 - In-situ synthesis of ZSM-5 on aluminum surfaces

F. Scheffier and W. Schwieger
Institute of Industrial Chemistry I, University of Erlangen-Nuremberg
Egerlandstr. 3, D-91058 Erlangen, Germany

In this study the hydrothermal formation of ZSM-5 zeolitic coatings o n the surface of
different pretreated flat aluminum sheets has been investigated. The specific feature of the
reported preparation method is the fact that the aluminum sheet acts as a support as well as an
aluminum source as well to achieve a good connection between the support and zeolite layer.
The reaction was carried out under various synthesis conditions. The obtained products were
characterized by XRD, SEM and chemical analysis.
 295

20-P-18 - Conceptual process design of an all zeolite membrane reactor for

the hydroisomerization of CJC6
E.E. McLeary a*, R.D. Sanderson a, C. Luteijn ~, E.J.W. Buijsse b, L. Gora b, T. Maschmeyer b
and J.C. Jansen a'b
~Institute of Polymer Science, Faculty of Natural Science, Stellenbosch University, South
Africa," bLaboratory of Applied Organic Chemistry and Catalysis, Delft University of
Technology, Delft, The Netherlands," CLaboratory of Process Systems Engineering, Delft
University of Technology, Delft, The Netherlands

Membrane reactors provide opportunities for overcoming thermodynamic limits on the

maximum attainable conversion of reversible reactions. A simple membrane reactor model
has been employed to investigate the performance of C5/C6 hydroisomerization process on
zeolites and compare it to a state-of-the-art total isomerization (TIP) process. A RON of 88.0
was obtained, slightly higher and promising compared to the TIP process with RON of 86.
296

21 - Nanocomposite Fundamentals and Applications (Wednesday)

21-P-06- Fabrication of hollow fibers and spheres composed of zeolites by

layer-by-layer adsorption method
Y. Tang (a), Y.-J. Wang (a), X.-D. Wang (a), W.-L. Yang (b)and Z. Gao (a)
a Department of Chemistry, Fudan University, Shanghai 200433, China, yitang@)Cudan.edu.cn
b Department of Macromolecular Science, Fudan University, Shanghai 200433, China

Hollow fibers and spheres of zeolite (labeled as HFZ and HSZ, respectively) were
successfully fabricated using carbon fibers and polystyrene (PS) spheres as templates
respectively, through layer-by-layer technique, coupled with removal of the templates by
calcination. The optimum performance conditions to obtain these kinds of materials were
systematically studied. The wall thickness and composition of these novel materials can be
readily tailored by varying the number of nanozeolite/PDDA (poly(diallyldimethyl
ammonium chloride)) deposition cycles and zeolite type used, respectively. The properties of
these novel materials were characterized by means of XRD, IR and SEM.

21-P-07- The zeolitisation of diatoms to create hierarchical pore structures

S.M. Holmes(a), R.J. Plaisted(b), P. Crow(b), P. Foran(b), C.S. Cundy(b) and M.W.
Anderson(b)
a Environmental Technology Centre, Chemical Engineering Dept. UMIST, Sackville Street,
Manchester, M60 1QD, UK. e-mail." stuart.holmes@umist.ac.uk, fax: +44 161 2004399
b UMIST Centre for Microporous Materials, Sackville Street, Manchester, M60 1QD, UK.

The synthesis of a hierarchical pore structure, combining the macroporous diatomaceous earth
with microporous zeolites, is reported. Diatomaceous earth is an abundant and varied source
of macroporous silica which has been 'zeolitisatised' to produce a bifunctional, hierarchical
composite. A range of different zeolites have been synthesised to generate different pore
architectures, hydrophobic/hydrophilic materials and ion-exchange/catalytic properties.

21-P-08 - Generating the narrowest single-walled carbon nanotubes in the

channels of AIPO4-5 single crystals
G.D. Li (a,b), Z.K. Tang (b), N. Wang (b), K.H. Wong (b) and J.-S. Chen* (a)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
chemcj@mail.jlu, edu. cn, Changchun, P. R. China
b Department of Physics, HKUST, Hong Kong, P. R. China

The pyrolysis of tripropylamine trapped in the framework structure of A1PO4-5 (AFI) single
crystal results in the formation of the narrowest single-walled carbon nanotubes. The diameter
of the nanotubes, which are stable enough when located in the AFI channels, is 0.42+0.02 nm.
As the nanotubes are strictly aligned in the one-dimensional channels, the AFI crystal
containing the tubes shows distinct anisotropic property. The growing process of the
nanotubes was monitored by polarized optical microscopy. It has been found that the optimal
temperature range for the growth of the nanotubes in A1PO4-5 single crystals is 773-873 K.
 297

2 1 - P - 0 9 - Zeolite- an effective nucleating agent of Na2HPO4"I2H20

J. Dong, X. Jing and Yu. Zhang
Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, Shanxi,
P. R. China, jxdong@public.ty.sx.cn
The use of zeolites, including LTA, Y, LTL, VPI-7, MFI and MOR, as nucleating agents of
phase-change-material Na2HPO4"12H20 was first reported. The results showed that all the
selected zeolites could inhibit the supercooling of Na2HPO4"12H20 to some extent. Among
them MOR displayed the best effect. When the amount is 5%, it can lower the supercooling to
2.03---1.02~ and this system showed good stability and reversibility. At the same time, the
morphology of samples after many times of re-crystallization was studied with SEM. The
photograph of the SEM and microprobe analysis results showed that these different zeolites
could form mixed isomorphous crystals with NazHPO4" 12H20. The function of zeolite on the
nucleation had no direct relation with its own crystal lattice and its cell parameters.

21-P-10 - Synthesis and characterization of SnO2 nano particles in zeolite

hosts
Yi. Zhang, Xi. Wang and Xu. Wang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116012,
China, yihzhang@263.net.

Zeolite-entrapped SnO2 nano-semiconductor was synthesized by microwave ion-exchange

method and chemical vapor deposition (CVD). The materials were studied by XRD, UV-Vis,
FS and l l9Sn MAS NMR. Sn(IV) can be effectively introduced into the channels of zeolite
hosts by microwave ion-exchange method. The hydration of Sn(IV) with H20 can be lessened
under microwave irradiation, which improves the incorporation of Sn(IV) ions into the
channels of the zeolites. For the CVD method, zeolite NH4Y is superior to NaY and HY as
the host for SnO2 nano-semiconductor. The chemisorption of SnCI4 on the zeolite is
correlated to the surface hydroxyl. SnO2 entrapped in zeolite has obvious quantum size effect.
The materials also have excellent gas sensing properties in detecting ethanol.

21-P-11 - Encapsulation of Mn(bipy)2 into the zeolite Y prepared via

different routes
B. Fan, W. Cheng and R. Li*
Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P.R.
China. E-mail. rfii@tyut, edu. cn

A series of zeolite Y, post-treated with various acids, synthesized in the organic-amine-

containing system, exchanged with Mn 2§ and prepared by direct addition of Mn(II) chloride
in the crystallized mixture of zeolite Y, are used as hosts for the encapsulation of Mn(bipy)2.
XRD, SEM, DTA, FTIR, and DRS measurements show that by flexible ligand method
Mn(bipy)2 can be effectively encapsulated in different hosts. The properties of the hosts
strongly influence the thermal stability and catalytic performances of encapsulated Mn(bipy)2.
Upon treatment of zeolite Y with acids and the use of Mn-containing Y and Y synthesized in
the system containing large-molecule organic amine as hosts, the catalytic activity can be
significantly increased.
298

21-P-12 - Preparation of zeolite Beta/polystyrene beads and the corres-

ponding hollow spheres
V. Valtchev and S. Sferdjella
Laboratoire de Mat~riaux Min~raux, U.P.R.E.S.-A-CNRS 7016, ENSCMu, Universitd de
Haute Alsace, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France
Zeolite shells on polystyrene beads were prepared by a combination of layer-by-layer (LbL)
and hydrothermal synthesis techniques. The negatively charged polystyrene beads were
surface modified in order to adsorb zeolite Beta nanocrystals. Such particles were then
adsorbed on the surface of the beads and induced to grow into a continuous film of intergrown
crystals of zeolite Beta. The effect of the preliminary treatment on the formation of the zeolite
film was studied. Finally the polystyrene beads used as macro-templates were removed by
calcination in air, yielding hollow spheres of zeolite Beta. The zeolite Beta/polystyrene
composites and the corresponding hollow zeolite spheres were characterized by XRD, SEM,
TG/DTA and BET surface area measurements.

21-P-13 - Synthesis, characterization and catalysis of manganese(II)

complexes encapsulated in NaX and NaY zeolites
J.M. Silva (a), R. Ferreira (b), C. Freire (b), B. de Castro (b)and J.L. Figueiredo (a)
a Faculdade de Engenharia da Univ. Porto, mabasto2OOO@yahoo.com
b CEQUP, Faculdade de Ci~ncias da Universidade do Porto, Portugal.

The encapsulation of manganese(II)salen complexes into the pores of synthetic zeolites (NaX
and NaY) was evaluated by different techniques: ICP-AES, XPS and SEM, TG-DSC, N2
adsorption, FTIR, UV-Vis. The results are consistent with the location of Mn complexes
inside the micropores; even at low loadings it was possible to confirm this evidence. Catalytic
tests in olefin epoxidation proved the existence of catalytic activity and the stereoselectivity of
the complex after encapsulation. These catalytic results indicate that Mn-salen-zeolites may
be promising heterogeneous catalytic systems.

21-P-14 - Guest-host interactions in systems containing liquid crystals

confined to molecular sieves
S. Frunza(a), L. Frunza(a,b), A. Sch6nhals(c), H.-L. Zubowa(b), H. Kosslick(b) and
R. Fricke(b)
~National Institute of Materials Physics, Bucharest, frunza@alphal.infim.ro, Romania
bInstitute of Applied Chemistry, Berlin-Adlershof Germany
~Bundesanstalt far Materialforschung und Prafung, Berlin-Dahlem, Germany

4-Pentyl-4'-cyanobiphenyl and 4-octyl-4'-cyanobiphenyl liquid crystals (LCs) confined in

molecular sieves of MCM-41 and cloverite types are studied in a wide temperature range by
dielectric spectroscopy, thermal analysis and in-situ FTIR spectroscopy. The phase transitions
of the bulk LCs cannot be detected when confined in MCM-41 sieve. A relaxational process
occurs due to the molecular motions in the layer at the pore walls; the temperature
dependence of the characteristic frequency obeys a Vogel-Fulcher-Tamman law associated to
a glassy state. In the cloverite cages, the LCs keep the phase transitions of the bulk but
shifted. Interactions between Lewis and BrOnsted sites and the LC molecules are monitored
by IR spectroscopy. DTA measurements put also in evidence strong guest-host interactions.
 299

2 1 - P - 1 5 - Zeolite Beta ordered macroporous structures with improved

mechanical strength and controlled mesoporosity
V. Valtchev, S. Sferdjella and H. Kessler
Laboratoire de Matdriaux Min&aux, U.P.R.E.S.-A-CNRS 7016, ENSCMu, Universit~ de
Haute Alsace, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France

Macroporous zeolite Beta structures were prepared by a self-assembly of monodisperse

polystyrene spheres and zeolite nanocrystals followed by a hydrothermal treatment. The
characteristic features of the self-assembled and hydrothermally treated macroporous
structures were studied by XRD, FTIR, SEM, TG/DTA and nitrogen adsorption
measurements. The hydrothermal treatment of the self-assembled composites led to
intergrowth and closing of the mesopores between the nanocrystals building the walls of
macropores. The mechanical properties of the macroporous zeolite structures were
substantially improved by the secondary growth of the zeolite crystals.

21-P-16 - Synthesis of zeolites with organic lattice

K. Yamamoto (a), Y. Takahashi (b) and T. Tatsumi (b)
a The University of Tokyo, Tokyo, Japan.
b Yokohama National University, Yokohama, ttatsumi@ynu.ac.jp, Japan.

Organic-inorganic hybrid zeolites with organic lattice were successfully synthesized by using
organically bridged silane as a silica source. 29Si and 13C MAS NMR spectra and IR spectra
proved the presence of organic lattice (Si-CH2-Si) partially replacing siloxane bond (Si-O-Si),
although some of Si-C bonds were cleaved. Their unit cell sizes were slightly larger than
those of their completely inorganic counterparts presumably due to the longer bond length of
Si-C than that of Si-O. When synthesized in the absence of organic template molecules, they
showed microporosity like ordinary zeolites. This is the first example of the successful
synthesis of zeolites having an organic group as lattice in a strict meaning.

2 I-P-17 - Crystallization mechanism of AIMepO-13

Y. Qi, G. Wang and Z. Liu
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023, China, zml@dicp.ac.cn

A microporous aluminum methylphosphonate, A1MepO-[3, was prepared by hydrothermal

method. The crystallization process was studied using XRD, PC-NMR, IR and SEM. It was
found that phase transformation occurred in the crystallization process. There is an inter-
mediate phase (nominated Phase A) between the starting gel and A1MepO-13. A1MepO-13 is
not stable in the crystallization condition, and apt to be converted to more stable products -
A1MepO-~ and amorphous phase. The scheme for the crystallization process is suggested as:
staring material ~ Phase A --~ A1MepO-13 --+ A1MepO-~ + amorphous phase.
300

21-P-18- Crystal structure and magnetic properties of rubidium clusters in

zeolite L T A
T. Ikeda a and T. Kodaira b
aNational Institute for Research in Inorganic Materials, 1-1, Tsukuba, 305-0044, Japan
bNational Institute of Materials and Chemical Research, 1-1, Tsukuba, 305-8565, Japan

The Rb metal-doped Rb-type LTA shows an interesting magnetic property whose magnetic
susceptibility obeys the Curie-Weiss law with a negative Weiss temperature. Rb atoms can be
loaded up to 5.4 atoms per Gt-cage. The crystal structure of the Rb loaded Rb-type LTA is
determined using X-ray powder diffraction under ultrahigh vacuum conditions. By increasing
the loaded density of the Rb cluster, arrangements of the Rb + ions in adjacent m-cages went
from equivalent to nonequivalent and the local symmetry for framework was degraded from
Oh to Yd. The structural arrangement is clearly revealed by electron density distribution using
the maximum entropy method. The magnetic property, which can be interpreted by the
Dzialoshinsky-Moriya (DM) interaction, is strongly related to the noncentrosymmetric
arrangement of the Rb clusters.
 301

26 - Catalysis for Oil Refining (Wednesday)

26-P-06 - Hydroisomerization of n-decane in the presence of sulfur. Effect of

m e t a l - a c i d balance and metal location
L.B. Galperin, S.A. Bradley and T.M. Mezza
UOP LLC, P.O. Box 5016, Des Plaines, Illinois, USA,"LBGalper@uop.com

Isomerization of n-decane in the presence of 1000 ppm H2S was studied on bifunctional Pt-
MAPSO-3! catalysts. Sulfur suppresses the catalyst metal function, thereby changing the
metal-acid balance which is required for high performance. Methods for controlling the
catalyst metal-acid balance by changing the ratio between metal and acid functions are
demonstrated. Catalysts with high isomerization selectivity in the presence of sulfur should
have a strong metal function. Close proximity of metal and acid sites, as well as highly
dispersed metal located on the binder, gives a catalyst with an isomerization selectivity of
about 90%. This is similar to selectivity of the same catalyst in the absence of sulfur.

2 6 - P - 0 7 - Hydrodesulfurization of benzothiophene over noble metals

supported on mesoporous silica MCM-41
M. Sugioka(a), A. Seino(a),T. Aizawa(a), J.K.A. Dapaah(a), Y. Uemichi(a) and
S. Namba(b)
a Muroran Institute of Technology, Muroran, msugioka@mmm.muroran-it.ac.jp, Japan
bTeikyo University of Science and Technology, Yamanashi, Japan

It was found that the Pt/MCM-41 catalyst showed high and stable catalytic activity for the
hydrodesulfurization of benzothiophene at 350 ~ and this activity was higher than that of
commercial CoMo/A1203 catalyst. The Pt/MCM-41 catalyst has high sulfur-tolerant property
towards hydrogen sulfide formed in hydrodesulfurization of benzothiophene. The silanol
group (Si-OH) of MCM-41 and the spillover hydrogen formed on Pt particle in Pt/MCM-41
catalyst play important roles in the hydrodesulfurization of benzothiophene. Pt/MCM-41
might be a promising new hydrodesulfurization catalyst for bulky organic sulfur compounds
in the petroleum feedstocks.

26-P-08 - Catalytic functionalities of USY zeolite supported hydrotreating

catalysts
K.S. Rawat, M.S. Rana and G. Murali Dhar*
Indian Institute of Petroleum, Dehradun, INDIA - gmurli@iip.res.in

USY zeolites of varying Si/A1 ratios were used as support for Mo, NiMo, CoMo and NiW
catalysts. Both the effect of variation of Si/A1 ratio of the zeolite and Mo content on support at
fixed Si/A1 ratio were studied. The catalysts were examined by XRD, oxygen chemisorption
and TPR techniques. The hydrodesulfurization and hydrogenation reaction studies indicated
that these catalysts are more active than y-A1203 supported catalysts and the increase in
activities may be attributed to an increase in Mo dispersion and reducibility. It was found that
oxygen uptake correlates well with the catalytic activity.
302

2 6 - P - 0 9 - Highly active, selective and stable ferrierite-based catalysts for

the skeletal isomerization of n-C5-C7
C.P. Nicolaides a, J. Makkonen b and M. Tiitta b
Chemical Process Engineering Research Institute, National Centre for Research and
Technology - Hellas, Thermi- Thessaloniki - cnicolai@alexandros, cperi, certh, gr, Greece;
6Fortum Oil and Gas, Oil Research and Development, Porvoo - marja.tiitta@fortum.com,
Finland
Various ferrierite zeolites prepared via different synthetic routes were tested as catalysts for
the skeletal isomerization of n-Cs-C7 olefins. The ferrierite samples having a small particle
size, low total aluminum content, but a high percentage of aluminum in framework positions,
showed the highest activity and selectivity for the reaction and stable catalytic performance
with time-on-stream.

26-P-10 - Producing synthetic steamcracker feed from cycloalkanes (or

aromatics) on various zeolite catalysts
A. Raichle, H. Scharl, Y. Traa and J. Weitkamp
Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany,
jens. weitkamp@po, uni-stuttgart, de

Methylcyclohexane (which can be readily manufactured from toluene by conventional ring

hydrogenation) is converted into a high-quality steamcracker feed over the acidic zeolites H-
Y, H-Beta, H-ZSM-11, H-ZSM-5, H-ZSM-22 and H-ZSM-35, thereby opening a new route
for the utilization of surplus aromatics. While the conversion decreases with increasing
geometrical constraints, the selectivity to the desired C2+-n-alkanes (mainly ethane, propane
and n-butane) shows the opposite behavior. This is attributed to a higher contribution of
Haag-Dessau cracking on zeolites with narrow pores.

26-P-11 - n-Heptane hydroconversion and methylcyclohexane cracking as

model reactions to investigate the pore topology of NU-88 zeolite
S. Lacombe, A. Patrigeon and E. Benazzi
IFP, Rueil-Malmaison Cedex, France - sylvie.lacombe@ifp.fr.

The n-heptane hydroconversion is a useful and simple tool to get primary ideas on the pore
topology of new zeolites, although a more precise investigation requires the use of more
complex molecules. This model reaction was used to investigate the pore topology of NU-88
zeolite. By working on the rate of appearance of the products and on the composition of the
isomers and cracked products, it could be proposed that NU-88 zeolite contains 10 MR
channels with large intemal void spaces, which could be intersections of 10 MR channels or
extra-cavities. The results were complemented with a methycyclohexane cracking test,
where the importance of hydrogen transfer reactions confirms the presence of large cavities.
 303

26-P-12 - New Mo and NiMo hydrodesulfurization catalysts supported on

AI-MCM-41. Effect of the support Si/A! molar ratio
T. Klimova, M. Calder6n and J. Ramirez
Departamento de Ingenieria Quimica, Facultad de Quimica, Universidad Nacional
Aut6noma de M~xico, Cd. Universitaria, M~xico D.F. -klimova@servidor.unam.mx, M~xico

A series of Mo and NiMo catalysts supported on Al-containing MCM-41 was prepared and
characterized. It was shown that the incorporation of A1 atoms into the siliceous MCM-41
framework causes a deterioration of the textural characteristics and some loss in the
periodicity of the MCM-41 pore structure. However, the acidity of the Al-containing MCM-
41 is substantially higher. The dispersion of Mo and Ni oxidic species increases with the
incorporation of aluminum in the MCM-41 support, that produces an increase in the total
conversion of dibenzothiophene. It was found that this effect is due to the interaction of Mo
and Ni oxidic species with aluminum atoms of the MCM-41 support.

2 6 - P - 1 3 - Hydrogenation and ring opening of mono- and diaromatics for

Diesel upgrading on Pt/Beta catalysts
M.A. Arribas, J.J. Mahiques and A. Martinez
Instituto de Tecnologia Quimica, UP V-CSIC, Valencia, amart@itq, upv. es, Spain

The combined hydrogenation and ring-opening of tetralin and 1-methylnaphthalene has been
carried out on bifunctional Pt/Beta catalysts. The influence of the acidic and textural
properties of the zeolite on activity and selectivity has been studied by varying the zeolite
crystal size and the Si/A1 ratio by means of acid and steaming treatments. Similar trends were
found for both aromatic reactants. Selectivity to products with the same number of carbon
atoms than the feed and yield to ring-opening products increased while decreasing the
BrOnsted acidity of the zeolite and by decreasing the size of the crystallites. Better catalytic
performance was obtained for the catalyst prepared from a Beta zeolite dealuminated by
steaming thus having a higher mesoporosity and reduced acidity.

26-P-14 - Hydro denitrogenation activity of N i O - MoO3 catalysts

supported on various mesoporous alumino silicates
K. Shanthi, N.R. Sasi Rekha, R. Moheswari and T. Sivakumar
Department of Chemistry, Anna University, Chennai, India.

Mesoporous alumino silicate molecular sieves with MCM-41 type structure synthesized using
various A1 sources (i.e.: aluminum sulphate, aluminum isopropoxide, pseudo boehomite and
sodium aluminate) have been used as supports for N i - Mo catalysts. The HDN of o-toluidine
and cyclohexylamine was studied in a fixed bed flow reactor at 450~ and PH2 = 1 atm. The
activity per unit of weight of the M C M - 41 supported catalysts was evaluated and compared
to that of supported catalysts prepared by sequential impregnation method. The XRD and
DRS data have been used to explain the observed trend in catalytic activity towards HDN
reaction
304

26-P-15 - Model hydrocracking catalysts combining NiMo sulfide and

large-pore zeolite" effect of the zeolite nature on the location of NiMo
sulfide in relation with catalytic properties
J. Leglise (a), D. Cornet (a), M. Ba~lala (a), C. Potvin (b) and J.-M. Manoli (b)
a Catalyse et Spectrochimie, ISMRA, Caen - Leglise@ismra.fr.
b Rdactivitd de Surface, Universitd P. & M. Curie, Paris- jmm@ccr.jussieu.fr
Ni and Mo ions were deposited into HBEA and HY zeolites, then sulfided. The solids were
characterized at all preparation stages by various methods, notably by MAS-NMR, FT-IR,
and TEM-EDX. The catalytic bifunctional properties were determined in the hydroconversion
of benzene (8 MPa H2, 1 h"l, 240-360~ With both zeolites, about half of the Ni-Mo is
located in cavities and mesopores, but the internal NiMo is better sulfided with the
nanocrystalline BEA zeolite. Catalyst NiMoS/BEA was much more active and slightly more
selective for hydrogenation than NiMoS/Y.

26-P-16 - Effect of zeolite acidity characteristics on the deactivation

behavior of bifunctional large-pore zeolite catalysts during cyclopentane
hydroconversion
S. Gopal and P.G. Smirniotis
Department of Chemical Engineering, University of Cincinnati, Cincinnati, USA
Panagiotis. Smirniotis@uc. edu
Time stability of Pt loaded zeolite Y, beta, mordenite and ZSM-12 was investigated at several
different Si/AI ratios using cyclopentane as a coke producing agent. Although zeolite pore
structure determined coking resistance to a large extent, significant differences in catalytic
performance were observed within a particular type of zeolite depending on the Si/A1 ratio.
This could be explained based on acid site density as it not only decreased the coking severity
but also controlled metal dispersion and metal acidity balance in the catalyst. In general
zeolites with Si/AI ratios between 15 and 40 showed the best stabilities in this study.

26-P-17 - Characterization and catalytic activities of MCM-41 supported

WS2 hydrotreating catalysts
T. Chiranjeevi, P. Kumar, M.S. Rana, G. Murali Dhar and T.S.R. Prasada Rao
Catalysis Division, Indian Institute of Petroleum, Dehradun,, INDIA
WO3-MCM-41 catalysts were prepared with good dispersion of WO3. The oxygen
chemisorption in the sulfided state indicated that WS2 is also well dispersed on MCM-41
surface. 02 chemisorption as a function of W loading indicated that maximum dispersion and
maximum number of anion vacancies are obtained with 19wt% W with highest catalytic
activities for HDS, HYD, HDO. The small crystallite size and its constancy as function of W
loading coupled with low surface coverage by WS2 indicated that monolayer WS2 patches are
formed on the selected regions of support surface. The correlation between 02 uptake and
catalytic activity indicated that oxygen chemisorption is not specific to any of the
functionalities of the overall dispersion of WS2. Co and Ni addition resulted in promotional
effect for both HYD and HDS; it is suggested that the three catalytic functionalities originate
from different set of sites on the WS2 and its promoted analogues.
 305

26-P-18 - Isomerization and hydrocracking of n-heptane and n-decane over

bifunctional mesoporous molecular sieves
C. Bischof and M. Hartmann
Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany,
hartmann@rhrk, uni-kl,de
n-Heptane and n-decane hydroconversion have been investigated on platinum-, palladium-
and ruthenium-containing A1MCM-41 (nsi/nal = 23) mesoporous molecular sieves. High
selectivities for branched isomers have been observed on 0.27 Pd/HAIMCM-41 at reaction
temperatures ranging from 250 to 380~ The product distribution is comparable with the one
found for ideal bifunctional catalysis. While on 0.27 Pd/HAIMCM-41 no cracking on the
metal function (hydrogenolysis) was observed, the cracked product distribution found on 0.5
Pt/HA1MCM-41 indicates that hydrogenolysis also occurs. Over 0.26 Ru/HAIMCM-41, the
high yields of methane, ethane and linear hydrocarbons reveal a high hydrogenolysis activity
of the ruthenium metal supported on AIMCM-41.

26-P-19 - Isomerization of cyclohexane, n-hexane and their mixtures on

zeolite catalyst
A. Holl6 (a*), J. Hancs6k (a) and D. Kall6 (b)
a University of Veszpr~m, Veszpr~m, hancsokj@almos.vein.hu, Hungary.
b Chemical Research Center, Hung. Acad. of Sci., Budapest, kallo@chemres.hu, Hungary
*Present address." Hungarian Oil and Gas Co., Sz6zhalombatta, AHollo@mol.hu, Hungary
Isomerization of c-C6, n-C6 and their mixtures has been investigated on Pt/H-MOR. The
effects of reaction conditions and feed composition on the yield of isomers, as well as on the
composition of cracked and other products were examined. Rate equations and parameters
involved were determined for the isomerization of pure alkanes and their mixtures.
Isomerization rate equation can be derived assuming rate determining skeletal rearrangement,
while in mixtures and at higher pressures the transport in micropores seems to control the
transformation.

2 6 - P - 2 0 - Application of adsorption Dubinin-Radushkevich equation for

study of n-pentane and m-xylene conversion catalysts microporous
structure
S.B. Agayeva, B.A. Dadashev, S.I. Abasov and D.B. Tagiyev
Institute of Petrochemical Processes, Azerbaijan Academy of Sciences
30, N.Rafiev st., 370025, Baku, Azerbaijan, E-mail." anipcp@dcacs.ab.az, ipcp@baku-az.net
The adsorptive and catalytic properties of zeolites HY, HZSM-5 and HM (natural and
synthetic) subjected to dealumination, ion exchange with rare-earth and transition elements
have been studied.The changes in conversion and selectivity for m-xylene and n-pentane are
shown to be connected with the changes of the zeolites microporous structure.These changes
are in conformity with DR equation parameters. The DR equation could be applied to the
simple test method elaboration of the starting and modified zeolites microporous structure
through their adsorptive properties.
306

26-P-21 - Hydroisomerization of n-hexadecane over Pt/AI-MCM-41

catalysts: Two different AI incorporation methods
K.-C. Park and S.-K. Ihm
Dept. of Chem. Eng., KAIST, Taejon, skihm@_mai!.kaist.ac.kr, Korea.

The hydroisomerization of n-hexadecane was carried out over Pt/A1-MCM-41 catalysts at

350~ and 103 bar. A1-MCM-41 was prepared by two different methods; a direct sol-gel
method (Pre) and a post-grafting method (Post). A1-MCM-41 was characterized by using
XRD, nitrogen adsorption, 27A1 NMR and ammonia TPD. The higher the amount of acid
sites was, the higher the reactivity and isomer yield were. Pt/A1-MCM-41-Post showed
higher conversions and higher isomerization yield than Pt/A1-MCM-41-Pre. Reaction
results did not agree with A1-NMR data but with ammonia TPD. This difference was
attributed to the better accessibility of tetrahedral sites (Broensted acid sites) in AI-MCM-
41-Post than those in A1-MCM-41-Pre.

26-P-22 - Zr-containing hexagonal mesoporous silicas as supports for

hydrotreating catalysts
N.G. Kostova, A.A. Spojakina, L.A. Petrov, O. Solcova a and K. Jiratova a
Institute of Catalysis, Bulgarian Academy of Science, Sofia, Bulgaria - nkostova@ic.bas.bg;
alnstitute of Chemical Process Fundamentals, Acad. Sci. czech Republic, Prague

This work reports the preparation of new supports for Mo- and NiMo-hydrotreating catalysts.
Zr-containing mesoporous silicas with Zr/Si ratio from 0 up to 0.04 were prepared using
TEOS, ZrOC102 and dodecylamine as a template. The materials and those modified with 12
% wt. Mo from 12-phosphomolybdic acid (HPMo) and its nickel salt were characterised by
IR, TPD of NH3, TPR and their activities were measured in thiophene HDS. Activities in
HDS of thiophene of Mo-containing catalysts prepared with the mesoporous silicas were
higher than those of the catalysts prepared with amorphous silica.

26-P-23 - New catalysts for isomerization of long-chain n-paraffins

M.I. Levinbuk,1 L.M. Kustov,2 T.V. Vasina,2 O.V. Masloboishchikova,2 M.L. Pavlov,3 I.E.
Gorbatkina 4 and V.A. Khavkin 4
1Moscow Oil and Gas University, 65 Leninsky prospect, 1117917 Moscow, Russia
2N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
3Salavat Catalyst Factory, Salavat, 4 Moscow Research Institute of Oil Refining, Russia

Novel Y-type zeolite-based catalysts for isomerization of long-chain paraffins (nCT-nCl6) and
aromatics hydrogenation have been developed. They provide high selectivity to isomerate
with minimal feed cracking. Isomerization of nC7 is accompanied by benzene hydrogenation
into methylcyclopentane and cyclohexane. Each reaction occurs on different sites and
proceeds without altering the other one. The effect of the ratio of iso to n paraffins in gasoline
fraction (IBP-62~ and 100-130~ was studied. Altenative methods to use the new catalysts
in oil processing have been considered.
 307

2 8 - Confinement and Physical Chemistry for Catalysis (Wednesday)

28-P-06- Use of coke-selectivated H-ZSM-5 in xylene isomerization

F. Bauer and A. Freyer
Institut fi~r Oberfli~chenmodifizierung, 5, Leipzig, Germany- fbauer@rz, uni-leipzig.de
The deposition of carbonaceous residues is used as modifying technique for the selectivation
of H-ZSM-5 during xylene isomerization. An enhanced selectivity and a reduction of xylene
loss was achieved by a thermal treatment of coke-selectivated H-ZSM-5 with hydrogen and
propane. In the presence of these reactive carrier gases internal coke may be effectively
removed and the remaining external coke covers those acid sites located on the crystallite
surface which are responsible for undesired transalkylation and secondary isomerization
reactions. Compared with samples selectivated with the xylene feed under high severity
conditions deposits of about 0.3 wt.-% modified pre-coke using methanol as coke precursor
are sufficient to reduce the xylene loss to 1.1% while maintaining the desired activity for
ethylbenzene conversion of about 55 %.

2 8 - P - 0 7 - Photocatalytic reactions on chromium containing mesoporous

molecular sieves under visible light irradiation: Decomposition of NO and
partial oxidation of propane
H. Yamashita*, K. Yoshizawa, M. Ariyuki, S. Higashimoto, and M. Anpo*
Osaka Prefecture University, yamashita@chem, osakafu-u, ac,/p, Japan
The photocatalytic reactivities of Cr-containing mesoporous molecular sieves (Cr-HMS) have
been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which
are highly dispersed and incorporated in the framework of molecular sieve with two terminal
Cr=O. In the presence of NO, Cr-HMS exhibited photocatalytic reactivity for the
decomposition of NO into N2, 02, and N20 not only under UV light irradiation but also
visible light irradiation. Especially, under visible light irradiation, a higher selectivity for N2
formation was observed. In the presence of propane and 02, a partial oxidation proceeded
under visible light irradiation to produce acetone and acrolein with a high selectivity, while a
complete oxidation proceeded under UV irradiation mainly to produce CO2. The charge
transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the
photocatalytic reactivities.

28-P-08 - Enhancing the shape selectivity of nanocrystalline HZSM-5 zeolite via

comprehensive modifications
H..C. Guo, X.S. Wang and G.R. Wang
Institute of Industrial Catalysis & State Key Lab. of Fine Chemicals, Dalian Universityof Technolog)4,
Dalian, P R. China- honghai@mbox.dl.cei.gov.cn
Fine tuning of a nano-HZSM-5 (20-50 nm, S I O 2 / A 1 2 0 3 = 25) was achieved by systematic
modifications. Evaluations were made through analyzing zeolitic overall acid strength,
external surface acid sites and microporous geometric constraints and the shape-selectivity in
ethylbenzene ethylation. It is concluded that nano-ZSM-5 can be trimmed into highly shape-
selective catalyst by exploiting the synergic effect of zeolitic overall acid strength
suppression, microporous geometric constraints regulation and external acid sites passivation.
308

28-P-09 - Nature of shape-selective catalysis in the ethylation and the

isopropylation of biphenyl over H - m o r d e n i t e s
Y. Sugi a*, S. Tawada a, T. Sugimura a, Y. Imada a, Y. Kubota a, T. Hanaoka b and T. Matsuzaki b
a Department of Chemistry, Gifu University, sugi@apchem.gifu-u.ac.jp, Japan
b National Institutes of Materials and Chemical Research, Tsukuba 305-8565, Japan

4-Isopropylbiphenyl (4-IPBP) was consumed much faster than 3-IPBP in their competitive
isopropylation. Selectivity for 4,4'-diisopropylbiphenyl (4,4'-DIPB) in bulk products
decreased with the increase of 3-IPBP, however, the selectivity in encapsulated products kept
constant. 4-Ethylbiphenyl (4-EBP) disappeared much faster than 3-EBP in their competitive
ethylation. Selectivity for 4,4'-diethylboiphenyl (4,4'-DEBP) was less than 2 %, whereas total
selectivity for DEBPs with 4-ethyl group was higher than 65 % in both products: DEBPs were
predominantly produced from 4-EBP. HM-pores were too loose to form 4,4'-DEBP.

28-P-10 - A d s o r p t i o n of selected amino acids from a q u e o u s solutions on

m e s o p o r o u s molecular sieves
S. Ernst, M. Hartmann and S. Munsch
Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany,
sernst@rhrk, uni-kl, de

The adsorption of various amino acids from aqueous solutions using MCM-41-type
mesoporous molecular sieves is discussed on the basis of their adsorption isotherms. The
amounts adsorbed strongly depend on the pH and the nature of the individual amino acid:
Amino acids with acidic side chains are hardly adsorbed, whereas basic amino acids show
very high affinities to the mesoporous adsorbent. The uptake of amino acids with non-polar
side chains increases with the chain length. The adsorption complex is proposed to consist of
the cationic form of the amino acid attached to the negatively charged silica surface.

28-P-11 - Influence of O H groups of Beta zeolites on the synthesis of M T B E

F. Collignon a and G. Poncelet
Universit~ Catholique de Louvain, Unit~ de Catalyse et Chimie des Mat~riaux Divis~s, Place
Croix du Sud 2/17, B-1348 Louvain-la-Neuve, Belgium.
a Katholieke Universiteit Leuven, Centrum voor Oppervlaktechemie en Katalyse, Kasteelpark
Arenberg 23, B-3001 Leuven, Belgium, francois.collignon@agr.kuleuven.ac.be

Vapor phase synthesis of MTBE over zeolite Beta is very efficient. For example, Beta zeolite
is three times more active than Amberlyst-15 for MTBE vapor phase synthesis at 50~ The
better catalytic performance of H-Beta was verified in liquid phase. The external surface area,
the amount of bridging A1OHSi, and silanol groups are important zeolite parameters for the
ether synthesis. The reaction occurs on bridging A1OHSi acid sites. The highest yields are
reached for low SiOH/A1OHSi ratios where methanol clusters bonded to silanol groups allow
accessibility of isobutene to the active AIOHSi groups.
 309

28-P-12 - About a possibilities of effectiveness increasing of porous catalyst

granules with controlled activity profile
v . v . Andreev
Dept. of Control and Informatics in Technical Systems, Chuvash State University, Moskovskii
pr. 15, 428015 Cheboksary, Russia; avv@chuvsu.ru
The possibilities of effectiveness increasing of the porous catalyst granules with controlled
activity profile are considered. Optimal control by the chemical reaction proceeding on such
catalyst granules under artificially created non-steady-state conditions allows to make their
productivity higher, than under steady-state conditions. On the base of analysis of critical
phenomena of multiplicity states form it is possible to reach of the more high productivity of
porous catalyst granule with controlled activity profile in case of a catalytic reaction
proceeding under non-steady-state conditions.

2 8 - P - 1 3 - Effects of channel structures of wide pore zeolites on m-cresol

transformation
F. L6pez a, L. Gonzdlez a, J.C. Herndndez a, A. Uzcdtegui a, F.E. Imbert a and G. Giannetto b
a
Laboratorio de Cin6tica y Cat6lisis, Grupo de Materiales Microporosos en Cat6lisis,
Departamento de Quimica, Facultad de Ciencias, Universidad ale Los Andes, La Hechicera -
b
M6rida 5101A. Venezuela. Fax." +58 74 401286, e-mail. imbeH@ciens.ula.ve ; Facultad de
Ingenieria, Universidad Central de Venezuela, Los Chaguaramos, Caracas Venezuela.

The m-cresol transformation was carried out on wide pore zeolites (HFAU, HBEA, HMOR
and HOFF). The activity follows the sequence HFAU > HBEA>> HMOR > HOFF. The order
of the acid strength determined by TPD-NH3 was HMOR>HOFF>HBEA>HFAU. On the
HBEA. HMOR and HOFF the isomerization was the main reaction due to their pore system
structure, that limits the formation of diphenylmethane intermediate of disproportionation,
while on HFAU the disproportionation reaction was not impeded at low conversion. The p/o
selectivity is mainly function of conversion.

28-P-14 - A study on the use of zeolite Beta as solid acid catalyst in liquid
and gas phase esterification reactions. The influence of the hydrophobicity
of the catalyst
M.J. Verhoef", R.M. Koster b, E. Poels b, A. Bliek b, J.A. Peters a and H. van Bekkum a
aTechnische Universiteit Delft, H. vanBekkum@tnw.tudelfi.nl, The Netherlands
blnstituut voor Technische Chemic, Universiteit van Amsterdam, The Netherlands

Zeolitic materials with Si to AI r a t i o s - with accent on zeolite B e t a - were tested in

esterification reactions. Hydrophilic materials proved to be inactive in the liquid phase
esterification of apolar substrates. This may be ascribed to strong adsorption of water formed.
More polar substrates are able to compete with water for the adsorption sites; thus, the
influence of the hydrophobicity of the catalyst on its activity becomes less pronounced. Such
influence is negligible on the activity of the catalysts in gas phase reactions. Here, the activity
is mainly dependent on the amount and the strength of acid sites.
310

2 8 - P - 1 5 - The influence of pore geometry on the alkylation of phenol with

methanol over zeolites
G. Moon, K.P. M611er, W. B6hringer and C.T. O'Connor
Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town,
Rondebosch, South Africa - gmoon@chemeng, uct.ac.za

The alkylation of phenol with methanol, in the liquid phase, has been investigated using
zeolites H-ZSM-5, H-beta, H-MCM-22, H-mordenite, H-USY as well as amorphous silica
alumina. At the low temperature of 200~ anisole was the major product over all the catalyst
investigated, second was cresols. H-Beta, H-USY, H-ZSM-5, H-mordenite and amorphous
silica alumina showed similar cresol distributions. H-MCM-22, which has the smallest pore
openings and the narrowest channel system among all zeolites studied, showed the highest
preference for p-cresol.

28-P-16 - Diffusion analysis of c u m e n e cracking over Z S M 5 using a jetioop

reactor
P. Schwan and K.P. M~ller
Department of Chemical Engineering, University of Cape Town, South Africa.

Cumene is cracked in a recycle reactor over commercial H-ZSM5 extrudates during a pulse
experiment. The results are compared to those obtained from steady state measurements. A
linear model for diffusion, adsorption and reaction rate is applied to reactants and products. In
contrast to literature it is shown that if the Thiele modulus is greater than 5, the system
becomes over parameterised. If additionally adsorption dynamics are negligible or not
measurable, only one lumped parameter can be extracted, which is the apparent reaction
constant found from steady state experiments. The pulse experiment of cumene is strongly
diffusion limited showing no adsorption dynamics of cumene. However, benzene adsorbed
strongly on the zeolite and could be used to extract transient model parameters.
 311

2 9 - New Approaches to Catalyst Preparation (Wednesday)

2 9 - P - 0 5 - Catalytic properties of MFI zincosilicates

s. Kowalac, E. Szymkowiak, I. Lehmann and G. Giordano*
Faculty of Chemistry, A. Mickiewicz University, Poznati, Poland. *Department of Chemical
Engineering, University of Calabria, Rende, Italy. skowalak@main:amu.edu.pl

A series of zincosilicates MFI was synthesized from the mixtures of even Zn/Si ratio and
various silicon sources. The properties of the resulting samples differed considerably regarding
their zinc content, the crystallite morphology and size and catalytic activity. The samples
modified with various cations (Ca, Cu, Zn, AI, H) showed some activity for 2-propanol
dehydration (no acetone was detected). The samples modified with AI cations showed the
highest activity. It is likely that part of A1 could attain the framework positions or facilitate a
generation of separated acidic OH groups. The lower activity of the H-forms could result from
the presence of hydrogen bonds between adjacent hydroxyls.

2 9 - P - 0 6 - Acidity characterization of dealuminated H-ZSM-5 zeolites by

isopropanol dehydration
C.S. Triantafillidis, V.A. Tsiatouras, A.G. Vlessidis and N.P. Evmiridis*
University of loannina, 45 110 Ioannina, nevmirid@cc.uoi.gr, Greece

A series of dealuminated ZSM-5 zeolites with various framework Si/A1 ratios were prepared by
different methods (HC1, ammonium hexafluorosilicate, steaming). The number of acid sites that
correspond to the high-temperature desorption peak of the ammonia-TPD spectra of all the
dealuminated samples is in 1:1 mole analogy to the framework A1 (FA1), irrespective the degree
and the type of dealumination method. The catalytic activity of the H-ZSM-5 zeolites for
isopropanol dehydration is linearly related to the number of acid sites that correspond to the
FAl-content (Brtinsted acidity). The Si-A1 amorphous phase that is formed in the high-
temperature steamed samples affects activity and induces different product selectivity for
propene and diisopropyl ether.

2 9 - P - 0 7 - A c i d i c Z r O 2 / S O 4 2 in mesoporous materials
Y. Sun, L. Zhu, H. Lu, D. Jiang, and F.-S. Xiao*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry & Department of Chemistry,
Jilin University, Changchun 130023, China,fsxiao@mail.jlu.edu.cn

ZrO2/SO42 supported in mesoporous hexagonal materials such as MCM-41 were prepared by

dispersion of ZrOC12.8HzO into the mesopores, followed by the hydrolysis and sulfation. They
have been characterized by X-ray diffraction, nitrogen adsorption isotherms, infrared
spectroscopy, and catalytic cracking of cumene and 1,3,5-triisopropylbenzene. The results show
that ZrO2/SO4 2" was successfully loaded into the inner pores of MCM-41 and the as-synthesized
catalyst showed favorable catalytic properties. The factors in the preparative process that
affected the final activity were discussed.
312

29-P-08- HMS catalysts containing transition metals or transition metal

complexes
z. Fu, D. Yin ,W. Zhao, Y. Chen, D. Yin, J. Guo, C. Xiong and Luxi Zhang
Institute of Fine Catalysis and Synthesis, Hunan Normal University, Changsha, 410081, P R
China

Copper, titanium, cobalt and iron substituted mesoporous silicas (Cu-, Ti-, Co-, and Fe-HMS)
were synthesized with dodecylamine surfactant as templating reagent. Three assembled
pathways were used to bond Ti tartrate complex over mesoporous silicas (HMS). The above
described catalysts were characterized by XRD and FT-IR, their metal loadings were measured
by chemical analysis method. In catalytic testing, Cu-HMS and especially Fe-HMS show the
best catalytic activity for hydroxylation of phenol with H202 in the presence of water. Ti-HMS
and especially Ti tartrate complex assembled HMS catalysts exhibit the best epoxidative activity
for catalyzing epoxidation of styrene with tert-butyl hydroperoxide.

29-P-09 - Synthesis of hydrophobic mesoporous molecular sieves by surface

modification
K.-K. Kang and H.-K. Rhee*
School of Chemical Engineering and Institute of Chemical Processes
Seoul National University, Seoul 151-742, hkrhee@snu.ac.kr, Korea

AlkyI-MCM-41 was prepared by surface modification technique. The modification was

conducted by chemically bonding an alkyl substituent to the surface of pure silica MCM-41 via
an organic reaction. In this work methyl and butyl groups were successfully introduced to
MCM-41.

29-P-10 - Guanidine catalysts supported on silica and micelle templated

silicas" new basic catalysts for organic chemistry
D.J. Macquarrie <a), D. Brunel <b), G. Renard Cb)and A.C. Blanc Cb)
aCentre for Clean Technology, Department of Chemistry, University of York, Heslington, York
-djml3@york.ac.uk, England, bLaboratoire r Mat6riaux Catalytiques et Catalyse en
Chimie Organique, ENSCM, UMR-5618-CNRS, Montpellier, France.

Supported guanidines are prepared via different routes, and their activity compared in two
reactions of interest. The base-catalysed epoxidation of electron-deficient alkenes is described,
and proceeds with excellent conversions and selectivities, when the surface is passivated by
silylation. The Linstead variation of the Knoevenagel condensation is also described, and gives
excellent conversions to partially decarboxylated products.
 313

29-P-11 - Texture of dealuminated mordenite catalysts modified with

cerium and catalytic properties in the isopropylation of biphenyl
M. Krfilik (a), J. Horniakova (a), D. Mravec (a), V. Jorik (a), M. Michvocik (a) and P. Moreau
a.Slovak University of Technology, Email." kralik@chtf.stuba.sk
b ENSCM, 8 rue de l 'Ecole Normale, 34296 Montpellier, Cedex 5, France

Formation of dispersed phase of ceria in the dealuminated mordenites modified with

ceria/cerium was registered by XRPD. Decrease in acidity at increased content of ceria may be
prescribed to ion-exchange of protons with cerium cations. An extra mesoporous structure of
ceria at higher metal loading (more than 10 wt. %) was found. On one side, a lower acidity and
narrower channels of catalysts resulted in the lower catalytic activity, on the other side higher
selectivity to the desired 4,4'-dialkylated biphenyl was achieved.

29-P-12 - Partially crystalline zeolitic material as novel solid acid catalysts

M. Liu, Z. Li, S. Lou, Q. Wang and S. Xiang*
Department of Chemistry, Nankai University, Tianjin 300071, shxiang@public.tpt.tj.cn, P. R.
China

Samples of zeolite beta varying in XRD crystallinity were prepared and used to catalyze the
reaction of methanol and isobutene to form MTBE (methyl tert-butyl ether). Considerable high
catalytic activity and selectivity to MTBE were maintained over partially crystalline zeolite
beta. The maximum conversion of isobutene over 30% crystalline sample was only slightly
lower than that of fully crystalline one, but the selectivity to MTBE was much higher. It was
evidenced further by TPDT method that the strong interaction between template and
aluminosilicate had occurred at the early stage of crystallization, the presence of X-ray
amorphous zeolitic species, the smaller crystallite and lowe~ Si/Ai ratio may account for the
observed catalytic characteristics.

29-P-13 - Novel mesoporous carbon as a catalyst support for Pt and Pd for

liquid phase hydrogenation reactions
W.S. Ahn a* , K.I. Min,a Y.M. Chung,b H.-K. Rhee,b S.H. JooC and R. Ryoo ~
School of Chemical Science and Engineering, Inha University, Inchon, Korea-
whasahn@inha.ac.kr; b School of Chemical Engineering and Institute of Chemical Processes,
Seoul National University, Kwanak-ku, Seoul, Korea, ~Department of Chemistry, Korea
Advanced Institute of Science and Technology, Taejon, Korea

Pt and Pd supported on a novel mes0porous carbon with regular pore diameter of 3 nm was
prepared, which showed significant improvement in liquid phase hydrogenation reactions.
314

29-P-14 - Investigation of catalytic activity of framework and extraframe-

work cobalt and manganese in MeAPO-34 prepared from fluoride medium
A. Ristid (a), G. Avgouropoulos (b), T. Ioannides (b) and V. Kau~i~ (a, c)
a National Institute of Chemistry, LjubO'ana, alenka.ristic@ki.si, Slovenia
b FORTH-ICE/HT, Patras, Greece
c University ofLjubljana, Slovenia

The surface acidity and catalytic activity of Co and Mg incorporated and impregnated in A1PO4-
34 were examined with ammonia adsorption, temperature-programmed desorption (TPD) and
with reaction of CO oxidation. Incorporation Of Co in the framework of A1PO4-34 leads to
enhancement of surface acidity and to formation of strong acid sites, while in MnAPO-34 this
effect is less pronounced. Samples with extraframework Co and Mg possess weak acid centres.
CoAPO-34 is one to two orders of magnitude more active than Co/A1PO4-34, while Me/A1PO4-
34 and MnAPO-34 are almost inactive in the reaction of CO oxidation.

2 9 - P - 1 5 - Preparation and characterization of bimetallic Pt-Zn catalysts

supported on zeolite NaX
J. Silvestre-Albero, F. Coloma, A. Sep61veda-Escribano and F. Rodriguez-Reinoso
Departamento de Quimica Inorg6nica. Universidad de Alicante, asepul@ua.es, Spain.

The effect of the zinc content and the reduction temperature on the characteristics and catalytic
properties of bimetallic Pt-Zn catalysts supported on zeolite NaX have been analyzed. Catalysts
have been characterized by TPR, XRD and XPS. Their catalytic behavior in the vapor phase
hydrogenation of crotonaldehyde (2-butenal) was studied after reduction a 632 and 773 K. The
presence of zinc causes a drastic decrease in catalytic activity, although the selectivity towards
the hydrogenation of the C=O bond is improved. Higher reduction temperature also improves
the catalytic selectivity. The formation of Pt-Zn alloyed phases upon reduction can explain this
catalytic behavior, although the contribution of a steric effect due to constraints creation in the
pores of the zeolite support can not be discarded.

29-P-16 - Surface modification of the uncalcined acid-made mesoporous silica

materials in a one-step procedure
H.-P. Lin(a), Y.-H. Liu(b), C.-P. Kao(a), S.-B. Liu(a) and C.-Y. Mou(b)*
a Academia Sinica,, Taipei, Taiwan,, hplin@gcn.net.tw
b National Taiwan University, TaipeL Taiwan 106. cymou@ms.cc.ntu.edu.tw

We investigate a new approach of surface functionalization of mesoporous silica. A direct

template displacement method has been developed to graft silane ligands onto the surface of
uncalcined mesoporous silica prepared from acidic condition. The organic surfactants can easily
be recovered and re-used as the templates of the mesoporous silicas. The high density of surface
silanol group in acid-synthesized silica leads to high loading of silanes. The mild reaction
condition and short reaction time lead to the preservation of morphology.
 315

29-P-17- Zirconia nanoparticles in ordered mesoporous material SBA-15

J. Sauer, S. Kaskel, M. Janicke and F. Schtith
Max-Planck-Institut fiir Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 M~ilheim an der
Ruhr, Germany, schueth@mpi-muelheim.mpg.de

Zirconia particles were incorporated in the ordered mesoporous material SBA-15 by

impregnating the calcined host material with zirconia precursor solutions and subsequent heat
treatments. The materials were characterized by XRD, Nz-Sorption, TEM and EDX. Different
analytical techniques indicate the incorporation of zirconia clusters inside the host structure with
particle sizes between 3 and 5 nm, and the existence of a small amount of zirconia particles
outside the host structure. According to the XRD pattern, the SBA-15 support stabilizes the
tetragonal phase and the particle size up to a temperature of 1373 K. The materials were
additionally sulfated by standard methods and showed in contrast to sulfated bulk zirconia a
lower catalytic activity in the n-butane isomerization.

29-P-18 - Preparation using ozone treatment, characterization and

application of isomorphously substituted Ti-, V- and Zr-MCM-41 catalysts
D. M~hn a, J. Halfisz a, E. Meretei a, Z. Kdnya a, A. Fonseca b, J. B.Nagy b and I. Kiricsi a
Department of Applied and Environmental Chemistry, University of Szeged
aRerrich tdr 1., H-6720 Szeged, Hungary, halas@chem.u-szeged.hu
bLaboratoire de RMN, Facultds Univer. Notre-Dame de la Paix, B-5000 Namur, Belgium
Si-, Ti-, V- and Zr-MCM-41 catalyst samples were synthesized, and two different methods were
used for removing the template from the as synthesized samples, either by the usual process at
high tempereture in the presence of O2, or oxidation at 150 ~ with ozone. After the physical
characterization (X-ray diffraction, 298i MAS NMR and IR spectroscopy, BET method) of the
samples, oxidation of cyclohexane, cyclohexene and vinyl cyclohexene with H202 as test
reactions were carried out. The catalytic activities and selectivities of the samples are different.
It has been shown that the activity and selectivity of these modified MCM-41 catalysts in the
oxidation reactions greatly depend on the method used for removing of template.

29-P-19- Preparation and catalytic evaluation of [Ga]MCM-58 and of MCM-

58-type catalysts with different aluminum contents
S. Ernst, M. Hartmann, T. Hecht and A. Weber
Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany,
sernst@rhrk, uni-kl, de

The large pore zeolite MCM-58 has been synthesized with nsi/nAi-ratios varying from 15 to 35
and also in its new gallosilicate form [Ga]MCM-58 with a nsi/nca ratio of 15. The catalytic
properties of these materials were characterized using the disproportionation of ethylbenzene
and the hydroconversion of n-decane as catalytic tests. MCM-58 and Pt-loaded MCM-58,
respectively, proved to be highly active catalysts in these reactions.
316

29-P-20- IR study on the reaction path of methanol decomposition over basic

zeolites
M. Rep (a), J.G. van Ommen (a), L. Lefferts (a) and J.A. Lercher (b)
a Faculty of Chemical Technology, University of Twente, Enschede, The Netherlands
b Institutfiir Technische Chemic, Technische Universitcit Mfinchen, Garching, Germany
Johannes. Lercher@ch. tum. de

On the basis of an infrared study of the adsorption and reaction of methanol and dimethyl ether
over alkali metal cation exchanged zeolites, we propose a reaction mechanism for the
decomposition of methanol over alkali cation exchanged zeolites. Additionally, formaldehyde
adsorption is performed on these molecular sieves and attempts will be made to correlate its
adsorption structure with the surface reactivity.

29-P-21 - Synthesis and characterization of highly ordered mono- and

bimetallic substituted MCM-41 molecular sieves and their catalytic
properties in selective oxidation of hydrocarbons
V. P~.rvulescu (a), C. D~.scalescu (a) and B.L. Su (b)
a Institute of Physical Chemistry, Bucharest, Romania; b The University of Namur (FUNDP),
bao-lian.su@fundp.ac.be, Belgium.
The mono- and bimetallic substituted MCM-41 catalysts with cobalt, vanadium or lanthanum
have been prepared by direct synthesis or impregnation and characterized by various
techniques, such as: XRD, Nz adsorption-desorption, SEM, TEM and TGA. The catalytic
activity in the selective oxidation of styrene with H202 has been evaluated. Adsorption of
benzene and ammonia on the mono- and bimetallic mesoporous molecular sieves with cobalt
and vanadium has been studied by IR spectroscopy and the results have been correlated with
their catalytic properties and the characteristics of the structure. Co-incorporated catalysts
prepared by direct synthesis show to be very active and selective.

29-P-22 - On the direct synthesis of noble metal cluster containing MCM-41

using surfactant stabilised metal nanoparticles
J.P.M. Niederer a, A.B.J. Arnolda,W.F. Hoelderich a, B. Spliethofb, B. Tesche b, M. Reetz b and H.
Boenneman b
aUniversity of Technology R WTH Aachen, Germany- Hoelderich@R WTH-Aachen.de
bMax-Planck-Institute for Coal Research, Muelheim, Germany
[Me]x-MCM-41 containing nanosized particles of platinum, palladium, rhodium, ruthenium and
iridium were directly synthesised from surfactant stabilised spherical metal nanoparticles in the
synthesis gel, and characterised with XRD, ICP-AES, TG/DSC, TEM, nitrogen physisorption
and carbonmonoxide chemisorption, and 29Si MAS NMR. During the synthesis some
agglomeration of the particles took place, but the metal particles were present inside the pore
system of MCM-41. The materials were active and selective catalysts in the hydrogenation of
cyclic olefins such as cyclohexene, cyclooctene, cyclododecene and norbornene.
 317

29-P-23 - M i c r o p o r o u s zincophosphates as solid base catalysts

L.A. Garcia-Serranoa; T. Blascob; J. P6rez-Pariente a and E. Sastre a
alnstituto de Cat6lisis y Petroleoquimica, C.S.I.C. - esastre@icp, csic. es, Madrid, Spain
blnstituto de Tecnologia Quimica, UP V-CSIC, Valencia, Spain
Samples of tridimensional microporous zinc phosphates with fully connected framework with
structures type FAU and CZP have been prepared. The influence of some synthesis parameters
on the nature of the crystalline phases obtained, such as crystallization time and temperature,
concentration of the different reactives or pH, are discussed. Physicochemical characterization
of the pure samples has been performed by different techniques: ICP, XRD, 13C and 31p MAS-
NMR, TG, TG-MS, in-situ thermal XRD analysis and SEM. These materials were tested in the
Knoevenagel condensation of different esters and benzaldehyde. They have demonstrated a
good selectivity and a higher activity than the basic zeolites previously described in the
literature with these reactions.

29-P-24 - Zirconium containing A I - M C M - 4 1 - synthesis, characterisation and

catalytic p e r f o r m a n c e in 1-hexene isomerisation
I. Eswaramoorthi a, V. Sundaramurthy a and N. Lingappan b
aDepartment of Chemistry, Anna University, Chennai. India - eswaramoorthi@lycos.com;
bScience and Humanities Division, Madras Institute of Technology, Chennai. India

Using the molar gel composition of SiO2:0.12 CTAB: x ZrO2: 0.01A1203: 0.19Na20: 35H20,
where x = 0.02-0.04, zirconium containing AI-MCM-41 samples were synthesised and
characterised by XRD, DRS, BET surface area, FT-IR and pyridine absorption studies. The
increase of d-spaceing with increase of Zr content indicates the incorporation of Zr in the
framework. In DRS, an absorption band around 210 nm confirms the presence of Zr (IV) in the
tetrahedral co-ordination. The pyridine adsorbed FT-IR studies shows that the increasing
incorporation of Zr in AI-MCM-41 increases the acidity of Zr-A1-MCM-41. Zirconium free AI-
MCM-41 and zirconium impregnated AI-MCM-41 show lower 1-hexene conversion and lower
selectivity of skeletal isomerised products than that of Zr-A1-MCM-41 catalysts. This confirms
the presence of Zr in the framework of MCM-41 and accounts for the increase in acidity.

29-P-25 - Iron containing zeolites and m e s o p o r o u s silica as sulfuric acid

catalyst
A. Wingen (a), W. Schmidt (a), F. SchOth (a), A.C. Wie (b), C.N. Liao (b) and K.J. Chao (b)
(a) MPI fiir Kohlenforschung, Mfilheim, Germany, schueth@mpi-muelheim.mpg.de
(b) National Tsing-Hua University, Taiwan - kjchao@mx, nthu. edu. tw

Iron modified zeolites and ordered mesoporous oxides have been studied as catalysts for the
sulfur dioxide oxidation in sulfur rich gases. Both zeolitic materials and mesoporous oxides
show very good activity in this reaction. Other than solid state or incipient wetness loaded
MCM-41 materials, the zeolites do not show an initial loss of activity. However, they loose
activity upon prolonged exposure to reaction conditions around 700~ The zeolitic samples
were analyzed via X-ray absorption spectroscopy, and the deactivation could be related to
removal of iron from framework sites to result in the formation of hematite-like species. If the
iron can be stabilized in the framework, these materials could be an interesting alternative to
other iron based catalysts for the commercial application in sulfur rich gases.
318

29-P-26 - Deep-bed dealumination of ZSM-5 zeolites. Changes in structure

and catalytic activity
P. Hudec, A. Smiegkovfi, Z. 2;idek, L. Sabo and B. Liptfikovfi
Department of Petroleum, Faculty of Chemical Technology, Slovak University of Technology,
Radlinskdho 9, Bratislava, Slovak Republic- phudec@chelin.chtfstuba.sk

Deep-bed dealumination of ZSM-5 zeolites with Si/A1 ratio of 15 and 21 at 560 and 780~
caused significantly changes in shape of adsorption isotherms t-plots. Low-pressure hystheresis
loop on adsorption isotherms and corresponding two-linear region on t-plots indicate the
framework dealumination to Si/Al>45. Total acidity of dealuminated samples was greater than
expected on the base of Si/AI framework ratio, confirming significant role of EFAL as Lewis
acid sites. TON of n-hexane cracking for deep-bed treated samples considerably increased,
documenting synergetic effect of the action of protic and aprotic acid sites.

29-P-27 - Fabrication of honeycomb structures with powder MCM-48 silica

Y.-S. Ahn (a), M.-H. Han (a), S. Jun (b) and R. Ryoo (b)
a Functional Materials Research Team, Korea Institute of Energy Research, Taejon, Korea-
ysahn@kier.re.kr; b Department of Chemistry (School of Molecular Science-BK21), Korea
Advanced Institute of Science and Technology, Taejon, Korea

Macroscopic honeycomb structures were fabricated with powder MCM-48 silicas by an

extrusion process using bentonite or pseudobohemite as binder. The products were
characterized by the X-ray diffraction patterns, specific BET surface areas and compressive
strengths after sintered at temperatures as high as 750~ The fabrication process for MCM-48
has been investigated thereby. The result shows that stabilities of the raw MCM-48 materials
are the bottleneck limiting the fabrication process. High-quality honeycombs retaining the well-
ordered mesoporous structure were obtained when MCM-48 was stabilized by the post-
synthesis hydrothermal treatments before the fabrication. However, without the post-synthesis
treatment, the MCM-48 structure was almost lost during the fabrication process.

29-P-28 - Acidic hybrid catalysts prepared by grafting large-pore silica M41S

materials
B. Lindlar (a), M. Ltichinger (a), M. Haouas (a), A. Kogelbauer (b) and R. Prins (a)
a Laboratory of Technical Chemistry, Swiss Federal Institute of Technology (ETH),
prins@tech, chem. ethz. ch, Switzerland
b Department of Chemical Engineering, Imperial College of STM, United Kingdom

Large-pore mesoporous materials with enhanced textural characteristics (surface area, pore size
distribution and pore volume) were obtained from a pH-adjusted synthesis with a surfactant
mixture of hexadecyl- and dodecyltrimethylammonium salts in combination with mesitylene-
swelling. This material was grafted with phenyl-alkoxysilanes and subsequently sulphonated.
Nitrogen adsorption and multinuclear MAS NMR were performed to monitor the different
synthesis steps.
 319

29-P-29 - Preparation of tungsten carbide supported on (AI-)FSM-16 and its

catalytic activity
M. Nagai, K. Kunieda, S. Izuhal and S. Omi
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture
and Technology, Koganei, Tokyo, Japan - mnagai@cc.tuat.ac.jp
The tungsten carbides on FSM-16 were prepared in carburizing of WO3/FSM-16 with 20%
CH4/H2 and characterized using nitrogen adsorption, XRD, TEM, and NMR. The relationship
between the surface properties and the catalytic activity of tungsten carbides on FSM-16 in
cyclohexene hydrogenolysis at 250~ was discussed.

29-P-30 - Ti-MCM-48 with different titanium loading: synthesis,

spectroscopic characterization and catalytic activity
V. Dellaroccaa; M.L. Pefiab; F. Reyb*; A. Cormab; S. Coluccia a and L. Marchese c
aUniversitgt di Torino, Torino, Italy," bUniversidad Polit6cnica de Valencia, Spain.
frey@itq.upv.es; c Universith del Piamonte Orientale 'A. Avogadro ', Alessandria, Italy.
A series of Ti-MCM-48 materials with different Ti contents has been synthesized and
characterized in the as-prepared and calcined states. Also, the catalytic activity for the
epoxidation of cyclohexene with tertbutylhydroperoxide on the different Ti-MCM-48 samples
was tested. From this study, it has been possible to establishe the dispersion of Ti(IV) sites on
the silica surface by means of DR-UV-Vis spectroscopy. These characterization results have
been correlated with the final catalytic activity found for these mesoporous catalysts.

29-P-31 - Comparison of 3-aminopropyisilane linked to MCM-41 and HMS

type silicas synthesised under biphasic and monophasic conditions
D.J. Macquarrie,a M. Rocchia,b B. Onida,b E. Garrone,b P. Lentz,c J. B.Nagyc, D. Brunel d, A.C.
Blanc d and F. Fajula d
~University of YORK, England. djm13@york.ac.uk; bPolitecnico di TORINO, Italy," CFacult~s
Universitaires Notre Dame de la Paix, NAMUR, Belgium; dCNRS-ENSCM, MONTPELLIER,
France.

Functionalised mesoporous silicas prepared by either grafting by silylation of MCM-41 or by

self-assembly co-condensation of organically functionalised silica precursors and silica
precursor (RO)4Si in presence of non-ionic surfactants feature different properties. Materials
were characterised by N2 sorption isotherms, FTIR and MAS-NMR. Imine formation during
contacting the different samples with probes such as acetone and benzaldehyde demonstrated
different environments of the anchored amine groups.
320

3 0 - E n v i r o n m e n t a l C a t a l y s i s (Wednesday)

3 0 - P - 0 6 - Effect o f the r e d u c t a n t n a t u r e on the catalytic r e m o v a l o f N 2 0 on

a Fe-zeolite-beta catalyst
G. Delahay (a), M. Mauvezin (a), B. Coq (a) and S. Kieger (b)
(a) Ecole Nationale de Chimie de Montpellier, delahay@cit.enscm.fr, France.
(b) Grande Paroisse, Paris-La D~fense, France
A Fe(97)-BEA catalyst, prepared by conventional ion-exchange procedure and calcined at
773 K, almost contains iron-binuclear-oxo-species in charge compensation of the BEA
structure. The re-oxidation of iron(II) species by N20 leads to new oxo-species reducible at
lower temperature than the dimer species. Among H2, CO, propene and NH3 in the reduction
of N20, CO, propene and NH3 are selective reductants. For these three reductants a similar
light-off temperature of ca 638 K is obtained in the selective catalytic reduction of N20. It
should be pointed out that CO is efficient from 473 K but its activity is limited by the re-
oxidation of Fe II to Fe III species by N20.

3 0 - P - 0 7 - D e g r a d a t i o n of N - n i t r o s a m i n e s on zeolites
J.H. Zhu*, B. Shen, Y. Xu, J. Xue, L.L. Ma and Q.H. Xu
Department of Chemistry, Nanjing University, Nanjing 210093, China

Degradation of N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) on

zeolites was investigated by use of temperature programmed surface reaction and GC-MS.
Activation of zeolite had almost no effect on TPSR of NPYR, because zeolite could selectively
adsorb N-nitrosamines. Cyano derivative appeared as the main product on NaZSM-5 or NaY
zeolites similar to that in pyrolysis while DNA became the dominant one on HZSM-5 or HY.
On the latter the Br6nsted acid sites probably play the role of main catalytic sites, hence N-
nitrosamines degrades to amines on BrOnsted acid sites while on the former N-nitrosamines
might decompose through radical reaction process, similar as pyrolysis. No desorption of the
N-nitrosamines occurs on zeolites even at elevated temperature, and protonation of zeolite

3 0 - P - 0 8 - Z r O 2 / N a Y : A n e w m a t e r i a l for r e m o v a l of N - n i t r o s a m i n e s
pollution
J.H. Zhu*, J.R. Xia, Ying Wang, G. Xie, J. Xue and Y. Chun
Department of Chemistry, Nanjing University, Nanjing 210093, China

Zirconia can be coated in NaY by microwave radiation and the content of ZrO2 was about 10 wt
%. Loading ZrO2 generated some basic sites on the surface of zeolite NaY so that more N-
nitrosopyrrolidine (NPYR) can be degraded at lower temperature than that on the parent zeolite.
When the carrier gas in the degradation reaction was changed from nitrogen to air, the maximum
concentration of NOx formed on ZrO2/NaY was dramatically decreased below 10 lamol/g though
most of the N-nitrosamines were confirmed to be degraded instead adsorbed on ZrO2/NaY.
Nitrogen is formed in degradation of NPYR as the main product over the ZrOa/NaY composite,
resulting from the special catalytic function of dispersed ZrO2. With high activity for
decomposition of N-nitrosamines and suppression for formation of NOx, ZrOz/NaY will be a
functional material to remove N-nitrosamines pollution from environment.
 321

3 0 - P - 0 9 - T o t a l oxidation of n-pentane, cyclohexane and their mixtures on

the Cu-containing Z S M - 5 zeolites
M.A. Botavina, N.V. Nekrasov and S.L. Kiperman
N.D.Zelinsky Institute of Organic Chemistry, Rus.Acad.Sci., Russia, botavina@ioc.ac.ru

The kinetics of total oxidation of n-pentane, cyclohexane and their mixtures on Cu-containing
ZSM-5 was studied to analyse possible effects of the critical size of reactant molecule on
these processes. Oxidation of n-CsHl2 seems to proceed in kinetic region whereas C6H12
conversion is affected by intracrystalline diffusion of reactants. This conclusion is in a good
accordance with hindrances for the mobility of investigated molecules. The oxidation of
normal pentane takes place on all catalysts surface and its rate does not change in the
presence of cyclohexane due to its low diffusivity, while cyclohexane conversion decreased
significantly in the presence of normal pentane. This investigation has shown a fruitfulness of
the kinetic approach to elucidation of diffusion effects in zeolite catalysis.

30-P-10 - Modified natural zeolite in catalytic clearing of exhaust and

ejected gases from nitric and carbon oxides.
L. Akhalbedashvili and S. Sidamonidze
Tbilisi State University, 380028, 3 Ave. Chavchavadze, e-mail: aklali@yahoo.com., Tbilisi,
Georgia

A catalyst for joint conversion of nitric and carbon oxides was developed on the basis of
natural zeolite-clinoptilolite from Georgian deposit. Catalyst making is accomplished with
copper cations introduced by ion-exchange following previous decationation. The high
activity in reduction of NO• by CH4, NH3, H2 and especially CO is explained by the presence
of copper-ions in the zeolite structure. The conversiom degree of (NO• reaction reaches
95-98% above 400~ This catalyst has the following advantages: cheapness and availability
of tuff, high zeolite content, simple making, low temperature of nitric and carbon oxides
conversion (150-500~ possibility of regeneration.

30-P-11 - Selective catalytic reduction of N20 with light alkanes over

different Fe-zeolite catalysts
S. Kameoka(a), S. Tanaka(a), K. Kita(a), T. Nobukawa(a), S. Ito(a), T. Miyadera(b) and K.
Kunimori(a)
a Institute of Materials Science, University ofTsukuba, kameoka@ims.tsukuba.ac.jp, Japan.
b National Institute for Resources and Environment, Tsukuba, Ibaraki, Japan
Fe ion-exchanged zeolite catalysts (Fe-zeolite; Fe-BEA was the most active) perform
effectively SCR of N20 with light alkanes (i.e., CH4, C2H6 and C3H8) even in the presence of
excess oxygen. CH4 reacted selectively with N20 even in the presence of excess 02 (> 250
~ 4N20 + CH4 ~ 4N2 + COz + 2H20), while the reaction of C2H6 and C3H8 with O2 was
drastically enhanced by the presence of N20. It was found that N20 played an important role
in the activation of alkanes at an initial step. On the basis of these results, we proposed a
mechanism in the SCR of N20 with light alkanes over Fe-BEA catalyst.
322

3 0 - P - 1 2 - Selective catalytic reduction o f NOx by NH3 over Mn supported

MCM-41 mesoporous materials
E.E. Iojoiu (a), P. Onu (a), S. Schmitzer (b) and W. Weisweiler (b)
a Technical University eGh.Asachb), Faculty of Industrial Chemistry, Bvd. D. Mangeron
Nr. 71, 6600 lasi, Romania, eiojoiu.@ch.tuiasi.ro, b University of Karlsruhe (TH), Institute of
Chemical Technology, Kaiserstr. 12, D-76128 Karlsruhe, Germany

Mn-MCM-41 catalysts were prepared and then tested using the selective catalytic reduction of
NOx by NH3. The influence of the support (siliceous or aluminosilicate MCM-41) as well as
the composition of the gas feed were investigated with respect to the catalytic activity. The
pure siliceous MCM-41 seems to offer much better catalytic properties to the catalyst. The
presence of a mixture of NO and NO2 in the gas feed causes an increase of SCR activity. The
catalysts analysed exhibit fairly high NO• conversion at temperatures above 250~

30-P-13 - Transition metal exchanged-MCM-22 catalysts for N20 decom-

position
A.J.S. Mascarenhas (a), H.M.C. Andrade (b) and H.O. Pastore (a)
a Grupo de Peneiras Moleculares Micro- e Mesoporosas, Instituto de Quimica, Universidade
Estadual de Campinas, lolly@iqm, unicamp, br, Campinas, Brazil.
b Instituto de Quimica, Universidade Federal da Bahia, Salvador, Brazil.

Transition metal exchanged-MCM-22 catalysts (Fe, Co and Cu) have shown high activity on
the decomposition of nitrous oxide (N20), comparable to the well-known ZSM-5 catalysts.
Cu-MCM-22 is highly active, but suffers inhibition by excess oxygen. Co-MCM-22 is not as
active as Co-ZSM-5 due to the formation of CoO, but is nearly insensitive to 02. Fe-MCM-
22 presents an intermediate behavior, and shows low tolerance to oxygen. Activities and
oxygen tolerance were explained on the basis of the nature of the active species formed in
each case.

30-P-14 - The NO and N 2 0 selective catalytic reduction on copper and iron

containing ZSM-5 catalysts: a comparative study
G. Fierro, G. Ferraris, M. Inversi, M. Lo Jacono and G. Moretti
Centro CNR SACSO, c/o Dipartimento di Chimica, Universith "La Sapienza", Roma,
giuseppe.fierro@uniroma l. it, Italy

In this work we report a comparison between the activities of H-ZSM-5, H-[Fe]-ZSM-5,

Cu-[Fe]-ZSM-5, Cu-ZSM-5 and Fe-ZSM-5 catalysts in the selective catalytic reduction
(SCR) of NO and N20 by C3H8 in the presence of oxygen. The results show that for the NO
reduction the order of activity is Cu-[Fe]-ZSM-5 ~ Cu-ZSM-5 > Fe-ZSM-5 > H-[Fe]-ZSM-5
H-ZSM-5. For the N20 reduction, the order of activity changed as follows: H-[Fe]-ZSM-5
> Fe-ZSM-5 > Cu-[Fe]-ZSM-5 -~ Cu-ZSM-5 > H-ZSM-5. Catalytic results for the N20
decomposition are also presented.
 323

3 0 - P - 1 5 - A comparison of different preparation methods of indium-

modified zeolites as catalysts for the selective reduction of NO
C. Schmidt (a), T. Sowade (a), F.-W. Schtitze (b), H. Berndt (b) and W. Gr~inert (a)
aLehrstuhl Technische Chemie, Ruhr-Universitcit Bochum, Bochum, Germany
blnstitut fiAr Angewandte Chemic Berlin-Adlershof e. V., Berlin, Germany

The influence of the preparation method of In-modified zeolite catalysts for the SCR of NOx
by methane on the structure of In species formed and the catalytic activity has been studied.
The structure of the catalysts has been investigated by XPS, ISS, XAFS, FTIR, electron
microscopy and TPR. Dependent on the preparation, indium may occupy zeolite cation sites
or form intra- and extra-zeolite oxide aggregates. It was found that indium ions at cation sites
provide a low-temperature SCR activity while clustered species are active at high
temperatures.

30-P-16 - Local structures of Ag+/ZSM-5 catalysts and their photocatalytic

reactivity for the decomposition of N20 into N2 and 02
M. Matsuoka, W.-S. Ju, and M. Anpo*
Department of Applied Chemistry, Graduate School of Engineering
Osaka Prefecture University, anpo@ok, chem. osakafu-u.ac.jp, Japan

Ag+/ZSM-5 catalysts were prepared by an ion-exchange method. In-situ characterization of

Ag+/ZSM-5 catalysts by means of UV-Vis, photoluminescence and XAFS spectroscopies
revealed that Ag § ions are anchored within the pore of ZSM-5 zeolite having a highly
dispersed and isolated state. In-situ FT-IR and UV-Vis investigations showed that N20
molecules reversibly adsorb onto the isolated Ag+ ions to form Ag+-N20 complexes. UV-
irradiation of the Ag+/ZSM-5 catalysts in the presence of N20 led to the photocatalytic
decomposition of N20 into N2 and 02 at 298 K. Investigations of the effective wavelengths of
the irradiated light for the reaction revealed that the photoexcitation of the absorption band
due to the Ag+-N20 complexes plays a significant role in this reaction.

30-P-17- One stage catalytic cracking of plastic waste on zeolitic catalysts

K. Gobin, D. Koumantaropoulos and G. Manos
Department of ChemicaI Engineering, University College London, g.manos@ucl.ac.uk

The catalytic degradation of polyethylene to hydrocarbon fuel was studied over zeolites, US-Y,
ZSM-5 and mixture of them (50% each), as well as zeolite-containing cracking catalysts. The
presence of ZSM-5 increased the gas formation. The cracking catalysts were able to degrade
polyethylene completely, resulting in high levels of yield to liquid products. The boiling point
distributions of the liquid fractions formed over the cracking catalysts were similar to this formed
over US-Y. The majority of the liquid products had boiling points below 500K, confirming the
high quality of the liquid hydrocarbons produced by the method. The study has demonstrated the
suitability of commercial cracking catalysts for the cracking of plastic waste and the potential of
plastic waste to be co-fed into existing refinery FCC units.
324

30-P-18 - Analysis of the deep catalytic oxidation of binary C V O C s

mixtures over H-ZSM-5 zeolite
R. L6pez-Fonseca, J.I. Guti6rrez-Ortiz, A. Aranzabal and J.R. Gonzfilez-Velasco*
Department of Chemical Engineering, Faculty of Sciences, Universidad del Pais Vasco/EHU,
P.O. Box 644, E-48080 Bilbao, Spain. E-mail." iqpgovej@lg.ehu.es

The oxidative decomposition of binary mixtures of chlorinated VOCs (1,2-dichloroethane,

dichloromethane and trichloroethylene) over H-ZSM-5 zeolite has been evaluated. The ease
of destruction decreased in the order: DCE>DCM>TCE. The main oxidation products were
CO, CO2, HC1 and C12. Some other chlorinated by-products were detected as well (vinyl
chloride, methyl chloride and tetrachloroethylene). The destruction of chlorinated mixtures
induced an inhibition of the oxidation of each CVOC. An important decrease in the formation
of intermediates was noticed and HC1 selectivity was largely improved.

30-P-19 - Solid state MAS N M R studies of zeolites and alumina reacted

with chlorofluorocarbons (CCI2F2, CHCIF2)
I. Hannus (a), Z. K6nya (a), P. Lentz (b), J. B.Nagy (b) and I. Kiricsi (a)
a Department of Applied and Environmental Chemistry, University of Szeged,
hannus@chem, u-szeged, hu, Hungary
b Laboratoire de RMN, Facultds Universitaires Notre-Dame de la Paix, Belgium

Multinuclear Magnetic Resonance of both the adsorbed and the solid phase allowed us to
follow the reaction of various chlorofluorocarbons (CC12F2 and CHC1F2) on NaY, HZSM-5
zeolites and 7-A1203. The intermediates and the final products were identified by 13C and 19F
NMR spectroscopy. At the same time the kinetics of the reactions could be determined at
various temperatures. Over alumina dismutation reactions take place as primary steps caused
by the Lewis acid sites. 29Si, 27A1 and 23Na NMR measurements were quite useful to identify
the solid reaction products.

30-P-20 - Zeolite-containing photocatalysts for treatment of waste-water

from petroleum refineries
A.K. Aboul-Gheit and S.M. Ahmed
Egyptian Petroleum Research Institute, Nasr City P.O. Box 9540, Cairo 11787, Egypt.
E Mail aboul-gheit@usa.net

Photocatalytic degradation of petroleum representative hydrocarbons (o-xylene > decaline >

n-hexadecane) was investigated using metal-phthalocyanines (Pcs) combined with Na-zeolites
(1:1) as photocatalysts. This combination was found significantly synergistic, n-Hexane
photodegradation was examined using : a) CuPc mixed with Na-mordenite, Na-Y, Na-Beta or
Na-ZSM-5, b) CuPc mixed with Na-, H- and dealuminated-mordenite, and c) Pcs having
different central oxidative metals: Ce, Co, Mn, Fe, Cr or Cu, mixed with Na-Beta zeolite.
Crude oil photodegradation was also examined using the catalysts of item c). The illumination
period for pure hydrocarbons testing was 15 minutes, whereas for crude oil was one week.
Kinetics using Langmuir-Hinshelwood models was successful.
 325

30-P-21 - Autoreduction of Cu 2+ species in Cu-ZSM-5 catalysts studied by

diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy,
thermogravimetry and elemental analysis
G. Moretti a, G. Ferraris a and P. Galli b
a Centro CNR "SACSO", bDipartimento di Chimica,
Universitdt "La Sapienza", ~uliano.moretti@uniromal.it, Roma- Italy

The autoreduction process of Cu 2+ species in Cu-ZSM-5 catalysts, with Si/A1 = 80 and copper
exchange levels 81 and 536 %, was studied by means of spectroscopic (in-situ diffuse
reflectance spectroscopy and X-ray photoelectron spectroscopy) and chemical methods
(thermogravimetry in N2, elemental analysis, adsorption-desorption of N2 at 77 K and
adsorption of N2 at 273 K). It appears that on the fresh catalysts (treated in air at 383 K) the
majority of Cu 2+ species may be reduced to Cu +, under vacuum or in a flow of inert gas at
high temperature, by means of the carbonaceous deposits left in the ZSM-5 matrix due to the
incomplete burning of the organic template used in the zeolite synthesis.

30-P-22 - Performance of bi-and tri-metallic mordenite catalysts for the

lean SCR of NOx by methane
F. Bustamante (a), P. Avila (b) and C. Montes de Correa (a)
a Dept. of Chemical Engineering, Universidad de Antioquia, cmontes@catios.udea.edu.co
b Instituto de Catdlisis y Petroleoquimica, CSIC 28049 Madrid. Espagta
The lean NOx reduction by CH4 in the presence of 10-15% water vapor was studied on bi-
and tri-metallic powder catalysts containing two or three of the following species: Co, Pd, Ce,
and Pt on HMOR. A cooperative effect in the Pd-Co, Pd-Ce, Pd-Ce-Co and Pd-Pt-Ce systems
was found for CH4-SCR under wet conditions. Pd-Ce/HMOR and Pd-Ce/Co-HMOR catalysts
were more tolerant to the coexistence of H20 and SO2 in the gas feed than Pd/Co-HMOR. Co,
Pd and Ce species were impregnated on ceramic monoliths washcoated with mordenite. The
results of NOx reduction were different for the monolithic and powdered catalysts. However,
a similar trend in the CH4-SCR activity of both catalyst types was observed.

30-P-23 - Total oxidation of volatile organic compounds - catalytic oxidation

of toluene over CuY zeolites
A.P. Antunes (a), J.M. Silva (b), M.F. Ribeiro (a), F.R. Ribeiro (a), P. Magnoux (c) and M.
Guisnet (c)
a lnstituto Superior T~cnico, DEQ, Lisboa, Portugal, e-mail.'filipa.ribeiro@ist.utl.pt
b Instituto Superior Engenharia de Lisboa, DEQ, Lisboa, Portugal
c Universit6 de Poitiers, UMR 6503, 40 Av. Recteur Pineau, 86022 Poitiers, France
Transformation of toluene in low concentration (800 ppm) in air over CuY zeolites containing
different copper contents and Si/A1 ratios was studied at temperatures between 150 and
500~ It was found that total oxidation is promoted on non dealuminated catalysts and
depends on the copper content. The most active catalysts correspond to the catalysts with Cu
contents that are close to the complete exchange of the zeolite. The presence of sodium
cocations in CuY zeolites increases their combustion efficiency, by improving the dispersion
of ionic copper species and preventing the formation of CuO clusters.
326

30-P-24 - Study on relationship between the local structures of Ti-HMS

mesoporous molecular sieves and their photocatalytic reactivity for the
decomposition of NO into N2 and 02
J. Zhang, a B. He, a M. Matsuoka, b H. Yamashita b and M. Anpob
a Institute of Fine Chemicals, East China University of Science and Technology, 7, China,"
jinlongzhang@hotmail.com; b Dept. of Applied Chemistry, Graduate School of Engineering
Osaka Prefecture University, 1-1, Gakuen-cho, Saka, Japan

Titanium oxide species included within the framework of mesoporous zeolites (Ti-HMS)
were studied using nitrogen adsorption/desorption. These mesoporous materials exhibited
high and unique photocatalytic reactivity for the direct decomposition of NO into N2, N20
and 02 at 275K.

30-P-25 - Influence of synergistic effects on the selective catalytic reduction

of NOx with CnHm over zeolites
S.N. Orlik and V.L. Struzhko
L. V. Pisarzhevsky Institute of Physical Chemistry of NAS of Ukraine
03039, Pr.Nauki, 31, Kiev, Ukraine, fax: (044) 265 62 16; e-mail: ipcukr@sovam.com

A synergistic effect leading to the increased catalyst activity and selectivity in selective
catalytic reduction (SCR) of NO with methane or propane-butane mixtures was found when
cobalt, calcium and lanthanum cations were introduced into the protic MFI-type zeolite. This
non-additive increase of the zeolite activity is attributed to increased concentration of the
BrOnsted acid sites and their defined location as result of interaction between those and
cations (Co, Ca, La). Activation of the hydrocarbon reductant occurs at these centers. Doping
the H-forms of zeolites (pentasils and mordenites) with alkaline earth metal and Mg cations
considerably increased the activity of these catalysts and their stability to sulfur oxides.

30-P-26 - Catalytic properties of Fe-Co double layered hydroxides

synthesised with beta zeolite for toluene oxidation
J. Carpentier, S. Siffert, J.F. Lamonier and A. Abouka'/s
Laboratoire de Catalyse et Environnement, E.A. 2598, Universit~ du Littoral- C6te d'Opale,
MREID, 145, avenue M. Schumann, 59140 Dunkerque, France, siffert@univ-littoral.fr.
Fe-Co layered double hydroxides with Co/Fe ratios of 2 and 3 were prepared with or without
the presence of Beta zeolite and their catalytic potential was tested in toluene total oxidation.
These calcined solids synthesised with [3-zeolite were less active and selective than those
prepared without zeolite. However, a mechanical mixture of 1/3 Fe,Co-LDH (Co/Fe - 3) +
2/3 Na[3-zeolite presented higher catalytic performance which could be explain by a
synergetic effect of the both Fe,Co-double oxide and [3-zeolite. The mechanism could undergo
through a spillover of the adsorbed toluene from zeolite, which has a high toluene
storage/release capacity, to the Fe,Co double Oxide, which is highly performant for this
oxidation.
 327

30-P-27 - Selective catalytic reduction of NO over Fe z e o l i t e s - catalytic and

i n - s i t u - D R I F T S studies
F. Heinrich, E. L6ffler and W. Grtinert
Lehrstuhl Technische Chemie, Ruhr-UniversitOt Bochum, P. O. Box 102148,
D-44 780 Bochum, Germany

An in-situ DRIFTS study of a Fe-ZSM-5 catalyst during the selective catalytic reduction of
NO by isobutane is reported. The catalyst was prepared by vapour-phase exchange of H-
ZSM-5 with FeC13. Catalytic data from in a micro-catalytic flow reactor have been in
principle reproduced by using the DRIFTS cell as a flow reactor. Adsorbates, transient
intermediates, and interactions of zeolite OH groups have been monitored at 873-523 K, with
concomitant NO conversion measurement. It has been found that the spectra of deposits
formed on H-ZSM-5 and Fe-ZSM-5 are identical at 523 K. In formation about the deposits
obtained at 523 K was not representative for the temperature of peak NO conversion

3 0 - P - 2 8 - Selective catalytic reduction of NO by methane over A g N a Z S M - 5

catalysts in the excess of oxygen
C. Shi a,b, M. Cheng a, Z. Qu a, X. Yangb and X. Bao a*
a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
The Chinese Academy Sciences, Dalian 116023, P. R. China, xhbao@dicp.ac.cn
b Laboratory of Plasma Physical Chemistry, Dalian University of Technology,
Dalian 116024, P. R. China

AgNaZSM-5 catalysts were investigated for the selectively catalytic reduction of NO by

methane in the excess of oxygen. It was clearly depicted that the conversion rate of NO to N2
had a linear dependence on the silver loading (4.32-~13.64%), which indicated that all silver
species in the zeolite were active for the CH4-SCR reaction. The presence of excessive
oxygen in the feed gas favored the CH4-SCR reaction. The temperature programmed
desorption profiles in He and 2%CH4/He after the co-adsorption of NO and 02 revealed that
surface nitrates were formed on silver catalyst, and could be effectively reduced by methane

30-P-29 - Z S M - 5 / R a n e y Fe composite used as D e N O x catalyst

B. Zong, W. Wang, L. Lu and X.T. Shu
Research Institute of Petroleum Processing, China Petrochemical Cooperation, Beijing,
China

Zeolite ZSM-5 was grown onto Raney Fe powder and wire gauze. ZSM-5/Raney Fe was used
as catalyst for the selective reduction of NO with NH3 in the presence of 02, SO2 and H20.
DeNOx activity of the composite catalysts were found to be increased after hydrothermal
treatment. Migration of Fe from Raney Fe into zeolite ZSM-5 during the treatment contributes
to the high performance of the ZSM-5/Raney Fe of DeNOx reaction. Using the technique of
growth the zeolite in situ on Raney Fe, high hydrothermal stability and high mechanically
strength catalytic packing of any required shape can be produced. The composite ZSM-
5/Raney Fe is promising catalyst for industrial DeNOx processing.
328

30-P-30 - Reduction of nitric oxide by hydrocarbons on Ni-ion exchanged

zeolites
B.I. Mosqueda-Jim6nez a'b, M. Brandmair a, A. Jentys a, K. Seshan b and J.A. Lercher a
a Technische Universit~it Mfinchen, Garching, lercher@ch.tum.de, Germany
b Faculty of Chemical Technology, University ofTwente, Enschede, The Netherlands

The reduction of NO in the presence of excess oxygen with propane and propene over Ni-
exchanged zeolites was studied. Incorporation of Ni led to the formation of Bronsted acid
sites resulting from the hydrolysis of divalent Ni ions. Calcined catalysts showed a high
selectivity to N2 formation, while after reduction of the Ni species significant concentrations
of NO2 and N20 were formed. Higher NO conversions were obtained with propane compared
to propene except for NiNaMOR catalysts with low nickel content. The concentration of acid
sites did not play a major role in the NO reduction, high acid site concentrations, however,
resulted in the formation of coke.

30-P-31- NOx Reactivity on microporous MeAPOs. spectroscopic and

catalytic studies
A. Frache a, M. Cadoni a, S. Coluccia b, L. Marchese a*, B. Palella c, R. Pirone ~ and P. Ciambelli e
aDitz~'mento a~Scienzee tecr~logieAvamate, Universitgtdel Piemonte On'entaleA l e s s ~ Italy.
~chese(~;h wTito.it,"bDipartimentodi Chimica IFM, Universitgtdi Torino CDi~mento di l n g e ~
Chimic~ (fniversithdi Ntg~oli "FedericolI", N#~ol~ Italy. dlstitutook"Ricerchesulla Combus#one, CNR, Ncg~oli,
Italy,"e o l ~ F l t O ~"I n g e ~ Chimicae Alimentare, Untversitgtdi Salerno, Italy.
NOx reactivity on microporous aluminophosphates and silico-aluminophosphates containing Co and Cu ions
in A1PO4-34, -5 and -11 type structures, is reported. CoAPO-34 is very efficient catalyst in the NO oxidation
to NOz reaching the equilibrium conversion value at 350~ wfiereas is inactive in the NO reduction by CO, a
reaction which, on the contrary, p ~ efficiently on Cu-based catalysts (specially in the 300-550~ range).
N20 decomposition and NO oxidation to NO2 are also effective on Cu-containing catalysts, and followed the
sequence of activity: Cu-SAPO-34 _>CuAPSO-34 > CuAPO-34 > CttAPO-5 ~ ChaAPO-11. NO adsorption
on the most active catalysts was investigated by FTIR and this showed that Cu2+ and Cu+ mononitrosyl
complexes were formed in much larger amount on the silicon-containingcatalysts.

30-P-32 - Adsorption characteristics on zeolite catalysts for hydrocarbon

removal under cold-start engine condition
H.K. Seo, J.W. Oh and S.J. Choung
School of Environmental and Applied Chemistry, KyungHee University, 449-701 Suwon,
Korea, sjchoung@nms.kyunghee.ac.kr

Air pollution, mainly contributed by the emission from automobiles, has become the most
serious urban environmental problems in many countries. In this study, so as to meet the
SULEV regulation, the main idea has been focused on the utilization of HCA(Hydro-Carbon
Adsorber) in order to adsorb the excess hydrocarbons emitted during the period of engine
cold-start. As a main recipe of HCA materials, many types of zeolite as well as the
combination of alumina, precious metals were used. In this study, physico-chemical factors of
zeolite such as acidic properties and hydrophobic properties etc. has been characterized, and
tried to find the optimum recipe of HCA materials. As results, among the acid properties of
zeolites, the Si/A1 ratio is found to be the most important factor to get higher hydro-carbon
adsorption capacity.
 329

3 0 - P - 3 3 - In-situ synthesized Z S M - 5 on cordierite substrate and NO

decomposition on the monolithic catalysts
N. Guan *a, X. Shan a, X. Zeng a, S. Liu a, S. Xiang a, U. Illgen b and M. Baerns b
aDepartment of Chemistry, Nankai University, Tianjin P.R. China; blnstitute of Applied
Chemistry, Rudower Chaussee 5, Berlin-Adlershof Berlin, Germany

For obtaining a monolithic catalyst with better mechanical and hydrothermal durability, ZSM-
5 zeolite with different Si/A1 ratios (60, 55, 40, 25, 15) have been synthesized in-situ on
cordierite honeycomb substrate. SEM photos showed the different crystal size from sample to
sample. Solid MAS NMR was used to determine Si/A1 ratios and the amount of zeolite on the
substrate by the peak intensity 29Si. Investigation of NO decomposition (2000 ppm NO in He)
on the Cu-exchanged ZSM-5/cordierite monolithic catalysts was performed at 723 K,
GHSV=I 0,000/h. Results proved that the TOF of NO decomposition on monolithic catalysts
is comparable with pure zeolite catalysts.

30-P-34 - Selective reduction of N O to N2 in the presence of oxygen

T. Furusawa (a), K. Seshan (b), S.E. Maisuls (b), J.A. Lercher (c), L. Lefferts (b) and K. Aika (a)
alnterdisciplinary Graduate School of Science & Technology, Tokyo Institute of Technology,
Japan kenaika@chemenv.titech.ac.]p; bFaculty of Chemical Technology, University of
Twente, The Netherlands," Clnstitutfiir Technische Chemic, Technische Universitgtt Mfmchen,
Garching Germany
Catalytic performance of Co-ZSM5 (Si/AI=I 1) prepared by SSIE (Solid State Ion Exchange)
method was compared with that of Ag-ZSM5 prepared by LSIE method for the selective
reduction of NO with propylene in the presence of oxygen. It was found that C3H6 acted as a
reductant more effectively for production of N2 over Ag-ZSM5 than Co-ZSM5 and that a
route for producing N2 exclusively existed over Ag-ZSM5 from the kinetic results.

30-P-35 - Catalytic behaviour of Co-exchanged ferrierite for lean N O x - S C R

with methane
D. Sannino, M. Concetta Gaudino and P. Ciambelli
Dipartimento di Ingegneria Chimica e Alimentare, Universith di Salerno, 84084 Fisciano
(SA), Italy. sannino@dica, unisa, it

Lean NOx-SCR with CH4 has been investigated on Co-modified synthetic ferrierite prepared
in different conditions of ion exchange (temperature, time, precursor zeolite composition). A
maximum NOx conversion (50% at 100% CH4 conversion) was obtained at 500~ Activity
and selectivity depend on the nature of Co species (from mononuclear to polynuclear cationic
to oxidised phases) formed into ferrierite. The effect of side reactions such as uncatalysed and
catalysed methane combustion on catalytic performance is discussed.
330

03- New Methods of Zeolite Synthesis (Thursday)

0 3 - P - 0 6 - Zeolitization of a spanish bentonite in seawater medium. Effect of

alkaline concentration and time
R. Ruiz, C. Blanco, C. Pesquera and F. Gonzzilez
Dept. de Quimica. Univ Cantabria, blancoc@unican.es, Santander (Spain).
In this study a bentonite was modified to a zeolitic material by alkaline treatment in a
seawater medium. The structural and textural characteristics of the clays modified in this
medium were determined and compared with those of the natural clay and with those of the
clays m.odified under the same conditions but in distilled water. The samples were
characterized by XRD, IR, TG and SEM. The modifications observed in the composition of
the resulting zeolitic products depend not only on the NaOH concentration and treatment
time but also on the nature of the synthesis media. The zeolitic products synthesized in
seawater showed higher crystallinity and less heterogeneity. The treatment can be designed
according to the characteristics required for the process in which the zeolitic product will be
applied.

03-P-07- Silicalite-I spheres prepared from preformed resin-silicate

composites
L. Tosheva and J. Sterte
Division of Chemical Technology, Luledt University of Technology, Luledt, Sweden,
luto@km.luth.se
Silicalite-1 spheres were prepared in two steps by treating resin-silicate composite particles
with structure-directing template solutions. In a first step resin-silicate composites were
obtained as a result of an ion exchange of silica species within macroporous anion exchange
resin beads. In a second step the composite particles were hydrothermally treated in structure-
directing template solutions at 170~ for 24 h. Finally, the organic components were removed
by combustion at 600~ A number of samples were prepared using TPAOH and TPABr
solutions of different concentrations as well as different weight ratios between template
solution and composites.

03-P-08 - The synthesis of offretite single crystals using pyrocatechoi as

complex agent
F. Gao (a), G. Zhu (a, b), Xiaotian Li (a), S. Qiu (a*), B. Wei (a), C. Shao (a) and O.
Terasaki(b)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of
Chemistry., Jilin University, Changchun, P. R. China, e-mail: sqiu@mail.jlu.cn
b CREST, Department of Physics, Tohoku University, Sendai, Japan.
Offretite single crystals with perfect morphology have been succesfully synthesized using
pyrocatechol as complex agent. Compared with other methods, zeolite offretite prepared in
this system has much larger size and better morphology. The influence of pyrocatechol has
been studied, and the XRD patterns and the SEM photographs of offretite single crystals have
been shown. The role of pyrocatechol has been characterized by 27 A1 NMR and 29 Si NMR,
which show that an aluminum-pyrocatechol complex is formed in the reaction gel.
 331

03-P-09 - Synthesis of FER type zeolite in presence of tetrahydrofuran

G.-Q. Guo (a, b), Y.-J. Sun (c) and Y.-C. Long (a*)
a Department of Chemistry, Fudan University, Shanghai 200433, P. R. China,
b Research Institute ofBeijng Yanshan Petrochemical Corporation, SINOPEC, Beijing
102500, P. R. China, guoqing_guo@263.net
c Center of Analysis and Measurement, Fudan University, Shanghai 200433, P. R. China

FER zeolite can be prepared by spontaneous crystallization under hydrothermal conditions

from the reactant with molar composition of 0.5 THF (tetrahydrofuran)-o0.215NazO
eSiOze0.05AlzO3e20H20. The influence of SIO2/A1203 molar ratio, alkalinity, amount of
template and reaction temperature was explored as well.

03-P-10 - Utilization of dry-gel conversion method for the synthesis of

gailosilicate zeolites beta, ZSM-5 and ZSM-12
R. Bandyopadhyay (a), Y. Kubota (a), S. Nakata (b) and Y. Sugi (a)*
a Department of Chemistry, Faculty of Engineering, Gifu University, Gifu-501-1193, Japan
Email" sugi@apchem.gifu-u.ac.jp; Fax. 81-58-293-2597
b Department of Materials-process Engineering and Applied Chemistry for Environment,
Faculty of Engineering and Resource Science, Akita University, Akita O10-8502, Japan

Synthesis of gallosilicate zeolites [Ga]-beta, [Ga]-ZSM-5 and [Ga]-ZSM-12 was performed

by dry-gel conversion (DGC) method. The crystallization of the dry gel was performed in
presence of small amount of water, without which the crystallization failed. The method was
convenient and as effective as conventional hydrothermal method. The samples were pure and
highly crystalline, and showed characteristic of typical gallosilicate zeolites.

03-P-I 1 - A novel method for the synthesis of cancrinite type zeolites

C.F. Linares (a), S. Madriz (b), M.R. Goldwasser (b) and C. Urbina de Navarro (c)
a Universidad de Carabobo. Dpto de Quimica, clinares@thor, uc. edu. re, Venezuela.
b Universidad Central de Venezuela, Caracas, Venezuela
c Centro de Microscopia Electr6nica, UCV, Caracas, Venezuela
A novel method for the synthesis of cancrinite type zeolites was developed by modification of
an X faujasite type zeolite. Synthesis parameters such as crystallization time (16 h), tempe-
rature (80~ and pressure (autogenous pressure) were highly reduced by this procedure
compared to previous synthesis methods. A 100% conversion of the ZX to cancrinite was
observed with crystallinity higher than 80%. No other phases different to that of the cancrinite
were observed. The basic character of the cancrinite was ascertained by means of its catalytic
activity in the Knoevenagel condensation reaction.
332

03-P-12 - High-throughput strategies for the hydrothermal synthesis of

zeolites and related materials
N. Stock (a), N. Hilbrandt (a), K. Choi (b) and T. Bein (a)
a Department Chemie, Ludwig-Maximilians-Universitgit Manchen, Butenandtstr. 5-13,
81377 Mfinchen, Germany
b Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA

We have developed an automated parallel synthesis methodology that permits the rapid and
detailed investigation of hydrothermal systems. The general procedure is as follows:
automatic dispensing of reagents into autoclave blocks followed by synthesis, product
isolation and automated structure analysis with X-ray diffractometry. Here we describe the
application of this technique to the exploration of the aluminophosphate synthesis field. The
effects of template, template concentration, A1 sources as well as mixed template systems are
investigated. Emphasis is put on the study of cooperative structure direction effects.

03-P-13 - Static zeolite MCM-22 synthesis using two-level factorial design

J. Warzywoda, S. Dumrul, S. Bazzana and A. Sacco, Jr.
Centerfor Advanced Microgravity Materials Processing, Chemical Engineering Department,
Northeastern University, Boston, MA 02115, USA, asacco@coe.neu.edu.
A 2 4 factorial experiment (factors: the SIO2/A1203 (A), H2SO4/Na20 (B), and
Hexamethyleneimine (HMI)/SiO2 (C) ratios of the synthesis mixture, and the synthesis time
(D)) was carried out to study the crystallization behavior of MCM-22 grown statically without
aging in a broad reaction composition range. The four-factor interaction was significant (i.e.,
none of the factors acted independently) in influencing the crystallization kinetics of MCM-
22. The two three-factor (A.B.C and A.B.D) interactions were significant (i.e., none of the
factors acted independently) in influencing the average MCM-22 particle size. The feasibility
of using the lower amounts of HMI, and more siliceous synthesis mixtures than before to
statically grow highly crystalline MCM-22 was demonstrated.

03-P-14 - Influence of nano-particle agglomeration on the catalytic

properties of MFI zeolite
S. Inagaki, I. Matsunaga, E. Kikuchi and M. Matsukata*
Department of Applied Chemistry, Waseda University,3-4-10kubo, Shinjuku, Tokyo, 169-
8555, Japan, *mmatsu@mn.waseda.ac.jp

Microstructures of spherical and coffin-shaped MFI zeolite and its influence on catalytic
activity for cumene cracking were investigated. While spherical MFI was composed of nano-
particles, coffin-shaped one possessed a layered structure where "nano-particles" with ca. 30
nm in size were accumulated on the dense core. Both the thickness of nano-particles layer and
mesopore volume linearly correlated with the activity for cumene cracking, suggesting that
the mesopores in MFI particles formed during "nano-particles" agglomeration, and that the
reaction rate of cumene cracking was significantly influenced by the diffusion of cumene
molecule in the nano-particles agglomerating layer.
 333

0 3 - P - 1 5 - Rapid and mass production of porous materials using a

continuous microwave equipment
D.S. Kim, J.M. Kim, J.-S. Chang and S.-E. Park*
Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical
Technology (KRICT), Yusung, Taejon 305-600, Korea," separk@pado.krict.re.kr

A continuous microwave equipment (CME) has been developed to achieve a rapid and mass
production for ZSM-5 and NaY zeolite. A precursor mixture for synthesis of ZSM-5 was
prepared by mixing aluminosilicate gel with a nanoseed solution obtained under microwave
irradiation, and pumped into the CME. Duration time in the CME was 5 min to accomplish
the crystallization of ZSM-5 under microwave irradiation. For NaY zeolite, the precursor gel
without nanoseeds was introduced into the CME and crystallization time was within 30 min.
XRD and SEM results indicate that the structural properties of ZSM-5 and NaY zeolite
obtained are similar to those obtained using batch-type microwave instrument and by
conventional hydrothermal synthesis.

0 3 - P - 1 6 - Hydrothermal synthesis of vanadium-containing microporous

aluminophosphates via the design of experiments approach
L. Frunza (a,b), P. Van Der Voort (c), E.F. Vansant (c), R.A. Schoonheydt (b) and B.M.
Weckhuysen (b)
a National Institute of Materials Physics, Bucharest, lfrunza@alphal.infim.ro, Romania
b Centrum voor Oppervlaktechemie en Katalyse, K. U Leuven, Belgium
c Department Scheikunde, U.I. Antwerpen, Belgium

An experimental design has been applied to the hydrothermal synthesis of VAPO-11

molecular sieve (AEL structure) from a VOSO,.5H20"AI(iPrO)3"Pr2NH'H,O gel. Statistical
models that relate the selected synthesis variables with the crystallinity are proposed. The
optimal synthesis conditions for the two structures (single phase or physical mixture with the
AFO (VAPO-41) structure) are inferred from the models and compared with the literature
data on single phase synthesis. Highly crystalline single-phase VAPO-11 can be best prepared
at 170~ from a synthesis gel with low vanadium content and high water content.

03-P-17 - Synthesis of a thin Silicalite-1 membrane, through sintering, for

use in a membrane reactor
E.E. McLearya, A.W. Hoogestegera, R.D. Sanderson a and J.C. Jansen a'b
alnstitute of Polymer Science, Faculty of Natural Science, Stellenbosch University, South
Africa," bLaboratory of Applied Organic Chemistry and Catalysis, Delft University of
Technology, Delft, The Netherlands

To meet the dual challenge of selectivity and permeability for membranes used in reactors,
there has been a thrust to support thin layers of highly selective membrane material on a
porous support with high permeability. In this report we present the synthesis of such a thin
molecular sieve layer of Silicalite-1 on a c~-A1203 support through the sintering of colloidal
zeolite crystals (---150 nm) deposited with the Langmuir-Blodgett technique on the support.
334

03-P-18 - Mixed alkali templating in the Si/A! = 3 and 10 systems" a combi-

natorial study
G.J. Lewis a, D.E. Akporiaye b, D. Bem a, C. Bratu a, I.M. Dahl b, A. Karlsson b, R.C. Murray a,
R.L. Patton a, M. Plassen b and R. Wendelbo b
aUOP LLC, g/lewis@uop.com, Des Plaines, IL USA ; bSINTEF, Blindern, Oslo, Norway

A combinatorial approach is used to investigate mixed alkali templating in the Si/A1 = 3 and
10 zeolitic systems. The experimental design includes 15 high-symmetry alkali combinations
of Li +, Na +, K + and Cs +, decoupled variations in total hydroxide and total alkali, and four
digestion conditions giving 960 reactions. Compositional fields for BEA, ANA, MER, LTL
and pollucite (ANA-Cs), interactions between alkali cations in the templating process, and the
use of Principle Components Analysis to streamline the analysis of large XRD data sets are
presented.

03-P-19 -Factors affecting composition and morphology of mordenite

F. Hamidil, M. Pamba 2, A. Bengueddach 3, F. Di Renzo4 and F. Fajula 4
ID6partement de Chimie, USTO, B.P. 1505 Elmenaouar, Oran, Algeria
2Lab. Physique de la Matibre Condens~e, Universit6 Montpellier 2, Montpellier, France
3Lab. Chimie des Mat6riaux, Universit6 0ran Es-Senia, Oran
4Lab. Mat6riaux Catalytiques et Catalyse en Chimie Organique, ENSCM, Montpellier

The shape and size of the crystals of mordenite, as well the Si/AI ratio, have implications on
industrial applications in hydrocarbon conversion and separation. The ratio between the
incorporation yields of silicon and aluminium is inversely proportional to the alkalinity level.
Increased solubility of silica at higher pH accounts for the decrease of incorporation of
silicon. The source of silica and the ageing of the synthesis gel also influence the final Si/AI
ratio. The alkalinity of the synthesis system is also the main factor affecting the morphology
of the mordenite crystals, flatter crystals being formed at low alkalinity.
 335

0 4 - Isomorphous substitutions (Thursday)

0 4 - P - 0 6 - Uniform distribution of nickel during the synthesis of Si-ZSM-5
through solid-state transformation
M. Salou, Y. Kiyozumi, F. Mizukami,* S. Niwa, M. Imamura and M. Haneda
National Institute of Materials and Chemical Research, mizukami@home.nirnc.go.jp, Japan

Ni-containing Si-ZSM-5 was prepared through solid-state transformation, from kanemite and
from TEOS, by adding nickel nitrate directly to the synthesis mixture. For both silica sources,
nickel was found to be present at the outer surface and in the main channels of the zeolite. The
outer surface nickel could be highly dispersed for a given Ni/Si ratio. In the case of TEOS,
most of the nickel was present at the surface whereas in the case of kanemite, the distribution
of nickel was more balanced between the surface and the bulk. The comparison with
impregnation showed that the interaction of nickel with the zeolite framework was increasing
in the order impregnation << direct synthesis-TEOS < direct synthesis-kanemite.

0 4 - P - 0 7 - Synthesis, characterization and catalytic activity of FeBEA and

FeMFI zeolite obtained by xerogel wetness impregnation
O.A. Anunziata (a), L.B. Pierella (a), E.J. Lede (b) and F.G. Requejo (b,c)
aCentro de Investigaci6n y Tecnologia Quimica(CITeQ) UTN-FC- Cordoba-Argentina
bDto. Fisica, Fac. Cs Ex, UNLP and IFILP (CONICET), La Plata, Argentina
~Present address." Material.Science Division., LBNL, Berkeley, CA, USA

Fe-containing zeolites with MFI and BEA type structure were prepared by a novel method
using amorphous SiO2/Fe203 xerogel. The dependence of the synthesis conditions on
crystallinity, structure and catalytic activity and its characterisation by BET, FT-IR, XRD,
EXAFS, XANES and TPD were investigated. XANES spectra are sensitive to the chemical
state of the element and depend on the oxidation state, the binding mode, and the ligand
atoms. The results obtained with the characterization methods confirmed that the Fe-zeolites
synthesis by new xerogel method gave Fe in framework position with tetrahedral symmetry.

04-P-08 - A novel method for the synthesis of chromium aluminosilicate

with BEA structure
X.-H. Tang, L.-R. Pan, J.-Z. Wang and H.-X. Li
Department of Material Science, College of Chemistry, Nankai University, Tianjin 300071,
xhtang@public.tpt.tj.cn, P. R. China

A novel method has been developed for hydrothermal synthesis of zeolite beta with high
chromium content and low aluminum content under static conditions. The crystalline phase
and spectroscopic property of this material were characterized by means of XRD, XRF, IR,
UV-Vis DRS, ESR and SEM. The results revealed that part of the chromium ions were
incorporated into the zeolite framework during crystallization. Using tris(acetylacetonato)
chromium(III), [Cr(C5H702)3], as a chromium source, Cr/Si molar ratio can be up to 1/48 in
the calcined and ion-exchanged sample. The chromium aluminosilicate exhibited a high
oxidative activity in the presence of dilute H202.
336

04-P-09 - Pure SAPO, CoAPSO and ZnAPSO ATO-like molecular sieves

through optimized synthesis procedures
A. Azzouz (a), N. Bilba (b), M. Attou (c), A. Zvolinschi (a) and S. Asaftei (a)
a Engineering Faculty, Bacau University, Romania, azzouz@ub.ro
b Faculty of Chemistry, The "AI.I. Cuza" University, Iasi, Romania
c Laboratoire de Synthese Organique, CDM, Draria, Algeria
Pure SAPO-31, CoAPSO-31 and ZnAPSO-31 were hydrothermally synthetized in the
presence of dipropylamine, using a 33 factorial experiment, in the temperature range 200-
210~ for 24-27 hours, from mixtures of molar composition: 1.2 A1203: 1.03P205: xSiO2:1.7
(n C3H7)zNH :IHF: 62H20 and A1203 : 1.03P205 : xSiO2 : y(Metal)205 : 1.7(n C3H7)zNH:
1HF: 62H20. Strong interactions were observed between the parameter effects but no synergy
phenomena occur. SAPO-31 can be obtained within relatively wide parameter ranges. Pure
CoAPSO-31 and ZnAPSO-31 can be synthesized using small Si content in the starting gels.

04-P-10- Relation between amount of the niobium ammonium complex in

the reaction mixture and the crystal size of a Nb- MFI zeolite
A.H. Munhoz jr.a; S. Rodriguesb; P.K. Kiyohara c and W. Sano c
aDepto.Eng. Materials-U.P.Mackenzie & Depto Eng. Quimica-UNIBAN- Brazil-
ahmunhoz@yahoo, corn bDepto.Eng. Quimica - U.S.P. - rodrigus@usp, br CInstituto de Fisica
- U.S.P. - sano@ifusp, br

A zeolite with MFI structure was synthesised with 3 different amounts of niobium ammonium
complex (NAC) in the reaction mixture. The samples obtained were characterised by scanning
electron microscopy (SEM) using secondary electron detector and energy dispersive spectrum
(EDS) detector, X-ray diffraction (XRD), differential thermal analysis (DTA), and electron
paramagnetic resonance (EPR). The increase of NAC in the reaction mixture results in the
decrease of the crystal size of the zeolite. The characterisation shows evidence that the
niobium was incorporated into MFI structure.

04-P-II - Spectroscopy of the formation of microporous transition-metal

ion containing aluminophosphates under hydrothermal conditions
B.M. Weckhuysen (a,b), D. Baetens (a) and R.A. Schoonheydt (a)
a Centrum voor Oppervlaktechemie en Katalyse, Departement Interfasechemie, K.U.Leuven,
Kardinaal Mercierlaan 92, 3001 Heverlee, Belgium. E-mail." Bert. Weckhuvsen~agr.kuleuven.ac.be
b Departement Anorganische Chemie en Katalyse, Debye lnstituut, Universiteit Utrecht, P.O.
Box 80083, 3508 TB Utrecht, The Netherlands

In-situ DRS spectroscopy has been used to investigate the crystallization process of MeAPO-
5 molecular sieves (with Me = Co, Cr, Ni and V) as a function of the synthesis time and
conditions. A specially developed synthesis cell was used, which allows to probe the
coordination environment of the transition metal ions in-situ during hydrothermal conditions
and to obtain high-quality molecular sieves starting from a homogeneous synthesis gel.
 337

04-P-12 - Co-templated synthesis of C r A P O - 5 with various organic acids

J. Kornatowski (a), G. Zadrozna (a), J.A. Lercher (a) and M. Rozwadowski (b)
a Technische Universitdit Manchen, TC 11,jan.kornatowski@ch.tum.de, Germany
b Nicholas Copernicus University, Faculty of Chemistry, Torun, Poland

Most of the 20 tested saturated, unsaturated, and bifunctional aliphatic acids can be used as
co-templates for CrAPO-5. The acid type and amount affect significantly the crystallinity, the
content of substituted Cr, as well as the dimensions and morphology of the crystals. The co-
templating role of the acids is clearly visible, however, a systematic correlation with the
resulting crystal properties is not observed. The acid has to be chosen with respect to the
required product properties. The highest crystallinity is observed with acetic, acrylic,
methacrylic or crotonic acids, the most perfect morphology is obtained with unsaturated acids
of C3 to C6 chain length and the highest substitution of Cr with C3 to C5 bifunctional acids. Only
methacrylic acid seems to satisfy all the above requirements to a relatively high extent.

04-P-13 - H o w to increase the a m o u n t of f r a m e w o r k Co 2+ in m i c r o p o r o u s

crystalline a l u m i n o p h o s p h a t e s ?
W. Fan a', R.A. Schoonheydt a and B.M. Weckhuysen a'b
aCentrum voor Oppervlaktechemie en Katalyse, Departement lnterfasechemie, K. U. Leuven,
E-mail." Bert. Weckhuysen@agr. kuleuven, ac. be
bDepartement Anorganische Chemie en Katalyse, Debye lnstituut, Universiteit Utrech

Using the synthesis of CoAPO-5 and CoAPO-CHA molecular sieves as examples, the
influence of the synthesis conditions the solvents as well as the presence of monovalent
countercations and structure-directing organic template molecules on the isomorphous
substitution degree of Co for A1 in microporous crystalline aluminophosphates are studied. It
was possible to prepare CoAPO-5 with more than 25% of the framework A1 sites substituted
by Co 2+, CoAPO-CHA with Co 2+ occupying most of the framework AI sites ([Co]:[A1]>I)
and a new cobalt phosphate material.

04-P-14 - Preparation of zinc containing zeolite catalysts

A. Katovic(a), E. Szymkowiak (b), G. Giordano (a), S. Kowalak (b), A. Fonseca (c) and J.
B.Nagy (c)
(a) Dipartimento di ]ngegneria Chimica e dei Materiali, Universit?~ della Calabria,
via P. Bucci, 1-87030 RENDE (CS), Italy
(b)Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznan, Poland
(c) Laboratoire de RMN, Facult6s Universitaires Notre-Dame de la Paix
rue de Bruxelles 61, B-5000 NAMUR, Belgium

A method is described for the preparation of zinc-containing zeolite by direct synthesis from
hydrogels. The synthesis of Zn-MFI type zeolite materials and the post synthesis introduction
of Cu are discussed. The samples are characterized by XRD, AAS, thermal analysis, SEM and
29Si-NMR spectroscopy. The catalytic results on the cumene conversion are discussed.
338

04-P-15 - Synthesis of Zn and Fe substituted mordenite using citric acid as

eomplexing agent
M. Dong, J.-G. Wang* and Y.-H. Sun
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry,
Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001, Shanxi, P. R. China
Email." iccjgw@sxicc, ac. cn

A complexing agent, citric acid, is employed in the synthesis of zincosilicate and ferrisilicate
mordenites. Evidences for the incorporation of heteroatoms in the lattice framework have
been obtained from ICP, CRD, FTIR, and SEM. The presence of citric acid enhances the
ratios of crystallization for the Zn- and Fe-substituted mordenites, promotes the crystallinity
of the products, and increases the heteroatomic contents in the lattice framework as well. It is
speculated that the citric acid may decrease the concentration of metal ions in the synthesis
gel, thereby prevent the unfavorable formation of oxide or hydroxide species.

04-P-16 - ET(Zr)S-4 molecular sieve: kinetic and morphological charac-

terization
D. Vuono a, P. De Luca a, A. Fonsecab, J. B.Nagyb and A. Nastro a
a) Department of Pianificazione Territoriale, University of Calabria, Arcavacata di Rende,
87030 Rende (Cs), Italy.
b) Laboratoire de R.M.N., Facult6s Universitaires Notre-Dame de la Paix, B-5000 Namur,
Belgium.

The purpose of this research is to study the crystallisation kinetics of ET(Zr)S-4 starting from
mixed systems containing titanium and zirconium and to connect the results obtained to the
observation, through electron microscopy (SEM), of the crystal morphology of ETS(Zr)-4
synthesised at different reaction times. The 29Si NMR data suggest that zirconium occupies
framework tetrahedral positions.

0 4 - P - 1 7 - Influence of alcali cations on the incorporation of iron into MFI

structure in fluoride media
F. Testa a, F. Crea a, R. Aiello a, K. Lfizfirb, P. Fejes c, P. Lentz d and J. B.Nagyd
~Dip. di Ingegneria Chimica e dei Materiali, Univ. della Calabria, 1-87030 Rende (CS) Italy
bInstitute of Isotope and Surface Chemistry, 1525 Budapest, P.O. Box 77, Hungary
~University of Szeged, Applied Chemistry Dept., Rerrich B6la t6r 1, 6720 Szeged, Hungary
dLaboratoire de RMN, FUNDP, 61 Rue de Bruxelles, 5000 Namur, Belgium

Up to three Fe/u.c. could be introduced into the MFI framework in fluoride-containing media.
The presence of Fe in tetrahedral framework position is shown by both the white colour of the
samples and the isomer shift in M6ssbauer spectra (IS<0.3 mm/s). During calcinations some
framework Fe atoms leave the structure. The crystal morphologies and the kinetic data show
that the cations exert specific effects in the stabilization of the crystals under development.
 339

04-P-18 - Synthesis and characterization of Co-containing zeolites of M F I

structure
E. Nigro a, F. Testa a, R. Aiello a, P. Lentz b, A. Fonseca b, A. Oszko c, P. Fejes d, A. Kukovecz d, I.
Kiricsi d and J. B.Nagy b
~Dipartimento di Ing. Chimica e dei Materiali, Univ.della Calabria, 1-87030 Rende (Cs), Italy
bLaboratoire de RMN, FUNDP, B-5000 Namur, Belgium
~Institute of Solid State and Radiochemistry, University of Szeged, H-6720 Szeged Hungary
dApplied Chemistry Department, University of Szeged, H-6720 Szeged Hungary

Co-containing zeolites of MFI structure were synthesized using alkaline media. The
orthorhombic-monoclinic symmetry transition suggests that at least the Co(II) ions occupy
tetrahedral framework positions. The XPS data clearly show that the samples contain both
framework tetrahedral and extraframework octahedral Co(II) ions at ion exchange positions.
340

13 - F r a m e w o r k s and Acid Sites (Thursday)

13-P-05 - In-situ F T I R studies of the acidity of H3PWl2040 and its porous

salts. Interaction with H20, NH3 and pyridine
N. Essayem(a), A. Holmqvist(a), G. Sapaly(a), J.C. V6drine(b) and Y. Ben T~arit(a)
(a)Institut de Recherches sur la Catalyse, Villeurbanne, France, essayem @catalyse.univ-
lyonl fr; (b)Leverhulme Centre for Innovative Catalysis, Liverpool, United Kingdom.

The dehydration-rehydration mechanism of H3PWI2040, has been investigated by in-

situ IR spectroscopy. Protonated water clusters (H20)nH + are observed both on the pure
non-porous acid and on its acidic porous/mesoporous salts. Further dehydration
induces the decomposition of these protonic species and leads to the formation of
hydroxyl groups. Strong modifications of the vibration bands of the Keggin unit occur
simultaneously. Adsorption of probe molecules such as water, ammonia and pyridine
has been performed on samples dehydrated at different temperatures. The adsorption
of pyridine over the pure acid H3P generated a peculiar IR spectrum. On the contrary
pyridine adsorption on the acidic salt gave rise to the regular pyridine vibrations.

13-P-06 - D y n a m i c s of p-nitroaniline in the micropore of zeolite Z S M - 5

studied by solid-state NMR
S. Hayashi and Y. Komori
National Institute of Materials and Chemical Research, hayashi@nimc.go.jp, Japan
Zeolite ZSM-5 with a high [Si]/[A1] ratio containing 3 to 4 p-nitroaniline (p-NA) molecules
per unit cell has been studied by solid-state NMR. 29Si NMR spectral change and detection
of the 29Si CP signals after incorporation ofp-nitroaniline demonstrate that the molecules
locate in the micropores. 13C CP/MAS NMR spectra of p-NA in ZSM-5 show line
broadenings in two C-H signals, which is related with motions of the benzene ring. The
frequency of the motion is of the order of 50 kHz, which is comparable to the strength of the
IH decoupling field. 2H NMR spectra demonstrate that 180 degree flip of the benzene ring
around the C2 axis of the molecule takes place, whose frequency is of the order of 100 kHz at
room temperature.

13-P-07 - The use of microcalorimetry to study the effects of post-synthesis

treatments on the modification of the acidity of s e v e r a l HY-type zeolites
A. Auroux (a) and M.L. Occelli (b)
a Institut de Recherches sur la Catalyse, Villeurbanne, France, auroux@catalyse.univ-
lyonl.fr; b MLO Consulting, Atlanta, USA
The effects on acidity of post-synthesis treatments on HY-type zeolites have been investigated
using NH3 adsorption calorimetry and 29Si and 27A1 NMR. The reaction of aqueous
(NH4)ESiF6 solutions with NHaY can yield HY crystals with a Si-enriched framework free
from measurable non-framework A1 species in which T(3Si, IA1)/T(4Si,0A1) > 1.0. LZ-210
type crystals with Si/A1=3.1-4.4 have greater acid site density and contain more acid sites
with strength > 100 kJ/mol than the reference LZY-82. Steam-aging causes a drastic decrease
in acid sites density. However, in the temperature range (760-815~ investigated, the
strength of the strongest acid sites in the reference LZY-82 remains practically unaffected
after hydrothermal treatment.
 341

1 3 - P - 0 8 - ESR investigations of the catalytic properties of Lewis acid sites

in H-mordenite
T.M. Leu and E. Roduner
Institut fiir Physikalische Chemie der Universitdit Stuttgart, Germany,
e. roduner@ipc, uni-stuttgart. de

The formation and the properties of Lewis acid sites (LAS) in the zeolite H-MOR were
investigated by means of ESR spectroscopy through the observation of the radical cation
formed upon adsorption of 2,5-dimethylhexa-l,5-diene (DMHD). The following facts have
been established: (i) LAS which bind ammonia are not the sites which are responsible for the
formation of radical cations. (ii) The amount of DMHD + formed is directly related to the
partial pressure of molecular oxygen present in the system. (iii) The addition of oxygen to H-
mordenite containing DMHD+'leads to a superoxide radical anion; furthermore, there is
strong evidence for a catalytic process involving DMHD+as a radical intermediate in the
oxidation of DMHD.

13-P-09- External surface acidity of modified zeolites: ESR via adsorption

of stable nitroxyl radicals and IR spectroscopy
A.B. Ayupov a, G.V. Echevsky a, E.A. Paukshtis a, D.J. O'Rear b and C.L. Kibby b
a Boreskov Institute of Catalysis, Ak. Lavrentieva Av. 5, Novosibirsk, 630090, Russia
b Chevron Research and Technology Co., 1O0 Chevron Way, Richmond, CA 94802, USA

The external surface Br~3nsted and Lewis acidity of modified zeolites were characterized by
FTIR of OH groups and adsorbed CO molecules and ESR of adsorbed nitroxyl radicals. The
catalytic properties of the samples were tested in reactions of aromatics conversion: toluene,
pseudocumene, and triisopropylbenzene. The correlation between acidity and catalytic
activity has been found and discussed. The three methods of external surface characterization
can lead to the entire view on zeolite acidity.

13-P-10 - Very strong acid site in HZSM-5 formed during the template
removal step; its control, structure and catalytic activity
A. Kohara, N. Katada and M. Niwa
Tottori University, Koyama, Tottori 680-8552 Japan
mikiniwa@chem, tottori-u.ac.jp, Fax +81-857-31-5256

Conditions of a step for template molecule removal affected strongly the concentration of
very strong acid site in HZSM-5. Treatment with ammonia water at ca 373 K was also studied
as a procedure to affect the solid acidity, and a similarity of acid sites created by both methods
was identified. From the quantitative measurements of acid sites, it was found that the very
strong acid site consisted of two A1 cations. Catalytic activity for octane cracking was
enhanced by the presence of very strong acid site.
342

13-P-I1- Correlation between ~B NMR isotropic chemical shifts and struc-

tural parameters in borates and boro-silicates
J. P16vert, F. Di Renzo and F. Fajula
Ecole Nationale Sup~rieure de Chimie de Montpellier, Franc. JPlevert@asu.edu

liB MAS NMR has been performed for a variety of borates and boro-silicates. Boron atoms in
tetrahedral coordination exhibit sharp resonance lines. The l~B isotropic chemical shift
displays dependence as a function of framework geometry parameters such as the mean
angles <BOT> and the mean distances <dBv>. Such correlation can be useful to characterize
the boron site in disordered zeolites.

13-P-12 - Investigation of the paramagnetic effect of oxygen in the 23Na

MAS N M R and 23Na MQMAS N M R spectra of LiNaX
R.J. Accardi (a), M. Kalwei (b) and R.F. Lobo (a)
a Center for Catalytic Science and Technology, Department of Chemical Engineering,
lobo@che.udel.edu, University of Delaware Newark, DE 19716, USA.
b Institute for Physical Chemistry, University ofMfinster Mfinster, Germany 48149.

The paramagnetic effects of oxygen molecules on the site III sodium cations in zeolite LiNaX
(~70% Li; ~30% Na) were investigated using variable temperature 23Na MAS NMR and 23Na
MQMAS NMR spectroscopy. The presence of the oxygen caused a down-field paramagnetic
shift for the site III resonance, although smaller than what was expected. 23Na MQMAS NMR
was used to calculate isotropic chemical shifts and 2 na order quadrupolar shifts. The
quadrupolar shifts of the room temperature sodium resonance remain the same irrespective of
the presence or absence of physisorbed oxygen, however, the quadrupolar shift was found to
increase at lower temperatures.

13-P-13 - Characterization of acidic sites in HY and LaY zeolites by laser-

induced fluorescence of adsorbed quinoline
A. Lassoued, J. Thoret, P. Batamack, A. G6d6on and J. Fraissard
Laboratoire de Chimie des Surfaces, UPMC-CNRS, ESA 7069, 4 place Jussieu, 75252 Paris
cedex 05, E-mail.'jfr@ccr.jussieu.fr, Fax : 33.(0)1.4427.5536, France.

We report the characterization of acidic sites in HY zeolite, dealuminated or not, and Y

zeolites exchanged with lanthanum (LAY), by the laser-induced fluorescence (LIF) method
using an N-heteroaromatic base, quinoline, which is adsorbed on the surface and photoexcited
at 240 nm. Spectra of quinoline reveal interactions between the adsorbate and surface sites.
Unstructured broad bands with lifetimes less than 1 gsec are observed in all samples. Strong
Bronsted acid sites interact with quinoline to form the quinolinum ion, that ion being revealed
by a band peaking at 390 nm. The acidity of LaY samples is a function of the La 3+ exchange
rate; this was fast highlighted by LIF spectroscopy.
 343

13-P-14 - D y n a m i c behaviour of acetonitrile molecules adsorbed in ALPO4-

5 and S A P O - 5 studied by solid N M R method
S. Ishimaru, M. Ichikawa, K. Gotoh and R. Ikeda
Department of Chemistry, University of Tsukuba, Tsukuba 305-8571, Japan

We studied characteristics of micropores in molecular sieves A1PO4-5 and SAPO-5 by

observing IH and 2H NMR to detect dynamic behaviour of acetonitrile molecules adsorbed in
the pores. From 2H spectra and ~H relaxation times, it was shown that the molecular motion
was strongly affected by the existence o f - O H groups on the pore-wall of SAPO-5. The
details of the motions are discussed from ~H NMR TI and T2 data.

13-P-15 - D e t e r m i n a t i o n of the Si/A! ratio of faujasite-type zeolites

C.H. Rtischer l*, J.-C. Buhl I and W. Lutz 2
llnstitut fiir Mineralogie, Universit~itHannover, Welfengarten 1 Hannover, Germany.
*C.Ruescher@mineralogie. uni-hannover,de
2WITEGA Angewandte Werkstoff-Forschungg. GmbHBerlin, Germany
Zeolites Y dealuminated by Si/A1 substitution using SIC14 (DAY-S) and dealuminated
thermochemically in steam (DAY-T) were investigated by X-ray powder diffraction, infrared
spectroscopy and wet chemical methods. The dependence of lattice constants (a) on the molar
ratio x = (I+Si/A1) z show non-ideal solid solution behaviour. In a first approximation the
change in a (in nm) can be described as: a = 0.187x+2.412, for 0.1 < x < 0.5. For x < 0.1 the
change in lattice constant saturates towards a = 2.425 nm. A similar shift in the double ring
mode (WDR)is observed, tailing off.

13-P-16 - Theoretical investigation of the chemical shift anisotropy of

toluene adsorbed on zeolite X
A. Simperler (a), A. Philippou (b), D.-P. Luigi (b), R.G. Bell (a) and M.W. Anderson (b)
a The Royal Institution of Great Britain, London, United Kingdom, rob@ri.ac.uk
b UMIST Centre for Microporous Materials, Manchester, United Kingdom

Adsorption of toluene on zeolites Li-X, Na-X, K-X, Rb-X, and Cs-X has been investigated
with quantum chemical methods. Calculations of geometries, Mulliken partial charges, and
13C chemical shift parameters of clusters representing the catalytically active site are
presented. The polarisation of the toluene carbons is the first step in alkylation reactions
catalysed by zeolites and, at an early stage, will influence the outcome of the reaction. We
show the simultaneous influence of the Lewis acidic cation and the basicity of the zeolite is
responsible for altering the electron distribution within the toluene and thus affecting the
outcome of an alkylation reaction.
344

13-P-17 - Acid properties of dexydroxylated ferrierites studied by IR

spectroscopy
J. Datka, B. Gil and K. G6ra-Marek
Faculty of Chemistry, Jagiellonian University, 30-060 Cracow, Ingardena 3, Poland.
datka@chemia, uj. edu.pl

Dehydroxylation was studied as one of methods of "tuning" the acid properties of ferrierite.
The concentration and acid strength of both Br6nsted and Lewis acid sites were determined
by IR spectroscopy. In non dehydroxylated ferrierite, the concentration of Br6nsted sites was
the same as the value calculated from the composition of zeolite. The maximal concentration
of Lewis acid sites in the most dehydroxylated zeolite was close to the stoichiometric value:
i.e. half of the concentration of Br6nsted sites. The acid strength of OH groups remaining in
partially dehydroxylated ferrierites decreased and the strength of Lewis sites formed increased
with the extent of dehydroxylation. The hydroxyls inside 10-ring channels and hydroxyls in
ferrierite cages are prone to dehydroxylation in the same degree.

13-P-18 - Aluminium species in activated zeolites: solid-state NMR

spectroscopy of the active sites
B.H. Wouters (a), T.-H. Chen (b) and P.J. Grobet (a)
a Center for Surface Chemistry and Catalysis, Department oflnterphase Chemistry,
K.U. Leuven, Piet.Grobet@agr.kuleuven.ac.be, Leuven, Belgium
b Department of Chemistry, Nankai University, Tianjin, 300071, PR China

Aluminium species in activated zeolites has been studied by solid-state NMR spectroscopy.
Framework A1-OH defect species are at the origin of reversible tetrahedral-octahedral
transformation in mild calcined zeolites. Depending on the calcination degree, the 30 ppm line
in the 27A1 MAS NMR spectra of zeolites is a superposition of deformed tetrahedrally
coordinated and penta-coordinated AI species.

13-P-19- Aluminium distribution in high silica pentasil ring zeolites

B. Wichterlov~i, J. D~de6,ek, Z. Sobalik and J. 12ejka
J. Heyrovsl@ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic;cejka@3"h-inst.cas.cz

Distribution of aluminium in the framework of ZSM-5 and Beta zeolites, represented by "A1
pairs" [A1-O-(Si-O)I,2-A1] and "single A1 atoms" far distant from each other, is estimated from
the distribution of divalent Co ions at the individual cationic sites, as obtained from the Co(II)
Vis spectra, and the changes in the concentration of OH groups and Lewis sites due to Co(II)
exchange, monitored by FTIR. It is shown that the distribution of framework A1 is not
random, but it is affected by the concentration of aluminium and procedure of zeolite
synthesis.
 345

1 3 - P - 2 0 - Effects of hydration on AIPO4-14 and AIPO4-18 structures: a~p

M A S a n d 27A! 3 Q - M A S N M R s t u d y b
C. V. Satyanarayanaa, R. Gupta, K. Damodaran, S. Sivasankera and S. Ganapathy b*
aCatalysisDivision bPhysical Chemistry Division,ganpat@ems.ncl.res.in, NCL, Pune, India

Structural transformations occurring in A1PO4-14 and A1PO4-18, upon calcination and

rehydration, have been studied by 31p and 27A1 MAS/3Q-MAS NMR spectroscopy. Isotropic
signals obtained from 31p MAS and 27A1 3Q-MAS aid in the direct detection of number of in
equivalent T-sites, which could be assigned based on the correlation of the isotropic shifts
with mean T-O-T angle. In calcined samples where only tetrahedral P and AI environments
exist, AIPO4-18 results clearly show a constrained geometry with minimal tetrahedral
distortion for the PO4 and AIO4 structure building units. Signal multiplicity in 3~p and 27A1
spectra of calcined-rehydrated samples of AIPO4-14 and -18 suggest that both respond to
hydration in a similar fashion to yield structures with lower space group symmetry.

13-P-21 - Comparative study of the acidity of the structurally related

faujasite type zeolites: FAU, EMT and ZSM-20
H. Kosslick (a), R. Fricke (a), H. Miessner (b), D.L. Hoang (a) and W. Storeck (c)
a Institute of Applied Chemistry Berlin-Adlershof kosslick@ aca-berlin.de, Germany
b Institute of Environmental Technologies, I. U. T, hm@iut-berlin.com, Germany
c Federal Institute of Materials Research and Testing (BAM),Berlin, Germany

Acidic properties of EMT and FAU type zeolites as well as their intergrowths with similar A1
content, which contain the same structural subunits but differ in stacking, have been studied
by different physico-chemical methods like NH3-FTIR. Small finestructure differences have
been found which might be the origin of different strengths of acid sites. Slight variations in
the acidity of Bronsted acid sites are indicated by the low frequency shift of the OH stretching
vibration band of hydroxy groups which are located in the large cavities. In consequence, the
protonic acidity is slightly enhanced in the following order: HFAU < HZSM-20 < HEMT.

13-P-22 - The effect of flexible lattice aluminum in zeolites during the

nitration of aromatics
M. Haouas (a), A. Kogelbauer (a,b) and R. Prins (a)
a Laboratory of Technical Chemistry, Swiss Federal Institute of Technology (ETH),
Zurich, prins@tech.chem.ethz.ch, Switzerland," b Department of Chemical
Engineering, Imperial College of STM, London, U.K.

The nitration of toluene with nitric acid and acetic anhydride with zeolite catalysts was
studied by means of multi-nuclear solid-state NMR spectroscopy in order to explain the
enhanced para-selectivity observed with zeolite beta. The reversible transformation of
framework aluminum from a tetrahedral into an octahedral environment was revealed by 27A1
NMR upon interaction of the zeolite with the different components of the nitrating system.
The flexibility of the lattice seems to play an important role in the regio-selectivity of nitration
catalyzed by zeolites.
346

13-P-23 - Characterization of acidic sites in zeolites by heteronuclear double

resonance solid state NMR
S.B. Waghmode, A. Abraham, S. Sivasanker, J.P. Amoureux a and S. Ganapathy*
National Chemical Laboratory, Pune 411 008, India
LDSMM, CNRS-8024, Universite de Lille, F-59655, France

The structural characterization of Br0nsted acid sites in zeolites can be investigated through
heteronuclear double resonance NMR experiments under Magic Angle Spinning (MAS).
With these experiments, we have recoupled the 1H-27AI heteronuclear dipolar interactions by
using the Rotational Echo Adiabatic Passage DOuble Resonance (REAPDOR) technique. The
signal evolution was followed and monitored under MAS and the REAPDOR fraction was
experimentally measured. Its time evolution is shown to reflect the differences in Br0nsted
acidity of three well known zeolites, namely, LTL, LTY and MOR.

13-P-24- Measurement of M Q M A S heteronuclear correlation spectra in

microporous aluminophosphates
C. Fernandez (a) and M. Pruski (b).
a) Laboratoire ale Catalyse et Spectrochimie, CNRS UMR 6506, ISMRA/Universit6 de Caen,
France; b) Ames Laboratory, Iowa State University, Ames, USA
Christian. Fernandez@ismra. ~.

We present a solid-state nuclear magnetic resonance (NMR) experiment that allows the
observation of a high-resolution two-dimensional heteronuclear correlation (2D HETCOR)
spectrum between aluminum and phosphorous in aluminophosphate molecular sieve VPI-5.
The experiment uses multiple quantum magic angle spinning (MQMAS) spectroscopy to
remove the second order quadrupolar broadening in 27A1 nuclei. The magnetization is then
transferred to spin-l/2 nuclei of 31P via cross polarization (CP) to produce for the first time
isotropic resolution in both dimensions.

13-P-25 - FTIR studies of the interaction of aromatic and branched

aliphatic compounds with internal, external and extraframework sites of
MFI-type zeolite materials
T. Armaroli (a), A. Guti6rrez Alejandre (b), M. Bevilacqua (a), M. Trombetta (a), F. Milella
(a), J. Ramirez (b) and G. Busca (a).
a DICheP, Universith di Genova, icibusca@csita, unige, it~ Italy
b UNICAT, UNAM, jrs@servidor.unam.mx, Mexico D.F, Mexico

The interaction of different nitriles (acetonitrile, pivalonitrile and benzonitrile), of branched

aliphatic compounds (2,2-dimethylbutane, tert-butyl-alcohol, methyl-tert-butylether, methyl
and dimethylcyclohexanes) and of aromatics (benzene, toluene, ortho-, meta- and para-
xylene, pyridine, picolines and lutidine) has been studied over four different ZSM5 zeolites,
over silicalite-1 and titanium silicalite-1 and over boralite BOR-C. Internal, external and
extraframework sites have been characterized and the access to the cavities discussed.
 347

1 4 - Frameworks, Cations, Clusters (Thursday)

14-P-06 - Relaxation processes of Na ion in dehydrated Nal2-A zeolite

T. Ohgushi and K. Ishimaru
Department of Materials Science, Toyohashi University of Technology,
ohgushi@tutms, tut. ac.jp, Japan.

Relaxation processes caused by Na § ion in Nala-A zeolite were studied by the dielectric
technique. Two loss peaks (two relaxations) were observed in the dehydrated state, and were
simultaneously influenced by the water adsorption in the extremely low vapor pressure or the
extremely low adsorbed amount. From the way of the influence and a character in the cation
distribution of the zeolite, both relaxations were related to the movements of Na + ion on the
site near the 4-membered oxygen ring (4MR). It was concluded by considering the
arrangements of some cation sites around 4MR that the loss observed in the higher frequency
region was caused by the jump of Na § ion between 4MR and 6MR, and the loss in the lower
frequency region by the jump ofNa + ion between 4MR and 8MR.

14-P-07 - Adsorption of DTBN at monovalent cations in zeolite Y as studied

by electron spin resonance spectroscopy
M. Gutjahr, W. B6hlmann, R. B6ttcher and A. P6ppl
University of Leipzig, poeppl@physik, uni-leipzig, de, Germany.
One major challenge in the research of microporous materials is the spectroscopic
characterization of acid sites. A promising approach is their complexation with paramagnetic
probe molecules and the subsequent characterization of the adsorption complex ESR
techniques. We used the continuous wave ESR method and modem high resolution pulsed
ESR techniques such as hyperfine sublevel correlation spectroscopy to study adsorption
complexes formed by paramagnetic Di-tert-butyl nitroxide probe molecules and zeolite
cations Li+, Na +, K +, Cs+ in Y zeolites. These investigations allow a determination of the
geometrical structure of the adsorption complexes and provide information about the
influence of the electronegativity of the various acid sites on the electron density distribution.

14-P-08 - Nature of the active sites of Mo-containing zeolites. XANES

studies at Mo K and Llll-edges
F.G. Requejo (a,b), E.J. Lede (a), L.B. Pierella (c) and O.A. Anunziata (c)
a Dto. Fisica, Fac. Cs Ex, UNLP and IFILP (CONICET), La Plata, Argentina
b Present address." Material.Sience Division., LBNL, Berkeley, CA, USA
c centro de Investigaci6n y Tecnologia Quimica(CfTe), UTN-FC-Cordoba-Argentina.

Molybdenum catalysts, prepared by incipient wetness impregnation of ammonium-MFI, MEL

and BEA zeolites, have been studied by XANES at the Mo L2,3-edge and FTIR. The catalytic
activity shows on the nature of Mo species. Due to the splitting at Mo La-edges obtain by
XANES, Mo atoms are mainly in tetrahedral surrounding in the samples. Linear XANES fit
provide information about concentration of Mo-sites related with their coordination.
Differences between linear XANES fits at L3 and K-edges can be attributed to different
measurement conditions, indicating different of Mo-sites according their hydration capability.
348

14-P-09 - EPR studies on nitrogen monoxide in zeolites

H. Yahiro (a), N. P. Benetis (b), A. Lund (b) and M. Shiotani (c)
(a) Faculty of Engineering, Ehime University, Matsuyama, hEahiro@en3.ehime-u.ac.jp,
Japan.
(b) Chemical Physics Laboratory, 1FM LinkOping University, LinkOping, Sweden
(c) Faculty of Engineering, Hiroshima University, Higashi-Hiroshima, Japan

Nitrogen monoxide (NO) introduced into Na-A(Na-LTA), Na-mordenite(Na-MOR), and Na-

ZSM-5(Na-MFI) zeolites was studied by X-band-EPR measurements. The EPR spectra of
NO introduced into Na-LTA revealed the presence of two monoradicals with different
rotational rates. The rotational motion of the NO monoradical formed in Na-LTA differed
from that in Na-MOR and Na-MFI. A (NO)2 biradical was present in Na-LTA, while it was
absent in the calcium ion-exchanged A-type zeolite, indicating that the pressure of Na + is
essential for the (NO)2 biradical formation.

14-P-10 - Evidence of partially broken bridging hydroxyls in molecular

sieves from IH MAS spin echo N M R spectroscopy
T.-H. Chen (a,b), B.H. Wouters (b) and P.J. Grobet (b)
aDepartment of Chemistry, Nankai University, Tianjin, 300071, PR China
bCenterfor Surface Chemistry and Catalysis, KU Leuven, Kardinaal Mercierlaan 92, B-3001
Heverlee (Leuven), Belgium, Piet. Grobet@agr.kuleuven.ac. be

By spin echo editing NMR method, combined with the lH{27Al}spin echo double resonance,
a new IH signal was found in the thermally treated molecular sieves, reflecting the complexity
of hydroxyls as well as the aluminum state in the dehydrated state. It represents an initial
stage of the dehydroxylation, or may be related with the initial stage of dealumination.

14-P-11 - Structure change of molecular sieve SAPO-37 at high tempe-

rature studied by 27A! MQ MAS N M R
T.-H. Chen (a,b), B. Wouters (b) and P. Grobet (b)
aDepartment of Chemistry, Nankai University, Tianjin, 300071, PR China
bCenterfor Surface Chemistry and Catalysis, KU Leuven, Kardinaal Mercierlaan 92, B-3001
Heverlee (Leuven), Belgium, Piet.Grobet@agr.kuleuven.ab.be

When SAPO-37 was calcined at 1173 K, Si atoms become mobile and detached from the
framework to aggregate to form polymorph silica, while AI-P dense phase was formed,
corresponding to a new AI signal which can be distinguished by the 27A1 MQMAS spectrum.
The move of atoms in SAPO-37 is the start of the collapse of the framework.
 349

14-P-12 - Effects of molecular confinement on structure and catalytic

behaviour of metal phthalocyanine complexes encapsulated in zeolite-Y
S. Seelan, D. Srinivas*, M.S. Agashe, N.E. Jacob and S. Sivasanker
National Chemical Laboratory, Pune 411 008, India, srinivas@cata.ncl.res.in
Metal phthalocyanine complexes (MPc; M = V, Co and Cu) encapsulated in zeolite-Y were
prepared by "in-situ ligand synthesis" and characterized by chemical and thermal analyses
and FT-IR, diffuse reflectance UV-vis and EPR spectroscopic techniques. The studies
provided evidence for the encapsulation of MPc inside the supercages of zeolite-Y. The Pc
moiety distorts from square planarity as a consequence of encapsulation. The encapsulated
complexes exhibited enhanced styrene epoxidation activity with tert-butylhydroperoxide
compared to the neat complexes in homogeneous medium. The activity and product
selectivity of the encapsulated complexes varies with the central metal atom.

14-P-13 - Investigations on isomorphous substitution and catalytically

active centres in MeAPO-31 (Me = Mn, Co, Zn, Ti)
N. Novak Tusar (a), A. Ristic (a), A. Ghanbari-Siahkali (b), J. Dwyer (b), G. Mali(a), I. Arcon
(c) and V. Kaucic (a)
a National Institute of Chemistry, Ljublj'ana, natasa.novak@ki.si, Slovenia; b Centre for
Microporous Materials, UMIST, Manchester, UK; c Nova Gorica Polytechnics, Nova Gorica,
Slovenia

An incorporation of manganese(II), cobalt(II), zinc(II) and titanium(IV) into the framework

aluminium sites of A1PO4-31 is studied. Isomorphous aluminium substitution with cobalt and
zinc was confirmed from static 3~p NMR spectrum and 31p MAS NMR spectrum,
respectively. UV-VIS and XANES spectra revealed a partial oxidation of framework
manganese(II) into manganese(III) in calcined MnAPO-31 and thus a presence of redox
centres in the product. The generation of acidic sites (Bronsted and Lewis) in MeAPO-31 was
supported by ammonia adsorption/desorption analysis. Strength of acid sites in the studied
catalysts decreases as following: MnAPO-31 > CoAPO-31 > ZnAPO-31. Titanium(IV) is
present in TAPO-31 as anatase and it is not incorporated into framework sites of AIPO4-31.

14-P-14 - A comparative study of Ti 4+ sites in titanium silicalite (TS-I)

synthetized by different methods
N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, M.V. Cagnoli, S.G. Marchetti and A.A. Yeramian
CINDECA, Fac. Cs. Exactas, Fac. Ingenieria, U.N.L.P., CIC, CONICET.,
norgal@quimica.unlp.edu.ar; Calle 47 N ~ 257 (1900) La Plata, Argentina.
Three TS-1 zeolites were prepared by three different methods. In order to determine that
all of them are "well manufactured", DRX, IR, SEM and DRS were used. The jointly use
of probe molecules (H202 and C6H6) and DRS allowed us to detect differences in the
population of the named "closed" and "open" Ti 4+ sites and in their geometries in the three
zeolites. These differences lead to distinct catalytic behavior when these solids are tested
in the oxidation of benzene with H202.
350

14-P-15 - Behaviour of F e ( l l l ) ions in Y zeolites in the presence of Cu(II)

and Ag(I) ions: an ESR study
A.L. Kustov (a), E.E. Knyazeva (a), E.A. Zhilinskaya (b), A. Aboukais (b) and B.V.
Romanovsky (a)
a Chemistry Department Moscow State University, Moscow, V-234, Russia,
bvromanovsky@mail, ru
b Laboratory of Catalysis and Environment, EA 2598, Littoral University, 59140 Dunkerque,
France, jilinska@univ-littoral.fr

Quenching effect of Cu(II) and Fe(III) paramagnetic ions when both present within NaY
large cages is evidenced. On the contrary, the presence of the same quantity of diamagnetic
Ag(I) ions in the NaY zeolite did not influenced on the EPR patterns of Fe(III). Observed
quenching effect is supposed to be explained caused by the strong dipole-dipole interaction
of paramagnetic species. Also, the catalytic activity of Fe-containing zeolite in methanol
oxidation decreases after loading a Cu compound.

14-P-16 - FT-Raman spectroscopic studies of host-guest interactions in

zeolites
Y. Huang,J.H. Leech and R.R. Poissant
University of Western Ontario, Department of Chemistry, London, ON, Canada N6A 5B7

FT-Raman spectroscopy is a powerful technique for investigating host-guest interactions in

zeolitic systems via monitoring the guest species. In this presentation, we report our recent
results on the investigations of host-guest interactions in two aspects of zeolite chemistry: (1)
examining the dynamic and conformational properties of several closely related alkyl-
cyclohexanes including cyclohexane, methylcyclohexane and trans-l,4-dimethylcyclohexane
adsorbed inside ZSM-5 framework and (2) probing the reactivity of organometallic species
such as (rl6-benzene)tricarbonylchromium(0) on the surface of zeolite Y.

14-P-17 - High-temperature MAS N M R investigation of the mobility of

cations and guest compounds in zeolites X and Y
M. Hunger, A. Buchholz and U. Schenk
Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany

By high-temperature 23Na MAS NMR spectroscopy could be shown that the rapid exchange
of sodium cations in dehydrated zeolite Na-Y starts at ca. 573 K and is characterized by an
activation energy of EA = 20+2 kJ/mol. The ra~3id exchange of cesium cations in dehydrated
zeolite CsNa-Y starts at ca. 423 K. Applying Cs MAS NMR spectroscopy, an activation
energy for the cesium exchange in zeolite Y equal to that for the sodium exchange was
determined. These activation energies are significantly lower than those estimated for cesium
exchange processes observed at temperatures of 423 to 773 K for dehydrated zeolites CsNa-Y
and CsNa-X impregnated with cesium hydroxide as guest compound (EA ca. 85 to 115
kJ/mol).
 351

14-P-18 - Generation of long-lived electron-hole pairs through sorption of

Biphenyl into acidic ZSM-5 zeolites
I. Gener (a), A. Moissette (a), H. Vezin (a), J. Patarin (b) and C. Br6mard (a)
a Universit6 des Sciences et Technologies de Lille, Villeneuve d'Ascq, France
Claude. Br~mard@univ-lille 1.fr
b Ecole Nationale Sup6rieure de Chimie de Mulhouse, France.

The EPR, UV-visible investigations as well as Raman scattering results provide informative
clues about the formation and nature of long-lived electron-hole pairs through spontaneous
biphenyl ionization upon sorption in the void space of activated ZSM-5 zeolites. The
transferred electron is trapped within the framework by electron accepting site, while biphenyl
radical cation captures one electron from electron donating sites of zeolite framework to
restore BP ground state and causes an electron deficient hole.

14-P-19 - Defects study in microporous materials by HRSEM, H R T E M and

diffraction techniques
G. Gonzalez*, Z. Lopez* and R. Reichelt**
*Laboratorio de Materiales, Centro Tecnol6gico, lnstituto Venezolano de Investigaciones
Cientificas, IVIC, Caracas 1020A, Venezuela. e-mail. gegonzal@ivic.ivic.ve.
**Institut fur Medizinische Physik und Biophysik der Universitat Munster, Munster, Germany

Control synthesis of MFI, MEL and MFI/MEL intergrowth systems has been performed by a
systematic variation of different parameters: SIO2/A1203, template/SiO2, Na20/SiO2, H20/
SiO2, templates ratio (TPABr/TBABr), temperature and crystallization time. The study of the
relationship between synthesis parameters, crystal morphology, crystal size and density of
defects has been carried out. Detailed characterization has been performed by HRSEM,
HRTEM, x-ray diffraction, electron diffraction and sorption measurements.

14-P-20- The effect of the framework structure on the chemical properties

of the vanadium oxide species incorporated within zeolites and their
photocatalytic reactivity
S. Higashimoto a, M. Matsuoka a, M. Che b and M. Anpo a*
a Dept. Appl. Chem., Osaka Prefecture University, anpo@ok.chem.osakafu-u.ac.jp, Japan
b Laboratoire de R6activit6 de Surface, Universit~ P. et M. Curie, UMR7609, CNRS, France

XAFS (XANES and FT-EXAFS) and phosphorescence studies including lifetime

measurements of several types of vanadium silicalite catalysts clearly showed the oxidation
state and coordination geometry of the highly dispersed V-oxides as well as the local
distortion structure of these species in their framework structures. Furthermore, dynamic
quenching studies of the phosphorescence by adding reactant molecules showed that the
charge transfer excited triplet state of these V-oxides, (V4+ - O-)*, acted as active sites for the
photocatalytic decomposition reactions of NO both in the presence and absence of propane,
their reactivity being strongly dependent on the framework structure of these catalysts.
352

14-P-21 -Characterization of aluminium and iron sites in MCM-22

J. (~ejka (a), J. D6de~ek (a), J. Kotrla (a), M. Tudor (a), N. Zilkovd (a) and S. Ernst (b)
a J. Heyrovsl~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic; cejka@l'h-inst.cas.cz
b Department of Chemistry, Chemical Technology, University of Kaiserslautern, Erwin
SchrOdinger Strasse 54, D-67663 Kaiserslautern, Germany
Type and distribution of aluminium and iron in the framework of zeolite
MCM-22 were investigated using adsorption of d3-acetonitrile, pyridine and 2,6-di-tert-
butylpyridine followed by FTIR spectroscopy, sodium ion-exchange and UV-Vis
spectroscopy of Co 2+ ions located in cationic positions. Detailed analysis of aluminium and
iron distribution among single ions, ion pairs, Br6nsted and Lewis sites and internal and
"external" surface is provided.

14-P-22 - Valency and coordination states of iron in FeAPO-11. An in-situ MSssbauer

study
K. L~zfir (a), N. Zilkovfi (b) and J. (~ejka(b)
a Institute of Isotope and Surface Chemistry, Chemical Research Center, P.O. Box 77, H-
1525 Budapest, Hungary; b 3{. Heyrovsl~ Institute of Physical Chemistry, Academy of
Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic;
cejka@l'h-inst, cas. cz
Distribution of Fe 2§ and Fe 3§ framework ions and their coordinations in FeAPO-11 structure
were investigated employing M6ssbauer spectroscopy and X-ray powder diffraction.
. . . .
Simultaneous stablhzatlon of Fe 2 + and Fe 3 + ions in various coordination states was observed.
It was shown that the structure of FeAPO-11 is rather flexible and the coordination of iron
strongly depends on the form of pretreatment. Among ferrous ions, facile transition between
octahedral and distorted trigonal coordinations was observed.

1 4 - P - 2 3 - Comparative properties of modified HEMT and HY zeolites from

the FTIR study of CO adsorption" effect of the dealumination and
amorphous debris on the Br~insted acidity
O. Cairon (a) and T. Chevreau (b)
a LCTPCM, UMR 5624, rue Jules Ferry, Pau, cairon@univ-pau.fr, France
b Catalyse et Spectrochimie, ISMtL4-Universitd Caen, chevreau@ismra.fr

Progressive CO adsorption has been studied by FTIR spectroscopy on two series of acid-
leached steamed HEMT and HY zeolites with various Si/A1F ratios. Acidity of structural OH
groups of steamed hexagonal faujasites was determined and compared with the results already
obtained with the cubic series. Moreover, quantitative estimation of Br6nsted acidity of
extraframework phase (numbers and strength) was carried out and allowed to complete the
comparison between the two structural varieties. Only minor differences were detectable.
 353

14-P-24- Raman spectroscopic study of 2,2'-bipyridine sorbed into ZSM5

A. Moissette, C. Brdmard, I. Gener and N. Louchart
Laboratoire de Spectrochimie Infrarouge et Raman, Universit~ des Sciences et Technologies
de Lille, 59655 Villeneuve d'Ascq cedex, France, alain.moissette@univ-lillel.fr

Sorption of 2,2'-bipyridine (bpy) into the void space of Mm/nZSM-5 (m = 0, 3, 6; M = Na +,

Zn 2+, H +) zeolites was studied by Raman spectrometry. The differences in the spectra
obtained from the loaded zeolites have been rationalized in terms of probable conformation
within the zeolite channels. It appears clearly that bpy conformation depends on the aluminum
content of the framework, nature of cations and zeolite acidity, bpy occluded in silicalite-1
was found to be in the trans conformation. The non bonding interactions between the
extraframework Na + cation and occluded bpy stabilize the cisoid non-planar conformer,
whereas the coordination bonding between Zn and N atoms constrains the cis planar
9 9 9 2+ 9

conformation. In HZSM-5, bpy sorption results in both mono and diprotonation of bpy.

14-P-25 - Fractals of silica aggregates

Z. Li a, D. Wu a, Y.-H. Sun a*, J. Wangb, Yi Liu b and B. Dong b
aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry,
Chinese Academy of Sciences, Taiyuan 030001, P. R. China
bSynchrotron Radiation Laboratory, Institute of High Energy Physics,
Chinese Academy of Sciences, P.O.Box 918, Beij'ing 100039, P R China

Small Angle X-ray Scattering was used to determine the fractal property of silica aggregates
prepared by base-catalyzed hydrolysis and condensation of alkoxides in alcohol. As-produced
samples were found to be mass fractals. The fractal dimensions spanned the regime 2.1---2.6
corresponding to more branched and compact structures. Both RLCA and Eden models
dominated the kinetic growth under base-catalyzed condition

14-P-26 - Structure of Mo species incorporated into SBA-1 and SBA-3

studied by XAFS and UV-VIS spectroscopies
H. Yoshitake, S.H. Lim, S. Che and T. Tatsumi
Yokohama National University, Yokohama, yosh@kan.ynu.ac.jp, Japan

Direct incorporation of Mo into template-directed mesoporous silica was carried out via
acidic (S'X+I-) route. High Mo-loading was achieved (9 wt%, as MOO3) without destructing
the regularity of SBA-1 and SBA-3. The local structural environment of Mo was analysed by
UV-vis and EXAFS spectroscopies in comparison with that of Mo-impregnated mesoporous
silicas. Edge energy of UV-vis spectra and coordination number obtained from EXAFS
showed that Mo agglomerates more easily than in the case of impregnation while the local
symmetry of Mo did not differ significantly among the molybdosilicates.
354

14-P-27 - Quantification of electric-field gradients in the supercage of Y

zeolites by comparing the chemical shifts of 131Xe (I = 3/2) and 129Xe (I =
1/2)
Y. Millot, P.P. Man, M.-A. Springuel-Huet and J. Fraissard
Laboratoire de Chimie des Surfaces, CNRS ESA 7069, SystOmes Interfaciaux fi l'Echelle
Nanomdtrique, Universit~ Pierre et Marie Curie, 4 Place Jussieu, Casier 196, Tour 55, 75252
Paris Cedex 05, pm@ccr.jussieu.fr, France

In the supercages of HY zeolite, the difference in chemical shift (Scs(131Xe) - ~cs(129Xe)) of

the two NMR-observable isotopes 131Xe, which is sensitive to the electric-field gradient
(EFG), and i29Xe, which is not sensitive to EFG, is -5 ~lPm at room temperature. The latter
value is due to the second-order quadrupole shift of I Xe and provides us with the EFG
generated by the framework of this microporous material: 16.3xl 0 ~9V.m -2.

14-P-28 - Iron species present in Fe/ZSM-5 catalysts prepared by ion

exchange in aqueous medium or in the solid state
M.S. Batista a, M.A.M. Tortes b, E. Baggio-Saitovich b and E.A. Urquieta-Gonzfilez a
Dep. Chem. Eng./UFSCar, S6o Carlos- SP, Brazil. e-mail." urquieta@power.ufscar.br
bBrazilian Center for Research in Physics, Rio de Janeiro, Brazil.

The Fe species formed during the preparation of Fe/ZSM-5 catalysts by ion exchange in
aqueous medium or in the solid state were studied. XRD, EPR, M6ssbauer spectrocopy
(MOSS) and chemical analysis (AAS) were used to sample characterization. The catalysts
were evaluated through the propane oxidation in the range from 373 to 773 K. The MOSS
data evidenced the presence of Fe +3 species in charge-compensation sites and a more content
of hematite (Fe203) in the catalysts prepared in aqueous medium. In the propane oxidation,
the activity of the Fe/ZSM-5 can be correlated with the amount of Fe-cationic species,
confirming that they are the responsible for the catalytic activity.

14-P-29 - Laser ablation mass spectrometry: a technique for observing

zeolite occluded molecules
S. Jeong(a), K.J. Fisher(a), G.D. Willett(a) and R.F. Howe(b)*
a School of Chemistry, University of New South Wales, Sydney NSW 2052, Australia
b Chemistry Department, University of Aberdeen, Aberdeen AB24 3 UE, UK,
r.howe@abdn.ac.uk

Laser ablation mass spectrometry (LAMS) uses a pulsed laser to destroy zeolite structures,
release and ionize molecules occluded within the zeolite pores. High resolution mass
spectrometry can then be used to study the ions produced. This paper describes LAMS studies
on two well defined model systems: hexamethylbenzene(HMB) adsorbed in NaFAU, and the
tetrapropylammonium(TPA) template in MFI. It is shown that LAMS can be used to identify
the adsorbed species.
 355

1 4 - P - 3 0 - Characterisation of TS-I active sites by adsorption of organic

probes
C. Flego*, A. Carati and M.G. Clerici
EniTecnologie S.p.A. cflego@enitecnologie.eni.it - S. Donato Mil. (MI) - Italy

UV-Vis-IR spectroscopy shows the involvement of Ti sites of TS-1 in the adsorption of

oxygenated probes (i-propanol, diethyl ether, propylene oxide, glycols) and pyridine. The
interaction affects the IR signal at 3725 cm l, which is tentatively attributed to TiOH groups.
In partially hydrated TS-1, lattice Ti is involved in the sorption of organic molecules directly
through one OH group and indirectly influencing the environment through the nearest SiOH
groups. S-1 shows in the comparison with TS-1 a lower density and a weaker strength of
adsorption of the organic probes. The interaction of the probes with Ti sites is reinforced
through co-operative H-bonds in MFI zeolitic structure, while in the amorphous mesoporous
titanium-silicalite this phenomenon is less relevant.

14-P-31 - NIR FT-Raman spectroscopy on molecular sieves

E. L6ffler and M. Bergmann
Lehrstuhl Technische Chemic, Ruhr-Universiti~t Bochum, P.O. Box 102148,
D-44780 Bochum, Germany

The potential of NIR FT-Raman spectroscopy for the investigation of zeolites (vanadyl-
containing MFI, TS-1) as well as alumophosphate-based molecular sieves (AEI, CHA, CLO)
are described. In Raman spectra of template containing samples bands of the organic species
dominate. By dispersive Raman microscopy a spatial distribution in a CoAPO-34 crystal is
observed. The Raman spectra allow a very rapid and sensitive detection of anatase formed
during thermal treatment of as-synthesised titanium-containing zeolites. Different vanadium
species are detected in vanadium-containing ZSM-5.

14-P-32 - Characterization of Zn and Fe substituted mordenite by X A F S

M. Dong, J.-G. Wang* and Y.-H. Sun
State Key Laboratory of Coal Conversion, Taiyuan, Shanxi, iccjgw@sxicc.ac.cn, P.R. China
The local structures of Zn (II) and Fe (III) in the lattice framework of mordenites have been
characterized by means of X-ray Absorption Fine Structure. The main absorption structure of
the XANES reveals the covalent bonding between the heteroatom and the lattice oxygen
atom. The pre-edge structure appeared in XANES spectra of (Si, Fe)-MOR suggests a
tetrahedral structure of Fe, which confirms the incorporation of Fe into the zeolite framework.
Furthermore, the tetrahedral structure of the heteroatoms in the framework and their
coordination distances are determined by using EXAFS technique.
356

14-P-33 - Identification of vanadium species in VAPO and V A P S O alumi-

nophosphate by UV resonance raman spectroscopy
Jia. Yu, Z. Liu*, Q. Xin and C. Li
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, P. O. Box 110, Dalian 116023, zml@dicp.ac.cn,
China

A sensitive UV resonance Raman spectroscopy has been used to characterize both VAPO-5
and VAPSO-5 aluminophosphate. UV-Raman spectra of VAPO-5 suggest that three different
vanadium species exist in VAPO-5, but the framework vanadium species are not observed.
However, the framework vanadium species exist in VAPSO-5 and are located in the matrix of
framework silica.

14-P-34 - On the interaction of H20 with TS-I: a spectroscopic and ab-initio

study
A. Damin (a), G. Ricchiardi (a), S. Bordiga (a), F. Bonino (a), A. Zecchina (a), F. Ricci (b),
G. Span6(b), F. Villain (c) and C. Lamberti (a)
a Dipartimento di Chimica 1FM, Via P. Giuria 7, 1-10125 Torino, Italy, Damin@ch.unito.it
b EniChem S.p.A., Centro Ricerche Novara, "lstituto Guido Donegani
d Laboratoire de Chimie lnorganique et Mat~riaux Mol&ulaires ESA CNRS 7071 Paris
We report an IR, EXAFS and ab-initio study on the interaction of TS-1 with water. IR
spectroscopy shows that water is reversibly adsorbed at RT, indicating a weak interaction
between H20 molecules and TS-1. EXAFS has evidenced an elongation of the 4 Ti-O bonds
of only 0.03 A upon water adsorption. On a theoretical ground, the adsorption of a water
molecule has been investigated on three clusters of increasing size: [Ti(OH)4)], [Ti(OSiH3)4]
and [TiOsSi6Hl2]. On the two bigger clusters a binding energy in the range of 10-15 kJ/mol
has been obtained. Our study confirms that TS-1 is a rather hydrophobic material.

14-P-35 - Spectroscopic study of the nature of vanadyl groups: influence of

the support (SiO2 and All] and SiB zeolites)
S. Dzwigaj (a,*), M. Matsuoka (a), M. Anpo (b) and M. Che (a,c)
(a) Laboratoire de R~activit~ de Surface, Paris, France
dzwie.ai(i~ccr./ussieu.fr; (b) Department of Applied Chemistry, Osaka Prefecture University, Osaka,
Japan," (c) Institut Universitaire de France

Diffuse reflectance UV-Visible and photoluminescence spectroscopies have been used to

study the local environment of vanadium ions dispersed on the surface of amorphous (SiO2)
and crystalline (non-dealuminated A1B and dealuminated SiB zeolites) supports. It is
demonstrated that the molecular structure of vanadium (V) species depend strongly on the
nature of the support. The application of photoluminescence spectroscopy allows to
distinguish in as prepared VSiO2, VA1B and VSiB materials one, two and three kinds of
tetrahedral vanadium (V) species, respectively.
 357

14-P-36 - Characterization of Ni, Pt zeolite catalysts by TEM and EDX

M.H. Jordgo and D. Cardoso
Chemical Engineering Department, Federal University orS. Carlos, S6o Carlos-SP, Brazil.
Fax." (+55-16) 260-8264. pmhj@iris.ufscar.br and dilson@power.ufscar.br

Bimetallic bifunctional catalysts containing different proportions of Ni and Pt supported in

HUSY zeolite were prepared and characterized by TEM, punctual EDX analysis and n-hexane
isomerization. The EDX analysis of the Ni and Pt bimetallic catalysts shows that the metal
particles contain both metals and from HRTEM it was observed that the bimetallic particles
have crystallographic parameters of metallic nickel. The presence of small platinum amounts
in the nickel catalysts produces more active catalysts for the n-hexane isomerization, and
presents also higher selectivity for the formation of dibranched hexane than the ones
containing only platinum.

14-P-37 - N M R and ESR investigations of alkali metal particles in NaY

zeolite
F. Rachdi a*and L.C. de M6norval b
~GDPC, UMR 5581 CNRS, UM2, Montpellier, France, ferid@gdpc.univ-montp2.fr
bLMC30, UMR 5618 CNRS, ENSCM, Montpellier, France, demenor@cit.enscm.fr
NaY zeolite loaded with sodium or rubidium metals vapor phase deposition has been
investigated by ESR, 129Xe, 23Na and 87Rb NMR. Exposure of the zeolite to a high Na
concentration leads to a single ESR line which is attributed to Na metallic particles inside the
zeolite cavities. 129XeNMR spectrum of NaY zeolite loaded with Na shows three lines at 88,
94 and 134 ppm which are interpreted in terms of domains of nonuniformely distributed metal
particles. By annealing at 670 K the spectrum collapses to a single line at 120 ppm,
characteristic of a narrow particle size distribution. 23Na and 87Rb NMR spectra in the
temperature range 260 K-300 K were obtained for Rb loaded NaY zeolite. The observed
resonances can be explained by the presence of Na/Rb alloy phase in the zeolite cavities.

14-P-38- Topochemical changes in large MFl-type crystals upon thermal

treatment in oxidizing and non-oxidizing atmosphere
O. Pachtovfi (a), B. Bernauer (b), J.-A. Dalmon (c), S. Miachon (c), I. Jirka (a), A. Zikfinovfi
(a) and M. Ko~ifik (a)
a *J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Praha, kocirik@jh-inst.cas.cz, Czech Republic; b Institute of Chemical Technology, Praha,
Czech Republic; c Institute de Recherches sur la Catalyse (CNRS), Villeurbanne, France

TPAOH removal from large as syntesized silicalite-1 crystals with internal morphology of
90~ has been investigated in regimes with gas flow in parallel to and through the
crystal layer both in absence and presence of oxygen. The void space accessibility of crystals
was estimated from sorption isotherms of N2 which exhibited as a rule two steps. The
topochemical changes in crystals after a partial template removal were evaluated using light
microscopy, ESCA measurements and elemental analysis of organic residues.
358

14-P-39- Structure of Fe(III) sites in iron substituted aluminophosphates: a

computational and X-ray spectroscopic investigation
C. Zenonos(a), A. Beale(a), G. Sankar(a), D.W. Lewis(b), J.M. Thomas(a) and C.R.A.
Catlow(a)
a Davy Faraday Research Laboratory, The Royal Institution ofGB, sankar@ri.ac.uk United
Kingdom; b Department of Chemistry, University College London, United Kingdom

We compare the structure of Fe(III) active sites in the small pore FeA1PO-18 and large pore
FeA1PO-5 catalysts prepared using appropriate structure directing agents. The present study
clearly points out that it is possible to substitute Fe(III) ions for tetrahedrally coordinated
AI(III) in the framework of A1PO-5 and A1PO-18 to yield an active and selective oxidation
catalysts. The use of atomistic simulations is again proven to provide accurate geometries
which, when combined with the analysis of the EXAFS data, yield accurate models for the
active sites.

14-P-40 - Possible formation of Cu +2(CO)2( H 20). complexes in a ZSM-5

zeolite prepared by direct synthesis: evidence for the occurrence of Cu+-Cu +
pairs?
F. Geobaldo 1, B. Onida ~, M. Rocchia l, S. Valange 2'3, Z. Gabelica 2 and E. Garrone l'*
/Dipartimento di Scienza dei Materiali e In~egneria Chimica, Politecnico di Torino, Torino
Italy E-Mail geobaldo@athena.polito.it; Universitd de Haute Alsace, ENSCMu, GSEC,
Mulhouse, France," 3LACCO, UMR CNRS 6503, ESIP, Poitiers, France

Cu-ZSM-5 zeolite prepared by direct synthesis via a methylamine route show Cu + species as
defined as those present in samples prepared by CuC1 vapour exchange. The IR study of the
reversible interaction of water with presorbed CO shows a variety of bands, the most plausible
interpretation of which is the formation of species (HzO)nCOCu+(OH)Cu+CO(HzO)m (n,m -
0,1,2), which suggests the occurrence of Cu + species in pairs.
 359

22 - A d v a n c e d Materials (Thursday)
22-P-06 - Tailored generation of titanium oxide species within porous
Si-MCM-41
P. Prochnow (a), G. Schulz-Ekloff (a), M. Wark (a,b), J.K. Thomas (b), A. Zukal (c) and J.
Rathousky (c)
a Institute of Applied and Physical Chemistry, University of Bremen, Germany,
mwark@chemie.uni-bremen.de; b Department of Chemistry and Biochemistry, Notre Dame
University, USA; c J. Heyrovsky Institute of Physical Chemistry, Prague, Czech Republic

It is elaborated, that the generation of titanium oxide species of tailored and uniform size into
Si-MCM-41 as host material does not only depend on the amount of titanium compounds
added in one step, but also on the repeated addition and hydrolysis of the titanium compound
in consecutive steps. Anatase nanoparticles of a well-defined size of up to 3 nm, Ti(IV) oxide
oligomers and mononuclear Ti(IV) oxide species, respectively, were generated without a
substantial enrichment of titanium oxide particles on the extemal surface of the Si-MCM-41
host. Depending on the size and content of the Ti(IV) oxide species, the fluorescence of
co-impregnated dye molecules was statically quenched to varying extent.

22-P-07 - Optical switching with photochromic dye molecules encapsulated

in the pores of molecular sieves by in-situ synthesis
C. Schomburg (a), D. W~hrle (a), G. Schulz-Ekloff (b) and M. Wark (b)
a Institute of Organic and Macromolecular Chemistry, University of Bremen, Germany ; b
Institute of Applied and Physical Chemistry, University of Bremen, Germany,
mwark@chemie, uni-bremen,de
Spiropyran or its configurational isomers (merocyanines), respectively, are incorporated in the
supercages of faujasite (NAY, HY and DAY) by in-situ synthesis. Luminescence spectra of
the colored isomers indicate the non-aggregated incorporation of merocyanine forms.
Photochromism experiments exhibit high quantum yields for the photoinduced switching
between the different configurational isomers. The strong retardation of the thermal relaxation
rate from the cis isomer to the trans isomer in the faujasite hosts is attributed to an increase of
the rotation barriers by the imposed spatial restrictions. A strongly increased stability towards
photobleaching is found with respect to spiropyrans stabilized in organic polymers or SiO2
based MCM-41 matrices.

22-P-08 - F o r m a t i o n of carbon nanotubes on various molecular sieves

supported metal oxides
A.M. Zhang, Q.H. Xu, J.J. Zhao and J.M. Cao
Department of Chemistry, Nanjing University, Nanjing, 210093, P. R. China
The carbon nanotubes were formed on metal oxide-supported zeolite by the decomposition of
acetylene hydrocarbon at 700~ The optimum reaction conditions of growth of nanotubes on
various molecular sieve catalysts, including Y, A, MOR, ZSM-5 and MCM-41, were studied.
Fe/Co-supported Y zeolite catalyst may be the best catalyst for growth of nanotubes in them.
Masses of carbon nanotubes with uniform diameter of about 30 nm were obtained over
pretreated Y zeolite. The states of iron in Fe-supported Y catalyst measured by M6ssbauer
spectrum during three stages of original, hydrogen reduced and catalytic synthetic nanotubes
indicated that the hydrogen generated during the reaction is enough to reduce the Fe(III) to
sub-valence active state. The nanotubes of larger diameter may be as the template of GaN
growth.
360

22-P-09 - Encapsulation of Tb[(CIBOEP)4P](acac) in Si-MCM-41 by the

method of ship-in-bottle and its luminescent properties at 77 K
Q. Xu(a), Z. Zhao(b), L. Li(a), G. Liu(b), H. Ding(a), J. Yu(a) and R. Xu(a)
a: Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130023, People's Republic of China. E-mail:rrxu@mailjlu.edu.cn
b." Chemistry Department, Jilin University, Changchun 130023, People's Republic of China.

Tb[5,10,15,20-tetra(para-(4-chlorobenzoyloxy)-meta-ethyloxyphenyl)Porphyrin] (acetylacet-
one) denoted as Tb[(C1BOEP)4P](acac) has been prepared by encapsulating Yb(acac)3 into
(CIBOEP)4P-doped Si-MCM-41. The properties of the samples are studied by ICP, XRD,
ESR, UV-vis, XPS and spectrofluorometry. It is found that the assembly has better
luminescent properties than the pure complex at 77 K.

2 2 - P - 1 0 - A new adsorbent with magnetic properties based on natural

clinoptilolite
V. Pode (a), V. Georgescu (b), V. Dalea (a), R. Pode (a) and E. Popovici (b)
a University "Politehnica" of Timisoara, Romania, Email: tcapm@rectorat.utt.ro
b University "AI. I. Cuza" oflasi, Bvd. Copou No. 11, 6600 Iasi, Romania

The present research aimed to use the Romanian volcanic tuff as an adsorbent material with
magnetic properties. The magnetic properties were induced by a chemical method for
covering the volcanic tuff particles with magnetite. The modified volcanic tuff was
synthesized by varying some parameters that could influence the adsorption and magnetic
properties. The magnetic characteristics of the samples were investigated by induction using a
Howling device. The adsorbent material could be used for pollution abatement in viscous
media contaminated by highly toxic metal ions that could be separated afterwards based on
their magnetic properties.

22-P-11 - Preparation of microcalorimetric gas sensors with C o A P O - 5

S. Mintova (a), J. Visser (b) and T. Bein (a)
aDepartment of Chemistry, University of Munich, Butenandtstr. 5-13 (E), 81377 Munich,
Germany, svetlana, mintova@cup, uni-muenchen, de
bFord Research Laboratory, MD 3028, Dearborn, M148121-2053, USA

Microcalorimetric sensors were prepared by direct synthesis and impregnation of Co in the

AFI type material. The synthesis of the CoAPO-5 samples was performed under hydrothermal
conditions in a microwave oven using various concentrations of Co, organic template and
different conditions of a microwave irradiation. The resulting powder samples used for further
preparation of calorimetric sensors were characterized using XRD, TG, nitrogen sorption and
UV-vis spectroscopy. The CoAPO-5 films were formed by a drop coating method and tested
as gas sensors toward carbon monoxide and cyclohexane. The temperature-change of the
sensors depends on the amount and the location of the Co in the AFI type structure and on the
accessible pore volume.
 361

22-P-12 - Study of cation-exchange properties of an organozeolite

V.A. Nikashina, E.M. Kats, I.V. Komarova, N.K. Galkina and K.I. Sheptovetskaja
Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences,
Kosygin str. 19, Moscow 117975, Russia."fax" (095)-938-2054,
e-mail" elkor@geokhi, msk. su

To evaluate the cation-exchange properties of organozeolite-Clinotsides obtained on the basis

of the natural clinoptilolite-containing tufts of Tedzami (Georgia) and Holinskoye (Russia)
deposits, an earlier developed method of determining their effective equilibrium and kinetic
characteristics including the comparison of theoretical and experimental breakthrough curves
was used. The quantitative characteristics of cation-exchange processes were obtained. It is
shown that there is significant influence of the modification on the kinetic of the cation-
exchange on Clinotsides.

22-P-13 - A d v a n c e d electrode materials based on m e s o p o r o u s a l u m i n u m -

stabilized anatase
A. Attia (a), S.H. Elder (b), R. Jir~isek (a), L. Kavan (a), P. Krtil (a), J. Rathousk~, (a) and A.
Zukal (a)
a J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolej~kova 3, 182 23 Prague 8, Czech Republic, rathous@/h-inst.cas.cz
b The William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest
National Laboratory, Richland, Washington 99352, U.S.A.

A novel mesoporous molecular sieve was prepared whose framework is composed of anatase
nanocrystals stabilized by aluminum. The material was characterized by X-ray diffraction,
Raman spectroscopy, nitrogen adsorption and lithium insertion electrochemistry. The faradaic
capacity and charge-transfer kinetics is considerably higher that those of analogous structures
stabilized by Zr.

22-P-14 - Dye-zeolite assemblies for optical sensing applications

J.L. Meinershagen and T. Bein*
Department of Chemistry, Ludwig Maximilians Universit~it, Butenandtstr. 11-13 (E),
81377 Munich, Germany. Julia.Meinershagen@cup. uni-muenchen.de

The aim of this work is to combine the shape selectivity of zeolites with the chemical
sensitivity of solvatochromic dyes; this has been explored for the application of size-selective
vapor sensing. Solvatochromic dyes are extremely sensitive to their surrounding environment
and display large wavelength shifts in visible and fluorescence spectra reflecting changes in
polarity. Dye / zeolite ensembles were prepared by ion exchange and inclusion synthesis as
well as direct adsorption. Optical responses to various organic analytes have been measured
using visible diffuse reflectance and fluorescence spectroscopy. Fast and reversible optical
changes have been observed for a wide range of molecules.
 362

2 2 - P - 1 5 - A new s o r b e n t based on c l i n o p t i l o l i t e - c o n t a i n i n g tuff modified by

polyethylene
I.N. Meshkova (a),V.A. Nikashina (b),T.M. Ushakova (a),V.G. Grinev (a) ,N.Yu. Kovaleva
(a), A.A. Zaborskii (b), T.A. Ladygina (a) and L.A. Novokshonova (a)
~Semenov Institute of Chemical Physics RAS, lnov@center.chph.ras.ru, Russia.
bVernadsky Institute of Geochemistry and Analytical Chemistry RAS, elkor@geokhi.su,
Russia.

Clinoptilolite-containing tuff (CT) dust was modified by the catalytic polymerization of

ethylene on the surface of CT particles. The compositions with 3-5wt.% of polyethylene (PE)
and 97-95 wt.% of CT were obtained. The thin PE coating formed on the CT particles was
permeable to the filtrating water solutions. As a result of encapsulation of the CT particles, the
filter properties of this sorbent were improved. The ion-exchange characteristics of the
modified CT (powder and pressed tablets) with respect to NH4 + and Sr2+ cations were
determined. It was shown that CT dust-PE compositions retained the ion-exchange properties
of initial CT.

22-P-16 - M o l e c u l a r sieves from pillaring of s o m e r o m a n i a n bentonite

E. Popovici a, I. Bedelean b, D. Pop b, G. Singurel a, D. Macocinschi c and H. Bedelean b
~"Al.I.Cuza" University of Iasi, Romania, eveline@uaic.ro; b"Babes Bolyai" University of
Cluj-Napoca, Romania; c "P.Poni" Institute of Macromolecular Chemistry

We report here preliminary results of the physicochemical characterization of a composite

material obtained by combining the cethyltrimethylammonium cations clay insertion
procedure with the room temperature synthesis of mesoporous materials inside of clay layers.
The Romanian bentonite, containing 64% montmorillonite was used. The organic cations are
incorporated within the interlayer region of the clay, serving to prop open the layers and to
allow incorporation of the silicon source for MCM-41 synthesis. The obtained materials
display a high thermal stability and molecular sieve properties.

22-P-17 - Electronic states and a r r a n g e m e n t s of AgI and CuI clusters

i n c o r p o r a t e d into zeolite L T A
T. Kodaira a and T. Ikeda b
aNational Institute of Materials and Chemical Research, Tsukuba, Ibaraki 305-8565, Japan,
kodairanimc.jp; bNational Institute for Research in Inorganic Materials, Tsukuba, Ibaraki
305-0044, Japan

Both AgI and CuI clusters were successfully incorporated into the cages of Na-type LTA. The
maximum loading densities of the AgI and CuI molecules per a-cage were 4.0 and 6.3,
respectively. In the optical spectra, the lowest absorption bands of both kinds of clusters show a
large shift to the higher energy side compared to that of the original bulks. It was found that the
space group of the original Na-LTA, Fm3 c, changed to lower symmetry ones by incorporation of
both kinds of clusters. These are determined by the appearance of new reflections in the X-ray
powder diffraction patterns. The physical properties of these two kinds of clusters seem to be
slightly different. CuI molecules adsorbed sparsely into the cage have the property to aggregate
and form a cluster. The CuI clusters have large electron-vibration interaction.
 363

22-P-18- PbI2 nanoclusters in zeolite LTL: host-guest chemistry and optical

properties
G. Telbiz(a),O. Shvets(a), V. Vozny(b) and M. Brodyn(b)
a. Institute of Physical Chemistry, National Acad. Sci.,Kyiv, gtelbiz@alfacom.net, Ukraine
b. Institute of Physics, National Acad. Sci., Kyiv, Ukraine

We report on the development of host-guest interaction and optical properties in course of

preparation procedures of semiconductor clusters PbI2 in the LTL matrix. For the samples
with relatively high PbI2 content the narrow emission peak only slightly blue-shifted from
Eex was observed. The gradual disappearance of this peak during the storage of the samples
in the air is explained by assuming that originally formed long clusters undergo fragmentation
into smaller species.

22-P-19 - Application of the molecular sieves as matrices for the pigments

S. Kowalak, A. Jankowska, N. Pietrzak and M. Str6zyk
Faculty of Chemistry, A. Mickiewicz University, Poznah, Poland.
sko walak~m ain. am u. edu. 191

The uniform intracrystalline voids of the molecular sieves can be employed for encapsulation
of molecules containing chromophore groups and they can result in forming pigments.
Natural lazurite is a good example of zeolite (sodalite) containing sulfur anion-radicals
encapsulated in ]3-cages. We demonstrate here that the above radical can be also introduced
into AIPO4 sodalite (A1PO4-20), but the attempts to encapsulate it to zincophosphate sodalite
were unsuccessful. The latter structure could, however, accommodate CdS molecules, when
they are encapsulated during the dry crystallization of SOD. The organic cation-radicals
generated in the MFI structure channels (HZSM-5, H-ferrosilicalite, H-zincosilicalite) as a
result of oligomerization of styrene and its derivatives form very stable pigments of various
colors.

22-P-20 - Laser dye doped mesoporous silica fibers: host-guest interaction

and fluorescence properties
G. Telbiz(a), O. Shvets(a), S. Boron(a), V. Vozny(b), M. Brodyn(b) and G.D. Stucky (c)
a. Institute of Physical Chemistry, National Acad. Sci.,Kyiv, gtelbiz@alfacom.net, Ukraine
b. Institute of Physics, National Acad. Sci., Kyiv, Ukraine," c. Department of Chemistry,
University of California,, Santa Barbara, CA, USA

Transparent mesoporous fibers with excellent order and parallel pores and doped by laser dye
are prepared with good reliability. Influence of the nature of laser dye on the host- guest
interaction is shown. Optical properties of Rhodamine 6G and Coumarine 120 embedded in
mesoporous fiber waveguide have demonstrated utility for new laser materials, microphotonic
devices or microreactors with increasing thermostability of dye component. The opportunity
of preparation of the composite materials mesoporous fiber / semiconductor is shown.
364

22-P-21 - Spectroscopic properties of dye-loaded mesoporous silicas of the

structural type MCM-41
B. Onida l, B. Bonellil, M. Lucco-Borleral, L. Floral, C. Otero Are~.n2 and E. Garrone l
1Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Italy,
onida@athena.polito.it," 2Departamento de Qu[mica, Universidad de Las Islas Baleares,
Palma de Mallorca, Spain.

Dye-containing mesostructured silica and zeolitic materials are interesting for their potential
application in optical devices and as chemical sensors. Congo Red and Curcumin, two pH
indicators, have been incorporated in MCM-41, precursors, which have been characterised by
means of X-ray diffraction, UV-Visible and FTIR spectroscopy. Dyes are located in the
micellar phase of the silica-surfactant mesophase and their spectroscopic properties confirm
that they are in a solvated state, where both surfactant and silica wall may act as a solvent.
Dyes maintain their pH indicator properties and are accessible to gases such as HC1 and NH3.
 365

27 - Selective Oxidation over Micro- and Mesoporous Catalysts (Thursday)

27-P-06 - Microporous metallosilicates for the oxidation of hydrocarbons:

preparation, characterization and catalytic activity
U. Arnold (a), R.S. da Cruz (b), D. Mandelli (c) and U. Schuchardt (a).
a Universidade Estadual de Campinas, ulf(-&iqm,unicamp, br, Brazil.
b Universidade Estadual de Santa Cruz, Ilh~us, Brazil.
c Pontificia Universidade Cat6lica de Campinas, Brazil.

Metallosilicates containing Cr, Cu or Mo have been prepared by an acid-catalyzed sol-gel

process. Structural information about the silicates were obtained by elemental analysis, TGA,
XRD, XRF, N2-physisorption, EPR, UV/VIS and FTIR spectroscopy. The silicates are active
catalysts for the oxidation of hydrocarbons with tert-butyl hydroperoxide. Catalyst stabilities
with regard to metal leaching during catalytic oxidations were investigated.

27-P-07 - High catalytic activity of Fe (Ill)-substituted aluminophosphate

molecular sieves (FeAPO) in oxidation of aromatic compounds
X. Meng, Y. Yu, L. Zhao, J. Sun, K. Lin, M. Yang, D, Jiang, S. Qiu and F.-S. Xiao*
Dept. of Chemistry, dilin Univ., Changchun 130023, China, E-mail.'fsxiao@mail.jlu.edu.cn

Iron substituted aluminophosphate molecular sieves (Fe-A1PO4-11, Fe-AIPO4-5 and Fe-VPI-

5) are catalytically active in oxidations of aromatic compounds such as hydroxylation of
phenol, benzene, and naphthol, as well as epoxidation of styrene. Catalytic data show that the
activities of Fe-A1PO4-11, Fe-AIPO4-5 are comparable with that of TS-1 in the oxidation of
aromatic compounds. Furthermore, Fe-VPI-5 shows high activity in naphthol hydroxylation
by H202, while TS-1 is completely inactive due to the small pore size. By comparison of
various catalysts, Fe (III) in the framework is considered to be the major active site in the
catalytic reactions.

27-P-08 - Selective oxidation of propyl alcohols over zeolites modified with

cations of the transition metals
A.M. Aliyev, D.B. Tagiyev, S.M. Medzhidova, S.S. Fatullayeva, A.R. Kuliyev, T.N.
Shakhtakhtinsky, G.A. Ali-zade and K.I. Matiyev
Institute of Theoretical Problems of Chemical Technology of the Academy of Sciences of
Azerbaijan, 370143, Baku, H.david ave., 29, Azerbaijan, E-maih ITPCHT@lan.ab.az.

Activity and selectivity of natural (pure and dealuminated clinoptilolite and mordenite) and A
synthetic zeolites modified with cations of the transition metals (Cu 2+, Co/+, Cr 2+, Zn 2+ and
Pd 2+) have been tested in vapor phase oxidation of iso-propyl and n-propyl alcohols. The
efficient catalyst, CuPdH-mordenite has been selected for the oxidation of iso-propyl alcohol
to acetone. It has been shown that this catalyst is not efficient in the oxidation of n-propyl
alcohol. The catalyst prepared from A synthetic zeolites and containing Pd 2+ and Cu 2+ shows
the highest activity in this reaction.
366

27-P-09 - Niobium leaching from the catalysts applied in the sulfoxidation

of thioethers with hydrogen peroxide
M. Ziolek, A. Lewandowska, M. Renn, I. Nowak, P. Decyk and J. Kujawa
Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 60-780 Poznan, Poland
E-mail: ziolek@amu.edu.pl

Micro- and mesoporous materials containing niobium in the framework or extra framework
positions were studied in the oxidation of dibutyl sulphide with H202. Leaching of Nb from
the solid to the liquid phase was considered. Some of the catalysts prepared via the
impregnation with Nb-salts show some leaching of Nb to the liquid phase and the oxidation
partially occurs homogeneously in the liquid phase. The reaction proceeds mainly on the
catalyst surface when the mesoporous molecular sieves containing Nb in the framework are
used.

27-P-10- Biomimetic oxygen transfer by Co and Cu complexes immobilized

in porous matrices
K. Hernadi (a), I. Pfilink6 (b), E. B6ngyik (a) and I. Kiricsi (a)
a Department of Applied and Environmental Chemistry, University of Szeged, Rerrich B. tdr
1, Szeged, H-6720 Hungary, hernadi@chem.u-szeged..hu; b Department of Organic
Chemistry, University of Szeged, D6m tdr 8, Szeged, H-6720 Hungary

Co(II) or Cu(II) histidine or imidazole complexes were immobilized in porous matrices

(montmorillonite and MCM-41) via two methods (introduction of preformed complex or
complex formation within the ion-exchanged host substances). It was found that
immobilization in general and the latter method in particular increased catalytic activity and
catalyst life time in the decomposition reactions of hydrogen peroxide relative to the matrix-
free complexes. The immobilized materials were characterized by experimental and
computational methods and the structures of the guest molecules inside the hosts were also
investigated.

27-P-11 - Titanium molecular sieves convert hydrogen peroxide into 102

F.M. van Laar, a D.E. De Vos, a P. Grobet, a J.-M. Aubry, b L. Fiermans c and P.A. Jacobs a
Centre for Surface Chemistry and Catalysis, Leuven, Belgium,
pierre.jacobs@agr.kuleuven.ac.be, bEquipe de Recherches sur les Radicaux Libres et
l'Oxygbne Singulet, Lille, France," ~Department of Solid State Sciences, Gent, Belgium

The interactions of Ti molecular sieves with H202 were investigated with near infrared
luminescence spectroscopy to detect the characteristic 1270 nm emission of the short-lived
excited singlet molecular oxygen (IO2). From these experiments it was concluded that (1) for
all titanium molecular sieves tested, part of the H202 is converted to 102, (2) higher H202
concentrations result in more singlet molecular oxygen, (3) increasing titanium content of the
molecular sieve does not result in more 102 production and (4) particularly the hydrophilic
(Ti,A1)-13 produces 102 at a high rate.
 367

27-P-12 - Propane oxidation on Cu/ZSM-5 catalyst: The effect of copper

and aluminum content in the reducibility and in the activity of Cu active
species
M.S. Batista and E.A. Urquieta-Gonzfilez
Dep. Chem. Eng./UFSCar, S~o Carlos- SP, Brazil. e-mail: urquieta@power.ufscar.br
The effect of Cu and A1 content in Cu/ZSM-5 catalysts on the nature of the formed Cu species
was studied. The samples were characterized by XRD, AAS, DRIFTS, EPR and Hz-TPR and
the activity was checked in the propane oxidation. The samples, irrespective of their Si/A1
ratio and Cu content, show a reduction peak at 210~ which, as evidenced by DRIFT of CO
adsorption, corresponds to the reduction of Cu +2 to Cu +l. The reduction peak of Cu +! shifts to
higher temperatures with the increase of Si/A1 ratio or with the diminution of Cu/A1 ratio,
evidencing that isolated Cu cations present a higher interaction with the zeolite structure. The
propane conversion, irrespective of Si/A1 ratio, increased with Cu content in the solid and the
TOF number correlated inversely with the Cu/A1 atomic ratio in the zeolite.

2 7 - P - 1 3 - Oxidizing conversion of isobutanol on zeolites

S.Zulfugarova
Institute of Inorganic and Physical Chemistry Azerbaijan Academy of Sciences
chem@dcacs.ab.az
Oxidizing conversion of isobutanol on Na, Cu, Co and F e - forms of zeolites of Y, erionite
and mordenite types was studied. Zeolite CuY shows the greatest activity in the formation of
isobutyric aldehyde (--30%); other samples are suitable for stronger oxidization and
dehydration reactions. It was demonstrated by thermodesorption that there is one form of
adsorbed oxygen with maximum temperatures of 100 -130~ on Na-erionite and Na-
mordenite. There are high-temperature adsorbed forms of oxygen with maximum
temperatures of 120-150, 400-450 and above 600~ on Ni-erionite and Cu-mordenite

27-P-14 - Photocatalytic production of H202 over heterogenized quinone in

zeolite
J.S. Hwang, C.W. Lee, H.S. Chai and S.-E. Park*
Catalysis Centerfor Molecular Engineering, KRICT, Taejon 305-606, Korea;
separk@pado, krict,re. kr

The photocatalytic production of H202 from ethanol and 02 is studied by using zeolite-
heterogenized quinone catalysts under UV light of 300-400 nm. The photochemical reaction
between ethanol an~ 02 initiated by quinone catalysts produces H202 and acetaldehyde
equivalently. The/qflinone compounds are heterogenized by both encapsulation method in
zeolite pore and anchoring method on zeolite surface. The anthraquinone-2-carboxylic acid
(AQCA) catalysts anchored on Pd~ zeolite exhibit enhanced catalytic activity in the
formation of H202 from ethanol and 02 as compared with encapsulated quinone catalysts of
the Pd~ The anchored AQCA does not leach out and prevent leaching of encapsulated
AQCA during the reaction.
368

27-P-15 - Liquid-phase oxidation of cyclohexane in the presence of

chromium and iron ETS-10 materials
A. Valente a, P. Brand~o b, Z. Lin a, F. Gon~alves a, I. Portugal a, M.W. Anderson b and J. Rocha a
a Departamento de Quimica, Universidade de Aveiro, 3810-193 Aveiro, Portugal
rocha@dq.ua.pt, Portugal.
b Department of Chemistry, UMIST, PO Box 88, Manchester M60 1QD, UK

The introduction of chromium or iron in microporous titanosilicate ETS-10 provides

interesting redox properties for cyclohexane oxidation, using H202 as oxidant, under moderate
reaction conditions, that ETS-10 alone does not possess. The main reaction products are
cyclohexanol and cyclohexanone. Selectivity to the latter is maximum when acetonitrile is the
solvent. The observed reactivity trend for these catalysts towards cyclohexane oxidation
decreases when the trapping efficiency of the solvent towards hydroxyl radicals increases.
Cyclohexane conversion increases with HEOE/cyclohexane ratios. Metal leaching from these
materials during oxidation accounts for loss of catalytic activity upon recycling.

2 7 - P - 1 6 - Effect of oxygen concentration on catalyst deactivation rate in

vapor phase Beckmann rearrangement over acid catalysts
T. Takahashi and T. Kai
Department of App. Chem. and Chem. Eng., Kagoshima Univ., Kagoshima 890-0065, JAPAN
E-mail." takahashi@cen.kagoshima-u.ac.jp, FAX +81-99-226-8360

The addition of a small amount of oxygen (up to 1000 ppm) in helium was effective to improve
the catalytic activity in vapor phase Beckmann rearrangement over HZSM-5 modified with
precious metals. The catalyst life time increased using oxygen as the diluent gas. When the
amount of oxygen exceeds 1.0 %, the dehydrogenation of the coke precursor is accelerated. The
combination of oxygen as the diluent gas and methanol as the diluent solvent was effective to
increase the life time of the acid catalysts including an amorphous SIO2-A1203, HZSM-5 type
zeolite and porous silica glass.

27-P-17 - On the role of the titanium active site in the phenol/anisole

hydroxylation over titanium substituted crystalline silicates
U. Wilkenh6ner 1, D.W. Gammon 2 and E. van Steen 1
Catalysis Research Unit, 1Dept. Chemical Engineering, 2Dept. Chemistry, University of Cape
Town, South Africa

Hydroxylation of phenol and anisole was investigated using TS-1, a silanised TS-1 and Al-
free Ti-Beta. Pore geometry, solvent, external surface and substrate govern the selectivity of
the hydroxylation reaction. In medium pore TS-1 the formation of hydroquinone in phenol
hydroxylation is favoured due to the geometric constraint on the formation of catechol in the
pores. A similar effect is observed for formation of ortho- and para hydroxy-anisoles in A1-
free Ti-Beta. Solvents affect activity and selectivity of the hydroxylation reactions through
adsorption and co-ordination to the titanium active site. The external surface of TS-1 plays a
substantial role in hydroxylation reactions.
 369

31 - Environment-Friendly Applications of Zeolites (Thursday)

31-P-05 - Application of sorbing composites on natural zeolite basis for

heavy metals contaminated territories rehabilitation
W. Sobolev (a), V. Ilyin (b), F. Bobonich (b) and S. B~ir~ny (c)
a S & P Department "Flegmin" ("Sventana" Ltd.), sable@kiev-page.com.ua, Ukraine
b Institute of Physical Chemistry of the National Academy of Sciences, Ukraine
c University of Miskolc, Institute of Chemistry, Hungary

Various compositions of natural zeolites modified for the remediation of soils contaminated
by heavy metals and radionuclides are discussed. Modified zeolites are selective adsorbents in
respect to bivalent cations including Sr, Cd, Cu, Pb, Zn. Incorporation of modified zeolites
into soils reduces the content of lead and other heavy metals by a factor of 4-5 and prevents or
diminishes the transport processes from soil into ground water and plant biomass. Using of
organo-mineral composites, containing 1-5 % selective sorbent "Zeolite P", is efficient to get
ecologically cleaned harvests of corn, bean and vegetable cultures under low contamination.

31-P-06- Investigation of lead removal from wastewater by Iranian

natural zeolites using 212pb as a radiotracer
H. Kazemian(a), P. Rajec(b), F. Macasek(b), and J.O. Kufacakova
a Jaber Ibn Hayan Research Labs., AEOI,, Tehran, IRAN- hkazemian@workmail.com
b Faculty of Natural Science, Comenius University, Bratislava, Slovak Republic

The uptake of lead from its aqueous solutions (1'10 .5 and 1'10 "2 mol.dm 3, buffered at
pH=3.7), by three clinoptilolite-rich tufts from Meyaneh, Firouzkouh, and Semnan; and a
natrolite-rich ore from Zahedan (Hormak) region of Iran, was investigated by plotting the ion-
exchange isotherms and calculating distribution coefficients (Ko). 212 Pb radioisotope was used
as a radiotracer. The results provide information on the suitability of the individual zeolites
for radioactive and industrial wastewater treatment. The removal of lead by the clinoptilolites-
rich tufts was effective and the uptake sequence was Meyaneh > Firouzkouh > Semnan;
whereas the take up of lead on the natrolite material was negligible.

3 1 - P - 0 7 - Purification of the waste liquid hydrocarbons using cation-

exchanged forms of clinoptilolite
M.K. Annagiyev, S.G. Aliyeva and T.M. Kuliyev.
Institute of Inorganic and Physical Chemistry, Academy of Sciences of Azerbaijan Republic,
Baku.

The use of adsorbents obtained on the basis of natural zeolites has a large practical and
theoretical importance for different branches of a national economy. Presence of even small
quantities of water and iron ions in liquid hydrocarbons of influences negatively upon the
quality of the products produced under manufacture of synthetic detergent- sulfonol;
corrosion of the industrial and transport equipment takes place too. Usually synthetic
adsorbents, which are deficient and expensive are used when drying liquid hydrocarbons.
370

3 1 - P - 0 8 - The use of transcarpathian zeolites for concentrating trace

contaminants in water
V.O. Vasylechko (a), L.O. Lebedynets (a), G.V. Gryshchouk (a), Y.B. Kuz'ma (a), L.O.
Vasylechko (b) and V.P. Zakordonskiy (a).
(a) Ivan Franko National University of L 'viv, L 'viv, Ukraine -granat@carat.lviv.ua
(b) Lvivska Polytechnika National Universitat, L 'viv, Ukraine
The adsorption properties of Ukrainian Transcarpathian natural zeolites (clinoptilolite and
mordenite) and of their chemically and acid-modified forms towards Cd, Cu and chloroform
have been investigated. The optimum conditions of concentrating trace contaminants of Cd,
Cu and chloroform in water were found. The possibility of the use Transcarpathian zeolites in
analyses of water has been demonstrated.

31-P-09 - Ammonia removal from drinking water using clinoptilolite and

lewatit S100
H.M. Abd E1-Hady, A. Grtinwald, K. Vlckova:[: and J. Zeithammerova
Civil Engineering Department, Department of Sanitary Engineering, Czech Technical
University In Prague - hoss.@fsv.cvut.cz, fax." 0042 02 24354607, Czech Rep.

High concentrations of ammonium in surface water make it unsuitable as drinking water, and
this is becoming a major problem in the world. The purpose of this study is to investigate the
possibility of removing ammonium from drinking water by means of an ion exchange
process. We used one material of natural origin: clinoptilolite and one synthetic material:
Lewatit S 100. Experimental results show that Lewatit S 100 has almost 4 and 1.7 times weight
capacity for ammonia removal compared to the capacity of clinoptilolite for concentrations 10
and 5 mg NH4+/L respectively, but for 2 mg NH4+/L the weight capacity of clinoptilolite was
found to be 1.9 times that of Lewatit S 100.

31-P-10 - Pilot plant of ammonium removal from nitrogen industry waste

waters by an Ukrainian clinoptilolite
Y.I. Tarasevich and V.E. Polyakov
Institute of Colloid Chemistry & Chemistry of Water, yuitaras@thomascat.kiev.ua, Ukraine

Laboratory studies and industrial tests had shown that to remove the ammonium ions from
nitrogen industry waste water, the application of the clinoptilolite is most promising.
Sulphuric acid involved in the industrial cycle can be conveniently used for the regeneration
of the worked-out clinoptilolite. Optimum conditions for water cleaning using the
clinoptilolite filter and for the subsequent regeneration of the filter by sulphuric acid were
determined. Eleven sorption/regeneration cycles were performed in industrial conditions; it
was shown that the dynamic exchange capacity of clinoptilolite, 0.52 geq/g, remains almost
unchanged. The 'hungry' regeneration is shown to be most efficient, enabling the recovery of
60-70% of the clinoptilolite exchange capacity. Cleaned industrial waste water can be used as
the make-up water in closed systems of industrial water supply. The worked-off regenerative
solutions, after their neutralisation and boiling down, are used as fertiliser.
 371

31-P-I I- Croatian clinoptilolite and montmorillonite-rich tuffs for ammo-

nium removal
M. Rozic (a) and S. Cerjan-Stefanovic (b)
(a)Faculty of Graphic Arts, Zagreb, Croatia, fax:385~1~2371-077
(b)Faculty of Chemical Engineering and Technology, Zagreb, Croatia
Clinoptilolite- and montmorillonite-rich tufts from Croatian deposits were examined to
evaluate their ability for ammonium ions uptake. Both tested materials have potential for
removing ammonium from waters. However, the montmorillonite-rich tuff is not as effective
as clinoptilolite-rich tuff, particularly in the presence of competing Ca 2+ cation. In all
experiments, the clinoptilolite-rich tuff exchanged a far more ammonium compared to the
montmorillonite-rich tuff.

31-P-12 - Ammonia removal from water by ion exchange using South

African and Zambian zeolite samples and its application in aquaculture
M. Mwale and H. Kaiser
DIFS, Rhodes University, Grahamstown -g98m5365@campus.ru.ac.za, RSA

The possibility of improving aquaculture water quality using a Zambian zeolite identified as
laumontite and a South African clinoptilolite sample is discussed. These were tested under
laboratory conditions and in a fresh water recirculating system. There were significant
differences in average ammonia CEC between clinoptilolite (14.94 rag/g) and laumontite
(2.77 mg/g). The average cation exchange capacity (CEC) values in the fresh water system
(5.80 mg/g and 4.12 mg/g for the 0.7-1.0 and 1.0-1.4 mm particle sizes, respectively) were
significantly lower than the column estimates for the same particle sizes. Mass balance of
nitrogen (N) indicated that only 22% of the 60% NH4+-N available for adsorption was
adsorbed by the zeolite. It was concluded that N budget studies make it possible to determine
the amount, nature and effect of the dissolved N load in a fish culture system and on the ion
exchange process. The results suggest that both samples can be used in water treatment.

31-P-13 - Permanent storage of chromium in hardened FAU-type zeolite

/cement pastes
C. Colella, D. Caputo and B. de Gennaro
Dipartimento d'Ingegneria dei Materiali e della Produzione, Universith Federico II, Napoli,
Italy

Cr removal from wastewater by ion exchange using FAU-type zeolites and the subsequent
stabilization of the resulting sludges in a cement matrix is reported. Amounts of 5 g/1 of
synthetic faujasite-like zeolite X or 8 g/1 of a faujasite- and phillipsite-rich tuff were able to
bring the Cr ~+ concentration in a wastewater of an electroplating plant, below the law limits
allowed for discharge in times of practical significance. The compressive strengths of the
compacts containing 10% to 75% of zeolitic materials were much higher than the value of
0.44 MPa, suggested by international protocols for handling and landfilling the solidified
wastes. Moreover, suitable leaching tests on the hardened pastes resulted in a Cr 3+
concentration in the leachates lower than the law limits allowed for discharge in water bodies
(2 mg/1).
372

31-P-14 - Phosphorus removal from wastewater in upgraded activated

sludge system with natural zeolite addition
J. Hrenovic a, y. Orhan b, H. Btiyiikgting6r b and D. Tiblja~ a

~Faculty of Science, University of Zagreb, Zagreb, Croatia-jasna.hrenovc@usa.net

bOndokuz Mayis University, Environment Eng. Dept.,, Samsun, Turkey- yukselo@omu.edu.tr
A new application of natural zeolites (NZ) in sewage treatment is presented in this paper. The
aim of this study was to investigate the enhanced performances of upgraded activated sludge
system with NZ addition; particularly as far as phosphorus removal, chemical oxygen demand
(COD) and sludge characteristics. Two experimental studies were run; an upgraded activated
sludge system with NZ addition and a conventional activated sludge system, run as a control
unit. The results point to the possibility of successful phosphorus and COD removal from
wastewater by activated sludge bioaugmented with phosphorus accumulating bacteria using
NZ as a support material.

31-P-15 - Application of natural zeolites to purify polluted river water

M. Okamotoa and E. Sakamotob
aDivision of Earth Sciences, Kyushu International University,, Yahata-higashi ku,
Kitakyushu, Japan, okamoto@econ.kiu.ac.jp; b Department of Biological and Environmental
Chemistry, Kyushu School of Engineering, Kinki University, Kayanomori, Iizuka, Japan
We have attempted to remove the ammonium ions contained in waste river water using
natural zeolites in an oxidative atmosphere using a laboratory-scale circulatory apparatus. The
ability of zeolites to purify waste-water was compared with that of regular river gravel, which
has no ion exchange ability. The results show that Ca-rich mordenite is superior to normal
river gravel to purify waste river water polluted by ammonium ions. The decrease of
ammonium ions in polluted water was a result not only of ion exchange with calcium ions in
zeolite, but also of microbiological oxidation on the surface of zeolite. The ability of natural
zeolites to oxidize ammonium ions into nitrate ions is a function of the zeolite contents of
minerals and the type of zeolite species.

31-P-16- Elimination of ammonium in seawater by zeolitic products

J.M. Lopez-Alcal~. and J.L. Lopez-Ruiz
Centro Andaluz Superior de Estudios Marinos. Departamento de C. Navales. Grupo Zeolitas,
C~tdiz University, Puerto Real (Cddiz) Spain. Jose.lopezruiz@uca.es

The problem of ammonium elimination by zeolites in seawater is studied in this paper. By

preparation of new zeolitic products, elimination of 20% of initial ammonium is reached. This
is the best result referenced in the literature up to date.
 373

32 - Zeolite Minerals and Health Sciences (Thursday)

32-P-06 - Effects of dietary inclusion of natural zeolite on broiler perfor-

mance and carcass characteristics
E. Christaki, P. Florou-Paneri, A. Tserveni-Gousi, A. Yannakopoulos, and P. Fortomaris
Department of Animal Production, Veterinary School Aristotle University of Thessaloniki,
54006 ThessalonikL yannaka@vet.auth, gr, Greece
The addition of 2% and 4% natural zeolite (NZ) to broiler diet was studied in a 42-day
experiment. Body weight gain, feed consumption, feed consumption ratio, some carcass
characteristics and chemical analysis in the muscular mass of breast and legs were
determined. The supplementation of 2% NZ in the broiler diet resulted in an improvement of
the feed conversion ratio and an increase of body weight, carcass yield as well as linoleic and
a-linolenic acid content, without any adverse effect on the other measured parameters. The
addition of 4% natural zeolite resulted in a significantly higher feed conversion ratio.

32-P-07- Interaction studies between aspirin and purified natural

clinoptilolite
A. Rivera (a), L.M. Rodriguez-Albelo (b), G. Rodriguez-Fuentes (a) and E. Altshuler (c)
a Zeolites Engineering Laboratory, University of Havana, jea@in[bmed.sld, cu, Cuba
b Organic Materials Laboratory, University of Havana, Cuba
c Superconductivity Laboratory, University of Havana, 10400 Havana, Cuba
Taking into account the antacid properties of a purified natural clinoptilolite, NZ, we have
examined its effects on aspirin (ASA) in an aqueous medium. We have studied by UV
spectroscopy the ASA in solution before and after the addition of NZ. Our results suggest that
the concentration of ASA is only affected by the interaction at high pH values (pH=8), at
which the ASA also starts to decompose. These results match the IR spectroscopy studies of
the incorporation of ASA to NZ. We also exchanged NZ with Ca, Cu and Na ions, and
studied the interaction of the modified zeolites with ASA. While no ASA was detected in the
zeolite in the first two cases at any pH value, the third one showed some incorporation for all
the pH values.

32-P-08 - Channel model for the theoretical study of aspirin adsorption on

clinoptilolite. W a t e r influence
A. Lain and A. Rivera
Zeolites Engineering Laboratory, University of Havana, anabel@laeJf oc.uh.cu, Cuba
A new zeolite model, that features the a and c channels of clinoptilolite has been used to
study the possible interactions of aspirin-water-zeolite, in order to know the behavior of the
drug in a more complex system and the influence of water present in the zeolite channel. The
calculations have been performed using the AM1 semi-empirical method and acid and sodic
clinoptilolite models. The results showed that the adsorption entalphy of aspirin in the acid
structure is in the same order than that obtained for the sodic structure, although the nature of
the interaction is different in each structure. The ester and aromatic groups were
preferentially oriented to the model. In any case the chemical stability of aspirin is affected
by the presence of water molecules in the system.
374

32-P-09 - In vitro and in vivo effect of natural clinoptilolite on m a l i g n a n t

tumors
M. Poljak Blazi, M. Katic, M. Kralj, N. Zarkovic, T. Marotti, B. Bosnjak, V. Sverko, T.
Balog and K. Pavelic
Division of Molecular Medicine, Rudjer Boskovic Institute, pavelic(~rud/er.irb.hr, Croatia

Many biochemical processes are closely related to ion exchange, adsorption and catalysis.
Zeolites reversibly bind small molecules such as oxygen or nitric oxide, they possess size and
shape selectivity, the possibility of metalloenzyme mimicry, and immunomodulatory activity.
These properties make them interesting for pharmaceutical industry and medicine. In vitro
experiments showed inhibition of tumour cell proliferation as well as MZ to be the possible
scavenger of HNE. After i.p. application of MZ, the number of peritoneal macrophages was
increased as well as their production of oxide anion. NO generation was totally abolished. At
the same time translocation of p65 subunit of NF~:B in spleen cells was observed. Thus, here
we report anticancer effect of MZ in vitro and immunostimulatory effect in vivo.

32-P-10 - Effects of natural c l i n o p t i l o l i t e - rich tuff and sodium bicar-

bonate on milk yield, milk composition and blood profile in Holstein cows
A. Nikkhah, A.R. Safamehr and M. Moradi- Shahrbabak
Department of Animal Science, Faculty of Agriculture, Tehran University, Tehran, Iran

An experiment was conducted to evaluate the effects of different levels of clinoptilolite- rich
tuff (CP) and sodium - bicarbonate (SB) on milk yield and its components in Holstein cows.
A balanced change - over design with 4 rations, 4 periods (28 days and 4 cows per ration)
was employed. Ingredients of the control ration (1) were alfalfa hay (17.1%), corn silage
(16.2%) and concentrate (66.7%) on dry matter basis. Experimental rations contained, 1% SB
(2) : 0.5% SB + 3% CP (3) and 6% CP (4), respectively. The actual means of daily milk yield
of the cows that received rations 1,2,3 and 4 were 23.53, 24.2, 25.24, 25.45 kg/d and milk fat
3.18, 3.39, 3.3 and 3.44%, respectively. The average dry matter intake per kg fat corrected
milk (4%fat) for rations 1-4 were, 0.9, 0.95, 0.96 and 0.95, respectively.

32-P-11 - Effect of natural clinoptillolite-rich tuff on the p e r f o r m a n c e of

V a r a m i n i male lambs
A. Nikkhah, A. Babapoor and M. Moradi- Shahrbabak
Department of Animal Science, Faculty of Agriculture, Tehran University, Tehran, Iran

In order to determine the effects of different levels of clinoptilolite-rich tuff (CP) on

performance of fat tail Varamini male four rations containing 0 (control), 2, 4 and 6% CP
which were named 1,2,3 and 4, were prepared, respectively. The rations were fed to four
groups of the lamb (12 lambs/group) individually for 100 days. Feed intake, average daily
gain (ADG), feed conversion rate (FCR), carcass dressing percentage and carcass quality
were measured. The obtained results were as follows: feed intake for rations were 1.32, 1.34,
1.38 and 1.41 kg DM/day, ADC were 166.0, 177.9, 196.9 and 184.8 g/day and FCR were
8.0, 7.6, 7.1 and 7.76, respectively. Dressing percentage of lamb which were fed ration 3,
washighest (53.9vs 52.5, 52.7 and 51.2).
 375

32-P-12 - Ciinoptilolite and the possibilities for its application in medicine

N. Izmirova (a), B. Aleksiev (b), E. Djourova (b), P. Blagoeva (d), Z. Gendjev (d), Tz.
Mircheva (d), D. Pressiyanov (c), L. Miner (c), T. Bozhkova (c), P. Uzunov (c), I. Tomova
(e), M. Baeva (f), A. Boyanova (f), T. Todorov (g) and R. Petrova (g)
a Sofia University, Faculty of Chemistry; b Faculty of Geology and Geography," c Faculty of
Physics, d National Oncological Center," e Sofia Sanitary Inspection,"f BAS Solid Body's
Physics Institute, g BAS Applied Mineralogy Inst. Central Mineralogy & Crystallography,
Laboratory, Sofia, Bulgaria.

Part I. Clinoptilolite (Cpt) is widespread in the NE part of the Rhodopes mountains in

Bulgaria. In respect to the possibilities of use of Bulgarian clinoptilolite in medicine, its
toxic, genotoxic and carcinogenic effects on laboratory animals, were studied. In the same
relation, the natural radioactivity of Cpt, of the animals' food, containing Cpt and of the
animals' faeces, was measured. The contents of 226Ra in drinking water, percolating through
Cpt rocks and the concentration of 222Rn in Cpt-built houses were also measured.
Part II. Products of biocrystallization in human urine dry residue after Cpt application per os
were observed too.
This Page Intentionally Left Blank
 377

AUTHOR INDEX

A Anfilov, B.G. 01-P-12

Angelescu, E. 24-P-29
Annagiyev, M.Kh. 3 l-P-07
Abasov, S.I. 25-P- 15 26-P-20 Anpo, M. 30-K-01 14-P-20 14-P-35 15-P-07
Abbasova, G.G. 25-P- 15 15-P-08 28-P-07 30-P-16 30-P-24
Abd EI-Hady, H.M. 3 l-P-09 Antoni, T. 02-P-24
Abe, Y. 24-0-02 Antoshin, G.V. 10-P-05
Aboukais, A. 14-P- 15 30-P-26 Antunes, A.P. 30-P-23
Aboul-Gheit, A.K. 30-P-20 Anunziata, O.A. 04-P-07 06-P-08 14-P-08
Abraham, A. 13-P-23 Aoyagi, J. 18-P- 12
Abramova, A.V. 11-P-23 Arabindoo, B. 25-0-02
Abramson, S. 29-0-02 Arafat, A. 02-P-38
Accardi, R.J. 13-P- 12 Aranzabal, A. 30-P-I 8
Afanassiev, I.S. 11-P-26 Arcon, I. 14-P- 13
Agashe, M.S. 14-P- 12 Arends, I.W.C.E. 30-0-02
Agayeva, S.B. 26-P-20 Ariyuki, M. 28-P-07
Agger, J.R. 02-0-05 Armaroli, T. 13-P-25
Aguado, J. 24-P-13 Armbruster, T. PL-2
,~,gueda, V.I. 18-P- 11 Arnold, A.B.J. 29-P-22
Aguilar-P, J. 25-P-13 Arnold, U. 27-P-06
Ahedi, R.K. 25-P-06 Asaftei, I. 24-P-30
Ahmed, S.M. 30-P-20 Asafiei, S. 04-P-09
Ahn, W.S. 01-P-14 02-P-19 23-P-14 29-P-13 Atal'yan, O.K. 10-P-05
Ahn, Y.-S. 29-P-27 Attia, A. 22-P- 13
Aiello, R. 02-P-29 04-P-17 04-P-18 06-P-28 Attou, M. 04-P-09
11-P-27 Aubry, J.-M. 27-P-11
Aika, K. 30-P-34 Auerbach, S.M. 16-0-04
Aizawa, T. 26-P-07 Auroux, A. 13-P-07
Akhalbedashvili, L. 23-P-09 30-P-10 Avalos, M. 1 l-P-20
Akiyama, Y. 02-P-25 Avalos-Borja, M. 0 I-P- 15
Akporiaye, D. 03-K-01 Avgouropoulos, G. 29-P-14
Akporiaye, D.E. 03-P- 18 Avil, P. 30-P-22
Akramzadeh Ardakani, M. 01-P-08 Ayupov, A.B. 13-P-09
Azuma, K. 11-P- 10
Alberti, A. 01-K-01
Azzouz, A. 04-P-09
Aleksiev, B. 32-P- 12
Aliyev, A.M. 27-P-08
Aliyeva, S.G. 3 I-P-07
Ali-zade, G.A. 27-P-08 B
AI-Khowaiter, S. 06-P-21
AI-Megren, H. 06-P-21
Altshuler, E. 32-P-07 B.Nagy, J. 02-P-29 04-0-03 04-P-14 04-P-I 6
Alvarez, A.M. 14-P- 14 24-P- 11 04-P- 17 04-P-I 8 11-P-27 29-P-18
Amokrane, S. 23-P-07
/
29-P-31 30-P-19
Amoureux, J.P. 13-P-2/3 Bahlala, M. 26-P- 15
Ananias, D. 0 5 - P - ! ~ Baba, T. 24-0-02
Anderson, M. 04-0-05 Babapoor, A. 32-P-11
Anderson, M.W. 02-0-05 13-P-16 21-P-07 Babonneau, F. 07-0-02
27-P-15 Baek, S.-W. 24-P-26
Andrade, H.M.C. 30-P-13 Baerlocher, C. 09-P-14 09-P-11
Andreev, V.V. 28-P-12 Baerns, M. 12-P-15 30-P-33
Andr6s, J.M. 18-P- 10 Baetens, D. 04-P-11
Andrews, R.D. 31-O-02 Baeva, M. 32-P-12
378

Baggio-Saitovich, E. 14-P-28 Birjega, R. 07-P-14

Bai, N. 07-P-07 Bischof, C. 26-P-18
Bakakin, V.V. 0 l-P- 11 Bitter, J.H. 12-O-02 19-P-08
Balmer, W. 23-P-06 Blagoeva, P. 32-P-12
Balog, T. 32-P-09 Blanc, A.C. 29-0-02 29-P-10 29-P-31
Bandyopadhyay, R. 03-P- 10 Blanco, C. 03-P-06
Bao, X. 30-P-28 Blanco, M.N. 23-P-19
B~ir~iny, S. 3 I-P-05 Blasco, T. 12-P-12 29-P-23
Barbosa, L.V. 24-P-17 Bliek, A. 28-P-14
Barker, C.M. 15-P- 18 Bobonich, F. 31-P-05
Barnes, P. 01-O-03 Boenneman, H. 29-P-22
Barrault, J. 07-P- 16 Bogdanchikova, N. 0 l-P- 15 1l-P-20
Barroudi, M. 06-P- 15 B6hlig, H. 12-P-08
Barsnick, U. 23-P-27 B6hlmann, W. 06-P-I 7 14-P-07
Barth, J.-O. 10-0-02 BOhringer, W. 11-O-02 28-P-15
Basaldella, E I. 20-P-14 20-P-13 Boissi6re, C. 08-O-01 08-P-05
Basler, W.D. 11-P-23 Bonardet, J.-L. 19-K-01 19-P-09
Bataille, T. 17-P-09 Bonelli, B. 22-P-21
Batamack, P. 13-P- 13 BOngyikand, E. 27-P-10
Batista, M.S. 14-P-28 27-P-12 Bonino, F. 14-P-34
Battiston, A.A. 12-O-02 Bonneviot, L. 06-0-03
Bauer, F. 28-P-06 Bonnin, D. 11-O-01
Bazzana, S. 03-P-13 Bordiga, S. 14-P-34 15-O-05 24-P-15
Beale, A. 14-P-39 Borello, L. 13-0-04
Beck, L.W. 03-0-04 Borges, C. 02-P-33
Bedard R.L. 05-P-16 Boron, S. 22-P-20
Bedekar, A.V. 24-0-04 Borovkov, V.Y. 12-O-04
Bedelean, H. 22-P- 16 Bosnjak, B. 32-P-09
Bedelean, I. 22-P- 16 Botavina, M.A. 30-P-09
Behrens, P. 02-P-41 06-P-25 10-O-03 B6ttcher, R. 14-P-07
Bein, T. 03-P-12 I1-P-15 20-0-04 22-P-11 Boutin, A. 16-0-03
22-P-14 Bouvier, F. 17-P-I 1
Belanova, E.P. 10-P-05 Boyanova, A. 32-P- 12
Bell, R.G. 13-P-16 16-P-13 16-P-14 Bozhkova, T. 32-P- 12
Bellat, J.P. 17-O-02 17-P-I 1 Bradley, S.A. 26-P-06
Bellussi, G. 25-0-03 29-O-01 Brand~io, P. 04-0-05 27-P-15
Bem, D. 03-K-01 03-P-I 8 05-P-16 Brandmair, M. 30-P-30
Ben T~arit, Y. 10-P-08 13-P-05 Braos-Garcia, P. 23-P-28
Benazzi, E. 26-P-11 Bratu, C. 03-P-18
Benco, L. 15-0-02 15-P-12 Br/iuer, P. 28-O-01
Benetis, N.P. 14-P-09 Brehm, M. 21-O-03
Bengoa, J.F. 14-P- 14 20-P- 13 24-P- 11 Br6mard, C. 14-P-18 14-P-24
Bengueddach, A. 03-P-19 17-P-14 Bricker, M. 03-K-01
Benmohammadi, I~. 21-O-04 Brieler, F. 21-O-03
Bergmann, M. 14-P-31 Broach, R.W. 05-P-16
Bernaue, B. 14-P-38 Broclawik, E. 15-P- 13
Berndt, H. 10-O-01 30-P-15 Brodyn, M. 22-P-18 22-P-20
Berthomieu, D. 15-P-23 Broersma, A. 19-P-08
Bertrand, O. 17-0-02 17-P-11 Bronic, J. 02-P-24 02-P-29
Bessho, H. 15-P-07 Brtihwiler, D. 14-0-04
Beta, I.A. 12-P-08 Brunel, D. 29-0-02 29-P- 10 29-P-31
Bevilacqua, M. 13-P-25 Buchholz, A. 14-P- 17
Beyer, H.K. 07-0-03 10-P-06 Budneva, A.A. 11-P-26
Bharathi, P. 15-P-09 Buhl, J.C. 02-P-07 13-P-15
Bichara, C. 15-P- 26 Buijsse, E.J.W. 20-P-18
Bilba, N. 24-P-30 04-P-09 Bulow, M. 12-O-04 03-0-05 18-O-03
Binet, C. 27-0-05 Burtica, G. 01-P-09 06-P-22
 379

Busca, G. 13-P-25 Chao, M.-C. 08-P-07

Buschmann, V. 02-0-01 02-P-06 Chaplin, M.F 16-P- 10
Busco, C. 15-0-05 Charkviani, M.K. 23-P-26
Bussaia, C. 15-P-28 Chatterjee, A. 15-P-06
Bustamante, F. 30-P-22 Chatterjee, M. 07-P-06
Buttefey, S. 16-0-03 Che, M. 14-P-20 14-P-35
Buttersack, C. 18-0-02 Che, S. 06-P-18 14-P-26
BtiyfikgtlngOr, H. 3 I-P- 14 Cheetham, A.K. 05-0-05 22-0-03
Byggningsbacka, R. 24-P- 16 Chelaru, C. 25-0-04
Chen, C.Y. 02-0-05 II-P-16 17-P-07
26-0-05
Chen, J. 05-0-02
C Chen, J.G. 26-0-04
Chen, J.-S. 05-P-11 l l - P - l l 1 l-P- 12 2 I-P-08
Chen, L. 21-O-03
Caceres, C. 23-P- 19 Chen, L.R. 1 I-P-08
Cadoni, M. 30-P-31 Chen, M. 05-P-06
Cagnoli, M.V. 14-P- 14 24-P- 11 Chen, Q. 12-P-05 24-P-06
Cai, T.-X. 25-P-09 Chen, T.-H. 13-P-18 14-P-10 14-P-11
Cairon, O. 14-P-23 Chen, W. 05-P-I 1
Calb, I. 01-P-09 Chen, We. 12-P-05 24-P-06
Calder6n, M. 26-P-12 Chen, X. 24-P-12
Callanan, L.H. 11-P-25 Chen, Y. 29-P-08
Calleja, G. 07-P-12 Chen, Y.B. 12-P- 11
Calzaferri, G. 14-O-04 Chen, Yo. 27-0-02
Camblor, M.A. 05-P-07 13-O-01 Cheng, M. 30-P-28
Campelo, J.M. 25-P-11 Cheng, W. 2 l-P-11
Cao, G. 1 l-P- 19 Cheng, X. 22-0-04
Cao, J.M. 22-P-08 Cheng, Z.L. 28-0-02
Cappelletti, P. 01-O-02 Cheralathan, K.K. 25-0-02
Caputo, D. 01-O-05 3 l-P-13 Chevreau, T. 14-P-23 27-0-05
Carati, A. 14-P-30 Chezeau, J.M. 09-P-I 1
Cardoso, D. 14-P-36 Chia, L.S. 05-P-20
Carlos, L.D. 05-P-12 Chihara, K. 18-P- 15
Carlsson, A. 03-0-02 Chiranjeevi, T. 26-P-17
Carlsson, K.A. 02-P- 16 Chiu, Y.W. 20-0-05
Carluccio, L. 29-0-01 Choi, E.Y. 09-P-06
Carpentier, J. 30-P-26 Choi, K. 03-P- 12
Cassiers, K. 06-P-11 Choi, S.-D. 23-P-10
Castagnola, N. 28-0-03 Choi, Y. 23-0-04
Castanheiro, J.E. 23-P- 19 Cholley, T. 24-0-03
Catlow, C.R.A. 01-O-03 14-P-39 15-P-18 Choung, S.J. 30-P-32
16-0-02 Christaki, E. 32-P-06
Caullet, P. 09-O-01 25-0-04 Chuichay, P. 15-0-04
Caumo, L. 24-P-17 Chun, Y. ll-P-09 30-P-08
t~ejka J. 06-P-20 13-0-02 13-P-19 14-P-21 Chun, Y.S. 20-0-01
14-P-22 25-P-10 Chung, Y.M. 29-P-13
Centi, G. 31-O-03 Ciambelli, P. 16-P-20 30-P-31 30-P-35
Cerjan-Stefanovic, 3 l-P-11 0 l-P-17 Clark, L.A. 15-P-19 16-O-05
Cerri, G. 01-O-02 Clerici, M.G. 14-P-30
Cesteros, Y. 23-P-16 Clet, G. 20-0-02
Chai, H.S. 27-P- 14 Climent, M.J. 23-P-21 23-P-22
Chanda, B. 24-0-04 Colella, A. 01-O-05
Chandwadkar, A.J. 07-P-20 Colella, C. 01-O-05 31-P-I 3
Chang, J.-S. 03-P-15 22-0-03 Colic, M. 32-O-01
Chang, S.H. 02-P-19 Collart, O. 29-0-04
Chao, K.J. 07-P-13 20-0-05 29-P-25 Collignon, F. 28-P-11
380

Coloma, F. 29-P- 15 de Jong, K.P. 14-O-01 19-P-08

Coluccia, S. 14-O-05 29-P-30 30-P-31 de los Reyes, J.A. 25-P- 13
Concepcion Rosabal, B. 01-P-15 De Luca, P. 04-P-I 6
Concetta Gaudino, M. 30-P-35 de M6norval, L.-C. 14-P-37 23-P-13
Conradsson, T. 09-0-03 09-P-12 de Souza, M.O. 24-P- 17
Conz, V. 24-P- 17 de Souza, R.F. 24-P- 17
Cook, B.R. 26-0-04 De Vos, D.E. 23-0-02 23-P-33 27-P-11
Cool, P. 06-P- 15 07-P- 18 deCastro, C. 29-0-03
Coq, B. 15-P-23 30-P-06 Decyk, P. 07-0-04 27-P-09
Corma, A. 11-P-29 23-K-01 25-P-13 23-P-21 D~,de~,ek J. 13-0-02 13-P- 19 14-P-21
23-P-22 24-P-20 29-P-30 32-0-05 Deere, J. 23-P- 17
Cornet, D. 26-P-15 27-0-05 Delabie, A. 15-P- 11
Corr~a, R.J. 24-P- 19 Delahay, G. 15-P-23 30-P-06
Costa, C. 15-P- 16 Dellarocca, V. 29-P-30
Coulomb, J-P. 17-O-02 17-O-03 17-P-05 Delmotte, L. 09-O-01
Cox, P.A. 05-0-03 Demuth, T. 15-0-02 15-P- 12
Crea, F. 04-P- 17 Deng, F. 08-P-08
Creaser, D. 02-0-03 20-P-09 Dereppe, J.-M. 19-K-01
Crow, P. 2 l-P-07 Derevyankin, A.Yu. 08-P-14
Cruciani, G. 01-K-01 09-P-13 Derewifiski M. 04-0-04 24-P-10
Cui, W. 24-P-28 Derouault, A. 07-P-I 6
Cundy, C.S. 02-0-02 02-P-08 21-P-07 Derriche, Z. 17-P- 14
Desplantier-Giscard, D. 06-P-27
Di Benedetto, A. 16-P-20
D Di Renzo, F. 03-P-I 9 04-0-01 06-P-27
06-P-28 13-P-I 1 29-0-02 29-0-04
Diaz, I. 07-P- 17 08-P-10
Diaz, L. 23-P-28
d'Espinose de la Caillerie, J.-B. 08-0-04 Diaz-Cabaflas, M.J. 24-P-20
da Cruz, R.S. 27-P-06 Dimitrov, M. 07-P- 19
Daage, M. 26-0-04 Ding, D. 16-P-07
Dadachov, M.S. 09-0-03 09-P-12 Ding, H. 22-P-09 28-0-02
Dadashev, B.A. 26-P-20 Djourova, E. 01-P-I 0 32-P-12
Daelen, G. 11-P-27 DObler, J. 12-O-03 12-P-08
Dahl, I. 03-K-01 03-P-18 Dolinsky, S.E. 24-P-09
Dahlhoff, G. 23-P-27 Domen, K. 07-P-I 5 12-P-06
Dai, Z. 22-0-02 Domiciano Fernandes, L. 06-P-24
Dakovic, A. 32-0-04 D6mine, M.E. 11-P-29
Dalea, V. 22-P- 10 Dominguez, J.M. 08-P-09
Dalloro, L. 15-0-05 Dondur, V. 32-0-04
Dalmon, J.-A. 14-P-38 Dong, B. 14-P-25
Damin, A. 14-P-34 Dong, J. 1 l-P-13 2 l-P-09
Damodaran, K. 13-P-20 Dong, M. 04-P-I 5 14-P-32
Dams, M. 23-0-02 dos Santos, J.H.Z. 24-P-17
Dapaah, J.K.A. 26-P-07 Dou, T. 06-P- 10
Darkrim, F. 17-P- 10 Drerman, J. 07-0-05
D,'iscalescu C. 29-P-21 Drijkoningen, L. 23-0-02
Datka, J. 13-P-17 15-P-13 Drozdov~, L. 11-O-05
Davidov~i, M. 14-0-03 Du, Z. 16-P-10
Davidson, A. 08-0-03 Duarte, M.T. 02-P-33
Davis, M.E. PL-3 02-P-27 02-P-28 Dubsk~, J. 24-P-10
De bruyn, M. 23-P-33 Duc6r6, J-M. 15-P-23
de Castro B. 2 l-P- 13 Dudarev, S.V. 02-P-20 02-P-31
de Gauw, F.J.M.M. 28-0-05 Duersch, B.S. 03-0-04
de Gennaro, B. 01-O-05 3 l-P- 13 Dufau, N. 17-0-03
de Gennaro, M. 01-O-02 01-O-05 Dumitriu, E. 25-0-04
de Jong, A.M. 19-P- 10 Dumrui, S. 03-P- 13
 381

Duncan, W.L. 19-0-03 Ferraris, G. 30-P- 14 30-P-21

Dunne, L.J. 16-P- 10 Ferreira, A. 05-P-12
Dutta, P.K. 28-0-03 Ferreira, P. 05-P-12
Dwyer, J. 14-P- 13 Ferreira, R. 2 I-P-I 3
Dzwigaj, S. 14-P-35 Ferrer, P. 18-P- 10
Fiermans, L. 27-P- 11
Fierro, G. 30-P- 14
E Figueiredo, J.L. 21 -P- 13
Fild, C. 13-0-01
Filip, D. 06-P-22
Finiels, A. 23-P-06 24-0-03
Ebigase, T. 24-P-25 Fisher, K.J. 14-P-29
Ebina, T. 07-P-06 Fitch, F.R. 03-0-05
Echavarria, A. 09-P-07 FjelMig, H. 05-0-05
Echevsky, G.V. 02-P-20 13-P-09 Flego, C. 14-P-30
Eckelt, R. 30-0-04 Fleitas, A. 32-0-03
Eckhard, J.-F. 23-P- 13 Floquet, N. 17-O-02 17-0-03 17-P-05
Edrissi, M. 02-P-09 Flora, L. 22-P-21
Ei4, M. 19-P-06 Florou-Paneri, P. 32-P-06
Eickelberg, W. 23-P-27 Fois, G.A. 15-0-05
Eimer, G.A. 06-P-08 Fomin, A.S. 10-P-05
Elder, S.H. 22-P-13 Fonseca, A. 04-0-03 04-P-14 04-P-16
Ellis, E.S. 26-0-04 04-P-I 8 11-P-27 29-P-18
Elomari, S.A. 03-0-03 Foran, P. 21-P-07
Elstner, M. 15-P-25 Fom4s, V. 23-K-01 23-P-21
Erdem-~;enatalar, A. 19-0-05 20-P- 15 Forrest, J.O. 02-0-02 02-P-08
Erdmann, K. 24-P-22 Forster, P.M. 22-0-03
Ernst, S. 04-0-02 14-P-21 28-P-10 29-P-19 Fortomaris, P. 32-P-06
Escalona Platero, E. 12-P- 13 Foster, M.D. 16-P- 13
Escola, J.M. 24-P- 13 Frache, A. 30-P-31
Essayem, N. 13-P-05 Fraissard, J. 06-P-16 11-O-01 13-P-13
Eswaramoorthi, I. 29-P-24 14-P-27 19-K-01 19-P-09
Evmiridis, N.P. 29-P-06 Franqois, V. 17-P- 11
Freire, C. 2 I-P-13
Freude, D. 14-0-02
F Freyer, A. 28-P-06
Fricke, R. 13-P-21 2 l-P- 14 30-0-04
Fripiat, J.J. 07-P-11
Fajula, F. 03-P-19 06-P-27 06-P-28 1 l-P-06 Fritzsche, S. 16-P- 18
13-P-11 23-P-13 24-0-03 29-0-02 FrOba, M. 07-P-19 17-P-12
29-0-04 29-P-31 Fromentin, E. 25-P-08
Falamaki, C. 02-P-09 Frontera, P. 02-P-29
Fan, B. 02-P-14 07-P-10 21-P-11 Frunza, L. 03-P-16 2 l-P- 14
Fan, J. 08-P-11 Frunza, S. 21-P-14
Fan, W. 04-P-13 07-P-10 Fu, J. 26-O-01
F~isi, A. 23-P- 15 Fu, Y. 05-0-02
Fatullayeva, S.S. 27-P-08 Fu, Z. 29-P-08
Fechete, I. 25-0-04 Fubini, B. 32-0-02
Fejes, P. 04-P- 17 04-P-I 8 Fuchs, A.H. 16-0-03
Fenelonov, V.B. 08-P- 14 Fukuoka, A. 22-0-05
Feng, S. 22-0-02 Fukushima, T. 11 -P- 10
Fenoglio, I. 32-0-02 Fukushima, Y. 02-P-27 17-O-04 22-0-05
Ferchiche, S. 02-P- 17 Furukawa, K. 1 I-P- 17
Ferey, G. 22-0-03 05-P-19 16-P-15 Furusawa, T. 30-P-34
Fermann, J.T. 16-0-04
Fernandez, C. 09-P-11 13-O-03 13-P-24
382

G Gisselquist, J. 05-P- 16
Gl~tser, R. 23-0-03
Gobin, K. 30-P- 17
Gabdrakipov, A.V. 15-P- 14 Goddard III, W.A. 16-P-09
Gabdrakipov, V.Z. 15-P- 14 Goddeeris, M. 23-P-20
Gabelica, Z. 02-P-33 04-0-01 07-P-16 Goh, N.K. 05-P-20
14-P-40 24-0-05 Goldwasser, M.R. 03-P-11
Galarneau, A. 06-P-27 29-0-02 29-0-04 Goletto, V. 07-0-02
Gale, J.D. 16-P- 15 G6mez, J.M. 18-P- 11
Galkina, N.K. 0 l-P- 12 22-P- 12 G6mt~ry, A. 23-P-15
Gallegos, N.G. 14-P-14 24-P-11 Gon~alves, F. 27-P- 15
Galli, E. 01 -K-01 Gong, Y. 08-P-08
Galli, P. 30-P-21 Gonzalez, G. 14-P- 19
Galperin, L.B. 26-P-06 Gonz~lez, F. 03-P-06
Gammon, D.W. 27-P-17 Gonz~ilez, L. 28-P-13
Ganapathy, S. 02-P-40 13-P-20 13-P-23 Gonz~lez-Pefia, V. 06-P-23
Ganea, R. 07-P- 14 Gonz~ilez-Velasco, J.R. 30-P- 18
Ganschow, M. 21-O-02 Goossens, A.M. 02-P-06
Gao, B. 09-P0-8 Gopal, S. 26-P-16
Gao, F. 03-P-08 09-P0-8 21-O-05 Gopinath, C.S. 07-P-20
Gao, X. 24-P-28 Gora, L. 20-0-02 20-P-18
Gao, Y.R. 28-0-02 G6ra-Marek, K. 13-P- 17
Gao, Z. 21-P-06 Gorbatkina, I.E. 26-P-23
Gaona, J.A. 11-P-29 Gorshkov, V.I. 1 l-P- 18
Garagorri, E. 24-P-13 Goryainov, S.V. 16-P- 19
Garcia, A. 25-P-11 Goto, Ya. 02-P-27 17-0-04
Garcia, R. 05-0-03 Goto, Yu. 17-0-04
Garcia, H. 23-P-21 Gotoh, K. 13-P- 14
Garcia-Serrano, L.A. 29-P-23 Goursot, A. 15-P-23 15-P-24 15-P-25
Garrone, E. 04-0-01 13-0-04 14-P-40 Graffin, P. 23-P-13
22-P-21 29-P-31 Gray, A.E. 16-P- 11
Gautier, S. 13-0-03 Green, M.L.H. 06-P-21
Gavlina, O.T. 1 I-P- 18 Grigoryan, A. 23-P-08
Gedanken, A. 06-P- 14 Grigoryan, F. 01-P-16
Gedeon, A. 08-P-14 08-0-04 13-P-I 3 Grill, W. 02-P-37
Geidel, E. 12-O-03 12-P-08 Grillet, Y. 17-P-05
Geier, O. 19-0-04 Grimm, A. 31-O-04
Gendjev, Z. 32-P-12 Grinev, V.G. 22-P-15
Gener, I. 14-P-I 8 14-P-24 Grobet, P. 13-P-18 14-P-10 14-P-11 23-P-33
Geobaldo, F. 04-O-01 13-O-04 14-P-40 27-P-11
Georgescu, V. 22-P-10 Groen, J.C. 17-P-08
Ghanbari-Siahkali, A. 14-P-13 Groothaert, M.H. 15-P- 11
Grtinert, W. 10-O-01 30-P-15 30-P-27
Ghorbel, A. 10-P-08
Grianwald, A. 3 l-P-09
Ghrir, A.M. 31-O-01
Gryshchouk, G.V. 3 l-P-08
Giamello, E. 14-0-05
Gualtieri, A.F. 01-O-04
Giannetto, G. 28-P- 13
Guan, N. 12-P-15 30-P-33
Gianotti, E. 14-0-05
Guillemot, D. 11-O-01
Gicquel, A. 17-P- 10
Guimon, C. 25-0-04
Gier, T.E. 05-0-05
Guisnet, M. 25-P-08 30-0-05 30-P-23
Gies, H. 09-0-05
Guo, C.J. 18-0-03
Gijzeman, O.L.J. 19-P-08
Guo, H.C. 28-P-08
GiI, B. 13-P-17 15-P-13
Gillespie, R. 03-K-01 Guo, J. 29-P-08
Gilson, J.-P. 12-O-01 27-0-05 Guo, S. 20-P-07
Giordano, G. 04-0-03 04-P-14 29-P-05 Guo, W. 02-P-35
Girard, S. 05-P-19 07-P-21 16-P-15 Guo, X. 27-0-02 24-P-14
Guo, Y. 1l-P-11
 383

Guo, G.-Q. 03-P-09 18-P-08 Heimbrodt, W. 21-O-03

Gupta, A. 16-0-05 Heine, T. 15-P-25
Gupta, R. 13-P-20 Heinrich, F. 30-P-27
Guth, J.-L. 18-P-06 Henriques, C. 02-P-33
Guti6rrez Alejandre, A. 13-P-25 Henriques, C.A. 24-0-05
Guti6rrez-Ortiz, J.I. 30-P- 18 Heo, N.H. 09-P-10
Gutjahr, M. 14-P-07 Herman, S. 0 l-P-09
Hernadi, K. 27-P-10
Hernfindez, I. 25-P-13
H Hem~ndez, J.C. 28-P- 13
Hern~indez, S. 18-P- 10
Herrier, G. 08-0-02
Ha, B.-H. 02-P- 10 Herrmann, R. 02-P-37
Ha, K. 20-O-01 Heydenrych, H. 11-P-24
Haberlandt, R. " 15-P-28 16-P- 18 Hidajat, K. 06-P-26
Haddad, E. 08-P-14 Higashimoto, S. 14-P-20 28-P-07 30-K-01
Hafner, J. 15-O-02 15-O-03 15-P-12 15-P-20 Hilbrandt, N. 03-P- 12
Hajnal, Z. 15-P-25 Hoang, D.L. 13-P-21
Hal,'tsz, J. 29-P- 18 Ho~evar, S. 19-P-06
Hailer, G.L. 06-P- 12 23-P-16 Hodnett, B.K. 23-P-17
Halsall-Whitney, H. 18-0-01 HC~lderich, W.F. 23-P-27 25-P-14 29-P-22
Hamada, H. 02-P-26 02-P-30 29-0-03
Hamdan, H. 25-P-12 Hol16, A. 26-P-19
Hambartsumyan, A. 0 I-P- 16 Holmes, S.M. 21-P-07
Hamidi, F. 03-P- 19 Holmgren, J. 03-K-01
Han, M. 1l-P-21 Holmqvist, A. 13-P-05
Han, M.-H. 29-P-27 Honda, T. 02-P-27
Han, Y. 05-P-09 06-P-07 Hong, S.B. 05-P-07 02-P-10
Han, Y.W. 09-P-06 Hoogesteger, A.W. 03-P-17
Hanaoka, T. 02-P-30 28-P-09 Horiuchi, T. 12-P- 11
Hancs6k, J. 26-P- 19 Horniakov~i, J. 25-P-07 29-P-11
Handan Tezel, F. 18-0-01 Houssin, C.J.Y. 02-0-01
Haneda, M. 04-P-06 Hou~vieka, J. 03-0-02 26-0-02
Hanif, N. 02-0-05 04-0-05 Hovnanian, N. 08-P-05
Hanika, J. 25-P-10 Howe, R.F. 14-P-29
Hannongbuai, S. 15-P-28 Hrenovic, J. 31 -P- 14
Hannus, I. 30-P- 19 Hronec, M. 25-P-07
Hantzer, S. 26-0-04 Huang, L. 08-P-13 20-P-I 1 22-0-04
Hao, J. 1 l-P- 13 Huang, W. 06-P-14
Haouas, M. 11-P-28 13-P-22 29-P-28 Huang, W.Y. 18-P-07
Harlick, P.J.E. 18-0-01 Huang, Y. 14-P- 16
Haroyan, H. 0 l-P- 16 HUbner, G. 12-P-09
Harrison, W.T.A. 05-0-01 Hudec, P. 24-P-10 29-P-26
Hartl, M. 10-0-03 Hudson, C.W. 26-0-04
Hartmann, M. 04-0-02 26-P-18 28-P-10 Hufnagel, V.J. 02-P-41
29-P-19 Hugeunard, C. 05-P-19 09-0-02
Hashimoto, K. 17-P- 13 Hulea, T. 25-0-04
Hattori, T. 24-P-25 30-0-03 Hulea, V. 25-0-04 29-0-02
Hayashi, H. 07-P-06 Hunger, B. 12-O-03 12-P-08
Hayashi, S. 1 l-P-07 13-P-06 Hunger, M. 14-P-17 23-P-12 23-P-23
He, H. 16-P-16 Hutschka, F. 15-O-02 15-O-03 15-P-12
He, M.-Y. 02-P-34 26-O-01 15-P-20 15-P-22
He, Y.J. 12-P- 11 Hwang, J.S. 27-P- 14
He, B. 30-P-24
Hecht, T. 29-P-19
Hedlund, J. 02-P-12 20-P-08 20-P-09
20-P-10
384

Jiang, D. 27-P-07 29-P-07

Jiang, Y.-S. 05-P- 11
Jim6nez-L6pez, A. 23-P-28
Jin, Q. 16-P-07
Iborra, S. 23-P-21
Jing, X. 1 l-P-13 21-P-09
Ibrahim, K.M. 31-O-01
Jing, Z. 16-P-16
Ichikawa, M. 13-P- 14 22-0-05
Jir~isek, R. 22-P- 13
Igarashi, N. 17-P- 13
Jiratova, K. 26-P-22
Ihm, S.-K. 24-P-26 26-P-21
Jirka, I. 14-P-38
ljiri, H. 1 l-P- 17
Jobic, H. 12-P-08 17-P-09
Ikeda, R. 13-P- 14
Joffre, J. 16-P-08 25-P-07
Ikeda, T. 02-P-25 21-P-18 22-P-17
Johnson, L. 18-P- 13
Iiiev, Tz. 01 -P- 13
Johnson, M.N. 01-O-03
Illgen, U. 30-P-33
Joo, S.H. 07-O-01 29-P-13
Ilyin, V. 3 l-P-05
Jord~io, M.H. 14-P-36
Imada, Y. 17-O-04 28-P-09
Jorik, V. 29-P-11
Imamura, M. 04-P-06
Joshi, V.N. 24-0-04
lmbert, F.E. 28-P- 13
Josien, L. 11-O-03
Imp6ror, M. 07-0-02 08-0-03
Jost, S. 15-P-28
Inagaki, S. 03-P-14 22-0-05
Ju, W.-S. 30-P-16
Inaki, Y. 24-P-25
Juan, R. 18-P-10
Inversi, M. 30-P- 14
Jun, S. 07-0-01 29-P-27
Ioannides, T. 29-P- 14
Jung, S.W. 09-P- 10
Iofcea, Gh. 24-P-30
Jungsuttiwong, S. 15-0-04 15-P-10
lojoiu, E.E. 30-P- 12
Juttu, G. 27-0-03
lone, K.G. 02-P-23
Iovi, A. 01-P-09
lshimaru, K. 14-P-06
lshimaru, S. 13-P- 14 K
ltabashi, K. 01-P-07
lto, S. 1 I-P-07 30-P-I 1
Ivanov, V.A. 11 -P- 18 Kai, T. 27-P-16
lvanova, I.I. 1 l-P-06 23-P-12 25-0-05 Kaiser, H. 31-P-12
lvanova, R. 0 l-P- 13 Kale, S.M. 23-P-30
Iwasaki, T. 07-P-06 15-P-06 Kaliaguine, S. 06-0-03
Izard, V. 29-0-02 Kalinin, V.P. 10-P-05
Izmirova, N. 32-P- 12 Kail6, D. 26-P-19
Izuhal, S. 29-P-29 Kallus, S. 02-P- 18
Izumi J. 18-P- 12 Kaltsoyannis, N. 15-P- 18
Kalwei, M. 13-O-01 13-P-12
Karnalakar, G. 28-0-04
Kameoka, S. 30-P-11
Kang, K.-K. 29-P-09
Kao, C.H. 20-0-05
Jacob, N.E. 14-P- 12 Kao, C.-P. 08-P-07 29-P-16
Jacobs, P.A. 02-0-01 02-0-04 12-P-10 23-0- Kapteijn, F. 18-O-04 30-0-02
02 23-P-20 23-P-33 27-P-11 Karapetyan, A. 01-P-16
Jacobsen, C.J.H. 03-0-02 26-0-02 Karetina, I.V. 02-P-42
Jfinchen, J. 31-O-04 K~irger, J. 19-0-04 28-0-01
Janicke, M. 29-P-17 Karlsson, A. 03-K-01 03-P-I 8
Jankowska, A. 22-P-19 Kartikeyan, S. 25-P-17
Jansen, J.C. 02-P-38 03-P-17 20-0-02 Kashia, L.D. 23-P-26
20-P- 18 Kaskel, S. 29-P-17
Janssen, A.H. 14-0-01 Kasture, B.B. 24-0-04
Jentys, A. 11-P-24 26-P-13 27-0-04 30-P-30 Kasture, M. 04-0-04
Jeong, S. 14-P-29 Katada, N. 13-P- 10
Ji, S.-F. 06-P-21 Kath, H. 23-0-03
 385

Katic, M. 32-P-09 Knops-Gerrits, P.-P.H.J.M. 16-P-09 12-P-10

Kato, M. 01-P-07 Knyazeva, E.E. 1 l-P-06 14-P-15 25-0-05
Katovic, A. 04-0-03 04-P-14 Ko, Y. 23-P-18
Kats, E.M. 22-P- 12 Ko, Y.S. 02-P- 19
Kaucic, V. 14-P- 13 29-P- 14 Kobayashi, S. 24-P-25
Kavan, L. 22-P-13 Ko~it'ik, M. 14-P-38 24-P-10
Kawamura, K. 06-P-05 Kodaira, T. 2 l-P-18 22-P- 17
Kawamura, Y. 30-0-03 Koermer, G. 11-O-04
Kawi, S. 06-P-26 Kogelbauer, A. 11-O-05 13-P-22 29-P-28
Kayiran, S. 09-O-01 17-P- 10 Kohara, A. 13-P- 10
Kazakov, A.V. 10-P-05 K6hn, R. 07-P- 19 17-P- 12
Kazansky, V.B. 12-0-04 Kolboe, S. 24-P-18
Kazemian, H. 0 l-P-08 3 l-P-06 Kolenda, F. 07-P-08
Keindl, M. 10-P-06 Koleva, E. 0 l-P- 13
Kennedy, G.J. 02-P-22 Koller, H. 13-0-01
Kessler, H. 21-P-15 25-0-04 Koltypin, Y. 06-P- 14
Kevan, L. 24-P-07 Kolyagin, Yu.G. 23-P-12
Khaddar-Zine, S. 10-P-08 Komarova, I.V. 01-P-12 22-P-12
Khavkin, V.A. 26-P-23 Komatsu, T. 27-0-01
Khelifa, A. 17-P- 14 Komiyama, H. 02-P-28
Khelkovskaya-Sergeeva, E.G. 26-0-03 Komori, Y. 13-P-06
Khongpracha, P. 15-0-04 15-P- 10 Kondo, J.N. 07-P-15 12-P-06
Khoury, H.N. 31-O-01 Kong, D. 24-P-06
Khvoshchev, S.S. 02-P-42 Kofigshaug, K.O. 05-0-05
Kibby, C.L. 02-P-20 13-P-09 Koningsberger, D.C. 12-O-02
Kieger, S. 30-P-06 K6nya, Z. 29-P-18 30-P-19
Kikot, A. 20-P-13 20-P-14 Kooyman, P.J. 06-P-20 23-P-25
Kikuchi, E. 03-P-14 07-P-24 ll-P-30 20-0-03 Koriabkina, A.O. 19-P- 10
Kim, A.M. 25-P-12 Komatowski, J. 04-P-12 10-O-02 24-P-22
Kim, D.S. 03-P- 15 22-0-03 Kosanovi, C. 02-P-32
Kim, G.-J. 23-P-10 23-P-11 Kosslick, H. 13-P-21 2 l-P-14 30-0-04
Kim, J.-H. 23-0-04 23-P-11 25-P-16 Koster, A.J. 14-0-01
Kim, J.M. 03-P-15 08-P-12 Koster, R.M. 28-P-14
Kim, K.-S. 23-0-04 Koster, S.C. 05-P-16
Kim, K.Y. 01-P-14 Kostova, N.G. 26-P-22
Kim, M.H. 01-P-14 23-P-18 Kotrla, J. 14-P-21
Kim, M.-W. 25-P-16 Kou, D. 18-P-09
Kim, N.-K. 23-P- 14 Kouli, A.L. 02-P-21
Kim, S.J. 23-P- 18 Koumantaropoulos, D. 30-P- 17
Kim, T.J. 02-P-37 Kovaleva, N.Yu. 22-P- 15
Kim, W.-G. 25-P- 16 Kowalac, S. 29-P-05
Kim, Y. 09-P-06 Kowalak, S. 04-P- 14 22-P- 19
Kimi, S.B. 31-O-02 Kozyra, P. 15-P- 13
King, L.M. 05-P-16 Krhlik, M. 25-P-07 29-P-11
Kiperman, S.L. 30-P-09 Kralj, D. 02-P-32 32-P-09
Kiricsi, I. 04-P-18 23-P- 15 27-P- 10 29-P- 18 Krasheninnikov, E.G. 1 l-P- 14
30-P-19 11-P-27 Krejcf, A. 25-P-10
Kirik, S.D. 08-P-14 Kremer, S. 02-0-04
Kirschhock, C. 02-0-01 02-0-04 Krishna, R. 16-P- 12
Kita, K. 30-P-11 Krtil, P. 22-P-13
Kitaev, L.Ye. 11-P-23 Krukovsky, I.M. 10-P-05
Kiyohara, P.K. 04-P- 10 Krygciak, J. 04-0-04
Kiyozumi, Y. 02-P-25 04-P-06 Kubasov, A.A. 11-P-23
Klar, P.J. 21-O-03 Kubota, Y. 03-P-10 17-0-04 25-P-06
Klein, D.P. 26-0-04 28-P-09 02-P-27
Klimova, T. 26-P-12 Kufacakova, J.O. 3 l-P-06
Klinowski, J. 16-P- 13 Kugita, T. 18-P- 12
386
Kujawa, J. 27-P-09
Kukovecz, A. 04-P- 18 11-P-27
Kulak, A. 20-0-01
Kuliyev, A.R. 27-P-08
Kuliyev, T.M. 3 l-P-07
Kulkami, S.J. 23-P-24 28-0-04
Kulprathipanja, S. 18-0-05
Kumakiri, I. 20-P- 16
Kumar, N. 23-P-25 24-P-16
Kumar, P. 26-P- 17
Kumar, R. 02-P-40 07-P-23 25-P-17
Kunieda, K. 29-P-29
Kunimori, K. 1 l-P-07 30-P-11
Kurata, Y. 02-P-30
Kuriyavar, S. 10-0-04
Kurpan, E. 02-P- 12
Kustov, A.L. 14-P- 15
Kustov, L.M. 26-0-03 26-P-23
Kuz'ma, Yu.B. 31-P-08
Kuznicki, S. 11-O-04
Kwon, S.P. 02-P- 10
L Li, H.-X. 04-P-08 06-P-09
Lacombe, S. 13-0-03 26-P-11
Ladygina, T.A. 22-P-15
Laeri, F. 21-O-04
Laha, S. 07-P-23
Laine, E. 23-P-25 24-P-16
Lam, A. 32-P-08
Lamberti, C. 14-P-34
Lamonier, J.F. 30-P-26
Langella, A. 0 I-O-02
Laniecki M. 24-P-23
Larbot, A. 08-O-01 08-P-05
Larin, A.V. 15-P-27
Lasp6ras, M. 23-P- 13
Lassinantti, M. 20-P- 10
Lassoued, A. 13-P- 13
Lau, M.-L. 03-0-05
Lavalley, J.C. 12-P-14
Lavren~i(,-~tangar, U. 19-P-06
L~zhr, K. 04-P-17 07-0-03 14-P-22
Lebaili, S. 23-P-07
Lebeau, B. 07-P-08
Lebedynets, L.O. 3 l-P-08
Lechert, H. 11-P-23
Lede, E.J. 04-P-07 14-P-08
Lee, B. 07-P- 15
Lee, C.W. 25-P-09 27-P-14
Lee, S.H. 09-P-06
Lee, W.M. 02-P- 10
Lee, Y.-J. 20-0-01
Leech, J.H. 14-P- 16
Lefferts, L. 29-P-20 30-P-34
Leglise, J. 26-P-15
Lehmann, E. 19-O-04
Lehmann, I. 29-P-05
Leiggener, C. 14-0-04
Lemos, F. 15-P-15 15-P-16
Lemos, M.A.N.D.A. 15-P- 16
Lentz, P. 04-P-17 04-P-18 11-P-27 29-P-31
30-P-19
Lercher, J.A. 04-P-12 10-O-02 26-P-13
27-0-04 29-P-20 30-P-30
30-P-34
Leu, T.M. 13-P-08
Levinbuk, M.I. 26-P-23
Levy, D. 09-P-09
Lewandowska, A. 27-P-09
Lewis, D.W. 14-P-39 16-P-I1
Lewis, G. 03-K-01 03-P-I 8
Lezanska, M. 24-P-22
Li, C. 12-P-07 14-P-33
Li, B. 16-P-07
Li, G. 27-0-02
Li, G.D. 21-P-08
Li, Gang 20-0-03 24-P-14
Li, L. 22-P-09
Li, N. 05-P-15
Li, Q. 02-P-35 08-P- 13
Li, Qi. 02-0-03
Li, R. 02-P- 14 07-P- 10 21 -P- 11
Li, Shi. 05-P-17
Li, Shu. 24-P-12
Li, X.-W. I I-P-21, 11-P-22
Li, X.-Y. 12-P-10
Li, Xiansen 20-P-12
Li, Xiaotan 03-P-08 21-O-05
Li, Y. 09-P08
Li, Y.S. 20-P-06 20-P-07
Li, Z. 08-P-08 14-P-25 18-P-09 29-P-12
Liao, C.N. 29-P-25
Lillerud, K.P. 05-0-05
Lim, S.H. 14-P-26
Lim, W.T. 09-P- 10
Lima, E. 23-P-13
Limtrakul, J. 15-0-04 15-P- 10
Lin, H.-P. 08-P-07 29-P-16
Lin, K. 27-P-07
Lin, X. 20-0-03
Lin, X.R. 20-0-05
Lin, Z. 05-P-13 27-P-15
Linares, C.F. 03-P-11
Lindfors, L.-E. 24-P-16
Lindlar, B. 29-P-28
Lingappan, N. 29-P-24
Linssen, T. 06-P- 15
Lipt~kov~i, B. 29-P-26
Lishchiner, I.I. 11 -P- 14
 387

Liu, C.-O. 20-P-06 M

Liu, G. 22-P-09
Liu, H.-O. 20-P-06
Liu, Min 27-0-02
Ma, B. 1 l-P-08 28-0-02
Liu, Ming 02-P-15 18-P-09 29-P-12
Ma, L.L. 18-P-07 30-P-07
Liu, N.N. 28-0-02
Macasek, F. 3 I-P-06
Liu, S. 06-P-14 30-P-33
Macocinschi, D. 22-P-16
Liu, S.-B. 29-P- 16
Macquarrie, D.J. 29-P-10 29-P-31
Liu, X. 02-P-39
Madriz, S. 03-P-11
Liu, Y.-H. 29-P-16
Maeda, K. 09-P-14
Liu, Yi 14-P-25
Maesen, T.L.M. 16-0-01
Liu, Yu 08-P-06
Magner, E. 23-P-17
Liu, Yun. 05-0-02 05-P-08
Magnoux, P. 25-P-08 30-0-05 30-P-23
Liu, Z. 05-P-17 05-P-18 14-P-33 21-P-17
Maireles-Torres, P. 23-P-28
24-O-01 24-P-28
Maisuls, S.E. 30-P-34
Liu, Z.-Q. 02-P-13
Majolo, F. 24-P-17
Llabr6s i Xamena, F.X. 24-P-15
Mfiki-Arvela, P. 23-P-25
Lledos, B. 09-0-01 Makkonen, J. 26-P-09
Llewellyn, P.L. 17-0-03 17-P-15 17-P-16
Malek, A. 02-P-22
Lo Jacono, M. 30-P- 14
Mali, G. 14-P- 13
Lobo, R.F. 13-O-01 13-P-12 27-0-03
Malova, O.V. 11 -P- 14
Loeser, T. 14-0-02 Man, P.P. 14-P-27
L6ffler, E. 14-P-31 30-P-27
Mandelli, D. 27-P-06
Loiseau, T. 05-P-19 Manoli, J.-M. 26-P- 15
Long, J. 26-0-01 Manos, G. 16-P-10 30-P-17
Long, Y.-C. 03-P-09 17-P-06 18-P-08
Manstein, H. 10-P-09
Lopes Bhering, D. 15-P-21
Mantein, H. 11-O-02
Lopez, B. 18-P-06
Marchese, L. 14-O-05 29-P-30 30-P-31
Lopez, Z. 14-P- 19
Marchetti, S.G. 14-P- 14 24-P- 11
L6pez, F. 28-P- 13 Marcilly, C. PL-4
Lopez-Alcal~t, J.M. 3 I-P- 16 Marcon, G. 23-P-07
L6pez-Fonseca, R. 30-P- 18
Margotti, M. 29-O-01
Lopez-Ruiz, J.L. 31 -P- 16 Marichal, C. 07-P-08 09-P-11
Lou, S. 29-P-12 Marie, O. 12-P- 14
Louchart, N. 14-P-24 Marinas, J.M. 25-P-11
Lourenqo, J.P. 02-P-33 Marlow, F. 06-0-02
Lu, D. 07-P- 15 Marotti, T. 32-P-09
Lu, G.Q. 07-0-05 07-P-18 Marques, A.L.S. 05-P- 14
Lu, H. 29-P-07 Marques, M.F.V. 24-0-05
Lu, L. 30-P-29 M~rquez-Alvarez, C. 06-P-23
Luan, Z. 24-P-07 Martens, J.A. 02-O-01 02-0-04 02-P-06
Lucco-Borlera, M. 22-P-21 Martin, C. 17-P-05
Lt~chinger, M. 29-P-28 Martin, T. 29-0-02
Ltlcke, B. 10-O-01 Martinez, A. 15-P-23
Luigi, D.-P. 13-P- 16 Martinez, C. 24-P-20
Luna, D. 25-P- 11 Martos, C. 06-P- 13
Lund, A. 14-P-09 Martra, G. 14-0-05
Luo, Q. 08-P-08 Martucci, A. 09-P-13
Luo, Y. 02-P-35 Marturano, P. 11-O-05
Luteijn, C. 20-P-18 Mascarenhas, A.J.S. 30-P- 13 05-P- 14
Lutz, W. 13-P-15 Maschmeyer, Th. 02-P-38 20-0-02 20-P-18
Masloboishchikova, O.V. 26-0-03 26-P-23
Massiani, P. 12-P- 14
Mathieu, M. 06-0-04 06-P-06
Matieva, Z.M. 11-P-23
Matijasic, A. 11-O-03
388

Matiyev, K.I. 27-P-08 Mizukami, F. 02-P-25 04-P-06

Matsukata, M. 03-P-14 07-P-24 1 I-P-30 Mizuno, R. 1 I-P- 10
20-0-03 Moheswari, R. 26-P- 14
Matsunaga, I. 03-P- 14 Mohino, F. 07-P- 17 08-P- 10
Mohd Muhid, M.N. 25-P-12
Matsuoka, M. 14-P-20 14-P-35 30-P- 16 Moissette, A. 14-P-18 14-P-24
30-P-24 Mojet, B.L. 02-0-01
Matsuzaki, T. 28-P-09 MOiler, K.P. 10-P-09 11-O-02 19-O-03
Mattos, L.V. 23-0-05 28-P-15 28-P-16
Maure, S. 17-P- 11 Monteiro, J.L.F. 24-0-05
Mauvezin, M. 30-P-06 Montes de Correa, C. 30-P-22
Maxwell, R S. 05-O-01 Montouillout, V. 13-0-03
Mazin, E.V. 25-0-05 Moon, G. 28-P-15
Mc Vicker, G.B. 26-0-04 Moradi- Shahrbabak, M. 32-P-10 32-P-11
McCusker, L.B. 09-P- 14 Morais, C.M. 05-P-12
McLeary, E.E. 03-P-I 7 20-P-18 Moreau, C. 23-P-06
Medina, F. 23-P-16 Moreau, P. 16-P-08 25-P-07 29-P-11
Medzhidova, S.M. 27-P-08 Moreau, V. 25-P-08
Mehn, D. 11-P-27 29-P- 18 Moreno, N. 18-P- 10
Meinershagen, J.L. 22-P-14 Moret, S. 17-P- 15
Melgares, A.M. 06-P-I 3 Moretti, G. 30-P-14 30-P-21
Mello, M. 19-P-06 Morishige, K. 17-0-01
Mellot-Draznieks, C. 05-P-19 07-P-21 16-P-I 5 Moroz, N.K. 11-P-26
Melo, R.A.A. 06-P- 19 Morris, R.E. 22-0-01
Mendes, F.M.T. 24-P-17 Mosqueda-Jim6nez, B.I. 30-P-30
Meng, X. 07-P-07 27-P-07 Mota, C.J.A. 15-P-21 24-P- 19
Meretei, E. 29-P- 18 Mou, C.-Y. 08-P-07 29-P-16
Merlino, S. 0 I-K-01 Mougenei, JC. 09-0-01
Meshkova, I.N. 22-P- 15 Moulijn, J.A. 18-O-04 30-0-02
M~thivier, A. 17-P-09 Mouloungui, Z. 23-P-32
Metzger, T.H. 20-0-04 Mravec, D. 16-P-08 25-P-07 29-P-11
Mezza, T.M. 26-P-06 Mskhiladze, A. 23-P-09
Mhamdi, M. 10-P-08 Mukherjee, P. 02-P-40 07-P-23
Miachon, S. 14-P-38 Mul, G. 30-0-02
Michel, D. 06-P- 17 Munhoz Jr., H. 04-P- 10
Michvocik, M. 29-P-11 Mufioz, G. 25-P-13
Miessner, H. 13-P-21 Mufioz-Pallares, J. 32-0-05
Mignot, C. 19-P-09 Munsch, S. 28-P-10
Mih~lyi, R.M. 10-P-06 Munshieva, M.K. 24-P-24
Mikhail, S. 18-P- 14 Munsignatti, M. 05-P-14
Miki, M. 08-P-09 Murali Dhar, G. 26-P-08 26-P-17
Milakovska, Z. 0 l-P- 10 Murray, R.C. 03-P- 18
Milella, F. 13-P-25 Murugesan, V. 25-0-02
Miller, M. 18-P- 13 Murzin, D.Yu. 23-P-25 24-P-16
Millini, R. 01-K-01 16-P-06 Mwale, M. 31 -P- 12
Millot, Y. 14-P-27
Min, K.I. 29-P- 13
Minagawa, K. 18-P- 12
Minchev, C. 07-P-I 9 N
Minev, L. 32-P-12
Mintova, S. 1 I-P- 15 20-0-04 22-P- 11 Naccache, C. 10-P-08
Miralles, J. 23-P-21 Nachtigall, P. 14-0-03
Mircheva, Tz. 32-P-12 Nachtigallov~t, D. 14-O-03
Mitchell, G.P. 12-P-16 Nagai, M. 12-P-17 29-P-29
Mitra, A. 20-P-11 22-0-04 Nagase, T. 07-P-06
Miyadera, T. 30-P- 11 Nair, S. 02-P-28
Miyazaki, T. 24-P-08 Naitza, S. 01-O-02
 389

Nakai, K. 17-P- 13 Ohrman, O. 20-P-09

Nakao, S.-I. 20-P- 16 Ojo, A.F. 03-0-05
Nakata, S. 03-P- 10 Okamoto, M. 3 l-P- 15
Nam, I.-S. 02-P-10 Okubo, T. 02-P-28 02-P-27 17-O-04
Namba, S. 18-P- 12 26-P-07 Ollonqvist, T. 23-P-25
Narender, N. 23-P-24 Olson, D.H. 09-0-04
Nastro, A. 04-P- 16 Omegna, A. 11-P-28
Naumov, M.V. 0 l-P-06 Omi, S. 12-P-17 29-P-29
Navarro, M.T. 11-P-29 Onida, B. 04-O-01 13-0-04 14-P-40 22-P-21
Nawata, S. 1 I-P- 10 29-P-31
Nekrasov, N.V. 30-P-09 Ono, Y. 24-0-02
Nenoff, T.M. 05-0-01 Onodera, Y. 07-P-06
Nenu, C. 07-P- 14 Onu, P. 30-P- 12
Nesterenko, S.N. 25-0-05 Onyestyhk, Gy. 19-P-07
N'Gokoli-Kekele, P. 19-K-01 19-P-09 Ookawa, M. 06-P-05
Nibou, D. 23-P-07 Orhan, Y. 3 l-P- 14
Nicolaides, C.P. 26-P-09 Orlik, S.N. 30-P-25
Nie, C. 08-P- 13 Ortiz, M.A. 18-P- 11
Niederer, J.P.M. 29-P-22 Oshuna, T. PL-5
Nieminen, V. 24-P-16 Oszko, A. 04-P- 18
Nigro, E. 04-P-18 11-P-27 Otero Arehn, C. 12-P-13 22-P-21 24-P-15
Niimi, T. 24-P-08 Oumi, Y. ll-P-10 24-P-08
Nikashina, V.A. 01-P-12 22-P-12 22-P-15 Oye, G. 06-P- 16
Nikkhah, A. 32-P-10 32-P-11
Nishide, T. 02-P-25
Nishimura, M. 15-P-07
Nishimura, T. 1 l-P-17
Niwa, M. 13-P-10
Niwa, S. 04-P-06 Pacheco, G. 07-P-I 1
Nobukawa, T. 30-P-11 Pachtov~i, O. 14-P-38
Noh, J.S. 09-P- 10 Padalino, G. 01-O-02
Nokbin, S. 15-0-04 Padurariu, D.M. 24-P-30
Nordgren, U. 20-P-09 Paganini, M.C. 14-0-05
Norefia, L. 25-P- 13 Paik, W.C. 02-P-10 05-P-07
Noronha, F.B. 23-0-05 Paillaud, J.L. 09-O-01 09-P-11
Novak Tusar, N. 14-P- 13 Pak, C. 06-P- 12
Novokshonova, L.A. 22-P- 15 Palacio, L.A. 09-P-07
Nowak, I. 07-0-04 27-P-09 Palanichamy, M. 25-0-02
Nulens, K.H.L. 12-0-03 P~il-Borb61y, G. 07-0-03
Nyman, M. 05-0-01 Palchik, O. 06-P-14
O' Brien, A. 16-P- 11 Palella, B. 16-P-20 30-P-31
P~ilink6, I. 23-P-15 27-P-10
Palomba, M. 01-O-02
O Pamba, M. 03-P-19
Pan, L.-R. 04-P-08
Pang, W. 05-0-02 05-P-08 07-P-07
O'Connor, C.T. 10-P-09 11-O-02 11-P-25 Paoli, H. 17-P-09
28-P-15 Parise, J.B. 05-O-01 09-0-05
O'Connor, D. 01-O-03 Park, K.-C. 24-P-26 26-P-21
O'Rear, D.J. 02-P-20 13-P-09 Park, M. 09-P- 10
Occelli, M.L. 13-P-07 Park, S.-E. 03-P-15 08-P-12 22-0-03 25-P-09
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Ogisu, Y. 17-0-01 Park, S.H. 09-0-05
Ogura, M. 07-P-24 1 I-P-30 Park, S.W. 09-P- 10
Oh, J.W. 30-P-32 Park, Y.-K. 24-P-26
Ohgushi, T. 14-P-06 Park, Y.S. 20-0-01
390

Parvulescu, V. 29-P-21 Poissant, R.R. 14-P- 16

Paschek, D. 16-P- 12 Polisset-Thfoin, M. 11-O-01
Pasqua, L. 06-P-28 Poljak Blazi, M. 32-P-09
Pastore, H.O. 05-P-14 30-P-13 Polyakov, V.E. 31 -P- 10
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Patra, C.R. 25-P- 17 Poncelet, G. 28-P-11
Patrigeon, A. 26-P-11 Ponomoreva, O.A. 25-0-05
Patton, R.L. 03-P-18 Pop, D. 22-P- 16
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Paulin, C. 17-P- 11 Popitsch, A. 10-0-03
Paulussen, S. 23-P-20 Popov, N. 01-P- 13
Pavel, C.C. 24-P-30 Popova, T. 01 -P- 13
Pavelic,-K. 32-0-01 32-P-09 Popovici, E. 06-P-22 22-P-10 22-P- 16
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Pefla, M.L. 29-P-30 Poyet, T. 17-P- 16
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Peng, L.M. 06-P-09 Prasada Rao, T.S.R. 26-P- 17
Perathoner, S. 31-O-03 Pressiyanov, D. 32-P-12
Perego, C. 25-0-03 29-O-01 Price, D. 01-O-03
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P6rez-Pariente, J. 06-P-23 07-P-17 08-P-10 Primo, J. 32-0-05
29-P-23 Prins, R. 11-O-05 11-P-28 13-P-22 29-P-28
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Perlberg, A. 18-0-02 Pruski, M. 13-P-24
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Pesquera, C. 03-P-06
Peters, J.A. 28-P- 14
Petranovskii, V. 01-P-15 1I-P-20 Q
Petrov, L.A. 26-P-22
Petrova, R. 32-P-12
Philippou, A. 04-0-05 13-P-16 Qi, X. 02-P-39
Philp, E.F. 05-0-03 Qi, Y. 21-P-17 24-P-28
Pierella, L.B. 04-P-07 06-P-08 14-P-08 Qian, B. 17-P-06
Pierloot, K. 15-P- 11 Qiu, S. 03-P-08 06-P-07 09-P-08 21-O-05
Pietrzak, N. 22-P-19 27-P-07
Pillep, B. 10-0-03 Qu, z. 30-P-28
Pinard, L. 30-0-05 Quartieri, S. 01-K-01 09-P-09
Pingei, U. 14-0-02 Querol, X. 18-P- 10
Pinnavaia, T.J. 08-P-06 Quoineaud, A.-A. 13-0-03
Pinto, A.C. 23-P-29
Pimgruber, G. 11-P-28
Pirone, R. 16-P-20 30-P-31
Pitu, M. 07-P- 14 R
Pizarro, P. 07-P- 12
Pizzio, L. 23-P-19
Plaisted, R.J. 02-0-02 21-P-07 Rachdi, F. 14-P-37
Plakhotnik, V.A. 24-P-09 Radha Kishan, M. 28-0-04
Plassen, M. 03-K-01 03-P-18 Raghavan, K.V. 28-0-04 23-P-24
Pl6vert, J. 02-P-27 02-P-28 13-P-11 Raichle, A. 26-P-10
Pode, R. 01-P-09 06-P-22 22-P-10 Rainho, J.P. 05-P- 12
Pode, V. 22-P- 10 Rajamohanan, P.R. 02-P-40
Poels, E. 28-P- 14 Rajec, P. 3 I-P-06
 391

Rakoczy, R.A. 19-0-04 Romeo, G. 31-O-03

Ramakrishna Prasad, M. 28-O-04 Romero, A.A. 25-P-11
Ramirez, A. 18-P-06 Romero, M.D. 18-P- 11
Ramirez, J. 13-P-25 26-P-12 Roth, W.J. 06-0-01
Ramirez-Solis, A. 15-P-21 Rottinghaus, G. 32-0-04
Ramishvili, Ts.M. 23-P-26 Rouquerol, F. 17-P- 15 17-P- 16
Ramos, A.M. 23-P- 19 Rouquerol, J. 17-0-03 17-P-I 5 17-P-16
Ramsahye, N.A. 16-P- 14 Roux, M. 09-P-11
Ramsay, J.D.F. 02-P- 18 Rouxhet, P. 02-0-04
Rana, M.S. 26-P-08 26-P-17 Rozanska, X. 15-0-03 15-P-20 15-P-22
Rao, B.S. 07-P-20 23-P-31 Rozic, M. 3 l-P-11
Rathousky, J. 06-P-20 22-P-06 22-P- 13 Rozwadowski, M. 04-P-12 24-P-22
Ratnasamy, P. 07-P-20 Ruan, T. 24-P-06
Rawat, K.S. 26-P-08 Ruiz, R. 03-P-06
Rebai, R. 23-P-07 Rtischer, C.H. 13-P- 15
Rebours, B. 17-P-09 Russell, P.C. 02-P-21
Rebrov, A.I. 23-P-12 Russo, G. 16-P-20
Reder, J.M. 1 l-P-15 Rustamov, M.I. 25-P-15
Rees, L.V.C. 19-O-02 19-P-07 28-0-02 Rymsa, U. 23-P-23
Reetz, M. 29-P-22 Ryoo, R. 07-0-01 29-P-13 29-P-27
Reichelt, R. 14-P- 19
Reinert, P. 06-0-03 11-O-03
Reisner, B.A. 09-0-04
Renard, G. 29-P-10
Renn, M. 27-P-09
Rep, M. 29-P-20 ~abo L. 29-P-26
Requejo, F.G. 04-P-07 14-P-08 Sacco, Jr, A. 02-P-16. 02-P-21 02-P-17
Rey, F. 11-P-29 29-P-30 03-P-13
Rhee, H.-K. 23-P-14 29-P-09 29-P-13 Sacerdoti, M. 09-P-13
Riahi, G. 11-O-01 Safamehr, A.R. 32-P- 10
Ribeiro, F.R. 15-P-15 15-P-16 30-P-23 Saito, T. 18-P- 15
Ribeiro, M.F. 02-P-33 30-P-23 Sakamoto, E. 3 l-P- 15
Ribera, A. 30-0-02 Sakamoto, Y. 22-0-05
Ricchiardi, G. 14-P-34 15-0-05 Sakata, Y. 24-P-25
Ricci, F. 14-P-34 Salagre, P. 23-P-16
Richter, M. 10-O-01 30-0-04 Saldarriaga, C. 09-P-07
Ristic, A. 14-P- 13 29-P- 14 Salmi, T. 23-P-25 24-P-16
Rivera, A. 32-P-07 32-P-08 Salou, M. 04-P-06
Rizzo, R. 01-O-02 Sanborn, M.J. 16-0-05
Roberge, D.M. 25-P-14 Sanchez, J.M. 25-P- 13
Rocchia, M. 14-P-40 29-P-31 S~inchez-Sfinchez, M. 12-P- 12
Rocha, J. 04-0-05 05-P-12 05-P-13 27-P-15 Sanderson, R.D. 03-P- 17 20-P- 18
Rodrigues da Rocha, S. 06-P-24 S~lndulescu, I. 24-P-27
Rodrigues, S. 04-P-10 Sani, A. 09-P-09
Rodriguez, I. 23-P-21 Sankar, G. 01-O-03 14-P-39
Rodriguez-Albelo, L.M. 32-P-07 Sannino, D. 30-P-35
Rodriguez-Castell6n, E. 23-P-28 Sano, T. 1 I-P-10 24-P-08
Rodriguez-Fuentes, G. 0 l-P- 15 1 l-P-20 Sano, W. 04-P- 10
32-0-03 32-P-07 Santos, E.N. 23-P-29
Rodriguez-lznaga, I. 1 l-P-20 Sanz, R. 07-P- 12
Rodriguez-Reinoso, F. 29-P- 15 Sapaly, G. 13-P-05
Roduner, E. 12-P-09 13-P-08 Sardashti, A.R. 01-P-08
ROger, H.P. 11-O-02 11-P-24 Sargsyan, S. 23-P-08
Rohlfing, Y. 21-O-02 Sarv, P. 24-P-10
Rojas-Hemfindez, A. 08-P-09 Sasaki, Y. 20-P-16
Romannikov, V.N. 08-P-14 Sasi Rekha, N.R. 26-P-14
Romanovsky, B.V. 14-P- 15 2 l-K-01
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Sastre, E. 06-P-23 07-P-I 7 08-P- 10 29-P-23 Shen, B. 30-P-07
Sato, M. 16-P- 17 Shen, J.-P. 25-0-01
Sato, T. 1 l-P-07 Sheptovetzkaya, K.I. 0 l-P- 12 22-P- 12
Satsuma, A. 24-P-25 30-0-03 Sheu, H.-S. 08-P-07
Satyanarayana, C.V. 13-P-20 23-P-31 Shi, C. 30-P-28
Sauer, J. 15-0-01 29-P- 17 Shi, Z. 05-0-04 05-P-06 05-P-10 22-0-02
Sauerbeck, S. 04-0-02 Shichi, A. 30-0-03
Sautet, P. 15-P- 17 Shimidzu, W. 20-P-16
Sawada, H. 24-0-02 Shimizu, S. 02-P-26
Scharf, O. 02-P-37 Shin, C.-H. 02-P- 10
Scharl, H. 26-P- 10 Shin, I.S. 07-P-22
Scheffler, F. 20-P- 17 Shiotani, M. 14-P-09
Schenk, M. 16-0-01 Shmakov, A.N. 08-P-14
Schenk, U. 14-P- 17 Shu, X.-T. 02-P-34 30-P-29
Schenkel, R. 10-0-02 Shvets, O. 22-P-18 22-P-20
Schertlen, R. 02-P-37 Sicard, L. 07-P-08
Schmachtl, M. 02-P-37 Sidamonidze, Sh. 23-P-09 30-P-10
Schmidt, C. 10-O-01 30-P-15 Sierka, M. 15-0-01
Schmidt, I. 03-0-02 26-0-02 Sierra, L. 18-P-06
Schmidt, W. 02-P-23 10-P-07 29-P-25 Siffert, S. 30-P-26
Schmitzer, S. 30-P- 12 ,~ilhan M. 14-0-03
Schneider, A.M. 02-P-41 Silva, I.F. 23-P-19
Schomburg, C. 22-P-07 Silva, J.M. 21-P-13 30-P-23
Sch6nhals, A. 2 I-P- 14 Silvestre-Albero, J. 29-P-15
Schoonheydt, R.A. 03-P- 16 04-P- 11 04-P- 13 Sim6n Carballo, R. 32-0-03
12-O-03 15-O-03 15-P- 11 Simon, A. 09-P-07 11-O-03
Schreier, E. 30-0-04 Simon, L. 26-P-13 27-0-04
Schuchardt, U. 27-P-06 Simperler, A. 13-P- 16
Schulz-Ekloff, G. 21-O-02 22-P-06 22-P-07 Singh, A.P. 23-P-30
Schuring, D. 19-P- 10 Singurei, G. 22-P- 16
Schtiring, A. 16-P- 18 Sivakumar, T. 26-P- 14
Schtith, F. PL-I 02-P-23 21-O-04 29-P-17 Sivasanker, S. 13-P-20 13-P-23 14-P-12
29-P-25 15-P-09
SchUtze, F.-W. 10-O-01 30-P-15 Sj6blom, J. 06-P-16
Schwan, P. 28-P- 16 Slabov~i, M. 06-P-20
Schwieger, W. 02-P-36 02-P-37 20-P-17 Slater, B. 16-0-02
Seelan, S. 14-P- 12 Slawin, A.M.Z. 05-0-03
Serf, K. 09-P-06 09-P-10 Slivinsky, Ye.V. 11-P-23
Seino, A. 26-P-07 Sloan, J. 06-P-21
Selvam, T. 02-P-36 Smaihi, M. 02-P- 18
Seo, G. 23-0-04 23-P-18 25-P-16 Smie~kov~, A. 24-P- 10 29-P-26
Seo, H.K. 30-P-32 Smimiotis, P.G. 26-P-16
Sep61veda-Escribano, A. 29-P-15 Smimov, A.V. 25-0-05
Serrano, D.P. 06-P-I 3 07-P- 12 24-P- 13 Smimov, M.B. 16-P- 19
Serykh, A.I. 12-0-04 Smit, B. 16-0-01
Seryotkin, Y.V. 11-P-26 Snurr, R.Q. 15-P-19 16-O-05
Seshan, K. 30-P-30 30-P-34 Sobalik, Z. 10-0-04 13-P-19
Setoyama, N. 17-0-04 Sobczak, I. 07-0-04
Sevcikov~, B. 23-P-25 Sobolev, W. 3 I-P-05
Sferdjella, S. 21-P-12 21-P-15 Sohrabi, M. 02-P-09
Shah, M.J. 11 -P- 19 Solcova, O. 26-P-22
Shakhtakhtinsky, T.N. 27-P-08 Solovyov, L.A. 08-P-14
Shan, X. 12-P-15 30-P-33 Sominski, E. 06-P-14
Shanthi, K. 26-P- 14 Son, T.-M. 23-P- 14
Shao, C. 03-P-08 21-O-05 Song, C. 25-O-01
She, L.-Q. 1 l-P-21 Song, L. 19-O-02 28-0-02
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Song, S.G. 05-P-16 Suzuki, H. 18-P- 15

Song, Y. 02-P- 11 Sverko, V. 32-P-09
Soni, H.S. 07-P-20 Szegedi,/~. 07-0-03
Sotelo, J.L. 18-P- 11 Szymkowiak, E. 04-P-14 29-P-05
Sowade, T. 10-O-01 30-P-I 5
Span6, G. 14-P-34 15-0-05
Spehlmann B. 18-0-05 T
Spliethof, B. 29-P-22
Spojakina, A.A. 26-P-22
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Taake, C. 02-P-07
Springuel-Huet, M.-A. 06-P-I 6 14-P-27
Tagiyev, D.B. 25-P-15 26-P-20 27-P-08
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Sridevi, U. 23-P-31 Takahashi, T. 27-P-16
Srinivas, D. 07-P-20 14-P-12
Takahashi, Y. 21-P-16
Srinivas, N. 28-0-04 Takeuchi, Y. 18-P- 15
Srinivasu, P. 23-P-24 Tan, C.S. 20-0-05
Stach, H. 31-O-04 Tanaka, S. 30-P-11
Stachurska, M. 04-0-04 Tang, X.-H. 04-P-08 06-P- 14
Stein, B. 1 I-P- 15 Tang, Y. 21-P-06
Stenzel, C. 02-P-37 Tang, Z.K. 21-P-08
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Stevens, C.L.T. 24-P-21 Tarasevich, Yu.I. 31 -P- 10
Stoch, J. 07-0-04 Tather, M. 19-0-05 20-P- 15
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Stojsic, D. 32-0-04 Taulelle, F. 05-P-19 09-0-02
Storeck, W. 13-P-21 Tawada, S. 25-P-06 28-P-09
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Stuhler, S.L. 02-P-21 Terr6s, E. 08-P-09
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Sueiras, J.E. 23-P- 16 Thangaraj, A. 11-O-04
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Sugimoto, N. 22-0-05 Thomas, J.K. 22-P-06
Sugimura, T. 28-P-09 Thomas, J.M. 14-P-39
Sugioka, M. 26-P-07 Thomas, K. 27-0-05
Sugiyama, K. 05-P-09 Thommes, M. 17-P- 12
Suh, Y.-W. 23-P- 14 Thoret, J. 13-P- 13
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Sundaramurthy, V. 29-P-24 Tomasevic-Canovic, M. 32-0-04
Suo, J. 24-P-12
394

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Tomova, I. 32-P-12
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Torosyan, G. 23-P-08 Vaini, M. 24-P-16
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Tosheva, L. 03-P-07 Valencia, S. 11-P-29 24-P-20
Toufar, H. 02-P-37 Valente, A. 27-P-15
Toukoniitty, E. 23-P-25 Valkenberg, M.H. 29-0-03
Toulhoat, H. 15-0-02 15-P- 12 Valtchev, V. 21-P-12 21-P-15
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Tsapatsis, M. 02-P-28 van Laar, F.M. 27-P-11
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Vasylechko, V.O. 31-P-08
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Vondrov~, A. 10-0-04
 395

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Vozny, V. 22-P-18 22-P-20 Weitkamp, J. 19-O-04 23-0-03 23-P-12
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Wang, J. 14-P-25
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Wang, J.-Q. 20-P-06 X
Wang, J.-Z. 04-P-08 06-P-09
Wang, K. 02-P-11
Wang, N. 21-P-08 Xi, C.-Y. 1 l-P- 12
Wang, Q. 29-P-12 Xia, J.R. 30-P-08
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Wang, X.S. 24-P-14 28-P-08 27-P-07 29-P-07
Wang, X.-Z. 06-P- 10 Xiao, T.-C. 06-P-21
Wang, Xi. 21-P-10 27-0-02 Xiao, Y.-Z. 06-P-10
Wang, Xu. 2 l-P- 10 Xie, G. 30-P-08
Wang, Y.-J. 21-P-06 Xie, K. 02-P- 14
Wang, Y.-M. 02-P-34 Xie, L. 1 l-P-13
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Weckhuysen, B.M. 03-P-16 04-P-I 1 04-P-13 Xu, Xin 05-P-06
Wei, B. 03-P-08 09-P0-8 Xu, Y. 05-P-20 30-P-07
Wei, Y. 05-P-17 24-O-01 Xue, J. 30-P-07 30-P-08
Weidenthaler, C. 10-P-07
WeiB, O. 21-0-04
396

Y Z

Yahiro, H. 14-P-09 Zaborskii, A.A. 22-P-15

Yamaguchi, H. 18-P- 15 Zadrozna, G. 04-P-12 24-P-22
Yamaguchi, T. 06-P-05 20-P-16 Zakarina, N.A. 15-P- 14
Yamakita, S. 02-P-28 Zaki, T. 18-P- 14
Yamamoto, K. 2 l-P- 16 Zakordonskiy, V.P. 3 l-P-08
Yamashita, H. 15-P-07 28-P-07 30-P-24 Zanardi, S. 01-K-01
Yamazaki, S. 11 -P- 17 Zanibelli, L. 29-0-0
Yan, A.-Z. 1l-P-09 Zarbaliyev, R.R. 25-P- 15
Yan, B. 05-P-20 Zarkovic, N. 32-P-09
Yan, D. 18-P-07 Zavoianu, R. 24-P-29
Yan, H.S. 24-P-14 Zecchina, A. 14-P-34 15-O-05 24-P-15
Yan, L.-J. 26-0-01 Zeithammerova, J. 3 l-P-09
Yan, W. 05-P-09 05-P-10 Zeng, X. 12-P-15 30-P-33
Yan, Y. 20-P-11 22-0-04 Zeng, Y. 17-P-06
Yanev, Y. 0 l-P- 13 Zenonos, C. 14-P-39
Yang, W.-L. 21-P-06 Zerbino, J.O. 20-P-14
Yang, C.M. 07-P- 13 Zeuthen, P. 26-0-03
Yang, H. 02-P-14 Zha, J. 07-P-09
Yang, L. 24-P-12 Zhang, A.M. 22-P-08
Yang, M. 27-P-07 Zhang, D. 22-0-02
Yang, S. 12-P-06 Zhang, H. 05-P-06 07-P-09
Yang, Xu. 30-P-28 Zhang, H.Y. 12-P- 11
Yannakopoulos, A. 32-P-06 Zhang, J. 30-P-24
Yao, J. 02-P-35 Zhang, J.Y. 11-P-22
Yashima, T. 27-0-01 Zhang, L. 05-P-08 22-0-02
Ye, X. 1 l-P-09 Zhang, Luxi 29-P-08
Yeramian, A.A. 14-P-14 24-P-11 Zhang, P. 05-P-08 07-P-07
Yin, Do. 29-P-08 Zhang, W. 08-P-06
Yin, Du. 29-P-08 Zhang, X.F. 20-P-06
Yogoro, Y. 06-P-05 Zhang, X.T. 28-0-02
Yomoda, D. 18-P- 12 Zhang, Xia. 24-P-12
Yoo, J.W. 23-P-32 Zhang, Xio. 20-P-07
Yoon, B.A. 02-P-22 Zhang, Yi. 21-P-10
Yoon, K.B. 20-0-01 Zhang, Yu. 21-P-09
Yoon, S.B. 07-P-22 Zhang, Zh. 07-P-09
York, A.P.E 06-P-21 Zhang, Zo. 06-P-07
Yoshida, H. 24-P-25 Zhanpeisov, N.U. 15-P-08
Yoshimura, M. 02-P-28 Zhao, D. 05-P-06 06-P-07 07-P-09 08-P-I 1
Yoshitake, H. 14-P-26 08-P-13
Yoshizawa, K. 28-P-07 Zhao, H. 22-0-02
Yu, C. 08-P-II Zhao, J.J. 22-P-08
Yu, J. 02-P-11 05-0-04 05-P-09 05-P-10 Zhao, L. 27-P-07
09-P0-8 22-P-09 Zhao, W. 29-P-08
Yu, J.-S. 07-P-22 Zhao, X.S. 07-0-05
Yu, Jia. 14-P-33 Zhao, Z. 22-P-09
Yu, N.-T. 12-P-10 Zheng, S. 11-P-24
Yu, S.-F. 1l-P- 12 Zhilinskaya, E.A. 14-P- 15
Yu, Y. 12-P-07 27-P-07 Zholobenko, V.L. 12-P-16 24-P-21
Yuan, H.-M. 05-P- 11 1l-P-12 Zhong, B. 06-P- 10
Yuan, Z.Y. 06-P-09 Zhou, H. 16-P- 16
Yue, Y. 08-0-04 08-P-08 Zhou, L.-P. I1-P-21 11-P-22
Yuschenko, V.V. 1 l-P-06 Zhou, W. 06-P-09 07-P- 17
Yushchenk, V.V. 1 I-P-23 Zhou, Y. 05-P-06
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Zhu, G. 03-P-08 09-P0-8

Zhu, H.Y. 07-P- 18
Zhu, J.H. 18-P-07 30-P-07 30-P-08
Zhu, L. 29-P-07
Zhu, W. 18-0-04
Zhu, Z. 24-P-06
Zidek Z. 29-P-26
Zik~inov~, A. 14-P-38 24-P- 10
~ilkov~ N. 14-P-21 14-P-22
Ziolek, M. 07-0-04 27-P-09
Zones, S.I. 02-0-05 03-0-03 1 l-P-16
17-P-07 26-0-05
Zong, B. 30-P-29
Zou, X. 09-0-03 09-P-12
Zou, Y. 02-P-11 05-0-02 05-0-02 05-P-08
II-P-11
Zu, Z. 12-P-05
Zubowa, H.-L. 2 l-P- 14
Zukal, A. 06-P-20 22-P-06 22-P-13
Zulfugarova, S. 27-P-13
Zvolinschi, A. 04-P-09
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 399

SUBJECT INDEX

A Acidity, Zr-HMS 26-P-22

Activated sludges 31-P- 14
AASBU method, structure prediction 07-P-21 Activation, catalyst, by plasma 1 l-P- 14
Ab initio calculations 15-0-01 Activation energy, proton jumps 15-0-01
Ab initio calculations, molecular orbital 15-P-07 Activation, MFI large crystals 14-P-38
Ab initio cluster calculation 15-P-08 15-P-21 Active sites 12-P-08
Ab initio simulation, dynamical processes 15-O-02 Activity profile, granular catalyst 28-P-12
ABW beryllophosphate 05-P-06 Activity-acidity relationship 15-P- 16
Acetal formation 23-P-21 Adjuvant in therapy 32-P-09
Acetaldehyde, aqueous 23-P-06 Adsorbate configuration, bipyridine/MFI 14-P-24
Acetic acid purification 18-O-05 Adsorbed phase ordering, AEL 17-O-03
Acetone dimerisation to MIBK 23-0-05 Adsorbed phase, phase transition 17-0-02
Acetonitrile adsorption, NMR study 13-P- 14 Adsorption 17-0-03 17-P- 17
Acetonitrile hydrogenation 23-P-28 Adsorption on adsorbed surfactant
Acetonitrile, synthesis 10-P-08 06-P-27 32-0-04
Acetylene 19-P-07 Adsorption, alkanes, silicalite- 1 19-P- 10
Acetylene oligomerisation 24-P- 15 Adsorption, Ar/N2 mixtures 17-P- 15
1-Acetyl-2-metoxynaphthalene isomerisation Adsorption, aromatics 19-0-02 18-P-08
25-P-08 Adsorption, aspirin on clinoptilolite 32-P-08
Acid/base properties 10-0-02 Adsorption, binary, organics 18-P- 15
Acid dealumination,BEA 11-P-22 Adsorption, chloroalkanes, Ag-FAU 24-P- 19
Acid, hybrid mesoporous 08-P- 10 Adsorption, chloroalkenes 17-P- 11
Acid leaching, zeolite Y 1 I-P-08 Adsorption, chloroform 16-P- 14
Acid sites 13-O-01 13-0-04 11-P-26 Adsorption, CO 15-P-10 12-P-13
Acid site, enhanced strength 13-P- 10 Adsorption, CO2 18-0-01 18-P- 10
Acid sites, FAU 13-P- 13 Adsorption, CO2 on Cu, Zn-FAU 17-P-14
Acid site location, MOR 12-P-16 Adsorption complexes 12-P-08
Acid sites, MCM-48 29-0-04 Adsorption complexes, geometry 14-P-07
Acid sites, mesoporous silica 24-P-25 Adsorption, dibenzothiophene 18-P- 11
Acid strength, MeAPO-31 14-P-13 Adsorption dynamics 19-P-07
Acid treatment, clinoptilolite 0 I-P-09 Adsorption enthalpies, Ar/N2 17-P- 15
Acidity 13-0-04 23-P- 15 24-0-01 Adsorption, H2 17-P- 10
Acidity-activity relationship 15-P- 16 Adsorption, H20, MCM-41 17-P- 13
Acidity, aluminophosphate 05-P-09 Adsorption, human bile 32-0-03
Acidity, dealuminated FAU 1 l-P-21 Adsorption, hydrocarbons 17-P-07 18-0-04 30-P-32
Acidity, EMT 13-P-21 Adsorption, isosteric heats 17-P- 14
Acidity, external surface 13-P-09 Adsorption isotherms, modelling 16-P- 10
Acidity, FAU 13-P-07 13-P-21 Adsorption, liquid phase
Acidity, M4 ls 29-0-03 18-O-02 18-P-07 28-P-10
Acidity, mesoporous silica 08-P-06 Adsorption, mesoporous silicas 17-P- 12
Acidity, mordenite 12-P-05 13-P-08 Adsorption models 16-O-03 26-P-20
Acidity, MTS 06-P-07 29-P-07 Adsorption, modelling 19-O-02 16-P-06 16-P-14
Acidity, by NH3 TPD 30-P- 18 Adsorption in MOR, modelling 15-P-12
Acidity, Pt/K-LTL 1l-P-07 Adsorption, mycotoxins 32-0-04
Acidity, SAPO 23-P-31 Adsorption, p-nitroaniline 13-P-06
Acidity, SAPO-34 24-P-26 Adsorption, N-nitrosamine 18-P-07
Acidity, zeolites 19-P-07 28-P- 15 Adsorption NMR, toluene/Na-X 13-P- 16
Acidity, zeolites by NMR 13-P-23 ,Adsorption, organics 14-P-30 17-P-06
Acidity, zeolite Y 15-P- 16 Adsorption, pheromones 32-0-05
400

Adsorption of probe molecules 13-0-04 AIPO4 deNOx catalysts 30-P-31

Adsorption properties, Na,Ca-LTA 17-P-09 AIPO4 heteronuclear NMR 13-P-24
Adsorption, proteins 23-P- 17 AIPO4 substituted, multipole moment 15-P-27
Adsorption, reactive 18-0-05 AIPO4 synthesis, templates 02-P-33
Adsorption, supercritical 17-P-05 17-P- 16 AIPO4, synthesis intermediate 02-P-11
AEL, commensurate phases 17-0-03 AIPO4-5 13-P-14
Affinity index 17-P-06 AIPOa-5/DCM resin composites 21-O-04
AFI, Co 04-P- 13 AIPO4-5 with Fe 14-P-39
AFI single crystal 2 l-P-08 AIPO4-5 host 21-O-05 21-P-08
AFM PL-2 02-0-05 A1PO4-11, adsorbed phase ordering 17-O-03
AFM, growth surface SSZ-24 13-P- 16 AI PO4-14, hydration 13-P-20
Ag diffuse reflectance 0 l-P- 15 AIPO4-18 with Fe 14-P-39
Ag dispersion, effect on SCR 30-P-28 AI PO4-18, hydration 13-P-20
Ag-clinoptilolite 0 l-P- 15 AIPO4-20 09-P- 11
Ag-FAU 18-O-05 24-0-02 24-P-19 AIPO4-20, host 22-P- 19
Ag-FER spectroscopy 14-0-03 AIPO4-31, substituted 14-P- 13
AgI clusters in LTA 22-P- 17 AIPO4-34, hydration 15-P- 17
Ag-LTA 14-O-04 AIPO4-CJ2, NMR crystallography 09-0-02
Ag-MFI 30-0-03 30-P-28 30-P-34 AI quantification 13-0-03
Ag-MFI spectroscopy 14-0-03 AI-SBA- 15, synthesis 08-0-04
Ag-MFI, adsorbent for CO 15-P- 10 AI sources, MCM-41 06-P- 17
Ag-MFI, deNOx catalyst 30-P-34 AI support, MFI films 20-P-I 7
AgS2 clusters in LTA 14-O-04 AI-Mn phosphate 05-P-11
Ag§ local structure 30-P- 16 AI, traces in TS-1 27-0-02
Agglomerated nanocrystals, reactivity 03-P- 14 Alcohol oxidation 27-P-08
Aggregates, silica, fractal 14-P-25 Aldehyde, unsaturated 29-P- 15
Aging 02-0-02 Aldol condensation 23-P-23
Aging, effect on synthesis 02-P- 19 02-P-21 Alkali cations, effect on adsorption 32-0-05
Aging, MCM-41 synthesis 06-P-21 Alkali cations, effect on photocatalysis 15-P-07
27A1-13Cdipole interaction 13-0-01 Alkali cations, effect in synthesis 03-0-05
27A1chemical shifts 15-P-21 Alkali cations in FAU, EPR 14-P-07
27A12D NMR 13-P- 19 Alkali cations in fluoride media 04-P-17
27Al(19F) WISE NMR 08-0-04 Alkali cation templates 03-P- 18
27A1MQ MAS NMR 13-O-03 13-P-20 14-P-11 Alkali-exchanged LSX 14-0-02
27A1 NMR 07-P-08 06-P- 17 Alkali-exchanged MCM-22 and MCM-36 10-O-02
09-0-02 09-P- 11 1 I-P- 10 11-P-28 13-P- 18 Alkali metal particles/FAU 14-P-37
13-P-22 13-P-24 18-P-13 21-P-17 30-P-19 Alkali treatment, bentonite 03-P-06
AI coordination, AIPO4-20 09-P-11 Alkali treatment, MFI 1 l-P-30
AI distribution by cation siting 13-P-19 Alkaline earth in LTL synthesis 02-P-17
AI distribution in MFI 13-O-02 Alkalinity, effect on crystallisation 03-P-19
AI, extraframework 13-P- 18 Alkane activation 25-0-05 25-P-15
AI, extra-framework, modelling 15-P-21 Alkane conversion 15-P- 15
AI insertion, CON and DON 1 I-P-16 Alkane cracking 15-P- 15
AI isopropoxide, MCM-41 secondary treatment Alkane diffusion, silicalite- 1 19-P- 10
23-P-33 Alkane formation, free energy 16-0-01
beta-Al methylphosphonate, crystallisation Alkane hydroconversion 16-0-01
21-P-17 Alkane isomerisation 26-0-02
AIMepO-beta, water adsorption 09-P- 14 n-Alkanes, long chain, isomerisation 26-P-23
AI-MCM-22 14-P-21 Alkanes, oxidation 27-0-01 27-P-06
AI-MCM-41, catalyst support 24-P-08 Alkene, s e e Olefin
AI-MCM-41, stability 06-P- 19 Alkoxy surface species from dechlorination 24-P-19
AIOH hydroxyls 14-P- 10 Alkoxysilanes 1 l-P-09
AI ordering 13-0-01 Alkoxysilane CVD 11-O-02
AI ordering, dachiardite 0 l-P-07 Alkylamine 06-P-23
AI pentacoordinated 13-P- 18 Alkylammonium in AIPO4 synthesis 02-P-33
A1 phosphites, microporous 05-P- 15 Alkylation 06-P-06 24-P-09 25-P-16
AIPO4, s e e a l s o aluminophosphate Alkylation, aniline 23-P- 12 25-P- 11
 401

Alkylation, benzene 24-P-06 25-P-15 29-0-01 Ammonium removal 3 I-P-09 3 l-P- 10

Alkylation, benzene, by alkanes 25-0-05 31-P-11 31-P-12 31-P-15 31-P-16
Alkylation, biphenyl 25-P-0 29-P-11 Ammoxidation, ethylene 10-P-08
Alkylation, bulky aromatics 25-P-12 Amorphisation at high pressure 16-P- 19
Alkylation, ethylbenzene 28-P-08 Amorphous aluminosilicate 02-P-32
Alkylation, isobutane 24-P-20 Amorphous aluminosilicate, zeolitic 29-P- 12
Alkylation, isopropylnaphthalene 25-P-16 Analcime crystal chemistry 01 -P- 11
Alkylation, naphthalene 25-0-03 25-P-13 Analcime from fly ash 18-P- I 0
Alkylation, ortho- 28-P-15 Anatase, aggregated nanocrystals 22-P- 13
Alkylation, phenol 23-P-31 25-P-09 28-P-15 Angle BOT-chemical shift correlation 13-P-I 1
Alkylation, polyaromatics Aniline methylation 23-P- 12
25-O-01 25-P-06 25-P-09 25-P-14 Aniline, N-methylation 25-P-11
Alkyl hydroperoxide, decomposition 27-P- 10 Animal feeding 32-P-06 32-P-10 32-P-11
Alkyl ketone photolysis 15-P-07 Anion exchanger 22-P- 12
N-alkylphenothiazines, photoionisation 24-P-07 Antarctica, zeolite occurrences 0 l-K-01
Alumina, anatase stabilizer 22-P- 13 Anthraquinone/BEA photocatalyst 27-P- 14
Alumina membrane support 20-0-03 Anticancer activity 32-P-09
Alumina, mesoporous 06-P-23 07-P- 16 07-P- 18 Apatite, crop enhancement 31-O-02
Alumina, mesostructured 07-P-08 APO-CJ3 02-P- 11
Alumina source 02-P-19 APO-CJ4 05-P- 10
Alumina support 30-P-19 Apple fragrance 23-P-22
Alumina-zirconia, mesoporous 07-P-09 Aquaculture 3 l-P- 12
Aluminate, sodium reagent 11-P-22 Aqueous solution 01 -P- 17
Alumination, BEA 1I-P- 10 11-P-22 Ar adsorption 17-P-05
Alumination, MCM-41 23-P-33 25-P-12 Ar adsorption, AEL 17-0-03
Alumination, MCM-48 29-0-04 Ar, supercritical adsorption, zeolites 17-P-I 6
Alumination of siliceous zeolites 11-P-28 Ar/N2 adsorption, FAU 17-P- 15
Aluminophosphates, s e e also AIPO4 Ar/N2 adsorption, LTA 17-P- 15
03-P-16 14-P-22 14-P-33 Armenia, natural mordenite 0 I-P- 16
Aluminophosphate, anionic 05-P-09 Aromatics, adsorption 19-0-02
Aluminophosphate, chiral 05-P- 10 Aromatics, adsorption on MFI 13-P-25
Aluminophosphates, hydration 15-P- 17 Aromatics, bulky, alkylation 25-P- 12
Aluminophosphate, lamellar 02-P- 11 Aromatic chloro compounds 23-P- 16
Aluminophosphates, lattice vibrations 14-P-31 Aromatics, diffusion 19-0-02
Aluminophosphate MIL-34 05-P- 19 Aromatics disproportionation 11-O-02
Aluminophosphates, Ni 09-P-08 Aromatics hydroalkylation 23-P-21
Aluminosilicate MCM-41 Aromatics hydrodecyclisation 26-P- 13
06-P-08 07-P-14 24-0-05 24-P-22 Aromatics, hydrogenation 26-P- 10
Aluminosilicate, mesoporous 06-P-07 06-P-15 Aromatics hydroxylation 2 I-P-07
06-P-22 06-P-27 08-P-06 08-P-14 29-0-04 Aromatics, nitration 13-P-22
Aluminosilicate UTD- 1 1 I-P-16 Aromatics oxidation 2 l-P-07
Aluminosilicate SSZ-33 1l-P-16 Aromatics oxyhalogenation 23-P-24
AM- 13, vanadosilicate 04-0-05 Aromatisation, C4 hydrocarbons 24-P-30 24-P-31
AM- 14, vanadosilicate 04-0-05 Aromatisation, cyclohexane 24-P-27
Amides in phosphate synthesis 02-P-33 Aromatisation, cyclohexene 24-P-27
Amination, methanol 11-P-25 Aromatisation, n-hexane 15-P-09 28-0-02
Amination, octanoi 23-P-07 Aspirin 32-P-07
Amines in beryllophosphates synthesis 05-P-06 Aspirin adsorption on clinoptilolite 32-P-08
Amine expander for MCM-48 06-0-04 ATO, substituted 14-P- 13
Amine extraction from HMS 06-P- 11 ATO, substituted, synthesis 04-P-09
Amines in phosphate synthesis 02-P-33 Au nanoparticles 11-O-01
Amine, template 02-P-41 03-0-03 07-0-05 Au, bimetallic clusters in FAU 11-O-01
Amine, zeolite template 05-0-02 Au2CI6 encapsulated 10-0-03
Amino acids 18-0-02 AV-6, stannosilicate 05-P- 13
Amino acids separation 28-P- 10 AV-7, stannosilicate 05-P- 13
3-Aminopropylsilane grafting 29-P-31 Avoidance rule 0 I-P-07
Ammonium exchange, clinoptilolite 0 I-P- 12 Azamacrocycles in synthesis 05-0-03
402

Aziridination, olefins 24-0-04 BEA, NiMo hydrotreatment catalyst 26-P-15

Azo dyes 21-O-02 BEA, partially crystalline 29-P-12
BEA, photocatalyst 30-P-20
BEA, polystyrene beads 2 l-P-12
B BEA, polytypism 0 l-K-01
BEA, Pt 17-P-08
liB NMR 13-P-11 BEA, Pt aromatisation catalyst 15-P-09
11B, quadrupolar interaction 13-P- 11 BEA, Pt hydrogenation catalyst 26-P-13
B distribution in MFI 13-O-02 BEA, Pt isomerisation catalyst 20-P-18
BN nanoparticles 21-O-05 BEA, Pt/Cs 26-0-05
B ordering 13-0-01 BEA, ring opening catalyst 26-0-03
B-substituted zeolites 13-P- 11 BEA, silylation 1 l-P-09
B-treated zeolites 11-P-23 BEA, synthesis, with DLH 30-P-26
Ba in alkaline synthesis 02-P-17 BEA, Ti 27-P- 11 27-P- 17
Ba-X, adsorbent 16-0-03 BEA, V 14-P-35
Basic catalysis Beckmann rearrangement 15-0-05
02-P-22 04-0-02 10-O-02 23-P-13 23-P-23 23-0-03 23-P-18 23-P-21 23-P-27 27-P-16
Basic catalysis, zincophosphates 29-P-23 Bentonite adsorbent 32-0-04
Basic catalyst, immobilised 23-0-04 Bentonite application 18-P- 14
Basic catalysts, mesoporous 29-P- 10 Bentonite, pillared 22-P- 16
Basic catalyst, MIBK synthesis 23-0-05 Bentonite zeolitisation 03-P-06
Basic probe molecules 13-P- 13 Benzaldehyde-ethylcyanoacetate condensation
Basic zeolites 23-0-04
10-O-02 23-P-12 23-P-13 23-P-29 29-P-20 Benzaldehyde, trimethylsilylcyanation 23-P- 11
Basic zeolites, synthesis 04-0-02 Benzene adsorption 14-P- 14 18-P- 15
Basicity of zeolites by NMR 13-P-23 Benzene adsorption, MFI 17-0-02 18-P-08
Basicity, zeolite oxygen 14-O-02 Benzene alkylation
BEA, adsorbent 18-0-02 24-P-06 25-0-05 25-P- 15 29-O-01
BEA, A! distribution 13-P- 19 Benzene diffusion, NMR imaging 19-K-01
BEA, alkylation catalyst 24-P-06 24-P-20 Benzene hydroconversion 26-P- 15
25-0-02 25-P-07 25-P-09 25-P-13 25-P-14 Benzene hydrogenation 27-0-04
BEA, all-silica, synthesis 02-P-35 Benzene oxidation to phenol 27-0-03
BEA/alumina membranes 20-P-18 Benzene removal, membrane 20-P- 12
BEA, alumination 1 I-P-10 11-P-28 Benzothiophene HDS 26-P-07
BEA, anthraquinone photocatalysts 27-P-14 N-benzyl- l-azoniumbicyclo[2,2,2]-octane template
BEA, aziridation catalyst 24-0-04 03-0-04
BEA, catalyst 28-P- 11 28-P- 15 Beryllophosphate synthesis 05-P-06
BEA/ceramic composite membrane 20-P-12 Beryllosilicates 05-O-05
BEA, Cr 04-P-08 Beta cage, encapsulation modelling 15-P-08
BEA, crystallisation kinetics 02-P-23 Bifunctional catalysis 23-0-05
BEA, dealumination and realumination 11-P-22 23-P-14 23-P-28 24-0-03 25-P-15 26-P-06
BEA-DLH oxidation catalyst 30-P-26 Bifunctional catalysts, MCM-41 26-P-18
BEA, drug carrier 32-0-05 Bifunctional catalysts, Pt,Ni-USY 14-P-36
BEA, effect of hydrophobicity on activity 28-P-14 Bile, adsorption 32-0-03
BEA, esterification catalyst 28-P-14 Bilirubin 32-0-03
BEA, Fe 04-P-07 10-O-04 30-P-11 30-P-27 Bimetallic catalysts 22-0-05 29-P-15
BEA, Fe, DeNOx catalyst 30-P-06 Bimetallic catalyst, Pt,Ni-USY 14-P-36
BEA, flexible lattice 13-P-22 Bimetallic clusters with Au 11-O-01
BEA, Ga 03-P- 10 Bimodal pore structure 06-P-20
BEA, hydroconversion catalyst 24-0-03 Bimodal porosity, MFI 03-0-02
BEA, In deNOx catalyst 10-O-01 Binary adsorption 17-P- 15 18-P- 15
BEA, isomerisation catalyst Binder, polymeric 22-P- 15
24-P-16 25-P-0 26-O-01 28-P-13 Biological wastewater treatment 3 l-P- 14
BEA, lattice vibrations 12-P-07 Biomedical applications 32-O-01 32-P-09
BEA, macroporous structures 2 l-P- 15 Biomimetic oxidation transfer 27-P- 10
BEA, Mo 14-P-08 Biphasic system, membrane separation 23-P-10
Biphenyl adsorption, MFI 14-P- 18
 403

Biphenyl alkylation CH4 in deNOx SCR 10-O-01 30-P-28

25-P-07 25-P-09 25-P-14 29-P- 11 CH4, photocatalytic oxidation 24-P- 12
Biphenyl isopropylation 29-P-11 CH4, supercritical adsorption, zeolites 17-P- 16
Biphenyl isopropylation, models 16-P-08 CH4-CF4 diffusion in FAU, modelling 16-O-05
2,2'-Bipyridine adsorption/MFI 14-P-24 Ca in LTL synthesis 02-P-17
Bipyridine complex, encapsulated 24-P-29 Ca promoters, DeNOx 30-P-25
Block copolymer surfactants 08-P-12 CaClz/Silica Gel 31-O-04
Boggsite, Xe-SF6 diffusion, modelling 16-0-05 Ca,Na-LTA 17-P-09
Borates NMR 13-P-11 Cadmium clusters 09-P-06
Borogermanates, layered 09-P-12 Cadmium exchange 3 l-P-08
Borosilicates NMR 13-P-11 Cafeine separation 20-0-05
Borosilicate zeolites 1 l-P-16 Calcination, exchanged zeolites 10-P-07
Borosilicate zeolite reforming catalyst 26-0-05 Calcination, mordenite 12-P-05
Branched paraffins, adsorption on MFI 13-P-25 Calcination, by ozone 11-P-27
Breakthrough curves 18-P- 15 19-P-06 Calcination, partial 1l-P-12
Bromamine-T 24-0-04 Calculations, ab initio 15-P- 14
Bronsted acid sites Calculation, framework vibrations 14-P-34
12-P-16 13-O-01 13-P-17 13-P-18 14-P-21 Calculations, semiempirical 15-P- 14
Bronsted acid sites in ZSM-5 13-P- 10 30-P-25 Calixpyrrole synthesis 28-0-04
Bronsted acidity 05-P-09 1 I-P-07 13-P-19 Calorimetric sensors 22-P-11
Br~nsted acidity, EMT 14-P-23 Calorimetry 31-O-04
Br~nsted acidity, ETS- 10 24-P-15 Cancrinite synthesis 02-P-07 03-P-I 1
Bronsted acidity, FAU 14-P-23 Cancrinite/sodalite overgrowth 02-P-28
Bronsted acidity, HPA 13-P-05 Capillary columns, LTA 18-P-09
Bulgaria, zeolite occurrences 0 l-P- 10 01-P-13 Caprolactam 23-P- 18 23-P-27 27-P-16
Bulk-material dissolution in MFI synthesis 02-P-26 Carbanium cation 24-P-09
Butadiene dehydrocyclodimerisation 22-0-03 Carbenium ions 12-P-06
Butane activation 24-P-09 Carbocation 15-P- 15
n-Butane dehydroisomerisation 24-0-01 Carbon intercalation 1 l-P-11
n-Butane isomerisation 24-P- 16 29-P-17 Carbon nanotubes 21-P-08
2-Butene in alkylation 24-P-20 Carbon nanotubes, formation 22-P-08
Butene isomerisation 14-P-22 24-P-21 Carbon number, effect on SCR 30-0-03
l-butene synthesis 24-P-17 Carbon replica 07-P-22
Butylamine templates 05-P-17 Carbon templates for MFI mesopores
n-Butyraldehyde aldol condensation 23-P-23 03-0-02 26-0-02
Carbon, mesoporous
PL-1 07-O-01 07-P-22 29-P-13
C Carbonisation 07-P-22
Catalyst deactivation 27-P- 16
13C chemical shift anisoptropy 13-P-16 Catalyst engineering 28-P- 12
13C MAS NMR Catalyst heterogeneity 23-0-02
~3C MAS NMR, molecular dynamics 13-P-06 Catalytic activity, external surface 13-P-09
13C NMR Catalytic cracking 08-P- 13
03-0-04 09-P-11 13-P-16 23-P-12 30-P-19 Catalytic tests of acidity and basicity 13-P-23
~3CNMR, MFI synthesis 02-P-40 Catalytic test reactions 26-P-11
~3CNMR probe, nitromethane 23-P-13 Catalysis, see individual reactions
t3C-27AI dipole interaction 13-O-01 Catalysis, effect of microwaves 28-0-02
C4 hydrocarbons aromatisation 24-P-30 Catechol 27-P- 17
C5-C7 olefins isomerisation 26-P-09 Cation distribution, MOR 16-P-11
C5-C6 hydroisomerisation 20-P-18 Cation distribution, Na,Ca-LTA 17-P-09
C6 isomer diffusion 19-P-10 Cation effect on aromatisation 15-P-09
C60 1 l-P-12 Cation effects in gas separation 18-O-03
CF4-CH4 diffusion in FAU, modelling 16-O-05 Cation effect in microwave heating 11-P-I 3
CH4 activation 24-0-02 Cation exchange 0 I-P- 17 09-0-05 10-0-02
CH4 adsorption, AEL 17-O-03 10-P-05 1 l-P- 18 1 l-P- 19 2 l-P-07 3 l-P-05
CH4 conversion 24-0-02 31-P-06 31-P-08 31-P-10 31-P-15 31-P-16
404

Cation exchange, clinoptilolite Chlorocarbon oxidation 30-P- 18

01-P-12 01-P-17 22-P-12 22-P-15 Chlorocarbon removal 30-0-05
Cation exchange, drying effect 1 l-P-20 Chiorofluorocarbon decomposition 30-P- 19
Cation exchange, ETS-4 1 l-P- 15 Chlorofluorocarbon-zeolite interaction 30-P- 19
Cation exchange, FAU 17-P-14 Chloroform adsorption 3 l-P-08
Cation exchange, indium 30-P- 15 Chloroform, adsorption in Na-Y 16-P- 14
Cation exchange, PHI 01-O-05 Cholesterol 32-0-03
Cation exchange, solid state Chromatography, LTA column 18-P-09
10-O-01 10-P-06 10-P-08 30-P-27 Chromatography, MSU-X application 08-O-01
Cation exchange, SOMS 05-0-01 Chromatography, stationary phases 18-P-06
Cation impurities, EPR 14-P- 15 Cigarette smoke 30-P-07
Cation location 15-P- 11 Cinchonidine 23-P-25
Cation location, clinoptilolite 01-O-03 Cinnamaldehyde hydrogenation 07-P- 16
Cation location, In-X 09-P- 10 Cinnamate ester synthesis 23-0-02
Cation location, MOR 09-P- 13 Cinnamyl alcohol 25-P-12
Cation mobility, high temperature 14-P- 17 Circular crystals, mesoporous silica 06-0-02
Cation properties, modelling 15-P-08 CIT-5 (CFI), Fe 16-P-09
Cation radicals 13-P-08 Citology 32-0-02
Cation radicals, biphenyl/MFI 14-P- 18 Citric acid, complexing agent 04-P- 15
Cation sites 03-0-03 CI-CIO hydrocarbons in SCR-NOx 30-0-03
Cation sites, MFI 15-P-24 Clays, polymer degradation catalyst 30-P-17
Cation sites, modelling 15-P-23 Clear solution synthesis 02-0-04
Cations sites by UV-visible spectroscopy 14-O-03 Clinoptilolite, acid sites 11-P-26
Cd clusters 09-P-06 Ciinoptilolite, acid treatment 0 l-P-09
Cd(l-x)Mn(x)S 21-O-03 Clinoptilolite, acidity 23-P-09
Cd-X 09-P-06 Clinoptilolite adsorbent 32-P-08
Ce,EU silicates 05-P- 12 Clinoptilolite, Ag 0 l-P- 15
Ce and Pd promoter 30-P-22 Clinoptilolite, applications
Ce-MCM-41 07-P-23 PL-2 3 l-P-07 3 l-P-08 3 l-P-10
Ce-MCM-41, stability 06-P- 19 31-P- 14 31-P-15 32-0-03 32-P-10 32-P-11
Ce-MFI 23-P-24 Clinoptilolite, Bulgaria 0 l-P- 10
Ce-MFI, oxihalogenation catalyst 23-P-24 Clinoptilolite, Ca 32-0-03
Ce-MOR 29-P-11 Clinoptilolite, cation exchange
Cellular reactions 32-P-09 01-P-12 31-P-12 32-0-04
Cement-zeolite composite 3 l-P- 13 Clinoptilolite, cation exchanger 3 l-P-09
Ceramic support 20-P-09 Clinoptilolite, crop enhancement 31-O-02
Ceramic from zeolites 10-P-07 Clinoptilolite, Cu 1 l-P-20 30-P- 10
CHA CoAPO 04-P- 13 Clinoptilolite, dehydration 23-P-09
CHA from fly ash 18-P- 10 Clipnotilolite dehydration catalyst 23-P-08
CHA, acidity, modelling 15-0-01 Clinoptilolite, deNOx catalyst 30-P-10
Chabazite, rare earth 1 I-P-19 Clinoptilolite, diffusion 19-0-04
Chabazite/sodalite overgrowth 02-P-28 Clinoptilolite and health 32-P-09
Chelate post-treatment 11-O-04 Clinoptilolite, host 22-P-10
Chelators, Fe 32-0-02 Clinoptilolite, hydrothermal transformation 32-P-07
Chemical liquid deposition 11-P-24 Clinoptilolite for lead removal 3 l-P-06
Chemical shift and electric gradient 14-P-27 Clinoptilolite, medical applications 32-P-12
Chemical shift-geometry correlation 13-P- 11 Clinoptilolite, modified, adsorbent 32-0-04
Chemical shift ~70-angle relationship 14-O-02 Clinoptilolite, occurrences 01-O-02
Chemisorption 17-P-08 Clinoptilolite, organic-modified 22-P- 12 22-P-15
Chiral hydrogenation 23-P-25 Clinoptilolite, oxidation catalyst 27-P-08
Chiral molecular sieve 05-P- 10 Clinoptilolite properties PL-2
Chiral templates 05-0-04 Clinoptilolite, purified 32-P-07
Chiral Ti (IV) Salen complex 23-P-11 Clinoptilolite stability 01 -O-03
Chlorination, diphenylmethane 23-P-30 Clinoptilolite, structure PL-2
Chloroalkane adsorption, Ag-FAU 24-P- 19 Clinoptilolite thermal behaviour 11-P-26
Chloroalkenes on MFI 17-P-I 1 Clinoptilolite tuff
Chloroaromatics dechlorination 23-P- 16 01-P-09 01-P-12 01-P-13 31-P-11
 405

Cloverite, host 2 l-P- 14 CO2 separation 18-0-01

Cluster calculations 15-P-09 CO2, supercritical solvent 20-0-05
Clusters, in LTA 22-P-17 Coating 20-P-09
CMK- 1 mesoporous carbon PL-1 Coating by LTA 20-P-15
J33Co MAS NMR 09-0-05 Coating, MFI/gold 20-P-14
Co 2+ in AIPO4 04-P- 11 04-P- 13 Coating by zeolites, Al alloy 22-0-04
CoAPO, deNOx catalysts 30-P-31 Coating, zeolites/diatoms 21-P-07
CoAPO-5 04-P-13 Coke 24-P-06
CoAPO-5, sensors 22-P-11 Coke, effect on catalysis 30-P-21
CoAPO- 18, Co site 14-0-05 Coke, effect on isomerisation 25-P-08
CoAPO-31 14-P-13 Coke formation, MFI 24-P-31
CoAPO-31, synthesis 04-P-09 Coke selectivation 28-P-06
CoAPO-34 29-P-14 Coke tolerance 26-P-16
CoAPO-34, Co site 14-0-05 Coking, in MTO 24-P-28
CoAPO-44 04-P- 13 Cold start exhaust gases 30-P-32
CoAPSO-31, synthesis 04-P-09 Colloidal FAU crystals 02-0-03 02-P-14
Co, cation site 15-P- 11 Colloidal MFI crystals 02-0-04
Co-ERI, oxidation catalyst 27-P- 13 Colloidal offretite 02-P-12
Co-FER catalyst 30-P-35 Colloidal templates 07-P-22
Co histidine complexes 27-P- 10 Combinatorial chemistry 03-P-12
Co-HMS 29-P-08 Combinatorial methods in synthesis
Co 2§ ion probes 14-P-21 03-K-01 03-P-13 03-P-16 03-P-18 06-P-25
Co-MCM-22 14-P-21 Commensurate phases, in AEL 17-O-03
Co-mesoporous silica 08-0-02 Compass forcefield 16-P-06
Co-MFI 04-P- 18 13-0-02 30-0-03 Complexing agent 03-P-08
Co-MFI, deNOx catalyst 30-P-34 Complexing agent, citric acid 04-P- 15
Co-MFI, by solid state ion exchange 10-P-08 Composite, BEA/polystyrene 2 l-P- 12 21-P-15
Co-MOR, oxidation catalyst 27-P- 13 Composite, diatom/zeolite 21-P-07
Co, Ni promotion 26-P-17 Composite, LTA/polystyrene 21-P-12
Co, Pd, Ce trimetallic catalysts 30-P-22 Composite, LTL/FAU 07-P-10
Co 2§ probe of AI distribution 13-P- 19 Composite membrane, BEA/ceramic 20-P-12
Co Salen complexes on MCM-41 23-P-10 Composite membrane, MFI/ceramic 20-P-12
Co site in CoAPO 14-O-05 Composite nanotube/AIPO4-5 2 l-P-08
Co spinel from zeolites 10-P-07 Composite, resin-silicate 03-P-07
Co, tungstophosphates 05-P-20 Composite, zeolite-cement 31-P-13
Co UV-Vis 04-P-18 13-P-19 Composite, zeolite/polymer 19-0-05
Co XPS 04-P- 18 Composite zeolitisation 21-P-07
Co-zeolites, oxidation catalysts 27-P-08 Composite, ZSM-5/Raney metal 30-P-29
Co-zeolite Y, oxidation catalyst 27-P-13 Computational analysis 16-P-08 16-P-15
CO adsorption 13-0-04 Confined system, 1-dimensional 17-P-17
CO adsorption equilibria 12-P- 13 Confined systems, phase transitions
CO adsorption, AEL 17-O-03 17-O-01 17-P-17
CO adsorption, Ag-MFI 15-P- 10 Conformational analysis 16-P-17
CO adsorption/cation MFI 15-P-24 Congo red in MCM-41 22-P-21
CO adsorption, Cu-MFI 14-P-40 Connectivities, by MQ MAS NMR 13-P-24
CO adsorption, EMT 14-P-23 Contaminant concentration 31-P-08
CO adsorption, FAU 14-P-23 Continuous microwave synthesis 03-P-15
CO adsorption, Pt-zeolites 17-P-08 Conversion, polyethylene 24-P-13
CO hydrogenation 24-P-11 Cordierite support 12-P- 15 20-P- 13 30-P-33
CO oxidation 29-P- 14 30-P- 10 Correlation functions 16-P-18
CO reduction, MeAPO-34 29-P-14 Corrosion pevention 22-0-04
CO2 adsorption, Cu, Zn-FAU 17-P-14 Cosurfactants 06-P-09 06-P- 18
CO2 adsorption isotherms 17-P- 14 CrAPO-5, synthesis 04-P-12
CO2 adsorption on zeolites 18-P- 10 Cr-BEA 04-P-08
CO2+H2 reaction 24-P-26 Cr cation exchange 31-P-13
CO2 and refining PL-4 Cr ETS- 10 27-P-15
CO2 removal 18-0-01 Cr-HMS 28-P-07
406

Cr-MCM-48 06-P-12 Crystallisation kinetics, ETS-4 04-P- 16

Cr-MFI 23-P-24 Crystallisation kinetics, KFI 02-P-21
Cr, oxidation catalyst 27-P-06 Crystallisation, LTA 02-P-29
Cr removal from wastewater 31-P-13 Crystallisation, MFI, phosphate-affected 02-P-40
Cr storage 31-P-13 Crystallisation models 02-P-24 02-P-31
Cr-zeolites, oxidation catalyst 27-P-08 Crystallisation, mordenite 03-P-19
Cr-ZSM-5, oxihalogenation catalyst 23-P-24 Crystallisation promotor, phosphate 02-P-40
Cracking, alkanes 15-P-15 Crystallisation, rapid 02-P-30
Cracking catalyst, treated USY 11-P-23 Crystallisation, silicalite- 1 02-P-16
Cracking, cumene Crystallisation, SSZ-24, AFM 02-O-05
03-P- 14 04-P- 14 1 l-P-30 28-P- 16 29-P-07 Crystallography 16-P-06
Cracking, cyclic oils 26-P-10 133CsNMR 14-P-17
Cracking, methylcyclohexane 26-P-11 Cs-BEA, Pt 26-0-05
Cracking, n-heptane 24-P-06 Cs cation exchange 1 l-P-18
Cracking, n-hexadecane 08-P-13 Cs-FAU, Pt catalyst 23-0-05
Cracking, n-hexane 26-0-01 29-P-26 Cs,Na-FAU 14-P-I 7 29-P-20
Cracking, polyethylene 24-P-13 Cs,Na-MFI 29-P-20
Cracking, polymers 30-P-17 Cs-zeolite condensation catalyst 23-P-29
Cracking, thiophene, modelling 15-P-22 Cu in AIPO4, deNOx catalyst 30-P-31
cracking, 1,3,5-trisopropylbenzene 29-P-07 Cu carbonyl complexes 14-P-40
m-Cresol transformation 28-P-13 Cu § cation 1 l-P-20
Croatian clinoptilolite 0 I-P- 17 31-P-11 Cu, cation exchange 1 l-P-20 31-P-08
Crop enhancement 31-O-01 31-O-02 Cu § cation site 15-P-11
Crotonaldehyde, hydrogenation 29-P-15 Cu 2+, cation site 15-P-11
Crotyl alcohol, synthesis 29-P-15 Cu-Clinoptilolite 30-P-10
Crystals, circular, mesoporous silica 06-0-02 Cu+-Cu2+ pairs in Cu-MFI 14-P-40
Crystal chemistry, analcime 01-P-11 Cu-ERI, oxidation catalyst 27-P-13
Crystal growth, FAU 20-P-16 Cu-exchanged zeolites 12-P-09
Crystal growth, LTA 20-P-16 Cu-FAU 17-P-14
Crystal growth, MFI 02-P-09 Cu-FAU oxidation catalyst 27-P-13 30-P-23
Crystal growth rate 02-P-08 Cu-FAU reforming catalyst 24-P-23
Crystal growth, ultrasound monitoring 02-P-37 Cu-FER spectroscopy 14-O-03
Crystal morphology, effect on diffusion 19-O-04 Cu histidine complexes 27-P-10
Crystal morphology, LTL 02-P- 17 Cu-HMS 29-P-08
Crystal morphology, TS- 1 16-P-16 Cu-MCM-41 07-0-04
Crystal orientation 20-0-04 Cu methylamino complexes 04-0-01
Crystal size, BEA 02-P-23 Cu-MFI 04-0-01 12-P-15
Crystal size, effect on catalysis 24-P-16 13-O-02 15-P-13 30-0-03 30-P-09 30-P-33
Crystal size, LTL 02-P- 17 Cu-MFI, aromatisation catalyst 24-P-30
Crystal size, MFI 02-P-09 02-P-15 Cu-MFI, deNOx catalyst 16-P-20 30-P-14
Crystal size, Nb-MFI 04-P-10 Cu-MFI diffuse reflectance spectroscopy 30-P-21
Crystal size tayloring 04-0-04 Cu § in MFI framework 15-P-13
Crystal structure, AlMepO 09-P-14 Cu 2+ in MFI framework 15-P-13
Crystal structure, AIPO4-20 09-P- 11 Cu-MFI oxidation catalyst 27-P-12
Crystal structure, Cd-FAU 09-P-06 Cu-MFI, spectroscopy 14-O-03
Crystal structure, Cu molybdate 09-P-07 Cu-MFI, synthesis 14-P-40
Crystal structure determination Cu molybdate structure 09-P-07
01-K-01 05-P-19 09-P-13 Cu-MOR 1 l-P-20
Crystal structure, layered germanate 09-P-12 Cu-MOR, oxidation catalyst 27-P-13
Crystal structure, SOMS 05-0-01 Cu,Na-Y 12-P-09
Crystallinity, partial, BEA 29-P-12 CuO-ZnO-ZrO2 24-P-26
Crystallisation 02-P-20 Cu, oxidation catalyst 27-P-06
Crystallisation, AIMepO 21-P-17 Cu oxides in MCM-41 07-P-19
Crystallisation fields 03-P-18 Cu 2+ reduction in Cu-ZSM-5 30-P-21
Crystallisation fields, K-Na system 03-0-05 Cu/silica 07-P-07
Crystallisation, in-situ monitoring 02-P-37 Cu, UV-visible 1 l-P-20
Crystallisation kinetics, BEA 02-P-23 Cu-zeolites 15-P-11
 407

Cu-zeolites, oxidation catalysts 27-P-08 Dealumination, FAU 14-P-23

Cu, Zn mesoporous alumina 07-P-16 Dealumination, FAU, chemical 1 l-P-21
Cubic mesoporous silica, functionalized 07-0-02 Dealumination, FAU, hydrothermal 1 l-P-21
CuI clusters in LTA 22-P-17 Dealumination, FER 13-P- 17
Cumene cracking Dealumination, MFI 29-P-06 29-P-26
03-P- 14 04-P- 14 1 l-P-30 29-P-07 Dealumination, MOR 12-P-05
Cumene cracking on H-ZSM-5 28-P-16 Deboration 1 l-P- 16
Cumene, diffusion in MFI 19-O-03 n-Decane 26-P- 18
Curcumin dye in MCM-41 22-P-21 Decane conversion 13-0-02
CVD 11-P-24 n-Decane hydroconversion 26-P-06 29-P- 19
CVD alkoxysilane 1 l-P-09 Decane, swelling agent 06-P-27
CVD alkoxysilane/MFI 10-P-09 11-O-02 Deca(oxyethylene)oleyl ether, surfactant 08-0-02
CVD FeC13 11-O-05 Decomposition of water, photochemical 28-0-03
CVD passivation 27-P- 17 Defects, MFI 14-P- 19
CVOC abatement 30-0-05 Degradation, polyethylene 24-P-25
Cycloalkane conversion 26-P- 10 Degradation, polymers, catalytic 30-P- 17
Cyclobutylamine template 05-P- 19 Dehydration, Cd-FAU 09-P-06
Cyclohexane aromatisation 24-P-27 Dehydration, clinoptilolite 11-P-26
Cyclohexane isomerisation 26-P- 19 Dehydration, isopropanol 29-P-06
Cyclohexane oxidation Dehydration, K-LSX 09-0-01
02-P-14 07-P-10 27-P-06 27-P-15 Dehydration, MOR 09-P- 13
Cyclohexane, oxidation, total 30-P-09 Dehydrocyclodimerisation, butadiene 22-0-03
Cyclohexane ring opening 26-0-03 Dehydrogenation, ethylbenzene 20-P-06
Cyclohexanol, diffusion in ZSM-5 19-0-03 Dehydrogenation, methanol 10-P-05
Cyclohexanone oxime Dehydroisomerisation, n-butane 24-0-01
15-O-05 23-0-03 23-P-18 23-P-27 27-P-16 Dehydroxylation, phenol 29-P-08
Cyclohexene aromatisation 02-P-42 Delaminated zeolites 23-P-21
Cyclohexene conversion 24-P-22 De novo simulation 16-P-09
Cyclohexene hydrogenation 26-P- 17 29-P-29 DeNOx catalyst 30-P-29
Cyclohexene oxidation 2 l-P- 13 29-P-30 DeNOx catalyst, aluminophosphate 30-P-31
Cyclohex-2-en- 1-one condensation 23-P-13 DeNOx catalyst, Fe-zeolites 30-P-27
Cyclopentane hydroconversion 26-P-16 DeNOx catalyst, MCM-22 30-P- 13
Cytochrome C, adsorption 23-P-17 DeNOx on Cu-MFI 16-P-20
CZP zincophosphate 29-P-23 DeNOx SCR ' 30-P- 10
DeNOx SCR by NH3 30-P-12 30-P-29
DeNOx SCR by CH4
D 10-O-01 30-P-I 5 30-P-22 30-P-28 30-P-35
DeNOx SCR by hydrocarbons 30-0-03 30-P-25
D-AI-MCM-41 23-P- 15 DeNOx SCR by propene 30-P-14 30-P-30 30-P-34
D-ZSM-5 23-P- 15 Densification, zeolite, thermal 10-P-07
1D confined system 17-P- 17 Design of experiments (DOE) method 03-P- 16
2D correlation IR spectroscopy 12-O-01 Desulfurisation, modelling 15-P-22
2DNMR 13-P-18 13-P-19 13-P-24 Deuterium exchange 23-P- 15
DABCO-based template 02-P-27 Dewaxing 26-P-23
Dachiardite, AI ordering 0 l-P-07 Dewaxing on Pt/AI-MCM-41 26-P-21
DC polarisation 22-0-04 DFT (density functional theory) 15-P-11
DCM resin/AIPO4-5 composites 21-O-04 DFT calculations 15-0-04
Deactivation, alkylation catalyst 24-P-06 15-P-06 15-P-17 15-P-21 15-P-24 15-P-25
Deactivation, reforming catalyst 24-P-23 DFT calculations, alkene epoxidation 15-P- 18
Dealkylation, trimethylbenzene 25-P- 10 DFT cluster calculations
Dealuminated mordenite 29-P-11 15-O-03 15-P-11 15-P-13 15-P-20 15-P-22
Dealuminated zeolite Y, Si/AI ratio 13-P-15 DFT periodic calculations 15-0-03
Dealumination Diagenetic zeolites 0 l-P-06
05-P-14 11-P-25 12-P- 16 13-P-07 24-P-21 Diamond anvil cell 09-P-09
Dealumination, BEA 1 I-P-10 11-P-22 Diaromatics hydrodecyclisation 26-P- 13
Dealumination, EMT 14-P-23 Diatomite, coating by zeolites 21-P-07
Diazine adsorption, FAU 12-0-03
408

Dibenzothiophene adsorption 18-P-11 DRIFTS, in-situ 30-P-27

Dibenzothiophene hydrodesulfurisation 12-P-17 DRIFTS/PY 30-P- 18
Diblock copolymer surfactants 08-P-12 Drinking water, deammoniation 3 l-P-09
Dichloromethane degradation 30-0-05 Drug carriers 32-O-01 32-0-05
Dielectric constant, zeolite films 20-P- 11 Drug carrier clinoptilolite 32-P-08
Dielectric spectroscopy 21-P-14 Drying, effect on ion exchange 1 I-P-20
Diesel pool PL-4 Dual temperature ion exchange I l-P-18
Diesel upgrading 26-P-13 Dubinin-Radushkevich equation 26-P-20
Diethylenetriamine template 02-P-41 Dust, health effect 32-0-02
Diffraction, anomalous 17-P-09 Dye molecules, encapsulation 21-O-02 22-P-06
Diffraction, microcrystal 22-0-01 Dyes in MCM-41 22-P-21
Diffuse reflectance, Ag 01-P-15 Dyes in mesoporous silica 22-P-20
Diffuse reflectance, Cu 1I-P-20 30-P-21 Dyes, photochromic, encapsulated 22-P-07
Diffuse reflectance, in situ 04-P- 11 Dyes in zeolites 22-P- 14
Diffuse reflectance spectroscopy Dynamic pulse method 17-P-08
07-P-14 15-P-11 26-P-14 26-P-22 Dynamical processes, modelling 15-0-02
Diffusion 16-P- 12 20-P-15
Diffusion, acetonitrile 13-P-14
Diffusion, acetylene 19-P-07
Diffusion, aromatics 19-0-02
Diffusion coefficients 19-P-08 20-P-15 E-Caprolactam 23-P-27
Diffusion coefficients, reaction conditions 28-P-16 Edingtonite from fly ash 18-P- 10
Diffusion constraints 28-P-16 Edingtonite, lattice vibrations 16-P- i 9
Diffusion, effect of crystal morphology 19-0-04 EDS 09-P-10
Diffusion, hydrocarbons 19-K-01 Effect of H20 and SO2 on catalytic activity 30-P-22
Diffusion, hydrocarbons, by 129XeNMR 19-P-09 Effluents, nitric oxide industry 30-P-34
Diffusion, MFI 19-P-09 Electric field gradient, FAU 14-P-27
Diffusion, MFI, organics 19-0-03 19-P-10 Electrochemistry 20-P- 14
Diffusion, MOR, n-hexane 19-P-08 Electrode, anatase 22-P- 13
Diffusion, PFG NMR 20-P-15 Electron density, SBA- 15 walls 08-0-03
Diffusion, single file 28-0-01 Electron diffraction, HREM 14-P- 19
Diffusivity, LTA coating 20-P-15 Electron-hole pairs, biphenyl/MFI 14-P- 18
Diffusivity, MFI, organics 19-O-03 Electron microscopy PL-5
2,5-Dihydrofuran adsorption 12-P-08 Electron transfer in zeolite Ru-Y 28-0-03
Dimerisation, olefins 24-P-29 Electron transfer, biphenyl/MFl 14-P- 18
2,2-Dimethylbutane isomerisation 28-0-05 Electronic materials 02-P-25
Dimethyldisulfide HDS 18-P-14 Electronic states 22-P- 17
Diphenylmethane, chlorination 23-P-30 EMT, acidity 13-P-21 14-P-23
2,6-Dimethylnaphthalene 25-0-03 EMT, transalkylation catalyst 25-0-04
Dipole-dipole coupling 14-P-15 EMT-MAZ overgrowth 02-P-06
Disproportionation, aromatics 11-O-02 Enantioselective catalysis 23-P-11
Disproportionation, cresols 28-P-13 Enantioselective hydrogenation 23-P-25
Disproportionation, ethylbenzene 29-P-19 Enantioselective synthesis, terminal epoxides
Disproportionation, toluene 23-P-10
10-P-09 11-P-24 24-P-06 29-P-26 Encapsulation 07-P- 10 2 l-K-01 21 -O-05
Dissolution, MFI 07-P-24 1l-P-30 Encapsulation, AgI/LTA 22-P- 17
DLH (double layered hydroxides), Fe,Co 30-P-26 Encapsulation, AgzS/LTA 14-0-04
n-Dodecane hydroisomerisation 08-P- 13 Encapsulation, anthraquinone/BEA 27-P-14
Dodecyl dimethyl benzylammonium surfactant Encapsulation, Au/FAU 11-O-01
06-P-09 Encapsulation, bipyridine/FAU 24-P-29
Dodecylamine, template 29-P-08 Encapsulation, bipyridine/MFI 14-P-24
Dodecylphosphate surfactant 07-P-08 Encapsulation, CuI/LTA 22-P- 17
DON, see U T D - 1 Encapsulation, dyes 21-0-02
Donor-acceptor interactions 22-P-06 Encapsulation, dyes, MCM-41 22-P-21
Double bond isomerisation 23-P-26 Encapsulation, Fe complexes/FAU 02-P-14
Double-mesopore silica 06-P- 10 Encapsulation, halides 10-O-03
DRIFT spectroscopy 12-O-04 12-P-09
 409

Encapsulation, HPA 23-P-19 Ethylcyanoacetate-benzaldehyde condensation

Encapsulation, metal oxide photocatalysts 30-K-01 23-0-04
Encapsulation, Mn complexes/FAU 21-P-13 Ethylene adsorption 12-P-09
Encapsulation, Mn-bipyridyl/FAU 21-P-11 Ethylene ammoxidation 10-P-08
Encapsulation, PbI2/LTL 22-P- 18 Ethylene conversion 24-P- 10
Encapsulation, photochromic dyes 22-P-07 Ethylene dimerisation 24-P-29
Encapsulation, phthalocyanines 14-P-12 Ethylene glycol in sodalite cage 16-P-17
Encapsulation, pigments 22-P-19 Ethylene polymerisation 24-0-05 24-P-17
Encapsulation, Rb clusters, LTA 2 l-P-18 Ethylenediamine template 05-P-08 09-P-08
Encapsulation, Tb[(CIBOEP)4P](acac)/MCM-41 Ethyleneimine, formation 23-P-08
22-P-09 ETS-4 11-P- 15
ENDOR spectroscopy 14-P-07 ETS-4, morphology 04-P- 16
Environment control 31-P-10 ETS-4, synthesis 04-P- 16
Environmental catalysis 30-P-08 30-P-32 ETS-4, Zr 04-P- 16
Epitaxial overgrowth CAN/SOD 02-P-28 ETS- 10, acid site NMR 13-P-23
Epitaxial overgrowth CHA/SOD 02-P-28 ETS-10, Bronsted acidity 24-P-15
Epitaxial overgrowth MAZ/EMT 02-P-06 ETS-10, Cr 27-P-15
Epoxide, terminal, hydrolysis 23-P-10 ETS-10, Fe 27-P-15
Epoxidation 2 l-P-07 27-P-06 ETS- 10, HRTEM PL-5
Epoxidation, cyclohexene 29-P-30 ETS- 10 modification 11-0-04
Epoxidation, fixed bed 24-P-14 ETS- 10, oligomerisation catalyst 24-P- 15
Epoxidation, olefins 11-P-29 14-P-12 15-P-18 p-Eugenol isomerisation 23-P-26
Epoxidation, alpha-pinene 23-P-14 Europium cerium silicates 05-P- 12
Epoxidation, propylene 24-P-14 27-0-02 EXAFS 01-O-03
Epoxidation, styrene 29-P-08 11-O-05 13-P-32 14-P-39 21-O-03 23-0-05
EPR spectroscopy 04-P- 10 EXAFS/XANES 07-P-13 29-P-25
04-P-I 1 05-P-I 1 13-P-08 13-P-09 14-O-05 Exhaust gas treatment 30-P-10 30-P-32
14-P-12 14-P-20 14-P-37 15-P-11 30-P-26 External sites, probing 13-P-25
EPR, cation impurities 14-P-15 External surface acidity 13-P-09
EPR, nitroxide 14-P-07 32-0-02 External surface properties 16-O-02
EPR, NO 14-P-09 Extraframework AI, modelling 15-P-21
EPR, polyaromatic ionisation 14-P-18 Extra-large pore zeolites PL-3
Erionite, Co 27-P-13
Erionite, Cu 27-P-13
Erionite, Fe 27-P-13
Erionite, health effect 32-0-02
Erionite, Ni 27-P-13 19F NMR 08-0-04 09-0-02 11-O-03 30-P-I 9
Erionite, oxidation catalyst 27-P-13 Factorial design 03-P- 13
Erionite, in zeolitic tuff 01-P-13 FAPO (Fe-AIPO4) 2 l-P-07
ERS- 10 alkylation catalyst 29-0-01 FAPO, deNOx catalysts 30-P-31
ERS- 10, pore structure 29-O-01 FAPO-5 14-P-39
ESR (see EPR) FAPO- 11 14-P-22
Esterification 08-P-10 FAPO-18 14-P-39
Esterification, effect of hydrophobicity 28-P-14 Fatty acids, selective adsorption in MFI 23-P-20
ETBE 28-P-11 Fatty oils, hydrogenation 23-P-20
Ethanol adsorption 18-P-15 FAU, see also LSX, LZ-210, SAPO-37, USY
Ethanol conversion 23-P-09 13-P-21
Ethanol, in H2Oz synthesis 27-P-14 FAU, acid sites 13-P-13
Ethanol, steam reforming 24-P-23 FAU, acid site NMR 13-P-23
Ethanolamine, dehydration 23-P-08 FAU, acidic and basic 23-P-12
Ethyl acetate adsorption 18-P-12 FAU, acidity
Ethyl acetoacetate condensation 23-P-29 13-P-07 13-P-21 14-P-23 15-P-16 23-P-09
Ethylbenzene 29-0-01 FAU, acidity, modelling 15-0-01
Ethylbenzene alkylation 28-P-08 FAU adsorbent 12-O-03
Ethylbenzene dehydrogenation 20-P-06 16-O-03 16-P-14 18-P-07 18-P-11 18-P-15
Ethylbenzene disproportionation 29-P-19 FAU adsorbent, Ar/N2 17-P-15
410

FAU, adsorption 12-P-08 FAU, Ni 24-P-24 27-P- 13

FAU, adsorption models 16-O-03 FAU, Ni oligomerisation catalyst 24-P-17 24-P-24
FAU, Ag 18-0-05 24-0-02 24-P- 19 FAU, Ni,W hydrocracking catalyst 1l-P-08
FAU, A1 site in activated 13-P-18 FAU, NiMo hydrotreatment catalyst 26-P-15
FAU, alkylation catalyst 24-P-09 FAU, nitroxide EPR 14-P-07
25-0-02 25-P-07 25-P-09 25-P-13 28-P-15 FAU oxidation catalyst 27-P-13
FAU, B-treated 11-P-23 FAU, P-treated 11-P-23
FAU, Ba, adsorbent 16-O-03 FAU, Pd/K,Na- 23-P-23
FAU, Cd 09-P-06 FAU, Pd, Heck catalyst 23-0-02
FAU, Co 27-P-13 FAU, photocatalyst 30-P-20
FAU, colloidal 02-0-03 02-P- 14 FAU, phthalocyanine epoxidation catalyst 14-P-12
FAU, Cr exchange 3 l-P- 13 FAU, polymer degradation catalyst 30-P-17
FAU cracking catalyst 11-P-23 FAU, porosity 26-P-20
FAU, crystallisation monitoring 02-P-37 FAU, proton tunnelling 16-0-04
FAU, Cs 29-P-20 FAU, Pt 17-P-08
FAU, Cs, Pt catalyst 23-0-05 FAU, Pt aromatisation catalyst 15-P-09
FAU, Cu 12-P-09 17-P-14 27-P-13 FAU, Pt bifunctional catalyst 30-0-05
FAU, Cu, oxidation catalyst 30-P-23 FAU, Pt-Pd hydrogenation catalysts 27-0-05
FAU, Cu, reforming catalyst 24-P-23 FAU, reagent 02-P-07 03-P-11
FAU, dealumination 1l-P-21 13-P-07 FAU, In-exchanged 09-P-lO
FAU, diffusion 19-P-07 FAU, Ru bipyridyl photocatalyst 28-0-03
FAU, diffusion, CH4-CF4, modelling 16-O-05 FAU, supercritical adsorption 17-P-16
FAU drug carrier 32-0-05 FAU (111) surface simulation 16-0-02
FAU, effect of H20 on xylene adsorption 16-O-03 FAU synthesis 02-0-03
FAU, electric field gradient 14-P-27 FAU synthesis, microwaves 03-P-15
FAU, Fe 27-P-13 30-P-I 1 FAU synthesis, role of K and Na 03-0-05
FAU, Fe, HDS catalyst 12-P- 17 FAU, toluene adsorption NMR 13-P-16
FAU, film synthesis 20-P-16 FAU, transalkylation catalyst 25-0-04
FAU, fluorination 11-P-I 7 FAU, unit cell constant 13-P-15
FAU-Ga 10-P-06 FA U zincophosphate 29-P-23
FAU, H form 12-P-06 25-P-15 FAU, Zn 17-P-14
FAU, host 02-P-14 11-O-01 FCC gasoline quality 26-0-01
14-P-12 14-P-29 14-P-37 21-P-10 21-P-II FCC heavy gasoline, reforming 26-0-05
2 l-P- 13 22-P-07 23-P- 19 24-P-29 30-P-08 Fe-AIPO4, s e e FAPO
FAU, hydration 15-0-04 Fe-BEA
FAU hydration catalyst 23-P- 19 04-P-07 10-O-04 30-P-06 30-P-11 30-P-27
FAU hydrotreatment catalyst 26-P-08 Fe in CIT-5, characterisation 16-P-09
FAU isomerisation catalyst FeCls, CVD 11-O-05
11-P-23 14-P-36 25-P-08 26-O-01 28-P-13 Fe,Co double layered hydroxides 30-P-26
FAU, K, adsorbent 16-O-03 Fe, coordination in FAPO-11 14-P-22
FAU, K-LSX, orthorhombic 09-O-01 Fe distribution in MFI 13-O-02
FAU, La 13-P-13 Fe effect on citotoxicity 32-0-02
FAU, La hydrogenation catalyst 26-0-03 Fe-ERI, oxidation catalyst 27-P- 13
FAU, La, proton sites 09-0-04 Fe-ETS-10 27-P-15
FAU, lattice vibrations 12-P-07 14-P-31 Fe, extra-lattice 30-0-02
FAU, Li,Na, 23Na NMR 13-P-12 Fe-FAU 30-P-11
FAU, Li,Na, pyrrole adsorption 12-P-12 Fe-FAU, HDS catalyst 12-P-17
FAU/LTA mixture, from fly ash 18-P-10 Fe-FAU, oxidation catalyst 27-P- 13
FAU/LTL composites 07-P- 10 Fe-FER 10-O-04
FAU membranes 20-0-02 Fe-FER oxidation catalyst 29-P-25
FAU, mesopore imaging 14-0-01 Fe(III) impurities, zeolite Y 14-P- 15
FAU, mesoporous 1l-P-08 Fe-LTL 07-P- 10 24-P- 11
FAU, Mn 21-P-11 21-P-13 Fe-MCM-22 14-P-21
FAU, modelling 15-P-25 Fe-MCM-41 06-P-28 07-P- 14
FAU, nanocrystals 02-P- 14 Fe-MCM-41 oxidation catalyst 29-P-25
FAU, nanotubes formation on 22-P-08 Fe-MCM-41, redox behaviour 07-0-03
FAU, Na 10-P-05 12-P-08 13-O-03 30-P-07 Fe-MEL oxidation catalyst 29-P-25
 411

Fe-MFI 04-P-07 Fisheries, deammoniation 3 l-P- 12

11-O-05 23-P-24 30-0-02 30-P-11 30-P-27 Flexibility, zeolite lattice 13-P-22
Fe in MFI, characterisation 12-O-02 16-P-09 Flue gas adsorption 18-P- 10
Fe-MFI, deNOx catalyst 12-O-02 30-P-14 Flue gas, screening 18-0-01
Fe-MFI oxidation catalyst 29-P-25 31-O-03 Fuorescence 22-P-06
Fe-MFI, oxihalogenation catalyst 23-P-24 Fluorescence, dyes in mesoporous silica 22-P-20
Fe-MFI, sulfide host 29-P-05 Fluorescence, laser induced 13-P- 13
Fe-MFI synthesis 04-0-03 Fluoride anion effect 06-P-26 06-P-28
Fe-MFI synthesis, fluoride 04-P- 17 Fluoride in CoAPO synthesis 04-P-09 04-P- 17
Fe-MOR 04-P-15 13-P-32 30-P-11 30-P-27 Fluoride in MCM-41 synthesis 06-P-28
Fe-MOR, oxidation catalyst 27-P-13 Fluoride in MFI synthesis 02-P-26
Fe-MTW oxidation catalyst 29-P-25 Fluoride in MOR synthesis 02-P-39
Fe-MTW, synthesis 04-0-03 Fluoride, location in IFR 22-O-01
Fe203 nanoparticles in MCM-41 07-P-13 Fluorination of zeolite Y 1 l-P- 17
Fe, oxidation state in FAPO-11 14-P-22 Fluorogallophosphate 11-O-03 16-P- 15
Fe oxo binuclear species 11-O-05 Fluorogermanates, layered 09-P- 12
Fe-phen complexes, encapsulated 02-P- 14 Fly ash, source of silica 18-P- 10
Fe Raney/MFI composite 30-P-29 Formation fields, M4 ls 06-P-25
Fe-SAPO-34 30-P-27 FOS-5, synthesis and structure 09-0-03
Fe sites, FAPO 14-P-39 Fractal, silica aggregates 14-P-25
Fe-TON 04-0-04 Fragrance synthesis 23-P-22
Fe-TON, synthesis 04-0-03 Framework enumeration, zeolites 16-P- 13
Fenton H202 chemistry 31-O-03 Framework polarity 32-0-05
FER, acidity 13-P- 17 Framework substitution 04-P-07
FER, adsorbent 17-P-06 Framework vibration, TS- 1 14-P-34
FER, Ag 14-0-03 Framework vibrations, zeolites 12-P- 10
FER, AI distribution 13-P- 19 Freezing in confined systems 17-0-01
FER, Co 30-P-35 Frequency response 19-0-02 19-P-07
FER, Cu 14-0-03 Friedel-Crafts alkylation 25-0-02 25-P-12 29-0-03
FER, dealumination 13-P- 17 FSM from saponite 06-P- 15
FER, Fe 10-0-04 FSM- 16 17-P-05 22-0-05
FER, Fe oxidation catalyst 29-P-25 FSM- 16, AI, host 29-P-29
FER, isomerisation catalyst FTIR, BEA dealumination, realumination 11-P-22
24-P-21 26-O-01 26-P-09 FTIR, 2D correlation 12-O-01
FER synthesis 03-P-09 FTIR, HPA 13-P-05
Ferrocene/MCM-41 07-P- 13 FTIR skeletal vibrations 13-P- 15
Ferromagnetic zeolites 22-P- 10 FTIR spectroscopy 09-0-04 1 I-P-21
Fertilizers, zeoponic delivery 31-O-02 12-O-03 12-O-04 12-P-06 12-P-09 12-P-13
Fibers, health effect 32-0-02 12-P-15 12-P-16 13-O-02 13-O-04 13-P-09
Fibers, mesoporous silica PL-1 06-0-02 22-P-20 13-P- 17 13-P-21 13-P-25 14-O-05 14-P-20
Fibers, MFI 2 l-P-06 14-P-23 14-P-30 14-P-34 14-P-40 15-O-05
Fibers, MFI, by bulk-material dissolution 02-P-26 15-P-13 17-P- 11 22-P-21 26-P-22 27-0-05
Film, MFI/ceramic 20-P-09 29-P- 19 29-P-20 30-P-16 30-P-31 32-P-07
Film, FAU 20-P-16 FTIR spectroscopy, in-situ 12-P- 14 23-P-23
Film, LTA 20-P- 10 20-P- 15 20-P- 16 FTIR-UV Vis 14-P- 12
Film, LTA/glass 20-0-01 Fuel cell catalyst 07-P-20
Film, MFI 20-0-04 Fukui functions 15-P-06
Film, MFI on AI 20-P- 17 Fukui function overlap method 15-P- 19
Film, MFI on cordierite 20-P- 13 Fumed silica 02-P-35
Film, MFI on gold 20-P- 14 Function groups 17-P-06
Film, zeolite, all-silica 20-P-11 Functionalized mesoporous silica 07-0-02
Film, zeolite, anti-corrosion 22-0-04 Furan adsorption 12-P-08
Filtration media 21 -P-07 Furfuryl alcohol, hydroxyethylation 23-P-06
Filtration, MSU-X application 08-O-01
Fine chemicals
23-K-01 23-P-21 23-P-22 23-P-29 24-0-04
Fischer-Tropsch synthesis 24-P- 11
412

G H

Ga-BEA 03-P-10 IH 2D NMR 13-P-19

Ga-CON 1 l-P- 16 ~H-MAS NMR, acid sites 1 l-P-07
Ga-DON 1 l-P- 16 ~H MAS spin echo NMR 14-P- 10
Ga-FAU 10-P-06 IH-NMR 08-0-04 09-P-I 1 11-P-28 13-P-14
Ga-MCM-22, activation 11-P-27 IH-NMR imaging 19-K-01
Ga-MCM-41 07-P- 14 tH NMR, MFI synthesis 02-P-40
Ga-MCM-58 29-P-19 lH-27AIdipolar coupling NMR 13-P-23
Ga-MFI 03-P-10 IH(E7AI) TRAPDOR NMR 08-0-04
Ga-MFI, activation 11-P-27 IH-29Si dipolar coupling NMR 13-P-23
Ga-MTW 03-P-10 2H-NMR 13-P-14
Gallophosphates 1 l-P- 12 H2 adsorption, LSX 12-0-04
Gallophosphates, activation 16-P- 15 H-, Ce-, Fe-, Mo-, Cr-ZSM-5 23-P-24
Gallophosphates, phase change 11-O-03 H202 20-P-14 21-P-07
Gallosilicate 05-P-07 Hz02 conversion 27-P-11
GaPO-42 (LTA), stability 1l-P-12 H202, Fenton chemistry 31-O-03
Gas purification 18-P- 10 H202, oxidation agent
Gas sensors 2 l-P- 10 22-P- 11 27-0-01 27-P-09 27-P- 15 29-P-18
Gas separation, CO2/C2 18-0-03 H~O2, in oxihalogenation 23-P-24
Gas separation, kinetic 18-0-03 H202, photocatalytic synthesis 27-P-14
Gases, structured 10-0-03 H3PO3 reactions 05-P-15
Gasoline pool PL-4 H2S effect 26-P-07
Gasoline quality, FCC 26-O-01 HAFS analysis 30-P-24
Gel composition 02-P-20 Haloaromatics olefination 23-0-02
Gel composition, effect on synthesis 02-P-21 Halogenide, K, in oxihalogenation 23-P-24
GeO2, FOS-5 structure 09-0-03 Hartree-Fock method 15-P-08 15-P-09
Germanates, fluoro, layered 09-P- 12 HDN (hydrodenitrogenation) 26-P-14
GIS beryllophosphate 05-P-06 HDS catalysts 26-P-08 26-P-12
GIS from fly ash 18-P-10 HDS, benzothiophene 26-P-07
GIS manganese phosphate 05-P-11 HDS, dibenzothiophene 12-P-17
Glass, controlled porosity 17-P- 12 HDS, dimethyldisulfide 18-P-14
Glass, porous, Beckmann catalyst 27-P-16 HDS, thiophene 26-P- 17 26-P-22
Glass support for LTA layer 20-0-01 Health, animals 32-P-06 32-P-I0 32-P- 11
Glass, volcanic, zeolitisation 0 I-P- 13 Health, human 32-O-01 32-0-02 32-P-09 32-P-12
Glycerol carbonate 23-P-32 Heat storage 2 I-P-09 31-O-04
Glycidol synthesis 23-P-32 Heating rate 02-P-08
Glycol solvent 05-P-11 Heavy metals 3 l-P-05
GME beryllophosphate 05-P-06 Heavy metal-exchanged zeolites 10-P-07
Gold 11-O-01 Heck olefination on Pd-zeolites 23-0-02
Gold support 20-P- 14 Heptane 13-0-02
GON (see GUS-I) n-Heptane 26-P-18
Grafted MCM-41 29-P-28 n-Heptane cracking 24-P-06
grafting 21-O-02 n-Heptane hydroconversion 26-P-11
Grafting, aluminium 29-0-04 Herschelite (CHA) from fly ash 18-P-10
Grafting, mesoporous silicas 18-P-06 29-P-09 Heteroatom distribution 13 -O-02
Grafting, one-step or two-step 29-P-31 Heteropoly acid, alkylation catalyst 25-P-16
Grains, porous catalysts 28-P- 12 Heteropoly acids, encapsulated 23-P-19
Gravimetry, Ar/N2 adsorption 17-P- 15 Heteropoly acid microporous salts 13-P-05
Grazing incidence X-ray diffraction 20-0-04 HEU (see clinoptilolite) 09-P-09
Green chemistry 16-P-09 Heulandite-type zeolites, Bulgaria 01-P-10
Grignard reagents 29-P-09 n-Hexadecane cracking 08-P-13
Growth surface, SSZ-24, AFM 02-0-05 n-Hexadecane hydroconversion 24-0-03
Guanidine, supported catalysts 29-P- 10 n-Hexadecane hydroisomerisation 26-P-21
GUS- 1 (GON) 02-P-27 n-Hexadecane isomerisation 26-P-21
Hexafluoroethane reagent 1 l-P-17
 413

Hexamethylbenzene, guest 14-P-29 Hydrocarbon pool, MTO 24-P-18

1,6-Hexamethylenediamine, template Hydrocarbon removal 3 l-P-07
02-P-22 02-P-42 Hydrocarbon removal, exhaust gases 30-P-32
Hexamethyldisiloxane in pore modification 1l-P-09 Hydroconversion, alkanes 16-0-01
n-Hexane aromatisation 15-P-09 28-0-02 Hydroconversion, benzene 26-P-15
n-Hexane conversion, silylated MFI 11-O-02 Hydroconversion, cyclopentane 26-P-16
n-Hexane cracking 26-0-01 29-P-26 Hydroconversion, n-decane 29-P-19
Hexane diamine template 16-P-16 Hydroconversion, n-heptane 26-P-11
n-Hexane diffusion, NMR imaging 19-K-01 Hydroconversion methylcyclopentane 11-O-01
n-Hexane diffusivity, MOR 19-P-08 Hydrocracking 1I-P-08 13-O-02 26-P-15 26-P-18
n-Hexane isomerisation 19-P-08 14-P-36 26-P-19 Hydrocracking, n-hexadecane 24-0-03
n-Hexane hydroisomerisation 06-P-23 Hydrodechlorination 23-P-16
Hexene formation 24-P-24 Hydrodecyclisation, aromatics 26-P-13
1-Hexene isomerisation 29-P-24 Hydrodesulfurisation 18-P-14
HgX2 encapsulated 10-O-03 Hydrogel milling 02-P-09
4-Hydroxybutan-2-one reagent 25-0-02 Hydrogen acceptor 25-0-05
High-silica zeolites 17-P-07 Hydrogen adsorption 17-P-10
High-silica zeolite adsorbent 18-P-15 Hydrogen in refining PL-4
High temperature treatment 10-P-07 Hydrogen transfer in ketone reduction 23-P-33
High-throughput strategies 03-P-I2 Hydrogenation 26-P-08 26-P-13 29-P-15
Histidine complexes, immobilized 27-P-10 Hydrogenation, acetonitrile 23-P-28
HLS silica 02-P-25 Hydrogenation, asymmetric 23-P-25
HMS alkylation catalysts 25-P-11 Hydrogenation, benzene 27-0-04
HMS, amine extraction 06-P- 11 Hydrogenation, CO 24-P-11
HMS catalysts 29-P-08 Hydrogenation, CO2 24-P-26
HMS, Co 29-P-08 Hydrogenation, crotonaldehyde 29-P-15
HMS, Cr photocatalysts 28-P-07 Hydrogenation, cyclohexene 26-P-17
HMS, Cu 29-P-08 Hydrogenation, cynnamaidehyde 07-P-16
HMS grafting 29-P-31 Hydrogenation, fatty oils 23-P-20
HMS, Ti 23-P- 14 29-P-08 Hydrogenation, liquid phase 29-P-13
HMS, V 14-P-20 Hydrogenation, olefins 29-P-22
HMS, Zr, support 26-P-22 Hydrogenation, rings 26-P-10
Hollow zeolite spheres 21-P-12 Hydrogenation, toluene 27-0-05
Honeycomb, cordierite 20-P-13 Hydrogenolysis, cyclohexene 29-P-29
Honeycomb, MCM-41 21 -O-03 Hydroisomerisation, C5/C6 20-P- 18
Honeycomb, MCM-48 29-P-27 Hydroisomerisation, n-decane 26-P-06
Host-guest interaction 14-P-16 Hydroisomerisation, n-dodecane 08-P-13
HPA, s e e heteropoly acids Hydroisomerisation, hexadecane 24-0-03 26-P-21
HPLC, mesoporous silicas for 18-P-06 Hydroisomerisation, long-chain n-alkanes 26-P-23
HRSEM 14-P-19 Hydrolysis, terminal epoxide 23-P-10
HRTEM PL-5 14-P-19 Hydrophobic MCM-41 17-P-13
HRTEM, Ag-clinoptilolite 01-P-15 Hydrophobic zeolites 19-P-06
Human byle 32-0-03 Hydrophobic zeolite in epoxidation 11-P-29
Hybrid acid catalyst 29-P-28 Hydrophobicity, BEA 28-P-14
Hybrid MCM-41 29-0-02 Hydrophobicity, MCM-41 29-0-02
Hybrid mesoporous acids 08-P-10 Hydrophobicity, MCM-48 06-P-06
Hybrid organic-inorganic materials 29-P-31 Hydrophobicity, mesoporous silica 06-P-27
Hybrid solids 22-0-02 Hydrophobisation, clinoptilolite 32-0-04
Hydration, AIPO4 13-P-20 15-P-17 Hydrophobisation, mesoporous silica 29-P-09
Hydration, FAU 15-0-04 Hydroquinone 27-P-17
Hydration, alpha-pinene 23-P-19 Hydrotalcite, basic catalyst 23-0-05
Hydrazine 20-P-14 Hydrothermal natural zeolites 0 l-P-06
Hydrocarbon adsorption 17-P-07 19-0-02 Hydrothermal stability, MTS 06-P-07
Hydrocarbons, C4, aromatisation 24-P-31 Hydrothermal transformation 02-P-36
Hydrocarbons, chloro-, in SCR-NOx 30-0-03 Hydrothermal transformation, clinoptilolite 32-P-07
Hydrocarbon conversion, silylated MFI 11-O-02 Hydrothermal treatment 11-P-25
Hydrocarbon diffusion, by 129XeNMR 19-P-09 Hydrotreatment 26-P-08 26-P-12 26-P- 17
414

Hydrotreatment, mesoporous catalyst Isobutene synthesis 24-0-01

26-P-14 26-P-22 Isobutyric aldehyde, formation 27-P- 13
Hydroxyalkylation of aromatics 23-P-21 Isodewaxing 26-P-23
Hydroxyalkylation of furfuryl alcohol 23-P-06 Isodimorphism of templates 0 I-P- 11
Hydroxyethylation with H-zeolites 23-P-06 Iso-eugenol 23-P-26
Hydroxyl groups, BEA 28-P- 11 Isomerisation 13-0-02 26-P- 18
Hydroxyl groups, silicalite 15-O-05 Isomerisation, 1-acetyl-2-metoxynaphthalene
Hydroxylation, aromatics 21 -P-07 25-P-08
Hydroxylation, phenol 07-P-07 27-P-17 Isomerisation, alkanes 26-0-02
Hydroxyls, bridging, NMR 14-P-10 Isomerisation, n-butane 24-P- 16 29-P- 17
Hydroxysilane 29-P-08 Isomerisation, butenes 24-P-21
Hypothetical framework 07-P-21 16-P-13 Isomerisation, n-butene, skeletal 14-P-22
Hypothetical framework, MCR- 16 16-P-07 Isomerisation, C6 hydrocarbons 26-P- 19
Isomerisation catalyst, treated USY 11-P-23
lsomerisation, cresols 28-P- 13
lsomerisation, cyclohexene 24-P-22
Isomerisation, 2,2-dimethylbutane 28-0-05
IFR 22-0-01 Isomerisation, p-eugenol 23-P-26
IFR, synthesis 03-0-04 Isomerisation, n-hexane 14-P-36 19-P-08 26-O-01
Imaging, ~H-NMR 19-K-01 Isomerisation, 1-hexene 29-P-24
Immobilisation in FAU 24-P-29 Isomerisation, light paraffins 06-P-23
Immobilized base 23-0-04 Isomerisation, long-chain n-alkanes 26-P-23
Immobilized enantioselective catalyst 23-P-11 Isomerisation, olefins 26-P-09
Immobilized Salen Co complexes 23-P-10 Isomerisation, toluene, modelling 15-P-20
Impact craters 0 l-P-06 lsomerisation, xylenes 12-P- 14 28-P-06
Impregnation 03-P-11 10-P-05 Isomerisation, xylenes, modelling 15-P-20
In exchange 09-P- 10 Isomerisation, xylene, NMR 12-0-01
In-MFI 30-P- 15 lsomorphous substitution, B 11 -P- 16 13-P- 11
ln-X 09-P-10 Isomorphous substitution, A! 1 I-P-16
ln-zeolites, deNOx catalysts 10-O-01 lsomorphous substitution, AIPO4 30-P-31
Indium silicates, microporous 05-P- 16 lsomorphous substitution, AIPO4-31 14-P- 13
Insertion compounds in porosil 10-O-03 lsomorphous substitution, Co
In-situ diffuse reflectance 04-P-11 04-P-II 04-P-13 04-P-18
In-situ DRIFTS 30-P-27 Isomorphous substitution, Cr 04-P-08
ln-situ IR spectroscopy 12-O-01 23-P-23 lsomorphous substitution, Fe
In-situ LTA synthesis 18-P-09 04-0-03 04-0-04 04-P-17
ln-situ NMR 02-P- 18 Isomorphous substitution, Fe/MCM-41 07-0-03
In-situ ultrasound monitoring 02-P-37 Isomorphous substitution, Ga 1 I-P-16 11-P-27
Interatomic potential technique 16-O-02 Isomorphous substitution, MCM-41 29-P- 18
Intercalation compounds 22-P- 16 Isomorphous substitution, MFI 13-O-02
Intercalation, MOR/magadiite 02-P-36 Isomorphous substitution, Nb 0 l-P- 14
Interfacial resistance, membrane 19-O-05 Isomorphous substitution, Ta 01 -P- 14
Interference microscopy 19-0-04 Isomorphous substitution, V 14-P-33 24-P-07
Internal reflection 21-O-04 Isomorphous substitution, Zn 04-P- 14
Iodide removal 18-0-05 Isomorphous substitution, Zr 04-P- 16
Ion dynamics 14-P-06 Isopropanol adsorption 18-P- 15
Ionic conduction, lithium silicate 09-0-05 Isopropanol dehydration 29-P-06
Ionisation, polyaromatics 14-P- 18 Isopropylation 25-P-09 25-P-16
IR spectroscopy, s e e FTIR Isopropylation, biphenyl 16-P-08 29-P-11
Iran, natrolite 0 l-P-08 Isopropylation, naphthalene 25-P-06
Iran, natural zeolites 3 l-P-06 lsopropylnaphthalene 25-P- 16
Iridium zeolites, hydrogenation catalyst 26-0-04 Isosteric heats of adsorption 17-P- 14
Isobutane alkylation 24-P-20 Isotherm of adsorption 17-P- 15
Isobutane diffusion 19-0-04 Isotopic labelling, MTO 24-P- 18
Isobutane in silicalite 16-P- 12 Isotopic traces technique 23-P- 15
lsobutanol oxidation 27-P- 13 IST- 1 02-P-33
IST-2 02-P-33
 415

ISV (see ITQ-7) Laser ablation 14-P-29

ITQ-2 acidity 13-0-04 Laser dyes, mesoporous silica 22-P-20
ITQ-2, fine chemistry catalyst 23-P-21 Laser-induced fluorescence 13-P-13
ITQ-4 (IFR) 22-0-01 Lattice dynamical calculations 16-P-19
ITQ-6, fine chemistry catalyst 23-P-21 Lattice energy calculation 07-P-21
ITQ-7, alkylation catalyst 24-P-20 Lattice model, adsorption 16-P-10
Lattice vibrations 12-P-07 14-P-31 16-P-18
Lattice vibrations, natrolite 16-P-19
Laumontite, cation exchange 31-P-12
Layer-by-layer shaping method 2 l-P-06
Jet-loop reactor 28-P- 16 Layered compounds 02-P- 11
Jordanian CHA-PHI tuff 31-O-01 Layered Cu molybdate 09-P-07
Layered double hydroxide, Fe,Co 30-P-26
Layered germanates 09-P-12
K Layered silicate 02-P-25 02-P-36
Layered zeolite menbranes 20-0-02
39KNMR 09-0-01 LCO, reforming 26-0-05
K exchange 1l-P- 18 Leaching, MFI 07-P-24
K cation in synthesis 03-0-05 Lead removal 3 I-P-06
K-FAU 09-0-01 Lewis acid 14-P-21 29-0-03
K-FAU, adsorbent 16-0-03 Lewis acid sites 13-P-08 13-P-17
K+ location, LSX 09-0-01 Lewis acidity 13-P-19
K-LTL, catalyst 23-P-30 Lewis basic sites 15-P-22
7Li'MAS NMR 09-0-05
K-M (see MER)
K, Sr-KFI, synthesis 02-P-21 7Li NMR, FAU adsorbent 12-P-12
Kanemite-derived mesoporous silica PL-1 Li exchange 01-0-04
Li,Na-FAU, 23Na NMR 13-P-12
Ketones, unsatutated 23-P-33
Keywords PL- 1 Li,Na-FAU, pyrrole adsorption 12-P-12
Kinetic modelling, NO-N20 interaction 16-P-20 Li-LSX 12-O-04
KIT-I 25-P-16 Li-LTA, H2 adsorbent 17-P-10
Knight shift 14-P-37 Li-Phillipsite 01-O-04
Knoevenagel condensation Li silicate RUB-29 09-0-05
04-0-02 23-0-04 23-P-29 29-P-23 Linde F (see EDI)
Kr adsorption, AEL 17-O-03 Linkers, covalent, LTA/glass 20-O-01
KSW-2, HRTEM PL- 1 Liquid crystals, confined 21-P-14
KZ-2 (TON), synthesis 04-0-04 Liquid phase sulfoxidation 27-P-09
Low silica zeolites, synthesis 05-P-07
LSX (low-silica X, FAU), JTo NMR 14-0-02
LSX, alkali-exchanged 14-0-02
LSX, K 09-0-01
LSX, La 09-0-04
La exchange 1 l-P-19
LSX, Li 12-0-04
La in AIPO4, deNOx catalyst 30-P-31 LSX, Na 12-0-04
La-FAU 09-0-04 13-P-13 LTA adsorbent 18-O-03 18-P-07
La-FAU ring opening catalyst 26-0-03 LTA adsorbent, Ar/N2 17-P-15
La-MCM-4 l, stability 06-P-19 LTA, adsorption, supercritical 17-P-16
La promoters, deNOx 30-P-25 LTA, Ag 14-0-04
Lactame 23-P-21 LTA, capillary column 18-P-09
Lake fresh water zeolitization 01-P-10 LTA, catalyst 23-P-32
Lamellar aluminophosphate 02-P- 11 LTA, cation relaxation 14-P-06
Large crystals activation 14-P-38 LTA, crystallisation monitoring 02-P-37
Large crystals, MFI 02-P-15 LTA, diffusion 19-P-07
Large pore Ni(II) phosphate VSB-1 22-0-03 LTA, encapsulation modelling 15-P-08
Large pore vanadosilicates 04-0-05 LTA/FAU mixture, from fly ash 18-P-10
Large pore zeolites PL-3 17-P-07 24-P-06 LTA, film, glass supported 20-0-01
Large pore zeolite catalysts LTA, film 20-P-10 20-P-16
25-P-06 25-P-10 26-P-15 26-P-16 28-P-13 LTA, GaPO 1 l-P-12
416

LTA, Hz adsorbent 17-P- 10 MAS-5 06-P-07

LTA host 14-0-04 2 l-P- 18 22-P- 17 MAS NMR (see individual nuclei)
LTA, host, sulfides 22-P- 19 MAS NMR, high temperature 14-P- 17
LTA, Li 17-P- 10 Mass spectrometry 14-P-29
LTA, membranes 20-0-02 MAZ-EMT overgrowth 02-P-06
LTA, Na 10-P-05 30-P-07 MBIK (methyl isobutyl ketone) synthesis 23-0-05
LTA, nanotubes formation on 22-P-08 MCM-22, see MWW
LTA reagent 03-P-11 MCM-36, basicity 10-0-02
LTA, synthesis 02-P-18 02-P-29 02-P-32 MCM-41
LTA, synthesis, in-situ 18-P-09 06-P-07 08-P-06 17-P-17 25-P-13 27-P-09
LTA, synthesis, role of K and Na 03-0-05 MCM-41, adsorbent 17-0-01
LTA, ~70 NMR 14-0-02 MCM-41 adsorbent, VOC removal 18-P- 12
LTA, P occlusion 18-P- 13 MCM-41, adsorption 17-P- 12
LTA, polystyrene beads 2 I-P- 12 MCM-41, fine chemistry catalyst 23-P-21
LTA, reagent 02-P-07 MCM-41, ZTAI-NMR 06-P- 17
LTL host, Pbl2 clusters 22-P-18 MCM-41 alumination 23-P-33 25-P-12
LTL synthesis 02-P- 19 MCM-41, aluminosilicate 06-P-08
LTL synthesis, alkaline earth effect 02-P-17 MCM-41 Beckmann catalyst 23-0-03
LTL, acid site NMR 13-P-23 MCM-41 bifunctional catalyst 26-P- 18
LTL/FAU composites 07-P- 10 MCM-41 catalysts 28-0-04
LTL, Fe 07-P-10 24-P-11 MCM-41, Ce 07-P-23
LTL, formation of nanotubes on 22-P-08 MCM-41, Cu 07-0-04
LTL, K, catalyst 23-P-30 MCM-41, deuterated 23-P- 15
LTL, lattice vibrations 12-P-07 MCM-41, Fe 06-P-28 07-0-03 07-P- 13 07-P-14
LTL, morphology 02-P- 17 MCM-41, Fe oxidation catalyst 29-P-25
LTL, Pd, Heck catalyst 23-0-02 MCM-41, functionalized, synthesis 07-0-02
LTL, Pt aromatisation catalyst 15-P-09 MCM-41, Ga 07-P- 14
LTL, Pt/K catalyst 1 l-P-07 MCM-41, grafting 17-P- 13 29-P-28 29-P-31
Luminescence spectroscopy 22-P-09 27-P-11 MCM-41, honeycomb 21-O-03
Luminescence, Ag-LTA 14-0-04 MCM-41, host 07-P- 19
Luminescence, PbljLTL 22-P- 18 21-O-05 21-P-14 22-P-09 22-P-21 22-P-08
LZ-210 (FAU) 18-O-05 MCM-41 hydrogenation catalyst 23-P-28
MCM-41 hydrophobisation 29-0-02 29-P-09
MCM-41 hydrotreatment catalyst 26-P-14 26-P-17
M MCM-41 in HPLC 18-P-06
MCM-41 isomerisation catalyst 24-P-22
M41 s synthesis 07-P-24 MCM-41, Mn, DeNOx catalyst 30-P- 12
M41 s, XRD 06-P-05 MCM-41, Nb 07-0-04 24-P-12
Macrocycles, aza- 05-0-03 MCM-41, Ni, hydrodechlorination catalyst 23-P-16
Macrocycle synthesis 28-0-04 MCM-41, Ni,Zr 23-P-28
Macroporosity, BEA 2 l-P- 15 MCM-41, noble metals 29-P-22
Magadiite-intercalated MCM-22 05-P- 14 MCM-41, porosity by positron annihilation 12-P-I 1
Magadiite in MOR synthesis 02-P-36 MCM-41, Pt chiral hydrogenation catalyst 23-P-25
Magadiite, pillared 23-P- 18 MCM-41, Pt hydroisomerisation catalyst 26-P-21
Magnetic properties 2 l-P- 18 22-P- 10 MCM-41, reagent 07-P- 10
Magnetic semiconductors, diluted 21-O-03 MCM-41 silylation 29-0-02
Magnetic susceptibility 11-O-05 MCM-41, size control 06-P-09
Magnetism, Rb clusters in LTA 21-P-I 8 MCM-41, spheres 06-P- 13
Magnetite, guest 22-P- 10 MCM-41, stability, effect of AI 06-P- 19
Manganese complexes in FAU 2 l-P-13 MCM-41, stability, effect of Ce 06-P- 19
Manganese phosphate, Al-substituted 05-P-11 MCM-41, stability, effect of La 06-P-19
Manometry, high-resolution 17-P- 15 MCM-41 support
MAPSO-31, Pt catalyst 26-P-06 24-0-05 26-P-07 26-P-12 27-P-10 29-P-22
MAPSO-56 (Co,Mn,Zr) 05-P- 18 MCM-41 support, chiral catalyst 23-P-10 23-P-11
Market, gasoline PL-4 MCM-41, synthesis
Market, zeolite PL-4 06-O-01 06-P-14 06-P-26 07-P-24
MCM-41, synthesis, aging effect 06-P-21
 417

MCM-41, synthesis, microwave 03-P- 15 Mesoporous aluminosilicate

MCM-41, synthesis, secondary 06-P- 10 06-P-07 06-P-08 06-P-22
MCM-41, Ti 07-P- 14 22-P-06 24-P- 12 29-P-30 Mesoporous anatase 22-P- 13
MCM-41, Ti, oxidation catalyst 29-P-18 Mesoporous basic catalysts 29-P- 10
MCM-41, transition metals 29-P-21 Mesoporous carbon
MCM-41, V, oxidation catalyst 29-P-18 PL- 1 07-0-01 07-P-22 29-P- 13
MCM-41, wall properties 08-P-14 Mesoporous-microporous mixed structures 06-0-03
MCM-41, washing effect 06-P-28 Mesoporous molecular sieve, keywords PL-1
MCM-41, XRD 06-P-05 Mesoporous molecular sieves
MCM-41, Zr, isomerisation catalyst 29-P-24 17-O-01 17-P-05 29-P-30
MCM-41, Zr, oxidation catalyst 29-P-18 Mesoporous silica (see also specific names, e.g.
MCM-48, adsorption 17-P-12 FSM-16, HMS, KIT-l, KSW-2, LMV-1, M41s,
MCM-48, alumination 29-0-04 MAS-5, MCM-41, MCM-48, MSU-X, MTS,
MCM-48, Beckmann catalyst 23-0-03 SBA-n) PL-1
MCM-48, Cr 06-P-12 06-P-07 06-P-20 07-P-24 08-P-05 08-P-06
MCM-48, honeycombs 29-P-27 08-P-07 17-P-17 25-P-13 27-P-09 29-P-30
MCM-48, HRTEM PL-5 Mesoporous silica, acidity 29-0-03
MCM-48, hydrophobicity 06-P-06 Mesoporous silica, activation 29-P- 16
MCM-48, morphology 29-P-27 Mesoporous silica, 27AI_NMR 06-P- 17
MCM-48, stability 06-P-06 Mesoporous silica adsorbent 17-0-01
MCM-48, swelling 06-0-04 06-P-06 17-P-05 17-P-12 18-P-12 23-P-17 28-P-10
MCM-48, synthesis 06-O-01 06-P-24 07-P-06 Mesoporous silica adsorbent, VOC removal 18-P-12
MCM-48, Ti 29-P-30 Mesoporous silicas, adsorption 17-P- 12
MCM-48, V 06-P-06 07-P-06 Mesoporous silica alumination
MCM-48, ~29XeNMR 06-P- 16 23-P-33 25-P-12 29-0-04
MCM-58 29-P-19 Mesoporous silica alkylation catalyst 25-P-11
MCR- 16, hypothetical structure 16-P-07 Mesoporous silica, Beckmann catalyst 23-0-03
MEL, Fe oxidation catalyst 29-P-25 Mesoporous silica, bifunctional catalyst 26-P-18
MEL, Mo 14-P-08 Mesoporous silica, Ce 07-P-23
MEL, V 14-P-20 Mesoporous silica, Co 08-0-02 29-P-08
Melting in confined systems 17-0-01 Mesoporous silica, Cr 06-P- 12
Membrane, asymmetric separation 23-P-10 Mesoporous silica, Cr photocatalysts 28-P-07
Membrane, BEA/alumina 20-P- 18 Mesoporous silica, cracking catalyst 08-P- 13
Membrane, BEA/ceramic 20-P-12 Mesoporous silica, Cu 07-0-04 29-P-08
Membrane, catalytic reactor 20-P-18 Mesoporous silica, Fe
Membrane, FAU 28-0-03 06-P-28 07-0-03 07-P-13 07-P-14 29-P-25
Membrane, MFI 03-P- 17 20-P-06 20-P- 17 Mesoporous silica, Fe oxidation catalyst 29-P-25
Membrane, MFI/alumina 20-O-05 Mesoporous silica fibers 06-0-02 22-P-20
Membrane, MFI/ceramic 20-P- 12 Mesoporous silica, fine chemistry catalyst 23-P-21
Membrane, MOR 20-0-03 Mesoporous silica, functionalized
Membrane, MOR/alumina 20-P- 18 07-0-02 07-P-17 08-P-08 08-P-I 0 29-P-16
Membrane, VOC removal 20-P-12 Mesoporous silica, Ga 07-P- 14
Membrane, zeolites 20-0-02 20-P-07 Mesoporous silica, grafting
Membrane, zeolite, modelling 16-O-05 17-P-I 3 29-P-28 29-P-31
Membrane, zeolite/polymer 19-0-05 Mesoporous silica, honeycomb 21-O-03 29-P-27
Membrane, zeolitic, supported 20-0-03 Mesoporous silica, host
Memory effect PL-2 07-P- 19 21-O-05 21 -P- 14 22-P-09
Menthene condensation 23-P-29 22-P-21 22-P-08 29-P-17 22-P-20 29-P-29
MER from fly ash 18-P-10 Mesoporous silica, HPA support 25-P-16
Mercapto functionalisation 07-P- 17 Mesoporous silica in HPLC 08-O-01 18-P-06
Mesophases 08-P-12 Mesoporous silica, HRTEM PL-1 PL-5
Mesopores, FAU 1 l-P-08 14-0-01 Mesoporous silica, hybrid acids 08-P-10
Mesopores, MFI 03-0-02 1l-P-30 26-0-02 Mesoporous silica, hydrodechlorination catalyst
Mesoporosity SBA-15 08-0-03 08-0-04 23-P-16
Mesoporous alumina 07-P-08 07-P- 18 Mesoporous silica hydrogenation catalyst 23-P-28
Mesoporous alumina, Cu, Zn 07-P- 16 Mesoporous silica, hydrogenation catalyst, chiral
23-P-25
418

Mesoporous silica, hydroisomerisation catalyst Mesoporous silica, wall properties 08-P- 14

08-P- 13 26-P-21 Mesoporous silica, washing effect 06-P-28
Mesoporous silica, hydrophobicity 06-P-06 Mesoporous silica, 129XeNMR 06-P- 16
Mesoporous silica hydrophobisation Mesoporous silica, Zr 26-P-22 29-P-18 29-P-24
29-0-02 29-P-09 Mesoporous single crystals 07-P-15
Mesoporous silica, hydrotreatment catalyst Mesoporous sulfides 1 I-P-11
26-P-14 26-P-22 Mesoporous titania 07-0-05 07-P-12
Mesoporous silica, isomerisation catalyst Mesoporous zirconia 07-P- 11
24-P-22 29-P-24 Mesoporous zirconia fuel cell catalyst 07-P-20
Mesoporous silica from kanemite PL-1 Mesostructural transformation 06-P-26
Mesoporous silica, Ni 08-0-02 Metal aluminophosphates 04-P-11 05-0-03
Mesoporous silica, Mn, DeNOx catalyst 30-P-12 Metal cations 32-P-07
Mesoporous silica, Mo 14-P-26 Metal cation reduction 04-0-01
Mesoporous silica, morphology 29-P-27 Metal cations in MeAPO synthesis 05-0-03
Mesoporous silica, Nb 07-0-04 24-P-12 Metal corrosion prevention 22-0-04
Mesoporous silica, Ni 23-P- 16 Metallocene, supported catalyst 24-0-05 24-P-08
Mesoporous silica, Ni,Zr 23-P-28 Metallosilicates, microporous 27-P-06
Mesoporous silica, noble metals 29-P-22 Methanol adsorption 29-P-20
Mesoporous silica, oxidation catalyst 29-P- 18 Methanol amination 11-P-25
Mesoporous silica, photocatalyst 24-P-07 24-P-12 Methanol conversion 07-P- 19 29-P-20
Mesoporous silica, polymer degradation catalyst Methanol dehydrogenation 10-P-05
24-P- 13 24-P-25 Methanol formation 24-P- 12 24-P-26
Mesoporous silica, porosity 08-0-03 Methanol in alkylation 15-0-03 25-0-03 25-P- 13
Mesoporous silica, redox catalyst 23-P- 14 Methanol to hydrocarbons 24-P-18
Mesoporous silica from saponite 06-P-15 Methanol, reagent 25-0-01
Mesoporous silica spheres 06-0-02 06-P-13 Methanol, steam reforming 24-P-23
Mesoporous silica spheres, SBA- 15 08-P-07 Methylamine in MFI synthesis 04-O-01
Mesoporous silicas, stability 06-O-01 N-Methylation, aniline 25-P-11
Mesoporous silica silylation 29-0-02 Methylation, 4-methylbiphenyl 25-0-01
Mesoporous silica, size control 06-P-09 Methylation, toluene, model 15-0-03
Mesoporous silica, spheres 06-P-13 4-methylbiphenyl, methylation 25-0-01
Mesoporous silica, stability Methylcyclohexane cracking 26-P-11
06-P-06 06-P- 19 08-P- 13 Methylcyclopentane hydroconversion 1 I-O-01
Mesoporous silica support Methylene silanes 2 I-P- 16
24-0-05 26-P-07 26-P-12 27-P-10 29-P-22 N-Methyl hexahydrojulodinium template 02-P-30
Mesoporous silica support, chiral catalyst Methylnaphtalene alkylation 25-P- 13
23-P- 10 23-P- 11 Methyloxirane ring opening 23-P- 15
Mesoporous silica, swelling 06-0-04 06-P-06 Methylpropyl ether 27-0-02
Mesoporous silica, synthesis MFI 02-P-31
06-0-01 06-P-14 06-P- 18 06-P-21 06-P-22 12-P-13 14-O-03 16-P-06 23-P-06 30-P-18
06-P-24 06-P-25 06-P-26 06-P-28 07-P-06 MFI, acid site NMR 13-P-23
07-P-24 08-0-02 08-P-09 08-P-11 08-P-12 MFI, acidity 13-P-08 13-P-25
Mesoporous silica, synthesis, acidic pH MFI, acidity, modelling 15-0-01
06-P-28 29-P-16 MFI adsorbent
Mesoporous silica, synthesis, aging effect 06-P-21 17-O-02 18-P-07 18-P-08 18-P-15 19-O-02
Mesoporous silica, synthesis, microwave 03-P-15 MFI, adsorption, biphenyl 14-P- 18
Mesoporous silica synthesis, pH effect 06-P-20 MFI, adsorption, bipyridine 14-P-24
Mesoporous silica, synthesis, secondary 06-P-10 MFI, adsorption, chloroalkenes 17-P- 11
Mesoporous silica, template extraction 06-P-11 MFI, adsorption modelling 16-P- 10 16-P- 12
Mesoporous silica, texture 08-P- 14 MFI, Ag 14-O-03 15-P-10 30-0-03 30-P-28
Mesoporous silica, Ti 07-P-14 22-P-06 MFI, Ag, deNOx catalyst 30-P-34
23-P-14 24-P-12 29-P-08 29-P-18 29-P-30 MFI, Ag, photocatalyst 30-P- 16
Mesoporous silica, transformation 06-P- 18 MFI, AI in activated 13-P- 18
Mesoporous silica, transition metals 29-P-21 MFI, A! distribution 13-P- 19
Mesoporous silica, V MFI, alkali leaching 07-P-24 1 l-P-30
06-P-06 07-P-06 14-P-20 24-P-07 29-P-18 MFI alkane conversion catalyst 15-P- 15
Mesoporous silica, XRD 06-P-05
 419

MFI alkylation catalyst MFI membrane 03-P-17 19-O-05 20-0-02 20-P-06

25-O-01 25-0-05 25-P-09 28-P-15 MFI, mesoporous 03-0-02 1 l-P-30 26-0-02
MFl/alumina membranes 20-0-05 MFI, Mo 14-P-08 30-K-01
MFI aromatisation catalyst 28-0-02 MFI, Mo, oxihalogenation catalyst 23-P-24
MFI, Beckmann catalyst 15-0-05 27-P- 16 MFI, modelling 15-P-06 15-P-25
MFI catalyst 24-P- 10 26-P- 10 MFI, nanoparticles agglomeration 03-P- 14
MFI, Ce, oxihalogenation catalyst 23-P-24 MFI, Na form 30-P-07
MFI/ceramic composite membrane 20-P- 12 MFI, Na synthesis 02-P-09
MFI, Co 10-P-08 04-P- 18 30-0-03 MFI nanoslabs 02-0-04
MFI, Co, deNOx catalyst 30-P-34 MFI, nanotubes formation on 22-P-08
MFI, coke-selectivated 28-P-06 MFI, Ni 04-P-06 23-P-20
MFI on cordierite 30-P-33 MFI, Ni deNOx catalyst 30-P-30
MFI, crystal size control 02-P- 15 MFI nucleation 02-0-02
MFI cracking catalyst 28-P- 16 MFI, organozeolite 2 I-P- 16
MFI, Cr, oxihalogenation catalyst 23-P-24 MFI, oxihalogenation catalyst 23-P-24
MFI, Cs 29-P-20 MFI photocatalyst 15-P-07 30-K-01 30-P-20
MFI, Cu 04-0-01 12-P- 15 MFI, polycrystalline film on cordierite 20-P-13
14-O-03 15-P-13 30-0-03 30-P-09 30-P-33 MFI, pore mouth plugging 11-O-02
MFI, Cu, aromatisation catalyst 24-P-30 MFI, pore mouthing 11-P-24
MFI, Cu, deNOx catalyst 16-P-20 30-P- 14 MFI porosity 26-P-20
MFI, Cu oxidation catalyst 27-P-12 MFI, Pt 17-P-08 23-P-20
MFI, Cu, synthesis 14-P-40 MFI/Raney composite catalyst 30-P-29
MFI, dealuminated, acidity 29-P-06 MFI-resin composite 03-P-07
MFI dealumination 29-P-26 MFI, silylated 19-0-03
MFI, defects 14-P- 19 MFI, silylated, hydrocarbon conversion 11-O-02
MFI, deNOx catalyst 30-P-13 30-P-25 MFI, silylation 10-P-09 11-O-02
MFI, deuterated 23-P- 15 MFI sites modelling 15-P-24
MFI, diffusion 19-0-04 19-P-09 19-P- 10 MFI, solid state synthesis 04-P-06
MFI, diffusion, hydrocarbon 19-K-01 MFI, supercritical adsorption 17-P- 16
MFI, electronic material 14-P- 18 MFI spheres 03-P-07 21-P-06
MFI, enhanced acidity 13-P- 10 MFI synthesis 02-O-01 02-P-31 02-P-41
MFI, Fe 04-P-07 11-O-05 MFI synthesis, bulk-material dissolution 02-P-26
12-O-02 16-P-09 30-P-11 30-P-27 31-O-03 MFI synthesis, clear solution 02-0-04 02-P-I 6
MFI, Fe, deNOx catalyst 30-P-14 MFI, synthesis, microwave 03-P- 15
MFI, Fe oxidation catalyst 29-P-25 MFI synthesis, phosphate-affected 02-P-40
MFI, Fe, oxihalogenation catalyst 23-P-24 MFI, synthesis precursors 02-O-01
MFI, Fe, sulfide host 22-P-19 MFI, template removal 13-P- 10
MFI, Fe, synthesis 04-0-03 MFI, thermal treatment 14-P-38
MFI, Fe, synthesis, fluoride 04-P- 17 MFI, Ti (see TS-1)
MFI fibers 2 l-P-06 MFI, V 14-P-20
MFI film 20-0-04 MFI, Zn 24-P-27
MFI film on AI support 20-P-17 MFI, Zn, aromatisation catalyst 24-P-30 24-P-31
MFI film on ceramic 20-P-09 MFI, Zn,Ni 28-0-02
MFI film on gold 20-P-14 MFI, Zn,Ni aromatisation catalyst 24-P-31
MFI, Ga 03-P- 10 MFI, Zn, sulfide host 29-P-05
MFI, Ga, activation 11-P-27 MFI, Zn, synthesis 04-P-14
MFI, growth rate 02-P-08 Mg in alkaline synthesis 02-P-17
MFI, heteroatom location 13-O-02 Michael condensation 23-P-13
MFI, hierarchically mesostructured 06-0-03 Microbalance, oscillating 19-P-08
MFI host 13-P-06 14-P-29 15-P-26 2 l-P- 10 Microbial oxidation 31-P-15
MFI, indium 30-P- 15 Microbicide 01-P-15
MFI, In deNOx catalyst 10-O-01 Microcalorimetry 13-P-07
MFI isomerisation catalyst Microcalorimetry, adsorption
12-O-01 25-P-08 26-0-01 17-0-02 17-0-03 17-P- 16
MFI, large crystals activation 14-P-38 Microcalorimetry, Ar/N2 adsorption 17-P- 15
MFI, lattice vibrations 12-P-07 Microcalorimetry, chloroalkene adsorption 17-P-11
MFI, macropores 19-0-03 Microlaser, potential 21-O-04
420

Microporosity SBA- 15 08-O-03 08-0-04 Molecular dynamics, experimental 13-P-06

Microporous-mesoporous mixed structures 06-0-03 Molecular dynamics, external surface 16-0-02
Microscopy, atomic force, s e e AFM Molecular modelling 16-0-01
Microscopy, electron PL-5 Molecular modelling, multicomponent diffusion
Microscopy, interference 19-0-04 16-O-05
Microwave heating 20-P-38 Molecular orbital calculation, Ag-LTA 14-O-04
Microwave heating, zeolites 1 l-P- 13 Molecular simulation, transition state 15-P- 19
Microwave in catalysis 28-0-02 Molecular traffic control 16-0-05 28-0-01
Microwave in synthesis 03-P- 15 Molybdate, Cu, structure 09-P-07
MIL-34 AIPO4 05-P- 19 Molybdenum sulfides, mesostructured 1 I-P-11
Milk yield, cows 32-P- 10 Monolayer, LTA crystal/glass 20-0-01
Miocene 01-O-02 Monomer for polyesters, synthesis 25-P-07
Mn(x)Cd(l-x)S 21-O-03 Monooctylamine, synthesis 23-P-07
MnAPO-31 14-P- 13 Monte Carlo docking 16-P- 16
MnAPO-34 29-P- 14 Monte Carlo energy minimisation 07-P-21 16-P-I 1
MnAPO-43 05-P- 11 Monte Carlo Simulation 16-O-01 16-O-03 16-P-12
Mn-Bipyridyl, encapsulated 2 l-P- 11 Montmorillonite support 27-P- 10
Mn-FAU 21-P-11 21-P-13 Montmorillonite tuff 3 l-P-11
Mn-MCM-41, deNOx catalyst 30-P- 12 MORacidity 12-P-05 12-P-14 13-P-08
Mn-zeolites, NOx storage 30-0-04 MOR, acid site 14-P- 10
Mo-BEA 14-P-08 MOR, acid site NMR 13-P-23
Mo incorporation in SBA-1 and-3 14-P-26 MOR adsorbent 18-P- 15 19-P-06
Mo-MEL 14-P-08 MOR, adsorption modelling 15-P- 12
Mo-MFI 14-P-08 23-P-24 30-K-01 MOR, AI distribution 13-P- 19
Mo-MFI, oxyhalogenation catalyst 23-P-24 MOR, AI in activated 13-P- 18
Mo,Zr-MCM-41 26-P-22 MOR alkylation catalyst
Mobility, adsorbed molecules 16-O-03 16-P-08 24-P-06 25-P-07 25-P-09
Modelling, adsorption MOR, alkylation catalyst, modelling 15-0-03
12-0-03 16-P-06 18-P- 15 19-0-02 MOR/alumina membranes 20-P- 18
Modelling, adsorption in MOR 15-P- 12 MOR, applications 3 I-P-08 3 l-P- 15
Modelling, ab initio cluster 15-0-04 MOR, Armenia 0 l-P- 16
Modelling, alkylation of aromatics 16-P-08 MOR catalyst 28-P- 15
Modelling, cation sites 15-P-23 MOR, cation location 09-P- 13
Modelling, chloroform adsorption 16-P- 14 MOR, Ce 29-P- 11
Modelling, desulfurisation 15-P-22 MOR, Co 27-P- 13
Modelling, DFT 15-P- 10 MOR, composition 03-P- 19
Modelling, dynamical processes 15-O-02 MOR, Cu 11 -P-20 27-P- 13
Modelling, embedded cluster 15-0-04 MOR, dealuminated 12-P- 16
Modelling, galiophosphate activation 16-P- 15 MOR, dealuminated 11-P-25 12-P-05 29-P-11
Modelling, hypothetical framework 16-P-07 MOR, dehydration 09-P- 13
Modelling methylation reaction 15-O-03 MOR dehydration catalyst 23-P-08
Modelling, MOR catalysis 15-P-12 MOR, diffusivity 19-P-08
Modelling proton mobility 15-0-01 16-0-04 MOR, Fe
Modelling reactivity 15-P- 15 04-P-I 5 13-P-32 27-P-13 30-P-11 30-P-27
Modelling, reaction mechanism 15-0-05 15-P-20 MOR, H form 27-0-04
Modelling structure changes 15-P- 17 MOR, high-silica 02-P-39
Modelling, synthesis, TS- 1 16-P- 16 MOR, host 22-P-08
Modelling, synthesis, zeolites 02-P-22 15-P-06 MOR, In deNOx catalyst 10-O-01
Modelling, transition state, cluster 15-P- 16 MOR isomerisation catalyst 26-0-01 28-P- 13
Modelling, zeolite framework MOR from magadiite 02-P-36
15-P-14 15-P-25 16-P-13 MOR membranes 20-0-03
Modification, MCM-41 surface 17-P- 13 MOR, morphology 03-P- 19
Modified H-MFI, alkylation catalyst 25-0-05 MOR, Ni 27-P- 13
Molecular confinement 14-P- 12 MOR, Ni deNOx catalyst 30-P-30
Molecular dynamics, adsorption 16-P- 14 MOR, occurrences 01-O-02
Molecular dynamics simulations MOR, oxidation catalyst 27-P-08 27-P- 13
15-P-28 16-O-03 16-P-06 16-P-17 16-P-18 MOR, Pd, Heck catalyst 23-0-02
 421

MOR, Pd,Co,Ce 30-P-22

MOR photocatalyst 30-P-20
MOR porosity 26-P-20 N
MOR, Pt 26-P- 19
MOR ring opening catalyst 26-0-03 14N NMR, MFI synthesis 02-P-40
MOR, sigma transformation 16-P-07 15N.NMR 13-P-22
MOR, synthesis 03-P- 19 N2 adsorption 17-P-05
MOR, structure modelling 16-P- 11 N2 adsorption, AEL 17-O-03
MOR, thermal stability 12-P-05 N2 adsorption, IR 12-P-09
MOR, vibrational spectroscopy 16-P- 11 N2 adsorption, LSX 12-0-04
MOR, in zeolitic tuff 0 l-P-13 N2, supercritical adsorption, zeolites 17-P-16
MOR, Zn 04-P-15 13-P-32 N2/Ar adsorption, FAU 17-P-15
Morphology, effect on diffusion 19-O-04 N2/Ar adsorption, LTA 17-P-15
Morphology, mesoporous silica PL- 1 06-P- 13 N2/O2 selectivity of adsorption 18-P-13
Morphology, MFI 02-P- 15 N20 decomposition, Fe-MFI 30-0-02
Morphology, MFI, internal 14-P-38 NzO decomposition, MCM-22 30-P-13
M0ssbauer spectroscopy 14-P-22 N20 in oxidation 27-0-03
MPV (Meerwein-Ponndorf-Verley) reduction N20 reduction 30-P-06 30-P-11
23-P-33 N20 SCR with propene 30-P-14
MSU-S, synthesis from zeolite seeds 08-P-06 N20-NO interaction 16-P-20
MSU-X 08-P-05 23Na 2D NMR 13-P-19
MSU-X in chromatography and filtration 08-0-01 23Na MAS NMR 09-0-05 14-P-17 14-P-37
MTBE 28-P- 11 29-P-12 23Na MQ MAS NMR, Li,Na-FAU 13-P-12
MTO, mechanism 24-P-18 23Na NMR, FAU adsorbent 12-P-12
MTO process 24-P-28 23Na NMR, paramagnetic effect of 02 13-P-12
MTO on SAPO-47 05-P-17 Na cations in synthesis 03-0-05
MTO on SAPO-56 05-P-18 Na exchange 1 l-P-18
MTS polymer degradation catalysts 24-P-13 Na forms of zeolites, NO adsorption 14-P-09
MTS, adsorbents 28-P-10 Na,Li-FAU, pyrrole adsorption 12-P-12
MTS, swelled 06-P-27 Na-LSX 12-0-04
MTW alkylation catalyst 25-0-03 Na nanoparticles 14-P-37
MTW, Fe oxidation catalyst 29-P-25 Na-Rb alloy 14-P-37
MTW, Fe, synthesis 04-0-03 Na-X, toluene adsorption NMR 13-P-16
MTW, Ga 03-P-10 Na-Y, adsorbent 16-O-03
MTW, Pt hydroconversion catalyst 26-P-16 Nanoclusters, Pblz/LTL 22-P- 18
MTW-related frameworks 02-P-27 Nanocomposite in zeolites 2 l-K-01
Mu-2 by Mu-3 transformation 11-O-03 Nanocrystailine FAU 02-0-03 02-P-14
Mu-3 stability 11-O-03 Nanocrystalline MFI 02-0-04 28-P-08
Multicomponent diffusion, modelling 16-O-05 Nanocrystals, anatase 22-P-13
Multipole moment, substituted AIPO4 15-P-27 Nanocrystals, offretite 02-P-12
Multiquanta 2D 27A1MAS-NMR 13-P-18 Nanoemulsion template 06-P-27
Multiquanta MAS-NMR 13-0-03 13-P-24 Nanoparticles agglomerates, MFI 03-P-14
MWW 27-O-01 Nanoparticles, Au 11-O-01
MWW acidity 13-0-04 Nanoparticles, Fe203 in MCM-41 07-P-13
MWW, acid oxidation catalyst 27-0-03 Nanoparticles, SnO2 21-P-10
MWW alkylation catalyst 28-P-15 Nanoparticles, surfactant stabilized 29-P-22
MWW, basicity 10-0-02 Nanoparticles, ZrO2 in SBA-15 29-P-17
MWW, Beckmann catalsyt 23-P-27 Nanoscopic precursor particles 02-0-01
MWW, Co 14-P-21 Nanoslabs, silicalite- 1 02-0-04
MWW, deNOx catalyst 30-P- 13 30-P-30 Nanowires in FSM- 16 22-0-05
MWW, Ni 30-P-30 Nanowires, Se in MFI 15-P-26
MWW, Fe 14-P-21 Naphtha isomerisation 26-P-23
MWW, magadiite-intercalated 05-P-14 Naphthalene isopropylation 25-P-06
MWW synthesis 02-P-34 02-P-42 03-P-13 Naphthalene alkylation 25-0-03 25-P- 13 25-P- 14
MWW, Ti 27-O-01 Naphthene ring opening 26-0-04
MWW, trivalent distribution 14-P-21 S-Naproxen synthesis 25-P-08
Mycotoxin, adsorption 32-0-04
422

Natrolite 09-P-09 Ni-MOR, oxidation catalyst 27-P- 13

Natrolite, applications 3 l-P-06 Ni phosphates 05-P-08
Natrolite, ion exchange 0 l-P-08 Ni phosphate, VSB- I 22-0-03
Natrolite, lattice vibrations 16-P- 19 Ni Raney/MFI composite 30-P-29
Natural zeolites, Antarctica 0 l-K-01 Ni,W/Y hydrocracking catalysts 1 l-P-08
Natural zeolites applications PL-2 0 l-P- 16 Ni,Zn/MFI aromatisation catalyst 24-P-31 28-0-02
22-P-10 22-P-15 30-P-10 31-O-01 31-P-06 Ni/Zr-MCM-41 23-P-28
31-P-08 31-P-12 31-P-14 31-P-15 32-O-01 Ni/ZrO2 fuel cell catalyst 07-P-20
32-0-04 32-P-06 32-P-09 32-P-10 32-P-12 Nine-member rings 09-P- 12
Natural zeolites, Armenia 0 l-P-16 Niobate molecular sieves 05-O-01
Natural zeolites, Bulgaria 0 l-P- 13 Niobium ammonium complex in MFI synthesis
Natural zeolites, Croatia 3 l-P- 11 04-P-10
Natural zeolites formation NIR spectroscopy 27-P-11
01-O-02 01-P-06 01-P-10 01-P-13 Nitrate cancrinite 02-P-07
Natural zeolites, Croatia01 -P- 17 Nitrate removal 3 l-P- 15
Natural zeolites, Iran 01-P-08 3 l-P-06 Nitration 29-P-28
Natural zeolites and health 32-O-01 32-P-09 Nitration, aromatics 13-P-22
Natural zeolites, Jordan 31-O-01 Nitration, zeolites 04-0-02
Natural zeolites, occurrencies 0 l-K-01 Nitrene 24-0-04
Natural zeolites, properties 01-O-05 Nitriles, source of template 03-0-03
Natural zeolites, Romania 0 l-P-09 p-Nitroaniline, adsorption 13-P-06
Natural zeolites, Russia 0 l-P- 12 Nitrogen industry, wastewater 30-P-34 3 I-P- 10
Natural zeolites, Sardinia 01-O-02 Nitromethane reagent 23-P- 13
Natural zeolites, South Africa 3 I-P-12 Nitromethane, ~3C NMR probe 23-P- 13
Natural zeolites, Ukraina 3 l-P-08 3 I-P- 10 N-Nitrosamines degradation 30-P-07 30-P-08
Natural zeolites, Zambia 3 I-P-12 N-Nitrosamine removal 18-P-07
Nb, see also Niobate Nitroxide, ditert-butyl 14-P-07
Nb-MCM-41 07-0-04 24-P-12 27-P-09 Nittoxide EPR label 32-0-02
Nb-MFI 01 -P- 14 Nitroxide EPR probe 14-P-07
Nb-MFI, synthesis 04-P- 10 Nitroxide radical adsorption 14-P-07
Nb nanoparticles 14-P-37 Nitroxyl radical probe 13-P-09
Neopentane diffusion 19-0-04 NMR (see individual nuclei)
Neutron diffraction 09-0-04 09-0-05 NMR cristallography, AIPOa-CJ2 09-0-02
Neutron diffraction, adsorbed phase 17-O-02 NMR, in-situ 02-P- 18
Neutron diffraction, AEL adsorbent 17-O-03 NMR spectroscopy 27-P-11
NH3, adsorption on zeolites 18-P- 10 NMR, MCM-48 07-P-06
NH3 TPD, see TPD NO adsorption 12-P-15 14-O-05 14-P-09
Ni-aluminophosphate 09-P-08 NO adsorption,Co-MFI 10-P-08
Ni-bentonite 18-P- 14 NO decomposition
Ni clusters in MFI 04-P-06 07-0-04 12-P-15 14-O-03 30-P-33
Ni-ERI, oxidation catalyst 27-P- 13 NO decomposition, photocatalytic 28-P-07 30-P-24
Ni-FAU 24-P-17 24-P-24 NO-NzO interaction 16-P-20
Ni-FAU, oxidation catalyst 27-P-13 NO reduction 30-P-15 30-P-27 30-P-28 30-P-34
Ni-MCM-22, deNOx catalyst 30-P-30 NO reduction with propene 30-P-14 30-P-30
Ni-MCM-41 hydrodechlorination catalyst 23-P-16 NO2 adsorption 14-0-05
Ni-mesoporous silica 08-0-02 NO2 decomposition
Ni-MFI 04-P-06 23-P-20 07-0-04 12-P-15 14-O-03 30-P-16 30-P-33
Ni-MFI, deNOx catalyst 30-P-30 NOx decomposition, photocatalytic 28-P-07 30-P-24
NiMo/H-BEA 26-P-15 NOx abatement, AIPO4 catalysts 30-P-31
NiMo/H-Y 26-P-15 NOx adsorption
NiMo hydrotreatment catalysts 26-P-08 10-0-04 10-P-08 12-P- 15 14-0-05 14-P-09
NiMo hydrotreatment catalyst on MCM-41 NOx decomposition 30-K-01
NiMo/MCM-41 hydrotreatment catalyst NOx reduction 30-P- 10
26-P-12 26-P-14 30-P-15 30-P-25 30-P-27 30-P-28 30-P-34
NiMo sulfide/large pore zeolites 26-P-15 NOx reduction by CH4 10-O-01 30-P-22 30-P-35
NiMo/Zr-HMS hydrotreatment catalyst 26-P-22 NOx reduction by NH3 30-P-12
Ni-MOR, deNOx catalyst 30-P-30 NOx reduction in propane 10-O-04
 423

NOx reduction by propene 30-P-14 30-P-30 Olefin polymerisation 24-P-15

NOx reduction with hydrocarbons 30-0-03 12-O-02 Olefination of haloaromatics 23-0-02
NOx sorption, metal zeolites 30-0-04 Oligocene 01-0-02
NOx storage, metal zeolites 30-0-04 Oligomerisation, acetylene 24-P-15
Noble metal zeolite 23-P-20 Oligomerisation, ethylene 24-P-17
Noble metals/MCM-41 26-P-07 Oligomerisation, olefins 24-P-15
Nonasil, synthesis 02-P-41 Optical properties 21 -O-03
Non-ionic surfactant 06-P-23 08-0-02 Optical properties, Ce-Eu silicates 05-P-12
Nu-86 synthesis 02-P-20 Optical properties, PbI//LTL 22-P- 18
NU-88, cracking catalyst 26-P-11 Optical sensors 22-P-14
NU-88, hydroconversion catalyst 26-P-11 Optical spectra 22-P-17
NU-88, pore topology 26-P-11 optical switching 22-P-07
nuclear waste 05-0-01 Optics, non-linear 22-0-01
Nucleation agent, zeolitic 2 l-P-09 Orange blossom fragrance 23-P-22
Nucleation and growth 02-P- 16 Ordering, adsorbed phases, AEL 17-O-03
Nucleation, FAU 02-0-03 Ordering, Al, in dachiardite 01-P-07
Nucleation, LTA 02-P-32 Ordering, B and AI 13-O-01
Nucleation, zeolites 02-0-02 Ordering, non-centrosymmetric 22-0-01
Nucleophilic Substitution 23-P-07 Organic acid templates 04-P-12
Organic adsorption, FER 17-P-06
Organic framework 21-P-16
O Organic functionalisation, mesoporous silica 29-P-31
Organic probe molecules 14-P-30
170 3Q MAS NMR 14-0-02 Organic removal, membrane 20-P-12
170 DOR NMR 09-0-02 14-0-02 Organic-modified clinoptilolite 22-P- 12 22-P-15
~70 NMR chemical shitt 14-0-02 Organometallic complexes, encapsulated
02 adsorption 17-0-01 07-P-10 14-P-16
02 adsorption, AEL 17-O-03 Organophosphates, microporous 22-0-02
02 as anti-coke agent 27-P-16 Organozeolites 2 l-P- 16
02 and Beckmann catalyst deactivation 27-P-16 Oriented crystal growth 02-P-28
02 and catalyst lifetime 27-P-16 Oriented crystals, mordenite 20-0-03
O2/N2 selectivity of adsorption 18-P-13 OSB-1 (OSO) 05-0-05
02, paramagnetic effect on 23Na NMR 13-P-12 OSB-2 05-0-05
02, singlet, molecular 27-P- 11 Over-exchanged Cu-ZSM 5 30-P-21
O2 substitution by organics 21-P-16 Oxalate in Fe-zeolite synthesis 04-0-03
02, supercritical adsorption, zeolites 17-P-16 Oxidation, alkanes, selective 27-O-01
03 in calcination 11-P-27 Oxidation, aromatics 2 I-P-07
03, template removal, MCM-41 29-P-18 Oxidation, benzene to phenol 27-0-03
Occluded salts 10-O-03 Oxidation, biological 3 I-P- 15
Occluded salts, LTA 22-P-17 Oxidation catalyst, Fe zeolites 07-P- 10
Octahedral molecular sieves 05-0-01 Oxidation catalyst, substituted MCM-41 29-P-18
Octahedral-tetrahedral frameworks Oxidation, CO 29-P- 14 30-P- 10
05-P-16 05-P-20 09-P-07 1 l-P- 15 27-P-15 Oxidation, CVOC 30-P- 18
Octane enhancers 28-P-11 Oxidation, cyclohexane
Octane, iso-, synthesis 24-P-20 02-P-14 07-P-10 27-P-15
Octanol, amination 23-P-07 Oxidation, cyclohexene 2 l-P- 13
Offretite, colloidal 02-P- 12 Oxidation, isobutanol 27-P- 13
Offretite isomerisation catalyst 28-P- 13 Oxidation, Fenton 31-O-03
Offretite single crystals 03-P-08 Oxidation, hydrocarbons 27-P-06
OH groups, ferrierite 13-P- 17 Oxidation, methane, photocatalytic 24-P- 12
Olefin adsorption 12-P-06 Oxidation by N20 27-0-03
Olefin epoxidation Oxidation, olefins 11-O-04
11-P-29 14-P- 12 15-P- 18 24-P- 14 27-0-02 Oxidation, phenol 04-0-01
Olefin hydrogenation 29-P-22 Oxidation, phytotoxic chemicals 31-O-03
Olefin isomerisation 26-P-09 Oxidation, propane, photocatalytic 28-P-07
Olefin oxidation, ETS- 10 11-O-04 Oxidation, propane, selective 27-P- 12
Oxidation, propyl alcohols 27-P-08
424

Oxidation, selective 24-P- 14 27-0-02 pH effect, MCM-41 synthesis 06-P-28

Oxidation, styrene 29-P-21 pH indicators 22-P-21
Oxidation, thioethers 27-P-09 30-P-26 pH of synthesis 02-P-19
Oxidation, toluene 30-P-23 Pharmacosiderite 1 l-P-15
Oxidation, total 30-P-09 Phase change, zeolites 10-P-07
Oxidation, VOC 30-P- 18 Phase diagram 03-P- 18
Oxides, mixed 24-P-26 Phase transformation, aluminium
Oxidizing atmosphere, effect on activation 14-P-38 methylphosphonate
Oxyhalogenation, aromatics 23-P-24 21-P-17
Phase transformation, Mu-3 11-O-03
Phase transition, confined system 17-O-01 17-P-17
Phase transition, host-guest systems 14-P-16
Phase-change material 2 l-P-09
31p NMR 09-0-02 09-P- 11 Phenol alkylation
11-O-03 13-P-20 13-P-24 14-P-11 18-P-13 23-P-31 25-0-02 25-P-09 28-P-15
31p NMR, MFI synthesis 02-P-40 Phenol dehydroxylation 29-P-08
P-treated zeolites 11-P-23 Phenol hydroxylation 07-P-07 27-P-17
Packing parameter 08-P-12 Phenol oxidation 04-0-01
aleogene 01-P-10 Phenol removal, membrane 20-P-12
para selectivity, toluene nitration 13-P-22 Phenol, synthesis 27-0-03
Paraffin isomerisation 26-0-02 Phenol-trimethylbenzene transalkylation 25-0-04
Parallel synthesis 06-P-25 Phenyl-functionalized mesoporous silica 07-0-02
Paramagnetic effect of 02 on 23Na NMR 13-P-12 1-Phenyl- 1,2-propanedione hydrogenation 23-P-25
Paramagnetic radicals 14-P-07 Pheromones 32-0-05
Para-selectivity 28-P-08 PHI, cation exchange 01 -O-05
Partially crystalline BEA 29-P-12 PHI, Li 01-O-04
Particle effects, membranes 19-O-05 Phosphate in Fe-zeolite synthesis 04-0-03
Particle size, BEA 02-P-23 Phosphate in MFI synthesis 02-P-40
Passivation, MFI 10-P-09 Phosphate, Ni, VSB- 1 22-0-03
212pb radiotracer 3 l-P-06 Phosphates, Ga, stability 16-P-15
PbI2 nanoclusters in LTL 22-P-18 Phospholipids 32-0-03
Pd-Au/H-Y 11-O-01 Phosphonate, AI methyl, polytypism 09-P-14
Pd/BEA 23-P-26 Phosphorescence spectra 14-P-20
Pd and Ce promoter 30-P-22 Phosphorus removal 31-P-14
Pd/FAU, Heck catalyst 23-0-02 Phosphites, aluminium, microporous 05-P-15
Pd/K,Na-X 23-P-23 Photocatalysis, NO2 decomposition 30-P-16
Pd/LTA, oxidation catalyst 27-P-08 Photocatalysis, transition metal oxides in zeolites
Pd/LTL, Heck catalyst 23-0-02 30-K-01
Pd/MCM-41 29-P-22 Photocatalytic decomposition, NO 28-P-07 30-P-24
Pd/MeAPSO- 1 l 24-O-01 Photocatalytic degradation 30-P-20
Pd/MOR 23-P-26 Photocatalytic oxidation of methane 24-P- 12
Pd/MOR, Heck catalyst 23-0-02 Photocatalytic oxidation of propane 28-P-07
Pd nanowires 22-0-05 Photocatalytic synthesis of H202 27-P- 14
Pd, Pt on mesoporous carbon 29-P-13 Photochemical H20 decomposition 28-0-03
Pd/SAPO- 11 24-O-01 photochromic dye 22-P-07
Pd-Pt/Y hydrogenation catalysts 27-0-05 Photoluminescence
Pd/Y 23-P-26 14-P-20 14-P-35 21-O-03 21-O-05 29-P-30
n-Pentane conversion 26-P-20 Photolysis of alkyl ketones 15-P-07
Pentane, neo-, diffusion 19-0-04 Photonic devices 22-P-20
Pentane, total oxidation 30-P-09 Photophysics 22-P-09
Permeability, composite membrane 19-O-05 Photo redox system 24-P-07
Permeance, membranes 20-P-07 Phtalocyanine 22-P-06
Peroxide decomposition, biomimetic 27-P-10 Phtalocyanine in FAU 14-P-12
Petrochemistry evolution PL-4 Phytotoxics oxidation 31-O-03
pH, effect on alumination 1 l-P-10 Pigments, encapsulated 22-P- 19
pH effect on ion exchange 31-P-11 Pillared clay 22-P- 16
Pillared clays, alkylation catalyst 25-P-13
 425

Pillared magadiite 23-P-18 Propane/propylene, separation 18-0-04

Pillared bentonite 22-P-16 n-Propanol adsorption 18-P- 15
Pillaring 09-P-08 2-Propanol conversion 29-P-05
Alpha-Pinene derivatives 23-P-14 Propyl alcohols oxidation 27-P-08
Alpha-Pinene epoxidation 23-P-14 Propylene adsorption 18-0-04
Alpha-Pinene hydration 23-P-19 Propylene in alkylation 25-P- 14
Pinene oxide, rearrangement 23-P-14 Propylene in deNOx SCR 30-P-30
Piperidine, formation 23-P-08 Propylene dimerisation 24-P-24
Plant growth enhancenent 31-O-02 Propylene epoxidation 24-P- 14 27-0-02
Plasma activation 1 l-P-14 Propylene oxide 24-P- 14
Plasma treatment, FAU 1 l-P-17 Propylene polymerisation 24-P-08
Polarity effects 18-P-07 Propylene/propane, separation 18-0-04
Polluted river water 31-P-15 Protein adsorption 23-P- 17
Polyamine binders 20-0-01 Proton mobility modelling 15-0-01
Polyaromatics adsorption 14-P-18 Proton positions, FAU 09-0-04
Polyaromatics alkylation 25-O-01 Proton transfer, modelling 15-0-02
Polyaromatics ionisation 14-P-18 Proton tunnelling, FAU 16-0-04
Polyethylene binder 22-P-15 PSA, CO2 18-0-01
Polyethylene conversion 24-P-13 PSA separation, ethyl acetate 18-P-12
Polyethylene cracking 30-P-17 Pt,Au/H-Y 11-O-01
Polyethylene degradation 24-P-25 Pt-2,2'-bipyridyl complex 24-P-29
Polymer degradation 30-P-17 Pt catalysts 29-P- 19
Polymerisation, acetylene 24-P-15 Pt dispersion 26-P- 16
Polymerisation catalysts 24-P-08 Pt/BEA 17-P-08 24-P- 16
Polymerisation, ethylene 24-0-05 Pt/BEA aromatisation catalyst 15-P-09
Polymerisation, olefins 24-P-15 Pt/BEA hydrogenation catalyst 26-P- 13
Polymer-zeolite membrane 19-O-05 Pt/BEA isomerisation catalyst 20-P- 18
Polystyrene beads support 21-P-12 21-P-15 Pt/Cs-BEA reforming catalyst 26-0-05
Polytypism, BEA 0 l-K-01 Pt/CsX basic catalyst 23-0-05
Population balance 02-P-24 02-P-29 Pt-FAU 17-P-08
Pore mouth catalysis 26-0-02 Pt-FAU aromatisation catalyst 15-P-09
Pore mouth plugging, MFI 11-O-02 Pt/FAU bifunctional catalyst 30-0-05
Pore mouthing, BEA 1 l-P-09 Pt/FAU catalyst, CH2C!2 conversion 30-0-05
Pore mouthing, MFI 11-P-24 Pt/K-LTL catalyst 1 l-P-07
Pore size distribution, modified MCM-41 17-P-13 Pt-LTL aromatisation catalyst 15-P-09
Pore size, effect on adsorption 17-P-07 Pt/MAPSO-31 hydroisomerisation catalyst 26-P-06
Pore size, effect on isomerisation 25-P-08 Pt/MCM-41 chiral hydrogenation catalyst 23-P-25
Pore size expansion, see swelling Pt/MCM-41 hydroisomerisation catalyst 26-P-21
Pore size, MCM-41 12-P-11 Pt/MOR, diffusivity 19-P-08 28-0-05
Pore structure, ERS- 10 29-0-01 Pt/MOR isomerisation catalyst 26-P-19
Pore topology, NU-88 26-P-11 Pt/MOR hydrogenation catalyst 27-0-04
Porosils, host 10-O-03 Pt-MOR hydroisomerisation catalyst 28-0-05
Porosils, synthesis 02-P-41 Pt/MFI 17-P-08 23-P-20
Porosity, hierarchical 21-P-07 Pt/MTW hydroconversion catalyst 26-P-16
Porous glass, Beckmann catalyst 27-P-16 Pt,Ni/USY isomerisation catalyst 14-P-36
Positron annihilation 12-P-11 Pt, Pd/mesoporous carbon 29-P-13
Positron emission profiling 19-P-10 Pt-Pd/Y hydrogenation catalysts 27-0-05
Post-synthetic treatment 06-P-06 08-P-13 1 l-P-16 Pt-Rh catalysts 22-0-05
Powder diffraction 01-O-04 09-P-09 (Pt,Rh,Pd,Ru,Ni)/HZSM-5 26-0-03
Pressure effect on natrolite 16-P-19 Pt zeolites, hydrogenation catalyst 26-0-04
Pressure effect on zeolite structure 09-P-09 Pt-Zn/zeolite X 29-P-15
Pressure swing adsorption (see PSA) Pyrocatechol in zeolite synthesis 03-P-08
Probe, ~3C NMR, nitromethane 23-P-13 Pyrolysis 2 l-P-08
Propane adsorption 18-0-04 Pyrrole adsorption, Li,Na-FAU 12-P-12
Propane formation 24-0-02
Propane selective oxidation 27-P-12
Propane, photocatalytic oxidation 28-P-07
426

Q Rietveld refinement
09-0-01 01-O-04 05-P- 19 09-P- 11 09-P-14
Quadrupolar interaction, ~B 13-P-11 Rietveld refinement, mesoporous silicas 08-P-14
Quantum chemical calculations 14-0-03 Ring opening, aromatics 26-P-13
Quantum confinement 21 -O-03 21 -O-05 Ring opening, cyclohexane 26-0-03
Quantum confinement, Ag-LTA 14-0-04 Ring opening, epoxides 23-P-10
Quantum-chemical calculations 15-O-05 Ring opening, methyloxirane 23-P-15
Quinoline, fluorescence 13-P-13 Ring opening, naphthenes 26-0-04
Quinone/BEA photocatalysts 27-P-14 3-Rings O5-0-O5
Rings, penetrability 15-P-14
Roboting synthesis 03-K-01
Romania, clinoptilolite occurrences 0 l-P-09
R
Ru bipyridyl complexes/FAU 28-0-03
RUB-29 lithium silicate 09-0-O5
Radical sites 24-P-25
Rubidium clusters in LTA 21-P-18
Radicals, adsorbed 24-P-07
Russia, clinoptilolite tuff 01-P-12
Radicals, health effect 32-0-02
Radioanalytical methods 3 l-P-06
Radionuclides 3 l-P-05 32-P-12
Raman spectroscopy 14-P- 18 14-P-24
Raman spectroscopy, host-guest interactions
14-P-16
Raman spectroscopy, NIR 14-P-31 Salen complex anchoring 29-P-08
Raman spectroscopy, vanadium 14-P-33 Salen complexes, Co, on MCM-41 23-P-10
Raman spectroscopy, zeolite lattice 12-P- 10 Salen complex, Yi (IV), chiral 23-P- 11
Raney metal/MFI composite 30-P-29 Salt occlusion, PbI2/LTL 22-P-18
Rare earth exchange 1 l-P-19 SANS, synthesis 02-0-01
Rare earth silicates 05-P- 12 SAPO-5 13-P-14
Raspberry ketone 25-0-02 SAPO-5, amination catalyst 23-P-07
STRb NMR 14-P-37 SAPO-56 05-P-18
Reaction dynamics, proton transfer 16-O-04 SAPO-I 1 alkylation catalyst 23-P-31
Reactivity enhancement 28-0-01 SAPO-I 1 dehydroisomerisation catalyst 24-O-01
Reactivity index 15-P-06 SAPO-11 synthesis 02-P-13
Reactivity, silicalite 15-0-05 SAPO-I 1 amination catalyst 23-P-07
Rearrangement of pinene oxide 23-P- 14 SAPO-31 alkylation catalyst 23-P-31
Reconstructive transformation 02-P-25 SAPO-31 amination catalyst 23-P-07
REDOR MAS NMR 13-0-01 13-P-23 SAPO-31, synthesis 04-P-09
Redox behaviour, Fe in MCM-41 07-0-03 SAPO-34 MTO catalyst 24-P-28
Redox behaviour, Ga-FAU 10-P-06 SAPO-34, acidity 24-P-26
Redox ion exchange 09-P- 10 SAPO-34, amination catalyst 23-P-07
Redox mesoporous molecular sieves 23-P- 14 SAPO-34, Fe 30-P-27
Reductibility, Cu/ZSM-5 27-P- 12 SAPO-34, host 24-P-26
Reduction, Cu 2+in MFI 30-P-21 SAPO-37, acid site 14-P-10
Reduction, Ga in FAU 10-P-06 SAPO-37, thermal decomposition 14-P-11
Reduction, metal ions 04-0-01 SAPO-41 alkylation catalyst 23-P-31
Reduction, regioselective, ketones 23-P-33 SAPO-47, characterisation 05-P-17
Refining evolution PL-4 SAPO-47, synthesis 05-P-17
Reflection, internal 21-O-04 Saponite, reagent 06-P- 15
Reforming, FCC gasoline and LCO 26-0-05 Sardinia, zeolite occurrences 01-O-02
Relaxation, lattice 16-P- 18 Saturation, unsaturated rings 26-P-10
Relaxation processes, cations 14-P-06 SAXS, synthesis 02-0-01
Renewable feedstock 23-P-32 SBA-1, functionalized, synthesis 07-0-02
REPDOR triple resonance 13-O-01 SBA-1, Mo 14-P-26
Resin-silicate composite 03-P-07 SBA- 1, synthesis 06-P- 18
Resonance Raman spectroscopy 14-P-34 SBA-2, functionalised 07-P-17
RHO, dealumination 11-P-25 SBA-3 in HPLC 18-P-06
Rietveld analysis, molecules in zeolites 16-P-06 SBA-3 synthesis 06-P-28
 427

SBA-3, Mo 14-P-26 295i 2D NMR 13-P- 19

SBA-3, synthesis 06-P- 18 29Si NMR
SBA-6, HRTEM PL-5 0 l-P-07 03-0-04 04-P- 18 09-0-01 1 I-P-07
SBA-15 08-P-07 l l-P-21 18-P-13 13-P-06 13-P-10 30-P-19
SBA- 15, adsorbent 17-0-01 29Si NMR, MFI synthesis 02-P-40
SBA- 15, AI, cracking catalyst 08-P- 13 29Si NMR, spectra prediction 15-P-25
SBA-I 5, AI, Pt hydroisomerisation catalyst 08-P- 13 Si/A1 distribution, clinoptilolite PL-2
SBA- 15, AI, template interaction 08-0-04 Si/AI ratio, dealuminated Y 13-P- 15
SBA-15 host 29-P-17 Si/AI ratio, effect of alkalinity 03-P- 19
SBA- 15 in HPLC 18-P-06 SiC nanoparticles 21-O-05
SBA- 15 porosity 08-0-03 Sigma transformation 16-P-07
SBA-15, stability 08-P-13 Silane, functionalisation by 29-P- 16
SBA- 15, V, photocatalyst 24-P-07 Silane, hydrophobisation by 06-P-06
SBA- 15, wall properties 08-P- 14 Silane, methylene framework 2 I-P- 16
SBA- 15, Y, HRTEM PL- 1 Silica adsorbents 18-0-04
Scaffolding 7-P- 11 Silica aggregates, fractal 14-P-25
Scolecite 09-P-09 Silica deposits 28-P-08
Sea water 3 l-P- 16 Silica fibers, zeolitisation 02-P-26
Sea water, bentonite zeolitisation 03-P-06 Silica MTS 06-P-27
Secondary synthesis, mesoporous silica 08-P-11 Silica source 02-P-I 9 02-P-20 06-P- 15
Sedimentary zeolites, properties 01-O-05 Silica source, effect on synthesis 02-P-23
Sedimentary zeolites, volcano- 01-O-02 Silica source, effect on synthesis of MOR 03-P- 19
Seeding 02-P-08 02-P-19 02-P-20 02-P-31 Silica spheres with Cu 07-P-07
Seeding, effect on synthesis 02-P-21 Silica template 07-P-22
Seeding, film 20-P-09 20-P-16 Silica BEA, pure 02-P-35
Seeding, zeolite layers 20-0-02 Silica, CaCI2 impregnated 31-O-04
Selectivation by coke 28-P-06 Silica, HLS 02-P-25
Selectivity, diffusion-controlled 28-0-01 Silica, reagent 02-P- 13
Selenium, nanowires in MFI 15-P-26 Silica-alumina, amorphous 27-0-05
SEM ETS- 10 27-P- 15 silica-alumina, amorphous catalyst 28-P- 15
Semiconductor, MoS I l-P-11 Silica-alumina, Beckmann catalyst 27-P- 16
Semiconductors, magnetic 21-O-03 Silicalite- 1 (see also MFI) 0 I-P- 14
Semi-empirical quantum-mechanical method Silicalite-1 adsorbent 17-0-02 19-0-02
16-P-16 Silicalite-1, adsorption modelling 16-P-10 16-P-12
Semiochemicals 32-O-05 Silicalite- 1, diffusion 19-P- 10
Sensor, calorimetric 22-P-11 Silicalite- 1 film 20-0-04
Sensor, gas 2 l-P- 10 Silicalite-1 membrane 03-P-17 19-O-05 20-0-02
Sensor, optical 22-P- 14 Silicalite- 1 nanoslabs 02-0-04
Separation, cafeine 20-0-05 Silicalite, supercritical adsorption 17-P- 16
Separation, CO2 18-0-01 Silica-rich mordenite 02-P-39
Separation, CO2/C2 hydrocarbons 18-O-03 Silica-zirconia, mesoporous 07-P-09
Separation of mixtures 17-P- 16 Siliceous ferrierite 17-P-06
Separation, membrane 19-0-05 Silicon incorporation in SAPO 23-P-31
Separation, membrane, asymmetric 23-P- 10 Silicon nanoparticles 21-O-05
Separation, propane/propylene 18-0-04 Silylation, effect on diffusivity 19-0-03
Separation, xylenes 18-P-08 Silylation, MCM-41 29-0-02
SF6-Xe diffusion in BOG, modelling 16-O-05 Silylation, mesoporous silica 18-P-06 29-P-31
Shape selectivity 11-P-24 25-P-07 25-P-09 Silylation, MFI 11-O-02
25-P- 14 28-P-08 28-P- 13 29-0-01 29-P- 11 Silylation, Ti-BEA 11-P-29
Shape selectivity enhancement 10-P-09 Simulation, FAU (111) surface 16-0-02
Shape selectivity simulation Single crystal mesoporous 07-P-15
15-P-19 16-O-01 16-P-08 Single crystals, offretite 03-P-08
Shape selectivity, test reactions 26-P-11 Single file diffusion 28-0-01
Shape-selective alkylation 25-0-01 Single file diffusion in MOR 28-0-05
Ship-in-the-bottle complexes Single file diffusion, effect on catalysis 28-0-05
07-P-10 14-P-12 21-K-01 Singlet molecular oxygen 27-P-11
21-P-11 22-P-07 22-P-09 24-P-29 27-P-10 Sintering in membrane preparation 03-P-17
428

Smectite adsorbent 32-0-04 Stability, mesoporous alumina 06-P-23

Smectite, reagent 06-P- 15 Stability, mesoporous silica
Sn NMR 05-P-13 06-O-01 06-P-06 06-P-07 08-P-06 08-P-14
SnO2 in Zeolites 21-P-10 Stability, SBA-15 08-P-13
Sn silicates 05-P-13 Stability, substituted MCM-41 06-P- 19
SO2 adsorption, effect of water 19-P-06 Stability, thermal, FAU 1 I-P-13
SO2 adsorption on zeolites 18-P-10 Stability, thermal, SAPO-37 14-P-11
SO2, effect on DeNOx activity 30-P-25 Statistical mechanics treatment, adsorption 16-P-10
SO2 oxidation 29-P-25 Steam dealumination 1 I-P-08 13-P-07 28-P-08
SO3H- anchored on mesoporous silica 08-P-10 Steam reforming 24-P-23
SOD AIPO4-20 09-P- 11 Steamcracker feed, synthetic 26-P-10
SOD-CAN composite 02-P-28 STF (see SSZ-35)
SOD-CHA composite 02-P-28 Stirring, effect on synthesis 02-P-19
SOD, encaspsulation, modelling 15-P-08 Storage, chromium 31-P-13
SOD from fly ash 18-P-10 Storage, heat 2 l-P-09 31-O-04
SOD, 170 NMR 14-0-02 Storage, Hz 17-P-10
SOD, sulfide host 22-P- 19 Storage, NOx 30-0-04
SOD synthesis 02-P-29 Strawberry crop enhancement 31-O-01
SOD synthesis, solid state 02-P-25 Structural modelling 08-P- 14 15-P-25
SOD, TMA 02-P-25 Structure analysis by NMR data 09-0-02
Sodalite building blocks 07-P-21 Structure determination 01-O-04 05-0-02
Sodalite cage 16-P-17 05-0-05 05-P-06 05-P-10 05-P-11 05-P-16
Soil amendment 31-O-01 05-P-20 09-0-04 09-P-08 09-P-09 1 l-P-12
Sol-gel, silica 14-P-25 Structure, FOS-5 09-0-03
Solid acid catalysts, partially crystalline 29-P-12 Structure, packing parameter 08-P-12
Solid state cation exchange 10-P-06 Structure prediction 07-P-21
Solidification, confined phase 17-P-17 Structure, rare earth silicates 05-P-12
Solid-state cation exchange 10-P-08 Structure resolution, HRTEM PL-5
Solid-state reactions by microwave heating 1 I-P-13 Structure, SBA- 15 08-0-03
Solvent effects 18-P-07 Structure, sigma transformation 16-P-07
Solvent extraction, mesoporous Ti02 07-P-12 Structure transformation, Mu-3 11-O-03
SOMS (Sandia octahedral molecular sieves) 05-O-01 Structure-directing agent (see template)
Sonochemistry in synthesis 06-P-14 Styrene epoxidation 29-P-08
Spaciousness index 29-0-01 Styrene oxidation 29-P-21
Sphares, silicalite 03-P-07 Sulfides, mesoporous 1 l-P-11
Spheres, mesoporous silica 06-P-13 Sulfide pigments 22-P-19
Spheres, MFI, hollow 2 l-P-06 Sulfonation 29-P-28
Spheres, zeolite, hollow 21-P-12 Sulfonic acids, supported 08-P-lO
Spin echo double resonance 14-P-10 Sulfoxidation, thioethers 27-P-09
Spinel ceramic from zeolites 10-P-07 Sulfur effect on catalysis 26-P-06
Spiropyrane in zeolite Y 22-P-07 Sulfur guard 18-P-14
Sr exchange 05-0-01 1 l-P-18 Sulfur in refining PL-4
Sr2+ removal 05-O-01 Sulfur resistance 27-0-05
Sr, K-KFI, synthesis 02-P-21 Sulfur tolerance 27-0-04
SSZ-33 (-CON) 1 l-P-16 Sulfuric acid synthesis 29-P-25
SSZ-35, synthesis 02-P-30 Supercooling avoidance 2 l-P-09
SSZ-42 26-0-05 Supercritical adsorption, zeolites 17-P-16
SSZ-53 03-0-03 Supercritical CO2 extraction 20-0-05
SSZ-55 03-0-03 Supercritical ethanol synthesis 07-P-09
STA-6 (SAS) 05-0-03 Supercritical fluid, adsorption 17-P-05
STA-7 (SAV) 05-0-03 Support effect in DeNOx SCR 30-P-12
STA-8 05-0-03 Supported metals 29-P-13
Stabilisation in cement matrix 31-P-13 Surface modification by silanes 29-P-16
Stability of AIPO4 vs. hydration 13-P-20 Surface modification, FAU 1 l-P-17
Stability, clinoptilolite 01-O-03 Surface modification, mesoporous silica 29-P-09
Stability, functionalized MCM-41 29-0-02 Surface properties, Mo-zeolites 14-P-08
Stability, MCM-48 06-P-06 Surface reactivity 32-0-02
 429

Surface species, ethylene conversion 24-P- 10 Synthesis, GUS- 1 02-P-27

Surface structure, FAU (111 ) 16-0-02 Synthesis, IFR 03-0-04
Surface topography, SSZ-24 02-0-05 Synthesis, K,Na-EDI 03-0-05
Surfactant extraction 06-P-11 Synthesis, K,Na-FAU 03-0-05
Surfactant on clinoptilolite PL-2 Synthesis, K,Na-LTA 03-0-05
Surfactant removal, mesoporous TiO2 07-P- 12 Synthesis, KFI 02-P-21
Surfactant, adsorbed adsorbent 06-P-27 32-0-04 Synthesis, LTA 02-P-29 02-P-32
Surfactant, cationic 06-P-09 Synthesis, LTA film 20-P- 16
Surfactant, deca(oxyethylene)oleyl ether 08-0-02 Synthesis, LTA, in-situ 18-P-09
Surfactant, mixed 08-P- 12 Synthesis, LTL, alkaline earth effect 02-P-17
Surfactant, non-ionic Synthesis, layer-by-layer 2 I-P- 12
08-0-03 08-P-05 08-P-11 08-P-12 06-P-18 Synthesis, layered germanates 09-P- 12
Surfactants, triblock copolymers 08-P-07 Synthesis, M41 s 07-P-24
Surfactant-silica interaction 08-P-05 Synthesis, MCM-22 02-P-34 03-P- 13
SUZ-4, isomerisation catalyst 24-P-21 Synthesis, MCM-41 06-0-01 07-P-24
Swelled mesoporous silica 06-P-27 Synthesis, MCM-41, aging, effect of 06-P-21
Swelling agents 06-P-27 17-P-05 Synthesis, MCM-41, aluminosilicate 06-P-08
Swelling agent, amine 06-0-04 Synthesis, MCM-41, Ce 07-P-23
Swelling, MCM-48 06-P-06 Synthesis, MCM-41, Fe 06-P-28
Sylilation, MFI 10-P-09 Synthesis, MCM-41, substituted 06-P- 19 29-P-21
Synchrotron diffraction Synthesis, MCM-41, time of 06-P-21
01-O-03 09-P-09 09-P- 13 20-0-04 Synthesis, MCM-41, Zr 29-P-24
Synthesis, acidic, mesoporous silica 29-P-16 Synthesis, MCM-48 06-O-01 06-P-06 06-P-24
Synthesis, aging effect 02-P-19 02-P-21 02-P-29 Synthesis, MeAPO 05-0-03
Synthesis, AIPO4, additives 02-P-33 Synthesis mechanism 02-P- 18
Synthesis, AIPO4, intermediates 02-P-11 Synthesis, mesoporous alumina 07-P-08 07-P-I 8
Synthesis AIPO4-31, substituted 04-P-09 Synthesis, mesoporous silica
Synthesis, AI-SBA- 15 08-0-04 06-P-07 06-P-09 06-P- 15
Synthesis, AI source, effect of 02-P- 19 06-P-I 8 06-P-26 08-P-I 1 08-P-12 17-P-05
Synthesis, alternate silica and surfactant 08-P-09 Synthesis, mesoporous silica, pH effect 06-P-20
Synthesis, anatase nanocrystals 22-P- 13 Synthesis, mesoporous silica, functionalized
Synthesis, asymmetric, terminal epoxides 23-P-10 07-0-02 08-P-08
Synthesis, BEA 02-P-23 Synthesis, mesoporous silica, temperature effect
Synthesis, BEA, all-silica 02-P-35 06-P-26
Synthesis, BEA, Cr, AI 04-P-08 Synthesis, mesoporous zirconia 7-P-11
Synthesis, cancrinite 03-P- 11 Synthesis with methylamine 04-O-01
Synthesis, cation effect 03-0-05 Synthesis, MFI 02-O-01 02-P-09 02-P-15
Synthesis, clear solution 02-0-02 02-P-29 20-P-16 Synthesis, MFI, bulk-material dissolution 02-P-26
Synthesis, combinatorial methods 03-K-01 Synthesis, MFI in carbon matrix 03-0-02
03-P-12 03-P-13 03-P-16 03-P-18 06-P-25 Synthesis, MFI on cordierite 30-P-33
Synthesis, Co-MFI 04-P- 18 Synthesis, MFI, Nb 04-P- 10
Synthesis, cosurfactants 06-P- 18 Synthesis, MFI, phosphate-affected 02-P-40
Synthesis, CrAPO-5 04-P- 12 Synthesis, MFI, solid state 04-P-06
Synthesis, dry-gel conversion 03-P- 10 Synthesis, MFI, supported 20-P- 17
Synthesis, ETS-4 04-P- 16 Synthesis, MFI, Zn 04-P- 14
Synthesis, FAU 02-0-03 Synthesis, microwave
Synthesis, FAU film 20-P-16 0 l-P- 14 02-0-02 02-P-08 03-P- 15
Synthesis, Fe-MFI 04-0-03 Synthesis, MIL-34 05-P- 19
Synthesis, Fe-MFI, fluoride 04-P-17 Synthesis, models 02-P-24
Synthesis, Fe-MOR 04-P- 15 Synthesis, MOR 02-P-39 03-P-19
Synthesis, Fe-MTW 04-0-03 Synthesis, MOR from magadiite 02-P-36
Synthesis, FER 03-P-09 Synthesis, MOR, Zn 04-P- 15
Synthesis, Fe-TON 04-0-03 Synthesis, MSU-X, two-step 08-P-05
Synthesis, fluoride medium 05-0-02 05-P-08 Synthesis, MWW 02-P-42
Synthesis, FOS-5 09-0-03 Synthesis, nanocrystalline FA U 02-P- 14
Synthesis by gel impregnation 04-P-07 , Synthesis, non-aqueous media 05-P-08 05-P-11
Synthesis gel, thermal treatment 02-P-32 Synthesis, organozeolite 2 I-P- 16
430

Synthesis, oxide mesostructures 07-0-05 Template (for mesoporous materials s e e also

Synthesis, parallel 03-P- 12 surfactant) 02-P-20
Synthesis parameters 02-0-02 02-P-08 02-P-20 Template, alkali cations 03-P-18
Synthesis, particulate precursors 02-O-01 Templates, AIPO4 synthesis 02-P-33
Synthesis, pH effect 06-P-28 Template, amine 03-0-03 05-0-02 07-0-05
Synthesis, phosphates, substituted 05-P-11 Template, butylamine 05-P- 17
Synthesis, phosphates, Ti 05-0-02 Template, chiral 05-0-04
Synthesis, phosphates, W 05-P-20 Template, colloidal 07-P-22
Synthesis, porosils 02-P-41 Template, concentration effect 02-P-41
Synthesis, rare earth silicates 05-P- 12 Template cyclobutylamine 05-P- 19
Synthesis, SAPO- 11 02-P- 13 Template, DABCO-based 02-P-27
Synthesis, SBA-15 08-0-04 08-P-07 Template degradation 02-P-22 11-P-27 20-P-38
Synthesis, seeding, effect of 02-P-21 Template degradation, MFI 14-P-38
Synthesis, silica source, effect of 02-P-19 Template, diethylenetriamine 02-P-41
Synthesis, silicalite on resin 03-P-07 Template, dodecylamine 29-P-08
Synthesis, silicalite, clear solution 02-P-16 Template, ethylenediamine 05-P-08 09-P-08
Synthesis, single crystals 03-P-08 Template, ex nitriles 03-0-03
Synthesis, SOD, solid state 02-P-25 Template extraction 06-P-11
Synthesis, sol-gel 0 I-P- 14 07-P-07 Template, hexamethylenediamine
Synthesis, solvothermal 05-P-09 02-P-22 02-P-42 16-P-16
Synthesis, SSZ-35 02-P-30 Template, N-methyl hexahydrojulodinium 02-P-30
Synthesis, stannosilicates 05-P- 13 Template modelling 16-P- 16
Synthesis, static 02-P-34 Templates, multiple 04-P- 12
Synthesis, stirring, effect of 02-P- 19 Template, nanoemulsion 06-P-27
Synthesis, zeolites, supported 2 l-P- 12 Template, nitrate 02-P-07
Synthesis, temperature dependence Template, non-ionic surfactant 08-0-03
02-P-34 03-P-12 Template ordering 22-0-01
Synthesis, TON 02-P-22 02-P- 10 04-0-04 Template, organic acids 04-P- 12
Synthesis, two-stage 02-0-03 02-P-34 Template, organic, choice 16-P-07
Synthesis, ultrasound 06-P- 14 Template removal, gallophosphates 16-P- 15
Synthesis, vanadosilicates 04-0-05 Template removal, MCM-41 29-P- 18
Synthesis, variable-temperature 20-P-07 Template removal, ZSM-5 13-P- 10
Synthesis, zeolites from bentonite 03-P-06 Template, silica 07-P-22
Synthesis, zeolites from fly ash 18-P- 10 Template, tetrahydrofuran 03-P-09
Synthesis, zeolites from MCM-41 07-P- 10 template-trivalent interaction 13-O-01
Synthesis, zeolites, modelling 02-P-22 15-P-06 TEOS, CVD on MFI 10-P-09
Synthesis, zeolites, substituted 05-P-I 1 Terpene valorisation 23-P-29
Synthesis, ZSM-34 02-P-22 Tert-butylation of biphenyl 25-P-07
Tetraalkylammonium degradation 20-P-38
2,4-di-Tetrabutylphenol, reagent 25-P- 12
Tetrachloethylene adsorption, MFI 17-O-02
Tetrafluoromethane reagent 1 l-P- 17
Ta-MFI 01-P-14 Tetrahydrofuran adsorption 12-P-08
Tantalum-pillared magadiite 23-P-18 Tetrahydrofuran template 03-P-09
Tartrate complexes 29-P-08 Tetrapropylammonium cation 14-P-29
Tb[(CIBOEP)4P](acac) encapsulation 22-P-09 Texture SBA- 15 08-0-03
TBHP in epoxidation 29-P-30 TG/DTA-MASS fluorinated FAU 1 l-P- 17
TEM 23-0-05 TGA 12-P-16 20-P-15
TEM, 3 D 14-0-01 Therapy, adjuvants 32-P-09
TEM Pt,Ni-USY 14-P-36 Thermal activation, clinoptilolite 3 l-P-09
TEM, overgrowth 02-P-06 Thermal analysis, ETS-4 04-P- 16
TEM-EDX 26-P-15 Thermal behavior, clinoptilolite 11-P-26
Temperature effect on ion exchange 1 l-P-18 Thermal desorption 17-P-09
Temperature effect on MCM-41 synthesis 06-P-26 Thermal stability, FAU 1 l-P-13
Temperature effect, FAU surface 16-0-02 Thermal stability, MOR 12-P-05
Temperature effect on synthesis 02-P-21 Thermal stability, zeolites 10-P-07
Thermal treatment, MFI 14-P-38
 431

Thermochemical storage of heat 31-O-04 Transformation, hydrothermal 02-P-36

Thioether sulfoxidation 27-P-09 Transformation, mesostructural 06-P-26
Thiol-functionalized SBA-2 07-P- 17 Transient uptake measurement 19-P-08
Thiophene cracking, modelling 15-P-22 Transition energies in UV-visible 14-O-03
Thiophene HDS 26-P-17 26-P-22 Transition metal cations
Ti (IV) Salen complex, chiral 23-P-11 04-P-11 15-P-I 1 15-P-23 27-P-08
Ti in AIPO4-31 14-P- 13 Transition metal cation-modified silica 24-P-07
Ti-BEA 27-P-11 27-P-17 Transition metal-exchanged MCM-22 30-P- 13
Ti-BEA, epoxidation catalyst 11-P-29 Transition metal halides in porosils 10-O-03
Ti-BEA, silylated 11-P-29 Transition metal incorporation 06-P- 12
Ti-ETS-10 11-O-04 27-P-15 Transition metal incorporation, mesoporous silica
Ti, framework, octahedral 1 I-P- 15 08-0-02
Ti-HMS 23-P-14 29-P-08 Transition metals in MCM-41 29-P-21
Ti-HMS deNOx catalyst 30-P-24 Transition metal mixed oxides 07-P-15
Ti-HMS, local structure 30-P-24 Transition metal oxide mesostructures 07-0-05
Ti-MCM-41 07-P-14 24-P-12 29-P-30 Transition metal oxides in zeolites, local structure
Ti-MCM-41 oxidation catalyst 29-P- 18 30-K-01
Ti-MCM-48 29-P-30 Transition metal oxides, supported catalysts 22-P-08
Ti-MFI (see TS-1) Transition metal-zeolite models 15-P- 13
Ti-MWW 27-O-01 Transition state modelling 15-P- 16 15-P- 19
TiO2, in MCM-41 22-P-06 Transition state selectivity 23-P-20
TiO2, mesoporous 07-0-05 07-P-12 Tribloc copolymer surfactants
Ti-peroxo species 15-P- 18 08-0-03 08-P-07 08-P-12 21-O-03
Ti phosphates, synthesis 05-0-02 1,2,4-trichlorobenzene 23-P- 16
Ti-zeolites 27-P- 17 Trichloroethylene adsorption 18-P- 15
Ti sites in TS- 1 14-P- 14 14-P-30 Trichloroethylene adsorption, MFI 17-0-02
Tiling theory 16-P- 13 Triethylmethylammonium in MFI 16-P-06
TI-X, exchange with In 09-P-10 1,3,5-Triisopropylbenzene conversion, silylated
TMA-SOD 02-P-25 MFI
Toluene adsorption 18-P- 15 11-O-02
Toluene, adsorption NMR, Na-X 13-P- 16 1,3,5-Trisopropyibenzene cracking 29-P-07
Toluene conversion, silylated MFI 11-O-02 trimetallic catalysts 30-P-22
Toluene disproportionation Trimethylamine, template 09-0-03
10-P-09 11-P-24 24-P-06 29-P-26 Trimethyl benzene, swelling agent 06-P-27
Toluene hydrogenation 27-0-05 1,2,4-Trimethylbenzene conversion, silylated MFI
Toluene isomerisation, modelling 15-P-20 11-O-02
Toluene methylation model 15-O-03 Trimethylbenzene transalkylation 25-P- 10
Toluene-Na-X interaction 13-P- 16 Trimethylbenzene-phenol transalkylation 25-0-04
Toluene nitration 13-P-22 Trimethylpentane synthesis 24-P-20
Toluene oxidation 30-P-23 Trimethylsilylcyanation, asymmetric 23-P-11
Toluene total oxidation 30-P-26 Tris (acetylacetonato)Cr 04-P-08
TON catalyst 26-P- 10 Trivalent distribution in MCM-22 14-P-21
TON, Fe 04-0-04 Trivalent distribution in MFI 13-0-02
TON, Fe, synthesis 04-0-03 Trivalent-template interaction 13-O-01
TON synthesis 02-P-22 04-0-04 TS-1 01-P-14 ll-P-15 27-P-11 27-P-17
Toxicity, clinoptilolite 32-P- 12 TS- 1 catalyst 15-P- 18
Toxicity, mineral dust 32-0-02 TS-1 catalyst, effect of AI 27-0-02
TPD (temperature-programmed desorption) 10-O-01 TS-1, crystal morphology 06-P-25
12-P-08 13-P-10 13-P-21 26-P-22 29-P-19 TS- 1, framework vibrations 14-P-34
TPD diazines/FAU 12-O-03 TS- 1, supported catalyst 24-P- 14
TPD NH3 12-P-17 13-P-10 29-P-14 30-P-18 TS- 1 synthesis 14-P- 14
TPD-MS 12-P-16 TS- 1 synthesis, modelling 16-P- 16
TPR 07-0-04 10-O-01 10-P-06 30-P-23 TS- 1, Ti sites 14-P- 14 14-P-30
Trace elements in crop growth 31-O-01 TS- 1, water adsorption 14-P-34
Transalkylation 25-0-03 29-0-01 Tschernichite (BEA) 0 l-K-01
Transalkylation, phenol/trimethylbenzene 25-0-04 Tuff, CHA, PHI-rich 31-O-01
Transalkylation, trimethylbenzene/toluene 25-P-10
432

Tuff, clinoptilolite-rich 0 l-P-09 01 -P- 12 Vibrational spectroscopy, MOR 16-P-11

22-P-12 22-P-15 31-P-11 32-P-10 32-P-11 VOC removal 18-P-15 30-0-05
Tuff, FAU-rich 3 I-P-13 VOC removal, MCM-41 adsorbent 18-P-12
Tuff, montmorillonite-rich 3 I-P-11 VOC deep oxidation 30-P-I 8 30-P-23
Tuff, zeolite-rich 0 I-P- 13 32-0-04 Volcano-sedimentary succession 01-O-02
Tungsten carbide/FSM- 16 29-P-29 Volumetric method, static 17-P-08
Tungstophosphate, Co 05-P-20 VPI-5 adsorbent 17-P-17
Tunneling, proton, FAU 16-O-04 VPI-5 story PL-3
Two-step synthesis, MSU-X 08-P-05 VSB-1 catalytic properties 22-0-03

Ukraina, natural zeolites 3 l-P-08 3 I-P- 10 W,Ni/FAU hydrocracking catalyst 1 l-P-08

Ultramarine, encapsulated 22-P- 19 W-based hydrotreatment catalyst 26-P-08
Ultrasound monitoring, crystallisation 02-P-37 Wall properties, mesoporous silica 08-P-14
Ultrasounds in synthesis 06-P- 14 Wall structure, mesoporous silica 06-P-05
Unit cell constant, FAU 13-P-15 Wall structure, SBA- 15 08-0-03
Unsaturated alcohol 23-P-33 Washing, effect on MCM-41 06-P-28
Unsaturated aldehydes 23-P-33 Waste streams, nuclear industry 05-O-01
Unsaturated ketone reduction 23-P-33 Wastewater treatment 3 l-P-14 31-P-15
USY (see also FAU) Wastewater, agroindustrial 31-0-03
USY hydrotreatment catalyst 26-P-08 Wastewater, Cr removal 31-P-13
USY alkylation catalyst 25-P-09 Wastewater, nitrogen industry 31-P-10
USY polymer degradation catalyst 30-P-17 Wastewater, Pb removal 3 I-P-06
USY, Pt,Ni isomerisation catalyst 14-P-36 Wastewater, petroleum refineries 30-P-20
USY, treated, isomerisation catalyst 11-P-23 Water adsorption models 16-O-03
USY, treated, cracking catalyst 11-P-23 Water adsorption, TS- 1 14-P-34
UTD-1 (DON) 1l-P-16 Water adsorption, AIMepO 09-P- 14
UTD- 1 host 10-0-03 Water clusters in FAU 15-0-04
UV Raman spectroscopy 12-P-07 14-P-33 Water desorption from LTA 17-P-09
UV-Visible spectroscopy Water desorption, modified MCM-41 17-P-13
04-P-I 1 04-P-18 10-P-08 lI-P-15 Water diffusion, simulation 15-P-28
1l-P-20 13-0-02 14-P-14 14-P-18 14-P-20 Water, drinking, deammoniation 3 I-P-09
14-P-26 14-P-35 22-P-21 30-P-31 32-P-07 Water effect on adsorption
Vis-UV spectroscopy 16-O-03 19-P-06 32-P-08
UV-Visible spectroscopy, models 14-O-03 Water, effect on NOx storage 30-0-04
UV-Visible-NIR 14-P-30 Water rolling 15-P-28
Water storage 31-O-04
Water treatment, fisheries 31 -P- 12
V WS2 HDS catalyst 26-P- 17

V-HMS 14-P-20
V-MCM-41 oxidation catalyst 29-P- 18 X
V-MCM-48 06-P-06 07-P-06
V-SBA- 15, photocatalyst 24-P-07 XAFS measurement 14-P-20 14-P-26 28-P-07
V-Silicalites 14-P-20 XAFS, Fe ZSM-5 12-O-02
Vanadium organophosphates 22-0-02 XANES 14-P-08 14-P-39
Vanadosilicate, large pore 04-0-05 129Xe-NMR, chemical shift 14-P-27
Vanadosilicates, synthesis 04-0-05 129Xe NMR in diffusion studies 19-P-09
Vanadyl/BEA, spectroscopic study 14-P-35 129Xe NMR, MCM-48 06-P- 16
VAPO 14-P-33 131Xe-NMR, chemical shift 14-P-27
VAPO-5 14-P-33 Xe-SF6 diffusion in BOG, modelling 16-O-05
VAPO-11, synthesis 03-P-16 XPS 04-P-18 09-P-10 26-P-14 30-P-26
VAPO-41, synthesis 03-P-16 XPS, Co 04-P- 18
VAPSO-5 14-P-33 XPS, Cu in MFI 30-P-21
 433

X-ray diffraction 05-0-04 Zorite 1 l-P-15

X-ray diffraction, Ag-clinoptilolite 01-P-15 Zr/AI-MCM-41 16-P-19
X-ray diffraction, chloroalkene adsorption 17-P-11 Zr/AI-MCM-41, synthesis 29-P-24
X-ray diffraction, grazing incidence 20-0-04 Zr-ETS-4 04-P- 16
X-ray diffraction, mesoporous silica 06-P-05 Zr-HMS, hydrotreatment catalyst 26-P-22
X-ray diffraction, temperature resolved 09-P-13 Zr-HMS, support 26-P-22
X-ray powder refinement 09-P-07 Zr-MCM-41 as Ni support 23-P-28
X-ray scattering, mesoporous silica 06-P-05 Zr-MCM-41 oxidation catalyst 29-P-18
Xylene adsorption models 16-O-03 ZrO2-CuO-ZnO 24-P-26
m-Xylene conversion 26-P-20 ZrO2 derivatives 07-P-09
Xylene isomerisation 12-P-14 28-P-06 ZrO2 nanoparticles in SBA-15 29-P-17
Xylene isomerisation, modelling 15-P-20 ZrO2 mesoporous 07-P-090 7-P-I 1 07-P-20
Xylene isomerisation, NMR 12-0-01 ZrO2/Na-Y 30-P-08
Xylene production 25-P-10 ZrO2, Ni fuel cell catalyst 07-P-20
Xylene separation 18-P-08 ZrO2/SO42" 29-P-07
Xylene separation, affected by water 16-O-03 ZSM-5, s e e MFI
ZSM-12, s e e MTW
ZSM-20 (FAU-EMT intergrowth) 13-P-21
Z ZSM-22, s e e TON
ZSM-25, synthesis 02-P-10
Zearalenone, adsorption 32-0-04 ZSM-34 (ERI/OFF), synthesis 02-P-22
Zeolite A, s e e LTA ZSM-35 (FER) catalyst 26-P-10
Zeolite adsorbents, from fly ash 18-P- 10 ZSM-48, synthesis 02-P-41
Zeolite Beta, s e e BEA
Zeolite F (EDI) synthesis, role of K and Na 03-0-05
Zeolite modification 3 l-P-08
Zeolite P (GIS) 3 I-P-05
Zeolite X, s e e FAU
Zeolite Y, s e e FAU
Zeolitisation, bentonite in sea water 03-P-06
Zeolitisation, diatoms 2 l-P-07
Zeolitisation of volcanic glass 0 I-P-I 3
Zeolitisation, volcano-sedimentary 01-O-02
Zeoponic fertilizer delivery 31-O-02
ZK-21, Ca form (LTA) 18-P-13
ZK-21, Na,TMA (LTA) 18-P-13
ZK-5, rare earth I l-P-19
ZK-5, synthesis 02-P-21
Zn-alumina, mesoporous 07-P- 16
ZnAPO-31 14-P- 13
ZnAPO-37 29-P-23
Zn-FAU 10-P-05 17-P-14
Zn-LTA 10-P-05
Zn-MFI 24-P-27
Zn-MFI, sulfide host 29-P-05
Zn-MFI, synthesis 04-P- 14
Zn-MOR 04-P-15 13-P-32
Zn,Ni-MFI, aromatisation catalyst
24-P-30 24-P-31 28-0-02
Zn phosphates 05-0-04
Zn phosphate catalysts 29-P-23
Zn spinel from zeolites 10-P-07
ZnO clusters 10-P-05
ZnO-CuO-ZrO2 24-P-26
Zn-Pt/zeolite X 29-P- 15
Zn-zeolites, oxidation catalyst 27-P-08
This Page Intentionally Left Blank
 435

STUDIES IN SURFACE SClENCEAND CATALYSIS

Advisory Editors:
B. Delmon, Universitd Catholique de Louvain, Louvain-la-Neuve, Belgium
J.T.Yates, University of Pittsburgh, Pittsburgh, PA, U.S.A.

Volume 1 Preparation of Catalysts I.Scientific Basesfor the Preparation of Heterogeneous

Catalysts. Proceedings of the First International Symposium, Brussels,
October 14-17,1975
edited by B. Delmon, RA. Jacobs and G. Poncelet
Volume 2 The Control of the Reactivity of Solids. A Critical Survey of the Factors that
Influence the Reactivity of Solids, with Special Emphasis on the Control of the
Chemical Processes in Relation to Practical Applications
by V.V. Boldyrev, M. Bulens and B. Delmon
Volume 3 Preparation of Catalysts II. Scientific Basesfor the Preparation of Heterogeneous
Catalysts. Proceedingsofthe Second International Symposium, Louvain-la-Neuve,
September 4-7, 1978
edited by B. Delmon, R Grange, R Jacobs and G. Poncelet
Volume 4 Growth and Properties of Metal Clusters. Applications to Catalysis and the
Photographic Process. Proceedings of the 32nd International Meeting of the
Soci6td de Chimie Physique, Villeurbanne, September 24-28,1979
edited by J. Bourdon
Volume 5 Catalysis by Zeolites. Proceedings of an International Symposium, Ecully (Lyon),
September 9-11,1980
edited by B. Imelik, C. Neccache,Y. BenTaadt, J.C.Veddne, G. Coududer and
H. Praliaud
Volume 6 Catalyst Deactivation. Proceedings of an International Symposium, Antwerp,
October 13-15,1980
edited by B. Delmon and G.E Froment
Volume 7 New Hodzons in Catalysis. Proceedings of the 7th International Congress on
Catalysis,Tokyo, June 30-July4, 1980. PartsA and B
edited by 1".Seiyama and K.Tanabe
Volume 8 Catalysis by Supported Complexes
by Yu.I.Yermakov, B.N. Kuznetsov andV.A. Zakharov
Volume 9 Physics of Solid Surfaces. Proceedings of a Symposium, Bechy~e,
September 29-October 3,1980
edited by M. L6zni~,ka
Volume 10 Adsorption at the Gas-Solid and Liquid-Solid Interface. Proceedings of an
International Symposium, Aix-en-Provence, September 21-23,1981
edited by J. Rouquerol and K.S.W. Sing
Volume 11 Metal-Support and Metal-Additive Effects in Catalysis. Proceedings of an
International Symposium, Ecully (Lyon), September 14-16,1982
edited by B. Imelik, C. Naccache, G. Coududer, H. Preliaud, R Medaudeau,
R Gallezot, G.A. Martin and J.C.Veddne
Volume 12 Metal Microstructures in Zeolites. Preparation - Properties-Applications.
Proceedings of aWorkshop, Bremen, September 22-24, 1982
edited by RA. Jacobs, N.I. Jaeger, R Jid= and G. Schulz-Ekloff
Volume 13 Adsorption on Metal Surfaces. An Integrated Approach
edited by J. B6nard
Volume 14 Vibrations at Surfaces. Proceedings of theThird International Conference,
Asilomar, CA, September 1-4,1982
edited by C.R. Brundle and H. Morawitz
Volume 15 Heterogeneous Catalytic Reactions Involving Molecular Oxygen
by G.I. Golodets
436

Volume 16 Preparation of Catalysts Ul. Scientific Basesfor the Preparation of Heterogeneous

Catalysts. Proceedings oftheThird International Symposium, Louvain-la-Neuve,
September 6-9, 1982
edited by G. Poncelet, R Grange and RA. Jacobs
Volume 17 Spillover of Adsorbed Species. Proceedings of an International Symposium,
Lyon-Villeurbanne, September 12-16,1983
edited by G.M. Pajonk, S.J.Teichner and J.E. Germain
Volume 18 Structure and Reactivity of Modified Zeolites. Proceedings of an International
Conference, Prague, July 9-13,1984
edited by RA. Jacobs, N.I. Jaeger, R Ji~,V.B. Kazansky and G. Schulz-Ekloff
Volume 19 Catalysis on the Energy Scene. Proceedings of the 9th Canadian Symposium
on Catalysis, Quebec, RQ., September 30-October 3,1984
edited by S. Kaliaguine andA. Mahay
Volume 20 Catalysis by Acids and Bases. Proceedings of an International Symposium,
Villeurbanne (Lyon), September 25-27,1984
edited by B. Imelik, C. Naccache, G. Coud.uder,Y. BenTaadt and J.C.Veddne
Volume 21 Adsorption and Catalysis on Oxide Surfaces. Proceedings of a Symposium,
Uxbridge, June 28-29,1984
edited by M. Che and G.C. Bond
Volume 22 Unsteady Processes in Catalytic Reactors
by Yu.Sh. Matros
Volume 23 Physics of Solid Surfaces 1984
edited by J. Koukal
Volume 24 Zeolites: Synthesis, Structure,Technology and Application. Proceedings of an
International Symposium, Portoroi-Portorose, September 3-8,1984
edited by B. Dr~aj, S. Ho(:evar and S. Pejovnik
Volume 25 Catalytic Polymerization of Olefins. Proceedings of the International Symposium
on Future Aspects of Olefin Polymerization,Tokyo, July 4-6,1985
edited by T. Keii and K. Soga
Volume 26 Vibrations at Surfaces 1985. Proceedings of the Fourth International Conference,
Bowness-on-Windermere, September 15-19,1985
edited by D.A. King, N.V. Richardson and S. Holloway
Volume 27 Catalytic Hydrogenation
edited by L. Cerven~
Volume 28 New Developments in Zeolite Science andTechnology. Proceedings of the
7th International Zeolite Conference,Tokyo, August 17-22,1986
edited by Y. Murakami, A. lijima and J.W.Ward
Volume 29 Metal Clusters in Catalysis
edited by B.C. Gates, L. Guczi and H. Kn6zinger
Volume 30 Catalysis andAutomotive Pollution Control. Proceedings of the First
International Symposium, Brussels, September 8-11,1986
edited by A. Crucq andA. Frennet
Volume 31 Preparation of Catalysts IV. Scientific Basesfor the Preparation of Heterogeneous
Catalysts. Proceedings of the Fourth International Symposium, Louvain-la-
Neuve, September 1-4,1986
edited by B. Delmon, R Grange, RA. Jacobs and G. Poncelet
Volume 32 Thin Metal Films and Gas Chemisorption
edited by RWissmann
Volume 33 Synthesis of High-silicaAluminosilicate Zeolites
edited by RA. Jacobs and J.A. Martens
Volume 34 Catalyst Deactivation 1987. Proceedings of the 4th International Symposium,
Antwerp, September 29-October 1,1987
edited by B. Delmon and G.E Froment
Volume 35 Keynotes in Energy-Related Catalysis
edited by S. Kaliaguine
 437

Volume 36 Methane Conversion. Proceedings of a Symposium on the Production of Fuels and

Chemicals from Natural Gas,Auckland, April 27-30, 1987
edited by D.M. Bibby, C.D. Chang, R.E Howe and S.Yurchak
Volume 37 Innovation in Zeolite Materials Science. Proceedings of an International
Symposium, Nieuwpoort, September 13-17,1987
edited by RJ. Grobet, W.J. Mortier, E.EVansant and G. Schulz-Ekloff
Volume 38 Catalysis 1987.Proceedings ofthe 10th North American Meeting ofthe Catalysis
Society, San Diego, CA, May 17-22,1987
edited by J.W.Ward
Volume 39 Characterization of Porous Solids. Proceedings of the IUPAC Symposium
(COPS I), Bad Soden a.Ts.,Apri126-29,1987
edited by K.K. Unger, J. Rouquerol, K.S.W. Sing and H. Kral
Volume 40 Physics of Solid Surfaces 1987. Proceedings of the Fourth Symposium on
Surface Physics, Bechyne Castle, September 7-11,1987
edited by J. Koukal
Volume 41 Heterogeneous Catalysis and Fine Chemicals. Proceedings of an International
Symposium, Poitiers, March 15-17,1988
edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier and
G. P6rot
Volume 42 Laboratory Studies of Heterogeneous Catalytic Processes
by E.G. Chdstoffel, revised and edited by Z. Pa61
Volume 43 Catalytic Processes under Unsteady-State Conditions
by Yu. Sh. Matros
Volume 44 Successful Design of Catalysts. Future Requirements and Development.
Proceedings 0ftheWorldwide Catalysis Seminars, July, 1988, on the Occasion of
the 30th Anniversary of the Catalysis Society of Japan
edited by T. Inui
Volume 45 Transition Metal Oxides. Surface Chemistry and Catalysis
by H.H. Kung
Volume 46 Zeolites as Catalysts, Sorbents and Detergent Builders. Applications and
Innovations. Proceedings of an International Symposium,W~irzburg,
September 4--8,1988
edited by H.G. Karge and J.Weitkamp
Volume 47 Photochemistry on Solid Surfaces
edited by M.Anpo andT. Matsuura
Volume 48 Structure and Reactivity of Surfaces. Proceedings of a European Conference,
Trieste, September 13-16,1988
edited by C. Morterra,A. Zecchina and G. Costa
Volume 49 Zeolites: Facts, Figures, Future. Proceedings of the 8th International Zeolite
Conference, Amsterdam, July 10-14,1989. Parts A and B
edited by P.A.Jacobs and R.A. van Santen
Volume 50 Hydrotreating Catalysts. Preparation, Characterization and Performance.
Proceedings of the Annual International AIChE Meeting,Washington, DC,
November 27-December 2,1988
edited by M.L. Occelli and R.G.Anthony
Volume 51 New Solid Acids and Bases.Their Catalytic Properties
by K.Tanabe, M. Misono,Y. Ono and H. Hattori
Volume 52 RecentAdvances in Zeolite Science. Proceedings of the 1989 Meeting of the
British Zeolite Association, Cambridge, April 17-19,1989
edited by J. Klinowsky and RJ. Barrie
Volume 53 Catalyst in Petroleum Refining 1989. Proceedings of the First International
Conference on Catalysts in Petroleum Refining, Kuwait, March 5-8,1989
edited by D.L.Tdmm,S.Akashah, M.Absi-Halabi andA. Bishara
Volume 54 Future Opportunities in Catalytic and Separation Technology
edited by M. Misono, Y. Moro-oka and S. Kimura
438

Volume 55 New Developments in Selective Oxidation. Proceedings of an International

Symposium, Rimini, Italy, September 18-22,1989
edited by G. Centi and I-.Tdfiro
Volume 56 Olefin Polymerization Catalysts. Proceedings of the International Symposium
on Recent Developments in Olefin Polymerization Catalysts,Tokyo,
October 23-25,1989
edited by T. Keii and K. Soga
Volume 57A SpectroscopicAnalysis of Heterogeneous Catalysts. Part A: Methods of
SurfaceAnalysis
edited by J.L.G. Fiewo
Volume 57B SpectroscopicAnalysis of Heterogeneous Catalysts. Part B: Chemisorption of
Probe Molecules
edited by J.L.G. Fierro
Volume 58 Introduction to Zeolite Science and Practice
edited by H. van Bekkum, E.M. Flanigen and J.C. Jansen
Volume 59 Heterogeneous Catalysis and Fine C.hemicals II. Proceedings of the 2nd
International Symposium, Poitiers, October 2-6,1990
edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, G. P6rot, R. Maurel
and C. Montassier
Volume 60 Chemistry of Microporous Crystals. Proceedings of the International Symposium
on Chemistry of Microporous Crystals,Tokyo, June 26-29,1990
edited by T. Inui, S. Namba andT.Tatsumi
Volume 61 Natural Gas Conversion. Proceedings of the Symposium on Natural Gas
Conversion, Oslo, August 12-17,1990
edited by A. Holmen, K.-J. Jens and S. Kolboe
Volume 62 Characterization of Porous Solidsll. Proceedings of the IUPAC Symposium
(COPS II),Alicante, May 6-9,1990
edited by F.Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing and K.K. Unger
Volume 63 Preparation of CatalystsV. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Fifth International Symposium, Louvain-la-Neuve,
September 3-6,1990
edited by G. Poncelet, P.A.Jacobs, P.Grange and B. Delmon
Volume 64 NewTrends in COActivation
edited by L. Guczi
Volume 65 Catalysis and Adsorption by Zeolites. Proceedings of ZEOCAT 90, Leipzig,
August 20-23,1990
edited by G. ~hlmann, H. Pfeifer and R. Fdcke
Volume 66 Dioxygen Activation and Homogeneous Catalytic Oxidation. Proceedings of the
Fourth International Symposium on Dioxygen Activation and Homogeneous
Catalytic Oxidation, Balatonf(ired, September 10-14,1990
edited by L.I. Sim~ndi
Volume 67 Structure-Activity and Selectivity Relationships in Heterogeneous Catalysis.
Proceedings of the ACS Symposium on Structure-Activity Relationships in
Heterogeneous Catalysis, Boston, MA, Apri122-27, 1990
edited by R.K. GrasseUi andA.W. Sleight
Volume 68 Catalyst Deactivation 1991. Proceedings of the Fifth International Symposium,
Evanston, IL, June 24-26,1991
edited by C.H. Bartholomew and J.B. Butt
Volume 69 Zeolite Chemistry and Catalysis. Proceedings of an International Symposium,
Prague, Czechoslovakia, September 8-13, 1991
edited by RA. Jacobs, N.I. Jaeger, L. Kubelkov6 and B.Wichtedov6
Volume 70 Poisoning and Promotion in Catalysis based on Surface Science Concepts and
Experiments
by M. Kiskinova
 439

Volume 71 Catalysis and Automotive Pollution Control II. Proceedings of the 2nd
International Symposium (CAPoC 2), Brussels, Belgium, September 10-13,1990
edited by A. Crucq
Volume 72 New Developments in Selective Oxidation by Heterogeneous Catalysis.
Proceedings of the 3rd European Workshop Meeting on New Developments in
Selective Oxidation by Heterogeneous Catalysis, Louvain-la-Neuve, Belgium,
April 8-10,1991
edited by R Ruiz and B. Delmon
Volume 73 Progress in Catalysis. Proceedings of the 12th Canadian Symposium on Catalysis,
Banff, Alberta, Canada, May 25-28, 1992
edited by K.J. Smith and E.C.Sanford
Volume 74 Angle-Resolved Photoemission.Theory and CurrentApplications
edited by S.D. Kevan
Volume 75 New Frontiers in Catalysis, PartsA-C. Proceedings of the 10th International
Congress on Catalysis, Budapest, Hungary, 19-24 July, 1992
edited by L. Guczi, F.Solymosi a~d RT6t6nyi
Volume 76 fluid Catalytic Cracking: Science andTechnology
edited by J.S. Magee and M.M. Mitchell, Jr.
Volume 77 NewAspects of Spillover Effect in Catalysis. For Development of HighlyActive
Catalysts. Proceedings of theThird International Conference on Spillover, Kyoto,
Japan,August 17-20,1993
edited by T. Inui, K. Fujimoto,T. Uchijima and M. Masai
Volume 78 Heterogeneous Catalysis and Fine Chemicals III.
Proceedings of the 3rd International Symposium, Poitiers, April 5 - 8,1993
edited by M. Guisnet, J. Barbier, J. Barrault, C. Bouchoule, D. Duprez,
G. P6rot and C. Montassier
Volume 79 Catalysis: An Integrated Approach to Homogeneous, Heterogeneous and
Industrial Catalysis
edited by J.A. Moulijn, RW.N.M. van Leeuwen and R.A. van Santen
Volume 80 Fundament=_!s of Adsorption. Proceedings of the Fourth International Conference
on Fundamentals ofAdsorption, Kyoto, Japan, May 17-22,1992
edited by M. Suzuki
Volume81 Natural Gas Conversion ~.. Proceedings of theThird Natural Gas Conversion
Symposium, Sydney, July 4-9,1993
edited by H.E. Curry-Hyde and R.F.Howe
Volume 82 New Developments in Selective Oxidation II. Proceedings of the SecondWorld
Congress and Fourth EuropeanWorkshop Meeting, Benalmddena, Spain,
September 20-24,1993
edited by V. Cort6s Corber6n and S.Vic Bell6n
Volume 83 Zeolites and Microporous Crystals. Proceedings of the International Symposium
on Zeolites and Microporous Crystals, Nagoya, Japan,August 22-25,1993
edited byT. Hattod andT.Yashima
Volume 84 Zeolites and Related Microporous Materials: State of theArt 1994.
Proceedings of the 10th International Zeolite Conference,
Garmisch-Partenkirchen, Germany, July 17-22,1994
edited by J.Weitkamp, H.G. Karge, H. Pfeifer andW. H61dedch
Volume 85 Advanced Zeolite Science and Applications
edited by J.C. Jansen, M. St6cker, H.G. Karge and J.Weitkamp
Volume 86 Oscillating Heterogeneous Catalytic Systems
by M.M. Slin'ko and N.I. Jaeger
Volume 87 Characterization of Porous Solids Ul. Proceedings of the IUPAC Symposium
(COPS III), Marseille, France, May 9-12,1993
edited by J.Rouquerol, F.Rodriguez-Reinoso, K.S.W. Sing and K.K. Unger
440

Volume 88 Catalyst Deactivation 1994. Proceedings of the 6th International Symposium,

Ostend, Belgium, October 3-5,1994
edited by B. Delmon and G.E Froment
Volume89 Catalyst Design forTailor-made Polyolefins. Proceedings of the International
Symposium on Catalyst Design forTailor-made Polyolefins, Kanazawa,
Japan, March 10-12,1994
edited by K. Soga and M.Terano
Volume 90 Acid-Base Catalysis II. Proceedings of the International Symposium on
Acid-Base Catalysis II, Sapporo, Japan, December 2-4,1993
edited by H. Hattori, M. Misono andY. Ono
Volume91 Preparation of CatalystsVI. Scientific Bases for the Preparation of
Heterogeneous Catalysts. Proceedings of the Sixth International Symposium,
Louvain-La-Neuve, September 5-8,1994
edited by G. Poncelet, J. Martens, B. Delmon, RA. Jacobs and R Grange
Volume 92 Science andTechnology in Catalysis 1994. Proceedings of the SecondTokyo
Conference on Advanced Catalytic Science andTechnology, Tokyo,
August 21-26,1994
edited by Y. Izumi, H.Arai and M. Iwamoto
Volume 93 Charactedzation and Chemical Modification of the Silica Surface
by E.EVansant, RVan DerVoort and K.C.Vrancken
Volume 94 Catalysis by Microporous Matedals. Proceedings of ZEOCAT'95, Szombathely,
Hungary, July 9-13,1995
edited by H.K. Beyer, H.G.Karge, I. Kiricsi and J.B. Nagy
Volume95 Catalysis by Metals andAIIoys
by V. Ponec and G.C. Bond
Volume 96 Catalysis and Automotive Pollution Control III. Proceedings of
theThird International Symposium (CAPoC3), Brussels, Belgium,
April 20-22,1994
edited by A. Frennet and J.-M. Bastin
Volume97 Zeolites:A RefinedTool for Designing Catalytic Sites. Proceedings of
the International Symposium, Qu6bec, Canada, October 15-20,1995
edited by L. Bonneviot and S. Kaliaguine
Volume 98 Zeolite Science 1994: Recent Progress and Discussions. Supplementary Materials
to the 10th International Zeolite Conference, Garmisch-Partenkirchen, Germany,
July 17-22,1994
edited by H.G. Karge and J.Weitkamp
Volume 99 Adsorption on New and Modified Inorganic Sorbents
edited by A. Dqbrowski andV.A.Tertykh
Volume 100 Catalysts in Petroleum Refining and Petrochemical Industdes 1995.
Proceedings ofthe 2nd International Conference on Catalysts in Petroleum
Refining and Petrochemical Industries, Kuwait, April 22-26,1995
edited by M.Absi-Halabi, J. Beshara, H. Qabazard andA. Stanislaus
Volume 101 11th International Congress on Catalysis - 40th Anniversary.
Proceedings ofthe 11th ICC, Baltimore, MD, USA, June 30-July 5,1996
edited by J.W. Hightower, W.N. Delgass, E. Iglesia andA.T. Bell
Volume 102 RecentAdvances and New Hodzons in Zeolite Science andTechnology
edited by H. Chon, S.I.Woo and S.-E. Park
Volume 103 Semiconductor Nanoclusters - Physical, Chemical, and CatalyticAspects
edited by RV. Kamat and D. Meisel
Volume 104 Equilibda and Dynamics of GasAdsorption on Heterogeneous Solid Surfaces
edited by W. Rudzir~ski,W.A. Steele and G. Zgrablich
Volume 105 Progress in Zeolite and Microporous Matedals
Proceedings of the 11th International Zeolite Conference, Seoui, Korea,
August 12-17,1996
edited by H. Chon, S.-K. Ihm andY.S. Uh
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Volume 106 Hydrotreatment and Hydrocracking of Oil Fractions

Proceedings of the 1st International Symposium / 6th EuropeanWorkshop,
Oostende, Belgium, February 17-19,1997
edited by G.F. Froment, B. Delmon and R Grange
Volume 107 Natural Gas Conversion IV
Proceedings of the 4th International Natural Gas Conversion Symposium,
Kruger Park, South Africa, November 19-23,1995
edited by M. de Pontes, R.L. Espinoza, C.R Nicolaides, J.H. Scholtz and
M.S. Scurrell
Volume 108 Heterogeneous Catalysis and Fine Chemicals IV
Proceedings of the 4th International Symposium on Heterogeneous Catalysis and
Fine Chemicals, Basel, Switzerland, September 8-12,1996
edited by H.U. Blaser,A. Balker and R. Pdns
Volume 109 Dynamics of Surfaces and Reaction Kinetics in Heterogeneous Catalysis.
Proceedings of the International Symposium,Antwerp, Belgium, September 15-17,1997
edited by G.F. Froment and K.C.Waugh
Volume 110 ThirdWorld Congress on Oxidation Catalysis.
Proceedings of theThirdWorld Congress on Oxidation Catalysis, San Diego, CA,
U.S.A., 21-26 September 1997
edited by R.K. Grasselli, S.T. Oyama, A.M. Gaffney and J.E. Lyons
Volume 111 Catalyst Deactivation 1997.
Proceedings of the 7th International Symposium, Cancun, Mexico, October 5-8,1997
edited by C.H. Bartholomew and G.A. Fuentes
Volume 112 Spillover and Migration of Surface Species on Catalysts.
Proceedings ofthe 4th International Conference on Spillover, Dalian, China,
September 15-18,1997
edited by Can Li and Qin Xin
Volume 113 RecentAdvances in Basic and Applied Aspects of Industrial Catalysis.
Proceedings ofthe 13th National Symposium and Silver Jubilee Symposium of
Catalysis of India, Dehradun, India, April 2-4,1997
edited by T.S.R. Prasada Rao and G. Murali Dhar
Volume 114 Advances in Chemical Conversions for Mitigating Carbon Dioxide.
Proceedings of the 4th International Conference on Carbon Dioxide Utilization,
Kyoto, Japan, September 7-11,1997
edited by T. Inui, M.Anpo, K. Izui, S.Yanagida andT.Yamaguchi
Volume 115 Methods for Monitoring and Diagnosing the Efficiency of Catalytic Converters.
A patent-oriented survey
by M. Sideris
Volume 116 Catalysis and Automotive Pollution Control IV.
Proceedings of the 4th International Symposium (CAPoC4), Brussels, Belgium,
April 9-11,1997
edited by N. Kruse, A. Frennet and J.-M. Bastin
Volume 117 Mesoporous Molecular Sieves 1998
Proceedings of the 1st International Symposium, Baltimore, MD, U.S.A.,
July 10-12,1998
edited by L.Bonneviot, E B61and,C. Danumah, S. Giasson and S. Kaliaguine
Volume 118 Preparation of Catalysts VII
Proceedings ofthe 7th International Symposium on Scientific Bases for the
Preparation of Heterogeneous Catalysts, Louvain-la-Neuve, Belgium,
September 1-4,1998
edited by B. Delmon, RA. Jacobs, R. Maggi, J.A. Martens, R Grange and G. Poncelet
Volume 119 Natural Gas ConversionV
Proceedings of the 5th International Gas Conversion Symposium, Giardini-Naxos,
Taormina, Italy, September 20-25,1998
edited by A. Parmaliana, D. Sanfilippo, E Frusted,A.Vaccad and F.Arena
442

Volume 120A Adsorption and its Applications in Industry and Environmental Protection.
Vol I: Applications in Industry
edited by A. D0browski
Volume 120B Adsorption and its Applications in Industry and Environmental Protection.
Vol I1:Applications in Environmental Protection
edited byA. Dsbrowski
Volume 121 Science andTechnology in Catalysis 1998
Proceedings of theThirdTokyo Conference in Advanced Catalytic Science and
Technology,Tokyo, July 19-24,1998
edited by H. Hattori and K. Otsuka
Volume 122 Reaction Kinetics and the Development of Catalytic Processes
Proceedings ofthe International Symposium, Brugge, Belgium, April 19-21,1999
edited by G.E Froment and K.C.Waugh
Volume 123 Catalysis: An Integrated Approach
Second, Revised and Enlarged Edition
edited by R.A. van Santen, RW.N.M. van Leeuwen, J.A. Moulijn and B.A.Averill
Volume 124 Experiments in Catalytic Reaction Engineering
by J.M. Berry
Volume 125 Porous Materials in Environmentally Friendly Processes
Proceedings ofthe 1st International FEZA Conference, Eger, Hungary,
September 1-4,1999
edited by I. Kiricsi, G. P=tl-Borb61y,J.B. Nagy and H.G. Karge
Volume 126 Catalyst Deactivation 1999
Proceedings of the 8th International Symposium, Brugge, Belgium,
October 10-13,1999
edited by B. Delmon andG.E Froment
Volume 127 Hydrotreatment and Hydrocracking of Oil Fractions
Proceedings of the 2nd International Symposium/7th European Workshop,
Antwerpen, Belgium, November 14-17,1999'
edited by B. Delmon, G.E Froment and R Grange
Volume 128 Characterisation of Porous SolidsV
Proceedings of the 5th International Symposium on the Characterisation of Porous
Solids (COPS-V), Heidelberg, Germany, May 30- June 2,1999
edited by K.K. Unger, G. Kreysa and J.R Baselt
Volume 129 Nanoporous Materials II
Proceedings of the 2nd Conference on Access in Nanoporous Materials,
Banff, Alberta, Canada, May 25-30, 2000
edited byA. Sayari, M. Jaronier andT.J. Pinnavaia
Volume 130 12th Intemational Congress on Catalysis
Proceedings of the 12th ICC, Granada, Spain, July 9-14, 2000
edited byA. Corma, EV. Melo, S. Mendioroz and J.L.G. Fierro
Volume 131 Catalytic Polymerization of Cycloolefins
Ionic, Ziegler-Natta and Ring-Opening Metathesis Polymerization
byV. Dragutan and R. Streck
Volume 132 Proceedings of the Intemational Conference on Colloid and Surface Science,
Tokyo, Japan, November 5-8, 2000
25th Anniversary ofthe Division of Colloid and Surface Chemistry,
The Chemical Society of Japan
edited byY. Iwasawa, N. Oyama and H. Kunieda
Volume 133 Reaction Kinetics and the Development and Operation of Catalytic Processes
Proceedings of the 3rd International Symposium, Oostende, Belgium, April 22-25,
2001
edited by G.E Froment and K.C.Waugh
Volume 134 Fluid Catalytic CrackingV
Materials and Technological Innovations
edited by M.L. Occelli and R O'Connor
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Volume 135 Zeolites and Mesoporous Materials at the Dawn of the 21st Century.
Proceedings of the 13th International Zeolite Conference, Montpellier, France,
8-13 July 2001
edited by A. Galameau, E di Renzo, E Fajula and J.Vedrine
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