Microporous and Mesoporous Materials 67 (2004) 1926

www.elsevier.com/locate/micromeso

Synthesis of mordenite nanocrystals

Beatriz O. Hincapie a, Luis J. Garces a, Qiuhua Zhang b, A. Sacco c, Steven L. Suib
a

a,d,*

Institute of Materials Sciences, Department of Chemical Engineering, University of Connecticut, U-3060, Storrs, CT 06269, USA
b
Technology Department, Carus Chemical Company 1500 8th St., LaSalle, IL 61301, USA
c
Department of Chemical Engineering, Northeastern University, 342 Snell Engineering, Boston, MA 02115, USA
d
Department of Chemistry, U-60, University of Connecticut, Storrs, CT 06269-3060, USA
Received 6 May 2003; received in revised form 16 September 2003; accepted 17 September 2003

Abstract
Mordenite is a zeolite that has been used as a selective adsorbent and as a catalyst. In reactions where the diusion of reagents
into the pore system is the rate-determining step, smaller particles of the catalyst improve the reaction rate. Mordenite with crystal
diameter smaller than 100 nm has been prepared by the modication of dierent synthetic parameters such as the source of aluminum, the presence of seeds, the use of low temperatures, longer crystallization times, and dierent silica to alumina ratios. The
decrease in the crystal diameter of the prepared mordenite was monitored by the application of the Scherrer equation that relates
the broadness of the X-ray diraction peaks to crystal sizes.

2003 Published by Elsevier Inc.
Keywords: Mordenite; Nanocrystals; Zeolites; Synthesis; Scherrer equation

1. Introduction
Mordenite is a zeolite with an ideal composition of
Na8 Al8 Si40 O96 nH2 O and a structure rened in the
Cmcm space group. The unit cell of sodium mordenite
, b: 20.517 A
, and c: 7.544 A

has dimensions a: 18.121 A
[1]. The most common morphology of mordenite is
characterized by needles with c direction elongation [2].
The micropore system of mordenite consists of two pore
) which
channels; an elliptical pore channel (6.7 7.0 A
runs parallel to the c-axis and, another pore channel
) [3].
which runs parallel to the b-axis (2.6 5.7 A
Due to its high thermal and acid stability, mordenite
has been used as a catalyst for important reactions such
as hydrocracking, hydroisomerization, alkylation, reforming, dewaxing, and the production of dimethylamines [26]. Mordenite has also been used in the
adsorptive separation of gas or liquid mixtures [6,7].
In addition, mordenite has been considered for appli*

Corresponding author. Address: Institute of Materials Sciences,

Department of Chemical Engineering, University of Connecticut,
U-3060, Storrs, CT 06269, USA. Tel.: +1-860-486-2797; fax: +1-860486-2981.
E-mail address: suib@uconnvm.uconn.edu (S.L. Suib).
1387-1811/$ - see front matter
2003 Published by Elsevier Inc.
doi:10.1016/j.micromeso.2003.09.026

cations in semiconductors, chemical sensors, and nonlinear optics [8].

Nanosized zeolites are important in catalytic and adsorptive applications. Smaller crystals of zeolites will
have larger surface areas and less diusion limitations
compared to zeolites with micrometer-sized crystals [9].
Nanometer-sized zeolites also oer advantages in supramolecular catalysis, photochemistry, nanochemistry, electrochemistry, and optoelectronics [10]. Zeolite
nanocrystals can also be used in the construction of other
geometries such as thin lms, bers, and self-standing
zeolite membranes [11]. Syntheses of nanoparticles of
zeolites A, Y, silicalite, sodalite, ZSM-5, zeolite L,
and zeolite beta have been previously reported [911].
Most of the reports on the synthesis of mordenite are
involved with an increase in the silica to alumina ratio
[4,7,12] or in the production of very large crystals of
mordenite (from 7 to 500 microns) [3,8,13,14]. Recently,
a polycrystalline mordenite membrane with a small
crystallite size was prepared using tetraethylammonium bromide as a template and by aging. The smallest
crystals obtained were around 45 microns [15]. Mordenite crystallites in the size range of 80120 nm were
previously synthesized by hydrothermal transformation
of Na-magadiite, a layered silicate in the presence of

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B.O. Hincapie et al. / Microporous and Mesoporous Materials 67 (2004) 1926

tetraethylammonium, sodium, and potassium hydroxide; these cations are required to obtain pure mordenite
[16]. To the best of our knowledge there are no reports
on the synthesis of mordenite with crystal diameters of
around 100 nm in the absence of organic templates. In
this study we have prepared mordenite nanocrystals by
adjusting gel compositions and crystallization conditions.

2. Experimental
Dierent parameters were studied to increase crystallinity and decrease the crystal diameter of mordenite.
Two dierent gel preparation procedures with dispersion (procedure 1) or dissolution of silica gel (procedure
2) and the addition of seeds were studied to increase
crystallinity. The eect of crystallization time and temperature, dierent source of Al2 O3 , and dierent silica
to alumina ratios (SAR) on the crystallinity and crystal
size of mordenite were also tested.
2.1. Gel preparation
The solubility of silica plays an important role in the
crystallization rate and crystal size of mordenite [13].
Gel preparation procedures aecting the dissolution of
silica gel were tested.
2.1.1. Procedure 1
The starting materials required to get a batch composition of 6Na2 O:Al2 O3 :30SiO2 :780H2 O, were added
in the following order: double deionized water (DDW),
sodium hydroxide (Alfa Aesar 97%), sodium aluminate
(EM Science, 85.53%), and silica gel (Fisher, 28200
mesh). The resulting mixture was stirred for 30 min, and
then transferred to Teon-lined stainless steel autoclaves. To study the eect of seeds, mordenite seeds (NaMordenite Strem chemicals, BET surface area 240 m2 /g,
SAR measured by EDX: 8.6) were added to one of the
autoclaves (0.1 g of seeds per 14 g gel). Crystallization
was carried out under hydrothermal conditions at 170
C, for 24 h.
2.1.2. Procedure 2
This procedure was used to prepare mordenite with
dierent batch compositions 6Na 2 O:Al 2 O 3 :30SiO 2 :
780H 2 O, 6Na 2 O:1.5Al 2 O 3 :30SiO 2 :780H 2 O, 6Na 2 O:
2.0Al 2 O 3 :30SiO 2 :780H 2 O, 6Na 2 O:3.0Al 2 O 3 :30SiO 2 :
780H2 O. The required amount of sodium hydroxide and
water (DDW) was divided into two parts to form two
solutions: solution (A) was prepared by dissolving silica
gel with stirring in an aqueous solution of sodium hydroxide. Solution (B) consisted of sodium aluminate and
sodium hydroxide dissolved in water. When aluminum

was used as the source of Al2 O3 , aluminum metal was

added very slowly to an aqueous solution of sodium
hydroxide (This is a very exothermic reaction!) and
dissolved slowly under stirring to prepare solution (B).
Solution (B) was then added to solution (A). A gel was
formed after stirring the mixture of solutions (A) and
(B) for periods of time from 1 to 2 h. In several experiments, mordenite seeds were added to the gel (0.1 g per
14 g gel). The homogenized gel was poured into Teonlined autoclaves and crystallization took place under
hydrothermal conditions (150 and 170 C, for 24, 48,
and 96 h). The SAR of the starting gels was calculated
without taking into account the SAR of the seeds.
Mordenite with the smallest crystal diameter (Mor-1)
was obtained by using this procedure (solution A:
DDW: 10 g, NaOH: 0.84 g, SiO2 : 5.6 g. This mixture
was stirred overnight (16 h). DDW (12 g) was added
before mixing with solution B. Solution B: DDW: 5.0 g,
NaOH: 0.7 g, Al: 0.33 g. After dissolution 16.8 g of
DDW was added and solution B was mixed with solution A. Seed (0.4 g) was added to the gel formed and
stirred for 1 h. The gel was crystallized at 150 C for
24 h).
2.2. Product recovery
The material resulting after crystallization was centrifuged and washed with double de-ionized water until
the pH of the remaining solution was less than 9. The
samples were dried overnight at 100 C.
2.3. Characterization
The XRD studies were carried out with a Scintag
XDS-200 powder diractometer on nely powdered,
unground samples using Cu(Ka) radiation and 45 kV
and 40 mA. The step size was 0.02 (2h) with a count
time of 0.6 s and a scan rate of 2.0/min. The XRD
patterns were recorded for 2hs between 5 and 40 and
compared with the XRD pattern of commercially
available mordenite (Na-Mordenite Strem Chemicals).
The crystal sizes of the prepared materials were determined using the Scherrer equation [17]. The instrumental line broadening was measured using a LaB6
standard. The crystallinity of the prepared samples was
calculated using the ratio of the sum of the areas of the
ve most intense peaks for the prepared samples (2h:
10.8, 20.6, 23.2, 26.6, 27.3) to that of the same
peaks for the standard (Na-Mordenite Strem Chemicals)
and multiplying by 100 [18].
Field emission scanning electron microscopy
(FESEM) experiments for the determination of particle
size and morphology were performed on a Zeiss DSM
982 Gemini eld emission scanning electron microscope
(FESEM) with a Schottky Emitter at an accelerating

B.O. Hincapie et al. / Microporous and Mesoporous Materials 67 (2004) 1926

voltage of 2 kV with a beam current of about 1 lA. An

ECON IV energy dispersive X-ray (EDX) analyzer
Model 9800 was used to determine the silica to alumina
ratios of the prepared zeolites. Samples for analysis by
transmission electron microscopy (TEM) were ground
with a mortar and pestle and sonicated in n-butanol
prior to dropping them on a 300 mesh holey carbon
coated copper grid (SPI). TEM measurements were
performed on a JEOL 2010 FasTEM 200 kV instrument
equipped with an EDAX energy dispersive spectrometer
and a Gatan EELS/GIF system. A micromeritics ASAP
2010 equipped with ASAP 2010 V4 software was used
for surface area determination. About 0.1 g of sample
was loaded into the glass sample bulb and degassed
under vacuum at 150 C. The BrunauerEmmettTeller
(BET) model was used to determine surface area. FTIR
experiments were done on a Nicolet Magna IR system
750 FTIR spectrometer with a resolution of 4 cm 1 .
KBr pellets of the samples were analyzed in the range
1500400 cm 1 .

3. Results
Mordenite with dierent degrees of crystallinity and
crystal size (measured by XRD) was obtained in all the
experiments. Experiments with initial SAR: 10 and 15
after 96 h of crystallization at 150 C produced analcime
and an unknown phase respectively as impurities (Figs.
1 and 5). In some cases values of crystallinity higher
than 100% were obtained. The area of the XRD peaks
for prepared samples was higher than the area of the
same XRD peaks for the standard. This result may be
due to the high crystallinity of prepared samples and

21

increased peak broadening due to the presence of

smaller crystals compared to the standard.
Figs. 24 show the eect of dierent parameters like
dissolution of silica gel, presence of seeds, source of
Al2 O3 , crystallization temperature and time, and SAR
on crystallinity and crystal size of mordenite, measured
by XRD. The size of crystals obtained with X-ray
methods is the eective length, measured in the direction of the diraction vector, along which diraction is coherent. The term crystal size is preferred over
particle size, since individual particles may contain
several crystals or domains having dierent orientations [19]. The crystal size obtained by applying Scherrers equation is interpreted as an average crystal
dimension, perpendicular to the reecting planes [20].
The accuracy of crystal size determination is usually
no better than 2040%, because the samples analyzed
do not have crystals of uniform size, but rather some
type of distribution [21]. Powders with needle shape
crystals (like those of mordenite) tend to become
aligned with the specimen axis in the preparation of
the sample [21]. The crystal dimension measured by
X-ray diraction could be the crystal diameter instead
of crystal length.
3.1. Eect of gel preparation procedure (dissolution of
silica gel) and the addition of seeds on the crystallinity of
mordenite
Fig. 2 shows that under similar crystallization conditions, mordenite produced by dissolving silica before
mixing with sodium aluminate (gel preparation procedure 2) is more crystalline and has a larger crystal size
than when silica was dispersed and mixed with other raw
materials (gel preparation procedure 1). The addition of
mordenite seeds also helped to produce more crystalline
mordenite.
3.2. Eect of the source of Al2 O3 , crystallization temperature and time on the crystallinity and crystal size of
mordenite (Fig. 3)

Fig. 1. XRD patterns of mordenite samples prepared with batch

composition 6Na2 O:3Al2 O3 :30SiO2 :780H2 O. Gel preparation procedure 2 (dissolution of silica gel), Al as source of Al2 O3 , seeds of
mordenite (0.1 g seed/14 g gel), crystallization temperature 150 C,
crystallization time (a) Standard Mordenite, (b) 24 h, (c) 48 h, (d) 96 h.
Extra peaks found in sample (c) correspond to analcime (ANA).

Crystallinity of mordenite prepared with NaAlO2 or

Al increases with time and temperature. Mordenite
prepared at 170 C and 24 h is more crystalline than
mordenite prepared at 150 C for 24 h. The crystal size
of mordenite decreases slightly with crystallization time
when NaAlO2 was used as the source of Al2 O3 and increased with crystallization time when Al was used. Increasing the crystallization temperature has a greater
impact on the crystal size of mordenite prepared with
NaAlO2 than when mordenite was prepared with Al.
The SAR of mordenite (by EDX) obtained when
using NaAlO2 is lower than when using Al as source
of Al2 O3 .

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B.O. Hincapie et al. / Microporous and Mesoporous Materials 67 (2004) 1926

160

Procedure 1 *

Procedure 2 *

140
120

Silica dissolved

Silica dispersed

100
80
Crystal size
(nm)
Crystallinity
(% Area)

60
40
20
0
seed

no seed

seed

no seed

Fig. 2. Eect of gel preparation procedure (silica dispersed or dissolved) and presence of seeds in the crystallinity of mordenite. Batch composition:
6Na2 O:Al2 O3 :30SiO2 :780H2 O, crystallization conditions 170 C, 24 h. Seeds: Na-Mordenite (Strem Chemicals).  See Section 2 for description of
gel preparation procedures 1 and 2.

Fig. 3. Eect of the source of Al2 O3 (NaAlO2 or Al), crystallization temperature and time in crystallinity and crystal size of mordenite. Batch
composition 6Na2 O:Al2 O3 :30SiO2 :780H2 O. Seeds Na-Mordenite (Strem chemicals), gel preparation procedure 2 (silica dissolved).  SiO2 /Al2 O3 of
product measured by EDX.

SiO2/Al2O3

SiO2/Al2O3

SiO2/Al2O3

SiO2/Al2O3

30

20

15

10

160
140
120

Crystal
size(nm)

MOR-2

100

MOR-1

Crystallinity
(%Area)

80
60
40
20
0
24

48

24

48

96

24

48

96

24

48

96

Crystallization time (h)

Fig. 4. Eect of changes in silica to alumina ratio in crystal size and crystallinity of mordenite. Gel preparation procedure 2 (silica dissolved), Na2 O/
SiO2 :0.2, H2 O/SiO2 :26, seeds Na-Mordenite from Strem Chemicals (0.1 g seed/14 g gel), Al as source of Al2 O3 , crystallization temperature 150 C.

3.3. Eect of changes in silica to alumina ratio

The eects of changing the silica to alumina ratio
(SAR) of the initial gel in the crystal size and crystal-

linity of mordenite are shown in Fig. 4. There is a decrease in the crystal size of mordenite, prepared under
the same crystallization conditions, as the SAR in the
starting gel is decreased from 30 to 15. Further decrease

B.O. Hincapie et al. / Microporous and Mesoporous Materials 67 (2004) 1926

in the SAR to 10 causes the formation of analcime as

impurity phase when the gel is treated at 150 C for 96 h.
The calculated crystallinity for samples with impurities
is decreased. The crystallinity of samples prepared with
SAR: 10 decreases with time because another phase
(analcime) is produced. Mordenite prepared with SAR:
15 after 96 h of crystallization time exhibits a decrease in
crystallinity and crystal size and additional low intensity
peaks of an unknown phase were detected by XRD
(Fig. 5, XRD pattern).
Fig. 5 presents the XRD pattern, TEM micrographs,
and FESEM micrograph of mordenite sample with the
smallest crystal size, crystallized at 150 C for 24
(Mor-1). Acicular crystals of mordenite are formed with

23

an average diameter of 63 nm (148 particles) and average length of 240 nm. The crystal size of this sample
determined by XRD is 42 nm; this value is closer to the
average diameter of the particles measured by SEM than
to the length.
Mordenite with the smallest crystal diameter
(MOR-1, Fig. 4) was prepared by using a batch composition of 6Na2 O:2Al2 O3 :30SiO2 :780H2 O (SAR 15),
dissolving the silica gel before mixing with the aqueous
solution of metallic aluminum in sodium hydroxide,
using seeds (0.1 g seed/14 g gel) and with crystallization
at 150 C for 24 h. This mordenite presents low crystallinity by XRD (80%). The peak broadening may affect the intensities of the XRD peaks. Peak heights

Fig. 5. (a) XRD patterns, (b) FESEM (Mor-1), (c) and (d) TEM micrographs of mordenite prepared with a batch composition 6Na2 O:
2Al2 O3 :30SiO2 :780H2 O, gel preparation procedure 2 (dissolution of silica), Al as source of Al2 O3 , mordenite seeds (0.1 g/14 g gel), crystallization
temperature 150 C, crystallization time (1) 24 h (Mor-1), (2) 48 h (Mor-2), (3) 96 h. Arrows indicate low intensity XRD peaks of an unknown phase
present in the sample (3). (e) Particle width (diameter, nm) and (f) length (nm) distributions of Mor-1 measured by FESEM are included.

24

B.O. Hincapie et al. / Microporous and Mesoporous Materials 67 (2004) 1926

80
70
60

%T

50
(b)

40
30
20

(a)

10
0
1400

1300

1200

1100

1000

900

800

700

600

500

400

-1

Wavelength (cm )
Fig. 6. FTIR mordenite (a) Mordenite standard, (b) Mor-1, sample prepared with batch composition 6Na2 O:2Al2 O3 :30SiO2 :780H2 O, gel preparation procedure 2 (dissolution of silica), Al as source of Al2 O3 , mordenite seeds (0.1 g/14 g gel), crystallization temperature 150 C, crystallization
time 24 h.

 (0.1
decrease when crystallite sizes are less than 1000 A
microns) [17].
The surface area of the sample labeled MOR-1 in Fig.
4 (mordenite with the smallest crystal diameter) was 389
m2 /g. This value is higher than the value obtained for
mordenite used as a seed and as a standard (240 m2 /g),
and is also higher than the surface area for mordenite
with a crystal size of around 0.1 lm reported previously
(340 m2 /g) [16]. This result indicates that a large port
mordenite, with good crystallinity was obtained [3]. Fig.
6 shows the FTIR spectra for MOR-1 and the standard
mordenite used as seed. Typical vibrations for mordenite
are observed (asymmetric stretching: external 1225 cm 1 ,
internal 1050 cm 1 ; symmetric stretching: external 800
cm 1 , internal 720 cm 1 ; double ring: 580 and 560 cm 1 ;
TO bending: 450 cm 1 ) [22].

4. Discussion
The crystal sizes of zeolites are a function of the ratio
between the nucleation rate and the rate of crystal
growth [23]. The synthesis of crystalline mordenite with
a small crystal size requires a high rate of nucleation and
a low rate of crystal growth. The parameters that can be
easily controlled and aect the crystal growth are crystallization time and temperature. According to the literature [23,24], decreasing the temperature and the time
result in smaller crystals. But under low temperature
conditions the rate of crystallization is also decreased
and a great deal of amorphous material will also be
present. The crystallization rate of mordenite was increased by modifying the dissolution of the silica source
and by addition of seeds.
As shown in this report, by dissolving the silica gel in
an alkaline solution previous to the addition of sodium
aluminate, more crystalline mordenite was obtained in

the same crystallization time as when the silica was not

previously dissolved; there is more availability of nutrients to start the nucleation and growth of zeolite crystals
[13]. In a previous study, using heat-treated silica that
dissolved slowly, an increase in the crystallization time
(140 h) and larger (250 m) crystals of mordenite were
obtained. The dissolution of amorphous silica particles
was found to be the rate-limiting step in the synthesis
of mordenite [13].
Seeding is a common strategy used to increase the
crystallization rate by adding crystals of the desired
phase. Seeds promote the crystallization by providing
additional surface area for the dissolved material to
grow [25]. The eect of seeds in increasing the crystallization rate of mordenite was observed in the experiments reported herein. By using seeds, more crystalline
mordenite can be obtained in less time than without
seeds. The reaction can be stopped before the crystals
continue growing. The addition of seeds also allowed
the use of lower temperatures (150 C) while still obtaining crystalline mordenite.
Partial isomorphous substitution of silicon by tetrahedron forming elements can inuence crystal size [23].
The crystal size of mordenite was decreased by decreasing the silica to alumina ratio of the starting gel
from 30 to 15. This result has been previously explained
by applying Lowensteins rule [25]. Aluminate ions in
solution could react only with silicate groups on the
growing crystal surface, while silicate ions in solution
could react with either silicate or aluminate surface
groups. The presence of aluminum is associated with
the formation of smaller crystals.
The decrease in crystal size of mordenite by decreasing the silica to alumina ratio has a limit because
contaminating phases can be produced. The lowest silica
to alumina ratio (SAR: 10) produced analcime after
long periods of time. Similar results have been previ-

B.O. Hincapie et al. / Microporous and Mesoporous Materials 67 (2004) 1926

ously reported [26]. Analcime is a denser phase with

irregular channels formed by highly distorted 8-mem [27]. The
bered rings and with dimensions 1.6 4.2 A
crystallinity of mordenite was also decreased by the
presence of an unknown phase obtained when the silica
to alumina ratio of the initial batch was very low (SAR
15 crystallized for 96 h). Dierent zeolite structures
can be synthesized in specic composition ranges and
conditions, called crystallization elds [26].
Aluminum was used as the source of Al2 O3 in the
experiments where the silica to alumina ratio was decreased. In those experiments the only modication was
the amount of aluminum used; the amounts of all of the
other raw materials were kept constant. The dissolution
of aluminum in a solution of sodium hydroxide releases
hydrogen [28] and some un-dissolved material was observed after the bubbling of hydrogen stopped. In the
experiments where powdered sodium aluminate was
used as the source of Al2 O3 no residue was observed
after mixing with water. Mordenite with lower silica to
alumina ratio was obtained when sodium aluminate
instead of aluminum was used as the source of Al2 O3 .
This result could be explained by the observed dierence
in solubility of the sources of Al2 O3 . Sodium aluminate
provided more available ions for reaction with dissolved
silicate than when aluminum was used.
The crystal size of mordenite prepared with sodium
aluminate decreased with crystallization time. The
crystals of mordenite initially formed may be dissolved
under the conditions used [29]. The crystal size of
mordenite prepared with aluminum as a source of Al2 O3
increased with crystallization time. This behavior may
be due to the slow release of aluminate ions from the undissolved aluminum into the solution and then slowly
added to the growing crystal surface. More silicate than
aluminate in solution favors crystal growth as previously discussed [25].

5. Conclusions
Mordenite with a crystal diameter as small as 62 nm
was obtained from a gel with a low silica to alumina
ratio, prepared with a solution of silica gel in sodium
hydroxide and aluminate ions from sodium aluminate
or metallic aluminum, using seeds and hydrothermal
conditions: 150 C, 24 or 48 h.
The parameter that most eectively decreased the
crystal diameter of mordenite was the reduction of the
silica to alumina ratio (SAR) of the starting gel from 30
to 15. But the decrease in crystal size by decreasing the
SAR is limited because a further decrease in SAR causes
the formation of analcime as an impurity phase.
Crystallinity of mordenite was improved by dissolving instead of dispersing the source of SiO2 previous to
mixing with the source of Al2 O3 and by adding seeds of

25

mordenite. This improvement in the gel preparation

procedure to obtain more crystalline mordenite allowed
us to use lower temperatures and shorter crystallization
times to obtain smaller crystals with good crystallinity.

Acknowledgements
We acknowledge support from NASA/CAMMP. We
also thank Dr. Francis Galasso for helpful discussions,
Dr. Kate Laubernds for TEM micrographs, IMSUCONN for TEM facilities, and Dr. James Romanow
(Physiology and Neurobiology Department-UCONN)
for providing access to FESEM facilities.

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