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Microporous and Mesoporous Materials 125 (2009) 170223

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Microporous and Mesoporous Materials


journal homepage: www.elsevier.com/locate/micromeso

Veried syntheses of mesoporous materials


V. Meynen, P. Cool *, E.F. Vansant
Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen, Universiteitsplein 1, 2610 Wilrijk, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: A very large number of different synthesis approaches for the preparation of mesoporous materials has
Received 30 March 2009 been reported in literature since the rst development of ordered mesoporous materials in the 1990s.
Accepted 31 March 2009 Since then, the synthesis of advanced mesoporous materials has undergone an explosive growth. More-
Available online 10 April 2009
over, this type of materials gains growing success in a wide variety of applications. For these reasons and
with the example of the book of veried microporous zeolite syntheses in mind, it is obvious that there is
Keywords: a growing need for veried synthesis methods of mesoporous materials. In this work, veried synthesis
Veried syntheses
methods have been compiled for a large number of selected relevant structured mesoporous silica and
Mesoporous
Super-microporous
titania materials as well as for some super-microporous materials (dened herein as materials with pore
diameters between 1.5 and 2 nm). In addition, for each material, a basic set of material characteristics
have been reported based on the most commonly applied characterization techniques (nitrogen sorption,
XRD, TEM, SEM, NMR, etc.) for mesoporous materials.
2009 Elsevier Inc. All rights reserved.

1. Introduction evant structured mesoporous silicas and titanias, followed by the


obtained material characterization results (surface area, pore
Microporous zeolites are among the best known and most widely dimensions, pore volume, XRD, TEM, SEM, NMR, etc.). Some of the
applied porous materials. Their uniform pore sizes with molecular materials listed are not strictly mesoporous, but super-microporous
dimensions, good stability, selectivity and activity due to their crys- (dened herein as pores between 1.5 and 2 nm). As this overview
tallinity, the possibility of incorporating heteroelements into the tries by no means to be complete, containing all existing and impor-
structure and their ion exchange capacities make zeolites unique tant mesoporous materials that have been developed, it should be
materials in several processes (catalysis, sorption, membrane sepa- seen as the start of the publication and documentation of proven
rations, etc.). Thanks to innovative synthesis strategies an evolution syntheses of mesoporous materials. It will be extended in the future
towards structured materials with larger pores could be obtained. with more veried syntheses of mesoporous materials.
After the rst reports, introducing the M41S family of ordered mes- The synthesis of nanoporous materials and more precisely mes-
oporous silicas at the beginning of the 1990s, the synthesis of ad- oporous materials, which are dened by IUPAC as materials with
vanced mesoporous materials has undergone explosive growth. pore sizes between 2 and 50 nm, is an active eld of research. As
The exploration of novel compositions and architectures in view of long as this continues, new mesoporous siliceous and non-siliceous
specic applications in areas as diverse as catalysis, sorption, sepa- or inorganic and inorganic-organic hybrid materials will be discov-
rations, sensing, optics, drug delivery, etc. has given rise to several ered and new techniques for preparing existing phases will appear.
national and international research programmes.
Within the framework of the EU-FP6 Network of Excellence IN- 2. Practical guide
SItu study and DEvelopment of processes involving nanoPORous
Solids (INSIDE-POReS) bringing together researchers from 16 lead- Synthesis experiments reported in the literature are often cryp-
ing European research groups, it became obvious that there is a tic, leaving the scientist who wants to reproduce the experiment
growing need for veried synthesis methods of mesoporous mate- many choices of reagents and procedures. Furthermore, the prod-
rials. The need and benet for this type of reference works can be uct characterization is often inadequate for an unambiguous choice
found in the previous similar work of the veried zeolite syntheses for a new application.
book coordinated by the International Zeolite Association, which In this paper, an outline, covering the essential points for
are indispensable in many laboratories in the eld [434]. Emphasis reporting a synthesis of nanoporous materials, was selected. The
will be put on various veried preparation methods for selected rel- format for all the recipes in this volume follows this outline. It is
intended to assist the scientist by placing the information in the
* Corresponding author. Tel.: +32 3 265 23 55; Fax: +32 3 265 23 74. same relative positions for all recipes. This form supposes that all
E-mail address: Pegie.Cool@ua.ac.be (P. Cool). synthesis experiments follow the general sequence:

1387-1811/$ - see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2009.03.046
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 171

List of acronyms and abbreviations

C degree Celsius M41S group name of mesoporous MCM materials (Mobil Com-
lm micrometer position of Matter)
16-12-16 gemini [C16H33(CH3)2NC12H24N(CH3)2C16H33]2Br MAS NMR magic angle spinning nuclear magnetic resonance
18-12-18 gemini [C18H37(CH3)2NC12H24N(CH3)2C18H37]2Br MCF mesostructured cellular foam
2D two-dimensional MCl metal chloride salt
3D three-dimensional MCM mobil composition of matter
3D-TEM three-dimensional transmission electron microscopy MDD molecular designed dispersion method
a.u. arbitrary units min minute
AAS atomic absorption spectroscopy mL milliliter
Ac autoclave MMA monolithic mesoporous aluminosilicate
ATR attenuated total reectance MOS molecular based organized systems
BEA specic framework type of a zeolite MQ MAS multiple-quantum magic angle spinning nuclear mag-
BET BrunauerEmmettTeller netic resonance
BJH BarretJoynerHalenda MSU Michigan State University
CASH combined assembly by soft and hard chemistries MW molecular weight
cm3 cubic centimeter NA Avogadro number
cmc critical micelle concentration Na-TTNT sodium trititanate nanotube
CP cross polarization NBB nanobuilding block
CRT cathode ray tube Nm nanometer
CTMABr cetyltrimethylammonium bromide NMR nuclear magnetic resonance
CVD chemical vapor deposition OMM ordered mesoporous material
DDMS decyldimethylsilyl p.a. pro analysis
DLCT direct liquid crystal templating P/PO relative pressure
DOR double-oriented rotation P123 poly(ethylene glycol)-block-poly(propylene glycol)-
DR DubininRadushkevich block-poly(ethylene glycol)
DRIFT diffuse reectance infrared Fourier transform PE polyethylene
DTMABr decyltrimethylammonium bromide PEO polyethylene glycol
ED-XRF energy dispersive-X-ray uorescence PHTS plugged hexagonal templated silica
EISA evaporation induced self-assembly PO propylene glycol
ENMIX European Nanoporous Materials Institute of Excellence POS polymeric based organized systems
EO ethylene glycol PP polypropylene
EPMA electron probe micro analysis ppb parts per billion
EtOH ethanol ppm parts per million
EU European Union PPO polypropylene glycol
EU-FP6 European Union Framework Programme 6 rpm rotations per minute
F127 poly(ethylene glycol)-block-poly(propylene glycol)- RT room temperature
block-poly(ethylene glycol) SBA Santa Barbara acids
FTIR Fourier Transform Infrared SBET specic surface area measured by the BET method
FTIR-PAS Fourier transform infraredphotoacoustic spectroscopy SEM scanning electron microscopy
FT-Raman Fourier transform Raman spectroscopy STP standard temperature and pressure
g gram t multilayer thickness
h hour T temperature
HCL hollow cathode lamp TDTMABr tetradecyltrimethylammonium bromide
HDMS hexyldimethylsilyl TEAOH tetraethylammonium hydroxide
HMS hexagonal mesoporous silica TEM transmission electron microscopy
HOM highly ordered silica monoliths TEOS tetraethyl orthosilicate/tetraethoxysilane
HRTEM high resolution transmission electron microscopy Ti(OiPr)4 titanium(IV) isopropoxide
H-TTNT proton exchanged trititanate nanotube TMOS tetramethyl orthosilicate/tetramethoxysilane
ICP/AES inductively coupled plasma atomic emission spectros- TTMABr tetradecyltrimethylammonium bromide
copy TTNT trititanate nanotubes
ICP-OES inductively coupled plasma-optical emission spectros- Vads volume of adsorbed gas
copy Vliq liquid volume
INSIDE POReS IN-SItu study and DEvelopment of processes Vmicro micropore volume
involving nanoPORous Solids Vtotal total pore volume
IUPAC International Union of Pure and Applied Chemistry W Watt
kHz Kilohertz WD-XRF wavelength dispersive-X-ray uorescence
LCT liquid crystal template XRD X-ray diffraction
M molar XRF X-ray uorescence
m2 square meter Hm magic angle

Batch preparation. (a) Name of porous materials


Product recovery. The product name is the name by which the product is usu-
Calcination conditions. ally referred to in the literature and its normal framework
Characterization. code (letter code followed by a number, reecting the struc-
172 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

ture). Furthermore, a short description of the material is Michael.Stocker@sintef.no


added to help the reader in selecting porous materials.
(b) Contributed by Prof. J. Weitkamp, Prof. R. Glser, Dr. S.C. Laha, Dr.
The names indicate the persons who actually prepared the D. Pufky-Heinrich, S.A.S. Rezai
mesoporous material. University of Stuttgart, Institute of Chemical Technology,
(c) Veried by Pfaffenwaldring 55, D 70569 Stuttgart, Germany.
Veriers are those independent investigators who repro- jens.weitkamp@itc.uni-stuttgart.de
duced the synthesis recipe and obtained a satisfactory prod-
uct by their own evaluation. Again, only names are given Prof. J. Caro, Prof. P. Behrens, Prof. M. Wark, I. Bannat, F.
here; for institutional afliations see the list of contributors. Heinroth, B. Seelandt, I. Krueger, N. Witteck, B. Yler, A. Zukal,
The verication reports, both positive and negative, are part R. Marshall, J. Rathousky
of the record of the recipe and are available on request at the University of Hannover, Callinstrasse 3-3A, D 30167 Hannover,
corresponding author P. Cool (pegie.cool@ua.ac.be). Germany.
(d) Type of material juergen.caro@pci.uni-hannover.de;peter.behrens@acb.uni-han-
The type of the material refers to the chemical content of the nover.de;michael.wark@pci.uni-hannover.de
unit cell as indicated by the elemental analysis after washing
and calcination.
Prof. F. Kapteijn, Dr. M.-O. Coppens, Dr. P.J. Kooyman, Dr. A.F.P.
(e) Batch composition
Ferreira, Dr. S. Aguado, Dr. J. Gascon, A. Denkova, Dr. A.
The batch composition refers to the product of the batch
Quintanilla
preparation stated in molar ratios of oxides, template mole-
Catalysis Engineering DCT TUDelft, Julianalaan 136, NL 2628
cules, neutralization products, reaction media, etc.
BL Delft, The Netherlands.
(f) Source of materials
f.kapteijn@tudelft.nl
The actual materials used to prepare the batch are given
along with their purities and suppliers.
Prof. F. Rodrguez-Reinoso, Prof. A. Seplveda-Escribano, Dr. J.
(g) Batch preparation
Silvestre-Albero, A. Silvestre-Albero, J. Ruiz-Martnez
The batch preparation refers to actual quantities of materials
University of Alicante, Department of Inorganic Chemistry, Lab-
plus the preparation steps used to prepare the material.
oratory of Advanced Materials, Carretera San Vicente del Ras-
(h) Product recovery
peig, s/n C.P. 03690, San Vicente del Raspeig (Alicante), Spain.
Product recovery refers to the procedure for separating the
reinoso@ua.es; asepul@ua.es; joaquin.silvestre@ua.es
desired product from the by-products.
(i) Post-synthesis treatment
These conditions refer to the experimental conditions and Dr. D.J. Jones, Prof. J. Rozire, Dr. N. Donzel, Dr. M. Taillades-
temperatures which convert the nished batch into the nal Jacquin
product. This includes the removal of the template by CNRS Agrgats, Interfaces et Matriaux pour lEnergie, Institut
extraction and calcination as well as recrystallization or sta- Charles Gerhardt for Molecular Chemistry and Materials, Uni-
bilization of the prepared materials.In order to obtain good versit Montpellier II, Place Eugne Bataillon, F 34095 Montpel-
quality materials it is advised never to put too much in a cal- lier cedex 5, France.
cination crucible. Deborah.Jones@univ-montp2.fr; Jacques.Roziere@univ-mon-
(j) Product characterization tp2.fr; Melanie.Taillades-Jacquin@univ-montp2.fr, Nicolas.
Product characterization identies the obtained (crystalline) Donzel@univ-montp2.fr
product and compares its properties to those of the known stan-
dards. For this publication, the basic characterizations are XRD, Prof. M-L. Saboungi, F. Meducin, F. Warmont, S. Serieye
N2 sorption at 196 C (determination of specic surface area, CNRS CRMD, Universit d Orleans, 1B rue de la Frollerie,
pore volume, pore diameter), SEM, TEM (HRTEM), NMR, etc. F 45071 Orlans Cedex 2, France.
(k) References mls@cnrs.orleans.fr
References indicate the primary literature reports dealing
with the nanoporous material plus selected general refer- Dr. N. Kanellopoulos, Dr. G. Karanikolos
ences recommended by the author. National Center for Scientic Research Demokritos, Patriarxou
Grigorio and Neapoleos, Agia Paraskevi, GR 15310 Athens,
3. Contributors Greece.
kanel@chem.demokritos.gr; g.karanikolos@chem.demokritos.gr
The following researchers and laboratories, which are members
of the Network of Excellence INSIDE-POReS, contributed recipes for Dr. K.S. Triantafyllidis, C. Nitsos, S. Karakoulia, Dr. S.D. Sklari
ordered mesoporous materials and/or the verication of recipes. Center for Research and Technology-Hellas (CERTH), Chemical
Process Engineering Research Institute (CPERI), 6th km. Chari-
Prof. P. Cool, Prof. E.F. Vansant, Dr. V. Meynen, F. Quiroz, K. De laou-Thermi Road, P.O. Box 60361 Thermi, GR 57001 Thessalo-
Witte, G. Smeulders, E. Beyers, S. Ribbens niki, Greece.
University of Antwerpen, Department of Chemistry, Laboratory ktrianta@chem.auth.gr
of Adsorption and Catalysis, Universiteitsplein 1, B 2610 Wilrijk,
Belgium.
pegie.cool@ua.ac.be; etienne.vansant@ua.ac.be 4. Overview of the main synthetic approaches to mesoporous
materials
Prof. M. Stcker, Dr. Arjen van Miltenburg, A.I. Spjelkavik, A.M.
Bouzga Most of the synthesis approaches to form inorganic mesoporous
SINTEF Materials and Chemistry, P.O. Box 124 Blindern, materials in general are based on the use of organic template mole-
Forskningsveien 1, N 0314 Oslo, Norway. cules that are used in different assembly processes or textural tem-
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 173

Fig. 4.1. Schematic overview of the main synthetic approaches to mesostructured materials. (A) Liquid crystal templating, (B) self-assembly and cooperative self-assembly,
(C) nanometric building blocks, and (D) sheet-folding mechanism of (titania) nanotubes. (Adapted from [4] and [10]).

plates, around which the inorganic precursor can condense [16] Table 4.1
Schematic overview of the main synthesis parameters to generate a diversity of
(Fig. 4.1). However, also template-free synthesis mechanisms like
mesoporous materials.
the nanobuilding block (NBB) mechanism [4] and other approaches
(e.g. folded sheet nanotubes) [79] (Fig. 4.1) have been reported. Surfactant Mechanism Interaction
A large diversity in synthesis approaches is known for the for- MOS LCT Direct Ionic
mation of different materials, and similar materials (e.g. MCM- POS Self-assembly Non-ionic
41, MCM-48, SBA-15, MSU etc.) can be made by different synthesis Textural templates Cooperative self-assembly Indirect Ionic
Nanometric building blocks Non-ionic
methods and surfactants, each of them allowing other parameters
to be altered and controlled. Next to differences in chemical ratios, MOS: molecular based organized systems, POS: polymeric based organized systems
the nature of the chemicals and additives that are applied as well [18], LCT: liquid crystal template.

as synthesis temperatures and times, also alternative synthesis set-


ups and combinations thereof are being used to obtain the neces- applied synthesis conditions [4,12,19]. SBA materials, on the other
sary synthesis conditions (reux setups, autoclaves for hand, have been made by use of POS (polymeric based organized
hydrothermal treatments and microwaves) [1117]. For this rea- system) surfactants that interact through an indirect reaction of
son, knowledge of the synthesis methods and parameters that the template with the positively charged silica source
inuence the nal material will allow pore size engineering and ((S0H+)(XI+)) in acid medium [2022]. A neutral interaction be-
control of the morphology and structural properties of the ob- tween MOS surfactants and an inorganic source results in the for-
tained material. Basically, the synthesis of mesoporous materials mation of e.g. HMS materials (S0I0) [4]. Moreover, also other
and its control can be limited to the altering of the combination parameters such as the pH, the presence of additives or not (e.g.
of the chosen surfactant type, the specic synthesis mechanism salts, swelling agents, co-solvents, co-surfactants etc.), concentra-
and the interaction of the silica source with the template mole- tions, specic silica source, solvent, temperature etc. [13,23,24]
cules (if present) (see Table 4.1) [4]. will allow ne-tuning of the nal material due to small changes
For example, M41S materials are made by a S+I direct interac- in the characteristics of the surfactant, the mechanism or the inter-
tion between an ionic, positively charged MOS (molecular based action. A detailed description of the different surfactants, mecha-
organized system) surfactant and a negatively charged silica source nisms and interactions has been reported in the review papers
in a basic environment. Three types of mechanisms, liquid crystal by Corma et al. [19] and Soler-Illia et al. [4].
templating, self-assembly and cooperative self-assembly have A general synthesis for the preparation of templated mesopor-
been suggested for the synthesis of M41S materials based on the ous materials can be described as the dissolution of the template
174 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

molecules in the solvent (with attention for pH, temperature, addi- nomically a good approach since it allows surfactant recycling, it
tives, co-solvents etc.) followed by addition of the silica source also has some important disadvantages: the surfactant cannot be
(TEOS, metasilicate, fumed silica etc.). After a stirring period at a removed completely by extraction and the condensation of the
certain temperature to allow hydrolysis and precondensation, the material is limited resulting in low structural and thermal stability.
temperature will be increased (sometimes combined with hydro- Moreover, the obtained material consists for a high percentage of an
thermal treatment or microwave synthesis, the addition of addi- amorphous phase. Therefore, when crystalline phases are crucial
tives or changes in the pH) in order to direct the condensation for their application (e.g. anatase in case of titania photocatalysts),
process. In a next step, the products will be recovered, washed heat treatments cannot be left out. For that reason, various in-situ
and dried. Finally, the template needs to be removed by calcination and post-treatment methods have been developed to stabilize mes-
procedures or extraction methods. The latter is environmentally oporous transition metal oxides. The most important stabilization
and economically the preferred procedure since it will allow the methods are summarized in Table 4.2.
recovery and recycling of the templates. However, extraction pro- Knowing the main mechanisms to form structured materials, a
cesses are often incomplete [25] and cannot be executed for all sur- short description of the veried mesoporous materials included in
factants and materials. Moreover, in contrast to calcination this publication will be given in order to assist the reader in the
procedures at high temperatures, extraction methods do not result selection of the optimal porous material for a given application.
in an additional condensation of the silica framework.
For non-siliceous materials, in addition to these important 4.1. M41S materials
parameters that control the formation of the structure, special
attention has to be paid to hydrolysis rates, redox reactions, phase The rst ordered mesoporous materials (IUPAC: 2 nm <
transformations etc. Indeed, the hydrolysis and condensation rates dp < 50 nm) that were reported are known as the M41S-type of sil-
of transition metal oxides are generally much faster than they are ica mesophases. They were rst reported in 1992 by Mobil [7177].
for silica. Therefore, various approaches have been applied to re- The Mobil researchers introduced self-assembling surfactants as
duce the uncontrolled hydrolysis and condensation in the synthe- structure directing agents to direct the formation of the SiO2 meso-
sis of transition metal oxides so that phase separations are avoided structured materials. Also, Chiola et al. [78], Di Renzo et al. [79] and
and good interactions between the inorganic source and the sur- Yanagisawa et al. [80] already reported on the formation of meso-
factant is obtained. The main factors to control the precursor reac- porous materials by making use of self-assembling molecules.
tivity are: (1) pH adjustment so that the solubility of the metal However, due to an only limited description of the synthesis and
oxides can be increased, in addition, the hydrolysis and condensa- characteristics of the materials, their synthesis did not lead to the
tion will be inhibited by the acid [2631], (2) retardation of great breakthrough as the publications and patents of Mobil.
hydrolysis through precursor complexation [3234], (3) use of M41S is the generic term for the various types of MCM (Mobil
non-aqueous solvents and a controlled amount of water to inhi- Composition of Matter) materials in the mesoporous range. All
bit/slow down the hydrolysis [29,31,35,36]. Some synthesis proce- M41S materials have well-dened uniform pores that are ordered
dures apply only one of the above-mentioned methods for the in the long range. However, the walls of the pores consist of amor-
formation of mesoporous transition metal oxides, others combine phous silica that can contain various heteroelements (e.g. Al [81
two or more of the synthesis approaches to obtain maximum con- 90], Ti [91,92], Co [93], Zr [94], Cu [88], Fe [88,95], Zn [88] etc.).
trol over the synthesis mechanism and properties of the nal mate- By changing the synthesis conditions, it is possible to alter the
rial. The best known example for the synthesis of transition metal ordering of the material and therefore create new types of struc-
oxides in this way is the evaporation induced self-assembly (EISA) tures belonging to the M41S family. The various types of M41S
which makes use of ethanol as the solvent, MCl as the metal oxide materials can be distinguished by the number after the acronym.
precursor and a MOS or POS template [2931,37,38]. Moreover, The three most important are: MCM-41 which is hexagonal
transition metal oxides are known to be less stable towards ther- [12,19,96101], cubic MCM-48 [19,81,101103] and lamellar
mal treatments due to possible redox reactions, phase transitions MCM-50 [104106]. In general, most M41S materials are made
and crystallization. Several strategies can be applied to prevent in basic environment with quaternary ammonium salts
structural collapse or the formation of unwanted crystal phases (CnH2n+1(CmH2m+1)3NX with n = 622, m = 14 and X = OH/Cl, OH,
etc. upon calcination or application of these materials. Furthermore, Cl, Br or HSO4) or gemini surfactants ([CmH2m+1(CH3)2NCsH2s
often extraction of the surfactant is done instead of calcination to N(CH3)2CnH2n+1]2Br with m and n = 1618 and s = 212). However,
avoid structural collapse. Although this is environmentally and eco- also sulphates, sulphonates, phosphates and carboxylic acids with

Table 4.2
Summary of various in-situ and post-treatment methods to increase the thermal stability of mesoporous transition metal oxides.

Stabilization method In-situ/Post- References


treatment
Pre-crystallized precursor particles In-situ [3943]
Hydrothermal (re)crystallization In-situ or Post- [4447]
treatment
POS surfactants and synthesis conditions for thicker walls In-situ [29,48]
Thermally stable surfactants/templates such as porous or non-porous carbon, CASH (combined assembly by soft and hard In-situ [4951]
chemistries), hydrocarbon additives, porous silica etc.
CVD (chemical vapour deposition) of metal tetraalkoxy groups with subsequent hydration to produce thicker pore walls Post-treatment [52]
Doping with sodium oxide (stability increase with increasing concentration of doped element) Post-treatment [53]
Ammonia treatment in gas or liquid phase (formation of small crystal domains before template removal) Post-treatment [5459]
Base treatment (formation of small crystal domains before template removal) Post-treatment [60]
Addition of mineral anions or cations (postponing crystallization to higher temperatures) In-situ or Post- [4,61,62]
treatment
Phosphate modication (postponing crystallization to higher temperatures) (high amounts will have negative inuence on Post-treatment [6370]
catalysis!)
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 175

Fig. 4.2. Schematic representation of the values of the packing parameters.

long alkyl chains are applied for the synthesis of MCM-41 and simplicity and ease in its preparation with negligible pore-net-
MCM-50 [107]. The key parameters for the M41S synthesis are working and pore-blocking effects [12]. It consists of an amor-
the hydrogel composition, the type and length of the surfactant, phous (alumino, metallo)-silicate framework forming hexagonal
the alkalinity, the temperature and the synthesis time. The type pores. MCM-41 has high surface areas of up to 1200 m2/g and large
of mesophase that will be obtained after a specic M41S synthesis pore volumes. The pores are very uniform causing narrow pore size
with quaternary ammonium salts can be predicted by the packing distributions [118]. The pores are unidirectional and arranged in a
factor (g-factor), which is a measure for the local effective surfac- honeycomb structure over micrometer length scales (Fig. 4.3).
tant packing [96,108110]. It includes the hydrophobichydro- A typical X-ray diffraction pattern of MCM-41 shows the hexag-
philic balance and therefore describes the tendency of the alkyl onal symmetry of the pore ordering (space group: p6m) (Fig. 4.4).
chains to minimize their water contact and maximize their inter- It typically contains four main reection lines (d100, d110, d200 and
organic interactions [110]. Also the Coulomb interactions between d210) or more at low angles (2h = 10). Since MCM-41 consists of
charged head groups are included. The solvating energies that also amorphous silica, it has no crystallinity at the atomic level. There-
determine the packing or shape of the surfactants in aqueous med- fore, no reections can be observed at higher degrees 2h.
ium are not included in this g-packing factor. It can be expressed as For classical MCM-41, the pores can be tailored to diameters be-
g aV0 l, where V represents the total volume of the surfactant chains tween dp = 1.5 and 20 nm. The largest pores can only be obtained
plus any co-solvent or organic additive between the chains, a0 the with the addition of swelling agents. The pore walls are quite thin
effective head group area at the micelles surface and l the kinetic with a thickness between 1 and 1.5 nm. The presence of these thin
surfactant tail length or curvature elastic energy (Fig. 4.2). The va- pore walls leads to low chemical and hydrothermal stabilities
lue of g increases as V increases or l or a0 decreases. [12,119]. In order to improve the stability of these materials,
In classical micelle chemistry, as the value of g increases above a
critical value, mesophase transitions occur. The expected meso-
phases as a function of the g packing factor can be summarized
as follows (Table 4.3) [1,96]:
These transitions reect a decrease of the surface curvature
from cubic through vesicular and lamellar. When the polar head
group has a large surface area, spherical structures are obtained.
On the other hand, lamellar or rod packing occurs when the head
groups are packed tightly with large aggregation numbers. By
changes in the synthesis conditions, the g packing factor and there-
fore also the ordering of the materials can be altered.
Additional information concerning the synthesis and character-
ization of M41S materials as well as the modication and applica-
Fig. 4.3. TEM image of the honeycomb structure of MCM-41 and a schematic
tions can be found in various reviews [5,12,19,96,111114]. The
representation of the hexagonal shaped one-dimensional pores.
M41S materials can be synthesized as powder materials, thin lms
on various supports or as monolithic materials. The monolithic
materials have, in addition to the ordered uniform micro- and mes-
opores, also controlled macropores and macroscopic morphologies
100
[115,116]. 110
Intensity / a.u.

200
4.1.1. MCM-41
Intensity / a.u.

MCM-41 is the most widely studied M41S material. It is often


210
used as a model to compare with other materials or to study fun-
damental aspects in sorption, catalysis [117] etc. This is due to the 3 4 5 6 7 8
2 /

Table 4.3
Overview of the value of g and the predicted mesophase [1,96]. 110 200

Packing factor (g) Mesophase 0 1 2 3 4 5 6 7 8


1/3 Cubic (Pm3n) 2 /
1/2 Hexagonal (p6m)
1/22/3 Cubic (Ia3d) Fig. 4.4. Typical XRD pattern of MCM-41 with indices of the diffraction planes.
1 Lamellar Inset: enlargement of the XRD pattern. The corresponding d-spacings:
(1 0 0) = 3.90 nm; (1 1 0) = 2.26 nm; (2 0 0) = 1.95 nm and (2 1 0) = 1.48 nm.
176 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

various techniques have been applied [12]. Some of these methods


include in-situ techniques like the addition of various salts
[120,121]. Other methods are post-modication methods such as
ion exchange [122], treatment in acid [123,124], grafting of orga-
nosilane functional groups to produce hydrophobic organic chains
on the surface [5,12,125,126] etc. On the other hand, attempts have
been made to increase the condensation and crystallization degree
in the pore walls of MCM-41 by hydrothermal treatments, intro-
duction of zeolite functionality by recrystallization in the presence
of zeolite templates, the formation of M41S materials with the in-
situ addition of molecular templates of zeolites or using zeolite
precursor particles as the inorganic source [127132].

4.1.2. MCM-48
Due to the smaller synthesis regime for MCM-48 when apply-
ing quaternary ammonium salts, the MCM-48 structure has been
far less studied than MCM-41 [133]. MCM-48 could be only
obtained with surfactant to silica ratios higher than 1
[104,108,133,134]. However, gemini surfactants have the intrinsic
ability to favour a cubic symmetry over a wide variety of condi-
tions [102]. MCM-48 is cubic and has BET surface areas, pore sizes
and volumes similar to MCM-41. The wall thickness of the pores
is thin for MCM-48 as for MCM-41 causing only limited chemical
and hydrothermal stabilities. The structure of MCM-48 is of par-
ticular interest since the pores are three-dimensional. The XRD Fig. 4.6. Cubic unit cell of MCM-48 with two independent micelle systems (red and
pattern consists of several lines in the region between 2h = 0 blue rods) separated by the pore wall (upper right). Mathematical representation of
and 10 (Fig. 4.5). Due to the amorphous nature of the pore walls, a G gyroid minimal surface (upper left). Representation of 2  4 cubic unit cells
again no diffraction patterns can be observed at high angles. Only without the pore walls. The rods represent two independent micelle systems (red
and blue) moving towards the (100) direction (bottom). (For interpretation of the
a broad band between 2h = 20 and 35 is present, indicating the references in colour in this gure legend, the reader is referred to the web version of
amorphous nature. this article.)
MCM-48 has a Ia3d symmetry that was conrmed by Monnier
et al. as being a 3D bicontinuous pore system [135]. The cubic pore
structure is mathematically ordered according to the minimal The interest in three-dimensional structured materials has in-
surface which was described for the rst time by Schoen [136]. creased over the last years. This can be attributed to the expecta-
The minimal surface dening the MCM-48 structure can be identi- tion that the 3D pore network could have some important
ed as a gyroid G or G-surface. Further mathematical aspects can advantages in catalysis and separation technology compared with
be found in the literature, see e.g. Ravikovitch and Neiman [137] one-dimensional systems. There is more agitation in the system
or Anderson [138]. The gyroid surface divides the cube into two due to an increased curvature in the pores. Moreover, the 3D net-
identical but separate compartments, creating two independent work reduces the chance of restrictions in diffusion, which is not
but intertwinning enantiomeric 3D pore systems. Fig. 4.6 shows limited to one dimension [111].
a schematic representation of the unit cell with two micelle sys-
tems (red and blue rods) following the pore system. The two inde- 4.2. SBA materials
pendent pore systems are interlocked and will run along the (111)
and (100) directions, but will never cross or join each other. The In 1998, a new family of highly ordered mesoporous silica
pore systems are represented by micelle rods that progress in spi- materials has been synthesized in an acid medium by the use of
rals around each other towards the (100) direction. commercially available non-ionic triblock copolymers (EOnPO-
mEOn) with large polyethyleneoxide (EO)n and polypropyleneoxide
(PO)m blocks [18,139,140]. Different materials with a diversity of
periodic arrangements have been prepared and denoted as SBA
materials (the acronym for Santa Barbara acids). A wide variety
332 of SBA materials has been reported in the literature, such as
211
420 SBA-1 (cubic) [141,142], SBA-11 (cubic) [139,143], SBA-12 (3D
Intensity / a.u.

422 hexagonal network) [139,143], SBA-14 (lamellar) [139], SBA-15


321400 431
Intensity / a.u.

(2D hexagonal) [139,140,143] and SBA-16 (cubic cage-structured)


[139,143145]. SBA-15 immediately attracted a lot of attention
3 4 5 6 7 8 because of its desirable features and is now the most intensely
2 /
studied SBA structure.
220
4.2.1. SBA-15
SBA-15 is a combined micro- and mesoporous material with
0 1 2 3 4 5 6 7 8 hexagonally ordered tuneable uniform mesopores (414 nm)
2 / [21,146]. The size of the micropores was found to depend on the
synthesis conditions and can vary between 0.5 and 3 nm in size
Fig. 4.5. Typical XRD pattern of MCM-48 (Ia3d space group) with indices of the
[147153]. It consists of thick microporous silica pore walls (3
diffraction planes. Inset: enlargement of the XRD pattern. The corresponding d-
spacings: (2 1 1) = 3.80 nm; (2 2 0) = 3.29 nm; (3 2 1) = 2.50 nm; (4 0 0) = 2.35 nm; 6 nm) responsible for the high hydrothermal stability of SBA-15
(4 2 0) = 2.10 nm; (3 3 2) = 2.00 nm; (4 2 2) = 1.93 nm and (4 3 1) = 1.85 nm compared to other mesoporous materials with thin pore walls like
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 177

MCM-41, MCM-48 and HMS [119,139]. X-ray diffraction patterns aqueous solution [22,146,153,159,160], whereas the polypropyl-
of the SBA-15 materials reveal the 2D hexagonally structured pores eneoxide blocks (PPO) are more hydrophobic and give rise to the
(p6mm space group) at low angles, whereas no diffraction pattern internal structure of the mesopore [18,22,159161]. A schematic
can be observed at high angles due to the amorphous nature of the representation of the structure-directing assembly of the PEO
pore walls (Fig. 4.7). and PPO blocks in SBA-15 can be seen in Fig. 4.10.
TEM investigation of the SBA-15 materials revealed the curved By changing the length of the polyethyleneoxide blocks, differ-
nature of the pores [154,155] (Fig. 4.8). ent amounts of micropores and changes in the pore wall thickness
However, it has been reported that SBA-15 materials with short could be obtained [21,160,161]. Moreover, the ratio of the number
or straight channels can be synthesized as well by, respectively, of polyethyleneoxide units to the number of polypropyleneoxide
decreasing the stirring time or adding salts during the synthesis units directs the mesophase (lamellar, hexagonal, cubic etc.) of
(Fig. 4.9) [156,157]. Moreover, these short-channel SBA-15 materi- the structure [5,160,162]. On the other hand, altering the length
als also give rise to smaller, less aggregated particles. of the polypropyleneoxide blocks will result in different mesopore
The shape and curvature of the pores was claimed to be impor- diameters [160]. Furthermore, synthesis parameters like tempera-
tant for the diffusion of molecules through the structure [154,158] ture [5,146,160,163165], pH [166] and the addition of additives
and the ultimate adsorption capacity [158]. The micropores in the such as co-surfactants, swelling agents, electrolytes, salts etc.
walls of the SBA-15 mesopores originate from the polyethyleneox- [5,167170] will allow pore size engineering and tuning of the gen-
ide blocks (PEO) in the triblockcopolymers that are directed to the eral properties and morphologies of SBA-15 to a large extent. A
wide diversity of morphologies [167175] has been reported for
SBA-15 such as rods, bers, gyroids, discoid-like, doughnut-like,
spheres (micrometer and millimeters sized), rope-like, etc.
100 (Fig. 4.11).
In addition, SBA-15 can be synthesized using low-cost silicon
sources [176180] and fast synthesis procedures [1417]. Due to
Intensity / a.u.

these desirable features, SBA-15 has attracted a lot of attention.


Since the development of SBA-15 a lot of research has been
done on the development and modication of materials with a
combined micro- and mesoporosity. It can be produced both as
bulk powder in large and small batches as well as in the form of
thin lms [181184] or as monoliths [185189]. In case of mono-
110 200
liths, the materials often are denoted differently, e.g. HOM-2
0 1 2 3 4 5 6 7 8 [188,189]. SBA-15 has been modied with a wide diversity of tran-
2 / sition metal oxides (V [190193], Ti [157,190,194197], Al [198
203], Zr [17], Ru [202], Rh [202], Fe [202] etc.) and organic func-
Fig. 4.7. Typical XRD pattern for SBA-15 materials (p6mm space group) with tional groups [204209] by post-synthesis and in-situ processes.
indices of the diffraction planes. The corresponding d-spacings: (1 0 0) = 9.80 nm;
(1 1 0) = 5.45 nm and (2 0 0) = 4.74 nm.
This gives the active SBA-15 materials the possibility to be used
in catalysis [190,192196,198200,202,210212], controlled re-
lease of drugs or antioxidants [213,214], removal of heavy metals
[215], photoluminescence [216,217], lithium batteries [218],
immobilization of enzymes [158,219], proton conductivity [209]
etc. Moreover, one of the interesting applications of SBA-15 is its
use as a template for the synthesis of (inverse) carbon replicas
[173,220224] and nanowires of various metals [225232].

4.2.2. SBA-16
When block copolymers with larger EO chains (e.g. EO106-
PO70EO106 = F127) are used as templates under acidic conditions,
SBA-16 can be formed at room temperature [20]. The large EO
chains will favour the formation of globular aggregated structures
[20,233]. SBA-16 can be obtained only in a narrow range of diluted
Fig. 4.8. TEM images and diffraction pattern showing the hexagonal ordering of
SBA-15 and the curved pores.

Calcination

PPO

PEO

mesopore
(4-14 nm)
micropore
Fig. 4.9. SEM image of SBA-15 (a) (inset: enlarged particle) and SBA-15 with short
channels (b). Fig. 4.10. Schematic representation of SBA-15 before and after calcination.
178 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Fig. 4.11. SEM images showing examples of a few different morphologies of SBA-15 (spheres, bers and rods).

surfactant concentration (35%) [20]. Similar to SBA-15, the tem- 110


plate can be removed by extraction in ethanol at low temperatures
or by calcination at elevated temperatures. After template removal, 200
a combined micro- and mesoporous material is obtained due to the

Intensity / a.u.
presence of PEO and PPO chains responsible for the formation of 211

Intensity / a.u.
220
the micropores and mesopores, respectively [146,249]. The narrow
pore size distributions, mesopore sizes around 6 nm, high surface
areas, large total pore volumes and thick pore walls (46 nm) of
1 1.5 2 2.5 3 3.5 4 4.5 5
SBA-16 resemble that of SBA-15. The thick pore walls result in high 2 /

chemical, thermal and hydrothermal stabilities of SBA-16 200


[119,234]. As in the case of SBA-15, the total pore volume, pore size
and relative fraction of micro- and mesopores can be controlled by
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
changes in the synthesis conditions (time, temperature, Si/surfac-
2 /
tant ratio, pH, type of surfactant, additives, cosurfactants etc.)
[235244,249,253]. Moreover, a wide variety of morphologies such Fig. 4.13. XRD pattern of SBA-16. Inset: enlargement of the diffraction pattern with
as spheres, cubes, rods etc. can be formed by careful control of the indices of the diffraction planes. The corresponding d-spacings: (1 1 0) = 11.31 nm;
synthesis method [240247]. Apart from various similarities with (2 0 0) = 8.02 nm; (2 1 1) = 6.39 nm and (2 2 0) = 5.88 nm.

SBA-15, the pore geometry and ordering of SBA-16 is different.


SBA-16 shows a broad hysteresis loop in nitrogen adsorption
desorption isotherms which closes around P/P0 = 0.45, indicating SBA-16 can be prepared in economically and environmentally
the presence of inkbottle pores (Fig. 4.12) [248250]. more friendly ways under fast [252] and mild conditions [253] or
X-ray diffraction patterns of SBA-16 reveal its three-dimen- via microwave synthesis [243,245]. SBA-16 materials can be made
sional cubic cage structure (Im3m space group) (Fig. 4.13) in bulk (powder) or deposited as lms on various substrates
[20,249]. A clear model of the structure based on TEM was pub- [254,255]. In accordance with all other mesoporous materials,
lished by Sakamoto et al. [251]. They observed that the cubic phase SBA-16 is often functionalized with various hetereoelements
consists of two non-interpenetrating 3D channel systems with [256,257] or organic functional groups [209,258,259] to improve
spherical cavities at the intersection of the channels. This 3D struc- their performance in various processes such as catalysis, sorption,
ture is expected to provide favourable mass transfer kinetics in separations etc. The functionalization can be achieved by in-situ
comparison to the 2D network of SBA-15. methods during synthesis or by post-modication processes.

4.3. Plugged hexagonal templated silica (PHTS): an analogue to SBA-15

By increasing the silica over surfactant ratio in the synthesis of


600
SBA-15, Plugged Hexagonal Templated Silica (PHTS) is formed
[154,224,260263].
500
-1

PHTS has the same basic characteristics as SBA-15. It consists of


Volume adsorbed STP / cm g

hexagonally ordered mesopores with diameters that are similar to


400
those of SBA-15. Moreover, it has thick pore walls (36 nm) perfo-
300
rated with micropores making PHTS a combined micro- and mes-
oporous material [264]. In addition, PHTS possesses microporous
200 amorphous nanoparticles (plugs) in the uniform mesoporous chan-
nels resulting in higher micropore volumes. The pillaring effect of
100 the nanoparticles gives PHTS a higher mechanical stability com-
pared to the pure SBA-15 [260,265]. In addition, PHTS possesses
0 a high hydrothermal stability, which improves when applying high
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
synthesis temperatures and longer synthesis times [260,266].
P/P 0
Therefore, PHTS is put forward as a good candidate for industrial
Fig. 4.12. Nitrogen sorption isotherm at 196 C for SBA-16 showing clearly a applications. Indeed, stability is one of the major factors that hin-
broad hysteresis loop. der prospective catalytic applications of mesoporous materials
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 179

[266]. Furthermore, PHTS materials have a characteristic nitrogen nanoparticles at the pore mouth) by simply adjusting the synthesis
sorption isotherm due to the presence of a tuneable amount of parameters [127,224,260]. In addition, altering the synthesis con-
both open and plugged sections induced by the dispersion of nano- ditions will allow controlling the size and stability of the plugs
particles in the mesopores (see Fig. 4.14 schematic representation) [266]. It was found that the minimum time required to obtain good
[224,260,262,267]. structural materials was 4 hours [262]. Moreover, increasing syn-
Nitrogen sorption isotherms at 196 C for both SBA-15 and thesis temperatures will result in increasing pore diameters and
PHTS are of type IV according to the IUPAC classication enlarged particle sizes. Changes in synthesis temperature result
(Fig. 4.14). The N2 sorption isotherms of PHTS show a one-step cap- in similar phenomena observed in SBA-15 materials and PHTS.
illary condensation in the adsorption branch, indicating the lling However, in contrast to SBA-15, the micropore volumes in PHTS in-
of the uniform mesopores. However, in contrast to SBA-15, PHTS crease when the synthesis temperature is raised, which was ex-
exhibits a two-step desorption. The rst desorption step is similar plained by the increase in the microporosity of the plugs [262].
to desorption from pure SBA-15 and can be assigned to desorption The synthesis mechanism of PHTS is described in the literature
of nitrogen from the open mesopores according to the normal Kel- [127]. By careful control of the stirring temperature and the
vin model. Desorption occurs at equilibrium conditions via a reced- amount of TEOS (tetraethylorthosilicate) used for the synthesis of
ing meniscus. The second desorption step can be attributed to the PHTS, different morphologies could be formed (Fig. 4.15).
nanoparticles (plugs) within the mesopores, plugging/narrowing At low temperatures and low TEOS concentrations smooth rods
part of the mesoporous channels and creating inkbottle-like sec- are formed, whereas at high temperatures spherical morphologies
tions. Therefore, nitrogen that is present between two nanoparti- will be obtained. The differences in morphologies were based on
cles can only be desorbed through the restricted pore entrance. the cloud point of the surfactant and the balance between the rate
For these plugged pores, desorption is delayed and results in a sec- of polymerization of the silica source and the rate of the meso-
ond desorption step at lower relative pressure compared to the structure formation [263].
open mesopores (rst desorption step). Catalytically active elements can be introduced in PHTS-type
Interpretations of the size of the nanoparticles and therefore materials in different ways. On the one hand, metal acetylaceto-
also the diameter of the pore at the plugs should be done with care. nate complexes can be deposited on the surface of the PHTS mate-
Indeed, the relative pressure at P/P0 = 0.42 depends weakly on the rials by use of the liquid-phase molecular designed dispersion
pore size and pore geometry in nitrogen sorption measurements method (MDD) [271]. This way, a dispersed layer of metal oxides
due to the lower closure point of the hysteresis (P/P0 = 0.42) for is formed on the surface of PHTS after calcination. Depending on
nitrogen [224,268270]. When this lower closure limit is reached, the size of the molecule and the temperature applied, molecules
capillary evaporation can no longer be delayed in the plugged sec- can be deposited in the entire pore or can be excluded from the
tions. Kruk et al. proved that using argon adsorptiondesorption plugged sections. Also other post-synthesis impregnation methods
isotherms (lower closure point limit at a relative pressure of ca. have been applied to introduce heteroelements on the surface of
0.3), all constrictions in the porous structure of PHTS, plugging PHTS materials [272,273]. On the other hand, PHTS materials can
the mesopores, are likely to exhibit diameters above ca. 45 nm be activated by introducing metal oxide or zeolitic nanoparticles
[224]. By modication with hexyldimethylsilyl (HDMS) and decyl- into SBA-15 [274279]. This way the catalytically active elements
dimethylsilyl (DDMS), it was estimated that the largest diameter of are introduced into the pores of SBA-15 at the same time as the
the constrictions were larger than 2.4 nm but smaller than 3.4 nm transformation of the material into a PHTS-type material. By an
[266]. Therefore, for materials with hysteresis loops closing at incipient wetness impregnation of a preformed nanoparticles sus-
P/P0 = 0.42, argon adsorptiondesorption measurements or surface pension in SBA-15, PHTS materials and their properties can be tai-
modication techniques should be carried out if information con- lor-made in a controlled way. Both the plugging as well as the
cerning the real size of the plugs and pore entrances are needed heteroelement are introduced by post-synthesis modications. Re-
[191,224,266,269]. The ratio of open to plugged pores can be tuned cently, also in-situ introduction of heteroelements in PHTS has
from 100% open pores to fully plugged pores (inkbottle pores with been achieved [280,281]. By carefully choosing the right method

600 350
-1

-1
Volume adsorbed STP / cm g

Volume adsorbed STP / cm g

500 300
Open
400
mesopore 250

plugged 200
300 mesopore
150
200
PHTS 100
100
SBA-15 50

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P /P 0 P /P 0

plug

open plugged
mesopore SBA-15 with
SBA-15 PHTS mesopore
inkbottle pores
Fig. 4.14. Nitrogen sorption isotherms at 196 C for SBA-15, PHTS and SBA-15 with inkbottle pores. Schematic representation of the different pore structures.
180 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Fig. 4.15. Different morphologies (smooth bers, rough bers, spherical) of PHTS synthesized by changes in the stirring temperature [263].

to introduce the heteroelements, it is possible to control the loca- ammonium uoride can selectively enlarge the windows by 50
tion of the active elements: (1) on the surface in the entire pore 80% [282,284].
system, (2) on the surface only in the open pores, (3) only in the The nitrogen sorption isotherms of MCF show inkbottle pores
plugs, (4) incorporated in the silica walls, and combinations of due to the presence of the large windows that provide accessibility
the previous. to the spherical cells. The structural properties of MCF materials
can be controlled by adjusting the synthesis parameters (time,
4.4. MCF temperature, pH, additives, swelling agent etc.) [157,282287].
Moreover, the morphology and particle size of the MCF materi-
Mesostructured cellular foam (MCF) is made by addition of a als can be altered by simple adjustments during the synthesis
swelling agent to the synthesis of SBA-15 [282284]. Often, mesit- [157,288]. Various heteroelements [289292,295] and functional
ylene (1,3,5-trimethylbenzene) is chosen, but other swelling groups [293,296302] have been introduced into MCFs via post-
agents are applied as well. The swelling agent causes an synthesis modication or in-situ techniques in order to increase
enlargement of the micelle resulting in a sponge-like foam with their performance in (bio)catalysis, sorption, controlled release,
three-dimensional structure with large uniform spherical cells separations etc. MCFs have been produced as bulk powders or
(1550 nm), accessible via large windows (520 nm) (Fig. 4.16). monoliths [303305].
Therefore, MCF is a very open structure with large uniform pore MCF materials are often desirable due to their fast mass transfer
diameters and large pore volumes (Fig. 4.17). It has thick pore kinetics, good accessibility for large molecules (e.g. polymers, en-
walls resulting in a high hydrothermal stability. The addition of zymes, etc.) and their large pore volumes that are benecial in var-
ious processes [157,290,294,298].

4.5. MSU

The acronym MSU stands for Michigan State University where


the synthesis of MSU was developed. MSU materials are prepared
with non-ionic polyethylene glycol polymers (not necessarily tri-
block copolymers) in neutral environment in contrast to SBA-15,
PHTS and MCF which are made in acidic media [306]. The various
types of MSU materials are often called the MSU-X family of
materials where X is a number or a letter. The numbers and let-
ters are used to distinguish among the different materials. For
example, MSU-1 is made with alkyl-PEO alcohols like tergitol,
MSU-2 with alkyl-aryl-PEO surfactants like triton-X or igepal,
MSU-3 with block copolymers like pluronic, MSU-4 with ethoxy-
Fig. 4.16. TEM image of an MCF structure. lated derivatives of the fatty esters of sorbitan like tween
[306,307]. Most of the MSU materials present only local structural
ordering and are called wormhole framework structures
2100
[306,308]. However, also highly ordered mesoporous MSU materi-
als have been developed that were denoted MSU-H (hexagonal)
-1

1800
Volume adsorbed STP / cm g

[307,309] as well as foam structures made with the addition of


1500
d v (r )

swelling agents (MSU-F) [308]. Other types of letters that can


1200 be placed after the acronym are MSU-S used for aluminosilicate
MSU materials that are synthesized using zeolite seeds and exhi-
900
bit improved hydrothermal stability compared to conventional
600 0 5 10 15 20 25 30 35 40 MCM-41 aluminosilicate materials. This often coincides with the
Radius / nm
addition of HBEA or WBEA to the nomenclature meaning that the
300
MCF SBA-15 structure was made by using zeolite beta (BEA) seeds and H
0 and W indicate the hexagonal or wormhole-like ordering of the
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
materials, respectively [310,311]. When vesicular particle archi-
P /P 0
tectures are obtained and a lamellar pore arrangement, the mate-
Fig. 4.17. Nitrogen adsorption-desorption isotherm at 196 C of SBA-15 and MCF. rial is denoted as MSU-V [312,313]. Also MSU-G exhibits a vesicle
Inset: pore size distribution deduced from the adsorption branches. like hierarchical structure [314].
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 181

Since the template is not necessarily a triblock copolymer, not way not only aluminium but noble and base metal ions have been
all MSU materials will possess micropores next to the controlled dispersed throughout mesoporous aluminosilicates and silica.
and uniform mesopores. Due to the fact that the synthesis occurs They can be either reduced to the metallic form (Rh, Pt, Ir, Ru)
in neutral environment, the interaction between surfactant and [346] or oxidized (Co, Ni, Cu, Ag) [347349].
the inorganic source is of the type S0I0 instead of the bridged inter- Through 27Al MAS NMR, the environment of aluminium in DLCT
action with the counterion of the acid ((S0H+)(XI +)) in case of SBA- aluminosilicates was shown to depend on the Si/Al ratio. The alu-
15, PHTS and MCF. This neutral interaction allows easy extraction minium was predominantly tetra-coordinated in materials of Si/Al
of the surfactant after synthesis. Therefore a more economical syn- ratio up to 15, tetra- and hexa-coordinate in samples of Si/Al of 10.
thesis is attained because of higher recovery yields of the surfac- Penta-coordination was observed in materials of low Si/Al ratio
tant after extraction. As in case of the preparation of all [347]. The strength of the acid sites has been investigated in detail
mesoporous templated materials, the structural and morphological using a combination of calorimetric, gas phase adsorption and
properties of MSU can be designed by careful control of the synthe- spectroscopic techniques [350]. For all Si/Al ratios, the acid
sis parameters (time, temperature, type of template, additives, etc.) strength is higher than that of aluminium substituted MCM-41
[315327]. Addition of uoride causes an in-depth mineralization types [351], which confers activity of interest in catalysis where
improving the structural quality of the nal material without medium acid strength is required. Bimetallic Pd/Pt and Pd/Rh par-
changing the pH of the solution [306,307,328]. For the synthesis ticles supported on DLCT aluminosilicates catalyse the hydrogena-
with tween surfactants, the addition of uoride ions is even a pre- tion and ring opening of polyaromatics components of light cycle
requisite to obtain good structures [307]. Moreover, cheap silicon oil to molecules of high cetane number [352354]. Copper and sil-
sources can be used to make the synthesis more cost-effective ver oxide functionalized DLCT aluminosilicates show activity in the
[308,329,330]. separation of propene from propane/propene mixtures [347,348],
To achieve high activity and performance in a variety of appli- while functionalization with supported cobalt, copper and iron oxi-
cations, MSUs can be modied with several heteroelements des confers de-NOx activity [349]. The direct liquid crystal tem-
[310,314,331335]. The MSU materials have been prepared as bulk plating approach has been extended from the use of oligomeric
materials as well as in lms [336] and monoliths [185,304,337 non-ionic surfactants to block copolymer templates [355357]
339]. The monolitic materials are designed to feature also a con- which enables preparation of large transparent aluminosilicate
trolled macroporosity and macroscopic morphologies next to the monolithic mesophases and pore sizes in corresponding calcined
adjustable micro- and mesoporosity. Their basic structure resem- materials in the range 37 nm [358].
bles that of MSUs but some special attention is needed in the syn-
thesis to allow control over the macroscopoic properties. In case of 4.7. Mesoporous titania
monoliths, the materials often have alternative terminology.
Templated mesoporous transition metal oxides are made in a
4.6. Direct liquid crystal templating (DLCT) similar way as their silica counterparts. However, special attention
needs to be given to the higher reactivity of the transition metal
An alternative synthesis route to mesoporous materials uses di- precursors in comparison to the silica sources. Only control over
rect templating by preformed lyotropic liquid crystal phases that the hydrolysis and condensation reactions and other aspects such
are prepared under high surfactant concentrations, generally >20 as phase transformations etc. will allow the formation of dened
wt.% [340345]. Both non-ionic and ionic surfactant types may porous structures. Therefore, various methods to temper the reac-
be used. The pore size can be controlled in the super-microporous tivity are applied in combination with a wide variety of in-situ or
to mesoporous range. Particular aspects of the synthesis are that: post-synthesis approaches to prevent the occurrence of uncon-
(1) It uses a molecular source of silicon (tetramethoxy- or tetraeth- trolled redox reactions, phase transformations etc. These are de-
oxysilane, TMOS, TEOS). (2) The synthesis is essentially solvent- scribed in the rst part of this chapter containing the general
free, TMOS or TEOS are being used as the solvent for heteroatom synthesis mechanisms and in several reviews [4,8]. Titania is one
salts (generally nitrates or metal organic compounds). (3) The syn- of these metal oxides that suffer fast hydrolysis and condensation
thesis takes place under conditions of controlled alkoxide hydroly- reactions resulting in poorly structured and even non-porous
sis and condensation, coupled with removal of the produced materials. This is regarded as the rst fundamental issue towards
alcohol in order to prevent disruption of the liquid crystal phase the synthesis of mesoporous titania. Various methods for the syn-
structure. The high concentration of surfactant required for direct thesis of mesoporous titania exist [4,8,65]. However, the best
liquid crystal templating is maintained throughout the whole pro- known synthesis approach to obtain the controlled formation of
cess and the phase structure is preserved by the solgel formation mesoporous titania is the evaporation induced self assembly
of silica in the hydrophilic domains. This results in a solid replica, a (EISA). This method combines different ways to temper reactivity
nanocast of the liquid crystal phase. Precipitation of a powder form such as synthesis in non-aqueous solvents (often ethanol) and
product is avoided and macroscopic (monolithic) porous objects acidic inhibition to temper condensation. The EISA method was
are obtained. The shape and size of the monoliths can be con- rst described by the group of Stucky for the formation of a wide
trolled. (4) The synthesis gel contains no cations other than pro- variety of transition metal oxides (TMOs) using ethanol as the sol-
tons, avoiding any need for an ion-exchange step. vent, MCln as the TMO source and a polymeric template [29,31]. La-
The DLCT methodology has been used for the preparation of ter, the EISA method was further optimized by Soler-Illia et al. via
super-microporous and mesoporous silica and aluminosilicates complexation of the titania precursor with alkoxides and the addi-
using a range of non-ionic surfactants of the Brij, Tergitol and tion of a controlled amount of water resulting in further retarda-
Montanox types [344]. Alkylene oxide segments of the surfactants tion of the hydrolysis and condensation kinetics [30]. This
can form crown ether-type complexes with inorganic ions through approach was done in combination with the use of MOS templates
weak coordination bonds, allowing direct preparation of hetero- such as CTABr (cetyltrimethylammonium bromide), inuencing
atom-containing mesoporous silicas [344,346]. The interaction be- the kinetics of hydrolysis and condensation even more strongly
tween metal ions and alkylene oxide segments ensures the due to ligand assisted templating. Although the mesoporous titania
dispersion of heteroatoms throughout the nascent mesophase, can be formed in a controlled way, it often possesses only local
while the strength of interaction can impact the extent to which ordering. Nevertheless, materials with high degree of ordering
a given metal ion is incorporated in the silica framework. In this can be obtained by mixing two types of titania precursors. It
182 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

consists of combining acidbase pairs which are titania precursors


such as a titanium salt (TiCl4) (inducing acidity) in combination
with a titaniumalkoxide (inducing alkalinity). They can easily react
to form low polymerized homogeneous precursors and self-control
of the inorganic polymerization is obtained [359361]. With the
EISA method, a critical micelle concentration (cmc) will be ob-
tained upon evaporation of the solvent. The synthesis should be
controlled in such a way that hydrolysis and condensation occur
upon micelle formation while a good interaction between the inor-
ganic titania source and the template is ensured. After formation of
the network, the material is subjected to a mild thermal treatment
to allow further condensation and strengthening of the network.
Afterwards, the template needs to be removed by extraction or cal- Fig. 4.18. HRTEM image of: (a) Na-TTNT, and (b) H-TTNT.
cination procedures. During calcination and any other heat treat-
ments, care must be taken to prevent structural collapse or
uncontrolled phase transformation. A wide variety of methods is
known. They are described in Table 4.2 in the rst part of this
chapter.

4.8. Titania nanotubes

Intensity / a.u.
Since the discovery of carbon nanotubes in 1991 by Iijima [362], b
much research has been devoted to the development of nanoscale
tubular materials. Especially, nanostructured titania has lately re-
ceived much attention due to its potential in a broad range of
a
applications like photocatalysis [9] (e.g. water purication), solar
cells [363], electronics [364,365] (e.g. lithium ion batteries), sen-
sors [366] (e.g. hydrogen sensing), membranes [367,368], medicine 0 10 20 30 40 50 60 70 80 90 100
2 /
[369,370] (e.g. bone tissue regeneration), adsorbers [371] (e.g.
treatment of radioactive liquid waste) and catalyst supports Fig. 4.19. X-ray diffraction patterns of: (a) Na2Ti3O7, and (b) acid washed H2Ti3O7
[372] (e.g. CO oxidation). In 1998, Kasuga et al. synthesized TiO2 nanotubes.
nanotubes for the rst time by a quick, cheap, simple and tem-
plate-free hydrothermal synthesis procedure [373]. The formation
mechanism of the Ti-based nanotubes is, however, still under dis- [387] based on the density functional theory were consistent with
cussion. According to Kasuga et al. [373] and other researchers the assumption that the intercalated sodium ions can be replaced,
[374,375], the acid washing process of the precipitate after hydro- even though the Na2Ti3O7 structure is very stable. This is possible
thermal treatment is essential for formation of trititanate nano- since the sodium ions are only weakly bonded to the negatively
tubes. However, several other authors [376,377] found evidence charged Ti3 O2
7 layers. Sodium can easily be exchanged for hydro-

that trititanate nanotubes are formed during hydrothermal treat- gen by acid washing, producing H-TTNT materials (Fig. 4.19). How-
ment. Nevertheless, there is a consensus that after chemical bond ever, also transition metals like Co2+ or Cu2+ can be intercalated
breaking of the bulk titania in NaOH, two-dimensional nanosheets [388]. This is interesting in view of photocatalysis under visible
are formed which can be converted into nanotubes by a sheet-fold- light.
ing mechanism [378381] (Fig. 4.1D). Also, the crystalline phase of Nitrogen sorption results reveal that there is a signicant differ-
the synthesized nanotubes is still a matter of controversy. Indeed, ence in the specic surface areas of the different trititanate nano-
various different crystalline phases were claimed to be obtained tubes (205 m2/g for Na-TTNT and 333 m2/g for H-TTNT) [9]. This
after hydrothermal treatment of a chosen TiO2 source in a NaOH can be explained by taking into consideration that the large so-
solution, such as TiO2 (anatase) [373], monoclinic sodium trititan- dium cations with large hydration spheres are exchanged by small,
ate (Na2Ti3O7)[382] or Na2Ti2O4(OH)2 crystal phases [383,384]. poorly hydrated protons during the acid treatment. The ion ex-
Trititanate nanotubes (TTNT) are prepared via a hydrothermal change process results in a smaller interlayer distance and a de-
synthesis method [9,385]. Hydrothermal treatment of a TiO2/NaOH crease in strain energy. The relaxation of these tensed bond
mixture yields a well formed tubularly shaped nanomaterial. These lengths and angles, originating from the curvature of the layers,
sodium-containing multiwall tubular structures consist of a num- leads to small differences in the nanotube dimensions which are
ber of shells with interlayer distances of about 0.74 nm and an in- responsible for the increase in surface area.
ner pore diameter of 44.2 nm (Fig. 4.18). The fact that the Next to ion exchange, anatase crystal domains can be obtained
nanotubes are not symmetric conrms the nanosheets fold up within the nanotubes by means of simple calcination processes or
according to a rolling up mechanism during hydrothermal treat- hydrothermal treatments [9,389,390]. This will result in a signi-
ment. Furthermore, the obtained nanotubes are open at both ends, cant increase in photocatalytic activity.
which makes the inner pore easily accessible. This is in contrast to Besides the classical synthesis of titania and trititanate nano-
most carbon nanotubes that have caps closing off their ends. tubes by hydrothermal treatment in conventional ovens, also
The titania and trititanate nanotubes consist of small nanocrys- microwave assisted syntheses have been reported [9,391394].
talline domains due to the nanometer size dimensions of the tubes.
The trititanate crystals are built up by the interconnection of three 5. Characterization techniques
TiO6 octahedra which share edges. These chains of octahedra join
at the corners to form a stepped, zigzag ribbon layered structure. This chapter involves characterization techniques briey de-
Between these negatively charged Ti3 O2 7 layers, sodium cations scribed, that have been used in order to characterize the synthe-
are located [386]. Results of ab initio calculations by Zhang et al. sized materials. Only a limited number of techniques are
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 183

described that are most commonly applied for the characterization (once all these requirements are fullled the systems jumps
of ordered mesoporous materials. It is clear that in addition other to the next point in the adsorption isotherm). The operator
more advanced techniques can be applied as well. should dene the stringency of the pressure readings criteria
Detailed descriptions of the techniques are given, together with depending on the nature of the sample. In this sense, care must
some recommendations for good practice. be taken when using samples where the presence of narrow
microporosity is expected.
5.1. Adsorption
A conclusive proof to asses the presence of true equilibrium
5.1.1. N2 adsorption isotherms conditions would be to check the effect on the adsorption isotherm
The correct characterization of the textural properties of nano- of either: (i) an increase in the stringency of the pressure readings
porous materials is very helpful to verify the success of the synthe- criteria, e.g. an increase in the equilibrium time, (ii) the effect of
sis process [395]. Additionally, the exact knowledge of the porous an increase in the adsorption temperature and/or (iii) to check the
network (micropores, mesopores and macropores) will be useful to uptake in the desorption branch. In the absence of kinetic restric-
understand the behavior of the new material in a future applica- tions: (i) the uptake must be independent of the pressure reading
tion. Commonly, the textural characterization of porous solids is criteria used over the whole relative pressure range, (ii) at a higher
performed using adsorption of probe molecules (Ar, N2, CO2, adsorption temperature the adsorption capacity must decrease
etc.). Among them, N2 adsorption at low temperature (196 C) over the whole relative pressure range, as it corresponds to an exo-
is the most widely used [396]. N2 adsorption covers the relative thermic process, and (iii) the desorption branch of the isotherm
pressure (P/P0) range from 106 to 1 and provides information must always close with the adsorption branch once the hysteresis
about the whole microporosity (up to 2 nm) and the mesoporosity. loop is closed (it must never remain above or below).
Although the use of N2 adsorption at 196 C for the character-
ization of porous materials is widely spread, the reported values 5.1.2. Analysis of the N2 adsorption isotherms
not always reect the real porous structure of the material. Usu- As stated above adsorptiondesorption of N2 at 196 C may be
ally, there are many inherent errors associated with the sample, used for the characterization of the porous texture on newly devel-
the equipment, the operator, etc., which must considered carefully oped materials. Prior to the measurement, the sample must be out-
in order to obtain reliable measurements. Although most of these gassed overnight under high vacuum at around 200 C. The N2
problems are not so important in mesoporous materials, they be- isotherm can provide information about the surface area, the
come very important when there is microporosity present [397 porosity and the pore volume [395,400].
399]: The adsorption isotherms for mesoporous materials are type IV
according to IUPAC classication [401], with capillary condensa-
Concerning the sample, there are critical parameters to be con- tion at medium relative pressure being indicative of mesoporosity
sidered such as the amount of sample used in each measure- [118]. In some cases the desorption branch is different to the
ment (commonly 0.1 g) and the shape of the sample (powder, adsorption path, the isotherm then exhibiting a hysteresis loop.
grain, pellet, monolith, etc.). It is noteworthy to mention that The shape of the hysteresis loop provides information about the
the textural properties of a certain sample should differ for the shape and the size of the mesopores.
powder or grain to the pellet or the monolith (e.g. breaking a The apparent or equivalent surface area is usually calculated
monolith to t the sample holder could provide an erroneous by application of the BET equation to the N2 adsorption isotherm.
characterization). Additionally, when using heavy pellets or The model calculates the volume of the monolayer of adsorbed
grains, care must be taken with the amount of sample since molecules on the surface and the surface area is directly obtained
the use of a single pellet or grain could differ considerable from by application of the following equation:
other individual pellets or grains. Thus, the use of several pellets
SBET nm  A  N A  1018 m2 =g
or grains in order to obtain an average value is highly encour-
aged. In these cases an increase of the amount of sample used with nm is the number of molecules adsorbed at the monolayer cov-
will drastically reduce the error. erage; A the mean cross-sectional area of the gas molecule (e.g. N2:
Concerning the automated equipment, the errors usually come 0.162 nm2); NA the Avogadro number.
from the lack of precision at low relative pressures. Automated In most mesoporous materials the range of linearity of the BET
equipments are frequently supplied with only a pressure-trans- equation, after plotting [(P/P0)/(n  (1  P/P0))] vs. P/P0, is in the rel-
ducer (1.33 105 Pa) which fails when trying to perform high-pre- ative pressure range (P/P0) from 0.05 to 0.30. However, if micropo-
cision isotherms (below P/P0  103104). The incorporation of rosity is also present this range will be leading to false values
a second pressure-transducer with a higher precision (133.3 or because the linearity of the BET plot will be greatly reduced to
1333 Pa) avoids the aforementioned drawbacks and allows about the 0.050.15 range. It is recommended to do the analysis
achieving high-precision adsorption measurement starting at of the BET equation after plotting the experimental data and check-
relatives pressures below 106. ing the range of linearity, not using the information directly pro-
Concerning the operator, the errors usually come from the lack vided by the automatic equipment. However, it is important to
of experience in the manipulation of the equipment, together remember that the intercept must be always positive indepen-
with the ignorance about the way the adsorption equipment dently of the porous nature of the material.
operates. First of all, the automated equipment must be fre- The micropore volume (Vmicro) can be estimated following three
quently calibrated (pressure reading, xed volumes, etc.) to approximations: applying the DubininRadushkevich (DR) equa-
avoid uncertainty in the adsorption data. Secondly, the opera- tion to the N2 adsorption data or using two different comparative
tor should ensure that the adsorption data are obtained under methods, the as-method and the t-method. In the DR method,
true equilibrium conditions. Usually, the software of the the logarithm of the amount adsorbed (log Vads) is plotted against
adsorption equipment allows to dene for each point in the the square logarithm of the inverse relative pressure (log2 (P0/P)).
adsorption isotherm: (i) the time left between consecutive Only the central region of the plot, which corresponds to the
pressure readings to ensure that the equilibrium has been micropores range (log2(P0/P) between 2 and 15), must be tted
reached, (ii) the number of pressure readings to be considered, to obtain a straight line. The extrapolation of this line provides
and (iii) the deviation allowed within these pressure readings the volume of micropores (log Vmicro).
184 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

The as and the t methods, both are based in the comparison of X-ray diffraction can also be carried out on powders, and this is
the adsorption isotherm with that of a non-porous reference sam- the way it is typically applied to mesoporous materials. Fig. 5.1
ple [400]. In the as-method the amount of N2 adsorbed is plotted shows powder X-ray diffraction patterns of different substances,
against the as value, which corresponds to the ratio Va/V0.4, ob- the basic composition of which is that of silica, SiO2 (disregarding
tained from the reference isotherm at each relative pressure (Va/ the presence of different amounts of surface silanol groups).
V0.4 represents the ratio between the amount adsorbed at each rel- Quartz, of course, is a crystalline material, and the regular periodic
ative pressure and that adsorbed at P/P0 = 0.4, once the monolayer arrangement of the atoms gives rise to sharp signals (Fig. 5.1a). On
is already formed and the micropores are already lled, on the ref- the other hand, silica gel is amorphous and does not show sharp
erence sample). The extrapolation of the initial linear part of the signals (Fig. 5.1c); only with magnication, a broad hump becomes
as-plot intercepts with the Y-axis and provides the volume of visible between 17 and 30 2h. As in the gel phase, the silica in
micropores. In the t-method the amount of N2 adsorbed is plotted mesoporous materials is amorphous. Correspondingly, in the mes-
against t, which corresponds to the multilayer thickness for the oporous sample (Fig. 5.1b), no sharp peaks are seen in the 2h region
adsorption of N2 on the non-porous reference solid. The t-values where crystalline quartz displays its Bragg reections. However,
are calculated from the reference isotherm as follows: mesoporous silicas do exhibit reection at low diffraction angles,
t n=nm  d typically in the region between 0.8 and 5 2h. In Fig. 5.1, this re-
gion is displayed on an enlarged 2h-scale in the inset. The presence
with n is the amount of gas adsorbed at each relative pressure; nm of these peaks is not due to a regular periodic arrangement of
the monolayer capacity calculated from the linear BET-equation; d atoms, but to a regular array of pores with diameters in the small
the mean thickness of the N2 monolayer (0.354 nm). nanometer range. The peaks can be indexed on a cubic lattice and
In the same way as the as-method, the extrapolation of the lin- from their arrangement, it can be deduced that the sample has the
ear part of the t plot intercepts with the Y-axis and provides the MCM-48 pore topology.
micropore volume of the material. Due to their similar principles, More precisely, as it is the electrons that scatter the X-ray
the micropore volume obtained from both methods must be quite beams, it is the difference in electron density between the pore
similar. walls and the empty pore space which gives rise to these reec-
The total pore volume (Vtotal) is obtained from the amount of tions. When there is some material inside the pores (for example
nitrogen adsorbed at a relative pressure P/P0  0.950.99. The re- the templating surfactant molecules in the as-synthesized state),
ported value can be expressed both as a volume of adsorbed gas this electron density contrast is smaller and, correspondingly, the
or, most commonly, as the volume of adsorbed liquid using the fol- intensity of these low-angle diffraction peaks is diminished. In ex-
lowing equation: treme cases, the intensity of these peaks can even vanish, in spite
of the fact that a perfectly ordered pore system is present.
V liq 1:54  103  V ads The MCM-48 material, the diffraction pattern of which is dis-
The pore size distribution in the mesopore range can be ob- played in Fig. 5.1b, can be considered as an ordered mesoporous
tained using the BJH (BarretJoynerHalenda) method. The meth- material (OMM). Often, products of surfactant-templated synthe-
od is based on the Kelvin equation, predicting the formation of ses only give a single, broadened diffraction peak at low angles.
liquid N2, at the capillary condensation step, in the larger pores Then, it can only be deduced that within the sample, the electron
of the material. The equation expresses the relation between the density varies with a certain periodicity. This periodicity corre-
condensation of N2 in the mesopores of a certain size. In this sponds to the d value which can be calculated from the peak posi-
way, based on the model the relation between P/P0 and the pore ra- tion 2h via the Bragg equation. The broadening indicates variations
dius can be deduced. This allows the formation of the pore size dis- of the periodicity around the calculated value. Whereas such
tribution of the material. samples can be highly mesoporous (as deduced for example from

5.2. X-ray diffraction (XRD)

X-ray diffraction is one of the most important and most powerful


methods for the investigation of materials. This method is based on
the scattering of X-rays by the electrons of atoms. The wavelengths
of X-rays are similar to interatomic distances, and so the X-rays scat-
tered by different atoms will interfere destructively or construc-
tively, in the latter case giving rise to diffracted beams. In the case
of crystalline samples, sharp diffraction phenomena result. The
geometry of the corresponding diffraction events can be described
by Braggs law, which combines a measure of the lattice of the crys-
tal structure, namely the distance d between lattice planes, the
wavelength k of the X-ray radiation and the diffraction angle h:
2d sin h k:
The Bragg equation treats diffraction as the reection of X-rays
at the lattice planes; correspondingly, a diffraction event is usually
called a reection.
By analyzing the geometry of the diffracted beams, information
can be gained on the geometry of the lattice of the structure under
investigation. By further analyzing the intensity distribution of the
reections, information on the positions of the atoms can be ob-
tained. This is usually carried out by measuring X-ray reections
on a single-crystal and forms the basis of X-ray single-crystal Fig. 5.1. Powder X-ray diffraction patterns of silica samples: (a) crystalline a-
structural analysis. quartz, (b) mesoporous MCM-48, and (c) amorphous silica gel.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 185

sorption measurements) they are not OMMs, as the characteristic series of TEM images taken at a tilt angle range of +70 to 70. Be-
order of the pores is missing. cause the beam direction is xed in electron tomography, the sam-
ple is rotated around a single axis to obtain the images at different
5.3. Scanning electron microscopy (SEM) tilt angles. The reconstruction can be visualized with contour sur-
faces that give information about the surface of the sample, as well
Scanning electron microscopy characterization is used primar- as with slices though the reconstruction that give detailed infor-
ily for the study of surface topography and morphology of solid mation on the interior porous structure of the sample. The resolu-
materials on a scale down to about 10 nm. Topographical features, tion of a 3D reconstruction is approximately given by the relation:
Q
void content, particle agglomeration as well as compositional and Resolution = * thickness of the sample/number of images. In the
structural differences within the material can be revealed. late 1960s, 3D TEM has already been pioneered in the eld of biol-
The technique works on the principle that an electron beam is ogy. Nowadays, with the power of the current generation of com-
passing through an evacuated column and focused by electromag- puters for the calculation of the reconstruction, advanced
netic lenses onto the material [402]. The beam is scanned over the tomography has evolved into a breakthrough technique for the
specimen surface in synchronism with the beam of a cathode ray characterization of nano-structured solid materials and catalysts.
tube (CRT) display screen. Inelastically scattered secondary elec- For any microscopy method, care has to be taken that the few
trons are emitted from the sample surface and collected by a scin- particles actually imaged are representative for the bulk of the
tillator, the signal from which is used to modulate the brightness of material under investigation. Many particles (or sample areas)
the cathode ray tube. In this way the secondary electron emission need to be inspected by the operator rst before deciding on which
from the sample is used to form an image on the CRT display particles or areas will be recorded. Especially, mesoporous materi-
screen. Differences in secondary emission result from changes in als can be very inhomogeneous, consisting of a mixture of ordered
surface topography. If (elastically) backscattered electrons are col- and disordered mesoporous material with dense amorphous mate-
lected to form the image, contrast results from compositional and rial. Additionally, specks of dust or of other samples can be caught
structural differences and often diffraction patterns can be ob- on the microscopy sample holder during sample preparation or
tained for crystalline materials. during transport to the microscope, giving rise to contaminated
Materials can only be studied properly when they are electri- data.
cally conducting, as the electrons otherwise give rise to charging
phenomena resulting in blurred images. Non-conducting materials 5.5. Nuclear magnetic resonance (NMR)
(amongst which silica-based materials) need to be sputtered with a
thin layer of conducting material before being inserted into the A number of atoms in the framework of solid materials possess
SEM, and connected to a conducting sample holder. In general, isotopes with nuclear spin, which makes these isotopes observable
Au or C is used for sputtering in a plasma sputter-coater. by NMR (nuclear magnetic resonance) spectroscopy. The informa-
tion obtained by solid-state NMR spectroscopy is complementary
5.4. High resolution transmission electron microscopy to that of diffraction techniques, such as X-ray and neutron diffrac-
tion, since the latter are long-range methods, while solid-state
5.4.1. Transmission electron microscopy (TEM) NMR spectroscopy allows the study of the local structure
The ultimate technique to obtain direct structural information [405,406]. 27Al and 29Si isotopes with the natural abundance of
at nanometer scale resolution for porous materials is transmission 100% and 4.7%, respectively, are important nuclei for investigating
electron microscopy. Whereas in SEM the detectors are mounted the local structure of mesoporous materials on the basis of silicates
on the same side of the sample as the impinging beam in order and aluminosilicates. In contrast to liquids with high mobility of
to detect the scattered secondary electrons, for TEM the detectors molecular compounds, the anisotropic nuclear interactions in sol-
are mounted behind the sample to detect the electrons transmitted ids are not averaged by mobility. Therefore, the NMR spectra of sol-
through a thin section (preferably less than 100 nm) of the mate- ids are too broad for a direct evaluation. The nuclear interactions
rial [403]. The image in TEM is the result of diffraction contrast. being responsible for this line broadening in the NMR spectra of
The sample is oriented so that some of the beam is transmitted solids are dipolar interactions of the resonating nuclei with neigh-
and some is diffracted out. Any local structural variation in the bouring nuclear spins, the anisotropic chemical shift due to the
sample causes a different fraction of the incident beam intensity anisotropic shielding effect of electrons, and the quadrupolar inter-
to be diffracted out, leading to a variation in image darkness on action of the nuclear electric quadrupole moment with the electric
a viewing screen at the base of the microscope. Magnication is eld gradient at the site of the nuclei. For nuclei with spin I = 1/2,
achieved by using lenses underneath the sample to project the im- only the rst two interactions are dominating broadening mecha-
age formed by the diffracted electrons onto a recording device. The nisms. For nuclei with spin I > 1/2, which exhibit an electric quad-
magnication is determined by the optical system and the resolu- rupole moment, also the quadrupolar interaction affects the shape
tion by the aberrations in the lens performance. of the solid-state NMR signal.
29
Atomic resolution can be obtained for crystalline materials. Si nuclei have a nuclear spin of I = 1/2 and sufcient line nar-
Powders can be crushed lightly, to separate primary particles, rowing is reached by the conventional magic angle spinning (MAS)
and supported on special, electrically conducting and partially NMR technique. On the other hand, 27Al nuclei are characterized by
electron transparent sample holders (TEM grids). Large particles a nuclear spin of I > 1/2 and, therefore, by an electric quadrupole
of non-conducting material will show charging phenomena lead- moment responsible for the quadrupolar interaction. The averag-
ing to blurred images. ing of this interaction may require the application of more sophis-
ticated solid-state NMR techniques, such as double-oriented
5.4.2. Three-dimensional TEM (3D TEM) or electron tomography rotation (DOR) or multiple-quantum MAS NMR (MQMAS).
Study of the shape and arrangement of individual pores at the The MAS technique is based on a rapid rotation of the sample
nanometer scale in three-dimensions can be done by electron with spinning frequencies between mrot = 3 and 30 kHz. Most of
tomography [404]. In contrast to TEM, which gives three-dimen- the above-mentioned nuclear interactions depend on the geomet-
sional information projected into a 2D image, tomography reveals ric term (3cos2H  1), where H denotes the angle between the
real structural information in the third dimension. With electron direction of the external magnetic eld and the sample spinning
tomography (3D-TEM) a 3D-reconstruction is calculated from a axis. The maximum averaging of solid-state interactions, i.e., best
186 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

line narrowing, is achieved for the magic angle of Hm = 54.74, i.e., Q


4

when (3cos2Hm  1) becomes zero. An important reason for the


residual line width of MAS NMR signals is the distribution of the Q
3

isotropic chemical shift. Often, this effect causes the line broaden-
ing in the spectra of mesoporous materials because of the distribu-
tion of structural parameters in the amorphous walls of these
materials.
The DOR technique removes the quadrupolar line broadening of
the central transition of nuclei by the simultaneous sample spin- Q2
ning around two axes. By this way, an averaging of the two geo-
metric terms in the equation describing the shape of the central
transition of quadrupole nuclei is reached. The DOR device consists
of a large outer rotor reaching a spinning frequency of up to -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0
1.5 kHz and a small inner rotor with a spinning frequency of up 29Si / ppm
to 7 kHz. The angle H1 between the external magnetic eld and
the rotational axis of the outer rotor corresponds to the magic an- Fig. 5.2. 29Si MAS NMR spectrum of SBA-15 consisting of signals due to Q4, Q3, and
Q2 silicon species.
gle Hm. The angle H2 between the rotational axes of the inner and
the outer rotor amounts to 30.5.
The MQMAS technique combines an excitation of non-observa- to silicon atoms at the outer surface or at internal framework de-
ble multiple-quantum transitions {+m, m} with the experimen- fects. Generally, silicon atoms bound to one (Q3: Si(3Si, 1OH)) or
tally observed single-quantum transition {+1/2, 1/2}. At a two (Q2: Si(2Si, 2OH)) hydroxyl groups can be distinguished by
specic time of the pulse-sequence, the anisotropic part of the their signals at chemical shifts of ca. 103 ppm and 90 ppm,
quadrupolar interaction, responsible for the line broadening, is respectively. It is important to note, that the signals of Si(1Al) spe-
refocused. In a simple form of the experiment, the multiple-quan- cies (d29Si = 95 to 105 ppm) occur at the similar resonance posi-
tum transitions are excited by a single high-power radio frequency tions to those of Si(3Si, 1OH) species. In this case, application of the
pulse. Subsequently, the multiple-quantum coherence is allowed cross polarization experiment has the advantage that this tech-
to evolve for the time t1. After the evolution period t1, a second nique causes a selective enhancement of the signals of silicon
pulse is applied, which converts the multiple-quantum coherences atoms with hydroxyl protons in their vicinity. This behavior sup-
into an observable single-quantum coherence, which is recorded ports the correct assignment of the nature of neighbouring species.
during the echo in the time period t2. Finally, the two-dimensional As an example, Fig. 5.2 shows the 29Si MAS NMR spectrum of a
Fourier transformation of the decays in the domain t2 for different mesoporous SBA-15 material consisting of signals due to Q4, Q3,
pulse delays t1 leads to a two-dimensional MQMAS spectrum with and Q2 silicon atoms at chemical shifts of 110, 102, and 91
narrow isotropic and featured signals along the frequency axes of ppm, respectively.
m1 and m2, respectively. According to Loewensteins rule, the formation of AlOAl
A suitable way to enhance the intensities of NMR signals of nu- bonds in aluminosilicates is forbidden, and only Al(4Si) species
clei with a small magnetogyric ratio or low concentration (rare can exist in the corresponding frameworks. Therefore, 27Al MAS
spins S, such as 29Si nuclei), which interact with abundant spins I NMR spectra of hydrated aluminosilicates consist, in general, of
(such as 1H nuclei), is the polarization transfer from the spins I only one signal of tetrahedrally coordinated framework aluminum
to the spin S ensemble via a cross polarization (CP). An additional (Altet) at chemical shifts of ca. 5060 ppm (referenced to a 0.1 M
advantage of this technique is the selective enhancement of the aqueous solution of Al(NO3)3 in D2O). In hydrated aluminosilicates,
NMR signals of rare spins S in the vicinity of abundant spins I. only small deviations from the ideal tetrahedral symmetry of the
The CP experiment starts with a p/2 pulse applied to the abundant AlO4 units may occur, which lead to weak quadrupolar interactions
spins I. Spin polarization is transferred from the spins I to the spins and weak second-order quadrupolar line broadenings.
S during the contact pulse, if the condition cI  B1I = cS  B1S is ful- Octahedrally coordinated aluminum species (Aloct) in hydrated
lled. In this case, B1I and B1S denote the amplitudes of the mag- aluminosilicates, which can be due to extra-framework aluminum
netic elds of the contact pulses applied to the spins I and S, compounds, induce 27Al MAS NMR signals at ca. 0 ppm. If these
while cI and cS are the magnetogyric ratios of the spins I and S, AlO6 species exists as polymeric aluminum oxides or oxide hy-
respectively. drates, a strong quadrupolar line broadening may occur owing to
The basic structural units of mesoporous materials on the basis distortions of the octahedral symmetry. In some cases, an addi-
of silicates and aluminosilicates are TO4 tetrahedra with silicon tional broad 27Al MAS NMR signal appears at 3050 ppm indicating
atoms at the central T-positions. In the second coordination sphere the presence of aluminum atoms in a disturbed tetrahedral coordi-
of these T-atoms, aluminum can be incorporated into the frame- nation or a vefold coordinated state.
work. Depending on the amount of aluminum atoms, which are As an example, Fig. 5.3 shows the 27Al MAS NMR spectrum of an
incorporated, the tetrahedrally coordinated silicon atoms (Q4) in aluminum-containing hydrated MCM-41 consisting of narrow sig-
aluminosilicates may be characterized by up to ve different envi- nals at 53 ppm due to tetrahedrally coordinated framework alumi-
ronments denoted as Si(nAl) with n = 0, 1, 2, 3, and 4. Each type of num and at ca. 0 ppm due to octahedrally coordinated aluminum
Si(nAl) species has a characteristic chemical shift. Typically, the species. The broad background signal at ca. 0 ppm indicates the
29
Si MAS NMR signal of Si(0Al) species occurs at ca. 110 ppm (ref- presence of polymeric aluminum oxides or oxide hydrates. An im-
erenced to tetramethylsilane). The addition of one tetrahedrally proved resolution, e.g., of the different signals at ca. 0 ppm would
coordinated aluminum atom in the local structure of Si(nAl) spe- require the application of the DOR or MQMAS technique.
cies leads to a shift of the corresponding 29Si MAS NMR signal by
ca. 5 ppm to positive values. For mesoporous materials, however, 5.6. Elemental analysis
the line broadening due to chemical shift distribution is so large
that the different signals of the various Si(nAl) species can not be 5.6.1. Atomic absorption spectroscopy (AAS)
resolved. Another important species inuencing the 29Si MAS Atomic absorption spectroscopy is a widely used method for the
NMR spectra of mesoporous materials are hydroxyl groups bound quantitative determination of single elements incorporated in a
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 187

tet
Al

oct
Al

180 160 140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140
27Al / ppm

Fig. 5.3. 27Al MAS NMR spectrum of an aluminum-containing hydrated MCM-41 with signals at 53 and 0 ppm due to tetrahedrally and octahedrally coordinated aluminum
species, respectively.

material [407]. When photons are sent in on an atom, an electron 5.6.3. X-ray uorescence (XRF)
of the outermost electron shell can be excited towards an elevated X-ray uorescence can be used for the qualitative and quantita-
energy level. Since the different energy levels in an atom are quan- tive determination of all elements in the periodic table with an
tisized, this excitation will only occur if the wavelength of the pho- atomic number greater than that of oxygen. The measurement of
ton is equal to an allowed transition state of the atom. The allowed lighter elements is less convenient, since difculties in detection
transitions are specic for each element. The amount of absorbed become progressively worse as atomic numbers become smaller
photons depends on the concentration of the element under deter- than 23 (vanadium) due to a competing process, namely Auger
mination. This results in the quantitative character of the emission [407].
technique. The samples are exposed to X-ray radiation, which causes ioni-
Before the actual measurement can be executed, it is necessary zation of inner shell electrons, creating vacancies in the inner shells
to atomize the investigated element. Different techniques can be (K, L, . . .). The transition of outer shell electrons into these vacan-
applied, whereby ame and electrothermal (using a graphite fur- cies can create the emission of characteristic X-ray uorescent
nace) atomizers are the most common. Flame atomization appears radiation. The measurement of the wavelength or the energy and
to be superior to the electrothermal method in terms of reproduc- intensity of the characteristic photons emitted from the sample
ibility. On the other hand, the sensitivity of the electrothermal are the basis of the XRF principle. This enables the identication
atomizing technique is markedly better since in this case the entire of the elements present in the sample and the determination of
sample is atomized in a short period, while for ame-AAS it is nec- their mass or concentration.
essary to rst destruct, dilute and vaporize the sample. Further- Different types of XRF instruments exist, whereby wavelength
more, the average residence time of the atoms in the optical path dispersive (WD) and energy dispersive (ED) instruments are the
is longer for the electrothermal method. The radiation with a most common. The primary difference is the way the uorescent
monochromatic source occurs after the atomization. The most X-rays are detected and analyzed. A wavelength dispersive XRF
common source for this type of measurements is a hollow cathode has a more complex set-up, which results in a lowered efciency
lamp (HCL). Since a HCL is an element specic source, the emitted compared to energy dispersive XRF. However, in comparison to
light possesses the proper wavelength to excite the atoms. The ex- ED-XRF, WD-XRF has a better resolution.
tent of absorption reects the element concentration of the
sample. 5.6.4. Inductively coupled plasma-optical emission spectroscopy/
atomic emission spectroscopy (ICP-OES/AES)
5.6.2. Electron probe microanalysis (EPMA) Inductively coupled plasma-atomic emission spectroscopy (ICP-
Electron probe microanalysis is a qualitative and quantitative AES), also referred to as inductively coupled plasma-optical emis-
technique, which is commonly used for the determination of the sion spectrometry (ICP-OES), is an analytical technique used to
elemental composition and distribution within a micro volume determine concentrations of a wide range of elements in solution.
of solid material [407]. The investigated materials are bombarded ICP-AES/OES is a fast multi-element technique with a dynamic lin-
with a high energy electron beam (compare with electron micros- ear range and moderate-low detection limits (0.2100 ppb). ICP-
copy), exciting the electrons from the lower K or L shells towards AES/OES makes use of the fact that the atoms of elements can take
elevated energy levels. Those electrons (primary electrons) will up energy from an inductively coupled plasma, are thereby excited,
emit characteristic X-rays while returning to their ground state. and fall back into their ground state again emitting electromag-
The element can be determined using Moseleys Law: k = K/ netic radiation at wavelengths characteristic of a particular ele-
(Z  r), whereby K and r are constants, Z the atomic number ment. The identication of this radiation permits the qualitative
and k the wavelength of the emitted radiation. The intensity of analysis of a sample. A quantitative determination takes place on
the radiation can be correlated to the concentration of the the basis of the proportionality of radiation intensity and element
element. concentration in calibration and analysis samples. Calibration can
The returning of excited primary electrons to lower energy lev- be performed with multi-element solutions mixed from standard
els, can give rise to the removal of secondary electrons out of more solutions.
innermost shells, so called Auger electrons. Since Auger electron To generate plasma, argon gas is supplied to a torch coil, and
emission predominates with atoms of low atomic numbers, this high frequency electric current is applied to the work coil at the
technique is more suitable for the determination of heavier ele- tip of the torch tube. Using the electromagnetic eld created in
ments (from boron to uranium). the torch tube by the high frequency current, argon gas is ionized
188 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

and plasma is generated. This plasma has high electron density 5.8. FT-infrared spectroscopy (FT-IR)
and temperature (67279727 C) and this energy is used in the
excitation of the sample. Solution samples are introduced into Fourier transform infrared spectroscopy (FT-IR) is an economic
the plasma in an atomized state through the narrow tube in the and multidisciplinary analytical tool, which yields information
center of the torch tube. A peristaltic pump delivers the aqueous concerning the structural details of a siliceous inorganic material
or organic liquid sample into a nebulizer where it is atomized and [402,406]. In addition, it can be used to conrm surface character-
introduced directly inside the plasma ame. The sample immedi- istics (such as acidity) and isomorphous substitution by other ele-
ately collides with the electrons and other charged ions in the ments in the material. The technique allows to relate different
plasma and is broken down into charged ions. The various mole- materials by their common structural features, such as a classi-
cules break up into their respective atoms which then lose elec- cation of zeolite structures. Analysis by FT-IR is based on the fact
trons and recombine repeatedly in the plasma, giving off the that molecules have specic frequencies of internal vibrations.
characteristic wavelengths of the elements involved. The emitted These frequencies occur in the infrared region of the electromag-
light is collected by a spectrometer and passes through a diffrac- netic spectrum. When a sample is placed in a beam of infrared
tion grating that serves to resolve the light into a spectrum of its radiation, the sample will absorb radiation at frequencies corre-
constituent wavelengths. Within the spectrometer, this diffracted sponding to molecular vibrational frequencies, and this is being
light is then collected by wavelength and amplied to yield an measured in the infrared spectrometer. The result is an infrared
intensity measurement that can be converted to an elemental spectrum which represents a plot of absorbed energy vs. fre-
concentration by comparison with the calibration standards. quency. The vibration frequency of a bond is related to the masses
Digestion methods such as microwave, high-pressure, fusion, of the vibrating atoms (m1 and m2 of atom 1 and atom 2, respec-
and acid digestion can be employed for the liquid sample prepa- tively) and the force constant (f in g  s2) of the vibrating bond,
ration of solid sample material. according to:
Some specics of the ICP-AES/OES methods are: s
1 m1 m2
Simultaneous, sequential analysis of multiple elements. t f
2pc m1 m2
Wide linear region of analytical curve.
Few chemical interference or ionization interference. Not all matter is capable of producing an IR-spectrum. In order
High sensitivity (low limit of detection for majority of elements to interact with IR-radiation, the molecule must have a permanent
is 10 ppb or lower). dipole moment and must vibrate with a variation in the bond
High number of measurable elementselements that are dif- length (stretching vibration) or the bond angle (bending vibration).
cult to analyze in atomic absorption spectrometry such as Zr, In general, for a non-linear n-atomic molecule, there are 3n  6
Ta, rare earth, P and B can be easily analyzed. fundamental vibrational modes. Standard FT-IR analysis requires
Stable. sample preparation such as rst measuring the background spec-
trum of a KBr pressed pellet, followed by measuring the sample,
The majority of the above features are derived from the struc- pressed and diluted (2%) in KBr.
ture and characteristics of the light source plasma. The mid-infrared region of the spectrum (4000 to 400 cm1) is
the most interesting part of the spectrum when dealing with sili-
ceous materials as it contains the fundamental framework vibra-
5.7. FTRaman spectroscopy tions of the Si(Al)O4 groupings. Identication of materials in this
region is possible because different materials will absorb at differ-
Raman spectroscopy is used to determine molecular structures ent frequencies. In addition to the characteristic nature of the
and compositions of materials. It is based on the principle of the absorptions, the magnitude of the absorption in the spectrum
interaction of monochromatic laser light with solid material due to a given species can be related to the concentration of that
[402]. The light can be scattered in all directions with the fre- species (quantitative analysis). Although any quantitative data de-
quency the same as that of the original light, this effect is known rived from the technique must be treated with caution. In fact,
as the Rayleigh scattering. Another type of scattering that can oc- there are some special methods that can be applied for quantita-
cur is known as the Raman effect. It occurs at frequencies both tive interpretation of the spectrum, such as the use of calibration
higher and lower than the original frequency and with dimin- graphs, analysis using absorbance ratio methods, standard addition
ished intensities. The differences Dv between the incident and techniques, and transformation of the FT-IR spectrum according to
scattered frequencies are equal to the actual vibrational frequen- the KubelkaMunk theory.
cies of the material. Therefore, Raman provides characteristic fre- Besides the standard applications of identication and quantita-
quencies of various functional groups. In a typical Raman tive analysis, there are a number of special FT-IR techniques. Some
spectrum the intensity is plotted against the Raman shift of these are briey listed as follows:
(cm1), the difference in frequency between the incident and FT-IR photoacoustic spectroscopy (FT-IR-PAS) involves infrared
scattered beam. All molecules vibrating giving rise to a change absorption in the sample, followed by conversion of the absorbed
in polarizability can be measured with Raman. Raman and infra- energy into heat [408]. The subsequent heat-induced thermal
red spectroscopy provide complementary information to struc- expansion in the sample and adjacent media produces a photoa-
ture determination. coustic signal when the incident beam intensity is modulated at
However, the primary limitation of the Raman technique re- a frequency in the acoustic range. Microphonic detection of this
sides in the intrinsic weakness of the Raman effect. As the total signal, processed by the normal detector amplication electronics
intensity of scattered radiation is only 0.1% of that of the source, of the FT-IR spectrometer yields the spectrum. FT-IR-PAS technique
it is essential that a very sensitive detector and efcient optical allows the measurement to take place under absolute dry condi-
systems are being used in the apparatus. In addition, if components tions (He gas atmosphere) and can be successfully applied for the
with uorescence are present in the samples, this gives interfer- study of the surface hydroxyl groups of a siliceous material.
ence when excited by visible laser radiation. Also heating effects, Special infrared reectance techniques involve attenuated total
especially for colored materials, can inuence the spectra in FT-Ra- reectance (ATR) and diffuse reectance infrared spectroscopy
man spectroscopy. (DRIFT).
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 189

ATR makes use of a crystal (zinc selenide or germanium) as the


reecting medium, and which is in close contact with the sample.
The ATR technique is very useful for obtaining spectra of very thin
samples, e.g. lms, coatings.

Intensity / a.u.
DRIFT is based on the principle of detection of diffusely scat-
tered radiation at a sample powder surface. The sample absorbs
some frequencies of the incident radiation so the scattered radia-
tion will be devoid of energy in some of these frequencies. When
scanning the scattered radiation a spectrum is obtained. The most
signicant advantage of DRIFT is that it allows spectra to be ob-
tained from solid powder samples, with virtually no sample prep-
aration other than scattering a small amount of the powdered 1 2 3 4 5 6 7 8
sample on a bed of powder KBr in a small cup. 2 /

Fig. 6.1. X-ray diffraction pattern of MCM-41 made from aerosil. The corresponding
6. Syntheses recipes d-spacings: (1 0 0) = 4.28 nm; (1 1 0) = 2.43 nm; (2 0 0) = 2.10 nm and
(2 1 0) = 1.59 nm.
6.1. MCM-41 (from fumed silica)
800
Short description of material: Hexagonally ordered mesoporous
material with small mesopores. 700

-1
Volume adsorbed STP / cm g
Contributed by: P. Cool, E.F. Vansant, V. Meynen

3
600
Veried by:
500
K.S. Triantafyllidis, C. Nitsos, S. Karakoulia, S.D. Sklari
A. Silvestre-Albero, J. Silvestre-Albero, A. Seplveda-Escribano, 400
F. Rodrguez-Reinoso 300
Type of material: Silica
200
Batch composition: 1 SiO2:0.25 CTMABr:39.36 H2O:0.20 TEAOH.
Source of materials: 100

Cetyltrimethylammonium bromide 99+% (CTMABr) (Acros 0


0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Organics).
P /P 0
Tetraethylammoniumhydroxide 20% (TEAOH 20%) (Sigma
Aldrich). Fig. 6.2. N2-sorption isotherm at 196 C of MCM-41 made from aerosil.
Fumed silica (aerosil 380, Degussa).
Batch preparation:

ads
1. Add 6.2 g CTMABr to 40.4 g H2O, stir at room temperature until
des
dissolved.
2. Add 10 g of TEAOH 20% solution.
3. Add 4.1 g fumed silica and stir at 70 C for 2 h (stirring is crucial.
If stirring is stopped due to a high viscosity, it is possible to add
d v (r )

between 1 and 5 ml of water to keep it stirring).


4. Stir for a duration of 24 h at room temperature.
5. Transfer the viscous solution into an autoclave and heat to 130
150 C for 48 h.
6. After the heat treatment, quench the autoclave and lter the
solution.
7. Wash the solid with 150 mL H2O.
8. Transfer the solid into an autoclave and add some fresh water
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
(until the solid is just covered) and heat it a second time to
Radius / nm
130150 C for 72 h.
Fig. 6.3. Pore size distribution of MCM-41 made from aerosil. It was obtained with
Product recovery: Filter, wash with 3  25 mL water and dry. the BJH method.
Post-synthesis treatment: Calcine the product at 550 C during
6 h with a heating rate of 1 C/min in ambient atmosphere. Cooling
down occurs slowly. Remarks:
Product characterization:
 MCM-41 can also be prepared with an alternative surfactant,
XRD: (See Fig. 6.1). gemini 16-8-16, following a similar synthesis procedure as for
N2-sorption: (See Figs. 6.2 and 6.3). MCM-48 [101] (recipe 6).
Range of data derived from the isotherms:
SBET = 10001100 m2/g.
Vtotal = 11.2 cm3/g. 6.2. MCM-41 (from metasilicate)
Pore diameter (BJH, adsorption branch) = 2.54.0 nm.
SEM: (See Fig. 6.4). Short description of material: Hexagonally ordered mesoporous
material with small mesopores.
190 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Tetradecyltrimethylammonium bromide P98% (TTMABr)


(Fluka).
Decyltrimethylammonium bromide P98% (DTMABr) (Fluka).
Ethyl alcohol P99% (EtOH) (Merck).
H2SO4 98% (Merck).

Batch preparation:
MCM-41 materials are synthesized using different templates.

1. Add 8.13 g sodium metasilicate to 120 g of demineralized water


and stir for 30 min in a PP-beaker (400 mL).
2. Add 4.84 g cetyltrimethylammonium bromide or 4.8 g tetrade-
cyltrimethylammonium bromide or 3.73 g decyltrimethylam-
monium bromide to 30 g demineralized water and 10 g EtOH,
mix and stir for 30 min.
3. Add (2) to (1) and stir for 30 min to obtain a clear gel.
4. Add 15 g of 2 M H2SO4 slowly to solution (3) within 7 min under
vigorous stirring then stir the mixture at room temperature
for 30 min. Cover the beaker with paralm during the synthesis
to prevent evaporation.
5. Add 15 g 2 M H2SO4 slowly to solution (4) within 7 min while
stirring vigorously then stir the mixture at room temperature
for 1 h. Cover with paralm to prevent evaporation.
6. Transfer the gel into a Teon-lined steel autoclave (Teon insert
200 mL) (only 2/3 of the gel can be transferred, the rest is
thrown away). Temperature: 150 C in air oven (preheated)
during 24 h, without agitation.
7. Quench the autoclave with cold water.

Product recovery:

1. Add 25 mL ethanol to the precipitate, mix and lter.


2. Wash the precipitate four times with 10 mL ethanol and three
times with 200 mL demineralized water.
3. Dry in air at 80 C overnight prior to calcination.

Post-synthesis treatment:
Calcine the solid at 540 C for 1 h in nitrogen with a heating rate
of 2 C/min. Substitute the nitrogen by air and continue the calci-
nation for 8 h at 540 C (gas ow 30 cm3/min).
Product characterization:

XRD: (See Fig. 6.5).


N2-sorption: (See Figs. 6.6 and 6.7).
Range of data derived from the isotherms:
SBET = 7701030 m2/g.
Vtotal = 0.60.95 cm3/g.
Pore diameter (BJH, adsorption branch) = 2.53.5 nm.
Fig. 6.4. SEM images of MCM-41 made from aerosil.

Contributed by: S.C. Laha, R. Glser, D. Pufky-Heinrich, J.


Weitkamp
Veried by:
Intensity / a.u.

F. Quiroz, V. Meynen, P. Cool, E.F. Vansant


A. Ferreira, S. Aguado, J. Gascon, F. Kapteijn

Type of material: Silica


Batch composition: 1 SiO2:1 Na2O:0.2 CTMABr (or TTMAB or
DTMABr):143 H2O:0.9 H2SO4.
Source of materials:
0 1 2 3 4 5 6 7 8
Sodium metasilicate 99% (Na2SiO3, Fluka). 2 /
Cetyltrimethylammonium bromide 95% (CTMABr) (Sigma
Aldrich). Fig. 6.5. X-ray diffraction pattern of MCM-41 from metasilicate. The corresponding
d-spacings: (1 0 0) = 3.58 nm; (1 1 0) = 2.05 nm; and (2 0 0) = 1.80 nm.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 191

600
-1

500
Volume adsorbed STP / cm g

400

300

200

100

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P /P 0

Fig. 6.6. N2-sorption isotherm at 196 C of MCM-41 made from metasilicate.


Based on material prepared using the C14 template (tetradecyltrimethylammonium
bromide).

ads
des
d v (r )

0 1 2 3 4 5 6 7 8 9 10
Radius / nm

Fig. 6.7. Pore size distribution of MCM-41(BJH) made from metasilicate. Based on
material prepared using the C14 template (tetradecyltrimethylammonium
bromide).

SEM: (See Fig. 6.8).


TEM: (See Fig. 6.9).

Fig. 6.9. TEM image of MCM-41 made from metasilicate.


6.3. MCM-41

Short description of material: Hexagonally ordered mesoporous


material with small mesopores. Veried by:
Contributed by: J. Rathousky, A. Zukal, R. Marschall, I. Bannat, J. F. Quiroz, V. Meynen, P. Cool, E.F. Vansant
Caro, M. Wark D. Pufky-Heinrich, J. Weitkamp

Type of material: Silica


Batch composition: 1 Na2SiO3:0.329 CTMABr:1.88
CH3COOC2H5:1018 H2O.
Source of materials:

Sodium metasilicate (Na2SiO3, SigmaAldrich).


Cetyltrimethylammonium bromide 95% (CTMABr) (Sigma
Aldrich).
Ethyl acetate p.a. >99% (Fluka).

Batch preparation:

1. Dissolve 2.61 g cetyltrimethylammonium bromide in 400 mL


water at 30 C.
2. Add 2.67 g sodium metasilicate and stir until completely
dissolved.
3. Add 4 mL ethyl acetate under vigorous stirring and stop stirring
Fig. 6.8. SEM image of MCM-41made from metasilicate. after 15 s.
192 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

4. Leave the mixture in a closed PE bottle for 24 h at room


temperature.
5. Treat the obtained mixture hydrothermally at 100 C for 48 h.

Product recovery:
Filter the hot precipitate, wash with ethanol and water and dry
at RT.
Post-synthesis treatment:
Calcine the product at 600 C for 20 h, with heating/cooling rate
of 1 C/min in ambient atmosphere.
Product characterization:

XRD: (See Fig. 6.10).


N2-sorption: (See Figs. 6.11 and 6.12).

Fig. 6.13. SEM images of MCM-41.


Intensity / a.u.

0 1 2 3 4 5 6 7 8
2 /

Fig. 6.10. X-ray diffraction pattern of MCM-41. The corresponding d-spacings:


(1 0 0) = 3.59 nm; (1 1 0) = 2.07 nm and (2 0 0) = 1.77 nm. Fig. 6.14. TEM images of MCM-41.

700 Range of data derived from the isotherms:


SBET = 9001200 m2/g.
600 Vtotal = 0.81.2 cm3/g.
-1
Volume adsorbed STP / cm g

Pore diameter (BJH, adsorption branch) = 2.04.0 nm.


500
SEM: (See Fig. 6.13).
400 TEM: (See Fig. 6.14).

300
6.4. MCM-41 (spherical)
200
Short description of material: Hexagonally ordered mesoporous
100 material with small mesopores and a spherical morphology.
Contributed by: F. Rodrguez-Reinoso, A. Seplveda-Escribano, J.
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Silvestre-Albero
P /P 0 Veried by:
F. Quiroz, V. Meynen, P. Cool, E.F. Vansant
Fig. 6.11. N2-sorption isotherm at 196 C of MCM-41. R. Marschall, M. Wark, J. Caro

Type of material: Silica


ads Batch composition: 1 SiO2:0.30 CTMABr:122.6 H2O:57.7
des EtOH:37.3 NH3.
Source of materials:

Cetyltrimethylammonium bromide 99+% (CTMABr) (Sigma


d v (r)

Aldrich).
Ammonia 30% (Panreac or ROTH or Acros Organics).
Ethanol absolute (Panreac).
Tetraethyl ortosilicate 98% (TEOS) (GC SigmaAldrich).
Methanol 99.8+% (SigmaAldrich).

Batch preparation:
0 1 2 3 4 5 6 7 8 9 10
Radius / nm
1. Add 7.5 g CTMABr to 150 g H2O and stir at room temperature
Fig. 6.12. Pore size distribution (BJH) of MCM-41. until complete dissolution.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 193

ads
des
Intensity / a.u.

dv (r )
1 2 3 4 5 6 7 8 9 10
2 / 0.0 1.0 2.0 3.0 4.0 5.0
Radius / nm
Fig. 6.15. X-ray diffraction pattern of spherical MCM-41. The corresponding
d-spacings: (1 0 0) = 3.66 nm; (1 1 0) = 2.08 nm and (2 0 0) = 1.83 nm. Fig. 6.17. Pore size distribution (BJH) of spherical MCM-41.

800 Post-synthesis treatment:


700
Calcine the product at 550 C during 5 h with a heating rate of
1 C/min in ambient atmosphere.
-1
Volume adsorbed STP / cm g

600 Product characterization:


500
XRD: (See Fig. 6.15).
400
N2-sorption: (See Figs. 6.16 and 6.17).
300 Range of data derived from the isotherms:
SBET = 11001500 m2/g.
200
Vtotal = 0.71.0 cm3/g.
100 Pore diameter (BJH, adsorption branch) = 2.03.0 nm.
SEM: (See Fig. 6.18).
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 TEM: (See Fig. 6.19).
P/P 0
Remarks:
Fig. 6.16. N2-sorption isotherm at 196 C of spherical MCM-41.

 Dissolving CTMABr at room temperature appears to be slow.


2. Add 42.9 g NH3 and 180 g ethanol. Increasing the temperature to 30 C results in faster dissolution.
3. Stir the solution for 30 min at 500 rpm.  When ethanol is applied, a homogeneous solution is obtained
4. Add 14.1 g TEOS. resulting in the spherical morphology [413].
5. Stir the solution for 3 h at 500 rpm and then for 12 h at 300 rpm
at 25 C.
6.5. Al-MCM-41
Product recovery:
Filtrate the solution and subsequently wash the solid with Short description of material: Hexagonally ordered mesoporous
300 mL distilled water and thereafter with 300 mL methanol. Dry material with small mesopores and Si/Al ratios of 20, 40 and 60.
the solid at 90 C for 20 h.

Fig. 6.18. SEM images of spherical MCM-41.


194 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Intensity / a.u.
0 1 2 3 4 5 6 7 8
2 /

Fig. 6.20. X-ray diffraction pattern of Al-MCM-41 (Si/Al 20). The corresponding d-
Fig. 6.19. TEM image of spherical MCM-41.
spacings: (1 0 0) = 3.59 nm; (1 1 0) = 2.09 nm and (2 0 0) = 1.80 nm.

Si/Al ratio:Chemical composition: Si/Al ratios of the (calcined)


parent mesoporous Al-MCM-41 materials (desired Si/Al ratios
Contributed by: M. Stcker indicated).
Veried by:
F. Quiroz, V. Meynen, P. Cool, E.F. Vansant
K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari Sample EPMA XRF AAS ICP-AES
Al-MCM-41 (20) 28.5 20.4 21.3 19.8
Type of material: Aluminosilicate
Al-MCM-41 (40) 34.5 34.2
Batch composition: 1 Si:0.06/0.02/0.01 Al:0.4 C14H29(CH3)3NBr:
Al-MCM-41 (60) 62.7 51.3 63.1
68 H2O.
Source of materials:

Tetradecyltrimethylammonium bromide ca. 99% (TDTMABr,


C14H29(CH3)3NBr) (SigmaAldrich).
Sodium aluminate (54% Al2O3, 41% Na2O) (Riedel-de Han). 700
Sodium silicate 5 hydrate (8.9% Na2O + 28% SiO2) (VWR BDH).
600
Sulfuric acid (H2SO4, 10%, 50% and 95%) (Merck p.a., 9597%).
-1
Volume adsorbed STP / cm g

500
Batch preparation:
400

1. Dissolve 15 g template (C14H29(CH3)3NBr) in 95 g water and stir.


300
2. Add sodium aluminate (0.43, 0.21 or 0.14 g, depending on the
Si/Al ratio) and continue stirring for 2 h. 200
3. Add 18.7 g sodium silicate under stirring, immediately followed
100
by 5.6 g 10% sulphuric acid.
4. Add 15 g water and stir the entire solution for 30 min. 0
5. Adjust the pH to 10 with 50% sulphuric acid. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
6. Transfer the nal solution to teon-lined autoclaves and heat P /P 0
for 144 h at 100 C or 150 C. MCM-41 is formed at both
Fig. 6.21. N2-sorption isotherm at 196 C of Al-MCM-41 (Si/Al 20).
temperatures.

Product recovery:
Filter the Al-MCM-41 samples, wash with water and dry at
room temperature until constant weight (three days).
Post-synthesis treatment: ads
des
Calcine the product at 540 C with a heating rate of 5 C/min,
during 1 h in owing nitrogen, followed by 6 h in owing air with
ow rates of 100 mL/min.
d v (r )

Product characterization:

XRD: (See Fig. 6.20).


N2-sorption: (See Figs. 6.21 and 6.22).
Range of data derived from the isotherms:
SBET = 850950 m2/g.
Vtotal = 0.71.3 cm3/g.
0 1 2 3 4 5 6 7 8 9 10
Pore diameter (BJH, adsorption branch) = 2.54.0 nm. Radius / nm
SEM: (See Fig. 6.23).
TEM: (See Fig. 6.24). Fig. 6.22. Pore size distribution of Al-MCM-41(Si/Al 20) by the BJH method.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 195

Veried by:

A. Ferreira, S. Aguado, J. Gascon, A. Quintanilla, F. Kapteijn


K.S. Triantafylidis, S. Karakoulia, C. Nitsos, S.D. Sklari
D. Pufky-Heinrich, J. Weitkamp

Type of material: Silica


Batch composition: 1 SiO2:100 H2O:0.26 NaOH:0.1 surfactant.
Source of materials:

Gemini surfactant:
1,12-Dibromododecane (Acros Organics).
N,N-dimethylhexadecylamine (Fluka)/N,N-dimethyloctadecyl-
amine (Acros Organics).
Acetone p.a. (Acros Organics).
MCM-48:
Fumed silica (aerosil 380, Degussa).
Fig. 6.23. SEM image of Al-MCM-41 (Si/Al 20).
Sodium hydroxide pellets p.a. (Acros Organics).
Gemini 16-12-16 or gemini 18-12-18 (home-made; see below).

Batch preparation:

(A) Synthesis gemini surfactant:


1. Add 12 g 1.12-dibromododecane and 25.5 mL N,N-dim-
ethylhexadecylamine to 50 mL acetone.
2. Increase temperature until reuxing starts (around the
boiling point of acetone), reux during 24 h.
3. Cool down (the gemini will start to crystallize).
4. Filter and wash with acetone p.a.
5. Recrystallize the gemini in a beaker (with a watch glass
on top) with acetone p.a.
6. Filter and wash with acetone p.a.
Fig. 6.24. TEM image of Al-MCM-41 (Si/Al 20).
The gemini crystals are recovered by ltration on a buch-
ner lter or with a rotavap. The gemini surfactant is dried
at room temperature in ambient conditions.
(B) Synthesis MCM-48
1. Add 60 mL H2O and 0.3461 g NaOH to 2.8867 g gemini
16-12-16 or to 3.0735 g gemini 18-12-18.
2. Stir in the teon part of an autoclave until gemini is
Intensity / a.u.

calcined sample
(Si/Al 60) dissolved.
3. Add 2 g aerosol and stir for 30 min.
4. Age the autoclave in an oven at 130 C during 3 days.
5. After heat treatment, quench the autoclave to room
calcined sample temperature.
(Si/Al 20)
6. Filter and wash with 30 mL water.
7. Transfer the residue back in an autoclave and add 30 mL
150 100 50 0 -50 -100 of fresh water.
Chemical shift/ ppm
8. Heat the autoclave in an oven at 130 C for 1 day.
Fig. 6.25. 27
Al MAS NMR spectra of the Al-MCM-41 sample with Si/Al ratio of 20
(Repeat 1  (total synthesis = 3 days base/1 day water/1
and 60. day water).

Product recovery:
NMR: (See Fig. 6.25). Filter, wash with 3  25 mL water and dry at room temperature.
Post-synthesis treatment:
Remarks: Calcine the product at 550 C during 6 h with a heating rate of
2 C/min in ambient atmosphere. Cooling down occurs slowly.
 Characterization of samples with other Si/Al ratios gives similar Product characterization:
results for XRD, N2-sorption, SEM and TEM.
XRD: (See Fig. 6.26).
N2-sorption: (See Figs. 6.27 and 6.28).
6.6. MCM-48 Range of data derived from the isotherms:
SBET = 12001700 m2/g.
Short description of material: Cubic structured mesoporous Vtotal = 1.01.4 cm3/g.
material with small mesopores. Pore diameter (BJH, adsorption branch) = 2.54.0 nm.
Contributed by: P. Cool, E.F. Vansant, V. Meynen SEM: (See Fig. 6.29).
196 Intensity / a.u. V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

1 2 3 4 5 6 7 8
2 /

Fig. 6.26. The X-ray diffraction pattern of MCM-48. The corresponding d-spacings:
(2 1 1) = 3.40 nm and (2 2 0) = 2.98 nm.

Fig. 6.29. SEM image of MCM-48.

800

700
-1
Volume adsorbed STP / cm g
3

600

500

400

300

200

100

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P /P 0

Fig. 6.27. N2-sorption isotherm at 196 C of MCM-48.

ads
des

Fig. 6.30. TEM image of MCM-48.


d v (r )

Intensity / a.u.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Radius / nm

Fig. 6.28. Pore size distribution of MCM-48 calculated with the BJH method.

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
TEM: (See Fig. 6.30).
2 /

Remarks: Fig. 6.31. X-ray diffraction pattern of the 16-12-16 gemini surfactant.

 16-12-16 gemini surfactant: The pattern should look like the


one shown in Fig. 6.31, otherwise another recrystallization is 6.7. SBA-15
necessary.
 Detailed information about the inuence and optimization of Short description of material: Large pore hexagonal mesoporous
the synthesis conditions on the properties of the materials can material with micropores in the walls.
be found in the literature [102,414]. Contributed by: P. Cool, E. F. Vansant, V. Meynen
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 197

Veried by: Product characterization:

A. Denkova, M.O. Coppens, F. Kapteijn XRD: (See Fig. 6.32).


K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari N2-sorption: (See Figs. 6.33 and 6.34).
A. Silvestre-Albero, J. Silvestre-Albero, A. Seplveda-Escribano, Range of data derived from the isotherms:
F. Rodrguez-Reinoso SBET = 650950 m2/g.
Vtotal = 0.651.0 cm3/g.
Type of material: Silica Vmicro = 0.100.3 cm3/g.
Batch composition: 1 TEOS:5.87 HCl:194 H2O:0.017 P123. Pore diameter (BJH, adsorption branch) = 5.07.0 nm.
Source of materials: SEM: (See Fig. 6.35).
TEM: (See Fig. 6.36).
Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma Remarks:
Aldrich).
HCl 37% (Acros Organics).  The morphology can be changed in a wide range [24,173].
Tetraethylorthosilicate 98% (TEOS) (Acros Organics).  It is also possible to use pluronic P123 from BASF (MW 5800)
(same product as from SigmaAldrich).
Batch preparation:

1. Add 4 g P123 to 130 mL H2O and 20 mL HCl. 6.8. SBA-15


2. Stir until complete dissolution.
3. Add 9.14 mL TEOS and stir during 7.5 h at 45 C. Short description of material: Large pore hexagonal mesoporous
4. Ageing for 15.5 h at 80 C (without stirring). material with micropores in the walls.
5. Cool down.

Product recovery:
Filter, wash with 3  25 mL water and dry. ads
Post-synthesis treatment: des

Calcine the product at 550 C during 6 h with a heating rate of


1 C/min in ambient atmosphere. Cooling down occurs slowly.
d v (r )
Intensity / a.u.

0 1 2 3 4 5 6 7 8 9 10
Radius / nm

Fig. 6.34. Pore size distribution of SBA-15 obtained by the BJH method.

0 0.5 1 1.5 2 2.5 3 3.5 4


2 /

Fig. 6.32. X-ray diffraction pattern of SBA-15. The corresponding d-spacings:


(1 0 0) = 9.70 nm; (1 1 0) = 5.58 nm and (2 0 0) = 4.82 nm.

700

600
-1
Volume adsorbed STP / cm g

500

400

300

200

100

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P /P 0

Fig. 6.33. N2-sorption isotherm at 196 C of SBA-15. Fig. 6.35. SEM images of SBA-15.
198 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Intensity / a.u.
0 1 2 3 4 5 6 7 8
2 /
Fig. 6.36. TEM images of SBA-15.
Fig. 6.37. X-ray diffraction pattern of SBA-15. The corresponding d-spacings:
(1 0 0) = 10.76 nm; (1 1 0) = 6.04 nm; (2 0 0) = 5.32 nm and (2 1 0) = 3.97 nm.
Contributed by: M. Stcker
Veried by:
1000

F. Quiroz, V. Meynen, P. Cool, E.F. Vansant 900

-1
K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari

Volume adsorbed STP / cm g


800

700
Type of material: Silica 600
Batch composition: 1 Si:0.018 EO20PO70EO20:2.08 HCl:112 H2O.
500
Source of materials:
400

300
Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma 200
Aldrich). 100
Tetraethylorthosilicate (TEOS) (SigmaAldrich, reagent grade 0
98%). 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Hydrochloric acid 1 M (HCl) (Merck). P/P 0

Fig. 6.38. N2-sorption isotherm at 196 C of SBA-15.


Batch preparation:

1. Add 20 g EO20PO70EO20 to 400 mL 1 M HCl and heat to 50 C.


ads
2. Stir the mixture over night at about 30 C to obtain a homoge-
des
neous mixture.
3. Heat the mixture to 40 C, add 40 g TEOS under stirring. A white
suspension (precipitation) is formed after 1 h.
4. Keep the mixture at 40 C under stirring for an additional 24 h.
5. Transfer the mixture into Teon-lined autoclaves and keep it at
d v (r )

100 C for 72 h.

Product recovery:
Centrifugate and wash with warm distilled water until pH of 4
5 is observed.
Dry the solid at 90 C over night.
Post-synthesis treatment:
Calcine the product at 500 C during 6 h in owing air (ow rate 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Radius / nm
of 100 mL/min). Heating rate: 1 C/min. Cooling down occurs slowly.
Product characterization: Fig. 6.39. Pore size distribution of SBA-15 determined by the BJH method.

XRD: (See Fig. 6.37). 6.9. SBA-15 (from sodium silicate)


N2-sorption: (See Figs. 6.38 and 6.39).
Range of data derived from the isotherms: Short description of material: Large pore hexagonal mesoporous
SBET = 550900 m2/g. material with micropores in the walls.
Vtotal = 1.01.4 cm3/g. Contributed by: S.C. Laha, R. Glser, J. Weitkamp
Vmicro = 0.020.06 cm3/g. Veried by:
Pore diameter (BJH, adsorption branch) = 7.08.0 nm.
SEM: (See Fig. 6.40). F. Quiroz, V. Meynen, P. Cool, E.F. Vansant
TEM: (See Fig. 6.41). B. Seelandt, M. Wark, J. Caro
Remarks:
Type of material: Silica
 Synthesis can be done in an autoclave or in PP bottles at temper- Batch composition: 1 SiO2:0.33 Na2O:0.017 P123:1.4 HCl:95
atures of 100 C. H2O.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 199

Post-synthesis treatment:
Calcine the solid at 540 C for 1 h in nitrogen with a heating rate
of 2 C/min. Substitute the nitrogen by air and continue the calci-
nation for 8 h at 540 C (gas ow 30 cm3/min).
Product characterization:

XRD: (See Fig. 6.42).


N2-sorption: (See Fig. 6.43 and 6.44).
Range of data derived from the isotherms:
SBET = 500700 m2/g.
Vtotal = 0.71.0 cm3/g.
Vmicro = 0.060.1 cm3/g.
Pore diameter (BJH, adsorption branch) = 5.58.0 nm.

Fig. 6.40. SEM image of SBA-15.

Intensity / a.u.
Source of materials:

Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly


(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma
Aldrich).
Sodium silicate solution extra-pure, (25.528.5% SiO2 and 7.5
8.5% Na2O) (Merck).
HCl 37 wt.% (Merck). 0 1 2 3 4 5 6 7 8
2 /

Batch preparation:
Fig. 6.42. X-ray diffraction pattern of SBA-15. The corresponding d-spacings:
(1 0 0) = 9.80 nm; (1 1 0) = 5.45 nm and (2 0 0) = 4.74 nm.
1. Add 43.2 g of dimineralized water to 8.5 g of concentrated HCl,
mix.
2. Add 6.92 g P123 triblock copolymer to (1), mix and stir for 1 h
at 35 C. 500

3. Add 69.5 g dimineralized water to 0.27 g NaOH, mix until 450


-1

dissolved.
Volume adsorbed STP / cm g

400
4. Add (3) to 15.9 g sodium silicate. 350
5. Add (4) to (2) and stir at 35 C for 24 h. 300
6. Hydrothermal treatment in a 300 mL Teon-lined steel auto-
250
clave at 100 C in a preheated oven, during 24 h, without any
200
agitation.
150

Product recovery: 100


50
1. Add 25 mL ethyl alcohol to the precipitate, mix and lter. 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
2. Wash the precipitate three times with 10 mL ethyl alcohol and
P /P 0
three times with 200 mL demineralized water.
3. Dry in air at 80 C. Fig. 6.43. N2-sorption isotherm of SBA-15.

Fig. 6.41. TEM images of SBA-15.


200 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

ads
des
d v (r )

0 1 2 3 4 5 6 7 8 9 10
Radius / nm

Fig. 6.44. Pore size distribution of SBA-15 obtained by the BJH method.

SEM: (See Fig. 6.45).


TEM: (See Fig. 6.46).
Fig. 6.46. TEM image of SBA-15.
6.10. SBA-15
4. After 24 h at 35 C, transfer the solution into a PP-bottle and
Short description of material: Large pore hexagonal mesoporous place it in an oven at 80 C for 24 h.
material with micropores in the walls.
Contributed by: F. Heinroth, P. Behrens Product recovery:
Veried by: Filter the reaction solution; wash the generated white powder
with water and dry at 50 C.
F. Quiroz, V. Meynen, P. Cool, E.F. Vansant Post-synthesis treatment:
A. Ferreira, S. Aguado, J. Gascon, F. Kapteijn Calcine the product at 500 C during 24 h in ambient atmo-
sphere with a heating rate of 1 C/min. Cooling down occurs slowly.
Type of material: Silica Product characterization:
Batch composition: 1 TEOS:6.2 4 M HCl:128.6 H2O:0.017 P123.
Source of materials: XRD: (See Fig. 6.47).
N2-sorption: (See Figs. 6.48 and 6.49).
Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly Range of data derived from the isotherms:
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma SBET = 600900 m2/g.
Aldrich). Vtotal = 0.81.1 cm3/g.
HCl 37% (SigmaAldrich). Vmicro = 0.090.17 cm3/g.
Tetraethylorthosilicate >98% (TEOS) (Fluka). Pore diameter (BJH, adsorption branch) = 5.06.5 nm.
SEM: (See Fig. 6.50).
Batch preparation: TEM: (See Fig. 6.51).
Remarks:
1. Add 34.2 g P123 to 810 mL H2O and 540 mL 4 M HCl and stir.
2. Heat the solution to 35 C.  Calcination at 500 C for 24 h without applying a heating ramp is
3. After 17.5 h, add 77 mL TEOS and stir. possible.

Fig. 6.45. SEM images of SBA-15.


V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 201

Contributed by: I. Bannat, J. Caro, M. Wark


Veried by:
G. Smeulders, V. Meynen, P. Cool, E.F. Vansant
A. Ferreira, S. Aguado, J. Gascon, F. Kapteijn
Intensity / a.u.

Type of material: Silica


Batch composition: 1 TEOS:8.14 HCl:168 H2O:0.017 P123.
Source of materials:
Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (BASF).
Tetraethylorthosilicate >98% p.s (TEOS) (Merck).
0 1 2 3 4 5 6 7 8
2 /
Concentrated hydrochloric acid >37% p.a. (Fluka).

Fig. 6.47. X-ray diffraction pattern of SBA-15. The corresponding d-spacings: Batch preparation:
(1 0 0) = 9.00 nm; (1 1 0) = 5.32 nm and (2 0 0) = 4.55 nm.

1. Dissolve 1 g P 123 in 25.63 mL of water.


700 2. Add 2.13 g of TEOS and add 8.13 g HCl quickly under vigorous
stirring.
600 3. Stir the mixture at 40 C for 4 h and transfer then into a teon-
based reaction vessel.
-1
Volume adsorbed STP / cm g

500 4. Carry out microwave treatment in a microwave system model


ETHOS 1 (MLS Company, Germany) for 2 h at 100 C. Use con-
400 tinuous microwave radiation with a maximum power of 400 W.

300 Product recovery:


Filter the solution and wash the white product with water.
200 Afterwards, dry the products at ambient temperature.
Post-synthesis treatment:
100
Calcine at 550 C for 6 h in ambient atmosphere and with a
heating rate of 1 C/min. Cooling down occurs slowly.
0
Product characterization:
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P /P 0 XRD: (See Fig. 6.52).
N2-sorption: (See Figs. 6.53 and 6.54).
Fig. 6.48. N2-sorption isotherm at 196 C of SBA-15. Range of data derived from the isotherms:
SBET = 700900 m2/g.
Vtotal = 0.81.0 cm3/g.
ads Vmicro = 0.100.20 cm3/g.
des Pore diameter (BJH, adsorption branch) = 5.07.0 nm.
SEM: (See Fig. 6.55).
TEM: (See Fig. 6.56).
d v (r )

Remarks:

 The template can also be removed by extraction instead of cal-


cination [418].

6.12. Short-channel SBA-15

0 1 2 3 4 5 6 7 8 9 10 Short description of material: Large pore hexagonal mesoporous


Radius / nm
material with micropores in the walls. In addition, the pore lengths
Fig. 6.49. Pore size distribution of SBA-15 obtained by the BJH method. are reduced in size allowing improved diffusion rate.
Contributed by: P. Cool, E.F. Vansant, V. Meynen
Veried by:
 This synthesis was made at a larger scale in the order of 20 g (3
4 times more compared to the other syntheses of SBA-15). A. Ferreira, S. Aguado, J. Gascon, F. Kapteijn
 Reduced reaction temperature circumvents hydrothermal treat- K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari
ment and allows to carry out the reaction in polypropylene (PP)
bottles. Type of material: Silica
Batch composition: 1 TEOS:5.87 HCl:194 H2O:0.017 P123.
Source of materials:
6.11. SBA-15 (microwave synthesis)
Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
Short description of material: Large pore hexagonal mesoporous (ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma
material with micropores in the walls. Aldrich).
202 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Fig. 6.50. SEM images of SBA-15.

HCl (37% Acros Organics). Remarks:


Tetraethylorthosilicate TEOS (98% Acros Organics).
 The short-channels can be identied both from the TEM
Batch preparation: images and the SEM images. Next to the shorter pores, also
the particles morphology consists of shorter rods that are not
1. Add 4 g P123 to 127 mL H2O and 20 mL HCl, stir until complete agglomerated in longer secondary particles as those of normal
dissolution (this takes about 1 h). SBA-15.
2. Heat till 40 C.  Addition of KCl during the synthesis (before TEOS is added) gives
3. Add 9.14 mL TEOS and stir for 8 min at 40 C. rise to SBA-15 with short straight channels [419].
4. Stop stirring and allow the mixture to age for 24 h at 40 C.  Addition of a swelling agent, mesitylene, during the synthesis
5. Hydrothermal treatment in an autoclave at 100 C for 24 h. (before TEOS is added) enlarges the pores of the short-channel
6. Quench the synthesis mixture. SBA-15 [172].
 Due to the short length of the mesopores, higher loadings can be
Product recovery: obtained upon impregnation [421].
Filter, wash with 3  20 mL water and dry in ambient
atmosphere.
Post-synthesis treatment: 6.13. Plugged hexagonal templated silica (PHTS)
Calcine the product at 550 C during 6 h, with a heating rate of
1 C/min. Cooling down occurs slowly. Short description of material: Large pore hexagonal mesoporous
Product characterization: material with micropores in the walls and amorphous microporous
silica plugs in the channels.
XRD: (See Fig. 6.57). Contributed by: P. Cool, E.F. Vansant, V. Meynen
N2-sorption: (See Figs. 6.58 and 6.59). Veried by:
Range of data derived from the isotherms:
SBET = 500800 m2/g. K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari
Vtotal = 0.91.2 cm3/g. A. Silvestre-Albero, J. Silvestre-Albero, A. Seplveda-Escribano,
Vmicro = 0.040.09 cm3/g. F. Rodrguez-Reinoso
Pore diameter (BJH, adsorption branch) = 6.08.0 nm. Literature verication by E.B. Celer et al. [266].
SEM: (See Fig. 6.60).
TEM: (See Fig. 6.61). Type of material: Silica
Batch composition: 1 TEOS:2.77 HCl:192 H2O:0.008 P123.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 203

Fig. 6.51. TEM images of SBA-15.

600

500
-1
Volume adsorbed STP / cm g

400
Intensity / a.u.

300

200

100

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
P/P 0
2 /

Fig. 6.52. X-ray diffraction pattern of SBA-15 made by microwave assisted Fig. 6.53. N2-sorption isotherm at 196 C of SBA-15 made by microwave assisted
synthesis. The corresponding d-spacings: (1 0 0) = 8.57 nm; (1 1 0) = 4.93 nm and synthesis.
(2 0 0) = 4.22 nm.

Source of materials: Batch preparation:

Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly 1. Add 4 g P123 to 130 mL H2O and 20 mL HCl; stir until complete
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma dissolution.
Aldrich). 2. Add 15 g (about 16 mL) TEOS and stir for 7.5 h at 60 C.
HCl 37% (Acros Organics). 3. Stop stirring and age for 15.5 h at 80 C.
Tetraethylorthosilicate 98% (TEOS) (Acros Organics). 4. Cool down to room temperature.
204 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

ads
des

Intensity / a.u.
dv (r )

0 1 2 3 4 5 6 7 8
2 /

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 Fig. 6.57. X-ray diffraction pattern of short channel SBA-15. The corresponding d-
Radius / nm spacings: (1 0 0) = 10.10 nm; (1 1 0) = 5.78 nm; (2 0 0) = 5.02 and (2 1 0) = 3.32 nm.

Fig. 6.54. Pore size distribution of SBA-15 made by microwave assisted synthesis
via the BJH method.

800

700

-1
Volume adsorbed STP / cm g
3
600

500

400

300

200

100

0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
P /P 0

Fig. 6.55. SEM image of microwave assisted synthesized SBA-15. Fig. 6.58. N2-sorption isotherm at 196 C of SBA-15 with short channels.

ads
des
d v (r )

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Fig. 6.56. TEM image of microwave assisted synthesized SBA-15. Radius / nm

Fig. 6.59. Mesopore size distribution of SBA-15 with short channels determined
Product recovery: with the BJH method.
Filter, wash with 3  25 mL water and dry at ambient
atmosphere.
Pore diameter (BJH, adsorption branch) = 5.07.0 nm for the
Post-synthesis treatment:
open pores. The plugged pores are smaller than 4 nm.
Calcine the product at 550 C during 6 h with a heating rate of
SEM: (See Fig. 6.65).
1 C/min in ambient atmosphere. Cooling down occurs slowly.
TEM: (See Fig. 6.66).
Product characterization:

XRD: (See Fig. 6.62). Remarks:


N2-sorption: (See Figs. 6.63 and 6.64).
Range of data derived from the isotherms:  Stability of the plugs is depending on the synthesis conditions
SBET = 700900 m2/g. [266].
Vtotal = 0.650.8 cm3/g.  For more information about the inuence of the TEOS amount,
Vmicro = 0.150.3 cm3/g. the stirring and ageing temperature [262].
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 205

Fig. 6.60. SEM images of short-channel SBA-15.

Fig. 6.61. TEM images of short-channel SBA-15.

600

500
-1
Volume adsorbed STP / cm g

400
Intensity / a.u.

300

200

100

0
0 1 2 3 4 5 6 7 8 9
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
2 /
P /P 0
Fig. 6.62. X-ray diffraction pattern of PHTS. The corresponding d-spacings:
(1 0 0) = 9.80 nm; (1 1 0) = 5.70 nm and (2 0 0) = 4.96 nm. Fig. 6.63. N2-sorption isotherm at 196 C of PHTS.

F. Quiroz, V. Meynen, P. Cool, E.F. Vansant


 PHTS can also be formed by post-synthesis depositions of nano- K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari
particles on SBA-15 [127].
Type of material: Aluminosilicate
Batch composition: 1 Si:0.06 Al:0.018 EO20PO70EO20:0.21
6.14. Al-SBA-15 HCl:115 H2O.
Source of materials:
Short description of material: Large pore hexagonal mesoporous
material with micropores in the walls and a Si/Al ratio of 32. Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
Contributed by: M. Stcker (ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma
Veried by: Aldrich).
206 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

ads
des
d v (r )

0 1 2 3 4 5 6 7 8 9 10
Radius / nm

Fig. 6.64. Mesopore size distribution of PHTS determined with the BJH method.

Tetraethylorthosilicate (TEOS) (SigmaAldrich, reagent grade


Fig. 6.66. TEM image of PHTS.
98%).
Sodiumaluminate (54% Al2O3, 41% Na2O) (Riedel-de Han).
HCl (0.1 M) (Merck).

Batch preparation:

1. Heat 20 g template (EO20PO70EO20) at 50 C and dissolve in


Intensity / a.u.

400 mL hydrochloric acid 0.1 M.


2. Stir the solution over night at 2530 C.
3. Add 40 g silicate source (TEOS) under stirring.
4. Stir the solution for 1 h.
5. Add 0.92 g sodiumaluminate.
6. Stir over night at 25 C.
7. Measure the pH in the solution; it should be around 2.
8. Change the temperature to 40 C, after about 30 min a gel is 0 1 2 3 4 5 6 7 8
formed, after 23 h a white precipitate is observed. 2 /
9. Stir the white precipitate solution for 4 h.
Fig. 6.67. X-ray diffraction pattern of Al-SBA-15 (Si/Al = 32). The corresponding d-
10. Change the pH of the solution to 2.5 at 40 C by addition of spacing: (1 0 0) = 8.02 nm.
4 M NaOH.
11. Stir the solution for 1 h.
12. Transfer the mixture to Teon bottles and keep it at 100 C Calcine the product at 500 C for 6 h in owing air with ow
for 72 h. rates of 100 mL/min and with a heating rate of 1 C/min.
Product characterization:
Product recovery:
Wash the formed white products with distilled water and cen- XRD: (See Fig. 6.67).
trifuge until pH 5. Dry the samples at 90 C for 3 days followed by N2-sorption: (See Figs. 6.68 and 6.69).
drying at 100 C overnight. Range of data derived from the isotherms:
Post-synthesis treatment:

Fig. 6.65. SEM images of PHTS.


V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 207

1200 6.15. Mesoporous silica lms


-1

1000 Short description of material: Mesoporous silica lm with pores


Volume adsorbed STP / cm g
3

in the nanometer range.


800 Contributed by: I. Krueger, N. Witteck, P. Behrens
Veried by:
600

K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari


400
V. Meynen, P. Cool, E.F. Vansant

200
Type of material: Silica
0
Batch composition: 1 TEOS:48.9 CH3CH2OH:0.06 2 N HCl:26.9
0.00 0.20 0.40 0.60 0.80 1.00 H2O:0.0135 EO20PO70EO20.
P /P 0 Source of materials:

Fig. 6.68. N2-sorption isotherm at 196 C of Al-SBA-15 (Si/Al = 32).


Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma
Aldrich).
ads Ethanol abs. for synthesis (Merck).
des Millipore water.
Hydrochloric acid purum p.a. (Fluka).
Tetraethoxysilane purum (TEOS) (Fluka).
Standard glass slides (Karl Hecht KG, Elka Objekttrger).
d v (r )

Batch preparation:
The nanostructured lm is prepared on standard glass slides in
a dip-coating procedure. The dip-coating solution:

1. Add 0.0135 mol of P123 to 48.9 mol of ethanol, 0.06 mol of


hydrochloric acid and 26.9 mol of millipore water until all the
block copolymer is dissolved.
0 2 4 6 8 10 12 14 16 18 20 2. Add 1 mol of TEOS to the mixture and stir for 10 min.
Radius / nm 3. Transfer the dip-coating solution to a modied desiccator (see
Fig. 6.73) wherein the air humidity is adjusted with a glucose
Fig. 6.69. Pore size distribution of Al-SBA-15 (Si/Al = 32) obtained with the BJH
method. solution (50 wt.%).
4. Position the glass slide for 5 min above the dip-coating solution
in the closed desiccator.
SBET = 8001100 m2/g. 5. Dip the glass slide into the solution for 30 s, pull out very slowly
Vtotal = 1.01.6 cm3/g. (approximately 2 mm/s) and keep in the closed desiccator for
Vmicro = 0.050.2 cm3/g. 5 min.
Pore diameter (BJH, adsorption branch) = 7.013.0 nm.
Chemical composition: Product recovery: Not applicable.
The Si/Al ratio of the different veried Al-SBA-15 samples were Post-synthesis treatment:
determined as 32 by XRF, 32 by EPMA and 42 by ICP/AES. The glass slides are put in a drying oven at 60 C in ambient
atmosphere overnight and are then calcined at 415 C for 4 h in
NMR: (See Fig. 6.70). ambient atmosphere without a heating rate.
SEM: (See Fig. 6.71). Product characterization:
TEM: (See Fig. 6.72).
XRD: (See Fig. 6.74).
SEM: (See Fig. 6.75).

Remarks:

 Successful deposition of the lm can also be observed by a


Intensity / a.u.

change in contact angle. For example: original glass slide about


28 and after deposition of the silica lm about 14.

calcined sample
(Si/Al 32) 6.16. SBA-16

Short description of material: Cubic mesoporous material with


150 100 50 0 -50 -100 micropores in the walls.
Chemical shift/ ppm Contributed by: W.J.J. Stevens, P. Cool, E.F. Vansant, V. Meynen
27
Veried by:
Fig. 6.70. Al MAS NMR spectra of the Al-SBA-15 sample with a Si/Al ratio of 32.
208 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Fig. 6.71. SEM images of calcined sample Al-SBA-15 (Si/Al = 32).

Intensity / a.u.

0 1 2 3 4 5 6
Fig. 6.72. TEM images of calcined sample Al-SBA-15 (Si/Al = 32). 2 /

Fig. 6.74. X-ray diffraction pattern of the SBA-15 lm. The corresponding d-
spacing: (1 0 0) = 5.81 nm.

Tetraethylorthosilicate 98% (TEOS) (Acros Organics).


1-Butanol.

Batch preparation:

1. Add 7 mL HCl to 190 mL H2O in a reux setup.


2. Add 14.8 mL BuOH.
3. Add 4 g F127 and stir until complete dissolution.
4. Add 21 mL TEOS and stir during 24 h at 45 C.
5. Stop stirring and age at 100 C during 24 h.

Product recovery:
Fig. 6.73. Schematic representation of the modied desiccator for dip-coating. Filter, wash with 3  25 mL water and dry at ambient
atmosphere.
Post-synthesis treatment:
D. Pufky-Heinrich, R. Glser, J. Weitkamp Calcine the product at 550 C during 6 h in ambient atmosphere
A. Silvestre-Albero, J. Silvestre-Albero, A. Seplveda-Escribano, and with a heating rate of 1 C/min. Cooling down occurs slowly.
F. Rodrguez-Reinoso Product characterization:

Type of material: Silica XRD: (See Fig. 6.76).


Batch composition: 1 TEOS:0.88 HCl:111 H2O:0.0032 F127:1.70 N2-sorption: (See Figs. 6.77 and 6.78).
BuOH. Range of data derived from the isotherms:
Source of materials: SBET = 700800 m2/g.
Vtotal = 0.550.65 cm3/g.
Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly Vmicro = 0.150.3 cm3/g.
(ethylene glycol) (MW 12600) (EO106PO70EO106, F127) (Sigma Pore diameter (BJH, adsorption branch) = 4.56.5 nm.
Aldrich). SEM: (See Fig. 6.79).
HCl 37% (Acros Organics). TEM: (See Fig. 6.80).
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 209

600

500

-1
Volume adsorbed STP / cm g
400

300

200

100

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P/P 0

Fig. 6.77. N2-sorption isotherm of cubic SBA-16 at 196 C.

ads
des

d v (r )

0 1 2 3 4 5 6 7 8 9 10
Radius / nm

Fig. 6.78. Pore size distribution of SBA-16 obtained by the BJH method.

Fig. 6.75. SEM images: surface structure of two different silica lms.
6.17. SBA-16

Short description of material: Cubic mesoporous material with


micropores in the walls.
Contributed by: F. Heinroth, P. Behrens
Veried by:
Intensity / a.u.

F. Quiroz, V. Meynen, P. Cool, E.F. Vansant


D. Pufky-Heinrich, S.A.S. Rezai, J. Weitkamp

Type of material: Silica


Batch composition: 1 TEOS:116 H2O:4 HCl:0.004 F-127.
Source of materials:

HCl (SigmaAldrich).
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
2 / (ethylene glycol) (MW 12600) (EO106PO70EO106, F-127)
(SigmaAldrich).
Fig. 6.76. X-ray diffraction pattern of cubic SBA-16. The corresponding d-spacings:
(1 1 0) = 11.31 nm; (2 0 0) = 8.02 nm; (2 1 1) = 6.39 and (2 2 0) = 5.88 nm. TEOS >98% (Fluka).

Batch preparation:
Remarks:
1. Add 134 mL concentrated HCl to 836 mL H2O.
 Addition of more or less butanol during the synthesis (before 2. Add 20 g Pluronic F-127 and stir.
TEOS is added) gives rise to differently ordered materials [426]. 3. Heat the solution to 35 C and add after 4.5 h 89.1 mL TEOS
 Changing the amount of TEOS added changes the observed mor- under stirring.
phology of the SBA-16 material as well as its porous character- 4. Transfer the solution after 20 h into a PP-bottle and treat it for
istics [246]. 24 h in an oven at 80 C.
210 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Fig. 6.79. SEM images of cubic SBA-16.


Intensity / a.u.

Fig. 6.80. TEM images of cubic SBA-16.


0 1 2 3 4 5 6 7 8
2 /

Product recovery: Fig. 6.81. X-ray diffraction pattern of SBA-16. The corresponding d-spacings:
Filter the reaction solution and wash the generated white pow- (1 1 0) = 10.14 nm; (2 0 0) = 6.35 nm and (2 1 1) = 2.15 nm.
der with water, dry at 50 C.
Post-synthesis treatment:
Calcine the product at 500 C during 24 h in ambient atmo-
SEM: (See Fig. 6.84).
sphere with a heating ramp of 1 C/min.
TEM: (See Fig. 6.85).
Product characterization:

XRD: (See Fig. 6.81). Remarks:


N2-sorption: (See Figs. 6.82 and 6.83).
Range of data derived from the isotherms:  Calcination at 500 C for 24 h without applying a heating ramp is
SBET = 550800 m2/g. possible.
Vtotal = 0.250.4 cm3/g.  This synthesis was made at a larger scale in the order of 20 g
Vmicro = 0.10.2 cm3/g. (34 times more compared to the other syntheses of
Pore diameter (BJH, adsorption branch) = 4.05.0 nm. SBA-16).
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 211

250
-1
Volume adsorbed STP / cm g

200

150

100

50

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P/P 0

Fig. 6.82. N2-sorption isotherm at 196 C of SBA-16.

ads
des

Fig. 6.85. TEM image of SBA-16.


dv (r )

6.18. MCF

Short description of material: Mesoporous cellular foam; porous


material with very large mesopores. Three-dimensional pore net-
work with cellular pore morphology.
Contributed by: P. Cool, E.F. Vansant, V. Meynen
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Veried by:
Radius / nm
M. Stcker, A.M. Bouzga
Fig. 6.83. Pore size distribution of SBA-16 calculated by the BJH method. K.S. Triantafyllidis, S. Karakoulia, C. Nitsos, S.D. Sklari

Fig. 6.84. SEM images of SBA-16.


212 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Type of material: Silica


ads
Batch composition: 1 TEOS:5.87 HCl:194 H2O:0.017 EO20- des
PO70EO20:0.031 NH4F:0.815 mesitylene.
Source of materials:

Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly

d v (r )
(ethylene glycol) (MW 5800) (EO20PO70EO20, P123) (Sigma
Aldrich).
HCl 37% (Acros Organics).
Tetraethylorthosilicate 98% (TEOS) (Acros Organics).
NH4F p.a. (Merck).
Mesitylene (=trimethylbenzene) 99% (Acros Organics).

0 5 10 15 20 25 30 35 40 45 50
Radius / nm
Batch preparation:
Fig. 6.87. Pore size distribution of MCF determined with the BJH method.
1. Add 4 g P123 and 20 mL HCl to 130 mL H2O; stir until the sur-
factant is dissolved.
2. Add 0.0467 g NH4F and 4.6 mL mesitylene.
3. Stir for 1 h at 3540 C.
4. Add 9.14 mL of TEOS; stir for 20 h at 3540 C.
5. Transfer the mixture to an autoclave and keep it at 100 C for
24 h.
6. After heat treatment, quench the autoclave to room
temperature.

Product recovery:
Filter, wash with 3  25 mL water and dry at ambient
Fig. 6.88. SEM images of MCF.
atmosphere.
Post-synthesis treatment:
Calcine the product at 550 C during 6 h in ambient atmosphere
with a heating rate of 1 C/min. Cooling down occurs slowly.
Product characterization:

XRD:The pores are too large for X-ray diffraction. The rst order
peak should appear below 0.2 2h.
N2-sorption: (See Figs. 6.86 and 6.87).
Range of data derived from the isotherms:
SBET = 550700 m2/g.
Vtotal = 2.12.6 cm3/g.
Vmicro = 0.070.1 cm3/g.
Pore diameter (BJH, adsorption branch) = 20.030.0 nm
(desorption about 10.015.0 nm).
SEM: (See Fig. 6.88).
TEM: (See Fig. 6.89).

Fig. 6.89. TEM image of MCF.

2000
Remarks:
1800
 The synthesis can also be executed without the addition of
-1

1600
NH4F. However, without the presence of F ions in the synthesis
Volume adsorbed STP / cmg

1400 mixture, the hysteresis loop will be much broader [282,284].


1200

1000

800 6.19. MMA (monolithic mesoporous aluminosilicates)


600
Short description of material:
400
Highlights :
200

0 Tunable porosity from super-micropores (1 nm < dp < 2 nm) to


0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
small mesopores.
P/P 0
Tunable concentration of surface acid sites (moderate acid
Fig. 6.86. N2-sorption isotherm at 196 C of MCF. strength).
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 213

Monolithic solid with controlled morphology. (7) Store at 40 C for 2 h.


Thermostabilityhydrostability. (8) Store at 60 C until solid phase condensation occurs (usually
One-step synthesis. 2 or 3-days period).

Applications: Product recovery:


The material contracts during the drying and calcination steps,
Heterogeneous catalysis. facilitating their removal form the moulds.
Adsorption, gas separation. . . Post-synthesis treatment:
Calcine at 560 C during 6 h in ambient atmosphere with a tem-
Contributed by: D. J. Jones, J. Rozire, N. Donzel, M. Taillades- perature ramp of 0.5 C/min.
Jacquin Product characterization:
Veried by:
XRD: (See Fig. 6.90).
A. Ferreira, S. Aguado, J. Gascon, F. Kapteijn N2-sorption: (See Figs. 6.916.96).
M. Stcker, A. van Miltenburg Pore diameter of the various MMA materials as determined by
Industrial verication by UOP-LLC (Des Plaines) [427]. the as-plot method

Type of material: Aluminosilicate MMA material dp/ nm


Batch composition: 1 TEOS:3.88 H2O:0.007 HNO3:0.19 Brij 30:
Al (NO3)3.9H20. Si/Al = 1 2.0
Source of materials: Si/Al = 40 2.2
Si/Al = 20 2.6
Tetraethoxysilane, purity 98%, Si(OC2H5)4 (SigmaAldrich). Si/Al = 15 2.5
65% Nitric acid solution (Fluka). Si/Al = 10 2.5
Aluminiumnitrate nonahydrate, purity 99+%, Al(NO3)3.9H2O Si/Al = 5 3.4
(Acros Organics).
Polyoxyethylene (4) lauryl ether (MW 362) (C12H25(OCH2-
CH2)4OH, Brij 30) (SigmaAldrich). Range of data derived from the isotherms:
SBET = 6501000 m2/g.
Batch preparation: Vtotal = 0.40.65 cm3/g.
Pore diameter (BJH, adsorption branch) = 1.55.0 nm.
(1) Add 4.5 g Brij 30 to 4.5 g 0.1 M HNO3 and 13.5 g TEOS while NMR: (See Fig. 6.97).
stirring the solution until complete dissolution (clear and SEM: (See Fig. 6.98).
transparent solution). The reaction vessel is kept at a con- TEM: (See Fig. 6.99).
stant temperature (usually 25 C) by means of a water bath.
(2) In case that Al is introduced in the system, the necessary Remarks:
amount of Al(NO3)3.9.H2O is added to the reaction mixture
while stirring. (e.g. 0.61 g in case of Si/Al = 40; 1.62 g for  The dilute 0.1 M HNO3 aqueous solution serves as both solvent
Si/Al = 15). and pH regulator.
(3) Remove the ethanol produced by the reaction by vacuum
treatment (water pump or reduced pressure of 2035 mbar) 300
-1
Volume adsorbed STP / cm g
3

at ambient temperature for 1 h. 250


(4) Store the solution in a drier at 60 C until an enough viscous
200
solution is obtained (usually between 1 and 2 h).
(5) Transfer the solution in a mould (glass tube) by means of a 150
syringe. 100
(6) Store at ambient temperature for 2 h.
50

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Si/Al = 10 P/P 0

Si/Al = 20
Fig. 6.91. Adsorption isotherms of nitrogen at 196 C of MMA (Si/Al = 1).
Intensity / a.u.

300
-1

Si/Al = 40
Volume adsorbed STP / cm g
3

250

Si/Al = 200

150

100

50
0 1 2 3 4 5 6 7 8 9 10
2 / 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Fig. 6.90. X-ray diffraction pattern of MMA. The corresponding d-spacings: (Si/ P/P0
Al = 10) = 4.67 nm; (Si/Al = 20) = 4.39 nm; (Si/Al = 40) = 3.63 and (Si/
Al = 1) = 3.38 nm. Fig. 6.92. Adsorption isotherms of nitrogen at 196 C of MMA (Si/Al = 40).
214 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

300
-1
Volume adsorbed STP / cm g
3

250

200

Intensity / a.u.
150 calcined sample
Si/Al = 15
100

50

0 calcined sample
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Si/Al = 40
P/P 0

Fig. 6.93. Adsorption isotherms of nitrogen at 196 C of MMA (Si/Al = 20). 150 100 50 0 -50 -100
Chemical shift / ppm

27
Fig. 6.97. Al MAS NMR spectra of various MMA materials.
350
-1
Volume adsorbed STP / cm g
3

300

250

200

150

100

50

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P/P 0

Fig. 6.94. Adsorption isotherms of nitrogen at 196 C of MMA (Si/Al = 15).

Fig. 6.98. SEM image of MMA.

300
-1
Volume adsorbed STP / cm g
3

250

200

150

100

50

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P/P 0

Fig. 6.95. Adsorption isotherms of nitrogen at 196 C of MMA (Si/Al = 10).

300
-1
Volume adsorbed STP / cm g
3

250

200

150

100

50

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Fig. 6.99. TEM image of MMA.
P/P 0

Fig. 6.96. Adsorption isotherms of nitrogen at 196 C of MMA (Si/Al = 5).

6.20. Monolithic material

 Adaptations of the above procedure were performed through the Short description of material: Monolithic material with super-
introduction of aluminium nitrate to the diluted HNO3 prior to micropores (1 nm < dp < 2 nm).
addition of surfactant and TEOS, using Si/Al ratio in the range Contributed by: B. Ufer, P. Behrens
5 < Si/Al < 40. Veried by:
 The materials can be successfully modied with Pt and Pd [428].
 Instead of applying moulds, the materials can also be made via K. De Witte, V. Meynen, P. Cool, E.F. Vansant
extrusion with or without the addition of binders. F. Meducin, F. Warmont, S. Serieye, M.-L. Saboungi
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 215

Type of material: Silica


Batch composition: 1 TMOS:0.196 tetraethylene glycol monod- ads
des
odecyl ether:0.00075 HCl:4.17 H2O.
Source of materials:
Tetraethylene glycol monododecyl ether >98% (Fluka).
Hydrochloric acid 0.01 mol/L (Riedel-de Han) Fixanal.

d v (r )
Tetramethylorthosilicate >98% (Fluka).

Batch preparation:

1. Mix 200 lL of tetraethylene glycol monododecyl ether with


200 lL 0.01 mol/L hydrochloric acid and 400 lL tetramethyl-
orthosilicate in a safe lock tube (Eppendorf). 0 1 2 3 4 5 6 7 8 9 10
2. Shake the used safe lock tube (Eppendorf) for 1 min. Radius / nm
3. Transfer the synthesis gel to a container providing the wanted
Fig. 6.102. Pore size distribution of the powdered monolithic material determined
geometry.
with the BJH method.
4. Leave the synthesis gel in the oven for one week at 40 C to
evaporate the resulting methanol and allow condensation to
take place.

Product recovery:
Recover the resulting monolithic material without further steps.
Post-synthesis treatment:
Calcine at 500 C during 24 h in ambient atmosphere with a
heating ramp that is as low as possible.
Product characterization:

XRD: (See Fig. 6.100).


N2-sorption: (See Figs. 6.101 and 6.102).

Fig. 6.103. SEM images of monolithic material.


Intensity / a.u.

Range of data derived from the isotherms:


SBET = 10601170 m2/g.
Vtotal = 0.400.50 cm3/g.
Pore diameter (BJH, adsorption branch) = 1.401.55 nm.
SEM: (See Fig. 6.103).
TEM: (See Fig. 6.104).
0 1 2 3 4 5 6 7 8 Remarks:
2 /
 The container to form the monoliths does not need to be of any
Fig. 6.100. XRD of the powdered monolithic material. The corresponding d-
spacings: (1 0 0) = 3.22 nm.
special type of material. Examples of materials that have been
used: cell-culture dishes, plastic drinking straws, etc.
 To obtain crack free monoliths, they should stay in an oven at
350 40 C for at least a week and evaporation or heating should
always be very slow to retain the monolithic structure.
300
 After calcination the monolith will show some crack formation
-1

and becomes super-microporous (1 nm < dp < 2 nm). Neverthe-


Volume adsorbed / cm g

250
less, it possesses short range order of the pores and high surface
200 areas.
 Due to the super-microporous nature of the materials, it must be
150
noted that the BJH method to determine the pore size needs to
100 be applied with care and is only indicative.

50

6.21. Stabilized mesoporous titania


0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P /P 0
Short description of material: mesoporous titania (partially ana-
tase). Stabilization of the structure by post-synthesis modication
Fig. 6.101. N2-sorption isotherm at 196 C of the powdered monolithic material. with NH4OH or NaOH.
216 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

Intensity / a.u.
20 25 30 35 40 45 50 55 60
2 /

Fig. 6.105. X-ray diffraction pattern of mesoporous titania stabilized with a base
treatment of NH4OH.

Intensity / a.u.

1000 900 800 700 600 500 400 300 200 100 0
-1
Raman shift / cm

Fig. 6.106. Raman spectrum of mesoporous titania after base treatment with
NH4OH and calcination.

250

Fig. 6.104. TEM images of monolithic material.


-1
Volume adsorbed STP / cm g

200

150
Contributed by: E. Beyers, P. Cool, E.F. Vansant, V. Meynen
Veried by:
100

M. Stcker, A.I. Spjelkavik


J. Ruiz-Martnez, J. Silvestre-Albero, A. Seplveda-Escribano, 50
F. Rodrguez-Reinoso
0
Type of material: Titania 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Batch composition: 1 Ti(OiPr)4:0.16 CTMABr:1.4 HCl:17 H2O:20 P /P 0

EtOH.
Fig. 6.107. N2-sorption at 196 C of mesoporous titania stabilized with NH4OH
Source of materials: treatment.

Ethanol p.a. (EtOH) (Merck, absolute GR for analysis).


HCl 37% (Acros Organics). 3. Add the CTMABr solution (1) to the Ti(OiPr)4 solution (2).
Titanium (IV) isopropoxide Ti(OiPr)4 97% (SigmaAldrich). 4. Add dropwise 2.06 mL H2O and stir during 15 min.
Cetyltrimethylammonium bromide CTMABr (Acros Organics). 5. Transfer the solution into an open Petri Dish and put this
NH4OH 2830 wt.% solution of NH3 in water p.a. (Acros in an oven at 60 C during 7 days.
Organics).
(B)
Batch preparation: Base treatment of the solid with NH4OH for stabilization:
1. Add 1 g of solid to 50 mL H2O (pH 910, by addition of
(A) NH4OH).
1. Add 0.59 g CTMABr to 6 mL EtOH. 2. Reux for 48 h, keep the pH constant between pH 910
2. Add 3 mL Ti(OiPr)4to 5.7 mL EtOH and 1.18 mL HCl. (NH4OH).
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 217

Product recovery:
Filter, wash with 3  25 mL water and dry at ambient
conditions.
Post-synthesis treatment:
Calcine the product at 300 C during 2 h with a heating rate of
2 C/min under air ow. Alternatively, it is possible to calcine the
material during 2 h at 450 C with a heating rate of 2 C/min with-
out air ow.
Product characterization:

XRD: (See Fig. 6.105).


Raman: (See Fig. 6.106).
N2-sorption: (See Figs. 6.107 and 6.108).
Range of data derived from the isotherms:
SBET = 250500 m2/g.
Vtotal = 0.250.8 cm3/g.
Pore diameter (BJH, adsorption branch) = 2.03.0 nm.
SEM: (See Fig. 6.109).
TEM: (See Fig. 6.110).

Remarks:
 The stabilization step with NH4OH is also possible with NaOH
and leads to products with a higher surface area and total pore
volume [60]. Fifty milliliter of 0.112 M NaOH solution was used
for each gram of product [60]. Fig. 6.110. TEM image (B and C) and diffraction pattern (A) of mesoporous titania
stabilized by the post-synthesis NH4OH treatment.

ads  The mechanism for stabilization can be found in the literature


des [56,60,431].

6.22. Titanate nanotubes


d v (r )

Short description of material: tubular-shaped material with inner


diameter of approximately 5 nm and outer diameter of approxi-
mately 10 nm. Titanate crystalline structure.
Contributed by: S. Ribbens, E. Beyers, E.F. Vansant, P. Cool, V.
Meynen
0 1 2 3 4 5 6 7 8 9 10 Veried by:
radius / nm

Fig. 6.108. Pore size distribution (BJH) of mesoporous titania stabilized with a I. Bannat, M. Wark, J. Caro
NH4OH treatment. A. Silvestre-Albero, J. Ruiz-Martnez, J. Silvestre-Albero, A. Sep-
lveda-Escribano, F. Rodrguez-Reinoso
N. Kanellopoulos, G. Karanikolos

Type of material: Sodium trititanate and after ion exchange


hydrogen trititanate.
Batch composition:
Source of materials:

TiO2-powder (Riedel-de Han).


HCl 37% (Acros Organics).
NaOH pellets (Acros Organics).

Batch preparation [432]:

1. Disperse 4.5 g TiO2 into 80 mL 10 M NaOH solution under


vigorous stirring.
2. Stir the mixture for an hour.
3. Transfer the mixture in an autoclave (AC).
4. Heat the AC to 150 C for 48 h.
5. Quench the AC to room temperature.
6. Recover the solid by centrifugation and wash three times
Fig. 6.109. SEM image of mesoporous titania stabilized with the NH4OH method. with deionized water.
218 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

7. Disperse the wet cake into 240 mL 0.1 M HCl and stir for H-tube
30 min. Na-tube
8. Recover the solid by centrifugation.
9. Wash with 0.1 M HCl to pH 56 to obtain the Na-titanate
tube.
10. Further washing up to pH 11.5 to convert the Na-titanate

d v (r )
tube into an H-titanate tube.

Product recovery:
Centrifugation, wash with water (3 times), ethanol (2 times)
and dry at 100 C in ambient atmosphere.
Post-synthesis treatment:
No further steps required
Product characterization: 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Radius / nm
XRD: (See Fig. 6.111).
Fig. 6.113. Pore size distribution (BJH, adsorption branch) of a sodium and
N2-sorption: (See Fig. 6.112 and 6.113).
hydrogen trititanate nanotube.
Range of data derived from the isotherms:
SBET = 200300 m2/g.
Vtotal = 0.50.9 cm3/g.
Pore diameter (BJH, adsorption branch) = 3.04.3 nm (inner
diameter).
TEM: (See Fig. 6.114).

Na2Ti 3O7
H2Ti 3O7
Intensity / a.u.

0 10 20 30 40 50 60 70 80 90 100
2 /

Fig. 6.111. X-ray diffraction pattern of Na2Ti3O7 and acid washed H2Ti3O7 Fig. 6.114. TEM and HRTEM of protonated titanate nanotubes (ac), sodium
nanotubes. titanate nanotubes (d). The nanotubes have outer diameters of 1015 nm and
lengths of 200400 nm.

Remarks:
1200
H-Tube
Na-tube
 The titanate nanotubes can be converted to anatase nanotubes
1000 by calcining under Ar atmosphere at 500 C [432] or in ambient
-1
Volume adsorbed STP / cm g

atmosphere [9].
800  The titanate nanotubes can also be prepared with microwave
assisted synthesis [9].
600

400
7. Conclusions

This publication covers the veried syntheses of the selected


200
relevant structured super-microporous and mesoporous siliceous
and titania materials. The number of listed materials is by no
0 means complete, containing all existing and important mesopor-
0 0.2 0.4 0.6 0.8 1
ous materials that have been developed in recent years. Moreover,
P /P 0
the number of veried syntheses is much smaller than the veried
Fig. 6.112. N2-sorption isotherm at 196 C of a sodium and hydrogen trititanate syntheses of zeolites collected in the well-known zeolite syntheses
nanotube. book [434]. However, this achievement should be seen as the start
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 219

of the publication and documentation for proven syntheses of mes- Mesoporous Molecular Sieves, Studies in Surface Science and Catalysis, vol.
117, Elsevier, Amsterdam, 1998, p. 1.
oporous materials, with the possibility to be further explored in the
[2] A.E.C. Palmqvist, Curr. Opin. Colloid Interface Sci. 8 (2003) 145.
future. [3] J. Patarin, B. Lebeau, R. Zana, Curr. Opin. Colloid Interface Sci. 7 (2002) 107.
The Network of Excellence (INSIDE POReS) was indispensable [4] G.J.A.A. Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chem. Rev. 102 (2002)
in accomplishing this publication on veried mesoporous materi- 4093.
[5] P. Cool, T. Linssen, K. Cassiers, E.F. Vansant, Recent Res. Devel. Mater. Sci. 3
als. It was the ideal network of researchers from different elds (2002) 871.
(synthesis, characterization, catalysis and membranes) that syn- [6] T. Linssen, K. Cassiers, P. Cool, E.F. Vansant, Adv. Colloid Interface Sci. 103
thesize and/or apply these mesoporous materials for different (2003) 121.
[7] B. Zhu, Y. Chen, J. Liu, W.D. Zhang, H.C. Zeng, Chem. Mater. 14 (2002) 1391.
application purposes. The publication was a joint work by ex- [8] O. Carp, C.L. Huisman, A. Reller, Prog. Solid Sate Chem. 32 (2004) 33.
perts in the eld working together to realize a large amount of [9] S. Ribbens, V. Meynen, G. Van Tendeloo, X. Ke, M. Mertens, B.U.W. Maes,
verication work in synthesizing and characterizing these mate- P. Cool, E.F. Vansant, Micropor. Mesopor. Mater. 144 (13) (2008) 401.
[10] M. Wei, Y. Konishi, H. Zhou, H. Sugihara, H. Arakawa, Solid State Commun.
rials. This work will be carried on in the future in the frame of 133 (2005) 493.
the European Nanoporous Materials Institute of Excellence (EN- [11] Y.K. Hwang, J.S. Chang, Y.U. Kwon, S.E. Park, in: S.E. Park (Ed.),
MIX), a collaboration within the Network of Excellence (NoE) IN- Nanotechnology in Mesostructured Materials, Studies in Surface Science
and Catalysis, vol. 146, Elsevier, Amsterdam, 2003, p. 101.
SIDE POReS. [12] P. Selvam, S.K. Bhatia, C.G. Sonwane, Ind. Eng. Chem. Res. 40 (2001) 3237.
As the number of mesoporous materials to be developed is still [13] Y.K. Hwang, J.-S. Chang, Y.-U. Kwon, S.-E. Park, Micropor. Mesopor. Mater. 68
growing, it is planned to come out with a second edition in the fu- (2004) 21.
[14] B.L. Newalkar, S. Komarneni, H. Katsuki, Chem. Commun. (2000) 2389.
ture containing new and more veried syntheses of mesoporous
[15] E.B. Celer, M. Jaroniec, J. Am. Chem. Soc. 128 (44) (2006) 14408.
materials. The eld is open for further additions as new materials [16] B.L. Newalkar, S. Komarneni, Chem. Commun. (2002) 1774.
will be added. Readers are invited to report their experience, suc- [17] K. Szczodrowki, B. Prlot, S. Antenois, J. Zajac, M. Lindheimer, D. Jones,
cess and ideas concerning the veried syntheses to the correspond- A. Julbe, A. Van Der Lee, Micropor. Mesopor. Mater. 110 (2008) 111.
[18] P. Alexandridis, T.A. Hatton, Colloid Surf. A 96 (1995) 1.
ing author. The authors will be pleased to include useful comments [19] A. Corma, Chem. Rev. 97 (1997) 2373.
from the readership in the second edition of this publication. [20] D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky, J. Am. Chem. Soc. 120
(1998) 6024.
[21] Y. Bennadja, P. Beaunier, D. Margolese, A. Davidson, Micropor. Mesopor.
Acknowledgments Mater. 4445 (2001) 147.
[22] S. Ruthstein, V. Frydman, S. Kababya, M. Landau, D. Goldfarb, J. Phys. Chem.
This work was funded by the EU and executed in the frame of B 107 (2003) 1739.
[23] J.M. Kim, Y.-J. Han, B.F. Chmelka, G.D. Stucky, Chem. Commun. (2000)
the European FP6 Network of Excellence INSIDE-POReS, coordi- 2437.
nated by Dr. N. Kanellopoulos. All contributors express their great [24] D. Zhao, J. Sun, Q. Li, G.D. Stucky, Chem. Mater. 12 (2000) 275.
appreciation for the support and encouragements of Dr. S. Bwadt [25] D. Huang, G.S. Lou, Y.J. Wang, Micropor. Mesopor. Mater. 84 (2005) 27.
[26] Q. Huo, D.I. Margolese, U. Ciesla, D.K. Demuth, P. Feng, T.E. Gier, P. Sieger,
(European Commission). A. Firouzi, B. Chmelka, F. Schth, G.D. Stucky, Chem. Mater. 6 (1994) 1176.
V. Meynen is grateful to the FWO-Flanders for nancial support. [27] G.J. De A.A. Soler-Illia, C. Sanchez, New J. Chem. 24 (2000) 493.
The authors would like to thank Prof. G. Van Tendeloo (EMAT, [28] G.J. De A.A. Soler-Illia, E. Scolan, A. Louis, P.A. Albouy, C. Sanchez, New J.
Chem. 25 (2001) 154.
University of Antwerpen), S. Brouwer (TUDelft), V. Butselaar-
[29] P. Yang, D. Zhao, D.I. Margolese, B.F. Schmelka, G.D. Stucky, Nature 396 (1998)
Orthelieb (TUDelft) and U. Lafont (TUDelft) for their aid in some 512.
of the SEM/TEM analyses, and M. Mertens from VITO (Flemish [30] G.J. De A.A. Soler-Illia, A. Louis, C. Sanchez, Chem. Mater. 14 (2002) 750.
Institute for Technological Research) for measuring part of the [31] P. Yang, D. Zhao, D.I. Margolese, B.F. Chmelka, G.D. Stucky, Chem. Mater. 11
(1999) 2813.
XRD patterns. Prof. Dr. M. Hunger from the Institute of Chemical [32] D.M. Antonelli, J.Y. Ying, Angew. Chem., Int. Ed. Engl. 34 (1995) 2014.
Technology, University of Stuttgart, is gratefully acknowledged [33] R.L. Putnam, N. Nakagawa, K.M. McGrath, N. Yao, I.A. Aksay, S.M. Gruner,
for the 27Al MAS NMR measurements. Linn Sommer from the A. Navrotsky, Chem. Mater. 9 (1997) 2690.
[34] D.M. Antonelli, A. Nakahira, J.Y. Ying, Inorg. Chem. 35 (1996) 3126.
Department of Chemistry, University of Oslo (Norway) is recog- [35] S.A. Bagshaw, T.J. Pinnavaia, Angew. Chem., Int. Ed. Engl. 35 (1996)
nized for recording some of the nitrogen adsorptiondesorption 1102.
isotherms. [36] D. Khushalani, G.A. Ozin, A. Kuperman, J. Mater. Chem. 9 (1999) 1491.
[37] L. Chen, B. Yao, Y. Cao, K. Fan, J. Phys. Chem. C 111 (2007) 11849.
The contributors, K.S. Triantafyllidis and C. Nitsos would like to [38] K. Liu, M. Zahng, K. Shi, H. Fu, Mater. Lett. 59 (2005) 3308.
acknowledge the aid of the Department of Chemistry of the Aris- [39] S.H. Elder, Y. Gao, X. Li, J. Liu, D.E. McCready, C.F. Windisch, Chem. Mater. 10
totle University of Thessaloniki for providing means and infrastruc- (1998) 3140.
[40] G. Bertoni, E. Beyers, J. Verbeeck, M. Mertens, P. Cool, E.F. Vansant, G. Van
ture for performing the synthesis of the mesoporous materials in Tendeloo, Ultramicroscopy 106 (7) (2006) 630.
cooperation with CERTH/CPERI. They would also like to thank the [41] I. Kartini, P. Meredith, J.C. Diniz Da Costa, G.Q. Lu, J. SolGel Sci. Technol. 31
Laboratory for Analysis and Characterization of Solids at CPERI/ (2004) 185189.
[42] I. Kartini, D. Menzies, D. Blake, J.C.D. Da Costa, P. Meredith, J.D. Tiches, G.Q. Lu,
CERTH and SINTEF (M. Stcker) for performing part of the charac-
J. Mater. Chem. 14 (2004) 29172921.
terization of the materials. [43] Q. Sheng, S. Yuan, J. Zhang, F. Chen, Micropor. Mesopor. Mater. 87 (2006) 177.
Chapter 4, The overview of the main synthetic approaches to [44] G.M.S. Elshafei, C.A. Philip, N.A. Moussa, Micropor. Mesopor. Mater. 79 (2005)
mesoporous materials was composed by V. Meynen, E. Beyers, S. 253.
[45] Y. Yue, Z. Gao, Chem. Commun. (2000) 1755.
Ribbens, D.J. Jones, P. Cool and E.F. Vansant. [46] D.S. Kim, S.-Y. Kwak, Appl. Catal. A: Gen. 323 (2007) 110.
Chapter 5, Characterization Techniques was composed by P. [47] C. Tian, Z. Zhang, J. Huo, N. Luo, Mater. Lett. 62 (2008) 77.
Cool, C. Van Oers, F. Rodrguez-Reinoso, K.S. Triantafyllidis, M. [48] E.L. Crepaldi, G.J. De A.A. Soler-Illia, D. Grosso, C. Sanchez, New J. Chem. 27
(2003) 9.
Hunger, P.J. Kooyman, P. Behrens and E.F. Vansant. [49] D.-W. Lee, S.-J. Park, S.-K. Ihm, K.-H. Lee, Chem. Mater. 19 (2007) 937.
Chapter 6 has been established by all researchers mentioned in [50] J. Lee, M.C. Orilall, S.C. Warren, M. Kamperman, F.J. Disalvo, U. Wiesner, Nat.
the contributors list (Chapter 3). Mater. 7 (2008) 222.
[51] J. Yao, H. Wang, Ind. Eng. Chem. Res. 46 (2007) 6264.
The authors gratefully acknowledge the Elsevier Inc. for their [52] H. Yoshitake, T. Sugihara, T. Tatsumi, Chem. Mater. 14 (2002) 1023.
help in connection with the production of the paper. [53] Q. Li, P. Hrter, W.M. Xue, J.L. Zou, W.A. Herrmann, J. Chem. Soc., Dalton Trans.
19 (2001) 2719.
[54] E. Beyers, P. Cool, E.F. Vansant, J. Phys. Chem. B 109 (2005) 10081.
References [55] D. Grosso, G.J. de A.A. Soler-Illia, F. Babonneau, C. Sanchez, P.-A. Albouy,
A. Brunet-Bruneau, A.R. Balkenende, Adv. Mater. 13 (2001) 1085.
[1] G.D. Stucky, D. Zhao, P. Yang, W. Lukens, N. Melosh, B.F. Chmelka, in: L. [56] K. Cassiers, T. Linssen, V. Meynen, P. Van Der Voort, P. Cool, E.F. Vansant,
Bonneviot, F. Bland, C. Danumah, S. Giasson, S. Kaliaguine (Eds.), Chem. Commun. (2003) 1178.
220 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

[57] K. Cassiers, T. Linssen, K. Aerts, P. Cool, O.I. Lebedev, G. Van Tendeloo, R. Van [102] O. Collart, P. Van Der Voort, E.F. Vansant, D. Desplantier, A. Galarneau, F. Di
Grieken, E.F. Vansant, J. Mater. Chem. 13 (2003) 3033. Renzo, F. Fajula, J. Phys. Chem. B 105 (2001) 12771.
[58] K. Cassiers, T. Linssen, M. Mathieu, Y.Q. Bai, H.Y. Zhu, P. Cool, E.F. Vansant, [103] M. Benjelloun, P. Van Der Voort, P. Cool, O. Collart, E.F. Vansant, Phys. Chem.
J. Phys. Chem. B 108 (2004) 3713. Chem. Phys. 3 (2001) 127.
[59] N. Kitazawa, H. Sato, Y. Watanabe, J. Mater. Sci. 42 (2007) 5074. [104] Q.S. Huo, D.I. Margolese, G.D. Stucky, Chem. Mater. 8 (5) (1996) 1147.
[60] E. Beyers, P. Cool, E.F. Vansant, Micropor. Mesopor. Mater. 99 (12) (2007) 12. [105] J.Y. Zhang, Z. Luz, D. Goldfarb, J. Phys. Chem. B 101 (36) (1997) 7087.
[61] M. Lindn, J. Blanchard, S. Schacht, S. Schunk, F. Schth, Chem. Mater. 11 [106] F.M. Bobonich, S.A. Kovalenko, Y.G. Voloshina, A.S. Korchev, V.N. Solomakha,
(1999) 3002. A.P. Philippov, V.G. Iln, Adsorp. Sci. Technol. 20 (6) (2002) 595.
[62] S. Yuan, Q. Sheng, J. Zhang, F. Chen, M. Anpo, Q. Zhang, Micropor. Mesopor. [107] Q. Huo, D.I. Margolese, U. Ciesla, D.G. Demth, P. Feng, T.E. Gier, P. Sieger,
Mater. 79 (2005) 93. A. Firouzi, B.F. Chmelka, F. Schth, G.D. Stucky, Chem. Mater. 6 (1994) 1176.
[63] L. Korsi, S. Papp, V. Meynen, P. Cool, E.F. Vansant, I. Dkny, Colloid Surf. [108] J.N. Israelochvili, D.J. Mitchell, B.W. Ninham, J. Chem. Soc., Faraday Trans. 2
A 268 (2005) 147. (72) (1976) 1525.
[64] U. Ciesla, S. Schacht, G.D. Stucky, K.K. Unger, F. Schth, Angew. Chem., Int. Ed. [109] J.N. Israelochvili, D.J. Mitchell, B.W. Ninham, Biochim. Biophys. Acta 470
Engl. 25 (1996) 541. (1977) 185.
[65] D.J. Jones, G. Aptel, M. Brandhorst, M. Jacquin, J. Jimnez-Jimnez, A. Jimnez- [110] S.M. Gruner, J. Phys. Chem. 93 (22) (1989) 7562.
Lpez, P. Maireles-Torres, I. Piwonski, E. Rodrguez-Castelln, J. Zajac, [111] G. ye, J. Sjblom, M. Stcker, Adv. Colloid Interface 89 (2001) 439.
J. Rozire, J. Mater. Chem. 10 (8) (2000) 1957. [112] J. Caro, in: E. Van Steen, L.H. Callanan, M. Claeys (Eds.), Recent Advances in
[66] J. Jimnez-Jimnez, P. Maireles-Torres, P. Olivera-Pastor, E. Rodrguez- the Science and Technology of Zeolites and Related Materials, Studies in
Castelln, A. Jimnez-Lpez, D.J. Jones, J. Rozire, Adv. Mater. 10 (10) (1998) Surface Science and Catalysis, Part AC, vol. 154, Elsevier, Amsterdam, 2004,
808. p. 80.
[67] L. Korsi, A. Oszko, G. Galbcs, A. Richardt, V. Zllmer, I. Dkny, Appl. Catal. [113] A. Taguchi, F. Schth, Micropor. Mesopor. Mater. 77 (2005) 145.
B Environ. 77 (2007) 175. [114] S. Battacharyya, G. Lelong, M.-L. Saboungi, J. Exp. Nanosci. 1 (3) (2006) 375.
[68] L. Korsi, S. Papp, I. Bertti, I. Dkny, Chem. Mater. 19 (2007) 4811. [115] C. Seebacher, C. Hellriegel, F.W. Deeg, C. Brauchle, S. Altmaier, P. Behrens,
[69] L. Korsi, I. Dkny, Colloid Surf. A 280 (2006) 146. K. Mullen, J. Phys. Chem. B 106 (22) (2002) 5591.
[70] D. Huang, Y.J. Wang, L.M. Yang, G.S. Luo, Micropor. Mesopor. Mater. 96 (2006) [116] M. Behrens, P.P. Saraber, H. Jansen, Z. Olujic, Chem. Biochem. Eng. Quart. 15
301. (2) (2001) 49.
[71] C.T. Kresge, M.E. Leonowics, W.J. Roth, J.C.Vartuli, US Patent 5 098 684, 1992. [117] J. Silvestre-Albero, J.C. Serrano-Ruiz, A. Seplveda-Escribano, F. Rodrguez-
[72] J.S. Beck, C.T. Chu, I.D. Johnson, C.T. Kresge, M.E. Leonowics, W.J. Roth, J.C. Reinoso, Appl. Catal. A: Gen. 135 (1) (2008) 16.
Vartuli, US Patent 5 108 725, 1992. [118] J. Silvestre-Albero, A. Seplveda-Escribano, F. Rodrguez-Reinoso, Micropor.
[73] J.S. Beck, D.C. Calabro, S.B. McCullen, B.P. Pelrine, K.D. Schmitt, J.C. Vartuli, US Mesopor. Mater. 113 (2008) 362.
Patent 5 145 816, 1992. [119] K. Cassiers, T. Linssen, M. Mathieu, M. Benjelloun, K. Schrijnemakers, P. Van
[74] J.S. Beck, C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, US Patent 5 264 Der Voort, P. Cool, E.F. Vansant, Chem. Mater. 14 (2002) 2317.
203, 1993. [120] J.M. Kim, S. Jun, R. Ryoo, J. Phys. Chem. B 103 (1999) 6200.
[75] J.S. Beck, K.D. Smith, J.C. Vartuli, US Patent, 5 334 368, 1994. [121] R. Ryoo, S. Jun, J. Phys. Chem. 101 (1997) 317.
[76] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.C. Beck, Nature 359 [122] J.M. Kim, J.H. Kwak, S. Jun, R. Ryoo, J. Phys. Chem. B 99 (1995) 16742.
(1992) 710. [123] K.J. Edler, J.W. White, J. Mater. Chem. 9 (1999) 2611.
[77] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, [124] D.T. On, S.M.J. Zaidi, S. Kaliaguine, Micropor. Mesopor. Mater. 22 (1998) 211.
C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L. [125] P. Van Der Voort, M. Mathieu, E.F. Vansant, in: A. Galarneau, F. Di Renzo,
Schlenker, J. Am. Chem. Soc. 14 (1992) 10834. F. Fajula, J. Vedrine (Eds.), Zeolites and Related Materials at the Dawn of
[78] V. Chiola, J.E. Ritsko, C.D. Vanderpool, US Patent 3 556 725, 1971. the 21st Century, Studies in Surface Science and Catalysis, vol. 135,
[79] F. Di Renzo, H. Cambon, R. Dutartre, Micropor. Mater. 2 (1993) 27. Elsevier, Amsterdam, 2001, p. 198.
[80] T . Yanagisawa, T. Shimizu, K. Kuroda, C. Kato, Bull. Chem. Soc. Jpn. 63 (1990) [126] K.A. Koyano, T. Tatsumi, Y. Tanaka, S. Nakata, J. Phys. Chem. B 101 (1997)
988. 9436.
[81] O. Collart, P. Cool, P. Van Der Voort, V. Meynen, E.F. Vansant, K. Houthoofd, [127] V. Meynen, P. Cool, E.F. Vansant, Micropor. Mesopor. Mater. 104 (2007) 26.
P.J. Grobet, O.I. Lebedev, G. Van Tendeloo, J. Phys. Chem. B 108 (2004) 13905. [128] M.J. Verhoef, P.J. Kooyman, J.C. Van der Wael, M.S. Rigutto, J.A. Peters, H. Van
[82] M.J. Meziani, J. Zajac, D.J. Jones, S. Partyka, J. Rozire, A. Auroux, Langmuir 16 Bekkum, Chem. Mater. 13 (2001) 683.
(5) (2000) 2262. [129] M.C. Xu, W. Wang, J. Weitkamp, M. Hunger, Z. Phys. Chem. 219 (7) (2005)
[83] M.J. Meziani, J. Zajac, J.-M. Douillard, D.J. Jones, S. Partyka, J. Rozire, J. Colloid 877890.
Interface Sci. 233 (2001) 219. [130] A. Karlsson, M. Stcker, K. Schfer, in: I. Kiricsi, G. Pl-Borbly, J.B. Nagy, H.G.
[84] M.J. Meziani, H. Benalla, J. Zajac, S. Partyka, D.J. Jones, J. Colloid Interface Sci. Karge (Eds.), Porous Materials in Environmentally Friendly Processes, Studies
262 (2003) 362. in Surface Science and Catalysis, vol. 125, Elsevier, Amsterdam, 1999, p. 61.
[85] R. Schmidt, D. Akporiaye, M. Stcker, O.H. Ellestad, J. Am. Chem. Soc. Chem. [131] A. Karlsson, M. Stcker, R. Schmidt, Micropor. Mesopor. Mater. 27 (1999) 181.
Commun. 12 (1994) 1493. [132] D. Trong-On, S. Kaliaguine, Angew. Chem., Int. Ed. 40 (17) (2001) 3248.
[86] R. Schmidt, H. Junggreen, M. Stcker, Chem. Commun. 7 (1996) 875. [133] J.C. Vartuli, K.D. Schmidt, C.T. Kreskge, W.T. Roth, M.E. Leonowicz, S.B.
[87] E. Antonakou, A. Lappas, M.H. Nilsen, A. Bouzga, M. Stcker, Fuel 85 (1415) McCullen, S.D. Hellring, J.S. Beck, J.L. Schlenker, D.H. Olson, E.W. Sheppard,
(2006) 2202. Chem. Mater. 6 (1994) 2317.
[88] M.H. Nilsen, E. Antonakou, A. Bouzga, A. Lappas, K. Mathisen, M. Stcker, [134] P. Behrens, A. Glaue, C. Haggenmller, G. Schechner, Solid State Ionic 101
Micropor. Mesopor. Mater. 105 (2007) 189. 103 (1997) 255.
[89] T. Boger, R. Roesky, R. Glser, S. Ernst, G. Eigenberger, J. Weitkamp, Micropor. [135] A. Monnier, F. Schth, Q. Huo, D. Kumar, D. Margolese, R.S. Maxwell, G.D.
Mater. 8 (1997) 79. Stucky, M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke, B.F. Chmelka,
[90] R. Schmidt, D. Akporiaye, M. Stcker, O.H. Ellestad, in: J. Weitkamp, H.G. Science 261 (1993) 1299.
Karge, H. Pfeifer, W. Holderich (Eds.), Zeolites and Related Microporous [136] A.H. Schoen, NASA Technical Note D-5541, Washington DC, 1970.
Materials: State of the Art 1994, Studies in Surface Science and Catalysis, Part [137] P.I. Ravickovitch, A.V. Neimar, Langmuir 16 (2000) 2419.
AC, vol. 84, Elsevier, Amsterdam, 1994, p. 61. [138] M.W. Anderson, Zeolites 19 (1997) 220.
[91] G. ye, E. Axelrod, Y. Feldman, J. Sjblom, M. Stcker, Colloid Polym. Sci. 278 [139] D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky, J. Am. Chem. Soc. 120
(6) (2000) 517. (1998) 6024.
[92] G. ye, J. Sjblom, M. Stcker, J. Disper. Sci. Technol. 21 (1) (2000) [140] D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Frederickson, B.F. Chmelka, G.D.
49. Stucky, Science 279 (1998) 548.
[93] T. Vrlstad, G. ye, M. Stcker, J. Sjblom, Micropor. Mesopor. Mater. 104 [141] H.-M. Kao, J.-D. Wu, C.-C. Cheng, A.S.T. Chiang, Micropor. Mesopor. Mater. 88
(2007) 10. (2006) 319.
[94] J. Rodrguez-Castelln, A. Jimnez-Lpez, P. Maireles-Torres, D.J. Jones, [142] M.J. Kim, R. Ryoo, Chem. Mater. 11 (1998) 487.
J. Rozire, M. Trombetta, G. Busca, M. Lenarda, L. Storaro, J. Solid State [143] J.M. Kim, G.D. Stucky, Chem. Commun. (2000) 1159.
Chem. 175 (2003) 159. [144] T.-W. Kim, R. Ryoo, K.P. Gierszal, M. Jaroniec, L.A. Solovyov, Y. Sakamoto, O.
[95] S. Liu, P. Cool, L. Lu, E. Beyers, P. Van Der Voort, E.F. Vansant, M. Jiang, Terasaki, J. Mater. Chem. 15 (2005) 8723.
Micropor. Mesopor. Mater. 79 (2005) 299. [145] P. Van Der Voort, M. Benjelloun, E.F. Vansant, J. Phys. Chem. B 106 (2002)
[96] U. Ciesla, F. Schth, Micropor. Mesopor. Mater. 27 (1999) 131. 9027.
[97] R. Schmidt, M. Stcker, E. Hansen, D. Akpoiaye, O.H. Ellestad, Micropor. Mater. [146] M. Kruk, M. Jaroniec, C.H. Ko, R. Ryoo, Chem. Mater. 12 (2000) 1961.
3 (1995) 443. [147] A. Nossov, E. Haddad, F. Guenneau, A. Galarneau, F. Di Renzo, F. Fajula,
[98] M. Hunger, U. Schenk, M. Breuninger, R. Glser, J. Weitkamp, Micropor. A. Gedeon, J. Phys. Chem. B 107 (2003) 12456.
Mesopor. Mater. 27 (1999) 261. [148] K. Miyazawa, S. Inagaki, Chem. Commun. (2000) 2121.
[99] R. Schmidt, M. Stcker, O.H. Ellestad, in: L. Bonneviot, S. Kaliaguine (Eds.), [149] A. Galarneau, H. Cambon, F. Di Renzo, R. Ryoo, M. Choi, F. Fajula, New.
Zeolites: A Rened Tool for Designing Catalytic Sites, Studies in Surface J. Chem. 27 (2003) 73.
Science and Catalysis, vol. 97, Elsevier, Amsterdam, 1995, p. 149. [150] A. Galarneau, H. Cambon, F. Di Renzo, F. Fajula, Langmuir 17 (2000)
[100] S. Liu, L. Lu, Z. Yang, P. Cool, E.F. Vansant, Mater. Chem. Phys. 97 (2006) 203. 8328.
[101] P. Van Der Voort, M. Mathieu, F. Mees, E.F. Vansant, J. Phys. Chem. B 102 [151] A.M. Silvestre-Albero, E.O. Jardim, E. Bruijn,V. Meynen, P. Cool, A. Seplveda-
(1998) 8847. Escribano, J. Silvestre-Albero, F. Rodrguez-Reinoso, Langmuir 25 (2009) 939.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 221

[152] Y. Ueno, A. Tate, O. Niwa, H.-S. Zhou, T. Yamada, I. Honma, Chem. Commun. [206] D. Margolese, J.A. Melero, S.C. Christiansen, B.F. Chmelka, G.D. Stucky, Chem.
(2004) 746. Mater. 12 (2000) 2448.
[153] R. Ryoo, C.H. Ko, M. Kruk, V. Antochshuk, M.J. Jaroniec, J. Phys. Chem. B 104 [207] B.-G. Park, W. Guo, X. Cui, J. Park, C.-S. Ha, Micropor. Mesopor. Mater. 66
(2000) 11465. (2003) 229.
[154] A.H. Janssen, P. Van Der Voort, A.J. Koster, K.P. De Jong, Chem. Commun. [208] M.A. Markowitz, J. Klaehn, R.A. Hendel, S.B. Qadriq, S.L. Golledge, D.G. Castner,
(2002) 1632. B.P. Gaber, J. Phys. Chem. B 104 (2000) 10820.
[155] P. Schmidt-Winkel, P. Yang, D.I. Largolese, B.F. Chmelka, G.D. Stucky, Adv. [209] R. Marchall, I. Bannat, J. Caro, M. Wark, Micropor. Mesopor. Mater. 99 (2007)
Mater. 11 (4) (1999) 303. 190.
[156] C. Yu, J. Fan, B. Tain, D. Zhao, G.D. Stucky, Adv. Mater. 14 (2002) 1742. [210] A. Taguchi, F. Schth, Micropor. Mesopor. Mater. 77 (2005) 1.
[157] K. De Witte, V. Meynen, M. Mertens, O.I. Lebedev, G. Van Tendeloo, [211] M.V. Landau, L. Vradman, A. Wolfson, P.M. Rao, M. Herskowitz, C.R. Chim. 8
A. Seplveda-Escribano, F. Rodrguez-Reinoso, E.F. Vansant, P. Cool, Appl. (34) (2005) 679.
Catal. B: Environ. 84 (12) (2008) 125. [212] M.S. Kumar, J. Prez-Ramirez, M.N. Debbagh, B. Smarsly, U. Bentrup, A. Brker,
[158] J. Fan, J. Lei, L. Wang, C. Yu, B. Tu, D. Zhao, Chem. Commun. 17 (2003) 2140. Appl. Catal. B: Environ. 62 (2006) 244.
[159] Y. Zheng, Y.-Y. Won, F.S. Bates, G.T. Davis, L.E. Scriven, Y. Talmon, J. Phys. [213] F. Balas, M. Manzano, P. Horcajada, M. Vallet-Regi, J. Am. Chem. Soc. 128
Chem. B 103 (1999) 10331. (2006) 8116.
[160] P. Kipkemboi, A. Fodgen, V. Alfredsson, K. Flodstrm, Langmuir 17 (2001) [214] F. Qu, G. Zhu, S. Huang, S. Li, J. Sun, D. Zhang, S. Qiu, Micropor. Mesopor.
5398. Mater. 92 (2006) 1.
[161] M. Impror-Clerc, P. Davidson, A. Davidson, J. Am. Chem. Soc. 122 (2000) [215] A.M. Liu, K. Hidajat, S. Kawi, D.Y. Zhao, Chem. Commun. (2000) 1145.
11925. [216] Q. Jiang, Z.Y. Wu, Y.M. Wang, Y. Cao, C.F. Zhou, J.H. Zhu, J. Mater. Chem. 16
[162] J.M. Kim, Y. Sakamoto, Y.K. Hwang, Y.-U. Kwon, O. Terasaki, S.-E. Park, (2006) 1536.
G.D. Stucky, J. Phys. Chem. B 106 (2002) 2552. [217] Z.C. Liu, H.R. Chen, W.M. Huang, J.L. Gu, W.B. Bu, Z.L. Hu, J.L. Shi, Micropor.
[163] P. Yang, D. Zhao, D. Margolese, B. Chmelka, G.D. Stucky, Nature 396 (1998) Mesopor. Mater. 89 (2006) 270.
152. [218] J. Xi, X. Qiu, X. Ma, M. Cui, J. Yang, X. Tang, W. Zhu, L. Chen, Solid State Ionics
[164] P.F. Fulvio, S. Pikus, M. Jaroniec, J. Mater. Chem. 15 (2005) 5049. 176 (1314) (2005) 1249.
[165] P. Feng, X. Bu, D. Pine, Langmuir 16 (2000) 5304. [219] M. Miyahara, A. Vinu, K.Z. Hossain, T. Nakanishi, K. Ariga, Thin Solid Films 499
[166] X. Cui, W.-C. Zhin, W.-J. Cho, C.-S. Ha, Mater. Lett. 59 (18) (2005) 2257. (2006) 13.
[167] D. Zhao, J. Sun, Q. Li, G.D. Stucky, Chem. Mater. 12 (2000) 275. [220] Z. Li, J. Zhang, Y. Li, Y. Guan, Z. Feng, C. Li, J. Mater. Chem. 16 (2006) 1350.
[168] A.G. Denkova, E. Mendes, M.O. Coppens, J. Phys. Chem. B 112 (3) (2008) 793. [221] H.J. Shin, R. Ryoo, M. Kruk, M. Jaroniec, Chem. Commun. (2001) 349.
[169] H. Zhang, J. Sun, D. Ma, X. Bao, A. Klein-Hoffmann, G. Weinberg, D. Su, [222] T.-W. Kim, R. Ryoo, K.P. Gierszal, M. Jaroniec, L.A. Solovyov, Y. Sakamoto, O.
R. Schlgl, J. Am. Chem. Soc. 126 (2004) 7440. Terasaki, J. Mater. Chem. 15 (2005) 1560.
[170] W.-H. Zhang, L. Zhang, J. Xiu, Z. Shen, Y. Li, P. Ying, C. Li, Micropor. Mesopor. [223] P. Dibandjo, F. Chassagneux, L. Bois, C. Sigala, P. Miele, J. Mater. Chem. 15
Mater. 89 (2006) 179. (2005) 1917.
[171] R. Pitchumani, W.J. Li, M.O. Coppens, in: A. Sayari, M. Jaroniec (Eds.), [224] M. Kruk, M. Jaroniec, S.H. Joo, R. Ryoo, J. Phys. Chem. B 107 (2003) 2205.
Nanoporous Materials IV, Studies in Surface Science and Catalysis, vol. 156, [225] Z. Liu, O. Terasaki, T. Ohsuna, K. Hiraga, H.J. Shin, R. Ryoo, Chem. Phys. Chem.
Elsevier, Amsterdam, 2005, p. 83. 4 (2001) 229.
[172] L. Wang, T. Qi, Y. Zhang, J. Chu, Micropor. Mesopor. Mater. 91 (2006) 156. [226] X. Ding, G. Briggs, W. Zhou, Q. Chen, L.-M. Peng, Nanotechnology 17 (2006)
[173] C. Yu, J. Fan, B. Tian, D. Zhao, G.D. Stucky, Chem. Mater. 14 (2002) 1742. 376.
[174] W. Stevens, K. Lebeau, M. Mertens, G. Van Tendeloo, P. Cool, E. Vansant, [227] L. Gai, Z. Chen, H. Jiang, Y. Tian, Q. Wang, D. Cui, J. Cryst. Growth 291 (2006)
J. Phys. Chem. B 110 (2006) 9183. 527.
[175] Z. Jin, X. Wang, X. Cui, Colloid Surf. A 316 (2008) 27. [228] F. Gao, Q. Lu, X. Liu, Y. Yan, D. Zhao, Nano Lett. 1 (12) (2001) 743.
[176] J.M. Kim, G.D. Stucky, Chem. Commun. (2000) 1159. [229] Y.J. Han, J.M. Kim, G.D. Stucky, Chem. Mater. 12 (2000) 2068.
[177] S.S. Kim, T.R. Pauly, T.J. Pinnavaia, Chem. Commun. (2000) 1661. [230] S.H. Joo, S.J. Choi, I. Oh, J. Kwak, Z. Liu, O. Terasaki, R. Ryoo, Nature 412 (2001)
[178] S.H. Joo, R. Ryoo, M. Kruk, M. Jaroniec, J. Phys. Chem. B. 106 (2002) 4640. 169.
[179] P.F. Fulvio, S. Pikus, M. Jaroniec, J. Colloid Interface Sci. 287 (2) (2005) 717. [231] J. Gu, J. Shi, L. Xiong, H. Chen, L. Li, M. Ruan, Solid State Sci. 6 (2004) 747.
[180] M. Choi, W. Heo, F. Kleitz, R. Ryoo, Chem. Commun. (2003) 1340. [232] M.H. Huang, A. Choudrey, P. Yang, Chem. Commun. (2000) 1063.
[181] P.C.A. Alberius, K.L. Frindell, R.C. Hayward, E.J. Kramer, G.D. Stucky, [233] G. Wanka, H. Hoffman, W. Ulbricht, Macromolecules 27 (1994) 4145.
B.F. Chmelka, Chem. Mater. 14 (2002) 3284. [234] R.M. Grudzien, B.E. Grabicka, M. Jaroniec, Appl. Surf. Sci. 253 (2007) 5660.
[182] W.A. Adams, M.G. Bakker, T.I. Quickenden, J. Photochem. Photobio. A 181 [235] L. Wang, J. Fan, B. Tian, H. Yang, C. Yu, B. Tu, D. Zaho, Micropor. Mesopor.
(2006) 166. Mater. 67 (2003) 135.
[183] L.C. Huang, E.K. Richman, L. Kirsch, S.H. Tolbert, Micropor. Mesopor. Mater. 96 [236] G. Chandrasekar, K.-S. You, J.-W. Ahn, W.-S. Ahn, Micropor. Mesopor. Mater.
(2006) 341. 111 (2008) 455.
[184] T. Yamada, H.S. Zhou, H. Uchida, I. Homma, T. Katsube, J. Phys. Chem. B 108 [237] C.-F. Cheng, Y.-C. Lin, H.-H. Cheng, Y.-C. Chen, Phys. Chem. Lett. 382 (2003)
(35) (2004) 13341. 496.
[185] B. Ammundsen, G.R. Burns, D.J. Jones, J. Roziere, J. SolGel Sci. Technol. 8 (13) [238] T.W. Kim, R. Ryoo, M. Kruk, K.P. Gierzal, M. Jaroniec, S. Kamiya, O. Terasaki, J.
(1997) 331. Phys. Chem. B 108 (31) (2004) 11480.
[186] S.Z. Zhang, J.J. Liu, K.C. Gong, Mater. Lett. 61 (2007) 4137. [239] P.E. Fulvio, B.E. Grabicka, R.M. Grudzien, M. Jaroniec, Adsorp. Sci. Technol. 25
[187] T. Amatani, K. Nakanishi, K. Hirao, T. Kodaira, Chem. Mater. 17 (2005) 2114. (6) (2007) 439.
[188] S.A. El-Safty, J. Porous Mater. 15 (2008) 369. [240] C.-L. Lin, Y.-S. Pang, M.-C. Chao, B.-C. Chen, H.-P. Lin, C.-Y. Tang, C.-Y. Lin,
[189] S.A. El-Safty, T. Hanaoka, Chem. Mater. 15 (15) (2003) 2892. J. Phys. Chem. Solids 69 (2008) 415.
[190] Y. Segura, P. Cool, P. Kustrowski, L. Chmielarz, R. Dziembaj, E.F. Vansant, [241] H. Jin, Q. Wu, C. Chen, D. Zhang, W. Pang, Micropor. Mesopor. Mater. 97
J. Phys. Chem. B 109 (2005) 12071. (2006) 141.
[191] V. Meynen, Y. Segura, M. Mertens, P. Cool, E.F. Vansant, Micropor. Mesopor. [242] M. Mesa, L. Sierra, J. Patarin, J.-L. Guth, Solid State Sci. 7 (2005) 990.
Mater. 85 (12) (2005) 119. [243] Y.K. Hwang, J.-S. Chang, Y.-U. Kwon, S.-E. Park, Micropor. Mesopor. Mater. 68
[192] Y.-M. Liu, Y. Cao, N. Yi, W.-L. Feng, W.-L. Dai, S.-R. Yan, H.Y. He, K.-N. Fan, (2004) 21.
J. Catal. 224 (2004) 417. [244] O.C. Gobin, Y. Wan, D.Y. Zhao, F. Kleitz, S. Kaliaguine, J. Phys. Chem. C 111 (7)
[193] K. Zhu, Z. Ma, Y. Zou, W. Zhou, T. Chen, H. He, Chem. Commun. (2001) 2552. (2007) 3053.
[194] M.S. Morey, S. OBrien, S. Schwarz, G.D. Stucky, Chem. Mater. 12 (2000) 898. [245] Y.K. Hwang, J.S. Chang, Y.U. Kwon, S.E. Park, in: S.E. Park, R. Ryoo, W.-S. Ahn,
[195] F. Chiker, J.Ph. Nogier, F. Launay, J.L. Bonardet, J. Appl. Catal. A Gen 240 (2) C.W. Lee, J.-S. Chang (Eds.), Nanotechnology in Mesostructured Materials,
(2003) 309. Studies is Surface Science and Catalysis, vol. 146, Elsevier, Amsterdam, 2003,
[196] A. Tuel, L.G. Hubert-Pfalzgraf, J. Catal. 217 (2003) 343. p. 101.
[197] G. Galleja, R. Van Grieken, R. Garcia, J.A. Melero, J. Iglesias, J. Mol. Catal. [246] W.J.J. Stevens, M. Mertens, S. Mullens, I. Thijs, G. Van Tendeloo, P. Cool
A Chem 182183 (2002) 215. , E.F. Vansant, Micropor. Mesopor. Mater. 93 (2006) 119.
[198] S. Sumiya, Y. Oumi, T. Uozumi, T. Sano, J. Mater. Chem. 11 (2001) 1111. [247] W.J.J. Stevens, K. Lebeau, M. Mertens, G. Van Tendeloo, P. Cool, E.F. Vansant,
[199] Y. Yue, A. Gdon, J.-L. Bonardet, N. Melosh, J.-B. DEspinose, J. Fraissard, J. Phys. Chem. B 110 (2006) 9183.
Chem. Commun. (1999) 1967. [248] P.I. Ravikovitch, A.V. Neimark, Langmuir 18 (2002) 911.
[200] Z. Luan, M. Hartmann, D. Zhao, W. Zhou, L. Kevan, Chem. Mater. 11 (1999) [249] P. Van Der Voort, M. Benjelloun, E.F. Vansant, J. Phys. Chem. B 106 (2002)
1621. 9027.
[201] H. Zhu, D.J. Jones, N. Donzel, J. Zajac, M. Lindheimer, Micropor. Mesopor. [250] K. Morishige, N. Tateishi, J. Chem. Phys. 119 (4) (2003) 2301.
Mater. 99 (2007) 47. [251] Y. Sakamoto, M. Kaneda, O. Terasaki, D.Y. Zhao, J.M. Kim, G.D. Stucky,
[202] X. Xu, H. Xu, F. Kapteijn, J.A. Moulijn, Appl. Catal. B: Environ. 53 (2004) 265. H.Y. Shin, R. Ryoo, Nature 408 (2000) 449.
[203] J. Adam, E. Anatonakou, A. Lappas, M. Stcker, M.H. Nilsen, A. Bouzga, [252] C.F. Cheng, Y.C. Lin, H.H. Cheng, S.M. Liu, H.S. Sheu, Chem. Lett. 33 (3) (2004)
J.E. Hustad, G. ye, Micropor. Mesopor. Mater. 96 (2006) 93. 262.
[204] C.-M. Yang, Y.Q. Wang, B. Zibrowius, F. Schth, Phys. Chem. Chem. Phys. 6 (9) [253] Z. Jin, X. Wang, X. Cui, J. Colloid Interface Sci. 307 (2007) 158.
(2004) 2461. [254] R.-H. Wang, J. Sun, Nanotechnology 18 (2007) 185705.
[205] Y. Wang, B. Zibrowius, C.-M. Yang, B. Spliethoff, F. Schth, Chem. Commun. [255] S. Kataoka, A. Endo, A. Harada, T. Ohmori, Mater. Lett. 62 (2008)
(2004) 46. 723.
222 V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

[256] S. Shen, Y. Deng, G. Zhu, D. Mao, Y. Wang, G. Wu, J. Li, X. Liu, G. Lu, D. Zhao, [304] J. Rozire, M. Brandhorst, R. Dutartre, M. Jacquin, D.J. Jones, P. Vitse, J. Zajac,
J. Mater. Sci. 42 (2007) 7057. J. Mater. Chem. 11 (2001) 3264.
[257] J.M.R. Gallo, C. Bisio, L. Marchese, H.O. Pastore, Micropor. Mesopor. Mater. [305] N. Leventis, S. Mulik, X. Wang, A. Dass, V.U. Patil, C. Sotiriou-Leventis, H. Lu,
111 (2008) 632. G. Churu, A. Capecelatro, J. Non-Cryst. Solids 354 (2008) 632.
[258] C. Knfel, J. Descarpentries, A. Benzaouia, V. Zeelnak, S. Mornet, P.L. Llewellyn, [306] S.A. Bagshaw, E. Prouzet, T.J. Pinnavaia, Science 269 (1995) 1242.
V. Hornebecq, Micropor. Mesopor. Mater. 99 (2007) 79. [307] E. Prouzet, F. Cot, G. Nabias, A. Larbot, P. Kooyman, T.J. Pinnavaia, Chem.
[259] R.M. Grudzien, B.E. Grabicka, M. Jaroniec, Adsorption 12 (2006) 293. Mater. 11 (1999) 1498.
[260] P. Van Der Voort, P.I. Ravikovitch, K.P. De Jong, M. Benjelloun, E. Van Bavel, [308] S.-S. Kim, T.R. Pauly, T.J. Pinnavaia, Chem. Commun. (2000) 1661.
A.H. Janssen, A.V. Neimark, B.M. Weckhuysen, E.F. Vansant, J. Phys. Chem. [309] W. Zhang, B. Glomski, T.R. Pauly, T.J. Pinnavaia, Chem. Commun. (1999) 1803.
B 106 (2002) 5873. [310] K.S. Triantafyllidis, T.J. Pinnavaia, A. Iosidis, P.J. Pomonis, J. Mater. Chem. 17
[261] P. Van Der Voort, P.I. Ravikovitch, K.P. De Jong, A.V. Neimark, A.H. Janssen, M. (2007) 3630.
Benjelloun, E. Van Bavel, P. Cool, B.M. Weckhuysen, E.F. Vansant, Chem. [311] K.S. Triantafyllidis, E.F. Iliopulou, E.V. Antonakou, A.A. Lappas, H. Wang,
Commun. (2002) 1010. T.J. Pinnavaia, Micropor. Mesopor. Mater. 99 (2007) 132.
[262] E. Van Bavel, P. Cool, K. Aerts, E.F. Vansant, J. Phys. Chem. B 108 (2004) 5263. [312] P.T. Tanev, T.J. Pinnavaia, Supramol. Sci. 5 (34) (1998) 399.
[263] E. Van Bavel, P. Cool, K. Aerts, E.F. Vansant, J. Porous Mater. 12 (2005) 65. [313] P.T. Tanev, Y. Liang, T.J. Pinnavaia, J. Am. Chem. Soc. 119 (37) (1997) 8616.
[264] C. Herdes, M.A. Santos, S. Abell, F. Medina, L.F. Vega, Appl. Surf. Sci. 252 (3) [314] S.S. Kim, W. Zhang, T.J. Pinnavaia, Science 282 (1998) 1302.
(2005) 538. [315] S.S. Kim, A. Karkambar, T.J. Pinnavaia, M. Kruk, M. Jaroniec, J. Phys. Chem.
[265] J. Lee, Y. Park, P. Kim, H. Kim, J. Yi, J. Mater. Chem. 14 (2004) 1050. B 105 (2001) 7663.
[266] E.B. Celer, M. Kruk, Y. Zuzek, M. Jaroniec, J. Mater. Chem. 16 (2006) 2824. [316] C. Boissire, A. Larbot, A. Van Der Lee, P. Kooyman, E. Prouzet, Chem. Mater.
[267] J. Sauer, S. Kaskel, M. Janicke, F. Schth, in: A. Galarneau, F. Di Renzo, 12 (2000) 2902.
F. Fajula, J. Vedrine (Eds.), Zeolites and Mesoporus Materials at the Dawn of [317] J.L. Bin, A. Leonard, B.L. Su, J. Phys. Chem. B 105 (2001) 6070.
the 21st Century, Studies in Surface Science and Catalysis, vol. 135, Elsevier, [318] J.L. Bin, A. Becue, B. Pauwels, G. Van Tendeloo, B.L. Su, Micropor. Mesopor.
Amsterdam, 2001, p. 315. Mater. 4445 (2001) 41.
[268] P.I. Ravikovitch, A.V. Neimark, Langmuir 18 (2002) 1550. [319] C. Boissire, M.A.U. Martines, M. Tokumoto, A. Larbot, E. Prouzet, Chem.
[269] J.C. Groen, L.A.A. Peffer, J. Perez-Ramirez, Micropor. Mesopor. Mater. 60 Mater. 15 (2003) 509.
(2003) 1. [320] C. Boissire, A. van der Lee, A.E. Mansouri, A. Larbot, E. Prouzet, Chem.
[270] F. Rouquerol, J. Rouquerol, K. Sing, Adsorption in Powders and Porous Solids: Commun. (1999) 2047.
Principles, Methodology and Applications, Academic Press, 1999. [321] E. Prouzet, F. Cot, C. Boussire, P.J. Kooyman, A. Larbot, J. Mater. Chem. 12
[271] V. Meynen, Y. Segura, M. Mertens, P. Cool, E.F. Vansant, Micropor. Mesopor. (2002) 1553.
Mater. 85 (12) (2005) 119. [322] S.A. Bagshaw, J. Mater. Chem. 11 (2001) 831.
[272] S.S. Reddy, V.S. Kumar, A.H. Padmasri, C.V.V. Styanarayana, B.D. Raju, K.S.R. [323] K. Biswas, J.C. Ray, J.-S. Choi, W.-S. Ahn, J. Non-Cryst. Solids 354 (2008) 1.
Rao, Catal. Commun. 8 (2007) 1080. [324] C. Boissire, A. Larbot, C. Bourgaux, E. Prouzet, C.A. Bunton, Chem. Mater. 13
[273] J. Lee, Y. Park, P. Kim, H. Kim, J. Yi, J. Mater. Chem. 14 (2004) 1050. (2001) 3580.
[274] V. Meynen, E. Beyers, P. Cool, E.F. Vansant, M. Mertens, H. Weyten, O.I. [325] Z. Jin, X. Wang, X. Cui, J. Non-Cryst. Solids 353 (2007) 2507.
Lebedev, G. Van Tendeloo, Chem. Commun. (2004) 898. [326] S.A. Bagshaw, I.J. Bruce, Micropor. Mesopor. Mater. 109 (2008) 199.
[275] V. Meynen, A. Busuioc, E. Beyers, P. Cool, E.F. Vansant, N. Bilba, M. Mertens, [327] S.A. Bagshaw, T. Kemmitt, N.B. Milestone, Micropor. Mesopor. Mater. 22
O.I. Lebedev, G. Van Tendeloo, in: R.W. Buckly (Ed.), Solid State Chemistry (1998) 419.
Research Trends, Nova Publishers, 2007. ISBN:1-60021-567-X (Chapter 3). [328] S.A. Bagshaw, T.J. Pinnavaia, Angew. Chem., Int. Ed. Engl. 35 (1996) 1102.
[276] K. De Witte, P. Cool, I. De Witte, L. Ruys, J. Rao, G. Van Tendeloo, E.F. Vansant, [329] L. Sierra, J.-L. Guth, Micropor. Mesopor. Mater. 27 (1999) 243.
J. Nanosci. Nanotechnol. 7 (7) (2007) 2511. [330] L. Sierra, B. Lopez, J. Gil, J.-L. Guth, Adv. Mater. 11 (1999) 307.
[277] V. Meynen, P. Cool, E.F. Vansant, P. Kortunov, F. Grinberg, J. Krger, [331] Y. Liu, W.Z. Zhang, T.J. Pinnavaia, Angew. Chem., Int. Ed. 40 (7) (2001) 1255.
M. Mertens, O.I. Lebedev, G. Van Tendeloo, Micropor. Mesopor. Mater. 99 [332] S.A. Bagshaw, F. Direnzo, F. Fajula, Chem. Commun. 18 (1996) 2209.
(2007) 14. [333] D.O. de Zarate, F. Bouyer, H. Zschiedrich, P.J. Kooyman, P. Trens, J. Iapichella,
[278] A.M. Busuioc, V. Meynen, E. Beyers, M. Mertens, P. Cool, N. Bilba, E.F. Vansant, R. Durand, C. Guillem, E. Prouzet, Chem. Mater. 20 (4) (2008) 1410.
Appl. Catal. A: Gen. 312 (2006) 153. [334] R. Ryoo, S. Jun, J.M. Kim, M.J. Kim, Chem. Commun. (1997) 2225.
[279] A. Busuioc, V. Meynen, E. Beyers, P. Cool, N. Bilba, E.F. Vansant, Catal. [335] H. Hamad, T. Hamieh, H. Mazoul, J. Toufaily, Adv. Powder Technol. 19 (2)
Commun. 8 (3) (2007) 527. (2008) 131.
[280] Z.Y. Wu, H.J. Wang, T.T. Zhyang, L.B. Sun, Y.M. Wang, J.H. Zhu, Adv. Funct. [336] Z. Sun, Y. Li, T. Shou, Y. Liu, G. Shi, L. Jin, Talanta 74 (2008) 1692.
Mater. 18 (2008) 82. [337] H. Zhong, G. Zhu, P. Wang, J. Liu, J. Yang, A. Yang, J. Chromatogr. A 1190
[281] A. Chen, W. Zhang, X. Li, D. Tan, X. Han, X. Bao, Catal. Lett. 119 (2007) 159. (2008) 232.
[282] P. Schmidt-Winkel, W.W. Lukens, D. Zhao, P. Yang, B.F. Chmelka, G.D. Stucky, [338] X. Ma, H. Sun, P. Yu, J. Mater. Sci. 43 (2008) 887.
J. Am. Chem. Soc. 121 (1999) 254. [339] S.A. El-Safty, J. Colloid Interface Sci. 319 (2008) 477.
[283] J.S. Lettow, Y.J. Han, P. Schmidt-Winkel, P.D. Yang, D.Y. Zhao, G.D. Stucky, [340] G.S. Attard, J.C. Glyde, C.G. Gltner, Nature (London) 378 (1995) 366.
J.Y. Ying, Langmuir 16 (22) (2000) 8291. [341] B.A. Ammundsen, G.R. Burns, D.J. Jones, J. Rozire, J. SolGel Sci. Technol. 8
[284] P. Schmidt-Winkel, W.W. Lukens, P. Yang, D.I. Margolese, J.S. Lettow, J.Y. Ying, (1997) 331.
G.D. Stucky, Chem. Mater. 12 (2000) 686. [342] C.G. Gltner, M. Antonietti, Adv. Mater. 9 (1997) 431.
[285] W. Zhu, Y. Han, L. An, Micropor. Mesopor. Mater. 72 (2004) 137. [343] B. Smarsly, S. Polarz, M. Antonietti, J. Phys. Chem. B 105 (2001) 10473.
[286] S.Y. Chen, S. Cheng, Chem. Mater. 19 (12) (2007) 3041. [344] J. Rozire, M. Brandhorst, R. Dutartre, M. Jacquin, D.J. Jones, P. Vitse, J. Zajac,
[287] J. Liu, C.M. Li, Q.H. Yang, J. Yang, C. Li, Langmuir 23 (13) (2007) 7255. J. Mater. Chem. 11 (2001) 3264.
[288] Y. Han, S.S. Lee, J.Y. Ying, Chem. Mater. 19 (9) (2007) 2292. [345] J.L. Blin, A. Leonard, B.L. Su, Chem. Mater. 13 (2001) 3542.
[289] R. Gao, W.-L. Dai, X. Yang, H. Li, K. Fan, Appl. Catal. A: Gen. 332 (2007) 138. [346] M. Jacquin, D.J. Jones, J. Rozire, S. Albertazzi, A. Vaccari, M. Lenarda,
[290] D. Trong-On, A. Ungureanu, S. Kaliaguine, Phys. Chem. Chem. Phys. 5 (2003) L. Storaro, R. Ganzerla, Appl. Catal. A Gen 251 (2003) 131.
3534. [347] M. Kargol, J. Zajac, D.J. Jones, T. Steriotis, J. Rozire, P. Vitse, Chem. Mater. 16
[291] Y.M. Liu, W.L. Feng, T.-C. Li, H.Y. He, W.-L. Dai, W. Huang, Y. Cao, K.-N. Fan, (2004) 3911.
J. Catal. 239 (2006) 125. [348] M. Kargol, J. Zajac, D.J. Jones, J. Rozire, T. Steriotis, A. Jimnez-Lpez, E.
[292] L. Chmierlarz, P. Kustrowksi, R. Dziembaj, P. Cool, E.F. Vansant, Appl. Catal. B: Rodrguez-Castelln, Chem. Mater. 17 (2005) 6117.
Environ. 62 (2006) 369. [349] M. Brandhorst, J. Zajac, D.J. Jones, J. Rozire, M. Womes, A. Jimnez-Lopez,
[293] H. Kim, J.C. Jung, P. Kim, S.H. Yeom, K.-Y. Lee, I.K. Song, J. Mol. Catal. A: Chem. E. Rodrguez-Castelln, Appl. Catal. B: Environ. 55 (2005) 267.
259 (2006) 150. [350] J. Zajac, R. Dutartre, D.J. Jones, J. Rozire, Thermochim. Acta 379 (2001) 123.
[294] Y.-M. Liu, W.-L. Feng, L.-C. Wang, Y. Cao, W.-L. Dai, H.-Y. He, K.-N. Fan, Catal. [351] M.J. Meziani, J. Zajac, J.M. Douillard, D.J. Jones, S. Partyka, J. Rozire, J. Colloid
Lett. 106 (34) (2006) 145. Interface Sci. 233 (2001) 219.
[295] Y. Su, Y.-M. Liu, L.-C. Wang, M. Chen, Y. Cao, W.-L. Dai, H.-Y. He, K.-N. Fan, [352] M. Jacquin, D.J. Jones, J. Rozire, A. Jimnez-Lopez, E. Rodrguez-Castelln,
Appl. Catal. A: Gen. 315 (2006) 91. J.M. Trejo-Menayo, M. Lenarda, L. Storaro, A. Vaccari, J. Catal. 228 (2004) 447.
[296] Z. Zhou, S. Zhu, D. Zhang, J. Mater. Chem. 17 (2007) 2428. [353] M. Jacquin, D.J. Jones, J. Rozire, Appl. Catal. A: Gen. 340 (2008) 250.
[297] H. Kim, J.C. Jung, S.H. Yeom, K.-Y. Lee, J. Yi, I.K. Song, Mater. Res. Bull. 42 [354] M. Jacquin, D.J. Jones, J. Rozire, A. Jimnez-Lpez, E. Rodrguez-Castelln,
(2007) 2132. J.M. Trejo-Menayo, M. Lenarda, L. Storaro, S.V. Albertazzi, Appl. Catal. A: Gen.
[298] S.S. Lee, S. Hadinoto, J.Y. Ying, Adv. Synth. Catal. 348 (2006) 1248. 340 (2008) 257.
[299] Y. Zhang, L. Zhao, S.S. Lee, J.Y. Ying, Adv. Synth. Catal. 348 (2006) [355] N.A. Melosh, P. Davidson, B.F. Chmelka, J. Am. Chem. Soc. 122 (2000) 823.
2027. [356] P. Feng, X. Bu, D.J. Pine, Langmuir 16 (2000) 5304.
[300] S.S. Lee, Y.Y. Ying, J. Mol. Catal. A: Chem. 256 (2006) 219. [357] P. Feng, X. Bu, G.D. Stucky, D.J. Pine, J. Am. Chem. Soc. 122 (2000) 994.
[301] K. Szymanska, J. Bryjak, J. Mrowiec-Bialon, A.B. Jarzebki, Micropor. Mesopor. [358] H.G. Zhu, D.J. Jones, N. Donzel, J. Zajac, M. Lindheimer, Micropor. Mesopor.
Mater. 99 (2007) 167. Mater. 99 (2007) 47.
[302] A.B. Jarzebski, K. Szymanska, J. Bryjak, J. Mrowiec-Bialon, Catal. Today 124 [359] B. Tian, H. Yang, X. Liu, S. Xie, C. Yu, J. Fan, B. Tu, D. Zaho, Chem. Commun.
(2007) 2. (2002) 1824.
[303] K. Nakanishi, Y. Kobayashi, T. Amatanni, K. Hirao, T. Kodaira, Chem. Mater. 16 [360] B. Tian, X. Liu, B. Tu, C. Yu, J. Fan, L. Wang, S. Xie, G.D. Stucky, D. Zaho, Nat.
(19) (2004) 3652. Mater. 2 (2003) 159.
V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223 223

[361] L. Chen, B. Yao, Y. Cao, K. Fan, J. Phys. Chem. C 111 (2007) 11849. [400] S.J. Gregg, K.S.W. Sing, Adsorption, Surface Area and Porosity, second ed.,
[362] S. Iijima, Nature 354 (1991) 5. Academic Press, London, 1982.
[363] A. Hagfeldt, M. Gratzel, Chem. Rev. 95 (1995) 49. [401] IUPAC Recommendations, Pure Appl. Chem. 57 (1985) 603.
[364] F. Croce, G.B. Appetecchi, L. Persi, B. Scrosati, Nature 394 (1998) 456. [402] J.P. Sibilia, A Guide to Materials Characterization and Chemical Analysis,
[365] M. Volel, M. Armand, W. Gorecki, M.L. Saboungi, Chem. Mater. 17 (8) (2005) VCH-Wiley, New York, 1996.
2028. [403] D.B. Williams, C.B. Carter, Transmission Electron Microscopy: A Textbook for
[366] O.K. Varghese, D. Gong, M. Paulose, K.G. Ong, C.A. Grimes, Sensor Actuat. B: Materials Science, Kluwer Academic/Plenum Publishers, New York, 1996.
Chem. 93 (2003) 338. [404] U. Ziese, K.P. de Jong, A.J. Koster, Appl. Catal. A: Gen. 260 (1) (2004) 71.
[367] X.B. Ke, Z.F. Zheng, H.W. Liu, H.Y. Zhu, X.P. Gao, L.X. Zhang, N.P. Xu, H. Wang, [405] G. Engelhard, D. Michel, High Resolution Solid State NMR of Silicates and
H.J. Zhao, J. Shi, K.R. Ratinac, J. Phys. Chem. B 112 (2008) 5000. Zeolites, John Wiley & Sons, 1987.
[368] X.B. Ke, H.Y. Zhu, X.P. Gao, J.W. Liu, Z.F. Zheng, Adv. Mater. 19 (2007) 785. [406] B.M. Weckhuysen, P. Van Der Voort, G. Catana, Spectroscopy of Transition
[369] T. Kasuga, Thin Solid Films 496 (2006) 141. Metal Ions on Surfaces, Leuven University Press, 2000.
[370] T. Lpez, E. Ortz-Islas, J. Manjarrez, F. Rodrguez-Reinoso, A. Seplveda, R.D. [407] D.A. Skoog, F.J. Holler, T.A. Nieman, Principles of Instrumental Analysis, fth
Gonzalez, Opt. Mater. 29 (2006) 70. ed., Harcourt, Brace and Company, Orlando, 1998.
[371] D.J. Corcoran, D.P. Tunstall, J.T. Irvine, Solid State Ionics 297 (2000) 135. [408] J. Ryczkowski, Catal. Today 124 (12) (2007) 1120.
[372] S.H. Chien, Y.C. Liou, M.C. Kuo, Synth. Met. 152 (2005) 333. [413] S. Liu, P. Cool, O. Collart, P. Van Der Voort, E. Vansant, O. Lebedev, G. Van
[373] T. Kasuga, M. Hiramatsu, A. Hoson, T. Sekino, K. Niihara, Langmuir 14 (1998) Tendeloo, M. Jian, J. Phys. Chem. B 107 (2003) 10405.
3160. [414] M. Mathieu, E. Van Bavel, P. Van Der Voort, E.F. Vansant, in: A. Galarneau, F.
[374] Y.Q. Wang, G.Q. Hu, X.F. Duan, H.L. Sun, Q.K. Xue, Chem. Phys. Lett. 365 Di Renzo, F. Fajula, J. Vedrine (Eds.), Zeolites and Mesoporous Materials at the
(2002) 427. Dawn of the 21st Century, Studies in Surface Science and Catalysis, vol. 135,
[375] D.S. Seo, J.K. Lee, H. Kim, J. Cryst. Growth 233 (2001) 298. Elsevier, Amsterdam, 2001, p. 135.
[376] X. Sun, Y. Li, Chem. Eur. J. 9 (2003) 2229. [418] Y.K. Bae, O.H. Han, Micropor. Mesopor. Mater. 106 (13) (2007) 304.
[377] D. Bavykin, A. Lapkin, P. Plucinski, J. Friedricht, F. Walsh, J. Catal. 235 (2005) [419] C. Yu, J. Fan, B. Tian, D. Zhao, G.D. Stucky, Adv. Mater. 14 (23) (2002) 1742.
10. [421] J. Fan, J. Lei, L. Wang, Y. Chengzhong, B. Tu, D. Zhao, Chem. Commun. 17
[378] B. Zhu, Y. Chen, J. Liu, W.D. Zhang, H.C. Zeng, Chem. Mater. 14 (2002) (2003) 2140.
1391. [426] F. Kleitz, L.A. Solovyov, G.M. Anilkumar, S.H. Choi, R. Ryoo, Chem. Commun.
[379] G.H. Du, Q. Chen, R.C. Che, Z.Y. Yuan, L.M. Peng, Appl. Phys. Lett. 79 (2001) (2004) 1536.
3702. [427] Industrial verication and scale up within the framework of an FP5 growth
[380] C.C. Tsai, H. Teng, Chem. Mater. 16 (2004) 4352. project, in: D.J. Jones (Ed.), Improvement of Diesel Quality by Catalytic
[381] R. Ma, Y. Bando, T. Sasaki, Chem. Phys. Lett. 380 (2003) 577. Processes, GR5D-2001-00537, Final Report, 2005.
[382] W. Wang, O.K. Varghese, M. Paulose, C.A. Grimes, J. Mater. Res. 19 (2004) 417. [428] M. Jacquin, D.J. Jones, J. Rozire, A. Jimnez-Lopez, E. Rodriguez-Castellon,
[383] J. Nian, H. Teng, J. Phys. Chem. B 110 (2006) 4193. J.M. Trejo-Menayo, M. Lenarda, L. Storaro, A. Vaccari, J. Catal. 228 (2004) 447.
[384] M. Zhang, Z. Jin, J. Zhang, X. Guo, J. Yang, W. Li, X. Wang, S. Zhang, J. Mol. Catal. [431] G. Bertoni, J. Verbeeck, M. Mertens, P. Cool, E.F. Vansant, G. Van Tendeloo,
A: Chem. 217 (2004) 203. Ultramicroscopy 106 (7) (2006) 630.
[385] H.Y. Zhu, Y. Lan, J. Am. Chem. Soc. 127 (2005) 6730. [432] T. Kasuga, M. Hiramatsu, A. Hoson, T. Sekino, K. Niihara, Adv. Mater. 11 (15)
[386] A. Thorne, A. Kruth, D. Tunstall, J.T.S. Irvine, W. Zhou, J. Phys. Chem. B 109 (1999) 1307.
(2005) 5439. [434] H. Robson, K.P. Lillerud (Eds.), Veried Syntheses of Zeolitic Materials, second
[387] S. Zhang, Q. Chen, L.M. Peng, Phys. Rev. B 71 (2005) 14104. revised ed., Published on Behalf of the Synthesis Commission of the
[388] X. Sung, Y. Li, Chem. Eur. J. 9 (2003) 2229. International Zeolite Association, Elsevier, Amsterdam, 2001.
[389] N. Wang, H. Lin, J. Li, L. Zhang, C. Lin, X. Li, J. Am. Chem. Soc. 89 (11) (2006)
3564.
[390] H. Zhu, X. Gao, Y. Lan, D. Song, Y. Xi, J. Zhao, J. Am. Chem. Soc. 126 (2004)
Further reading
8380.
[391] X. Wu, Q.-Z. Jiang, Z.-F. Ma, M. Fu, W.-F. Shangguan, Solid State Commun. 136 [409] L. Chen, H.W. Shen, A. Eisenberg, J. Phys. Chem. B 103 (1999) 1216.
(2005) 513. [410] J. Rathousky, M. Zukalova, A. Zukal, J. Had, Collect. Czech. Chem. C 63
[392] H.H. Ou, S.L. Lo, Y.H. Liou, Nanotechnology 18 (2007) 175702. (1998) 1893.
[393] M. Fu, Z.D. Jiang, Z.F. Ma, W.F. Shangguan, J. Inorg. Mater. 20 (4) (2005) [411] H. Wellmann, J. Rathousky, M. Wark, A. Zukal, G. Schulz-Ekloff, Micropor.
808. Mesopor. Mater. 4445 (2001) 419.
[394] Y.A. Wang, J.J. Yang, J.W. Zhang, H .J. Liu, Z.J. Zhang, Chem. Lett. 34 (8) (2005) [412] R. Marschall, I. Bannat, J. Caro, M. Wark, Micropor. Mesopor. Mater. 99
1168. (2007) 190196.
[395] H. Marsh, F. Rodrguez-Reinoso, Activated Carbon, Elsevier, London, 2006. [415] M. Grn, K. Unger, A. Matsumoto, K. Tsutsumi, Micropor. Mesopor. Mater.
[396] K.S.W. Sing, Adv. Colloid Interface Sci. 7677 (1998) 3. 27 (1999) 207.
[397] R.V.R.A. Rios, J. Silvestre-Albero, A. Seplveda-Escribano, M. Molina-Sabio, F. [416] K. Flodtrm, V. Alfredsson, Micropor. Mesopor. Mater. 59 (2003) 167176.
Rodrguez-Reinoso, J. Phys. Chem. C 111 (2007) 3803. [417] S.-E. Park, J.S. Chang, Y.K. Hwang, D.S. Kim, S.H. Jhung, J.S. Hwang, Catal.
[398] J. Silvestre-Albero, A. Seplveda-Escribano, F. Rodrguez-Reinoso, V. Surv. Asia 8 (2004) 91.
Kouvelos, G. Pilatos, N.K. Kanellopoulos, M. Krutyeva, F. Grinberg, J. Krger, [420] A. Sayari, B. Han, Y. Yang, J. Am. Chem. Soc. 126 (2004) 14348.
A.I. Spjelkavik, M. Stcker, A. Ferreira, S. Brouwer, F. Kapteijn, J. Weitkamp, [422] I. Krger, Dissertation, Universitt Hannover, 2006.
S.D. Sklari, V.T. Zaspalis, D.J. Jones, L.C. de Menorval, M. Lindheimer, P. [423] T. Sato, Md.K. Hossain, D.P. Acharya, O. Glatter, J. Phys. Chem. B. 108 (2004)
Caffarelli, E. Borsella, A.A.G. Tomlinson, M.J.G. Linders, J.L. Tempelman, E.A. 12927.
Bal in: N. Seaton, F.R. Reinoso, P. Llewellyn, S. Kaskel (Eds.), Characterisation [424] E. Prouzet, T.J. Pinnavaia, Angew. Chem., Int. Ed. Engl. 36 (1997) 516.
of porous solids VIII: Proceedings of the 8th International Symposium on the [425] K.J. Edler, S.J. Roser, Int. Rev. Phys. Chem. 20 (3) (2001) 387.
characterisation of Porous Solids, Royal Society of Chemistry, Edinburgh, [429] G.S. Attard, J.C. Glyde, C.G. Gltner, Nature 378 (1995) 366.
2009, p. 9, ISBN: 978-1-84755-904-3. [430] H. Miyata, T. Noma, M. Watanabe, K. Kuroda, Chem. Mater. 14 (2002) 766.
[399] J.M. Jurez-Galn, A. Silvestre-Albero, J. Silvestre-Albero, F. Rodrguez- [433] X.P. Gao, Y. Lan, H.Y. Zhu, J.W. Liu, Y.P. Ge, F. Wu, D.Y. Song, Electrochem.
Reinoso, Micropor. Mesopor. Mater. 117 (2009) 519. Solid State 8 (1) (2005) A26.