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Mechanism of self-assembly in the synthesis of silica

Cite this: Chem. Soc. Rev., 2013,
mesoporous materials: in situ studies by X-ray and
42, 4071
neutron scattering†
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H

J. L. Blin*ab and M. Impéror-Clerc*c

In this review, recent progress in the understanding of the formation of various silica mesoporous
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Received 30th August 2012
DOI: 10.1039/c2cs35362h
www.rsc.org/csr
materials is reported. Owing to time-resolved experiments using Small Angle X-ray or Neutron
Scattering (SAXS or SANS), it is possible to follow in situ the formation of a material during its synthesis
via the Cooperative Templating Mechanism (CTM). Such experiments directly provide unique
information about the structural properties of the material inside the synthesis solution. One of the
main findings is that phase transformations often occur in the material prior to the stabilisation of its
final structure. Moreover, during the very early stages of the synthesis, it is also possible to detect the
first hybrid silica–surfactant micellar aggregates, prior to the precipitation of the material, as reported in
the case of the SBA-15 materials. All these experiments allow a better understanding of the formation
mechanisms and of the influence of the many synthesis parameters. These results open the way to a
better prediction and control of the structure of mesoporous materials.

a
Université de Lorraine, SRSMC, UMR7565, F-54506 Vandoeuvre-lès-Nancy cedex,
Introduction
France. E-mail: jean-luc.blin@univ-lorraine.fr, marianne.imperor@u-psud.fr
b Recently, there has been a rapid growth in emerging areas such
CNRS, UMR7565, F-54506 Vandoeuvre-lès-Nancy cedex, France
c
CNRS, UMR8502, Université Paris-Sud, Bat 510, F-91405 Orsay cedex, France as nanotechnology, photonics and bioengineering, which require
† Part of the mesoporous materials themed issue. porous structures with well-defined structural, interfacial,

Jean-Luc Blin, 41 years old, Marianne Impéror-Clerc, 45 years

received his PhD in 1997 at the
University of Lille-1 (France).
Then he was an assistant
professor at the laboratory of
Inorganic Materials in Namur
University (Belgium). At this
time he started his studies on
porous materials. In 2002 he
joined the laboratory of Structure
and Reactivity of Complex
Molecular System of the
J. L. Blin Lorraine University (France)
where he became a professor in
2006. His research interests focus on the design of porous
inorganic and/or hybrid materials (SiO2, TiO2). In particular,
he investigates their formation mechanism in relation to the
surfactant based-systems used for their preparation. He is a
co-author of 77 publications.
M. Impéror-Clerc
X-ray/neutron scattering. She is a co-author of 60 scientific
publications in the field.
old, received her PhD in Physics
in 1992 at the University of
Paris-Sud (France). Since 1992,
she has been a research fellow at
the CNRS (Centre National de la
Recherche Scientifique) at the
Solid State Physics Laboratory
at the University of Paris-Sud.
In the Soft Matter Physics
group, her research interests
are centered on the structural
analysis of complex fluids and
mesoporous materials using

This journal is c The Royal Society of Chemistry 2013 Chem. Soc. Rev., 2013, 42, 4071--4082 4071

Review Article
compositional and morphological properties. Mesoporous
materials are excellent candidates for such applications. As a
matter of fact, they have tuneable pore sizes (2–30 nm), high
specific surface areas (>800 m2 g1) and high pore volumes
(>0.7 cm3 g1).1,2 These characteristics afford their use for
several potential applications in many fields such as adsor-
bents, catalysts, host matrices for electronic and photonic
devices, drug delivery and sensors.3–7
The synthesis of these compounds combined the sol–gel
chemistry and the use of assemblies of surfactant molecules as
framework templates. Depending on the starting block two
mechanisms can lead to the formation of these ordered meso-
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
structures. The first one is the cooperative templating mecha-
nism (CTM) and in this case the building blocks are the
micelles; so the CTM occurs at low surfactant concentrations.8
In such a mechanism, the interactions between the surfactant
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and the inorganic precursor are responsible for the mesoporous
materials formation. The synthesis can be achieved through either
an electrostatic pathway, based on a supramolecular assembly of
charged surfactants with charged inorganic precursors or a
neutral pathway, in which hydrogen bonding is responsible for
the cohesiveness between the surfactant and the inorganic
precursor.8 The self-assembly mechanism is widely employed to
prepare the ordered mesoporous materials and numerous hydro-
genated and fluorinated surfactant-based systems have been
investigated as structure directing agents and different kinds of
materials such as MCM (Mobil Crystalline Materials),1,2 SBA
(Santa Barbara),9 MSU (Michigan State University)10 etc. have
been obtained. The second way to prepare ordered mesostruc-
tures is the liquid crystal templating (LCT) pathway.11,12 In this
case the surfactants are present at much larger concentrations
and the structure of the recovered materials can be designed a
priori based on the corresponding surfactant phase diagram.
Nevertheless, whatever the synthesis pathways, the charac-
teristics of the recovered materials, such as the structure and
the pore diameter, are strongly related to the phase diagram of
the surfactant used for their preparation. For example, using
both hydrogenated and fluorinated systems, it has been evi-
denced that the cooperative templating mechanism (CTM) is
favored when the temperature at which the silica source is
added to the micellar solution is less enough than the phase
separation temperature (lower consolute point).13,14 The synthesis
conditions such as the hydrothermal treatment temperature and
duration, the quantity of silica source or the pH also play a key
role to get a well-defined architecture with control of both the
morphology and the pore diameter.15–18 For example MCM-41,
48 and 50 have been obtained under the same conditions just by
changing the silica source quantity.19 The pH is an important
factor which affects the material structure; the hexagonal ordering
of MCM-41 and SBA-15 materials can be improved by adjustment
of the pH during the hydrothermal treatment.20 The hydro-
thermal treatment conditions have also a great influence on the
structure, the porosity and also the stability of the materials.21–23
To develop the applications, the mesopore diameter can be
tailored by the addition of a swelling agent. In the literature,
1,3,5-trimethylbenzene (TMB), triisopropylbenzene, amines,
4072 Chem. Soc. Rev., 2013, 42, 4071--4082
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toluene, alkanes or fluorocarbons have been used as expanders
to prepare large pore mesoporous materials.24–28
When mesoporous materials are prepared from a micellar
solution (CTM route), it is now admitted that the interactions
between the surfactant and the silica are the driving force for
the formation of the materials. In the initial stage, the inter-
actions between small silica oligomers and surfactants drive
the formation of hybrid organic–inorganic micelles or aggre-
gates. Then, the condensation of the inorganic precursor at the
external surface of the micelles occurs. The ordered mesophase
is obtained after intermicellar condensation. Finally, the hydro-
thermal treatment at higher temperature achieves the rigidity
of the material owing to a complete polymerization of the silica
source. The ordered mesoporous material is recovered after
surfactant removal either by solvent extraction or by calcina-
tion. However, some disagreements concerning the first stage
of the CTM appeared and several studies have been carried out
to understand better how the surfactant micelles and the
inorganic precursor could affect the formation of the hybrid
mesophase. Thus, many studies are focused on the formation
of organized mesoporous materials through the CTM. Several
experimental techniques29–35 such as Raman spectroscopy,29
NMR,30,31 fluorescence probing techniques,32 EPR,33 transmis-
sion electron microscopy (TEM),30,34 and IR spectroscopy35
have been used to investigate the formation of the mesoporous
materials. For example in a paper dealing with the in situ
investigations of the synthesis of mesoporous silica prepared
from an ionic surfactant, using a fluorescence probe such as
pyrene or dipyrenylpropane, Lebeau et al.32 have proposed a
mechanism based on the existence of silica pre-polymers to
explain the formation of the silica materials. These pre-
polymers bind with free surfactant molecules in solution. The
size of the pre-polymers grows with time and more and more
surfactant molecules can be attached to them, leading to the
formation of organic–inorganic hybrid aggregates. The micelles
act as a reservoir of surfactant molecules which are consumed
in proportion with the formation of the inorganic framework.
Finally the precipitation of a surfactant ion–polymerized silica
complex occurs, leading to the ordered material. All of the
above cited techniques present advantages and disadvantages,29
for instance the spectroscopic and TEM experiments are
generally carried out ex situ and some modifications of the
system can occur during the sample preparation.
In this review, we focus on the use of small angle scattering
experiments using X-rays (SAXS) or neutrons (SANS). They allow
exploring structural properties on scales ranging from a few
nanometres up to a fraction of micron (the typical range of the
scattering vector modulus is between 103 Å1 and 1 Å1). For
example, only SAXS and SANS experiments can determine the
micelles structure at the nanoscale and changes in the micelles
shape when interacting with silica oligomers. As illustrated in
this review, SAXS and SANS offer the main advantage to carry
out in situ experiments. Compared to SAXS, SANS affords the
additional possibility to use the contrast variation method with
different H2O–D2O isotopic compositions as water. This method
allows obtaining a scattering curve, which feature varies as a
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Chem Soc Rev
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Fig. 1 Schematic drawing of an in situ SAXS/SANS setup used for time-resolved analysis. The synthesis mixture continuously flows inside a quartz flow-cell. The
asterisk (*) stands for the incoming X-rays/neutrons. Reprinted with permission from ref. 41. Copyright 2008, Elsevier, Adv. Colloid Interface Sci.
function of the isotopic composition, as illustrated later in this
review. One typical example is the work of Stébé et al.36 where
an ex situ SANS study was performed to establish the relation-
ship between the micelles structure and the type of silica
mesostructures (ordered 2D-hexagonal or wormlike) synthesized
from nonionic fluorinated systems.
To get a better insight into the formation mechanism of
mesoporous materials SAXS and SANS can be combined with
other techniques and in situ analyses by SAXS or SANS can be
performed to observe the transformations of the system in the
moment they are taking place. For example Alfredsson et al.30
combined SAXS and 1H NMR to follow the synthesis of meso-
porous silica in the presence of block copolymers as templates
at low pH. However as the reaction of formation of the hybrid
mesophase is fast, time-resolved measurements usually require
the use of a high-flux X-ray source such as synchrotron radia-
tion. As a matter of fact in material science where processing is
the main concern synchrotron radiation has become a standard
tool for the characterization of the material.37 The time resolu-
tion is usually in the range of seconds and many non-crystalline
systems such as polymers have been investigated using this
technique. Applied to the study of the formation mechanism of
ordered mesoporous materials, due to the fast kinetics of the
formation reaction of the organic–inorganic hybrid mesophase,
synchrotron radiation is well adapted for the investigation of
the hybrid mesophase38 and this technique has been used by
different groups to perform such studies.39 When the experi-
ments are carried out ex situ no particular setup is needed.
A crucial point to perform in situ studies is then the design of
well adapted sample reactors and the development of experi-
ment setups, allowing the SAXS/SANS experiments.40–42 First in
1998, Lindén et al.40 have constructed a tubular reactor to study
the initial stages of formation of MCM-41 materials. The
reactor is connected to a cell especially designed for XRD
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measurements of liquids. In this way the authors have studied
the continuous preparation of MCM-41 materials. Their results
have shown that the hexagonal phase is already developed after
a reaction time of three minutes. Then only the condensation
of silica goes on within the walls of the material. After,
Zholobenko et al.41,43 have developed a simple experimental
setup to investigate by SAXS and SANS analysis the initial steps
of the SBA-15. This setup is depicted in Fig. 1. More recently,
Jammaer et al.42 designed a more complex continuous synthesis
reactor suited to SAXS experiments.
One of the main challenges in the field is to predict from the
surfactant self-assembly properties the structure of the final
material after surfactant removal. In this article, we review the
main recent progress made to reach this aim using SAXS/SANS
in situ experiments. In the first section, we explain that one
major finding is that structural transformations upon time
often occur within the hybrid mesophase, before getting the
final stable state. The second section reviews experiments that
are devoted to the study of the initial stages of the CTM, and
that contribute to a better understanding of the interactions
between surfactant micelles and silica precursors.
1. In situ characterization of the material
1.1. 2D-hexagonal mesophase
The most common structure encountered in mesoporous
materials is the 2D-hexagonal one. The powder pattern of a
2D-hexagonal mesoporous material exhibits typically three
Bragg peaks with a very strong one at low angles (10 reflection
line) and two other weaker peaks at higher angles (11 and
20 reflection lines). A typical example is shown in Fig. 2. Higher
order peaks can be observed for very well ordered materials.44,45
From these reflection lines, the hexagonal unit cell parameter
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Fig. 2 Formation of a silica–CTAB mesophase in the presence of solubilized benzene under acidic conditions. (a) In situ SAXS results show a structural transition from a
2D-hexagonal to a lamellar mesophase upon time. (b) Lowering of the mean curvature of the surfactant–silica aggregates due to the progressive incorporation of the
benzene molecules. Reprinted with permission from ref. 60. Copyright 2002, American Chemical Society, Langmuir.
pffiffiffi
ða0 ¼ 2d10 = 3Þ can be determined, which corresponds to the
sum of the pore diameter and the thickness of the silica wall.
In the absence of such Bragg peaks, a broad peak can be
observed instead on the SAXS pattern, and it corresponds to a
disordered structure of the mesoporous molecular sieves hav-
ing wormhole like channel systems, without long-range order,
analogous to MSU-type materials.
A general behavior of 2D-hexagonal mesophases is that a
continuous decrease in the lattice spacing values, and thus in
pffiffiffi
the unit cell parameter ða0 ¼ 2d10 = 3Þ, is observed with time
during the mesophase formation. This is a general phenomenon,
due to an increase in the density of silica, which involves a
decrease in the wall thickness and consequently a shrinkage of
the unit cell parameter. This evolution can be observed for
example in Fig. 2 and further examples will be illustrated for
other systems in the following.
Moreover, variations in the intensity of the Bragg reflections
are observed during the formation of mesoporous materials.
They are linked to modifications with time of both the amount
of material in solution and the form factor of the unit cell.44,46
Then in situ SAXS and SANS experiments give direct access to
structural modifications inside the material. For example,
Morris et al.47 observed such variations in the Bragg peak
intensities during the synthesis of mesoporous silica obtained
from P123 as a surfactant and TMOS as a silica source. The
intensity of the 10 reflection increases between 0 and 105
minutes of the silica condensation. The authors explain this
phenomenon by a gradual inclusion of inorganic moieties into
an already ordered or partly ordered surfactant mesostructure.
Then, between 105 and 155 minutes, the intensity of the
10 reflection decreases due to the increase in rigidity of the gel.
4074 Chem. Soc. Rev., 2013, 42, 4071--4082
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Highly ordered mesoporous silica was obtained after surfactant
removal.
Lindén et al.48 have performed in situ synchrotron experi-
ments to study the formation of MCM-41 materials synthesized
from alkyltrimethylammoniumbromide surfactants of different
chains and their mixtures. They have shown that under the
used conditions, where the silicate hydrolysis and condensa-
tion reactions are fast (pH = 10.7), the hexagonal mesophase is
formed after 80 s and that its formation is kinetically controlled
by the rate of the silicate condensation. An increase in the
intensity of the 10, 11 and 20 reflections and in the intensity
ratio between the 11 and 20 reflections is noted with time. This
phenomenon is more pronounced when the number of carbon
atoms (nc) in the surfactant chains is increased. However,
this variation in nc does not affect strongly the kinetics of
formation of the hexagonal mesophase. The authors have
proposed a six steps mechanism: hydrolysis of the silica pre-
cursor, formation of silicate oligomers in solution, clustering of
poorly condensed silica–surfactant hybrid micelles into flocs,
elongation of the surfactant micelles accompanied by the
formation of hexagonal ordered domains, increased inter-
micellar condensation and finally the growth of the particle
by agglomeration.
1.2. Cubic phases and phase transformations
Compared with the 2D-hexagonal phases, much less examples
are devoted to cubic structures. This is probably due to the fact
that they are more difficult to obtain. In this section, we review
different examples for which cubic phases are induced using
additives such as alcohol. As detailed hereafter, a general trend
is that cubic phases often result from a phase transformation
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from another mesophase, that is a transformation from a
hexagonal to a cubic phase, or from a lamellar to a cubic phase.
Indeed, different phase transitions can be induced by the
presence of an alcohol. For example, by increasing the amount
of alcohol (methanol, ethanol or propanol) added to the syn-
thesis mixture of a CTAB surfactant based system, Cool et al.49
have observed the following mesophase sequence: hexagonal -
cubic - lamellar - radially arranged hexagonal close packing.
When the alcohol concentration is further increased, it acts as a
cosolvent and spherical particles are formed. A TEM analysis
shows a radial arrangement of the pores within the spherical
particles. A hexagonal close packing of the pores is observed on
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
a local scale around the center of the spherical particles. To
explain these phase transitions the authors consider a variation
in the surfactant packing parameter, a widespread concept in
surfactant systems which was introduced by J. Israelachvili.50
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They postulate that at the lower concentration, short alcohol
molecules could penetrate into the surfactant micelles. How-
ever, the used alcohols (methanol, ethanol and propanol) are
too short to act as co-surfactants. Kim et al.51 have succeeded in
preparing MCM-48 like ordered large mesoporous silica
belonging to the Ia3% d space group. This cubic mesostructure
is synthesized from the Pluronic P123 at low HCl concentration
in the presence of n-butanol, which acts as a co-surfactant. The
limits of the domain of the silica cubic mesostructure can be
shifted by both the amount of n-butanol and the silica source
i.e. TEOS or sodium silicate. SAXS results upon time show that
the cubic structure is due to a transformation from a lamellar
phase after 4–6 hours of reaction. Ruthstein et al.52 have
demonstrated that the same type of cubic phase can also result
from a transformation from a hexagonal structure. The concept
of the packing parameter is used to explain the phase transfor-
mation. In situ SAXS experiments carried out by Pevzner and
Regev53 also demonstrate that the bicontinuous phase is
obtained through several phase transformations: hexagonal to
lamellar then lamellar to hexagonal and finally hexagonal to
cubic. Once again a variation in the packing parameter, which
is modified by both the time and the temperature of the
reaction, is proposed to explain the different evolutions. The
final cubic phase is recovered after heating at 100 1C and it
results from the transformation of the hexagonal phase where the
10 planes evolve to the 211 planes of the cubic structure, both
planes having the same interplanar distance (epitaxial relation).
Using a continuous flow reactor, Ågren et al.54 have per-
formed in situ SAXS analysis to follow the formation at room
temperature of mesostructured silica obtained from the
TEOS–H2O–CTAB–NH3 mixture in the presence of different
alcohols, which act as a co-surfactant. Without alcohol the
hexagonal mesophase is formed within the first 5 minutes after
mixing the reactants and no intermediate phases are observed.
When hexanol or butanol molecules are added, the authors
observed that the kinetics of mesophase formation is not
modified but a much more complex phase behavior is noted.
Depending on the amount of alcohol, one, two or three phases
coexist. At low butanol or hexanol content, a swelling of the
hexagonal phase occurs. Then a transition from the hexagonal
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to a lamellar phase (coexistence of the two phases) occurs with
the increase in the alcohol amount. A similar trend has been
reported with short chain amines as co-surfactants.55 Depending
on the amine chain length and the concentration, the amine can
be adsorbed onto the silicate polymer or co-adsorbed onto the
silicate polymer and onto the CTAB through hydrogen bonding
to the silanol groups.
In conclusion, all these studies show that the addition of
alcohols which act as co-surfactants (like butanol) induces
other mesophases like cubic phases. It is often invoked that
the observed phase transformations can be understood in
terms of changes in the packing parameter. Indeed, the
presence of alcohol is expected to already modify the surfactant
phase behavior itself, and afterwards the structure of the
mesoporous material. However, in most of the reported articles,
the effect of alcohol addition on the surfactant phase behavior
(prior to the addition of a silica precursor) was not investigated.
This should help to determine the changes in the packing
parameter due to the presence of a co-surfactant.
1.3. Pore size enlargement
As mentioned above, additives can also be used to tailor the
mesopore size. Several groups attempt to expand the pore size
of mesoporous materials, but only few of them have tried to
suggest a detailed swelling mechanism. Moreover, few studies
deal with pore size enlargement of mesostructure using a non-
ionic surfactant and most of them are related to the ionic ones.
For example, Ulagappan and Rao56 have studied the effect of
alkane incorporation on the formation of a mesoporous silica
using a cationic surfactant. On the basis of SAXS and nitrogen
adsorption results, they found that short alkanes penetrate
between the tails of the surfactant molecules. In contrast,
higher alkanes, such as decane, form a hydrophobic droplet
stabilized by a layer of the cationic surfactant molecules. In the
latter case, the swelling mechanism involves one molecule of
surfactant for one molecule of alkane. Galarneau et al.57 used
trimethylbenzene (TMB) to enlarge the size of the micelles of
cetyltrimethylammonium bromide surfactant in order to prepare
large pore MTS (Micelle Template Silica) materials. Based on
EPR and 1H NMR analysis, the authors conclude that TMB partly
localizes around the headgroup of the surfactant. To explain the
pore size enlargement of MCM-41 or SBA materials, Jana et al.58
consider that hydrophobic organic species, such as methyl-
substituted benzene, isopropyl-substituted benzene or alkane,
added as organic swelling agents are incorporated into the
hydrophobic region of the rod-like micelles, causing an increase
in pore diameter. Using a non-ionic polyoxyethylene surfactant,
Boissière et al.59 also consider a swelling effect of the micelle
core to explain the effect of the addition of a swelling agent
(TMB) on the pore size of MSU mesoporous silica.
However, only a few reports deal with the in situ SAXS
characterization of the oil solubilization in the silica--surfactant
hybrid mesophase. Lindén et al.25,26,60 have led this kind of
study for CTAB-based systems. They have studied the effect of
the solubilization of various oils such as hexane,26 benzene60
or toluene25,26,60 on the formation of the silicate surfactant
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mesophase under various conditions. These authors have
evidenced that upon the addition of oil, the appearance of
the hexagonal mesophase is delayed. Concerning the swelling
effect, they have concluded that the hybrid mesophase can
accommodate a higher amount of oil than the hexagonal liquid
crystal phase of the CTAB–water phase diagram. They have
attributed this phenomenon to the non-equilibrium nature of
the silica–surfactant mesophase. They have also outlined that
the solubility of the oil and the degree of silica polymerization
are the key parameters for the pore size enlargement.26
Looking at the solubilization of benzene under acidic
conditions, Lindén et al.26 found that the benzene molecules
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the cationic template stabilizes micro-emulsion droplets that
serve as building blocks for the final material. The d-spacing of
the hybrid mesophase increases with both the fatty acid/CTAB
and toluene/CTAB molar ratios. The time at which the hexagonal
mesophase is detected is related to the toluene/CTAB molar
ratio. However the swollen hexagonal silica–cationic surfactant
mesophase is not obtained alone, it is in kinetic equilibrium
with a lamellar phase. The extent of the latter is determined by
the amount of toluene and the countersurfactant added to the
synthesis mixture at a constant stirring rate.
1.4. Mesoporous organosilicas (PMOs)

rather penetrate between the hydrophobic chains. Benzene can
also be dissolved in water due to the presence of ethanol
released during the hydrolysis of TEOS, the silica precursor.
When the quantity of benzene is increased, more and more oil
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The hydrolysis and the condensation of a modified silica
precursor of the formula (OR)3Si–R 0 –Si(OR)3 (where R is a
methyl or ethyl group and R 0 represents any organic unit) in
the presence of a surfactant lead to the periodic mesoporous

molecules penetrate deeper along the hydrophobic chains. This
phenomenon induces a decrease in the curvature and a transi-
tion from the hexagonal to a lamellar structure (Fig. 2). The
solubilization capacity can be enhanced by the presence of a
co-surfactant.
The same group has investigated the ability to solubilize
toluene using a mixture of fatty acids and CTAB.25 The synthesis
is carried out at room temperature. Time resolved SAXS experi-
ments have shown that in almost all cases the addition of the
fatty acids in the absence of toluene leads to the gradual swelling
of the hexagonal mesophase and finally to the transition from a
hexagonal to a lamellar structure. Upon the addition of toluene,
organosilica (PMOs) materials.61–63 These PMOs constitute a
new class of mesoporous materials and they have applications
in different domains,64 but their formation mechanism has
been rarely investigated. In a paper dealing with the prepara-
tion of phenylene-bridged periodic mesoporous organosilicas,
Funari et al.65,66 have performed in situ SAXS analysis to shed
some light on the PMOs formation (Fig. 3). Materials are
prepared from a series of polyoxyethylene alkyl ether [Cm(EO)n]
surfactants under mild acidic conditions. 1,4-Bis(triethoxysilyl)-
benzene (BTEB) is used as an organosilica precursor. This study
has shown that the highly hydrolyzed organosilica species
induce the appearance of the hybrid mesophase. When PMOs

Fig. 3 In situ SAXS results for a thiophene-bridged periodic mesoporous organo-silica (PMOs). Brij 76 (polyethylene (10) stearylether) is used as a surfactant and
2,5-bis(triethoxysilyl)thiophene (BTET) as an organo-silica source. Several Bragg peaks were recorded with time as can be seen both on the 3D-plot (a) and the 2D-plot
(b) of the data. The corresponding d-spacings (c) are attributed to a coexistence of a 3D-hexagonal phase (P63/mmc space-group) with a 2D-hexagonal phase during
the early stages of the material formation. The broad scattering could be attributed to the presence of hybrid organic–inorganic micelles in the solution. Reprinted
with permission from ref. 65. Copyright 2010, American Chemical Society, Chem. Mater.

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are synthesized with C18(EO)6 or C16(EO)6, the obtained structure
is lamellar at the beginning. Then the balance of charges between
the organic and the inorganic species is responsible for a transi-
tion from the lamellar to a hexagonal structure. If C12(EO)6 is
used as a template, the situation is quite different. Indeed, no
phase transition is observed and a cubic mesostructure is
obtained. The authors explain these behaviors by considering
variations in the packing parameter, due to a change in the
conformation of the oxyethylene group. It should be noted that,
whatever the surfactant, no ordered structure is recovered when
the template is removed. After surfactant removal, no reflection is
detected on the SAXS pattern of PMOs prepared with C18(EO)6
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and only one reflection is detected for the materials synthesized
from C16(EO)6 or C12(EO)6. The authors explain that the ordering
of the silica–hybrid mesophase obtained in solution is due to
strong interactions between the headgroup of the surfactant and
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the charged silica species mediated by the counterion.
A similar study has been led by the same authors for phenylene
and thiophene bridged PMOs.67 In that case, Brij 76 [C18(EO)10]
and 1,4-bis(triethoxysilyl)benzene (BTEB) or 2,5-bis(triethoxysilyl)-
thiophene (BTET) are, respectively, used as a surfactant and an
organosilica precursor. Once again the formation process is
governed by the polymerizing organo-silica species. The ordering
of the hybrid mesophase is induced by the varying number of
charges on the surface of the silica species during the hydrolysis
and condensation. At the early stages of the reaction, the partly
hydrolyzed and condensed silica species are connected to the
headgroup of the surfactant molecules by electrostatic and van
der Waals interactions. In addition, the in situ SAXS experiment
performed at 50 1C has evidenced that a mixture of 3D-hexagonal
and 2D-hexagonal structures is formed, as shown in Fig. 3.
However, a hydrothermal treatment at higher temperatures
involves the complete transition from 3D to 2D hexagonal, which
is the final structure. It is also observed that both BTEB and BTET
react in the same way under the conditions reported.
Recently, Morris et al.68 have synthesized oriented PMO
filaments in the channels of anodic alumina membranes (AAMs).
SAXS allowed the identification of the mesopores’ orientation
within the AAMs channels. The PMOs filaments were prepared by
the evaporation induced self-assembly (EISA) method. It appears
that humidity plays a key role in the process. As a matter of fact,
ex situ SAXS analysis reveals that at low humidity samples exhibit
scattering patterns where only in-plane reflections are present.
In this case, the 2D-hexagonal filaments are well oriented along
the channels direction. In contrast, at higher humidity, the
presence of out-of-plane reflections shows that the filaments
are oriented in a circular fashion inside the channels. The
humidity controls the evaporation rate of both water and ethanol.
The authors have correlated the rate of evolution of the meso-
porous structure with the rate of the solvent evaporation.
1.5. Coupling with complementary techniques
As already mentioned, one main advantage of SAXS/SANS
experiments is to combine in situ the structural analysis with
other types of measurements. Even if this subject is not the
main topic of this review, let us just illustrate this point with
This journal is c The Royal Society of Chemistry 2013
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Review Article
one important example in the field, the combination with
adsorption–desorption measurements (BET). They are known
to be crucial to investigate the porosity of mesoporous materials
(after surfactant removal). In the pioneering work of Albouy and
Ayral,69 nitrogen adsorption data at low temperature were com-
bined in situ with SAXS measurements for a 2D-hexagonal silica
material (with CTAB used as a template) and it was found that
the capillary condensation of nitrogen within the pores induces
unexpectedly a slight increase in the lattice parameter. From
these measurements, it was shown that both contributions of
the mesopores and micropores could be determined separately,
and that an accurate measurement of the wall density could be
obtained. More recently, this type of approach has been refined
and applied to other mesoporous silica materials like the
2D-hexagonal SBA-15 material70 or to even more complex
architectures with hierarchical porosity,71 and combining
in situ adsorption measurements with both SAXS70,71 and
SANS.71 The adsorption behavior of different fluids (nitrogen,71
dibromomethane,71 pentane/perfluoropentane70) was fully
quantitatively determined thanks to the modeling of the scattered
intensity, based either on the chord-length distribution analysis71
or on the direct modeling of the Bragg peak intensities and the
disordered micropores contribution.70
2. Investigation of the early stages of
the CTM
Since around 2007, to obtain deeper insight into the under-
standing of the formation mechanism of mesoporous materials,
some in situ SAXS and SANS studies have combined both the
determination of the micelle structure as well as the evolution of
the ordered surfactant–silica hybrid mesophase during the
materials synthesis. The main purpose is then to make the link
between the evolution of the micellar phase and the formation
of an ordered mesophase. Different families of mesoporous
materials have been investigated in this way: materials pre-
pared using Gemini surfactants (Section 2.1), with CTAB under
basic conditions (Section 2.2), and with Pluronic copolymers,
SBA-15 materials (Section 2.3). For the latter materials, several
studies are compared.
2.1. Formation mechanism of MCM-41 obtained from
a Gemini surfactant
Based on a SAXS time resolved analysis, Gianotti et al.72 have
proposed a two-step mechanism to describe the formation
process of MCM-41 materials prepared from a Gemini (C16-4-16)
surfactant. The main advantage of this family is that the MCM-41
can be synthesized at room temperature without hydrothermal
treatment. For the data analysis, the spectra of the solution
measured before the addition of the silica precursor (TEOS)
were subtracted as background. At the beginning of the reac-
tion, SAXS patterns indicate the presence of isolated cylindrical
particles covered by silica. Their size is around 6.2 nm. Then a
detailed analysis of both the shift of the d-spacing and of
its full-width at half maximum (FWHM) indicates that these
Chem. Soc. Rev., 2013, 42, 4071--4082 4077

Review Article
primary cylindrical particles merged to form small domains
without long range order. Finally, these small domains joined
together to give rise to the 2D hexagonal mesostructure with
long range order. The 11 and 20 reflections appear only at this
stage and it is concluded that the final ordered materials are
obtained after 450 s. The evolution of the d10 spacing with time
allows calculating the fraction of MCM-41 material. Moreover,
from the Bragg peaks intensity evolution with time, it is deduced
that the particles are growing with a rod-like morphology.
2.2. Growth of mesoporous silica particles templated with
CTAB under basic conditions
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
A recent in situ SANS study dealing with the growth of meso-
porous silica nanoparticles has been reported by Hollamby
et al.73 The contrast variation method has been applied to
distinguish the contribution of the different parts of the
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samples, i.e. the micelles and the silica nanoparticles. The
latter are fully formed after 840 s. A multiform model has been
employed to fit the SANS data. The influence of different
parameters such as the methanol released during the hydro-
lysis of TMOS, the changing contrast due to the change in
composition of the particles during their growth have been
taken into account for the fitting. These parameters can affect
the value of the scale factor and as a consequence the results of
the fitting. Based on the analysis of the SANS curves obtained
under different experimental conditions, a cooperative mecha-
nism is proposed to explain the growth of the mesoporous
silica nanoparticles. After hydrolysis and initial condensation,
small silica oligomers adsorb onto the CTAB micelles surface.
This lowers the intermicellar repulsion. The decrease in repulsion
allows the formation of small aggregates of silica–surfactant
hybrid structures. The micellar aggregation is accompanied by
the condensation of silica into the gaps. The final particles consist
of walls of condensed silica surrounding micelles in a hexagonally
packed structure. The effect of both the temperature and the
TMOS concentration on the growth of the silica nanoparticles has
Fig. 4 Modeling of in situ SAXS results using a core–shell model for the surfactant micelles. (a) Theoretical electron density profile of the cross-section of a rod-like
micelle with a constant density in the core and a smeared profile for the shell. (b) Evolution with time of this profile derived from the data modeling in the case of the
SBA-15 synthesis. The increase in the density in the shell region is interpreted by an increasing amount of silica in the shell upon time. Reprinted with permission from
ref. 75. Copyright 2009, American Chemical Society, J. Phys. Chem. C.
4078 Chem. Soc. Rev., 2013, 42, 4071--4082
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Chem Soc Rev
also been investigated. It appears that while the temperature does
not affect the size of the particles, the latter depends on the
quantity of TMOS. Decreasing the TMOS concentration leads to
smaller particles, whereas larger particles with higher silica con-
tent are prepared when the TMOS amount is increased.
2.3. 2D-hexagonal SBA-15 materials
Several studies have been devoted to the formation of the SBA-15
2D-hexagonal silica material using both in situ SAXS38,46,74–77
and SANS43,78 and the influence of many synthesis parameters
could be investigated. Moreover, because the kinetic times for
the formation of the material are large enough (typically 10 to
60 minutes), it was possible for this material to follow in situ the
structural relationships between the micelles in solution and
the material upon time.38,43,46,75 The structure directing agent is
a commercial triblock copolymer (P1239 or P10479 – Pluronic@
BASF trademark) consisting of a central PPO hydrophobic block
with two PEO hydrophilic blocks linked at its two extremities.
For P123, a detailed quantitative study of the micellar structure
prior to the silica precursor addition has been performed under
typical synthesis conditions (P123 concentration of 2.5% w/w),
varying the temperature, the concentration and the nature of
the acidic source (HNO3, HBr, HCl, H2SO4, H3PO4).80 It has
been found that it forms always spherical micelles, with a
progressive dehydration of the PPO core upon temperature,
and deep influence of the acid nature on the overall size of the
micelles. Salting-in/chaotropic anions (like Br) have a ten-
dency to confine inside the micelles and to reduce their size
as salting-out/kosmotropic anions (like H3PO4) give rise to
larger micelles. After the addition of the silica source, in situ
SAXS experiments have been interpreted using complete
modeling of the scattering curves.38,75 In these models, the
micelles are described using a core–shell model as illustrated in
Fig. 4. The main finding is that the micelles in solution
undergo a sphere-to-rod shape transition prior to the formation
of the 2D-hexagonal mesophase, and that this phenomenon is
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 View Article Online

Chem Soc Rev Review Article

Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
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Fig. 5 Formation mechanism of the 2D-hexagonal SBA-15 material derived from in situ SAXS experiments. (a) Initial solution of P123 spherical micelles. (b) Addition
of the TEOS silica precursor. (c) Hydrolysis step and beginning of the condensation. (d) Shape transformation of the hybrid organic–inorganic micelles from spherical to
rod-like. (e) Nucleation of the 2D-hexagonal phase. (f) Growth of the 2D-hexagonal phase. Reprinted with permission from ref. 38. Copyright 2011, American Chemical
Society, J. Phys. Chem. B.

linked to the fact that silica oligomers are present within the It has been found that salting-out/kosmotropic anions (like
shell of the micelles, as shown by the increase in the shell H3PO4 or SO42) lead to better ordered materials than salting-in/
density upon time (Fig. 4). The formation mechanism derived chaotropic anions (like Br).38 The influence of the nature of
from this analysis is summarized in Fig. 5. It consists of three the silica sources (TMOS, TEOS, TPOS,78 silicate42) has also
main steps. During the hydrolysis of the silica precursor (TEOS been reported. In Fig. 6, the time evolution of the 2D-hexagonal
in this case), no modification of the spherical micelles occurs. spacing followed by in situ SANS for five different synthesis
Then the condensation of the silica starts and some oligomers conditions with P104 as a template is shown.78 It can be
begin to interact with the EO groups at the surface of the observed for example that in the presence of 1 M NaBr the
micelles. Upon further silica condensation, a sphere to rod d-spacing decreases from 12 to 10 nm, which is probably due a
shape transition of the micelles occurs. When a sufficient decrease in the micelle size prior to the precursor addition.
amount of silica oligomers are present within the shell, the Even if many parameters have already been investigated, addi-
precipitation of the 2D-hexagonal mesophase is observed. tional systematic studies using in situ experiments are required
It can be explained by the fact that the attractive van der Waals aiming to achieve a complete control of the material structure.
interaction between the hydrophobic cores of the micelles
becomes the dominant interaction, inducing the formation of
micelles aggregates. Inside this mesophase, the silica conden-
sation continues and the progressive formation of the solid
walls in-between the micelles has also been followed by in situ
SAXS46,74,81 and SANS.78 The silica wall formation has been
derived from SAXS results using either direct modeling46 or
electron density reconstruction.74 As mentioned previously (see
Section 1.1), this step is associated with a global shrinkage of
the lattice parameter upon time because of the densification of
the silica network during condensation. Moreover, the conco-
mitant decrease in the hydration of the wall upon time has
been revealed by in situ SANS experiments, where the contrast is
Fig. 6 Evolution of the (10) 2D-hexagonal d-spacing, for five different synthesis
very sensitive to the amount of water within the walls.78
conditions of the SBA-15 material, obtained during in situ SANS measurements.
Among the many synthesis parameters of SBA-15, it has been Three different silica precursors (TMOS, TEOS and TPOS) are compared and the
shown that the nature of the acidic source38 as well as the addition addition of 1 M salt (NaCl and NaBr) was also investigated. Reprinted with
of salt77 affect the whole kinetics of the material formation. permission from ref. 78. Copyright 2011, Elsevier, Solid State Sci.

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Review Article
One main aspect in future studies will be to understand the
control of the morphology82 of the particles obtained via the
CTM route. Indeed, it has been demonstrated recently that
the stirring rate of the solution during the precursor hydrolysis
step is a crucial synthesis parameter that controls directly the
morphology of the grains, ranging from platelets to elongated
rods or even to closed donut-like shapes.82
3. Conclusion
During the past ten years, in situ SAXS and SANS experiments
have helped to understand the elaboration of silica mesoporous
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
materials. In the near future, one of the main challenges will be
to gather in situ structural information on a wide range of
length-scales, from a fraction of nanometer up to a few
microns. The use of ultra small angle scattering experiments
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(USAXS79 and USANS) should provide very interesting informa-
tion about the nucleation/growth of mesoporous material via
the CTM route and open the way to the morphology control
of the particles. In addition, at length-scales of only a few
Angströms, a better characterization by SAXS of the silica
clusters formed by condensation in solution during the early
stages of reaction should also be developed.
To date, as shown in this review, the majority of the
mesoporous materials that have been investigated by in situ
experiments contain only silica. One can expect that the
methods that have been developed in this case will be extended
to more and more complex materials, including completely
different inorganic sources83 or the incorporation of metals84 or
metal oxides. For the latter, Anomalous Small Angle X-ray
Scattering (ASAXS) experiments should provide interesting
new perspectives by varying the energy of the X-rays. This will
be however restricted to the case of materials containing heavy
elements, because the absorption threshold needs to be experi-
mentally accessible.
One key parameter to study the formation mechanism of
non-silica mesoporous materials with a mesopore ordering
concerns the control of the alkoxide precursor hydrolysis and
condensation that is much faster than for silicium. Indeed,
alkoxides other than silicium ones usually exhibit a high
reactivity towards hydrolysis and condensation. It is especially
the case for titanium oxide, which is a very important oxide
because of its semiconductor properties. As a consequence of
the high condensation rate, poorly ordered non-silica materials
are often recovered. However, some attempts to investigate the
in situ formation of non-silica mesoporous materials already
exist. For example based on in situ time-resolved SAXS and
SANS experiments, Né et al.85 have proposed a two-step mecha-
nism to describe the formation of a 2D-hexagonal meso-
structured zirconia by using hexadecyltrimethylammonium
bromide (CTAB) as a surfactant and zirconium oxychloride as
an inorganic precursor. No preexisting cylinders coated with
zirconium seem to be involved in the synthesis of the meso-
porous ZrO2. The first step is the nucleation/growth process of
the grains. The second is a first-order reorganization inside
the grains from locally ordered cylinders to a hexagonal lattice.
4080 Chem. Soc. Rev., 2013, 42, 4071--4082
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Chem Soc Rev
The micelles act simply as a reservoir of surfactants. This
mechanism is different from the one proposed for the silica
2D-hexagonal SBA-15 material, but it is similar to the one
proposed by Lebeau et al.32 for the preparation of mesoporous
silica from cationic surfactants. Then, the development of new
experimental setups suited to very fast kinetics is required to
shed some light on the different possible synthesis mecha-
nisms for ordered non-silica mesostructured materials in
particular titania.
References
1 C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and
J. S. Beck, Nature, 1992, 359, 710–712.
2 J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz,
C. T. Kresge, K. D. Schmitt, C. T. W. Chu, D. H. Olson,
E. W. Sheppard, S. B. McCulle, J. B. Higgins and J. L.
Schender, J. Am. Chem. Soc., 1992, 114, 10834–10843.
3 P. Botella, A. Corma and M. S. Quesada, J. Mater. Chem.,
2012, 22, 6394–6401.
4 S. Y. Park, M. Barton and M. Pendleton, Colloids Surf., A,
2011, 385, 256–261.
5 X. Zhang, V. Thavasi, S. G. Mhaisalkar and S. Ramakrishna,
Nanoscale, 2012, 4, 1707–1716.
6 L. F. F. P. G. Braganca, M. Ojeda, J. L. G. Fierro and
M. I. Pais da Silva, Appl. Catal., A, 2012, 423–424,
146–153.
7 J. L. Blin, C. Gérardin, C. Carteret, L. Rodehüser, C. Selve
and M. J. Stébé, Chem. Mater., 2005, 17, 1479–1486.
8 Y. Wan and D. Zhao, Chem. Rev., 2007, 107, 2821–2860.
9 D. Zhao, Q. Hhuo, J. Feng, B. F. Chmelka and G. D. Stucky,
J. Am. Chem. Soc., 1998, 120, 6024–6036.
10 E. Prouzet and T. J. Pinnavaia, Angew. Chem., Int. Ed. Engl.,
1997, 36, 516–518.
11 A. El-Safty, Y. Kiozumi, T. Hanaoka and F. Mizukami,
J. Phys. Chem. C, 2008, 112, 5476–5489.
12 K. Zimny, J. L. Blin and M. J. Stébé, J. Phys. Chem. C, 2009,
113, 11285–11293.
13 J. L. Blin, R. Bleta and M. J. Stébé, J. Colloid Interface Sci.,
2006, 300, 765–773.
14 F. Michaux, J. L. Blin and M. J. Stébé, Langmuir, 2008, 24,
1044–1052.
15 A. Galarneau, M. Nader, F. Guenneau, F. Di Renzo and
A. Gedeon, J. Phys. Chem. C, 2007, 111, 8268–8277.
16 T. Benamor, L. Vidal, B. Lebeau and C. Marichal, Micro-
porous Mesoporous Mater., 2012, 153, 100–114.
17 J. L. Blin, A. Leonard and B. L. Su, Chem. Mater., 2001, 13,
3542–3553.
18 F. Michaux, M. J. Stébé and J. L. Blin, Microporous Meso-
porous Mater., 2012, 151, 201–210.
19 M. Kruk, M. Jaroniec, H. J. Shin and R. Ryoo, Stud. Surf. Sci.
Catal., 2005, 156, 55–62.
20 Z. Lou, R. Wang, H. Sun, Y. Chen and Y. Yang, Microporous
Mesoporous Mater., 2008, 110, 347–354.
21 A. Galarneau, H. Cambon, F. Di Renzo, R. Ryoo, M. Choi
and F. Fajula, New J. Chem., 2003, 27, 73–79.
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
22 P. F. Fulvio, S. Pikus and M. Jaroniec, J. Mater. Chem., 2005,
15, 5049–5053.
23 A. Leonard, J. L. Blin, P. A. Jacobs, P. Grange and B. L. Su,
Microporous Mesoporous Mater., 2003, 63, 59–73.
24 L. Cao, T. Man and M. Kruk, Chem. Mater., 2009, 21,
1144–1153.
25 A. Lind, J. Andersson, S. Karlsson, P. Ågren, P. Bussian,
H. Amenitsch and M. Lindén, Langmuir, 2002, 18,
1380–1385.
26 M. Lindén, P. Ågren, S. Karlsson, P. Bussian and
H. Amenitsch, Langmuir, 2000, 16, 5831–5836.
27 R. Bleta, J. L. Blin and M. J. Stébé, J. Phys. Chem. B, 2006,
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
110, 23547–23556.
28 J. L. Blin and M. J. Stébé, Microporous Mesoporous Mater.,
2005, 87, 67–76.
29 N. Baccile, C. V. Teixeira, H. Amenitsch, F. Villain,
Downloaded by University of Chicago on 20/04/2013 17:38:22.
M. Lindén and F. Babonneau, Chem. Mater., 2008, 20,
1161–1172.
30 K. Flodstrom, H. Wennerstrom and V. Alfredsson, Langmuir,
2004, 20, 680–688.
31 C. C. Egger, M. W. Anderson, G. J. T. Tiddy and J. L. Casci,
Phys. Chem. Chem. Phys., 2005, 7, 1845–1855.
32 J. Frasch, B. Lebeau, M. Soulard, J. Patarin and R. Zana,
Langmuir, 2000, 16, 9049–9057.
33 S. Ruthstein, V. Frydman and D. Goldfarb, J. Phys. Chem. B,
2004, 108, 9016–9022.
34 S. Schacht, M. Janicke and F. Schuth, Microporous Meso-
porous Mater., 1998, 22, 485–493.
35 S. M. Holmes, V. L. Zholobenko, A. Thursfield, R. J. Plaisted,
C. S. Cundy and J. Dwyer, J. Chem. Soc., Faraday Trans.,
1998, 94, 2025–2032.
36 F. Michaux, J. L. Blin, J. Teixeira and M. J. Stébé, J. Phys.
Chem. B, 2012, 116, 261–268.
37 M. H. J. Koch and W. Bras, Annu. Rep. Prog. Chem., Sect. C:
Phys. Chem., 2008, 104, 35–80.
38 S. Manet, J. Schmitt, M. Imperor-Clerc, V. Zholobenko,
D. Durand, C. L. P. Oliveira, J. S. Pedersen, C. Gervais,
N. Baccile, F. Babonneau, I. Grillo, F. Meneau and
C. Rochas, J. Phys. Chem. B, 2011, 115, 11330–11344.
39 F. Babonneau, N. Baccile, D. Grosso and M. Imperor, Actual.
Chim., 2011, 34–39.
40 M. Lindén, S. A. Schunk and F. Schuth, Angew. Chem., Int.
Ed., 1998, 37, 821–823.
41 V. L. Zholobenko, A. Y. Khodakov, M. Imperor-Clerc,
D. Durand and I. Grillo, Adv. Colloid Interface Sci., 2008,
142, 67–74.
42 J. Jammaer, T. S. van Erp, A. Aerts, C. E. A. Kirschhock and
J. A. Martens, J. Am. Chem. Soc., 2011, 133, 13737–13745.
43 M. Imperor-Clerc, I. Grillo, A. Y. Khodakov, D. Durand and
V. L. Zholobenko, Chem. Commun., 2007, 834–836.
44 M. Imperor-Clerc, P. Davidson and A. Davidson, J. Am.
Chem. Soc., 2000, 122, 11925–11933.
45 K. J. Edler and J. W. White, Chem. Mater., 1997, 9,
1226–1233.
46 A. Y. Khodakov, V. L. Zholobenko, M. Imperor-Clerc and
D. Durand, J. Phys. Chem. B, 2005, 109, 22780–22790.
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
47 J. P. Hanrahan, M. P. Copley, T. R. Spalding, J. D. Holmes,
D. C. Steytler, H. Amenitsch, M. Steinhart and M. A. Morris,
J. Non-Cryst. Solids, 2007, 353, 4823–4829.
48 I. Beurroies, P. Agren, G. Buchel, J. B. Rosenholm,
H. Amenitsch, R. Denoyel and M. Lindén, J. Phys. Chem. B,
2006, 110, 16254–16260.
49 S. Liu, P. Cool, O. Collart, P. Van Der Voort, E. F. Vansant,
O. I. Lebedev, G. Van Tendeloo and M. Jiang, J. Phys. Chem.
B, 2003, 107, 10405–10411.
50 J. Israelachvili, Intermolecular and Surface Forces: Revised
Third Edition, 2011.
51 T. W. Kim, F. Kleitz, B. Paul and R. Ryoo, J. Am. Chem. Soc.,
2005, 127, 7601–7610.
52 S. Ruthstein, J. Schmidt, E. Kesselman, R. Popovitz-Biro,
L. Omer, V. Frydman, Y. Talmon and D. Goldfarb, Chem.
Mater., 2008, 20, 2779–2792.
53 S. Pevzner and O. Regev, Microporous Mesoporous Mater.,
2000, 38, 413–421.
54 P. Ågren, M. Lindén, J. B. Rosenholm, R. Schwarzenbacher,
M. Kriechbaum, H. Amenitsch, P. Laggner, J. Blanchard and
F. Schüth, J. Phys. Chem. B, 1999, 103, 5943–5948.
55 P. Agren, M. Lindén, J. B. Rosenholm, J. Blanchard,
F. Schuth and H. Amenitsch, Langmuir, 2000, 16, 8809–8813.
56 N. Ulagappan and C. N. R. Rao, Chem. Commun., 1996,
2759–2760.
57 M. F. Ottaviani, A. Moscatelli, D. Desplantier-Giscard,
F. Di Renzo, P. Kooyman and A. Galarneau, J. Phys. Chem. B,
2004, 108, 12123–12129.
58 S. K. Jana, R. Nishida, K. Shindo, T. Kugita and S. Namba,
Microporous Mesoporous Mater., 2004, 68, 133–142.
59 C. Boissière, M. A. U. Marines, M. Tokumoto, A. Larbot and
E. Prouzet, Chem. Mater., 2003, 15, 509–515.
60 M. Tiemann, V. Goletto, R. Blum, F. Babonneau,
H. Amenitsch and M. Lindén, Langmuir, 2002, 18,
10053–10057.
61 B. J. Melde, B. T. Holland, C. F. Blanford and A. Stein, Chem.
Mater., 1999, 11, 3302–3308.
62 S. Inaki, S. Guan, Y. Fukushima, T. Ohsuna and O. Terasaki,
J. Am. Chem. Soc., 1999, 121, 9611–9614.
63 Q. H. Yang, J. Liu, L. Zhang and C. Li, J. Mater. Chem., 2009,
19, 1945–1955.
64 F. Hoffmann, M. Cornelius, J. Morell and M. Froba,
J. Nanosci. Nanotechnol., 2006, 6, 265–268.
65 V. Rebbin, A. Rothkirch, M. Froba and S. S. Funari, Chem.
Mater., 2010, 22, 3746–3751.
66 V. Rebbin, A. Rothkirch, U. Vaino and S. S. Funari, J. Phys.:
Conf. Ser., 2012, 351, 012015.
67 V. Rebbin, A. Rothkirch, N. Ohta and S. S. Funari, Langmuir,
2010, 26, 9017–9022.
68 J. M. O’Callaghan, N. Petkov, M. P. Copley, D. C. Arnold,
M. A. Morris, H. Amenitsch and J. D. Holmes, Microporous
Mesoporous Mater., 2010, 130, 203–207.
69 P. A. Albouy and A. Ayral, Chem. Mater., 2002, 14,
3391–3397.
70 G. H. Findenegg, S. Jahnert, D. Muter, J. Prass and O. Paris,
Phys. Chem. Chem. Phys., 2010, 12, 7211–7220.
Chem. Soc. Rev., 2013, 42, 4071--4082 4081

Review Article
71 S. Mascotto, D. Wallacher, A. Brandt, T. Hauss,
M. Thommes, G. A. Zickler, S. S. Funari, A. Timmann and
B. M. Smarsly, Langmuir, 2009, 25, 12670–12681.
72 E. Gianotti, G. Berlier, K. Costabello, S. Coluccia and
F. Meneau, Catal. Today, 2007, 126, 203–210.
73 M. J. Hollamby, D. Borisova, P. Brown, J. Eastoe, I. Grillo
and D. Shchukin, Langmuir, 2012, 28, 4425–4433.
74 K. Flodstrom, C. V. Teixeira, H. Amenitsch, V. Alfredsson
and M. Lindén, Langmuir, 2004, 20, 4885–4891.
75 A. Sundblom, C. L. P. Oliveira, A. E. C. Palmqvist and
J. S. Pedersen, J. Phys. Chem. C, 2009, 113, 7706–7713.
76 A. Sundblom, C. L. P. Oliveira, J. S. Pedersen and
Published on 21 December 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35362H
A. E. C. Palmqvist, J. Phys. Chem. C, 2010, 114,
3483–3492.
77 C. V. Teixeira, H. Amenitsch, P. Linton, M. Lindén and
V. Alfredsson, Langmuir, 2011, 27, 7121–7131.
Downloaded by University of Chicago on 20/04/2013 17:38:22.
4082 Chem. Soc. Rev., 2013, 42, 4071--4082
View Article Online
Chem Soc Rev
78 P. Linton, A. R. Rennie and V. Alfredsson, Solid State Sci.,
2011, 13, 793–799.
79 P. Linton, A. R. Rennie, M. Zackrisson and V. Alfredsson,
Langmuir, 2009, 25, 4685–4691.
80 S. Manet, A. Lecchi, M. Imperor-Clerc, V. Zholobenko,
D. Durand, C. L. P. Oliveira, J. S. Pedersen, I. Grillo, F. Meneau
and C. Rochas, J. Phys. Chem. B, 2011, 115, 11318–11329.
81 M. Impéror-Clerc, Interface Focus, 2012, 2, 589–601.
82 H. I. Lee, J. H. Kim, G. D. Stucky, Y. F. Shi, C. Pak and
J. M. Kim, J. Mater. Chem., 2010, 20, 8483–8487.
83 M. Tiemann, M. Froba, G. Rapp and S. S. Funari, Chem.
Mater., 2000, 12, 1342–1348.
84 D. Kumar, P. U. Sastry, D. Sen and N. M. Gupta, Microporous
Mesoporous Mater., 2006, 89, 132–137.
85 F. Né, F. Testard, T. Zemb and I. Grillo, Langmuir, 2003, 19,
8503–8510.
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