Advances in Colloid and Interface Science 189–190 (2013) 21–41

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Advances in Colloid and Interface Science

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Soft templating strategies for the synthesis of mesoporous materials:

Inorganic, organic–inorganic hybrid and purely organic solids
Nabanita Pal, Asim Bhaumik ⁎
Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700 032, India

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

Available online 2 January 2013 With the discovery of MCM-41 by Mobil researchers in 1992 the journey of the research on mesoporous mate-
rials started and in the 21st century this area of scientific investigation have extended into numerous branches,
Keywords: many of which contribute significantly in emerging areas like catalysis, energy, environment and biomedical re-
Self-assembly search. As a consequence thousands of publications came out in large varieties of national and international
Soft templating journals. In this review, we have tried to summarize the published works on various synthetic pathways and for-
Mesoporous materials
mation mechanisms of different mesoporous materials viz. inorganic, organic–inorganic hybrid and purely or-
Surfactants
Porous organic materials
ganic solids via soft templating pathways. Generation of nanoscale porosity in a solid material usually requires
participation of organic template (more specifically surfactants and their supramolecular assemblies) called
structure-directing agent (SDA) in the bottom-up chemical reaction process. Different techniques employed
for the syntheses of inorganic mesoporous solids, like silicas, metal doped silicas, transition and non-transition
metal oxides, mixed oxides, metallophosphates, organic–inorganic hybrids as well as purely organic mesoporous
materials like carbons, polymers etc. using surfactants are depicted schematically and elaborately in this paper.
Moreover, some of the frontline applications of these mesoporous solids, which are directly related to their func-
tionality, composition and surface properties are discussed at the appropriate places.
© 2012 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2. Synthesis pathway and mechanism of formation of mesoporous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1. Role of template in generating the porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2. Surfactants as structure-directing agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3. Interaction pathways of surfactants and inorganic metal precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4. Factors affecting the surfactant self-assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.5. General formation methods of mesoporous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.5.1. Synthesis method and mechanism of purely inorganic mesoporous materials . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5.2. Synthesis method and mechanism of organic–inorganic hybrid mesoporous materials and Periodic Mesoporous Organosilicas (PMOs) 32
2.5.3. Synthesis method and mechanism of purely organic mesoporous materials . . . . . . . . . . . . . . . . . . . . . . . . . 35
3. Properties and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5. Future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

1. Introduction

Since “the overwhelming tendency for solids to minimize void space

⁎ Corresponding author. Tel.: +91 33 2473 4971; fax: +91 33 2473 2805. within their structures” is inherent, porous materials are difficult to
E-mail address: msab@iacs.res.in (A. Bhaumik). make naturally. But Albert Einstein said “In the middle of difficulty

0001-8686/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cis.2012.12.002
22 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
lies opportunity.” This impossible task is made possible in 1992 by the
scientists of Mobil Oil Corporation (USA), when they first successfully
synthesized MCM (Mobil Composition of Matters)-41/48 through
surfactant-mediated self-assembly method [1]. This surfactant-
assisted templating pathway or soft templating strategy opens a
new class of materials named as mesoporous materials. The history of
porous materials began with zeolites having aluminosilicate frame-
works, which are conventionally synthesized via non-surfactant
assisted route employing single molecule template and having small
pores (micropore) inside it [2]. The most generalized definition of a
porous material is a continuous and solid network material filled
through voids. In the case of nanoporous materials the pore or voids
are of the order of ≈1–100 nm. A material can be recognized as porous
if its internal voids can be filled with gas. Sometimes, the voids might be
filled with a liquid or even a solid [3]. Generally, pores are classified into
two types: open pores which connect to the outside of the material and
closed pores which are isolated from the outside. Porosity provides
materials with lower density and higher surface area compared to
dense materials. For most industrial applications including separation,
catalysis and bioreactors open pores can play a crucial rule. Closed
porous materials are used mainly for thermal insulation and low
density structural components [4]. According to IUPAC convention,
depending upon size of the pore, the porous materials are of three
types: mesoporous, microporous and macroporous. Whereas, based
on the framework building blocks porous materials can be classified
as: purely inorganic, hybrid organic–inorganic and all-organic
porous polymers and carbonaceous materials. The classification
of porous materials is given in a flowchart (Scheme 1). This review
mainly highlights the soft templating strategies involved in the
synthesis of purely inorganic, organic–inorganic hybrid and all-
organic porous polymers and carbons materials, which are mesoporous
in nature. We do not discuss in this review about metal–organic
framework (MOF) [5] and metal phosphonates [6] since those solids
are commonly synthesized via non-templating route and having mi-
cropores in the framework.
Meso, the Greek prefix, meaning “in between”, has been adopted
by IUPAC to define porous materials having dimension of pores in
between micropore and macropore i.e. typically between 2 and
50 nm [7]. Owing to their high stability, surface areas and large
Scheme 1. Schematic representation of the classification of nanoporous materials.
pore volumes they are used technically as adsorbents, ion-exchangers,
catalysts, catalyst supports and in many other related applications
[8–10]. According to IUPAC classifications, mesoporous materials
can be ordered or disordered in nature. Ordered mesoporous mate-
rials such as MCM-41/48, SBA-15 have uniform and regular arrange-
ments of pore (or channel) widths whereas, atomic arrangements
are not ordered [1]. Disordered mesoporous solids like KIT-1 has
uniform channel width but they are not regularly arranged i.e. nei-
ther the pore arrangements nor the atomic arrangements are or-
dered. Both the pore and atomic arrangements are observed ordered
in microporous zeolites [11,12]. Mobil scientists employed long chain
organic surfactant molecules as the structure-directing agent (SDA)
during the synthesis of highly ordered mesoporous material MCM-41
instead of using small organic molecules, which are conventionally
used as the single molecule template as in the case of zeolites or related
microporous solids [2]. Rather than individual molecule being used
as void filler in the ordering of the reagents to form the microporous
materials, assemblies of molecules dictated by solution energetic are re-
sponsible for the formation of these pore systems. During the synthesis
process, the SDA molecules, in the form of a lyotropic liquid-crystalline
phase, lead to the assembly of an ordered mesostructured composite
during the condensation with the silica precursors. The mesoporous
materials are obtained by subsequent removal of the surfactant by
extraction or calcination. Since the discovery of mesoporous materials
through this type of supramolecular templating pathway, this research
area has tremendously expanded and has been reviewed intensively in
the recent time [13–15]. Surfactant templating routes have also been
used successfully in the preparation of non-silica based mesoporous
transition and non-transition metal oxides [16], metal sulfides [17],
metal phosphates [18] etc. In the following section a brief account of
the synthetic chemistry as well as mechanism behind the surfactant
assisted synthesis along with the various applications regarding these
mesoporous materials has been reviewed minutely. That is, the scope
of this review is mainly focused on various soft templating strategies
employed (discussed in Section 2.5) in synthesizing different mesoporous
solids. However, we have taken a chance to discuss in brief about
the hard templating approach (Section 2.5) in order to differenti-
ate, and highlight the merits and demerits of it from that of soft
templating strategy.
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
2. Synthesis pathway and mechanism of formation of
mesoporous materials
In the synthesis of mesoporous material organic surfactant mole-
cules play a decisive role to generate porosity within the building
blocks and thus act as template or structure directing agent (SDA).
This soft templating method is the most successful pathway for the
synthesis of ordered and disordered mesoporous matrices. Before
going to the main topic it is essential to know what is template or
what kind of interaction occurs between a template and precursor
species forming the mesoporous framework during the synthesis.
2.1. Role of template in generating the porosity
In broad sense, template means a stencil, pattern or overlay used
in graphic arts (drawing, painting, etc.) and sewing to replicate let-
ters, shapes or designs. In nanoporous regime template represents
that particular molecule, which helps to generate or design porosity
in the matrix. Thus a template acts as structure directing agent
(SDA) in the synthesis of porous materials [19]. The SDAs can be of
different types. Surfactant can be employed as a SDA, the essential
feature of which is the coexistence of chemically bonded hydrophobic
(non-polar) hydrocarbon ‘tail’ and a hydrophilic (polar) ‘head’ group
in a molecule. These molecules have high molecular weight and they
aggregate in solvent to form self-assembled micelle [1,20]. There are
some other SDAs bearing hydrophobic-hydrophilic groups in a single
molecule, which are not surfactants but play the role of template in
designing mesopores in a material. These template molecules may
or may not form self-assembly [21]. Another type of SDA is dendrimer
or polymer, which can be macromolecular single molecule having
high molecular weight [22,23]. All the above templates are soft tem-
plates (discussed in Section 2.5).
There are also hard templates like porous silica or colloidal silica
spheres, polystyrene etc. to generate porosity within the matrix [24].
Strictly speaking, a template is a structure (usually organic, though
hard template may be inorganic) around which a material (often
inorganic) nucleates and grows in a “skin-tight” fashion, so that
upon the removal of the templating structure, its geometric and
electronic characteristics are replicated in the (inorganic) materials
[25,26]. The classification of soft template SDAs has been illustrated
in the flowchart Scheme 2. Sustainable design and fabrication of
mesoporous materials can provide breakthroughs in the advance-
ment of energy conversion and storage devices. In this context
block copolymers has emerged as a powerful and affordable tool in
Template or structure
directing agents
Depending upon
functionality
Cationic
e.g. CTAB, CPC, etc.
Surfactants Non-surfactant
Large molecule, high
molecular wt, form
micelle, e.g. CTAB,
SDS etc. Single molecule
template, no self-
assembly e.g. TPA etc.
Scheme 2. Schematic representation of various categories of soft templates.
23
directing the structure of nanomaterials for photovoltaics, batteries
and fuel cells, where the morphologies of the mesoporous hybrids can
ranged from hexagonally arranged cylinders to three-dimensional
bi-continuous cubic networks [27]. In this review we will mainly em-
phasize upon the surfactant type template associated in the synthesis
of mesoporous materials.
2.2. Surfactants as structure-directing agent
Amphiphilic surfactant templating pathway has been defined as a
process in which an organic species functions as a central structure
about which precursor moieties organize to form long range ordered
material [25]. The molecules have both hydrophobic and hydrophilic
parts and the hydrophobic component of surfactant can solubilize or-
ganic species, while the hydrophilic or ‘water-loving’ component in-
teracts with charged inorganic precursors to direct the formation of
the inorganic framework (Fig. 1A).
Surfactants have both hydrophobic and hydrophilic components in
the molecule, which could behave distinctly in polar and non-polar sol-
vents. In aqueous media the polar part of the molecule interacts with
water, while the non-polar part stays away from the water molecules.
There are two ways by which such amphilic molecule stabilizes in
water. The amphiphilic surfactant molecule (Fig. 1A) can arrange itself
at the surface of the water such that the polar part interacts with the
water and the non-polar part is held above the surface (either in the
air or in a non-polar liquid) as shown in Fig. 1B. The presence of these
molecules on the surface disrupts the cohesive energy at the surface
and thus lowers the surface tension. That's why, such molecules are
called ‘surface active’ molecules or surfactants. Another arrangement
of these molecules can allow each component to interact with its
favored environment. Molecules can form aggregates in which the hy-
drophobic portions are oriented within the cluster and the hydrophilic
portions are exposed to the solvent [28]. Such aggregates are called
micelles (Fig. 1C). The proportion of molecules present at the surface
or as micelles in the bulk of the liquid depends on the concentration
of the amphiphile. At low concentrations surfactants will favor arrange-
ment on the surface. As the surface becomes crowded with surfactant
more molecules will arrange into micelles. At certain concentration
the surface becomes completely loaded with surfactant and any further
additions must arrange as micelles. This concentration is called the Crit-
ical Micelle Concentration (CMC). Different SDAs has different CMC
value in water [29]. Beyond the CMC value the self-assembly of micelle
occurs to form 3D spherical or 2D rod like array with further increasing
concentration and this self-assembly helps in the pore generation. This
Depending upon
the charge
Anionic Nonionic
e.g. SDS, lauric acid etc. e.g. P123, F127 etc.
Small molecule, low Single macromolecule
molecular wt, self- template, high molecular
assembly, e.g. urea, wt, do not form micelle,
sodium salicylate etc. e.g. dendrimers.
24 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
Air
Water
Hydrophobic Hydrophilic
(non-polar) (polar) ‘water
hydrocarbon ‘tail’ loving’ head gr.
A B
Fig. 1. Surfactant molecule and its behavior in aqueous media.
self-assembled micelle formed by the association of individual amphi-
philic templating molecules bonded through weak forces like van
der Waals, hydrogen bonding etc. but there is no covalent linkage
between those amphiphiles [30]. Actually, these SDA molecules are
the ‘placeholder’, what becomes the void space to produce nanoporous
material. They not only allow controlling the variation of pore size but
also the shape of the pores i.e. the total architecture of the template
molecule, its size and shape are imprinted in the porous solid (Fig. 2)
[3].
Depending upon the dissociation of surfactant molecule in aqueous
media there are three types of amphiphilic surfactant molecules [31].
a. Cationic surfactants dissociates in water into an amphiphilic cation
and an anion, most often halide type. A large portion of this class
belongs to nitrogenous compounds such as amine salts and qua-
ternary ammoniums, with one or several long chain alkyl group,
often coming from natural fatty acids. The common examples are
cetyltrimethylammonium bromide or hexadecyltrimethylammonium
bromide (CTAB), cetylpyridinium chloride (CPC), N-Dodecyl
pyridinium chloride etc.
b. Anionic surfactants dissociates in water into an amphiphilic
anion, and a cation, which is in general an alkaline metal (Na +,
K +) or a quaternary ammonium ion. Anionic surfactants include
alkylbenzene sulfonates (detergents), (fatty acid) soaps, lauryl
sulfate (foaming agent), di-alkyl sulphosuccinate (wetting agent),
lignosulfonates (dispersants) etc. Few common examples are sodi-
um dodecyl sulphate (SDS), sodium dodecylbenzene sulphonate etc.
c. Nonionic surfactants are another type which does not ionize in
water, because their hydrophilic components are non-dissociable
like alcohol, ether, ester, amide etc. A large variety of this type sur-
factant is made hydrophilic by the presence of polyethylene glycol
chain obtained by the polycondensation of ethylene oxide. Polycon-
densation of propylene oxide results a polyether which is slightly
hydrophobic. This polyether chain is used as lipophilic group i.e.
non-polar group in the so-called poly-EO-poly-PO block copoly-
mers. These copolymers are often included in different class
named polymeric surfactants. Common examples of non-ionic
surfactants are Pluronic P123, F127 etc [31].
Fig. 2. A common pathway for the formation of mesoporous solid [3].
Water
C
Beside these, there is another type of surfactant which is called
amphoteric or zwitterionic surfactants. In this case a single surfactant
molecule shows both cationic and anionic dissociations. Synthetic prod-
ucts like betaines, sulphobetaines, natural substances such as amino
acids and phospholipids etc. belong to this category [32]. Dodecyl beta-
ines, lauryl betaines are common examples. The structures of some
commonly used surfactants are depicted here for clarity (Fig. 3).
2.3. Interaction pathways of surfactants and inorganic metal precursors
Six different synthesis pathways that reflect the metal-template
molecular interaction have been readily employed to prepare ordered
mesoporous materials under wide range of pHs, temperatures and
surfactant nature and their concentrations [33]. The pathways are
S +I −, S −I +, S −M +I −, S +X −I +, S 0I 0 and N 0I 0, where S is the surfac-
tant, I is the inorganic phase and X is the mediating anionic species,
M is intermediate cation, S 0 is neutral amine, I 0 is hydrated inorganic
oligomer and N 0 is non-ionic template (Table 1).
For pathways involving electrostatic interaction, charge of the
inorganic source is controlled by the pH and isoelectric point. The
pH at which the charge of molecules is zero is called isoelectric pH.
Silica species (isoelectric point = 2) has a positive charge at pH b 2
(acidic conditions), neutral charge at pH = 2 and a negative charge
at pH > 2 (alkaline conditions) (Fig. 4). M41S silica molecular sieves
were originally fabricated at alkaline condition when anionic inor-
ganic species (I −) stabilize with cationic surfactant (S +) through
the S +I − strong interaction [1]. Likewise, silica mesostructure can
be formed with anionic surfactant (S −) at acidic condition (inorganic
species I +) using the S − I + approach [34]. The synthetic pathways
involving a mediating ion (e.g., S +X −I +) have a weaker electrostatic
interaction between the cationic precursor I + and the S +X − active
sites which leads to products with rich morphologies [35]. In case of
S −M +I − type the metal salt of aliphatic acid are generally used as
template. Hence, in highly basic media metal hydroxo species for
e.g. Zn(OH) 2−, Zn(OH)42−, Zn2(OH)62− components from zinc precur-
sor generated which interact with anionic template through metal
counter ion to form lamellar oxide [36]. Non-ionic template and amines
are also used as templates which interact with metal precursor through
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41 25

Fig. 3. Some common surfactants used in different field of science.

H-bonding in acidic media (S0I0/N0I0 interaction). MSU-X, hexagonal 2.4. Factors affecting the surfactant self-assembly
mesoporous silica HMS are synthesized in these fashions [37–40]. All
these types of interactions are beautifully shown in Fig. 5. Besides, there As it is already discussed that the formation of pore and its size,
are some examples of interaction between organic and inorganic species shape and dimension are entirely dependent on the surfactant supra-
through coordination and covalent bond formation. Mesostructured nio- molecular self-aggregation, depending upon the various factors like
bium oxide synthesized in non-aqueous media is a good example of the nature of template molecule, temperature, presence of counter ions
former case whereas hydrolysable silane group containing surfactant in the reaction media, the concentration of surfactants, role of sol-
type precursor can condensed through covalent interaction between or- vents etc. the size and shape of the surfactant micelle varies as well
ganic and inorganic parts of same molecule to form ordered mesoporous as that of the pore system of mesoporous solids. The structure or ge-
solid without template [41,42]. Stucky et al. have developed a wide range ometry of the template micelle may be of different patterns such as
of mesostructured optical materials using a one-step synthesis procedure spherical, cylindrical, lamellar, bilayer and so on [29] (Fig. 6). CMC,
where the inorganic/surfactant/optically active species co-assemble dur- which is the determining parameter of the formation and stability
ing the synthesis [43]. The corresponding regularly arranged pores found of micelle are governed by all these factors mentioned above and is
in mesoporous metal oxide frameworks provide a high surface area for a characteristic of a particular surfactant.
better dispersion of optically active components and allow for rapid dif- The counter ions like intermediate anions or cations have strong
fusion, which are essential for optical applications. effect on the metal–template interaction. Generally anions have stron-
ger effect than cation and as in majority of cases for the synthesis
Table 1 of mesoporous solids are carried out in the presence of cationic or
Types of interaction between template head group and inorganic precursor. non-ionic surfactants [44]. The transformation of spherical micelle of
Surfactant type Interaction Interaction Examples cationic surfactants to rod like geometry is more favorable when the
pathway type hydrated size of anion present in the media decreases and polarizability
Cationic S+ Electrostatic S +I − Tungsten oxide, MCM-41 increases. Upon neutralization the surfactant charge by the counter ion,
interaction S +X −I + Lamellar zinc phosphate, cubic Pm3n
rod like micelle formation observed and thus small hydrated anion
silica with high polarizability are more effective in this case. Well known
Anionic S− Electrostatic S −I + Lamellar Iron oxide Hofmeister series of anions, SCN− > NO3− > Br− >Cl− >OH− >F − are
interaction S −M +I Lameller aluminium oxide, zinc oxide
found to induce the sphere to rod transition of alkyltrimethylammonium
surfactants [45]. On the other hand high concentration of salts like NaCl,
Neutral S0/N0 H-bonding S0I0 Hexagonal silica HMS
interaction KCl, NaBr, Na2SO4 etc. may lead spherical micelle to transform into
N0I0 Silica MSU-X
lamellar form (Fig. 6). The CMC of non-ionic surfactants is also
26 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41

HO OH2
pH < 2 Si O O
H2O OH Controlled Si
condensation
Hydrolysis Ionic inorganic O O O
Si(OR)4
Silica species (I) Si Si
precursor HO O O O O
Si
pH > 2
O OH

Fig. 4. Silica precursor at variable pH condition.

O O
HO Si HO
O Si OH2 -
O O

HO
Si O
HO
Si OH2 -
O O

HO Si O HO Si OH2 -
O O
O Si
OH2 -
Si HO
HO
S+I- Interaction S+X-I+ Interaction

HO
O
M
M
O O
O O
H
M
M O +
H O
O O
HO M O +
HO M H
O
O O
H O +
M
M

O O
H O +
O
M
M
S-I+ Interaction HO S-M+I- Interaction
HO
O O
Si

O O

Si
OH
O

Si OH

O O

Si
OH S0I0/ N0I0 Interaction
Fig. 5. Different types of metal surfactant interactions.
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
greatly influenced by anions, which lower the respective CMC value
leading to increment of the attractive interactions between non-ionic
micelles [46].
The nature of surfactants and the concentration of it in aqueous
media have large impact on the size and shape of the self-assembled
superstructure. In aqueous media when the concentration of amphi-
philes changes from low to high, growth of spherical to rod shape mi-
celle results though more high concentration leads to lamellar phase.
Double-tailed surfactants generally furnish bilayer phase and lamellar
aggregate can also be formed from mixed surfactants aqueous solution
[46]. Surfactants with large hydrophilic group and small hydrophobic
chain form normal spherical micelle whereas if surfactants have small
polar head group but large brunched tail then spherical reverse micelle
will be formed i.e. the head group is inside and tail is outside (Fig. 6). If
oil is present in aqueous media the shape and size of all the self-assembly
changes and if more water is present surfactants organize themselves as
lamellar type [47]. Beside this normal micelle can be reversed in totally
non-polar media.
Thermal effect on the salt induced spherical to rod like micelle for-
mation of different alkyltrimethylammonium and non-ionic surfactants
were studied by Zieliński et al. and Lindman et al., respectively [48,49].
It has been found experimentally that the size of ionic surfactant micelle
decreases with rise of temperature although for non-ionic surfactants
reverse trend is observed. The temperature effect is more prominent
in case of rod like micelle than spherical one [50].
2.5. General formation methods of mesoporous materials
Thorough investigation and continuous research to understand the
formation mechanism for the mesostructured materials is going on till
date since 1992 [35,51]. Surfactant-assisted synthesis of mesoporous
materials can occur in two pathways: in endotemplate methods
(“soft-matter templating”) and in exotemplate methods (“nanocasting”).
In endotemplate (‘endo’ means within) or soft-templating route,
around the self-assembly of SDA in liquid medium inorganic precursors
Fig. 6. Different types of surfactant structures.
27
arrange themselves in regular ordered array to form an inorganic–
organic composite solid i.e. template self-assembly remains within
the inorganic materials. In this method usually there are three steps to
form a mesoporous solid. First, the surfactant self-assembly (about
which we have discussed in the previous section), second is the orga-
nization of inorganic precursor over this surfactant self-assembly
and formation of a stable inorganic–organic hybrid and third or last
is the successful subsequent removal of organic template to get the
mesoporous solid. Detailed study about the formation process of
these inorganic-surfactant composite materials has revealed that
two different mechanisms are involved in endotemplate route. One
is cooperative self-assembly (CSA) mechanism and another is ‘true’
liquid crystal template (TLCT) mechanism [13,52,53]. In former case
(CSA) there is a simultaneous aggregation of self-assembled SDA
along with the already added inorganic species and a liquid–crystal
phase with hexagonal, cubic, or laminar arrangement containing both
the organic micelle and inorganic precursor can be developed
(Fig. 7a). On the other hand, the TLCT mechanism first proposed by
Mobil scientists is ‘true’ since this pathway covers all the possibility be-
hind mesophase formation [1,20]. Here, the concentration of the surfac-
tant is so high that under the prevailing conditions (temperature, pH) a
lyotropic liquid-crystalline phase is formed without requiring the pres-
ence of the precursor inorganic framework materials (Fig. 7b) [54].
After the formation of the inorganic–organic nanocomposite material
and its further condensation it is necessary to remove the template
from this composite (called as-synthesized) to obtain the porosity. Cal-
cination in aerial atmosphere is the most familiar method to eliminate
the organic template completely and used widely for mesoporous silica,
oxides and phosphates. Different temperatures are required for remov-
ing different templates. Further, high temperature treatment increases
the degree of crystallinity in the mesoporous material [55]. But in case
of organic modified and unstable, air sensitive materials this method
is not suitable owing to loss of porosity. This problem has been solved
by introduction of solvent extraction method which is mild but very
effective for removal of surfactant without disturbing the framework
28 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
structure. Solvents like ethanol, THF with small quantity of dilute hy-
drochloride acid, ethylene diammine or ammonium acetate are used
in solvent extraction methods [56,57].
Exotemplate (‘exo’ means outside) (“nanocasting”) method is that
where a porous solid like silica or carbon or sometimes colloidal crys-
talline silica microsphere, polystyrene beads etc. is used as the tem-
plate in place of the surfactant. Thus, this method is also known as
“hard-matter templating” or hard-templating. In this case template
remains outside the inorganic material and the hollow space that
provided by the exotemplate framework (usually mesoporous silica
or carbon) are filled with that inorganic precursor, which is then
transformed (cured) under suitable conditions. In this way, the
pore system of the template is copied as a “negative image” in the
material. The now-filled exotemplate is removed by HF or NaOH
solution or by high temperature [58]. After removal of the template
framework, the incorporated material is obtained with a large specif-
ic surface area. This replication method was used for first time by
Ryoo et al. [59,60] for the synthesis of mesoporous carbon (CMK-1)
(Fig. 8).
Note that the terms endo- and exotemplate are formally derived
from the terms endo- and exo-skeleton used in biology. In addition,
there is another method named evaporation induced self-assembly
(EISA) (discussed later) for synthesis of mesostructured silicates and
transition metal oxides (TMOs) [61–63]. Brinker et al. have reported
the synthesis of mesostructured thin silica films derived from
methyltriethoxysilane (MTES) and/or tetraethyl orthosilicate (TEOS)
silica precursors and polystyrene-block-poly(ethylene oxide) (PS-b-
PEO) diblock copolymers via EISA process [61]. The meso- and micro-
structure of the calcined films consists of cubic-ordered arrays of spher-
ical mesopores of ca. 5-7 nm in diameter, together with PEO-induced
interconnected micropores of ca. 1 nm in diameter, as determined
by HRTEM, N2 sorption, gas permeation and grazing incidence
small-angle X-ray scattering studies. Mesoporous organic polymer
resin and carbon based solids are also synthesized in this strategy
[64]. Beside these general methods each type porous solids like sili-
ca, phosphates, mesoporous polymers, carbons, oxides etc. have in-
dividual specific methods which are applied to synthesize those
under variable conditions. In addition Ariga et al. have reviewed
the recent research to design nanomaterials into organized struc-
tures, called nanoarchitectonics which involve the syntheses of
mesoporous silicas, metal oxides, semiconductive materials, metals,
alloys, organic composites, biomaterial composites, carbons, carbon
nitrides, and boron nitrides, as innovative components [65]. All
these materials are being discussed in the following section under
Fig. 7. Formation of mesoporous structures: (a) via co-operative self-assembly, (b) via true liquid–crystal templating process.
the category of purely inorganic, organic–inorganic hybrid and
purely organic porous materials (Scheme 1).
2.5.1. Synthesis method and mechanism of purely inorganic mesoporous
materials
Syntheses of silica, non-silica transition and non-transition metal
oxide, metallophosphate, sulphide based materials are illustrated under
this topic.
2.5.1.1. Silica based mesoporous materials. Due to several advantages like
a great variety of possible structures (flexibility of tetra-coordinated
silicon atom), a precise control of the hydrolysis-condensation reac-
tions (because of lower reactivity), enhanced thermal stability of the
obtained amorphous networks (no crystallization upon thermal treat-
ment) and strong grafting of organic functions as well as for the appli-
cations in numerous promising fields extensive work is going on over
silica-based mesoporous materials since the discovery of M41S family
of mesoporous silicas. Mesoporous pure silica and silica based mate-
rials are generally prepared in endotemplate method under hydrother-
mal condition using basic or acidic media.
Hydrothermal condition is actually a sol-gel process consisting of a
number of steps. Initially, formation of surfactant self-assembly occurs
via TLCT mechanism to form a homogeneous surfactant solution in com-
mon solvent media (usually aqueous). Then silicate precursor, such as
tetraethyl or tetramethyl orthosilicate (TEOS or TMOS) or inorganic so-
dium silicate is added to the surfactant solution when it gets hydrolyzed
under acidic or basic condition to form a silicate oligomer sol. Next,
these oligomers are condensed with surfactant micelle via coopera-
tive assembly and aggregated to form inorganic–organic hybrid,
which finally precipitates in the form of a gel. The gel is treated hy-
drothermally for further condensation, solidification and reorganiza-
tion of the material to an ordered arrangement [51,66]. Finally, after
certain time the resultant product is cooled, filtered, washed and
dried (Fig. 9). Ordered mesostructured silica material is obtained from
this as-synthesized solid after the removal of surfactant through calci-
nation or solvent extraction [67,68].
In basic condition during hydrolysis silica precursor remains as sili-
cate anion (Fig. 9) and condensation, polymerization as well as cross-
linking take place in the pH range of 9.5 to 12.5 [51]. This is the most
well-known, old and convenient method of silica synthesis. Mesoporous
MCM-41, MCM-48 [69], etc. and various transition as well as non-
transition metal doped silica [70,71] are synthesized using this strategy.
Commonly, CTAB, SDS are used as surfactants [70], sodium hydroxide
(NaOH), potassium hydroxide (KOH), ammonia solution (NH3.H2O),
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41 29

Fig. 8. Schematic representation of ‘exotemplate’ method.

tetramethylammonium hydroxide or TMAOH [(CH3)4NOH] and
tetraethylammonium hydroxide or TEAOH [(C2H5)4NOH] are used as
base to control the pH of the synthesis gel. There is also example of
mesoporous silica (HMS-3) synthesis in basic media at freezing tem-
perature [72]. The discovery of SBA type ordered mesoporous silica
materials having thick pore walls and large pores synthesized with
the use of non-ionic triblock copolymers like Pluronic P123 and
F127 as SDAs under acidic conditions is an important milestone in
this context [73]. In highly acidic media the oxide linkage of Pluronic
surfactants breaks through protonation and micelle formation oc-
curs. Silica precursor forms cationic species (Fig. 9) which condenses
with surfactant micelle [74]. It is believed that acidic condensation of
silica is slower than basic. Hydrochloric acid (HCl), nitric acid
(HNO3), sulphuric acid (H2SO4) sometimes weak acids like phospho-
ric acid (H3PO4), acetic acid (CH3COOH) etc. are also used as catalyst
for silica synthesis under this condition. The hydrothermal tempera-
ture for silica remains in the range of 263 K to 303 K depending upon
the surfactant nature [51]. Though medium room temperature is
preferred for gaining high crystallinity owing to slow hydrolysis. A
large mesopore of 6–7 nm with consecutive generation of small mi-
cropore on the amorphous pore wall of SBA type material is the
main characteristic of using this type of Pluronic surfactant.
Miyazawa et al. has also beautifully established that this micropore
volume within mesoporous pore wall can be controlled by varying
temperature as well as Si/surfactant ratio [75]. Following the above
strategies other heteroelements like Ti, V, Co, Fe, Mn, Cr, Zn, Cu, W
etc. which have similar cationic size and coordination sites same as
Si, are experimentally incorporated into the silicate framework,
which showed high thermal stability and high surface area together
with multipurpose applications [76–79]. Most of these doping with

Fig. 9. Stepwise formation of mesoporous silica material [68].

30 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
high loading occurs in basic media having S +I − interaction whereas
there are few reports of acidic media synthesis with low metal incor-
poration [80].
2.5.1.2. Non-silica based mesoporous materials. The surfactant templating
strategy to the synthesis of non-silica based mesostructure; mainly
metal oxides have been commenced since 1993 [81]. Other several
types of non-siliceous mesostructured materials like phosphate, sulphide
based materials and also different types of mesoporous metals are
known [82–85]. Sayari has summarized the synthesis of mesoporous
molecular sieves (pure and modified silicates, other metallic oxides
and sulfides as well as aluminophosphates of MCM-41, MCM-48, SBA-n,
MSU-n structures) under a wide range of conditions in the presence of
cationic, anionic, gemini, or neutral surfactants [86]. The pore size of
these mesostructured materials may be adjusted from ca. 2–10 nm
using different strategies. Because of their unique flexibility in terms
of synthesis conditions, pore size tuning and framework composition,
these materials have been targeted for a number of potential applica-
tions, particularly in catalysis.
Mesoporous oxides have the great potential to various fields such
as heterogeneous liquid phase catalysis [87], photocatalysis [56],
magnetism [88], optoelectronics [89], integrated optics [90] and bio-
technology [63] etc. It is often observed for transition metal ions that
the multitude of possible coordination numbers and oxidation states
has a pronounced influence on the observed composite mesoporous
materials as expected. After the first successful approach towards the
synthesis of mesostructured titania [16] various mesoporous metal
oxides and mixed oxides of Nb, Ta, V, W, Zr, Sn, Hf, Al, Zn, Cu, Ni,
Al etc. have been synthesized through the mediation of electrostatic,
hydrogen-bonding, covalent and van der Waals interactions be-
tween metal and template [91–94].
Mesoporous oxides having same type of extended frame-
work containing metal-oxygen bonds like silica and silica based
mesostructured materials should have similar synthetic conditions.
However, very little attention was paid on oxide based mesostructured
materials compare to other silica based composites. The reason behind
is mainly [34]:
A. The high reactivity toward hydrolysis and condensation of transi-
tion metal oxide leads to uncontrolled phase separation between
organic and inorganic components, yielding non-mesostructured
materials, but porous gels.
B. The redox reactions, the possible phase transitions and the crystalli-
zation processes are often accompanied by the collapse of the struc-
tural integrity.
C. Synthesis procedures are extremely sensitive to many external pa-
rameters, leading to irreproducible results in some cases.
The first stable oxide (mesoporous titania) was prepared by
controlled hydrolysis of titanium isopropoxide in the presence of
tetradecylphosphates through ‘modified sol-gel method’, using
acetylacetone as a chelating agent [16]. Though, IR spectroscopy mea-
surements revealed the presence of phosphate groups after calcination
of the sample at 623 K. This result prompted the researchers to
design other mesostructured transition metal oxides via different
synthetic routes.
The synthesis of porous oxides can be carried out via both
‘exotemplate’ and ‘endotemplate’ methods. For all the methods it was
found that in order to form a successful mesophase of oxides, three con-
ditions should be satisfied [30]. First is the ability of formation
polyanions or polycations by the inorganic metal precursor to
allow multidendicity. Second must be the ability of polyanions or
polycations to condense into rigid walls (Fig. 10A). Finally, a charge
density matching, which is an essential to explain the interaction
between the surfactant and the inorganic species and thus to direct
the formation of a particular mesophase [94]. Recently, P. Bruce
and his co-workers have reviewed different template synthesis and
applications of ordered mesoporous metal oxides supplying clear in-
formation about the mechanism [95].
In ‘endotemplate’ or soft-templating route mesoporous oxide ma-
terials are generally synthesized in hydrothermal method [91], at low
temperature (freezing) [90] or at room temperature [96]. In all the
above methods template molecules self-assemble prior or simulta-
neously with the inorganic metal precursor (Fig. 7) which form a
hydroxo species and interact with template molecules in electro-
static way to form metal–template composite in aqueous sol–gel
process [34]. After the removal of template by calcination or
solvent-extraction we get the desired solid porous metal oxide
(Fig. 10B). A large variety of metal oxides have been synthesized
through supramolecular self-assembly method by proper selection
of a cationic, anionic or non-ionic surfactants. Hydrothermal synthe-
sis of hydrous crystalline mesoporous RuO2 is reported by Oh et al.
using cationic surfactant hexadecyltrimethylammonium chloride
(C16TMA +Cl −) via chloride anion mediated S +X -I + interaction
of cationic surfactant and ruthenium nitrosyl precursor [97].
Mesoporous mixed oxides can be prepared through hydrothermal
method using Pluronic P123 template which is observed in case of
mesoporous titania-silica or Ga-Nb mixed oxide (synthesized via
self-assembly hydrothermal assisted approach or SAHA method)
[98,99]. Anionic template SDS is also employed for the synthesis of high-
ly ordered mesoporous mixed oxide TiO2-Fe2O3 phase [100]. In the EISA
method [101,102] nonaqueous sol–gel route is employed, where organ-
ic solvents like ethanol, propanol etc. are used as reaction medium. This
method for the synthesis of mesostructured materials has proven to be
an extremely useful process for both controlling macroscopic form (thin
films, membranes, and monoliths) and enabling the synthesis of a series
of mesostructured metal oxides [62]. Because of using non-aqueous
media and block copolymer SDA the hydrolysis rate as well as the
redox reaction, phase transformation etc. have been minimized in this
nonaqueous sol–gel method [35]. This method based on supramolecular
self-assembly of surfactant has several advantages than aqueous sol–gel
process for achieving better control over particle formation, high crys-
tallinity at relatively moderate reaction temperature (373–573 K) and
homogeneous particle morphology within one reaction system [103].
Here, the evaporation of the volatile solvent (usually ethanol) following
deposition concentrates the surfactant molecules and inorganic precur-
sors, driving their co-assembly to form ordered mesophases. Subse-
quent aging, heat or chemical treatments induce inorganic precursor
condensation and lock in the mesostructure (Fig. 11). The addition of
metal chlorides to an alcohol generates HCl in situ, yielding stable
chloroalkoxy precursors. The slow introduction of moisture from the
ambient environment causes these precursors to partially hydro-
lyze. These stable, hydrophilic precursors are arranged by the
block copolymer SDA. Different mesoporous transition and non-
transition metal oxide and mixed oxides with semicrystalline
frameworks have been synthesized in EISA route in highly acidic
alcoholic solutions in presence of non-ionic Pluronic surfactants
F127, P123 etc. [64,104,105]. Mesoporous titania thin film with con-
trolled size and wall thickness is produced recently in this method
using a new triblock copolymer template PEO–PB–PEO structure
(PEO = poly(ethylene oxide) and PB = polybutadiene) [106]. This
EISA method is widely employed for the synthesis of a huge number
of mesoporous binary and ternary mixed oxides [107–109]. A delayed
hydrolysis and condensation of the reacting precursors in order to
achieve sufficiently ordered arrangement and homogeneous mixture
of multiple oxides via EISA method is observed in case of silica–germa-
nia mixed oxide [110].
Another process for mesoporous oxide synthesis is ‘exotemplate’
or hard-templating or nanocasting method (Fig. 8) pioneered by the
group of Ryoo [59,60]. It is one of the most important strategies for
synthesizing mesostructured transition pure or multi metal oxides.
Recently, many interesting porous metal oxides and mixed oxides
have been synthesized using this method [111,112]. The method is
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41 31

Fig. 10. A: Stabilized highly reactive metal precursor for metal oxide synthesis and B: interaction of metal-surfactant to form mesostructure.

Fig. 11. Schematic model for EISA method.

32 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
not discussed here elaborately since this is beyond the scope of this
review.
Although many open-framework and layered metal phosphates
with diverse compositions and properties have been developed
[113–115] their applications are constrained by the lack of large sur-
face areas and the dominance of small pores or interlayer spaces.
Mesoporous metallophosphates having good surface area are of
keen attention in this respect, due to their applications in the fields
of catalysis, ion exchange, proton conductivity, intercalation chemis-
try, photochemistry, and materials chemistry [116]. For playing a
crucial role as active solid catalysts in various acid-base catalysis,
redox catalysis and photocatalytic processes [117,118] much works
have been devoted to the synthesis of mesoporous metal phosphate
materials [119,120]. The discovery of aluminophosphates (AlPO,
similar to zeolite), AlPO4, in 1980s with reasonable thermal stability
and novel structures is an important development in this area [121].
But the material was microporous in nature synthesized using non-
surfactant organic amine salt. Probably the first mesoporous phos-
phate synthesized in surfactant mediated pathway was aluminium
and gallophosphate reported by Holland et al. [119]. In this context
a rich varities of metal phosphates/phosphonates with mesoporous
framework have been reported, synthesized via ionic, non-ionic
templating routes [122–125].
Porous inorganic phosphates are oxide type materials with open
framework and the synthesis of those phosphates can be carried out
following the same procedures utilized for mesoporous silica as well
as oxides i.e. the same supramolecular self-assembly of surfactants
followed by the interaction of ionic or non-ionic inorganic metal phos-
phate with charged or neutral template and further condensation to
form mesoporous solid. Mesoporous phosphates generally have the
framework structure alike porous oxide consisting tetrahedral or octa-
hedral MO4 or MO6 unit, but here is alternation of MO4 and PO4 unites
in the moiety. Mesoporous aluminophosphate shows an alternative
tetrahedral AlO4 and PO4 unites, whereas silicoaluminophosphate has
another additional SiO4 unit connected by shared oxygen molecule
[126]. Similar to oxides, phosphates can be synthesized both in aqueous
and nonaqueous sol–gel routes. In aqueous sol-gel route generally, CTAB
[126], SDS, tetradecyltrimethylammonium bromide (TTBr) [127] etc. are
used as surfactants, inorganic phosphorous sources are phosphoric acid
(H3PO4) [126], disodium hydrogen phosphate (Na2HPO4), diammonium
hydrogen phosphate etc. [127] and pH is adjusted by liquid ammonia,
TMAOH, NaOH etc, though preferably TMAOH results more stable struc-
ture [126]. For e.g. surfactant template approach using CTAB has been
successfully employed for the synthesis of mesoporous highly acidic
zirconium phosphate at room temperature in aqueous sol–gel method
[128]. Nonaqueous sol–gel route is also important to synthesize well
arranged mesoporous phosphates where ethanol, propanol etc. are
used as nonaqueous solvents [129]. Hydrothermal treatment or some-
times room temperature helps to form the desired mesostructure
[126,127]. Sometimes EISA method is effective to form mesoporous
metallophosphates and bioactive glasses [130–132] In Fig. 12 we have
provided a schematic presentation of the synthesis of mesoporous
metallophosphate by using EISA method. Kapoor et al. has established
convenient room temperature sol–gel method for the synthesis of
mesoporous high surface area zirconium–titanium mixed phosphate
using cationic surfactant octadecyltrimethylammonium chloride
(C18TA +Cl −) [133]. Synthesis of mesoporous metallophosphate
via hard-template route or exotemplate' method are also very common
now-a-days. A report by Luo et al. for the synthesis of cubic ordered
yttrium phosphate using KIT-6 as hard template [134] and by Xia et
al. for mesoporous hydroxyapatite (Ca10(PO4)6(OH)2) using CMK-3
[135] is worthy to mention here.
Analogous to the oxide-based porous materials there are inorganic
chalcogenides (sulfides and selenides), which have received an in-
creasing amount of attention in modern time after Stupp et al. first re-
port of mesoporous cadmium sulfide and selenide in the year 1996
[136]. Use of porous sulfides as semiconductors, sensing material,
electronics [137] etc. makes those an imperative in nanoscience and
nanotechnology for which many sulfides and selenides of Zn, Sn, Cd,
Mo, Fe, Ga and so on are synthesized in surfactant mediated supramo-
lecular pathway [138] similar to silica. In case of porous sulfide syn-
thesis hydrogen sulfide (H2S) is used as sulfide source along with
the respective metal salt precursor and ionic or non-ionic organic
template leads to the formation of the particular metal sulfides via
LCT mechanism [94].
Zero valent transition metals are very important in many catalytic
processes and hence the synthesis of nanostructured metals with high
surface areas and controlled porosity imposes a significant challenge
on materials scientists. In 2008, Yamauchi et al. reported the aqueous
syntheses of mesostructured metallic platinum with large pore diame-
ter exceeding 10 nm, i.e. giant mesocages by surfactant liquid–crystal
templating pathway [84]. Hao et al. has nicely summarized main
principles governing the usage of soft vesicle in the synthesis of
hard materials (mainly porous metals and metalic nanoparticles)
and detailed procedures for vesicle templating and the characteriza-
tion of the synthetic mechanisms [139].
2.5.2. Synthesis method and mechanism of organic–inorganic hybrid
mesoporous materials and Periodic Mesoporous Organosilicas (PMOs)
In addition to the purely inorganic porous materials, another impor-
tant way of modifying the framework structure of nanoporous material
is the incorporation of organic components, either on the silicate sur-
face, inside the silicate wall, or trapped within the channels. Organic
functionalization of these solids permits the tuning of surface properties
(e.g. hydrophilicity, hydrophobicity, binding to guest molecules), alter-
ation of the surface reactivity, protection of the surface from attack
along with modification of the bulk properties of the materials, and at
the same time stabilization of the materials towards hydrolysis [140].
In view of the advantages and properties of these materials, they can
find wide range of applications in catalysis [141], adsorption chemistry
[142], electronics [143], sensors [144], environmental technology [145]
and bioapplication [146] etc. introducing suitable functional groups
into the walls. Stein et al. have described the generalized methods
of preparing organic–inorganic hybrid mesoporous silicates with
uniform channel structures bearing both reactive and passive
organic groups in the porous solids by grafting methods or by co-
condensation under surfactant control [147]. Functional groups
could be placed selectively on the internal or external pore surfaces or
even within walls of the mesoporous solids. Such functionalized hybrid
mesoporous silicates are especially important in catalysis, sorption of
metals anions, and organics reactors for polymerization, fixation of bio-
logically active species, and optoelectronics.
After successful introduction in 1999 [148], a number of organic–
inorganic hybrid silica or periodic mesoporous organosilica (PMO)
materials with various organic bridging groups have been synthe-
sized [149–157]. Owing to the stability, selectivity, high density of
binding sites and ease of modification these organic-inorganic hybrid
materials have versatile potential in different fields of research. These
PMOs can be synthesized by using a large variety of organosilane
compounds [(R′O)3Si\R\Si(OR′)3, R = CH2CH2, C6H4, etc., R′ = CH3,
C2H5 etc.], where two trialkoxysilyl groups connected by an organic
bridge. These materials have a homogeneous distribution of organic
fragments and silica moieties within the framework. Thus these ma-
terials can be designed to carry from simple to bulky functionalities.
A large variety of organic bridging groups starting from ethylene,
benzene to complex large heterocyclic bridging groups [150] as well
as fluorophore moieties [157] can be incorporated inside the
mesporous pore walls of these PMOs using soft-templating routes.
Corma et al. have developed a chiral periodic mesoporous organosilica
ChiMO with 2D-hexagonal periodicity in the PMO framework using
chiral vanadyl salen complex bearing two peripheral trimethoxysilyl
groups as organosilane precursor [155]. This chiral PMO gave 30%
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
Fig. 12. Schematic representation of mesoporous phosphate synthesis in EISA method [132].
enantioselectivity in the cyanosilylation of benzaldehyde. Self-
organization in these organic-inorganic hybrid materials leads to
molecular-scale and mesoscale periodicities. Inagaki et al. has de-
scribed the synthesis of organosilicas with molecular periodicity
of organic units formed by self-organization of bissilylated organic
monomers without employing templates, as well as PMOs with meso-
scale periodicity in the presence of soft templates [156]. The unique
structural features of these materials make them potentially useful in
a wide range of advanced applications, such as selective separation,
sensing, catalysis, optoelectronics, light-harvesting, etc [156].
Organic–inorganic hybrid materials comprise mainly the silica
based materials though there are some reports on hybrid phosphates
[6,158], microporous metal organic frameworks or MOFs [159] and
polymers (discussed later). Hybrid phosphates and phosphonates
are mainly synthesized in the absence of template or by using single
molecule templates. Kimura has synthesized few organic-inorganic
hybrid mesoporous alumnophosphates via surfactant templating
route [160]. One of the aluminum organophosphonates (AOPs) with
methylene groups inside the inorganic-organic hybrid frameworks
have been synthesized by using oligomeric surfactants (C(16)EO(10)
and C(16)EO(20)) and triblock copolymers (EO(80)PO(30)EO(80), EO(106)
PO(70)EO(106), and EO(20)PO(70)EO(20)). Some of these materials have
periodicity in pore arrangement and are potential candidates for
adsorption, ion-exchange and catalytic applications.
Organic functionalized silica molecules can be synthesized in
three pathways depending upon supramolecular templating mecha-
nism (Fig. 13). First one is the “grafting” method where the pore sur-
face of a purely inorganic silica material is ‘grafted’ by subsequent
modification with other organic groups or organosilica precursors.
Second one is the “co-condensation” method where simultaneous
condensation of corresponding silica and organosilica precursors
‘co-condensed’ to form hybrid silica. If uniform surface coverage with
organic groups is desired in a single step, the direct co-condensation
may be the first choice which provides better control over the amount
of organic groups incorporated in the structure. However, products
obtained by post-synthesis grafting are often structurally better
33
defined and hydrolytically more stable. The third type is periodic
mesoporous organosilica (PMO) formation method i.e. bridging or-
ganic units are directly incorporated in the three-dimensional net-
work structure of the silica matrix through two covalent bonds
generally in “co-condensation” route [161–163] and thus distributed
homogeneously in the pore walls, which could effectively bind an
active catalytic site at the mesopore surface.
At the very beginning organic functionalized mesoporous silicas
were synthesized via post-synthetic modification or post-grafting of
the inner surfaces of mesostructured silica materials. In this proce-
dure, generally the condensation of organosilanes is carried out
with free surface silanol groups of the mesostructured silica resulting
in an inorganic framework with an organic layer grafted onto this
framework. Different organosilane precursors commercially available
can be used in this purpose (Fig. 14). On proper modification with
other organic functional groups before or after grafting a great variety
of organo functional groups can be incorporated into the silica frame-
work. For example \SH group on oxidation by dilute aqueous hydro-
gen peroxide can be converted into reactive \SO3H group, \NH2 or
\Cl group on condensation with aldehydes, other amines can gener-
ate newly functionalized silica. Synthesis of an \COOH functionlized
SBA-15 material [164] using APTES as organosilane source has been
depicted schematically in Fig. 15A. Utilization of azide functionalized
SBA-15 to form a new free amine based organosilica via [3 + 2] Azide–
alkyne cycloaddition ‘click’ reaction is an effective strategy for post-
functionalization of the surface of mesopores by a reactive organic moi-
ety [165]. Post-grafting method has several advantages. Firstly, the
initial mesostructure of the silica material is generally preserved,
depending on the amount of grafted organosilane. Secondly, owing to
a huge number of suitable organosilanes, a wide range of organic func-
tionalized silicas can be synthesized with different chemical and physi-
cal properties. Again if bulky organosilanes are used, these groups can
selectively be grafted at the pore openings, leading to complete
closure of the pores thus sealing the air within and giving rise to
low-к materials [162]. Many large highly reactive, chiral organic groups
like 2,2′-bis(diphenylphosphinooxide)-1,1′-binaphthyl (I-BINAPO) has
34 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
been successfully utilized to synthesize highly ordered 2D-hexagonal
PMO [166]. Using these post-synthesized modification procedures or-
ganic functional groups incorporated in the silica matrix may be found
both on surface i.e. inner and outer surface of the silica pore wall. A
very useful technique for controlling the site-selective functionalization
of mesoporous silica is the condensation organosilane with template
filled as-synthesized silica particles in order to minimize the inner
wall functionalization of silica to a great extent. Here the amount and
density of organic group on the outer surface of silica can be controlled
by adjusting organosilane to silane ratio [167].
Compared to the post-grafting technique, the co-condensation
method is a one-pot synthesis procedure. Here, the hybrid material
is prepared through co-condensation of tetraalkoxysilanes with
terminal trialkoxyorganosilanes or bis trialkoxysilane (some of
which are shown in Fig. 14) in the presence of a structure directing
organic template (Fig. 15B). There are also a number of interesting
organosilanes which can be prepared in the laboratory to synthe-
size new PMO [154]. The organic functionalities of these materials
are incorporated into the framework during the formation of
mesostructure and hence more regularly distributed throughout
the network compared to the organosilica materials obtained via
the grafting method [168]. However, the homogeneous distribution
of the organic units is largely dependent on the hydrolysis and con-
densation rates of the silica and organosilica precursors. Rate differ-
ences for the hydrolysis or condensation process of the different
precursors can lead to a significant amount of self condensation.
Fig. 13. Synthetic pathways of organic–inorganic hybrid mesoporous silica: 1. Post-synthesis functionalization or post grafting, 2. Co-condensation or in situ grafting, and 3. Organic
bridged periodic mesoporous silica.
The integration of organic bridges in the pore channel walls make
organic-inorganic hybrid materials very unique as in the case of PMO.
Having a high organic loading these PMOs can have very narrow pore
size distributions, high specific surface areas, large pores, thick pore
walls and large pore volumes. Furthermore, as the organic units are
embedded in the channel walls, these functionalities are easily acces-
sible for further modification. The most obvious advantage is their
pore sizes, which can be engineered from 2 to 30 nm, while retaining
narrow pore size distributions. This broadens the applicability of
PMOs in industrial as well as pharmaceutical world. The higher cata-
lytic activity is attributed to the textural and morphological features
of these materials in addition to the improved hydrophobicity inside
the pore channels.
In a generalized synthesis of a PMO via co-condensation route, the
bridging organosilane precursor of the type (R1O)3Si\R\Si(OR1)3 is
allowed to hydrolyze along with TEOS under acidic or basic pH condi-
tions in the presence of a soft template. This is followed by hydrother-
mal treatment to yield the as-synthesized hybrid material, which on
template removal by acid extraction results PMO material grafted
with organic group (R) in the pore wall (Fig. 16). Calcination is not
suitable to remove the template molecules as in this case the materi-
al itself bearing organic group at its pore wall, which could be burnt
out from the material during calcination. Initially, bridging R was
limited to simple organic groups such as ethylene, phenylene and
thiophene etc. [148,170], but recent improvement of synthetic pro-
cedures of organosilane precursors has enhanced the possibility of
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
Fig. 14. Different organosilane precursors for synthesizing organic–inorganic hybrid mesoporous silicas including PMOs.
incorporation of a variety of organic groups ranging from hydrocar-
bon and metal complexes to heteroaromatics in the silica framework
[150]. Multifunctional PMO can be synthesized using two or more
different organosilane precursors. Beside these organically function-
alized silicas or organosilicas synthesized via any of the above proce-
dures, introduction of metal or metal complex in the organic
functionalized mesoporous silica are an interesting material for ca-
talysis, adsorption study, optics, magnetism or sensors. Mesoporous
organosilica having large tunable porosity, high surface area as well
as containing donor sites like \NH2, \SO3H, \COOH, \OH, \CN
groups offer a good possibility of metal incorporation and their stabi-
lization on the silica pore wall via coordination or covalent bonding.
Various transition metal ion or complexes of Mn, Fe, Co, Cu, Pd, Pt etc.
are extensively used in this purpose to introduce new property in the
PMO material. Periodic mesoporous silica containing diimine moiety
found an excellent scavenger for grafting of oxo-vanadium Schiff
base complex and the resulting material showed excellent catalytic
efficiency in the liquid phase partial oxidation reactions [169].
2.5.3. Synthesis method and mechanism of purely organic mesoporous
materials
Porous organic polymers are attracting increasing attentions in re-
cent time for their wide scope in surface chemistry, especially in
35
adsorption and catalysis [171–174]. Carbon based porous materials
are also indispensable due to their abundance and sustainability.
Their applications vary widely, e.g. as electrode materials for batte-
ries, fuel cells, and supercapacitors, as sorbents for separation pro-
cesses and gas storage, bioapplication and as supports for many
important catalytic processes [175–179]. Their use in such diverse ap-
plications is directly related not only to their superior physical and
chemical properties, such as electrical and thermal conductivity,
chemical stability, and low density, but also to their wide availability.
Extensive applications of these porous ordered carbons as ‘hard tem-
plate’ for designing highly ordered mesoporous transition metal ox-
ides and mixed oxides, zeolites, nitrides are also well established
[180–182].
2.5.3.1. Mesoporous polymers. Only a few studies have appeared so
far on the soft templating strategy for the synthesis of ordered
mesoporous polymers [183–187]. The choice of the polymer precursor
is the key to the successful organization of the organic-organic
mesostructures. The conditions for polymer formation which have to
be fulfilled are (a) dissolution in the same medium as the surfactants,
(b) interaction with the template molecules, (c) organizing itself neatly
around the template, (d) further polymerization, preferably forming a
rigid polymer structure, without losing the interaction with the
36 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
Fig. 15. A: Schematic diagram for the synthesis of an acid (\COOH) functionalized
silica SBA-15 (AFS-1). B: Schematic pathway of synthesis of a \NH2 functionalized
silica in co-condensation method.
template and (e) finally the removal of template without destroying
the polymer mesostructure. Prior to the development of self-
assembly soft-templating syntheses, mesoporous polymers were main-
ly synthesized by a hard-templating approach. In this approach, a
monomer is infiltrated into a hard template (for example, an
opal-like colloidal assembly of silica), which is removed after polymeri-
zation to give mesoporous polymer networks [188]. The soft-templating
self-assembly approach represents a breakthrough allowing the efficient
synthesis of mesoporous polymers (Fig. 17). A review on the designed
synthesis of mesoporous solids, including mesoporous polymers, via the
nonionic surfactant templating method, has been published recently
[189]. Most of the mesoporous polymers are prepared by the EISA (evap-
oration induced self-assembly) method, typically using ethanol as solvent
(Fig. 17). However, similar materials can also be prepared in basic aque-
ous media by a liquid crystal templating or cooperative assembling
pathway [190].
Most of the reported mesoporous polymers are phenol-formaldehyde
(resol) resins (template polymer), mainly synthesized as a precursor for
mesoporous carbon. Mesoporous phenol-formaldehyde resin can be
readily prepared through the assembly of oligomers with surfactant,
followed by polymerization and surfactant removal. More specifically,
the phenolic oligomers are prepared readily by heating phenol and
formaldehyde in a molar ratio of 1:2 in a basic aqueous medium at
343 K for 1 h. After the reaction, the solution is neutralized with
hydrochloric acid and the water is removed under vacuum, forming
the oligomers. This oligomer and a Pluronic surfactant on evaporation
induced self-assembly (EISA) process lead to formation of an or-
dered surfactant-oligomer nanocomposite thin film which on sub-
sequent heating at 373 K for 24 h polymerizes further and forms
mesostructured surfactant-polymer nanocomposite containing
liquid-crystalline surfactant [64]. Decomposition of the surfactant
by heating at 623 K for 5 h in nitrogen inert atmosphere or by
sulphuric acid (H2SO4) extraction method produces mesoporous poly-
mer thin films (Fig. 17). Mesoporous polymers with ordered two di-
mensional hexagonal (p6mm), three dimensional cubic (Im3m) or
lamellar structures [64] can be synthesized using Pluronic surfactant
F127 (EO107PO70EO107) or P123 (EO20PO70EO20, EO = ethylene oxide,
PO = propylene oxide). In similar fashion, phloroglucinolic oligomers
can be prepared by heating phloroglucinol with formaldehyde in
acidic water-ethanol at room temperature. Like silicate clusters,
these oligomers contain a large number of hydrophilic hydroxyl
groups, which allow them to form hydrogen bond with a Pluronic
surfactant.
2.5.3.2. Mesoporous carbons. Mesoporous carbons are often produced
by using a mesoporous ordered silica material as a hard-template
[191]. More recently, also polymers (e.g. polyacrylonitrile) synthe-
sized in situ in the pores or voids of mesoporous silicas have been
used as carbon precursors, leading to mesoporous carbons which
are in some cases even partially graphitic [192]. Microporous carbon
can be prepared using zeolite hard template as reported by Kyotani
et al. [193]. Polymer beads, anodic aluminium oxide, silica/alumino-
silicate gel etc. are also reported hard-template for synthesizing
mesoporous carbon [194]. The process of producing mesoporous car-
bon using exocasting is indirect and needs aggressive chemicals to re-
move the silica matrix. This hard-template route used to synthesize
mesoporous carbon materials are also time-consuming or produces
carbon with a disordered pore structure [195]. Therefore it would be
more elegant and desirable to produce mesoporous carbon by a di-
rect templating mechanism using amphiphilic molecules.
But, the preparation of mesoporous carbon materials with ordered
open pore structures via a supramolecular templating approach is
difficult, due to the intrinsic characteristics of organic molecules
and high formation energy of C\C bonds. The basic requirements
for synthesizing porous carbon using soft-template are (a) high
ability of the precursors to self-assemble within the nanostructures,
(b) simultaneous presence of minimum one pore-generating as well
as one carbon-generating precursors, (c) pore-generating component
should have the stability to maintain the temperature required for curing
the carbon-yielding component but must be readily decomposed during
carbonization having least carbon yield and 4) carbon-yielding com-
ponent must have the ability to form a highly cross-linked polymeric
material which retains its nanostructure during the removal of the
pore-generating template [195]. There are very few precursors
which fulfill the above requirements. Although, some very interesting
studies on the soft-templated synthesis of mesoporous carbons have re-
cently been reported [196,197]. One of the most successful ways in
achieving mesoporous carbon through this soft-templating pathway is
to synthesize mesoporous polymers, with high content of carbon.
Mesoporous polymers obtained by using various precursors (as discussed
earlier) can be converted to their corresponding carbons with controlled
pore structures by simply carbonizing the polymer template in inert
atmosphere (nitrogen or argon) applying temperature up to 1173 K.
In presence of block copolymer F127 mesoporous polymer is derived
from self-assembled resorcinol-formaldehyde precursors mediated
by the I +X −S + and H-bonding interaction in highly acidic media. Fi-
nally mesoporous carbon is obtained from this polymer in a well repro-
ducible approach [198]. A very interesting pathway to produce
mesoporous carbon with increased microporosity is reported by
Jaroniec and co-workers, where KOH is used for the activation of phe-
nolic resin polymer derived porous carbon in order to simultaneous
preservation of micro and mesopores [199].
3. Properties and applications
The physical and chemical properties of the mesoporous materials
depend on the specific surface area, tunable pore diameter, pore
volume and cubic, hexagonal arrangements of pores as well as
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41 37

Fig. 16. General synthetic pathway for periodic mesoporous silica (PMO). R = bridging organic group.

Fig. 17. Surfactant directed synthesis of a mesoporous phenol–formaldehyde polymer from oligomer building blocks. Mesoporous carbon is obtained after carbonization.
38 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41

Table 2
Various applications of mesoporous materials.

Field Type of Name of the material Applications References

properties

Adsorption Biomolecular MCM-41, MCM-48, SBA-15, CMK-3, CMK-1, OMS Separation of biochemicals, adsorption of amino acid, vitamins, [178,206,207]
adsorption proteins, CO2
properties

Toxic ion Mesoporous alumina, PMO, titanium-silico phosphate Fluoride, As(III/V), Cd(II), Hg(II), Fe(III), Cu(II), Zn(II) etc. [130,154]
adsorption adsorption to purify water
properties

Gas adsorption Mesoporous polymers, Organically functionalized N2, H2, CO2 gas adsorption and storage [72,142,173,208]
properties silica

Adsorption and Mesoporous SiO2\ZrO2, silica nanoparticles, calcium Drug delivery of bisphosphonate, adsorption and desorption of [209–212]
release phosphate, Au capped silica, DNA, dyes and drugs in human cell
properties

Catalysis Redox properties Mesoporous titanium–phosphorous mixed oxide, Partial oxidation of styrene, oxidation of cyclohexene to adipic [91,130,213]
Ti\Al\SBA-15, mesoporous mixed oxides acid, reduction of nitroarenes

Acid-base Mesoporous zinc-titanate, Zn doped silica, \COOH Friedel-Crafts benzylation, esterification, transesterification, base [55,57,70,104,141]
properties functionalized SBA-15, zirconium phosphate catalyzed Knoevenagel condensation, Xanthenes preparation,
biofuel production via esterification

Other synthetic Mesoporous NiO\ZrO2, Pd doped porous polymer, C-S cross coupling, C-C cross coupling, Mannich reaction, [93,187,214,215]
name reactions polyoxometalate doped silica, Fe3O4@silica Biginelli condensation reaction

Photocatalytic Mesoporous TiO2, ZnO\CeO2 binary oxide, tantalum Photodegradation of dye, decomposition of dye, photosplitting of [6,216,217]
properties oxide water

Optics, Magnetic Mesoporous Fe3O4 Ferromagnetism [218]

electricity, property
magnetism

Optical Luminescent PMO, rare earth doped silica, tungsten Chemosensing [157,219,220]
properties oxide

Electrical Nanostructured SnO2 Dielectric effect [221]

properties

Optoelectronics Mesoporous TiO2, ZnO, TiO2 nanoparticles Photocurrent enhancement on dye doping, DSSC [56,90]

Sensing Gas sensing Mesoporous SnO2, TiO2 materials, ordered CO, NH3, H2, NO2, CH4 etc. gas sensing, [222–224]
property mesoporous ZnO, In2O3, WO3

Ion sensing Azo compound functionalized organosilica, Optical and electro-chemical sensing of cations like Fe(III), [144,225–229]
property fluorescent grafted silica, dye doped silica, porous Zn(II), Cu(II), \NH2 gr. etc. and anions like \CN, citrate, borate,
carbon nitride carboxylate etc.

Biosensing Mesoporous titania MSN, organically functionalized Detection and sensing of glucose oxidase, protein, glucose etc. [230,231]
property silica,

pH sensing role Functionalized silica pH sensor of a particular medium [227,232]

on the framework building metals and non-metals present in
the mesostructures. As a consequence, versatile applications of
mesoporous materials in different fields highlight it an indispensable
topic of research in nanoscience and technology. For example the
field of heterogeneous catalysis is highly benefited from the
surfactant-assisted synthesis of novel mesoporous materials and
will grow day by day with ongoing increased surface modification
and new composition of mesoporous framework [15]. The semicon-
ducting properties of Ti, Zn etc. based mesoporous oxides have found
tremendous importance in dye sensitized solar cell (DSSC), optical
device, photocatalysis etc. Simultaniously, electronics, magnetism,
biotechnology, medicinal, adsorption chemistry, sensors and so on
have got the chance of visualizing the crucial role of these materials
[137,143]. Magnetic nanocomposites of different shape and size can
be derived by embedding monodisperse magnetic nanocrystals in
mesoporous nanospheres or inside the porous channels and cages
of ordered mesoporous materials [200]. These nanocomposites based
on mesoporous structures have huge potentials in the areas of heath
care, catalysis, and environmental separation.
Moller and Bein have reviewed different aspects of inclusion
chemistry in ordered mesoporous host materials, which includes sorp-
tion, ion exchange, immobilization followed by reduction, grafting of re-
active metal alkoxides, halides etc., grafting of silane coupling agents
(sometimes followed by subsequent reactions), grafting of reactive
metal complexes, and polymerization in the channels [201]. Co-
condensation of a reactive species during the mesopore synthesis
is described as an effective strategy to incorporate a reactive func-
tionality into the walls of the mesoporous channel system. Impor-
tant applications of these modified and functionalized mesoporous
systems are heterogeneous catalysis, photocatalysis, ion exchange
and separations, removal of heavy metals, chromatography, stabili-
zation of quantum wires, stabilization of dyes, and polymer compos-
ites. Surface-functionalized mesoporous silica nanoparticle (MSN)
materials have been extensively studied as efficient drug delivery
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
carriers [202–204]. Slowing et al. have described the synthesis of dif-
ferent class of MSN materials and their biocompatibility in vitro,
where various contemporary methods for controlling the structural
properties and chemical functionalization for biotechnological and
biomedical applications are given [202]. Progress made on using
MSN to penetrate various cell membranes in animal and plant cells,
the concept of gatekeeping in the design of a variety of stimuli-
responsive nanodevices suggest that MSN-based systems have a
great potential for the site-specific delivery and intracellular con-
trolled release of drugs, genes, and other therapeutic agents.
Further, due to the necessity of refining industry for heavier feed-
stocks, there is considerable demand for zeolites with mesopores,
which can utilize its accessible surface areas and higher pore volumes.
In this context different synthesis strategies involving ‘destructive’
structure breaking together with ‘constructive’ structure building
synthesis pathways have been developed to synthesize mesoporous
zeolitic materials combining micropores with mesopores [205]. In
Table 2 we have summarized some of the important applications of
mesoporous materials synthesized through soft templating pathway
in a tabular form.
4. Summary
From purely inorganic, organic-inorganic hybrid to purely organic—an
overview of the surfactant-assisted synthetic pathways of all these or-
dered and disordered mesoporous materials are depicted elaborately in
this review. Since there is a large number of research and synthesis
works randomly reported on a wide spectrum of mesoporous materials,
a good review on the formation mechanism of these materials is essential
for further study and development in this frontier area of research. Hence
a deep insight on the formation of mesopores via self-assembly of surfac-
tants is discussed here with well recognized schematic models and good
fitting references. Along with this respective interaction pathways in-
volved in synthesis of mesoporous oxide, silica, organic–inorganic hybrid
silica, phosphate, sulphides, carbon and polymer using high molecular
weight large amphiphilic molecules, are systematically demonstrated
here in tabular form. Further, potential applications of these mesoporous
solids in the field of surface science, nanotechnology and materials chem-
istry in general have been highlighted.
5. Future prospects
All the mechanistic pathways described herein to create mesoporosity
within silica, metal oxide, phosphate or carbon based materials are a
successful approach towards the additional effort in the mesoporous
world. A variety of mesoporous solids can be prepared employing these
synthesis protocols like, organically functionalized mesoporous silicas,
PMOs, new lanthanide and actinide metal doped silicas, oxides or organic
polymers and their carbons. When a variation of metals is able generate
new porous mixed oxides similarly variation in condensation of
new organosilane precursor with TEOS or other sources can produce
multicomponent hybrid silica. Organic monomers synthesized in our
everyday research can be employed to synthesize porous polymers of
different types which are not yet been prepared. An apparent idea of
metal-template interaction will help to generate porous network in
these materials as well as conventional nonporous materials using surfac-
tants molecules will open multiple branches in the research area of
nanoporous solids. Moreover, there are numerous porous oxides, mixed
oxides, phosphates, organic-inorganic hybrid silica and carbons which
have been fabricated and characterized till date but their application
potentials are not being explored so far. So in future the in-depth study
on catalysis, sensing, adsorption, optoelectronics, light-harvesting behav-
ior may open good opportunity for the further research on these
materials.
39
Acknowledgments
AB wishes to thank Department of Science & Technology, New Delhi
for providing the instrumental facilities through DST Unit on Nanoscience.
NP expresses gratitude to Council of Scientific and Industrial Research
(CSIR), New Delhi for a senior research fellowship.
References
[1] Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS. Nature 1992;359:710–2.
[2] Beck JS, Vartuli JC, Kennedy GJ, Kresge CT, Roth WJ, Schramm SE. Chem Mater
1994;6:1816–21.
[3] Polarz S. Encycl nanosci nanotechno 2004;8:239–58.
[4] Nguyen TQ, Wu J, Tolbert SH, Schwartz BJ. Adv Mater 2001;13:609–11.
[5] Rao CNR, Natarajan S, Vaidhyanathan R. Angew Chem Int Ed 2004;43:1466–96.
[6] Groves JA, Miller SR, Warrender SJ, Mellot-Draznieks C, Lightfoot P, Wright PA.
Chem Commun 2006:3305–7.
[7] Behrens P. Adv Mater 1993;5:127–32.
[8] Davis ME, Lobo RF. Chem Mater 1992;4:756–68.
[9] Ozin GA. Adv Mater 1992;4:612–49.
[10] Mal NK, Bhaumik A, Kumar R, Ramaswamy AV. Catal Lett 1995;33:387–94.
[11] Ryoo R, Kim JM, Ko CH, Shin CH. J Phys Chem 1996;100:17718–21.
[12] Ni YM, Sun AM, Wu XL, Hai GL, Hu JL, Li T, et al. J Colloid Interface Sci 2011;361:
521–6.
[13] Ying JY, Mehnert CP, Wong MS. Angew Chem Int Ed 1999;38:56–77.
[14] Ciesla U, Schüth F. Microporous Mesoporous Mater 1999;27:131–49.
[15] Lee J, Kim J, Hyeon T. Adv Mater 2006;18:2073–94.
[16] Antonelli DM, Ying JY. Angew Chem Int Ed Engl 1995;34:2014–7.
[17] MacLachlan MJ, Coombs N, Ozin GA. Nature 1999;397:681–4.
[18] Tiemann M, Fröba M. Chem Mater 2001;13:3211–7.
[19] Cheng C-F, Luan Z, Klinowski J. Langmuir 1995;11:2815–9.
[20] Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, et al. J Am
Chem Soc 1992;114:10834–43.
[21] Zheng J-Y, Pang J-B, Qiu K-Y, Wei Y. J Mater Chem 2001;11:3367–72.
[22] Larsen G, Lotero E, Marquez M. Chem Mater 2000;12:1513–5.
[23] Muylaert I, Verberckmoes A, De Decker J, Van der Voort P. Adv Colloid Interface
Sci 2012;175:39–51.
[24] Li Z, Jaroniec M. J Am Chem Soc 2001;123:9208–9.
[25] Flaigen EM, Patton RL, Wison ST. Stud Surf Sci Catal 1988;37:13–27.
[26] Sayari A. Stud Surf Sci Catal 1996;102:1–46.
[27] Orilall MC, Wiesner U. Chem Soc Rev 2011;40:520–35.
[28] Alexandridis P, Olsson U, Lindman B. Langmuir 1998;14:2627–38.
[29] Britoand RMM, Vaz WLC. Anal Biochem 1986;152:250–5.
[30] de A GJ, Soler-Illia A, Sanchez C, Lebeau B, Patarin J. Chem Rev 2002;102:4093–138.
[31] Huo QS, Margolese DI, Ciesla U, Feng PY, Gier TE, Sieger P, et al. Nature 1994;368:
317–21.
[32] Faustino CMC, Calado ART, Garcia-Rio L. J Colloid Interface Sci 2011;359:493–8.
[33] Tanev PT, Pinnavaia TJ. Science 1995;267:865–7.
[34] Che S, Garcia-Bennett AE, Yokoi T, Sakamoto K, Kunieda H, Terasaki O, et al. Nat
Mater 2003;2:801–5.
[35] Monnier A, Schuth F, Huo Q, Kumar D, Margolese D, Maxwell RS, et al. Science
1993;261:1299–303.
[36] Huo Q, Margolese DI, Ciesla U, Demuth DG, Feng P, Gier TE, et al. Chem Mater
1994;6:1176–91.
[37] Bagshaw SA, Kemmitt T, Milestone NB. Microporous Mesoporous Mater 1998;22:
419–33.
[38] Van Der Voort P, Ravikovitch PI, De Jong KP, Benjelloun M, Van Bavel E, Janssen
AH, et al. J Phys Chem B 2002;106:5873–7.
[39] Foerster S, Fischer S, Zielske K, Schellbach C, Sztucki M, Lindner P, et al. Adv Col-
loid Interface Sci 2011;163:53–83.
[40] Zhao W, Li JJ, He C, Wang LN, Chu JL, Qu JK, et al. Catal Today 2010;158:427–31.
[41] Shimojima A, Kuroda K. Angew Chem Int Ed 2003;42:4057–60.
[42] Shimojima A, Liu Z, Ohsuna T, Terasaki O, Kuroda K. J Am Chem Soc 2005;127:
14108–16.
[43] Scott BJ, Wirnsberger G, Stucky GD. Chem Mater 2001;13:3140–50.
[44] Leontidis E. Curr Opin Colloid Interface Sci 2002;7:81–91.
[45] Nguyen D, Bertrand GL. Curr Opin Colloid Interface Sci 1992;150:143–57.
[46] Sein A, Engberts JBFN. Langmuir 1995;11:455–65.
[47] Pileni M-P. Nat Mater 2003;2:145–50.
[48] Zieliński R, Ikeda S, Nomura H, Kato S. J Chem Soc Faraday Trans I 1989;85:
1619–29.
[49] Lindman B, Wennerstroem H. J Phys Chem 1991;95:6053–4.
[50] Hayashi S, Ikeda S. J Phys Chem 1980;84:744–51.
[51] Wan Y, Zhao D. Chem Rev 2007;107:2821–60.
[52] Corma A. Chem Rev 1997;97:2373–419.
[53] Zimny K, Carteret C, Stebe MJ, Blin JL. J Phys Chem C 2011;115:8684–92.
[54] Vartuli JC, Kresge CT, Leonowicz ME, Chu AS, Mc-Cullen SB, Johnson ID, et al.
Chem Mater 1994;6:2070–7.
[55] Pal N, Paul M, Bera A, Basak D, Bhaumik A. Anal Chim Acta 2010;674:96–101.
[56] Prado AGS, Airoldi C. J Mater Chem 2002;12:3823–6.
[57] Knoefel C, Lutecki M, Martin C, Mertens M, Hornebecq V, Llewellyn PL. Micropo-
rous Mesoporous Mater 2010;128:26–33.
[58] Jiao F, Harrison A, Jumas J-C, Chadwick AV, Kockelmann W, Bruce PG. J Am Chem
Soc 2006;128:5468–74.
40 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41
[59] Ryoo R, Joo SH, Jun S. J Phys Chem B 1999;103:7743–6.
[60] Joo SH, Choi SJ, Oh I, Kwak J, Liu Z, Terasaki O, et al. Nature 2001;412:169–72.
[61] Smarsly B, Xomeritakis G, Yu K, Liu NG, Fan HY, Assink RA, et al. Langmuir
2003;19:7295–301.
[62] Grosso D, Cagnol F, Soler-Illia GJDA, Crepaldi EL, Amenitsch H, B.-Bruneau A,
et al. Adv Funct Mater 2004;14:309–22.
[63] Schuster J, Koehn R, Doeblinger M, Keilbach A, Amenitsch H, Bein T. J Am Chem
Soc 2012;134:11136–45.
[64] Meng Y, Gu D, Zhang FQ, Shi YF, Yang HF, Li Z, et al. Angew Chem Int Ed 2005;44:
7053–9.
[65] Ariga K, Vinu A, Yamauchi Y, Ji Q, Hill JP. Bull Chem Soc Jpn 2012;85:1–32.
[66] Berggren A, Palmqvist AEC, Holmberg K. Soft Matter 2005;1:219–26.
[67] Chandra D, Bhaumik A. Ind Eng Chem Res 2006;45:4879–83.
[68] Vivero-Escoto JL, Chiang Y-D, Wu KC-W, Yamauchi Y. Sci Technol Adv Mater
2012;13 [013003-1-9].
[69] Wang S, Wu D, Sun Y, Zhong B. Mater Res Bull 2001;36:1717–20.
[70] Guidotti M, Gavrilova E, Galarneau A, Coq B, Psaroa R, Ravasio N. Green Chem
2011;13:1806–11.
[71] Wangcheng Z, Guanzhong L, Yanglong G, Yun G, Yunsong W. J Rare Earth
2008;26:59–65.
[72] Nandi M, Sarkar M, Sarkar K, Bhaumik A. J Phys Chem C 2009;113:6839–44.
[73] Zhao DY, Feng JL, Huo QS, Melosh N, Fredrickson GH, Chmelka BF, et al. Science
1998;279:548–52.
[74] Ryoo R, Ko CH, Kruk M, Antochshuk V, Jaroniec M. J Phys Chem B 2000;104:
11465–71.
[75] Miyazawa K, Inagaki S. Chem Commun 2000:2121–2.
[76] Szegedi A, Popova M, Minchev C. J Mater Sci 2009;44:6710–6.
[77] Chen L-F, Guo P-J, Zhu L-J, Qiao M-H, Shen W, Xu H-L, et al. Appl Catal A Gen
2009;356:129–36.
[78] Ying F, Li J, Huang C, Weng W, Wan H. Catal Lett 2007;115:3–4.
[79] Selvaraj M, Lee TG. J Phys Chem B 2006;110:21793–802.
[80] Zhang W, Wang J, Tanev PT, Pinnavaia TJ. Chem Commun 1996:979–80.
[81] Davis ME. Nature 1993;364:391–3.
[82] Wang J, Neaton JB, Zheng H, Nagarajan V, Ogale SB, Lie B. Science 2003;299:
1719–22.
[83] Jiang J, Lough A, Ozin G, Bedard RL, Broach R. J Mater Chem 1998;8:721–32.
[84] Yamauchi Y, Sugiyama A, Morimoto R, Takai A, Kuroda K. Angew Chem Int Ed
2008;120:5451–3.
[85] Warren SC, Messina LC, Slaughter LS, Kamperman M, Zhou Q, Gruner SM, et al.
Science 2008;320:1748–52.
[86] Sayari A. Chem Mater 1996;8:1840–52.
[87] Hu C, Xing S, Qu J, He H. J Phys Chem C 2008;112:5978–83.
[88] Liong M, Lu J, Kovochich M, Xia T, Ruehm SG, Nel AE, et al. ACS Nano 2008;2:
889–96.
[89] Lee J-K, Kim G-P, Song IK, Baeck S-H. Electrochem Commun 2009;11:1571–4.
[90] Chandra D, Mridha S, Basak D, Bhaumik A. Chem Commun 2009:2384–6.
[91] Sayari A, Liu P. Microporous Mater 1997;12:149–77.
[92] Wu ZX, Li QA, Peng D, Webley PA, Zhao DY. J Am Chem Soc 2010;132:12042–50.
[93] Sun SM, Wang WZ, Shang M, Ren J, Zhang L. J Mol Catal A Chem 2010;320:72–8.
[94] Ji HJ, Liu XH, Wang X, Yao XX. J Colloid Interface Sci 2011;353:356–62.
[95] Ren Y, Ma Z, Bruce PG. Chem Soc Rev 2012;41:4909–27.
[96] Shibata H, Ogura T, Mukai T, Ohkubo T, Sakai H, Abe M. J Am Chem Soc
2005;127:16396–7.
[97] Oh SH, Nazar LF. J Mater Chem 2010;20:3834–9.
[98] Wu ZY, Tao YF, Lin Z, Liu L, Fan XX, Wang Y. J Phys Chem C 2009;113:20335–48.
[99] Deshmane CA, Jasinski JB, Ratnasamy P, Carreon MA. Chem Commun 2010;46:
6347–9.
[100] Patra AK, Dutta A, Bhaumik A. ACS Appl Mater Interfaces 2012;4(9):5022–8.
[101] Katou T, Lu D, Kondo JN, Domen K. J Mater Chem 2002;12:1480–3.
[102] Lee YF, Chang KH, Chu CY, Chen HL, Hu CC. RSC Adv 2011;1:401–7.
[103] Sanchez C, Livage J. New J Chem 1990;14:513–8.
[104] Pal N, Paul M, Bhaumik A. Appl Catal A Gen 2011;393:153–60.
[105] Fan J, Boettcher SW, Stucky GD. Chem Mater 2006;18:6391–6.
[106] Ortel E, Fischer A, Chuenchom L, Polte J, Emmerling F, Smarsly B, et al. Small
2012;8:298–309.
[107] Tagusagawa C, Takagaki A, Iguchi A, Takanabe K, Kondo JN, Ebitani K, et al.
Angew Chem Int Ed 2010;49:1128–32.
[108] Cai WQ, Yu JG, Jaroniec M. J Mater Chem 2011;21:9066–72.
[109] Li S, Zhou H, Han B, Deng F, Liu X, Xiao L, et al. Catal Sci Technol 2012;2:719–21.
[110] Szczech JR, Lukowski MA, Jin S. J Mater Chem 2010;20:8389–93.
[111] Wang Y, Ren J, Wang Y, Zhang F, Liu X, Guo Y, et al. J Phys Chem C 2008;112:
15293–8.
[112] Lai X, Li X, Geng W, Tu J, Li J, Qiu S. Angew Chem Int Ed 2007;46:738–41.
[113] Murugavel R, Choudhury A, Walawalkar MG, Pothiraja R, Rao CNR. Chem Rev
2008;108:3549–655.
[114] Poojary DM, Shpeizer B, Clearfield A. J Chem Soc Dalton Trans 1995:111–3.
[115] Bruque S, Aranda MAG, Losilla ER, O.-Pastor P, M.-Torres P. Inorg Chem 1995;34:
893–9.
[116] Bardeen J, Cooper LN, Schrieffer JR. Phys Rev 1957;108:1175–204.
[117] Moffat JB. Catal Rev Sci Eng 1978;18:199–258.
[118] Blanco A, Campelo JM, Garcia A, Luna D. J Catal 1992;137:51–68.
[119] Holland BT, Isbester PK, Blanford CF, Munson EJ, Stein A. J Am Chem Soc
1997;119:6796–803.
[120] Ma TY, Yuan ZY. ChemSusChem 2011;4:1407–19.
[121] Wilson ST, Lok BM, Mesina CA, Cannan TR, Flanigen ED. J Am Chem Soc
1982;104:1146–7.
[122] Ma TY, Li H, Tang AN, Yuan ZY. Small 2011;7:1827–37.
[123] Bhaumik A, Inagaki S. J Am Chem Soc 2001;123:691–6.
[124] Jones DJ, Aptel G, Brandhorst M, Jacquin M, Jiménez-Jiménez J, Jiménez-López A,
et al. J Mater Chem 2000;10:1957–63.
[125] Yu D, Qian J, Xue N, Zhang D, Wang C, Guo X, et al. Langmuir 2007;23:382–6.
[126] Luan Z, Zhao D, He H, Klinowski J, Kevan L. J Phys Chem B 1998;102:1250–9.
[127] Sarkar A, Pramanik P. Microporous Mesoporous Mater 2009;117:580–5.
[128] Jiménez-Jiménez J, Maireles-Torres P, Olivera-Pastor P, Rodríguez-Castellón E,
Jiménez-López A, Jones DJ, et al. Adv Mater 1998;10:812–5.
[129] Tian BZ, Liu XY, Zhang ZD, Tu B, Zhao DY. J Solid State Chem 2002;167:324–9.
[130] Salinas AJ, Shruti S, Malavasi G, Menabue L, Vallet-Regi M. Acta Biomater 2011;7:
3452–8.
[131] Garcia A, Cicuendez M, Izquierdo-Barba I, Arcos D, Vallet-Regi M. Chem Mater
2009;21:5474–84.
[132] Feng W, Sun L-D, Zhang Y-W, Yan C-H. Coord Chem Rev 2010;254:1038–53.
[133] Kapoor MP, Inagaki S, Yoshida H. J Phys Chem B 2005;109:9231–8.
[134] Luo Q, Shen S, Lu G, Xiao X, Mao D, Wang Y. J Mater Chem 2009;19:8079–85.
[135] Xia Z, Liao L, Zhao S. Mater Res Bull 2009;44:1626–9.
[136] Braun PV, Osenar P, Stupp SI. Nature 1996;380:325–8.
[137] He X, Antonelli D. Angew Chem Int Ed 2002;41:214–29.
[138] Anderson MT, Newcomer P. Mater Res Soc Symp Proc 1995;371:117–21.
[139] Dong RH, Liu WM, Hao JC. Acc Chem Res 2012;45:504–13.
[140] Sanchez C, Soler-Illia GJDA, Ribot F, Lalot T, Mayer CR, Cabuil V. Chem Mater
2001;13:3061–83.
[141] Diaz U, Garcia T, Velty A, Corma A. Chem Eur J 2012;18:8659–72.
[142] Choi S, Drese JH, Jones CW. ChemSusChem 2009;2:796–854.
[143] Lu YF, Fan HY, Doke N, Loy DA, Assink RA, LaVan DA, et al. J Am Chem Soc
2000;122:5258–61.
[144] Sarkar K, Dhara K, Nandi M, Roy P, Bhaumik A, Banerjee P. Adv Funct Mater
2009;19:223–34.
[145] Zhang LX, Zhang WH, Shi JL, Hua Z, Li YS, Yan J. Chem Commun 2003:210–1.
[146] Sanchez C, Lebeau B, Chaput F, Boilot JP. Adv Mater 2003;15:1969–94.
[147] Stein A, Melde BJ, Schroden RC. Adv Mater 2000;12:1403–19.
[148] Inagaki S, Guan S, Fukushima Y, Ohsuna T, Terasaki O. J Am Chem Soc 1999;121:
9611–4.
[149] Asefa T, MacLachlan MJ, Coombs N, Ozin GA. Nature 1999;402:867–71.
[150] Olkhovyk O, Jaroniec M. J Am Chem Soc 2005;127:60–1.
[151] Xia YD, Wang WX, Mokaya R. J Am Chem Soc 2005;127:790–8.
[152] Hoffmann F, Cornelius M, Morell J, Fröba M. Angew Chem Int Ed 2006;45:
3216–51.
[153] Wight AP, Davis ME. Chem Rev 2002;102:3589–613.
[154] Paul M, Pal N, Rajamohanan PR, Rana BS, Sinha AK, Bhaumik A. Phys Chem Chem
Phys 2010;12:9389–94.
[155] Baleizao C, Gigante B, Das D, Alvaro M, Garcia H, Corma A. Chem Commun 2003:
1860–1.
[156] Fujita S, Inagaki S. Chem Mater 2008;20:891–908.
[157] Chandra D, Yokoi T, Tatsumi T, Bhaumik A. Chem Mater 2007;19:5347–54.
[158] Ferey G, Mellot-Draznieks C, Serre C, Millange F. Acc Chem Res 2005;38:217–25.
[159] Kitawaga S, Kitaura R, Noro S. Angew Chem Int Ed 2004;43:2334–75.
[160] Kimura T. Chem Mater 2005;17:5521–8.
[161] Seki T, McEleney K, Crudden CM. Chem Commun 2012;48:6369–71.
[162] Petkov N, Mintova S, Jean B, Metzger T, Bein T. Mater Sci Eng C 2003;23:827–31.
[163] Mizoshita N, Tani T, Inagaki S. Chem Soc Rev 2011;40:789–800.
[164] Nandi M, Mondal J, Sarkar K, Yamauchi Y, Bhaumik A. Chem Commun 2011;47:
6677–9.
[165] Jain SL, Modak A, Bhaumik A. Green Chem 2011;13:586–90.
[166] Wang P, Liu X, Yang J, Yang Y, Zhang L, Yang Q, et al. J Mater Chem 2009;19:
8009–14.
[167] Kecht J, Schlossbauer A, Bein T. Chem Mater 2008;20:7207–14.
[168] Candu N, Coman S, Parvulescu VI, El Haskouri J, Amoros P, Beltran D. Top Catal
2009;52:571–8.
[169] Verma S, Nandi M, Modak A, Jain SL, Bhaumik A. Adv Synth Catal 2011;353:
1897–902.
[170] Silva AR, Wilson K, Whitwood AC, Clark JH, Freire C. Eur J Inorg Chem 2006:
1275–83.
[171] Houbenov N, Haataja JS, Iatrou H, Hadjichristidis N, Ruokolainen J, Faul CFJ, et al.
Angew Chem Int Ed 2011;50:2516–20.
[172] Chandra D, Bhaumik A. J Mater Chem 2009;19:1901–7.
[173] Volkov VV, Lebedeva VI, Petrova IV, Bobyl AV, Konnikov SG, Roldughin VI, et al.
Adv Colloid Interface Sci 2011;164:144–55.
[174] Wang W, Ren H, Sun FX, Cai K, Ma HP, Du JS, et al. Dalton Trans 2012;41:3933–6.
[175] Oka K, Shibata Y, Itoi T, Izumi Y. J Phys Chem C 2010;114:1260–7.
[176] Wang D-W, Li F, Chen Z-G, Lu GQ, Cheng H-M. Chem Mater 2008;20:7195–200.
[177] Peng X, Cao D, Wang W. J Phys Chem C 2008;112:13024–36.
[178] Hartmann M, Vinu A, Chandrasekar G. Chem Mater 2005;17:829–33.
[179] Zhang S, Chen L, Zhou S, Zhao D, Wu L. Chem Mater 2010;22:3433–40.
[180] Zhu K, Egeblad K, Christensen CH. Eur J Inorg Chem 2007:3955–60.
[181] Li J, Dai W-L, Fan K. J Phys Chem C 2008;112:17657–63.
[182] Fischer A, Müller JO, Antonietti M, Thomas A. ACS Nano 2008;2:2489–96.
[183] Castelvetro V, De Vita C. Adv Colloid Interface Sci 2004;108:167–85.
[184] Meng Y, Gu D, Zhang FQ, Shi YF, Cheng L, Feng D, et al. Chem Mater 2006;18:
4447–64.
[185] Chandra D, Jena BK, Raj CR, Bhaumik A. Chem Mater 2007;19:6290–6.
[186] Xing R, Liu N, Liu YM, Wu HH, Jiang YW, Chen L, et al. Adv Funct Mater 2007;17:
2455–61.
[187] Modak A, Mondal J, Sasidharan M, Bhaumik A. Green Chem 2011;13:1317–31.
 N. Pal, A. Bhaumik / Advances in Colloid and Interface Science 189–190 (2013) 21–41 41

[188] Liang C, Dai S. J Am Chem Soc 2006;128:5316–7. [212] Vivero-Escoto JL, Slowing II, Wu C-W, Lin VS-Y. J Am Chem Soc 2009;131:3462–3.
[189] Wan Y, Shi YF, Zhao DY. Chem Commun 2007:897–926. [213] Lapisardi G, Chiker F, Launay F, Nogier J-P, Bonardet J-L. Catal Commun 2004;5:
[190] Hang F, Meng Y, Gu D, Yan Y, Yu C, Tu B, et al. J Am Chem Soc 2005;127:13508–9. 277–81.
[191] Xing L, Huang J, Wu S, Wang H, Song K, Xu H, et al. Carbon 2007;45:203–28. [214] Rafiee E, Eavani S. Green Chem 2011;13:2116–22.
[192] Kruk M, Dufour B, Celer EB, Kowalewski T, Jaroniec M, Matyjaszewski K. J Phys [215] Mondal J, Sen T, Bhaumik A. Dalton Trans 2012;41:6173–81.
Chem B 2005;109:9216–25. [216] Ma T-Y, Yuan Z-Y, Cao J-L. Eur J Inorg Chem 2010:716–24.
[193] Kyotani T, Ma ZX, Tomita A. Carbon 2003;41:1451–9. [217] Noda Y, Lee B, Domen K, Kondo JN. Chem Mater 2008;20:5361–7.
[194] Liang C, Li Z, Dai S. Angew Chem Int Ed 2008;47:3696–717. [218] Huang ZB, Tang FQ. J Colloid Interface Sci 2005;281:432–6.
[195] Ryoo R, Joo SH, Kruk M, Jaroniec M. Adv Mater 2001;13:677–81. [219] Muralidharan MN, Rasmitha CA, Ratheesh R. J Porous Mater 2009;16:635–40.
[196] Liang CD, Hong KL, Guiochon GA, Mays JW, Dai S. Angew Chem Int Ed 2004;43: [220] Ozkan E, Lee S-H, Liu P, Tracy CE, Tepehan FZ, Pitts JR, et al. Solid State Ionics
5785–9. 2002;149:139–46.
[197] Tanaka S, Nishiyama N, Egashira Y, Ueyama K. Chem Commun 2005:2125–7. [221] Chandra D, Mukherjee N, Mondal A, Bhaumik A. J Phys Chem C 2008;112:
[198] Wang X, Liang C, Dai S. Langmuir 2008;24(14):7500–5. 8668–74.
[199] Górka J, Zawislak A, Choma J, Jaroniec M. Carbon 2008;46:1159–61. [222] Waitz T, Wagner T, Sauerwald T, Kohl CD, Tiemann M. Adv Funct Mater 2009;19:
[200] Liu J, Qiao SZ, Hu QH, Lu GQ. Small 2011;7:425–43. 653–61.
[201] Moller K, Bein T. Chem Mater 1998;10:2950–63. [223] Teoh LG, Hung IM, Shieh J, Lai WH, Hon MH. Electrochem Solid-State Lett
[202] Slowing II, Vivero-Escoto JL, Wu CW, Lin VSY. Adv Drug Deliv Rev 2008;60:1278–88. 2003;6:G108–11.
[203] Jarvis KL, Barnes TJ, Prestidge CA. Adv Colloid Interface Sci 2012;175:25–38. [224] Wagner T, Kohl C-D, Fröba M, Tiemann M. Sensors 2006;6:318–23.
[204] Das SK, Bhunia MK, Chakraborty D, Khuda-Bukhsh AR, Bhaumik A. Chem [225] Wang J-Q, Huang L, Xue M, Wang Y, Gao L, Zhu JH, et al. J Phys Chem C 2008;112:
Commun 2012;48:2891–3. 5014–22.
[205] Chal R, Gerardin C, Bulut M, van Donk S. ChemCatChem 2011;3:67–81. [226] Descalzo AB, Rurack K, Weisshoff H, Martínez-Máñez R, Marcos MD, Amorós P,
[206] Vinu A, Hossain KZ, Kumar GS, Sivamurugan V, Ariga K. Stud Surf Sci Catal et al. J Am Chem Soc 2005;127:184–200.
2005;156:631–6. [227] Melde BJ, Johnson BJ, Charles PT. Sensors 2008;8:5202–28.
[207] Chew TL, Ahmad AL, Bhatia S. Adv Colloid Interface Sci 2010;153:43–57. [228] Zoo Lee E, Lee SU, Heo N-S, Stucky GD, Jun Y-S, Hong WH. Chem Commun
[208] Vaidhyanathan R, Iremonger SS, Shimizu GKH, Boyd PG, Alavi S, Woo TK. Science 2012;48:3942–4.
2010;330:650–3. [229] Martínez-Máñez R, Sancenón F. Coord Chem Rev 2006;250:3081–93.
[209] Colilla M, Manzano M, Izquierdo-Barba I, Vallet-Regí M, Boissière C, Sanchez C. [230] Melde BJ, Johnson BJ. Anal Bioanal Chem 2010;398:1565–73.
Chem Mater 2010;22:1821–30. [231] Slowing II, Trewyn BG, Giri S, Lin VS-Y. Adv Funct Mater 2007;17:1225–36.
[210] Li X, Zhang J, Gu H. Langmuir 2011;27:6099–106. [232] Li LL, Sun H, Fang CJ, Xu J, Jin JY, Yan CH. J Mater Chem 2007;17:4492–8.
[211] Min KH, Lee HJ, Kim K, Kwon IC, Jeong SY, Lee SC. Biomaterials 2012;33:5788–97.