Block Copolymer-Templated Mesoporous Oxides

Current Opinion in Colloid and Interface Science 8 (2003) 109126
Block copolymer-templated mesoporous oxides
Galo J. de A.A. Soler-Illiaa,b,*, Eduardo L. Crepaldia,c, David Grossoa, Clement

Sancheza,*
a
` Condensee,
CNRS UMR 7574, Universite Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05,
Laboratoire de Chimie de la Matiere
France
b
Nacional de Energa
Atomica,
Unidad de Actividad Qumica,

Comision
Centro Atomico
Constituyentes, Av. Gral. Paz 1499 (1650),
San Martin, Pcia. de Buenos Aires, Argentina
c
Francisco syno, C.P. 07 13140-000 Paulinia, SP, Brazil

Rhodia Brasil Ltda. CPP, Fsico-Qumica,
Fazenda Sao
Abstract
Block copolymers (BC) are indeed suitable and versatile templates for the creation of mesostructured and mesoporous materials.
Great advances have been achieved in the last 3 years. Nowadays, it is possible to obtain highly controlled large-pore and highly
stable mesostructured and mesoporous materials (silica, non-silica oxides, carbons,) shaped as powders, films, monoliths or
aerosols. This paper reviews mainly the synthesis of BC-templated mesostructured oxides, stressing in the physical, chemical and
processing parameters, which have to be thoroughly controlled to reproducibly obtain mesoporous materials.
2003 Elsevier Science Ltd. All rights reserved.
Keywords: Polymer; Mesoporous materials; Surfactant; Block copolymer; SBA-15
1. Mesotextured and mesoporous materials

The physical chemistry of organized matter relies
on the successful combination of solgel chemistry and
self-assembly procedures, to uniquely control the texture
of materials at the nanometer scale w1,2x. The growth
of soft chemistry derived inorganic or hybrid networks
templated by organized surfactant assemblies (structure
directing agents) allowed to construct a new kind of
materials organized in the mesoscopic scale (250 nm):
the best example is the ever growing family of mesostructured hybrids and derived mesoporous inorganic
materials.
Since the pioneering work of the Mobil scientists
w3x, a permanent effort is made to develop mesotextured inorganic or hybrid phases, which are potential
candidates for a variety of applications, in the fields of
catalysis, optics, photonics, sensors, separation, drug
Abbreviations: BC, block copolymer; EISA, evaporation-induced
self assembly; TLCT, true liquid crystal templating; HI, hybrid
interface; PEO, poly(ethylene oxide); PPO, poly(propylene oxide);
PI, polyisoprene; PS, polystyrene; PAA, poly(acrylic acid); P123,
pluronics P123 (PEO)20(PPO)70(PEO)20 ; F127, pluronics F127
(PEO)106(PPO)70(PEO)106 ; HLB, hydrophilicylipophilic balance
*Corresponding authors. Tel.: q33-1-44-27-55-45; fax: q33-1-4427-47-69.
E-mail addresses: gsoler@cnea.gov.ar (G.J.d.A. Soler-Illia),
clems@ccr.jussieu.fr (C. Sanchez).
delivery, sorption, acoustic or electrical insulation

w4,5x. The choice of the organic template to spatially
control the mineralization process in the mesoscale, is a
key issue in the synthesis of textured or porous materials.
In the case of mesoporous oxides, the templating relies
on supramolecular arrays: micellar systems formed by
surfactants or block copolymers (BC) w6x. BC w7x
are indeed interesting as supramolecular templates
because they are capable to impart larger pores and
thicker walls, apart from being industrially available,
hazard-free and easy to remove from the mineral framework (by thermal treatment or solvent extraction). Since
the first successful syntheses of these exciting mesoorganized materials, the number of publications is steadily increasing w8x. However, the understanding of their
synthesis procedures is limited.
In the last 3 years, the main advances in the texturing
of inorganic or hybrid materials by BC can be summarized as follows:
a. The fine structure of these composite materials (i.e.
the nature of the inorganic walls, the organic domains,
and the hybrid interface) is beginning to be unveiled
w8,9,10x, helping to understand the role of synthesis and processing variables.
b. The porosity and pore structure of these materials are
beginning to be understood, in correlation with the
synthesis variables w8,11 x. This is fundamental for
1359-0294/03/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1359-029403.00002-5
110
c.
d.
e.
f.
g.
h.
G.J.d.A. Soler-Illia et al. / Current Opinion in Colloid and Interface Science 8 (2003) 109126
the reproducible synthesis of materials with targeted

applications.
Synthesis methods have been extended to non-silica
frameworks (particularly single or mixed metal oxides
w12,13,14,15,16,17x).
New synthesis methods have been developed, which
involve low cost precursors w18x, and to control the
processing of the obtained mesophases, especially as
films w16,17x, or particles with well defined shape
w19x.
Pore and wall modification has become possible;
following the concepts applied to MCM-41-like silica
w20x, organic functions can be grafted on the inorganic
walls w21x, within the framework w22,23x, or both
w24x.
Mesoporous aluminosilicates with partially crystalline
walls have been obtained w25,26x, which are more
resistant to extreme conditions (such as those found
in membranes or catalysis).
Multiscale textured materials (i.e. macroymesoporous, or microymesoporous, or microymesoymacroporous) have been designed by combining templating
techniques at different scales (integrative synthesis
paths) w27,28x.
The formation mechanisms of mesosotructured
hybrids are on the way to being understood
w29,30x, thanks to in situ methods.
In this paper, we will discuss recent work dealing on

BC (diblock and triblock) as templating agents for
mesostructured and mesoporous oxides. While we do
not aim at giving an exhaustive description, which can
be found in recent reviews w6,31,32,33,34x, we
will focus on the chemical and physicalchemical concepts behind the reported syntheses, trying to shed some
light on the trends issuing from an analysis of recent
literature.
2. Block copolymers as templates: why and when
The first papers related to mesostructured oxides
described the use of ionic surfactants such as the cationic
alkyltrimethylammonium (CnTAq, ns818), anionic
alkylsulfonates (CnSO2y
3 , ns1218) or alkylphosphates
as supramolecular templates. These synthesis were performed in extreme (acid or alkaline) pH conditions,
yielding materials with controlled pore size (15100
However, two main limitations exist: (a) typical
A).
which is a serious limitation
wall thickness of 813 A,
regarding stability for catalysis; (b) limited pore size
offered by molecular surfactants. The only way to go
pore size consisted in employing swelling
beyond 50 A
agents (such as trimethylbenzene), involving complicated synthesis, and irreproducibility (linked to emulsion
formation or phase separation). Thus, more versatile
supramolecular templates were needed. Amphiphilic BC
Table 1
Characteristics of surfactants and BC
Surfactant
Solution and mesophase behavior
Molecularymonodisperse
Headqchain structure object shape
controlled by the g packing
parametera
Simple micelle-like or bicontinuous mesostructures
Micellization driven by
hydrophilicyhydrophobic
character
Cosolvent swelling modifies
curvature
Use in the design of
mesostructured materials
Hard well-defined HI
Thin walls (11.5 nm)
Walls not entangled with the
template
Pore size limited by micelle size
BC
Polymericycan be polydisperse
Enormous range of
architectures: linear, branched,
star, shape controlled by
xAB, N and f A, f B,b
Possibility of complex
multiscale mesostructures (e.g.
knitting patterns)
Micellization driven by
hydrophilicyhydrophobic
character, block size and
conformation
Differential swelling of domains
by cosolvents
Blurry interface, swollen by

the inorganic phase
Thick walls (210 nm)
Walls entangled with the
template (multiphase)
Pore size tailorable by
modifying the polymerization
degree, monomer nature or
polymer fraction
gsVyLcA0, according to (Israelachvili N, et al. J Chem Soc Farad

Trans II 1976;72:1525); see also Ref. w6x.
b
xAB is the FloryHuggins parameter; NsNAqNB q is the total
degree of polymerization (NA, NB, are the respective degrees of polymerization of each block); f A, f B are the volume fractions of each block;
see Refs. w35,36x.
belong to an important family of surfactants, widely

used in detergency, emulsifying, coating, thickening, etc.
The self-assembly characteristics of these BC permit to
control the superstructure, to vary the typical length
scales and to add specific functions. Indeed, the properties of BC can be continuously tuned by adjusting
solvent composition, molecular weight or polymer architecture w35,36x. Table 1 compares the characteristics
of BC vs. low-weight ionic surfactants. Fig. 1 shows
typical BC used as templates, accompanied by typical
XRD and TEM information of BC-templated phases.
Alkyl-poly(ethylene oxide) oligomeric nonionic surfactants (Brij, Triton, Igepal families, Cn(EO)mOH, where
Cn is an alkyl or alkylyaryl chain), although not strictly
BC, have been widely used and compared to true BC
templates; hereafter, we will also comment on this kind
of polymers.
2.1. Precipitation-based methods
Pinnavaia and coworkers were the first to bring the
idea of using nonionic surfactants (alkylamines
(CnNH2), oligomeric alkyl-poly(ethylene oxide)
(Cn(PEO)mOH), or (PEO)m(PPO)n (PEO)m , EOs
CH2CH2O, and POsCH(CH3)CH2O) as porogen
species, in neutral media w37,38x. Some advantages

of using neutral non-ionic surfactants over the ionic
ones were immediately noticed: (a) larger inorganic wall
enhancing the hydrothermal stathickness (1540 A),
bility of the mesoporous oxides; (b) easier pore diameter
tuning, by varying both the type and the concentration
of the surfactant, (c) easier solvent removal, by solvent
extraction; H-bonding (instead of electrostatic) interactions between the template and the inorganic framework
should be easier to dissociate. The first materials issued
from the so-called neutral route (S 0I 0)1 presented loworder wormlike structures. This has been overcome by
optimizing precipitation conditions; indeed, a two-step
method has been recently reported w39x, which yields
excellent organization.
The Stucky group w40,41x obtained highly organ thick-wall (3070 A)
silica
ized large-pore (45300 A)
by precipitation, using triblock (EO)n(PO)m (EO)n templates. The 2D-hexagonal SBA-15 is subject of increasing studies, being the large-pore equivalent to MCM-41.
The cubic SBA-16 has been fully characterized by
electron microscopy and diffraction w42x. Other groups
have used templates containing hydrophobic groups such
as poly(butylene oxide),w43x or poly(DL-lactic acid coglycolic acid), PLGA w44x.
2.2. True liquid crystal templating
Attard et al. performed silica solgel polymerization
in lyotropic liquid crystals (LC), creating an alternative
to conventional precipitation methods (the true liquid
crystal templating, TLCT route w45 x). This path leads
to mesostructured hexagonal, cubic or lamellar silica, as
gels, cast monoliths or membranes. Metallic mesoporous
materials are obtained by chemical or electrochemical
reduction of metal salts, dissolved in the hydrophilic
regions of the LC phase w46x. A similar approach leads
to ordered arrays of semiconductor nanoparticles w47x.
TLCT methods permit one to obtain a cast replica of
the LC phase; the final phase should be in principle
controlled by knowing the phase diagram of the surfactant (a kind of thermodynamic control). However, a
major drawback is the inhomogeneity that can result
either by inadequate diffusion of the inorganic moieties
within the pre-formed LC phase, or uncontrolled phase
111
separation due to inorganic polymerization taking place

in viscous LC media.
While PEOPPOPEO or PEO-alkyl copolymers are
the most usual templates, Wiesner and coworkers performed pioneering work in organoaluminosilicates templated with high mass (PI-b-PEO) diblock copolymer
templates w10,48x. Antonietti and coworkers extended the TLCT approach to a great variety of inorganic
frameworks and polymeric templates, particularly to
high molecular mass ionic copolymers w33,49x, or
poly(ethylene-co-butylene)-b-(ethylene oxide), which
afford very large pore size (2030 nm) w50x. This group
has also used PS-PEO BC, which lead to quasi-hexagonal pore arrangements w51x.
2.3. Evaporation-induced self assembly
The evaporation-induced self assembly (EISA)
denomination was coined by Brinker et al. w52x to
encompass the synthesis methods leading to ordered
hybrid mesophases from dilute solutions, upon solvent
evaporation. EISA can be considered an LCT-based
method (after solvent evaporation, a hybrid LC phase is
formed). Starting from solutions below the critical
micellar concentration, permits one to obtain thin films
or gels with excellent homogeneity (high dilution discouraging inorganic polymerization). BC-templated silica mesoporous films w53 x and monoliths w9,54x were
obtained by EISA. This method is particularly interesting
to work with non-silica systems, where condensation
has to be thoroughly controlled. In the last 3 years,
EISA-based methods were developed to include practically all possible oxides, as xerogels w12,13,14x, thin
films w16,17x or aerosols w55x.
In all three outlined routes (precipitation, TLCT and
EISA), an interplay of physical and chemical factors
has to be considered, if aiming to design mesostructured
materials in a rational way. A fourth route (nanocasting
on already formed mesoporous materials), mainly developed by Ryoo and coworkers, is useful for frameworks
that are difficult to form using LC templates (reactive
oxides, polymers, carbon, non-oxides,) w56 x. Hereafter, we will focus on the first three routes, by discussing selected examples.
3. Hybrid mesostructures: striving forces in action
In the usual nomenclature for mesostructured materials, I stands

for the inorganic skeleton, and S for the template. The term S 0I 0
describes routes relying on non-ionic surfactants; the main interactions
between the template and the inorganic species are H-bonding or
dipolar, giving birth to the so-called neutral path. See for example
Ref. w6x. However, there seems to be an abuse of terminology when
supposing a neutral inorganic network I 0 for pH )pHiepSiO2, which
is typically between 2 and 3. Note that although the negative charge
remains low in neutral media (pH f7), silica is negatively charged
above pH 2 (See Iler RK. The chemistry of silica, New York: Wiley;
1979, p. 186, 659 ss.).
Two main processes can be recognized in the formation of these mesophases, which is schematized in Fig.
2:
a. The creation of an organized texture, due to the selfassembly properties of the template. This process
results in a microphase separation, which divides the
space in two domains: hydrophilic and hydrophobic,
in the case of the simplest BC surfactants.
112
Fig. 1. (a) BC templates used in mesostructure generation. (b) Typical XRD and TEM characterization of a 2D hexagonal SBA-15 material. (c)
2D-XRD and TEM information for an Im3m cubic oriented silica film.
b. The formation of an inorganic network. The inorganic

components are placed in one of the spatially separated parts of these nanoheterogeneous systems. Condensation reactions will give rise to an extended
inorganic network; these reactions can be tuned to
take place simultaneously or subsequently as organization proceeds.
The simplest analysis will evidence three fundamental
interactions that will control the final obtained structure:
surfactantsurfactant (SS), inorganicinorganic (II)
and surfactantinorganic (SI); these interactions take
place in each of the microsegregated phases, or at the
inorganic-template hybrid interface (HI). The solvent
will also take part in mesophase formation. The most
relevant thermodynamic aspects in the formation of a
hybrid mesophase (DGms) have been defined by Huo et
al. in their description of the cooperative assembly
model w57x.
DGmssDGinterqDGinorgqDGorgqDGsol
(1)
The central points to a well-defined mesophase formation (details discussed elsewhere w6 x) are (a) the
adequate segregation of hydrophilic and hydrophobic
regions of the template (mainly DGorg) (b) the selective
positioning of the inorganic counterpart in one of these
regions, without disrupting organization; this is related
to the creation of a well-defined and compatible HI
between the inorganic walls and the organic templates
(i.e. DGinter is important). In principle, NDGinorgNNDGinterN or NDGorgN to permit the latter two terms to
direct the formation of organized assemblies.
Obtaining a well-defined templated hybrid is a matter
of controlling a delicate thermodynamic and kinetic
balance between multiple phenomena. Fig. 3 shows the
three main components of a mesostructured hybrid

(template, inorganic and solvent), connected by their
binary relationships. This gives a first-order general
picture of the important variables.
An important advantage of BC compared to ordinary
surfactants is that all relevant terms leading to order
(i.e. DGinter and DGorg) can be pre-designed from the
synthesis. The hydrophilicylipophilic balance (HLB)
and shape can be tuned by changing the polymerization
degree (i.e. DGorgAxAB, NA and NB w7,35,36x).
Moreover, the intrinsic chemistry of each block can be
changed, modulating the interactions with the inorganic
units that build up the framework.
Solventtemplate interactions have been thoroughly
studied from the thermodynamic point of view. The
complexity of PEOPPOPEOywaterycosolvent systems has been unveiled by Alexandridis and coworkers,
who established correlations between the cosolvent
polarity and its location within each block, or the
different interfaces w58,59 x. With the solventpolymercosolvent phase diagram in mind, it is in principle
possible to design different mesostructures. The inorganic monomers or polymers can swell one of the blocks;
therefore, the polarity of the inorganic species should
affect the final mesostructure (see below).
A thermodynamic analysis can be useful to explain
solventyBC and possibly inorganicyBC interactions.
However, the behavior of the inorganic components is
more complex, and will depend markedly in kinetic
features, mostly related to inorganic polymerization,
which can freeze a given mesostructure w14,60x,
113
Fig. 3. Scheme of the main relationships between the solvent, the

template and the inorganic center.
even a metastable one. Inorganic condensation is often

controlled by the solvent (i.e. the inorganic-solvent
relationship: in a solgel system, relevant variables are
solvent and cosolvent nature, pH, concentration, condensation inhibitors or catalysts,w61x). Examples involving these factors will be shortly discussed below.
4. The role of the hybrid interface
The SI interaction is particularly important in BCmetal oxide hybrids, especially in PEOPPO based
ones. Different possible interactions taking place at the
HI are schematized in Fig. 4. Most of the fine HI
characterization has been performed on PEO-based (di-
Fig. 2. Schematic view of the steps leading from a solution to a mesoporous oxide network.
114
Fig. 4. (a) Schematic view of the (S 0 H q )(X y I q ), S 0 I 0 , and (S 0 M q )(X y I 0 ) HIs. (b) Three possible structures of a HI composed by a nonionic
polymer and an inorganic framework. Left: a three-phase HI; the PEO block is completely segregated from the inorganic phase. Right: a twophase HI, where the inorganic polymer is completely integrated into the PEO block. Center: an intermediate situation, where a fraction of the
PEO is free.
or triblock) templates. Melosh et al. w9x determined

that in F127-templated silica monoliths, organization
arose for polymer weight fractions higher than 40%. For
lower polymerysilica ratios, non-ordered gels were
formed. This lack of order was due to a relatively strong
interaction (probably of H-bonding type) of the (SiOSi) polymers forming the inorganic skeleton with
both PEO and PPO blocks, as demonstrated by CPMAS NMR. These strong interactions extend the HI,
hindering PPO segregation. For higher polymer concentrations, the PPOyPPO (SS) attractions take over the
SiOyPPO (SI) interactions, and microsegregation
takes place, resulting in mesostructural order. In all
examined cases, a strong interaction was observed
between the PEO block and the silica polymer. A similar
feature has been proposed to explain the microporosity
of SBA-15. Quantitative XRD analysis of as-synthetized
SBA-15 leads to a pore model where a low-density
corona (formed by interpenetrated PEO and silica, Fig.
4b) is located between the pore center and the silica
wall w62x; this less dense zone can be held responsible
for the observed microporosity (see below). However,
recent work by Haddad et al. suggests that microporosity

is rather related to incomplete silica condensation w63x.
A synthesis approach developed by Wiesner and
coworkers w10x using hybrid precursors (GLYMOs
(CH3O)3Si(CH2)3CH(O)CH2 ), and Al(OsecBu)3 ) and
PEO-b-PI (polyisoprene) templates leads to a continuum
of mesoporous phases (for low polymer contents) to
dispersions of nanometric objects (for higher contents)
w64x. Using PI as the hydrophobic block has two
advantages: (a) an enhanced phase segregation, due to
a higher solubility difference between both blocks; (b)
no interaction is expected between the PI block and the
inorganic framework, as opposed to PPO. These points
are determinant in obtaining an efficient segregation.
Solid-state NMR of the PEOyinorganic interface w65x
demonstrates that the aluminosilicate network and the
PEO blocks are continuously interpenetrated (two-phase
model, Fig. 4b). The compatibility of the inorganic
network with PEO has been advantageously used in the
creation of mesostructured ORMOCER-based electro
lytes w66x. Goltner
et al. applied a combination of N2
adsorption and SAXS to study the pore nature of PS-b-
PEO templated silica, and propose an alternative model

for these hybrid materials, where a gradual transition
from a two-phase to a three-phase system takes place
along the HI (Fig. 4b) w67x.
Recent work in silica and titania mesostructured films
w68x showed that it is possible to obtain different phases
by varying the templateysilica volume fraction (VTSs
Vtempl y(VtemplqVSiO2)), in line with the phase diagram
approach of TLCT. However, the solvent role is indeed
important. Recent work in oriented silica membranes
w69x reveals that worm-like or hexagonal phases can
be obtained in conditions where cubic phases are expected (VTS-70% for F127 w58x). In these silicatropic
hybrids, the final mesostructure can be tailored by the
water contents in solution (h), at a constant VTS. The
crucial role of h can be envisaged as follows: the
mesostructure is not only directed by the VTS, but also
by the amount of the silicatemplate interface. Water
helps to fold the template in a more curved form
w60x, but also generates more hydrophilic silanol ends.
A more hydrophilic HI (wateryinorganic) tends to maximize interactions with the hydrophilic block, and
enhance curvature. It seems that this modulation of the
hydrophilicyhydrophobic character of the interface
(MHHI) model is quite general in EISA-derived xerogels or films w6x.
A similar role of the interface is observed in TiO2based gels bearing different hydrophilic character w14x.
While evaporation from low-water containing solutions
leads to worm-like mesostructures, addition of acidic
water results in enhanced organization. Water plays a
twofold role: (a) by promoting Ti(IV) hydrolysis (acid
hinders condensation), hydrophilic Ti-oxohydroxo species are generated, which can swell the PEO block; (b)
water helps to better define the HI, enhancing microphase separation. Both possible routes are shown in Fig.
4. Again, the enhanced phase separation (between PEO
and PPO) results in improved mesophases. In these
systems which are more reactive towards condensation,
however, kinetic considerations (i.e. differential evaporation, effects of condensation and gel viscosity w70x)
must be considered to give a complete picture of
mesophase formation.
In summary, a thermodynamic point of view is
extremely useful, but the compatibility between two
polymers (the BC and the inorganic part, which is a
polymer itself) should be taken into account. Better
order is related to an adequate balance of the SS
interactions (DGorg) that form the mesophase, with the
SI (DGhybrid) interactions at the HI, via adjusting VTS,
h or the HLB of the template andyor the inorganic
precursor. Too strong interactions at the HI can disrupt
the formation of an organized mesophase, yielding an
intimately mixed hybrid material, presenting no ordered
segregation at the mesoscopic scale w9x. Temperature,
an essential variable, should be more thoroughly
115
explored before clear trends arise, because of the crossed

kinetic effects. It should be very interesting to apply the
theoretical tools extensively developed for BC w35x to
take into account the presence of an inorganic framework; some works in simulation of these complex
systems have recently emerged w7173x, which are an
interesting starting point to comprehension.
5. Role of the inorganic condensation: a race towards
order
From the kinetics point of view, the formation of an
organized hybrid mesostructure is the result of the
balance between two competitive processes: phase separationyorganization of the template vs. inorganic
polymerization.
5.1. Silica
In precipitation-based synthesis, it seems that a surfactant-rich precipitate is first formed, which evolves
into a more or less organized solid, depending on the
synthesis conditions. The first near-neutral pH synthesis
conditions introduced by Pinnavaia and coworkers lead
to worm-like materials. Silica condensation rates are
slower in mild acidic media (pH f pHiepsilica 2); this
should permit to attain a higher order in this pH range,
the kinetic constants (ki) of the different processes
should be ordered as follows: w57x
kinter)korg)kinorg.
In these conditions, the precipitation of ordered phases
is controlled by the self-assembly involving the HI (Fig.
4a). Under this view, it is natural that less organized
phases are obtained at higher pH (57), where fast
silica polymerization prevails over order.
Addition of Fy anions helps to obtain well-defined
mesostructures even in conditions where silica condensation is fast. Kim et al. reported that highly ordered
mesophases can be obtained between pH 0 and 9 w74x.
Addition of Fy anions (known as condensation catalysts) can control both hydrolysis and condensation;
alternatively, fluoride ions could compete for the water
molecules or exert a salting out effect on PEO blocks
w75,76x. It is also possible that fluoride could assist
silica dissolutionreprecipitation, leading to better order.
More information is needed to answer this issue. Cations
also seem to affect organization; indeed, Zhang et al.
created highly ordered silica by adding M nq cations
(Liq, Co2q, Ni2q,) to the reaction media. A new
(S 0M nq)I 0 pathway was invoked (Fig. 4a) w77x. In a
thorough study on the effect of electrolytes, Bagshaw
proposed a more complete (S 0M q)(X yI 0) model for
the HI, where cations and anions play different roles
w78x. Another Fy based method is the elegant two-step
116
Fig. 5. (A) Thickness evolution along time of a mesostructured TiO2 -F127 film; corresponding 2D-SAXS in situ images are also shown. Organization comes after the drying line. (B) Acidity controls Ti(IV)-oxo condensation. (a) For low acidic solutions wHq xywTix-1, inorganic condensation is faster than mesophase formation, and worm-like mesostructures are obtained. (b) When wHq xywTix)1, condensation is hindered and
rearrangements leading to a well-ordered cubic phase are possible. Adapted from Ref. w70x.
` et al. w39x, where

synthesis developed by Boissiere
hydrolysis and condensation are separated. Hybrid silicacovered micelles are formed in the first stage, which
present an alkyl core, PEO inner shell and silica outer
shell w79x. The following step involves condensation of
the outer silica by dilute Fy, leading to organized
materials between pH 2 and 4. Synthesis performed at
higher or lower pH values, where silica condensation is
faster, lead to less ordered materials.
5.2. Non-silica
These systems present very fast inorganic condensation kinetics. There are several strategies to retard
condensation, such as complexation, acidification or
controlled hydrolysis w6x. The most successful is to
directly turn on hydrolysis and turn off condensation
by using highly acidic aqueous media (pH-1), and
work in EISA conditions w12,13,14 x. This has been
applied to xerogels w12,13,14x, films w16,17x and
aerosols w55x. An interesting alternative is to use preformed entities, such as titanium-oxo clusters w14,80x
or nanoparticles w81x. Non-hydrolytic conditions yield
thick wall mixed oxides from complex molecular precursors w15x.
5.3. Films
Mesoporous thin films and membranes are particularly
interesting for optical, membrane or photovoltaic applications. PEOPPOPEO and alkyl-PEO templated films
showing worm-like, cubic or hexagonal symmetry have
been synthesized w16,17,29,53x. The mesostructure
symmetry and orientation in space are determined by
2D-SAXS. At the same time, interferometry measurements can determine film thickness. Both techniques
can be coupled to follow film formation in situ
w29,70,82,83x (Fig. 5a). Some interesting trends
arise: (a) ordered phases appear after the drying line
(i.e. after the film reaches its final thickness), where a
hybrid LC is formed. (b) The presence of water favors
order. Indeed, external humidity (RH%) is a crucial
variable, as it can control the water flux to or from the
film. (c) As-prepared films are flexible hybrid mesophases, presenting low inorganic condensation; therefore, post-processing can help to improve ordering or
even change the initial phase. (d) A low inorganic
condensation degree favors order. A successful mesostructured film formation arises from a competition
between two parallel processes: (a) efficient solvent
evaporation will trigger the formation of a mesophase;
here, the relevant factors are the template concentration,

the solvent nature and external RH (water evaporationy
accretion). (b) The stiffening rate of the resulting hybrid
mesophase (or gel); this is basically affected by the
water and acid contents, wMx (MsSi, Ti, Zr,), and
viscosity w70x. These concepts can also be applied to
the formation of xerogels, taking into account the scaling
up (film thickness is approximately 100300 nm for a
thin film, and 1001000 mm for a xerogel) w69x.
6. From organised hybrids to mesoporous oxides:
porosity and accessibility
6.1. Silica
The successive steps leading to a mesoporous oxide
from a mesostructured hybrid are shown in Fig. 2. Most
of the work has been performed on PEO-based templated
silica. Recurrently, the obtained oxides show micro-and
mesoporosity; this has been attributed to the capacity of
the PEO block to interpenetrate the inorganic network,
as previously discussed. Smarsly et al. w84x developed
a multiphase model, in which the mesopore size
depends on both NA and NB the lengths of the hydrophobic and hydrophilic blocks, respectively. A single
relationship can describe the conformation of the surfactant along the hydrophobicyhydrophilic interface. The
interface area per molecule (b) obeys an empirical
scaling law b 2sb02 NA0.16NB0.4. This model seems to be
more complete than the classical two phase model
(Fig. 4b), where only the hydrophobic block was related
to the pore size.
Processing of a mesostructured hybrid prior to calcination is also determinant for pore size, surface area
and porosity. These issues affect wall thickness and
stability, which is utterly important regarding stability
in demanding conditions (catalysis, membranes,). For
SBA-15 materials, aging time and temperature are particularly important w8,11,40,41,63x. Kruk et al.
found that mesoporous SBA-15 prepared from calcination of an as-prepared hybrid precursor contained a
significant fraction of microporosity; further aging of
the precursor in the mother liquors leads to an improvement on the pore size distribution (Fig. 6) w11x, in
agreement with the first work by Zhao et al. w40,41x,
and elimination of the residual microporosity; a similar
trend is found for AlSi systems w63x. Aging of an asprepared precipitate at 80100 8C seems to help segregation of the PEO blocks and the inorganic framework,
by promoting condensation of the latter. High temperatures also change the polymer behavior. It is known that
for T)60 8C, PEO blocks become less hydrophilic and
expel water w85x (the same is valid for the more
hydrophobic PPO blocks, for T)40 8C).
117
6.2. Non-silica
The principal issue regarding non-silica mesoporous
oxides is high temperature treatment. While silica walls
keep their amorphous nature upon thermal treatment,
crystalline phases arise in transition metal-based frameworks. Growth of nanocrystals beyond the wall thickness
deteriorates the mesostructure. This is one of the advantages of BC templates: walls are thicker than in the case
of molecular amphiphiles, and the first works by Yang
et al. w12,13x showed partially crystallized inorganic
walls. However, a careful post treatment of the hybrid
precursors has to be undertaken to obtain higher crystallite fractions, which are indeed exciting for applications where mesoporous crystalline materials are needed
((photo)catalytic, electronic, or energy conversion). This
has been recently demonstrated for nanocrystalline titania and zirconia films w86x, and for ultrastable (T)700
8C) mesoporous yttriazirconia and ceriazirconia
films, which can be tuned by post-treatment w87x.
7. Perspectives and implications
In the last 3 years, major advances have been performed in this field, after the first successful synthesis
of BC-templated silica. In summary, a better knowledge
of the nature of the HI (particularly in PEO-based
templates) led to improve the synthesis routes, permitting one to generate tuned porosity (from micro-mesoporous to purely mesoporous) robust silica. The
possibilities have been extended to non-silica oxides
with crystalline walls, which is itself a great advance.
Thanks to a variety of procedures, it is possible to
process these oxides as powders (with controlled particle
size), films, monoliths or membranes. Systematic studies
are leading to a better description of the role of synthesis
and processing variables. This better understanding with
no doubt conveys to reproducible syntheses; applications
based on thoroughly characterized materials can be now
envisaged.
Such an innovative field of research should strongly
benefit and become more mature through better system
understanding and further developments in areas such
as: interfacial chemistry and physical chemistry of nanocomposites, study of pseudo phase diagrams of hybrid
composites, study of order-disorder transition in hybrid
nanosystems, synthesis of new BC with tuned functionalities (carrying chirality for example), development of
BC based hybrid materials that can adapt their structure
and response to external stimuli w36x, and application
of modern theoretical techniques w7173x.
A strong effort is currently devoted to understand and
rationalize the formation mechanism of mesostructured
oxides in order to be able to control their design for
targeted properties. In situ methods are indeed allowing
a breakthrough in the understanding of the formation
118
Fig. 6. (a) Evolution of d100 (h), mean pore diameter (3) and BET surface area (j) along aging for SBA-15, data from Ref. w41x. (b)
Evolution of BET surface area (j) and microporosity fraction (h) along aging for SBA-15 silica; data from Ref. w11 x. (c) Scheme of the pore
evolution upon thermal treatment, depending on pre-treatment and aging.
processes of these materials w29 x. The numerous examples reported in the literature clearly demonstrate that
the nanostructure of these materials, their degree of
organization and their final properties strongly depend
not only on the chemical nature of their components,
but also on the synergy between these components.
Thus, a key point for the design of new materials is the
tuning of the nature, the extent and the accessibility of
the inner interfaces w6,20x. Optimized formation paths
of these materials result from the delicate adjustment of
the balance andyor of the correct sequencing of different
physicochemical processes under thermodynamic and
kinetic control. Moreover, not only the chemical parameters but also the processing conditions are of paramount importance to obtain robust and reproducible
systems w86,87x.
However, the development of this area is still on its
infancy: indeed, most of the performed research is based
on commercially available macromolecules, spurred by
the first successful PEO-based materials. The horizon is
broader: BC can be precisely tailored by controlled
polymerization techniques w7x. Work devoted to the
synthesis of new BC specifically designed to construct
novel hybrid or inorganic architectures should conduct
to exciting opportunities. Recent work on zwitterionic

BC w88x, double-hydrophilic BC w89x or rodcoil
BC w36x emphasize the richness and versatility provided
by tailor-made BC. New polymeric ABC triblocks
should be explored, selectively functionalized to allow
the formation of hybrid assemblies presenting spatial
ordering at different length scales (i.e. knitting patterns
w7x). Other important future branch is related to the
repercussion of chirality from the molecular level to the
micrometer or even to the macroscopic length scales.
Multiscale texturation can be achieved by combining
different approaches: controlled phase separation
w90,91x, cooperative self-assembly and liquid crystal
topological defects as templates w92x, micromoulding
w27x with macromolecular organic or biological templates and their combination w27x. The creation of
multifunctional materials having hierarchical structures
and the specific localization of a given function at a
given scale will be the next challenge. The design of
intelligent membranes that would be able to associate
sensing, separation and catalytic processes is an
example.
In many senses, Nature can be considered as a model
or a school of design for advanced materials w93x.
Since millions of years, Nature produces inorganic
materials and hybrid composites with a remarkable
efficiency by employing highly selective structures. In
diatoms and sponges, the formation of inorganic components (i.e. silica) with precisely controlled and beautiful morphologies is directed by biopolymers such as
proteins and polysaccharides in water under mild conditions. The magnificence and the complexity of these
biomineralized architectures, associated with the growing demand for friendly environmental synthesis conditions, spurred much interest in biomimetic approaches
in materials science w94x. Several biopolymers such as
collagen w95,96x, chitin w97x or chitosan w98x have been
used to texture inorganic silica based materials at mesoand macroscopic scales. Modified biopolymers are also
useful templates for microymacrostructured nanoparticle-based superstructures w91 x. The demonstration that
silicatein (a protein found in some silica sponge spicules) can lead to silica structures with controlled shapes
w99x spurred interesting work in bio-derived BC
w100x. This bio-BC can also template the assembly of
complex multiphase systems, due to their selective
functions w101x.
Regarding applications, BC-templated materials
should present improved properties in catalysis (SBA15 is being intensively studied w11x) or water remediation w21x. Separation is another interesting area,
where the full advantages of pore tailoring can be
revealed w102,103x.
In this mushrooming field, future approaches should
include integrative synthesis pathways: coupling of multiscale templating and morphosynthesis, associated to
119
external stimuli (applied fields, fluxes, mechanical constraints, imprinting,). This land of research is by
essence multidisciplinary and the success of this race to
advanced materials will strongly depend on the ability
of physicists, chemists, biologists and chemical engineers to collaborate efficiently.
Acknowledgments
The authors are indebted to F. Warmont for the TEM
images. GJAASI acknowledges financial support from
Antorchas
St Gobain Recherche, SECyT, Fundacion
(RG 14056-18), and Gabbos Re-entry Grants.
References and recommended reading
of special interest
of outstanding interest
w1x This subject has received attention in a previous issue; see
e.g. Blume A, Zemb T, editors. Self-assembly: weak molecular forces at work for building mesoscopic architectures.
Curr Opinion Colloid Interf Sci 2002; p. 7, 66 and subsequent
articles.
w2x Mann S, Burkett SL, Davis SA, et al. Chem Mater
1997;9:2300.
An interesting conceptual review where the different approaches
to build inorganic or hybrid networks through Organized Matter
Chemistry are presented in a tutorial fashion.
w3x Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS.
Nature 1992;359:710.
This paper launched the field of mesoporous materials.
w4x For a state of the art in the field of nanostructured materials,
see Chem Mater 2001, p. 13, Special Issue on Nanostructured
and functional materials. Eckert H, Ward M, editors, and all
articles therein.
w5x Many recent symposia and meetings have been dedicated to
nano-, mesostructured and meso-ordered materials. See for
example (a) Stud Surf Sci Catal, Nanoporous Materials III,
Sayari A, Jaroniec M, editors, Amsterdam: Elsevier; 2002.
(b) Mater Res Soc Symp, 2002, vol. 726, OrganicyInorganic
Hybrid Materials 2002, Laine RM, Sanchez C, Yang S,
Brinker CJ, editors (c) Mater Res Soc Symp, 2002, vol.
728, Functional nanostructured materials through multiscale
assembly and novel patterning techniques, Tolbert SH, Dickson RM, Hammond PT, editors. (d) 3rd International Mesostructured Materials Symposium (IMMS), Jeju, Korea, July
811 2002. Available from http:yywww.imma.cay
imms2002.html.
w6x Soler-Illia GJAA, Sanchez C, Lebeau B, Patar J. Chemical
strategies to design textured materials: from microporous and
mesoporous oxides to nanonetworks and hierarchical structures. Chem Rev 2002;102:4093 138.
A complete, updated and comprehensive review on the synthesis
routes leading to templated solids, from zeolites to mesoporous,
macroporous and multiscale materials, which includes recent work
and discussion of the proposed formation mechanisms of textured
hybrid phases.
w7x Forster
S, Plantenberg T. Functional structural hierarchies

from self-organizing polymers. Angew Chem Int Ed
2002;41:688 714.
An excellent review on the use of block copolymers, covering
every relevant aspect, from self-organization aspects, liquid crystal
phases, use of BC as supramolecular templates for hybrid struc-
120
tures or nanoreactors for precipitation of nano-objects, to the

possibility of creation of hierarchical assemblies.
w8x Davidson A. Modifying the walls of mesoporous silicas
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A complete review discussing the effect of synthesis and postsynthesis treatments in the wall stability of MCM-41 and SBA15 type mesoporous silicas, which is a central subject for catalytic
applications.
w9x Melosh NA, Lipic P, Bates FA, Wudl F, Stucky GD, Chmelka
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In this remarkable paper, a mesostructured monolith templated
with F127 ((EO)106(PO)70(EO)106), is completely characterised by XRD, TEM and multinuclear NMR. It is clearly established
that the silica network is entangled with the EO fragments. In
addition, for low polymerysilica ratios, PO blocks also interact
with silica, leading to non-ordered hybrids. For higher polymer
contents, the POyPO interaction takes over the silicayPO interactions, the mesostructure is better defined, and highly ordered
hybrid mesophases are obtained.
w10x Simon PFW, Ulrich R, Spiess H, Wiesner U. Block copoly mer-ceramic hybrid materials from organically modified
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This is a short review of the work by Wiesner and coworkers in
the synthesis of organically modified aluminosilicates presenting
mesoscale preiodicity. The use of PEO-PI (polyisoprene) diblock
copolymers as a template leads to mesostructured hybrids presenting cubic Plumbers nightmare symmetry. Selective solvent swelling of the hydrophobic regions of the templates leads to a whole
array of controlled nanometric objects, such as fibres or nanospheres. Heat treatment permits to obtain mesoporous full ceramic
materials.
w11x Kruk M, Jaroniec M, Ko CH, Ryoo R. Characterization of
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8.
This paper demonstrates that the pore size and features (microy
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parameters (hydrothermal treatment time and temperature, washing,). The cell shrinkage was found to be relatively high, if
compared to CTAB-templated MCM-41. The observed structural
properties and porosity features are explained in the basis of
changes in the degree of penetration of the EO chains in the silica
wall. Pore size and can be tailored by judiciously changing the
synthesis and aging steps.
w12x Yang P, Zhao D, Margolese DI, Chmelka BF, Stucky GD.
Generalised syntheses of large-pore mesoporous metal oxides
with semicrystalline frameworks. Nature 1998;356:152 5.
A very simple and pioneering approach to obtain thermally stable,
mesoporous metal oxides, from
ordered, large-pore (up to 140 A)
highly reactive metal centers (Ti, Zr, Sn,), by resorting to EISA
method in highly acidic solutions resulting from dissolution of the
metal chlorides in ethanol.
w13x Yang P, Zhao D, Margolese DI, Chmelka BF, Stucky GD.
Block copolymer templating syntheses of mesoporous metal
oxides with large ordering lengths and semicrystalline framework. Chem Mater 1999;11:2813 26.
The full paper of the preceding article, states in more detail the
synthesis and characterization of mesoporous TiO2, ZrO2, SnO2,
and mixed SiyTi and ZryTi oxides. In principle, it is possible to
obtain hexagonal and cubic mesophases, by varying the surfactant
(PEOPPOPEO or PEOPBO block copolymers).
w14x Soler-Illia GJAA, Scolan E, Louis A, Albouy PA, Sanchez
C. Design of mesostructured titanium oxo based hybrid
organicinorganic networks. New J Chem 2001;25:156 65.
A detailed study on the EISA-based synthesis of titania-nonionic

surfactant hybrid composites (using PEOPPOPEO block copolymers, or PEO-alkyl surfactants as templates). The authors demonstrate the essential role of water in the mesoscopic organization.
In low water conditions, worm-like structures are obtained; strong
PEOyTi(OH)y(OR)x interactions are responsible for poor polymer
folding. Organised mesophases require the presence of acidic water
in order to enhance phase separation and hinder inorganic polymerization. In this way, organized mesostructures are obtained, where
the pore size is commensurate with the template mass. The
proposed model for mesophase formation is focused on the competition between the hydrophobicyhydrophilic character of the
inorganic precursor and the template, and the complexing power
of the latter.
w15x Kriesel JW, Tilley TD. General route to homogeneous,
mesoporous, multicomponent oxides based on the thermolytic transformation of molecular precursors in non-polar
media. Adv Mater 2001;13:331 5.
Unlike most of the synthesis routes reported, this route relies on
the non-hydrolytic condensation of mixed alkoxides (ZrySi, TaySi,
FeySi,) in non-polar media. Worm-like mesostructures bearing
pore, 6080 A
thick walls and 400600 m2 ygy1 surface
2540 A
area are obtained after thermal treatment of these complex alkoxides in toluene solutions at 135 8C using ABA triblock copolymers.
This route is interesting for the possibility of obtaining very welldispersed and homogeneous mixed metal oxides.
w16x Grosso D, Soler-Illia GJAA, Babonneau F, et al. Highly
organised mesoporous titania thin films showing monooriented 2D hexagonal channels. Adv Mater 2001;13:1085.
The first report on oriented titania mesoporous films, with a
complete characterization by 2D-XRD and TEM. The necessary
role of water to obtain well-defined mesophases is stressed.
w17x Crepaldi EL, Soler-Illia GJAA, Grosso D, Albouy PA, San chez C. Design and post-functionalisation of highly ordered
mesoporous zirconia thin films. Chem Commun 2001;1582
3.
Hexagonally textured zirconia films are synthesized by a two-step
EISA-based method using Brij 58 as template. Once the surfactant
is removed, organic functions can be grafted on the pore surface,
by taking advantage of phosphate, acetylacetonate or carboxylate
groups, which are able to complex Zr.
w18x Kim SS, Pauly TR, Pinnavaia TJ. Non-ionic surfactant
assembly of ordered, very large pore molecular sieve silicas
from water soluble silicates. Chem Commun 2000;1661 2.
Mesoporous silica is obtained from silicates and P123 triblock
copolymer. See also Kim JM, Stucky GD. Synthesis of highly
ordered mesoporous silica materials using sodium silicate and
amphiphilic block copolymers. Chem Commun 2000, pp. 1159
1160.
w19x Yu C, Tian B, Fan J, Stucky GD, Zhao D. Nonionic block
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2002;124:4556 7.
Monodisperse 1 mm rhombododecaedron single crystals of mesoporous silica (Im3m cubic structure) have been produced by
precipitation from silicon alkoxides using F108 block copolymer
(PEO)108(PPO)50(PEO)108 . Particle size control is apparently related to the presence of high concentrations of inorganic salts
(K2SO4).
w20x The essential concepts of pore modification have been
developed by the groups of MacQuarrie, Mann, Stein, Ozin,
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A, Hammoudi S. Periodic mesoporous silica-based organic
inorganic
nanocomposite
materials.
Chem
Mater
2001;13:31513168.
Although most of the reported works are of MCM-41 like materials,
this is an excellent review.
w21x Richer R, Mercier L. Direct synthesis of functional meso porous silica by neutral pH nonionic surfactant assembly:
factors affecting framework structure and composition. Chem
Mater 2001;13:2999 3008.
This paper presents a very nice study on the direct preparation of
thiol-grafted mesoporous silica of controlled particle size by Fy
catalyzed precipitation in the presence of nonionic oligomeric
templates. A complete analysis of the synthesis variables such as
template, reaction temperature and thiol contents is presented.
Worm-like phases are generally obtained, except in the case of Brij
76 (C18H37(PEO)10OH)), which leads to well-organized hexagonal
mesostructures.
w22x Muth O, Schellbach C, Froba
M. Triblock copolymer assisted
synthesis of periodic mesoporous organosilicas (PMO) with
large pores. Chem Commun 2001;2032 3.
Large-pore silica bearing CH2CH2 groups within the walls is
synthesized using P123 as template. This is the first report on a
large pore full organosilica framework.
w23x Lu Y, Fan H, Doke N, et al. Evaporation-induced self
assembly of hybrid bridged silsesquioxane film and particulate mesophases with integral organic functionality. J Am
Chem Soc 2000;122:5258 61.
Mesoporous silica with organic functions within the walls is
produced in the shape of films or aerosols, using ionic or oligomeric
nonionic surfactants.
w24x Corriu RJP, Mehdi A, Reye C, Thieuleux C. Mesoporous
hybrid materials containing functional organic groups inside
both the framework and the channel pores. Chem Commun
2002;1382 3.
A metal chelating species, (1,4,8,11-tetraazacyclotetradecane,
cyclam) is incorporated in the walls of a hybrid mesoporous silica
by a precipitation one-pot route, using P123 as template and Fy
as catalyst. After template extraction, other organic groups can be
post-grafted, leading to bifunctional mesoporous silica.
w25x Trong On D, Kaliaguine S. Ultrastable and highly acidic,
zeolite-coated mesoporous aluminosilicates. Angew Chem
Int Ed 2002;41:1036 40.
ZSM-5 zeolite seeds are used to coat the mesopores of a SBA-15like aluminosilicate. While the pore size (from the parent meso
porous oxide to the modified one) diminishes from 70 to 54 A,
and the surface area, from 800 to 465 m2 gy1 , the pore coating by
zeolite crystallites imparts strong surface acidity and high stability
to these highly ordered mesoporous aluminosilicates.
w26x Liu Y, Pinnavaia TJ. Assembly of hydrothermally stable
aluminosilicate foams and large-pore hexagonal mesostructures from zeolite seeds under strongly acidic conditions.
Chem Mater 2002;14:3 5.
Mesostructured aluminosilicate cellular foams were prepared by
from zeolite seeds FAU, MFI or BEA, using P123 as template,
and trimethylbenzene as swelling agent. This direct synthesis
approach leads to mesostructures composed of partially crystallized
zeolitic walls, which retain at least 80% of their initial porosity
and surface area after steaming tests. The approach can be extended
to the assembly of large-pore hexagonal SBA-15-like structures,
which also show a better resistance than SBA-15 to severe steaming
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w27x Yang P, Deng T, Zhao D, et al. Hierarchically ordered oxides.
Science 1998;282:2244 6.
Although not so recent, this paper remains a high standard. Porous
silica, titania and niobia patterned at multiple scale were obtained
by combining micromolding (patterning a PDMS template), polystyrene sphere templating and cooperative assembly of inorganic
species and amphiphilic poly (ethylene oxide) block copolymers.
The mesoporous structure is generated in the voids of the PS
121
colloidal crystal, via a cooperative self-assembly of the inorganic

species and the ABC template.
w28x Zhao D, Yang P, Chmelka BF, Stucky GD. Multiphase
assembly of mesoporousmacroporous membranes. Chem
Mater 1999;11:1174 8.
Sponge-like silica membranes with 3D structures have been synthesized that have adjustable macro-and mesoporosities, by combining multiscale phase segregation (microemulsion controlled
phase separation) with precipitation of a mesostructured silica,
templated with P123 block copolymer.
w29x Grosso D, Balkenende AR, Albouy PA, Ayral A, Amenitsch
H, Babonneau F. Two-dimensional hexagonal mesoporous
silica thin films prepared from block copolymers: detailed
characterization and formation mechanism. Chem Mater
2001;13:1848 56.
Synchrotron SAXS in situ is used to follow the formation of F127templated silica films made by dip-coating (EISA). Organization
takes place upon solvent removal, by a disorder to order transition.
A worm-like mesostructure is first formed, which evolves into a
highly organized p6m after drying. A complete characterization of
the oxide films is performed.
w30x Patarin J, Lebeau B, Zana R. Recent advances in the
formation mechanisms of organized mesoporous materials.
Curr Opinion Colloid Surf Sci 2001;7:107 15.
An interesting review describing the efforts to shade light on the
formation mechanisms of MCM-41 and block-copolymer templated
materials. The authors stress the importance of the interactions
between the inorganic framework and the organic template in the
development of a mesostructured phase.
w31x Ying JY, Mehnert CP, Wong MS. Synthesis and applications
of supramolecular-templated mesoporous materials. Angew
Chem Int Ed 1999;38:57.
Although not recent, this is a well-written and documented review,
which gives particular emphasis to applications.
w32x Goltner
CG, Antonietti M. Mesoporous materials by tem plating of liquid crystalline phases. Adv Mater 1997;9:431.
A short and conceptual paper, dealing with the important features
that control production of ceramic mesostructures using polymeric
liquid crystalline phases. There is also a short discussion about
templated polymeric materials.
w33x Polarz S, Antonietti M. Porous materials via nanocasting
procedures: innovative materials, and learning about softmatter organization. Chem Commun 2002; 25932604.
A basic and recent review on nanocasting techniques, describing the
current routes to construct mesostructured hybrids by self-assembly
of surfactants and polymers.
w34x Schuth
F. Non-siliceous mesostructured and mesoporous

materials. Chem Mater 2001;13:3184.
A very complete review of mesoporous non-silica phases, including
carbons and other non-oxide composites.
w35x Bates FS, Fredrickson GH. Block copolymersdesigner soft
materials.
Phys.
Today,
February
1999,
32.
A tutorial paper; an interesting source of advances in block copolymer synthesis, application, and understanding of the theoretical
models beneath the great variety of possible mesostructures.
w36x Klok HA, Lecommandoux S. Supramolecular materials via
block copolymer self-assembly. Adv Mater 2001;13:1217
29.
An interesting review about tailor-made block copolymers, with
particular emphasis in rodcoil (the rod segments are rigid) diblock
copolymers or oligomers. The most interesting discussion concerns
the possibilities of integrating these copolymers in stimuli-sensitive
materials.
w37x Tanev P, Pinnavaia TJ. A neutral templating route to meso porous molecular sieves. Science 1995;267:865 7.
122
This is a pioneering paper that demonstrated a neutral templating

route for preparing mesoporous molecular sieves based on hydrogen-bonding self-assembly between neutral primary amine micelles
(S 0) and neutral inorganic precursors (I 0). The S 0I 0 templating
route is also useful for the synthesis of other oxide mesostructures
(aluminas) that may be less readily accessible by electrostatic
templating pathways.
w38x Bagshaw SA, Prouzet E, Pinnavaia TJ. Templating of meso porous molecular sieves by nonionic polyethylene oxide
surfactants. Science 1995;269:1242.
The use of PEO-based surfactants (alkyl-PEO and triblock PEO
PPOPEO) as templates for mesoporous sieves is demonstrated
for the first time. Worm-like or disordered hexagonal MSU-1 to 3
silica present up to ca. 1200 m2 gy1 surface area and 2.55.8 nm
pore size.
w39x Boissiere
` C, Larbot A, van der Lee A, Kooyman P, Prouzet
E. A new synthesis of Mesoporous MSU-X silica controlled
by a two-step pathway. Chem Mater 2000;12:2902 13.
A two-step synthesis is developed to obtain mesoporous silica with
controlled particle size using nonionic surfactants or BC as templates. A first step at low pH generates a stable solution of micellar
hybrid objects. A subsequent condensation step is triggered by
increasing pH or adding Fy as condensation catalyst; the latter
method permits a higher control on nanostructure and particle
morphology.
w40x Zhao D, Feng J, Huo Q, et al. Science 1998;279:
548.
A seminal paper on the synthesis and characterization of BCtemplated silica. Synthesis using large block copolymers (P123
and F127) is reported for the first time.
w41x Zhao D, Huo Q, Feng J, Chmelka BF, Stucky GD. Nonionic
triblock and star diblock copolymer and oligomeric surfactant
synthesis of highly ordered, hydrothermally stable, mesoporous silica structure. J Am Chem Soc 1998;120:6024 36.
This is a central paper reporting a family of highly ordered
silica structures (SBA-11, SBA-12, SBAmesoporous (20300 A)
15, SBA-16,) by using commercially available PEO-based polymers, to obtain cubic (Im3m or Pm3m), 3Dhex (P63 ymmc), 2D
hexagonal (p6mm) or lamellar (La) symmetries. Synthesis are
performed in acidic medium; it is proposed that the assembly of
the inorganic and organic periodic composite materials takes place
by an H-bonding based (S 0H q)(X yI q) pathway. The assembly
rate varies according to rsk wHqx0.3 wCly x0.3 . The easy to reproduce SBA-15 (2D-hex) is the most studied large-pore phase;
however, the pore features and the wall structure vary with thermal
treatment (see below). The cubic SBA-16 is more difficult to
reproduce.
w42x Sakamoto Y, Kaneda M, Terasaki O, et al. Direct imaging
of the 3D pores and cages of mesoporous materials. Nature
2000;408:449.
This is a superb characterization of the complex mesostructures of
3D-cubic silica-based materials.
w43x Yu C, Yu Y, Zhao D. Highly ordered large caged cubic
mesoporous silica structures templated by triblock PEO
PBOPEO copolymer. Chem Commun 2000;575:576.
Large pore silica is obtained from polymers presenting enhanced
phase separation due to the presence of poly(butylene oxide)
blocks.
w44x Cho EB, Kwon KW, Char K. Mesoporous organosilicas
prepared with PEO-containing triblock copolymers with different hydrophobic moieties. Chem Mater 2001;13:3837 9.
PEOPLGAPEO block copolymers are used to template organosilica frameworks, which are less polar than pure silica inorganic
structures.
w45x Attard GS, Glyde JC, Goltner
CG. Liquid-crystalline phases

as templates for the synthesis of mesoporous silica. Nature
1995;378:366 8.
This is the first report on the templating of silica mesostructures

from ordered liquid-crystalline mesophases; the resulting silica
phase, with pores of ca. 3 nm diameter, is a cast of the organic
mesophase. This is the first attempt to use phase diagrams as a
guideline to predict the synthesis of mesoporous silica from the
assumption that the phase diagrams of the surfactantysilicaywater
system at high surfactant concentration is similar to the (known)
phase diagram of surfactant water alone. Ordered and oriented
mesostructured monoliths can be synthesized this way.
w46x Attard GS, Bartlett PN, Coleman NRB, Elliott JM, Owen
JR, Wang JH. Mesoporous platinum films from lyotropic
liquid crystalline phases. Science 1997;278:838 40.
Mesoporous platinum films are produced by electrochemical reduction of platinum salts confined to the aqueous environments of
lyotropic LC phases. The films present well-defined long-ranged
porous nanostructure and high specific surface areas. For a recent
review on electrochemical deposition of periodic non-oxide materials, see Braun PV, Wiltzius P. Curr Opin Colloid Interf Sci 2002,
p. 7, 116.
w47x Braun PV, Osenar P, Tohver V, Kennedy SB, Stupp SI.
Nanostructure templating in inorganic solids with organic
lyotropic liquidcrystals. J Am Chem Soc 1999;121:7302 9.
A very interesting approach to create dispersions of semiconductor
nanoparticles, by in situ precipitation in LC phases.
w48x Templin M, Franck A, Du Chesne A, et al. Organically
modified aluminosilicate mesostructures from block copolymer phases. Science 1997;278:1795 8.
A pioneer paper in the field, although less popular than the Stucky
work w40,41x because of the less common inorganic and
template used. Organically modified aluminosilicate mesostructures
were synthesized from two metal alkoxides with the use of
poly(isoprene-b-ethylene oxide) block copolymers (Pl-b-PEO) as
structure directors. By increasing the fraction of the inorganic
precursors with respect to the polymer, morphologies expected
from the phase diagrams of diblock copolymers were obtained.
The length scale of the microstructures and the state of alignment
were varied using concepts known from the study of block
copolymers. These results suggest that the use of higher molecular
weight block copolymer mesophases instead of conventional lowmolecular weight surfactants provides a simple, easily controlled
pathway for the preparation of various silica-type mesostructures
that extends the accessible length scale of these structures by about
an order of magnitude.
w49x Kramer
E, Forster
S, Goltner
C, Antonietti M. Synthesis of
nanoporous silica with new pore morphologies by templating
the assemblies of ionic block copolymers. Langmuir
1998;14:2027 31.
w50x Goltner
C, Berton B, Kramer
E, Antonietti M. Nanoporous
silica from amphiphilic block copolymer (ABC) aggregates:
control over correlation and architecture of cylindrical pores.
Chem Commun 1998;2287 8.
w51x Goltner
CG, Henke S, Weissenberger MC, Antonietti M.

Mesoporous silica from lyotropic liquid crystal polymer
templates. Angew Chem Int Ed 1998;37:613 6.
w52x Brinker CJ, Lu Y, Sellinger A, Fan H. Evaporation-induced
self-assembly: nanostructures made easy. Adv Mater
1999;11:579.
The EISA method is useful for creating mesostructures from
relatively dilute solutions. Films, xerogels or powders showing a
great degree of organization and orientation are formed by selectively evaporating volatile solvents from relatively dilute solutions.
All the essential concepts that permit to develop synthesis methods
for this versatile route are summarized in this paper.
w53x Zhao D, Yang P, Melosh N, Feng J, Chmelka BF, Stucky
GD. Continuous mesoporous silica films with highly ordered
large pore structures. Adv Mater 1998;10:1380.
The first report on transparent silica films presenting large-size
pores, using block copolymer templates and hydrolysis of silica
alkoxides. Cubic (Pm3m and Im3m) or hexagonal (p63 ymmc, 3D
hex; or p6mm, 2Dhex) structures are obtained. While hexagonal
structures are obtained using templates with a higher PPO fraction,
F127-based systems lead to cubic or 3D hexagonal mesostructures.
w54x Melosh NA, Davidson P, Chmelka BF. J Am Chem Soc
2000;122:823.
2D-XRD studies on the monoliths of reference w9x show that
oriented 2D-hexagonal phases are obtained with a minor cubic
phase.
w55x Grosso D, Soler-Illia GJAA, Crepaldi E, Sanchez C. Nano crystalline Transition Metal Oxide Spheres with controlled
multi-scale porosity. Adv Funct Mater 2003;13:37 42.
Multiscale porous nanocrystalline transition metal oxide materials
(MO2, MsTi, Zr, Ce) were prepared through a one-step aerosolbased method. By combining aerosol processing and specific
treatments, micronic spheres presenting periodically organized
meso-porous crystalline network were synthesised. Multi-scale
templating by latex beads can also be applied, resulting in spheres
presenting macro- and mesopores, in which each single porosity
can be easily and independently adjusted. In addition, a porosity
gradient can be generated. The strategy highlighted in the present
report can be easily applied to elaborate many solgel hierarchically structured derived materials.
w56x Joo R, Kruk SH, Jaroniec M. Ordered mesoporous carbons.
Adv Mater 2001;13:677 81.
This paper reviews the synthesis methods for ordered mesoporous
carbons. The synthesis procedure involves infiltration of the pores
of the template with appropriate carbon precursor, its carbonization,
and subsequent template removal. MCM-48, SBA-1, and SBA-15
silicas were successfully used to synthesize carbons with cubic or
hexagonal frameworks, narrow mesopore size distributions, high
BET specific surface areas (up to 1800 m2 gy1), and large pore
volumes. See also Joo SH, Ryoo R, Kruk M, Jaroniec M. Evidence
for general nature of pore interconnectivity in 2-dimensional
hexagonal mesoporous silicas prepared using block copolymer
templates. J Phys Chem B 2002;106:46404646. A recent paper
describing the synthesis of mesoporous CMK-3 carbons using twodimensional (2-D) ordered mesoporous silicas as casts. Highly
ordered SBA-15 and MSU-H silicas were synthesized using different silica sources and (PEO)(PPO)(PEO) triblock copolymer
templates. The ordered mesoporous silicas (pore size range 7.5
10 nm) were used as templates for the synthesis of carbon inverse
replicas, leading to 2D-Hex CMK-3 mesoporous carbons.
w57x Huo Q, Margolese DI, Ciesla U, et al. Chem Mater
1994;6:1176 91.
This is a central paper concerning mesostructured and mesoporous
materials in general. After describing the synthesis of silica and
non-silica hybrid mesophases templated with cationic or anionic
surfactants, a cooperative assembly mechanism is proposed to
explain the formation of these organized periodic hybrid composites. According to a general model, the free energy of mesostructure
formation (DGms) is composed of four main terms, which represent,
respectively the contributions of the inorganicorganic interface
(DGinter), the inorganic framework (DGinorg ), the self-assembly of
the organic molecules (DGorg ) and the contribution of the solution
(DGsol). Thus, DGmssDGinterqDGinorgqDGorg qDGsol . The cooperative templating pathway proposed in this paper emphasizes the
role of the inorganic-template interactions, i.e. the DGinter. An
excellent analysis of the effect of the different synthesis variables
(thermodynamic and kinetic aspects) in the control of the final
structure is given.
w58x Ivanova R, Alexandridis P, Lindmann B. Interaction of
poloxamer block copolymers with cosolvents and surfactants.
Colloids Surf A 2001;183185:41 53.
123
This an important paper clarifying the behavior of triblock PEO

PPOPEO block copolymers with cosolvents and other surfactants
(SDS, CTAB, C8(EO)4,). The ternary diagrams of the widely
used F127 with water and different cosolvents (ethanol, glycerol,
propylene glycol, triacetin,) are reported, and the different
regions presenting lyotropic behavior identified by SAXS. The
effects of different polarity cosolvents are interpreted in terms of
the preference of the cosolvent molecules to locate in the different
domains of the BC self-assembly, modifying the interfacial area
per BC molecule. Hydrophobic cosolvents preferentially dissolve
in the PPO rich domains; molecules presenting amphiphilic behavior (alcohols) may act as cosurfactants, and locate at the interface
between PEO and PPO blocks.
w59x Ivanova R, Alexandridis P, Lindmann B. Modification of the
lyotropic liquid crystalline microstructure of amphiphilic
block copolymers in the presence of cosolvents. Adv Colloid
Interf Sci 2001;8990:351 82.
A complete review on the effects of cosolvents on copolymer
phase behavior. By analyzing recent trends, the authors develop a
model to explain and predict cosolvent effect in PEOPPOPEO
triblock copolymer phases, by selective swelling of the block
domains with solvents presenting different polarity. The relevant
variable to fine tune the self assembly seems to be the relative
swelling per cosolvent content, per copolymer content. There
appears to be a competition between water and the cosolvent for
the swelling of the PEO sites. The presence of water results in
mesostructures presenting higher curvature (i.e., cubic instead of
hexagonal, for example).
w60x Soler-Illia GJAA, Sanchez C. Interactions between
poly(ethylene oxide)-based surfactants and transition metal
alkoxides: their role in the templated construction of mesostructured hybrid organicinorganic composites. New J Chem
2000;24:493 9.
The interactions between triblock PEO-based surfactants and metal
centers (Ti, Zr, V) are studied by coupling NMR and UVVis
spectroscopy. It has been observed that in scarce water conditions,
bicontinuous worm-like textured phases are systematically
obtained; the polymer acts as a separator, but in no way segregation
of an ordered phase takes place. An excess of acid water gives rise
to hybrid hexagonal phases; in these conditions, the mesostructure
parameters depend on the template size. These results lead to
propose an assembly mechanism that depends on the hydrophilicy
hydrophobic matching of the inorganic precursor and the template.
w61x Brinker CJ, Scherer GW. SolGel science. New York: Academic Press, 1990.
The Bible of SolGel synthesis, characterization and properties.
Everything needed to understand the complexity of solgel procedures (mainly, the control of the reaction kinetics of inorganic
hydrolysis and condensation, to obtain controlled inorganic oxide
frameworks) is here. For a classic review on non-silica polymerization, see Livage J, Henry M, Sanchez C. SolGel chemistry of
transition metal oxides. Progr Solid State Chem 1988;18:259341.
w62x Imperor-Clerc M, Davidson P, Davidson A. Existence of a
microporous corona around the mesopores of silica-based
SBA-15 materials templated by triblock copolymers. J Am
Chem Soc 2000;122:11925 33.
The XRD intensities of SBA-15-like hybrid and calcined
silica,
templated
with
(PEO)20(PPO)70 (PEO)20
and
(PEO)17(PPO)60(PEO)17 are compared in a quantitative way. The
study shows that the cylindrical mesopores are in fact surrounded
by a corona region, presenting low electronic density, which
becomes microporous after calcination. This less dense region is
still observed by XRD even after hydrothermal treatment, even if
not detected by N2 adsorption.
w63x Haddad E, dEspinose JB, Nossov A, Guenneau F, Mignon

C, Gedeon
A. Organicinorganic phase interaction in Al-
124
SBA-15 mesoporous solids by double resonance NMR spectroscopy. Stud Surf Sci Catal 2002;141:423 8.
The surface area and porosity of AlSBA-15 are shown to be
dramatically modified by hydrothermal treatment (sample aging of
0 to 48 h at 100 8C changes the SBET from 525 to 908 m2 gy1, the
pore diameter from 4.5 to 8.3 nm, and the micropore volume from
0.045 to 2=10y3 cm3 gy1). NMR double resonance studies show
that the PEO fragments are increasingly rigidified with thermal
treatment, due to a strong interaction between PEO fragments and
the inorganic skeleton; this interaction becomes larger upon aging,
suggesting that more hybrid interface is created. However, TRAPDOR 1H{27Al} experiments showed that the strength of the
polymerinorganic framework interaction remained the same, irrespective of the maturation time. This result is in disagreement with
the microporous corona proposed in other work (see Ref. w62x).
w64x Ulrich R, Du Chesne A, Templin M, Wiesner U. Nanoobjects with controlled shape, size and composition from
block copolymer mesophases. Adv Mater 1999;11:141 6.
Nanoscopic spheres, tubes or lamellae were obtained by varying
the inorganic contents of inorganic precursoryPIPEO polymer
mixtures. Nanocolloids can be obtained as hairy objects containing an inorganic core and an organic (polymer) shell, or smooth
objects, after firing.
w65x De Paul SM, Zwanziger JW, Ulrich R, Wiesner U, Spiess
HW. Structure, mobility, and interface characterization of
self-organized organicinorganic hybrid materials by solidstate NMR. J Am Chem Soc 1999;121:5727 36.
Solid state NMR is used to characterize the local chemical
environments, dynamic heterogeneities and interface nature of
mesostructured hybrid inorganicorganic composites made from
PI-b-PEO block copolymers and alkoxide precursors. The inorganic
component selectively dissolves in the PEO phase; moreover, these
two phases are intimately mixed on a molecular level.
w66x Ulrich R, Zwanziger JW, De Paul SM, et al. Solid hybrid
polymer electrolyte networks: nano-structurable materials for
lithium batteries. Adv Mater 2002;14:1134 7.
The structural and electrical (conductivity) properties of a solid
hybrid polymer (SHyP) electrolyte network are presented. The
basis of the ShyP material is an epoxide-modified aluminosilica
framework, which is templated by a PI-b-PEO polymer. The
presence of PEO moieties facilitates diffusion of Liq cations.
Lewis acid Al sites provide an enhanced conductivity, and PEO
crystallization is efficiently suppressed. This kind of electrolyte
provides a nanostructured lithium ion conductor, with interesting
mechanical and conductive properties.
w67x Goltner
CG, Smarsly B, Berton B, Antonietti M. On the

microporous nature of mesoporous molecular sieves. Chem
Mater 2001;13:1617.
A combination of SAXS and N2 adsorption is used to shed light
on the nature of mesoporous silica, prepared by TLCT, using PSb-PEO or pure PEO templates. Micropores are generated by the
penetration of the PEO chains in the silica structure; this is
particularly marked for low PEO concentrations, where each EO
chain acts as a non-specific template in the micropore scale. At
higher PEO fractions, PEO contributes both to micro- and mesopores. A gradual transition from a two-phase (i.e. hydrophobic
polymeryhydrophilic polymer embedded into the inorganic wall)
to a three phase (hydrophobicyhydrophilicyinorganic) system is
proposed, where the PEO chains are partially dissolved in the
inorganic framework, but a saturation limit dictates the beginning
of a microphase separation.
w68x Alberius-Henning PCA, Frindell KL, Hayward RC, Kramer
EJ, Stucky GD, Chmelka BF. General predictive synthesis
of cubic, hexagonal and lamellar silica and titania mesostructured thin films. Chem Mater 2002;14.
P123-templated titania films are obtained and characterized. Cubic

or hexagonal mesostructures are obtained depending on the relative
templateysilica volume fraction (VTS).
w69x Soler-Illia GJAA, Crepaldi E, Grosso D, Sanchez C. Struc tural control in self-standing mesostructured silica oriented
membranes and xerogels. Chem Commun 2002;2298 9.
An EISA-based simple and reproducible method gives rise to a
mesostructures by changing
variety of large pore (as150200 A)
a key parameter, the wH2Ox y wSix ratio (h). These mesostructures
are analogues to the already known MSU-X (wormlike), SBA-15
(2D-hexagonal p6m) or SBA-16 (Im3m space group); the cubic
and hexagonal xerogels show a high degree of organisation and
orientation. Mesostructure control can also be attained by changing
the template (nonionic block copolymer).
w70x Soler-Illia GJAA, Grosso D, Crepaldi EL, Cagnol F, Sanchez
C. Controlled design of mesostructured titania based materials. Mater Res Soc Symp Proc 2002;766 (paper Q7.3).
EISA-based mesostructured TiO2 -surfactant hybrid xerogels and
thin films are tailored by tuning the hydrolysis-condensation of the
metallic cations with the self-assembly of the organic counterparts
(hydrophilic matching approach). The formation kinetics of the
mesophase is followed by SAXS, interferometry and mass spectrometry (MS). Thermal treatment leads to high surface (100400
m2 gy1) phosphorus-free mesoporous titania films or powders,
presenting nanocrystalline walls (anatase). This approach can be
successfully extended to other non-silicate based meso-structured
materials. See also Sanchez C, Crepaldi EL, Bouchara A, Cagnol
F, Grosso D, Soler-Illia GJAA. Design of transition metal oxide
and hybrid mesoporous materials. Mater Res Soc Symp Proc 2002,
768, paper S1.2. The EISA approach can be extended to a great
variety of systems.
w71x Bhattacharya A, Mahanti SD. Self-assembly of ionic surfactants and formation of mesostructures. J Phys Condens
Matter 2001;13:1413 28.
A 2D-Monte Carlo analysis of self-assembly of silica and ionic
surfactants.
w72x Rankin SE, Malanoski AP, van Swol F. Monte Carlo simulation of amphiphile self-assembly during dip-coating. Mater
Res Symp Proc 2001;636:D1.2.1 D1.2.6.
A very interesting attempt to describe the self-assembly processes
taking place in dip-coating. A surfactantyoilywater model system
is used; upon water removal, most features of the dip-coating
process are found. The effect of a hydrophilic or hydrophobic wall
is also explored.
w73x Siperstein F, Gubbins KE. Synthesis and characterization of
templated mesoporous materials using molecular simulation.
Mol Simulation 2001;27:339 52.
An interesting paper, where the Monte Carlo method is used to
calculate equilibrium properties of surfactantysolventysilica LC
systems. A three-dimensional large cell is used for the calculations,
permitting to accurately depict the different phases obtained by
variation of the surfactantyinorganic ratio. Ar adsorption properties
modeled on the resulting material are in qualitative agreement with
experimental data.
w74x Kim JM, Han YJ, Chmelka BF, Stucky GD. One-step
synthesis of ordered mesocomposites with non-ionic amphiphile block copolymers: implications of isoelectric point,
hydrolysis rate and fluoride. Chem Commun 2000;2437 8.
This interesting work describes the effect of important synthesis
variables (pH, hydrolysis and fluoride contents) in the precipitation
of ordered hexagonal silica, templated with P123 BC. The use of
fluoride anions permits one to expand the pH scale of synthesis of
well ordered 2D hexagonal materials from 0 to 9. This is apparently
due to the quick formation of suitable fully hydrolyzed silica
species, which can adequately interact with the structure-directing
block copolymer, to yield ordered mesostructures. The presence of
residual alkoxide moieties attached to the silica centers leads to
weaker SI interactions. Fluoride anions help to complete the
hydrolysis of the inorganic precursor (TMOS, Si(OCH3 )4 ), before
significant condensation takes place. If condensation rates are
higher than hydrolysis rates, as in the case of TEOS
(Si(OCH2CH3)4), organization is not possible for pH )2.7. This
problem can be overcome if pre-hydrolyzed sols are used as
precursors.
w75x Alexandridis P, Holzwarth JF. Differential scanning calorimetry investigation of the effect of salts on aqueous solution
properties of an amphiphilic block copolymer (poloxamer).
Langmuir 1997;13:6074 82.
w76x Leontidis E. Hofmeister anion effects on surfactant selfassembly and the formation of mesoporous solids. Curr Opin
Colloid Interf Sci 2002;7:81 91.
An excellent recent review on the ion effects in the synthesis of
mesostructured and mesoporous materials. The analysis shows that
anions affect the formation of mesoporous silica in a significant
way, by different albeit complex and still misunderstood paths.
Regarding non-ionic surfactants, ions can promote ordering by
interfacial dehydration or through charging by adsorption. A very
important conclusion is that non-ionic templating in the presence
of Hofmeister salts may not always be non-ionic. These ions
should also have a relevant role along thermal treatment.
w77x Zhang W, Glomski B, Pauly TR, Pinnavaia TJ. A new
nonionic surfactant pathway to mesoporous molecular sieve
silicas with long range framework order. Chem Commun
1999;1803 4.
Mesoporous silica presenting enhanced order (3D hexagonal or
cubic) are synthesized in neutral media, using alkyl(PEO) surfactants. Electrostatic forces are introduced by adding small metal
cations (Liq, Co2q, Ni2q, Mn2q and Zn2q) that are complexed
by the EO block. Charge balance at the HI is achieved through ion
pairing with the counter anions of the metal salt.
w78x Bagshaw SA. The effect of dilute electrolytes on the forma tion of non-ionically templated wSix-MSU-X mesoporous
silica molecular sieves. J Mater Chem 2001;11:831 40.
This paper discusses important general trends which affect the final
texture of mesostructured and mesoporous silica obtained by
precipitation. While cations can modify the micelle packing by
PEO complexation; anions can modify the rate and extent of silica
hydrolysis and condensation, through the formation of pentacoordinate intermediates, fluoride being a special case.
w79x Boissiere
` C, Larbot A, Bourgaux C, Prouzet E, Bunton CA.
A study of the assembly mechanism of the mesoporous
MSU-X silica two-step synthesis. Chem Mater
2001;13:3580 6.
NMR, SAXS and DLS techniques are used to propose a structural
model for the synthesis reported in Ref. w39x.
w80x Steunou N, Forster
S, Florian P, Sanchez C, Antonietti M.

Synthesis of nanostructured polymer-titanium oxide composites through the assembly of titanium-oxo clusters and
amphiphilic block copolymers micelles. J Mater Chem
2002;12:3426 30.
A titanium-oxo cluster, Ti16O16(OEt)32 is used as pre-condensed
block for the solgel synthesis of hybrid mesostructures, using a
PS-b-PMAA block copolymer template. Cluster dispersions or a
hexagonal ordered hybrid mesostructure can be obtained by varying
the initial conditions.
w81x Hwang YK, Lee KC, Kwon YU. Nanoparticle routes to
mesoporous titania films. Chem Commun 2001;1738 9.
Anatase nanoparticles are synthesised by forced hydrolysisycondensation of peroxide complexes in acidic media. Mesostructured
thin films are prepared by dip-coating dilute solutions using PEOalkyl templates. Cubic or hexagonal phases are obtained, depending
on the aging temperature, if films are kept at high humidity.
Although anatase is used as the inorganic building block, the wall
crystallinity is low.
125
w82x Crepaldi EL, Soler-Illia GJAA, Grosso D, Albouy PA, Amen itsch H, Sanchez C. Design of transition metal oxide mesoporous thin films. Stud Surf Sci Catal 2002;141:235 42.
A combination of time-resolved synchrotron SAXS and interferometry is used to study the first steps in the formation of nonsilica oxide BC hybrid films. See also Crepaldi EL, Grosso D,
Soler-Illia GJAA, Albouy PA, Sanchez C. Formation and stabilization of mesostructured vanadium oxide thin films. Chem Mater
2002;14:33163325, and Pidol L, Grosso D, Soler-Illia GJAA,
Crepaldi E, Sanchez C, Albouy PA, Amenitsch H. Hexagonally
organised mesoporous Aluminium-oxo-hydroxide thin films prepared by the template approach. In-situ study of the structural
formation. J Mater Chem, 2002;12:557564. In situ SAXS is used
to follow the formation of vanadium (IV) oxide and Al-oxohydroxide mesostructured hybrids.
w83x Grosso D, Babonneau F, Sanchez C, et al. A first insight of
the mechanisms involved in the self-assembly of templated
SiO2 and TiO2 meso-organised films during dip-coating. J
SolGel Sci Tech 2003;26:561 5.
In situ SAXS and interferometry are used to follow the formation
of BC-templated silica and titania films. It seems that, although
the chemical differences between both systems, a general trend is
observed: organization arises after drying, a worm-like intermediate
phase is observed before the final order, and the presence of
interfaces is essential for good alignment.
w84x Smarsly B, Polarz S, Antonietti M. Preparation of porous
silica materials via solgel nanocasting of non-ionic surfactants: a mechanistic study on the self-aggregation of amphiphiles for the precise prediction of pore size. J Phys Chem
B 2001;105:10473 83.
An interesting paper in which SAXS, N2 adsorption and TEM are
used to investigate the dependence of the porosity on the characteristics (block length and volume) of alkyl(PEO) templates. A
model is developed that relates the amphiphilic organization during
nanocasting to the resulting porosity, in a thermodynamically
controlled approach. The PEO block partially dissolves in the
inorganic walls, leading to a three phase HI. Unfortunately, no
indication of the effects of post-treatment are presented.
w85x Guo C, Liu HZ, Chen JY. A Fourier transform infrared study
of the phase transition in aqueous solutions of ethylene
oxidepropylene oxide triblock copolymer. Colloid Polym
Sci 1999;277:376 81.
The phase transition between unimer and micellar phases of the
BC P105 (PEOPPOPEO) in aqueous solution has been investigated as a function of temperature using FTIR spectroscopy. The
transition of 8 wt.% Pluronic P105 in aqueous solution was found
to occur at 25 8C. As temperature increases, PO blocks appear to
be stretched conformers with strong interchain interaction, and the
formation of a hydrophobic core in the micellar phase. The EO
chains are found to change to a more disordered structure with
low-chain packing density from the unimer phase to the micellar
phase. Both the EO and PO blocks exhibit dehydration during the
phase transition.
w86x Crepaldi E, Soler-Illia GJAA, Grosso D, Sanchez C. Transition metal oxide mesoporous thin films exhibiting enhanced
thermal stability: high surface area semicrystalline coatings.
New J Chem 2003;27:9 13.
This important paper discusses the effect of post-treatment of
hybrid BC-oxide (titania, zirconia) mesophases on the thermal
treatment, particularly in high temperature stability, wall crystallinity, and contraction. It is clearly shown that the obtained hybrid
structure is largely uncondensed, and that aging under a humid
environment helps to enhance the thermal performance of BCtemplated non-silica mesoporous coatings.
w87x Crepaldi E, Soler-Illia GJAA, Grosso D, Durand D, Sanchez
C. Controlled formation of cubic and hexagonal mesoporous
yttriazirconia and ceriazirconia thin films exhibiting
126
unprecedented thermal stability. Angew Chem Int Ed

2002;42:347 51.
This paper presents thin mesoporous mixed films, presenting cubic
or 2D hexagonal mesostructure with excellent thermal stability.
w88x Schopps
M, Leist H, DuChesne A, Wiesner U. Salt-induced

switching of microdomain morphology of ionically functionalized diblock copolymers. Macromolecules 1999;32:2806
9.
Macrozwitterionic m, v PS-b-PI diblock copolymers are synthesized, by inserting a tertiary amino group at the block junction
point, and a sulfonate capping group. The self-assembly features
of this novel macromolecule are very interesting; indeed, saltinduced transitions (switching) are easier than in ordinary noncharged systems.
w89x Colfen
H. Double-hydrophilic block copolymers: synthesis

and application as novel surfactants and crystal growth
modifiers. Macromol Rapid Commun 2001;22:219 52.
Double-hydrophilic block copolymers (DHBC), a new class of
amphiphilic molecules with unique properties is presented. These
BC do not self-assemble in water, they behave as soluble polymers
or polyelectrolytes in solution, being able to ensure a simultaneous
control of particle growth and stabilization of inorganic powders.
Their amphiphilicity is just induced by the presence of an organic
or mineral substrate or by temperature or pH changes.
w90x Nakanishi K. Pore structure control of silica gels based on
phase separation. J Porous Mater 1997;4:67 111.
A complete review on phase separation-based templating. Bimodal
mesoporousmacroporous silicas can easily obtained by adjusting
hydrolysis-condensation kinetics of silicon alkoxide precursors and
a controlled phase separation phenomena between a continuous
solvent phase containing hydrosoluble polymers and a growing
inorganic network. These silica phases are being developed as
chromatographic supports.
w91x Bouchara A, Soler-Illia GJAA, Chane-Ching JY, Sanchez C.
Nanotectonic approach of the texturation of CeO2-based
nanomaterials. Chem Commun 2002;1234 5.
Phase-separation templating is used to create macroporous films.
CeO2 nanocrystalline particles are selectively functionalized to
create a compatible hybrid interface with a polypeptide template
(poly-g-benzyl-L-glutamate, PBLG). By adjusting a single parameter, such as the template to inorganic ratio, a versatile tuning
between templating effect and phase separation yields hierarchical
porous materials presenting both micro and macro porosity with
inorganic walls constituted of nano-crystalline cerium oxide
particles.
w92x Yang H, Ozin GAO, Kresge CT. The role of defect in the
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Block Copolymer-Templated Mesoporous Oxides

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Current Opinion in Colloid and Interface Science 8 (2003) 109126

Block copolymer-templated mesoporous oxides

Galo J. de A.A. Soler-Illiaa,b,*, Eduardo L. Crepaldia,c, David Grossoa, Clement

Unidad de Actividad Qumica,

Francisco syno, C.P. 07 13140-000 Paulinia, SP, Brazil

1. Mesotextured and mesoporous materials

delivery, sorption, acoustic or electrical insulation

the reproducible synthesis of materials with targeted

In this paper, we will discuss recent work dealing on

Blurry interface, swollen by

gsVyLcA0, according to (Israelachvili N, et al. J Chem Soc Farad

belong to an important family of surfactants, widely

species, in neutral media w37,38x. Some advantages

separation due to inorganic polymerization taking place

In the usual nomenclature for mesostructured materials, I stands

b. The formation of an inorganic network. The inorganic

three main components of a mesostructured hybrid

Fig. 3. Scheme of the main relationships between the solvent, the

even a metastable one. Inorganic condensation is often

or triblock) templates. Melosh et al. w9x determined

recent work by Haddad et al. suggests that microporosity

PEO templated silica, and propose an alternative model

explored before clear trends arise, because of the crossed

` et al. w39x, where

here, the relevant factors are the template concentration,

to exciting opportunities. Recent work on zwitterionic

S, Plantenberg T. Functional structural hierarchies

tures or nanoreactors for precipitation of nano-objects, to the

A detailed study on the EISA-based synthesis of titania-nonionic

colloidal crystal, via a cooperative self-assembly of the inorganic

F. Non-siliceous mesostructured and mesoporous

This is a pioneering paper that demonstrated a neutral templating

CG. Liquid-crystalline phases

This is the first report on the templating of silica mesostructures

CG, Henke S, Weissenberger MC, Antonietti M.

This an important paper clarifying the behavior of triblock PEO

CG, Smarsly B, Berton B, Antonietti M. On the

P123-templated titania films are obtained and characterized. Cubic

S, Florian P, Sanchez C, Antonietti M.

unprecedented thermal stability. Angew Chem Int Ed

M, Leist H, DuChesne A, Wiesner U. Salt-induced

H. Double-hydrophilic block copolymers: synthesis

A recent and complete progress report dealing on this exciting

Press; 2001. See also Biomimetisme

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