Chem Soc Rev

View Article Online

REVIEW ARTICLE View Journal

Ecodesign of ordered mesoporous silica materials†

Cite this: DOI: 10.1039/c3cs35451b Corine Gérardin,*a Julien Reboul,za Magali Bonneb and Bénédicte Lebeaub

Characterized by a regular porosity in terms of pore size and pore network arrangement, ordered
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B

Received 1st November 2012
DOI: 10.1039/c3cs35451b
www.rsc.org/csr
Downloaded by RMIT Uni on 19 February 2013
mesoporous solids have attracted increasing interest in the last two decades. These materials have been
identified as potential candidates for several applications. However, more environmentally friendly and
economical synthesis routes of mesoporous silica materials were found to be necessary in order to develop
these applications on an industrial scale. Consequently, ecodesign of ordered mesoporous silica has been
considerably developed with the objective of optimizing the chemistry and the processing aspects of the
material synthesis. In this review, the main strategies developed with this aim are presented and discussed.

1. Introduction Mobil Oil Company.2 The unique characteristics of periodic

Mesoporous materials have known a great development since
their discovery in the early 1990s by Kuroda et al.1 and by the
a
Equipe MACS, Institut Charles Gerhardt Montpellier, CNRS-ENSCM-UM2-UM1,
France. E-mail: gerardin@enscm.fr, jreboul@icems.kyoto-u.ac.jp;
Fax: +33 467163470; Tel: +33 467163465
b
Equipe MPC, IS2M, CNRS-UHA-ENSCMu, Mulhouse, France.
E-mail: benedicte.lebeau@uha.fr, magali.bonne@uha.fr; Fax: +33 389336885;
Tel: +33 389336882
† Part of the mesoporous materials themed issue.
‡ Present address: Institute for Integrated Cell-Material Sciences (WPI-iCeMS),
Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
mesoporous materials with very large specific surface areas
usually above 1000 m2 g1, well-defined mesopores of controlled
size (2 nm r size r 20 nm) and morphology are obtained
owing to the use of assemblies of amphiphilic organic mole-
cules as pore-forming agents and structure-directing agents,
which ensure the formation of ordered hybrid organic–inorganic
mesophases as precursors of the inorganic porous structures.2–4
Due to their very interesting surface properties, mesoporous
materials have found a great utility in different domains such
as catalysis, separation, adsorption, sensor technology, gas
storage, nanocasting, chromatography, and medicine. Since
the number of their potential applications has continued to

Corine Gérardin received her PhD
in 1992 from P. et M. Curie
University in Paris. She was
then a post-doctoral fellow in
Princeton University. Since 1994,
she has been a CNRS research
scientist; she first developed
hydrothermal NMR methodologies
for investigating the formation
mechanisms of inorganic and
microporous materials in L.
Pasteur University in Strasbourg.
Corine Gérardin After 4 years back in Princeton
University and the Complex
Fluid CNRS-Rhodia Laboratory (Cranbury), she moved to Institut
C. Gerhardt, Montpellier, in 2000. Her research focuses on
understanding the self-assembly of polymer-based complex
systems towards hybrid nanomaterials, and on the design of
nanoparticles, functional ordered mesoporous materials and
hierarchically porous zeolites.
Julien Reboul received his PhD
degree in chemistry from the
University of Montpellier II
(France) in 2009. Then he
worked as a postdoctoral fellow
in the group of Prof. Susumu
Kitagawa in the ERATO ‘‘Kitagawa
Integrated Pores Project’’ and in
the Institute for Integrated Cell-
Material Sciences (iCeMS) in
Kyoto University where he is
currently an assistant professor.
Julien Reboul His research interests include
the synthesis of hybrid porous
materials through self-assembly
processes.

This journal is c The Royal Society of Chemistry 2013 Chem. Soc. Rev.

Review Article
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
Fig. 1 Number of papers in the field of ‘‘mesoporous silica’’ and their applications
in either ‘‘separation’’ or ‘‘drug delivery’’ or ‘‘sensing’’ over the last 10 years.
grow in those different domains during the last twenty years
(Fig. 1), there has been an increasing need to develop more
ecologically sustainable procedures for the manufacture of
Downloaded by RMIT Uni on 19 February 2013
mesoporous silica and related metal oxides taking into considera-
tion the increasing concern for environmental protection. Indeed,
governments and environmental groups keep on pushing for the
development of processes and products with a minimal impact on
the environment (EuP (Energy using product) 2005/32/CE and
REACH). Since 2006, the REACH European Union Regulation
((EC) No. 1907/2006) has been addressing the production and
use of chemical substances, and their potential impacts on both
human health and the environment. Considerable efforts have
therefore been undertaken to propose greener synthesis routes,
which take into account the whole life cycle of mesoporous
materials from raw material extraction to disposal at the end of
their lifetime and consider environmental criteria such as con-
sumption of raw materials, water and energy, emissions in water
and air, waste. . .. Herein we give an overview of ecodesign of
ordered mesoporous materials. Ecodesign is an approach to
Magali Bonne received her PhD
degree in chemistry from the
University of Poitiers (France) in
2010. Then she moved to the
Nagoya Institute where she
studied the reactivity of hydro-
carbon oxidation catalysts. Then
she moved to CNEA, Buenos
Aires, where she worked on the
functionalisation of mesoporous
thin films for catalytic applica-
tions. In 2011, she got the
Magali Bonne position of Associate Professor at
the Institut de Science des
Matériaux de Mulhouse, équipe Matériaux à Porosité Contrôlée.
Her actual research focuses on synthesis and characterization of
mesoporous silica. She pays particular attention to their
functionalisation by different methods.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
design a product taking into consideration the environmental
effects of the product during its whole lifecycle: from resource
extraction to manufacture, use and disposal. Ecodesign in materi-
als science is precisely a preventive approach which aims to
propose products and processes in agreement with the funda-
mental principles of green chemistry, which include the following
different aspects: the use of ecofriendly reactants, the use of
renewable resources, the use of non-toxic solvents, the recyclabil-
ity of reactants and products, the reduction of gases emitted into
the atmosphere, and the development of integrative, fast and low
cost processes with easy implementation.5–7 Recently, a discus-
sion on the ecodesign of sol–gel chemistry has been published.8
Since most of the synthesis strategies involved in the preparation
of ordered mesoporous materials are based on the sol–gel pro-
cess, the ecodesign of mesoporous solids has been briefly dis-
cussed in that review.
Besides the environmental concern regarding mesoporous
silica materials production, the development at an industrial level
of these materials is also largely limited by the high cost of their
production. This cost is partly the result of the use of expensive
structuring agents, which need to be eliminated during the last
step of material elaboration. It is also due to the use of expensive
silica precursors such as silicon alkoxides. Therefore efforts have
recently been made to develop more economical synthesis routes
in order to favour large scale development.
The main focus of the review will be on the ecosynthesis of
ordered mesoporous silica (OMS) which present amorphous
silica pore walls. Indeed, mesoporous silica are the most
studied and well-known mesoporous materials, since silica is
ideal for controlling the structure, texture and shape of the final
materials and also presents the advantage of being safe for
medical and biological applications.
The OMS synthesis procedures usually consist of several steps
whose success, cost and degree of impact on the environment are
dependent on numerous chemical and physical parameters.
Bénédicte Lebeau carried out her
graduate work with Dr Clément
Sanchez in Paris, specializing in
the synthesis and characteriza-
tion of sol–gel hybrid materials
for optical applications. After
earning her PhD degree in 1995,
she carried out postdoctoral
research in the biomimetism
area with Prof. Stephen Mann at
the University of Bath, UK. Since
1998, Bénédicte Lebeau has been
Bénédicte Lebeau a CNRS research scientist. Her
current research in the team
Materials with Controlled Porosity of the Institute of Material
Science of Mulhouse, CNRS-UHA, France, is focused on the
synthesis of ordered mesoporous oxide-based materials. Her
primary interests are the study of the formation mechanisms of
these solids and their organic functionalization.
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
The first part of this review will introduce the different
chemical reactants which were used in the synthesis of meso-
porous materials, it will discuss the advantages and disadvan-
tages of the most classical reactants and of the newly developed
ones with regard to their ecopotential and their influence on
the properties of the resulting materials: it concerns reactants
which will be integrated after transformation into the final
material and those which do not end up in the final material.
Reactants include precursors for the silica framework on one
hand, and the organic structure-directing agents on the other
hand. The most common silica precursors are alkoxides
and salts. The former ones are usually expensive, fragile and
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
sometimes unsafe, but their advantage is that their reactivity is
easier to control. Salts are cheaper and are available in aqueous
solution. Although first studies devoted to ordered mesoporous
silica have used TEOS§ as a silica source, it was quickly reported that
sodium silicate is preferable for low-cost synthesis processes.9,10
Cost and environmental impacts of mesoporous silica synthesis
were further reduced with the utilization of silica sources derived
Downloaded by RMIT Uni on 19 February 2013
from the biomass and recycled wastes. Silica extracted from
natural mineral deposits or derived from fly ashes or rice husk
ashes was considered. And more recently, the use of industrial
wastes as silica sources was also investigated. In the latter cases,
extraction of silica precursors from the raw material is usually
achieved by a silica etching process under acidic or alkali
conditions. Although obtaining high-purity silica precursors
from these alternative resources is still challenging, synthesis
of materials with similar mesostructures and performances to
the ones derived from synthetic precursors was reported.
Several templating agents have been used since the discov-
ery of mesoporous materials. Classical surfactants, well known
for their ability to form lyotropic liquid crystalline phases, were
first used. Cationic alkylammonium surfactants were the first
to be reported, then structuring agents were quickly extended
to nonionic amine surfactants and neutral amphiphilic block
copolymers based on polyethylene oxide. But the production
method and toxicity of these amphiphilic systems remain a
major concern for the environment. Recently greener surfactant
molecules or polymers and colloids have been considered,
which include surfactants synthesized from renewable raw
materials or biologically produced surfactants. Different
polymers resulting from biomass transformation have also
been tested as pore-forming agents. However, in many cases,
replacement of classical surfactants for such new porogens did
not allow comparable materials in terms of structure and
texture to be obtained. Another approach consisted of using
structure-directing agents which can be recovered and recycled
under sustainable conditions, leading to more environmentally
friendly and less expensive production processes: the use of
porogens which are hydrosoluble or dissociable in water and
§ Lexical for common labels and abbreviations: TEOS: tetraethylorthosilicate;
TMOS: tetramethylorthosilicate; PEO: poly(ethylene oxide); PPO: poly(propylene
oxide); P123: amphiphilic triblock copolymer (PEO)20–(PPO)70–(PEO)20; F127:
amphiphilic triblock copolymer (PEO)106–(PPO)70–(PEO)106; CTAB: cetyltrimethyl-
ammonium bromide; EISA: evaporation induced self-assembly;240LISA: light
induced self-assembly.252
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
recoverable under very mild conditions has emerged as a
very promising approach. The progress in that domain was
considerable thanks to the recent development in block
copolymer synthesis techniques and in the related soft matter
studies on assembly phenomena. Some smart assemblies
of double-hydrophilic block copolymers sensitive to specific
physico-chemical parameters in water have shown to be
promising structure directing agents of silica.
The second part of the review concerns ecostrategies developed
for the processes involved in the synthesis of OMS from an
economical and environmental point of view. The processes
concern those implemented for the formation of the material
(from precursors to as-synthesized hybrid solids) and for the
template removal step. The physical parameters associated with
these processes, and thus also called processing parameters,
concern temperature and durations. They are mainly controlled
by the technologies used. Since ecodesign and scale-up for
industrialization target similar aims such as low cost, time and
energy saving processes, these two close concepts are often
considered together. Most of the OMS synthesis procedures
reported in the literature have been developed on the research
laboratory scale. But most of the laboratory-scale processes
are not appropriate for industrial developments (magnetic
stirring, Büchner funnel filtration). Improvements in ecodesign
and/or industrial development are therefore moderate. In this
review, processes involved in the synthesis of OMS have been
considered according to their application in the two main
synthesis routes: precipitation or assisted self-assembly. In
particular, progress in terms of duration, energy consumption
and scale-up has been analyzed. The template removal step is
very important since it can have significant consequences
on surface, chemical and textural properties of the porous
materials, thus affecting their use in different applications.
To eliminate the organic template, the two most common
methods are calcination and solvent extraction. However, the
high energy consumption, CO2 emissions, the long operation
time, and the use of organic solvents are not consistent with
ecofriendly design. Numerous different template removal processes
have then been studied with the objective of improving at least
one of these aspects: process time, reduction of solvents, and
also both aspects simultaneously. In all cases, the degree of
removal of the template and the impact on the surface and
textural properties have been evaluated.
Selected examples as well as an overview as comprehensive
as possible of the state of research will then be given on the
chemical reactants, on one hand, and on the physical processes
on the other hand involved in the eco-synthesis of ordered
mesoporous silica.
2. Structure-directing agents of silica
2.1. Classical surfactants as structure-directing agents
Utilization of surfactant self-assemblies to direct the silica
mineralization process is the most commonly studied route
towards the synthesis of highly ordered mesoporous silica.2,4
The general idea of using amphiphilic molecules as templates
Chem. Soc. Rev.

Review Article
is based on the fact that such systems can simultaneously form
a hybrid surfactant/silica interface and self-assemble into robust
and regular superstructures. Surfactants which are commonly
used in the synthesis of OMS are frequently classified according
to the nature of the interactions between their polar group
and the hydrolyzed silica precursors. Cationic surfactants are
efficient directing agents owing to the strong ionic interactions
between their cationic head-group and the negatively charged
silica precursors under basic conditions (synthetic route S+I
where S+ = surfactant cations and I = inorganic precursor
anions). Since the first ordered materials were synthesized
with the quaternary cationic surfactants CnH2n+1N(CH3)3Br
(with n = 8–22),2 various mesostructures were synthesized with
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
gemini,11 bolaform12 and fluorinated13 surfactants. Utilization
of neutral alkylamines was also demonstrated under neutral pH
conditions.14 In this case, the synthesis mechanism relies on
the formation of H-bonds between primary amines and neutral
inorganic species (synthetic route S0I0, where S0 = nonionic
surfactants and I0 = neutral silica species). Stabilization of the
Downloaded by RMIT Uni on 19 February 2013
hybrid interface is also possible via the formation of H-bonds
between the silicic acid and the ether oxygens of a PEO§ chain
of nonionic surfactants (synthetic route S0I0 or S0H+XI+ under
strong acidic conditions, where X = inorganic counter ions
such as Cl, Br, I, SO42 or NO3).15 The higher molecular
weight and the wide variability in size and composition of this
family of surfactants (that includes the commercial oligomeric
acid alkyl–PEO, alkyl–phenol–PEO, sorbitan ester and PEO-based
block copolymers) considerably extend the range of accessible
pore size as well as the diversity of mesopore structures attain-
able.16 A last synthetic route consists in using surfactants with
an anionic polar head under basic conditions. The charge
matching effect is ensured by the addition of cationic amino
groups of organoalkoxysilanes to the reaction mixture (synthetic
route SN+–I, where S = anionic surfactants, I = silicate
species and N+ = cationic amino groups).17
Development of silica structuring by means of supramole-
cular assemblies generated a huge amount of studies that focus
on both the design of the pore characteristics and the setting of
synthesis procedures towards milder conditions, with the
objectives of energy saving and reduced ecological impact.
The choice of alkylated quaternary ammonium salts to synthe-
size the first ordered mesoporous silica was motivated by their
similarities with the ammonium salts commonly used as molecular
templates in the synthesis of zeolites. The first ordered mesoporous
alumino-silicates synthesized by Mobil scientists in 1992 were
achieved in basic solution by using the cationic surfactant CTAB§
through the (S+I) synthetic pathway. The synthesis was achieved
under hydrothermal conditions with temperatures ranging from
100 1C to 150 1C.2 Well ordered mesoporous silica were then
produced with the same quaternary ammonium-base cationic
surfactants under acidic conditions (the S+XI+ synthetic route
where S+ = cationic surfactants, I = silicate species and X =
inorganic counterions such as Cl, Br, I, SO42 or NO3). This
acidic route presents the advantage of shorter synthesis time and
lower surfactant concentrations. Furthermore, synthesis under
acidic conditions could be achieved at room temperature.18–20
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
The success of this strategy has been tempered by the
recognition of the toxicity21 and poor biodegradability of alkyl
ammonium cationic surfactants. Cytotoxicity tests performed
on established cell lines proved that such ionic surfactants
show higher toxicity values than the nonionic ones, and
that cationic surfactants are more potent than their anionic
counterparts.22,23 Due to their relative ability to solubilize
phospholipids and cholesterol in lipid membranes, quaternary
ammonium salts affect cell permeability which may lead to cell
death. Furthermore ammonium-based surfactants denature pro-
teins and are accompanied by generalized tissue irritation.24–26
Though the impact of quaternary ammonium surfactants on the
environment is not well established yet, their poor biodegradability
as well as their inhibitory effects on biogas production were
demonstrated.27–29 Also, Sigma safety data mentioned their toxicity
to fish and aquatic invertebrates.30
The utilization of neutral primary amines for the synthesis
of hexagonal mesoporous silica in 1995 was the first example of
a neutral synthesis route S0I0.14 Advantageously, syntheses
by using neutral alkylamines are performed under mild pH
conditions, avoiding the addition of a high amount of mineral
base (NaOH) or acid (HCl). Furthermore, this route makes
possible the easy and efficient removal of the template.31,32
However, neutral primary amines are poorly soluble in water
and the addition of organic solvents to the reaction mixture is
necessary.14 Also, toxicity of alkylamines is not so different
from toxicity of quaternary ammonium surfactants.
PEO-based nonionic surfactants such as polymeric (Pluronic
P123§ and F127,§ respectively) and Tween surfactants (ethoxylated
derivatives of fatty esters of sorbitan) enabled the synthesis of
highly ordered silica phases in relatively dilute aqueous solution.16
A highly acidic pH is yet required to generate the long range
organic–inorganic coulombic interactions at the start of the
cooperative assembly process. Boissière et al. established a neutral
pathway that avoids the addition of high amounts of HCl.33–35
Nonionic PEO-containing polymeric surfactants Pluronic P123
and F127, respectively are commonly considered as biodegradable
and non-toxic compared to quaternary ammonium surfactants.
However, to the best of our knowledge, no report on their actual
toxic effects is available. Studies revealed the poor biodegradability
of both surfactants and their toxicity to several biological organisms
at relatively high concentration.8
Che et al. followed an anionic surfactant templating route
to mesoporous silica.17,36 This approach is based on the
co-structure directing effect imparted with aminosilane or
quaternized amino silane. Regarding the sustainability of this
strategy, positive points are that syntheses were achieved under
mild pH (pH = 8.5–10.2) conditions and the anionic surfactants
used are biodegradable and obtainable from sustainable
resources.37 However, the aminosilane or quaternized amino
silane used as co-structure directing agents are rather toxic.38
Synthesis procedures of the organic templates largely contribute
to the overall environmental impact of the mesoporous silica
synthesis. So far, the large majority of mesostructured silica-based
materials were synthesized from commercial surfactants for
which the hydrocarbon-rich hydrophobic segments are derived
This journal is c The Royal Society of Chemistry 2013
 View Article Online

Chem Soc Rev Review Article

from petroleum.39 Production of saturated linear alkylates is
either based on the extraction of linear paraffins from refinery
cuts containing a mixture of linear and isomerized substances40,41
or on the ethylene oligomerization.42,43 Synthetic procedures
established for the connection of the polar heads to the hydro-
phobic tails are briefly described in the following.44
Synthesis of cationic surfactants is based on the attachment of
a nitrogen atom or nitrogen-containing fragment to either fatty
carboxylic acid alpha olefins or fatty alcohols. The formation of a
primary or tertiary amine is followed by an alkylation step that
leads to the quatenary amine. Alkylation is commonly performed
under high pressure with flammable gas reactants such as
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
and clean because the only side product is water. PEO-based
low-molecular weight surfactants are derived from the polymeriza-
tion of ethylene oxide (EO). However ethylene oxide is a toxic
monomer45 and the process of alkoxylation is highly exothermic.
Toxicity of EO and the sophistication of the implementation
required for its safe manipulation are rarely mentioned, PEO-based
surfactants being usually claimed to be safe chemicals. Similarly,
PEO-based block copolymers and copolymers composed of PEO
segments covalently linked to hydrophobic PPO§ segments
(Pluronic-type copolymers) are produced by the polymerization
of ethylene oxide and propylene oxide, two toxic, flammable
and pollutant precursors.

chloromethane or with highly hazardous liquid alkylating agents
such as dimethylsulfate or diethylsulfate.
Anionic surfactants usually engaged in silica mesostructuration
are mainly composed of sulfate, phosphonate or carboxylate polar
functions. Sulfate based anionic surfactants are produced either by
sulfation of a fatty alcohol with a sulfating agent such as sulfur
trioxide, sulfuric acid, chlorosulfonic acid or sulfamic acid or by a
Downloaded by RMIT Uni on 19 February 2013
The consequent amount of CO2 generated during the consump-
tion of petrochemical intermediates and the toxicity of reagents
engaged in the synthesis procedures directed researchers’ attention
towards alternative surfactant resources. For instance, utilization of
hydrophobic tails derived from renewable resources is seen as a
promising route towards the generation of ‘‘bio-derived templates’’
with a low ecological impact.

sulfonation step, which produces a carbon–sulfur bond with
sulfuric acid as a sulfonating agent. The sustainability of these
procedures is limited by the release of the SO2 and SO3 gas as well
as volatile organic compounds. The major process in the synthesis
of phosphonated surfactants is the reaction of fatty alcohols with
P2O5, phosphoric acid or polyphosphoric acids. Carboxylated
surfactants are synthesized through the reaction of sodium
monochloroacetate with a base to form a carboxymethylether
with sodium chloride as a by-product. A second route consists in
the oxidation of the terminal hydroxyl ethyl group of an alcohol
ethoxylate using nitric acid or other strong oxidizing systems.
Nonionic surfactants based on an unsaturated hydrophobic
hydrocarbon tail are composed of either alkanolamines or PEO
as the polar part. Alkanolamines are the reaction products of
mono- or dialkanolamines with fatty acids or their esters. The
reaction leads to the formation of the respective secondary and
tertiary amides. This synthesis procedure is considered safe
Waste generation is another criterion that should be
considered when estimating sustainability of synthesis pro-
cesses. The E-factor concept has been developed in order to
estimate the waste generation in the manufacture of chemicals.
It measures the actual amount of waste produced in the process
of fabrication, defined as everything but the desired product. It
takes the chemical yield into account and includes reagent
and solvent losses; it only excludes water from the calculation.
The E-factors of different usual ordered mesoporous silicas
have been calculated according to the method reported by
R. A. Sheldon:46
E-factor = kg waste/kg product
E-factors were calculated with classical recipes where
OMS (Ordered Mesoporous Silica, see Table 1) are obtained
by precipitation. Results are reported for calcined materials

Table 1 Labels for ordered mesoporous solids, type of used surfactant, crystallographic structure

Label Origin of name Surfactant Structure Ref.

+ 
MCM-41 Mobil composition of matter Alkyltrimethyl ammonium salt CnH2n+1N (CH3)3X P6mm, hexagonal 2
(with n = 12, 14, 16 or 18 and X = Cl or Br)
MCM-48 Mobil composition of matter Alkyltrimethyl ammonium CnH2n+1N+(CH3)3X Ia3d, cubic 2
(with n = 12, 14, 16 or 18 and X = X or Br)
FSM-16a Folder sheet mesoporous Alkyltrimethyl ammonium CnH2n+1N+(CH3)3X P6mm, hexagonal 1
(with n = 12, 14, 16 or 18 and X = X or Br)
HMS Hexagonal mesoporous silica Uncharged amine surfactant CnH2n+1NH2 Wormhole framework 14
structure
SBA-15 Santa Barbara amorphous P123 P6mm, hexagonal 16
SBA-16 Santa Barbara amorphous F127 Im3m, cubic 243
KIT-6b Korea Advanced Institute of P123 Ia3d, cubic 48
Science and Technology
FDU-1c FuDan University Poly(ethylene oxide)–poly(butylene oxide)– Fm3m, cubic
poly(ethylene oxide) triblock copolymer
B50-6600 (EO39BO47EO39, Dow Chemicals)
COK-12d Centrum voor Oppervlakte- P123 P6m, hexagonal 230, 258
chemie & Katalyse
358a FSM-16 materials are obtained from kanemite, a layered silicate. b KIT-6 is synthesized by utilizing a triblock copolymer (EO20PO70EO20)–butanol
mixture. c FDU-1 is synthesized in the presence of the NaCl salt. d COK-12 are synthesized in a buffered (citrate/citric acid) surfactant solution.

This journal is c The Royal Society of Chemistry 2013 Chem. Soc. Rev.
 View Article Online

Review Article Chem Soc Rev

Table 2 E-factors of different usual OMS and production processes of the structuring agent, (ii) elabora-
tion procedures of the mesoporous material, including the
OMS type Ref. E-factor
template removal, performed under milder conditions, thus
SBA-15 13 16/2.3 B 7.0 allowing energy and atom saving, and (iii) degradation of the
KIT-6 48 25/4 B 6.2
MCM-41 49 41.9/21 B 2.0 structuring agents, after their elimination, which is safer for the
MCM-48 50 45.3/1 = 45.3 environment. In that context, several trends related to the use
of new structuring agents appeared in the last few years, which
allow fulfilling one or several of the previously cited criteria:
in Table 2. As recognised by R. A. Sheldon, water was not taken
(i) the elaboration of surfactants from building blocks derived
into account.
from renewable resources, (ii) the synthesis and the use
E-factors of usual OMS are quite low in comparison to the
of cleavable surfactants for improved biodegradability, (iii)
nanomaterials studied by Eckelmann et al.47 and comparable to
the use of biosurfactants synthesized by enzymes or micro-
those of industrial bulk chemicals.46 It is noteworthy that the
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B

organisms, and finally, (iv) the design of new organic templates

E-factor of MCM-48 silica materials is much higher than the
recoverable in water such as reversible assemblies. Tables 3–7
others. This higher value is due to the use of ethanol as a solvent
show the main templates, which will be described in the
in the synthesis. An easy way of lowering E-factors is therefore to
following sections. For many years, the need for products
use water as the only solvent. Let us also note that if recycling of
that address environmental issues has driven innovation in
the reactants can be envisaged, then that will lead to a strong
surfactant technology and many new surfactants with lower
decrease of the mass of waste and therefore of the E-factor.
toxicity and increased biodegradability were developed. First,
Downloaded by RMIT Uni on 19 February 2013

there has been a considerable development in the synthesis of

2.2. Surfactants from renewable resources
Since the number of potential applications for mesoporous
silica and related metal oxides continues to grow, there is
an increasing need to develop and to use more ecologically
sustainable and more economical porogens. It is necessary
to propose new structuring agents, which should have the
following specifications: (i) environmentally friendly synthesis
surfactants from building blocks (polar head and hydrophobic
tail) derived from renewable resources (Table 3).
2.2.1. Renewable raw materials for the hydrophobic part
of the surfactant: fatty acids. The synthesis of surfactant
molecules from natural fats and oils has been developed in
order to replace their synthesis from synthetic products of the
petrochemistry. Indeed due to the petroleum shortage, preparation

Table 3 Surfactants from renewable sources

Hydrophobic part based on renewable raw materials Hydrophilic part based on renewable raw materials Ref.

52

58

64

Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
Table 4 Cleavable surfactants
Glycine betaine ester-type
Table 5 Biosurfactants
Sophorolipids Phospholipids
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
Downloaded by RMIT Uni on 19 February 2013
Amino acid-based surfactants produced by enzymes
Table 6 Biopolymers
Chitosan Chitin
of surfactants from renewable sources has become more impor-
tant. The hydrocarbon-rich hydrophobic segment of surfactants
can be derived from natural oils such as coconut, avocado,
peach oils etc. The availability of these natural oils and their
fast biodegradability are the main advantages of the surfactants
derived from renewable resources. Depending on the markets,
some products require the use of vegetable derived oils but
several others allow the use of tallow fats, derived from animals
(pork or beef) and obtained by a saponification process. Tallow
is a hard fat which consists of glyceryl esters of oleic, palmitic,
and stearic acids (16–18 carbon chains). It is extracted from
fatty deposits of animals, especially from suet (fatty tissues
around the kidneys of cattle and sheep). It is used for produ-
cing tallow alkyl amines, which are widely used in the synthesis
of cationic and amphoteric surfactants. About 80% of the
global oil and fat production are vegetable oils and only 20%
are of animal origin.51 Thus, natural fats and oils are expected
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
Glycine betaine amide-type Ref.
69
Ref.
74–77
Cellulose Ref.
80, 82–84
to remain an attractive source of renewable hydrophobes for
surfactants in the future.
Triglyceride oils are one of the most important sources for
the preparation of surfactants. Among the triglyceride oils,
linseed, sunflower, soybean, coconut, palm, tall and rapeseed
oils are largely used for the synthesis of surfactants. About one
quarter of global production comes from soybean, followed by
palm oil, rapeseed, and sunflower. Fatty acids are commonly
obtained by the transformation of tallow fats or vegetable
oils and they can then be transformed into other surfactant
molecules such as fatty amines. Hydrophobes from fatty acids
consist of linear alkyl chains from C8 to C22. For example,
coconut oil serves as a source of the shorter C8–C14 acids while
tallow, palm oil and soya bean oil are rich in C16–C18 acids; the
longer C20–C22 chains can be obtained from rapeseed. Natural
fats and oils are triglycerides comprised of distribution of
different fatty acids and, therefore, the surfactants derived from
Chem. Soc. Rev.

Review Article
Table 7 Hydrosoluble templates
Hyperbranched dendritic polyglycerol Amphiphilic dendritic polyamidoamine
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
Downloaded by RMIT Uni on 19 February 2013
Poly(acrylic acid)-b-poly(ethylene oxide) Poly(acrylic acid)-b-poly(acrylate methoxy poly(ethylene oxide))
them contain a mixture of chain lengths. As an example,
coconut fatty acids are made up of C12 acids (45–50%), C14 acids
(15–20%), C16 acids (8–10%), oleic acid (5–6%), and 10–15% of
smaller carbon chains. Tallow acids are made up of oleic acid
(40–45%), palmitic acid (25–30%), and stearic acid (15–20%).
In the naturally derived fatty acids, there are also differences
in the degree of unsaturation of the hydrophobic chains. For
example, soybean oil is a highly unsaturated acid, which contains
the following C18 acids: oleic acid, linoleic acid and linolenic
acid, with one, two and three double bonds, respectively. These
differences allow providing a large palette of compositions
and properties of surfactants, which can then be used in
many applications including structure directing agents of
mesoporous silica.
Canlas and Pinnavaia described the use of naturally derived
oleyl amine in place of the usual alkyl amine surfactants for the
preparation of mesostructured silica based materials.52 They
showed that plant derived oleyl primary amine surfactants were
effective templating agents of mesoporous silicas with well
organized wormhole and lamellar framework structures.
N-alkylated oleylamines, which have the compromised hydro-
gen bonding ability with silica precursors, were able to act
as effective structuring agents in less polar media (higher
ethanol : water ratio). The procedures used for the oleyl
amine-templated synthesis of mesoporous silica via the S0I0
hydrogen bond pathway were similar to those described in the
literature for the preparation of mesoporous silicas using
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
Ref.
92, 97
Ref.
98, 101
classical alkyl amine porogens. Ethanol : water mixtures over
the range of 10 : 90 to 100 : 0 (v/v) were used with temperatures
varying from 25 to 60 1C in order to tune the solvent polarity. In
all cases, the surfactant removal was done by calcination at
600 1C because this method remains the most convenient route
for completely removing the structuring agent. Moreover, under
appropriate reaction conditions these surfactants allowed
templating mesoporous silica with framework pore size within
the supermicroporous range through solvent polarity modifica-
tion. It was suggested that the ability for unsaturated alkyl
amines to yield supermicropores in low polarity media was
due to the possible adoption of a hairpin conformation of the
hydrophobic chain of the surfactant under such conditions. The
use of other unsaturated C18 hydrophobic moieties found in
vegetable oils (e.g., linoleic and linolenic esters) would certainly
afford different pore sizes owing to different conformations
of the hydrophobic chain. It appeared that due to their
ability to adopt hairpin as well as extended chain structures
depending on solvent polarity, oleyl amine surfactants are more
versatile than saturated amines in templating both super-
microporous and mesoporous forms of silica. Supermicroporous
materials could offer new perspectives in size- and shape-
selective separation and catalysis in comparison to mesoporous
or microporous analogues.
Oleyl amine can be obtained by transformation of oleic acid
which is obtained either from tallow fats or from vegetable oils
such as soya and palm oils. This C18 fatty acid with one double
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
bond between C9 and C10 is largely used as a detergent or in
cosmetics, because it is mild to the skin and has good cleaning
properties. Fatty amines are the most important nitrogen
derivatives of fatty acids. They can be produced by the reaction
of fatty acids with ammonia and hydrogen. Intermediates are
alkyl nitriles, which are formed from carboxylic acids and
ammonia over dehydrating catalysts (Al2O3, ZnO, or salts of
Mn or Co) in liquid-phase reactors or liquid- and vapor-phase
reactors at 280–360 1C. The nitriles are hydrogenated at a tempera-
ture of 80–180 1C and a pressure of 1 to 10 MPa in the presence of
nickel or cobalt hydrogenation catalysts.
Fatty amines are biodegradable; they are subject to microbial
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
degradation by soil microorganisms. Alkylamines were shown to
be readily biodegradable, fulfilling the 10-days-window criterion.53
Fatty amines are also used as bases in the manufacture of
corresponding quaternary ammonium compounds, and as
suggested by Pinnavaia et al., quaternary forms of oleyl surfac-
tants could be used in the preparation of mesoporous silica and
would certainly allow obtaining more ordered mesostructures
Downloaded by RMIT Uni on 19 February 2013
such as hexagonal and cubic mesophases analogous to MCM-41
and MCM-48 through electrostatic S+I assembly pathways.
Galarneau et al. reported the direct use of tallow fats derived
surfactants for preparing MCM-41 type mesoporous silica
materials.54 They showed the formation of well ordered 2D
hexagonal phases. The conditions of material synthesis were
similar to those for obtaining MCM-41 type materials with
CTAB.§ Commercial raw materials used as cationic surfactants
in industrial applications are normally derived from natural
oils, which implies that mixtures of surfactants with different
alkyl chain lengths are used in the products.
It is important to mention the degradation properties of
such cationic surfactants. Cationic surfactants are widely used
as detergents, they are thus released into the environment
and their environmental acceptability is justified if they are
eliminated by biodegradation. Biodegradation of cationic
surfactants is therefore important in addressing environmental
issues. Cationic surfactants were shown to be readily biodegrad-
able in aerobic environments, nevertheless they remain toxic
even at low concentrations.55
The versatility of the natural products-derived surfactants is
considerable and this opens the way to a rich diversity of
materials templated by these surfactants. Moreover, oleochemical-
derived and animal oil-derived surfactants have many advantages
(often readily biodegradable and cheaper) compared with surfac-
tants prepared from petroleum-based sources and therefore appear
to be promising porogens for mesoporous silicas.
2.2.2. Renewable raw materials for the hydrophilic part of
the surfactant: amino acids and sugars
Amino acids as raw materials for natural resources-derived
surfactants. Amino acid-based surfactants constitute an inter-
esting group of surfactants known for their excellent surface
active properties, biocompatibility and antimicrobial activity.
They are known to be environmentally friendly, and are biode-
gradable under aerobic and anaerobic conditions.
Recently, the synthesis of hybrid mesostructured silica
was reported from aqueous solutions of C12-glutamic acid
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
and C12-leucine based surfactant formulations and sodium silicate
under neutral pH and atmospheric conditions.56 The use of
surfactants derived from glutamic acid and leucine leads to the
precipitation of mixtures of hybrid mesostructures including
lamellar phases. This approach involves the challenging task
of organizing silica from entirely sustainable organic and
inorganic sources under environmentally benign conditions.
Amino acid-based amphoteric type-surfactants were also
used for elaborating mesoporous silica (Table 3).57
Ordered hollow mesoporous silica materials with a vesicular
structure were synthesized using an amphoteric amino acid
surfactant sodium N-dodecyl glycine (Me(CH2)11–NH–CH2–
COOH) template in the presence of a 3-aminopropyltriethox-
ysilane as the co-structure-directing agent (CSDA). The addition
of tetrapropylammonium bromide (TPABr) as a co-templating
agent allowed forming an hexagonal phase. The authors also
showed that an increase in the CSDA/surfactant ratio led to the
mesophase changing from the lamellar phase into the hexago-
nal phase. The synthesis procedure involves the mixing of
dodecylglycine in acidified water with the TPABr surfactant
and then, the addition of TEOS and the CSDA. After 24 h
stirring, the reaction product is collected and washed with
deionized water and anhydrous ethanol, and then dried at
60 1C. Finally the product is calcined at 550 1C.
Mesoporous silica were also obtained by using naturally
derived amphoteric surfactants: sodium and potassium
N-dodecyl glycine (C12H25NHCH2COO), which were synthesized
by reacting coconut amine with monochloroacetic acid in
alkaline medium.58 Typical commercial coconut fatty acids
have a carbon chain length distribution centered around C12
and C14. Mesoporous silica with hexagonal structure and Pm3n
cubic structure with an ordered and parallelly arranged pore
channel were synthesized using two amphoteric surfactants,
potassium N-dodecyl glycine and sodium N-dodecyl glycine, as
templates, respectively. The synthesis pathway using the
amphoteric surfactants together with 3-aminopropyltriethoxy-
silane as a CSDA was considered as a charge neutralization
SN+I pathway where S denotes the negatively charged
N-dodecyl glycine surfactant, N+ denotes the ammonium cation
of APS, and I the silicate species. An interesting feature is that
the use of the anionic dodecyl glycine surfactant allows prepar-
ing mesostructures different from lamellar, and more precisely,
the synthesis of hexagonal and cubic ordered pore structures
with narrow pore size distributions could be directed by amino
acid-type amphoteric surfactants.
An important step in the search for sustainability is to use
green surfactants with a polar head and a hydrophobic chain both
obtained from renewable resources. They may be prepared from
sterols or triglycerides, which are precursors of the hydrophobic
chains, and from sugars or amino acid precursors for the polar
heads. Amphoteric amino acid surfactants, such as those based
on glutamate functions, for example, are known for their excellent
bactericide properties, low toxicity and high degradability.59
To the best of our knowledge, those naturally derived
surfactants were not used yet as structure directing agents of
silica, but there seems to be no limitation to the use of these
Chem. Soc. Rev.

Review Article
amino acid based surfactants as porogens in the preparation of
mesoporous silica.
Finally, even if they are not surfactants, it is interesting to cite
here an original work based on the use of folic acid assemblies.
Folic acid is composed of a pterin group, chemically and
structurally similar to guanine, conjugated to the L-glutamate
moiety via a p-amino benzoic acid; folic acid molecules may
form chiral columnar stacks, which arrange into hexagonal
mesostructures. These non-amphiphilic assemblies were used
as structuring agents of ordered mesoporous silica;60 it is
expected that other molecules containing pterin or guanosine
groups would be suitable for use as silica templates.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
Sugars as raw materials for natural resources-derived surfactants.
Another class of surfactants derived from natural building blocks
is the one in which the polar head is based on one or several sugar
entities. Alkyl glycosides synthesized from renewable resources
are interesting non-ionic surfactants because of their ability to
form liquid crystalline phases, their chiral properties and their
Downloaded by RMIT Uni on 19 February 2013
biodegradability. The development of well-ordered materials
using these compounds as structuring agents was nevertheless
limited because the interactions between the neutral surfactant
and the weakly charged inorganic precursor are short-range
hydrogen bonding forces, often resulting in disordered meso-
structures. In 2003, Hüsing and Stangar reported the use of
commercially available alkyl glycosides as templating surfactants
in the sol–gel process of thin silica films.61 They used n-octyl
b-D-glucopyranoside (b-C8Glc), n-dodecyl b-D-maltopyranoside
(b-C12Mal) and n-decyl b-D-maltopyranoside (b-C10Mal), the
liquid crystalline phase behavior in water being well known
for b-C8Glc and b-C12Mal, and studied the self-assembly
capability in combination with a prehydrolyzed silicate solution.
They prepared sols from a prehydrolyzed silicate solution
with the addition of a glucoside or a maltoside surfactant and
showed that the siloxane condensation rate in the silica–
glycoside sol was considerably reduced compared to a pure
silica system due to hydrogen bonding interactions between the
silanols and the sugar head groups. The use of the glucoside
surfactant only resulted in temperature unstable lamellar phases,
whereas the maltosides lead to curved mesophases that were
stable to template removal by extraction or calcination.
More recently, Botella et al. used biocompatible alkyl malto-
side surfactants for preparing mesostructured silica materials
under biomimetic conditions (room temperature and physio-
logical pH).62 By tailoring synthesis conditions, they obtained
ordered mesostructures with some disaccharide surfactants,
as n-decyl-b-D-maltoside (C10M) and n-dodecyl-b-D-maltoside
(C12M), alone or combined with CTAB. Short-range ordered
mesoporous structures with disordered hexagonal or bicontinuous
cubic Ia3d symmetry were obtained depending on the surfac-
tant length and concentration. The synthesis leads always to a
disordered hexagonal wormhole-like mesophase with C10M,
whereas C12M could give a poorly ordered hexagonal or
the bicontinuous cubic Ia3d symmetry. In all cases, a weak
H-bonding interaction between the Si–OH species of the
inorganic matrix and the polar head of the structure-directing
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
agents was observed both for the C10 and the C12 chain length.
Furthermore, they intercalated ibuprofen as a reference drug
within surfactant micelles, in order to build a surfactant-
assisted delivery system whereby the release performance was
related to the surfactant dissolution and diffusion into the liquid
phase of the therapeutic agent encapsulated, which offers better
control and slower release than the standard surfactant-free
material.
Alkyl polyglucosides. Alkyl polyglucosides (AGs) including
several glucose molecules are produced from raw renewable
materials such as starch, fats, often by acid-catalyzed reaction
of glucose with fatty alcohols; the industrial process leads to a
mixture of mono-, di-, tri- and oligoglycosides. The products are
generally characterized by the length of the alkyl chain and the
average number of glucose units. They could be produced with
a higher selectivity by enzymatic syntheses but this is now limited
to the laboratory scale due to the high manufacturing costs and due
to the problem of availability of the suitable enzymes. The physico-
chemical parameters and interfacial properties of various alkyl
(poly)glycosides were reported. For example, Castro et al. studied
mono-glycosides and geminis obtained by connecting two alkyl
glycoside molecules through a spacer of ester or ether type.63 The
same authors also showed that alkylglycosides present environ-
mentally friendly properties, such as fast biodegradability and non-
toxicity, and are mild to the skin.
Ai Guo Kong et al. used industrial grade cation alkyl poly-
glycosides as structure-directing agents to prepare ordered
mesoporous silica through inorganic–organic self-assembling in
weak basic aqueous solution.64 They obtained worm-like meso-
structures with narrow pore size distribution centered at 3.6 nm.
Moreover, alkyl polyglucosides were used as carbon precursors; the
direct pyrolysis of silica–cation alkyl polyglucoside composites with
H2SO4 as a catalyst and the subsequent silica removal lead to the
formation of mesoporous carbon material.
2.3. Cleavable surfactants for improved biodegradability
Environmental concern is a driving force for surfactant develop-
ment. An original approach was proposed for the development of
greener surfactants: the elaboration of cleavable surfactants. The
development of surfactants with weak bonds deliberately built
into the structure, between the polar head and the hydrophobic
tail, was driven by the need for better biodegradability of the
surfactants. A range of possible ‘‘switches’’ for the decomposi-
tion of surfactants by chemical means was developed; they
include cleavage induced by acid, alkali, ultraviolet light, heat,
or ozone.65 Acid- and alkali-labile surfactants are particularly
interesting, but there is always a compromise between required
stability at one stage and ease of breakdown at a subsequent
stage. Acid-labile surfactants include molecules with cyclic and
acyclic acetals, ketals, and ortho ester types of bonds, whereas
alkali-labile surfactants are usually based on ester bonds.
The ester bond approach has been particularly developed for
cationic surfactants, giving rise to the so-called esterquats
which have found various industrial applications. Betaine
esters are interesting labile surfactants, which present a pH
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
dependence (Table 4). UV-labile surfactants based, for example,
on an azo bond also appear to be promising amphiphilic
molecules.
During the nineties, quaternary ammonium salts containing
ester bonds have started to largely replace traditional cationic
surfactants. There was an environment risk evaluation concern-
ing the largely used ditallowdimethylammonium chloride,
which pushed the detergent industry to replace those surfac-
tants with readily biodegradable analogues. Cleavable cationic
surfactants with an ortho-ester link were then developed, which
appeared to be very interesting chemodegradable surfactants.
Ester bond-containing surfactants, which undergo hydrolysis of
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
their ester bond, lose their surfactant properties and are less
toxic to the living organisms. The rates of chemical hydrolysis
of esterquats and of betaine ester type cleavable cationic
surfactants and their gemini analogues were compared and it
was shown that esterquats are hydrolyzed much slower than
betaine esters. Both families were shown to degrade very fast
under aerobic conditions, whereas gemini analogues were
Downloaded by RMIT Uni on 19 February 2013
not readily biodegradable. Biodegradation tests show that
many cationic surfactants undergo complete degradation, but
interestingly, the rate of chemical hydrolysis is not directly
correlated with the biodegradability of the surfactants.66,67
The biodegradability of alkyltrimethylammonium chloride
(ATMAC) has been studied following standard tests of oxygen
uptake or carbon dioxide evolution. It was shown that it
decreases when the chain length increases and it decreases
from about 70% down to zero after 10 days when the chain
length increases from C8 to C18.66,67 The surfactants never-
theless can be ultimately degraded in aerobic screening tests.
Moreover, the oral toxicity was shown to be much higher in the
case of alkyltrimethylammonium cationic surfactants than in
the case of anionic or neutral surfactants. The acute toxicity of
ATMAC after oral administration was characterized by an LD50
which increases from 250 to 1000 mg per kg of body weight (rat)
when analyzing the effects of C12 to C18-TMAC.68
Those surfactants appear to be a promising class of switch-
able amphiphiles, nevertheless environmental groups targeted
such cleavable surfactants that may be disposed of with
aqueous waste, eliminating the remediation cost; they ques-
tioned about the environmental impact of such surfactants and
their ability to break down into fragments that may be soluble
in water, which may represent an important source of water
pollution. A prerequisite for the development of smart and
switchable surfactants would then be the formation of either
gas or non-ionic hydrophobic moieties upon decomposition of
the surfactants.
Cleavable surfactants that are derived from only renewable
resources. Glycine betaine derived cationic surfactants were
prepared from glycine betain and plant oils. Glycine betaine
(GB) is a natural cheap substance possessing a quaternary
trimethylalkylammonium moiety and a carboxylate function.
It constitutes a promising raw material for the preparation of
biodegradable and biocompatible cationic surfactants (Table 4).
GB accounts for 27% by weight of molasses of sugar beet, and it
is obtained after extraction of saccharose. It is a by-product of
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
the sugar industry, which could be advantageously utilized.
T. Benvegnu et al. showed that it was possible to produce GB
esters and amides from tropical or european oils by following
an economically and environmentally acceptable process (no
solvent, no waste).69 The introduction of an ester-type or an
amide-type linkage between the hydrophilic moiety (polar head
group) and the hydrophobic backbone (alkyl chain) was again
proposed for ensuring a high biodegradability. Convenient
procedures were developed on a multigram scale using green
solvent-free processes to provide glycine betaine-derived esters
and amides. Readily biodegradable formulations containing
ester-type surfactants were found to exhibit remarkable surface
active properties.69 The ultimate aerobic biodegradability of
glycine betaine derived ester cationic surfactants was evaluated
using the ‘‘CO2 evolution’’ test, which is included in the
European Regulation on biodegradability of detergent surfac-
tants. A high biodegradation level (70% within 28 days) was
reached that allowed the surfactants to be classified as readily
biodegradable. It is of great advantage to replace cationic
surfactants derived from petrochemicals by surfactants that
are derived from 100% vegetable products while maintaining
the same surface active properties. The glycine betaine
approach allows producing cationic surfactants while avoiding
the classical quaternization process of tertiary amines.69
To our knowledge, such surfactants were not tested as
structuring agents yet but they should be able to act as efficient
porogens for ordered mesoporous silica.
2.4. Biosurfactants (biologically produced surfactants)
Numerous microorganisms are known to produce substances
with surface-active properties. The function of these compounds
is often to facilitate the uptake of hydrophobic substrates such as
triglycerides or alkanes. The common name for these biologically
produced surface-active agents is biosurfactants.70 Recently, there
has been a great deal of interest in biosurfactants produced by
either microorganisms or isolated enzymes since they possess a
number of potential advantages over their chemically manu-
factured counterparts, including low toxicity, biodegradability,
a wide variety of controlled structures and ease of synthesis
from renewable raw materials (Table 5).
It was long thought that surfactants could not be produced
on a large scale by enzymatic syntheses but several industrial
processes have now shown that it is possible to manufacture
bulk quantities of chemicals by such methods.71 Biocatalysis
is attracting more and more attention as there is a need to
shift the resource base of the chemical industry from fossil
feedstocks to renewable raw materials. Moreover it seems that
by using a small group of different enzymes, it will be possible to
produce a large number of different structures of surfactants.70
Lipases have now been recognized as the most convenient
enzymes having the largest potential for the synthesis of
surfactants.72 It is partly due to their high stability and hence
the possibility of recycling the enzymatic catalysts in several
consecutive runs, thus reducing the costs of production. Never-
theless, enzymes are expensive, that is why new biotechnology
processes are now being developed to create more effective
Chem. Soc. Rev.

Review Article
tools for producing enzymes at a lower cost and on a larger
scale, making it possible to produce bulk quantities of target
enzymes when there is a well identified demand.
2.4.1. Sophorolipids. Among the biosurfactants, sophoro-
lipids are in the best position when considered by industries or
academia. This is due to a high production yield using a
nonpathogenic organism. Thus, sophorolipids find a variety
of applications from detergents to therapeutics via oil recovery
and bioremediation.73 C. bombicola is the species most studied
by researchers for the production of sophorolipids. It exhibits
both the highest yield and productivity among the different
strains of the Candida genus.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
The sophorolipid biosurfactant consists of sophorose, a
diglucose, bound to a hydroxy fatty acid. This glycolipid exhi-
bits significant emulsifying properties, moreover, it possesses
bactericidal activity, but it is also active against plant patho-
genic fungi. As sophorolipids are synthesized with high produc-
tion yields (over 400 g l1), and from renewable resources or
even waste streams, their current production price amounts
Downloaded by RMIT Uni on 19 February 2013
to 2 to 5 h kg1, depending on the substrate cost and the
production scale.
In view of the different advantages of sophorolipds, Baccile
et al. recently used them as structuring agents of silica.74 They
showed that sophorolipids can form nanometer-sized micelles
with various morphologies in water depending on their concen-
tration. This property allowed using them, for the first time, as
structure directing agents in the synthesis of nanostructured
silica thin films via the EISA (Evaporation Induced Self-Assembly)§
process. They used a culture broth of the yeast Candida bombi-
cola with glucose and oleic acid. The sophorolipid molecule,
which contains a COOH group at the end of the hydrocarbon
chain, exhibits some pH sensitivity, which was profitably
exploited for tuning the pore morphology and dimensions by
changing the pH of the medium.
2.4.2. Phospholipids and lecithin
Phospholipids. For a long time, phospholipid surfactants
have not been investigated as potential structure directing
agents of silica. Phospholipids are known as components of
cell membranes and liposomes, but their use in directing
inorganic mesophases has long been unexplored. In 2009,
Brinker et al. demonstrated that, using short chain (C6) phos-
pholipids, nanostructured films formed via an EISA§ process
could be assembled with living cells, to create a biocompatible
encapsulation matrix for whole-cell biosensor devices that
preserves cell viability for months under desiccating condi-
tions.75 Diacyl phosphatidylcholines with two tails of 6 to 14
carbons were found to template 1D, 2D or 3D mesophases,
depending on the chain length; moreover, the removal of the
lipids by thermal or UV/O3 processing was shown to strongly
depend on the phospholipid-based structure. An interesting
feature is that the biocompatibility of the lipid–silica material
was confirmed with encapsulated cell viability increased
compared to that in pure silica materials.
Lecithin. Commercial lecithin is the most important by-product
of the oil processing industry because of its functionality and
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
wide application in food systems and industry. The recovery of
lecithin from oil is a relatively simple process. Hydration of
the phosphatides by water or steam followed by recovery by
centrifugation allows phosphatidylcholines to be obtained.
They may be extracted from eggs, which contain up to 70% of
phosphatidylcholine, or soybeans, and rapeseed (up to 20% of
phosphatidylcholine); they are actually mainly produced from
soybeans. Phosphatidylcholines belong to the phospholipids,
they are bio-derived zwitterionic phospholipids, the head group
is composed of a choline (positively charged) and a phosphate
(negatively charged) while the hydrophobic tail is composed of
two fatty acids (palmitic or oleic acids for example). A glycerol
group allows binding the head and the tail (Table 5).
Galarneau et al. used lecithins directly as structuring agents
of silica.76 They reported the use of natural surfactants such
as lecithin to prepare micelle-templated silica for enzyme
encapsulation systems. The use of lecithin allowed protecting
the enzyme and avoiding the direct interaction between silica
and enzyme, which usually inhibits the enzyme activity. The
addition of amines allowed creating a curvature in the lecithin–
amine (dodecylamine) system and generating a mesoporous
framework. Lactose was also added to protect the enzyme
activity. They showed that this route leads to a well-organized
mesoporous material with a sponge-like structure, a controlled
pore size and a high surface area and finally that the enzyme
(lipase) was active in this environment.
The previous studies based on the use of phospholipids and
lecithin open interesting perspectives for biocatalysis applications.
2.4.3. Amino acid based surfactants synthesized with
enzymes. Amino acid-based surfactants with a naturally derived
hydrophobic chain (from palm oils) are a particularly interest-
ing class of biosurfactants. Amino acid based biosurfactants
can be prepared by lipase catalyzed acylation of amino acids
with a range of long-chain fatty acids (or their esters) as acyl
donors.77 Lipase-catalyzed transacylation of palm oil fractions with
amino acids was shown to be useful for the production of mixed
medium to long chain surfactants for specific applications.78
Amino acid based surfactants prepared by chemical synth-
esis have been used as structure-directing agents of silica but
enzyme-synthesized amino acid surfactants have never been
utilized for this purpose. Amino acid-based surfactants consti-
tute an interesting group of biosurfactants owing to their
excellent surface active properties, biocompatibility and strong
antimicrobial activity. They have been extensively studied,
however, their synthesis using enzymes was not perfectly
mastered.79 The feasibility of lipases catalyzed acylation of
amino acids with a range of long-chain fatty acids (or their
esters) as acyl donors was not satisfactory, because the reaction
rates were poor and the yields were low. The low conversions
obtained were attributed in part to the low solubility of the
amino acids in the oil phase. Chen et al. utilized an interesting
strategy to prepare amino acid-based surfactants under the
catalysis of lipase.77 Glycerol was chosen as a linker between
amino acids and fatty acids as alcohols are known to be good
substrates for lipases. The compounds obtained have the
following characteristic structural features: they contain a
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
long-chain alkyl group in the hydrophobic moiety; they have an
amino acid moiety as the hydrophilic moiety, a hydroxyl group
between the hydrophobic and hydrophilic moieties, which has
the hydrogen-bonding ability, and finally they possess a chiral
carbon atom in the amino acid moiety which creates the chiral
aggregate forming ability (Table 5).
2.5. Polymers and colloids from renewable resources
Various biomacromolecules and polymer colloids have
been used as structure directing agents of silica, they include
polysaccharides such as chitosane and colloids of chitin or
cellulose (Table 6).
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
Chitosan polymers. Chitin is a largely abundant organic
material, which is the main constituent of the shell of crusta-
ceans such as shrimps, crabs and lobsters. Due to its low
solubility, it is rarely readily used in chemistry, but its partial
deacetylation results in chitosan having several amino groups
and being soluble in acidic aqueous solution. Due to its
water-solubility in acidic media, biocompatibility and ability
Downloaded by RMIT Uni on 19 February 2013
to interact with silica, chitosan has been used for structuring
silica-based materials. Most often, hybrid chitosan–silica
materials yield after calcination of the polymer poorly ordered
mesoporous or meso-macroporous materials.80,81
Chitin colloids. Chitin colloids were recently used by
B. Alonso and Belamie for structuring silica.82 Chitin nanorods
were obtained from shrimp shells after purification (L = 260 
80 nm, D = 23  3 nm); they are bundles of chitin monocrystals
(D = 3.2  0.6 nm) with amino groups at their surface. These
authors first prepared siloxane oligomers with polysaccharide
chitin nanorods in alcoholic suspension; after evaporation of
the suspensions, they obtained materials, whose mechanical
and optical properties could be tuned by varying the chitin
volume fraction. Moreover, long-range arrangement of aligned
nanorods inside these materials could be achieved under
moderate magnetic fields (9 T), generating highly oriented
textures. Spray-dried chitin–silica nanocomposite particles
could be prepared, yielding mesoporous silica particles after
calcination.
Cellulose nematic liquid crystals. Cellulose is the most
abundant natural biopolymer, which is renewable, biodegrad-
able, and non-toxic. It is a polysaccharide composed of b(1-4)
linked D-glucose units. Its structure explains its characteristic
properties, such as hydrophilicity, chirality, biodegradability
and high functionality. This renewable polymer is more
and more considered as a green alternative to fossil-fuel
based polymers. It has been recently used as a template for
hierarchical hybrid mesostructures.83 Mesoporous silica
materials were synthesised by sol–gel mineralisation using
nematic liquid crystals of cellulose nanorods.84 Nanorods can
be prepared by acid hydrolysis of cellulose. Removal of the
cellulose nanorod template produced a birefringent silica
replica that exhibited patterned mesoporosity due to the
presence of co-aligned cylindrical pores, approximately 15 nm
in diameter and 10 nm in wall thickness. As cellulose nanorods
can be prepared from renewable, inexpensive sources, they
offer a cost-effective, environmentally benign route to the
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
template-directed synthesis of mesoporous materials. Then,
using the chiral nematic phase of hydroxypropylcellulose as a
template, Thomas and Antonietti obtained high-surface area
porous silica but no long-range chiral organization was
observed.85 Later on, the development of a free standing film
of a photonic mesoporous inorganic solid that is a cast of
a chiral nematic liquid crystal formed from nanocrystalline
cellulose was described by Shopsowitz.86 It was the first example
of materials to combine mesoporosity with long-range chiral
ordering that produces photonic properties. Finally, cellulose
was also associated with PEG and pluronics F127§ polymers for
forming micrometer-sized mesoporous silica spheres.87
2.6. Synthetic hydrosoluble structuring agents: removable in
water
The ideal specific properties of a structure-directing agent
include the following ones: an ideal structuring agent would
be readily recoverable by a simple washing process. Or it would
be decomposed in a simple way for its easy removal from the
material. Its decomposition products would be inert and easily
recoverable under sustainable conditions. Its decomposition
products could be reconstituted into the original molecule
for reuse. If the structuring agent results from non-covalent
assembly of molecular entities, it would present a reversible
assembly process of its entities by using a controllable and non-
energy intensive switch to trigger the assembly under environ-
mentally friendly conditions.
Among the structure directing agents that are recoverable
under sustainable conditions, those which can be washed out
in water at room temperature are especially interesting. Indeed
the most efficient way to remove the structuring agent is
calcination at high temperature, which presents the following
disadvantages: it leads to the loss of the organic template which
can represent up to 70% of the cost of the mesoporous silica
manufacture, it leads to the emission of CO2 which is noxious
for the environment, it is time and energy-consuming, and this
increases the cost of manufacture of the final material, and
finally it yields highly condensed silica frameworks and may
lead to some deterioration of the framework, which is often
inorganic but which can also be a hybrid containing organic
functions.
In that case, calcination is forbidden and a washing procedure
in a solvent which is a good solvent for the template must be
envisaged. Water-soluble or water-dissociable structuring
agents include some small hydrophilic molecules, polymers
and dendrimers and some specific micellar assemblies of hydro-
soluble polymers. These molecules are illustrated in Table 7.
Among the small hydrophilic molecules which have been
used as templates of silica, citric acid is one of the simplest and
cheapest structuring agents.88 Y. Wang et al. used citric acid as
a template and a catalyst for preparing mesoporous silica
starting from TEOS§ as the silica source. The material presents
a wormlike mesostructure, and interestingly the silica surface
possesses abundant silanol groups. Citric acid could then be
extracted by a water washing procedure leading to mesoporous
silica and the recycling ratio was high, close to 97%.
Chem. Soc. Rev.

Review Article
The disadvantage of citric acid as a pore-forming agent is that it
obviously cannot produce ordered hybrid organic–inorganic
mesophases and then ordered mesopores.
Pluronic-type small triblock copolymers have been largely
used as templates of silica; they are amphiphilic polymers and
are usually removed from silica by calcination or by an ethanol
washing procedure, but some of them present a rather good
solubility in water depending on temperature and therefore
they may be extracted from water solution. Whereas the P123§
polymer PEO20–PPO70–PEO20 could not be removed easily by a
water extraction procedure (only 24% compared to 74% in
ethanol, which is a better solvent) from a SBA-15-type hybrid
material,89 other Pluronic polymers which are richer in PEO
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
could be extracted in higher proportion by washing in water. C.
Knöfel showed that when the F127§ polymer, PEO106–PPO70–
PEO106, was used as a template, it could be totally removed by a
water extraction procedure under reflux at 80 1C, leading to a
higher pore volume in comparison with the calcination
procedure.90
Downloaded by RMIT Uni on 19 February 2013
Due to the high uniformity of their molecular weight and
structure, dendrimers appeared to be very attractive templates
for preparing porous materials with a narrow mesopore size
distribution. They have then been used by several groups for
directing the structure of silica91 and some of them were shown
to be removable from the silica framework by a simple washing
procedure in water. Y. Xu et al. prepared mesoporous silica with
a narrow pore size distribution centered at 3.8 nm by using a
dendritic polyglycerol as the template.92 They showed that the
template could be completely removed from silica by means of
a simple water extraction procedure. Hyperbranched or den-
dritic polyglycerols appear to be promising versatile structuring
agents, which are highly biocompatible,93 which can be hydro-
soluble and which can be functionalized either as polycationic
or polyanionic macromolecules depending on the needs.94,95 In
2003, J. Hukkamaki and Pakkanen used amine-terminated
polyamidoamine (PAMAM) dendrimers for the preparation
of mesoporous silica following a material synthesis pathway
similar to that developed with classical linear alkylamines.96
H. Dai et al. reported mesoporous silica materials with control-
lable pore diameters (3–9 nm), narrow pore size distributions,
high surface area (>700 m2 g1) and pore volume (>1 cm3 g–1)
using a dendritic polyamidoamine (PAMAM of generation G2
with ethylenediamine as an initiator core) with TEOS as the silica
precursor by an HCl catalyzed sol–gel process. The dendritic
template could be completely removed and recycled by means of
a simple water extraction treatment.97 Furthermore, they showed
that the mesopore diameter could be controlled using dendritic
polyamidoamines of different generations and with different
functional groups. Despite the attractive properties of such
monodisperse and well-defined macromolecules, which may
be hydrosoluble and biocompatible, disadvantages of using
dendrimers as structure directing agents are their cost and the
difficulty in their multi-stage synthesis. Moreover, dendrimers
do not allow preparing ordered porous mesophases.
Dendrimers are hyperbranched macromolecules with a well-
defined target architecture, which are removable from silica
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
structures in water solution due to their high water solubility.
Recently, other large structures of hydrosoluble polymers
appeared to be very attractive water-removable structure
directing agents: they are smart polymer micelles which result
from the controlled non-covalent assembly of hydrosoluble
polymers. In 2008, polyion complex (PIC) micelles resulting
from the electrostatic complexation between charged double-
hydrophilic block copolymers (DHBC) and oppositely charged
homopolymers were used as structuring agents of silica. A great
advantage of such micelles in comparison with classical
micelles of permanent amphiphilic polymers or surfactants is
that the process of PIC micelle formation is reversible in water
by applying a physicochemical stimulus such as a change in the
pH or the ionic strength of the solution; this property ensures
that PIC micelles are dissociable and recoverable by washing
the hybrid material in water at an adequate pH or ionic
strength. N. Baccile et al. showed that PIC micelles allowed
preparing highly ordered hybrid silica–PIC micelle mesostruc-
tures with either a 2D hexagonal arrangement of cylindrical
micelles or a lamellar symmetry (Fig. 2).98 PIC micelles used in
that study were formed by complexing a poly(acrylic acid)-b-
poly(ethylene oxide) or a poly(methacrylic acid)-b-poly(ethylene
oxide) DHBC with an oligochitosan (OCL) (see Tables 6 and 7).
An oligochitosan is a naturally derived polyamine prepared
from shells of shrimps or other crustacean species upon
deacetylation of chitin; it is therefore an abundant product
easily obtained from shrimp processing waste. Rather small
chitosans are used in that study (molecular weight smaller than
5000 g mol1) since water solubility is required. Such PAA-b-
POE–OCL micelles are stable in a pH domain between the pKa
of the polyacid (about 4.5) and that of the polybase (about 6.5)
and they dissociate beyond this pH range. It was shown that the
use of PIC micelles allowed preparing mesoporous silica mate-
rials in water as the only solvent, at room temperature, and
under mild pH conditions (above pH 4.5 for the hybrid material
synthesis and above 7.7 for the micelle removal). The PIC
micelle size and consequently the mean mesopore size could
be tuned by varying the polymer block lengths.99,100 It was also
shown that polymers could be recycled for further re-use and
Fig. 2 Double-hydrophilic block copolymers-based polyion complex micelles:
switchable micelles in aqueous solution for the preparation of ordered meso-
porous silica.
This journal is c The Royal Society of Chemistry 2013
 View Article Online

Chem Soc Rev Review Article

formation of new mesoporous silica. DHBC polymers with a
different architecture were also used, such as PAA-b-PAPOE
(poly(acrylate methoxy poly(ethyleneoxide))) block copolymers
(Table 7), which present a comb-type POE-based neutral
block.101 Associated with silica precursors, they also lead to
the formation of mesostructured silica, revealing that inter-
actions between silica and PAPOE comb blocks were as efficient
as those with linear POE blocks in the precipitation of the
hybrid material. This study revealed that PIC micelles formed
by complexation between hydrosoluble polymers can behave as
classical amphiphilic block copolymers and produce ordered
hybrid mesophases upon interacting with silica precursors with
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
economical and environmentally friendly synthetic procedures
for mesoporous materials. As they can be recovered and
recycled in aqueous solution, they allow fulfilling the following
criteria of green chemistry: atom and energy saving, and
reduction of the use of hazardous solvents and substances. If
ordered mesoporous materials are sought, micellar assemblies
of hydrosoluble polymers such as polyion electrostatic complex
micelles should be preferred to individual small molecules,
polymers or dendrimers, which do not allow the formation of
ordered porous mesophases.
Table 8 summarizes and compares the different types of
templates that are described in this section.

a considerable advantage of the ability to dissociate in water.

Moreover, this type of system is highly versatile in comparison
with one component-amphiphilic polymers since PIC micelles
combine two polymers, which possess different acidic and
basic functions. Finally, the polymers constituting the PIC
micelles were shown to be biocompatible and they may be
partly derived from renewable resources.
Downloaded by RMIT Uni on 19 February 2013
3. Silica sources
Development of sustainable strategies for the synthesis of
ordered mesoporous silica implies the careful choice of silica
precursor. The environmental impact of its manufacturing
procedure, the by-product release during its utilization and

In conclusion of this part, water-soluble or water-dissociable its cost must be taken into account. The need for reducing or
structuring agents are highly promising for the development of eliminating the use of hazardous chemical compounds and

Table 8 Comparison and summary of templates described in this review

Type Characteristics (examples) Advantages Drawbacks

Surfactants From petroleum High surface-active properties Acute toxicity (category 4)b
(CTAB§) Highly ordered mesopores can be prepared Low biodegradability
Produced from toxic reagents
A large amount of CO2 generated for the
production of the hydrocarbon-rich
hydrophobic segments
Cost-extensive production processes
From renewable resources Environmentally-friendly synthesis procedures Extraction from natural resources: affects
(Oleyl-amines, alkyl Unsaturated hydrophobic chains from vegetable the biodiversity
glucosides) oils: supermicropore generation A sugar-based hydrophilic part: short-range
hydrogen bonding forces. Only disordered
mesostructures
Cleavable Synthesized from natural resources The fragments obtained after cleavage are
(Glycine betaine) Economical and environmentally acceptable soluble in water: disposal issue
production processes Not tested yet as porogens
‘‘Switchable’’ amphiphiles
Readily biodegradable
Biocompatible
High surface-active properties
Biosurfactants Environmentally acceptable production processes Bulk quantities of enzymes are required for
(sophorolipids, Low toxicity a large scale production
phospholipids) Easy synthesis Enzymes are expensive
Biodegradable
A large variety of structures

Polymers From petroleum Low toxicity Produced from highly toxic and flammable
(Pluronic) A wide range of sizes and compositions lead to a monomers (EO, PO)
high diversity in pore sizes and structures Cost-extensive production processes
Biopolymers Environmentally acceptable production processes No surface-active properties
(chitosan, chitin, cellulose) Easy synthesis
Low toxicity (category 2)b
Biodegradable
Hydrosolubles Highly biocompatible Expensivea
(dendrimers, DHBC/ Removable from silica by a simple washing Arduous multistep synthesis
chitosan complexes) procedure in water
Micelle formation reversible in water under the
application of a stimulus
Recyclable
a
PEO-b-PMAA (polymer source) is approximately 350 times more expensive than CTAB§ and 2500 times more expensive than Pluronic F127§
(Sigma-Aldrich). b Toxicity obtained from the Sigma-Aldrich safety data sheet, where available.

This journal is c The Royal Society of Chemistry 2013 Chem. Soc. Rev.
 View Article Online

Review Article Chem Soc Rev

Table 9 Comparison of the different silica sources available for the synthesis of silica-based mesoporous materials

Origin Type Advantages Drawbacks Ref.

Silicon alkoxides (TEOS, TMOS)
Soluble silicates (sodium silicate
solution, colloidal silica,
fumed silica)
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
Homogeneous silicate oligomers
composition in solution
Suitable for syntheses of highly
organized mesostructures at any pH
CheapSimple synthesis procedure
Soluble in water
Energy-intensive and expensive 14, 102
synthesis procedures
Synthesized from toxic precursors
Require the use of catalysts
Soluble in organic solvents only
Release of alcohols during the
hydrolysis/condensation process
Silicate solutions composed of a 9, 20, 33, 35,
variety of silicate oligomers with 102, 112–135
different degrees of polymerization
Inorganic polycondensation difficult
to control under neutral and
acidic pH

Natural Natural clays, diatomaceous
earth, natural zeolites, other
natural silica-containing miner-
als,
gramineae plants (rice husk)
Downloaded by RMIT Uni on 19 February 2013
AbundantCheap The same drawbacks as soluble 144–147, 161
Non-toxic silicates
Possibility of forming mesoporous Strong acids and high temperatures
materials without the addition of are used for purification
organic surfactants: by taking
advantage of metal cation impurities
(K+) or residual natural organic
molecules (lignin)

Recycling Industrial wastes (coal ash, rice
husk ash), electronic wastes
(packaging resin), domestic
wastes (glassware), regeneration
of porous silica materials (hard
templates used for nanocasting)
AbundantCheap and non-toxic Slightly lower surface area and pore 183–199,
Additional functionality (acidity) volume than with synthetic 216–220,
conferred by the residual metal ions precursors 224–227
included within the silica matrix
An answer to the problem of
waste disposal

energy-intensive synthesis procedures led recently to the use of
silica precursors derived from natural mineral deposits, bio-
mass or industrial wastes (Table 9). Silica species extracted
from these raw materials constitute a huge resource of silica
precursors and thereby represent a great opportunity for the
future sustainable and large-scale development of ordered meso-
porous silica materials. Table 2 summarizes the advantages
and the drawbacks of the synthetic, natural and waste-derived
silica sources.
3.1. Synthetic silica sources
3.1.1. Silicon alkoxides. Development of ordered mesoporous
silica materials is tightly related to the development of the sol–gel
process. Indeed, the mild experimental conditions required for
this synthetic route enable the coexistence of both organic and
inorganic species. Also, the versatility of the sol–gel process in
terms of pH, temperature and precursor concentration makes it
possible to adjust the rate of the inorganic polymerization reactions
as well as the nature of the interactions at the hybrid interface, two
key parameters to be controlled in order to obtain homogeneous
porous siliceous materials. Conventional sol–gel procedures involve
the successive hydrolysis and condensation of metal alkoxide or
halide derivatives, resulting in the coordination of the metal
centers to oxo- or hydroxo-bridges, thus generating metal–oxo
or metal–hydroxopolymers in solution.
Historically, sol–gel technology to form silica originates
from the hydrolysis of tetraalkoxysilanes (Si(OR)4) in the
presence of either acid or basic catalysts. Mesoporous silica
materials are typically synthesized by using tetraethoxysilane
(Si(OCH2CH3)4), TEOS,§ and TMOS§ (Si(OCH3)4). Because of its
lower price and lower toxicity, TEOS is much more often used
than TMOS. Indeed, methanol vapors released as a by-product
of TMOS hydrolysis are known to be toxic to eyes and can cause
blindness.
Successful use of TEOS in the synthesis of organized meso-
porous silica14,102 is due to the possibility of tailoring the
silicate oligomers present in solution by regulating the experi-
mental conditions of hydrolysis and condensation. Structures
and different degrees of polymerization of the polysilicic acids
can indeed affect their ability to interact with the organic
templates through electrostatic interaction or hydrogen bond
formation. Major drawbacks of silicon alkoxides are their
toxicity and high cost that limit their development from the
laboratory to the industrial scale. These limits are essentially
related to their production procedures commonly based on
energy-intensive processes and involving harmful chemicals.
TEOS is traditionally obtained either by alcoholysis of silicon
tetrachloride:
SiCl4 + 4ROH - Si(OR)4 + 4HCl (1)
(R = alkyl groups such as methyl, ethyl, propyl, etc.).
or by the reaction of anhydrous alcohol with the
silicon metal:
Si + 4ROH + catalyst - Si(OR)4 + 2H2 (2)
(R = alkyl groups such as methyl, ethyl, propyl).
Alkoxysilane production from tetrachlorosilane (SiCl4) is
limited by the high cost of this chemical and the toxic and
corrosive nature of the hydrogen chloride vapors produced as a

Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
by-product. Silicon tetrachloride is either prepared by treating
silicon metal with chlorine according to the following equation:
Si + 2Cl2 - SiCl4 (3)
or by mixing powdered metallic silicon with anhydrous hydrogen
chloride gas over a fluidized bed at 575 1C:103
Si + 3HCl - HSiCl3 + H2 (4)
and
Si + 4HCl - SiCl4 + 2H2 (5)
As chlorine gas is a highly toxic gas and trichlorosilane and
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
tetrachlorosilane react violently with water to form HCl, the
reaction must be performed very carefully for both health and
safety reasons.
Production of the silicon metal is typically achieved by using
an open electric furnace, wherein an AC electric current is passed
through graphite electrodes into a mixture of quartz or gravel
and carbon sources such as charcoal, coal, wood chips and/or
Downloaded by RMIT Uni on 19 February 2013
petroleum coke. This carbothermic reduction of silicon dioxide
is performed at T = 1800–2000 1C, well above the melting point of
silicon (1700 1C).104,105 The reaction is expressed as follows:
SiO2 + 2C - Si + 2CO (6)
From the standpoint of energy utilization, reductive
furnaces for silicon production are rather inefficient. Indeed,
only 31% of the total energy input to the furnace both in the
form of electrical and chemical energy from the reductant is
used for reduction of quartz. Remaining energy is lost, most of
it in the form of by-product off-gas.105 Second, carbon mon-
oxide resulting from the silica reduction (eqn (6)) reacts
with oxygen outside of the furnace to produce carbon dioxide
(2CO + O2 - 2CO2). Hence, this process results in a significant
carbon dioxide emission with 4.5 tons of CO2 per ton of silicon
metal yielded.106 To this should be added the indirect emissions
resulting from the production of electricity required for reduction,
which vary according to the power source used. 97 kg of CO2 is
emitted for each kilowatt-hour in the case of a typical coal plant
while 0.004 kg is emitted with a hydropower.107
3.1.2. Soluble silicates. In the case of more sustainable
production of silica mesostructures, soluble silicates have
recently attracted much attention owing to their low price
and low toxicity compared to silicon alkoxides. Soluble silicates
are purely inorganic amorphous glasses and are mainly used in
the form of aqueous alkaline sodium silicate solution (Na2SiO3,
also known as water glass or liquid glass), fumed silica and
colloidal silica.108 Soluble silicates have been successfully used
in chemical grouting and other geotechnical applications. They
are also used as detergents and flocculating agents.109 Sodium
silicate solutions, colloidal silica and fumed silica are the most
commonly used inorganic silica sources for the preparation of
organized mesoporous silica. The low cost of these inorganic
precursors is due to their methods of production that involve
the direct transformation of natural quartz deposits. Sodium
silicate solutions are usually obtained by the fusion of silica
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
sand with soda ash (sodium carbonate or sodium hydroxide) at
1100–1200 1C, followed by the dissolution of the resulting
molten salt into water, according to the equation:110
Na2CO3 + SiO2 - Na2SiO3 + CO2 (7)
Fumed silica is produced from flame pyrolysis of quartz
sand or silicon tetrachloride vaporized in a 3000 1C electric
arc.111 Colloidal silica is obtained either by acidification of
silicates or by using an ion exchange resin. In addition to
economic and ecological consideration, the higher chemical
stability of inorganic silica precursors makes them easier to
handle and store than the silicon alkoxides.
Since the pioneering work on M41S materials using precipitated
silica as a silicon source and alkylammonium salts as templates,112
inorganic silica precursors were commonly utilized for the
production of the mesoporous silica MCM-41 and MCM-48
under basic conditions.102,113–116 Sierra and Guth first reported
the synthesis of mesoporous silica via the neutral route using a
low-cost sodium silicate solution in place of silicon alkoxide
and Triton X100 (polyethyleneglycol-4-ter-octylphenylether with
9–10 ethoxy groups) as a neutral surfactant.117 Soluble silica
sources were then successfully applied by following various
synthetic strategies, which were often adapted from procedures
using TEOS.§ Hexagonal and 3D cubic mesostructures were
obtained under acidic conditions,20,118–121 worm-like and hexagonal
mesostructures under near neutral pH conditions,10,35,114–122
and hexagonal mesostructures under basic conditions.109–113
Regarding the large variety of the silica mesostructures
generated, differences between silicon alkoxides and soluble
silicate precursors are not so obvious. Nevertheless, some
characteristic features of soluble silicates should be mentioned.
The main difference between silicates and alkoxides consists
in the nature of the molecular precursors that are released
after solubilization and involved in the silica polymerization
reaction. In contrast to the freshly hydrolyzed silicon alkoxide
monomers, silicate solutions are composed of a variety of silica
oligomers with different degrees of polymerization. 29Si NMR
spectroscopy of silicate solutions has been a powerful method
for studying the connectivity of silicon and oxygen atoms
in silicate solutions. The nomenclature Si(Qn) indicates the
number (n) of siloxane bound in which silicon atoms are
implicated. TEOS displays signals from Si(Q0) while soluble
silicates generally display signals from Si(Q1) to Si(Q4) and
rarely Si(Q0). The significance of the Si(Qn) distribution and
its effect on the formation of mesostructured silica were
studied by comparing the synthesis using different silica
sources.20 The authors found that the absence of Si(Q4) species
was the critical factor in determining the synthesis conditions
of mesoporous silica materials. Mesoporous silica could not be
synthesized when using as received colloidal silica in which
only the Si(Q4) state was detected by NMR spectroscopy. The
first step of dissolution by adding NaOH to the medium was
found to be necessary. Also, utilization of sodium silicate
solution containing Si(Q4) species did not result in any meso-
structures. Klotz et al. also demonstrated the importance of
Chem. Soc. Rev.

Review Article
controlling the Si(Qn) distribution.123 They showed that the
predominance of Si(Q1) species at the early stages of the reaction
resulted in well ordered materials and that the formation of less
well organized materials after ageing was related to the appear-
ance of Si(Q3) species. Formation of silica oligomers with size
and charge suitable to bind the surfactant in a cooperative
manner is known to be critical to the surfactant-templating
assembly process. The advantage of alkoxide species over soluble
silicate species is the possibility of precisely controlling both the
hydrolysis and the condensation kinetics prior or simultaneously
to the surfactant self-assembly process.33,124,125
Silicate species are commonly used to form MCM-41
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
type materials. Under basic conditions, silicate species are
essentially composed of small negatively charged oligomers,
which are suitable for the formation of silica-surfactant
assemblies.126–128 However, the formation of organized meso-
structures from soluble silicates under neutral or acidic
conditions was found to be less straightforward than with
TEOS. This is because, compared to monomeric silicon
Downloaded by RMIT Uni on 19 February 2013
alkoxides, sodium silicate species polymerize very quickly with
a decrease of pH.127 This excessively high polymerization
kinetics was shown to affect both the quality of the meso-
structures and their hydrothermal stability.35,117 Recently,
improvement of the mesostructure quality and reproducibility
of the syntheses under acidic pH conditions by using PEO-
containing block copolymers were achieved through a rapid
mixing of the reactants. Jo et al. synthesized SBA-15 and KIT-6
materials with a quality comparable to the samples resulting
from TEOS§ by very rapidly mixing the reactants using an
electric mixer.120 The authors claimed that the rapid change of
pH from basic to acidic results in the quenching of the silicate
structures and hence prevents undesirable polymerization.
Furthermore, due to a higher content of sodium counterions
within the reaction mixture, the degree of condensation of the
silica matrix obtained from sodium silicate is usually lower
than with TEOS.129 It has been shown that this feature can
result in materials with lower chemical stability.130 However, a
silicic acid sol can be obtained by passing the solution of
sodium silicate through a H+-saturated cation-exchange resin.129
Sierra and Guth improved the chemical stability of mesoporous
materials synthesized under near neutral pH conditions with
PEO-based templates by the addition of sodium counterions that
compensated the negative charges of the silica oligomers.117
Boissière et al. also improved the chemical stability of similar
hybrid systems by the addition of sodium fluoride salts, which
helped the silica polycondensation to occur.33
Morphology of mesostructures synthesized from sodium
silicates was recently the subject of several studies. As the
morphology of mesostructured materials obtained through
the [S0H+][XI+] synthetic pathway (under acidic pH conditions
and using nonionic triblock copolymers) can be significantly
affected by the inorganic salts,131,132 sodium silicate is believed
to act as both a silica precursor and a ‘‘morphology directing
agent’’. Particles with rod-like morphologies were mainly
observed.116,121,133,134 Processing of the silica material derived
from sodium silicate was also recently reported and spherical
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
mesoporous silica particles were synthesized via an aerosol-
assisted evaporation induced self-assembly (EISA) process.135
Finally, routes for the production of neutral alkoxysilanes
from the dissolution of silica (sand, fumed silica or silica gel)
were developed using ethylene glycol (EG) and organic amines.136
To the best of our knowledge, these silica-derived alkoxides
have not been explored yet as alternative silica precursors for
the production of mesoporous silica materials.
3.2. Natural silica sources
In this section, a natural silica source is defined as a non-toxic
silica-containing mineral that is extracted from natural depos-
its and that can be straightaway used as a reagent in the
synthesis of mesoporous silica. Synthesis procedures starting
from natural silica sources involved a first step of pretreatment
under acidic or basic conditions and at mild temperatures in
order to extract silicate species from the material. But in contrast
to synthetic silica sources reported in the previous section
(TEOS, water glass, colloidal silica, fumed silica, etc.), both
chemical composition and structure of the natural silica source
are very close to that of the corresponding raw material. The
exploitation of these silica sources does not imply any energy-
intensive and non-ecological silicon extraction or chemical
transformation steps and therefore they can be considered as
readily available chemical sources.
3.2.1. Layered silicates (natural clays). Interest in using
layered silicates for the production of MCM-41 materials origi-
nates from the abundant resources and the similarities of their
standard units to those of mesoporous materials.137 In 1990,
Yanagisawa et al. reported the first porous silica with controlled
mesopores (designated as FSM-16) obtained from the reaction
of the sodium form of a layered polysilicate ‘‘kanemite’’
(NaHSi2O53H2O) with an aqueous solution of alkyltrimethyl-
ammonium (CnTMA) surfactants.1 The synthesized meso-
porous product presented pores of 2–4 nm and a surface area
of 900 m2 g1. This discovery is at the origin of mesoporous
silica. Layered silicates used as a silica source are commonly
composed of silicate layers constructed by only tetrahedral SiO4
units and exchangeable metal cations between the layers. A
‘‘folded sheet’’ mechanism was proposed to explain the for-
mation of the silica mesostructures from layered silicates, in
which the cationic surfactants are intercalated by the silicate
sheets and the transformation into the hexagonal phase occurs
during the hydrothermal treatment.138 Recently, this mecha-
nism was proposed in a different way. Sakamoto et al. proposed
that a hexagonal structure is created by condensation of
silicates consisting of derivatives of kanemite sheets via the
formation of a mosaic of hexagonal domains.139 Utilization of
both synthetic and natural kanemites as silica sources was
investigated.140–143 Formation of mesostructured materials
from various natural clays like kaolinite,144 talc,145 bento-
nite,146 and attapulgite147 was then examined. Syntheses with
layered silica involve a first step of acidic leaching of the
raw material, which typically consists in the treatment with
concentrated solutions of hydrochloric acid (HCl) or sulfuric
acid (H2SO4) followed by thermal treatment. During this acid
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
‘‘activation’’, variable amounts of structural (octahedral) cations
are removed from the raw material while the tetrahedral sheets
form an amorphous silicate gel. This step determines the
amount of silicates or aluminosilicates involved in the formation
of the mesostructured material, which is therefore crucial in
order to adjust the final structural properties.
Saponite is a trioctahedral smectite obtained as a product of
the hydrothermal alteration and weathering of basalta and
ultramafic rocks.148 It is composed of an octahedral layer
consisting of mainly Mg(O,OH)6-octahedra condensed between
two tetrahedral layers consisting of mainly Si(O,OH)4-tetra-
hedra. Starting from saponite as a silica source, Linssen et al.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
synthesized FSM-16 materials with high porous volume (max.
0.6 cm3 g1), high specific surface area (max. 900 m2 g1) in a
very short synthesis time (3 days instead of 15 days from
kanemite) and low surfactant concentration (3 wt% instead of
26 wt% for the MCM-41 synthesis).149,150 Saponite was treated
with HCl aqueous solution prior to utilization in order to
remove the magnesium contained in octahedral layers. Also
Downloaded by RMIT Uni on 19 February 2013
using saponite as a silica source, Okada et al. performed a
selective leaching step under much milder acidic conditions in
order to preserve characteristics of saponite within the final
mesostructured materials.151
Bentonite is the product of volcanic ash weathering and is
mainly composed of montmorillonite. This natural clay was
used as Si and Al source for the formation of Al-MCM-41.147
Aluminosilicates were extracted by first mixing the clay with
solid NaOH and heated at 6001C for 2 h. The obtained soluble
sodium aluminosilicates were then dispersed in water.
After filtration, the supernatant was mixed with a CTAB§
aqueous solution and the reaction mixture was subjected to
hydrothermal treatment at 1101C for 24 h. Highly ordered
mesoporous Al-MCM-41 were obtained with specific surface
areas (548–1018 m2 g1) and Si : Al molar ratio (8.3–59.6)
varying depending on the mass ratio of bentonite to solid
NaOH set for the leaching treatment and on the pH of the
hydrothermal reaction mixture.
Attapulgite (Si8O2)Mg5(OH)2(H2O)44H2O is a hydrated mag-
nesium silicate with a needle-like morphology.152 Attapulgite
was transformed into an aluminum-containing mesoporous
silica (Al-MCM41) after grinding and acid-leaching.147 Grinding
of the attapulgite resulting in its amorphization played a crucial
role in the formation of Al-MCM-41. The mechanism of for-
mation of the mesoporous material was proposed (Fig. 3). First,
grinding results in the amorphization of the layered structure
of the natural attapulgite. The process of breakdown and
Fig. 3 Proposed mechanisms from natural attapulgite to mesoporous material Al-MCM-41: (A) original attapulgite; (B) ground attapulgite; (C) acid-leached sample;
(D) reactants for hydrothermal synthesis; (E) as-synthesized sample; (F) calcined sample Al-MCM-41.147
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
disordering of the mineral structure resulted in the migration
of a part of the Al3+ ions within the SiO2 tetrahedral sheets.
Subsequent acid leaching produces progressive dissolution of
the octahedral sheet and the removal of their constituent Mg2+,
Fe3+ and Al3+ ions. Simultaneously, acid leaching leads to the
polycondensation of the Si–O tetrahedral sheets, which results
in the formation of amorphous silica on the surface of the
remaining layered silicate. Surface adsorption of Al3+ species
such as [Al(H2O)6]3+ also occurs. The material obtained is
microporous and presents a high surface area and pore volume.
Then, this material acts as a source of Si and Al for the
production of a hexagonally ordered silica-surfactant
mesophase under hydrothermal treatment via a conventional
templating mechanism.18,153
3.2.2. Natural zeolites and diatomaceous earth. Similar to
clays, natural zeolites and diatomaceous earth are abundant
and low cost resources.154 Owing to their porosity and high
silica content, these natural minerals are commonly used as
adsorbents, pozzolanic materials for the concrete industry and
coatings among others.155–157 Diatomaceous earth consists of
macroporous amorphous silica frameworks organized in a
multitude of architectures.158 Because of their macroporous
channel structures and their high silica content, diatoms were
mainly utilized as precursors for the construction of hierarch-
ical and multiporous materials. Synthesis routes generally
involve a dissolution–reprecipitation mechanism where the
coupling of the diatom dissolution and the new porous phase
precipitation kinetics enables the preservation of the original
diatom morphology. Multiporous zeolite macrostructures
were hence synthesized through the transformation of the
diatomaceous silica walls into a zeolite.159,160 Lebeau et al.
introduced additional mesopores into the walls of diatom
skeletons through a similar ‘‘pseudomorphic transformation’’
by the conversion of the diatom skeleton under hydrothermal
conditions and in the presence of ionic surfactants (CTAB§).161
To the best of our knowledge, no example of mesostructured
silica synthesized from natural zeolites was reported in the
literature yet. Nevertheless, the potential of these minerals as
silica precursors was emphasized by the syntheses of meso-
porous zeolites with enhanced catalytic activity from synthetic
zeolites.162 Al-MCM-41 or Al-SBA-15 type materials possessing
strong Brönsted acidity were synthesized by using soluble
aluminosilicate precursors containing tiny fragments of zeolite
structure. Typical synthesis procedures consist in disassembling
the zeolite into unit structures in an alkali solution and in the
presence of organic surfactants, followed by hydrothermal
Chem. Soc. Rev.

Review Article
Fig. 4 TEM images of (A) the parent zeolite Y crystals and (C) calcined HY mesoporous zeolite prepared by recrystallisation with CTAB and TMAOH. High resolution
images of the micropores within the parent (B) and the recrystallised zeolite HY crystal (D).166
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
treatment.163,164 Recently, Gérardin et al. synthesized meso-
porous zeolite Y crystals with narrow intracrystalline mesopore
size distribution by the recrystallization of zeolite HY crystals in
the presence of tetramethylammonium hydroxide and hexade-
cyltrimethylammonium bromide (CTAB) as surfactants (Fig. 4).165
Downloaded by RMIT Uni on 19 February 2013
The recrystallised materials possess a hierarchical structure with
long-range zeolite crystallinity and a high mesoscopic order of
the mesopores located in the same crystals. A bimodal pore
system was obtained with narrow size distributions of micro-
pores (7.4 Å) and mesopores (43 Å).
3.3. Recycled silica sources
Recycled industrial and agricultural by-products that contain
silica were recently considered as abundant silica resources. In
addition to converting toxic wastes into high value silica-based
materials, recycling processes afford solutions to solve the
problem of waste disposal and to guarantee the long-term
availability of natural silicon resources.
3.3.1. Fly ash and bottom ash. Fly ash and bottom ash are
residual by-products of coal power plants in the production
of electricity. After pulverization, coal enters a boiler where
temperature reaches up to 1500 1C. During the cooling process,
the vapor-phase inorganic matters solidify into individual and
spherical particles when suspended in the exhaust gases.
Particles that rise with the flue gases are named ‘‘fly ash’’.
The others, that do not rise, are called ‘‘bottom ash’’. The
annual production of coal ash is estimated to be around
600 million tons, with fly ash constituting 500 million tons of
the total ash produced.166 Fly ash particles are regarded as
highly contaminating, due to their enrichment in potentially
toxic trace elements, which condense from the flue gas.167,168
Disposal of this large amount of industrial waste in landfills,
holding ponds or lagoons throughout the world is becoming an
increasing environmental and economical issue.169 Utilization
of these materials as potential resources for preparation of
value added products appears to be an economically viable
solution to this problem.170–172 Primary components of fly ash
are silica, alumina and iron oxides with varying amounts of
carbon, calcium, magnesium and sulfur. Depending on the
nature of parent coal, conditions of combustion, storage and
handling methods, their physico-chemical properties and
mineral composition vary, making them suitable for a variety
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
of applications that require large amounts of materials such as
production of concrete for the cement industry,173,174 road construc-
tion,175 as soil-additives176,177 and as low-cost adsorbents.178–180
From the perspective of sustainable and economical meth-
ods of mesoporous silica-based materials production, coal ash
is an extensive, cheap and readily available source of Si and Al.
Extraction of sodium silicates and sodium aluminosilicates
from coal ash was first investigated for the synthesis of zeo-
lites181–185 and geopolymers.186–188 Manufacture of these two
types of aluminosilicate materials is commonly achieved by a
hydrothermal process, whereby the coal ash phase is dissolved
within an alkaline solution (mainly NaOH and KOH solutions).
A step of solid-state fusion of the coal ash with sodium
hydroxide prior to the hydrothermal reaction was applied in
order to improve the yield of zeolites as well as the purity of the
final compound. By this method, silica incorporated within
coal ash in the dense form of quartz and mullite is converted
into more soluble sodium silicate and other sodium alumino-
silicate phases.189 Methods of mesoporous silica synthesis from
coal ash are closely related to those of zeolite production. Based
on the procedure established by Kumar et al., a typical synth-
esis applies the alkali-fusion strategy, directly adapted from the
zeolite synthesis.190 Typically, coal ash is treated with sodium
hydroxide at around 500 1C for 1 h to obtain the fused mass,
which is then cooled at room temperature and milled over-
night. The obtained fused powder is then dissolved in water
and aged for at least one day. The suspension is subsequently
filtered resulting in a clear sodium silicate solution. This
solution is finally added to an organic template solution and
the obtained mixture is hydrothermally treated at around
100 1C for a few days. Aluminosilica Al-MCM-41 and pure
silica MCM-41 were obtained with cetyl trimethylammonium
bromide (CTAB), water–ethanol and ammonium solution. The
alkali-fusion strategy for the dissolution of coal ash is largely
preferred to hydrothermal reaction because the much higher
concentration of Si and Al species in the solutions of fused
fly ash critically promotes the formation of mesoporous
materials.191 On the other hand, fusion with sodium hydroxide
also results in significantly higher Na concentrations within the
reaction mixtures.
It was shown that high Na content in the precursor solution
enhances the formation of zeolites183 and can impede the
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
formation of the MCM-41 phase.190,192 However, the negative
effect of Na can be minimized by an adequate control of the
pH.193,194 Besides the method of silicon/aluminum extraction
(alkali-fusion or hydrothermal treatment) and the size of coal
particles, Si content and the Si : Al ratio within the fused fly ash
solutions are critical parameters influencing the formation of
MCM-41 materials from coal ashes.190–194 Indeed, the amount
of Si and Al species available after extraction must satisfy the
Si : Al ratio ranging from 1.35 to the limit of pure Si which was
established from tests using pure precursors.112 Majchrzak-
Kuce ˛ba and Nowak discussed the effect of the mineralogical
composition and structure of the coal ash on the formation
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
of mesoporous materials and their quality based on the com-
parison of ten fly ashes of different types and origin.192 The
authors showed that extract solutions containing the highest
amount of Si do not systematically originate from the highest
Si-content coal ashes but rather from ashes containing
the highest amount of readily dissolvable aluminosilicate
glasses composed of ‘‘reactive’’ silica species. Nevertheless,
Downloaded by RMIT Uni on 19 February 2013
the disappearance of quartz and mullite phases reported in
some studies suggests that silica even in its natural crystalline
form can react with NaOH resulting in soluble sodium silicate
species during the fusion process.192,193 Hence, the careful
selection of the coal ash and the adjustment of the experi-
mental conditions for the extraction of the silicate species are
critical to obtain the Si : Al ratio and Na content suitable for the
formation of MCM-41 materials. Notably, SBA-15 and SBA-16
were obtained with a solution of amphiphilic triblock copolymers
((EO)20(PO)70(EO)20 and (EO)106(PO)70(EO)106 respectively), hydro-
chloric acid and sodium metasilicate.190,195,196
MCM-41 synthesized from coal ashes in an alkaline medium
showed degrees of arrangement of the pores, surface areas and
pore volumes generally slightly lower than those of materials
synthesized from pure silica precursors.192,193 Lower values of
structural parameters were attributed to the incorporation of
aluminum cations and other metal ions derived from the coal
ash within the inorganic matrix under alkaline conditions197 or
to the lower reactivity of the silicate species from the industrial
waste compared to commercial precursors.190,193 The pore
volume reduction may result from the inclusion of coal ash
residues and traces of metal oxide present in the supernatant
solution after the fusion step, which partially block the meso-
pores.191,196 SBA-15 and SBA-16 obtained were mostly free from
alkali and other impurities, which remain in the dissolved state
in the supernatant due to the highly acidic conditions of the
material synthesis. These materials were shown to possess
significantly larger average pore size and pore volume than
the analogous materials prepared using pure chemicals.198
Noteworthily, optimization of SBA-type textural properties still
requires the addition of extra-silica sources.
Formation of mesoporous silica phases from coal ashes is
hence not as straightforward as in the case of pure chemicals.
Nevertheless, materials of similar quality and with equivalent
performances to those of conventional mesoporous materials
could be synthesized. SBA-15 type materials from coal ashes were
successfully used for CO2 adsorption after polyethyleneimine
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
(PEI) impregnation.196,198 CO2 adsorption performances observed
with these materials competed favorably with the ones of
conventional SBA-15. Dhokte et al. took advantage of the
moderate acidity provided by the incorporation of aluminum
species within the inorganic framework to use MCM-41 from
coal ash as a solid heterogeneous catalyst for the classical
Mannich reaction.199
The material showed much shorter reaction times and
higher yields compared to classical catalysts such as adenine
as an aminocatalyst, acidic ionic liquid TMBSA[HSO4],
Al(CH3SO3)34H2O. Recyclability of this new ‘‘green’’ catalyst
was also demonstrated. The high overall porosity and uniform
pore structure with long-range order of recycling derived
materials were also recently exploited for the production of high-
quality mesoporous carbons through a nano-casting process.196
‘‘Greener’’ strategies were recently developed by using
sodium silicate from coal ashes. Production of MCM-41 using
a one-step synthesis method at room temperature (without
using hydrothermal treatment) was achieved by the addition
of acetic acid.200 Park et al. optimized the recyclability of the
silicate species by collectively preparing SBA-15, MCM-41 and
zeolite 13X from coal ashes. In this procedure, the mesoporous
materials were synthesized from the extracted supernatant
recovered after alkali-fusion while the precipitated solid part
was then used to produce zeolite 13X. As the Si–Al ratio of the
precipitate decreases after the silicate extraction, the authors
took advantage of the more favorable composition of the
precipitate for preparing zeolites.201
3.3.2. Rice husk. Rice is a member of the Graminae family,
which also includes grasses, bamboos, wheat, barley, oats
and maize. In all of these plants, silica is taken up through
the roots as dissolved Si(OH)4 and is reprecipitated within and
around the cells as hydrated opaline deposits. All of the aerial
parts of the grass plants have silicified cells in varying
amounts.202 Hence, not only grasses (Gramineae) but also
horsetails (Esquisetum) and sedges (Cyperaceae) are potential
silica resources for the production of silica-based materials.203
In this sense, rice husk itself is considered as a natural silica
source. However, rice husk, the main ‘‘natural silica-source’’, is
generally recovered as the major by-product from the rice-
milling industries. It constitutes the part of the rice plant that
surrounds the paddy grain and contains silica in the range
of 20–25 wt%. According to the United Nation ‘‘Food and
Agriculture Organization’’ (FAO), the world rice production in
2011–2012 was estimated to be 482.4 million tons.204 As rice
husk constitutes approximately 20% of the paddy produced,
on a weight basis, it represents a huge silica resource. As
abundantly available biomass, it is commonly transformed
into fuels, chemicals or electric power via thermochemical
processing.205 Its combustion produces rice husk ashes
containing over 90% of silica, which are commonly used as a
pozzolan in the cement industry206 as well as for the manufac-
ture of sodium silicate used in the fine chemical industry. The
latter application requires a preliminary step of purification.
After combustion, silica contains impurities such as oxide of
alkali metal and carbon residues, which are usually removed by
Chem. Soc. Rev.

Review Article
a preliminary leaching step with a boiling solution of HCl,
HNO3, H2SO4, NaOH and NH4OH and a subsequent thermal
treatment with temperatures ranging from 500 1C to
1400 1C.207–209 Highly pure silica was used as a silica source
for the synthesis of silicon carbide, silicon tetrachloride, silicon
nitride210,211 and recently for the production of porous materi-
als like zeolite212–215 and mesoporous silica-based materials.
The preliminary preparation of the purified sodium silicate
solutions is followed by synthesis procedures of mesoporous
materials that are similar to procedures starting from synthetic
soluble silica sources mentioned previously. MCM-41, MCM-48
and SBA-15 type materials synthesized using sodium silicate
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
solutions extracted from rice husk were successfully used as
molecular sieves for the adsorption of chlorinated volatile
organic compounds,216 as supports for heterogeneous cataly-
sis217,218 and as carbon dioxide adsorbents.219,220
Recent approaches attempted to lower the environmental
impact of mesoporous material formation from rice husk silica
by tailoring the silica extraction conditions and by taking
Downloaded by RMIT Uni on 19 February 2013
advantage of the multicomponent husk composition. Qu
et al.221 used lignin, one of the carbonaceous components of
the husk, as a template to form hybrid mesoporous materials.
Solutions composed of sodium silicate and lignin were prepared
through the thermal treatment of the rice husks in the presence
of sodium hydroxide. Sols were then obtained by heating the
solution in which sulfuric acid was added. Hybrid lignin–silica
materials recovered after precipitation possessed surface areas
ranging from 235 to 472 m2 g1 depending on the lignin–silica
composition of the materials. Wang et al.222 reported the for-
mation of porous silica nanoparticles from HCl-treated rice husk
via controlled pyrolysis. The authors claimed that the potassium
cations still remaining within the silica after purification cata-
lyzed the melting of silica primary nanoparticles to form porous
structures. After doping the synthesized silica nanoparticles with
potassium cations and a pyrolysis step, semicrystalline meso/
macroporous frameworks with mesopore diameters ranging
from 2 to 9 nm and a (BET) surface area of 164 m2 g1 were
synthesized (Fig. 5). Although the latter two approaches are not
conducive to the formation of any organized mesostructures,
they pave the way towards strategies that will essentially rely on
natural resources and significantly reduce the number of
chemical modification steps.
Fig. 5 Schematic view of the synthesis of hierarchical meso-macroporous silica nanoparticles from rice husk.222
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
3.3.3. Other industrial wastes. The use of electronic products
has grown substantially over the last five decades. Since the
useful life of electronic devices is relatively short, e-waste is
becoming one of the rapidly growing environmental problems
of the world. Recycling programs and collection methods were
established to recover materials from these types of wastes.223
Liou recovered high purity silica from the combustion
of packaging resin wastes commonly used for the encapsula-
tion of electronic devices such as integrated circuits.224 In
a recent study, this author reported the synthesis of well-
ordered MCM-41 type materials using packaging resins as raw
materials.225 Extraction of silica from the e-waste was achieved
as follows: a powdered resin was placed in a tubular reactor
made of quartz and heated under purified air at 800 1C for 1 h.
The residual metal impurities within the sample were then
removed using an acid-leaching process. Subsequent treatment
in a hot hydrochloric acid solution, washing and neutralization
steps resulted in ashes. Extraction of the silica from the ash was
achieved by an alkali-extraction technique. The sodium silicate
solution recovered was then used as a silica precursor in
the synthesis of mesoporous materials. Following the same
concept, mesoporous silicas were synthesized from silica pre-
cursors extracted from photonic industry wastes226 and iron ore
tailings.227 An interesting recent study was performed on the
synthesis of giant zeolite crystals by means of a bulk material
dissolution technique.228 Shimizu et al. demonstrated the
growth of millimeter scale silicalite-1 and anacime from
the surface of silica tubes through hydrothermal treatment in
the presence of structure directing agents (Fig. 6). To the best of
our knowledge, this result is the first example of domestic glass
recycling that is exploited for the synthesis of valuable porous
materials. It can be anticipated that this abundant silica
resource will be soon used for the production of ordered
mesoporous silica materials.
3.3.4. Recycling of silica based mesoporous silica. Kim et al.
recently reported a method for the recycling of silica wastes
based on the regeneration of mesoporous silica materials.229
The authors showed that dissolution of silica-based hard
templates used for the generation of mesoporous carbons
(by means of nanocasting) results in silicate species reusable
for subsequent formation of well-ordered mesostructured
materials (Fig. 7). Characteristics of synthetic, natural and
This journal is c The Royal Society of Chemistry 2013
 View Article Online

Chem Soc Rev Review Article

efforts have been made on ecodesign and the adaptation to the

scale-up of processes.231
Synthesis procedures usually involve several steps when the
precipitation route (also called the aqueous route) is followed.
Concerning the assisted self-assembly routes, most of the proce-
dures to prepare dry surfactant-containing materials are based on
a few steps. In any case, a common final step consisting in the
surfactant extraction has also to be considered.

4.1. Precipitation synthesis route

Most of the synthesis routes developed for OMS are based on
the precipitation of the solids and they involve different steps:
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B

a reaction step usually in the liquid phase, solid recovery,

washing and drying (Fig. 8).
Fig. 6 Growth of giant zeolite crystals from the surface of a glass tube.228
4.1.1. Reaction step. In this first step, reactants are mixed
and left to react. After mixing of the reactants, the solid phase
precipitates with characteristic time depending on the process
parameters. This step can be very fast as it is usually observed
and followed when silica precursors such as sodium silicate are
Downloaded by RMIT Uni on 19 February 2013

used. This precursor is highly reactive and it is difficult to

control condensation. When alkoxysilanes are used as a silica
precursor, the reaction step takes usually more time. With this
type of precursor it is easier to control silica condensation. In
any case, a ripening or gestation stage can be considered and
consists usually in the micelle/silicate species self-assembly
and ordering. It is often followed by an ageing or maturation
stage which aims to consolidate the silica walls by increasing
the condensation degree. These stages are characterized by
long duration and high reaction medium temperature and thus
they are time and energy consumers. These two physical para-
meters need to be optimized. Concerning the synthesis of OMS
from sodium silicate and in the presence of a cationic surfac-
tant such as cetyltrimethylammonium bromide, it was quickly
demonstrated that rapid precipitation of the mesostructured
material can be obtained at room temperature.49 For the
syntheses performed in the presence of neutral surfactants

Fig. 7 Schematic procedure for conventional nanocasting (a) and for the
regeneration of mesoporous silica materials from the silicate waste (b).229

recycling-derived silica sources are summarized and compared

in Table 8.

4. Processes involved in the synthesis

Designing more ecological and more economical processes for
the OMS synthesis has been less addressed than ecodesign
focused on reactants of the synthesis. One of the main reasons
is probably due to the fact that most of the laboratory-scale
processes are not adapted to the ecodesign and the scale-up
(magnetic stirring, Büchner funnel filtration. . .). However
quickly after their discovery, simple synthesis protocols for
OMS have been developed by varying the nature of reactants Fig. 8 Steps involved in the precipitation and assisted self-assembly routes for
(ref. 230 and references therein). It is more recently that some the synthesis of OMS.

This journal is c The Royal Society of Chemistry 2013 Chem. Soc. Rev.

Review Article
which are temperature sensitive, these two parameters play a
primordial role. This point has been widely studied for the
synthesis of OMS with SBA-15 architecture.232–234 Ripening or
gestation is performed in the 15–60 1C temperature range
where micellization occurs.235 The initial synthesis protocol
has a duration of 24 h236 and was found to be possibly reduced
to 2 hours when ripening was performed at 40 1C. It could be
further reduced to 30 min at this ripening temperature but with
lower textural characteristics (lower specific surface area, pore
volume and pore size) or at a higher ripening temperature.234 It
was shown by dynamic light scattering that mesostructured
silica/P123 particles precipitate at about 30 min after the silica
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
source (TEOS§) addition with a ripening temperature of 40 1C.
This precipitation time corresponds to the minimal duration to
consider if pore ordering and narrow particle size distribution
are desired. It could be reduced to 5 min when ripening is
performed at 55 1C. The temperature during this stage was also
found to influence particle morphology.232,234
During this synthesis stage stirring is often required at least
Downloaded by RMIT Uni on 19 February 2013
at the beginning. Indeed, stirring is performed for reactant
mixing and sometimes maintained for an additional period. In
some cases, synthesis of SBA-15 type OMS for example, the
stirring process and the rate influence strongly the morphology
of particle aggregates.232,234,237 When magnetic or mechanical
stirring is applied, the shear flow created in the synthesis
volume favors the aggregation of rod-like particles to form
fiber-like macrostructures.238 Without stirring, unaggregated
rod-like particles were obtained.236 Mixing time will depend on
the duration of the reactant addition. The latter also has a
strong influence on the material formation according to the
nature of the reactant. In particular, the nature of the used
silica source needs a particular attention in regard of the
mixing method. Recently Ryoo et al. studied the influence of
the duration of silica source addition on the formation of OMS
with SBA-15 and Kit-6 architecture.120 When sodium silicate is
used as the silica source, fast addition under vigorous stirring
conditions is preferable for obtaining a homogenous solid with
desired characteristics. A home-scale mixer which can be
compared to a mechanical stirring process has been used for
this purpose. Mixing is a crucial point and often makes the
scale-up difficult. It is noteworthy that magnetic stirring is
mainly used but it is not adaptable on the industrial scale.
Mechanical stirring is more appropriate for such purposes.
After the formation of the mesostructured solid, heating is
often applied to promote silica condensation and consolidate
the silica framework. Ageing or maturation is usually performed
under static conditions and by placing the reaction flask in an
oven. OMS such as MCM-41 are synthesized using cationic
surfactants that are sensitive to pH, ionic strength and concen-
tration. The synthesis procedures have been quickly optimized
in terms of total duration and temperature, and protocols at
room temperature with fast precipitation were developed.2,231
An additional thermal treatment applied to the reaction
mixture under hydrothermal conditions or not is often per-
formed to improve silica network condensation and thus
hydrothermal stability. In the case where non-ionic surfactants
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
are used as structuring agents such as P123 block copolymers,
the aggregation of the amphiphilic copolymers is mainly con-
trolled by the temperature. Thus, temperature becomes a
predominant parameter for controlling micelle formation,
micelle/silicate species self-assembly, rigidity of the silica net-
work, pore structuring. . .. This additional stage called ageing
or maturation may strongly modify structural and textural
characteristics as observed for SBA-15-type OMS. During this
stage the heating process is energy consuming. Temperatures
from 80 to 150 1C and durations from 12 to 48 h usually
recommended are parameters to optimize. Such parametric
studies have been reported on SBA-15-type OMS.232–234 Strong
structural and textural modifications mainly take place during
the 6 first hours and a 14 h-thermal treatment should be
sufficient since minor changes occur for longer durations.234
An interesting approach was the use of micro-wave (MW)
heating, which was found to reduce considerably the durations
of the ageing stage. T. Bein has first reported the synthesis of
highly ordered MCM-41 type OMS with hexagonal channel pore
structure in a temperature-controlled microwave oven from
aged precursor gels within about one hour.239 The use of
microwave energy to synthesize highly ordered MCM-41 OMS
with homogeneous morphology was later reported by S. E. Park
et al.240 They introduced ethylene glycol as another dielectric
medium in addition to the water solvent. The microwave route
has been extended to other OMS types such as MCM-48,241 SBA-
15,242 SBA-16243 and FDU-1.244 SBA-15 type OMS with compar-
able structural and textural characteristics were obtained after
MW thermal treatment for 2 h at 90 1C against 24 h at 90 1C in a
classical oven. However, a minimum ripening or maturation
time is required to avoid the collapse of the structure upon MW
heating.234 It was also reported that the MW route is adaptable
for short time synthesis of periodic mesoporous organosilicas.245
More recently Jaroniec et al. took advantage of the recent
microwave technology to develop temperature-programmed
microwave-assisted synthesis (TPMS) of ordered mesoporous
silicas (OMS).246 SBA-15 type OMS were prepared by following
this new route where temperature and time were programmed
for the entire synthesis. Synthesis at higher temperatures
than conventional protocols was investigated. Resulting SBA-15
materials showed better hydrothermal stability than those
synthesized at commonly used temperatures either under
conventional or microwave conditions. Moreover, partial decom-
position of the template during high-temperature microwave-
assisted syntheses was observed and found to not compromise
the formation of well-ordered SBA-15 materials. Such a combined
synthesis protocol is highly desirable since it is time saving.
Ultrasonication was also used and reported as a fast method
for the preparation of OMS such as MCM-41247 and SBA-15.248
Sonication involves an acoustic cavitation phenomenon that
creates high transient temperatures and high pressures of
several thousand bars in the solution. Significant changes in
the processing medium occur during sonication. Tang et al.
reported the synthesis of MCM-41 OMS solids with thick
walls and a very narrow pore size distribution by using ultra-
sound radiation.247 Later, a rapid sonochemical route to
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
prepare SBA-15 and Ti-SBA-15 was reported by Lee et al.249
However an additional hydrothermal treatment was necessary
at 85 1C for 1–3 h. More recently a temperature-assisted
sonochemical method was reported for the fast synthesis of
SBA-15 type OMS.248 When the ripening or gestation step is not
applied (ultrasound radiation was applied immediately after
silica source addition), strong modifications of the pore shape,
porous characteristics and particle morphology were observed.
Very short synthesis times have also been reported for the
synthesis of periodic mesoporous organosilicas in the presence
of cationic ammonium surfactants or neutral amphiphilic
block copolymers.250 In this study, sonication has also been
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
judiciously used for template removal. A total experiment time
of 1 h was reported when cationic ammonium surfactants were
used. With amphiphilic block copolymers the synthesis time
was 30 min but an additional treatment in the acetone–HCl
mixture for 24 h was found to be necessary for complete
surfactant removal.
Microwave heating and sonication are economical processes
Downloaded by RMIT Uni on 19 February 2013
because they are time and energy savers and can be developed
at the industrial level. However, in reported studies, no energy
balance was observed.
4.1.2. Solid recovery. At the end of the reaction step, solid
recovery is necessary and induces another process. The
solid recovery step is rarely considered in studies concerning
ecodesign. However this step is of paramount importance.
Indeed filtering is usually applied for recovering the solids
and removing the major part of solvent, usually water. Lowering
the amount of solvent will reduce time for drying and thus
associated energy consumption. The filtering step needs to be
optimized in terms of process because it is usually done with
a Büchner funnel, which is not compatible with industrial develop-
ment. An alternative way for solid recovery is centrifugation.251 This
process has to be optimized in terms of rotating rate and duration
depending on the particle size. Some other solid–liquid separation
technologies could be considered such as press filters and studied in
terms of efficiency, and time and energy saving.
4.1.3. Washing. The washing step is also rarely optimized.
However this step is necessary to remove by-products and can
help to remove surfactants, even partially. The triblock copoly-
mer remaining in SBA-15 OMS after solvent washing has been
studied by solid state NMR.89 The as-synthesized SBA-15 mate-
rial recovered by filtration, washed with distilled water and air
dried at room temperature was subjected to solvent washing
under the same conditions with water and ethanol for compar-
ison. 13C solid-state NMR results showed that the water wash-
ing process disturbed the overall molecular ordering of P123.§
After water washing, PEO block carbons exist in two motional
states, rigid and mobile. 24 %wt of P123 was removed, which
probably corresponds to PEO§ blocks weakly bound to meso-
porous materials. Water washing affects more the hydrophilic
PEO blocks of P123. After ethanol washing, wider and feature-
less resonances were observed suggesting a wide structural
distribution and reduced motion of both PEO and PPO§ blocks
of the remaining P123 (26 %wt). It is assumed that the small
amount of P123 remaining in SBA-15 after ethanol washing
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
must have adhered onto the SBA-15 surface rather than being
retained in the micellar structure. The intensity of the reso-
nance characteristics of PEO chains is higher and this was
explained by a stronger adhesion of some PEO blocks to the
inorganic materials surface because both are hydrophilic.
Washing with an appropriate solvent could be a way to remove
quickly a large amount of template molecules under mild
conditions. It is also expected to allow the partial recycling of
the templating agents.
During this washing step, change of solvent can be easily
done and can be helpful to facilitate the drying step. It is note-
worthy that washing involves supplementary filtration steps. The
amount of solvent used for washing is of paramount importance
when considering ecodesign since it has to be integrated in the
E-factor calculation (except when water is used).46,47 However, this
parameter is often not precise and not optimized.
4.1.4. Drying. The drying step is crucial since several reac-
tion phenomena such as condensation and mesostructuration
as a consequence of micelle rearrangement, growth and assem-
bly take place along this step. During this step, the evaporation
of the residual solvent occurs thus modifying the characteris-
tics of the final product. Moreover, solvent is characterized with
superficial tension that can control particle aggregation.
The drying stage can be considered as a supplementary
reaction step with increasing solid-phase concentration. Struc-
tural and textural changes that take place during this step have
been little studied for OMS. Phase transition upon drying
has been reported for precipitated OMS.251 The mesophase
transformation strongly depends on the flexibility of the silica
network and thus synthesis duration before drying is of para-
mount importance. It was reported that a long synthesis time
would lead to a too rigid silica network which undergoes further
structuration changes upon drying. On the other hand, a short
synthesis time would lead to a more flexible silica network which
could lose ordering upon high temperature drying. Synthesis
time and drying temperature have to be adjusted to control the
structure and texture of the final material.
The synthesis of a SBA-15 type OMS was recently reported
with a very short synthesis time of 30 min.234 On the basis of
the work of Rushtein et al., it was assumed that mesostructura-
tion of micelle/silica species aggregates occurred during the
drying step.252 Drying is often performed in an oven at low
temperatures of about 50–70 1C. Since at the beginning, the
silica network is weakly condensed and flexible, amphiphilic
molecules can be temperature sensitive and modify their
aggregation state, consequently strong changes in the material
structure and texture can occur. The presence of water mole-
cules at the surfactant/inorganic framework interface was
found to play a primordial role in the phase transition upon
drying, depending on the flexibility of the silica network.
When drying is performed at room temperature, it takes
long time (several days), but it is a low energy cost process. The
dimension of the bed could be optimized in order to increase
drying efficiency and reduce time.
Some studies have reported the influence of the drying
methods such as oven, microwave and spray on the physical
Chem. Soc. Rev.

Review Article
(oil and water adsorption, tapping density) and textural
(porosity) properties of mesoporous silica solids.253,254 MW
and spray drying can reduce considerably the drying time. In
conventional oven drying, heat energy is transferred to the
interior of the gel by conduction. Consequently, the rate of
heat conduction depends mainly on the gel conductivity, which
decreases with decreasing moisture content upon drying. In the
MW process, water molecules present in the gel absorb the
microwaves simultaneously in the total volume causing mole-
cular vibrations with respect to the oscillating electric field of
the microwaves and thus heating uniformly the whole gel. With
MW radiation the drying process is accelerated and, the total
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
drying time and the production cost as well are reduced. For
spray drying, the size-controlled drops of precursor solution or
slurry are dispersed into a hot air chamber. The uniform
heating of the whole sample mass is facilitated by the size of
the droplets. There are very few studies on the influence of
drying on the characteristics of OMS. L. Pei et al. have studied
the effect of the drying rate on the structure of mesoporous
Downloaded by RMIT Uni on 19 February 2013
silicas templated by pluronic P123 block copolymers and in
particular on the formation of closed pores in the mesoscopic
structure of silica.255 A fast drying process is more favorable for
the replication of isolated P123 micelles which results in closed
pores formation in the mesoporous silica.
All these synthesis steps are time and energy consuming. An
alternative low cost and environmentally benign synthesis
route has been described for OMS particles. A dry-gel conver-
sion process instead of hydrothermal reaction in strong acid
solution has been performed to reduce the cost of the synthesis
of SBA-15 type OMS.256 This procedure consists in the prepara-
tion of a precursor gel by hydrolysis of the alkoxysilane pre-
cursor (TEOS) in aqueous surfactant (P123) solution. After
recovery, these gels were dried and they underwent steam-
assisted dry-gel conversion at 100 1C with time varying from 2
to 24 h. Moreover, it was demonstrated that the acidic filtrate
recovered by separation of the as-synthesized solid particles
was reusable for the synthesis of SBA-15 materials. Although
this synthesis strategy was claimed cost-effective and environ-
mentally benign compared to classical procedures, tempera-
tures, durations and technologies implemented are similar.
Only a reduction in the HCl amount can be noticed.
4.1.5. Continuous process. Most of the synthesis procedures
developed by precipitation involve at least four steps: (i) pre-
cursor sol preparation, (ii) solid recovery, (iii) washing and (iv)
drying. Reduction of the number of synthesis steps is highly
desirable in order to decrease the time and cost of the total
procedure. It is also favorable to facilitate the implementation
of the continuous synthesis process, which allows large-scale
production. Consequently the continuous synthesis process
appears to be essential in the ecodesign context. M. Linden
et al.257 were the first to report a continuous preparation of
MCM-41 type OMS in a tubular reactor. This work was not
motivated by the search for ecodesign methods but it was
performed to study by time-resolved in situ XRD the kinetics
of mesostructuration of such materials. Feeding of aqueous
reactants and the silica source was controlled by peristaltic
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
pumps. An ultrasonic bath and static mixers were used to
homogenize the reactants mixture. The mixture was fed at a
constant flow rate into the XRD measurement cells in a tube
with length adjusted to the desired reaction time. Recently, a
very fast synthesis protocol for COK-12 type OMS which are very
similar to SBA-15 type OMS was reported and adapted for the
continuous synthesis process that allows large scale produc-
tion.258 Surfactant solution and the silica source are separately
pumped with controlled flow and mixed in a glass Y piece. The
mixture is fed into a glass tube at a controlled flow rate and for
short synthesis time (4 min). Extra steps such as solid recovery
(vacuum filtration), washing and drying (in air at 60 1C) are also
performed. Therefore, this continuous synthesis process allows
integrating all stages of the reaction step.
4.2. Assisted self-assembly routes
Synthesis procedures based on the assisted self-assembly
of silica precursors species and structuring agents such as
Evaporation Induced Self-Assembly (EISA§)259 lead to the
formation of mesostructured material in a very few steps. This
synthesis method is presented in detail in a review of the
present themed issue on Mesoporous Materials. Therefore, it
is briefly discussed only from an ecodesign point of view in the
present paper. This process has been recognized as a time and
energy saving process.260 Indeed, the main part of the reaction
step (species assembly and ordering), solid recovery and drying
are integrated in one step. The precursor sol is prepared by
mixing reactants (silica precursors, pore structuring agents,
organic solvent and water). Then the process consists in the
solvent evaporation from the sol during which siliceous species
and surfactant molecules self-assemble and self-organize with
both increasing water concentration of the liquid phase and
condensation of siliceous species. This process is particularly
well adapted for controlling the shape-modeling such as films,
fibers, monoliths. . .. Moreover it was also found to be adapta-
ble for the formation of mesostructured non-siliceous oxides
such as titania, zirconia261. . .. However, compared to the pre-
cipitation route, the EISA process required the use of an organic
solvent which evaporates and thus leads to volatile organic
compounds (VOC). This process has recently inspired a LISA§
process to make thick and thin mesoporous silica films.262 The
LISA procedure is very interesting in terms of the ecofriendly
process because it does not involve the use of any solvent.
Moreover, silica precursors, which are polydimethoxysilane
oligomers, are quasi-nonvolatile. Polycondensation of siliceous
species at the P123 amphiphilic copolymer interface is gener-
ated by light and a photoacid. Processes such as the EISA start
with the preparation of a stable precursor solution. Depending
on the UV rays source and the deposition technique (conveyor
or spin-coating), thick and thin films can be prepared. The
Si/P123 ratio and humidity rate were also found to have a
crucial influence on the pore network ordering.
The EISA process is widely used for the production of thin
or thick film, coating, and monoliths. In these cases, the
formation of a long-range continuous network is observed.
However, an aerosol technique can be used to produce
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
spherical particles based on the EISA process. First reports on
the spray-drying technique described the preparation of poly-
disperse spherical ordered mesoporous silica particles.263,264
Optimisation of experimental conditions and processing para-
meters has been the aim of several studies in order to improve
pore structuration265 and particle size distribution.266 It was
reported that monodisperse mesoporous silica microspheres
can be formed by using a vibrating orifice aerosol generator
(VOAG).267 Further improvement of this method allowed
increasing the production yield.268 Initially developed with
alkoxysilane, it was adapted to a lower cost silica source such
as sodium metasilicate.269 It is noteworthy that this technique
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
is limited to the production of particles with spherical mor-
phology. Spray drying can also be used to produce OMS film.261
Aerosol is a technique already used in industries and offers
several perspectives for industrial developments.
Compared to precipitation routes, the assisted self-assembly
synthesis procedures do not need supplementary solid recov-
ery, washing and drying steps (Fig. 8). Moreover, except for
Downloaded by RMIT Uni on 19 February 2013
volatile species formed upon precursor hydrolysis and conden-
sation, and the solvent, all reactants are integrated in the final
material. Wastes are lower in comparison to the precipitation
route. It is noteworthy that some film deposition or particle
formation processes such as dip-coating or spray drying,
respectively, allow the use of the whole (or almost whole)
precursor sol. This is not the case when film deposition
methods such as spin-coating or spray-coating are used.
Indeed, these methods are known to generate a large amount
of waste sol precursor. Because of the low thickness of thin
films prepared by EISA or LISA, the template removal is easier
than that for powders or monoliths and thus less energy
consuming.270 Using Brij 56, Pluronic F127§ and CTAB§ as
templates for their films, Losurdo et al. showed that the
template removal is a rapid process that occurs at temperatures
as low as 160 1C.271 In general the temperature used for the
elimination of these templates is between 200 and 300 1C.
The low thickness of thin films is favorable to internal heat
diffusion and consequently a faster network condensation
upon thermal treatment for consolidation is expected.
Another rapid synthesis route involving a few steps is the
instant direct templating strategy developed for the elaboration
of OMS monoliths.272 It consists of mixing the reactant alkox-
ysilane as a silica source, a neutral templating agent and water
in right proportions to form instantly a liquid-crystalline phase.
Acid is present in the water phase to quickly initiate silica
condensation around the liquid crystalline phase assembly of
the surfactants. Alcohol produced by alkoxysilane hydrolysis
and condensation is simultaneously removed under vacuum.
The obtained xerogel is aged for 10 hours in an oven at
moderate temperature (45 1C). In this process the only waste
produced is alcohol.
4.3. Surfactant removal
To obtain porous materials, the final step is the removal of the
organic template from the inorganic framework. This step plays
an important role in determining the final structural and
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
textural properties of the porous materials and different
methods are described in the literature. Typically, the most
commonly used ones are calcination preceded or not by a
chemical extraction with an organic solvent.
The extraction processes described here deal with the most
common structuring agents used in templating pathways.
Table 10 summarizes the different ways used for the elimina-
tion of the templates.
4.3.1. Calcination process. Regarding the calcination proce-
dure, the temperature used depends on the nature of the
template to be removed.
The triblock copolymer type neutral template and a cationic
template such as CTAB§ often used can be decomposed at
300 1C according to TG analysis. However the calcination
temperature often applied is higher, 500–550 1C for 3 h and
even more. At these temperatures the template removal is
complete, but dehydroxylation occurs, and the shrinkage273
due to long time treatment implies the modification of textural
properties of the OMS.
Numerous studies have been done to demonstrate the
impact of high temperature calcination on shrinkage and
textural properties of OMS and hence the advantage of using
another template extraction method.
Decomposition of the P123 type copolymer by TG-DTA
analysis has been studied by Kleitz et al. in the case of SBA-15
materials.274 They demonstrated that at 150–200 1C the major
part of the PEO§ is transformed into carbonaceous species.
XRD measurements at different temperatures also confirm the
creation of porosity with the increase in the intensities of the
low angle reflections at these temperatures. The oxidation of
the block copolymer occurred at 200–250 1C and produced CO2
and H2O. Moreover, the total pore volume is reached at
calcination temperatures between 175 and 270 1C. Bérubé
et al.275,276 also showed that the lattice contraction begins at
a temperature around 300 1C and a decrease of the pore
diameter can be observed. The materials calcined under an
inert atmosphere at 450 1C show essentially the same residual
organic content as the one calcined at 175 1C under air. The
alkyltrimethylammonium surfactant can be decomposed in
three steps: a first degradation step at temperatures between
150 and 250 1C corresponds to the elimination of the trimethyl-
amine head group, then oxidation in two steps is observed: around
250 1C and then around 300 1C. From 400 1C the loss observed is
essentially due to the elimination of carbonaceous species and to
condensation of silanols.274,277,278 However the total removal
of carbonaceous species seems to occur at temperatures between
600 1C and 800 1C,279 indeed, 13C MAS NMR shows that there is no
more carbon traces at temperatures around 700 1C.
By increasing the time of calcination, the temperature used
can be lower than the conventional one. Goworek et al.280,281
showed that 15 h at 250 1C under hydrogen flow is a convenient
method to remove the entire CTAB§ template in MCM-41
materials. Indeed, a low temperature calcination is necessary
to completely remove the template from the as-synthesized
silica. Moreover the use of a hydrogen flux avoids the formation
of stable chemical species that are normally found at this
Chem. Soc. Rev.

Review Article
temperature under an oxidative atmosphere. This study also
demonstrates that the elimination can be done under another
atmosphere other than air. Indeed, Zalewski et al. indicated
that the main part of the organic template can be removed at
580 1C under an argon atmosphere.282 However using an inert
gas for a calcination process costs more than using air.
According to these temperature calcination profiles, syntheses
of different mesoporous silica materials have been performed
at calcination temperature T r 300 1C for the elimination of
triblock copolymers.283,284
After the total removal of the template, an increase in the
calcination temperature can be explained by the need to
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
decrease the amount of hydroxyl groups in the materials.
29
Si MAS NMR combined with 1H ultrafast MAS NMR allow
characterizing quantitatively the SiOH groups285 and depend-
ing on the aimed application, the number of SiOH will vary and
so the calcination temperature chosen can be different.
Most of the studies do not deal with the temperature of
template elimination. For most of them, the calcination tem-
Downloaded by RMIT Uni on 19 February 2013
peratures often used are Z540 1C for removing the ammonium
surfactant2,286,287 and 500–550 1C for removing the non-ionic
surfactant.16,131,236,288–290 Poly(ethylene oxide) based surfac-
tants291 and hybrid templates292 have been removed at 600 1C.
The calcination process is a very efficient way to remove all the
templates involved in the synthesis. But, after this step the template
is totally destroyed and no reuse is possible by this technique.
Moreover, high temperatures and long treatment times applied
during the calcination processes are energy consuming. Chemical
extraction methods were hence proposed.
4.3.2. Chemical extraction. The chemical extraction is performed
in liquid medium and involves supplementary synthesis steps
such as washing, solid recovery and drying. It is a long time
process for template removal because several runs are often
necessary to remove the entire surfactant template occluded
within the pores. However, this method allows the elimination
of the template without its decomposition and permits thus its
recovery and reuse. Chemical extraction requires a high
amount of solvent, which limits the sustainability of the
method. However, where applicable, the Soxhlet method allows
saving solvent. Indeed the average quantity of ethanol used for
a total extraction is about 60–250 mL per gram of template.
Cassiers et al.293 demonstrated that the amine template can
be easily removed using acidified water. Using water alone for
the extraction is totally inefficient because of the low solubility
of the amine template in water, even at high temperature. The
addition of HCl in the medium allows the conversion of
dodecylamine (DDA) into dodecylammonium chloride, which
facilitates the extraction. The template extracted can then be
reused. Moreover, this method was shown to be fast, the
extraction being achieved after 1 h under reflux.
The efficiency of two surfactant removal methods, washing
in an ethanol reflux Soxhlet system for 72 h and calcination at
730 1C for 4 h, was studied on previously dried OMS (air drying
for 72 h, drying in an oven at 150 1C for 72 h, drying in vacuo at
25 1C, at 100 1C for 12 h). Both methods lead to mesoporous
silicas with large specific surface area, pore volume, pore
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
diameter and unit-cell parameter, except for the one obtained
by the oven drying process at 150 1C. This can be explained by
partial oxidation of the amine at this temperature.31
AlOthman and Apblett294 described a synthetic route for
preparing an hexagonal mesoporous silica using 1-hexadecyl-
amine as a templating agent. The template extraction was
conducted either by calcination at 550 1C or using acidic
ethanolic solution. In this case, both recovered mesoporous
materials exhibit similar textural and structural properties.
Nevertheless, more silanol groups were observed at the silica
surface of the ethanol washed material.
Aluminosilicate mesoporous molecular sieves have been
prepared using hexadecylamine as a template. Elimination of
the latter was conducted using different extraction solutions
(ethanol, sodium acetate in ethanol, ammonium acetate in
ethanol) prior to calcination. Using ethanol alone does not
allow the total removal of the template. Only the neutral part
which is not associated with the Al framework could be removed.
In contrast, the presence of a cation allows the total extraction of
the template. In this work, extracted samples were not character-
ized just after the extraction, but rather after calcination. Samples
that are treated previously with ethanol or ethanol–NH4+ were
stable upon calcination and possess textural properties similar to
the ones directly calcined. But samples treated with ethanol–Na+
exhibit structural degradation.295
The use of ethanol under reflux for 16 or 24 h is a common
method to remove the P123 template. The specific surface area,
pore volume and pore diameter of the mesoporous silicas
obtained are similar to or higher than those of the corres-
ponding mesoporous silicas obtained by calcination.296–298
Mesoporous silicas obtained after alcoholic solution extraction
exhibit a higher number of surface silanols. But the use of
ethanol alone seems to be not totally efficient. Some studies
showed that the removal of the template using HCl in ethanol
is more efficient and leads to a higher surface specific area,
pore volume and pore diameter.299–302 It is also noteworthy that
the chemical extraction of the surfactant from ordered meso-
porous silica using HCl–ethanol solution leads to the formation
of ethoxy groups.303 These ethoxy groups modify the surface
properties of the porous material. Moreover they are less
reactive than silanols and their presence can limit an organic
post-grafting functionalization with organosilane. However, the
combination of extraction using ethanol + HCl prior to calcina-
tion allows the total removal of the template.304,305 Whatever
the calcination temperature (from 350 to 900 1C), the chemical
extraction step leads to mesoporous silica materials with a
higher surface specific area, pore volume and pore diameter
compared to materials obtained only by calcination.306
In comparison to this traditional method, acidic extraction
using H2SO4 is performed for the removal of F127. It seems that
the use of H2SO4 after 2 cycles (24 h + 24 h) of extraction is more
efficient than ethanol extraction, and the shrinkage of the
structure is reduced compared to calcined materials.307
As it is said above, H2SO4 treatment seems to be a good
method to remove the triblock copolymer template.308 But after
treatment with sulfuric acid on different SBA-15 type mesoporous
This journal is c The Royal Society of Chemistry 2013
 View Article Online

Chem Soc Rev Review Article

Table 10 Comparison of different extraction processes on silica mesoporous materials

Mesoporous Temperature of Process Extraction SBET Vt Dp

Ref. material Template Extraction process the process (1C) length (min) efficiency (%) (m2 g1) (cm3 g1) (nm)
275 SBA-15 P123 Calcination 270 150 98.6 1120 1.20 9.0
131 500 360 100 710 1.30 8.0
277 MCM-41 CTAB 550 99

312 MCM-48 CTAB EtOH–HCl extraction 120 92.7

EtOH extraction 120 50.4

331 MCM-41 CTAB Ion exchange 60 15  3 Z99 1085 1.00 3.2

Calcination 527 360 100 976 0.90 3.2

333 SBA-15 P123 Flash calcination 300 15 Z99 1000 1.10 7.7
Calcination 300 15 846 0.96 7.7
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B

300 120 928 1.10 7.6

336 SBA-15 P123 Microwave assisted 200 2 >90 853 1.40 8.8
extraction: H2O2–HNO3
Calcination 550 100 679 1.10 7.8
337 SBA-15 P123 Microwave assisted 6 >90 1000
extraction: EtOH–hexane
Calcination 550 360 100 560
Downloaded by RMIT Uni on 19 February 2013

339 Silica mesoporous F127 O2 plasma 10 63 595 0.70 3.7

thin film
Calcination 425 300 54 563 0.40 3.7

344 MCM-41 CTAB Sonication 40 15 1219 0.43

Calcination 450 300 100 1055 0.37

345 MCM-41 CTAB O3 oxidation 1440 Z99 710 3.6

Calcination 550 240 100 Close to 710 o3.6
353 Periodic mesoporous P123 Perchlorates oxidation 80 720 589 1.40 7.2
organosilicas
Ethanol extraction 70 480 605 1.06 5.8
351 SBA-15 P123 H2O2 oxidation 124 120 95 609 0.86 6.3
Calcination 550 360 100 760 1.10 6.3
324 SBA-15 P123 KMnO4 oxidation 90 240 >90 827 1.24 9.6
Calcination 550 100 816 1.03 7.8

325 SBA-15 P123 SFE CO2/ethanol 90 1440 81 681 1.10 9.5

Calcination 550 420 100 605 0.92 8.6

silicas, both mesopore and micropore distributions are totally
different. It seems that these distributions are strongly dependent
on the HCl concentration of the synthesis media.309 To overcome
the problem of partial template removal, calcination at low
temperature (473 K) can be applied after the sulfuric acid treat-
ment in order to remove completely the P123 template.310,311
When using ammonium salts as templates, the most common
solvent for their extraction are alcohols: methanol,312 ethanol,312,313
and isopropanol.314 In the last case, elimination was achieved by
refluxing the as-synthesized material in isopropanol for 24 h. The
total removal of the template was examined by 13C MAS NMR and
no residual trace was visible. Here again, the addition of acid in the
extraction process enhances the extraction efficiency.315 For
instance, Ji et al.312 estimated an extraction efficiency of 92.7%
when using EtOH–HCl vs. 50.4% when using EtOH alone, 86.7%
when using MeOH–HCl vs. 72% when using MeOH alone and
10.4% when using acetone–HCl vs. 8.5% when using acetone alone.
It clearly appears that whatever the solvent used, adding HCl
enhances the efficiency of the extraction, even if the best solvent
seems to be EtOH–HCl. Moreover it is demonstrated that 24 h of
extraction time is enough to remove all the templates. Indeed,
92.7% extraction efficiency is obtained using EtOH–HCl during
24 h and 93.4% is obtained after 120 h. Time of extraction varies
from 6 h to 24 h.316–320 Indeed, in the synthesis of silica thin films
or silica membranes, where the support can be damaged by the
solvent used, time of exposure to solvent is shorter i.e. 1 h to obtain
a hybrid mesoporous silica membrane.321
Some hazardous solvents have also been used for surfactant
extraction. For example, an original one-step method to simulta-
neously remove the template and make MCM-41 material hydro-
phobic was described by Antochshuk and Jaroniec.322 To do so,
the mesoporous material was dispersed in a solution of trialk-
ylsilane under reflux for 36 h, and then anhydrous pyridine was
added and left under reflux for 18 h, in order to eliminate the
template. After filtration and washing, a hydrophobic meso-
porous MCM-41 is obtained. From an ecodesign point of view
this method is not interesting since it requires a long time and
the solvent is hazardous.
The first template elimination by supercritical fluid extraction
was done on MCM-41 and HMS materials.323,324 This method

This journal is c The Royal Society of Chemistry 2013 Chem. Soc. Rev.

Review Article
has been repeated and also tried on SBA-15 materials.325 No
structure shrinkage was observed after the treatment, and the
efficiency of the template removal was equivalent to what was
obtained by solvent extraction. After a few hours, a removal
efficiency of higher than 90% can be obtained depending on
exposure time and pressure.325–327 Using alcohol as co-solvent
enhances the efficiency of the extraction.323,328 This extraction
method has been widely used to remove the template from
mesoporous thin films too where the microporosity is easier to
remove than in a mesoporous bulk solid.329,330
The main problems with classical template removal
processes are: long duration of the procedure and energy
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
consumption. Indeed, for example, when the calcination
process is used to remove the template, the process takes more
than 10 hours and the power output is about 12.5 kWh to
achieve 500 1C at a heating rate of 1 1C min1 (conditions often
used) for a 1.5 kWh muffle furnace. In terms of energy
consumption, it seems better to use solvent extraction for the
removal of the template. But in this case, the nature of solvent,
Downloaded by RMIT Uni on 19 February 2013
its quantity when used without the Soxhlet apparatus, the
duration and number of runs make this process a long one.
4.3.3. Fast extraction processes. Different fast procedures,
involving short operation time, use of less hazardous chemicals
and low effects on material’s structure, have been developed.
Lang and Tuel331 developed a fast and efficient ion exchange
process in order to remove organic cationic surfactants from
pure silica MCM-41 and aluminosilicates. The ion exchange
was achieved between CTMA+ and NH4+ ions by stirring for
15 min the materials in an alcoholic solution of ammonium
nitrate. The treatment was repeated twice. No specific equip-
ment was required in this process. The method was not only
applied to siliceous compounds but also to aluminosilicates.
Moreover, to improve the ecodesign process, the recovery of the
template is possible.
The effect of the heating rate (2 to 100 1C min1) during
calcination at 600 1C for 4 h was studied by Bagshaw and
Bruce.332 They demonstrated that rapid calcination at 200–300 1C
is efficient to remove all the surfactants. In this case, the energy
consumption is clearly lower than in traditional calcination. As it
is said previously, the power output for the elimination of the
template in a traditional muffle furnace is 12.5 kWh. By using the
procedure described by Bagshaw et al., the elimination of the
template in a muffle furnace takes place with a power output of
0.075 kWh. Benamor et al.333 have developed a rapid calcination
method by using an induction furnace between 300 and 700 1C for
15 and 5 min, respectively, in order to considerably reduce the
energy consumption process. Here the power output for the
elimination of the template is about 0.42 kWh compared to
12.5 kWh in a traditional furnace. This method was applied to
various types of OMS. The overall organic template was removed
at 300 1C for 15 min by this method.
Microwave digestion of the template is also a fast and
efficient procedure for organic template removal. This procedure
involves the use of oxidants such as H2O2/HNO3 and a maximum
duration of 15 min. In all cases, the surfactant removal
was complete and the OMS structure was maintained,334–336
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
the specific surface area, pore diameter and pore volume are
high. Another microwave digestion was studied using a mixture
of EtOH–hexane.337 The procedure was fast (2 min) and was
repeated three times to enable the complete removal of the
template.338 In these cases, as the removal of the template
needs the use of hazardous solvent and/or strong oxidants, the
low energy consumption is the only advantage of the procedure,
with an average power output of 0.05 kWh.
The Plasma process was also used for rapid removal of
template. This process was essentially applied to remove the
template from mesoporous thin films. This was done using
oxygen plasma for 10 (ref. 339) or 20 (ref. 340) min, or using an
argon plasma341 for 30 min. Solution plasma342 was also used
for template removal in mesoporous thin films. In this case the
efficiency of the process depends on the solution pH, which was
adjusted by addition of HCl or NaOH343 where better results are
obtained for pH between 3 and 5.
Jabariyan and Zanjanchi used an ultrasound assisted method
to eliminate the template from a MCM-41 mesoporous silica. In
a short time (from 1 to 60 min) and at relatively low temperatures
(from 25 to 60 1C) sonication in ethanol solvent allowed for the
removal of templates. The use of the ethanol as solvent allowed
the re-use of the template. Materials obtained by means of
sonication exhibit a higher specific surface area, pore volume,
pore diameter and unit-cell parameter than the calcined ones.
The short time, low cost of solvent and the easy manipulation of
the sonication make the method very interesting.344
4.3.4. Other surfactant extraction methods. In parallel to
conventional calcination and chemical extraction methods,
other strategies have been developed to remove organic
structuring agents. These alternative methods which can be
considered chemical (oxidation assisted or not) or physical
(photocalcination, sublimation) extraction processes lead often
to the decomposition of the templating agent.
Oxidation of the organic template by ozone seems to be
efficient. In the latter case ozone is produced by UV light. Ozone
can also be produced by an electric discharge. Keene et al.345 made
a comparison between these two processes for the elimination of
the organic template from MCM-41. Similar results were obtained.
However, Heng et al.346 showed that the ozone treatment, obtained
by electric discharge, was efficient only at T > 150 1C for the removal
of the organic template (TPAOH) from the membrane zeolite.347
H2O2 oxidation treatment appears to be an efficient way to
eliminate the CTA template.348 The removal at room tempera-
ture overnight allowed obtaining mesoporous materials with
higher specific surface area, pore volume, pore diameter and
unit cell parameter. Colloidal mesoporous silica (CMS) nano-
particles were obtained using this oxidation template removal
method. After the extraction, a step of reflux in acidic ethanol
was necessary. This additional step allowed for the stabilization
of the CMS nanoparticles, also for the eventual removal of
organic fragments occluded within the pores. This double
treatment leads to materials with higher specific surface area,
pore volume and pore diameter.349,350
In order to prevent shrinkage in SBA-15 mesoporous silica,
hydrothermal treatment in H2O2, for various durations and at
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
various temperatures, is applied after the aging step. In addition
to the lower shrinkage observed after calcination of the material,
this method also enabled the elimination of the template.
Efficiency of the template removal depends on treatment condi-
tions: time, temperature, H2O2 concentrations. As-synthesized
mesoporous materials exhibit higher specific surface areas,
larger pore volumes and uniform particles sizes for an oxidative
treatment of 6 h at 130 1C without further calcination. 2 h at
124 1C was enough to remove 95% of the template. A H2O2
concentration of 12.5 wt% minimum was necessary to achieve
100% removal efficiency.351
A method combining UV irradiation and dilute H2O2 treat-
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
ment has been developed in order to remove the P123 template
from SBA-15 materials. The elimination was complete after 4 h
treatment at room temperature. UV irradiation results in the
formation of HO radicals from dilute H2O2. These radicals
oxidize the organic template and create organic intermediate
radicals which lead to the formation of CO2 and H2O after a
series of oxidation and degradation reactions. Moreover, as HO
Downloaded by RMIT Uni on 19 February 2013
radicals are small, they diffuse into micropores and eliminate
the template completely. The formation of these radicals
depends on the pH. Xiao et al.352 demonstrated that better
results were obtained at pH 3.5, where the extracted mesoporous
silica exhibited better structural and textural properties.
Cai and Zhao353 showed that the use of ammonium perchlo-
rate (AP) appears to be efficient in removal of the P123 template.
The extraction must occur at 80 1C to be efficient and depends
on the pH of the medium. Indeed, it is known that the oxidation
of AP under acidic conditions is affected. In order to remove
completely the template in a short time (t o 10 h), the extraction
must be done under strong acidic conditions, pH o 1. Under
low acidic conditions, pH o 5, the extraction can be complete
with a longer time required (t > 5 h). If the process is done under
pH > 5, whatever the time reaction required, the extraction
cannot be done. By this method, mesoporous silica with high
specific surface area and pore volume can be obtained. Other
perchlorates i.e. LiClO4, NaClO4, MgClO4 can also be used in
order to remove copolymer triblock templates.
The efficient use of MnO4 solution to remove the template
at low temperature has been demonstrated by Lu et al.354 The
reaction between KMnO4 depends on the temperature and time
treatment. Indeed, higher temperatures enable the formation
of soluble manganese species contrary to room temperature
that generates MnO2 formation. The extraction is more efficient
at 90 1C. Moreover for low temperature treatment a longer contact
time is required, but at 90 1C only 4 h is necessary. Contrary to the
calcination process, the as treated SBA-15 exhibits larger open
porosity. High specific surface area, pore volume, pore diameter
and unit cell parameter are obtained for samples treated by this
low temperature oxidative removal treatment.
However these extraction methods required the use of
strong oxidants that are hazardous chemicals and do not follow
ecodesign rules.
The photocalcination process using UV light was shown to
be efficient after hours of treatment; however this process could
not be done at ambient temperature. In this case, the organic
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
templates were destroyed by the combination of UV light with
ozone. The proposed mechanism is as follows: the use of a UV
light below 245 nm allows for the dissociation of ambient air
oxygen in order to produce ozone and atomic oxygen. Simulta-
neously, the same lamp emitted a 253.7 nm line in order to
dissociate the organic template and produce activated species.
Ozone and atomic oxygen then attack these species and form
volatile molecules, CO2, H2O, N2, that can escape from the
material or be washed off.355 Even if this process involves long
time duration, the removal of the organic template from
mesoporous thin films was efficient.355,356
Template removal was also achieved by sublimation, an efficient
method at low temperature, which preserves the integrity of the
template. However, it is a long process and the use of a minimum
quantity of the template appeared to be critical. With a 40 wt%
amount, the extraction was not complete.357
5. Conclusions
The considerable mastery attained in the last few years in the
synthesis of mesoporous silica materials with controlled
chemical, structural and textural characteristics allowed the
identification and the development of numerous applications
in diverse areas. In order to promote the development of these
applications on an industrial scale, it was therefore necessary to
search for more environmentally-friendly and economical
synthesis routes for mesoporous silica. Ecodesign of meso-
porous silica has therefore considerably developed in the past
decades with the objective of optimizing the chemistry and the
processing aspects of the material synthesis.
A great effort has been made towards the use of greener
structuring agents. The first improvement in that direction was
the replacement of petroleum-derived conventional surfactants
by surfactants prepared from building blocks derived from
renewable raw materials: this was implemented for providing
the hydrophobic part as well as the hydrophilic part of the
surfactant from renewable resources. Another class of greener
surfactants was also used, they are biologically produced
surfactants (biosurfactants). Another interesting aspect in the
search for chemical approaches with a low impact on the
environment consists in using cleavable surfactants which
present a higher biodegradability. Nature derived polymers or
colloids, most of them being polysaccharide-type biopolymers,
proved to be efficient porogens, which do not allow ordered
mesoporous solids to be obtained but allow high pore volumes
to be reached. Finally, an interesting trend consists in using
structuring agents that can be recovered and recycled in
aqueous solution at room temperature: hydrosoluble dendri-
mers, on one hand, and on the other hand, stimuli-sensitive
micelles based on double-hydrophilic block copolymers,
dissociable in water, appeared to be promising synthetic struc-
turing agents. One often has to accept a compromise between
optimal structural properties and the use of green chemical
reactants. Nevertheless, nature derived amphiphiles or poly-
mers provide an infinite richness of structures and functions
that one should profitably exploit for confering new
Chem. Soc. Rev.

Review Article
functionalities and properties to the final material. If long
range ordered mesoporous materials are definitely sought, then
amphiphilic systems, including polyion complex micelles of
hydrosoluble polymers, should be used.
Besides the synthetic silica sources traditionally used for
processing silica via sol–gel processes (silicon alkoxides, sodium
silicate etc.), cheap and abundant alternative silica sources
derived from natural minerals (natural clays, diatomaceous
earth, zeolites etc.), biomass (rice husk) or from the recycling
of industrial wastes (e-wastes) were shown to behave as efficient
precursors for the synthesis of mesoporous materials. Compared
to synthetic silica sources, utilization of natural silica sources
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
makes possible the generation of readily applicable silica
precursors from raw silicon-containing materials by significantly
reducing the number of chemical modifications and energy
consumption. The choice of natural raw material as well as
methods used for the extraction of the silicate species deter-
mines the quality of the synthesized mesostructure. Natural
silica sources usually allow for the synthesis of well-ordered
Downloaded by RMIT Uni on 19 February 2013
mesoporous materials with applications in gas adsorption,
molecular separation or catalysis, which favorably compete
with the applications of analogous materials synthesized from
conventional silica sources. Especially promising is the recycling
of silica-containing wastes, which avoids the use of synthetic
silica sources, addresses the issue of waste disposal and avoids
to draw on natural silica resources. Since silica is involved in the
composition of a large variety of manufactured materials (cement,
domestic glass-based items), utilization of silica precursors
extracted from recycled wastes is expected to be reported to a
greater extent in the near future.
Concerning processes involved in the formation of OMS,
most of the efforts made on the ecodesign of processes have
been done for the reaction and the template removal steps.
Several studies have focused on the optimization of duration
and temperature required for the synthesis of OMS with desired
structural and textural properties. Some technologies such as
microwave heating and sonication have been used to replace
the original ones. Time and energy saving strategies are asso-
ciated with the reduction of synthesis steps and the continuous
process was found to be highly desirable. When synthesis of
OMS in powder form is concerned, the aerosol technique based
on the EISA strategy seems to fulfill the best the specifications
of ecodesign. Moreover, it is adaptable for scaling-up and thus
for industrial development. However, this technique is
restricted to the formation of OMS with spherical morphology.
Synthesis steps such as solid recovery, washing and drying that
are involved in the OMS precipitation route have been rarely
studied and optimized. For this synthesis route some
continuous strategies have been developed but they are still
incomplete. If the synthesis of OMS in continuous networks
such as film, fibers, monoliths is desired, EISA or LISA strate-
gies can be used, which readily offer synthesis procedures with
a few steps and short durations.
Processes involved in the synthesis of OMS can hardly be
considered green since no real energy and carbon balance was
done. However some efforts are currently done. In both synthesis
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
strategies, precipitation or assisted self-assembly, the continuous
procedure allows integrating all steps and thus offers more
potentialities for reducing costs and for scaling-up.
In most of the targeted applications for OMS, accessible
porosity is required. Many different template removal processes
have been developed. The most commonly used ones, thermal
calcination and chemical extraction, are energy and time
consuming, but they present different advantages. Indeed,
using the calcination process allows the removing of all the
surfactants used in the templating pathways. However, in this
case, the choice of temperature is important and often
arbitrarily chosen as a function of what is most currently
reported. Concerning the chemical extraction, one of the major
advantages is the possible reuse of the template for other
syntheses.
On the other hand, structure shrinkage in high temperature
calcination and the partial template removal sometimes
occurring when using chemical template extraction, the use
of solvents and the long time process are disadvantages of these
processes.
The development of the rapid processes, such as ion
exchange, fast calcination, microwave digestion plasma process
and sonication, overcomes these drawbacks. The necessary
time to remove the template varies from 2 to 45 min depending
on the method used. The mesostructured materials synthesized
by these rapid extraction procedures exhibit better structural
and textural properties than the ones obtained by the classical
calcination procedure. Many other methods of template removal
were studied; although in those cases only one of the drawbacks
was overcome (time, use of less hazardous chemicals or low
effects on material’s structure), structured materials with superior
textural and structural properties were formed compared to the
ones obtained by classical calcination.
Notes and references
1 T. Yanagisawa, S. Tsuneo, T. Shimizu, K. Kuroda and
C. Kato, Bull. Chem. Soc. Jpn., 1990, 63, 988–992.
2 J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz,
C. T. Kresge, K. D. Schmitt, C. T. Chu, D. H. Olson,
E. W. Sheppard, S. B. McCullen, J. B. Higgins and
J. L. Schlenker, J. Am. Chem. Soc., 1992, 114, 10834–10843.
3 G. J. de A. A. Soler-Illia, E. L. Crepaldi, D. Grosso and
C. Sanchez, Curr. Opin. Colloid Interface Sci., 2008, 8,
109–126.
4 Y. Wan and D. Zhao, Chem. Rev., 2007, 107, 2821–2860.
5 C. Luttropp and J. Lagerstedt, J. Cleaner Prod., 2006, 14,
1396–1408.
6 T. Aoe, J. Cleaner Prod., 2007, 15, 1406–1414.
7 P. Knight and J. O. Jenkins, J. Cleaner Prod., 2009, 17,
549–558.
8 N. Baccile, F. Babonneau, B. Thomas and T. Coradin,
J. Mater. Chem., 2009, 19, 8537–8559.
9 S.-S. Kim, T. R. Pauly and T. J. Pinnavaia, Chem. Commun.,
2000, 835–836.
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
10 S.-S. Kim, T. R. Pauly and T. J. Pinnavaia, Chem. Commun.,
2000, 1661–1662.
11 Q. Huo, R. Leon, P. M. Petroff and G. D. Stucky, Science,
1995, 268, 1324–1327.
12 D. Zhao, Q. Huo, J. Feng, J. Kim, Y. Han and G. D. Stucky,
Chem. Mater., 1999, 11, 2668–2672.
13 B. Tan, H.-J. Lehmler, S. M. Vyas, B. L. Knutson and
S. E. Rankin, Chem. Mater., 2005, 17, 916–925.
14 P. T. Tanev and T. J. Pinnavaia, Science, 1995, 267,
865–867.
15 S. A. Bagshaw, E. Prouzet and T. Pinnavaia, Science, 1995,
269, 1242–1244.
16 D. Zhao, Q. Huo, J. Feng, B. F. Chmelka and G. D. Stucky,
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
J. Am. Chem. Soc., 1998, 120, 6024–6036.
17 S. Che, A. E. Garcia-Bennett, T. Yokoi, K. Sakamoto,
H. Kunieda, O. Terasaki and T. Tatsumi, Nat. Mater.,
2003, 2, 801–805.
18 Q. Huo, D. L. Margolese, U. Ciesla, P. Feng, T. E. Gier,
P. Sieger, R. Leon, P. M. Petroff, F. Schüth and G. D. Stucky,
Downloaded by RMIT Uni on 19 February 2013
Nature, 1994, 368, 317–321.
19 A. Huo, D. I. Margolese, U. Ciesla, D. G. Demuth, P. Feng,
T. E. Gier, P. Sieger, A. Firouzi, B. F. Chmelka, F. Schüth
and G. D. Stucky, Chem. Mater., 1994, 6, 1176–1191.
20 Y. M. Setoguchi, Y. Teraoka, I. Moriguchi, S. Kagawa,
N. Tomonaga, A. Yasutake and J. Izumi, J. Porous Mater.,
1997, 4, 129–134.
21 B. Isomaa, J. Reuter and B. M. Djupsund, Arch. Toxicol.,
1976, 35, 91–96.
22 N. Vlachy, D. Touraud, J. Heilmann and W. Kunz, Colloids
Surf., B, 2009, 70, 278–280.
23 R. L. Grant, C. Yao, D. Gabaldon and D. Acosta, Toxicology,
1992, 76, 153–176.
24 R. W. Lewis, J. C. McCall and P. A. Botham, Toxicol. In
Vitro, 1993, 7, 155–158.
25 T. Imamura, in Encyclopedia of Surface and Colloid
Science, ed. P. Somasundaran, CRC Press, 2nd edn, 2006,
pp. 5252–5263.
26 F. van Ruissen, M. Le, J. M. Carroll, P. G. M. van der Valk
and J. Schalkwijk, J. Invest. Dermatol., 1998, 110, 358–363.
27 M. T. Garcia, E. Campos, J. Sanchez-Leal and I. Ribosa,
Chemosphere, 1999, 38, 3473–3483.
28 M. T. Garcı́a, E. Campos, J. Sánchez-Leal and I. Ribosa,
Chemosphere, 2000, 41, 705–710.
29 G. Zeng, H. Fu, H. Zhong, X. Yuan, M. Fu, W. Wang and
G. Huang, Biodegradation, 2007, 18, 303–310.
30 Sigma-Aldrich Safety data Sheet according to Regulation
(EC) No. 1907/2006 Version 5.1, Revision Date 09.08.2012,
Print Date 25.08.2012.
31 A. G. S. Prado and C. Airoldi, J. Mater. Chem., 2002, 12,
3823–3826.
32 Q. M. Zhang, Y. Li, F. Z. Huang and Z. N. Gu, Chin. Chem.
Lett., 2001, 12, 275–278.
33 C. Boissière, A. Larbot, A. van der Lee, P. J. Kooyman and
E. Prouzet, Chem. Mater., 2000, 12, 2902–2913.
34 E. Prouzet, F. Cot, C. Boissière, P. J. Kooyman and
A. Larbot, J. Mater. Chem., 2002, 12, 1553–1556.
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
35 C. Boissière, A. Larbot and E. Prouzet, Chem. Mater., 2000,
12, 1937–1940.
36 C. Gao, H. Qiu, W. Zeng, Y. Sakamoto, O. Terasaki,
K. Sakamoto, Q. Chen and S. Che, Chem. Mater., 2006,
18, 3904–3914.
37 K. Sakamoto, in Surfactant Science Series, ed. J. Xia and
I. A. Nnanna, Dekker, New York, 2001, ch. 10, vol. 101,
pp. 261–280.
38 Sigma-Aldrich safety data sheets.
39 CTAB Sigma-Aldrich Certificate of origin.
40 D. J. Safarik and R. B. Eldridge, Ind. Eng. Chem. Res., 1998,
37, 2571–2581.
41 R. B. Eldridge, Ind. Eng. Chem. Res., 1993, 32, 2208–2212.
42 L. K. Johnson, C. M. Killian and M. Brookhart, J. Am. Chem.
Soc., 1995, 117, 6414–6415.
43 J. Skupińska, Chem. Rev., 1991, 91, 613–648.
44 M. I. Levinson, in Surfactant production: present realities
and future perspectives, ed. U. Zoller and P. Sosis, CRC
Press, Taylor and Francis Group, Boca Raton, 2009, ch. 1,
vol. 142, pp. 1–36.
45 ETHYLENE OXIDE Concise international chemical assess-
ment document; 54 WHO Library Cataloguing-in-
Publication Data.
46 R. A. Sheldon, Green Chem., 2007, 9, 1273–1283.
47 M. J. Eckelman, J. B. Zimmermann and P. T. Anastas,
J. Ind. Ecol., 2008, 12, 316–328.
48 F. Kleitz, S. H. Choi and R. Ryoo, Chem. Commun., 2003,
2136–2137.
49 A.-C. Voetglin, A. Matijasic, J. Patarin, C. Sauerland, Y. Grillet
and L. Huve, Microporous Mater., 1997, 10, 137–147.
50 K. Schumacher, C. du Fresne von Hohenesche,
K. K. Unger, R. Ulrich, A. Du Chesne, U. Wiesner and
H. W. Spiess, Adv. Mater., 1999, 11, 1194–1198.
51 J. O. Metzger and U. Bornscheuer, Appl. Microbiol. Biotech-
nol., 2006, 71, 13–22.
52 C. P. Canlas and T. J. Pinnavaia, RSC Adv., 2012, 2,
7449–7455.
53 European Union Risk Assessment Report on primary alkyl
amines, Rapporteur: Federal Institute for Occupational
Safety and Health Division for Chemicals and Biocides
Regulation 2008.
54 J. Iapichella, J.-M. Meneses, I. Beurroies, R. Denoyel,
Z. Bayram-Hahn, K. Unger and A. Galarneau, Microporous
Mesoporous Mater., 2007, 102, 111–121.
55 M. J. Scott and M. N. Jones, Biochim. Biophys. Acta, 2000,
1508, 235–251.
56 B. Thomas, N. Baccile, S. Masse, C. Rondel, I. Alric,
R. Valentin, Z. Mouloungui, F. Babonneau and T. Coradin,
J. Sol-Gel. Sci. Technol., 2011, 58, 170–174.
57 Y.-X. Yang, Z. Huang, W.-J. Deng, J.-G. Shao, Y.-R. Chen and
X.-N. Liu, Microporous Mesoporous Mater., 2008, 116, 267–276.
58 W.-D. Xiang, Y.-X. Yang, J. Chen, Z. Wang and X.-N. Liu,
J. Am. Ceram. Soc., 2008, 91, 1517–1521.
59 M. C. Morán, A. Pinazo, L. Pérez, P. Clapés, M. Angelet,
M. T. Garcı́a, M. P. Vinardell and M. R. Infante, Green
Chem., 2004, 6, 233–240.
Chem. Soc. Rev.

Review Article
60 R. Atluri, N. Hedin and A. E. Garcia-Bennett, J. Am. Chem.
Soc., 2009, 131, 3189–3191.
61 U. L. Stangar and N. Hüsing, Silicon Chem., 2003, 2,
157–165.
62 P. Botella, A. Corma and M. Quesada, J. Mater. Chem.,
2012, 22, 6394–6401.
63 M. J. L. Castro, J. Kovensky and A. F. Cirelli, Langmuir,
2002, 18, 2477–2482.
64 A. G. Kong, H. W. Wang, Z. He, H. Ming Ding and
Y. K. Shan, Mater. Lett., 2008, 62, 2973–2976.
65 P.-E. Hellberg, K. Bergström and K. Holmberg,
J. Surfactants Deterg., 2000, 3, 81–91.
66 C. G. van Ginkel, Handbook of detergents: Part B Environ-
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
mental Impact, Surfactant Science Series, Marcel Dekker,
Inc., New York, 2004, vol. 121, pp. 523–549.
67 A. R. Tehrani-Bagha, H. Oskarsson, C. G. van Ginkel and
K. Holmberg, J. Colloid Interface Sci., 2007, 15, 444–452.
68 Kirk-Othmer Encyclopedia of Chemical Technology. Dialog on
Disc, John Wiley & Sons, Inc. Dialog Information
Downloaded by RMIT Uni on 19 February 2013
Services, Inc., Palo Alto, United States, 3rd edn, 1994.
69 F. Goursaud, M. Berchel, J. Guilbot, N. Legros, L. Lemiegre,
J. Marcilloux, D. Plusquellec and T. Benvegnu, Green
Chem., 2008, 10, 310–320.
70 Surfactants from Renewable Resources, ed. M. Kjellin and
I. Johansson, Wiley Series in Renewable Resources, 2010.
71 Applied Biocatalysis, ed. A. J. J. Straathof and P. Adlercreutz,
Harwood Academic, Amsterdam, 2010.
72 H. C. Holm and D. Cowan, Eur. J. Lipid Sci. Technol., 2008,
110, 679–691.
73 J. D. Desai and I. M. Banat, Microbiol. Mol. Rev., 1997, 61,
47–64.
74 N. Baccile, N. Nassif, L. Malfatti, I. N. A. Van Bogaert,
W. Soetaert, G. Pehau-Arnaudet and F. Babonneau, Green
Chem., 2010, 12, 1564–1567.
75 D. R. Dunphy, T. M. Alam, M. P. Tate, H. W. Hillhouse,
B. Smarsly, A. D. Collord, E. Carnes, H. K. Baca, R. Köhn,
M. Sprung, J. Wang and C. J. Brinker, Langmuir, 2009, 25,
9500–9509.
76 A. Galarneau, G. Renard, M. Mureseanu, A. Tourrette,
C. Biolley, M. Choi, R. Ryoo, F. Di Renzo and F. Fajula,
Microporous Mesoporous Mater., 2007, 104, 103–114.
77 Q. Chen, S. F. Chen and Z. Y. Li, Chin. Chem. Lett., 1999, 10,
789–792.
78 E. L. Soo, A. B. Salleh, M. Basri, R. N. Zaliha Raja Abdul
Rahman and K. Kamaruddin, J. Biosci. Bioeng., 2003, 95,
361–367.
79 A. J. J. Straathof, S. Panke and A. Shmid, Curr. Opin.
Biotechnol., 2002, 13, 548–556.
80 T. Witoon, M. Chareonpanich and J. Limtrakul, J. Sol-Gel
Sci. Technol., 2009, 51, 146–152.
81 A. El Kadib and M. Bousmina, Chem.–Eur. J., 2012, 18,
8264–8277.
82 B. Alonso and E. Belamie, Angew. Chem., Int. Ed., 2010, 122,
8377–8380.
83 P. Tingaut, T. Zimmermann and G. Sebe, J. Mater. Chem.,
2012, 22, 20105–20111.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
84 E. Dujardin, M. Blaseby and S. Mann, J. Mater. Chem.,
2003, 13, 696–699.
85 A. Thomas and M. Antonietti, Adv. Funct. Mater., 2003, 13,
763–766.
86 K. E. Shopsowitz, H. Qi, W. Y. Hamad and M. J. MacLachlan,
Nature, 2010, 468, 422–425.
87 Z. Zhang, L. Yang, Y. Wang, G. Luo and Y. Dai, Microporous
Mesoporous Mater., 2008, 115, 447–453.
88 Y. Wang, S. Huang, S. Kang, C. Zhang and X. Li, Mater.
Chem. Phys., 2012, 132, 1053–1059.
89 O. H. Han and Y. K. Bae, Bull. Korean Chem. Soc., 2008, 29,
911–912.
90 C. Knöfel, M. Lutecki, C. Martin, M. Mertens, V. Hornebecq
and P. L. Llewellyn, Microporous Mesoporous Mater., 2012,
128, 26–33.
91 A. El Kadib, N. Katir, M. Bousmina and J.-P. Majoral, New J.
Chem., 2012, 36, 241–255.
92 Y. Xu, S. Xu, T. Emmler, F. Roelofs, C. Boettcher, R. Haag
and G. Buntkowsky, Chem.–Eur. J., 2008, 14, 3311–3315.
93 J. Khandare, A. Mohr, M. Calderón, P. Welker, K. Licha and
R. Haag, Biomaterials, 2010, 31, 4268–4277.
94 D. Steinhilber, S. Seiffert, J. A. Heyman, F. Paulus,
D. A. Weitz and R. Haag, Biomaterials, 2011, 32, 1311–1316.
95 J. Dernedde, A. Rausch, M. Weinhart, S. Enders,
R. Tauber, K. Licha, M. Schirner, U. Zügel, A. von Bonin
and R. Haag, Proc. Natl. Acad. Sci. U. S. A., 2010, 107,
19679–19684.
96 J. Hukkamaki and T. T. Pakkanen, Microporous Mesoporous
Mater., 2003, 65, 189–196.
97 H. Dai, J. Yang, J. Ma, F. Chen, Z. Fei and M. Zhong,
Microporous Mesoporous Mater., 2012, 147, 281–285.
98 N. Baccile, J. Reboul, B. Blanc, B. Coq, P. Lacroix-
Desmazes, M. In and C. Gérardin, Angew. Chem., Int. Ed.,
2008, 47, 8433–8437.
99 J. Reboul, T. Nugay, N. Anik, H. Cottet, M. In, P. Lacroix-
Desmazes and C. Gérardin, Soft Matter, 2011, 7, 5836–5846.
100 J. Warnant, N. Marcotte, J. Reboul, G. Layrac, A. Aqil,
C. Jerôme, D. A. Lerner and C. Gérardin, Anal. Bioanal.
Chem., 2012, 403, 1395–1404.
101 J. Warnant, J. Reboul, T. Cacciaguerra, C. Jérôme and
C. Gérardin, Powder Technol., 2011, 208, 461–466.
102 Q. Huo, D. I. Margolese and G. D. Stucky, Chem. Mater.,
1996, 8, 1147–1160.
103 Handbook of Semiconductor Silicon Technology, ed.
W. C. O’Mara, R. B. Herring and L. P. Hunt, Noyes
Publications, Park Ridge, New Jersey, 1990.
104 A. Schei, J. K. Tuset and H. Tveit, Production of High Silicon
Alloys, Tapir Forlag, Trondheim, 1998.
105 V. Dosaj, M. Kroupa and R. Bittar, Silicon and silicon alloys,
chemical and metallurgical, in Kirk-Othmer Encyclopedia of
Chemical Technology, John Wiley & Sons, Inc., New York,
4th edn, 1997, vol. 15, pp. 104–1122.
106 G. J. M. Phylipsen and E. A. Alsema, Environmental life-cycle
assessment of multicrystalline silicon solar cell modules,
Report 95057 of Department of Science, Technology, and
Society, Utrecht University, 1995.
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
107 Y. Demirel, Energy and Energy types, Green Energy and
Technology, Springer-Verlag, London Limited, 2012, ch. 2,
pp. 27–70.
108 H. P. van Dokkum, J. H. J. Hulskotte, K. J. M. Kramer and
J. Wilmot, Environ. Sci. Technol., 2004, 38, 515–521.
109 J. G. Vails, Soluble silicates in industry, American Chemical
Society and Monograph Series, 1928, vol. 48, p. 48.
110 H. P. Bauer, in Handbook of detergents, ed. U. Zoller and
P. Sosis, CRC Press Taylor and Francis Group, 2009, ch. 22,
pp. 387–419.
111 H. E. Bergna, in Colloidal Silica: Fundamentals and Applica-
tions, ed. H. E. Bergna and W. O. Roberts, CRC Press Taylor
and Francis Group, Boca Raton, ch. 1–2, vol. 131, pp. 1–8.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
112 C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and
J. S. Beck, Nature, 1992, 359, 710–712.
113 P. Van Der Voort, M. Mathieu, F. Mees and E. F. Vansant,
J. Phys. Chem. B, 1998, 102, 8847–8851.
114 L. Chen, T. Horiuchi, T. Mori and K. Maeda, J. Phys. Chem.
B, 1999, 103, 1216–1222.
Downloaded by RMIT Uni on 19 February 2013
115 P. B. Amama, S. Lim, D. Ciuparu, L. Pfefferle and
G. L. Haller, Microporous Mesoporous Mater., 2005, 81,
191–200.
116 S. Han, W. Hou, W. Dang, J. Xu, J. Hu and D. Li, Colloid
Polym. Sci., 2004, 282, 761–765.
117 L. Sierra and J.-L. Guth, Microporous Mesoporous Mater.,
1999, 27, 243–253.
118 J. M. Kim and G. D. Stucky, Chem. Commun., 2000,
1159–1160.
119 J. M. Kim, Y. Sakamoto, Y. K. Hwang, Y.-U. Kwon,
O. Terasaki, S.-E. Park and G. D. Stucky, J. Phys. Chem. B,
2002, 106, 2552–2558.
120 C. Jo, K. Kim and R. Ryoo, Microporous Mesoporous Mater.,
2009, 124, 45–51.
121 K. Kosuge, T. Sato, N. Kikukawa and M. Takemori, Chem.
Mater., 2004, 16, 899–905.
122 S.-S. Kim and T. J. Pinnavaia, Chem. Commun., 2001,
2418–2419.
123 M. Klotz, A. Ayral, C. Guizard and L. Cot, J. Mater. Chem.,
2000, 10, 663–669.
124 A. Firouzi, D. Kumar, L. M. Bull, T. Besier, P. Sieger,
Q. Huo, S. A. Walker, J. A. Zasadzinski, C. Glinka,
J. Nicol, D. Margolese, G. D. Stucky and B. F. Chmelka,
Science, 1995, 267, 1138–1143.
125 C. A. Fyfe and G. Y. Fu, J. Am. Chem. Soc., 1995, 117,
9709–9714.
126 J. Frasch, B. Lebeau, M. Soulard and J. Patarin, Langmuir,
2000, 16, 9049–9057.
127 R. K. Iler, The Chemistry of Silica, John Wiley & Sons,
New York, 1979.
128 J. L. Bass and G. L. Turner, J. Phys. Chem. B, 1997, 101,
10638–10644.
129 X. Hou, R. J. Kirkpatrick, L. J. Struble and P. J. M. Monteiro,
J. Am. Ceram. Soc., 2005, 88, 943–949.
130 K. Cassiers, T. Linssen, M. Mathieu, M. Benjelloun,
K. Schrijnemakers, P. Van Der Voort, P. Cool and
E. F. Vansant, Chem. Mater., 2002, 14, 2317–2324.
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
131 D. Zhao, J. Sun, Q. Li and G. D. Stucky, Chem. Mater., 2000,
12, 275–279.
132 P. Schmidt-Winkel, P. Yang, D. I. Margolese, B. F. Chmelka
and G. D. Stucky, Adv. Mater., 1999, 11, 303–307.
133 S. Shio, A. Kimura, M. Yamaguchi, K. Yoshida and
K. Kuroda, Chem. Commun., 1998, 2461–2462.
134 S. P. Naik and I. Sokolov, Microporous Mesoporous Mater.,
2008, 116, 581–585.
135 L.-Y. Lin and H. Bai, Microporous Mesoporous Mater., 2012,
136, 25–32.
136 H. Cheng, R. Tamaki, R. M. Laine, F. Babonneau, Y. Chujo
and D. R. Treadwell, J. Am. Chem. Soc., 2000, 122,
10063–10072.
137 T. Kimura and K. Kuroda, Adv. Funct. Mater., 2009, 19,
511–527.
138 S. Inagaki, Y. Fukushima and K. Kuroda, J. Chem. Soc.,
Chem. Commun., 1993, 680–682.
139 Y. Sakamoto, S. Inagaki, T. Ohsuna, N. Ohnishi,
Y. Fukushima, Y. Nozue and O. Terasaki, Microporous
Mesoporous Mater., 1998, 21, 589–596.
140 S. Inagaki, Y. Fukushima and K. Kuroda, Stud. Surf. Sci.
Catal., 1994, 84, 125–132.
141 S. Inagaki, A. Koiwai, N. Suzuki, Y. Fukushima and
K. Kuroda, Bull. Chem. Soc. Jpn., 1996, 69, 1449–1457.
142 S. Inagaki, Y. Fukushima and K. Kuroda, Chem. Commun.,
1993, 680–682.
143 Y. Fukushima and S. Inagaki, Mater. Sci. Eng., A, 1996,
217/218, 116–118.
144 K. Okada, H. Yoshizaki, Y. Kameshima and A. Nakajima,
Appl. Clay Sci., 2008, 41, 10–16.
145 H. Yang, C. Du, S. Jin, A. Tang and G. Li, Microporous
Mesoporous Mater., 2007, 102, 204–211.
146 H. Yang, Y. Deng, C. Du and S. Jin, Appl. Clay Sci., 2010, 47,
351–355.
147 H. Yang, A. Tang, J. Ouyang, M. Li and S. Mann, J. Phys.
Chem. B, 2010, 114, 2390–2398.
148 J. L. Post, Clays Clay Miner., 1984, 32, 147–153.
149 T. Linssen, P. Cool, M. Baroudi, K. Cassiers, E. F. Vansant,
O. Lebedev and J. van Landuyt, J. Phys. Chem. B, 2002, 106,
4470–4476.
150 T. Linssen, K. Cassiers, P. Cool, O. Lebedev, A. Whittaker
and E. F. Vansant, Chem. Mater., 2003, 15, 4863–4873.
151 K. Okada, H. Yoshizaki, Y. Kameshima, A. Nakajima and
C. D. Madhusoodana, J. Colloid Interface Sci., 2007, 314,
176–183.
152 W. L. Haden Jr. and I. A. Schwint, Ind. Eng. chem., 1967, 59,
58–59.
153 A. Monnier, F. Schüth, Q. Huo, D. Kumar, D. Margolese,
R. S. Maxwell, G. D. Stucky, M. Krishnamurty, P. Petroff,
A. Firouzi, M. Janicke and B. F. Chmelka, Science, 1993,
261, 1299–1303.
154 A. H. Englert and J. Rubio, Int. J. Miner. Process., 2005, 75,
21–29.
155 S. Wanga and Y. Peng, Chem. Eng. J., 2012, 156, 11–24.
156 W. T. Tsai, K. J. Hsien and J. M. Yang, J. Colloid Interface
Sci., 2004, 275, 428–433.
Chem. Soc. Rev.

Review Article
157 C. S. Poona, L. Lama, S. C. Koua and Z. S. Lin, Constr. Build.
Mater., 1999, 13, 427–432.
158 E. G. Vrieling, T. P. M. Beelen, R. A. van Santen and
W. W. C. Gieskes, J. Biotechnol., 1999, 70, 39–51.
159 Y. Wang, Y. Tang, A. Dong, X. Wang, N. Ren and Z. Gao,
J. Mater. Chem., 2002, 12, 1812–1818.
160 M. W. Anderson, S. M. Holmes, N. Hanif and C. S. Cundy,
Angew. Chem., Int. Ed., 2000, 39, 2707–2710.
161 C. E. Fowler, Y. Hoog, L. Vidal and B. Lebeau, Chem. Phys.
Lett., 2004, 398, 414–417.
162 S. van Donk, A. H. Janssen, J. H. Bitter and K. P. de Jong,
Catal. Rev., 2003, 45, 297–319.
163 S. Inagaki, M. Ogura, T. Inami, Y. Sasaki, E. Kikuchi and
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
M. Matsukata, Microporous Mesoporous Mater., 2004, 74,
163–170.
164 S. Jeong, H. Kim, J.-H. Bae, D. H. Kim, C. H. F. Peden,
Y.-K. Park and J.-K. Jeon, Catal. Today, 2012, 185, 191–197.
165 R. Chal, T. Cacciaguerra, S. van Donk and C. Gérardin,
Chem. Commun., 2010, 46, 7840–7842.
Downloaded by RMIT Uni on 19 February 2013
166 R. C. Joshi and R. P. Lothia, in Advances in concrete
technology, Gordon and Breach Science Publishers,
Amsterdam, 1997, vol. 2.
167 R. L. Davison, D. F. S. Natusch, J. R. Wallace and
C. A. Evans Jr., Environ. Sci. Technol., 1974, 8, 1107–1113.
168 M. H. Wong and J. W. C. Wong, Environ. Pollut., 1986, 40,
127–144.
169 G. Ferraiolo, M. Zilli and A. Converti, J. Chem. Technol.
Biotechnol., 1990, 41, 281–305.
170 R. S. Blissett and N. A. Rowson, Fuel, 2012, 97, 1–23.
171 R. S. Iyer and J. A. Scott, Resour., Conserv. Recycl., 2001, 31,
217–228.
172 M. Ahmaruzzaman, Prog. Energy Combust. Sci., 2010, 36,
327–363.
173 K. G. Babu and G. S. N. Rao, Cem. Concr. Compos., 1993, 15,
223–229.
174 E. E. Berry and V. M. Malhotra, ACI J., Proc., 1980, 77, 59–73.
175 B. Kim, M. Prezzi and R. Salgado, J. Geotech. Geoenviron.
Eng., 2005, 131, 914–924.
176 S. Jala and D. Goyal, Bioresour. Technol., 2006, 97,
1136–1147.
177 V. C. Pandey and N. Singh, Agric., Ecosyst. Environ., 2010,
136, 16–27.
178 S. Wang and H. Wu, J. Hazard. Mater., 2006, 136, 482–501.
179 A. K. Sen and A. K. De, Water Res., 1987, 21, 885–888.
180 M. Nascimento, P. S. Moreira Soares and V. P. de Souza,
Fuel, 2009, 88, 1714–1719.
181 T. Hemni, Soil Sci. Plant Nutr., 1987, 33, 517–521.
182 H. Höller and U. Wirsching, Fortschr. Mineral., 1985, 63,
21–43.
183 K. S. Hui, C. Y. H. Chao and S. C. Kot, J. Hazard. Mater.,
2005, 127, 89–101.
184 C. F. Lin and H. C. His, Environ. Sci. Technol., 1995, 29,
1109–1117.
185 X. Querol, N. Moreno, J. C. Umaña, A. Alastuey,
E. Hernández, A. López-Soler and F. Plana, Int. J. Coal
Geol., 2002, 50, 413–423.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
186 J. Davidovits, J. Therm. Anal., 1991, 37, 1633–1656.
187 L. Li, S. Wang and Z. Zhu, J. Colloid Interface Sci., 2006, 300,
52–59.
188 K. Al-Zboon, M. S. Al-Harahsheh and F. Bani Hani,
J. Hazard. Mater., 2011, 188, 414–421.
189 M. Shigemoto, H. Hayashi and K. Miyaura, J. Mater. Sci.,
1993, 28, 4781–4786.
190 P. Kumar, N. Mal, Y. Oumi, K. Yamana and T. Sano,
J. Mater. Chem., 2001, 11, 3285–3290.
191 H.-L. Chang, C.-M. Chun, I. A. Aksay and W.-H. Shih, Ind.
Eng. Chem. Res., 1999, 38, 973–977.
192 I. Majchrzak-Kucȩba and W. Nowak, Int. J. Miner. Process.,
2011, 101, 100–111.
193 H. Misran, R. Sing, S. Begum and M. A. Yarmo, J. Mater.
Process. Technol., 2007, 186, 8–13.
194 H. Misran, S. Ramesh, M. A. Yarmo and R. A. Kamarudin,
Mater. Chem. Phys., 2007, 101, 344–351.
195 G. Chandrasekar, W.-J. Son and W.-S. Ahn, J. Porous Mater.,
2009, 16, 545–551.
196 G. Chandrasekar and W.-S. Ahn, J. Non-Cryst. Solids, 2008,
354, 4027–4030.
197 K. S. Hui and C. Y. H. Chao, J. Hazard. Mater., 2006, 137,
1135–1148.
198 C. Chen, K.-S. You, J.-W. Ahn and W.-S. Ahn, Korean J.
Chem. Eng., 2010, 27, 1010–1014.
199 A. O. Dhokte, S. L. Khillare, M. K. Lande and B. R. Arbad,
J. Ind. Eng. Chem., 2011, 17, 742–746.
200 M. Halina, S. Ramesh, M. A. Yarmo and R. A. Kamarudin,
Mater. Chem. Phys., 2007, 101, 344–351.
201 J.-E. Park, H.-K. Youn, S.-T. Yang and W.-S. Ahn, Catal.
Today, 2012, 190, 15–22.
202 B. M. Jenkins, in Biogeochemical cycling of mineral-forming
elements, ed. P. A. Trudinger and D. J. Swaine, Elsevier/
North-Holland, Inc., New York, 1979, pp. 467–483.
203 J. Eames and L. H. McDaniels, An introduction to plant
anatomy, McGraw-Hill Book Co., Inc., New York, 1947,
p. 427.
204 FAO lowers global rice forecast for 2012, in http://www.fao.
org/news/story/en/item/154122/icode.
205 B. M. Jenkins, Physical properties of biomass, in Biomass-
Handbook, ed. O. Kitani and C. W. Hall, Gorden and
Breach, New York, 1989, pp. 860–891.
206 G. A. Habeeb and M. M. Fayyadh, Aust. J. Basic Appl. Sci.,
2009, 3, 1616–1622.
207 E. L. Foletto, E. Gratieri, L. Hadlich de Oliveira and
S. L. Jahn, Mater. Res., 2006, 9, 335–338.
208 D. An, Y. Guo, Y. Zhu and Z. Wang, Chem. Eng. J., 2010,
162, 509–514.
209 L. Sun and K. Gong, Ind. Eng. Chem. Res., 2001, 40,
5861–5877.
210 T.-H. Liou, F.-W. Chang and J.-J. Lo, Ind. Eng. Chem. Res.,
1997, 36, 568–573.
211 N. K. Sharma, W. S. Williams and A. Zangvil, J. Am. Ceram.
Soc., 1984, 67, 715–720.
212 P. Khemthong, S. Prayoonpokarach and J. Wittayakun,
J. Sci. Technol., 2007, 14, 367–379.
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
213 J. Wittayakun, P. Khemthong and S. Prayoonpokarach,
Korean J. Chem. Eng., 2008, 25, 861–864.
214 K. Kordatos, S. Gavela, A. Ntziouni, K. N. Pistiolas,
A. Kyritsi and V. Kasselouri-Rigopoulou, Microporous
Mesoporous Mater., 2008, 115, 189–196.
215 W. Panpa and S. Jinawath, Appl. Catal. B, 2009, 90,
389–394.
216 N. Grisdanurak, S. Chiarakorn and J. Wittayakun, Korean J.
Chem. Eng., 2003, 20, 950–955.
217 S. Artkla, W. Kim, W. Choi and J. Wittayakun, Appl. Catal.
B, 2009, 91, 157–164.
218 J. Chumee, N. Grisdanurak, S. Neramittagapong and
J. Wittayakun, Braz. J. Chem. Eng., 2009, 26, 367–373.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
219 H. T. Jang, Y. K. Park, Y. S. Ko, J. Y. Lee and B. Margandan,
Int. J. Greenhouse Gas Control, 2009, 3, 545–549.
220 M. Bhagiyalakshmi, L. J. Yun, R. Anuradha and H. T. Jang,
J. Hazard. Mater., 2010, 175, 928–938.
221 Y. Qu, Y. Tian, B. Zou, J. Zhang, Y. Zheng, L. Wang, Y. Li,
C. Rong and Z. Wang, Bioresour. Technol., 2010, 101,
Downloaded by RMIT Uni on 19 February 2013
8402–8405.
222 W. Wang, J. C. Martin, X. Fan, A. Han, Z. Luo and L. Sun,
Appl. Mater. Interfaces, 2012, 4, 977–981.
223 H.-Y. Kang and J. M. Schoenung, Resour., Conserv. Recycl.,
2005, 45, 368–400.
224 T. H. Liou, Chem. Eng. J., 2004, 98, 39–51.
225 T. H. Liou, Chem. Eng. J., 2011, 171, 1458–1468.
226 L.-Y. Lin, J.-T. Kuo and H. Bai, J. Hazard. Mater., 2011, 192,
255–262.
227 H. Yu, X. Xue and D. Huang, Mater. Res. Bull., 2009, 44,
2112–2115.
228 S. Shimizu and H. Hamada, Microporous Mesoporous
Mater., 2001, 48, 39–46.
229 J. H. Kim, M. Kim and J.-S. Yu, Environ. Sci. Technol., 2011,
45, 3695–3701.
230 J. A. Martens, J. Jammaer, S. Bajpe, A. Aerts,
Y. Lorguouilloux and C. E. A. Kirschhock, Microporous
Mesoporous Mater., 2011, 140, 2–8.
231 J. M. Morales, J. Latorre, C. Guillem, A. Beltrán-Porter,
D. Beltrán-Porter and P. Amorós, Solid State Sci., 2005, 7,
415–421.
232 P. F. Fulvio, S. Pikus and M. Jaroniec, J. Mater. Chem., 2005,
15, 5049–5053.
233 H. I. Lee, J. H. Kim, G. D. Stucky, Y. Shi, C. Pak and
J. M. Kim, J. Mater. Chem., 2010, 20, 8483–8487.
234 T. Benamor, L. Vidal, B. Lebeau and C. Marichal, Microporous
Mesoporous Mater., 2012, 153, 100–114.
235 G. Wanka, H. Hoffmannand and W. Ulbricht, Macromole-
cules, 1994, 27, 4145–4159.
236 D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson,
B. F. Chmelka and G. D. Stucky, Science, 1998, 279,
548–552.
237 A. Sayari, B. H. Han and Y. Yang, J. Am. Chem. Soc., 2004,
126, 14348–14349.
238 M.-C. Chao, C.-H. Chang, H.-P. Lin, C.-Y. Tang and
C.-Y. Lin, J. Mater. Sci., 2009, 44, 6453–6462.
239 C. G. Wu and T. Bein, Chem. Commun., 1996, 925–926.
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
240 S. E. Park, D. S. Kim, J.-S. Chang and W. Y. Kim, Catal.
Today, 1998, 44, 301–308.
241 Y. J. Zhang, S. L. Zhao, L. Q. Lu and G. D. Sun, Acta Chim.
Sinica, 2001, 59, 820.
242 B. L. Newalkar, S. Komarneni and H. Katsuki, Chem.
Commun., 2000, 2389–2390.
243 Y. K. Hwang, J. S. Chang, Y. U. Kwon and S. E. Park,
Microporous Mesoporous Mater., 2004, 68, 21–27.
244 C. A. Fantini, J. R. Matos, L. C. Cides da Silva, L. P. Mercuri,
G. O. Chiereci, E. B. Celer and M. Jaroniec, Mater. Sci. Eng.,
B., 2004, 112, 106–110.
245 B. C. Grabicka and M. Jarociec, Microporous Mesoporous
Mater., 2009, 119, 144–149.
246 E. B. Celer and M. Jaroniec, J. Am. Chem. Soc., 2006, 128,
14408–14414.
247 X. Tang, S. Liu, Y. Wang, W. Huang, E. Sominski,
O. Palchik, Y. Koltypin and A. Gedanken, Chem. Commun.,
2000, 2119–2120.
248 A. Palani, H.-Y. Wu, C.-C. Ting, S. Vetrivel, K. Shanmugapriya,
A. S. T. Chiang and H.-M. Kao, Microporous Mesoporous
Mater., 2010, 131, 385–392.
249 S. K. Lee, J. Lee, J. Joo, T. Hyeon, W. S. Ahn, H. Lee and
W. Choi, J. Ind. Eng. Chem., 2003, 9, 83–88.
250 P. Mohanty, N. M. K. Linn and K. Landskron, Langmuir,
2010, 26, 1147–1151.
251 M. Ogura, H. Miyoshi, S. P. Naik and T. Okubo, J. Am.
Chem. Soc., 2004, 126, 10937–10944.
252 S. Ruthstein, J. Schmidt, E. Kesselman, Y. Talmon and
D. Goldfarb, J. Am. Chem. Soc., 2006, 128, 3366–3374;
L. Omer, S. Ruthstein, D. Goldfarb and Y. Talmon, J. Am.
Chem. Soc., 2009, 131, 12466–12473.
253 S. D. Bhagat, Y.-H. Kim, G. Yi, Y.-S. Ahn, J.-G. Yeo and
Y.-T. Choi, Microporous Mesoporous Mater., 2008, 108,
333–339.
254 P. B. Sarawade, Appl. Surf. Sci., 2011, 258, 955–961.
255 L. Pei, K.-I. Kurumada, M. Tanigaki, M. Hiro and K. Susa,
J. Mater. Sci., 2004, 39, 4045–4047.
256 S. Shen, F. Chen, P. S. Chow, P. Phanapavudhikul, K. Zhu
and R. B. H. Pan, Microporous Mesoporous Mater., 2006, 92,
300–308.
257 M. Linden, S. A. Schunk and F. Schüth, Angew. Chem., Int.
Ed., 1998, 37, 821–823.
258 J. Jammaer, T. S. van Erp, A. Aerts, C. E. A. Kirschhock and
J. Martens, J. Am. Chem. Soc., 2011, 133, 13737–13745.
259 C. J. Brinker, Y. lu, A. Sellinger and H. Fan, Adv. Mater.,
1999, 11, 579–585.
260 J. Rathousky, V. Kalousek, V. Yarovyi, M. Wark and
J. Jirkovsky, J. Photochem. Photobiol., A, 2010, 216, 126–132.
261 G. J. de A. A. Soler-Illia, A. Louis and C. Sanchez, Chem.
Mater., 2002, 14, 750–759.
262 H. Depaz, A. Chemtob, C. Croutxé-Barghorn, S. Rigolet and
B. Lebeau, Microporous Mesoporous Mater., 2012, 151,
88–92; H. Depaz, A. Chemtob, F. Crest, C. Croutxé-Barghorn,
S. Rigolet and B. Lebeau, RSC Adv., 2012, 2, 11944–11952.
263 N. Baccile, D. Grosso and C. Sanchez, J. Mater. Chem., 2003,
13, 3011–3016.
Chem. Soc. Rev.

Review Article
264 Y. Lu, H. Fan, A. Stump, T. L. Ward, T. Rieker and
C. J. Brinker, Nature, 1999, 398, 223–226.
265 S. Nagamine, A. Endo, M. Nakaiwa, T. Nakane,
K.-I. Kurumada and M. Tanigaki, Microporous Mesoporous
Mater., 2001, 43, 181–189.
266 M. Ide, E. Wallaert, I. Van Driessche, F. Lynen, P. Sandra
and P. van der Voort, Microporous Mesoporous Mater., 2011,
142, 282–291.
267 G. V. R. Rao, G. P. Lopez, J. Bravo, H. N. Pham, A. K. Datye,
H. F. Xu and T. L. Ward, Adv. Mater., 2002, 14, 1301–1304.
268 Y. Yamauchi, P. Gupta, K. Sako, N. Fukata, S.-I. Todoroki,
S. Inoue and S. Kishimoto, J. Ceram. Soc. Jpn., 2009, 117,
198–202.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
269 L.-Y. Lin and H. Bai, Microporous Mesoporous Mater., 2010,
136, 25–32.
270 P. Innocenzi, L. Malfatti and G. J. A. A. Soler-Illia, Chem.
Mater., 2011, 23, 2501–2509.
271 M. Losurdo, M. M. Giangregorio, G. Bruno, F. Poli,
L. Armelao and E. Tondello, Sens. Actuators, B, 2007, 126,
Downloaded by RMIT Uni on 19 February 2013
168–173.
272 S. El-Shafty, T. Hanaoka and F. Mizukami, Adv. Mater.,
2005, 17, 47–53.
273 M. Kruk and C. Hui, J. Am. Chem. Soc., 2008, 130,
1528–1529.
274 F. Kleitz, W. Schmidt and F. Schüth, Microporous
Mesoporous Mater., 2003, 65, 1–29.
275 F. Bérubé and S. Kaliaguine, Microporous Mesoporous
Mater., 2008, 115, 469–479.
276 F. Bérubé and S. Kaliaguine, in Recent Progress in
Mesostructured Materials Proceedings of the 5th International
Mesostructured Materials Symposium (IMMS2006), Elsevier,
2007, vol. 165, pp. 189–193.
277 M. T. J. Keene, R. D. M. Gougeon, R. Denoyel, R. K. Harris,
J. Rouquerol and P. L. Llewellyn, J. Mater. Chem., 1999, 9,
2843–2849.
278 F. Kleitz, W. Schmidt and F. Schüth, Microporous Meso-
porous Mater., 2001, 44–45, 95–109.
279 J. Ryczkowski, J. Goworek, W. Gac, S. Pasieczna and
T. Borowiecki, Thermochim. Acta, 2005, 434, 2–8.
280 J. Goworek, A. Kierys and R. Kusak, Microporous Meso-
porous Mater., 2007, 98, 242–248.
281 J. Goworek, A. Kierys, W. Gac, A. Borówka and R. Kusak,
J. Therm. Anal. Calorim., 2009, 96, 375–382.
282 R. Zaleski, J. Wawryszczuk, J. Goworek, A. Borówka and
T. Goworek, J. Colloid Interface Sci., 2003, 262, 466–473.
283 K. Morishige and Y. Kondou, J. Phys. Chem. C, 2012, 116,
3702–3706.
284 N. Xiao, L. Wang, S. Liu, Y. Zou, C. Wang, Y. Ji, J. Song, F. Li,
X. Meng and F.-S. Xiao, J. Mater. Chem., 2009, 19, 661–665.
285 L. Shi, Y. Zou and H. He, Chem. Lett., 2001, 1164–1165.
286 D. Khushalani, A. Kuperman, N. Coombs and G. A. Ozin,
Chem. Mater., 1996, 8, 2188–2193.
287 D. P. Das, K. M. Parida and B. K. Mishra, Res. Lett. Mater.
Sci., 2009, 2009, 1–5.
288 F. Bérubé, A. Khadhraoui, M. T. Janicke, F. Kleitz and
S. Kaliaguine, Ind. Eng. Chem. Res., 2010, 49, 6977–6985.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
289 K. Ikari, K. Suzuki and H. Imai, Langmuir, 2006, 22,
802–806.
290 S. Hoon Joo, R. Ryoo, M. Kruk and M. Jaroniec, in
Nanotechnology in Mesostructured Materials Proceedings of
the 3rd International Materials Symposium, Elsevier, 2003,
vol. 146, pp. 49–52.
291 M. A. Aramendı́a, V. Borau, C. Jiménez, J. M. Marinas and
F. J. Romero, J. Colloid Interface Sci., 2004, 269, 394–402.
292 J. Jiu, K. Kurumada, F. Wang and L. Pei, Mater. Chem.
Phys., 2004, 86, 435–439.
293 K. Cassiers, P. V. D. Voort and E. F. Vansant, Chem.
Commun., 2000, 2489–2490.
294 Z. A. AlOthman and A. W. Apblett, Appl. Surf. Sci., 2010,
256, 3573–3580.
295 R. Mokaya and W. Jones, J. Mater. Chem., 1998, 8,
2819–2826.
296 L. Wang and R. T. Yang, J. Phys. Chem. C, 2011, 115,
21264–21272.
297 Q. Wei, Z. Nie, Y. Hao, Z. Chen, J. Zou and W. Wang, Mater.
Lett., 2005, 59, 3611–3615.
298 D. Margolese, J. A. Melero, S. C. Christiansen,
B. F. Chmelka and G. D. Stucky, Chem. Mater., 2000, 12,
2448–2459.
299 W. Guo, X. Li and X. S. Zhao, Microporous Mesoporous
Mater., 2006, 93, 285–293.
300 W. J. Hunks and G. A. Ozin, Adv. Funct. Mater., 2005, 15,
259–266.
301 S. Inagaki, S. Guan, Y. Fukushima, T. Ohsuna and
O. Terasaki, J. Am. Chem. Soc., 1999, 121, 9611–9614.
302 W. Guo, I. Kim and C.-S. Ha, Chem. Commun., 2003,
2692–2693.
303 V. Goletto, M. Imperor and F. Babonneau, Stud. Surf. Sci.
Catal., 2001, 135, 1129–1136.
304 R. M. Grudzien, B. E. Grabicka and M. Jaroniec, J. Mater.
Chem., 2006, 16, 819–823.
305 T. Tsoncheva, J. Rosenholm, M. Linden, L. Ivanova and
C. Minchev, Appl. Catal., A, 2007, 318, 234–243.
306 R. M. Grudzien, B. E. Grabicka and M. Jaroniec, Appl. Surf.
Sci., 2007, 253, 5660–5665.
307 X. Zhuang, X. Qian, J. Lv and Y. Wan, Appl. Surf. Sci., 2010,
256, 5343–5348.
308 C. Yang, B. Zibrowius and F. Schüth, Chem. Commun.,
2003, 1772–1773.
309 A. Rumplecker, B. Zibrowius, W. Schmidt, C.-M. Yang and
F. Schüth, in Recent Progress in Mesostructured
Materials Proceedings of the 5th International Mesostructured
Materials Symposium (IMMS2006), Elsevier, 2007, vol. 165,
pp. 195–198.
310 C.-M. Yang, B. Zibrowius, W. Schmidt and F. Schüth,
Chem. Mater., 2003, 15, 3739–3741.
311 C.-M. Yang, B. Zibrowius, W. Schmidt and F. Schüth,
Chem. Mater., 2004, 16, 2918–2925.
312 H. Ji, Y. Fan, W. Jin, C. Chen and N. Xu, J. Non-Cryst. Solids,
2008, 354, 2010–2016.
313 V. V. Kovalenko, G. M. Tel’biz and F. M. Bobonich, Theor.
Exp. Chem., 2004, 40, 64–68.
This journal is c The Royal Society of Chemistry 2013

Chem Soc Rev
314 G. Toussaint, M. A. Rodriguez, R. Cloots, J. Rubio,
F. Rubio, B. Vertruyen and C. Henrist, J. Non-Cryst. Solids,
2011, 357, 951–957.
315 C.-Y. Chen, H.-X. Li and M. E. Davis, Microporous Mater.,
1993, 2, 17–26.
316 Y. Luo and J. Lin, Microporous Mesoporous Mater., 2005, 86,
23–30.
317 M. C. Burleigh, M. A. Markowitz, M. S. Spector and
B. P. Gaber, J. Phys. Chem. B, 2001, 105, 9935–9942.
318 H. Mao, X. Gao, J. Yang and B. Li, Appl. Surf. Sci., 2011, 257,
4655–4662.
319 H. Xu, X. Wang, L. Tao and S. Wu, Sci. China: Chem., 2010,
53, 556–561.
Published on 13 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CS35451B
320 A. Doyle and B. K. Hodnett, Microporous Mesoporous
Mater., 2003, 58, 255–261.
321 Y. Chen, H. Wu, S. Gan, Y. Wang and X. Sun, J. Membr. Sci.,
2012, 403–404, 94–100.
322 V. Antochshuk and M. Jaroniec, Chem. Commun., 1999,
2373–2374.
Downloaded by RMIT Uni on 19 February 2013
323 S. Kawi and S. Lai, Chem. Commun., 1998, 1407–1408;
S. Kawi and A. H. Goh, Stud. Surf. Sci. Catal., 2000, 129,
131–138.
324 X.-B. Lu, W.-H. Zhang, J.-H. Xiu, R. He, L.-G. Chen and
X. Li, Ind. Eng. Chem. Res., 2003, 42, 653–656.
325 R. van Grieken, G. Calleja, G. D. Stucky, J. A. Melero,
R. A. Garcı́a and J. Iglesias, Langmuir, 2003, 19, 3966–3973.
326 L. Huang, C. Poh, S. C. Ng, K. Hidajat and S. Kawi,
Langmuir, 2005, 21, 1171; L. Huang, S. Kawi, C. Poh,
K. Hidajat and S. C. Ng, Talanta, 2005, 66, 943–951.
327 Z. Huang, L. Xu and J.-H. Li, Chem. Eng. J., 2011, 166, 461–467.
328 Z. Huang, L. Xu, J.-H. Li, S. Kawi and A. H. Goh, Sep. Purif.
Technol., 2011, 77, 112–119.
329 A. A. Lubgyban, J. A. Lubguban, M. T. Othman,
R. V. Shende, S. Gangopadhyay, R. D. Miller, W. Volksen
and H.-C. Kim, Thin Solid Films, 2008, 516, 4733–4741.
330 Z. Huang, D.-Y. Luan, S.-C. Shen, K. Hidajat and S. Kawi,
J. Supercrit. Fluids, 2005, 35, 40–48.
331 N. Lang and A. Tuel, Chem. Mater., 2004, 16, 1961–1966.
332 S. A. Bagshaw and I. J. Bruce, Microporous Mesoporous
Mater., 2008, 109, 199–209.
333 T. Benamor, L. Michelin, B. Lebeau and C. Marichal,
Microporous Mesoporous Mater., 2012, 147, 334–342.
334 S. A. Idris, C. M. Davidson, C. McManamon, M. A. Morris,
P. Anderson and L. T. Gibson, J. Hazard. Mater., 2011, 185,
898–904.
335 B. Tian, X. Liu, H. Yang, S. Xie, C. Yu, B. Tu and D. Zhao,
Adv. Mater., 2003, 15, 1370–1374.
This journal is c The Royal Society of Chemistry 2013
View Article Online
Review Article
336 B. Tian, X. Liu, C. Yu, F. Gao, Q. Luo, S. Xie, B. Tu and
D. Zhao, Chem. Commun., 2002, 1186–1187.
337 T.-L. Lai, Y.-Y. Shu, Y.-C. Lin, W.-N. Chen and C.-B. Wang,
Mater. Lett., 2009, 63, 1693–1695.
338 M. Guli, L. Zhang, J. Yao and X. Li, Powder Technol., 2012,
219, 271–275.
339 Y. Hu, Y. Peng, L. Brousseau, A. Bouamrani, X. Liu and
M. Ferrari, Sci. China: Chem., 2010, 53, 2257–2264.
340 J. M. Gomez-Vega, K. Teshima, A. Hozumi, H. Sugimura
and O. Takai, Surf. Coat. Technol., 2003, 169–170, 504–507.
341 J. Zhang, A. Palaniappan, X. Su and F. E. H. Tay, Appl. Surf.
Sci., 2005, 245, 304–309.
342 P. Pootawang, N. Saito and O. Takai, Thin Solid Films, 2011,
519, 7030–7035.
343 J. He, S. Fujikawa, T. Kunitake and A. Nakao, Chem. Mater.,
2003, 15, 3308–3313.
344 S. Jabariyan and M. A. Zanjanchi, Ultrason. Sonochem.,
2012, 19, 1087–1093.
345 M. T. J. Keene, R. Denoyel and P. L. Llewellyn, Chem.
Commun., 1998, 2203–2204.
346 S. Heng, P. P. S. Lau, K. L. Yeung, M. Djafer and
J.-C. Schrotter, J. Membr. Sci., 2004, 243, 69–78.
347 N. Chemin, M. Klotz, V. Rouessac, A. Ayral and E. Barthel,
Thin Solid Films, 2006, 495, 210–213.
348 Y. Xia and R. Mokaya, J. Phys. Chem. B, 2006, 110,
9122–9131.
349 J. Kecht and T. Bein, Microporous Mesoporous Mater., 2008,
116, 123–130.
350 H. Kang, Y. Zhu, J. Shen, X. Yang, C. Chen, H. Cao and
C. Li, Mater. Res. Bull., 2010, 45, 830–837.
351 L. M. Yang, Y. J. Wang, G. S. Luo and Y. Y. Dai, Microporous
Mesoporous Mater., 2005, 81, 107–114.
352 L. Xiao, J. Li, H. Jin and R. Xu, Microporous Mesoporous
Mater., 2006, 96, 413–418.
353 H. Cai and D. Zhao, Microporous Mesoporous Mater., 2009,
118, 513–517.
354 A.-H. Lu, W.-C. Li, W. Schmidt and F. Schüth, J. Mater.
Chem., 2006, 16, 3396–3401.
355 T. Clark Jr., J. D. Ruiz, H. Fan, C. J. Brinker, B. I. Swanson
and A. N. Parikh, Chem. Mater., 2000, 12, 3879–3884.
356 A. Hozumi, Y. Yokogawa, T. Kameyama, K. Hiraku,
H. Sugimura, O. Takai and M. Okido, Adv. Mater., 2000,
12, 985–987.
357 I. Mukherjee, J. Chen, H. Yin and Y. Wei, Powder Technol.,
2011, 206, 214–217.
358 C. Yu, B. Tian, J. Fan, G. D. Stucky and D. Zhao, J. Am.
Chem. Soc., 2002, 124, 4556–4557.
Chem. Soc. Rev.