Recent Patents on Nanotechnology 2009, 3, 213-224

213

A Review on Chemical Methodologies for Preparation of Mesoporous

Silica and Alumina Based Materials
Bhanudas Naik and Narendra Nath Ghosh*
Chemistry Group, Birla Institute of Technology and Science - Pilani, Goa Campus, Goa- 403726, India
Received: November 27, 2008; Accepted: May 15, 2009; Revised: May 29, 2009

Abstract: The discovery of novel family of molecular sieves called M41S aroused a worldwide resurgence in the field of
porous materials. According to IUPAC definition inorganic solids that contain pores with diameter in the size range of 20500 are considered mesoporous materials. Mesoporous silica and alumina based materials find applications in catalysis,
adsorption, host- guest encapsulation etc. This article reviews the current state of art and outline the recent patents in
mesoporous materials research in three general areas: Synthesis, various mechanisms involved for porous structure
formation and applications of silica and alumina based mesoporous materials.

Keywords: Mesoporous, silica, alumina, zeolite, SBA-n, M41S, liquid crystal, catalyst.
1. INTRODUCTION
Synthesis of silica and alumina based mesoporous
materials have gained immense importance since 1990 after
the discovery of M41S type of molecular sieves by the
scientists of Mobil Oil Corp. [1-3]. These materials have
attracted the attention of material scientists due to their high
surface area (~1000 m2/g) and narrow pore size distribution
with long range ordering [3]. These features made these
materials potential candidates for various scientific as well as
industrial applications, such as, heterogeneous catalysts,
separation process, host guest chemistry, adsorbents host for
quantum structures, separation of large biological molecules,
environmental pollution control etc [4-9]. Due to growing
interest in this area a special issue of Journal of porous
materials has been dedicated on Zeolites and Novel Microand Mesoporous Materials [10] and excellent reviews have
been published by several experts [4, 5, 8]. There are several
researchers reported various synthetic methodologies and
applications of zeolites and other macro and micro porous
materials. Due to high demand of silica and alumina based
mesoporous materials in various industry several patents
have been filed disclosing variety of synthetic methods and
their utility for specific applications [11-28]
According to the IUPAC definition, solids that contain
pores with pore diameter (i) >50 nm are called as macroporous, (ii) between 2-50 nm are mesoporous and (iii) <2 nm
are microporous [4, 5]. Some of the examples of different
porous materials are listed in the Table 1.
Several researchers have reported various synthesis
methodologies to prepare mesoporous oxide materials and
proposed different mechanisms to explain the porous
structures [4-9, 29]. Various factors, such as starting materials (e.g., alkoxides, metal salts etc), surfactants as structure
directing agent), reaction parameters (e.g. pH, temperature,
solvent, co-solvent etc.) influence the formation of porous
*Address correspondence to this author at the Chemistry Group, Birla
Institute of Technology and Science - Pilani, Goa Campus, Goa- 403726,
India; Tel/Fax: 91 832 2580318/ 2557033; E-mail: naren70@yahoo.com

1872-2105/09 $100.00+.00

structures and dictate the pore size, its distribution and

ordering [37-44]. So, it is very important to critically compile the reported synthesis methods, proposed mechanisms
and the factors, which influence the porous structure and to
correlate synthetic methods with the resultant structures for
preparation of tailor-made materials.
In this paper, we have reviewed different synthesis routes
employed for preparation of various types of porous silica
and alumina based materials, mechanisms of formation of
porous structures and factors which influence their
structures.
2. POROUS SILICA BASED MATERIALS
There are number of silica based porous materials
available, which are widely studied and characterized, such
as microporous zeolites, mesoporous silicates (e.g. M41S,
SBA -15 etc.), mesoprous aluminosilicates etc. In the following sections, we have discussed about several synthetic
routes, which are used for their preparation with some
typical examples, mechanisms associated with their structure
formations and effect of different reaction conditions on
structures.
2.1. Synthesis Methodologies
One of the oldest members of the porous materials family
is zeolite. Zeolites are hydrated crystalline aluminosilicates
(MxDy[Alx+2ySin-(x+2y)O2n]mH20) [where x, y and m is number
of monovalent cations, bivalent cations and water molecules
respectively, and n is valence of cations] [35]. Zeolite is a
Greek word that means boiling stone. This is because of
naturally occurring zeolites are the minerals which absorb
water and boil when heated. Historically zeolites were
discovered from the mineral stilbit in 1756 by Cronsted [5,
35]. Thereafter, huge progress has been made in their
synthesis, structural elucidation, modification, preparation of
synthetic zeolites, development of new zeolites and zeolitelike materials (aluminophosphates) etc. Aluminum phosphates were discovered in 1982 [45]. Since then, they have
attracted the attention due to their structural characteristics
2009 Bentham Science Publishers Ltd.

214 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

Table 1.

Naik and Ghosh

Different Types of Porous Materials

Type of Material

Pore Size

Examples

Pore Size Range ()

Reference Number

Macroporous

>500

Porous glasses

>500

[4,7]

Mesoporous

20-500

Pillared layered clays

10 , 100

[4,7]

Microporous

<20

M41S

16-100

[4]

SBA-15

80 - 100

[29,30]

SBA-16

50

[31]

Diatom biosilica

20-500

[32,33]

Mesoporous alumina

20

[34]

Zeolites

<14.2

[9,35,36]

Activated carbon

[4]

ZSM-5

4.5-6

[9,35,36]

Zeolite A

3-4.5

[35]

Beta and Mordernite- Zeolites

6-8

[35]

Faujasite

7.4

[9]

Cloverite

6-1.32

[9]

and applications in the field of catalysis and molecular

sieving [46, 47]. Three dimensional structures of zeolite
form by linking AlO4 and SiO4 tetrahedra though sharing of
oxygen ions [35]. Zeolites are synthesized by using small
cationic molecules as structure directing agents [47-49]. Pore
structure of zeolites lies in the region of microporosity. The
discovery of M41S family of mesoporous silica helped in
zeolite synthesis by providing methodologies to expand the
pore size into mesopore range [50-54].
Synthesis of mesoporous silica was first reported in the
year 1990 independently by the researchers of Mobil Oil
Corporation [1-3] and Kurodas group [55, 56]. Self organized surfactant molecules were used as structure directing
agents [57, 58]. Stucky et al. in Santa Barbara synthesized
SBA-n materials, which were analogous to M41S [59]. Some
of the important mesoporous silica materials are M41S
family members (MCM-41, MCM-48, MCM-50) and SBA-n
type materials (SBA-1, SBA-3, and SBA-15) [1-4, 59-63].
Synthesis methodologies which are generally used for
preparation of these materials are discussed below:
M41S type molecular sieves were synthesized by using
stoichiometric amounts of silica source (TEOS, Ludox,
fumed silica, sodium silicate), alkyltrimethylammonium
halide surfactant (cetyltrimethylammoniam bromide
(CTAB)), sodium hydroxide or tetramethylammonium hydroxide (TMAOH) and water. CTAB played the role of
structure directing agent. White precipitate obtained after
mixing the reactants and aged at higher temperatures for 24
to 144 hr. Surfactant template was removed by calcining the
precipitate [1, 2].
Stucky et al. synthesized SBA-15 by using triblock
copolymer pluronic P123 ((EO)20(PO)70(EO)20), where EO is
hydrophilic ethylene oxide groups and PO is hydrophobic
propylene oxide group) as template, TEOS as source of silica
and hydrochloric acid. After mixing, the resultant solution
was heated at 308 K with stirring and aged to obtain a white

precipitate. Calcination of this precipitate resulted in

formation of SBA-15 [60, 64].
Chao et al. [65] have prepared SBA-1 crystals using
C18TMACl, sodium silicate and H2O. pH was maintained in
between 1 to 2, which was around isoelectric point of silica.
Feng et al. [66] have demonstrated the control of pore sizes
in mesoporous silica. They have synthesized mesoporous
silica by using colloidal silica, pluronic F127 or P123 and
water as solvent, with butanol, pentanol, or hexanol as
cosolvent. Kim et al. [67] have synthesized well ordered
silica mesostructures using Pluronic P123 and TMOS.
Hydrolysis of TMOS was controlled by the presence of
fluoride (NH4F) and amphiphilic surfactants over a wide
range of pH 0 to 9. Fluoride was used as it catalyzed the
hydrolysis and polymerization of silica species [68] and
helped to improve the structural order [69]. Setoguchi et al.
[70] have synthesized mesoporous silica using one step
synthesis route employing different types of silica sources
(such as sodium silicate, colloidal silicate, waterglass or
TEOS) with C16 PyCl template in highly acidic medium
(pH<1). Sun et al. [71] have reported the synthesis of high
quality MCM-48 through hydrothermal post-synthesis route.
The gel resulted from the mixture of TEOS, CTAB, H2O,
ethanol and ammonium hydroxide was autoclaved and
finally calcined to obtain the mesoporous MCM-48. Huo et
al. [72] studied the effect of different surfactants on the
synthesis of mesoporous silica. They have reported the
synthesis of MCM-41, MCM-48, MCM-50, SBA-1, SBA-2
and SBA-3 by using different quaternary ammonium
surfactants with various silica sources, such as TEOS,
TMOS, fumed silica, sodium silicate at different pH
conditions. Choi and Yang [37] investigated the effect of pH
change on mesoporous silica structures such as SBA-15 and
the mesocellular silica forms (MCF). They have synthesized
SBA-15 by using Pluronic P123, TMOS and HCl.
Ammonium hydroxide was added stepwise to control pH of
the reaction medium. Similarly, MCFs were synthesized by

A Review on Chemical Methodologies for Preparation of Mesoporous

adding xylene as hydrophobic swelling agent in the synthesis

medium. Clavier et al. [73] developed a method for synthesis
of transparent mesoporous silica monoliths containing grafted organic functional groups. Diamine grafted monoliths
was synthesized by hydrolysis of Si(OMe)4 in methanol in
presence of ethylene glycol and then reacting the product,
formed due to hydrolysis, with chelating diamines. Wu et al.
[74] reported the synthesis of mesoporous Ti-SBA-15 by
titanation of SBA-15 in glycerol with the assistance of
quaternary organic ammonium hydroxides. They have also
synthesized Ti-MCM-41 by hydrothermal method with Si/Ti
ratios of 37 to 320. Ghosh et al. [75] have reported a novel
building block technique for preparation of mesoporous site
isolated vanadium silica catalysts, where cubic Si8O20
spherosilicate unit was used as building block.
2.2. Mechanisms of Formation of Porous Silica
(i). Formation of Zeolites
In synthesis of ZSM-5, single molecule template acted as
structure directing agent, which was responsible for
microporous structure formation. The template used for
ZSM-5 synthesis was tetrapropylammonium cation. Initial
step in this synthesis involved condensation of silicate ions
around the structure of the template and formation of ordered
aggregates of silica framework [76, 77]. Nucleation of these
initial assemblies led to crystal growth and final structure
[5].
(ii). Formation of Mesostructured Silicates
In pursue to explain the mechanistic route of mesostructure formation several models have been proposed. At
basic level, all these models suggest that, surfactant supramolecular assemblies provides template structure and this
finally leads to the formation of pore structure in the
inorganic matrix. Considering different mode of interaction
of inorganic precursors with surfactants, several models have
been proposed [4]. Surfactant molecules are made-up of two
distinct entities within the same molecule: hydrophilic head
group and hydrophobic tail group. In aqueous medium, these
molecules act as surface active agents and change the
structural orientation depending on their concentration [64,
78,79]. At low concentration, surfactant molecules exist as
monomolecules. When the concentration of surfactant
increases, they aggregate together to form micelles. The
micelle concentration threshold, at which surfactant molecules aggregate to form isotropic micelles is called critical
micellization concentration (CMC). Further increase in
concentration results in formation of hexagonal closed
packed arrays [78]. Next step in this process is the
coalescence of adjacent, mutually parallel cylinders to form
lamellar phase [5]. The cubic phase is generally consists of
complex, interwoven networks of rod shaped aggregates
[80]. Kresge and Beck et al. [1-3] have proposed liquid
crystal templating mechanism for synthesis of M41S
materials based on resemblance between lyotropic phases
and M41S. The factors which influence the mesostructures
are hydrocarbon chain length of surfactant molecules,
concentration of surfactant and presence of organic swelling
agents [57]. For MCM-41 two mechanistic pathways have
been proposed (I) liquid crystal templating mechanism and
(II) charge density matching mechanism [1-5].

Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

215

Pathway 1:Liquid Crystal Templating Mechanism

This mechanism was proposed based on the similarity
between liquid crystalline surfactant assemblies (i.e.,
lyotropic phases) and M41S. Two mechanistic pathways
were postulated by the Mobil researchers:
1) Surfactant in solution forms lyotropic liquid crystal
phase (LC). Deposition of inorganic precursors occurs
on the micelle rods of preformed liquid crystalline
phase. Subsequent polymerization of inorganic precursors leads to the formation of organic-inorganic
mesostructure. This can be viewed as hexagonal array of
surfactant micellar rods embedded in silica matrix.
Removal of surfactants produces open, mesoporous
framework.
2) Ordering of surfactant molecule into hexagonal liquid
crystal phase is influenced by inorganic precursors. This
was postulated as a cooperative self assembly of ammonium surfactants and silicate precursors below CMC.
Davis et al. [81] investigated in situ 14N NMR
spectroscopy study of synthesis of MCM -41 under the same
synthetic conditions reported by Mobil scientists and the
results confirmed that LC did not form during MCM-41
synthesis. They proposed that, silicate deposition occurred
on the surfactant micelle rods which were randomly
arranged, followed by ordering of silicate deposited rods into
hexagonal mesostructures. Aging of these mesostuctures at a
favorable temperature helped in condensation of silicates
into the MCM-41. However, according to Steel et al. [82]
silicate precursors directed the surfactant molecules into
hexagonal LC phase. This result was supported by 14N NMR
spectroscopy study. It was postulated that, the silicate
precursors were present as organized layers in between the
rows of the cylindrical miceller rods. Puckering of layers
around the rods resulted in formation of hexagonal mesoporous structures.
Pathway 2: Charge Density Matching Mechanism
Stucky et al. [83] have introduced a new concept, known
as Charge Density Matching Mechanism, to explain the
mechanism of mesostructure formation. This model provided
a general mechanism for mesoporous materials formation.
From X-Ray diffraction study, it was confirmed that during
synthesis the initial phase formed was layered structured.
This was due to the electrostatic force of attraction between
oppositely charged cationic surfactant head groups and
anionic precursor species. Subsequent condensation step
caused reduction in charge density of silicate species, which
forced them to balance the charge density by introducing
curvature into layers. As a result, lamellar structure transformed to hexagonal mesophase.
Apart from these two models, another model was
proposed by Firouzi et al. [84], known as silicatropic liquid
crystals. They investigated the effect of electrolyte on
miceller phase transitions through 1H, 29Si NMR spectroscopy and neutron scattering study of CTAB phase transition. CTAB transformed to hexagonal phase in presence of
silicate ions. It was also proved that, in addition to charge
balance requirement, the preferential bonding of ammonium
group to the D4R silicate anions occurred under high pH

216 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

condition [84, 85]. Silicate precursors, which were negatively charged ions, ion-exchanged with surfactant halide
counter ions and produced silicatropic liquid crystals,
phase (SLC). Heat treatment of SLC resulted in irreversible
condensation of silicates and formation of MCM-41. SLC
phase displayed same characteristic features of lyotropic
systems at low surfactant concentration.
Huo et al. presented a generalized model to explain the
interaction of surfactant head group (S) and inorganic
precursor (I) [59, 86]. This liquid crystal mechanism could
be classified as S+I- pathway, where charge density matching
occurred between oppositely charged surfactant and
inorganic silicate ions through S-I+ pathway (where surfactant was anionic and inorganic precursors were positively
charged). Charge interaction pathways could also proceed
through same charge surfaces by S+X-I+ and S-M+I- (M+ is
metal cation and X- is counteranion) pathways. Oppositely
charged counter ions helped to neutralize the repulsion
between same charged surfaces by serving as a charge
balancing intermediates though hydrogen bonding.
(iii). Formation of M41S Family
Silicate mesophases of M41S family of molecular sieves,
mainly MCM-41, MCM-48 and MCM-50 [87], derived from
basic medium via S+I- route and by variation of surfactant to
silicon molar ratio. MCM-41 possesses hexagonal mesosphere belonging to p6m space group, MCM-48 structure
shows cubic mesophase, which can be visualized as a two
interlinked networks of spherical cages separated by
continuous silicate frameworks. MCM-50, in uncalcined
form, shows lamellar structure (p2), but after surfactant
removal and post treatment, results into pillared layer material. Formation of phases of M41S is dependant on surfactant
to silicon molar ratio. MCM-41, MCM-48 and MCM-50
forms when this ratio is <1, 1 -1.5, and 1.2 2 respectively
[87].
(iv). Formation of SBA-n Materials
SBA-1 and SBA-3 are generally synthesized by using
cationic surfactants in acidic medium, which is below the
isoelectric point of silica, through S+X-I+ pathway [59].
These materials are termed as acid prepared materials
(APM) [4]. SBA-1 is cubic structure but not bicontinuous
like MCM-48, where as, SBA-3 is hexagonal structure (p6m)
similar to that of MCM-41 [59, 72]. These materials are
having thicker pore walls and the framework charge is
different from that of base derived materials. This is due to
the different precipitation conditions and charge balance
system [4].
One of the important SBA group materials is SBA-15,
which is different from other members of this family. It can
be synthesized in acidic medium with non ionic pluronic
surfactant [31]. SBA-15 has hexagonal structure similar to
MCM-41. SBA-16 is another material, synthesized with
pluronic surfactant F127 (Im3m). These materials are synthesized in the highly acidic mediums with cationic silica
precursor. At low pH, protonated PEO chains of surfactants
associate with cationic silica species though weak electrostatic interactions and pathway proceeds through S0H+X-I+
route [37, 88]. Silica, prepared with non ionic surfactants,
posses thicker pore walls, due to slower self-assembly of

Naik and Ghosh

silica-surfactant mesophase in gel compared to ionic

surfactants [89].
Kim and Stucky reported the synthesis of highly ordered
two dimentional hexagonal SBA-15 (P6mm), three dimentional hexagonal SBA-12 (P63/mmc), and cubic SBA-16 and
SBA-11 (Im3m and Pm3m) using sodium matasilicate as
silica source and nonionic amphiphilic block copolymers as
structure directing agents [90].
3. MESOPOROUS ALUMINA
3.1. Synthesis of Mesoporous Alumina
Based on the synthesis strategy, the synthesized mesoporous alumina may possess amorphous walls or crystalline
walls [91, 92]. Alumina exists in different crystalline phases
such as ,  , and
[92, 93]. -Al203 transforms to
-Al203
when heated at higher temperature [93, 94]. However,
collapse of mesoporous framework walls was observed at
elevated temperatures [95, 96]. -Al203 can be obtained by
heat treatment of Al(OH)3 or AlOOH at intermediate
temperatures [ 97 ].
Several researchers have reported different synthetic
routes for preparation of mesoporous alumina. Some of the
typical methodologies have been discussed below:
Baumann et al. [98] and Hao et al. [99] have used
aluminum salts, propylene oxide and ethanol to prepare Al2O3 through calcination at 8000C. Davis et al. have
reported the preparation of mesoporous aluminas using
Al(sec-BuO)3 as aluminum source, alcohol as solvent and
different carboxylic acids as structure directing agents [34].
Liu et al. have described the synthesis of ordered crystalline
molecular sieves via nanocasting route using mesoporous
carbon (CMK-3) as template, aluminium nitrate as aluminum
precursor and ethanol as solvent [100]. Liu et al. have
prepared -alumina single crystal nano leaves via hydrothermal route using AlCl3, NaOH, CTAB, ethanol (solvent)
at 1600C [101]. Seki et al. have reported mesoporous
alumina synthesis using Al(sec-BuO)3,1-propanol, lauric
acid and autoclaving the reaction mixture at 1100C for 24
hrs. The precursor was calcined at 6000C for 5 hrs [102].
Kim et al. have employed post-hydrolysis method for
synthesis of -alumina using Al(sec-BuO)3, stearic acid and
sec-butyl alcohol [92]. Yada et al. have reported the use of
dodecyl sulfate as surface directing agent [103, 104].
Cabrera et al. have used triethanolamine with CTAB for
synthesis of organized mesoporous aluminas (OMA)
[105].Cejka et al. have used Al(sec-BuO)3, lauric acid or
stearic acid and 1-propanol for preparation of OMA [97].
Alvine et al. have electrochemically prepared mesoporous
membranes using a two step anodization technique [106].
Mesoporous alumina molecular sieves (MSU-X) were
synthesized by using polyethylene oxide and aluminium
alkoxide [39, 107]. A neutral synthesis route for mesoporous
alumina using triblock copolymer was described by Deng et
al. [108]. A sol-gel synthesis route for mesoporous alumina
has been reported by Niesz et al. using aluminium tri-tert
butoxide, Pluronic P123, ethyl alcohol (solvent) [109].
Ghosh et al. have developed an aqueous solution based
method for synthesis of mesoporous alumina by using
aluminium nitrate, carboxylic acids and TEA. Pore structure

A Review on Chemical Methodologies for Preparation of Mesoporous

Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

was controlled by varying the chain length of carboxylic acid

[110].
3.2. Mechanism of Formation of Mesoporous Alumina
The synthesis route employed by Davis et al. [34] was
hydrolysis of aluminium alkoxides in presence of carboxylate surfactant. In this method S-I complexation reaction
between surfactant (S) and inorganic precursor (I) was
involved [96]. Hydrolysis of aluminium alkoxides took place
by one of the two following reactions given below [111,
112]:
Al(OR)3 + 3H20  Al(OH)3 + 3 ROH

(1)

Al(OR)3 + 2H20  AlO(OH) + 3ROH

(2)

Bayerite (Al(OH)3) was the final phase formed when

hydrolysis was conducted in water (Al3+: H2O >20) at a
temperature < 3500C [112]. It was observed that, bayerite
phase did not form when hydrolysis was performed in
presence of carboxylic acid and large excess of water at 298
K for 24 h. So presence of carboxylic acid inhibited the
formation of bayerite phase [111]. Pseudoboehmite was the
major species formed in Vaudry-Davis method [34, 111].
Here, assembly of carboxylic acidic coordinated with small
Al(O(OH) clusters formed and resulted in formation of
mesophase consisting of organic core and inorganic shell.
Yada et al. [113] proposed S-I+ assembly pathway when
starting materials were dodecyl sulfate and aluminium
nitrate. Zhang and Pinnavaia synthesized mesoporoue
alumina (MSU-X) by N0I0 assembly, using electrically
neutral polyethylene oxide surfactants (N0) and aluminium
alkoxides (I0) [39, 96, 107]. In this method pore structure
was formed via supramolecular assembly process.
Liu et al. [114] synthesized mesoporous crystalline
alumina by using boehmite sols in presence of non-ionic
surfactant (P123). They have proposed the possibility of a
different mechanistic pathway other than widely accepted
supramolecular self-assembly process. Unusual results of
large surface area accompanied by high pore volume and
large pore size in boehmite-P123 system were not observed
before for mesoporous aluminas. Characterization results
revealed that, weak interaction between precursor and P123
molecules had negligible influence on morphology of
crystalline structure of boehmite. But, this interaction had
capability to induce change in the stacking mode of boehmite layers as building blocks [115]. This mechanism was
more closely analogous to boehmite-surfactant sandwich
structure proposed by Gonzlez-Pea et al. [116]. Cejka et
al. reported the synthesis of organized mesoporous aluminas
(OMA) by using carboxylic acids surfactants (lauric acid and
stearic acids) [97]. Length of the hydrophobic hydrocarbon
chain of carboxylic acids played the similar role like alkyl
trimethylammonium surfactants in the synthesis of MCM41, i.e. increase of pore size with increasing chain length
[117].
4. FACTORS INFLUENCE THE STRUCTURE OF
MESOPOROUS MATERIALS
4.1. Effect of Surfactant
Surfactant chemistry is the fundamental subject matter in
the study for mesoporous material synthesis and also in

217

understanding of the detailed mechanism of formation of

mesoporous structures. The nature of surfactant governs the
pore size, structure of pores, thickness of walls, phase and
symmetry of materials [8]. Surfactant molecules consist of
hydrophilic polar head group and hydrophobic nonpolar
hydrocarbon tail [64,78]. Due to this amphiphilic nature, the
surfactant molecules behave as active agents in aqueous
solution showing high affinity to the surfaces and interfaces.
Depending on the nature of surfactant polar head group,
surfactants are classified as anionic, cationic, zwitterionic
and non ionic surfactants [64, 118-128]. At CMC, surfactant
molecules self organize into micelles aggregates [5]. Further
increase in surfactant concentration or addition of some polar
compounds results in their transformation to liquid
crystalline phases. Structures of mesoporous materials are
related to the shape and concentration of surfactant and can
be expressed in terms of simple expression of surfactant
packing parameter g, for lyotropic LC phase [129, 130].
g = V/al, where V is volume of surfactant tail, a is effective
head group area and l is length of the extended surfactant
tail. Value of g differs for different surfactants. This is due to
the variation of different types of surfactant tails and heads
groups. Hence, relative sizes of surfactant tail and head
group are governing factors for optimum packing of the
surfactants into different geometrical structures. g less then
1/3, produces spherical micelles, further increase in
concentration produces cubic phase (Pm3n), when g= 1/3.
When the value of g is
hexagonal arrays (p6m) form.
When g value lies in between 1/3 and
formation of cubic
phase (Ia3d) occurs. Lamellar structure forms when g is
equal to 1 [131,132]. The effect g value was observed in
synthesis SBA-1 and SBA-3. When cationic surfactants are
used in acidic medium, at g = 1/3 SBA-1, having cubic phase
(pm3n), forms. But hexagonal (p6m) phase forms when g
=1/2 [4, 72]. Surfactants with larger head group (such as
CnH2n+1(C2H5)3N+, n=12, 14, 16, 18) favor the synthesis of
SBA-1 in the acidic medium. Larger head groups decrease
the value of surface packing parameter in order to generate
maximum surface curvature [129, 131]. SBA-3 forms when
head group of surfactant changes from C2H5 to CH3 [72].
Mobil scientists produced three types of mesoporous silica
(MCM-41, MCM-48 and MCM-50) by varying the
concentration of CTAB surfactant in basic pH [87].
CnH2n+1(CH3)3N+ with n=12, 13, 14, 15, 16, 18 can also be
used for synthesis of MCM-41 [72]. Chiral surfactants
(C16H33N+(CH3)2CH(CH3)C6H5) was also applied for
production of MCM-41 and MCM-50 [72]. Stuky et al.
synthesized hexagonal SBA-15 with nonionic P123 ((EO)20
(PO)70(EO)20) block copolymer in acidic medium [31, 60].
Use of Gemini surfactant was reported for synthesis of high
quality mesoporous silica with cubic geometry (ia3d) [120].
Gemini surfactant is known for self assembling at lower
concentration compared to monomeric surfactants.
Pannasvaia and coworkers [39, 40] used nonionic surfactants
and partially ionized silica in neutral pH to obtain worm like
mesostructures with monodispersed pore size.
4.2. Effect of pH
pH is the important parameter which influences the
synthetic chemistry of mesoporous materials. This is because
of pH of medium, which influences charge of inorganic

218 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

precursor species and surfactant head groups and consequently their mutual interaction. M41S family of molecular
sieves was synthesized in basic pH by using CTAB, whereas
Stuky et al. synthesized SBA materials in acid medium [1-3,
60, 64].
Due to high pH value, negatively charged inorganic
precursors preferentially interacted with positively charged
ammonium head groups of the surfactants and resulting in
condensation of inorganic silicate ions into solid organicinorganic mesoporous structure. In case of SBA-15, at low
pH polyethylene oxide chains gets protonated and interacts
with positively charged silica species mediated by negatively
charged halide ions to form S0H+X-I+ intermediate [31].
Using same surfactant different mesophases can also be
obtained by changing the pH of reaction medium from acidic
to basic [72]. Change of pH values leads to phase
transformation of silica from lamellar to hexagonal phase
[133]. Mechanism of formation of mesophases at acidic and
basic extremes is completely different [86].This is because
of negatively charged silicate ions act as counter ions above
isoelectric point (pH~2.0) [134]. Whereas below isoelectric
point, positively charged silicate ions act as co-counter ions
in acidic medium [72]. Generally, in strong acidic medium
rate of hydrolysis of TEOS is faster than condensation.
Therefore, well ordered hexagonal arrangement of mesopores is obtained at acidic pH, whereas the rate of
condensation is faster then hydrolysis in neutral or basic
conditions [37]. Thus, pH plays a critical role in hydrolysis
and condensation of inorganic silica species. Hydrolysis and
condensation of silicon alkoxides can be expressed by the
following three equations [68].
Hydrolysis:  Si-OR + H2O
 Si-OH + ROH (a)
Alcohol condensation: Si-OR + HO-Si
 Si-O-Si  +
ROH (b)
Water condensation: Si-OH + HO-Si
 Si-O-Si  + H 2
O (c)
When pH is 2, charge on silica becomes zero [134] and
pH above 2, the silica species [Si(OH)4] condense into small
silica aggregates, as shown in equation c [68] and have
negative charge on the surface due to silanol groups.
It has been observed that, slow growth rate is the
fundamental requirement for formation of crystals with wellshape morphology. Silica condensation is slowest and
surface charge is electronically neutral around isoelectric
point at pH=2. pH dependency of condensation rate was
exhibited by SBA-1 when its crystal shape showed transitions from sphere
decaoctahedron
truncated cube

cube with chage in pH from 1.0 to 2 [65]. The electrolyte
concentration is also a factor which effects mesophase
formation [135].
The effect of amines on the distribution of silica and
aluminosilicate species was observed in the synthesis of
mesoporous silica. Solubility and distribution of silicate
structures can be altered by addition of organic alkyl ammoniums to the silica source [136]. Commonly tetramethylammonium hydroxide (TMOH) is used to dissolve silica.
Major forms of silica structures produce are D3R(Q36),
D4R(Q38), and D5R(Q310) [137]. Firouzi et al. showed that
there is a preferential bonding of ammonium head group of

Naik and Ghosh

alkyl trimethylammonim surfactant to D4R silicate anions at

high pH. This was proved by the formation of D4R in
solution of silicate anions which did not contain D4R
species. Alkyl trimethylammonim surfactant forced non D4R
species to reequilibrate and formed D4R [84, 85]. One of the
suggestions for this observation was that the projected areas
of D4R anion and ammonium head group were matching [4,
84, 85].
4.3. Effect of Silica Source
Mesoporous silica synthesis is vibrant with respect to
source of silica used. Mesoporous structures have been
synthesized by making use of several sources of silica, such
as silicon alkoxides (e.g., TEOS, TMOS), sodium silicate,
Ludox, fumed silica, water glass etc. [4, 5, 8]. Silicon
alkoxides are not soluble in water but can be dissolved in a
mixture of water and water miscible organic solvent (e g.,
ethanol). They can be hydrolyzed by acid catalyzed or base
catalyzed reaction resulting in cleavage of ester bond. They
condense into aggregates containing Si-O-Si species and
have negative charge due to silanol groups [68].
In TEOS and other simple alkoxides, number of siloxane
bonds is zero. Thus, TEOS shows 29Si-NMR Si(Qn) signal to
be Si(Q0), where value of n represent coordination number of
silicon with siloxane bonds. Colloidal silica shows Si(Q4 )
whereas water glass can exhibit maximum of five signals [8].
It is found that, silica sources displaying Si(Q4) signals are
unsuitable as starting material in synthesis of mesoporous
silica [70].
Klotz et al. showed that for the formation of ordered
mesoporous materials require Si(Q1) species in the initial
stage of synthesis. Presence of Si(Q3) species in initial stage
of the synthesis resulted in disordered mesoporous silica
[138]. Setoguchi et al. studied the effect of various silica
sources under strong acidic conditions (pH<1) with C16PyCl
surfactant. They found that use of sodium silicate produced
high quality mesoporous silica analogous to MCM-41, where
as use of as received colloidal silica resulted in formation of
non-mesoporous silica [70]. Mesoporous silica produced
from water glass also showed interesting results. Type I
water glass produced maesoporous silica but type III did not
[70]. Setoguchi et al. have [70] also synthesized mesoporous
silica using Huo et al.s method [59,86]. TEOS produced
mesoporous silica with high surface area and narrow pore
size distribution. This can be compared with mesoporous
silica, prepared by using sodium silicate. Kim et al. showed
that in rapid hydrolysis condition TMOS acted as
preferential precursor source than TEOS [37, 67].
5. DIFFERENT METAL INCORPORATED POROUS
MATERIALS
Porous materials with high surface area and narrow pore
size with long range ordering makes these materials suitable
for loading catalytically active species (e.g., metals). This
leads to the development of variety of advanced catalysts.
Amount of metal species can be incorporated into mesoporous silica depends on the stability of resultant mesoporous structure as well as method of synthesis. Several
metal incorporated porous materials are listed in Table 2.

A Review on Chemical Methodologies for Preparation of Mesoporous

Table 2.

Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

219

(Table 2) Contd.

Metal Loaded Mesoporous Silica and Alumina

Type of Porous
Material

Type of Metal
Incorporated

Ref.

Alumina coated
SBA-15

Fe

Lim et al. [163]

MCM-41

Al

Beck et al. [2]

Mesoporous
alumina

Fe

Liu et al. [114]

MCM-41

Ti

Corma et al. [139]

Liu et al. [114]

Reddy et al. [140]

Mesoporous
alumina

Pd

MCM-41
MCM-41

Ti

Tanev et al. [141]

Kim [92]

Sayari et al. [142]

Mesoporous
alumina

Ni

MCM-41
MCM-41

Al

Luan et al. [143]

MCM-41

Al

Fu et al. [144]

MCM-41

Mn

Zhao,Goldfarb [145]

MCM-41

Sn

Abdel-Fattah, Pinnavaia [146]

MCM-41

Ga

Cheng et al. [147]

MCM-41

Ga, Al

Cheng, Kinowsk [148]

MCM-41

Al

Tuel, Gontier [149]

MCM-41

Ga

Tuel, Gontier [149]

MCM-41

Fe

Tuel, Gontier [149]

MCM-41

Tuel, Gontier [149]

MCM-41

Zr

Tuel et al. [150]

MCM-41

Cr

Ulgappan, Roa [151]

MCM-41

Ti

Zhang et al. [152]

MCM-41

Zhang et al. [152]

MCM-41

Cr

Zhang et al. [152]

MCM-41

Mn

Zhang et al. [152]

MCM-41

Mo

Zhang et al. [152]

MCM-41

Fe

He et al. [153]

MCM-41

Zr

Jones et al. [154]

MCM-41

Nb

Zhang Ying [155]

MCM-41

Ti

Wu et al. [74]

MCM-48

Ti

Koyano,Tatsumi [156]

MCM-48

Ti

Zhang, Pinnavaia [157]

MCM-48

Cr

Zhang, Pinnavaia [157]

MCM-48

Zhang, Pinnavaia [157]

MCM-48

Fe

Echchahed et al. [158]

MCM-48

Mn

Gomez et al. [159]

SBA-15

Zn

Jiang et al. [160]

SBA-15

Eu

Gu et al. [161]

SBA-15

Ti

Wu et al. [74]

SBA-15

Sn

Shah et al. [162]

6. APPLICATIONS OF THE POROUS MATERIALS

6.1. Applications of Porous Silicates
Zeolites are widely used in various catalytic and non
catalytic applications. They find their applications as catalyst
in refineries, petrochemical and chemical industries. Zeolite
X is used as cracking catalyst, zeolite Y as isommarization
catalyst and ZSM-5 in fluid catalytic reactions. Rayalu et al.
have prepared novel zeolite-based photocatalysts, having
visible light activity and pronounced photoreduction
property [36]. Zeolite-based composite photocatalysts have
been designed by incorporation of HPA (Heteropolyacid),
semiconductor (TiO2) and transition metal (Co) on Zeolite.
These metallozeolite photocatalysts showed efficiency in
photoreduction of methyl orange. These catalysts also
showed encouraging results for hydrogen production from
water. Qi and Yang have reported the use of Fe/ZSM-5
catalyst for selective catalytic oxidation of ammonia to
nitrogen [164]. Metal-containing zeolites have been found to
be very active as catalyst in selective reduction of NOx,
especially Cu-ZSM-5 when propene is used as reductant
[165,166]. Cobalt containing zeolites exhibited their catalytic
activity in NOx reduction reaction in presence of methane
[166]. Tabata et al. observed that the activity of cobaltcontaining zeolites with propane was highest for zeolites,
having large pore size. This was attributed to less diffusion
hindrances in these catalysts [167,168].
Metal ion loaded M41S and SBA-15 based materials are
having several applications such as, in heterogeneous
catalyzed reactions (oxidation, acid catalyses, hydroxylation
and polymerization), adsorbents, separation processes, host
guest encapsulation, host of quantum structures etc. Some
applications of various metal ion incorporates mesoporous
silica are listed in Table 3.
6.2. Applications of Mesoporous Aluminas
High surface area aluminas with porous structure have
gained importance due to their potential applications as
catalysts and catalyst supports as well as adsorptive material
in the separation processes [98]. Favorable textural properties and intrinsic acid base properties have resulted in
their extensive use as a catalyst supports [114]. Transition
alumina especially
-alumina, has potential to be a major
catalytic support in automotive, petroleum industries [92,
114] and in adsorption technology [92]. The acidic function
of the support accomplishes the isomerization and cycli-

220 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

Table 3.

Naik and Ghosh

Applications of Various Mesoporous Silicates

Materials

Application

Remarks

Ref.

NiMo-MCM-41

Catalysts for gas oil

hydrocracking.

NiMo-MCM-41 showed higher hydrodesulurization and

hydrodenitrogenetaion activity than NiMo loaded on USY or
amorphous aluminosilicate.

Corma et al. [169]

Cr-MCM-41 and
Cr-MCM-48

oxidation of
ethylbenzene

These catalysts showed quite promising results for liquid phase

oxidation of ethylbenzene.

Sakthivel et al.
[170]

Al-MCM-41

Diels-Alder reaction of
cyclopentadiene with
several unsaturated
aldehydes,

Al-MCM-41 catalyst showed highest activity compared to the HZSM-5 in all the reactions tested.

Kugita et al. [171]

Cobalt containing SBA-15

Fischer-Tropsch
reaction

Highly dispersed Co in SBA-15 exhibited high catalytic activity

which was attributed to the ordered pore structure of SBA-15.

Khodakov et al.
[172]

Ni-

Catalyst for selective

hydrodechlorination of

Park et al. [173]

1,1,2-trichloroethane

Ni-SBA-16 sample showed highest activity. This was due to its

three-dimensional pore structure, which allowed rapid diffusion of
molecules through the pore system.

Fe- and Pt- containing

MCM-41

De-NOx reaction

Promising results for de-NOx reaction was observed.

Yang et al. [174]

and Long et al.
[175]

Na-MCM-41 and
Cs-MCM-41

Base catalysis

In knoevenagel condensation of benzaldehyde with ethyl

cyanoacetate, excellent conversion of benzaldehyde and selectivity
was observed.

Ti-MCM-41

Catalysts for
hydroxylation of
benzene

Excellent catalytic oxidation performance in presence of hydrogen

peroxide.

Tanev et al. [141]

Pt-MCM-48

Hydrogenation of
benzene and toluene

This catalyst showed high activity in the hydrogenation of benzene

and toluene.

Chatterjee et al.
[177]

Pt and Rh nanowires and/or

particles were prepared in
mesopores of FSM-16

Hydrogenation and
isomerisation catalist

Pt nanowire showed high activity for butane hydrogenation, while Pt-

Fukuoka et al. [178]

Bimetallic nanoparticles were

prepared from

Hydrogenation and

Under solvent-free and low temperature condition showed selective

hydrogenation.

SBA-15 and Ni-SBA-16

chiral catalys

Ru6Pd6 and Ru6CSn carbonyl

clusters

Kloetstra
et al. [176]

Rh nanowire exhibitd high activity for butane isomerization to

isobutene.
Johnson et al. [179]

Superior performance by chiral catalyst confined within mesoporous

silica.

were anchored along the

interior walls of
mesoporous silica MCM-41
Gold Nanoparticles in SBA15

Catalyst for CO
oxidation,

SBA-15 was functionalized with positively charged groups, and

[AuCl4]
-species were subsequently incorporated into the channel
system via ion exchange. Upon reduction with NaBH4, highly
dispersed nanoparticles of gold were formed in the channels of the
mesoporous host

Yang et al. [180]

Sulfide ion within MCM-41

Catalytic reduction of
methyl viologen

Methyl viologen in the presence of mesoporous MCM-41 and sulfide

ions is found to undergo a spontaneous catalytic reduction

Liao et al. [181]

to methyl viologen radical (MV+).

zation of normal paraffins, the supported metal convert lowoctane components to high-octane isoparaffins [182]. In
addition, micro and nanocrystalline aluminas are commonly
used for Al2O3- based ceramics [183].

7. CURRENT & FUTURE DEVELOPMENTS

In this paper, we have reviewed the current state of art in
mesoporous materials research in three general areas: syn-

A Review on Chemical Methodologies for Preparation of Mesoporous

thesis, various mechanisms which are proposed to explain

porous structure formation and different applications of
silica and alumina based mesoporous materials. Several
chemical methods which are used for synthesis of silica and
alumina based mesoporous materials and the factors which
influence the pore structure have been discussed with typical
examples. In pursue to explain the formation of pore structures; the mechanistic routes proposed by several researchers, such as liquid crystal template mechanism, charge
density matching mechanism have been discussed.
High surface area and porous structure of these materials
made them potential candidate to be used for various scientific as well as industrial applications. The use of mesoporous materials as catalysts has already been demonstrated
in a number of applications. Apart from catalysis
applications, they can be used in separation process, host
guest chemistry, adsorbents, host for quantum structures,
separation of large biological molecules, environmental
pollution control etc. In spite of the large amount of synthesis work already been done, still development of simple
chemical methodology is required for synthesis of hierarchical meso structures possessing well defined patterned
features on different length and size scale .

Recent Patents on Nanotechnology 2009, Vol. 3, No. 3

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[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
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[27]
[28]
[29]
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[32]

ACKNOWLEDGEMENT
Narendra N. Ghosh gratefully acknowledges support
from Department of Science and Technology, New Delhi
India ( Project no: SR/S1/IC-39/2006).

[33]

[34]

CONFLICT OF INTEREST
No conflict of interest pertaining to the authors exists
regarding any of the patents and patent applications cited in
this manuscript
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