Synthesis of Fluorescein

Procedure

Step 1: Take 0.3g Resorcinol and 0.2 g of ground powdered Pthalic anhydride in a 50 ml round

bottom flask.

Step 2: Add 5-6 drops of 2M H2SO4 dropwise and heat the mixture between 180 -200 oC for 30

minutes on sand bath. Mix the reactants during heating using a glass-rod. The color of the

mixture should turn yellowish red. Then take the round bottom flask out from sand bath and

allow it to cool to room temperature.

Step 3: Then add 10 ml of acetone and stir for 5 min using glassrod. The solution should turn

yellow as the crude fluorescein dissolves. Filter the solution.

Step 4: From filtrate boil off the acetone. Take this crude orange residue in a beaker and dissolve

it in 30 mL of diethyl ether and 1.5 mL of water.

Step 5: Place a stir bar in the solution and put the beaker over a magnetic stir plate for several

minutes until all the solids dissolve.

Step 6: Transfer this organic solution in a separatory funnel and add 15 mL water for washing.

Discard the aqueous wash.

Step 7: Dry the organic layer over anhydrous sodium sulfate.

Step 8: Pre-weigh a small beaker. Place the dried organic solution in the beaker and evaporate it

to dryness on a water bath. Weigh the product (orange solid) and calculate the % of yield.

Product analysis

The TLC, UV-Visible spectrophotometer and IR spectrophotometer will be used to check the

formation and purity of the synthesized product compared with commercial Fluorescein.
 Synthesis of mesoporous Silica (MCM 41)

Objective: Synthesis and characterization of mesoporous Silica (MCM 41)

Materials required:

I) Glassware and equipment: Beaker (100 ml) x 2, Dropper, Funnel, Glass rod, Measuring

cylinder (50 ml), Magnetic stirrer.

II) Chemicals: CTAB, TEOS, Ammonia solution.

Procedure: For synthesis of 500 mg of MCM 41

(i) 0.48 g CTAB will be dissolved in 23 ml water with 1.65 ml ammonia solution (~30%). The

mixture will be stirred until the formation of clear solution.

(ii) 1.725 g tetraethyl orthosilicate will be added to the clear solution of CTAB and stirred for 4

h.

(iii) The resulting mixture then allowed to age for 24 h for condensation at room temperature.

(iv) The organic –inorganic hybrid precursor thus formed to be filtered and wash with 150 ml

distilled water, followed by drying in an oven at 100 oC for 24 h.

(v) Then finally dried precursor will be calcined at 550 oC for 3 h in air atmosphere to obtained

MCM 41.

Characterization of materials:

The functional groups present in dry precursor will be characterized by using FTIR (assignment

of finger print region)

Calcined powder (MCM 41) will be characterized by using powder X-ray diffractometer.

Calculation:

Finally you need to calculate the % of Yield.

Reference:
1) C.T. Kresge, M.E. Leonowicz, W. J. Roth, J. C. Vartuli, and J. S. Beck, Nature 359, 710

(1992).

2) B, Naik, S. Hazra, P. Muktesh, V. S. Prasad, N. N. Ghosh, Science of Advanced Materials 3,

1025 (2011).

3) J. Y. Ying, C. P. Mehnert, and M. S. Wong, Angew. Chem. Int. Ed. 38, 56 (1999)

4) B Naik and N N Ghosh, Recent Patents on Nanotechnology 3, 213 (2009)

 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 20-
500 Å 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 Micro-
and 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 macro-
porous, (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 mate-
rials (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
structures and dictate the pore size, its distribution and
ordering [37-44]. So, it is very important to critically com-
pile 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 follow-
ing 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 zeolite-
like materials (aluminophosphates) etc. Aluminum phos-
phates were discovered in 1982 [45]. Since then, they have
attracted the attention due to their structural characteristics

1872-2105/09 $100.00+.00 © 2009 Bentham Science Publishers Ltd.

214 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3
Table 1. Different Types of Porous Materials
Type of Material Pore Size Examples
Macroporous >500 Å Porous glasses
Mesoporous 20-500 Å Pillared layered clays
M41S
SBA-15
SBA-16
Diatom biosilica
Mesoporous alumina
Microporous <20 Å Zeolites
Activated carbon
ZSM-5
Zeolite A
Beta and Mordernite- Zeolites
Faujasite
Cloverite
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 Kuroda’s group [55, 56]. Self orga-
nized 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 hyd-
roxide (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
Naik and Ghosh
Pore Size Range (Å) Reference Number
>500 [4,7]
10 , 100 [4,7]
16-100 [4]
80 - 100 [29,30]
50 [31]
20-500 [32,33]
20 [34]
<14.2 [9,35,36]
6 [4]
4.5-6 [9,35,36]
3-4.5 [35]
6-8 [35]
7.4 [9]
6-1.32 [9]
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 graf-
ted 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 meso-
structure formation several models have been proposed. At
basic level, all these models suggest that, surfactant supra-
molecular 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 mole-
cules 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 pre-
cursors 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 ammo-
nium 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 meso-
porous 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 trans-
formed 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 spectro-
scopy and neutron scattering study of CTAB phase transi-
tion. 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 negati-
vely 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 surfac-
tant 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 mesos-
phere 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 mate-
rial. 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 synthe-
sized in the highly acidic mediums with cationic silica
precursor. At low pH, protonated PEO chains of surfactants
associate with cationic silica species though weak electro-
static 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 dimen-
tional 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 meso-
porous 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 hydro-
thermal 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
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 carboxy-
late 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
Al(OR)3 + 2H20  AlO(OH) + 3ROH
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 boeh-
mite layers as building blocks [115]. This mechanism was
more closely analogous to boehmite-surfactant sandwich
structure proposed by González-Peña 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 MCM-
41, 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
Recent Patents on Nanotechnology 2009, Vol. 3, No. 3 217
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
(1)
increase in surfactant concentration or addition of some polar
(2) 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 conse-
quently 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 organic-
inorganic 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 meso-
pores 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 well-
shape 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 transi-
tions 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 ammo-
niums to the silica source [136]. Commonly tetramethyl-
ammonium 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 meso-
porous silica depends on the stability of resultant meso-
porous 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 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3 219

Table 2. Metal Loaded Mesoporous Silica and Alumina (Table 2) Contd….

Type of Porous Type of Metal Ref. Alumina coated Fe Lim et al. [163]
Material Incorporated SBA-15

MCM-41 Al Beck et al. [2] Mesoporous Fe Liu et al. [114]

alumina
MCM-41 Ti Corma et al. [139]
Mesoporous Pd Liu et al. [114]
MCM-41 V Reddy et al. [140] alumina
MCM-41 Ti Tanev et al. [141] Mesoporous Ni Kim [92]
MCM-41 B Sayari et al. [142] alumina

MCM-41 Al Luan et al. [143]

6. APPLICATIONS OF THE POROUS MATERIALS
MCM-41 Al Fu et al. [144]

MCM-41 Mn Zhao,Goldfarb [145]

6.1. Applications of Porous Silicates

MCM-41 Sn Abdel-Fattah, Pinnavaia [146]

Zeolites are widely used in various catalytic and non
catalytic applications. They find their applications as catalyst
MCM-41 Ga Cheng et al. [147] in refineries, petrochemical and chemical industries. Zeolite
X is used as cracking catalyst, zeolite Y as isommarization
MCM-41 Ga, Al Cheng, Kinowsk [148]
catalyst and ZSM-5 in fluid catalytic reactions. Rayalu et al.
MCM-41 Al Tuel, Gontier [149] have prepared novel zeolite-based photocatalysts, having
visible light activity and pronounced photoreduction
MCM-41 Ga Tuel, Gontier [149] property [36]. Zeolite-based composite photocatalysts have
MCM-41 Fe Tuel, Gontier [149] been designed by incorporation of HPA (Heteropolyacid),
semiconductor (TiO2) and transition metal (Co) on Zeolite.
MCM-41 B Tuel, Gontier [149] These metallozeolite photocatalysts showed efficiency in
MCM-41 Zr Tuel et al. [150]
photoreduction of methyl orange. These catalysts also
showed encouraging results for hydrogen production from
MCM-41 Cr Ulgappan, Roa [151] water. Qi and Yang have reported the use of Fe/ZSM-5
catalyst for selective catalytic oxidation of ammonia to
MCM-41 Ti Zhang et al. [152]
nitrogen [164]. Metal-containing zeolites have been found to
MCM-41 V Zhang et al. [152] be very active as catalyst in selective reduction of NOx,
especially Cu-ZSM-5 when propene is used as reductant
MCM-41 Cr Zhang et al. [152] [165,166]. Cobalt containing zeolites exhibited their catalytic
MCM-41 Mn Zhang et al. [152] activity in NOx reduction reaction in presence of methane
[166]. Tabata et al. observed that the activity of cobalt-
MCM-41 Mo Zhang et al. [152] containing zeolites with propane was highest for zeolites,
MCM-41 Fe He et al. [153]
having large pore size. This was attributed to less diffusion
hindrances in these catalysts [167,168].
MCM-41 Zr Jones et al. [154]
Metal ion loaded M41S and SBA-15 based materials are
MCM-41 Nb Zhang Ying [155] having several applications such as, in heterogeneous
catalyzed reactions (oxidation, acid catalyses, hydroxylation
MCM-41 Ti Wu et al. [74] and polymerization), adsorbents, separation processes, host
MCM-48 Ti Koyano,Tatsumi [156] guest encapsulation, host of quantum structures etc. Some
applications of various metal ion incorporates mesoporous
MCM-48 Ti Zhang, Pinnavaia [157] silica are listed in Table 3.
MCM-48 Cr Zhang, Pinnavaia [157]
6.2. Applications of Mesoporous Aluminas
MCM-48 V Zhang, Pinnavaia [157]
High surface area aluminas with porous structure have
MCM-48 Fe Echchahed et al. [158] gained importance due to their potential applications as
catalysts and catalyst supports as well as adsorptive material
MCM-48 Mn Go´mez et al. [159]
in the separation processes [98]. Favorable textural pro-
SBA-15 Zn Jiang et al. [160] perties and intrinsic acid base properties have resulted in
their extensive use as a catalyst supports [114]. Transition
SBA-15 Eu Gu et al. [161] alumina especially
-alumina, has potential to be a major
SBA-15 Ti Wu et al. [74]
catalytic support in automotive, petroleum industries [92,
114] and in adsorption technology [92]. The acidic function
SBA-15 Sn Shah et al. [162] of the support accomplishes the isomerization and cycli-
220 Recent Patents on Nanotechnology 2009, Vol. 3, No. 3 Naik and Ghosh

Table 3. Applications of Various Mesoporous Silicates

Materials Application Remarks Ref.

NiMo-MCM-41 Catalysts for gas oil NiMo-MCM-41 showed higher hydrodesulurization and Corma et al. [169]
hydrocracking. hydrodenitrogenetaion activity than NiMo loaded on USY or
amorphous aluminosilicate.

Cr-MCM-41 and oxidation of These catalysts showed quite promising results for liquid phase Sakthivel et al.
Cr-MCM-48 ethylbenzene oxidation of ethylbenzene. [170]

Al-MCM-41 Diels-Alder reaction of Al-MCM-41 catalyst showed highest activity compared to the H- Kugita et al. [171]
cyclopentadiene with ZSM-5 in all the reactions tested.
several unsaturated
aldehydes,

Cobalt containing SBA-15 Fischer-Tropsch Highly dispersed Co in SBA-15 exhibited high catalytic activity Khodakov et al.
reaction which was attributed to the ordered pore structure of SBA-15. [172]

Ni- Catalyst for selective Ni-SBA-16 sample showed highest activity. This was due to its Park et al. [173]
SBA-15 and Ni-SBA-16 hydrodechlorination of three-dimensional pore structure, which allowed rapid diffusion of
1,1,2-trichloroethane molecules through the pore system.

Fe- and Pt- containing De-NOx reaction Promising results for de-NOx reaction was observed. Yang et al. [174]
MCM-41 and Long et al.
[175]

Na-MCM-41 and Base catalysis In knoevenagel condensation of benzaldehyde with ethyl Kloetstra
Cs-MCM-41 cyanoacetate, excellent conversion of benzaldehyde and selectivity et al. [176]
was observed.

Ti-MCM-41 Catalysts for Excellent catalytic oxidation performance in presence of hydrogen Tanev et al. [141]
hydroxylation of peroxide.
benzene

Pt-MCM-48 Hydrogenation of This catalyst showed high activity in the hydrogenation of benzene Chatterjee et al.
benzene and toluene and toluene. [177]

Pt and Rh nanowires and/or Hydrogenation and Pt nanowire showed high activity for butane hydrogenation, while Pt- Fukuoka et al. [178]
particles were prepared in isomerisation catalist Rh nanowire exhibitd high activity for butane isomerization to
mesopores of FSM-16 isobutene.

Bimetallic nanoparticles were Hydrogenation and Under solvent-free and low temperature condition showed selective Johnson et al. [179]
prepared from chiral catalys hydrogenation.
Ru6Pd6 and Ru6CSn carbonyl Superior performance by chiral catalyst confined within mesoporous
clusters silica.
were anchored along the
interior walls of
mesoporous silica MCM-41

Gold Nanoparticles in SBA- Catalyst for CO SBA-15 was functionalized with positively charged groups, and Yang et al. [180]
15 oxidation, [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

Sulfide ion within MCM-41 Catalytic reduction of Methyl viologen in the presence of mesoporous MCM-41 and sulfide Liao et al. [181]
methyl viologen ions is found to undergo a spontaneous catalytic reduction
to methyl viologen radical (MV+).

zation of normal paraffins, the supported metal convert low- 7. CURRENT & FUTURE DEVELOPMENTS
octane components to high-octane isoparaffins [182]. In
In this paper, we have reviewed the current state of art in
addition, micro and nanocrystalline aluminas are commonly
mesoporous materials research in three general areas: syn-
used for Al2O3- based ceramics [183].
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 struc-
tures; the mechanistic routes proposed by several resear-
chers, 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 scien-
tific as well as industrial applications. The use of meso-
porous 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 syn-
thesis work already been done, still development of simple
chemical methodology is required for synthesis of hierar-
chical meso structures possessing well defined patterned
features on different length and size scale .
ACKNOWLEDGEMENT
Narendra N. Ghosh gratefully acknowledges support
from Department of Science and Technology, New Delhi
India ( Project no: SR/S1/IC-39/2006).
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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 As exemplified by Pd-
grafted ultra-large pore
silicate Pd-TMS11 (TEM
image presented above), su-
pramolecular-templated meso-
porous materials find many uses,
for example (starting at the left and go-
ing clockwise) in polymerization, for
immobilization of well-defined ho-
mogeneous catalysts, in Heck
catalysis, in acid catalysis,
and as an encapsulation
host for ferrocenyl
units.
 REVIEWS

Synthesis and Applications of Supramolecular-Templated

Mesoporous Materials**
Jackie Y. Ying,* Christian P. Mehnert, and Michael S. Wong

Research in supramolecular-templated
mesoporous materials began in the
early 1990s with the announcement of
MCM-41 and the M41S family of
molecular sieves. These materials are
highly unusual in their textural char-
acteristics: uniform pore sizes greater
than 20 Š, surface areas in excess of
1000 m2 gÿ1, and long-range ordering of
the packing of pores. The mesoporous
materials are derived with supramo-
lecular assemblies of surfactants, which
template the inorganic components
during synthesis. Many researchers
have since exploited this technique of
supramolecular templating to produce
materials with different compositions,
new pore systems, and novel proper-
ties. This article reviews the current
state of the art in mesoporous materi-
als research in three general areas:
synthesis, catalytic properties, and oth-
er applications that take advantage of
bulk morphologies. Various mecha-
nisms formulated to explain the for-
mation of mesostructures are discussed
in the context of compositional con-
trol. The catalytic applications of mes-
oporous materials are examined, with
a significant fraction based on recent
patent literature. Other directions in
the utilization of mesoporous materials
are also presented.
Keywords: amphiphiles ´ hetero-
geneous catalysis ´ mesoporosity ´
molecular sieves ´ template synthesis

1. Introduction silicate precursors),[5] Antonelli and Ying (mesoporous tran-

Only six years have passed since the exciting discovery of
the novel family of molecular sieves called M41S was reported
by the researchers at Mobil Research and Development
Corporation.[1] These mesoporous (alumino)silicate materials,
with well-defined pore sizes of 15 ± 100 Š, break past the
pore-size constraint (< 15 Š) of microporous zeolites. The
extremely high surface areas (> 1000 m2 gÿ1) and the precise
tuning of pore sizes are among the many desirable properties
that have made such materials the focus of great interest. The
M41S materials also ushered in a new approach in materials
synthesis where, instead of the use of single molecules as
templating agents (as in the case of zeolites), self-assembled
molecular aggregates or supramolecular assemblies are em-
ployed as the structure-directing agents. Various aspects of
M41S and related mesoporous materials have been reviewed
by Brinker (recent advances in porous inorganic materials),[2]
Vartuli et al. (synthesis of the M41S family),[3] Stucky et al.
(biomimetic synthesis of mesoporous materials),[4] Raman
et al. (porous silicates templated by surfactants and organo-
[*] Prof. J. Y. Ying, Dr. C. P. Mehnert, M. S. Wong
Department of Chemical Engineering
Massachusetts Institute of Technology
Cambridge, MA 02139 (USA)
Fax: (‡ 1) 617-258-5766
E-mail: jyying@mit.edu
[**] A list of abbreviations is provided in the Appendix.
sition metal oxide (TMS) family),[6] Behrens (mesoporous
transition metal oxides),[7] Zhao et al. (aluminosilicate MCM-
41),[8] and Sayari (catalytic applications of MCM-41).[9] Here
we review the current state of mesoporous materials research
from the standpoint of compositional control. The synthesis of
not only (alumino)silicate M41S materials but also transition
metal doped and pure transition metal oxide mesoporous
materials is addressed. After discussion of the major synthesis
routes and mechanisms of formation, the applications of these
materials are surveyed, with particular emphasis on hetero-
geneous catalysis.
Inorganic solids that contain pores with diameters in the
size range of 20 ± 500 Š are considered mesoporous materials,
according to IUPAC definition. Examples of mesoporous
materials include M41S, aerogels, and pillared layered struc-
tures, as listed in Table 1.[10] In this paper, we will focus only on
ªmesoporous materialsº that have been prepared by supra-
molecular templating, such as M41S. The demarcation at 20 Š
between the micropore and mesopore regimes is convenient,
in that all zeolites and related zeotypes are microporous;
however, some types of the supramolecular-templated struc-
tures can be microporous (see Section 2.4). Mesoporous
materials derived by means of surfactant templating are
occasionally called ªzeolitesº and described as ªcrystallineº
materials in reference to their long-range ordering of the pore
packing. Such references are not correct, as the pore walls of
these materials are amorphous and lack long-range order.

Angew. Chem. Int. Ed. 1999, 38, 56 ± 77  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 1433-7851/99/3801-0057 $ 17.50+.50/0 57
REVIEWS J. Y. Ying et al.

Table 1. Pore-size regimes and representative porous inorganic materials.

Pore-size Definition Examples Actual size range
regimes
macroporous > 500 Š glasses > 500 Š
mesoporous 20 ± 500 Š aerogels > 100 Š
pillared layered clays 10 Š, 100 Š[a]
M41S 16 ± 100 Š
microporous < 20 Š zeolites, zeotypes < 14.2 Š
activated carbon 6Š

[a] Bimodal pore-size distribution. Scheme 1. Schematic representation of the general formation of MCM-41
from inorganic precursors and organic surfactants.

2. Mechanisms of Mesostructure Formation

There have been a number of models proposed to explain
the formation of mesoporous materials and to provide a
rational basis for the various synthesis routes. On the most
common level, these models are predicated upon the presence
of surfactants in a solution to guide the formation of the
inorganic mesostructure from the solubilized inorganic pre-
cursors (Scheme 1). Surfactants contain a hydrophilic head
group and a long hydrophobic tail group within the same
molecule and will self-organize in such a way as to minimize
contact between the incompatible ends. How the inorganic
precursor interacts with the surfactant is the issue whereby the
models diverge; the type of interaction between the sur-
factant and the inorganic precursor will be seen as a significant
difference among the various synthesis routes, the formation
models, and the resulting classes of mesoporous materials.

Jackie Y. Ying was born in Taiwan

and raised in Singapore. She grad-
uated summa cum laude from The
Cooper Union in 1987, and com-
pleted her Ph.D. degree as an AT&T
Bell Laboratories Scholar at Prince-
ton University in 1991. She was a
NSF-NATO Postdoctoral Fellow
and Alexander von Humboldt Re-
search Fellow at the University of
Saarland with Prof. H. Gleiter, and
she currently holds the St. Laurent J. Y. Ying C. P. Mehnert M. S. Wong
Associate Professorship at the
Chemical Engineering Department
of the Massachusetts Institute of Technology. Her research is focused on the synthesis of nanostructured inorganic materials
for catalytic, membrane, and advanced ceramic applications. She is the author of over eighty publications, and the recipient
of the American Ceramic Society Ross C. Purdy Award, David and Lucile Packard Fellowship, National Science
Foundation and Office of Naval Research Young Investigator Awards, Camille Dreyfus Teacher-Scholar Award, Royal
Academy of Engineering ICI Faculty Fellowship, and American Chemical Society Faculty Fellowship Award in Solid-State
Chemistry. She serves on the Board of Directors of the Alexander von Humboldt Association of America as well as the
editorial boards of several journals.

Christian P. Mehnert studied chemistry at the Technische Universität München (1985 ± 1992). During this time he carried
out research with Dr. D. OHare at Oxford University (1990) and Prof. J. Lewis at Cambridge University (1991), before he
completed his research thesis which focused on the synthesis of new aminocarbyne complexes of chromium with Prof. W. A.
Herrmann and Prof. A. C. Filippou (1992). He then moved to England, where he became a graduate student at Oxford
University with Prof. M. L. H. Green to work on the synthesis of new organometallic complexes with metal vapor synthesis
techniques and the investigation of the reaction chemistry of highly Lewis acidic perfluorinated borane complexes. After
receiving his doctorate (D.Phil.) as a student at Balliol College (1996), he moved to the United States and joined Prof. J. Y.
Yings laboratory at the Massachusetts Institute of Technology as a postdoctoral research associate. The area of his current
research is the synthesis and application of new nanostructured materials for catalysis, with a special focus on the
incorporation of organometallic catalysts into mesoporous molecular sieves.

Michael S. Wong is a Ph.D. student in Chemical Engineering at the Massachusetts Institute of Technology. He received a
B.S. degree in Chemical Engineering from the California Institute of Technology (1990 ± 1994) and a M.S. degree in
Chemical Engineering Practice from the Massachusetts Institute of Technology (1997). His research interests include the
synthesis and characterization of nanostructured zirconia-based material for acid catalytic applications.

58 Angew. Chem. Int. Ed. 1999, 38, 56 ± 77

Mesoporous Materials REVIEWS
2.1. Pure Silicate Composition far below the critical micelle concentration (CMC) required
for hexagonal LC formation.[12] This mechanistic pathway was
2.1.1. Liquid Crystal Templating Mechanism shown possible recently under different synthesis conditions
(see Section 2.1.5).
The original M41S family of mesoporous molecular sieves
The second mechanistic pathway of LCT was vaguely
was synthesized, in general, by the combination of appropri-
postulated as a cooperative self-assembly of the ammonium
ate amounts of a silica source (e.g. tetraethylorthosilicate
surfactant and the silicate precursor species below the CMC.
(TEOS), Ludox, fumed silica, sodium silicate), an alkyltrime-
It has been known that no preformed LC phase was necessary
thylammonium halide surfactant (e.g. cetyltrimethylammoni-
for MCM-41 formation but, to date, the actual details of
um bromide (CTAB)), a base (e.g. sodium hydroxide or
MCM-41 formation have not yet been fully agreed upon.
tetramethylammonium hydroxide (TMAOH)), and water.
Several mechanistic models have been advanced which share
Aluminosilicate M41S was synthesized by the addition of an
the basic idea that the silicate species promoted LC phase
aluminum source to the synthesis mixture. The mixture was
formation below the CMC.
aged at elevated temperatures ( 100 8C) for 24 to 144 hours,
which resulted in a solid precipitate. The organic ± inorganic
mesostructured product was filtered, washed with water, and
air-dried. The product was calcined at about 500 8C under a 2.1.1.1. Silicate Rod Assembly
flowing gas to burn off the surfactant, to yield the mesoporous Davis and co-workers[13] found that the hexagonal LC phase
material. did not develop during MCM-41 synthesis, based on in situ 14N
A ªliquid crystal templatingº (LCT) mechanism was NMR spectroscopy. They proposed that, under the synthesis
proposed by the Mobil researchers, based on the similarity conditions reported by Mobil, the formation of MCM-41
between liquid crystalline surfactant assemblies (i.e., lyotrop- began with the deposition of two to three monolayers of
ic phases) and M41S.[1] The common traits were the meso- silicate precursor onto isolated surfactant micellar rods
structure dependence on the hydrocarbon chain length of the (Scheme 3). The silicate-encapsulated rods were randomly
surfactant tail group,[11] the effect of variation of the surfactant
concentrations, and the influence of organic swelling agents.
With MCM-41 (which has hexagonally packed cylindrical
mesopores) as the representative M41S material, two mech-
anistic pathways were postulated by the Mobil researchers
(Scheme 2):
1) The aluminosilicate precursor species occupied the space Scheme 3. Assembly of silicate-encapsulated rods (adapted from
between a preexisting hexagonal lyotropic liquid crystal ref. [13]).
(LC) phase and deposited on the micellar rods of the LC
phase. ordered, eventually packing into a hexagonal mesostructure.
2) The inorganics mediated, in some manner, the ordering of Heating and aging then completed the condensation of the
the surfactants into the hexagonal arrangement. silicates into the as-synthesized MCM-41 mesostructure.
In either case, the inorganic components (which were
negatively charged at the high pH values used) preferentially
interacted with the positively charged ammonium head
2.1.1.2. Silicate Layer Puckering
groups of the surfactants and condensed into a solid,
continuous framework. The resulting organic ± inorganic Instead of the formation of silicate-covered micellar rods,
mesostructure could be alternatively viewed as a hexagonal Steel et al.[14] postulated that surfactant molecules assembled
array of surfactant micellar rods embedded in a silica matrix; directly into the hexagonal LC phase upon addition of the
removal of the surfactants produced the open, mesoporous silicate species, based on 14N NMR spectroscopy. The silicates
MCM-41 framework. It is now known that pathway 1 did not were organized into layers, with rows of the cylindrical rods
take place because the surfactant concentrations used were intercalated between the layers (Scheme 4). Aging the

Scheme 2. Two possible

pathways for the LCT
mechanism.[1b]

Angew. Chem. Int. Ed. 1999, 38, 56 ± 77 59

REVIEWS
Scheme 4. Puckering of silicate layers in the direction shown (adapted
from ref. [14]).
mixture caused the layers to pucker and collapse around the
rods, which then transformed into the surfactant-containing
MCM-41 hexagonal-phase mesostructure.
2.1.1.3. ªCharge Density Matchingº
A ªcharge density matchingº mechanistic model was
proposed by Monnier et al.[15] and Stucky et al.[16] and
suggested that MCM-41 could be derived from a lamellar
phase. The initial phase of the synthesis mixture was layered
(as detected by X-ray diffractometry (XRD)), and was
formed from the electrostatic attraction between the anionic
silicates and the cationic surfactant head groups (Scheme 5).
Scheme 5. Curvature induced by charge density matching.[15] The arrow
indicates the reaction coordinate.
As the silicate species began to condense, the charge density
was reduced. Accompanying this process, curvature was
introduced into the layers to maintain the charge density
balance with the surfactant head groups, which transformed
the lamellar mesostructure into the hexagonal mesostructure.
2.1.1.4. ªFolding Sheetsº
The lamellar-to-hexagonal phase motif also appeared in
materials called FSM prepared from the intercalation of the
ammonium surfactant in kanemite, a type of hydrated sodium
silicate composed of single-layered silica sheets.[17] After the
surfactants were ion-exchanged into the layered structure, the
silicate sheets were thought to fold around the surfactants and
condense into a hexagonal mesostructure (Scheme 6). The
60
J. Y. Ying et al.
Scheme 6. Folding of silicate sheets around intercalated surfactant mole-
cules.[17b] a) Ion exchange, b) calcination.
final product was claimed to be very similar to MCM-41, with
no resemblance to the original kanemite structure. However,
Vartuli et al.[12] found that the layered structures were still
retained in the kanemite-derived mesoporous materials.
2.1.1.5. ªSilicatropic Liquid Crystalsº
Under synthesis conditions that prevented condensation of
the silicate species, such as low temperatures and high pH
( 14), a true cooperative self-assembly of the silicates and
surfactants was found possible. Firouzi et al.[18] conclusively
showed, through 2H and 29Si NMR spectroscopy, and neutron
scattering, that a micellar solution of CTAB transformed to a
hexagonal phase in the presence of silicate anions; this was
consistent with the effect of electrolytes on micellar phase
transitions.[19] The silicate anions ion-exchanged with the
surfactant halide counterions, to form a ªsilicatropic liquid
crystalº (SLC) phase that involved silicate-encrusted cylin-
drical micelles (Scheme 7). The SLC phase exhibited behavior
Scheme 7. Formation of a silicatropic liquid crystal phase.[18]
very similar to typical lyotropic systems, except that the
surfactant concentrations were much lower and the silicate
counterions were reactive.[20] Heating the SLC phase caused
the silicates to condense irreversibly into MCM-41.
Firouzi and co-workers[18, 20] also demonstrated that in
addition to the charge balance requirement (i.e., electrostatic
interaction) there was preferential bonding of the ammonium
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
Mesoporous Materials REVIEWS
head group to multi-charged D4R (double four-ring,
[Si8O20]8ÿ) silicate anions under the high pH conditions. The
interaction was so strong that an alkyltrimethylammonium
surfactant solution could force a silicate solution that did not
contain D4R oligomers to re-equilibrate and form D4R
species. It was suggested that this behavior came from the
closely matched projected areas of a D4R anion and an
ammonium head group (0.098 nm2 vs. 0.094 nm2) and the
correct distribution of charges on the projected surfaces.
Fyfe and Fu[21] were able to prepare mesostructured
silicates with D4R silicates. Combination of the D4R pre-
cursors with cetyltrimethylammonium chloride (CTAC) sur-
factants produced mesostructured precipitates. Control of the
condensation of the silicates within the mesostructure by
acidic vapor treatment led to the observation of cubic,
lamellar, and hexagonal phases as intermediate transforma-
tion phases (see Section 2.1.3).

2.1.1.6. Silicate Rod Clusters

The previous theories have regarded the formation of
MCM-41 as a series of events that occur homogeneously
throughout an aqueous solution. Recent work has shown that
MCM-41 might be formed heterogeneously. Regev[22] found
evidence for MCM-41 intermediate structures in the form of Figure 1. Schematic representation of the various types of inorganic ±
clusters of rodlike micelles ªwrappedº by a coating of silicate surfactant head group interactions: electrostatic: a) S‡Iÿ, b) SÿI‡,
c) S‡XÿI‡, and d) SÿM‡Iÿ ; hydrogen bonding: e) S0I0 and f) N0I0 ; and
through low-temperature transmission electron microscopy covalent bonding: g) SÿI.
(TEM) and small-angle X-ray scattering. The clusters of
elongated micelles were found before precipitation occurred.
As the reaction progressed, Regev proposed, the silicate
species diffused to and deposited onto the individual surfaces
of the micelles within the cluster; the clusters of elongated
micelles eventually became clusters of silicate-covered mi-
celles. Thus, the clusters of micelles served as nucleation sites
for MCM-41 formation.

2.1.2. Generalized Liquid Crystal Templating Mechanism:

Electrostatic Interaction
A generalized mechanism of formation based on the
specific type of electrostatic interaction between a given
inorganic precursor I and surfactant head group S was
proposed by Huo and co-workers.[23] Based on the nomencla-
ture, pathway 2 of the original LCT mechanism (Scheme 2),
which involved anionic silicate species and cationic quater-
nary ammonium surfactant, could be categorized as the S‡Iÿ
pathway. By extension, the other charge-interaction pathways
are SÿI‡, S‡XÿI‡ (Xÿ is a counteranion), and SÿM‡Iÿ (M‡ is a
metal cation). This classification system is useful, especially
when other types of inorganic ± organic interactions are
considered (Figure 1). The success of the cooperative tem-
plating model, referred to here as the generalized LCT
mechanism (Scheme 8), was illustrated by the diverse com-
positions of organic ± inorganic mesostructures found possible
(see Section 2.3.1). As for silicate mesostructures, Huo and
co-workers[23] found them possible through the S‡XÿI‡ path-
way. By operating below the isoelectric point of silica (pH  2) Scheme 8. Cooperative templating of the generalized LCT mechanism.[23b]
under acidic conditions, the silicate species were cationic (I‡). a) Cooperative nucleation; b), c) liquid crystal formation with molecular
The same ammonium surfactant S‡ could be used as a inorganic compounds; d) inorganic polymerization and condensation.

Angew. Chem. Int. Ed. 1999, 38, 56 ± 77 61

REVIEWS
templating agent but the halide counteranion Xÿ became
involved through this pathway as it served to buffer the
repulsion between the I‡ and S‡ by means of weak hydrogen-
bonding forces. The resulting materials are known as ªacid-
prepared mesostructuresº or APM materials.
2.1.3. Formation of Non-Hexagonal Mesophases
There are two synthesis routes for the derivation of silicate
mesoporous molecular sieves of various mesophases: the
basic route (S‡Iÿ) and the acidic route (S‡XÿI‡). Synthesized
in basic medium, the M41S family is made up of three well-
defined mesostructures: MCM-41, MCM-48, and MCM-50[24]
(Table 2, Figure 2). MCM-41 has a hexagonally packed array
Table 2. Mesophases of silicate molecular sieves and governing synthesis
parameters.
Name Mesophase Space group Parameter
MCM-41[1, 24] hexagonal[a] p6m [surfactant]/[Si] < 1
MCM-48[1, 24] cubic Ia3Åd [surfactant]/[Si] ˆ 1 ± 1.5
MCM-50[1, 25] lamellar p2 [surfactant]/[Si] ˆ 1.2 ± 2
SBA-1[23, 26] cubic Pm3Ån g ˆ 1/3[b]
SBA-2[29] hexagonal[c] P63/mmc g < 1/3[b]
SBA-3[26] hexagonal[a] p6m g ˆ 1/2[b]
[a] Two-dimensional array. [b] g ˆ V/a0l. [c] Three-dimensional array.
Figure 2. Illustrations of mesoporous M41S materials: a) MCM-41,
b) MCM-48, and c) MCM-50.[3]
of noninterconnecting cylindrical pores. The structure of
MCM-48 belongs to the cubic space group Ia3Åd. The structure
can be thought of as two intertwined networks of spherical
cages separated by a continuous silicate framework. MCM-50
contains a lamellar structure in the uncalcined form; a
mesoporous pillared layered material results when the
surfactant is removed after post-treatment with TEOS.[25]
Vartuli et al.[24] found that the surfactant:silicon molar ratio
was the key synthesis parameter that determined the meso-
phase (Table 2). At ratios approaching 2:1, a ªcubic octamerº
structure was formed. The uncondensed material was com-
posed of D4R silicate anions complexed with the surfactant;
this molecular compound further supports the preferential
binding of D4R silicates with ammonium surfactants.
Through the acidic route, APM materials termed SBA have
been synthesized.[26] SBA-1 is cubic (space group Pm3Ån,
Figure 3),[23, 26] but not bicontinuous as in MCM-48 (Ia3Åd);
SBA-3 (space group p6m) is the APM mesostructural
analogue of MCM-41. The acid-derived materials have
thicker pore walls and a framework charge different from
the base-derived mesoporous materials, due to the different
precipitation conditions and charge balance requirements. For
example, the overall framework charge of SBA-3 was slightly
positive and so the surfactant and counterion species (S‡Xÿ)
62
J. Y. Ying et al.
could be removed in
ethanol under reflux. In
contrast, the inorganic
framework of MCM-41
was negatively charged
and the surfactants could
be washed out only with
acidic alcohol under re-
flux.
Another aspect of mes-
ophase formation is the Figure 3. The Pm3Ån cubic phase, in
which the polyhedra represent
manner in which the sur-
micelles.[27]
factant tail groups pack
in the material. Huo
et al.[26] applied the concept of an effective surfactant packing
parameter g (g ˆ V/a0l) used for lyotropic LC phases to the
silicate mesophases.[28] The packing parameter can be used to
predict the phase of a given LC system as a first approx-
imation; it is affected by the overall volume V of the
surfactant, the effective head group area a0 , and the surfactant
chain length l. Huo et al.[29] exploited this concept with the use
of gemini surfactants (two ammonium surfactant molecules
covalently linked through the head groups) to create SBA-2.
The space group of SBA-2 is P63/mmc. Its structure consists of
a hexagonal close-packed (hcp) array of spheres; the spheres
can be thought of as spherical micelles. This structure is not
found in the traditional LC systems. The preparation of
MCM-48 (Ia3Åd) was also demonstrated by adjustment of g
with alcohol addition to the synthesis mixture[30] or with mixed
cationic-anionic surfactants.[31]
2.1.4. Hydrogen-Bonding Interaction
Tanev and Pinnavaia[32] showed that mesoporous silica
could be prepared by the hydrogen-bonding interaction of an
alkylamine (S0) head group and hydroxylated TEOS (I0 ;
Figure 1 e). The materials lacked long-range ordering of pores
and had higher amounts of interparticle mesoporosity,
because the long-range effects of the electrostatic interaction
that would normally control the packing of micellar rods were
absent. This neutral templating synthesis route produced
mesoporous silicates with thicker walls and higher thermal
stability compared to the LCT-derived silicates.[33] The silicate
framework in the resulting mesophase was neutrally charged,
so the surfactants could be removed by solvent extraction.
Tanev and Pinnavaia[34] further exploited the S0I0 route by the
use of double-headed alkylamines (a,w-dialkylamine) to
create porous lamellar mesostructures.
Another hydrogen-bonding synthesis route used surfac-
tants with a polyethylene oxide head group (Figure 1 f).[35]
Because the length of the head group and that of the tail
group could be adjusted, pores as large as 58 Š could be
synthesized without the use of swelling agents. The poly-
ethylene oxide head group is nonionic (N0), unlike the amine
head group (S0) which is uncharged and can be ionized. The
nonionic route (N0I0) seemed to provide greater pore ordering
than the neutral route (S0I0), but still lacked long-range
hexagonal packing order. The pores were more ªwormlikeº
than rodlike cylinders.
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
Mesoporous Materials
2.1.5. True Liquid Crystal Templating Mechanism
By operating in the liquid crystal phase region of a
polyethylene oxide surfactant solution, Attard et al.[36]
showed that monolithic mesoporous silicates could be pre-
pared. Tetramethylorthosilicate (TMOS) was gelled in the LC
solution with removal of the LC-destabilizing methanol, to
produce a hexagonal mesophase; the Ia3Åd and layered phases
were found possible also, depending on the chain length of the
tail group. This synthesis approach could be considered a true
LCT route, which supports the viability of pathway 1 of the
originally proposed LCT mechanism for MCM-41
(Scheme 2).[1b] In this method of preparation, the organic ±
inorganic interaction was less important than the actual
presence of a LC phase. Göltner and co-workers[37] showed
that amphiphilic diblock copolymers (with a polyethylene
oxide head group and a polystyrene tail group) could also be
used as templates to create crack-free monoliths of meso-
porous silica.
2.1.6. Formation of Other Mesophases
Mesoporous silicates with pore systems not as well-defined
as those of the M41S and SBA materials could result when an
additional salt is added to the synthesis mixture. The structures
of these materials deviate from the ideal hexagonal pore
packing of MCM-41, as detected through XRD and TEM. The
long-range ordering of the materials is not definitive proof for
ªbetterº materials, however. McGrath et al.[38] showed that a
ªspongeº phase (L3) of mesoporous silicates could be induced
by the use of cetylpyridinium bromide surfactant, hexanol co-
surfactant, sodium chloride, and water as precursors. After the
addition of TMOS and aging, the solution gelled into a
monolithic form. The L3 phase exists in lyotropic surfactant
solutions but has no long-range ordering (Figure 4). Because
of the special characteristics of the L3 phase (which can be
thought of as a random, bicontinuous cubic phase), the pore
volume of the material could be controlled simply with the
amount of water in solution, and surfactant removal was not
required for mesoporosity.
Figure 4. The silicate framework separates the water from the surfactants
in the L3 phase.[38]
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
REVIEWS
In another approach, Ryoo and co-workers[39] added ethyl-
enediaminetetraacetic acid (EDTA) to a high pH synthesis
mixture, to create a hydrothermally stable mesoporous
silicate with a highly branched network of pores similar to
the L3 surfactant phase (termed KIT-1). It was proposed that
the EDTA polyacid salt caused the transformation of the
hexagonal phase to the L3-like mesophase.[39] For these
disordered mesoporous materials, at least one strong XRD
peak could still be detected in the low-angle region.
2.2. Doped Silicate Compositions
The interest in doping mesoporous silicates with metals lies
primarily in the development of catalytically active materials.
The incorporation of a metal is seemingly straightforward in
light of the various mechanistic pathways, but the amount of
dopant incorporation, the reproduction of the mesophase that
is obtained in the pure silica system and the stability of the
resulting mesoporous material cannot be predicted. In the
original Mobil recipe, tetrahedrally coordinated aluminum
atoms could be substituted isomorphously for silicon atoms in
the MCM-41 framework as in the case for zeolites, but the
degree of substitution depended on the aluminum precursor
and method of preparation.[40, 45] The highest amount of
aluminum that could be incorporated into the framework
without formation of octahedrally coordinated aluminum
(which does not belong to the framework) was reported to be
about 9 mol %.[45] Fu et al.[46] reported the incorporation of up
to 50 mol % Al into MCM-41 by means of special alumino-
silicate ions ([Al4Si4(OH)8O12]4ÿ) with a similar cubelike
structure as D4R silicates; however, the resulting materials
showed little resemblance to MCM-41 and dealumination was
reported. Ryoo et al.[40] showed that aluminum could be
added to the synthesis mixture and be incorporated into
MCM-41 even after the precipitation of the pure mesostruc-
tured silicate.
There are numerous reports that concern the doping of
MCM-41 with a variety of metals (Table 3); the doped MCM-
41 materials have been primarily used for catalytic applica-
tions (see Section 3.1). The amorphous silicate framework of
MCM-41 could accept metal dopants other than aluminum
but beyond a certain limit, the stability of the calcined
material would become affected. Thus, the reported levels of
doping for calcined MCM-41 were usually low, at most 1 ±
2 mol %. The small amounts of metals that could be incorpo-
rated contrasted that of aluminum, probably due to the ease
of substitution of the latter (which has a similar cation size and
same coordination state as Si) into the silicate framework.
Tuel and Gontier[52] showed that much higher loadings of
tetrahedrally coordinated trivalent metal cations were possi-
ble through the ªneutralº S0I0 route, rather than the electro-
static approach. The incorporation levels were apparently
highly dependent on the synthesis route and sensitive to the
pH of the synthesis mixture. Most doped MCM-41 materials
were prepared under basic pH conditions (S‡Iÿ), whereas one
set was prepared under acidic conditions (S‡XÿI‡)[56] with low
incorporation levels (Table 3). In contrast, Wong et al. showed
that MCM-41 type materials could be doped with very high
63
REVIEWS J. Y. Ying et al.

Table 3. Reports of dopant incorporation in silicate M41S materials. as the metal precursor since, like other transition metal
Authors Metal Si/dopant Synthesis alkoxides, it is highly reactive in the presence of water. Left
dopant molar ratio route[a] uncontrolled, titanium alkoxide would react and form an
Beck et al.[1b] Al 15 S‡Iÿ insoluble titanium oxide gel precipitate. Antonelli and Ying
Corma et al.[41] Ti 56 S‡Iÿ reasoned that if the hydrolysis and condensation rates were
Reddy et al.[42] V 60 S‡Iÿ controlled with a chelating agent such as acetylacetone,
Tanev et al.[43] Ti 100[b] S0I0
titanium isopropoxide could form mesostructured titania in
Sayari et al.[44] B 6.25[b] S‡Iÿ
Luan et al.[45] Al 10 S‡Iÿ the presence of a surfactant solution.[63] This ªmodified sol ±
Fu et al.[46] Al  1[b] S‡Iÿ gel methodº was successful in yielding the mesoporous
Zhao, Goldfarb[47] Mn 11 S‡Iÿ materials, with the resulting product characterized with
Abdel-Fattah, Pinnavaia[48] Sn 99 S0I0 XRD, nitrogen adsorption and TEM. Surfactants with head
Cheng et al.[49] Ga 30 S‡Iÿ
groups that could interact with the titanium alkoxide led to
Cheng, Klinowski[50] Ga, Al 57, 57 S‡Iÿ
Koyano, Tatsumi[51] Ti 80 S‡Iÿ (MCM-48) titania mesostructures, and the phosphate surfactants were
Tuel, Gontier[52] Al 6 S0I0 preferred for their thermal stability to 100 8C during aging.
Ga 31 S0I0 The resulting mesoporous materials were termed TMS1 (Tech
Fe 55 S0I0
molecular sieves). Though not quite as well-defined in its
B 17 S0I0
Tuel et al.[53] Zr 17 S0I0 long-range hexagonal packing order as the MCM-41 silicates,
Ulagappan, Rao[54] Cr 30[b] S‡Iÿ Ti-TMS1 still possessed a narrow pore-size distribution and a
Zhang, Pinnavaia[55] Ti 50[b] S‡Iÿ (MCM-48) high surface area of about 200 m2 gÿ1.
Cr 50[b] S‡Iÿ (MCM-48)
V 50[b] S‡Iÿ (MCM-48)
Zhang et al.[56] Ti 277, 76 S‡XÿI‡, S0I0
2.3.3. Ligand-Assisted Templating: Covalent Interactions
V 434, 131 S‡XÿI‡, S0I0
Cr 163, 70 S‡XÿI‡, S0I0 In a different synthesis approach, our laboratory has
Mn 3332, 118 S‡XÿI‡, S0I0
Mo 95, 199 S‡XÿI‡, S0I0
successfully derived mesoporous niobium oxide (Nb-TMS1)
Echchahed et al.[57] Fe 40 S‡Iÿ (MCM-48) and tantalum oxide (Ta-TMS1) molecular sieves without the
He et al.[58] Fe 52 S0I0 addition of chelating agents.[64±66] Instead of relying on charge
Jones et al.[59] Zr 25 S‡Iÿ interaction, the surfactants were pretreated with the metal
Zhang, Ying[60] Nb 10 S‡Iÿ
alkoxides in the absence of water to form metal-ligated
Wong et al.[61] Zr 5 S‡XÿI‡
surfactants. The highest quality materials came from the use
[a] MCM-41 structure, unless otherwise noted. [b] Molar ratio values of of amine surfactants, due to the strong affinity for nitrogen ±
precursor mixture, not of calcined materials.
metal bond formation between the surfactant head group and
loadings of zirconium ( 17 mol %) through the S‡XÿI‡ the niobium or tantalum alkoxide precursor. Upon addition to
route.[61] Zhang and Ying[60] found that up to 10 mol % Nb the alkoxide ± surfactant solution, water acted as both a
could be introduced into MCM-41 at high pH, which could solvent and a reactant, to initiate surfactant self-assembly and
then be used to anchor amine-substituted porphyrin mole- alkoxide hydrolysis/condensation, respectively. In this ligand-
cules[151] (see Section 3.3). assisted templating (LAT) approach, control of mesostructure
phases was found possible by adjustment of the metal/
surfactant ratio, and led to a family of mesoporous transition
2.3. Non-Silicate Compositions metal oxides analogous to the M41S family of aluminosilicates
(Table 4).
2.3.1. Generalized Liquid Crystal Templating MechanismÐ Table 4. Mesophases of niobium oxide molecular sieves.
Early Efforts
Name Mesophase Space group Parameter
The first foray into mesostructured materials of non-silicate Nb-TMS1[64] hexagonal[a] p6m [surfactant]/[Nb] < 1.25
compositions started with the generalized LCT mechanism of Nb-TMS2[65] hexagonal[b] P63/mmc [surfactant]/[Nb] ˆ 1.5
Huo and co-workers.[23] Mesostructured oxides were found Nb-TMS3[65] cubic Pm3Ån [surfactant]/[Nb] ˆ 1[c]
possible for such metals as Sb, Fe, Zn, Pb, W, and Mo.[23, 62] Nb-TMS4[65] lamellar p2 [surfactant]/[Nb] ˆ 2
However, most mesophases were layered and did not yield [a] Two-dimensional array. [b] Three-dimensional array. [c] Prepared by
porous materials when the surfactants were removed. The few vapor diffusion of water into synthesis mixture.
hexagonal phases derived underwent mesostructure collapse
upon surfactant removal (either by solvent extraction or by Our laboratory has also extended the LAT approach to
calcination) probably due to the lack of complete condensa- synthesize mesoporous zirconium oxide, Zr-TMS.[67] Zr-TMS
tion of the inorganic framework. was derived with very high surface areas (as high as
560 m2 gÿ1) from zirconium n-propoxide and phosphate sur-
factant, though not with a well-defined mesoporous phase.
2.3.2. A Modified Sol ± Gel Method
Wong and Ying were able to show that surface areas, pore
Our laboratorys initial research efforts led to the first sizes, and pore volumes could be controlled in accordance
reported synthesis of mesoporous transition metal oxides.[63] with the chain lengths of templating alkylphosphate mole-
Mesoporous titanium oxide was obtained with titanium ethoxide cules (for carbon number n ˆ 4 ± 16).[68] As in the case of Ti-

64 Angew. Chem. Int. Ed. 1999, 38, 56 ± 77

Mesoporous Materials
TMS1, some phosphate head groups remained in the material
after calcination, which could be exploited for acid catalysis
(see Section 2.3.4.3). The interactions between zirconium alk-
oxide and various anionic and nonionic amphiphiles were
explored;[68] the covalency of the interaction was deduced
from NMR spectroscopic studies and the templating of Zr-
TMS by short-chained amphiphilic molecules (see Section 2.4).
2.3.4. Other Compositions
Before we developed the modified sol ± gel and LAT routes,
we too began with the electrostatic approach in the attempt to
prepare mesoporous transition metal oxides. Many of our
attempts resulted in non-mesostructured amorphous oxides,
in spite of the careful control of pH, aging temperature and
period, and choice of metal-surfactant ratios and precursor
salts. The generalized LCT mechanism could be used to
explain the formation of mesostructures but, unfortunately it
could not be used a priori to predict mesostructure formation,
given a metal salt and a surfactant precursor.
For many mesostructured metal oxides prepared through
an electrostatic approach via the generalized LCT pathway,
the isolated mesostructured products were uncondensed
transition metal salts and were unstable upon surfactant
removal. Stein et al.[69] found this to be the case for tungstate
([H2W12O40]6ÿ) and niobotungstate ([NbxW6ÿxO19](2‡x)ÿ, x ˆ
2 ± 4) Keggin ions, as did others, including Janauer et al.[70]
(W, Mo, V) and Luca and co-workers[71] (V). Suib and co-
workers found that mesoporous manganese oxides (termed
MOMS) could be synthesized by adjustment of the oxidation
state of the Mn-containing precursor.[72, 73] The pore structure
of the resulting materials was less well-defined after calcina-
tion than that of mesoporous MCM-41 and TMS1. Interest-
ingly, the framework walls were crystalline, and the material
exhibited semiconducting properties.
2.3.4.1. Alumina
Bagshaw and Pinnavaia[74] used polyethylene oxide surfac-
tants in the N0I0 nonionic route to template mesoporous
alumina (termed MSU). The materials contained wormlike
pore channels with surface areas of greater than 400 m2 gÿ1.
Vaudry et al.[75] synthesized mesoporous alumina with higher
surface areas (710 m2 gÿ1). Carboxylate surfactants were used
as the templates but the average pore sizes could not be
tailored by variation of surfactant chain lengths; an LCT
mechanism (SÿI‡ pathway) was not apparent. Yada et al.[76]
found that careful control of pH led to the preparation of
mesoporous alumina (with the retention of the main XRD
peak) by the SÿI‡ route.
2.3.4.2. Aluminophosphates and Vanadophosphates
There have been attempts to extend the surfactant templat-
ing synthesis technique to aluminophosphates. Lamellar
aluminophosphates were prepared.[77, 78] Vesicular templating
of the inorganic components was proposed to explain the
formation of inorganic ± organic bilayers organized as cylin-
ders,[79] and particles patterned like exoskeletons of radio-
larian organisms.[80]
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
REVIEWS
Fluoride ions were used in the synthesis mixture as
mineralizing agents by Feng et al.[81] to produce layered,
hexagonal, and cubic phases of aluminophosphates. The
mesostructures were unstable to calcination, however. Hex-
agonally packed mesoporous aluminophosphates were ob-
tained by Zhao et al.[82] by the use of TMAOH to carefully
control the pH. Chakraborty et al.[83] were able to substitute
silicon atoms into mesostructured aluminophosphates, where
upon calcination, mesoporous silicoaluminophosphates were
obtained.
Vanadium phosphorus oxides (VPO) are useful as selective
oxidation catalysts, and mesoporous VPO synthesis has been
attempted by several groups.[84, 85] Mesostructured VPO
materials were found possible, but accounts on surfactant
removal either indicated collapse of the mesostructure[84] or
provided insufficient information on the mesoporosity.[85]
2.3.4.3. Zirconia
Zirconium oxide is an interesting material catalytically and
much effort has been devoted to the generation of a
mesoporous form. Hudson and Knowles[86] used alkyltrime-
thylammonium halide to template zirconium hydroxide to
produce pure zirconia with a high surface area. The templat-
ing effect was not seen in this synthesis, which resulted in
broad pore-size distributions. A ªscaffoldingº mechanism was
proposed in which the occluded surfactant basically acted as a
filler to prevent the zirconia framework from collapsing
during heat treatment. Reddy and Sayari[87] found that a
zirconium oxide mesostructure could be produced with
zirconium sulfate as the inorganic precursor in a S‡XÿI‡
synthesis route. The material was found to collapse upon
calcination. Ciesla et al.[88] and Liu et al.[89] found that by ion-
exchanging the occluded sulfate counteranions with phos-
phates, a microporous zirconium oxo-phosphate could be
obtained. Ciesla et al.[88] also found that a microporous
zirconium oxide stabilized with sulfates could be produced
by use of a different precursor, for example a zirconium n-
propoxide at low pH. A microporous oxide form of hafnium, a
heavier congener of zirconium, was derived similarly.[90]
Pure zirconium oxide is a weakly acidic catalyst and is not
useful for reactions that demand strong acidity. To increase
acidic strength, modification of the pure zirconium oxide with
anions or metal dopants is required. Mesoporous phosphated
zirconium oxide, a moderately acidic material, was prepared
through a one-pot synthesis with zirconium n-propoxide and
alkylphosphates.[67, 68] The phosphate groups that remained
after calcination enhanced the thermal stability (as in the case
of microporous zirconium oxo-phosphates), and increased the
acidic strength of the zirconia framework.
2.3.4.4. Metal Sulfides
A few examples of mesostructured metal sulfides have been
reported. Stupp and co-workers[91] used a polyethylene oxide
surfactant with a cadmium salt solution to obtain a hexagonal
mesophase. The material was then exposed to hydrogen
sulfide gas, which converted the cadmium salt to cadmium
sulfide. Li et al.[92] derived a lamellar tin sulfide material with
CTAB and tin chloride as precursors, and sodium sulfide as
65
REVIEWS
the reducing agent. Surfactant removal was not possible from
the CdS materials and probably not possible from the SnS2
layered mesostructures.
2.3.4.5. Other Examples
Zhao and Goldfarb[93] reported the use of non-amphiphilic
compounds to template oxides of magnesium and zinc into
lamellar mesostructures. Disodium chromoglycate and flufe-
namic acid compounds self-assembled into a lyotropic chro-
monic phase and interacted with the metal precursor by
means of S‡Iÿ electrostatic attraction. Self-assembly occurred
with the flat aromatic molecules containing edgewise polar
groups, which differed from the amphiphilic molecules
normally used.
Attard et al.[94] templated platinum salts with the hexagonal
phase of polyethylene oxide surfactants, and reduced the
mesostructure (with hydrazine hydrate or less noble metals)
to give mesoporous platinum metal with an average pore size
of 30 Š. The mesoporous platinum did not possess a long-
range hexagonal packing of the pores.
2.4. Control of Pore Sizes
There is no energetic limitation to the pore sizes possible in
microporous and mesoporous silicates, as shown by Navrotsky
et al.[95] It was found that MCM-41 and zeolites are only
slightly less stable relative to the thermodynamically stable
phase of silica, a-quartz, which suggests that the only
limitation to the synthesis of porous structures is to find the
appropriate kinetic pathways. In this respect, it may be easier
to synthesize amorphous mesoporous MCM-41-like materials
with smaller pores, rather than crystalline microporous
zeolites with larger pores.
Sun and Ying[96] were able to control pore sizes between 5 Š
and 20 Š by the use of short-chain alkylamines as supra-
molecular templates, allowing for systematic bridging of the
mesoporous and microporous regimes. This work demon-
strated for the first time that non-zeolitic microporous
materials (TMS5) could be synthesized by supramolecular
templating of small molecules, and could be composed of pure
niobia. The amphiphilic molecules with a hydrocarbon chain
length of n less than eight are normally too small to self-
assemble in an aqueous solution and would be expected to
behave as molecular templating agents (as in zeolite syn-
thesis). However, the ligand-assisted templating technique
provided a shielding effect by the inorganic components on
the amphiphile head groups in such a way as to favor self-
assembly versus solubilization of the templating agents. Thus,
supramolecular templating was successfully extended to the
systematic synthesis of microporous materials. This approach
was further modified by Sun and Ying to produce micro-
porous Nb-TMS6 with use of a,w-dialkylamines.[97]
The use of short-chained amphiphiles has also led to the
systematic derivation of micropores in zirconium oxide. Wong
and Ying[68] used short-chained alkylphosphates to produce
high surface area porous zirconium oxides modified by
surface phosphate groups.
66
J. Y. Ying et al.
At the other end of the pore-size spectrum, hexagonally
ordered mesoporous silicates with pores as large as 300 Š
(SBA-15) were found possible by researchers at the Univer-
sity of California at Santa Barbara.[98] Nonionic triblock
copolymers (polyethylene oxide/polypropylene oxide/poly-
ethylene oxide) were used under acidic conditions (pH  1),
and the templating was thought to occur through both
electrostatic and hydrogen-bonding interactions.
3. Catalytic Applications
The unique physical properties of MCM-41 have made
these materials highly desirable for catalytic applications. The
extremely high specific surface areas are conducive to high
catalytic activity. The large pore size (relative to that of
microporous zeolites) allows for the fixation of large active
complexes, reduces diffusional restriction of reactants, and
enables reactions involving bulky molecules to take place. In
spite of the one-dimensionality of its pore channels, MCM-41
has been the main focus of catalytic studies (rather than the
other M41S mesoporous structures) because of its ease of
preparation.
The first catalytic studies with mesoporous molecular sieves
focused on metal-substituted MCM-41 materials in which the
active species were incorporated into the silicate matrix. The
reactions studied were mainly oxidation reactions and acid
catalysis. The next stage of development of MCM-41-based
catalysts involved the deposition of heteroatoms onto the
surface of the mesoporous framework. Since then, a wide
variety of applications have been established and the field is
still expanding rapidly. More recently, research has been
devoted to the fixation of catalytically active complexes onto
the walls of the MCM-41 porous framework to combine the
advantages of homogeneous catalysis with a heterogeneous
catalyst support. Although extensive research efforts have
been undertaken to explore the catalytic applications of
modified MCM-41 materials, industrial use has so far been
limited. Only a longer time frame will reveal if commercial
applications of these systems will become feasible.
3.1. Metal-Substituted Mesoporous Molecular Sieves
3.1.1. Oxidation Reactions
Titanium silicate materials with MFI or MEL zeolite
structure types (e.g. TS-1 or TS-2) have been investigated as
olefin epoxidation catalysts.[99] Although zeolites such as TS-1
showed very high catalytic activity and selectivity, they could
only be effective in the oxidation of small molecules. Larger
molecules like cyclohexene were excluded from catalytic
conversion due to the rather small pore size of the TS-1
material (5.3  5.5 Š). Consequently, a considerable amount
of research was dedicated to the preparation of titanium-
containing zeolites with large pores. The synthesis of a
titanium-substituted b zeolite with BEA structure (7.6 
6.4 Š) enabled the epoxidation of long-chain aliphatic olefins.
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
Mesoporous Materials
To catalyze bulkier substrates, it would be critical to develop
molecular sieves with even larger pore sizes.
Soon after the Mobil announcement of the M41S materials,
the synthesis of MCM-41 doped with titanium was reported
simultaneously by two groups. Corma et al.[41] prepared Ti-
MCM-41 with ionic surfactants under hydrothermal condi-
tion, while Tanev et al.[43] synthesized Ti-HMS with neutral
primary amine surfactants in a room-temperature prepara-
tion. Both synthesis procedures led to the incorporation of
catalytically active titanium sites into the mesoporous silicate
matrix without significantly affecting the surface area and
pore size, although the Ti-HMS material contained more
interparticle mesoporosity.
Comparison study[41] of Ti-MCM-41 with Ti-b zeolite and
Ti-ZSM-5 showed a higher catalytic activity for the former in
the epoxidation of norbornene with tert-butyl hydroperoxide
(TBHP) as oxidant. In the evaluation of the Ti-HMS
catalyst,[43] the sterically more demanding substrate 2,6-di-
tert-butylphenol (2,6-DTBP) was investigated. The aromatic
compound was selectively oxidized to the corresponding
quinone with H2O2 . This study further illustrated that Ti-HMS
gave a higher conversion rate than Ti-MCM-41 in the
oxidation of 2,6-DTBP. The authors suggested that due to
the exceptionally high textural mesoporosity of the catalyst,
Ti-HMS has less diffusional limitation than Ti-MCM-41 and
therefore superior catalytic activity for the oxidation of large
organic substrates.
A further study on the selective oxidation of large organic
molecules was undertaken by Reddy et al.[42] By the substi-
tution of vanadium into the porous framework of MCM-41
through hydrothermal synthesis, they were able to prepare a
highly active and selective catalyst for the partial oxidation of
cyclododecane and 1-naphthol with H2O2 as oxidant. The
same group also prepared a vanadium-containing mesoporous
material, V-HMS, by a room-temperature synthesis route.[100]
The resulting catalyst was evaluated for the oxidation of 2,6-
DTBP with either H2O2 or TBHP. Compared to the Ti-HMS
described earlier,[43] the V-HMS material showed higher
catalytic activity for this reaction.
Gontier and Tuel[101] reported the successful application of
transition metal (Ti and V) substituted mesoporous and
microporous molecular sieves for the liquid-phase oxidation
of aniline. Although conventional oxidation catalysts like TS-
1 and ZSM-48 exhibited good activity, the reaction was
limited by pore diffusion of products and reactants in the
zeolites. By the use of ultra-large pore materials like the
doped MCM-41, diffusion limitation was overcome and
higher catalytic activities were observed.
Tuel et al.[53] showed that zirconium-containing mesoporous
MCM-41 could be synthesized with hexadecylamine surfac-
tant and zirconium isopropoxide at room temperature. The
resulting material, designated Zr-MS, showed similar catalytic
activity in the oxidation of aniline as the titanium-containing
mesoporous material. However, it gave higher selectivity for
alcohol in the epoxidation of norbonylene.
An interesting approach was undertaken by Vankelecom
et al.[102] which involved the incorporation of Ti-MCM-41
catalyst into a partially polymerized polymethylsiloxane
matrix. Catalytic results for the epoxidation of cis-cyclooctene
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
REVIEWS
with TBHP suggested an even higher conversion for the
polymer-embedded Ti-MCM-41 than the free catalyst. This
example illustrated that a combination of membrane tech-
nique and materials design could have a significant impact in
the development of future catalyst technology. Although a
variety of MCM-41 materials containing early transition
metals has been prepared and investigated for oxidation
catalysis, their activities were lower than the existing zeolite
systems. In order to make a real impact in the area of
oxidation catalysis, new systems must be as active as TS-1
materials while providing a mesoporous structure.
3.1.2. Acid-Catalyzed Reactions
The cracking activity and hydrothermal stability of alumi-
num-substituted MCM-41 materials were investigated by
Corma et al.[103] It was shown that the activity of MCM-41
for a reaction catalyzed by strong acid sites, such as n-heptane
cracking, was much lower than that of an ultra-stabilized Y
(USY) zeolite, and similar to that of amorphous aluminosi-
licate. However, in the case of gasoil cracking, the greater
accessibility of the large molecules to acid sites in MCM-41
relative to USY made the difference in activity much smaller
between these two catalysts. In order to simulate fluidized
catalytic cracking conditions, MCM-41 was steam treated. The
resulting material showed a collapse of the porous structure,
and the gasoil cracking activity was greatly diminished. The
steam-treated MCM-41 was a much less active catalyst than
steam-treated amorphous aluminosilicate.
An investigation of the hydrocracking abilities of alumi-
num-substituted MCM-41 for larger size molecules was
carried out by Reddy and Song.[104, 105] Significant catalytic
activity was obtained with 1,3,5-triisopropylbenzene (TIPB),
to form mainly mono- and di-substituted isopropylbenzene. A
conversion as high as 100 % was achieved for the hydro-
cracking of TIPB by loading the MCM-41 aluminosilicate
with platinum metal.
Extensive studies on cracking[106±112] and hydrocracking[113±119]
over MCM-41 were undertaken by the Mobil researchers, but
no commercial use has been established yet. An interesting
approach was described by Degnan et al.[116] that combined
modified MCM-41 materials with zeolites to give a mixed
hydroprocessing catalyst. In this catalyst, MCM-41 provided an
ultra-high surface area supporting the metal components (Ni/
W or Pt) for hydrogenation reactions, while the zeolite provided
the acidic functionality required for cracking. The resulting
catalyst exhibited good activities in both hydrogenation and
cracking, and could be used in fuel hydrocracking processes,
especially where high conversion levels were desired.
An application of aluminum-containing MCM-41 was
reported by Aguado et al.,[120] which showed the conversion
of low-density polyethylene (LDPE) to hydrocarbon feed-
stock. Cracking of polyolefins typically involves solid acid
catalysts, such as amorphous aluminosilicates and zeolites.
Due to the bulky nature of the polymeric feedstock, catalytic
activity has been mainly governed and limited by the catalyst
pore size. Consequently, despite its lower aluminum content,
aluminosilicate MCM-41 was found to be more active for
LDPE cracking than amorphous aluminosilicate, due to its
67
REVIEWS J. Y. Ying et al.

greater mesoporosity. Although the reaction was hindered by CH2OH

OH
its small pore size ( 5.5 Š), ZSM-5 showed the highest OH

activity for the LDPE cracking since, in the earlier reaction

stages, only acid sites located on or near the external surface
were involved. The superior activity of ZSM-5 compared to
MCM-41 was attributed to the higher acid strength of ZSM-5.
However, the product distribution obtained with MCM-41 1 2
consisted of more liquid hydrocarbons in the range of gasoline
and middle distillates with lower aromatic content relative to
amorphous aluminosilicate and ZSM-5. This example showed
quite nicely that even though MCM-41 materials could not O Ph
compete in catalytic activity, they could produce new product
distributions (i.e., favorable selectivity) that could be useful
towards existing processes. 3
The application of aluminosilicate MCM-41 as a catalyst in OH

the production of acetals was reported by Climent et al.,[121] CH2OH

and it represented a good example where the moderate O Ph

acidity and the mesoporous structure of MCM-41 were well
utilized. These acetal compounds are interesting for use in
pharmaceuticals and as fragrances in perfumes and deter-
gents. MCM-41 was shown to be an active and selective 4 5
catalyst for the acetalization of aldehydes. For small aldehyde Scheme 9. Alkylation of 2,4-DTBP with cinnamyl alcohol over alumino-
reactant molecules, zeolites were found to be more active than silicate MCM-41.
mesoporous MCM-41. However, when reactants larger than
7 Š were involved, geometrical constraints did not allow them By introducing titanium into the framework of aluminosi-
to diffuse into the microporous framework of zeolites. The licate MCM-41, a bifunctional catalyst was prepared by
ultra-large pores of MCM-41 made this material more Corma et al.[128] for the conversion of linalool into cyclic
attractive for the acetalization of many fine chemicals. furan and pyran hydroxyl ethers (Scheme 10). The authors
Tetrahydropyranylation of alcohols and phenols represents
a common synthetic tool to protect the hydroxyl functionality
OH
in peptide, nucleotide, carbohydrate and steroid chemistry.
Kloetstra and van Bekkum[122] used aluminosilicate MCM-41 O H
TBHP
as a mild and efficient acid catalyst for the tetrahydropyr-
[Ti]/CH2Cl2
anylation of primary, secondary, and tertiary alcohols and O H
phenols. It was also shown that aluminosilicate MCM-41
provided excellent catalytic activity and selectivity with
respect to bulky substrates like cholesterol, superior to the OH
current commercial heterogeneous aluminosilicate catalysts. OH

The application of aluminosilicate MCM-41 as acid catalyst O

for Friedel ± Crafts alkylation was reported by Armengol
et al.[123] In this study, the bulky substrate 2,4-di-tert-butyl-
phenol (2,4-DTBP, 1) was alkylated with cinnamyl alcohol, to
give a mixture of 3 and 4 together with minor amounts of 5
(Scheme 9). The formation of dihydrobenzopyran 3 was
attributed to an intramolecular ring closure of the primary
cinnamylphenol 2 that arose from the Friedel ± Crafts alkyla-
tion of phenol 1. The formation of 4 and 5 was suggested to be
based on acid-catalyzed dealkylation, which has been fre-
quently observed for tert-butyl-substituted aromatic com-
pounds. MCM-41 was shown to give higher yields of 3 than
conventional catalysis with sulfuric acid or amorphous
aluminosilicate. No reaction occurred over acid faujasites
(HY) and only very little activity was noted for steam-treated
HY zeolite.
Alkylation reactions of naphthalene, paraffin, and benzene
with short- and long-chain olefins were also examined over
MCM-41.[124±127] MCM-41 was found to be less reactive than
ZSM-5 in the synthesis of ethylbenzene, but it yielded more
polyalkylated products than the latter.
O
OH
OH
O
O
Scheme 10. Conversion of linalool into cyclic furan and pyran hydroxyl
ethers with Ti-MCM-41 ([Ti]).
postulated that epoxidation took place over the titanium sites,
and acid-catalyzed intramolecular ring opening of the epoxide
then occurred by the 3-hydroxyl group. The conversion for this
reaction was as high as 80 % with the Ti-MCM-41 material. In
comparison, titanium-modified zeolite b gave somewhat
lower conversion. Although Ti-b zeolite usually exhibited
higher activity than Ti-MCM-41 in epoxidation reactions, Ti-
MCM-41 provided greater activity in this case, possibly due to
increased diffusion of reagents through its larger pores.
Deviating from the typical aluminosilicate compositions,
phosphated mesoporous zirconium oxide (Zr-TMS) was
developed for mild acid catalysis.[67, 68] The Zr-TMS material

68 Angew. Chem. Int. Ed. 1999, 38, 56 ± 77

Mesoporous Materials
was found to be active for the gas-phase double-bond
isomerization of 1-butene at temperatures of 100 ± 350 8C.
The material should also be useful for other types of reactions
that require moderate acidity, and was seen as an improve-
ment over crystalline layered zirconium phosphates for acid
catalytic applications.
3.1.3. Hydroxylation Reactions
The catalytic hydroxylation of benzene to phenol over a
variety of transition metal substituted mesoporous molecular
sieves was reported by Zhang et al.[56] Ti-, V-, Cr-, Mo-, and
Mn-substituted MCM-41 and HMS silicates (with typical
transition metal contents of 0.2 ± 1.5 wt %) were prepared by
electrostatic and neutral templating pathways, and examined
for the peroxide hydroxylation of benzene. All materials were
catalytically active, and in particular the Ti-HMS material
gave  100 % selectivity at low conversion. In a further study
by the same group,[55] transition metal (Ti, V, Cr) substituted
cubic-phased MCM-48 mesoporous silicates were prepared by
hydrothermal synthesis, and successfully applied for the
selective peroxide oxidation of styrene and methyl methacry-
late to benzaldehyde and methyl pyruvate, respectively.
3.1.4. Polymerization Reactions
In a study by Abdel-Fattah and Pinnavaia,[48] tin-substituted
mesoporous silicate was prepared by neutral amine surfactant
assembly of silicon and tin(iv) alkoxides at ambient temper-
ature. The resulting material was successfully applied to
lactide ring-opening polymerization. Sn-HMS yielded higher
conversion than tin-doped silica and pure tin oxide. Com-
pared to homogeneous catalysts, Sn-HMS improved the
average molecular weight and polydispersity of polymers
produced, possibly by imposing steric constraints on the
propagating polymer chain with its ordered pore structure,
and by minimizing ªback-bitingº and intermolecular trans-
esterification reactions.
3.2. Metal-Deposited Mesoporous Silicates
One of the earliest catalytic applications of MCM-41
involved supported NiMo in gasoil hydrocracking.[103] The
molybdenum and nickel components were introduced by the
incipient wetness impregnation technique, followed by calci-
nation. Despite a loading of 12 wt % MoO3 and 3 wt % NiO,
the surface area of the MCM-41 support was only slightly
reduced. The NiMo-MCM-41 catalyst showed a higher
hydrodesulfurization and hydrodenitrogenation activity than
NiMo loaded on USY or amorphous aluminosilicate. The
better performance of NiMo-MCM-41 was attributed to the
mesoporous structure and the high surface area that provided
access to bulky molecules and a high dispersion of active
metal components.
The application of modified MCM-41 material in the
reduction of nitrogen oxides (NOx) from emission gases has
been reported by Beck et al.[129] The molecular sieves were
used as a framework for the deposition of vanadium and
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
REVIEWS
titanium oxides. It was found that the modified MCM-41
material exhibited higher activity for NOx reduction by
ammonia than vanadium oxide and titanium oxide loaded
amorphous silica gel.
Another interesting application of modified MCM-41
material was reported by Kresge et al.[130] for the demetalation
of hydrocarbon feedstock. MCM-41 was loaded with MoO3
and NiO by impregnation. This catalyst showed a high
efficiency for the removal of iron and nickel, and was also
active for arsenic removal and desulfurization.
For the oligomerization of a-olefins, Pelrine and co-work-
ers[131, 132] reported the use of chromium-modified MCM-41
material. The metal component was introduced through
impregnation, followed by calcination to give chromia-loaded
MCM-41. Prior to polymerization experiments, the material
was activated by carbon monoxide to reduce the chromium to
a lower valence state. Oligomerization of 1-decene over this
catalyst produced a wide variety of lubricants with higher
viscosity values than those obtained with chromia on silica.
The use of nickel-impregnated MCM-41 aluminosilicate for
oligomerization of olefins was reported by Bhore et al.[133]
Compared to zeolites with medium pore sizes, the impreg-
nated MCM-41 material showed higher activity and greater
selectivity for the formation of trimers and tetramers of
propylene. Furthermore, they offered control over the degree
of branching through variation of the reaction conditions.
The isomerization of n-hexane with platinum-modified
MCM-41 aluminosilicate was reported by Del Rossi et al.[134]
The platinum precursor [Pt(NH3)4Cl2] was introduced by ion
exchange, and the material was then calcined. Although
platinum on amorphous SiO2-Al2O3 showed a slightly higher
conversion of n-hexane than Pt-MCM-41, the selectivity for
isohexane was significantly higher over Pt-MCM-41 with its
uniform pore structure.
Borghard et al. investigated the hydrogenation of benzene
to cyclohexane, and showed that Pd-impregnated MCM-41
has higher activity than palladium supported on other
materials.[135] The enhanced reactivity was attributed to the
higher surface area and pore volume of the MCM-41 support.
An alternative approach in acid catalysis was described by
Kresge et al.[136] Instead of modification of the silicate frame-
work of MCM-41 with trivalent cations (e.g. Al3‡) to generate
Brùnsted acid sites, they deposited heteropolymetallic acids
inside the porous framework. Although heteropolymetallic
acids have very strong acid sites, their surface areas are rather
small. By utilizing supports with high surface areas, acid site
dispersion was achieved. The catalyst was prepared by loading
the mesoporous material with phosphotungstic acid
(H3PW12O40) with the incipient wetness method, and was
investigated for four different paraffin substrates. In n-butane
conversion, isobutane was obtained with a selectivity exceed-
ing 80 %, which was substantially higher than that achieved
over ZSM-5. For the conversion of n-hexane, the heteropo-
lymetallic acid loaded MCM-41 exhibited higher activity
(with comparable selectivity), compared to Pt-MCM-41. The
excellent activity was attributed to the high dispersion of the
heteropolymetallic acid on MCM-41.
Aluminosilicate MCM-41 materials cation-exchanged with
sodium and cesium have been successfully used for the base-
69
REVIEWS J. Y. Ying et al.

catalyzed Knoevenagel condensation.[137] The reaction of and their applications as oxidation catalysts were demon-
benzaldehyde and ethyl cyanoacetate in aqueous solution in strated.
the presence of Na-MCM-41 (Scheme 11) led to a conversion A major drawback of the ªwetº impregnation method is the
undesired cluster growth during the deposition of the active
O species. In order to overcome this problem and to ensure a
high dispersion of active species, a new methodology, termed
CN CO2Et
H
H2C
vapor grafting, was developed by Ying and Mehnert.[141] By
–H2O
CO2Et CN use of volatile organometallic precursors, it was possible to
deposit active species in a highly dispersed and uniform
Scheme 11. Base-catalyzed Knoevenagel condensation over MCM-41 fashion throughout the entire porous system of MCM-41
cation-exchanged with sodium and cesium.
(Figure 5). The resulting variety of metal and metal oxide

of about 90 % within three hours with almost 100 % selectiv-

ity. In contrast, the same reaction in boiling ethanol led to the
acetalization of benzaldehyde due to the presence of residual
acid sites. Furthermore, both H-MCM-41 and Na-MCM-41
catalyzed the condensation of benzaldehyde with acetophe-
none to yield chalcone. They were also successfully employed
for aldol condensations with bulky ketones. In addition, if an
a-hydroxyl group was present on the benzophenone, an
intramolecular Michael addition giving flavanone would
follow the aldol condensation (Scheme 12).

O O O

H Me
–H2O
R R

R = OH

O
Figure 5. TEM image of the palladium-grafted mesoporous silicate
material Pd-TMS11.[142]

grafted mesoporous materials (termed TMS11) presented an

O attractive combination of ultra-high catalyst dispersion and
tunable pore sizes (15 ± 100 Š). The Pd-TMS11 material[142, 143]
was conveniently prepared by vacuum sublimation of
Scheme 12. Aldol condensation between benzaldehyde and acetophe-
none, followed by a Michael addition to give flavone, over H-MCM-41 and [CpPd(h3-C3H5)] through the hexagonally packed MCM-41
Na-MCM-41. mesopores, followed by reduction under hydrogen. Inves-
tigation of Pd-TMS11 for carbon ± carbon coupling reactions
One of the first examples of the deposition of active metal (Heck reaction, Scheme 13) showed that its catalytic activity
oxide sites on MCM-41 through the fixation of organometallic was superior to that of other heterogeneous Heck catalysts
complexes onto the inside walls of
MCM-41 was reported by Maschmeyer
Pd-TMS11
et al.[138] Treatment of the porous + base
R X +
MCM-41 material with a solution of – HX•base
[(C5H5)2TiCl2] in the presence of NEt3
R
anchored the titanocene complex
through oxygen atoms onto the pore E/Z
surface. Calcination under a stream of
oxygen removed the cyclopentadienyl O
O
ligand and generated an active epox- Pd-TMS11
+ base C nBu
X + C nBu
idation catalyst. The resulting system R
O O
– HX•base
showed good activity, and was particu-
R
larly useful in the conversion of bulky
substrates, which could have access to E/Z
the active centers inside the ultra-large R: H H NO2 C(=O)CH3
pores. With the same approach, vana-
dium-grafted[139] and manganese-graft- X: Cl Br Br Br
ed[140] MCM-41 materials were derived Scheme 13. Carbon ± carbon coupling reactions catalyzed by mesoporous Pd-TMS11 material.

70 Angew. Chem. Int. Ed. 1999, 38, 56 ± 77

Mesoporous Materials
and even surpassed that of many homogeneous catalysts. This
heterogeneous Heck catalyst demonstrated how bulky sub-
strates could be effectively and selectively coupled to an even
larger molecule inside the mesoporous framework. The highly
dispersed Pd-grafted catalyst provided a less expensive and
more thermally robust alternative to homogeneous Pd com-
plexes.
3.3. Organometallic Complexes Anchored to
Mesoporous Silicates
An early example for the anchoring of an organometallic
complex onto the porous walls of aluminosilicate MCM-41
was reported by Liu et al.[144] They treated ion-exchanged
MCM-41 with phenanthrolineiron(ii) chloride and were able
to immobilize the complex. The resulting material was
investigated for the oxidation of phenol with H2O2 as the
oxidant. A higher activity was obtained with the immobilized
iron complex than for the free iron complex. However, a
significant amount (9.5 %) of leaching was noted in the
former, which could be overcome when the transition metal
complexes were anchored onto the walls of MCM-41 with an
organic linker.
Sutra and Brunel[145] treated MCM-41 material with
(MeO)3Si(CH2)3Cl, which generated surface-bound 3-chloro-
propylsilane moieties that could be allowed to react with bis-
3-(3,5-di-tert-butylsalicylidenaminopropyl)amine, to yield sur-
face-bound Schiff base ligands (Scheme 14). The metal was
O N O
III
Mn Cl
MCM-41 O Si N
O N O
Scheme 14. Surface-fixated Schiff base ligand with coordinated manga-
nese for epoxidation reactions.
then introduced by means of a solution of [MnII(acac)2]
(acac ˆ acetylacetone) in methanol. Air oxidation of the
solution gave the final MnIII complex. The immobilization of
such epoxidation catalysts offered the advantage of easy
separation and the potential of increased selectivity with the
well-defined pore structure of the support material.
Surface-immobilized manganese ± triazacyclononane com-
plexes have also been developed for epoxidation catalysis.[146]
By anchoring 1,4,7-triazacyclononane on glycidylated MCM-
41, followed by the introduction of the manganese metal, a
catalyst with remarkable epoxidation activity and high selec-
tivity for styrene and cyclohexene was achieved.
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
REVIEWS
Cobalt(ii) complexes have been immobilized onto the inside
walls of ethylenediamine-grafted mesoporous materials.[147]
For the functionalization of the support, the surface-bound
silanol groups were allowed to react with alkoxysilyl com-
pounds that possessed donor amine groups to produce
chelating ligands that were then used in the complexation of
metal ions such as CoII. The ability of the cobalt ± amine
complexes to form reversible dioxygen adducts was also
demonstrated and might be useful to some biological reac-
tions.
Although numerous efforts have focused on the fixation of
metalloporphyrins, as in the elegant work of Herron and co-
workers[148, 149] who reported the entrapment of phthalocya-
nine within large pore zeolites, turnover frequency and
selectivity were rather poor. More recently, the encapsulation
of ruthenium porphyrins in modified MCM-41 was reported
by Liu et al.[150] In this work, the surface of MCM-41 was
treated with 3-aminopropyltriethoxylsilane to provide a two-
electron donor anchor (NH2 group) to which the ruthenium
porphyrin was attached (Scheme 15). The catalyst derived was
O
MCM-41 O Si(CH2)3NH2 EtOH Ru CO
O
O
MCM-41 O Si(CH2)3N Ru CO EtOH
H2
O
Scheme 15. Surface-immobilized ruthenium porphyrin complex on MCM-41.
investigated for the oxidation of olefins, giving turnover
numbers that were 20 ± 40 times higher than that for the free
porphyrin. Also of interest was the observation that in the
oxidation of cis-stilbene with the modified MCM-41 material,
the major product was trans-stilbene oxide. In contrast,
oxidation of cis-stilbene catalyzed by free ruthenium por-
phyrin gave a 1:1 mixture of cis- and trans-stilbene oxides. The
high selectivity to trans-stilbene oxide was attributed to the
steric constraint imposed by the straight channels of the
MCM-41 support. This example demonstrated nicely the
potential of mesoporous materials in size- and shape-selective
catalysis.
An alternative approach in the anchoring of metallopor-
phyrin onto the inside walls of mesoporous MCM-41 has been
developed by Zhang et al.[151] with amine-substituted porphyr-
in systems. The active complex was attached by means of a
covalent interaction between the amine terminal groups of
the complex and the niobium dopants in the support matrix.
Such ligation ensured that the active sites would not undergo
self-oxidation. Excellent cyclohexane hydroxylation and cy-
clohexene epoxidation activities have been obtained with this
catalyst system, and the material could be recycled for
71
REVIEWS
repeated use without loss of activity or leaching of porphyrin
complexes.
An interesting approach was taken by OBrien et al.,[152]
whereby the MCM-41 material was modified with ferrocenyl
end groups attached to the silicate surface. By means of the
ring-opening reaction of the strained metallocenophane
[Fe{(h-C5H4)2SiMe2}], it was possible to anchor ferrocenyl
units inside the pore channels of MCM-41. This fixation
reaction demonstrated the potential of these mesoporous
molecular sieves as a matrix for the encapsulation of defined
organometallic complexes.
A further example for the attachment of a well-defined
cobalt oxide species was reported by Maschmeyer et al.[153]
They investigated the selective oxidation of cyclohexane to
cyclohexanone using a cobalt complex that was bound either
directly to a hydroxyl group of the MCM-41 surface or to a
surface-anchored spacer compound which contained a car-
boxylic acid group. The evaluation of the catalysts showed
that the directly anchored complex had a lower conversion
than the complex that was attached through the spacer.
Although this catalyst system exhibited only mediocre activity
(12 % conversion after 24 hours), no leaching of the cobalt
cluster was apparent. The high stability against leaching was
attributed to the anchoring of the cluster to the functionalized
MCM-41 surface.
Two independent groups have reported the preparation of
MCM-41 grafted with methylalumoxane (MAO) for use as
support for catalysts in Ziegler ± Natta polymerization.[154, 155]
The immobilization of homogeneous metallocene catalysts
onto support materials has been of great interest since fixation
of the polymerization catalysts to a surface might enable
polymers to be replicated with higher density and larger
particle size than those produced by unsupported homoge-
neous catalysts. In the catalyst preparation by Tudor and
OHare,[155] dehydrated MCM-41 material was first treated
with an excess of MAO, and then with the chiral polymer-
ization catalyst rac-ethenebis(indenyl)zirconium dichloride. It
was found that the polypropylene produced by the metal-
locene-grafted MCM-41 was fourfold higher in number-
averaged molecular weight and has higher isotacticity and
melting point than that produced by the homogeneous
catalyst.
An alternative approach in the fixation of polymerization
catalysts has been developed by immobilizing zirconocene
complexes[156] that have modified cyclopentadienyl ligands.
These zirconocene complexes could be conveniently anch-
ored onto the walls of MCM-41 materials through their siloxy
groups (Scheme 16). This catalyst system showed remarkable
reactivity for ethylene polymerization; however, low activity
was observed for propylene polymerization.
Me Me
. films.
Si
O Si
Me
Me Cl
MCM-41 Zr
Me Me Cl
O Si Si
Me Me
Scheme 16. Zirconocene complex anchored on the MCM-41 surface.
72
J. Y. Ying et al.
4. Other Applications
4.1. Thin Films and Membranes
In addition to catalytic applications, the well-defined
mesoporous M41S family of materials also offer interesting
potential for use in membrane separation, adsorption, and
electronic/optical applications. For membrane applications, it
is important to be able to process mesoporous structures in
the form of defect-free, oriented thin films. Synthesis of
ordered films of hexagonally packed mesoporous silica was
first reported by Yang et al., who used an acidic aqueous
mixture of cationic CTAC surfactant and TEOS.[157] Thin films
(0.2 ± 1.0 mm) could be grown from the bottom side of a
cleaved mica substrate held horizontally in the synthesis
vessel. Mesoporosity of the thin films became accessible upon
calcination, and TEM revealed that the pore channels ran
predominantly parallel to the mica surface. The formation of
the oriented mesoporous silica films was thought to begin with
nucleation which involved silica-surfactant-mica interfacial
interactions that facilitated the assembly of silica-surfactant
micellar seeds on the mica. A later study by Yang et al.[158]
showed that ordered mesoporous films could be grown
without a solid substrate by surfactant templating at the
interface between air and water. These continuous films were
believed to be formed through a dual-templating role of the
surfactants. The authors suggested that the surfactant over-
structure at the air ± water interface and the micellar aggre-
gates in solution interacted collectively with the soluble
silicate building blocks to polymerize mesostructured silicates
as free-standing films.
Aksay et al.[159] showed that continuous mesostructured
silica films could be grown on many substrates, with the
corresponding structure determined by the specifics of the
substrate ± surfactant interaction. For example, not only the
hydrophilic surface of mica but hydrophobic surfaces such as
graphite could be used as binding sites for the silica ±
surfactant micellar precursor species to orient a hexagonal
phase of mesostructured silica in the form of a continuous thin
film. This study presented XRD results that illustrated
epitaxial alignment of the adsorbed surfactant layer with
crystalline mica and graphite substrates. The presence of
significant strain in the mesostructured silica overlayer was
verified, and as the films grew thicker, accumulated strain was
released, which resulted in the growth of hierarchical
structures from the ordered film.
By slow evaporation of a sol mixture containing TMOS, two
equivalents of water, CTAC, and a mineral acid, Ogawa[160]
prepared a self-supporting transparent film of hexagonal-
phase mesostructured silica. Transparency was retained after
calcination, but the author did not discuss the orientation of
the hexagonally packed pores or the retention of crack-free
For many potential applications, such as membranes for
biomolecular separations and sensors for large molecules, it
would be particularly useful to have the axis of the pore
channel oriented vertically (instead of parallel) with respect
to the solid substrate or liquid surface. The use of external
forces to influence the ordering of pores in mesoporous films
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
Mesoporous Materials
has been examined recently. Hillhouse et al.[161] have prepared
hexagonally packed mesoporous silica layers on glass sub-
strates in a continuous flow cell, and showed that an external
flow field could induce a preferred orientation for film
formation. Tolbert et al.[162] demonstrated that the application
of a strong magnetic field (11.7 T) could force the long-range
orientational ordering of the pores in MCM-41 during the co-
assembly process.
Lu et al.[163] found that oriented mesostructured films could
be obtained by dip-coating substrates with dilute precursor
sols. Slow evaporation of the solvent in the entrained solution
drove the surfactant concentration past the CMC, and the co-
assembly of the silicate and surfactant into a well-defined
mesostructure. Depending on the initial surfactant concen-
tration, mesostructured films with hexagonal, cubic, and
layered phases could be prepared. With calcination, support-
ed mesoporous films of the two-dimensional hexagonal phase
(with pore channels parallel to the air ± solid interface) and a
mixed cubic and three-dimensional hexagonal phase were
obtained. The mixed-phase film contained three-dimensional
pore channels accessible from the air ± solid interface. Lu and
co-workers further reported the in situ study of the
lamellar ! cubic ! hexagonal mesostructure phase transfor-
mations. Whereas Lu et al.[163] used CTAB as the templating
surfactant, Tolbert et al.[164] employed a gemini surfactant to
prepare a mesoporous silicate film with the three-dimensional
P63/mmc mesophase structure.[26, 29]
4.2. Hollow Tubules and Other Bulk Morphologies
The processing of mesoporous materials into designed bulk
morphologies is not limited to thin films. Lin and Mou[165] have
found that hollow tubules of 0.3 ± 3 mm in diameter could be
produced by careful control of the surfactant-water content
and the rate of silica condensation at high pH values. The wall
of these tubules consisted of coaxial cylindrical MCM-41
mesopores. It was proposed that solvent-separated multi-
layers of periodic hexagonal MCM-41 silicates could be
formed and further ªbentº into hollow microtubules with the
nanochannels constituting the walls of these tubules. The
hierarchical order of this ªtubules-within-a-tubuleº organiza-
tion is similar in nature to that of the frustules of marine
diatoms, and may find applications in catalysis, separation
technologies, and optoelectronics.
While MCM-41 synthesis typically resulted in precipitated
powders, Huo et al.[166] demonstrated that mesoporous silica
could be produced in the form of marblelike spheres of about
1 mm in diameter. The authors prepared a basic CTAB
solution and slowly added tetrabutylorthosilicate (TBOS)
while stirring; the stirring speed controlled the size of the
spheres. The surfactant was removed by calcination to yield
smaller-diameter spheres of mesoporous silica. The authors
suggested that the formation of the spheres was based on an
emulsion synthesis, wherein the mixture of butanol (from
hydrolyzed TBOS) was stabilized by the CTAB surfactant.
The use of microemulsions was shown earlier in the formation
of mesoporous silicate spherical shells by Schacht et al.[167]
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
REVIEWS
MCM-41 powders typically have little form, because of the
uncontrolled precipitation of these materials. Exceptions have
illustrated the hexagonal habit of MCM-41[1b] and Nb-
TMS1.[65] Interesting particle morphologies of APM materials
(mesoporous silicates prepared under acidic conditions) were
demonstrated by Ozin and co-workers.[168] The materials were
synthesized under very low pH conditions and high dilution of
TEOS and surfactant. These extreme synthesis conditions
prevented uncontrolled precipitation of the mesostructured
silicates, which allowed for high-curvature particles to nucle-
ate and grow.
4.3. Other Templated Mesostructures and
Hierarchical Structures
In the synthesis of MCM-41, ordered arrangements of
mesoporous channels were produced in silica-based materials
upon surfactant removal. The resulting pore sizes were
governed by the diameter of the templating micelles, and
have been limited to  30 nm. Recently, Davis et al.[169]
showed that a bacterial superstructure, which consisted of a
thread of coaligned multicellular filaments of Bacillus subtilis,
could be used to extend the length scale of inorganic materials
patterning. Ordered macroporous fibers of either amorphous
silica or MCM-41 mesostructured silica were obtained by
template-directed mineralization of the interfilament spaces,
followed by removal of organic material by calcination. The
resulting inorganic structures consisted of a macroporous
framework of 0.5 mm wide channels with curved walls of
either amorphous or mesoporous silica, 50 ± 200 nm in thick-
ness. This work illustrated how supramolecular and super-
cellular templates might be combined for the fabrication of
inorganic materials with hierarchical structures.
The concept of supramolecular templating was also ex-
tended to porous silicates with a layered structure.[34, 170]
Galarneau et al.[170] showed that mesoporosity could be
introduced into layered silicate clays by a gallery-template
synthesis, which extended the range of pore sizes possible in
pillared layered silicates (from spacings of < 10 Š to 14 ±
22 Š). A cationic ammonium surfactant was used to swell a
silicate clay before shorter chained alkylamines and TEOS
were added; the organic components were later removed by
calcination to yield porous clay heterostructures (PCH). The
templating organics not only swelled the layers for the TEOS
to pillar, but also controlled the spacing between the pillars
within the galleries, an advantage not offered by traditional
pillaring methods. Although the resulting materials did not
resemble the typical M41S-type mesoporous materials, this
approach could be applied to other classes of layered
materials, such as zirconium phosphates.
4.4. Adsorbents
Beside catalysis and membrane separation, a major poten-
tial application of mesoporous materials lies in adsorbents.
The huge pore volume and the compositional flexibility of
MCM-41 type materials can be widely exploited for selective
73
REVIEWS
adsorption of gases and liquids, and binding of metals. For
example, Ioneva et al.[171] have shown that adsorptive storage
of methane in silicate-based MCM-41 was possible at 25 8C up
to 6.9 MPa. An increase in methane storage could be attained
with increasing surface area per unit volume of adsorbent.
MCM-41 allowed for a 75 % improvement in the methane
storage density over that of the compressed gas at 3.45 MPa. It
also has higher total storage capacities for argon, nitrogen and
light hydrocarbon vapors than typical microporous sorbents.
In some applications, such as methane adsorption, pores
smaller than 20 Š might be desirable for optimization of the
gas affinity.
Mesoporous materials are also being used by Mitsubishi
Heavy Industries, Ltd.[172] for a volatile organic compounds
(VOC) recovery process. The high surface area of mesoporous
aluminosilicates can be utilized to adsorb VOC at room
temperature with great capacity. The saturated sorbent can be
reactivated with hot air (120 ± 150 8C) and the recovered VOC
can be concentrated by 3 ± 10 times. This process does not
require the use of steam for adsorbent reactivation, and is
flexible for recovery of various kinds of VOC. Izumi[172] has
demonstrated that mesoporous materials can out-perform
leading zeolite sorbents in the adsorption of methyl ethyl
ketone by about twofold for a high SiO2/Al2O3 ratio. The
acidic, low-temperature synthesis developed also holds prom-
ise for the manufacture of mesoporous materials at a lower
cost than high-silica zeolites.
For effective binding of heavy metals, Feng et al.[173] have
functionalized the surface of mesoporous silicate supports
with a monolayer of tris(methoxy)sulfanylpropylsilane mol-
ecules with thiol terminal groups. This strategy enabled
mercury, silver, and lead ions to be proficiently adsorbed
from tainted water so that the samples were rendered clean
enough to drink. The adsorptive power of this new material
was more than an order of magnitude higher than that of
conventional sorbents. The sorbent was highly selective for
certain metals; metal ions such as sodium, barium, and zinc
were not taken up. It was also reusable; treatment of the
mercury-loaded material with concentrated HCl would re-
lease the mercury, and the sorbent remained functional after
multiple cycles. This example represented a powerful appli-
cation of functionalized mesoporous materials as a selective
sorbent with ultra-high surface activity.
4.5. Hosts for Quantum Structures
The well-defined mesoporous structure of M41S materials
can be used as hosts for quantum semiconductor structures of
low dimensionality. The cylindrical channels of the mesopo-
rous structure of MCM-41 allow for matrix-mediated syn-
thesis of molecular wires and quantum wires, and the silicate-
based framework can provide electrical isolation of the
conducting wires. Wu and Bein[174] have reported the adsorp-
tion of aniline and its polymerization in the pores of a
transition metal containing mesoporous MCM-41 host. The
resulting polyaniline filaments encapsulated in the 3 nm wide
pore channels showed significant low-field conductivity,
74
J. Y. Ying et al.
which indicated that they still supported mobile charge
carriers.
Leon et al.[175] have demonstrated the feasibility of filling
the mesopores with a semiconductor. Using vapor phase
epitaxy, germanium filaments were deposited in the pore
channels whereby surface hydroxyls acted as anchor points for
seeding the nucleation of semiconductor clusters. The Ge
crystallites took the shape and periodicity of the mesopores of
the silicate matrix. While only some of the pores were filled
and more complete semiconductor loading awaits future
development, such fabrication techniques are promising
towards generating quantum wire and dot arrays with high
packing density.
For device fabrication, it would be of interest to derive the
host inorganic materials in the form of thin films (instead of
particulates), with ordered mesopores preferably oriented
perpendicular to the plane of the films. It would also be
important for many applications to achieve the quantum wires
as continuous, single crystals.[176] This area of research holds a
great deal of potential for significant technological impact,
and may capitalize on the pore-size tunability of well-defined
MCM-41 mesostructures for unique quantum confinement
effects.
5. Summary and Outlook
The field of heterogeneous catalysis has benefited tremen-
dously from the research in supramolecular-templated meso-
porous materials and will continue to grow, especially with the
development of materials of new compositions and surface
modifications. The potential of mesoporous materials as
catalysts has already been demonstrated in a number of
areas, but only time will tell if these novel materials will find
widespread commercial applications. Research in the prepa-
ration of materials that contain both surfactant-templated
mesoporosity and controlled bulk features has just begun, and
it remains to be seen if these systems can be developed for
macrostructure-dependent applications, such as membrane
separations. In spite of the large amount of synthesis work
done already, relatively little research has been devoted to
further elucidate the mechanisms of formation for the variety
of mesostructures. Insights on self-assembly mechanisms will
be useful towards expanding our capability to derive system-
atically tuned pore dimensions which span the microporous,
mesoporous and macroporous regimes. Hierarchical meso-
structures possessing patterned features on different length
scales processed in the desired bulk morphologies also await
further development as unique multifunctional devices.
Appendix
Abbreviations of mesoporous materials, proposed mecha-
nisms, and substrates.
APM acid-prepared mesostructures
CMC critical micelle concentration
CTAB cetyltrimethylammonium bromide
CTAC cetyltrimethylammonium chloride
Angew. Chem. Int. Ed. 1999, 38, 56 ± 77
Mesoporous Materials REVIEWS
D4R double four-ring [12] J. C. Vartuli, C. T. Kresge, M. E. Leonowicz, A. S. Chu, S. B. McCull-
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