523

Mesoporous materials
David M Antonelli* and Jackie Y Ying t

There have been advances in mesoporous structures in
extending the composition to include transition metal oxide
analogs of MCM-41, in understanding the mechanism of
formation of these exciting materials, and in the application
of these materials to catalysis and nanoscale electronics.
Addresses
'Department of Chemistry and Molecular Sciences,
University of Sussex, Falmer, Brighton BN1 9HR, UK;
e-mail: d.m.antonelli@sussex.ac.uk
tDepartment of Chemical Engineering, Massachusetts Institute of
Technology, Cambridge, MA 02139, USA; e-mail: jyying@mit.edu
'Current Opinion in Colloid & Interface Science 1996, 1:523-529
© Current Science ltd ISSN 1359-0294
Abbreviations
HMS hexagonal mesoporous silica
LAT ligand-assisted templating
Introduction
Since Mobil first reported the discovery of MCM-41 in
199Z [1,Z), there has been a great surge in interest in
the study of mesoporous materials [3-10). This silicate
material and its recently prepared transition metal oxide
analogs ~I-T~ISI (M = Nb,Ta,Ti) [11--,IZ--,13-,14--,Pl)
consist of a high surface area (up to 1400 m 2 g-l),
hexagonally packed array of inorganic tubules ranging from
Zo-100 A in diameter. They are formed by rernplating
inorganic oxides onto a self-assembled liquid crystal
mesostructure. Mesoporous materials are of great interest
to catalysis [15-Z5) because of their large and uniform
pore sizes, which allow sterically hindered molecules,
which are unable to diffuse effectively through the smaller
microporous channels of zeolites, to diffuse facilely to
internal active sites. These same properties could also
lead to application in gas sorption processes. Mesoporous
materials are also important because the regular pore
structure can serve as a support for conductive and
magnetic materials, leading to quantum wires for smart
electronic devices [Z6-Z9). The compositional extension
of the mesostructures to the transition metal oxide based
M-TMSI family provides further flexibility in the tailoring
of oxidation states, coordination chemistry and electronic
properties. This review will cover three main areas in
the study of meso porous materials since 1995> first,
compositional and mesostructured phase variation; second,
the mechanism of formation; and third, the applications of
these materials to catalysis and nanoscale electronics.
from a source of silica and a cationic trimethylammonium
bromide surfactant at concentrations under which micelle
formation of the organic phase is favorable (Fig. 1).
This approach relies on the Coulombic attraction be-
tween the inorganic phase, consisting of polysilicate and
polyaluminosilicate anions, and the organic template. By
adding dopants such as titanium isopropoxide [30) the
composition of the silicate or aluminosilicate walls of
MCM-41 can be altered such that small amounts of other
metals are included in the mesostructure. Tanev et 0/.
[30) also described how neutral amine surfactants can be
used in place of charged surfactants to form MCM-41-like
structures (termed H~IS [hexagonal mesoporous silica))
of lower crystallinity than the Mobil material [1,Z). On
the basis of a lack of a signal in the 14N-magic angle
sample spinning (~IAS) NMR spectrum, the authors
concluded that the amine head group remained' in the
neutral form in the as-synthesized, material. Using this
approach, a purely alumina analog of HMS was also
synthesized [31--); however, no purely transition metal
analog was reported. Although neutral surfactants do not
yield materials with high crystallinity, the amine could be
easily washed out with ethanol, hence avoiding calcination.
Recent work [3Z-] demonstrated that, by using well
defined aluminosilicate clusters as precursors, rather than
bulk oxides or alkoxides, it was possible to control the
amount of aluminium in the wall and in some cases retain
the local geometry about each aluminium atom throughout
the synthesis procedure.
Figure 1
Liquid crystal templating used to form mesoporous hexagonally
packed channels of silica.

Composition and mesostructured phase

variation The extension of MCl\I-41-like structures into the realm
MCr-.I-41 is synthesized using a micelle-based liquid of pure transition metal oxides would represent an impor-
crystal templating method at a variety of pH values, tant leap from both catalytic and electronic standpoints
524 Applications in chemistry I chemical engineering
because transition metal oxides have variable oxidation
states that are useful towards tailoring catalytic, electronic
and magnetic properties; aluminium and silica oxides
do not have this advantage. Early attempts to prepare
transition metal oxide analogs of l\ICM-41 without any
silica or alumina employed a liquid crystal templating
approach using trialkylammonium bromide surfactants (0
synthesize hexagonally packed mesostructures of W, Pb,
Sb, and Fe oxides [33-35]. Other researchers showed that
a mesostructured vanadyl phosphate material could be
prepared using a similar methodology [36]. None of these
materials, however, were stable to surfactant removal, and
hence. no mesoporous materials were obtained. Further
studies- [37--] revealed that the W-based material was
actually a mesostructured salt in which the individual
W oxo-clusters comprising the walls had not condensed.
Although this work did not lead (0 the derivation
of mesoporous materials of novel composition, it was
important in showing that it .was possible to synthesize
rnesostructured phases out of transition metal oxides.
It also showed that, by subtly varying the pH and
surfactant: metal oxide ratios, cubic and layered phases of
these materials could be obtained. This study in many
ways paralleled work by Mobil on the MCM-41 system
which showed that with increasing surfactant: silica ratios
they could isolate hexagonal (MCM-4l), cubic (MCM-48),
and finally layered (MCM-50) phases [3,4].
In 1995, two approaches to synthesize the first stable
hexagonally packed, mesoporous transition metal oxide
molecular sieves were developed [1l--,lZ--,13-,14--,Pl].
Prior approaches for synthesizing mesoporous materials
such as MCM-41 relied on the presence of a soluble
inorganic oxide monomer or oligomer and could not be
successfully applied to the synthesis of early transition
metaloxide rnesostructures. This is because such oxides
and related' oxo-clusters are normally either highly inert or
irisoluble. Because of this, metal alkoxides, which are both
more soluble and more reactive than the corresponding
oxides and oxo-clusters, were employed instead. In
all previous approaches to mesoporous materials, the
surfactant was first dissolved in water or water/ethanol
Figure 2
Ligand-assisted templating as a method
of synthesizing transition metal oxide
MCM·41 analogs, such as Nb-TMS1.
NbIOEt)s
r"
+ CJ2112\NII2
before addition of the inorganic precursor. This approach
was only successful in the synthesis of Ti-TMSI [11--]
(the first hexagonally packed mesoporous transition metal
oxide molecular sieve) if acetylacetone was added to the
alkoxide precursor prior to hydrolysis with an aqueous
solution of a phosphate surfactant. We proposed [11--]
that the acerylacerone slows down hydrolysis of the highly
reactive transition metal alkoxide long enough for it to
achieve the appropriate interaction with the phosphate
surfactant head groups for mesostructure formation to
take place. Ti-TMS 1 was partially stable (0 calcination,
and yielded materials with mesoporosity stable to several
hundred degrees and surface areas of up (0 ZOO m 2 g-I.
Infrared evidence indicated that at least some of the
phosphate head groups remained in the structure after
calcination, while nitrogen adsorption showed that some
degree of pore collapse had occurred during calcination.
The second approach (0 transition metal oxide meso-
porous materials [1Z--,13-,14--,Pl] used ligation of the
surfactant head group directly to the metal alkoxide prior
(0 hydrolysis and condensation" thus establishing the
required interaction between the organic and inorganic
phases before introduction of water (Fig. Z). Another
key feature of this ligand-assisted ternplating (LAT)
approach was that the metal was directly ligated to the
inorganic precursor without a charge matching or hydrogen
bonding interaction as previously described in this review.
This LAT method yielded mesostructures of Nb and
Ta oxides with surface areas of up to 600 m 2 g-I after
surfactant removal by acid washes. These structures had
remarkable thermal and hydrothermal stabilities ranging
from 300-800·C. The LAT method is advantageous
because the ligand-metal bond was easily cleaved by acid
for surfactant removal, thus avoiding calcination which
could damage the structure. It also allows for NMR studies
to be conducted, yielding direct information through both
scalar and dipolar Nl\IR coupling constants between the
ligand head group .and the metal center. The synthesis
conditions of Nb-TMSI could also be easily varied to
yield cubic and layered mesostructures, as well as crystals
as large as several millimeters [14--].
 Mesoporous materials Antonelli and Ying 525

Figure 3

S denotes surfactant head group

x, y and n denote the stoichiometries in the cluster of
the metal, hydrogen, and oxygen respectively
m denotes the.charge on the entire cluster; the charge
depends on the number of oxygen and hydrog en atoms
in the cluster, as well as on the nature of m

Organic-Inorganic Interactions

Charge Matched: S' [MxOnHylOt- , Coulombic Forces

J
s~

A general scheme for the formation of inorganic tubular mesostructures using charged or neutral surfaclants in which the .forces bringing
the ensemble together are either Coulombic in nature or hydrogen bonds. In pathway A1, as proposed by Chen et al. [41 I, the surfactants
first self-assemble into randomly ordered rod ·like micelles before contact with the inorganic species. Because of either a charge interaction
between cationic or anionic head groups with anionic or cationic inorganic spec ies respectively, or hydrogen bon'ding of neutral head groups to
hydrophilic silicates as demonstrated by Tanev et al. [301, the inorganic spec ies, which may be monomeric or oligomeric in nature and at various
stages of condensation, is attracted to the surface of the rod-like micelle. In pathway A2, this same ensemble is formed without the use of
preformed rod-like micelles. Such a charge-rnatchinq mechanism, proposed by Huo et a/. [341, is believed to operate under conditions in which
mesostructures precipitate out of solutions at concentrations well below the critical micelle concentration of the surfactant. It proposes that the
balancing of the size and charge density of the surfactant head groups is the .lmportant element in determining the type of mesostructure formed
on precipitation. Pathways A1 and A2 converge in step 8, where condensation of the walls and ordering of the tubes into a hexagonally packed
mesostructure occur.

The recent surge in interest in MCl\I-41-like materials has
led coefforts to not only vary the wall compo sition, but also
create new mesostructurcd morphologies with different
templating agents. Surfactants wirh more than one head
group have been used successfully in the synthesis
of 'new mesostructures of silica. In one study, gemini
surfacrants, which have an additional charged ammonium
group tethered on a small chain to the first ammonium
head group, were used to synthesize a new silica phase
which crystallized in the hexagonal space group P63/mme
[38). This material retained its structure on calcining
to give a material with an intricate three-dimensional
pore structure. Two other groups independently showed
that environmentally friendly neutral ethylene oxide
surfactants could be used ro make MCl\I-41 analogs of
varying crystallinity [39,40). It is anticipated that this
cleaner technology will aid l\ICl\I-41 synthesis on an
industrial scale.
M~chanism of formation
Since the discovery of the mesoporous silicate molec -
ular sieve l\ICl\I-41, the mechanism of formation of
organic-inorganic mesostructures in general has been a
subject of great' interest and debate [34,37··,41]. While
there are many well understood examples of remplating
of an inorganic materi al onto stable preformed structures
such as bacterial fibers [42,43), phospholipid tubules [44}.
or metallic surfaces [45,46], the mechanism of remplating
onto metastable organic liquid crystal rnesostructures
important in l\ICM-41 and M-Tl\ISl formation is not
clear. The main issue of contention concerning the
mech anism of formation of MCl\I-41 in the literature
526 Applications in chemistry I chemical engineering
centers around whether or not the individual alkyl
trimethylammonium surfactants form tubular micelles
before [41] or after [34,37--] addition of the silicate,
which is attracted to the head groups of the surfactant
through a Coulombic interaction between the anionic
silicate oligomers and the cationic alkyl ammonium
moieties. Condensation of these silicate units into the
walls of the mesostructure occurs after self-assembly in
both of these proposed mechanisms. Figure 3 shows
the two previously established mechanisms for MCM-41
mesostructure formation. In the first mechanism (Fig. 3,
path At), proposed by Chen et 01. [41], the presence of
preformed alkyl trimethylammonium micelles onto which
the .anionic silicate species condense is the important
feature. In this study, a series of 14N-NMR experiments
showed that, under the surfactant concentrations studied,
the HI hexagonal liquid crystal phase was not involved
at any stage of MC~I-41 formation and that individual
micellar rods in solution were first coated with two to three
monolayers of silica before assembly into a more highly
ordered precipitate. X-ray diffraction studies [41] of the
precipitate in real time showed that the first detectable
phase was hexagonal and that no layered phase existed as
an intermediate. In other studies [47], it had been shown
that layered silica mesostructures could reassemble into
hexagonal structures under different conditions.
Figure 4
Schematic drawing showing active
metal site on internal wall of MCM·41. (a)
(a) MCM-41 'Iig~nd sheet' (M denotes
a metal and L denotes a ligand). (b)
Functionalized MCM-41 surface.
Building active sites onto the walls of
MCM-41-like materials can be more
effective in catalytic processes than
imbedding the active component into the
walls.
(b)
In the second mechanism (Fig. 3,. path A2), proposed
by Huo et 01. [34], preformed micelles are not necessary
in the formation of mesostructures. This mechanism
accounts for the observation that mesostructures form
under conditions where no micelles are present. The
important feature in this case is the cooperative assembly
of the mesostructure via charge matching of inorganic
species to the surfactant head group. For reasons of
charge interactions and solubility, this approach causes
the precipitation of hexagonal salt mesostructures prior
to condensation of the walls under conditions where
micelles are not present in solution. This mechanism is
strongly supported by a series of 2H-NMR and 29Si-N~IR
experiments [37--].
The mechanism of mesostructure formation under the
LAT approach is not yet fully understood. It was found
that Nb-T~ISI can be synthesized using highly dilute
ethanol solutions with only steady-state concentrations of
water introduced by vapor diffusion [14--]. Under these
conditions, micelle formation is highly unfavorable and
hence this rules out any mechanism involving preformed
micelles. The cooperative assembly mechanism is ruled
out since this mechanism necessitates charge-governed
self-assembly prior to any condensation of the inorganic
phase. In the synthesis of Nb-TMS1, mesostructure
~10oA-..j

formation is intimately coupled with condensation. This
suggests that the LAT approach may involve not only a
new way of establishing an interaction between the organic
and inorganic phases, but also a different mechanism of
self-assembly than those previously proposed for other
mesoporous materials, possibly involving helical coiling of
propagating niobium oxide-alkoxide polymer chains with
pendant surfactant chains. The mechanism of this process
is currently under study (D~I Antonelli, C Rienstra,
R Griffin, JY Ying, unpublished data).
The above work demonstrates that there is more than
one mechanism for the formation of organic/inorganic
mesostructures, and that no noe mechanism is operative
under all conditions, even for the same material.
Applications
Although MCM-41 was only recently discovered, its
applications to catalysis and nanoelectronics are already
being explored. The first catalytic study appeared in 1994,
demonstrating that ?\IC?\I-41 was indeed advantageous
over its microporous counterparts in catalysis involving
large molecules, where a diffusion bottleneck might be
expected [30]. This work showed that Ti-doped MCM-41
and HMS outperformed Ti-silicalite in catalytic peroxide-
based oxidations of a wide range of substituted aromatics,
including relatively inert2,6-di-tert-butylphenol. Tanev
et 0/. [30] attributed this improvement to the enhanced
rate of diffusion of the substrate through the mesoporous
channels of MCM-41 and Hfo,lS as compared with that in
microporous silicalite. Later work by Maschrneyer et 0/.
[480 ] showed that the activity of similar catalytic processes
using mesoporous ~aterials could be further improved
if the active Ti was introduced not as a component of
the wall, as in the work of Tanev et 0/. [30], but as a
pendant group on the surface of the wall. This is illustrated
in Figure 4. In this study [48 titanocene was used to
0
),
graft isolated and easily accessible Ti sites onto the inner
walls of MCM-41. After calcination, the material proved
highly active towards olefin epoxidation. The integrity
of the catalytic sites was probed using a wide variety of
spectroscopic techniques, which were able to show that
the Ti units were monomeric and bound exclusively to
Si-O units on the walls of the material. Most recently,
Zr-doped Hfo,lS was found useful in the oxidation of a
wide range of alkanes and substituted aromatics [49]. The
relatively large size of Zr has thwarted many attempts
to incorporate it into the strained and inflexible walls of
microporous zeolites. Tuel et 0/. [49] attribute this to the
amorphous character of the walls of mesoporous materials,
which have a greater tolerance for incorporation of large
ions.
Applications of mesoporous materials to small-scale elec-
tronic devices are also being explored. In 1994, researchers
showed that conductive polyaniline wires could be placed
inside ?\IC~I-41 channels by 'a ship in bottle' approach, in
Mesoporous materials Antonelli and Ying 527
which monomeric aniline units were polymerized inside
the channels using a Cu catalyst [26). The accessibility
now of large millimeter-sized crystals of Nb-TMSI
should lead to further electronic, optical and magnetic
applications in the future. The pores of these crystals
could be easily filled with semiconductors or magnetic
materials to yield quantum wires with unique properties.
Conclusions
The past two years have seen a great increase in interest
in mesoporous materials. While catalytic and electronic
applications of these exciting new materials are being
explored, their full potential has not yet been achieved.
While their mechanism of formation was at first a
mystery, a series of elegant NMR and neutron scattering
studies has elucidated the various pathways which can
lead to mesostructure formation. With the advent of
transition metal oxide ?\ICM-41 analogs as well as new
environmentally friendly methods of making these porous
mesostructures, it appears that the field will continue to
expand as it has since the discovery of MCM-41 in 1992
and that commercial applications are not too far off in the
future.
The future directions of research in this area should
include further extension of the composition of the
mesoporous materials to include other transition metals
for wider range of catalytic applicability, as well as
materials other than oxides (e.g., nitrides and selenides),
for semiconductor semiconductor applications; refining the
techniques for docking well defined catalysts at the inner
walls of the porous structures' and applications to novel
electronic and magnetic materials through host-guest
interactions.
Acknowledgements
The authors would like to acknowledge the support of the National Science
foundation (CTS-9257223 and D:\IR-9400334) and the US Department of
Energy (DE-fG02-94ER30231) in the nanostructurcd catalysts research and
survey conducted, respectively.
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Patent
• of special interest
•• of outstanding interest
PI. Ying JY, Antonelli OM: Composition and method for producing
hexagonally-packed meso porous metal oxides. US patent
pending, serial no 08/415695.