Journal of Membrane Science 235 (2004) 53–72

Ordered mesoporous and macroporous inorganic films and membranes

V.V. Guliants∗ , M.A. Carreon, Y.S. Lin1
Department of Chemical and Materials Engineering, University of Cincinnati, Cincinnati, OH 45221-0012, USA

Received 21 April 2003; received in revised form 29 December 2003; accepted 12 January 2004

Abstract

This article reviews synthesis, structures and emerging applications of ordered inorganic meso- and macroporous films and membranes.
Thin films or membranes of these groups of porous materials can be prepared by various techniques commonly used for film formation
from liquid solution, including solvent evaporation, in situ growth from solution and other alternative methods. Although these techniques
allow control over the thickness and pore structures in thin films or membranes, they currently offer limited control over the pore alignment
relative to the substrate surface. The ordered mesoporous and macroporous thin films and membranes are highly promising for a range of
potential applications in separations, chemical sensing, heterogenous catalysis, microelectronics and photonics as insulating layers of low
dielectric constant and photonic bandgap materials. Furthermore, functionalization of the internal pore surfaces in these films and deposition
of functional nanoparticles within the pores offer numerous new possibilities for molecular engineering of catalytic, photonic, and magnetic
materials for advanced nanotechnological applications based on quantum confinement effect.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Mesoporous; Macroporous; Pore structures

1. Introduction films and membranes were made by compacting nano- or

According to IUPAC [1], mesoporous and macroporous
films or membranes refer to materials with pore diameters in
the 2–50 and >50 nm ranges, respectively. The term “film”
is used to describe a material in a specific planar geometry,
while the membrane is defined as a thin physical barrier al-
lowing selective transport of mass species. Thin films can
be formed on any support (substrate), whereas membranes
must be prepared on a porous support (or substrate), which
allows transport of mass species. Mesoporous and macrop-
orous films and membranes have been studied extensively
in the past decades and many of them have found commer-
cial applications [2,3]. Examples of these applications in-
clude a large number of inorganic membrane microfiltration
and ultrafiltration processes being used in industry for bev-
erage and drinking water purification and wastewater treat-
ment. The majority of these mesoporous and macroporous
∗ Corresponding author. Tel.: +1-513-556-0203;
fax: +1-513-556-3473.
E-mail addresses: vguliant@alpha.che.uc.edu (V.V. Guliants),
jlin@alpha.che.uc.edu (Y.S. Lin).
1 Co-corresponding author.
micron-sized dense crystallites (such as ␥- or ␣-alumina
crystals). Their pore structure is defined by the crystallite
size and the manner in which they are packed. The pores
of these films or membranes are not arranged in an ordered
fashion as opposed to those in ordered mesoporous and
macroporous films or membranes.
The first ordered mesoporous materials, belonging to alu-
minosilicate molecular sieves called M41S, were reported
by researchers at Mobil over a decade ago [4]. The meso-
porous aluminosilicate and other metal oxide materials with
well-defined pore sizes up to 33 nm break past the pore-size
constraint (<1.5 nm) of microporous zeolites. The ex-
tremely high surface areas (>1000 m2 /g) and precise tuning
of pore sizes are among the many desirable properties that
have made such materials the focus of great attention. 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. Since the initial
discovery of the M41S materials, many other ordered pore
structures corresponding to different surfactant assemblies
have been synthesized. Various aspects of these ordered

0376-7388/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2004.01.019
54 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
mesoporous materials have been reviewed by Brinker (re-
cent advances in porous inorganic materials) [5], Vartuli
et al. (synthesis of the M41S family) [6], Stucky et al.
(biomimetic synthesis of mesoporous materials) [7], Ra-
man et al. (porous silicates templated by surfactants and
organo-silicate precursors) [8], Antonelli and Ying (meso-
porous transition metal oxide (TMS) family) [9], Behrens
(mesoporous transition metal oxides) [10], Zhao et al.
(aluminosilicate MCM-41) [11], and Sayari (catalytic ap-
plications of MCM-41 and HMS) [12].
The most common ordered mesoporous structure is the
two-dimensional hexagonal phase with the P6mm symme-
try, consisting of close-packed hexagonal arrays of cylindri-
cal surfactant micelles. Lamellar silicate-surfactant phases
are also obtained, which are not stable to the removal of
the surfactant which leads to a collapse of the silica lay-
ers. Various cubic phases have also been reported. The bi-
continuous cubic gyroid phase with the Ia3d symmetry is
found in alkaline-catalyzed syntheses. This phase with its
network of interconnected pores is much more attractive
than the two-dimensional hexagonal phase for applications
requiring diffusion of species into and out of the pore net-
work. The Pm3n phase composed of spherical micelles in a
cubic close-packed arrangement is found in both acid- and
alkaline-catalyzed preparations.
The initial work of the Mobil researchers involved
only alkaline-catalyzed preparations and materials re-
ported in these papers are referred to as MCM-41 (P6mm
two-dimensional hexagonal phase), MCM-48 (Ia3d cubic
phase) and MCM-50 (lamellar phase). Two-dimensional
hexagonal mesoporous materials prepared by Inagaki and
co-workers [13] from surfactant-intercalated kanemite are
referred to as FSM-16. Subsequent preparation of materials
in acidic medium led to ordered mesoporous materials with
similar symmetries, but distinct wall properties: SBA-1
(Pm3n, cubic phase), SBA-2 (P63 /mmc, three-dimensional
hexagonally packed spherical micelle phase) and SBA-3
(P6mm, two-dimensional hexagonally packed cylinders)
[14]. Other surfactant-templated phases include disor-
dered materials with a worm-like network of channels:
KIT-1 [15], MSU-1 [16], a well-defined intergrown cu-
bic hexagonal phase STAC-1 [17] and ordered non-ionic
alkyl-EOx -templated materials, e.g. cubic SBA-11 (Pm-3m),
three-dimensional hexagonal SBA-12 (P63 /mmc) [18]. Us-
ing the same methodology, triblock-copolymer-templated
materials with much larger pores have also been synthesized
in acidic systems, e.g. two-dimensional hexagonal SBA-15
(P6mm) [19] and SBA-16 cubic cage structure (Im-3m) [18].
The technological potential of mesoporous materials for
chemical separations and heterogeneous catalysis was rec-
ognized at the time of their discovery [20]. An important
feature of mesoporous materials is the recently discovered
ability to form thin films. While the early work focused
on the synthesis of bulk materials, methods for preparation
of mesoporous materials in a thin film configuration at a
thickness range of tens of nanometers to micrometers were
reported in the last few years. The motivation for synthesis
of mesoporous thin films originates from the appreciation
of their technological potential as membranes, sensors [20],
heterogeneous catalysts [20], and insulating layers of low
dielectric constant for microelectronics [21]. These applica-
tions require the ordered material in the form of thin film.
Mesoporous thin films or membranes are characterized by
bulk properties, such as symmetry, pore diameter, surface
area and stability, and film-related parameters, such as pore
orientation, film thickness, continuity and surface roughness.
Although a number of reviews have appeared on bulk or-
dered mesoporous materials, only one review on ordered
mesoporous films has emerged to date with the emphasis on
self-standing, unsupported films prepared at the liquid and
air interface [22] despite increasing number of published
studies on thin film ordered mesoporous materials and their
technological importance. Ordered macroporous materials
templated by ordered arrays of colloidal spheres and other
shapes have also recently received interest from scientific
community [23]. The present review is focused on solid
substrate-supported thin films of the ordered mesoporous
and macroporous materials that are promising for applica-
tions in chemical sensing, separations and catalysis. We will
first discuss the major preparation routes and mechanisms of
formation of mesoporous thin films and then review poten-
tial applications of these materials in membrane separations,
heterogeneous catalysis and nanotechnology. The subjects
of mesoporous and macroporous films will be discussed in
separate sections because of the fundamentally different for-
mation mechanisms and resulting pore structures.
2. Mechanisms of self-assembly
2.1. Ordered mesoporous materials
2.1.1. Liquid crystal templating mechanism
The original M41S family of mesoporous molecular
sieves is synthesized by reacting a silica source (e.g.
tetraethylorthosilicate (TEOS), Ludox, fumed silica, sodium
silicate), an alkyltrimethylammonium halide surfactant (e.g.
cetyltrimethylammonium bromide (CTAB)), a base (e.g.
sodium hydroxide or tetramethylammonium hydroxide
(TMAOH)), and water at ≥100 ◦ C for 24–144 h. Alumi-
nosilicate M41S is synthesized by addition of an aluminum
source to the synthesis mixture. The as-synthesized product
contains occluded organic surfactant, which is removed by
calcination at ∼500 ◦ C in air to yield an ordered mesoporous
material.
A “liquid crystal templating” (LCT) mechanism of forma-
tion was proposed by the Mobil researchers (Fig. 1), based
on the similarity between liquid crystalline surfactant as-
semblies (i.e. lyotropic phases) and M41S [4]. The common
traits were the mesostructure dependence on the hydrocar-
bon chain length of the surfactant tail group [24,26], the ef-
fect of surfactant concentration, and the influence of organic
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72 55

Fig. 1. Formation of mesoporous structures by liquid crystal templating mechanism (redrawn from [22]): (path a) via pre-existing surfactant liquid crystal
phase; (path b) via the formation of silica-coated surfactant species that (path c) either form micelles which agglomerate to form ordered and disordered
arrays or (path d) a lamellar phase which undergoes a phase transition into the final hexagonal phase. Mesoporous phase exhibiting a hexagonal array
of ordered pores is obtained after calcination to remove the surfactant.

swelling agents. Two mechanistic pathways were proposed
by the Mobil researchers to explain formation of MCM-41
containing two-dimensional hexagonal arrays of cylindrical
mesopores: (1) via condensation and cross-linking of the in-
organic species at the interface with a pre-existing hexago-
nal lyotropic liquid crystal (LC) phase; and (2) via ordering
of the surfactant molecules into the two-dimensional hexag-
onal mesophase mediated by the inorganic species and fol-
lowed by their condensation and cross-linking.
In the both pathways, the inorganic species, which are
negatively charged at the high synthesis pH preferen-
tially interact with the positively charged alkyl ammonium
head groups of the surfactants and condense into a solid,
continuous framework. The resulting organic-inorganic
mesostructure could be alternatively viewed as a hexagonal
array of surfactant micellar rods embedded in a silica ma-
trix. The surfactant removal produces the open mesoporous
MCM-41 framework. Typical TEM images of mesoporous
two-dimensional hexagonal mesostructures are shown in
Fig. 2 [25]. These mesophases with pore sizes >2.5 nm
generally display type IV nitrogen adsorption–desorption
isotherms at 77 K characteristic of mesoporous materials
with ordered unimodal pore size distribution shown in Fig. 3.
M41S type materials with smaller mesopores (1.7–2.5 nm)
exhibit type I isotherms characteristic of microporous ma-
terials. It is now known that pathway 1 did not take place
in the Mobil syntheses because the surfactant concentra-
tions used were far below the critical micelle concentration
(CMC) required for the hexagonal LC formation [26]. This
mechanism was recently shown to be valid under different
synthesis conditions (see Section 2.2).
The second mechanistic pathway of LCT was proposed as
a cooperative self-assembly of the alkyl ammonium surfac-
tant and the silicate precursor species below the CMC. It is
well established that no preformed LC phase is necessary for
the MCM-41 formation, but to date the mechanistic details
of MCM-41 synthesis have not yet been fully agreed upon.
Several mechanistic models have been advanced which share
the basic idea that the silicate species promoted LC phase
formation below the CMC.
2.1.2. Inorganic species-driven self-assembly
Davis and co-workers [27] found that the hexagonal LC
phase did not develop during the MCM-41 synthesis, based
56 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72

rods. The silicate-encapsulated rods were randomly ordered,

Fig. 2. High resolution TEM image of two-dimensional hexagonal meso-
porous SBA-15 silica in the direction along (A) and perpendicular (B) to
the c-axis [25].
on in situ 14 N NMR spectroscopy. They proposed that, under
the synthesis conditions reported by Mobil, the formation of
MCM-41 began with the deposition of two to three mono-
layers of silicate precursor onto isolated surfactant micellar
BJH Adsorption dV/dlog(D) Pore Volume
10
8 SLC phase caused the silicates to condense irreversibly into
Pore Volume (cm3/g)
eventually packing into a hexagonal mesostructure. Heating
and aging completed the condensation of the silicates into
the as-synthesized MCM-41 mesostructure.
Instead of the formation of silicate-covered micellar rods,
Steel et al. [28] postulated that surfactant molecules assem-
bled directly into the hexagonal LC phase upon addition of
the silicate species, based on 14 N NMR spectroscopy. The
silicates were organized into layers with rows of the cylin-
drical rods intercalated between the layers. Aging the mix-
ture caused the layers to pucker and collapse around the
rods, which then transformed into the surfactant-containing
two-dimensional hexagonal MCM-41 structure.
A “charge density matching” mechanistic model proposed
by Monnier et al. [29] and Stucky et al. [30] suggested that
MCM-41 could be derived from a lamellar phase. The ini-
tial phase of the synthesis mixture was layered as detected
by X-ray diffraction (XRD) formed due to the electrostatic
attraction between the anionic silicates and the cationic sur-
factant head groups. As the silicate species began to con-
dense, the charge density was reduced. Accompanying this
process, the 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.
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. [31] con-
clusively showed, through 2 H and 29 Si 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 [32]. The silicate anions
ion-exchanged with the surfactant halide counterions, to
form a “silicatropic liquid crystal” (SLC) phase that involved
silicate-encrusted cylindrical micelles. The SLC phase ex-
hibited behavior very similar to typical lyotropic systems,
except that the surfactant concentrations were much lower
and the silicate counterions were reactive [33]. Heating the

MCM-41. Firouzi et al. [31,33] also demonstrated that in

addition to the charge balance requirement (i.e. electrostatic
6 interaction) there was preferential bonding of the alkyl
ammonium head groups to multi-charged D4R (double
4 four-ring, [Si8 O20 ]8− ) silicate anions under the high pH con-
ditions. The interaction was so strong that an alkyltrimethy-
lammonium surfactant solution could force a silicate solu-
2 tion that did not contain D4R oligomers to re-equilibrate and
form D4R species. It was suggested that this behavior came
0 from the closely matched projected areas of a D4R anion and
2 4 6 8 10 12 14 an ammonium head group (0.098 nm2 versus 0.094 nm2 ) and
the correct distribution of charges on the projected surfaces.
Pore Size (nm) Fyfe and Fu [34] were able to prepare mesostructured sili-
Fig. 3. Pore size distribution of a typical two-dimensional hexagonal cates with D4R silicates. Combination of the D4R precursors
SBA-15 mesoporous silica [25]. with cetyltrimethylammonium chloride (CTAC) surfactants
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72 57

produced mesostructured precipitates. Control of the con-

densation of the silicates within the mesostructure by acidic
vapor treatment led to the observation of cubic, lamellar and
hexagonal phases as intermediate transformation phases.
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 [35]
found evidence for MCM-41 intermediate structures in the
form of clusters of rod-like micelles “wrapped” by a coat-
ing of silicate through low-temperature transmission elec-
tron microscopy (TEM) and small-angle X-ray scattering.
The clusters of elongated micelles were found before pre-
cipitation occurred. According to Regev [35], as the reac-
tion progressed, the silicate species diffused to and deposited
Fig. 5. SEM image of colloidal array of ∼400 nm polystyrene spheres
onto the individual surfaces of the micelles within the clus-
[130].
ter. The clusters of elongated micelles eventually became
clusters of silicate-covered micelles. Thus, the clusters of
micelles served as nucleation sites for MCM-41 formation. condense and form a solid framework around the spheres.
Finally, the spheres are removed by either calcination or sol-
2.2. Ordered macroporous materials vent extraction.
The success of forming macroporous ordered structures
Colloidal crystals consisting of three-dimensional ordered is mainly determined by van der Waals interactions, wetting
arrays of monodispersed spheres, represent novel templates of the template surface, filling of the voids between the
for the preparation of highly ordered macroporous inor- spheres and volume shrinkage of the precursors during so-
ganic solids, exhibiting precisely controlled pore sizes and lidification process. The colloidal crystal templating method
highly ordered three-dimensional porous structures. This may be used in combination with sol–gel, salt solution,
macroscale templating approach typically consists of three nanocrystalline and other precursors to produce the inor-
steps as shown in Fig. 4. First, the interstitial voids of the ganic three-dimensional macrostructures [23]. The colloidal
monodisperse sphere arrays are filled with precursors of var- crystal templates used to prepare three-dimensional macro-
ious classes of materials, such as ceramics, semiconductors, porous materials include monodisperse polystyrene (PS),
metals, monomers, etc. In the second step, the precursors poly(methyl methacrylate) (PMMA) and silica spheres.

Fig. 4. Experimental procedure to generate three-dimensional macroporous inorganic materials by templating against crystalline arrays of colloidal spheres
(modified from [124]).
58 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72

3. Preparation of films and membranes

3.1. Mesoporous films and membranes

3.1.1. Solvent evaporation techniques

Fig. 6. SEM image of macroporous inorganic material. The walls are com-
posed from vanadium–phosphorus oxide crystals (modified from [130]).
A typical SEM image of a colloidal array of polystyrene
spheres used as a template in the synthesis of macroporous
inorganic materials is shown in Fig. 5. Prior to precursor
infiltration, these monodisperse spheres are ordered into
close-packed arrays by sedimentation, centrifugation, verti-
cal deposition or electrophoresis [36]. The final inorganic
macroporous structure after the removal of spheres contains
ordered interconnected pore structure shown in Fig. 6.
The solvent evaporation techniques involve formation of
a liquid film containing the solvent, surfactant and silica pre-
cursor followed by evaporation of the solvent. Several meth-
ods can be used to form liquid films. These include dip-,
spin-coating and film casting. Solvent evaporation has been
suggested as the driving force for the organization of surfac-
tant species into mesoscale aggregates (i.e. lamellar, hexag-
onal, cubic) around which condensation of silicate species
takes place. The various mesostructured inorganic films and
membranes prepared by the solvent evaporation techniques
are summarized in Tables 1–3 [37–83].
The mesostructured films prepared by a dip-coating
method are shown in Table 1. In this method, the substrates
are withdrawn from a homogeneous precursor solution and
the dip-coated solution is allowed to drain to a particular
thickness [84]. The thickness of the film is mainly deter-
mined by the rate of evaporation of the solvent and the
viscosity of the solution. One of the advantages of this
method is the facile formation of films on non-planar sur-
faces. Casting is another solvent evaporation method that
has been used for the preparation of mesostructured films.

Table 1
Ordered mesostructured films prepared by dip-coating
Thin film structure Precursors Support Reference
Three-dimensional cubic silica TEOS, ethanol, HCl, CTAB Alumina [37]
Hexagonal and three-dimensional cubic silica  TEOS, ethanol, HCl, PEO-PPO-PEO Silicon wafers and glass [38]
slides
Two-dimensional hexagonal silica  TEOS, PEO-PPO-PEO, ethanol, HCl, pluronic Si(1 0 0) wafers [39]
F-127
Two-dimensional hexagonal and rectangular titania  TiCl4 , ethanol, pluronic F-127, Brij 58 Glass or silicon substrates [40]
Disordered tungsten oxide WCl6 , pluronic P-123, ethanol Tin-doped indium oxide [41]
(ITO)-coated glass
Hexagonal silica TEOS, Glass slides [42]
3-(2,4-dinitrophenylamino)propyltriethoxysilane,
CTAB
Two-dimensional hexagonal and two-dimensional ZrCl4 , C16 H33 (CH2 CH2 O)20 OH ethanol, H2 O Silicon [43]
rectangular ZrO2
Two-dimensional hexagonal aluminum oxide normal AlCl3 , C16 H33 (CH2 CH2 O)20 OH ethanol, H2 O, Glass plates or silicon wafers [44]
to the substrate NH4 OH
Hexagonal silica  TEOS, CTAB, ethanol, H2 O, HCl Glass slide [45]
Hexagonal silica TMOS, NaOH, NH3 , H2 O, CTABr Silicon wafers, borosilicate [46]
glass
One-dimensional hexagonal silica TEOS, HCl, H2 O, F-127, EtOH Glass and silicon [47]
One-dimensional hexagonal and cubic silica  TEOS, HCl, H2 O, EtOH, Brij 56 Silicon with oxide [48]
overlayer (SiO2 /Si) and Au
Three-dimensional hexagonal silica, c-axes ⊥ TEOS, HCl, H2 O, CTABr, EtOH Silicon wafers [49]
Hexagonal and cubic silica  TEOS, HCl, H2 O, CTABr Silicon [50]
One-dimensional hexagonal, three-dimensional TEOS, CTAB, Brij 56, HCl, H2 O Silicon [51]
hexagonal, lamellar and cubic silica
Two-dimensional hexagonal silica membranes  TEOS, HCl, H2 O, alkyl trimethyl ammonium Glass or silicon [52]
bromides (C12 –C16 )
Three-dimensional hexagonal and cubic silica  TEOS, HCl, H2 O, gemini surfactants Silicon wafers or glass [53]
One- and two-dimensional hexagonal silica  TEOS, EtOH, HCl, H2 O, CTAB, F-127 Glass or silicon wafers [54]
Cubic and three-dimensional hexagonal silica  TEOS, HCl, EtOH, CTAB Silicon wafers [55]
: Parallel to interface; ⊥: normal to interface.
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72 59

Table 2
Ordered mesostructured films prepared by casting
Thin film structure Precursors Support Reference

Hexagonal silica  TEOS, CTAC, HCl Functionalized Si(1 0 0) [56]

wafers
Hexagonal silica  TEOS, C12 EO10 C16 EO10 , C16 TAC, HCl, H2 O Silica glass substrate coated [57]
with polyimide film
Hexagonal silica  TEOS, cetylpyridinium chloride, H2 O HCl Glass slides [58]
Hexagonal silica  TEOS, HCl, H2 O, gemini surfactants, alkyl Glass [59]
ammonium bromides (C12 –C18 )
Hexagonal silica  TEOS, HCl, H2 O, CTACl Silicon wafers [60]
Hexagonal silica  TEOS, HCl, H2 O, CTACl Mica–gold layer [61]
Hexagonal silica  TEOS, HCl, H2 O, CTABr, EtOH Unsupported [62]
Lamellar, one-dimensional TEOS, PrOH, HCl, CTACl, H2 O Glass [63]
hexagonal and cubic silica
Two-dimensional hexagonal TMOS, NaOH, NH3 , CTAB, CTAHS Silicon or glass [64]
silica
: Parallel to interface.

In this method, the solution is dropped on to the substrate
and allowed to solidify, resulting in much thicker films.
Some examples of mesostructured films prepared by casting
and modified casting techniques are shown in Table 2.
Spin-coating has been widely used for the preparation of
mesostructured films by solvent evaporation summarized in
Table 3. Four stages of spin-coating can be distinguished:
deposition of the surfactant/inorganic solution, spin-up,
spin-off and evaporation [84]. Initially, an excess of liquid
is deposited on the surface of the substrate during the first
stage. In the spin-up stage, the liquid flows radially outward
by centrifugal force. In the spin-off stage, the excess of liq-
uid flows to the perimeter and leaves in a form of droplets.
In the final stage, evaporation takes place leading to the
formation of uniform thin films. One of the most important
advantages of this method is that the film tends to become
very uniform in thickness. The main disadvantage of this
method is that it can only be used with flat substrates.

Table 3
Ordered mesostructured films prepared by spin-coating
Thin film structure Precursors Support Reference

Hexagonal silica  TMOS, HCl, CnTAC Pyrex glass [65]

Hexagonal silica  TEOS, CTACl, HCl Glass [66]
Three-dimensional hexagonal silica c-axis ⊥ to TEOS, HCl, CTAB, ethanol Glass plates [67]
the film plane
Three-dimensional hexagonal silica ⊥ TEOS, CTAB, HCl, ethanol Glass plates [68]
Hexagonal titania Ti(OCH(CH3 )2 )4 , HCl, propanol Glass slides [69]
Hexagonal silica  TEOS, CTAC, HCl, pluronic P-123 Microslide glass, titanium, [70]
silicon
Hexagonal disordered titania Ti(OC4 H9 )4 , ethanol, HCl, CTAC, BTAC Soda lime silica glass plates [71]
Disordered silica TEOS, pluronic P-123, ethanol, Si(1 0 0) single crystal [72]
polypropylene glycol wafers or at-cut piezoelectric
crystalline quartz
Oriented lamellar silica TEOS, ethanol, HCl, Fe-TMA Glass [73]
Hexagonal silica Sodium silicate solution, H2 SO4 , CTACl ITO-coated glass [74]
Hexagonal and cubic SiO2  TEOS, P-123, F-127, ethanol, H2 O, HCl N-type silicon with SiO2 and Si3 N4 [75]
Disordered tungsten oxide WCl6 , ethanol, P-123 ITO-coated glass, Pyrex glass [76]
Hexagonal silica TMOS, NaOH, NH3 , H2 O, CTABr Silicon wafers, borosilicate glass [46]
One-dimensional hexagonal silica  TEOS, HCl, H2 O, P-123 Glass [77]
Hexagonal silica  TEOS, HCl, H2 O, P-123 Glass [78]
One-dimensional hexagonal and cubic silica  TEOS, HCl, H2 O, EtOH, Brij 56 Silicon with oxide overlayer [48]
(SiO2 /Si) and Au
Hexagonal silica TEOS, HCl, H2 O, CTABr, EtOH Surface aluminum hydroxide [79]
on glass
One-dimensional hexagonal silica  TEOS, HCl, H2 O, CTACl, PrOH Glass [80]
Lamellar, one-dimensional hexagonal silica  TEOS, HCl, H2 O, CTACl, PrOH Glass [81]
Hexagonal and cubic silica  TEOS, HCl, H2 O, CTABr Silicon [50]
Disordered titania Ti(OC4 H9 )4 , EtOH, HCl, CTACl Glass plates [82]
Lamellar, hexagonal and cubic silica  TMOS, CTACl, HCl, H2 O Glass [83]
: Parallel to interface; ⊥: normal to interface.
60 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72

In a very interesting alternative synthesis approach,
Chan et al. [85] prepared three-dimensional cubic ceramic
mesostructured films via spin-casting by employing silicon-
containing triblock copolymers. In this proposed method, a
bifunctional oxidation process consisted in ozonolysis and
UV radiation, was used to selectively remove hydrocarbon
blocks and convert the remaining silicon-containing tem-
plate composite into a mesostructured silicon oxycarbide.
Different pore structures (i.e. hexagonal, cubic, rect-
angular) and pore symmetries (P6mm two-dimensional
hexagonal, Ia3d cubic, P63 /mmc three-dimensional hexag-
onally packed spherical micelle, etc.) with one-, two- and
three-dimensional pores have been observed on the films
prepared by these three methods. However, the control over
pore orientation relative to the substrate surface still remains
a major synthesis challenge for two-dimensional hexagonal
structures in particular, because the pore alignment normal
to the substrate surface is required for making these pores
accessible in membranes and thin films.
3.1.2. Growth from solution
The basic principle for the synthesis of ordered meso-
porous films by growth from solution is to bring the syn-
thesis solution (including a solvent, surfactant and inorganic
precursor) in contact with a second phase, e.g. solid (ce-
ramic), gas (air) or another liquid (oil). The two-phase sys-
tem is kept under specific conditions and the ordered film
is formed at the interface. When the second phase is solid,
it is the support on which the ordered film or membrane is
grown. When the second phase is air or oil, the solid films are
self-standing. The formation of the ordered films in the pres-
ence of different second phases is briefly discussed further.
Ordering of inorganic-surfactant species can occur spon-
taneously at the solid support interface submerged in the
synthesis solution. It has been shown that films of this
type grow only in acidic solutions [22]. The first example
of silicate-surfactant films formed spontaneously from an
acidic synthesis medium on mica substrates was reported
by Yang et al. [86]. A formation mechanism was proposed,
in which nucleation of silica-surfactant micelles on the
freshly cleaved mica surface takes place. Crystal growth
is then regulated by charge and structure matching at the
surface. Some of the relevant work on growth of mesostruc-
tured films at the solution–support interface [86–103] is
summarized in Table 4. Mostly cubic and two-dimensional
hexagonal films with pores oriented parallel to the substrate
have been reported. Interestingly, Tolbert et al. [98] re-
ported two-dimensional hexagonal films with the preferred
alignment of pores normal to the plane of the film either
at the solution–support or air–water interface. It was pro-
posed that the films nucleate on micellar structures in an
oriented fashion and then grow into the solution. It should
be pointed out that most solid substrates used in these
studies were dense, whereas porous substrates are required
for membrane applications.
Yang et al. [89] reported for the first time an example of
a free-standing silicate-surfactant film spontaneously grown
at the air–solution interface. The films were prepared from
dilute acidic solutions. The silicate film formation was pro-
posed to occur by the polymerization of silicate species in
the surfactant head group regions of the hexagonal phase
that was concentrated at the liquid surface overstructure [22].
Three-dimensional hexagonal silicate films have been grown
at the air–water interface [98]. Mesostructured films grown
at the air–solution interface [104–114] are summarized in
Table 5.
Growth at an oil–solution interface involves the solu-
bilization of the silica precursor in the oil phase. When

Table 4
Ordered mesostructured films grown at solution–support interface
Support Growth method Pore orientation References

M Heteronucleation of two-dimensional H phase  For mica [86]

M, G, SiO2 Heteronucleation of two-dimensional H phase  For M and G disordered for SiO2 [87,88]
G Heteronucleation of two-dimensional H phase  [89]
SAM/Au Heteronucleation of two-dimensional H phase  [61,90]
SAM/Si Heteronucleation of two-dimensional H phase  [56]
SiO2 Nucleation in applied dc field Slightly distorted two-dimensional H  [91,92]
SiO2 , NbO, TiO, other oxides Micromolding, colloidal sphere templating Three-dimensional C, two-dimensional H  [93]
B–Si glass Two-dimensional H  along flow direction [94]
B–Si glass Shear field in continuous-flow cell Three-dimensional H  along flow direction [95]
M ∼50% ⊥ [96]
M Gemini surfactant assemblies Two-dimensional H  [97]
M Gemini surfactant assemblies Two-dimensional H ⊥ [98]
Si Heteronucleation of two-dimensional H phase two-dimensional H  [66,99,100]
SiO2 , Si “Rubbing method” for polyimide overlayer Two-dimensional H  [66,99]
Porous SS Heteronucleation of MCM-48 Three-dimensional C [101]
Porous Al2 O3 Heteronucleation of MCM-48 Three-dimensional C [102]
Porous SS Growth of silica in the pores of support C [103]
M: Freshly cleaved mica; G: graphite; SiO2 : amorphous silica; NbO: niobia; TiO: titania; SAM/Au: self-assembled monolayer of hexadecanethiolate on
gold; SAM/Si: self-assembled monolayer of octadecylsilyl groups on Si; B–Si: borosilicate; SS: stainless steel; H: hexagonal; C: cubic; : parallel to
interface; ⊥: normal to interface.
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72 61

Table 5
Ordered mesostructured films grown at air–water interface
Precursors Pore orientation References

Dilute acidic TEOS and C16 TACl Two-dimensional H  [89,104–106]

Dilute acidic TEOS and C16 TAB Two-dimensional H  [107,108]
Dilute acidic TEOS and C16 TAB Three-dimensional C, two-dimensional H  [109]
Dilute acidic TMOS and C16 TAB Two-dimensional H  [110,111]
Alkaline TEOS and C16 TAB Disordered two-dimensional H [112]
Dilute acidic TEOS and gemini surfactants Three-dimensional H with pore component ⊥ to interface [98]
Dilute acidic TEOS and C16 TACl H and C  [88]
Dilute acidic TEOS and PEO–PPO–PEO triblock copolymers Two-dimensional H and three-dimensional  [113]
Acidic TEOS, glycerol–H2 O and C16 TAB Disordered mesostructure [114]
H: Hexagonal; C: cubic; : parallel to interface; ⊥: normal to interface.

separated from the aqueous solution, the silica precursors
react with the surfactant at the oil droplet interface forming
the desirable mesoporous silica particles (i.e. hexagonal or
cubic). The most representative examples of films grown at
the oil–solution interface [115,116] are shown in Table 6.
Schacht et al. [115] showed the possibility of pore align-
ment by growing mesoporous silicate films at the oil–water
interface.
3.1.3. Alternative deposition techniques
Alternative deposition techniques reported to date in-
clude electrodeposition and pulsed laser deposition. Various
mesostructured inorganic films prepared by these techniques
are summarized in Table 7 [117–122]. Electrodeposition of
mesoporous thin films was employed to create continuous
thin films of mesostructured materials on a variety of sub-
strates. This method was reported by Attard et al. [117],
Elliott et al. [118,119], Whitehead et al. [120] and Gollas
et al. [121]. They used a direct liquid crystal templating
method, which required a high surfactant concentration
(>30 wt.%) to provide a homogeneous liquid crystal phase
during the entire electrodeposition process. Mesoporous Pt
or Sn films were deposited via the reduction of hexachloro-
platinic acid or Sn(II) sulfate, respectively, in an electro-
plating solution containing a two-dimensional lyotropic
hexagonal mesophase of non-ionic oligoethylene glycol
monoalkyl ether surfactants (Cn EO8 , n = 12–16). The pore
diameters varied from 17.5 to 35 Å depending on the sur-
factant chain length and a hydrophobic swelling agent used,
such as n-heptane. The pores appeared to be tilted 20◦ away
from the normal orientation relative to the substrate surface.
The electrodeposition method has an advantage that it can

Table 6
Ordered mesostructured films grown at oil–water interface
Growth method Pore orientation Reference

TEOS in oil (n-C6 H14 , C6 H6 , toluene, mesitylene) Two-dimensional H ⊥ to interface [115]

HCl in water, and C16 TAB at interface
TEOS in oil (n-C7 H16 ), HCl in water, and C16 TACl at interface Two-dimensional H  to interface bicontinuos C [116]
TEOS in oil (n-C7 H16 ), NaOH in water, and C16 TAB at interface
H: Hexagonal; : parallel to interface; ⊥: normal to interface.

Table 7
Ordered mesostructured films prepared by alternative deposition techniques
Thin film type Precursors Support type Deposition method Reference

Hexagonal Pt C16 EO8 , H2 O, H2 PtCl6 Au electrodes Electrodeposition [117]

Hexagonal Pt Hexachloroplatinic acid hydrate, H2 O, C16 EO8 Au wire and Au plate electrodes Electrodeposition [118]
Hexagonal Pt Platinic acid hexahydrate, H2 O, C16 EO8 Au microelectrodes Electrodeposition [119]
Hexagonal metallic Sn SnSO4 , C16 EO8 , C18 EO8 , C18 EO20 , H2 SO4 Cu or Au electrodes Electrodeposition [120]
Hexagonal Pt Hexachloroplatinic acid hydrate, H2 O, H2 SO4 , Au-coated quartz crystals Electrodeposition [121]
C16 EO8
Hexagonal silica ⊥ to SiO2 , NaOH, CTAB, H2 SO4 Si or SS porous substrates Pulsed laser deposition [122]
the substrates
One-dimensional Selenium dioxide, H2 SO4 , C16 EO8 , H2 O Ni sheet electrodes, Pt electrodes, Electrodeposition [123]
hexagonal Se Au on glass films
SS: Stainless steel; ⊥: normal to interface.
62 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72

Table 8
Bulk macroporous materials prepared using colloidal sphere templates by sol–gel method
Colloidal template Macroporous framework Pore structure References

0.2–1.0 ␮m ps SiO2 150–1000 nm, hcp [124]

∼0.35 ␮m oil microemulsion droplets TiO2 , SiO2 ZrO2 >50 nm, hcp [125]
∼0.47 ␮m ps TiO2 , ZrO2 , Al2 O3 320–360 nm, hcp [126]
0.4–0.7 ␮m ps SiO2 , TiO2 , ZrO2 , Al2 O3 , Fe2 O3 , Sb4 O6 , WO3 , YZrO2 250–500 nm, ffc/hcp [127]
∼0.526 ␮m ps SiO2 Disordered hcp, ∼250 nm [128]
∼0.4 ␮m ps Vanadium phosphorus oxides 300–400 nm, hcp [129,130]
∼1 ␮m ps SiO2 , TiO2 , ZrO2 , PbTiO3 , Pb(ZrTi)O3 Disordered hcp, 800–1000 nm [131]
∼0.7–0.85 ␮m ps Eu2 O3 , Nd2 O3 , Sm2 O3 , ∼300–350 nm, hcp [132]
0.64 ␮m ps TiO2 , SiO2 ZrO2 Disordered hcp, ∼400 nm [133]

be used to deposit thin films onto non-planar substrates.
However, it is limited to electrodeposition of metals under
mild conditions (temperature, pH, reactant concentration)
needed to provide stable liquid crystal phases.
Pulsed laser deposition (PLD) is another alternative de-
position technique for creating continuous mesoporous thin
films on non-planar surfaces. The laser ablation process in-
volves irradiating a bulk mesoporous target with an intense
laser beam, which results in the ejection and deposition
of nanoscale fragments of the mesoporous structure on a
substrate surface. Balkus Jr. et al. [122] have developed
a guest assisted laser ablation technique which consisted
of exchanging the bis(pentamethylcyclopentadienyl) cobal-
tocenium ion (Cp2 *Co+ ) or ferrocene followed by PLD.
The exchanged species absorbed the UV laser irradia-
tion during ablation preventing the generation of defects
in the bulk mesoporous structure and resulting in deposi-
tion of continuous, well-adhered and ordered mesoporous
films. A post-PLD hydrothermal treatment resulted in a
two-dimensional hexagonal MCM-41 phase without the
preferential alignment of the pore channels relative to the
substrate surface and the transition metal oxide meso-
porous molecular sieve Nb-TMS1 exhibiting a worm-like
interconnected pore structure. Although the pulsed laser
deposition method can produce good quality ordered meso-
porous films, sophisticated equipment is required for film
production. It is unlikely that this method will be able to
compete with solvent evaporation techniques in speed and
degree of control over resulting film structures and pore
orientations.
3.2. Macroporous films and membranes
3.2.1. Synthesis of macroporous materials
Several synthesis methods have been used in the past to
prepare three-dimensional macroporous inorganic materials.
These include sol–gel, salt precipitation, nanocrystal infil-
tration and polymerization. All the synthesis methods rely
on the use of polymeric or inorganic template, usually in a
form of spheres packed in a periodic fashion. Bulk ordered
macroporous materials prepared by the sol–gel [124–133]
and other methods [134–146] are summarized in Tables 8
and 9, respectively. The most representative methods to pre-
pare inorganic macrostructures are briefly discussed further.

Table 9
Bulk macroporous materials prepared using colloidal sphere templates by other synthesis methods
Colloidal template Macroporous framework Pore structure Synthesis method References

0.36–2.92 ␮m ps TiO2 240–2000 nm, hcp Liquid phase chemical reaction [134]
∼0.4–0.7 ␮m ps NiO 250–500 nm, hcp Salt precipitation and chemical [135]
conversion
0.6–0.8 ␮m ps MgO, NiO, Cr2 O3 , Mn2 O3 , Fe2 O3 , Co3 O4 , 380–550 nm, hcp Salt precipitation and chemical [136]
conversion
0.56 ␮m ps SiO2 , TiO2 320–525 nm, fcc Nanocrystal incorporation [137]
0.21–0.26 ␮m silica spheres CdSe ∼200–250 nm, fcc Nanocrystal incorporation [138]
0.23–0.48 ␮m ps Polyurethane, polyacrylate, epoxy > 50 nm, ccp Polymerization [139]
>0.1 ␮m PS or silica spheres Polyacrylate-methacrylate, copolymer PAMC, > 60 nm, ccp, fcc Infiltration/polymerization [140]
polyurethanes
0.2–0.4 ␮m silica spheres Polyurethane, polystyrene, poly(methyl 200–400 nm, hcp Polymerization [141]
acrylate)
0.13–0.3 ␮m ps Ni, SnCo, Au, Si, Pt 150–200 nm, hcp Ion spraying/laser spraying [142]
0.466 ␮m ps and 1 ␮m silica CdS, CdSe 400–800 nm, hcp Electrodeposition [143,144]
spheres
0.5–0.75 ␮m ps Polypyrrole, polyaniline, polybiothiophene 300–700 nm, hcp Electrodeposition/polymerization [145]
0.33 ␮m ps/0.336 ␮m silica TiO2 , ZrO2 , Al2 O3 , polypyrrole, PPV, CdS, ∼270–330 nm, hcp Inverse opal templating [146]
spheres, 0.33 ␮m PMMA/ AgCl, Au, Ni
0.336 ␮m silica spheres
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
Macroporous inorganic frameworks have been success-
fully prepared using the sol–gel method, in which metal
alkoxides dissolved in alcohol are impregnated into the voids
of the colloidal (polymer) sphere arrays. Hydrolysis and
condensation take place at the sphere surface, leading to the
formation of the inorganic framework. Subsequent heat
treatment to remove the polymer spheres results in an
ordered macroporous metal oxide. The final macropore di-
mensions are ∼15–30% smaller than the original size of the
spheres due to the shrinkage of the inorganic framework.
This is caused by a large volume loss during sol–gel pro-
cess as an alcohol is evaporated. Significant shrinkage of
the inorganic framework during template removal by heat
treatment results in severe cracking and loss of long-range
order. Therefore, the sol–gel method in combination with
heat treatment to remove polymer spheres has not resulted
to date in highly ordered macroporous materials for pho-
tonic bandgap applications for which long-range order is
required. Several single, binary and tertiary oxides have
been prepared using the sol–gel chemistry: SiO2 [124];
TiO2 , ZrO2 , SiO2 [125]; TiO2 , ZrO2 , Al2 O3 [126]; SiO2 ,
TiO2 , ZrO2 , Al2 O3 , Fe2 O3 , Sb4 O6 , WO3 , YZrO2 [127];
SiO2 [128]; V-P-O [129,130]; SiO2 , TiO2 , ZrO2 , PbTiO3 ,
Pb(ZrTi)O3 [131]; Eu2 O3 , Nd2 O3 , Sm2 O3 [132]; TiO2 ,
TiO2 /SiO2 [133]; TiO2 [134].
Precipitation of metal salts, such as acetates and ox-
alates, and oxides within the colloidal polymer sphere
arrays and subsequent chemical conversion of the inor-
ganic precursors is an alternative method to prepare ordered
macroporous structures. This procedure is less sensitive to
atmospheric humidity and allows the formation of ordered
three-dimensional macroporous structures for compositions
difficult to prepare by the sol–gel chemistry [23]. Yan et al.
[135] reported the synthesis of macroporous NiO with
250–500 nm voids using templated precipitation and subse-
quent chemical conversion of the inorganic precursors. The
metal salt solution (acetates or nitrates) penetrated the void
spaces between the spheres, and subsequent calcination of
the macrocomposite removed the spheres and produced the
desirable metal oxide. A number of ordered macroporous
inorganic oxides have been prepared using the salt pre-
cipitation method: MgO, Cr2 O3 , Mn2 O3 , Fe2 O3 , Co3 O4
[136].
Ordered macroporous materials may be prepared by fill-
ing the void spaces of colloidal sphere arrays with nanopar-
ticles. This method offers the great advantage of incorporat-
ing specific nanoparticles of desirable crystalline phases into
the wall structure of the macroporous framework. Another
major advantage of this method is that it results in a minor
shrinking and cracking of the three-dimensional framework
developed during template removal. Typically, the pore
shrinkage is limited to 5–10%. Subramania et al. [137] used
monodisperse PS spheres to template colloidal dispersions
of silica and titania which led to three-dimensional struc-
tures with 320–525 nm macropores. Vlasov et al. [138]
used CdSe nanocrystals templated against monodisperse
63
silica spheres to synthesize macroporous CdSe semicon-
ductor.
Polymerization of organic precursors around colloidal
silica sphere arrays is a common method to produce ordered
macroporous polymeric materials. The colloidal arrays of
spheres are filled with a liquid monomer, which is subse-
quently polymerized by a heat treatment or UV irradiation.
Macroporous polyurethane, poly(acrylate–methacrylate),
PMMA, polystyrene, epoxy, poly(methyl acrylate) have
been prepared using this methodology [139–141].
Other miscellaneous techniques for the preparation of
inorganic macrostructures include spraying techniques
[142,147], electrodeposition [143–145,148] and inverse
opal templating [140,146]. Spraying techniques have been
used mainly in the preparation of macroporous films.
Macroporous TiO2 was prepared using spray pyrolysis by
depositing titanyl acetylacetonate onto silica spheres [142].
Macroporous Au was synthesized by ion spraying [147].
Electrodeposition techniques offer excellent control over
the degree of filling and wall thickness. Growth of the
desirable macrostructure occur galvanostatically or poten-
tiostatically. Macrostructures of CdS, CdSe [143,144], ZnO
[148], polypyrrole, polyaniline and polybithiophene [145]
have been successfully prepared by electrodeposition. In
inverse opal templating method, three-dimensional macrop-
orous structures prepared by templating with opal structures
can be subsequently used to form another opal replica. A
wide range of compositions, (TiO2 , ZrO2 , Al2 O3 , polypyr-
role, PPV, CdS, AgCl, Au, Ni) [146] have been prepared
by this method.
The ability to control wall thickness, pore size, elemen-
tal and phase compositions makes the colloidal sphere
array templating a versatile, attractive and flexible route
for the synthesis of highly ordered macroporous materials
with fine-tuned pore and framework architectures. The wall
thickness of macroporous structures can be controlled by
the hydrolysis/condensation rates of the inorganic precur-
sors [127], the PS spheres packing [130] and by forming
core-shell structures at the sphere surface (i.e. deposition
of polyelectrolyte multilayers at the sphere surface) [133].
The pore size can be easily manipulated in the range of the
sphere sizes, which are typically 100 nm to 50 ␮m in di-
ameter. Even smaller spheres (20 nm) can be prepared and
used to template small-pore materials [36]. Furthermore,
it is possible to build macroporous structures containing a
specific crystalline phase by incorporating nanoparticles of
desired phases in the voids of sphere arrays [137,138]. De-
pending on the choice of the inorganic sources and template
removal method, various crystalline phases can be obtained
[130]. This suggests that the most critical aspects in the
preparation of these macroporous structures are the ability
of the precursors to infiltrate and condense between the
spaces of the colloidal spheres without swelling or destroy-
ing the template as well as the ability to avoid excessive
grain growth which leads to a decrease in macroporosity
and structural order.
64 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72

Fig. 7. Cross sectional view of a ∼2.5 ␮m copper film with ∼325 nm diameter voids prepared by the template self-assembly approach [149].

3.2.2. Macroporous thin films and membranes After the film formation, PS spheres were removed by
Several examples of macroporous thin films and mem- extraction with chloroform.
branes have been also reported in recent years. Jiang et al. Akin et al. [155] reported the synthesis of macroporous
[149] disclosed a general methodology for preparation of TiO2 films displaying 0.5, 16 and ∼50 ␮m diameter pores.
macroporous metal films from colloidal arrays of silica The ∼1 mm thick films were grown by forming colloidal
spheres. Macroporous Ni, Cu, Ag, Au and Pt films were mixtures of submicron-sized PS latex spheres that were
prepared by introducing metal nanocrystals in multilayer interspersed in 50 nm sized ultrafine TiO2 powder. Ye et al.
colloidal arrays of silica spheres. After the metals were de- [156] synthesized ordered three-dimensional macroporous
posited in the interstitial spaces, the silica template was re- silica films by colloidal crystal templating. Optical mea-
moved by etching in dilute HF. The final macroporous sam- surements indicated that these films exhibited the typical
ples displayed highly ordered free-standing ∼2 ␮m thick behavior of a photonic bandgap material, indicating a crys-
metal films with three-dimensional interconnected spherical talline order in the sample. A robust Si–O–Si network was
voids (200–400 nm). The SEM image of a ∼2.5 ␮m thick formed in the silica gel throughout the voids of PS sphere
Cu film prepared by this technique is shown in Fig. 7. The template prior to heat treatment, resulting in large-area
removal of the template at room temperature is most likely
responsible for the formation of highly ordered macrop-
orous structures without significant framework shrinkage.
Subramania et al. [150–152] described a novel ceramic
fabrication technique for thin-film TiO2 photonic crystals
at visible wavelengths. Ordering of the PS spheres and for-
mation of titania network were performed simultaneously.
The colloidal PS suspension was spread on glass or silicon
substrates and upon slow drying produced a thin film of or-
dered PS spheres embedded in TiO2 matrix, followed by the
removal of the spheres by heat treatment. The reflectance
spectra of these films shifted systematically with the pore
size (Fig. 8), providing the evidence of photonic crystal
effects.
Synthesis of macroporous TiO2 films by a modified
sol–gel technique using silica spheres as a template was also
reported by Turner et al. [153]. A typical film thicknesses
of ∼3 ␮m were obtained. Since the pores (∼300 nm) were
highly ordered, the films possessed intense optical diffrac-
tion properties. Khramov et al. [154] prepared macroporous Fig. 8. Wavelength of the primary reflective peak as a function of the
silicate films by condensing a silica sol synthesized via polystyrene sphere diameter indicating photonic crystal effect of macro-
sol–gel method with 0.1–1 ␮m polystyrene latex spheres. porous TiO2 (modified from [150]).
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
Table 10
Macroporous thin films prepared using colloidal sphere templates by various synthesis methods
Colloidal template Macroporous framework
0.1–1 ␮m ps ∼1 ␮m films, SiO2
0.3–0.4 ␮m ps Films, SiO2
∼0.4 ␮m silica spheres ∼2 ␮m films, Ni, Cu, Ag, Au, Pt
∼0.4–0.8 ␮m ps >10 ␮m films, TiO2
0.5–50 ␮m ps ∼0.1 mm films, TiO2
0.5–0.75 ␮m ps Films, Au, Pt
∼0.22–0.37 ␮m ps Multilayer films, Ni
continuous films. Ordered macroporous Au and Pt films
were prepared by electrochemical reduction of Au and Pt
complex ions (cyanide-free Au plating solution and hex-
achloroplatinic acid) in aqueous solution in the void spaces
between PS spheres [157]. Toluene was used to remove
the spheres. The films displayed regular three-dimensional
(fcc) macroporous structures. The optical reflectivity of
macroporous Ag and Pt films displayed strong diffractive
optical properties due to the highly ordered structure of the
spherical voids and because of the pore diameters in the
range of the visible light wavelengths.
Opaline macroporous ordered Ni films were made by
a tacking method using colloid multilayers as building
blocks [158]. Ni was incorporated in the colloidal multi-
layers by electrochemical deposition of aqueous solutions
NiSO4 ·6H2 O and NiCl2 . These macroporous films in which
the diameters of macropores and chemical compositions
are controlled layer-by-layer may be potentially used as
photonic bandgap materials. One of the advantages of the
macroporous approach is that the self-assembly process
can lead to three-dimensional structures of different com-
positions. However, the current lack of long-range order in
macroporous films is a limitation that needs to be overcome
if these films are to be used as photonic bandgap materials.
Different inorganic macroporous films synthesized us-
ing colloidal sphere templates are summarized in Table 10
[149–158]. Since these macroporous films have relatively
large pore size (submicron to several microns), their mass
transfer resistance is much smaller than the mesoporous
membranes. Therefore, even thick macroporous films can
offer sufficiently high gas or liquid transport rates and may
be employed in various practical applications without the
need of a support.
4. Emerging applications
4.1. Separations and catalysis
4.1.1. Mesoporous films and membranes
Several separation and catalytic applications have
been reported for mesoporous bulk phases. Corriu et al.
65
Pore structure Synthesis method References
Not shown Sol–gel [154]
∼250–300 nm, hcp Sol–gel [156]
200–400 nm, hcp Nanoparticle deposition and [149]
electroless plating
300–700 nm, hcp Ceramic slurry technique [151,152]
Disordered hcp, 0.5–50 ␮m Ceramic slurry technique [155]
500–750 nm, fcc Electrochemical deposition [157]
∼250–300 nm, fcc Stacking [158]
technique/electrochemical
deposition
[159] reported a mesoporous organic-inorganic hybrid
silica functionalized with 5-azanonane-1,9-diamine or
5,8-diazadodecane-1, 12-diamine and complexed with
CuCl2 for N2 /O2 separation by selective adsorption. Meso-
porous matrices have been used to immobilize proteins for
bioseparation applications. Ackerman et al. [160] reported
a protein system bound to a matrix with 50–400 Å pores.
The activity of such immobilized protein was at least two
times greater than the activity of a protein system immobi-
lized under identical conditions on a normal silica matrix
material. The greater activity of the protein–mesoporous
host system is likely related to the better dispersion of
the protein entities as well as with the higher superficial
contact between the proteins and the compounds to be
degraded. Organophosphorus hydrolase (OPH) was the
protein used to degrade organophosphorus compounds
found in pesticides and chemical weapons.The separa-
tion of heavy metals by functionalized mesoporous ma-
terials is of great interest for environmental applications.
Robert et al. found that mesoporous silica functionalized
with 3-mercaptopropyltrimethoxysilane ligands were ex-
tremely effective in the removal of Hg and Ag ions from
aqueous solutions [161]. Zhao and co-workers reported
thiolamino-functionalized SBA-15 silicas for the removal of
heavy metal ions from wastewater [162]. Another examples
of heavy metal ion separation by mesoporous functional-
ized materials have been reported by Etienne et al. [163],
Ryoo and co-workers [164] and Brown et al. [165].
Ordered mesoporous mixed metal vanadium–phosphorus
oxides promising for selective oxidation of n-butane have
been reported by Carreon and Guliants [166,167]. Lin and
co-workers [168] prepared acenaphthene diimine nickel(II)
dibromide catalyst supported on mesoporous particles with
a hexagonal pore structure for ethylene polymerization. It
was observed that a significant reduction in activity was
observed with the supported catalyst in ethylene polymer-
ization as compared to homogeneous catalysts. Soga et al.
[169] prepared aluminoxanes adsorbed on mesoporous sil-
ica displaying ethylene polymerization activity in a catalytic
system containing bis(cyclopentadienyl) zirconium dichlo-
ride. Furuya et al. [170] used Ti-mesoporous silica to oxidize
cyclohexene by t-BuOOH in the presence of benzene and
66 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
cyclohexane to cyclohexene oxide with 99% selectivity at
98% conversion. Examples of bulk mesoporous acid, redox
and other catalysts have been reviewed by Sayari [12].
Few separation and catalytic applications for mesoporous
films and membranes have been proposed. Nishiyama et al.
[102] reported the preparation of an MCM-48 membrane
with a cubic pore structure on a porous alumina support by
growth at the solution–support interface. The calcined mem-
brane was evaluated for the permeation of He, H2 , CH4 ,
O2 , N2 and CO2 , showing Knudsen regime permeation be-
havior, which was expected for gas diffusion in mesopores.
The permeance of these gases decreased considerably with
temperature. In a different separation application, Park et al.
[171] used non-silylated and trimethyl-silylated MCM-48
membranes for the separation of an ethanol/water mixture. It
was found that the separation factor was 16 for the silylated
membrane, and only 0.3 for the non-silylated membrane due
to hydrophobicity of the former membrane.
Ordered mesoporous silicas containing surface-attached
functional groups are highly promising materials for a va-
riety of separation applications. The major advantage of
these materials is that the specificity of these materials to-
wards different species may be controlled via the nature of
a surface-attached group and the pore size of these mate-
rials. Guliants and co-workers [172] have recently synthe-
sized MCM-48 and MCM-41 silicas displaying 1.6–2.8 nm
pores and containing surface attached 3-aminopropylsilyl
groups highly promising for the separation of CO2 from
dilute sources, such as flue gas. For example, at 298 K and
101,325 Pa (1 atm) these materials displayed high CO2 ca-
pacity (0.9 mmol/g) and negligible N2 adsorption.
Several catalytic applications of mesoporous films have
been reported. Ogawa et al. [173] reported the preparation of
Al-containing mesoporous silica films used as nanoreactors
for organic photochemical reactions. Adsorbed azobenzene
derivative incorporated in the film exhibited photochemical
isomerization upon UV and visible light irradiation at tem-
peratures as low as 80–300 K. Ikeue et al. [174] reported
Ti-containing porous silica films exhibiting high photocat-
alytic activity in the reaction of CO2 with H2 O to produce
CH4 and CH3 OH. Yusuf et al. [71] reported catalytic appli-
cations of mesoporous titania films. The photocatalytic ac-
tivity of the films for the oxidation of NOX was higher for
the mesoporous films as compared to conventional gel films.
The high surface areas displayed by these mesoporous films
are responsible for their better catalytic performance. Be-
cause of finely tuned pore sizes and structures, flexibility of
framework compositions, high surface areas and enhanced
accessibility of the active surface sites, ordered mesoporous
materials are highly promising not only as bulk catalysts,
but also as catalytic membrane systems.
4.1.2. Macroporous films and membranes
Ordered macroporous films and membranes are novel
monolithic materials with potential applications in het-
erogeneous catalysis, bioseparations as well as membrane
supports for the separation of small molecules. Due to high
surface area (up to 230 m2 /g) and unimodal large pores,
these macroporous structures are highly attractive for a va-
riety of separation and catalytic applications involving large
molecules.
A few examples of catalytic applications have been
already reported for bulk macroporous solids. Stein and
co-workers [175,176] used ordered macroporous silica as
a support for catalytically active species. For instance, the
Stein group found that ␥-SiW10 O36 polyoxometallate clus-
ters incorporated into the walls of macroporous silica ex-
hibited catalytic activity for the epoxidation of cyclooctene
[175]. In another study, Johnson and Stein [176] compared
different pore structures (macro, meso and non-porous sil-
ica surfaces) with the activity of silica samples doped with
transition metal substituted polyoxometallates (TMSP).
Although the three types of catalysts showed comparable
conversions in the epoxidation of cyclohexene to cyclo-
hexene oxide, the open macroporous structure supported
a greater number of TMSP clusters at its surface leading
to improved cluster retention during the catalytic reaction.
Carreon and Guliants [129,130] reported novel macrop-
orous vanadium–phosphorous oxides displaying desirable
chemical environment (i.e. V oxidation states, bulk chem-
ical compositions), the active (VO)2 P2 O7 phase as well as
high surface areas (∼75 m2 /g) for the partial oxidation of
n-butane to maleic anhydride. The successful preparation
of these catalytically active bulk phases ushers in new and
exciting opportunities for the design of macroporous films
and membranes for various applications in biocatalysis and
bioseparations.
4.2. Nanotechnological applications of meso- and
macroporous films and membranes
4.2.1. Mesoporous films and membranes
Mesoporous inorganic films or membranes synthesized
by supramolecular templating approach are attractive for
potential applications as sensors, electrochromic devices,
selective electrodes, etc. Stucky and co-workers [177] syn-
thesized optically transparent mesoporous silica films doped
with fluorescein entities, which function very effectively as
pH sensors. Cheng et al. [41] reported the electrochromic
properties of mesoporous tungsten oxide films. The unique
microstructure of WO3 leads to better electrochemical and
optical properties as compared to standard sol–gel-derived
tungsten oxides. Innocenzi et al. [178] synthesized meso-
porous silica films deposited on alumina substrates. The
films exhibited a change in the current intensity as a func-
tion of relative humidity indicating its potential use as hu-
midity sensors. Domansky et al. [179] studied the dielectric
response of mesoporous silica films as a function of several
gas-phase chemical species. The dielectric constant and
dissipation factor of partially dehydroxylated films were
highly sensitive to water vapor and ammonia in air showing
their potential as chemical sensors.
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
Ordered mesoporous silica coatings displaying bioactive
properties can be used in biomedical applications, e.g. as
medical implants as suggested by Gomez-Vega et al. [70].
Dag et al. [180] reported the preparation of silicon clus-
ters inside hexagonal mesoporous silica films displaying
photoluminescence and nanosecond luminescence lifetimes.
These composites are promising as light-emitting diodes,
optical interconnections and chemical sensors.
Several examples of mesoporous silica films displaying
low dielectric constants have been reported [181–186]. Yu
et al. [181,182] prepared silica mesoporous thin films with
low dielectric constant via sol–gel method. Preliminary re-
sults on these silica films show a very positive prospective for
intermetal dielectric applications. MacDougall et al. [183]
synthesized mesoporous silica films with block copolymers
showing very low dielectric constant (<2.3) which makes
them useful for current and future microelectronic applica-
tions.
Ordered mesoporous materials are suitable hosts for the
incorporation of nanoparticles with unique size-dependent
properties for potential applications in adsorption, sensing,
and catalysis. In particular, the discovery of the SBA-15
mesoporous silica has generated considerable interest in
the areas of catalysis, separation and membrane reactors.
However, the presence of framework microporosity in early
SBA-15 materials that led to a three-dimensional-connected
pore channel system limited their application as a model
host system to investigate size-dependent behavior of matter
in confined space.
Tang et al. [187] prepared SiGe quantum dots in the pores
of ordered mesoporous silica films. According to photolu-
minescence measurements, these confined dots showed im-
proved light emission required for optoelectronic devices.
Guliants and co-workers [25,188] have recently reported
synthesis of SBA-15 silica with low fraction of microp-
ores and its use as a host for the nucleation and growth
of 3–15 nm CdS crystals. Boilot and co-workers [189] and
Rathousky and co-workers [190] incorporated CdS nanopar-
ticles inside mesoporous silicate materials for potential ap-
plications in nanoscale optoelectronic devices. Hirai et al.
[191] incorporated CdS nanoparticles in reverse micellar
systems into thiol-modified MCM-41. The resulting com-
posite showed photocatalytic activity for H2 generation from
water. Other nanoparticles have been successfully incorpo-
rated inside mesoporous silica hosts. Fischer and co-workers
[192] reported the confinement of CdSe nanoparticles inside
MCM-41 pores. Zhang et al. [193] incorporated CdS, CuS
and ZnS nanoclusters inside an MCM-41 host for potential
applications in optoelectronics. These composites represent
promising materials for the fabrication of light absorbers,
quantum-dot lasers and as optical probes in biological stain-
ing and diagnostics.
It should be noted that several disordered mesoporous
inorganic membranes, such as ␥-alumina membranes with
∼4 nm pores, are commercially available [3]. These mem-
branes are very robust and used in many commercial
67
processes for filtration and separation. Amorphous and
crystalline microporous inorganic membranes exhibiting
excellent gas separation properties are also available and
some of these have been commercialized for gas and liquid
separations [194]. It is difficult for the ordered mesoporous
membranes to compete with the well-established, robust
disordered mesoporous inorganic membranes in conven-
tional separation and filtration applications. A representative
disordered mesoporous membrane is the 4 nm pore ceramic
membrane made of ␥-alumina which has been studied ex-
tensively for several decades. Furthermore, the disordered
mesoporous ␥-alumina membrane has been commercialized
for about two decades and offers good chemical, thermal and
mechanical stability for a large number of industrial applica-
tions. Nevertheless, these ordered mesoporous membranes
can find new applications, which take advantages of their
ordered pore structures and unique surface chemistries. One
such potential application is the production of high quality
polyethylene fibers using ordered mesoporous membranes
with two-dimensional hexagonal pores oriented normal to
the substrate surface as a molecular extruder [195].
4.2.2. Macroporous films and membranes
Ordered macroporous structures with pore sizes of a few
hundred nanometers are highly attractive for new appli-
cations in chromatography, (bio)catalysis, (bio)separations
and photonics. Macroporous TiO2 films diffract visible light
(i.e. photonic crystal effect) and can also be used in pho-
tocatalysis and photonics [150,152,153]. Khramov et al.
[154] described macroporous silica films that can selec-
tively discriminate different probe compounds based on their
charge. Therefore, various guest species may be trapped in
the macropores and used in chemical sensing applications.
Furthermore, macroporous bioceramic TiO2 films on Ti sur-
faces can find applications in bone tissue–Ti implant inter-
faces [155]. Tessier et al. [196] described the use of ordered
macroporous Au structures in analytical applications, such
as surface-enhanced Raman spectroscopy (SERS). Macro-
porous structures containing semiconductor quantum dots
show unique size-dependent optical and electronic proper-
ties, which are not observed in corresponding bulk materials
[138].
5. Concluding remarks
We have reviewed the synthesis, structures and emerg-
ing applications of ordered meso- and macroporous inor-
ganic films and membranes. Thin films and membranes of
these porous materials can be prepared by various tech-
niques commonly used for film formation from liquid so-
lution. Although these techniques allow control over the
thickness and the pore structure of the thin films, they have
a limited ability to control the pore alignment relative to
the substrate surface. The ordered mesoporous thin films
and membranes are promising for potential applications in
68 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
(bio)separations, chemical sensing, heterogeneous catalysis
and optoelectronics. Furthermore, facile functionalization of
the internal pore surfaces in these films and deposition of
nanoparticles in the pores offer numerous possibilities for the
design of novel optical, magnetic and electrically active ma-
terials (i.e. these novel materials can be used as capacitors,
chemical sensors based on dielectric response of function-
alized mesoporous silica films and low dielectric constant
materials). Macrostructured films displaying pore diameters
of a few hundred nanometers similar to the wavelength of
visible light are promising as photonic crystals exhibiting
unique optical properties. The emission of light through a
photonic crystal can be manipulated in the region of the pho-
tonic bandgap, which is of great interest for optoelectronics
and photocatalytic applications. Therefore, the ability to en-
gineer porosity on the meso- and macroscales is expected
to lead to advanced materials with unique and remarkable
properties for a wide variety of emerging nanotechnological
applications.
References
[1] W.J. Koros, Y.H. Ma, T. Shimidzu, Terminology for membranes
and membrane processes, J. Membr. Sci. 120 (1996) 149.
[2] A.J. Burggraaf, L. Cot (Eds.), Fundamentals of Inorganic Membrane
Science and Technology, Elsevier, Amsterdam, 1996.
[3] P. Hsieh, Inorganic Membranes for Separation and Reaction, Else-
vier, Amsterdam, 1996.
[4] (a) C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S.
Beck, Ordered mesoporous molecular sieves synthesized by a liquid-
crystal template mechanism, Nature 359 (1992) 710–712;
(b) J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge,
K.D. Schmitt, C.T.-W. Chu, D.H. Olson, E.W. Sheppard, S.B. Mc-
Cullen, J.B. Higgins, J.L. Schlenker, A new family of mesoporous
molecular sieves prepared with liquid crystal templates, J. Am.
Chem. Soc. 114 (1992) 10834–10843;
(c) C.T Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, Synthetic
mesoporous crystalline materials having high adsorption capacity
for benzene, US Patent 5,098,684 (1992), to Mobil Oil Corp.
[5] C.J. Brinker, Porous inorganic materials, Curr. Opin. Solid State
Mater. Sci. 1 (1996) 798–805.
[6] J.C. Vartuli, C.T. Kresge, W.J. Roth, S.B. McCullen, J.S. Beck, K.D.
Schmitt, M.E. Leonowicz, J.D. Lutner, E.W. Sheppard, in: W.R.
Moser (Ed.), Advanced Catalysts and Nanostructured Materials:
Modern Synthesis Methods, Academic Press, New York, 1996,
pp. 1–19.
[7] G.D. Stucky, Q. Huo, A. Firouzi, B.F. Chmelka, S. Schacht, I.G.
Voigt-Martin, F. Schüth, in: H. Chon, S.-K. Ihm, Y.S. Uh (Eds.),
Progress in Zeolite and Microporous Materials, Studies in Sur-
face Science and Catalysis, vol. 105, Elsevier, Amsterdam, 1997,
pp. 3–28.
[8] N.K. Raman, M.T. Anderson, C.J. Brinker, Template-based ap-
proaches to the preparation of amorphous, nanoporous silicas,
Chem. Mater. 8 (1996) 1682–1701.
[9] D.M. Antonelli, J.Y. Ying, Mesoporous materials, Curr. Opin. Col-
loid Interface Sci. 1 (1996) 523–529.
[10] P. Behrens, Voids in variable chemical surroundings: mesoporous
metal oxides, Angew. Chem. Int. Ed. Engl. 35 (1996) 515–518.
[11] X.S. Zhao, G.O. Lu, G.J. Millar, Advances in mesoporous molecular
sieve MCM-41, Ind. Eng. Chem. Res. 35 (1996) 2075–2090.
[12] A. Sayari, Catalysis by crystalline mesoporous molecular sieves,
Chem. Mater. 8 (1996) 1840–1852.
[13] (a) S. Inagaki, Y. Fukushima, K. Kuroda, Synthesis of highly or-
dered mesoporous materials from a layered polysilicate, J. Chem.
Soc., Chem. Commun. (1993) 680–682;
(b) Y. Fukushima, S. Inagaki, Nano-scale structure control of meso-
porous silica, Mater. Sci. Eng. A 217–218 (1996) 116–118.
[14] Q. Huo, D.I. Margolese, G.D. Stucky, Surfactant control of phases
in the synthesis of mesoporous silica-based materials, Chem. Mater.
8 (1996) 1147.
[15] R. Ryoo, J.M. Kim, C.H. Ko, C.H. Shin, Disordered molecular
sieve with branched mesoporous channel network, J. Phys. Chem.
100 (1996) 17718.
[16] S.A. Bagshaw, E. Prouzet, T.J. Pinnavaia, Templating of meso-
porous molecular sieves by non-ionic polyethylene oxide surfac-
tants, Science 269 (1995) 1242.
[17] W. Zhou, J. Klinowski, The mechanism of channel formation in
the mesoporous molecular sieve MCM-41, Chem. Phys. Lett. 292
(1998) 207.
[18] D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky, Non-ionic
triblock and star diblock copolymer and oligomeric surfactant syn-
theses of highly ordered, hydrothermally stable, mesoporous silica
structures, J. Am. Chem. Soc. 120 (1998) 6024.
[19] D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredickson, B.F.
Chmelka, G.D. Stucky, Triblock copolymer syntheses of meso-
porous silica with periodic 50 to 300 Angstrom pores, Science 279
(1998) 548.
[20] H. Yang, N. Coombs, I. Sokolov, G.A. Ozin, Registered growth
of mesoporous silica films on graphite, J. Mater. Chem. 7 (1997)
1285–1290.
[21] A.E. Braun, Thermal processing options. Focus and specialize,
Semiconductor Int. 22 (5) (1999) 56–58.
[22] K.J. Edler, S.J. Roser, Growth and characterization of mesoporous
silica films, Int. Rev. Phys. Chem. 3 (20) (2001) 387–466.
[23] A. Stein, R.C. Schroden, Colloidal crystal templating of three-
dimensionally ordered macroporous solids: materials for photonics
and beyond, Curr. Opin. Solid State Mater. Sci. 5 (2001) 553–564.
[24] J.S. Beck, J.C. Vartuli, G.J. Kennedy, C.T. Kresge, W.J. Roth, S.E.
Schramm, Molecular or supramolecular templating: defining the
role of surfactant chemistry in the formation of microporous and
mesoporous molecular sieves, Chem. Mater. 6 (1994) 1816–1821.
[25] P. Kumar, G. Beaucage, V.V. Guliants, The effects of pore size and
structure on formation of CdS nanocrystals inside mesoporous SBA-
15 and SBA-16 silicas, Chem. Mater., submitted for publication.
[26] J.C. Vartuli, C.T. Kresge, M.E. Leonowicz, A.S. Chu, S.B. Mc-
Cullen, I.D. Johnson, E.W. Sheppard, Synthesis of mesoporous
materials: liquid-crystal templating versus intercalation of layered
silicates, Chem. Mater. 6 (1994) 2070–2077.
[27] C.Y. Chen, S.L. Burkett, H.X. Li, M.E. Davis, Studies on meso-
porous materials. II. Synthesis mechanism of MCM-41, Microp-
orous Mater. 2 (1993) 27–34.
[28] A. Steel, S.W. Carr, M.W. Anderson, 14 N NMR study of surfactant
mesophases in the synthesis of mesoporous silicates, J. Chem. Soc.,
Chem. Commun. (1994) 1571–1572.
[29] A. Monnier, F. Schüth, Q. Huo, D. Kumar, D. Margolese, R.S.
Maxwell, G.D. Stucky, M. Krishnamurty, P. Petroff, A. Firouzi, M.
Janicke, B.F. Chmelka, Cooperative formation of inorganic–organic
interfaces in the synthesis of silicate mesostructures, Science 261
(1993) 1299–1303.
[30] G.D. Stucky, A. Monnier, F. Schüth, Q. Huo, D. Margolese, D.
Kumar, M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke, B.F.
Chmelka, Molecular and atomic arrays in nano-and mesoporous
materials synthesis, Mol. Cryst. Liq. Cryst. 240 (1994) 187–200.
[31] A. Firouzi, D. Kumar, L.M. Bull, T. Besier, R. Sieger, Q. Huo,
S.A. Walker, J.A. Zasadzinski, C. Glinka, J. Nicol, D. Margolese,
G.D. Stucky, B.F. Chmelka, Cooperative organization of inorganic-
surfactant and biomimetic assemblies, Science 267 (1995) 1138–
1143.
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
[32] S. Ikeda, in: K.L. Mittal, B. Lindman (Eds.), Surfactants in Solution,
vol. 2, Plenum Press, New York, 1984, pp. 825–840.
[33] A. Firouzi, F. Atef, A.G. Oertli, G.D. Stucky, B.F. Chmelka, Alka-
line lyotropic silicate-surfactant liquid crystals, J. Am. Chem. Soc.
119 (1997) 3596–3610.
[34] C.A. Fyfe, G. Fu, Structure organization of silicate polyanions with
surfactants: a new approach to the syntheses, structure transfor-
mations, and formation mechanisms of mesostructural materials, J.
Am. Chem. Soc. 117 (1995) 9709–9714.
[35] O. Regev, Nucleation events during the synthesis of mesoporous
materials using liquid crystalline templating, Langmuir 12 (1996)
4940–4944.
[36] Y. Xia, B. Gates, Y. Yin, Y. Lu, Monodispersed colloidal spheres:
old materials with new applications, Adv. Mater. 12 (10) (2000)
693–713.
[37] B.A. McCool, N. Hill, J. DiCarlo, W.J. DeSisto, Synthesis and
characterization of mesoporous silica membranes via dip-coating
and hydrothermal deposition techniques, J. Membr. Sci. 218 (2003)
55–67.
[38] D. Zhao, P. Yang, N. Melosh, J. Feng, B.F. Chmelka, G.D. Stucky,
Continuos mesoporous silica films with highly ordered large pore
structures, Adv. Mater. 10 (16) (1998) 1380–1385.
[39] D. Grosso, A.R. Balkenende, P.A. Albouy, A. Ayral, H. Amenitsch,
F. Babonneau, Two-dimensional hexagonal mesoporous silica thin
films prepared from block copolymers: detailed characterization and
formation mechanism, Chem. Mater. 13 (2001) 1848.
[40] D. Grosso, G.J. Soler-Illia, F. Babonneau, C. Sanchez, P. Albouy, A.
Brunet-Bruneau, A.R. Balkenende, Highly organized mesoporous
titania thin films showing mono-oriented 2D hexagonal channels,
Adv. Mater. 13 (14) (2001) 1085.
[41] W. Cheng, E. Baudrin, B. Dunn, J.I. Zink, Synthesis and elec-
trochromic properties of mesoporous tungsten oxide, J. Mater.
Chem. 11 (2001) 92.
[42] B. Lebeau, C.E. Fowler, S.R. Hall, S. Mann, Transparent thin
films and monoliths prepared from dye-functionalized ordered silica
mesostructures, J. Mater. Chem. 9 (1999) 2279.
[43] E.L. Crepaldi, G.J. Soler-Illia, D. Grosso, P. Albouy, C. Sanchez,
Design and post-functionalisation of ordered mesoporous zirconia
thin films, Chem. Commun. (2001) 1582.
[44] L. Pidol, D. Grosso, G.J. Soler-Illia, E.L. Crepaldi, C. Sanchez,
P.A. Albouy, H. Anenitsch, P. Euzen, Hexagonally organized meso-
porous aluminum-oxo-hydroxide thin films prepared by the tem-
plate approach. In situ study of the structural formation, J. Mater.
Chem. 12 (2002) 557.
[45] Z. Hua, J. Shi, L. Wang, W. Zhang, Preparation of mesoporous
silica films on a glass slide: surfactant template removal by solvent
extraction, J. Non-Cryst. Solids 292 (2001) 177.
[46] M.T. Anderson, J.E. Martin, J.G. Odinek, P. Newcomer, Synthesis
of periodic mesoporous silica films, Mater. Res. Symp. Proc. 431
(1996) 217–222.
[47] D. Grosso, A.R. Balkenende, P.A. Albouy, F. Babonneau, Struc-
tural analysis of hexagonal mesoporous silica films produced from
triblock-copolymer structuring sol–gel, Stud. Surf. Sci. Catal. 129
(2000) 673–682.
[48] T. Clark Jr., J.D. Ruiz, H. Fan, C.J. Brinker, B.I. Swanson, A.N.
Parikh, A new application of UV–ozone treatment in the preparation
of substrate-supported mesoporous thin films, Chem. Mater. 12
(2000) 3879–3884.
[49] D. Grosso, P.A. Albouy, H. Amenitsch, A.R. Balkenende, F. Babon-
neau, Time resolved in situ X-ray diffraction study of the forma-
tion of 3D hexagonal mesoporous silica films, Mater. Res. Soc.
Symp. Proc. 628 (2002) CC6.17.1–CC6.17.6.
[50] Y. Goto, N. Sugimoto, Y. Fukushima, Y. Imada, Y. Kubota, Y.
Sugi, Preparation of highly ordered mesoporous thin film with
alkyltrimethylammonium (Cn TMA+ ), Mater. Res. Soc. Symp. Proc.
581 (2000) 423–428.
69
[51] H. Fan, Y. Lu, R.A. Assink, G.P. Lopez, C.J. Brinker, Surfac-
tant templated mesoporous hybrid thin films, Mater. Res. Soc.
Symp. Proc. 628 (2000) CC6.41.1–CC6.41.7.
[52] M. Klotz, A. Ayral, C. Guizard, L. Cot, Synthesis and characteriza-
tion of silica membranes exhibiting an ordered mesoporosity. Con-
trol of the porous texture and effect on the membrane permeability,
Sep. Purif. Technol. 25 (2001) 71–78.
[53] D. Zhao, P. Yang, D.I. Margolese, B.F. Chmelka, G.D. Stucky,
Synthesis of continuous mesoporous silica thin films with three-
dimensional accessible pore structures, Chem. Commun. (1998)
2499–2500.
[54] M. Klotz, P. Albouy, A. Ayral, C. Menager, D. Grosso, A. Lee, V.
Cabuil, F. Babonneau, C. Guizard, The true structure of hexagonal
mesophase templated silica films as revealed by X-ray scattering:
effects of thermal treatments and of nanoparticle seeding, Chem.
Mater. 12 (2000) 1721–1728.
[55] Y. Lu, R. Ganguli, C.A. Drewien, M.T. Anderson, C.J. Brinker,
W. Gong, Y. Guo, H. Soyez, B. Dunn, M.H. Huang, J.I. Zink,
Continuos formation of supported cubic and hexagonal mesoporous
films by sol–gel dip-coating, Nature 389 (1997) 364–368.
[56] A. Hozumi, Y. Yokogawa, T. Kameyama, K. Hiraku, H. Sugimura,
O. Takai, M. Okido, Morphology of mesoporous silica grown on or-
ganic surfaces: effects of surface functional groups and microstruc-
tures, Mater. Res. Soc. Symp. Proc. 255 (2000) 599.
[57] H. Miyata, T. Noma, M. Watanabe, K. Kuroda, Preparation of
mesoporous silica films with fully aligned large mesochannels using
non-ionic surfactants, Chem. Mater. 14 (2002) 766.
[58] R. Ryoo, C.H. Ko, S.J. Cho, J.M. Kim, Optically transparent single-
crystal like oriented mesoporous silica films and plates, J. Phys.
Chem. B 101 (1997) 10610–10613.
[59] C.H. Ko, J.M. Kim, R. Ryoo, Mesocrystal engineering using non-
bonded interaction to obtain optically transparent mesoporous silica
films and plates with uniform orientation, Microporous Mesoporous
Mater. 21 (1998) 235–243.
[60] A. Hozumi, Y. Yokogawa, T. Kameyama, K. Hiraku, H. Sugimura,
O. Takai, M. Okido, Photocalcination of mesoporous silica films
using vacuum ultraviolet light, Adv. Mater. 12 (13) (2000) 985–987.
[61] H. Yang, N. Coombs, G.A. Ozin, Mesoporous silica with
micrometer-scale designs, Adv. Mater. 9 (1997) 811–814.
[62] S. Nagamine, A. Endo, M. Nakaiwa, T. Nakane, K. Kurumada,
M. Tanigaki, Synthesis of submillimeter-thick films of surfactant
templated mesoporous silica, Microporous Mesoporous Mater. 43
(2001) 181–189.
[63] I. Honma, H. Zhou, D. Kundu, A. Endo, Structural control of
surfactant templated hexagonal, cubic and lamellar mesoporous
silicate thin films prepared by spin coating, Adv. Mater. 12 (2000)
1529.
[64] J.E. Martin, M.T. Anderson, J. Odinek, P. Newcomer, Synthesis of
periodic mesoporous silica thin films, Langmuir 13 (1997) 4133–
4141.
[65] M. Ogawa, H. Ishikawa, T. Kikuchi, Preparation of transparent
mesoporous silica films by rapid solvent evaporation method, J.
Mater. Chem. 8 (1998) 1783.
[66] H. Miyata, K. Kuroda, Alignment of mesoporous silica on glass
substrate by a rubbing method, Chem. Mater. 11 (1999) 1609.
[67] S. Besson, T. Gacoin, C. Jacquiod, C. Ricolleau, D. Babonneau, J.P.
Boilot, Structural study of 3D-hexagonal mesoporous spin-coated
sol–gel films, J. Mater. Chem. 10 (2000) 1331.
[68] S. Besson, C. Ricolleau, T. Gacoin, C. Jacquiod, J.P. Boilot, A
new 3D organization of mesoporous oriented CTAB silica films, J.
Phys. Chem. B 104 (2000) 12095.
[69] H. Yun, K. Miyazawa, H. Zhou, I. Honma, M. Kuwabara, Synthesis
of mesoporous thin TiO2 films with hexagonal pore structures using
triblock copolymer templates, Adv. Mater. 13 (2001) 18.
[70] J.M. Gomez-Vega, M. Iyoshi, K.Y. Kim, A. Hozumi, H. Sugimura,
O. Takai, Spin coated mesoporous silica coatings for medical ap-
plications, Thin Solid Films 398–399 (2001) 615.
70 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
[71] M.M. Yusuf, H. Imai, H. Hirashima, Preparation of porous titania
film by modified sol–gel method and its application to photocatalyst,
J. Sol–Gel Sci. Technol. 25 (2002) 65.
[72] H. Fan, H.R. Bentley, K.R. Kathan, P. Clem, Y. Lu, C.J. Brinker,
Self-assembled aerogel-like low dielectric constant films, J. Non-
Cryst. Solids 285 (2001) 79.
[73] H. Zhou, I. Honma, Conductive self-assembled mesostructured silica
films synthesized by ferrocenyl surfactant, Jpn. J. Appl. Phys. 38
(1999) L958.
[74] C. Song, G. Villemure, Electrode modification with spin-coated
films of mesoporous molecular sieve silicas, Microporous Meso-
porous Mater. 44–45 (2001) 679.
[75] T. Yamada, H. Zhou, H. Uchida, M. Tomita, Y. Ueno, T. Ichino,
I. Honma, K. Asai, T. Katsube, Surface photovoltage NO gas sen-
sor with properties dependent on the structure of the self-ordered
mesoporous silicate film, Adv. Mater. 14 (11) (2002) 812.
[76] E. Ozkan, S. Lee, P. Liu, C.E. Tracy, F.Z. Tepehan, J.R. Pitts, S.K.
Deb, Electrochromic and optical properties of mesoporous tungsten
oxide films, Solid State Ionics 149 (2002) 139.
[77] T. Yamada, K. Asai, A. Endo, H.S. Zhou, I. Honma, Size control
of oriented hexagonal mesoporous silicate thin film prepared by
triblock copolymer templates, J. Mater. Sci. Lett. 19 (2000) 2167–
2169.
[78] T. Yamada, K. Asai, A. Endo, H.S. Zhou, I. Honma, Size controlled
mesoporous silicate thin films using block copolymers as template
(I), Stud. Surf. Sci. Catal. 132 (2001) 631–634.
[79] J.M. Berquier, L. Teysseedre, C. Jacquiod, Synthesis of transparent
mesoporous and mesostructured thin silica films, J. Sol–Gel Sci.
Technol. 13 (1998) 739–742.
[80] D. Kunda, H.S. Zhou, I. Honma, Thermally induced structural
changes of lamellar and one-dimensional hexagonal mesoporous
silica thin films, J. Mater. Sci. Lett. 17 (1998) 2089–2092.
[81] I. Honma, A. Endo, D. Kunda, H.S. Zhou, Thermal stability of
structurally controlled lamellar and hexagonal mesoporous silicate
thin films, Mater. Res. Soc. Symp. Proc. 576 (1999) 235–240.
[82] H.M. Yusuf, H. Imai, H. Hirashima, Preparation of mesoporous
TiO2 thin films by surfactant templating, J. Non-Cryst. Solids 285
(2001) 90–95.
[83] M. Ogawa, N. Masukara, Preparation of transparent thin films of
lamellar, hexagonal and cubic silica-surfactant mesostructured ma-
terials by rapid solvent evaporation methods, Microporous Meso-
porous Mater. 38 (2000) 35–41.
[84] C.J. Brinker, G.W. Scherer, Sol–Gel Science. The Physics and
Chemistry of Sol–Gel Processing, Academic Press, 1990.
[85] V.Z.-H. Chan, J. Hoffman, V.Y. Lee, H. Latrou, A. Avgeropoulos,
N. Hadjichristidis, R.D. Miller, E.L. Thomas, Ordered bicontin-
uos nanoporous and nanorelief ceramic films from self-assembling
polymer precursors, Science 286 (1999) 1716–1719.
[86] H. Yang, A. Kuperman, N. Coombs, S. Mamiche-Afara, G.A. Ozin,
Synthesis of oriented films of mesoporous silica on mica, Nature
379 (1996) 703.
[87] I.A. Aksay, M. Trau, S. Manne, I. Honma, N. Yao, L. Zhou, P.
Fenter, P.M. Eisenberger, S.M. Gruner, Biomimetic pathways for
assembling inorganic thin films, Science 273 (1996) 892.
[88] N. Yao, A.Y. Ku, N. Nakagawa, T. Lee, D.A. Saville, I.A. Aksay,
Disorder–order transition in mesoscopic silica thin films, Chem.
Mater. 12 (2000) 1536.
[89] H. Yang, N. Coombs, I. Sokolov, G.A. Ozin, Free-standing and
oriented mesoporous silica films grown at the air–water interface,
Nature 381 (1996) 589.
[90] N. Coombs, D. Khushalani, S. Oliver, G.A. Ozin, G.C. Shen, I.
Sokolov, H. Yang, Blueprints for inorganic materials with natural
form: inorganic liquid crystals and a language of inorganic shape,
J. Chem. Soc., Dalton Trans. (1997) 3941.
[91] A.Y.-C. Ku, Guided self-assembly and directed restructuring of
mesoscopic silica using electric fields, Ph.D. thesis, Princeton Uni-
versity, 2003.
[92] M. Trau, N. Yao, E. Kim, Y. Xia, G.M. Whitesides, I.A. Aksay, Mi-
croscopic patterning of orientated mesoscopic silica through guided
growth, Nature 390 (1997) 674.
[93] P. Yang, T. Deng, D. Zhao, P. Feng, D. Pine, B.F. Chmelka, G.M.
Whitesides, G.D. Stucky, Hierarchically ordered oxides, Science
282 (1998) 2244.
[94] H.W. Hillhouse, T. Okubo, J.W. Van Egmond, M. Tsapatsis, Prepa-
ration of supported mesoporous silica layers in a continuos flow
cell, Chem. Mater. 9 (1997) 1505.
[95] H.W. Hillhouse, J.W. Van Egmond, M. Tsapatsis, Highly oriented
mesostructured thin films: shear-induced deposition of optically
anisotropic coatings of tungsten oxide/surfactant composites, Lang-
muir 15 (1999) 4544.
[96] H.W. Hillhouse, J.W. Van Egmond, M. Tsapatsis, J.C. Hanson,
J.Z. Larese, Synthesis and characterization of ordered arrays of
topological defects in mesoporous silica films, Chem. Mater. 12
(2000) 2888.
[97] S. Manne, T.E. Schaffer, Q. Huo, P.K. Hansma, D.E. Morse, G.D.
Stucky, I.A. Aksay, Gemini surfactants at solid–liquid interfaces:
control of interfacial aggregate geometry, Langmuir 13 (1997) 6382.
[98] S.H. Tolbert, T.E. Schaffer, J. Feng, P.K. Hansma, G.D. Stucky, A
new phase of oriented mesoporous silicate thin films, Chem. Mater.
9 (1997) 1962–1967.
[99] H. Miyata, K. Kuroda, Preferred alignment of mesochannels in a
mesoporous silica film grow on a silica (1 1 0) surface, J. Am.
Chem. Soc. 121 (1999) 7618–7624.
[100] H. Miyata, K. Kuroda, Formation of a continuos mesoporous silica
film with fully aligned mesochannels on a glass substrate, Chem.
Mater. 12 (2000) 49.
[101] N. Nishiyama, A. Koide, Y. Egashira, K. Ueyama, Mesoporous
MCM-48 membrane synthesized on a porous stainless steel support,
J. Am. Soc., Chem. Commun. (1998) 2147.
[102] N. Nishiyama, D.H. Park, A. Koide, Y. Egashira, K. Ueyama, A
mesoporous silica MCM-48 membrane: preparation and character-
ization, J. Membr. Sci. 182 (2001) 235–244.
[103] N. Nishiyama, A. Koide, Y. Egashira, K. Ueyama, Mesoporous
MCM-48 membrane synthesized on a porous stainless steel support,
Chem. Commun. (1998) 2147–2148.
[104] H. Yang, N. Coombs, O. Dag, I. Sokolov, G.A. Ozin, Free-standing
mesoporous silica films: morphogenesis of channel and surface
patterns, J. Mater. Chem. 7 (1997) 1755.
[105] H. Yang, G.A. Ozin, C.T. Kresge, The role of defects in the for-
mation of mesoporous silica fibers, films and curved shapes, Adv.
Mater. 10 (1998) 883.
[106] P.D. Yang, G. Wirnsberger, H.C. Huang, S.R. Cordero, M.D. McGe-
hee, B. Scott, T. Deng, G.M. Whitesides, B.F. Chmelka, S.K. Bu-
ratto, G.D. Stucky, Mirrorless lasing from mesostructured waveg-
uides patterned by soft lithography, Science 287 (2000) 465.
[107] A.S. Brown, S.A. Holt, T. Dam, M. Trau, J.W. White, Mesoporous
silicate film growth at the air–water interface. Direct observation
by X-ray reflectivity, Langmuir 13 (1997) 6363–6365.
[108] S.A. Holt, G.J. Foran, J.W. White, Observation of hexagonal crys-
talline diffraction from growing silicate films, Langmuir 15 (1999)
2540.
[109] J.L. Ruggles, S.A. Holt, P.A. Reynolds, A.S. Brown, D.C. Creagh,
J.W. White, Observation of a cubic phase in mesoporous silicate
films grown at the air/water interface, Phys. Chem. Chem. Phys. 1
(1999) 323.
[110] K.J. Edler, S.J. Roser, S. Mann, In situ Brewster angle microscopy
and surface pressure studies on the interfacial growth of mesostruc-
tured silica thin films, J. Chem. Soc., Chem. Commun. (2000) 773.
[111] K.S. Edler, A. Goldar, A.V. Hughes, S.J. Roser, S. Mann, Structural
studies on surfactant templated silica films grown at the air/water
interface, Microporous Mesoporous Mater. 44–45 (2001) 661–670.
[112] S. Roser, H.M. Patel, M.R. Lovell, J.E. Muir, S. Mann, X-ray reflec-
tion studies on the monolayer-mediated growth of mesostructured
 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
MCM-41 silica at the air/water interface, J. Chem. Soc., Chem.
Commun. (1998) 829.
[113] D. Zhao, P. Yang, B.F. Chmelka, G.D. Stucky, Multiphase assembly
of mesoporous–macroporous membranes, Chem. Mater. 11 (1999)
1174–1178.
[114] J.-L. Zhang, W. Li, X.-K. Meng, L. Wang, L. Zhu, Synthesis of
mesoporous silica membranes oriented by self-assembles of surfac-
tants, J. Membr. Sci. 222 (2003) 219–224.
[115] S. Schacht, Q. Huo, I.G. Voigt-Martin, G.D. Stucky, F. Schuth, Oil
water interface templating of mesoporous macroscale structures,
Science 273 (1996) 768.
[116] L. Faget, A. Berman, O. Regev, Synthesis of unsupported meso-
porous silica interphasic films at the oil–water boundary, Thin Solid
Films 386 (1) (2001) 6–13.
[117] G.S. Attard, P.N. Bartlett, N.R.B. Coleman, J.M. Elliot, J.R. Owen,
J.H. Wang, Mesoporous platinum films from lyotropic liquid crys-
talline phases, Science 278 (1997) 838–840.
[118] J.M. Elliot, G.S. Attard, P.N. Bartlett, N.R. Coleman, Nanostruc-
tured platinum (HI -ePt) films: effects of electrodeposition condi-
tions on films properties, Chem. Mater. 11 (1999) 3602.
[119] J.M. Elliot, P.R. Birkin, P.N. Bartlett, G.S. Attard, Platinum mi-
croelectrodes with unique high surface areas, Langmuir 15 (1999)
7411.
[120] A.H. Whitehead, J.M. Elliot, J.R. Owen, G.S. Attard, Electrodepo-
sition of mesoporous tin films, Chem. Commun. (1999) 331–332.
[121] B. Gollas, J.M. Elliot, P.N. Bartlett, Electrodeposition and proper-
ties of nanostructured platinum films studied by quartz impedance
measurements at 10 MHz, Electrochim. Acta 45 (2000) 3711.
[122] K.J. Balkus Jr., A.S. Scott, M.E. Gimon-Kinsel, J.H. Blanco,
Oriented films of mesoporous MCM-41 macroporous tubules via
pulsed laser deposition, Microporous Mesoporous Mater. 38 (2000)
97–105.
[123] I. Nandhakumar, J.M. Elliott, G.S. Attard, Electrodeposition of
nanostructured mesoporous selenium films (HI -eSe), Chem. Mater.
13 (2001) 3840.
[124] (a) O.D. Velev, T.A. Jede, R.F. Lobo, A.M. Lenhoff, Porous silica
via colloidal crystallization, Nature 389 (1997) 447–448;
(b) O.D. Velev, T.A. Jede, R.F. Lobo, A.M. Lenhoff, Microstructured
porous silica obtained via colloidal crystal templates, Chem. Mater.
10 (1998) 3597–3602.
[125] A. Imhof, D.J. Pine, Ordered macroporous materials by emulsion
templating, Nature 389 (1997) 948–951.
[126] B.T. Holland, C.F. Blanford, A. Stein, Synthesis of macroporous
minerals with highly ordered three-dimensional arrays of spheroidal
voids, Science 281 (1998) 538–540.
[127] B.T. Holland, C.F. Blanford, T. Do, A. Stein, Synthesis of highly
ordered, three dimensional, macroporous structures of amorphous
or crystalline inorganic oxides, phosphates, and hybrid composites,
Chem. Mater. 11 (1999) 795–805.
[128] B.T. Holland, L. Abrams, A. Stein, Dual templating of macroporous
silicates with zeolitic microporous frameworks, J. Am. Chem. Soc.
121 (1999) 4308–4309.
[129] M.A. Carreon, V.V. Guliants, Hierarchical design of mixed metal
oxides: novel macroporous VPO phases, Chem. Commun. (2001)
1438–1439.
[130] M.A. Carreon, V.V. Guliants, Macroporous vanadium phosphorus
oxide phases displaying three-dimensional arrays of spherical voids,
Chem. Mater. 14 (6) (2002) 2670–2675.
[131] G. Gundiah, C.N.R. Rao, Macroporous oxide materials with three-
dimensionally interconnected pores, Solid State Sci. 2 (2000) 877–
882.
[132] Y. Zhang, Z. Lein, J. Li, S. Lu, A new route to three-dimensionally
well-ordered macroporous rare-earth oxides, New J. Chem. 25
(2001) 1118–1120.
[133] D. Wang, R.A. Caruso, F. Caruso, Synthesis of macroporous titania
and inorganic composite materials from coated colloidal spheres.
71
A novel route to tune pore morphology, Chem. Mater. 13 (2001)
364–371.
[134] J.E.G. Wijnhoven, W.L. Vos, Preparation of photonic crystals made
of air spheres in titania, Science 281 (1998) 802–804.
[135] H. Yan, C.F. Blanford, B.T. Holland, M. Parent, W.H. Smyrl, A.
Stein, A chemical synthesis of periodic macroporous NiO and
metallic Ni, Adv. Mater. 11 (12) (1999) 1003–1006.
[136] H. Yan, C.F. Blanford, B.T. Holland, W.H. Smyrl, A. Stein, General
synthesis of periodic macroporous solids by templated salt precipita-
tion and chemical conversion, Chem. Mater. 12 (2000) 1134–1141.
[137] G. Subramanian, V.N. Manoharan, J.D. Thorne, D.J. Pine, Ordered
macroporous materials by colloidal assembly: a possible route to
photonic gap materials, Adv. Mater. 11 (15) (1999) 1261–1265.
[138] Y.A. Vlasov, N. Yao, D.J. Norris, Synthesis of photonic crystals
for optical wavelengths from semiconductor quantum dots, Adv.
Mater. 11 (2) (1999) 165–169.
[139] S.H. Park, Y. Xia, Macroporous membranes with highly ordered
and three-dimensionally interconnected spherical pores, Adv. Mater.
10 (1998) 1045–1048.
[140] B. Gates, Y. Yin, Y. Xia, Fabrication and characterization of porous
membranes with highly ordered three-dimensional periodic struc-
tures, Chem. Mater. 11 (1999) 2827–2836.
[141] P. Jiang, K.S. Hwang, D.M. Mittleman, J.F. Bertone, V.L. Colvin,
Template-directed preparation of macroporous polymers with ori-
ented and crystalline arrays of voids, J. Am. Chem. Soc. 121 (1999)
11630–11637.
[142] Q. Luo, Z. Liu, L. Li, S. Xie, J. Kong, D. Zhao, Creating highly or-
dered metal, alloy, and semiconductor macrostructures by electrode-
position, ion spraying and laser spraying, Adv. Mater. 13 (2001)
286–289.
[143] P.V. Braun, P. Wiltzius, Electrochemically grown photonic crystals,
Nature 402 (1999) 603–604.
[144] P.V. Braun, P. Wiltzius, Electrochemical fabrication of 3D micrope-
riodic porous materials, Adv. Mater. 13 (2001) 482–485.
[145] P.N. Bartlett, P.R. Birkin, M.A. Ghanem, C.S. Toh, Electrochemi-
cal syntheses of highly ordered macroporous conducting polymers
grown around self-assembled colloidal templates, J. Mater. Chem.
11 (2001) 849–853.
[146] P. Jian, J.F. Bertone, V.L. Colvin, A lost-wax approach to monodis-
perse colloids and their crystals, Science 291 (2001) 453–457.
[147] S. Matsushita, T. Miwa, A. Fujishima, Preparation of a new nanos-
tructured TiO2 surface using a two-dimensional array-based tem-
plate, Chem. Lett. 309 (1997) 925–926.
[148] T. Sumida, Y. Wada, T. Kitamura, S. Yanagida, Macroporous ZnO
films electrochemically prepared by templating of opal films, Chem.
Lett. (2001) 38–39.
[149] P. Jiang, J. Cizeron, J.F. Bertone, V.L. Colvin, Preparation of macro-
porous metal films from colloidal crystals, J. Am. Chem. Soc. 121
(1999) 7957–7958.
[150] G. Subramania, K. Constant, R. Biswas, M.M. Sigalas, K.M. Ho,
Optical photonic crystals fabricated from colloidal systems, Appl.
Phys. Lett. 74 (26) (1999) 3933–3935.
[151] G. Subramania, K. Constant, R. Biswas, M.M. Sigalas, K.M. Ho,
Synthesis of thin film photonic crystals, Synth. Met. 116 (2001)
445–448.
[152] G. Subramania, K. Constant, R. Biswas, M.M. Sigalas, K.M. Ho,
Inverse face-centered cubic thin film photonic crystals, Adv. Mater.
13 (6) (2001) 443–446.
[153] M.E. Turner, T.J. Trentler, V.L. Colvin, Thin films of macroporous
metal oxides, Adv. Mater. 13 (3) (2001) 180–183.
[154] A.N. Khramov, J. Munos, M.M. Collinson, Preparation and charac-
terization of macroporous silicate films, Langmuir 17 (2001) 8112–
8117.
[155] F.A. Akin, H. Zreigat, S. Jordan, M.B.J. Wijesundara, L. Hanley,
Preparation and analysis of macroporous TiO2 films on Ti surfaces
for bone–tissue implants, J. Biomed. Mater. Res. 57 (2001) 588–
596.
72 V.V. Guliants et al. / Journal of Membrane Science 235 (2004) 53–72
[156] Y.H. Ye, S. Badilescu, V.V. Truong, Large-scale ordered macrop-
orous SiO2 thin films by a template-directed method, Appl. Phys.
Lett. 4 (2002) 81.
[157] P.N. Bartlett, J.J. Baumberg, P.R. Birkin, M.A. Ghanem, M.C. Netti,
Highly ordered macroporous gold and platinum films formed by
electrochemical deposition through templates assembled from sub-
micron diameter monodisperse polystyrene spheres, Chem. Mater.
14 (2002) 2199–2208.
[158] T. Sumida, Y. Wada, T. Kitamura, S. Yanagida, Construction of
stacked opaline films and electrochemical deposition of ordered
macroporous nickel, Langmuir 18 (2002) 3886–3894.
[159] R. Corriu, A. Mehdi, C. Reye, H. Ledon, Mesoporous silica-based
organic–inorganic hybrid materials, especially for gas separations,
Patent WO 2002076991 (2002).
[160] J.E. Ackerman, J. Liu, C. Lei, Proteins in a porous support, Patent
WO 2002068454 (2002).
[161] N. Robert, K. Mohan, K. Gordon, M. Edward, Heavy metal re-
mediation using functionalized mesoporous silicas with controlled
macrostructure, Langmuir 17 (2) (2001) 528–533.
[162] A.M. Liu, K. Hidajat, S. Kawi, D.Y. Zhao, A new class of hybrid
mesoporous materials with functionalized organic monolayers for
selective adsorption of heavy metal ions, Chem. Commun. 13 (2000)
1145–1146.
[163] M. Etienne, S. Sayen, B. Lebeau, A. Walcarius, Organically-
modified mesoporous silica spheres with MCM-41 architecture as
sorbents for heavy metals, Stud. Surf. Sci. Catal. 141 (2002) 615–
622.
[164] V. Antochshuk, M. Jaroniec, S.H. Joo, R. Ryoo, Mesoporous ma-
terials for heavy metal ion adsorption synthesized by displacement
of polymeric template, Stud. Surf. Sci. Catal. 141 (2002) 607–614.
[165] J. Brown, R. Richer, L. Mercier, One-step synthesis of high capacity
mesoporous Hg2+ adsorbents by non-ionic surfactant assembly,
Microporous Mesoporous Mater. 37 (1–2) (2000) 41–48.
[166] M.A. Carreon, V.V. Guliants, Mesostructured vanadium–phosphorus
oxide phases, Microporous Mesoporous Mater. 55 (3) (2002) 297–
304.
[167] M.A. Carreon, V.V. Guliants, Synthesis and characterization of
mesostructured vanadium–phosphorus oxide phases, Stud. Surf. Sci.
Catal. 141 (2002) 301–308.
[168] Z. Ye, H. Alsyouri, S. Zhu, Y.S. Lin, Catalyst impregnation and
ethylene polymerization with mesoporous particle supported nickel-
diimine catalyst, Polymer 44 (2003) 969–980.
[169] K. Soga, Y. Sano, T. Uozumi, Organic aluminoxanes and poly-
merization catalysts using them for olefins, Patent JP 2000063387
(2000).
[170] M. Furuya, S. Riku, Oxidation of cyclohexene using silica meso-
porous catalysts. Patent JP 2002069015 (2002).
[171] D.H. Park, N. Nishiyama, Y. Egashira, K. Ueyama, Enhancement
of hydrothermal stability and hydrophobicity of a silica MCM-48
membrane by silylation, Ind. Eng. Chem. Res. 40 (2001) 6105.
[172] (a) S. Kim, C. Gauer, V.V. Guliants, J.Y.S. Lin, Amine-modified
silica membranes for separation of carbon dioxide under ambient
conditions, in: Proceedings of the Seventh International Conference
on Inorganic Membranes, 23–26 June 2002, Dalian, China;
(b) S. Kim, J. Ida, V.V. Guliants, Tayloring surface prop-
erties of MCM-41 and MCM-48 silicas by bonding 3-
aminopropyltriethoxysilane for selective adsorption of carbon diox-
ide, Chem. Mater., submitted for publication.
[173] M. Ogawa, K. Kuroda, J. Mori, Aluminum-containing mesoporous
silica films as nano-vessels for organic photochemical reactions,
Chem. Commun. (2000) 241.
[174] K. Ikeue, S. Nozaki, M. Ogawa, M. Anpo, Photocatalytic reduction
of CO2 with H2 O on Ti-containing porous silica thin film photo-
catalysts, Catal. Lett. 80 (2002) 3.
[175] R.C. Schroden, C.F. Blanford, B.J. Melde, B.J.S. Johnson, A. Stein,
Direct synthesis of ordered macroporous silica materials functional-
ized with polyoxometalate clusters, Chem. Mater. 13 (2001) 1074.
[176] B.J.S. Johnson, A. Stein, Surface modification of mesoporous,
macroporous and amorphous silica with catalytically active poly-
oxometallate clusters, Inorg. Chem. 40 (2001) 801.
[177] G. Wirnsberger, B.J. Scott, G.D. Stucky, pH sensing with meso-
porous thin films, Chem. Commun. (2001) 119.
[178] P. Innocenzi, A. Martucci, M. Guglielmi, A. Berzotti, E. Traversa,
Electrical and structural characterization of mesoporous silica thin
films as humidity sensors, Sens. Actuators B 76 (2001) 299.
[179] K. Domansky, J. Liu, L. Wang, M.H. Engelhard, S. Baskaran,
Chemical sensors based on dielectric response of functionalized
mesoporous silica films, J. Mater. Res. 16 (10) (2001) 2810–
2816.
[180] O. Dag, G.A. Ozin, H. Yang, C. Reber, G. Bussiere, Photolumines-
cent silicon clusters in oriented hexagonal mesoporous silica films,
Adv. Mater. 11 (6) (1999) 474.
[181] S. Yu, T. Wong, K. Pita, X. Hu, Synthesis of organically modified
mesoporous silica as a low dielectric constant intermetal dielectric,
J. Vac. Sci. Technol. B: Microelectron. Nanometer Struct. 20 (5)
(2002) 2036–2042.
[182] S. Yu, T. Wong, K. Pita, X. Hu, V. Ligatchev, Surface modified silica
mesoporous films as a low dielectric constant intermetal dielectric,
J. Appl. Phys. 92 (6) (2002) 3338–3344.
[183] J.E. MacDougall, K.R. Heier, S.J. Weigel, Sol–gel preparation of
mesoporous silica films with reduced dielectric constants and low
halide and metal contents using non-ionic catalysts, US Patent
6,365,266 (2002).
[184] C. Yang, A. Cho, F. Pan, T. Tsai, K. Chao, Spin-on mesoporous sil-
ica films with ultralow dielectric constants, ordered pore structures,
and hydrophobic surfaces, Adv. Mater. 13 (14) (2001) 1099–1102.
[185] S. Seraji, Y. Wu, M. Forbess, S.J. Limmer, T. Chou, G. Cao, Sol–gel-
derived mesoporous silica films with low dielectric constants, Adv.
Mater. 12 (22) (2000) 1695–1698.
[186] S. Baskaran, J. Liu, K. Domansky, N. Kohler, L. Nathan, C. Coyle,
G.E. Fryxell, S. Thevuthasan, R.E. Williford, Low dielectric con-
stant mesoporous silica films through molecularly templated syn-
thesis, Adv. Mater. 12 (4) (2000) 291–294.
[187] Y.S. Tang, S. Cai, G. Jin, J. Duan, K.L. Wang, H.M. Soyez, B.S.
Dunn, SiGe quantum dots prepared on an ordered mesoporous silica
coated Si substrate, Appl. Phys. Lett. 71 (17) (1997) 2448.
[188] M.A. Carreon, V.V. Guliants, P. Kumar, G. Beaucage, Oriented
periodic mesoporous thin films for the fabrication of nanoelectronic
devices, in: Proceedings of the Seventh International Conference
on Inorganic Membranes, 23–26 June 2002, Dalian, China.
[189] S. Besson, T. Gacoin, C. Ricolleau, C. Jacquiod, J.P. Boilot, 3D
Quantum dot lattice inside mesoporous silica films, Nanoletters
2 (4) (2002) 409.
[190] H. Wellmann, J. Rathousky, M. Wark, A. Zukal, G. Schulz-Ekloff,
Formation of CdS nanoparticles within functionalized siliceous
MCM-41, Microporous Mesoporous Mater. 44–45 (2001) 419.
[191] T. Hirai, H. Okubo, I. Komasawa, Size-selective incorporation of
CdS nanoparticles into mesoporous silica, J. Phys. Chem. B 103
(1999) 4228–4230.
[192] H. Parala, H. Winkler, M. Kolbe, A. Wohlfart, R.A. Fischer, R.
Schmechel, H. Von Seggern, Confinement of CdSe nanoparticles
inside MCM-41, Adv. Mater. 12 (14) (2000) 1050–1055.
[193] W. Zhang, J. Shi, H. Chen, Z. Hua, D. Yan, Synthesis and charac-
terization of nanosized ZnS confined in ordered mesoporous silica,
Chem. Mater. 13 (2001) 648–654.
[194] Y.S. Lin, I. Kumakiri, B.N. Nair, H. Alsyouri, Microporous inor-
ganic membranes, Sep. Purif. Methods 31 (2) (2002) 229.
[195] K. Kageyama, J.I. Tamazawa, T. Aida, Extrusion polymerization:
catalyzed synthesis of crystalline linear polyethylene nanofibers
within mesoporous silica, Science 285 (1999) 2113.
[196] P.M. Tessier, O.D. Velev, A.T. Kalambur, J.F. Rabolt, A.M. Lenhoff,
E.W. Kaler, Assembly of gold nanostructured films templated by
colloidal crystals and use in surface-enhanced Raman spectroscopy,
J. Am. Chem. Soc. 122 (2000) 9554.