Nanocrystallised titania and zirconia mesoporous thin films exhibiting enhanced thermal stability

Article abstract of DOI:10.1039/b205497n

Tuned chemical conditions complemented with a set of treatments have been developed to enhance the thermal stability of transition metal oxide mesoporous thin films (up to 500°C for TiO₂ and 450°C for ZrO₂), allowing the formation of crack-free coatings presenting excellent optical quality (transmittance higher than 85% in the visible region), tailored thickness (from 50 to 700 nm), a highly organised cubic (Im3m space group for TiO₂) or 2D-hexagonal (P6m space group for ZrO₂) mesostructure, high surface area (140-200 m² g^-1), controlled and narrowly distributed mesopore size (25-80 A), and a nanocrystalline inorganic framework (anatase or tetragonal zirconia).

Full text of DOI:10.1039/b205497n

View Article Online / Journal Homepage / Table of Contents for this issue
Nanocrystallised titania and zirconia mesoporous thin films
exhibiting enhanced thermal stability
´
Eduardo L. Crepaldi, Galo J. de A. A. Soler-Illia, David Grosso and Clement Sanchez*
`
´
´
Laboratoire de Chimie de la Matiere Condensee, Universite Pierre et Marie Curie (Paris VI) -
CNRS, 4, place Jussieu (T54-E5), 75252, Paris cedex 05, France. E-mail: clems@ccr.jussieu.fr;
Fax: +33 1 44 27 47 69; Tel: +33 1 44 27 33 65
L e t t e r
Received (in Montpellier, France) 4th June 2002, Accepted 9th September 2002
First published as an Advance Article on the web 18th October 2002
the inorganic framework can enhance chemical and/or
mechanical stability.
Tuned chemical conditions complemented with a set of treat-
ments have been developed to enhance the thermal stability of
transition metal oxide mesoporous thin films (up to 500 ꢀC for
TiO2 and 450 ꢀC for ZrO2), allowing the formation of crack-free
coatings presenting excellent optical quality (transmittance
higher than 85% in the visible region), tailored thickness (from
50 to 700 nm), a highly organised cubic (Im3m space group for
TiO2) or 2D-hexagonal (P6m space group for ZrO2) mesostruc-
In the present work we report for the first time, to the best of
our knowledge, the reproducible synthesis of thermally stable
transition metal oxide thin films presenting a periodically orga-
nised mesoporosity with high surface area associated with
nanocrystalline inorganic walls and an excellent optical qual-
ity. The strategies employed to reduce the contraction of the
mesostructure and enhance the thermal stability are based on
the controlled ageing of the films at increasing temperatures
to gradually eliminate volatile species and to further tune the
condensation steps, consolidating the inorganic framework
before the elimination of the template. Such coatings present
a pre-stiffened inorganic network that can be slowly heated
up to temperatures of 450 ꢀC for TiO2 and 400 ꢀC for ZrO2
to result in highly organised nanocrystalline transition metal
oxide mesoporous films.
TiCl4 or ZrCl4 was first reacted with a solution of the tem-
plate in anhydrous ethanol (ethanol was chosen as solvent
due to its substrate wetting properties and the good solubility
of all inorganic and organic precursors) to form, as previously
described, metallic chloroethoxide precursors [MCl4 ꢁ x(OEt)x ;
M ¼ Ti, Zr].18,19 To this highly acidic system (on average two
moles of HCl are generated for each mole of metal chloride),
water was added in controlled quantities. From these sols,
the deposition process was conducted in controlled atmo-
spheric relative humidity (RH), a parameter of paramount
importance for combining good optical quality and high struc-
tural order in the resulting coatings.
ture, high surface area (140–200 m2
g
ꢁ1), controlled and
˚
narrowly distributed mesopore size (25–80 A), and a nanocrys-
talline inorganic framework (anatase or tetragonal zirconia).
The field of mesoporous materials has experienced a burst of
activity in the last decade following the supramolecular tem-
plate approach introduced by scientists at Mobil Research
and Development Co.1 In this field most of the research has
been devoted to silica-based materials,1,2 which are very versa-
tile in terms of functionalisation with organic groups3 and
stable under thermal treatment. Indeed, the resulting periodi-
cally organised mesoporous and amorphous silica frameworks
easily keep their integrity upon calcination at temperatures of
about 600 ꢀC. The synthesis of transition metal (TM) oxide
based mesoporous materials is more difficult than that of
silica-based ones, in view of the complexity of TM chemistry,
such as high reactivity towards hydrolysis/condensation, and
their variable oxidation states and co-ordination numbers. In
addition, metal-oxo polymers tend to form crystalline phases
upon thermal treatment, whose formation is usually associated
with the collapse of the mesoporous network.4–6
In-situ SAXS coupled to interferometry analysis showed20–23
that the formation of meso-organised coatings takes place
through a disorder-to-order transition, from an isotropic sol
or gel to a worm-like mesophase, to a highly organised cubic
Im3m [for TiO2 , Fig. 1(a)]24 or 2D-hexagonal P6m [for
ZrO2 , Fig. 1(b)] mesostructure. For TiO2 , to allow such a
transition, two main conditions must be respected: (1) the con-
densation of the inorganic framework should be quenched and
(2) the solvent evaporation (especially water) should be slow.
Both conditions contribute to reduction of the viscosity of
the deposited gel and allow the formation of micelles, their
organisation in a ‘‘titanotropic’’ hybrid liquid crystal meso-
phase,10 and their alignment along the film–substrate and
film–air interfaces. These conditions can be obtained by using
very acidic initial solutions (the applied dipping sols display
pH < 0) and carrying out the deposition process at high
(ꢂ50%) RH.20,21
Among the developed methods, the so-called evaporation-
induced self-assembly (EISA)7,8 is one that has been proven
to be especially well-adapted to the design of TM oxide based
mesoporous materials.9–12 In our approach, metal chlorides in
alcoholic water media are used as the inorganic source and
non-ionic poly(ethylene oxide) based surfactants or block co-
polymers as the structure-directing agents.11–14More recently,
other methods based on the use of titania nanoparticles15 or
16,17
Ti(OEt)4
as inorganic precursors and non-ionic poly(ethy-
lene oxide) based surfactants have been developed for the for-
mation of mesoporous TiO2 based thin films. These authors
claimed that the mesostructured coatings are stable up to
400–450 ꢀC, but no evidence for the presence of crystalline
anatase phases was presented in these works. Especially for
TiO2 , many potential applications (such as photocatalysis and
energy conversion) are directly dependent on the presence of
anatase. For ZrO2 , even though not essential for the expected
potential applications (based on the high stability of this
oxide, such as heavy-duty membranes), the crystallisation of
Indeed, at low temperature (25–35 ꢀC) and in such highly
acidic conditions (pH < 0) the ability of titanium(IV) precur-
sors to undergo condensation reactions is strongly quenched
and therefore mainly monomeric or small oligomeric titanium
DOI: 10.1039/b205497n
New J. Chem., 2003, 27, 9–13
9
This journal is # The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2003

View Article Online
treatments allow a progressive condensation of the titanium-
oxo network. Indeed, the decrease in acidity, the increase of
the water concentration, and the rise in temperature (steps at
60 and 130 ꢀC) produce highly favourable conditions to permit
further condensation without surfactant removal. Such a pre-
treatment, aimed at pre-consolidating the network, is followed
by the removal of templates at temperatures higher than
300 ꢀC without destroying the periodically organised meso-
structure. Moreover, when large amphiphilic block copolymers
are used as the template they provide thicker amorphous
metal-oxo walls that can more easily accommodate the crystal-
lisation of titania nano-anatase.
For ZrO2 based systems, the formation of extended metal-
oxo polymers is much more dependent on the concentration
than for Ti(IV).25 As a result, the evaporation process readily
results in the formation of condensed inorganic species and a
worm-like mesophase is ‘‘frozen’’. However, the freshly
formed zirconium-oxo polymers contain many hydroxo
bridges (olation is kinetically favoured27) and can be ‘‘dis-
solved’’.12 Therefore, a treatment at very high humidity (satu-
rated, exposition to water vapours) for a short time (10–15 s)
results in a fast swelling of the film, allowing the disorder-to-
order transition. The second drying process takes place homo-
geneously, enhancing the optical quality. This treatment is
more efficient if applied as soon as the first drying process is
finished (oxolation is thermodynamically favoured27), so the
deposition should be carried out in a low humidily atmosphere
(10%) for fast evaporation.12 The further steps of ageing and
calcination induce in a first approximation the same effects
as those described for titania-based films.
The adhesion of the TiO2 and ZrO2 based films to the sub-
strate results in an anisotropic contraction,28 clearly observed
by XRD, 2D-XRD, 2D-SAXS and TEM, resulting in a dis-
torted cubic or 2D-hexagonal structure, which can be respec-
tively described as triclinic or 2D-centred rectangular [space
group C2m, see inset in Fig. 1(b)].11,12,18 Results acquired by
XRD in y ꢁ 2y mode (Fig. 2) show the importance of ageing
and gradually heating the films before calcination at tempera-
tures high enough to eliminate the template. A 1 day old (at
room temperature and RH ¼ 50%) F127-templated TiO2 film
(Conditions 1) treated at 350 ꢀC undergoes a structural con-
traction of about 70% (d110 , from approximately 130 to 39
Fig. 1 2D-SAXS patterns for as-prepared F127-templated (a) TiO2
and (b) ZrO2 based hybrid mesostructured thin films. The insets in
parts (a) and (b) are representations of the cubic (Im3m) and hexagonal
(P6m) unit cells, respectively. The latter is indexed following the C2m
space group symmetry.
hydroxy species are formed.25 These species are small, hydro-
philic (hydroxylated and hydrated) and may be positively
charged when larger amounts of water are present in the solu-
tion;26 these advantages allow a good matching of the hybrid
organic-inorganic interface, therefore facilitating co-operative
self-assembly processes with the surfactant.10
˚
A). On the other hand, a 2 week old film (at room temperature
and RH ¼ 50%), heated at 60 ꢀC for 24 hours followed by
130 ꢀC for 24 hours (Conditions 2), and finally calcined at
350 ꢀC displays a much smaller structural contraction, around
57%. Similar results are observed for both templates (Brij 58
and Pluronic F127) and also for ZrO2 based systems. A lower
degree of contraction means that the resulting coatings
can have larger and less distorted pores. In addition, an
Once the cubic hybrid mesophase has been formed a series
of chemical and thermal treatments have been developed to
enhance the thermal stability of TiO2 mesoporous thin films,
allowing the formation of highly organised, high surface area
mesoporous coatings, exhibiting semicrystalline frameworks.
Since the as-prepared film is almost uncondensed, it presents
a relatively fragile mesostructure (as-prepared films can be dis-
solved in water and they contain a large amount of volatile
species (15–20 mass % eliminated up to 100 ꢀC, as observed
by TG/DSC analysis) and chloride (0.3 to 1 Cl/Ti molar ratio,
as observed by EDX)). As a consequence, the method chosen
to eliminate the volatile species, to increase the condensation
of the inorganic moieties and eliminate the template, is of para-
mount importance because it determines the integrity of the
organisation, the degree of contraction and the thermal stabi-
lity of the final mesoporous coating. Therefore, a set of ageing
treatments under controlled relative humidity followed by
progressive thermal treatments (from 60 ꢀC to 500 ꢀC) were
carried out.
During these steps, while water from controlled air humidity
is provided to the hybrid film, HCl molecules are progressively
removed (as determined by EDX for different ageing
times). These chemical conditions combined with the thermal
Fig. 2 X-Ray diffraction diagrams for 350 ꢀC treated F127-templated
TiO2 films previously aged following (a) conditions 1 and (b) condi-
tions 2.
10
New J. Chem., 2003, 27, 9–13

View Article Online
enhancement in the thermal stability has been observed, with
films treated under conditions 2 undergoing mesostructural
collapse in temperatures about 50 to 100 ꢀC higher than those
treated under conditions 1, which is crucial for the formation
of highly organised, high surface area semicrystalline coatings
(see below).
Fig. 3 summarises the results obtained for the thermal treat-
ment of Pluronic F127-templated TiO2 based mesostructured
films. Low-angle XRD in y ꢁ 2y mode [Fig. 3(a)] shows a
gradual reduction of d110 and a decrease in the peak intensity
for treatment between 350 and 450 ꢀC. The intense and narrow
peaks (FWHM ꢃ 0.1ꢀ) suggest a very highly organised and
oriented mesostructure, which can be seen by TEM [Fig.
3(c)]. At 500 ꢀC a marked reduction in intensity and broaden-
ing of the [110] peak (FWHM ꢃ 0.4ꢀ) suggests a degradation of
the structure, with further heating resulting in mesostructural
collapse. Wide-angle XRD in parallel mode clearly shows the
formation of anatase from 400 ꢀC [Fig. 3(b)]. At 450 and
500 ꢀC, besides the presence of anatase, low intensity peaks
arising from the presence of brookite (JCPDS, PDF card no.
29–1360) can be observed. Finally, heating at 600 ꢀC results
in coatings presenting only anatase, showing that the brookite
phase is metastable. HRTEM [Fig. 3(e)] analysis showed the
presence of an important quantity of anatase crystallites for
films treated at 350 ꢀC and above. The problem to detect such
a phase by XRD for the 350 ꢀC treated film is strictly related
to the small quantity of matter in the coatings associated with
the small size of the crystallites (broad peaks). Thick films
(4 layers) were prepared by a dip-coating/stabilisation at
130 ꢀC/dip-coating process to increase the deposited quantity
of matter. Analysing the resulting film treated at 350 ꢀC (fol-
lowing conditions 2) by XRD showed the presence of an
intense peak at ca. 1.73ꢀ (2y), very close to that observed for
a similar monolayer film. The peak is slightly broader
(FWHM ꢃ 0.2ꢀ), which indicates a lower order and/or lower
orientation of the mesophase. In such a film, the deposited
quantity of matter is enough to detect the crystalline phase
(anatase) by XRD, as one can see in Fig. 3(d).
As revealed by TEM and HRTEM [Figs. 3(c) and 3(e)], the
thickness of the pore walls of films treated at and above 300 ꢀC
˚
is approximately 100 A (dark areas). From the results pre-
sented in Figs. 3(a) and 3(b) one can see that the degradation
of the structure can be directly related to the formation of ana-
tase crystallites [see inset in Fig. 3(b)] that exceed this size,
which occurs from 450 to 500 ꢀC. Therefore, highly organised
mesoporous TiO2 thin films exhibiting a semicrystalline (ana-
tase) framework can be obtained by thermally treating aged
films at temperatures ranging from 350 and 450 ꢀC. Under
such conditions, the 300–400 nm thick (as determined by ellip-
sometry11 and checked by TEM and SEM) coatings present
excellent optical quality (transmittance > 85% from 350 to
1100 nm), high surface area (148 m2 gꢁ1 for a 350 ꢀC treated
film, see Fig. 4) and are totally crack-free on the micrometric
scale (as observed by SEM). The pore size of the resulting
˚
coatings is large, around 58 A, and narrowly distributed
˚
(FWHM ꢃ 25 A), in good agreement with the elliptical
˚
(approximately 40 ꢄ 80 A) pores observed by TEM. As one
Fig. 3 F127-templated TiO2 films prepared following conditions 2:
(a) low-angle (y ꢁ 2y mode) and (b) wide-angle (parallel mode) XRD
diagrams for films treated at the indicated temperatures. The inset in
part (b) shows the variation of the anatase crystallite size as a function
of temperature. (c) TEM image along the [111] zone axis for a 350 ꢀC
treated film. The inset in part (c) is the modulus of the Fourier trans-
form of the full image. (d) Wide-angle XRD pattern for a multilayer (4
coatings) 350 ꢀC treated film together with the lines for anatase
(JCPDS, PDF card no. 21-1272), from which the crystallite size for
the 350 ꢀC treated sample was calculated. (e) HRTEM images along
the [100] zone axis for a 400 ꢀC treated film showing the presence of
anatase crystallites.
Fig. 4 Nitrogen adsorption-desorption isotherms and pore size dis-
tribution plot for 350 ꢀC treated a F127-templated TiO2 film.
New J. Chem., 2003, 27, 9–13
11

View Article Online
collapse. However, the coatings treated between 300 and
400 ꢀC exhibit excellent optical quality (films are crack-
free and transparent, with transmittance higher than 90% in
the 200 to 1100 nm region for a typical thickness of 300
nm), high structural order and a semicrystalline (tetragonal
zirconia) framework.
can see in Fig. 4, the volume adsorbed at low pressure is not
large, showing that the surface area comes practically only
from the mesopores, unlike PEO based block copolymer tem-
plated silicas.29 In this type IV isotherm it is difficult to identify
the hysteresis loop as H1 or H2.30 Usually, the N2 adsorption
isotherms of materials presenting a cage-like structure (such as
the mesostructure observed here for F127-templated TiO2
films, Im3m symmetry) have a H2 hysteresis loop, associated
with the presence of large pores connected by smaller openings
(ink-bottle pores), typical of SBA-1629 and also observed for
F127-templated silica films.31 Here, this effect seems to be
minimised by the presence of defects in the pore walls, as
one can see in Fig. 3(c).
When Brij 58 (B58) was used as the structure-directing agent
a much lower thermal stability was attained for both ZrO2 and
TiO2 based systems. TiO2 based coatings maintain their mesos-
tructural stability up to 350 ꢀC,11 while the stability of ZrO2
based ones is limited to 300 ꢀC.12 The B58-templated coatings
have similar porosity (estimated based on the organic/inor-
ganic ratio) to those templated by F127, however, the size of
the micelles of B58 are much smaller, resulting in much smaller
ZrO2 based mesostructured films treated up to 300 ꢀC pre-
sent very high structural order [Figs. 5(a) and 5(c)]. Treatment
at 350 and 400 ꢀC results in a gradual reduction in intensity
and broadening of the (02) XRD peak, as well as a progressive
structural contraction. A very broad, low intensity peak can be
observed at 450 ꢀC, while at 500 ꢀC the mesostructure is com-
pletely lost. Wide-angle XRD showed very broad, low inten-
sity peaks [indicated by arrows in Fig. 5(b)] for films treated
between 300 and 400 ꢀC. The broadness (FWHM > 2ꢀ) of
˚
pores and thinner walls (around 25 Afor both TiO2 and ZrO2
based thin films). These thin walls cannot accommodate the
crystallites formed at temperatures higher than those indicated
above. These results support the hypothesis that the meso-
structural degradation can be related to indiscriminate crystal-
lisation of the inorganic framework, with crystallites growing
to a size that exceeds the thickness of the pore walls. Neverthe-
less, anatase nanocrystallites could be observed in the inor-
ganic walls of 350 ꢀC treated B58-templated TiO2 films by
HRTEM.20–23
Moreover, preliminary results indicate that following the
same synthesis strategy the preparation of mixed oxide (such
as ZrO2–CeO2) mesoporous films is feasible and results in
higher thermally stable mesoporous coatings, in which the high
structural order can be retained up to 500 ꢀC.
˚
such peaks indicates that crystallites smaller than 40 Aare pre-
sent in the ZrO2 framework, which can be easily detected by
HRTEM [Fig. 5(d)]. Further heating (to 450 and 500 ꢀC)
results in a massive crystallisation of the inorganic network,
and the resulting wide-angle XRD patterns display intense
peaks that show the presence of tetragonal zirconia (JCPDS,
PDF card no. 50-1089). The sizeꢀ of the crystallites quickly
˚
˚
grows from less than 40 A (at 400 C) to more than 100 A (at
450–500 ꢀC), exceeding the thickness of the pore walls (around
The results presented in this letter open a wealth of oppor-
tunities to synthesise non-silicate nanocrystalline mesoporous
coatings with relevance for use as materials in the field of cat-
alysis, photocatalysis and nano-membranes working under
extreme conditions (for instance high pH and temperature).
˚
80 A, as estimated by TEM), which results in mesostructural
Experimental
Film preparation
The starting solutions contain 1 TiCl4:t template:40 EtOH:10
H2O or 1 ZrCl4:t template:40 EtOH:20 H2O, where t is 0.05
for Brij 58 [C16H33(OCH2CH2)20OH] or 0.005 for Pluronic F-
127 [HO(CH2CH2O)106(CH2CH(CH3)O)70(CH2CH2O)106H].
In both cases, t was adjusted in order to give approximately
one ethylene oxide (EO) group per metal, resulting in an inor-
ganic (MO2)/organic ratio around 0.3–0.4 (v/v). The prepara-
tion of a typical dipping solution can be described as follows:
0.01 mol of anhydrous metal chloride (1.93 g for TiCl4 or 2.33
g for ZrCl4) was slowly added to a solution containing 0.57 g
of Brij 58 or 0.67 g of Pluronic F-127 in 18.43 g of ethanol. To
this solution 1.80 g (for Ti) or 3.60 g (for Zr) of water was
slowly added.
Films were prepared by dip-coating glass or silicon sub-
strates at a constant withdrawal rate (1–5 mm sꢁ1) at con-
trolled temperature (25–35 ꢀC) and relative humidity (RH,
10–80%). After a given ageing time at controlled RH, the films
were thermally treated in air (ramp of 1 ꢀC minꢁ1) at tempera-
tures ranging from 60 to 600 ꢀC.
Film characterisation
Low-angle X-ray diffraction (XRD) diagrams were collected in
y ꢁ 2y mode using a conventional goniometer, PW 1820 Phi-
˚
lips (Cu-Ka1 radiation, l ¼ 1.5406 A). Wide-angle XRD pat-
terns were collected in parallel mode (o ¼ 0.5ꢀ, 2y varied from
10 to 70ꢀ, Cu-Ka1 radiation) using a Philips X’Pert PW-3050
with a thin film optic. The crystallite size was estimated by
applying the Scherrer equation to the FWHM of the (101)
peak for anatase and tetragonal zirconia, with silicon as a
standard for the instrumental line broadening. Synchrotron
Fig. 5 F127-templated ZrO2 films prepared following conditions 2:
(a) low-angle (y ꢁ 2y mode) and (b) wide-angle (parallel mode) XRD
diagrams for films treated at the indicated temperatures. The inset in
part (a) is a 2D-SAXS pattern for a 300 ꢀC treated film. (c) TEM
and (d) HRTEM images along the [001] zone axis for a 300 ꢀC treated
film. The inset in part (c) is the modulus of the Fourier transform of
the full image.
12
New J. Chem., 2003, 27, 9–13

View Article Online
7
Y. Lu, R. Ganguli, C. A. Drewien, M. T. Anderson, C. J. Brinker,
W. Gong, Y. Guo, H. Soyez, B. Dunn, M. H. Huang and J. I.
Zink, Nature, 1997, 389, 364.
C. J. Brinker, Y. Lu, A. Sellinger and H. Fan, Adv. Mater., 1999,
11, 579.
(a) P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka and G. D.
Stucky, Nature, 1998, 395, 583; (b) P. Yang, D. Zhao, D. I.
Margolese, B. F. Chmelka and G. D. Stucky, Chem. Mater.,
1999, 11, 2813.
small-angle X-ray scattering (SAXS) analysis was performed
in transmission mode using the synchrotron radiation of
the SAXS beam-line of ELETTRA (Trieste, Italy). Full
details regarding such experiments can be found else-
where.13,14,20,21,32,33
Transmission electron microscopy images in ordinary
(TEM) or high (HRTEM) resolution were collected using a
Philips EM 208 (120 kV) or a Philips CM 20 (200 kV) micro-
scope, respectively, for samples scratched from the substrate,
embedded in epoxy resin, and ultramicrotomised. Scanning
electron microscopy coupled to EDX investigations (JEOL
JSM-5200 scanning microscope operating at 20 kV, coupled
to an Oxford Link Pentafet 6880 for surface elemental ana-
lysis) were performed to evaluate the morphology and the
chemical composition of the film surface.
8
9
10 (a) G. J. de A. A. Soler-Illia, E. Scolan, A. Louis, P. A. Albouy
and C. Sanchez, New J. Chem., 2001, 25, 156; (b) G. J. de A. A.
Soler-Illia, A. Louis and C. Sanchez, Chem. Mater., 2002, 14,
750; (c) G. J. de A. A. Soler-Illia and C. Sanchez, New J. Chem.,
2000, 24, 493.
11 D. Grosso, G. J. de A. A. Soler-Illia, F. Babonneau, C. Sanchez,
P.-A. Albouy, A. Brunet-Bruneau and A. R. Balkenende, Adv.
Mater., 2001, 13, 1085.
12 E. L. Crepaldi, G. J. de A. A. Soler-Illia, D. Grosso, P.-A. Albouy
and C. Sanchez, Chem. Commun., 2001, 1582.
13 L. Pidol, D. Grosso, G. J. de A. A. Soler-Illia, E. L. Crepaldi, C.
Sanchez, P.-A. Albouy, H. Amenitsch and P. Euzen, J. Mater.
Chem., 2002, 12, 557.
14 E. L. Crepaldi, D. Grosso, G. J. de A. A. Soler-Illia, P.-A.
Albouy, H. Amenitsch and Cle´ment Sanchez, Chem. Mater.,
2002, 14, 3316.
15 Y. K. Hwang, K.-C. Lee and Y.-U. Kwon, Chem. Commun., 2001,
1738.
16 H. Yun, K. Miyazawa, H. Zhou, I. Honma and M. Kuwabara,
Adv. Mater., 2001, 13, 1377.
17 K. L. Frindell, M. H. Bartl, A. Popitsch and G. D. Stucky,
Angew. Chem., Int. Ed., 2002, 41, 960.
Ultraviolet-visible spectrophotometry was performed using
a Bio-Tek Instruments UVIKON XS spectrophotometer for
films deposited on fused silica substrates.
Thermogravimetric (TGA)/differential scanning calori-
metric (DSC) analysis was performed in air (100 cm3 minꢁ1
)
using a TA Instruments SDT 2960 from room temperature
to 700 ꢀC at a heating rate of 1 ꢀC minꢁ1. Nitrogen adsorp-
tion-desorption isotherms were collected at ꢁ196 ꢀC for films
scratched from the substrate using Micromeritics ASAP 2010
equipment (BET and BJH models, respectively, used for sur-
face area and porosity evaluation).
18 D. C. Bradley, R. C. Mehrotra and D. P. Gaur, Metal Alkoxides,
Academic Press, London, 1978.
19 M. Nabavi, S. Doeuff, C. Sanchez and J. Livage, J. Non-Cryst.
Solids, 1990, 121, 31.
Acknowledgements
20 E. L. Crepaldi, G. J. de A. A. Soler-Illia, D. Grosso, P.-A.
Albouy, H. Amenitsch and C. Sanchez, Stud. Surf. Sci. Catal.,
2002, 141, 235.
This work was financially supported by the French Ministry of
Research, CNRS, CNPq (Brazil, grant no. 200636/00-0), and
21 D. Grosso, F. Babonneau, C. Sanchez, G. J. de A. A. Soler-Illia,
E. L. Crepaldi, P.-A. Albouy, H. Amenitsch, A. R. Balkenende
and A. Brunet-Bruneau, J. Sol-Gel Sci. Technol., 2003, in press.
22 C. Sanchez, E. L. Crepaldi, A. Bouchara, F. Cagnol, D. Grosso
and G. J. de A. A. Soler-Illia, Mater. Res. Soc. Symp. Proc.,
2002, 728, S1-2.
´
Fundacion Antorchas (Argentina). The authors thank Dr.
Pierre-Antoine Albouy and Dr. Heinz Amenitsch for their help
with the Synchrotron-SAXS measurements. The authors also
´
thank Jose A. Maulin and Maria T. P. Maglia, and the Labor-
atorio de Microscopia Eletronica of the Depto. de Biologia
´
ˆ
23 G. J. de A. A. Soler-Illia, D. Grosso, E. L. Crepaldi, F. Cagnol
and C. Sanchez, Mater. Res. Soc. Symp. Proc., 2002, 726, Q7.3.
24 According to the angles between the in-plane and out-of-plane
spots in the 2D-SAXS pattern, the cubic domains are oriented
with the (110) plane (the most densely packed in the lattice)
parallel to the substrate. A complete indexation of a similar
mesophase presenting the same orientation was reported for
F127-templated silica thick films in: G. J. de A. A. Soler-Illia,
E. L. Crepaldi, D. Grosso, D. Durand and C. Sanchez, Chem.
Commun., 2002, 2298.
25 C. F. Baes and R. E. Mesmer, The Hydrolysis of Cations, John
Wiley & Sons, New York, 1976.
26 M. G. Reichmann, F. J. Hollander and A. T. Bell, Acta Crystal-
logr., Sect. C, 1987, 43, 1681.
27 E. M. Larsen, in Advances in Inorganic Chemistry and Radiochem-
ˆ
Celular Molecular e Bioagentes Patogenicos, Faculdade de
Medicina de Ribeira˜o Preto, University of Sa˜o Paulo, for
TEM measurements.
References
1
(a) C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and
J. S. Beck, Nature, 1992, 359, 710; (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. McCullen,
J. B. Higgins and J. L. Schlenker, J. Am. Chem. Soc., 1992,
114, 10 834.
´
istry, eds. H. J. Emeleus and A. G. Sharpe, Academic Press,
New York, 1970, vol. 13, p. 1.
2
(a) A. Corma, Chem. Rev., 1997, 97, 2373; (b) J. Y. Ying, C.
Mehnert and M. S. Wong, Angew. Chem., Int. Ed., 1999, 38, 57;
(c) T. J. Barton, L. M. Bull, W. G. Klemperer, D. A. Loy,
B. McEnaney, M. Misono, P. A. Monson, G. Pez, G. W. Scherer,
J. C. Vartuli and O. M. Yaghi, Chem. Mater., 1999, 11, 2633; (d )
D. Zhao, P. Yang, Q. Huo, B. F. Chmelka and G. D. Stucky,
Curr. Opin. Solid State Mater. Sci., 1998, 3, 111; (e) N. K. Raman,
M. T. Anderson and C. J. Brinker, Chem. Mater., 1996, 8, 1682.
(a) A. Stein, B. J. Melde and R. C. Schroden, Adv. Mater., 2000,
12, 1403; (b) A. Sayari and S. Hamoudi, Chem. Mater., 2001,
13, 3151.
´
28 M. Klotz, P.-A. Albouy, A. Ayral, C. Menager, D. Grosso, A.
Van der Lee, V. Cabuil, F. Babonneau and C. Guizard, Chem.
Mater., 2000, 12, 1721.
29 D. Zhao, Q. Huo, J. Feng, B. F. Chmelka and G. D. Stucky,
J. Am. Chem. Soc., 1998, 120, 6024.
30 M. Kruk and M. Jaroniec, Chem. Mater., 2001, 13, 3169.
31 D. Zhao, P. Yang, N. Melosh, J. Feng, B. F. Chmelka and G. D.
Stucky, Adv. Mater., 1998, 10, 1380.
32 D. Grosso, A. R. Balkenende, P.-A. Albouy, A. Ayral, H.
Amenitsch and F. Babonneau, Chem. Mater., 2001, 13, 1848.
33 D. Grosso, F. Babonneau, P.-A. Albouy, H. Amenitsch, A. R.
Balkenende, A. Brunet-Bruneau and J. Rivory, Chem. Mater.,
2002, 14, 931.
3
4
5
6
A. Sayari and P. Liu, Microporous Mater., 1997, 12, 149.
F. Schuth, Chem. Mater., 2001, 13, 3184.
¨
G. J. de A. A. Soler-Illia, C. Sanchez, B. Lebeau and J. Patarin,
Chem. Rev., 2002, 102(11), in press.
New J. Chem., 2003, 27, 9–13
13