Journal of Non-Crystalline Solids 225 Ž1998.

146–152

Section 4. Catalysts. Surface function

High-temperature catalysts through sol–gel synthesis
A.J. Lecloux ) , J.P. Pirard
UniÕersite´ de Liege,
` Laboratoire de Genie
´ Chimique, Institut de Chimie B6, B-4000 Liege,
` Belgium

Abstract

Sol–gel chemistry is an efficient tool for controlling morphology and reactivity of solids and its potential in the
development of tailor-made and thermally stable industrial catalysts is discussed. The key targets in catalyst preparation are
mechanically and thermally stable morphology, highly dispersed active phase on homogeneous carrier and porosity
minimising diffusional limitation. Sol–gel chemistry approach to the development of such catalysts is illustrated through
examples. By controlling gelation and drying steps, ‘aerogel-like’ morphologies with good mechanical properties in which
the reactants molecules have an open access to the active sites, practically without mass transfer limitation are obtained
under non-hypercritical conditions. Highly dispersed supported metallic catalysts as well as homogeneous mixed oxides
carriers have been prepared which remain very stable at high temperature. This opens the way to prepare high-performance
industrial catalysts which could not be prepared without the sol–gel approach. q 1998 Elsevier Science B.V. All rights
reserved.

Keywords: Catalyst synthesis; Sol–gel chemistry; Morphology

1. Introduction chemistry in the aqueous phase is widely used in

preparation of industrial heterogeneous catalysts. De-
Heterogeneous catalysis is one of the most de-
velopments of the preparative inorganic chemistry in
manding applications of the solid state chemistry. It
organic media open new possibilities in catalyst syn-
is indeed essential to have a very good control, not
thesis, in particular the preparation of high pore
only of the chemistry of the reaction at the catalyst’s
volume solids, homogeneous mixed oxides and
surface, but also of the physical phenomena linked to
highly dispersed metallic catalysts. Gel formation
heat and mass transfer processes. ‘Aerogel-like’
and drying process are discussed in relationship with
solids can help to solve some of the pending ques-
the morphology control and the solid-state reactivity
tions in heterogeneous catalysis, i.e., the high disper-
of the resulting solids. Attention is given to improve-
sion of an active species on a carrier having an
ment of mechanical properties of aerogel-like struc-
homogeneous surface, acceptable mechanical proper-
tures and to preparation of multicomponent gels, in
ties and a porous texture which allows the easy
particular highly dispersed supported metallic cata-
diffusion of reactants to those active sites. Sol–gel
lysts as well as homogeneous mixed oxides carriers
which remain stable at high temperature. Examples
)
Corresponding author. Tel.: q32-2 676 7306; fax: q32-2 illustrate the synthetic potential and flexibility of
676 7241; e-mail: ale@cefic.be. sol–gel chemistry in catalysis.

0022-3093r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 0 2 2 - 3 0 9 3 Ž 9 8 . 0 0 0 3 4 - 9
 A.J. Lecloux, J.P. Pirardr Journal of Non-Crystalline Solids 225 (1998) 146–152 147

2. Basic chemistry and growth process
The purpose of this paper is not to present a
detailed review of the sol–gel process chemistry
because books w1,2x and review papers w3–5x are
already published on this subject. But it intends to
contribute to the discussion on the potential of sol–
gel chemistry in the field of catalysis. Its potential
clearly depends on the flexibility of this type of
chemistry and, in particular, on its most recent devel-
opments implying the use of organic compounds
andror solvents.
The most popular raw materials for the synthesis
of oxides through organic sol–gel chemistry are the
corresponding alkoxides, which are carefully hydrol-
ysed, and then dried and calcined in well controlled
conditions. Similarly, metallic salts of organic acids,
like oxalate, acetate, citrate, acetylacetonate, etc. can
also be used as precursors for sol–gel processes. In
both cases, the ratio of the kinetic constants of

Fig. 1. Aggregation patterns of ‘elementary particles’: Ža. relatively linear aggregate; Žb. branched aggregate.
148 A.J. Lecloux, J.P. Pirardr Journal of Non-Crystalline Solids 225 (1998) 146–152
hydrolysis and condensation is one of the key-con-
trolling factors of the gel morphology. This ratio
depends on a large number of parameters, such as
the nature of the organic moiety, the type of solvent,
the use of a complexing agent, the presence of a
catalyst and its nature, the absolute and relative
concentrations of reactants and temperature.
It is also known that the time has to be considered
as a very important parameter because the degree of
reaction continuously varies with time and modifies
the relative kinetics of hydrolysis and condensation.
Moreover, as the reaction steps are partially re-
versible, the reaction time and the aging conditions
can affect the molecular structure of the resulting
gel.
When several metallic species are involved, their
relative reactivity towards hydrolysis and condensa-
tion can be very different. In this case, to get a
homogeneous solid, the relative reactivity must be
adjusted by modifying the reaction conditions. The
choice of the right solvent as well as the use of
complexing agents can be particularly effective w1x.
When mixed oxides are used as catalysts or as
catalyst’s carriers, the homogeneity of the composi-
tion is a crucial factor in controlling the surface
reactivity. Through sol–gel chemistry, highly homo-
geneous mixed oxides can be produced which cannot
be obtained through classical methods, leading for
example to an enhanced number of active sites. This
will be discussed later on.
One of the most important feature of the sol–gel
process is the three-dimensional development of the
metal–oxygen–metal bonds. Depending on the rela-
tive importance of the hydrolysis and condensation
reactions, the growing process produces ‘polymeric
species’ which can be relatively linear, branched or
particulate. In a first step, micelles of about 10 to 20
nm in diameter are formed through a nucleation
process, the rate of which depends on the reaction
conditions. The faster the nucleation process, the
larger the number of nuclei formed and the smaller
the micelle size.
Either these nuclei will grow independently: in
this case, particles are formed which can grow in a
very homogeneous and well-controlled way w6–8x.
This growing process is largely used in the prepara-
tion of catalysts when a well-defined micro- or
meso-porous texture is requested. Or the nuclei will
interact with each other to form a three-dimensional
network leading progressively to a gel. In this case,
the growth process occurs through the progressive
aggregation of micelles, also called ‘elementary par-
ticles’. Depending on the reaction conditions and on
the metallic species involved, the aggregates can be
relatively linear or branched, reproducing at an ‘ele-
mentary particle’ level the similar three-dimensional
development as at the molecular level Žsee Fig. 1 and
Ref. w9x.. The fractal character of the resulting solids
w10–12x, as well as the analysis of the viscoelastic
behaviour during the gelation w13,14x, supports the
similarity of the growth patterns observed at differ-
ent scales.
Even if the main challenge is to retain after drying
the morphology created at the gelation step, the way
this gelation has been conducted is crucial for the
final properties of the dried solid.
3. Aging and drying
During the aging process, even at normal temper-
ature and pressure, some reconstruction of the ‘poly-
meric’ entities and of the ‘aggregates’ can occur to
minimise the global free energy of the system. This
reconstruction generally leads first to a consolidation
of the aggregates and then to a progressive densifica-
tion of the solid part of the gel. Depending on the
initial shapes of aggregates and on the aging condi-
tions, the densification may lead, either to high-den-
sity particles, which can even crystallise like in the
case of zeolite synthesis, or to a three-dimensional
network of elementary particles, which can progres-
sively shrink by expelling the solvent.
During the drying of the gel, the capillary forces,
originated by the surface tension of the liquid phase,
tend to densify the solid by closely packing together
the elementary particles, destroying the most fragile
part of the three-dimensional network and reducing
the porous volume of the resulting solid. In such a
process, quasi-non-porous monoliths can be formed.
The nature of the liquid phase and the way of
removing it are two determinant factors to control
the morphology of the dried product. Classically, the
preparation’s techniques used to produce industrial
catalysts take place in aqueous phase and, due to the
high surface tension of water, an important shrinkage
 A.J. Lecloux, J.P. Pirardr Journal of Non-Crystalline Solids 225 (1998) 146–152
of the gel cannot be avoided during the drying step.
The pore volume of the resulting solid is then limited
to maximum 1 cm3rg in the best conditions. The use
of organic solvents with a smaller surface tension
enlarges the range of possibilities even in a classical
drying process.
4. Preparation of solids with ‘aerogel-like’ mor-
phology
Ideally, the drying step should avoid the destruc-
tion of the morphology created during the gelation
step or at least be conducted in such a way, that the
morphological changes remain under control. To pre-
serve after drying the morphology created in the
liquid phase, the effects of the capillary forces should
be minimised or ideally avoided. Classically this
objective can be reached by working in hypercritical
conditions directly on the reaction medium or after
having replaced the solvent by liquid carbon dioxide.
These processes are unfortunately very expensive
and difficult to scale up at industrial level.
The development of a classical drying process
able to produce highly porous solids with an ‘aero-
gel-like’ morphology has been studied by Haereid et
al. w15,16x at the lab scale. These studies as well as
research projects carried out in our laboratory intend
to minimise the effects of the capillary forces during
the drying step both by reducing the surface tension
of the liquid phase Žorganic solvent. and by increas-
ing the mechanical properties of the wet solid net-
work. If the mechanical strength of this wet network
can be made high enough to resist to a large extend
the capillary forces, the porous structure will not
collapse and an ‘aerogel-like’ morphology can be
produced in classical drying conditions. By using
such an approach, high pore volume catalysts could
then be obtained in acceptable economical condi-
tions.
The wet solid network in a gel consists of strands
of ‘polymeric substances’ or chains of particles
joined at nodes and forming a three-dimensional
cross-linked structure w1,17,18x. The mechanical sta-
bility of this network depends on the size and shape
of the unit cells and in particular on the ratio be-
tween the diameter, d, of the chains and the distance,
L, between the nodes. The value of d is closely
149
linked to the size of the ‘elementary particles’ formed
during the nucleation process and is independent of
the pore size w18,19x. The value of L depends on the
type of aggregation Žlinear or branched. as well as
on the total solid concentration in the synthesis
medium. Obviously the mechanical strength of the
network decreases when the ratio drL decreases but
increases with the degree of interconnection Žbranch-
ing. within the network. To minimise the shrinkage
of the wet network during the drying, the synthesis
and aging conditions must be chosen to have rela-
tively large ‘elementary particles’ Žlarge d value.
combined with a high degree of branching. The
existence of a dilution effect has also been reported
in the literature w20x.
‘Low-density xerogels’ have been compared to
aerogels of similar composition on the basis of nitro-
gen adsorption–desorption isotherms analysed ac-
cording to the scheme proposed by Lecloux w21x and
of mercury porosimetry curves analysed by using the
model of Pirard et al. w18,22,23x. The results, which
are discussed elsewhere w24,25x, indicated that high
pore volume values about 4 to 6 cm3rg can be
measured in xerogels with a porous texture similar to
that observed in aerogels. The macropore volume
increases with the basicity of the medium, probably
due to the formation of a highly interconnected
network, and decreases when the nucleation rate
increases w25x, most probably because smaller ele-
mentary particles are formed.
If the preparation of tailor-made catalysts is con-
sidered, it is interesting to note that it is possible to
control the relative importance of macroporosity
measured by mercury compression w18,23x and meso-
porosity measured by nitrogen adsorption. As it will
be discussed later on through some practical exam-
ples, the possibility of adjusting the porosity of a
catalyst is essential to control the diffusion phenom-
ena during the reaction. In this respect, the low-den-
sity xerogels seem to be particularly attractive on the
industrial point of view.
5. Thermally stable solids and catalysts
The stability of catalysts is essential when an
industrial application is considered. In particular the
thermal stability of highly dispersed species on or in
150 A.J. Lecloux, J.P. Pirardr Journal of Non-Crystalline Solids 225 (1998) 146–152
the catalyst carrier is still an important practical
question. Examples are given hereafter to illustrate
the potential of the sol–gel chemistry in preparing
thermally stable solids.
5.1. Homogeneous mixed oxides
In catalysis, mixed oxides are very often used
either as carrier or as active component. In many
cases, it is however very difficult, not only to pre-
pare highly homogeneous mixed oxides of some
compositions, but also to avoid the separate crystalli-
sation of one component during thermal treatments
or in operative conditions.
In his review paper on aerogel catalysts, Pajonk
w3x indicated that aerogels are very stable materials.
Even when treated at high temperature, they exhibit
high surface area and large pore volume. He also
demonstrated the high flexibility of the sol–gel ap-
proach in preparing mixed oxides of various types by
co-gelling several metal derivatives in appropriate
organic solvents by reaction with water at the re-
quired pH. Binary and tertiary aerogels have been
prepared and used as heterogeneous catalysts in a lot
of reactions. For example, nickel oxide, chromium
oxides and iron oxides have been associated with
alumina, silica, zirconia or magnesia.
The key condition to obtain homogeneous mixed
oxides is to adjust the relative reactivity of the
metallic precursors in such a way that they have
similar rates of hydrolysis andror condensation. To
reach this objective, 2-methoxy-ethanol has been
used for several years in our lab as solvent in
combination with complexing agents like acetic acid,
acetylacetone or diamines. This approach makes pos-
sible the preparation of various mixed oxides charac-
terised by a high homogeneity. Homogeneous
silica–zirconia gels containing up to 80% Zr have
been prepared w26x and dried both in hypercritical
and low pressure conditions. Aerogels and low-den-
sity xerogels with similar porous structures are ob-
tained. Due to the high homogeneity of the solids
prepared in this way, the silica–zirconia demixing
and the crystallisation of zirconium oxide is post-
poned up to very high temperature. As an example,
silica–zirconia aerogels containing up to 40% Zr
appear to be stable at temperatures as high as 8008C.
At this temperature the solids remain amorphous, the
pore volume and the specific surface area are rather
modified. The collapse of the texture due to the
crystallisation of ZrO 2 and the partial softening of
the silica backbone is observed only for higher con-
tent in Zr or for treatment at higher temperature.
This type of solids cannot be obtained by classical
techniques. As such or chemically modified, they
could be of industrial importance, in particular for
the development of high efficiency acid–base cata-
lysts or for incorporating well-dispersed, transition
metal active sites in silica or alumina backbones.
5.2. Supported metallic catalysts
Heinrichs et al. w24,27–30x and Delhez et al. w31x
described the synthesis and properties of metallic-
supported catalysts obtained by the sol–gel route. Pd
and Ag complexes, containing both amine functions
and siloxane moiety, are added to alcoholic solutions
of TEOS and the mixture is hydrolysed with ammo-
niated water in ethanol. A nanocomposite gel is
obtained which is aged at 708C, dried under vacuum
at 1508C, calcined and reduced. The most interesting
features of this study are enumerated below.
Ø Finely dispersed particles of palladium–silver
alloys in a highly porous silica matrix are obtained.
Pore volumes from 3 to 6 cm3rg and specific sur-
face areas between 250 and 450 m2rg are measured,
indicating the formation of an ‘aerogel-like’ struc-
ture.
Ø The metallic particles size Žfrom 2.5 to 3.5 nm.
remains unchanged even at temperature at which the
sintering process should normally occur. It appears
that the Pd–Ag particles are located inside the silica
‘elementary particles’ Žwith an apparent diameter of
about 20 to 30 nm. which form the backbone of the
low-density xerogels. During the gelation process,
the Pd complexes seem to play the role of nucleating
agents and the silica particles exhibit and retain an
internal microporosity.
Ø The resulting catalysts have a remarkable cat-
alytic activity in hydrodechloration reactions leading
selectively to olefines with a very limited formation
of the corresponding alkanes.
Ø Moreover, the catalytic reaction occurs without
any observable transfer limitation. The Weisz’s crite-
rion, which compares reaction and diffusion rates
w32x, has been used to study the possible diffusion at
 A.J. Lecloux, J.P. Pirardr Journal of Non-Crystalline Solids 225 (1998) 146–152
three discrete levels: elementary particles, aggregates
and pellets. The results clearly show w29,30x that
there is no internal diffusional limitation. The diffu-
sion in such a porous structure proceeds as follow: in
order to reach the active sites, reagents have to
diffuse in pores of decreasing size located in entities
of decreasing size and decreasing void fraction. Those
antagonist effects globally lead to very small values
of the Weisz’s criterion indicating that catalysts with
such a texture offers very good mass transfer proper-
ties.
This last point, which seems to be linked to the
‘aerogel-like’ morphology of the solids and which
gives the reactants molecules an open access to the
active sites, is particularly interesting in heteroge-
neous catalysis where the mass transfer properties
can drastically affect the activity and the selectivity
of reactions.
It is, however, interesting to point out that the
drying conditions have a significant effect on the
catalytic properties of the solids. The metallic parti-
cles, which are trapped in the ‘elementary particles’
of silica, are accessible to the reactants through the
microporosity present in the silica particles. But this
microporosity almost disappears if the drying take
place in hypercritical conditions leading to inactive
catalysts. In this particular case, low-density xerogels
are much more efficient than true aerogels.
6. Conclusion
In the sol–gel process applied to catalyst’s syn-
thesis, the gelation and drying steps must be particu-
larly well-defined and managed for controlling the
morphology of the resulting solids.
The practical examples presented in this paper
show that it is possible to prepare, in classical drying
conditions, low-density xerogels with textural prop-
erties similar to those obtained in aerogels dried in
hypercritical conditions.
By controlling the synthesis parameters of low-
density xerogels it is indeed possible to produce
highly porous solids with well defined surface prop-
erties and acceptable mechanical strength. In particu-
lar, very homogeneous, highly-porous, thermally sta-
ble, mixed oxides have been prepared which can
open new application fields in acid–base and oxida-
151
tion catalysis. Similarly, the one-step synthesis of
metallic catalysts supported on low-density xerogels
backbone lead to particularly active and selective
hydrogenation catalysts, characterised by remarkable
mass transfer properties.
The application of those results to the preparation
of other types of catalytic compositions, like those
studied by Lopez and Gomez w33,34x, or by Schubert
w5,35x, can open the door to new interesting indus-
trial developments in particular, if the porous texture
can be controlled to avoid diffusional limitations.
However, a detailed study of the extrapolation
from the lab scale experiments to the industrial scale
must still be carried out, the main difficulty being
linked to the increasing viscosity of the reaction
medium in which the sol–gel chemistry takes place.
Huge mass transfer limitations are occurring which
have to be understood and overcome before develop-
ing industrial applications.
Acknowledgements
Many co-workers contributed to the progressive
building of the knowledge presented in this paper.
Many thanks to all of them, in particular to R. Pirard
and B. Heinrichs.
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