Applied Catalysis A: General 265 (2004) 207–219

Review
Preparation of catalysts from microemulsions and their
applications in heterogeneous catalysis
Sara Eriksson, Ulf Nylén, Sergio Rojas1 , Magali Boutonnet∗
Department of Chemical Engineering and Technology, Chemical Technology, Royal Institute of Technology (KTH),
Teknikringen 42, SE-100 44 Stockholm, Sweden

Received 20 March 2003; received in revised form 13 January 2004; accepted 16 January 2004

Available online 05 March 2004

Abstract

Microemulsions have a wide range of applications from oil recovery to synthesis of nanoparticles. The first implementation of water-in-oil
(w/o) microemulsions for synthesis of nanoparticles was introduced in 1982 and concerns nanoparticles of noble metals for catalytic uses.
Since this time, the method has been employed quite extensively in the field of catalysis, from room-temperature reactions such as butene
isomerisation to high-temperature reactions such as catalytic combustion of methane.
The present review paper will introduce the term microemulsion with emphasis on the microemulsion properties essential for heterogeneous
catalyst preparation followed by a general description of the mode of catalytic materials prepared from microemulsions. Several examples
of the use of these materials in heterogeneous catalysis are then described. It is shown that nanoparticles obtained from microemulsions
have specific properties with respect to size, size distribution and surface structure. Consequently, these particles are in some cases superior
regarding catalytic activity and/or selectivity.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Microemulsion; Nanoparticles; Catalyst preparation; Catalysis

1. Introduction have found a wide range of applications, from oil recovery

The term microemulsion was first defined by Schulman
and Friend in the 1940s [1]. Since this time, microemulsions
Abbreviations: AOT, sodium bis(2-ethylhexyl)sulphosuccinate; Berol
02, alkyl phenol ethoxylate; Berol 050, pentaethyleneglycol dodecyl
ether (PEGDE); BHA, barium hexaaluminate; CTAB, cetyltrimethylam-
monium bromide; CTAC, cetyltrimethylammonium chloride; FCC, fluid
catalytic cracking; 1 H NMR, proton nuclear magnetic resonance; Marli-
pal O13/70, ethoxylated iso-tridecanoles containing 7 moles of ethylene
oxide per mole of alcohol; Neodol 91-6, C9 –C11 alcohol containing 6
moles of ethylene oxide per mole of alcohol; NP-X, poly(oxyethylene)x
nonylphenol ether;  (omega), water to surfactant molar ratio; OP-
10, polyoxyethylene(10)octylphenyl ether; OSC, oxygen storage capacity;
PFPE-PO4 , perfluoropolyether phosphate; RCH/RP, Ruhrchemie/Rhône-
Poulenc; TEM, transmission electron microscopy; TEOS, tetraethyl or-
thosilicate; THF, tetrahydrofuran; TOF, turn over frequency; Triton X-
100, polyoxyethylene(10)iso-octylphenyl ether; Tween 80, polyoxyethy-
lene(20)sorbitan monooleate; VOC, volatile organic compounds; XRD,
X-ray diffraction; w/o, water-in-oil microemulsion
∗ Corresponding author. Tel.: +46-8-790-82-45; fax: +46-8-10-85-79.
to synthesis of nanoparticles, as reported by Chhabra et al.
in their review article from 1997 [2].
The idea of using microemulsion systems for catalyst
preparation was first suggested by Gault in collaboration
with Friberg. Gault was at this time investigating the rela-
tionship between the particle size of a transition metal-based
catalyst and the selectivity in the hydrogenolysis and iso-
merisation reactions of hexanes [3]. The method usually em-
ployed at this time, and still now, for preparation of metal
catalysts was the impregnation technique. With this method,
it is possible to prepare small metal particles although it is
quite difficult to obtain a narrow particle size distribution.
Using impregnation, the morphology of the catalyst support
will have some effect on the structure and size of the metal
particles. Moreover, it is rather difficult to control the com-
position of bimetallic particles. Due to the specific structure
of a microemulsion, it was expected to be a suitable envi-
ronment for producing small metal nanoparticles of narrow

E-mail address: magali@ket.kth.se (M. Boutonnet).

size distribution as well as bimetallic particles of controlled
1 Present address: Instituto de Catálisis y Petroleoquı́mica (CSIC), composition. Synthesis of metal nanoparticles was first re-
C/Marie Curie s/n, 28049 Cantoblanco Madrid, Spain. ported by Boutonnet et al. in the early 1980s [4].

0926-860X/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.01.014
208 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
This present review gives an introduction to microemul-
sion systems and explains why these systems are interesting
for nanoparticle preparation, especially for catalytic appli-
cations. For other types of microemulsion applications, the
reader should consult the reviews published by Kon-No [5],
Schomäcker et al. [6] and Klier et al. [7]. Since the first
report on the use of microemulsions in the preparation of
noble-metal catalysts, Pt in particular, other types of active
components such as Cu, bimetallic particles (e.g. Au–Pt)
and oxide-based materials (e.g. perovskites) have been ob-
tained successfully by this method. Different examples are
reported in this review showing the wide range of appli-
cations for this method in the field of catalysis. It must
be emphasised that the present review article only takes
into account literature references where the catalytic per-
formance of the microemulsion-prepared catalysts has been
demonstrated.
2. The microemulsion technique
2.1. Microemulsion: definition
A microemulsion is defined as a system of water, oil
and amphiphile (surfactant). This system is an optically
isotropic and thermodynamically stable solution. At macro-
scopic scale, a microemulsion looks like a homogeneous so-
lution but at molecular scale, it appears to be heterogeneous.
The internal structure of a microemulsion, at a given tem-
perature, is determined by the ratio of its constituents. The
structure consists either of nanospherical monosized droplets
or a bicontinuous phase. In Fig. 1, the different structures of
a microemulsion at a given concentration of surfactant are
schematised.
At high concentration of water, the internal structure of
the microemulsion consists of small oil droplets in a contin-
uous water phase (micelles). With increased oil concentra-
tion, a bicontinuous phase without any clearly defined shape
is formed. At high oil concentration, the bicontinuous phase
is transformed into a structure of small water droplets in a
Fig. 1. The microscopic structure of a microemulsion at a given concentration of surfactant as function of temperature and water concentration [6].
continuous oil phase (reverse micelles), also known as a w/o
microemulsion. The size of the different droplets varies from
10 to 100 nm depending on the type of surfactant. It should
be pointed out that the system is strongly sensitive with re-
spect to temperature, particularly in the case of non-ionic
surfactants. As can be seen in Fig. 1, increasing the temper-
ature will destroy the oil droplets while the water droplets
will be destroyed by a temperature decrease. Outside the
area corresponding to microemulsion solution, a two-phase
system exists.
2.2. Preparation of nanoparticles
From a particle-preparation point of view, the microemul-
sion system with an internal structure consisting of small
droplets is the most interesting. The w/o microemulsion is
of particular interest since it can be conceived as tiny com-
partments made up of the hydrophilic moiety of the surfac-
tant filled with water. In the hydrophilic interior of these
droplets, a certain amount of water-soluble material can be
dissolved; for example, transition metal salts that then serve
as precursor(s) for the final metal particles. As stated previ-
ously, this system is very sensitive to temperature due to the
physical and chemical properties of its constituents. There-
fore, it is of importance in the case of nanoparticle prepara-
tion to choose microemulsion systems, which are stable at
room temperature or at slightly higher temperature (70 ◦ C).
There are two main ways of preparation in order to obtain
nanoparticles from microemulsions:
1. By mixing two microemulsions, one containing the pre-
cursor and the other the precipitating agent (Fig. 2a).
2. By adding the precipitating agent directly to the mi-
croemulsion containing the metal precursor (Fig. 2b).
2.3. Influence of various factors on the particle size
2.3.1. Size of the water droplets
The size of the final metallic particle will much depend
on the size of the droplets in the microemulsion. The droplet
 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
Fig. 2. Modes of particle preparation from microemulsion: (a) mixing of two microemulsions; (b) direct addition of precipitating (reducing) agent to the
microemulsion.
size will be influenced by the water-to-surfactant ratio, ω.
An increase of this ratio at constant concentration of sur-
factant will increase the average diameter of the droplets.
Lisiecki and Pileni [8] reported that the size of Cu nanopar-
ticles prepared in a system consisting of AOT, cyclohexane
and water increased from 2 to 10 nm as ω changed from
1 to 10.
2.3.2. Surfactant concentration
When the amount of water and oil is kept at fixed values,
an increase of the amount of surfactant will increase the
number of droplets. That means that the number of metal
ions per droplet will decrease and consequently the size of
the particles [8].
Several studies have shown that the size of the droplets
has a great influence on the size of the particles that
are formed after precipitation of the precursor. However,
there is not any direct correlation between the size of the
droplets (10–100 nm) and the size of the obtained parti-
cles. In the case of platinum particles, the concentration
of PtCl6 2− ions in a microemulsion of PEGDE (pen-
taethyleneglycol dodecylether), hexane and water, was equal
to 1.55 × 1020 ions/dm3 and the number of PtCl6 2− ions
in each droplet was estimated to 5. TEM analysis revealed
that the average size of the Pt particle was equal to 35 Å,
which corresponds to 100–1500 metal atoms depending on
the shape of the particle [9]. This shows that the final parti-
cle is not formed inside the droplet but only the nuclei. The
209
microemulsion system is dynamic which means that during
the process of particle formation a constant collision of
the aggregates takes place. Consequently the formation of
particles proceeds in two steps, first the nucleation process
inside the droplet, then the aggregation process to form the
final particle. The rate of particle growth is controlled by the
presence of the surfactant, which sterically prevents the nu-
clei from growing too fast. Consequently the particles will
grow at the same rate, favouring the formation of particles
of homogeneous size distribution. The result is a suspension
of small particles stabilised by the surfactant molecules
prohibiting coalescence that otherwise would lead to fur-
ther agglomeration. The size of the droplet will influence
the size of the nuclei but the size of the final particle
will be controlled by the surrounding surfactant molecules
[10].
2.3.3. Nature of the precipitating agent (reducing agent)
Hydrazine is an efficient reducing agent for transition
metal salts such as dihydrogen hexachloroplatinate. The
reduction process is in this case completed instantly and
is very fast in comparison to when using pure hydrogen.
As a general rule, a fast nucleation process will result in
the production of small particles [4]. Furthermore, when
increasing the concentration of hydrazine while the con-
centration of metal salt is kept constant, a decrease in the
particle size is observed. This was shown when Ni particles
were prepared in a microemulsion containing cetyltriammo-
210 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219

Table 1
Influence of several parameters on the particle size of Pd-based catalysts prepared by different methodologies
Metal precursor Particle size (nm) Surfactant Oil phase Reducing agent Preparation method Reference

PdCl2 5 PEGDE Hexane Hydrazine ME [4]

PdCl2 6–7 NP-5 Cyclohexane Hydrazine ME [44]
12 IM
Pd(NH3 )4 5–8 AOT iso-Octane Hydrazine ME [53]
K2 PdCl4 2.4–3.8 AOT n-Heptane Hydrazine ME [59]
PdCl2 5 AOT iso-Octane Hydrazine ME [60]
PdCl2 3–10 NP-5 Cyclohexane Hydrazine ME [61]
12 IM
PdCl2 5 Marlipal O13/40 Cyclohexane NaH2 PO2 ME [62]
3 and 11a HM
ME, microemulsion; IM, impregnation; HM, homogeneous aqueous solution.
a Bimodal particle size distribution.

nium bromide (CTAB) as surfactant, n-hexanol and water
at a temperature of 73 ◦ C. The diameter of the nickel par-
ticles decreases when the ratio of the hydrazine to nickel
chloride concentrations increases. The diameter of the par-
ticles reaches a constant value when this ratio is above
10 [11].
The modes of preparation of Pd particles from different
microemulsion systems are presented in Table 1. Depending
on the nature of the surfactant, the reducing agent, the metal
precursor and the solvent, particles of different sizes varying
from 3 to 12 nm could be obtained.
2.4. Preparation of supported catalysts from
microemulsions
As nanoparticle-containing microemulsions constitute a
very stable suspension, it is still a challenge to separate the
particles from the constituents of the microemulsion, espe-
cially from the surfactant as its molecules are strongly ad-
sorbed onto the particles. In order to obtain a homogeneous
supported catalyst, it is necessary to maintain the homoge-
neous distribution when transferring the particles onto the
support. Besides, the particles have to adhere strongly to the
support in order to minimise the sintering of the particles at
high temperatures.
The most common way until now to carry out this pro-
cess is to add a solvent like tetrahydrofuran (THF) to the
microemulsion, which will destabilise the solution and bring
about sedimentation of the particles. THF will compete with
the surfactant molecules adsorbed onto the particle and dis-
place them resulting in an unstable suspension. If the sup-
port powder is added at the same time as the solvent, the
particles will stick onto the support. A proper mixing of the
solution together with the powder will increase the possibil-
ity of obtaining a homogeneous distribution of the particles
on the support. Based on experience, this is a difficult task
and the success of the method is very much dependent on
the properties of the support. Some particular aspects of the
preparation of supported catalysts will be discussed in more
detail in the following sections.
2.5. New developments of the microemulsion-mediated
synthesis
2.5.1. Supercritical microemulsion
Recent developments regarding particle preparation from
microemulsion systems are based on the use of supercritical
CO2 . Sun et al. [12] have developed a novel method called
RESOLV based on the rapid expansion of a supercritical
microemulsion into a liquid containing the reducing agent
for production of metal particles. In this case, silver nitrate
was incorporated in reversed micelles formed by perfluo-
ropolyether ammonium carboxylate molecules in supercrit-
ical CO2 . The formation of silver particles takes place when
the micellar solution is expanded in a room-temperature so-
lution of sodium borohydride.
2.5.2. Novel preparation of supported catalysts from
microemulsions
A new method developed by Bonini et al. [13] may bring
about a solution to the deposition of metallic particles onto
suitable supports. This method consists of spraying the mi-
croemulsion solution into an air/acetylene flame. According
to the authors, the original structure of the nanoparticles is
preserved during the process. In addition, this method al-
lows the deposition of large amounts of particles, which is
of great interest for industrial applications where large quan-
tities of catalysts are needed.
Higgins [14] proposes a method based on low-cost ce-
ramic cross-flow ultrafiltration to recover metal particles
prepared in microemulsions. Moreover, the method allows
the possibility to recycle the remaining components of the
microemulsion. With this in mind, the industrial commer-
cialisation of the microemulsion technique for nanoparticle
production becomes more realistic.
3. Catalytic applications
Since the development of the microemulsion technique
in the early 1980s several publications have been presented
 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
where the technique is demonstrated for catalyst preparation
and where the catalysts have been tested in various reac-
tions. Applications such as reforming, combustion, methanol
synthesis, CO and CO2 hydrogenation and hydrogen pro-
duction, among others, will be presented in the following
section.
Tables 2 and 3 summarise the most relevant aspects of
the preparation and application of selected microemulsion-
based catalysts reported in literature and patents, respec-
tively.
3.1. Hydrogenation, hydrogenolysis and isomerisation
catalysts
One of the first applications of microemulsion catalysts
was in the liquid phase hydrogenation of 1-hexene and
2-hexene using 3 nm size platinum particles on alumina
support [15]. However, kinetic experiments carried out at
atmospheric pressure and at temperatures between −14 and
50 ◦ C showed that a commercial Pt/SiO2 reference catalyst,
EUROPT-1, generally displayed higher reaction rates than
the microemulsion counterpart.
In order to elucidate the catalytic properties of platinum
in absence of a support, Boutonnet et al. studied the deuter-
ation, isomerisation and hydrogen–deuterium exchange
reaction of but-1-ene [16]. Monodispersed colloidal plat-
inum particles obtained in different microemulsions and
non-aqueous environments were employed. Suspensions
containing Pt particles were in general very active catalysts
as such. However, it was observed that the accessibility of
surface metal was influenced by the presence of surfac-
tant molecules adsorbed on the metal particles. Although
well-dispersed particles (3–5 nm) were obtained, the cat-
alytic activity in the liquid phase (batch reactor) compared
to the gas phase (flow reactor) using a supported catalyst is
lower and differs approximately by a factor of 10. Another
important observation was that reduction with hydrazine
compared to pure hydrogen results in a higher metal dis-
persion, thus yielding a more active catalyst, see Fig. 3.
Next Boutonnet et al. investigated the catalytic behaviour
of platinum, palladium and rhodium particles prepared from
microemulsions supported on pumice in the deuteration, iso-
merisation and hydrogen–deuterium exchange reaction of
but-1-ene with focus on retrieving reaction-mechanistic in-
Fig. 3. Hydrogenation of but-1-ene on Pt particles in microemulsions containing CTAB: (A) Pt4+ reduced by hydrazine; (G) Pt4+ reduced by hydrogen [16].
211
formation [17]. It was demonstrated that for catalysts pre-
pared from microemulsions, the surfactant does not decrease
the activity of the catalysts. Mild catalytic pretreatments are
sufficient to eliminate the effect of these large molecules that
might have been expected to act as poisons. Monodispersed
supported catalysts, Pt (2.5 nm), Rh (2.5 nm), Pd (5.0 nm)
were obtained from particles prepared by microemulsion
technique and they were as active as catalysts prepared by
the impregnation method. The product selectivity of Pd and
Rh catalysts did not depend on the preparation mode while
the Pt catalysts exhibited a high selectivity when prepared
from microemulsion. This was explained by the fact that
hydrogen treatment at 200 ◦ C, prior to the reaction, affects
only the hydrogenation sites of the catalysts keeping the iso-
merisation sites intact. This effect was not observed in the
case of Pt catalysts prepared by impregnation.
The isomerisation and hydrogenolysis reactions of differ-
ent hexanes have been thoroughly investigated for monodis-
persed colloidal platinum particles on alumina [18], titania
[19] and for colloidal platinum/palladium alloy particles on
alumina [20]. The possibility to prepare nanosized metal
alloys of narrow size distribution at room temperature is
a very attractive feature and is successfully demonstrated
[20]. In addition, it was shown for the first time that true
platinum/palladium alloys can be prepared at room temper-
ature when a microemulsion is used as synthesis environ-
ment. After preparation, the particles originally suspended
in a microemulsion are transferred onto the supports with-
out agglomeration. In the case of Pt/Al2 O3 [18], although
the platinum particle size displayed a peak maximum at ∼
2 nm, see Fig. 4, this microemulsion catalyst did not follow
the non-selective ring opening mechanism and the cyclic
isomerisation mechanism, respectively, normally ascribed to
highly dispersed platinum particles. As the size distribution
of Pt catalysts from microemulsion is quite narrow with only
a very little fraction of particles having a diameter less than
1 nm, it leads to the conclusion that the cyclic mechanism
takes place exclusively on particles smaller than 1 nm. In
addition, the activity of the corresponding classical catalyst
prepared from impregnation was higher. The authors claim
that this reduced activity is due to surfactant molecules still
bound to the metal surface, thereby inhibiting the catalytic
reaction. Regarding the Pt/TiO2 catalysts, it was shown
that no metal–support interaction was observed when the
 212
Table 2
Survey of the most representative microemulsion-based catalytic process in the literature
Catalyst Use Microemulsion Metal precursor Particle size (nm) Surface area (m2 /g) Reference

Pt/Al2 O3 , pumice Hydrogenation PEGDE/hexadecane/water H2 PtCl6 2.5–3.5 154 [15]

Pt, Pd, Rh/pumice Hydrogenation PEGDE/hexadecane or hexane/water H2 PtCl6 , PdCl2 , RhCl3 2.5–5 – [17]
Pt/Al2 O3 , TiO2 Hydrogenolysis isomerisation PEGDE/hexadecane/water H2 PtCl6 0.5–3.5 154 [18,19]
Pt–Pd/Al2 O3 Hydrogenolysis isomerisation PEGDE/hexadecane/water H2 PtCl6 , PdCl2 10–100 – [20]
Pt/S–ZrO2 Isomerisation PEGDE/n-octane/water H2 PtCl6 29–41 – [21]
Pt/TiO2 Selective hydrogenation PEGDE/n-octane/water H2 PtCl6 – – [22]

S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219

Pd, Rh particles Hydrogenation AOT + PFPE-PO4 /water/ PdCl2 , RhCl3 5–10 (Pd), 3–5 (Rh) – [24,25]
supercritical CO2
Pt–Ir/boehmite Selective ring opening PEGDE/iso-octane/water H2 PtCl6 , IrCl3 20–100 370 [26]
CeO2 /Al2 O3 CO oxidation OP-10/cyclohexane/n-hexyl Cerium nitrate 2.6–4.9 153–185, 73 after [29]
alcohol/water 5 h at 1000 ◦ C
Pd/Cex Zr1−x O2 /Al2 O3 CO oxidation NO reduction Triton X-100/heptane/hexanol/water/ Zirconyl nitrate cerium 2–5 96–186 [32,33]
tetramethylammonium hydroxide nitrate
Pt/Al2 O3 Combustion of toluene Tween 80/cyclohexane or H2 PtCl6 35 145–166 [34]
heptane/cyclohexanol/water
BaAl11 O19 Combustion of methane Neodol Barium and aluminium 4–40 112 (2 h at [35]
91-6/1-pentanol/iso-octane/water iso-propoxide 1300 ◦ C)
Pd/Al2 O3 Combustion of methane Berol 02/cyclohexane/water Pd(NO3 )3 20–40 150 [36]
Pd/ZrO2 , TiO2 , Al2 O3 Methanol synthesis NP-5/cyclohexane/water PdCl2 /Zr, Ti and Al 2–10 – [37]
alkoxides
Cu/ZnO Hydrogen production Berol 02/cyclohexane/water Cu(NO3 )2 , Zn(NO3 )2 – – [38]
Pt/C, Pt–Ru/C, Pt–Pd/C Electrocatalysts Berol 050/iso-octane/water H2 PtCl6 , RuCl3 , PdCl2 2–5 – [39]
Pt–Ru/C Electrocatalysts NP-5 or NP-9/cyclohexane/water H2 PtCl6 , RuCl3 4–20 – [40]
Rh/SiO2 CO2 hydrogenation NP-5/cyclohexane/water RhCl3 4.5a or 6.7b – [44]
Rh/SiO2 CO2 hydrogenation NP-5/cyclohexane/water RhCl3 3.2a or 4.5b – [45]
Rh/SiO2 Particle preparation NP-5 or NP-7 or NP-10 or NP-15, RhCl3 1.5–6 – [46]
polyoxyethylene(15)oleylether,
polyoxyethylene(23)dodecylether,
CTAB or CTAC or
AOT/cyclohexane or alcohols/water
Rh/SiO2 CO hydrogenation CTAB/hexanol/water RhCl3 5–7 – [47]
Rh/SiO2 CO hydrogenation CTAB/hexanol/water RhCl3 3.4a or 7.5b – [50]
Rh/SiO2 CO hydrogenation CTAC/hexanol/water RhCl3 4 – [51]
Pd/ZrO2 CO hydrogenation CTAB/hexanol/water PdCl2 and Zr(BuOH)4 2–12 – [53]
Fe/SiO2 CO hydrogenation NP-5 or NP-10 or NP-20/hexanol Fe(NO3 )3 4.8–13 – [54]
or butanol/water
a Particle size as determined by TEM analysis.
b Particle size as determined by CO chemisorption analysis.
 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219 213

Fig. 4. TEM picture of 2% Pt/Al2 O3 prepared from microemulsion (a) and histogram, D1 = Ni / Ni (b) [18].

catalysts were prepared from a microemulsion giving high
selectivity and activity compared to the catalysts prepared
by impregnation.
Boutonnet-Kizling and Regali successfully prepared a
series of platinum-promoted sulphated zirconia catalysts
[21]. Support synthesis, sulphating and platinum deposition
were performed using different techniques and combined
in different orders. The zirconia support was synthesised
either by microemulsion or precipitation, the sulphating
was carried out either simultaneously together with the
zirconia support synthesis or by impregnation of sulphuric
acid and the platinum deposition was accomplished using

Table 3
Survey of selected patents concerning the use of microemulsions in catalyst preparation
Year Catalytic nanoparticle Composition of w/o Mode of particle production Application/catalytic reactions Reference
microemulsion

1981 Platinum metals Non-ionic surfactant, Reduction of metal complexes Deposition on carrier [63]
hydrocarbon, water, metal salt with hydrazine, hydrogen
1987 Ruthenium on support Non-ionic, anionic, cationic The microemulsion is used as Preparation of Fischer–Tropsch [55]
surfactants, hydrocarbon, impregnation solution catalysts
water, metal salt
1987 Platinum metals and Non-ionic, anionic, cationic The microemulsion is used as Deposition on carrier [64]
Group VIII metals surfactants, hydrocarbon, impregnation solution
water, metal salt
1997 Platinum metals No details The microemulsion is used as Catalytic combustion of ethanol [65]
impregnation solution
1997 Pd–Au on ␣-Al2 O3 Genepol (amongst Reduction of metal complexes Production of vinyl acetate [66]
others)/pentane/water with hydrazine
1997 Ferromagnetic particles Non-ionic, anionic, cationic Hydrolysis and hydrogen Photocatalysts [67]
in semi-conducting surfactants, hydrocarbon, reduction
metal oxide water, metal salt
1998 Various metal particles Ethoxylated alkyl phenol, Reduction of metal complexes Deposition on carrier [68]
hydrocarbon, water, metal salt with sodium or ammonium
hypophosphite
1998 Pd, Cu and Fe metal Nonionic surfactants alcoholic The microemulsion is the Olefin oxidation [69]
particles co-surfactant, hydrocarbons, reaction medium for the
water, metal salt catalytic reaction
1999 Composite oxide Water-in-oil microemulsion Spraying and burning of the Preparation of carrier material [70]
powder, aluminium, microemulsion
barium
2002 Hexaaluminates Non-ionic surfactant, Hydrolysis Preparation of combustion [71]
hydrocarbon, water, metal catalysts
alkoxide, nitrate
2002 Hexaaluminates Ionic and non-ionic Hydrolysis of the precursors Oxidation of hydrocarbons [72]
surfactants, hydrocarbon, followed by a supercritical
water, metal alkoxide, nitrate drying step
214 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
microemulsion-made particles or by impregnation with
hexachloroplatinic acid. The zirconia particles prepared in
microemulsion present a pure tetragonal structure and have
smaller particle size than those prepared by precipitation.
All the catalysts (2 wt.% metal loading) together with a
10 wt.% Pt/Al2 O3 reference catalyst were tested for iso-
merisation of 2-methylpentane at 300 ◦ C and atmospheric
pressure. The results showed that the zirconia supports pre-
pared by the microemulsion method displayed enhanced
isomerisation selectivity at the cost of decreased activity.
The microemulsion method has been adopted successfully
in combination with the sol–gel process to obtain monodis-
persed platinum particles of narrow size distribution on ti-
tanium oxide for selective hydrogenation of crotonaldehyde
[22]. An increased platinum–titanium oxide (metal–metal
oxide) interface interaction is believed to be responsible for
the selective hydrogenation of ␣–␤ unsaturated aldehydes
into unsaturated alcohols. Ordinary impregnation catalysts
as well as catalysts with platinum particles prepared in mi-
croemulsions before deposition onto the TiO2 support did
not display the desired selectivity.
The microemulsion technique has also been used in the
development of cracking catalyst additives for sulphur re-
moval from FCC gasoline [23]. Metal oxide particles were
prepared by mixing a microemulsion system containing the
metal nitrate with a second microemulsion system contain-
ing oxalic acid solution. Upon calcination, the desired metal
oxide was formed. The additives were mixed with a com-
mercial reference FCC catalyst to an amount of 10 wt.%.
These mixtures successfully reduced the sulphur content in
the gasoline but, at the same time, resulted in a lower yield
of gasoline than for the reference catalyst alone. The loss in
gasoline was due to an increased amount of gas production
and/or an increased production of carbonaceous deposits,
the latter responsible for the sulphur-reducing ability by hy-
drogen transfer reactions.
Two recent publications demonstrate the use of nano-
sized noble metal particles in water-supercritical CO2
microemulsion in the hydrogenation of various hydrocar-
bons such as 4-methoxyhydrocinnamic acid, trans-stilbene,
maleic acid, nitrobenzene [24] and naphthalene and phe-
nol [25]. The reactions were carried out at high pressure
and the metal particles were reduced prior to the hydro-
carbon injection by bubbling hydrogen gas through the
microemulsion. Nanosize particle formation was confirmed
by TEM. In most cases, the extent of reaction was moni-
tored by in situ UV-Vis spectrometry, otherwise 1 H NMR
spectroscopy was adopted to monitor the rate of reaction.
In the absence of metal precursor or hydrogen gas, no
hydrogenation activity was observed. The advantages of
performing hydrogenation reactions in supercritical CO2
compared to conventional solvent systems are: enhanced
diffusion rates and solubility of hydrogen gas, easy product
separation and less waste generation. A possible industrial
application could be the production of low-aromatic diesel
fuels.
Moreover, microemulsion-based bimetallic Pt–Ir/boehmite
catalysts have been found to be active in the selective ring
opening of naphthenic molecules such as indan [26]. The
objective is to improve the diesel fuel quality, i.e. increase
the paraffinic functionality in order to increase the cetane
number.
3.2. Combustion catalysts
Catalytic combustion is a promising technology for power
generation and pollution abatement that has received increas-
ing attention during the past few years [27]. In the following
section, a summary of combustion catalysts prepared by the
microemulsion technique is presented. The section is divided
in two main parts, low-temperature and high-temperature
applications.
3.2.1. Low-temperature catalysts
Cerium oxide plays an important role in the three-way cat-
alysts (TWCs) used for pollution abatement in automobiles.
The properties that make CeO2 a promising material for use
in catalytic applications are primarily (i) the ability to shift
easily between reduced and oxidised state (i.e. Ce3+ /Ce4+ )
and (ii) the high oxygen storage capacity (OSC) [28].
Nanosize CeO2 particles have successfully been prepared
in a reverse microemulsion system [29]. The particle size
could be controlled in the range of 2–5 nm by varying the
concentration of the reactants, cerium nitrate and ammo-
nium hydroxide. The catalytic activity of CeO2 on alumina
(Al2 O3 ) for the oxidation of CO was tested for catalysts
prepared both by the microemulsion technique and the co-
precipitation method. The results presented by Masui et al.
show that a higher activity was obtained for the catalysts
prepared by the microemulsion method, despite the fact that
equal surface areas were obtained by both preparation pro-
cedures. The authors do not offer a clear explanation for this
behaviour. However, properties such as fine size, morphol-
ogy and high OSC are suggested to have a positive effect
on the activity.
The OSC effectiveness of CeO2 can be considerably im-
proved by the addition of zirconium oxide (ZrO2 ) [30]. The
preparation method for the mixed oxides is important as it
affects the surface area, homogeneity and phase formation
of the material [31]. The preparation of ceria–zirconia mixed
oxides by the microemulsion technique was reported by
Fernández-Garcı́a and coworkers [32,33]. Palladium was de-
posited on CeO2 –ZrO2 or CeO2 –ZrO2 /Al2 O3 by the incip-
ient wetness method and the resulting catalysts were tested
for CO oxidation and NO reduction. The Ce–Zr mixed ox-
ide was prepared by mixing two microemulsion systems of
Triton X-100, heptane, hexanol and water, one containing
the metal salts and the other the precipitating agent. The
CO conversion was significantly improved when compared
to a Pd/Al2 O3 reference catalyst. The highest activity was
observed for the Pd/CeO2 –ZrO2 catalyst, which achieved
100% conversion at room temperature. The results indicate
 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
Fig. 5. Light-off curves of toluene obtained with platinum catalysts pre-
pared by impregnation of ␥-alumina (curves 1, 2) and ␪-alumina (curves
3, 4) by heptane–Tween 80-water microemulsion (curves 1, 3) or water
solution of H2 PtCl6 (curves 2, 4) [34].
that the presence of CeO2 –ZrO2 promotes the formation of
active metallic Pd(0) sites for CO adsorption. A promoting
effect of CeO2 –ZrO2 was also detected for the NO reduc-
tion reaction. However, NO had an inhibiting effect on CO
oxidation at low temperatures due to formation of palladium
oxide.
Rymeš et al. [34] studied the preparation of platinum cat-
alysts by the reverse microemulsion method for combustion
of volatile organic compounds (VOC). The corresponding
catalysts were also prepared by traditional impregnation
for comparison. The model reaction chosen in this work
was the combustion of toluene. The inlet temperature for
50% conversion, T50 , was found to decrease by 50 ◦ C when
a microemulsion catalyst was used, as depicted in Fig. 5.
The effect of oil and water-to-surfactant molar ratio used
in the microemulsion system was found to be insignificant
for the activity. The increased activity of microemulsion
catalysts is suggested to result from a smaller Pt parti-
cle size and a higher concentration of noble metal in the
outer shell of the support particles, as confirmed by TEM
analysis.
3.2.2. High-temperature catalysts
Barium hexaaluminate (BHA) catalysts have been pre-
pared by a reverse microemulsion-mediated sol–gel method
and tested for methane combustion activity [35]. A number
of preparation parameters, such as microemulsion composi-
tion, water-to-alkoxide ratio, ageing time, powder recovery
and drying techniques, were investigated. Nanoparticles of
high thermal stability could be obtained under optimal prepa-
ration conditions compared to conventional sol–gel derived
materials. This enhancement in stability is suggested to oc-
cur since crystallisation to the desired hexaaluminate phase
took place at a relatively low temperature. The light-off tem-
215
perature for 1 vol.% CH4 in air using pure BHA as catalyst,
was found to be 590 ◦ C. This temperature could be lowered
to ∼400 ◦ C by depositing CeO2 on the catalyst.
Catalysts consisting of palladium deposited on alumina
have been prepared by incipient wetness and microemulsion
techniques [36]. Palladium nitrate was reduced in a mi-
croemulsion system of Berol 02, cyclohexane and water by
adding hydrazine. The effect of palladium particle size and
dispersion on the activity for methane combustion under
diesel-engine exhaust conditions was studied. The results
indicate that small particles of less than 2 nm exhibit early
ignition. However, larger particles (about 10 nm) increase
the reaction rate and complete conversion is obtained at a
lower temperature. The use of a microemulsion-mediated
preparation route did not improve the activity of the
catalysts.
3.3. Catalysts for methanol synthesis and hydrogen
production
Methanol synthesis over catalysts prepared using w/o
microemulsions has been studied by Kim et al. [37]. The
authors have described the preparation of Pd particles sup-
ported on ZrO2 , TiO2 and Al2 O3 from their metal salt
and alkoxide precursors, respectively. The catalytic per-
formance of these catalysts in the production of methanol
was compared to the corresponding catalysts prepared by
impregnation. Even though the catalysts prepared by mi-
croemulsion displayed higher activities, the product selec-
tivity was found to be similar for both sets of catalysts. This
behaviour was due to the smaller particle size displayed by
the catalysts prepared by microemulsion. When catalysts
displaying similar particle sizes were compared, analogous
conversions were achieved both by the microemulsion- and
impregnation-based catalysts.
Hydrogen production by partial oxidation of methanol has
been studied by Agrell et al. [38] using Cu/ZnO catalysts
prepared by the microemulsion technique. The catalysts
prepared by microemulsion exhibited lower surface areas
(ca. 22–36 m2 /g) than the reference catalysts (60 m2 /g).
Furthermore, Cu was better dispersed on the surface of the
latter catalysts. In spite of those facts, the activity of the
microemulsion catalysts was higher than that of the refer-
ence catalyst. The authors suggest that the higher activity of
the microemulsion catalyst could be due to interactions be-
tween CuO and ZnO lattices. However, other explanations
could not be ruled out.
3.4. Electrocatalysts
Potentially, fuel cells represent a suitable alternative for
energy production. In the last decades, there has been a
great interest in the development and improvement of fuel
cells, particularly in the field of polymeric fuel cells. Among
other issues, the development of more active electrocatalysts
is mandatory if the technology is to be commercialised.
216 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
Electrocatalysts are mostly based on Pt or Pt–Ru parti-
cles deposited on carbon. Key requirements for an optimal
electrocatalyst, particularly for those based on bimetallic
formulations, are a high dispersion and an adequate particle
size. The preparation of Pt, Pt–Ru and Pt–Pd-based electro-
catalysts from microemulsions has been reported by Escud-
ero et al. [39]. The activity of the materials was tested in a
H2 /O2 or H2 /air fuel cell using the prepared electrocatalysts
as the anode of the fuel cell and a commercial electrocatalyst
as cathode. Catalysts containing ca. 0.37–0.50 mg Pt/cm2
displaying a particle size from 2 to 5 nm were obtained.
However, for higher metal loadings, aggregates of approx-
imately 20 nm were also observed by TEM. The activity
displayed by the microemulsion-based electrocatalysts is
similar to the one displayed by commercial electrocatalysts.
Liu et al. [40] have described the preparation of Pt–Ru
electrocatalysts from microemulsions and emulsions. They
prepared three sets of catalysts by varying the concentration
of the components (i.e. water, surfactant and oil phase) thus
obtaining a microemulsion, a transparent liquid and a turbid
emulsion. The particle size increased with the water con-
centration in the mixtures, from ca. 4.3 nm obtained from a
microemulsion to 9.2 and 20.6 nm from a transparent liquid
and a turbid emulsion, respectively. As expected, the solid
obtained by microemulsion displayed the highest active area
due to the small particle size.
Yang et al. [41] have explored the preparation of highly
dispersed Pt–Ru/C catalysts by microemulsion. The samples
displayed an outstanding performance towards methanol ox-
idation when compared with literature results. The authors
ascribed this behaviour both to the high dispersion of the
metallic phase and to the presence of RuOx Hy species in the
sample. However, a proper evaluation of the results is diffi-
cult due to the wide range of experimental conditions stud-
ied. Recently, Zhang and Chan [42] have prepared Pt–Ru
nanoparticles in w/o microemulsions using Triton X-100
as surfactant and propanol as cosurfactant. They also re-
ported the presence of RuOx Hy species in their samples.
These species are proposed to be responsible for oxidis-
ing CO to CO2 , thereby minimising the poisonous effect
of CO. Similar results have been obtained in our laboratory
[43].
3.5. CO and CO2 hydrogenation
The activation of the CO bond by catalysts prepared by
microemulsion has been profoundly studied by Kishida
et al., who proposed an alternative route for preparing
microemulsion-based supported catalysts for such applica-
tions [44,45]. For instance, CO2 hydrogenation with cata-
lysts prepared by the microemulsion method has been stud-
ied. Both Rh/SiO2 and Rh/ZrO2 catalysts (metal loading
ca. 1.6 wt.%) were prepared by microemulsion technique
and their inherent catalytic activities were compared to
analogous catalysts prepared by deposition and impregna-
tion. The particle size, as determined by CO chemisorption,
was 4.5 nm and ca. 10 nm for the catalysts prepared by
microemulsion and impregnation, respectively. Regarding
the CO2 hydrogenation activity, the catalysts prepared by
microemulsion showed a higher activity than the impreg-
nation counterpart. In both cases, methane was the main
product. The authors suggest that the higher activity of the
microemulsion-based catalysts could be explained by the
metal particle size, the location of rhodium particles in the
support and the strong metal–support interaction (SMSI).
Subsequently, the preparation of Rh, Pd and Pt supported
on SiO2 was described [44]. In their approach, while metal
particles were prepared following a procedure analogous
to the one described by Boutonnet et al. [15,16], the sup-
port was added in its precursor form. That is, TEOS was
added to the microemulsion and hydrolysed in situ due to
the presence of ammonia. XRD and CO chemisorption anal-
ysis led to the conclusion that small Rh particles, with a
narrow size distribution, were obtained. Unfortunately, the
authors gave no indication about the Rh/CO stoichiometry
for the chemisorption experiments. Furthermore, some Rh
particles were buried in the support. All the catalysts were
tested in the CO2 hydrogenation reaction. The catalytic re-
sults reported by the authors were compared to the results
from impregnation-based catalysts. Higher conversions (al-
most one order of magnitude) were obtained with catalysts
prepared by microemulsion, possibly due to their smaller
particle size, thus increasing the active metal area.
A comprehensive study of the influence of microemul-
sion components and their relative concentration on the final
morphology of the catalysts is detailed in a series of pa-
pers by Kishida and coworkers [46–49]. The most relevant
conclusions regarding the preparation of Rh catalysts are as
follows: (i) the nature of the surfactant plays a key role in
the size of the metal particles; (ii) for the silica-supported
rhodium catalysts, the rhodium particles are, at least, partly
embedded in the support. The ratio of the surface-exposed
rhodium could be modified by controlling the hydrolysis
time of the support precursor; (iii) particle size can be con-
trolled irrespectively of the metal content and the catalyst
surface area.
Concerning the hydrogenation of CO, the activity of
Pd, Rh and Fe catalysts prepared by the microemulsion
technique has been studied. Hanaoka et al. described the
preparation of Rh/SiO2 catalysts both by the microemul-
sion method and by impregnation, and their behaviour
in the CO hydrogenation reaction [50]. They found that
microemulsion-based catalysts were more active than the
impregnated counterparts, even though the total amount of
metal was lower in the former case. This behaviour was
explained by the smaller particle size (ca. 3.4 nm) displayed
by the microemulsion catalysts. Also, the TOF for the for-
mation of C2 oxygenates was higher for the microemulsion
catalysts.
Very interesting results were obtained by Tago et al. dur-
ing the study of CO hydrogenation by Rh/SiO2 catalysts pre-
pared by the microemulsion technique [51]. They found that
 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
the selectivity towards C2 oxygenated compounds increases
when increasing the Rh content. This effect could neither be
due to the particle size nor to the amount of Rh exposed on
the surface since, according to the authors, these parameters
were kept constant for all the samples. Apparently, the only
difference between the catalysts, besides the Rh loading,
was the distance between the metallic particles. For a larger
amount of rhodium, a smaller inter-particle distance was ob-
tained. The authors suggest that the difference in selectiv-
ity could be ascribed to the reduction of the inter-particle
distance. In that sense, they recognise that “some of the
rhodium particles began to touch each other with increas-
ing the rhodium content”. It is well known that the chain
growth is favoured on larger particles. Furthermore, it has
been reported that the higher the metal loading, the higher
the selectivity towards long chain paraffins [52].
Kim et al. have tested Pd-supported catalysts prepared
from microemulsions in the CO hydrogenation reaction [53].
The microemulsion-based catalysts were more active than
the catalysts prepared by impregnation, even for catalysts
having the same particle size. However, the product selec-
tivity was independent of the Pd particle size.
Recently, Hayashi et al. studied the catalytic properties
of Fe/SiO2 samples prepared by the microemulsion method
[54]. They found that these catalysts displayed a more than
two-fold CO conversion as compared to the analogous cata-
lysts prepared by impregnation. Further, and more interest-
ing, in spite of the tendency of Fe catalysts to produce hydro-
carbons the production of oxygenates was found to be very
high for the catalysts prepared in microemulsions. Also, the
selectivity was found independent of the particle size. This
fact was explained by the presence of Fe ␦+ species, which
are stable even after reduction at high temperatures. The
Fe ␦+ species are considered responsible for the production
of oxygenated compounds [52]. Thus, when both the mi-
croemulsion and the impregnation catalysts were reduced at
high temperature (600 ◦ C), the former displayed twice the
CO conversion and three times the C2+ oxygenates as com-
pared to the latter.
Syngas conversion by means of Ru catalysts prepared
from microemulsions has been patented by Abrevaya and
Targos [55]. The catalysts were prepared with the aim of ob-
taining samples containing the same amount of active metal
while modifying the particle size. The behaviour of the cat-
alysts was compared to two Fe-based reference catalysts.
Ru-based catalysts displayed a higher selectivity towards
heavier hydrocarbons than the Fe-based catalyst.
3.6. Photocatalysts
Titanium dioxide has been prepared by the microemul-
sion technique and studied as a photocatalyst for the degra-
dation of organic pollutants. Mori et al. prepared TiO2 in
several w/o microemulsion systems of different constituents
[56]. Two dissimilar types of microemulsions were formed
depending on the water content, the reverse micelle (RM)
217
region and the swelling reversed micelle (SM) region. The
particles formed in the RM region were smaller than the
size of the water droplets in the microemulsion while parti-
cles produced in the SM region were larger than the droplet
size. Anatase phase titania could be formed at a relative low
temperature of 227 ◦ C for some samples. The photodecom-
position of methylene blue was tested resulting in a poor
performance of the microemulsion-derived catalysts when
compared to a commercial reference catalyst. This inferior
catalytic behaviour was not explained by the authors.
The photocatalytic activity of TiO2 for wet oxidation of
phenol has been investigated [57]. The material was syn-
thesised using the method of hydrothermal treatment of
microemulsions. Nanoparticles of both anatase and rutile
phases could be prepared by adding nitric acid and hy-
drochloric acid, respectively. The results showed that both
phases were active for the photodegradation of phenol, how-
ever, a difference in the reaction kinetics was observed. The
rutile phase initially decomposed phenol much faster than
anatase but the latter showed a superior rate taking into ac-
count the overall photodecomposition reaction.
The catalytic behaviour of Ti–W mixed oxides has been
investigated for the photoelimination of toluene using
sunlight-type excitation [58]. Nanosize particles were pre-
pared in a microemulsion consisting of ammonium tungsten
oxide (aq)/n-heptane/Triton X-100/hexanol. Ti–W mixed
oxides of anatase phase with up to 20 at.% W incorporated
in the anatase structure could be obtained. The catalytic
activity for toluene degradation was found to increase upon
W doping. This enhanced activity was explained to arise
due to the formation of W-related charge trapping centres
at the surface and a decrease of the photoabsorption band
gap energy related to the electronic influence of W in the
creation of electronic states in the anatase band gap. No
comparison with similar Ti–W catalysts prepared by other
techniques was made in this study.
3.7. Advantages and disadvantages of the microemulsion
technique
The most remarkable features of the microemulsion tech-
nique for catalyst preparation are:
• The metal particles are reduced directly in the microemul-
sion and can be used as a catalyst in suspension without
further thermal treatment.
• A narrow particle size distribution can be obtained.
• The particle size can be controlled to a great extent.
• Bimetallic particles can be obtained at room temperature.
• No effect of the support on the formation of the particles.
The open challenges for the microemulsion technology
before its implementation as a commercial route for catalyst
preparation are:
• Amount of catalyst prepared from a single microemulsion.
• Recovery and recycling of the liquid phase.
218 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
4. Conclusions
This paper covers most of the applications concerning
heterogeneous catalysts prepared from microemulsions.
Monometallic particles, bimetallic particles as well as
mixed metal oxides have been successfully prepared by the
method. These catalytic materials have been used in a wide
range of applications such as hydrogenation and isomerisa-
tion of alkanes, oxidation of alcohols, catalytic combustion
of methane or volatile organic compounds, electrocatalysts
for fuel cells, etc. The majority of the catalysts obtained
from microemulsions show high catalytic activity. The
main advantages of using the microemulsion technique
in the preparation of catalytic materials are related to the
possibility of controlling properties such as particle size,
morphology and size distribution. Nanosize particles with
a narrow size distribution can often be achieved and, there-
fore, structure-sensitive catalytic reactions can benefit from
this preparation procedure as well as support materials
where a high surface area and thermal stability are required.
Other interesting aspects are associated with the deposition
of active material on the support as previously mentioned.
The number of research work in this field is accelerating
and progress is expected to emerge from fruitful collabora-
tion with scientists in the field of physical chemistry, ma-
terial science, colloid chemistry and catalysis. Even though
the scaling-up of catalyst preparation is a challenge, cata-
lysts prepared from microemulsions show very interesting
properties in certain reactions at laboratory scale.
Acknowledgements
S. Rojas gratefully acknowledge the Ministerio de Ed-
ucación, Cultura y Deporte of Spain, for a postdoctoral
grant. The European Commission and the Swiss Govern-
ment are acknowledged by S. Eriksson for financial support
to the AZEP project, contract no. ENK5-CT-2001-00514.
U. Nylén wishes to express his thanks to the Euro-
pean fifth framework project RESCATS, contract no.
GR01-2000-25596, for funding.
References
[1] J.H. Schulman, J.A. Friend, J. Colloid Interface Sci. 4 (1949) 497.
[2] V. Chhabra, M.L. Free, P.K. Kang, S.E. Truesdail, D.O. Shah, Tensile
Surfact. Det. 34 (1997) 156.
[3] C. Corolleur, D. Tomanova, F.G. Gault, J. Catal. 24 (1972) 401.
[4] M. Boutonnet, J. Kizling, P. Stenius, G. Maire, Colloid Surf. 5 (1982)
209.
[5] K. Kon-No, Structure–performance relationships in surfactants, Sur-
fact. Sci. Ser. 70 (1997) 551.
[6] R. Schomäcker, M.-J. Schwuger, K. Stickdorn, Chem. Rev. 95 (1995)
849.
[7] J. Klier, C.J. Tucker, T.H. Kalantar, D.P. Green, Adv. Mater. 12
(2000) 1751.
[8] I. Lisiecki, M.P. Pileni, J. Am. Chem. Soc. 115 (1993) 3887.
[9] J. Kizling, PhD Thesis, Royal Institute of Technology, Stockholm,
1991.
[10] L. Yongcheng, C.-W. Park, Langmuir 15 (1999) 952.
[11] D.-H. Chen, S.-H. Wu, Chem. Mater. 12 (2000) 1354.
[12] P. Sun, P. Atorngitjawat, M.J. Meziani, Langmuir 17 (2001) 5707.
[13] M. Bonini, U. Bardi, D. Berti, C. Neto, P. Baglioni, J. Phys. Chem.
B 106 (2002) 6178.
[14] R.J. Higgins, An economical process for manufacture of nano-sized
inorganic powders based on microemulsion-mediated synthesis, Pro-
posal to NSF Program Solicitation Nos. 96–67, 1996.
[15] M. Boutonnet, C. Andersson, R. Larsson, Acta Chem. Scand. A 34
(1980) 639.
[16] M. Boutonnet, J. Kizling, R. Touroude, G. Maire, P. Stenius, Appl.
Catal. 20 (1986) 163.
[17] M. Boutonnet, J. Kizling, V. Mintsa-Eya, A. Choplin, R. Touroude,
G. Maire, P. Stenius, J. Catal. 103 (1987) 95.
[18] M. Boutonnet, J. Kizling, R. Touroude, G. Maire, P. Stenius, Catal.
Lett. 9 (1991) 347.
[19] A. Dauscher, R. Touroude, G. Maire, J. Kizling, M.
Boutonnet-Kizling, J. Catal. 143 (1993) 155.
[20] R. Touroude, P. Girard, G. Maire, J. Kizling, M. Boutonnet-Kizling,
P. Stenius, Colloid Surf. 67 (1992) 9.
[21] M. Boutonnet-Kizling, F. Regali, Stud. Surf. Sci. Catal. 118 (1998)
495.
[22] M. Boutonnet-Kizling, C. Bigey, R. Touroude, Appl. Catal. A: Gen.
135 (1996) L13–L17.
[23] P.-O.F. Andersson, M. Pirjamali, S.G. Järås, M. Boutonnet-Kizling,
Catal. Today 53 (1999) 565.
[24] H. Ohde, C.M. Wai, H. Kim, J. Kim, M. Ohde, J. Am. Chem. Soc.
124 (2002) 4540.
[25] M. Ohde, H. Ohde, C.M. Wai, Chem. Commun. 20 (2002) 2388.
[26] U. Nylén, J.F. Delgado, S. Järås, M. Boutonnet, Low and
high-pressure ring opening of indan over 2 wt.% Pt, Ir and Pt25 Ir75 /
boehmite catalysts prepared from microemulsion systems, Appl.
Catal. A: Gen., in press.
[27] E.M. Johansson, D. Papadias, P.O. Thevenin, A.G. Ersson, R.
Gabrielsson, P.G. Menon, P.H. Björnbom, S.G. Järås, Catalytic com-
bustion for gas turbine applications, Catalysis—Specialist Periodi-
cal Reports, vol. 14, Royal Society of Chemistry, Cambridge, 1999,
p. 183.
[28] A. Trovarelli, M. Boaro, E. Rocchini, C. de Leitenburg, G. Dolcetti,
J. Alloy Compd. 323/324 (2001) 584.
[29] T. Masui, K. Fujiwara, K. Machida, G. Adachi, T. Sakata, H. Mori,
Chem. Mater. 9 (1997) 2197.
[30] R.J. Farrauto, R.M. Heck, Catal. Today 51 (1999) 351.
[31] J. Kašpar, P. Fornasiero, M. Graziani, Catal. Today 50 (1999) 285.
[32] M. Fernández-Garcı́a, A. Martı́nez-Arias, A. Iglesias-Juez, A.B.
Hungrı́a, J.A. Anderson, J.C. Conesa, J. Soria, Appl. Catal. B 31
(2001) 39.
[33] A. Martı́nez-Arias, M. Fernández-Garcı́a, A. Iglesias-Juez, A.B.
Hungrı́a, J.A. Anderson, J.C. Conesa, J. Soria, Appl. Catal. B: En-
viron. 31 (2001) 51.
[34] J. Rymeš, G. Ehret, L. Hilaire, M. Boutonnet, K. Jirátová, Catal.
Today 75 (2002) 297.
[35] A.J. Zarur, J.Y. Ying, Nature 403 (2000) 65.
[36] E. Pocoroba, L.J. Pettersson, J. Agrell, M. Boutonnet, K. Jansson,
Top. Catal. 16/17 (2001) 407.
[37] W.Y. Kim, H. Hayashi, M. Kishida, H. Nagata, K. Wakabayashi,
Appl. Catal. A: Gen. 169 (1998) 157.
[38] J. Agrell, K. Hasselbo, K. Jansson, S.G. Järås, M. Boutonnet, Appl.
Catal. A: Gen. 211 (2001) 239.
[39] M.J. Escudero, E. Hontañón, S. Schwartz, M. Boutonnet, L. Daza,
J. Power Sour. 106 (2002) 206.
[40] Z. Liu, J.Y. Lee, M. Han, W. Chen, L.M. Gan, J. Mater. Chem. 12
(2002) 2453.
[41] B. Yang, Q. Lu, Y. Wang, L. Zhuang, J. Lu, P. Liu, J. Wang, R.
Wang, Chem. Mater. 15 (2003) 3552.
 S. Eriksson et al. / Applied Catalysis A: General 265 (2004) 207–219
[42] X. Zhang, K.-Y. Chan, Chem. Mater. 15 (2003) 451.
[43] S. Rojas, M. Boutonnet, F.J. Garcı́a-Garcı́a, J.L.G. Fierro, in prepa-
ration.
[44] M. Kishida, K. Umakoshi, J. Ishiyama, H. Nagata, K. Wakabayashi,
Catal. Today 29 (1996) 355.
[45] M. Kishida, T. Fujita, K. Umakoshi, J. Ishiyama, H. Nagata, K.
Wakabayashi, J. Chem. Soc., Chem. Commun. 7 (1995) 763.
[46] M. Kishida, T. Hanaoka, W.Y. Kim, H. Nagata, K. Wakabayashi,
Appl. Surf. Sci. 121/122 (1997) 347.
[47] M. Kishida, K. Ichiki, T. Hanaoka, H. Nagata, K. Wakabayashi,
Catal. Today 45 (1998) 203.
[48] M. Kishida, T. Hanaoka, H. Hayashi, S. Tashiro, K. Wakabayashi,
Stud. Surf. Sci. Catal. 118 (1998) 265.
[49] T. Hanaoka, T. Hatsuta, T. Tago, M. Kishida, K. Wakabayashi, Appl.
Catal. A: Gen. 190 (2000) 291.
[50] T. Hanaoka, W.Y. Kim, M. Kishida, H. Nagata, K. Wakabayashi,
Chem. Lett. 7 (1997) 645.
[51] T. Tago, T. Hanaoka, P. Dhupatemiya, H. Hayashi, M. Kishida, K.
Wakabayashi, Catal. Lett. 64 (2000) 27.
[52] J.P. Hindermann, G.J. Hutchings, A. Kiennenmann, Catal. Rev. 35
(1993) 1.
[53] W.Y. Kim, T. Hanaoka, M. Kishida, K. Wakabayashi, Appl. Catal.
A: Gen. 155 (1997) 283.
[54] H. Hayashi, L.Z. Chen, T. Tago, M. Kishida, K. Wakabayashi, Appl.
Catal. A: Gen. 231 (2002) 81.
[55] H. Abrevaya, W.M. Targos, US Patent 4 714 692 (1987), to UOP
Inc., USA.
[56] Y. Mori, Y. Okastu, Y. Tsujimoto, J. Nanoparticle Res. 3 (2001) 219.
[57] M. Andersson, L. Österlund, S. Ljungström, A. Palmqvist, J. Phys.
Chem. B 106 (2002) 10674.
[58] A. Fuerte, M.D. Hernández-Alonso, A.J. Maira, A. Martı́nez-Arias,
M. Fernández-Garcı́a, J.C. Conesa, J. Soria, G. Munuera, J. Catal.
212 (2002) 1.
219
[59] B.H. Robinson, A.N. Khan-Lodhi, T. Towey, in: M.P. Pileni (Ed.),
Structure and Reactivity in Reverse Micelles, Elsevier, Amsterdam,
1989, p. 198.
[60] M.-L. Wu, D.-H. Chen, T.-C. Huang, J. Colloid Interface Sci. 243
(2001) 102.
[61] J. Agrell, M. Boutonnet, U. Jacobsson, J. C. Eriksson, Unpublished
results from 1999.
[62] M. Lade, H. Mays, J. Schmidt, R. Willumeit, R. Schomäcker, Colloid
Surf. A 163 (2000) 3.
[63] P. Stenius, J. Kizling, M. Boutonnet, WO Patent 8102688 (1981), to
Ytkemiska Institutet, Sweden.
[64] W.M. Targos, US Patent 4 714 693 (1987) to UOP Inc., USA.
[65] M. Boutonnet-Kizling, S. Järås, L.J. Pettersson, U. Winter, M.
Zwinkels, WO Patent 97/09114 (1997), to Institutionen för
Kemiteknik Kemisk Teknologi KTH, Sweden.
[66] S.R. Tanke, WO Patent 97/33690 (1997), to Hoechst Celanese Cor-
poration, USA.
[67] A. Towata, M. Sando, US Patent 5 703 002 (1997), to Agency of
Industrial Science & Technology, Ministry of International Trade &
Industry, Japan.
[68] G.V. Odegova, T.O. Zajkova, V.V. Boldyrev, L.A. Pavljukhina, S.A.
Savintseva, RU patent 2 115 474 (1998), to Inst Khim Tverdogo Tela
i Per Nogo Syr Ja So Ran L, Russia.
[69] L. Imre, R. Schomäcker, J. Daun, US Patent 5 710 342 (1998), to
Bayer Aktiengesellschaft, Germany.
[70] Y. Koichi, T. Shinji, M. Naoto, K. Oji, S. Masahiko, T. Kazumasa, T.
Takao, K. Nobuo, EP Patent 0 940 176 A2 (1999), to Toyota Jidosha
Kabushiki Kaisha, Japan.
[71] K. Anflo, J. Agrell, A. Ersson, S. Järås, M. Boutonnet, J. Brandt,
O. Lyckfeldt, WO Patent 02/094716 A1 (2002), to Svenska Rym-
daktiebolaget, Sweden.
[72] J.Y. Ying, A. Zarur, US Patent 6 413 489 (2002), to MIT, USA.