Applied Catalysis A: General 291 (2005) 6272

www.elsevier.com/locate/apcata

Mechanism of deposition of gold precursors onto TiO2

during the preparation by cation adsorption and
depositionprecipitation with NaOH and urea
Rodolfo Zanella 1, Laurent Delannoy, Catherine Louis *
Laboratoire de Reactivite de Surface, UMR 7609 CNRS Universite Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05, France
Received 5 November 2004; received in revised form 23 February 2005; accepted 23 February 2005
Available online 11 May 2005

Abstract

Gold on TiO2 prepared by cation adsorption (CA) and depositionprecipitation with urea (DP urea) and NaOH (DP NaOH) were
characterized by various techniques during the preparation in order to determine the nature of the species deposited and the chemical
phenomena occurring during these preparations. In the case of cationic adsorption of the [Au(en)2]3+ complex, we showed that the preparation
has to be performed at room temperature to avoid the decomposition of the complex and the reduction of gold. In such a way, small gold
particles are obtained after calcination, but the gold loading is low. The methods of depositionprecipitation (DP NaOH and DP urea) involve
both the deposition of a gold(III) species on the TiO2 surface, but the nature of these species is different. For the DP NaOH, we propose that
[AuCl(OH)3]
, the main species present at the pH 8 of the preparation, reacts with hydroxyl groups of the TiO2 surface, and forms a grafted
hydroxy-gold compound. This may explain the limited amount of gold deposited on TiO2 by this method. For the DP urea method, all the gold
present in solution is deposited on the TiO2 surface as a gold(III) precipitate, which is not gold(III) hydroxide, but an amorphous compound
containing nitrogen, oxygen and carbon. This compound arises from a reaction between the gold precursor and the products of decomposition
of urea. The metallic gold particles obtained after calcination exhibit a decreasing size when the time of DP urea increases. We propose that the
progressive increase of pH, due to urea decomposition at 80 8C, results in changes in the surface charge density of the gold precipitate
particles, and leads to a fragmentation of the particles.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Gold; TiO2; Depositionprecipitation; Cation adsorption; EXAFS

1. Introduction Haruta offers better results in terms of catalytic activity than

Since the discovery in the late eighties that gold can be
catalytically active when it is dispersed as small particles
(<5 nm) on an oxide support, the preparation of gold-based
catalysts has been widely studied in order to prepare active
and stable catalysts [15]. It has been previously shown that
the preparation method has a strong influence on the
catalysts performances [2,3,6]. The depositionprecipitation
method using sodium hydroxide (DP NaOH) developed by
* Corresponding author. Tel.: +33 1 44 27 30 50; fax: +33 1 44 27 60 33.
E-mail address: louisc@ccr.jussieu.fr (C. Louis).
1
Present address: CCADET, UNAM, Circuito Exterior S/N Ciudad
Universitaria, A.P. 70-186, C.P. 04510 Mexico, DF, Mexico.
impregnation, which leads to large gold particles (>10 nm)
or than coprecipitation. Moreover, the DP NaOH method is
easier to handle than the deposition of organogold complex
in gas or liquid phase on a support in absence of moisture,
which is also an efficient method to prepare nanosize gold
particles (23 nm) [4,7,8]. For these reasons, the DP NaOH
method was selected for the production of reference gold
catalysts (World Gold Council, www.gold.org). However,
this method also presents some disadvantages. First, it does
not seem to be effective for the deposition of gold
nanoparticles on metal oxides with a point of zero charge
(PZC) below 5 or on activated carbon [9,10]. Hence, silica or
tungsten oxide supported gold catalysts cannot be prepared
using the DP NaOH method. Grafting in gas and liquid

0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.02.045
 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272
phase, using for example, dimethyl-gold acetylacetonate, is
preferred in this case, but this organogold complex is very
expensive and the catalyst preparation has to be done in
absence of air [8]. Another disadvantage of the DP NaOH
method is that the totality of gold present in solution cannot
be deposited on the support. Indeed, on the most commonly
studied amphoteric support TiO2, the maximum gold
loading is much lower (3 wt.%) than the nominal amount
of gold presents in solution (13 wt.%) when the pH is in the
range 710, but it is higher (8 wt.%) at a pH closed to the
point of zero charge of the oxide (PZCTiO2  6) [11]. An
increase of the gold loading could be achieved by decreasing
the pH of the solution below 6, but that occurs at the expense
of the gold particles size which strongly increases [11,12].
Recently, we compared the suitability of several
preparation methods to obtain Au/TiO2 catalysts with small
metal particles [13]. The amphoteric character of TiO2
allowed us to modulate the charge of the oxide surface by
adjusting the solution pH below or above its PZC. Then, it
was possible to use the procedures of anion adsorption (AA)
with the [AuCl4]
complex and cation adsorption (CA) with
the [Au(en)2]3+ complex, in addition to other methods, such
as depositionprecipitation with NaOH and deposition
precipitation with urea (DP urea). We observed that it was
possible to achieve small particles size (<5 nm) after
calcination under air at 300 8C. However, the gold loadings
resulting from these various preparations were quite different.
Indeed, with a gold concentration in solution corresponding to
a Au loading of 8 wt.% in the case of a complete deposition of
gold on the TiO2 support, the weight percentage obtained
ranged from 1 wt.% for the anion adsorption method to about
8 wt.% for the depositionprecipitation with urea, depending
on the time of contact and the temperature of the solution. As
previously observed by Haruta, the maximal loading for the
DP NaOH preparation was around 3 wt.% at a pH close to 8.
The most interesting result was that depositionprecipitation
with urea led to small Au particle sizes (23 nm) even at a very
high metal loading (8 wt.% since all the gold in solution was
deposited on the support).
In a former paper [13], we proposed some assumptions,
based on the literature data, regarding the chemical
mechanisms involved in the deposition of gold by these
various methods. We decided to perform extended
characterization experiments, especially extended X-ray
absorption fine structure (EXAFS), in order to validate or not
these hypotheses. We focused our work on three preparation
methods: DP NaOH, cation adsorption with [Au(en)2]3+ and
especially DP urea.
2. Experimental
2.1. Au/TiO2 preparations
The catalysts preparations are given in details in reference
[13]. For summary, 1 g of TiO2 (Titania Degussa P25) was
63
dispersed in 100 mL of an aqueous solution of HAuCl4 or
[Au(en)2]Cl3 (4.2  10
3 M), the gold concentration corre-
sponding to a theoretical Au loading of 8 wt.% in the case of a
complete deposition. Commercial HAuCl43H2O [Acros] and
freshly prepared [Au(en)2]Cl3 [14] were used. The solution
temperature was usually fixed at 80 8C and the pH was
adjusted to 8 with NaOH for the DP NaOH and to about 9 with
ethanediamine for the cation adsorption method. The time
of contact between the support and the solution was 1 h for
DP NaOH and between 1 and 16 h for CA samples. In the case
of the DP urea preparation, urea (CO(NH2)2) was added to the
HAuCl4 solution to achieve a concentration of 0.42 M. The
main parameters studied were the DP time, the HAuCl4
concentration and the solution temperature. All the prepara-
tions were performed in the absence of light, which is known
to decompose the gold precursors.
After deposition of gold onto TiO2, the solids were
separated from the precursor solution by centrifugation. A
small part of each sample was kept wet and unwashed for
characterization, but the main part was washed several times
with distilled water and dried under vacuum at room
temperature or 100 8C and were characterized after drying.
Finally, when it was necessary to obtain metallic gold,
calcinations under a flow of industrial air (50 mL min
1)
were performed at 300 8C for 4 h.
All the samples were stored at room temperature under
vacuum in a desiccator, away from light in order to prevent
any alteration [15].
2.2. Techniques of characterization
Chemical analyses were performed by inductively
coupled plasma atom emission spectroscopy at the CNRS
Center of Chemical Analysis (Vernaison, France).
Calcined Au/TiO2 samples were examined by transmis-
sion electron microscopy (TEM) with a JEOL 2000FX
electron microscope. The histograms of the metal particle
sizes were established from the measurement of 3001000
particles. The size limit for the detection of gold particles on
TiO2 is about 1 nm.
X-ray absorption near edge structure (XANES) and
extended X-ray absorption fine structure (EXAFS) mea-
surements of the Au/TiO2 samples were performed at the
Au-LIII edge at the XAS 13 beam line of the DCI storage ring
of LURE synchrotron radiation facility (Orsay, France). The
samples were diluted with cellulose and pressed as a pellet.
The XANES and EXAFS spectra were recorded at room
temperature, in transmission mode using two argon-filled
ionization chambers and a channel-cut Si[1 1 1] mono-
chromator. For each sample, the XANES spectra were
scanned 2 times with 0.5 eV steps from 11870 to 12020 eV
and the EXAFS signals were scanned 5 times with 2 eV
steps from 11750 to 12750 eV. The energy was calibrated
using a Au metal foil. The XANES spectra of HAuCl4,
Au(OH)3 [Au(en)2]Cl3 and a gold foil were also recorded.
After background correction, the XANES spectra were
64 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272

normalized in the middle of the first EXAFS oscillation. The Table 2

EXAFS analyses were done in the framework of single Best parameters for the fit of EXAFS signals of Au references and Au/TiO2
samples for DP NaOH, CA and DP urea series
scattering treatments with the package of programs
Sample Backscatterers N s (A) R (A) DE0 (eV) r (%)
EXAFS pour le Mac [16] since data analysis was limited
to the first shell only. The kx[k] functions were extracted Gold foil Au 12 0.089 2.85 3.4 0.9
Au(OH)3 O 4.0 0.059 1.98 7.1 0.4
from the data following the procedure proposed by Lengeler
HAuCl4 Cl 4.0 0.049 2.27 6.9 1.1
and Eisenberger [17] using a linear pre-edge background and [Au(en)2]Cl3 N 4.0 0.054 2.03 7.6 0.5
a cubic spline atomic absorption background. The Fourier DP NaOH O 4.0 0.064 1.98 8.1 1.5
transforms (FT) were calculated on w[k]kx[k], where w[k] is CA 3 h/80 N 2.0 0.058 2.03 6.8 1.7
a KaiserBessel window with a smoothness parameter equal Au 3.0 0.080 2.85 2.0
to 3. The k limits are 3 and 14 A
1. It may be noted that the C 2.0 0.141 2.89 8.8
FTs are presented without phase correction in the figures. DP urea 16 h O or N 4.0 0.057 2.03 5.4 1.6
Single scattering fits of experimental curves were performed N: number of neighbors; s: DebyeWaller factor; R: distance between Au
with the Round Midnight program [16], which uses the and a backscatterer; DE0 (eV): energy shift; r: agreement factors, GAu
minimization capabilities of the Minuit code [18]. The Au = 0.82 GAuN = 0.375 and GAuO = 0.4.
constant of the mean free path Gi was extracted from
references (metallic gold foil) and Au(OH)3, GAuAu = 0.82
and GAuO = 0.4. The inelastic reduction factor S02, and the fully deprotonated surface (TiO2 Degussa contains 6OH/
functions jf i[k, Ri]j (amplitude) and jfi[k, Ri]j (phase shift) nm2 according to the manufacturer). The gold loading
were calculated from the structures of metallic gold, and reached after 16 h is much higher, approximately 6 wt.%
Au2O3 using the FEFF 7.0 code [19,20]. (Table 1). The same preparation procedure was repeated at
The Raman spectrometer is a commercial RAMAN 25 8C. Table 2 shows that, under these conditions, the gold
RXN1 analyser from Kaiser optical systems Inc. (KOSI). It loading and particle size after 1 and 16 h are quite the same,
incorporates a laser working at 785 nm, a CCD detector 1 wt.% and 2 nm. This indicates that the evolution of the
providing full spectral collection of Raman data from 200 to gold loading and particle size with the time of contact occurs
3500 cm
1 with a resolution of at least 4 cm
1 and at 80 8C and not at room temperature.
holographic notch filters. The comparison of the XANES spectrum of the sample
The infrared study were conducted with an IFS 66V prepared at 80 8C for 3 h (CA 3 h/80) (Fig. 1b) with those of
(Bruker) using a DRIFTS cell. The sample compartment was the reference compounds, Au foil and [Au(en)2]Cl3, reveals
filled with the sample powder diluted in synthetic diamond. the presence of metallic gold (Fig. 1a and d). Indeed, the
lower intensity of the white line and the resonance above the
maximum of the white line, indexed on the figure by a dotted
3. Results line, are typical of metallic gold [21,22]. The modulus of the
Fourier transform of the EXAFS signal of the same sample
3.1. Cation adsorption (Fig. 2a) is clearly different from that of the reference
[Au(en)2]Cl3 (Fig. 2b). The simulation indicates that the first
It has been previously shown [13] that, for the samples shell is related to AuN bonds with a distance of 2.03 A.
prepared at 80 8C at pH 9 with [Au(en)2]3+, the adsorption The second shell corresponds to the simultaneous presence
time had a strong influence on the gold loading and particle of carbon atoms (coming from the ligand en: NH2CH2
size (Table 1). Indeed, when the contact time increases (1, 3,
and 16 h) both the Au loading (1, 3, and 6 wt.%) and the
average particle size (2, 3.5, and 4 nm) clearly increase. A
change in the solution pH (9 or 10) did not drastically
modify this trend [13]. A maximum gold content of 3 wt.%
was expected, based on the assumption of the interaction of
one [Au(en)2]3+ cation with 3O
of the TiO2 surface and of a

Table 1
Au/TiO2 samples prepared by cation adsorption with [Au(en)2]3+
Sample Time of T (8C) Au Average particle
contact (h) loading (wt.%) size (nm)
CA 1 h/80 1 80 1.1 2.1
CA 3 h/80 3 80 3.0 3.5
CA 16 h/80 16 80 6.1 4.1
CA 1 h/25 1 25 1.2 2.5 Fig. 1. Au-LIII XANES spectrum of Au foil (a), CA 3 h/80 (b), CA 16 h/25
CA 16 h/25 16 25 1.1 2.7 (c), and [Au(en)2]Cl3 (d).
 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272
Fig. 2. Modulus of the Fourier transform of the k3-weighted EXAFS signal
of CA 3 h/80 (dotted line) (a) and [Au(en)2]Cl3 (b).
CH2NH2) (dAu
C  2.9 A) and to a AuAu pair correlation
at a bond distance of 2.85 A, characteristic of metallic Au
(Fig. 2 and Table 2). The presence of metallic gold is
highlighted by the higher intensity and the broader width of
the second peak for sample CA 3 h/80 than for [Au(en)2]Cl3.
Regarding the sample prepared at room temperature for 16 h
(CA 16 h/25)], the shape of the XANES spectra (Fig. 1c) is
similar to that of the reference [Au(en)2]Cl3 (Fig. 1d) with no
evidence for the presence of metallic gold. However, the
weak signal to noise ratio of the EXAFS spectrum made it
non usable for simulation.
3.2. Depositionprecipitation with NaOH
In a previous work, we proposed a possible mechanism of
deposition of gold in the case of the DP NaOH method [13].
We assumed that a gold surface complex could form from
the reaction between the chloro-hydroxo gold species
[AuCl2(OH)2]
or [AuCl(OH)3]
with the TiO2 surface
hydroxyl groups:
65
Fig. 3. Modulus of the Fourier transform of the k3-weighted EXAFS signal
of Au(OH)3 (a), DP NaOH (b), HAuCl4 (c), and Au foil (d).
Fig. 3 shows the Fourier transform of the EXAFS signal
of this sample and of the references HAuCl4 and Au(OH)3,
without phase correction. The EXAFS signal of the DP
NaOH sample looks like more that of Au(OH)3 than that of
HAuCl4. It appears that the AuO coordination is the
dominating one with a mean distance AuO equal to 1.98 A
(Table 2). There is no contribution, which can be attributed
to an AuCl coordination (dAuCl = 2.28 A). The XANES
spectra of the DP NaOH, Au(OH)3 and HAuCl4 samples also
reveal that the spectrum of the deposited gold species is
much closer to that of gold hydroxide than that of
chloroauric acid (Fig. 4). Obviously, the deposited gold
species does not contain chloride ligands. Haruta [11],
Moulijn [24] and more recently Lin [25] reported the same
conclusions. However, the direct comparison of the Fourier
transform of the DP NaOH EXAFS signal with that of the
reference Au(OH)3 (Fig. 3) does not lead to an unambiguous
identification of the deposited gold as the hydroxide. Indeed,
gold hydroxide reveals, in addition to the AuO coordina-
tion, an another feature at a distance of 3.7 A, which can be
tentatively attributed to the AuAu distance in the AuOAu
shell resulting from the formation of Au(OH)3 oligomers in
the commercial product. Indeed, gold hydroxide is often
TiOH AuCl2 OH2 
! TiOAuCl2 H2 O OH

(1)

Indeed, these chloro-hydroxo gold species are expected

to be the prevailing ones under our conditions of preparation
(pH 8, T = 80 8C and concentration 5  10
3 M),
according to [23]. Moreover, earlier studies are in agreement
with the formation of a gold surface complex, and also
showed that the maximum gold loading coincides with a pH
close to the point of zero charge of the support, i.e. when the
amount of surface hydroxyl groups is maximal [11].
However, gold hydroxide Au(OH)3 is usually considered
as the gold species deposited on the support surface by the
DP NaOH [11,24]. In order to collect additional data, we
prepared a sample of Au/TiO2 by the DP NaOH method. The
sample was kept unwashed to avoid changes in the gold Fig. 4. Au-LIII XANES spectrum of HAuCl4 (a), DP NaOH (b), and
speciation during washing, and dried at room temperature. Au(OH)3 (c).
66 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272

described as an hydrous Au2O3, in which such AuOAu

coordination exist [26]. This feature is not clearly observed
in the DP NaOH sample. In a recent work, Lin et al. [25]
reported that they could observe the presence of AuOAl
shell at a distance of 3.2 A, which would indicate that gold-
alumina interaction takes place during the deposition. We
estimate that the signal to noise ratio is too low to make any
simulation at so long distance.

3.3. Depositionprecipitation with urea

The method of depositionprecipitation with urea,

developped by Geus [27] for the preparation of Ni and
Cu supported catalysts, has been deeply studied, and
especially its mechanism, in the case of the preparation of
Ni/SiO2 catalysts by one of us [2831]. The progressive
decomposition of urea in solution at temperature above
60 8C releases OH
ions, which gradually increase the
medium pH. This method makes possible the slow
precipitation of hydroxides onto the support, and avoids a
brutal and local increase of pH, which could induce
precipitation in solution. Regarding the preparation of
supported gold catalysts, we observed that using the DP urea
procedure, almost all the gold in solution was deposited on
the TiO2 support [13]. Thus, using the DP urea method, a
high gold loading could be achieved (8 wt.%) whereas the
DP NaOH method only allowed to deposit up to 3 wt.% of
Au (only 35% of gold could be deposited). The high yield
of deposition in the case of the DP urea method was also
observed on various supports by other groups, but not
explained [3235]. More astonishing, the precipitation of
gold takes place very quickly since it is complete within the
first hour when the pH of the solution is still acidic (pH 3)
(Table 3). Moreover, as shown in Table 3, the average
metallic particle size obtained after one hour of DP, then
calcination, is rather large, but when the DP time in solution
increases, the size decreases. All these features, i.e. the fast
deposition of gold and the evolution of gold particle size
versus the DP time, indicate that the mechanism of gold
deposition occurring during DP urea is different from that
observed during the preparation of Ni/SiO2 system by DP
urea [27,28], and also from the mechanisms of DP NaOH
and cation adsorption. This is confirmed visually by the
orange color of the wet samples prepared by DP urea
compared with the white color of those prepared by DP
NaOH and cation exchange. We previously proposed [13]
that gold was deposited on the TiO2 surface via the
Fig. 5. Au-LIII XANES spectra of Au foil (a), HAuCl4 (b), Au(en)2Cl3 (c),
and DP urea 16 h (d).
formation of gold surface complex and then of gold colloids
arising from the reduction of AuIII species by the Ti3+ ions
present in the support. The gold colloids, negatively charged
on the surface, could interact with the positively charged
TiO2 surface at low pH. In order to establish the possible
presence of metal gold colloids in the samples prepared by
DP urea, the samples have been characterized by XANES
analysis. The white line intensity of the XANES spectrum of
DP urea 16 h sample clearly reflects the presence of gold in
the oxidation state III, when it is compared to the references
HAuCl4 [Au(en)2]Cl3 and Au foil (Fig. 5). It is worth noting
that the XANES spectrum of DP urea 16 h is very similar to
that of [Au(en)2]Cl3 and rather different from that of
HAuCl4. This could indicate the absence of chloride ligands
in the gold species deposited by DP urea, which is confirmed
by the chemical analysis (Cl < 0.2 wt.%). Moreover, the
comparison of the XANES spectrum of the gold foil with
that of the DP urea 16 h sample (Fig. 5a) also clearly shows
that the supported gold species in DP urea sample is gold(III)
and not gold(0), as assumed in our former paper [13].
Fig. 6 shows the comparison of the Fourier transform of
the EXAFS signals of the DP urea 16 h and the DP NaOH

Table 3
Au/TiO2 samples prepared by DP urea at 80 8C
Sample DP pH Au loading Average particle
time (h) (wt.%) size (nm)
DP urea 1h 1 3 7.2 7.1
DP urea 2h 2 6.2 6.5 3.2
DP urea 4h 4 7 7.7 2.7 Fig. 6. Modulus of the Fourier transform of the k3-weighted EXAFS signal
DP urea 16 h 16 7.3 6.8 2.5 of DP urea 16 h (a) and of DP NaOH 1 h (b).
 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272
samples. The gold species present on the TiO2 surface for
both methods seem to be different. Indeed, for the DP urea
sample, the first peak is at R = 2.03 A whereas for the DP
NaOH sample, the peak is located at R = 1.98 A (Table 1,
Fig. 6). Although it is not possible to distinguish an oxygen
from a nitrogen neighbor because of the close atomic
number of this two elements, the distance at 2.03 A may
correspond to a AuN environment since the value is close to
that obtained for nitrogen atoms as first neighbors in
[Au(en)2]Cl3 (Table 2) [36]. This could imply that some
nitrogen atoms are present in the close vicinity of gold. The
possible presence of nitrogen atoms as first neighbors could
indicate that urea, or a product resulting from its
decomposition, could have reacted with the gold species
in solution to form a compound which would have
precipitated on the support.
In order to check this assumption, we studied the
evolution of the speciation of gold in solution by Raman
spectroscopy (2501200 cm
1 range) when urea was added
and the temperature of the solution was raised. The
concentrations of HAuCl4 and urea used during this
experiment were the same as those used during the DP
urea preparations. The Raman spectrum of the HAuCl4
solution at pH 3 (Fig. 7) shows two peaks at 322 and
347 cm
1, which can be attributed to the out-of phase
stretching mode (n5) and the symmetric stretching vibrations
(n1) for [AuCl4]
, respectively [37]. The addition of urea at
room temperature results in the appearance of a new intense
peak at 1002 cm
1 (symmetric NCN stretching) and two
very weak peaks barely visible on Fig. 7 at 523 (NCN in-
plane bending mode) and 585 cm
1 (NCN in-plane
rocking mode). They are all characteristic of urea [38]. As
long as the solution was kept at room temperature, no
changes in the shape of the spectrum or in the pH of the
solution occurred. At 50 8C, the hydrolysis of urea has not
begun yet, and the Raman spectrum remained unchanged.
Fig. 7. Evolution of the Raman spectrum of a fresh HAuCl4 solution (4.2
10
3 M), after addition of urea (0.42 M) at RT, and during heating of the
mixture.
67
When the solution was heated up to 80 8C, the peaks at 322
and 347 cm
1 became broader and weaker. These changes
coincide with the appearance of an orange gold precipitate in
the solution. After 2 h at 80 8C, the pH of the solution has
reached 6.9 and the orange gold precipitate was still present.
Peck et al. [37] reported that at a pH close to 7, the gold
speciation is [Au(OH)Cl3]
, and two Raman peaks at 339
and 569 cm
1, corresponding to the AuCl and AuOH
stretching modes, respectively, can be observed. The
absence of these peaks indicates that most of the gold has
precipitated as the orange compound. We repeated the same
experiment in a UVvis liquid cell, and observed that there
was almost no more gold left in the solution after one hour of
heating at 80 8C (spectra not shown). The orange gold
precipitate was filtered off the hot solution, washed with
distilled water and dried at room temperature. The elemental
analysis gave: Au (74 wt.%), N (11.5 %), O (7.5 %), C (4 %),
H (1.6 %), and Cl (1.4 %), which corresponds to the
following atomic composition: AuN2.2O1.2C0.9H4.2Cl0.1. It
may be noted that the Cl content is very low. No diffraction
peak could be observed by X-ray diffraction analysis,
indicating that this compound is amorphous.
The XANES spectrum and the Fourier transform of the
EXAFS signal of the gold precipitate were compared to
those of the DP urea 16 h sample (Fig. 8). It is remarkable
that they are perfectly superposable in both cases. This
shows that the gold species deposited on TiO2 during DP
urea is of the same nature as the gold precipitate. The
XANES spectra also prove that gold is in the oxidation state
III in the precipitate as in the DP urea sample. The fast
formation of the gold precipitate at acidic pH, explains the
fact that the totality of gold is deposited on TiO2 during the
first hour of DP urea (Table 3). Since no reaction occurs as
long as the solution of HAuCl4 and urea remains at room
temperature, the gold precipitate and therefore the supported
gold phase are proposed to arise from the decomposition of
urea. Indeed, in acidic solution, the hydrolysis of urea can be
written as:
CONH2 2 3H2 O ! 2NH4 CO2 g 2OH
(2)
The thermal decomposition of solid urea at 140 8C leads
to the formation of isocyanate and ammonium ions:
CONH2 2 ! NH4 OCN
(3)
Isocyanate ions are also considered as intermediate
species in the reaction of urea hydrolysis [39].
The gold precipitate has been analyzed by Infrared and
Raman spectroscopies (Fig. 9). Both spectra confirmed the
presence of nitrogen in the precipitate. Indeed, the I.R.
spectrum shows the presence of NHx groups (bands at 3220
and 3000 cm
1 corresponding, respectively to yas(NH) and
ys(NH) and at 1575 cm
1 corresponding to das(NH2))
[40,41]. Other bands at 3435, 3305, 1620, and 1445 cm
1
could be related to the presence of OH (dOH) or carbonates
groups [41]. The band at 2177 cm
1 is more difficult to
68 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272
Fig. 8. Au-LIII XANES (A) and modulus of the Fourier-transformed of the EXAFS signal (B) of the DP urea 16 h sample (a) and the orange gold precipitate
(dotted line) (b).
attribute, but could be related to isocyanate vibration
(NCO) [41]. Interestingly, the intensity of this band
increases when the precipitate is heated under argon. As
indicated previously in the text, the thermal decomposition
of urea leads to the formation of isocyanate ions (Eq. (3)).
Since there is no visible band around 1685 cm
1, related to
the CO stretching vibration of urea coordinated to a metal
atom, the presence of coordinated urea molecule can be
Fig. 9. (a) Infrared and (b) Raman spectra of the orange gold precipitate
formed by reaction between HAuCl4 and urea.
ruled out. Therefore, urea could be present as impurity in the
precipitate. The Raman spectrum also reveals the presence
of AuN coordination (band at 541 cm
1 y(AuN)) but Au
O coordination can not be excluded (band at 569 cm
1
ys(AuN or AuO)) [40,41].
In order to establish whether the high gold loading
deposited on TiO2 really reflects a phenomenon of
depositionprecipitation of gold onto the support as
described in [2729] for other systems, or a precipitation
in solution, the following experiment was performed. The
gold precipitate was mechanically mixed with the TiO2
powder, and submitted to the same conditions as for DP
urea: (i) The mixture was added to an aqueous solution
containing urea with the same concentration as for DP urea.
(ii) The suspension was acidified with HCl in order to start
the experiment at the same pH as for DP urea (pH 2). (iii)
The suspension was then heated at 80 8C for 16 h. After
washing, drying and calcination under air at 300 8C, very
large gold metal particles (3040 nm) were detected by
XRD, indicating that the precipitation of gold during the DP
urea preparation occured essentially on the support surface.
4. Discussion
4.1. Cation adsorption
In the case of cation adsorption, it appears that the high
Au loading and the relatively large particle size obtained for
the samples prepared at 80 8C, after a contact time longer
than 1 h, are related to the presence of metallic gold in the
supported gold phase. The low stability of the [Au(en)2]3+
complex is certainly at the origin of the metallic gold.
Indeed, Guillemot [42] in a work on the preparation of gold
catalysts supported on zeolithe showed that the [Au(en)2]3+
complex tends to decompose when it is heated at
temperature above 60 8C. They proposed as a consequence
that gold is reduced by the ethanediamine ligands. Hence,
the metallic gold present in the CA samples prepared at
 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272 69

80 8C probably arises from the decomposition of the proposed that the deposition could occur via a grafting
[Au(en)]2]3+ complex in the solution during the adsorption reaction of the metal complexes with hydroxyl groups of the
and the subsequent deposition of metal gold colloids. support surface.
Moreover, it is possible that the adsorbed [Au(en)2]3+
complex could act as nucleation sites for colloid growth,
which would explain that the gold particle size increases
with the gold loading and with time. In contrast, the samples
prepared at 25 8C do not seem to contain metallic gold. The
Au loading does not depend on time and is lower (1 wt.%)
than the maximum theoretical gold loading (3 wt.%). This
indicates that the deposition of gold probably takes place
according to a cation adsorption mechanism. This cation
adsorption mechanism leads to a high dispersion of the gold
precursors, and to small metal particles after calcination, but
it does not allow to obtain high Au loading, and most of the
gold precursors remain in the solution.
4.2. Depositionprecipitation with NaOH
The depositionprecipitation using sodium hydroxide is
certainly the most usually employed method for preparing
supported gold based catalysts. The XAS characterization
showed that the gold species deposited during the DP NaOH
is not a chloro-hydroxo compound but a species whose
structure is close to that of gold hydroxide. It is worth noting
that gold hydroxide does not form spontaneously in
solution, when the preparation is performed without the
presence of the support, in the range of pH and HAuCl4
concentration used in this study. We are aware that the pH at
the solidliquid interface could be appreciably different
from that in solution, and could lead to different speciation
of the metal complexes [43,44]. However, since the PZCTiO2
is close to 6, the gold complexes at the TiO2-solution
interface are probably not very different from those in
solution (pH 8), or are slightly less hydrolyzed. Thus,
precipitation of Au(OH)3 can be ruled out when TiO2 is
added to the solution.
The dominating species in solution at the preparation pH
(pH 8) and the temperature of 80 8C, are [AuCl2(OH)2]
and
[AuCl(OH)]3]
[23]. According to previous studies, these
two species present the highest adsorption constants on g-
Al2O3 and the adsorption could occur via the following
surface reactions [45,46].
TiOH AuClOH3 
! Ti
O
AuOH3 

H Cl
(6)
Such a reaction could lead to the formation of a grafted
hydroxy-gold species. The amount of hydroxyl groups
available on the TiO2 surface is lower at pH 8 than at the pH
corresponding to the PZCTiO2  6. This limits the number of
adsorption sites, and can explain the restricted gold content
obtained in the samples prepared by DP NaOH. This
interpretation is also consistent with Harutas results, who
observed a lower gold loading at pH 8 than at pH 6 [11]. It
may be added that this mechanism of deposition of gold onto
titania is not a mechanism of depositionprecipitation, as
described by Geus et al. [27] and Burattin et al. [28,29] in the
case of other metals.
4.3. Depositionprecipitation with urea
For the DP urea preparation, the deposition of gold onto
the TiO2 surface occurs from the precipitation of a gold
compound. According to the XANES data (Fig. 5), the
supported gold compound is gold(III) and not gold(0) as
assumed in our former paper [13]. The absence of plasmon
resonance band at 550 nm in the UVvis spectrum (figure
not shown), appearing when metallic gold particles with size
above 2 nm are present, is also an indication that metallic
gold does not form during DP urea preparation.
The supported gold compound is different from gold
hydroxide. Indeed, the EXAFS signal and the XANES
spectrum are identical to the orange precipitate formed
under the same condition, but in the absence of support,
whose elemental analysis revealed a large amount of
nitrogen (AuN2.2O1.2C0.9H4.2Cl0.1). Thus, it is reasonable to
consider that the gold species in the solution of HAuCl4 at
pH 3 reacts with either the ammonium ions, or the
isocyanate ions arising from the decomposition of urea
(Eqs. (2) and (3)).
We did not find any information in the literature regarding
the reaction of gold with isocyanate ions except for the
existence of the gold (I) fulminate [Au(OCN)2]
, but this
AlOH AuClOH3 
! Al
O
AuOH2  H2 O compound was reported to be rather unstable [47], which is
Cl
(4) not the case of the orange gold precipitate. The reactivity of
gold complexes with ammonia and its derivatives is more
AlOH AuCl2 OH2 
! Al
O
AuClOH H2 O
Cl
(5)
However, our XAS results show that there is no chlorine
in the close vicinity of gold in the catalyst prepared by DP
NaOH. Moreover, the number of neighbors is found to be
four and not three which is consistent with the usual square
planar geometry of AuIII species. This is also in contra-
diction with the possible formation of Au(OH)3. Thus, we
documented. Among these compounds, which have all the
typical square plane geometry of the AuIII complexes, the
tetraammine gold(III) ion [Au(NH3)4]3+ has been the most
studied [40,48,49]. Its synthesis is not easy, and it can only
be obtained by very slow addition of concentrated ammonia
to a solution of HAuCl4 while keeping the pH lower than 5
[50]. If the ammonia solution is added too fast or in large
excess, the explosive compound called fulminating gold is
formed [50,51]. Therefore, the process of synthesis of
70 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272
tetraammine gold(III) is not very different from what is
occurring during urea hydrolysis, with the progressive
release of ammonium ions. However, the [Au(NH3)4]3+ ion
has only been isolated in the solid state as nitrate, phosphate
or perchlorate salts [49,51]. [Au(NH3)4]3+ can also be
present in solution, but it does not easily precipitate with
other counter-ions [51]. In our case, the anions available in
solution are chlorides, hydroxides, isocyanates and may be
hydrogenocarbonates resulting from the decomposition of
urea. Moreover [Au(NH3)4]3+ undergoes reduction when it
is exposed to light [40]. This is not the case of our gold
precipitate, which is not altered when it is stored in air and
exposed to daylight during several weeks. Some chlorinated
derivatives of this species, such as [Au(NH3)Cl3] [52]
and [Au(NH3)2Cl2]+ [48] also exist, but the absence of
chlorine atoms as first neighbors, attested by EXAFS and
chemical analysis, rules out this possibility. This precipitate
could also be fulminating gold, which appears as various
gold compounds or mixtures, depending on the preparative
route [53]. Fulminating gold is variously described as a dirty
olivegreen powder when it is prepared from auric
hydroxide and ammonia, as a yellow precipitate or as a
black powder, when it is prepared from auric oxide and
concentrated ammonia [51]. Several formulas are proposed:
Au2O33NH3 + NH(AuNH2Cl)2 or gold hydrazide (AuHN
NH2)3H2O, but it may be also an ammine [Au(NH3)2(O-
H)2]OH [50,51]. In the present study, neither the gold
precipitate, nor the supported gold formed during DP urea,
ever showed any explosive character, even during drying, so
we do not believe that they are fulminating gold, but they
could be a close compound.
The small size of the gold particles observed by TEM
after calcination for the Au/TiO2 samples prepared by
DP urea implies that a strong interaction occurs between
the TiO2 support and the gold precipitate during the
deposition, which leads to a high dispersion of metallic
gold. Since at acidic pH, the surface of TiO2 is positively
charged, and the gold species in solution are [AuCl4]

or [Au(OH)Cl3]
, the gold species could interact with
the support, then act as nucleation centers for the growth
of particles of the orange gold precipitate on the
support.
Table 4
Au/support samples prepared by DP urea at 80 8C
Support PZC DP time (h) Final pH
TiO2 6 1 3
P25 45 m2/g 16 7.3
SiO2 2 1 5.2
Aerosil 300 16 7 3.7
250 m2/g
g-Al2O3 7.5 1 4.3
100 m2/g 16 7.1
CeO2 6 1 4.4
256 m2/g 16 6.6
a
Estimated by XRD (poor contrast between gold particles and CeO2 by TEM).
Fig. 10. Evolution of the pH and the gold particle size estimated by TEM
with the time of preparation by DP urea for Au/TiO2.
Other groups used the methods of depositionprecipita-
tion with urea to deposit gold on various supports, but they
never focused their studies on the characterization of the
freshly prepared catalysts [3235]. They all observed that it
was possible to deposit almost all the gold in solution
whatever the support, but their results showed that the gold
dispersion strongly depends on the nature of the support.
Indeed, the gold particle size after calcination under air or
pure oxygen was rather large in the case of Au/SiO2 samples
(1015 nm) [33] and clearly smaller for Al2O3 (510 nm)
[33], TiO2 (7.5 nm) [32] and Co3O4 (4 nm) [35]. It is worth
noting that the TiO2 support used by Dekkers et al. [32] was
different from ours. Unfortunately, in most cases, the authors
did not specify the duration of the procedure of deposition
precipitation by urea, which appears to be an important
parameter since, as shown in Table 3 and Fig. 10, the gold
particle size depends on the time of preparation.
We also prepared several samples, according to the DP
urea procedure, using SiO2, Al2O3, and CeO2 as supports.
For a deposition time of 1 h or 16 h, the gold loading was
high for all the supports except SiO2 (Table 4). In addition,
the average particle size decreases according to the sequence
SiO2 > Al2O3  CeO2  TiO2. This is in agreement with
the literature data mentioned above. The largest particles are
obtained for the silica support, which possesses the lowest
point of zero charge (PZC 2). The adsorption of negatively
Au loading (%) Average particle size (nm)
7.2 7.1
6.8 2.5
2.9 >20
>20
6.9 6.9
7.2 2.3
7.9 8.1a
8.2 <5a
 R. Zanella et al. / Applied Catalysis A: General 291 (2005) 6272
charged gold species [AuCl4]
or [Au(OH)Cl3]
is not
possible on the silica surface since it is negatively charged
throughout the whole DP urea preparation. Thus, the
interaction between the gold precipitate and the silica
support, if it exists, must be weaker, and this could be the
reason for the lower gold loading and the larger particle size.
Indeed, previous works showed that the strength of the metal
precursor-support interaction can affect the metal dispersion
after reduction [54]. For example, cobalt has been shown to
spread on titania during reduction whereas it sinters on silica
[55]. Then, the metal oxides, which could induce strong
gold-support interactions, such as TiO2, Al2O3 and CeO2,
would be able to preserve small gold particle sizes.
Another general feature observed for all the supports is
that the particle size decreases when the deposition time
increases, i.e. during the increase of the pH (Tables 3 and 4,
Fig. 10). Since gold precipitates very quickly on the supports
at pH around 3, the decrease in the gold particle size with the
time is due to a redispersion of the particles of gold
precipitate, and is independent of the nature of the support
(the same trend was observed for Al2O3 and CeO2, and to a
lower extent for SiO2). Such a phenomenon of segregation
and fragmentation is well known in colloidal chemistry, and it
depends on the changes in the surface charge density of the
particles and in the electrical repulsive forces between the
particles [56,57]. The process is described by the rapid
precipitation of large aggregates, followed by a slow
peptization (deaggregation), for example, when the pH of
the solution increases [58]. It is possible that the surface of the
gold precipitate is charged in solution and that the progressive
increase in pH resulting from the hydrolysis of urea modifies
the surface potential charge, inducing repulsions and leading
to a fragmentation of the precipitate particles.
In conclusion, the DP urea method shows some remarkable
characteristics. The main one is that, in the presence of
supports such as TiO2, Al2O3, or CeO2, a gold compound
formed by reaction between gold and the products of
hydrolysis of urea completely precipitates on the support. The
supported phase is a gold(III) compound and not gold(0) as
assumed in our former paper [13]. We can infer that the
precipitation of gold on the support surface initially requires
the adsorption of an anionic gold species, which later acts as
nucleation sites for the precipitation of gold on the oxide
support. The gold precipitate evolves then with the deposition
time and its particles split up. The fast deposition of a gold
compound containing nitrogen instead of the slow precipita-
tion of an hydroxide, and the decrease of gold particle size
versus the DP time, indicate that the mechanism of gold
deposition during DP urea is different from that occurring
during the preparation of Ni/SiO2 system by DP urea [27,28].
5. Conclusion
In the present work, we performed a characterization
study to determine the chemical mechanisms involved in the
71
preparation of Au/TiO2 catalysts by different procedures of
gold deposition. In the case of the cation adsorption with
[Au(en)2]3+, we found that, when it is performed at 80 8C,
cation adsorption is accompanied by the decomposition of
the thermally unstable [Au(en)2]3+ in Au0. Hence, the
resulting samples contain metallic gold particles formed
during the preparation. In contrast, when the preparation is
performed at 25 8C, the deposition is exclusively a
mechanism of cation adsorption of [Au(en)2]3+, and both
the gold loading (1 wt.%) and the average gold particle size
(2.5 nm) are small.
The DP NaOH and the DP urea methods involve the
deposition of a gold(III) compound on the support surface.
However, the gold species deposited are different. Indeed,
for the DP NaOH method, a AuIII hydroxy-type species
seems to be grafted on the support, i.e. Ti[OAu(OH)3]
. Its
formation would result from a reaction between
[AuCl(OH)3]
, which is the main species in solution at
pH 8, and the hydroxyl groups of the TiO2 surface still
present at this pH. For the DP urea method, the mechanism
of gold deposition on titania is a mechanism of deposition
precipitation, since we have clearly established that when
the pH increased, there is precipitation of a gold compound,
which it is not Au(OH)3, onto the support. The fast
formation of this gold precipitate at pH close to 3 explains
the fact that gold is totally deposited on the support within
the first hour of the preparation. The depositionprecipita-
tion mechanism could first involve an initial electrostatic
interaction between anionic gold species [AuCl4]
and/or
[AuCl3(OH)]
and the positively charged TiO2 surface at
acidic pH, then the growth of the particles of gold precipitate
on these sites, which act as nuclei. When the pH increases
during the DP urea, the surface charge density of the gold
precipitate particles is modified, leading to a fragmentation,
and then to a decrease in the gold particle size with
increasing deposition time. Finally, the DP urea, like the DP
NaOH method, is a suitable method for the preparation of
gold catalysts on various oxide supports with point of zero
charge in the range 68 (TiO2, Al2O3, CeO2) but not for
silica (PZC 2).
Acknowledgments
Rodolfo Zanella is indebted to CONACYT (Mexico) and
SFERE (France) for his Ph.D. grant, and to FESC, UNAM.
We also thank the technical staff of LURE synchrotron
facility (Orsay, France) and especially Dr Francoise Villain.
We also want to thank Jean-Marc Krafft for his help for the
Raman and DRIFTS recording of the spectra and analysis.
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