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The best current way to prepare Au/TiO2 catalysts is the method of deposition-precipitation with NaOH (DP
NaOH) developed by Haruta and co-workers. With this method, it is possible to obtain small gold metal
particles (2-3 nm), but the corresponding gold loading remains rather low (3 wt %). The main goal of this
work is to investigate other methods of preparation of Au/TiO2 catalysts to obtain small gold metal particles
(2-3 nm) and a higher Au loading. It is shown that anion adsorption with AuCl4- (AA) does not produce Au
loading higher than 1.5 wt % and the average particle size is not very small (4 nm). Cation adsorption with
Au(en)23+ (CA) leads to small particles (2 nm) when the solution/support contact time is moderate (1 h), but
the Au loading does not exceed 2 wt %. The most promising method of preparation appears to be depositionprecipitation with urea (DP urea). Indeed, samples with gold particles as small as those obtained with DP
NaOH (2 nm) can be prepared, and all gold in solution is deposited on TiO2 in contrast to DP NaOH. The
DP urea samples reported in this paper can reach a Au loading as high as 8 wt % using a TiO2 support with
a surface area of 45 m2 g-1. The possible mechanisms of deposition of gold on the TiO2 support by the
different methods of preparation are discussed.
I. Introduction
Gold metal becomes catalytically active in several chemical
reactions when it is finely divided and supported on metal
oxides.1-3 The most remarkable catalytic properties of supported
gold were observed by Haruta et al. in 19874-6 in CO oxidation
at subambient temperature. Since then, the most studied catalyst
has been gold supported on TiO2. Taken separately, Au and
the TiO2 support are catalytically inactive for this reaction, but
Au/TiO2 shows a drastic synergetic effect for the reaction of
CO oxidation. The optimum size of gold particles is smaller
than 5 nm for catalytic applications and about 2-3 nm for CO
oxidation.2,7,8 Such particle sizes can be achieved by a careful
control of the conditions of preparation.
The catalytic activity of Au/TiO2 for CO oxidation depends
on the preparation method; for example, Au/TiO2 catalysts
prepared by coprecipitation are less active than catalysts
prepared by deposition-precipitation.9,10 The parameters used
in the preparations are also important. For instance, for the
deposition-precipitation method, Haruta et al.3 described how
the catalytic activity is sensitive to gold concentration, pH and
temperature of the solution, calcination temperature, and addition
of magnesium citrate.
Haruta developed a preparation method of Au/TiO2 catalysts
by deposition-precipitation with NaOH as precipitating agent
(DP NaOH).11,12 With a nominal amount of 13 wt % of Au in
solution and within a pH range between 7 and 10, this method
permits the deposition of up to 3 wt % of Au and the formation
of small metal particles with an average size of about 3 nm.
Higher Au loading of 8 wt % could be achieved at pH 5.5, but
* To whom correspondence should be addressed. E-mail: louisc@
ccr.jussieu.fr.
Universite
Pierre et Marie Curie.
CRMC2 CNRS.
Associated with the Universities of Aix-Marseille II and III.
Zanella et al.
results
DP
theor Au Au
Cl
average standard particle size
time
loading loading loading particle deviation distribution
sample (h) pH (wt %) (wt %) (wt %) size (nm) (nm)
(nm)
DPN1
1
DPN2
2
DPN3
4
DPN4 16
DPN5a 1
DPN6
1
DPN7
1
a
8
8
8
8
8
7
8
8
8
8
8
8
8
16
1.8
2.4
2.1
2.4
3.1
3.3
3.6
0.026
0.025
0.035
0.077
0.09
0.031
0.030
1.8
1.5
1.6
1.5
1.4
1.4
3.3
0.62
0.40
0.36
0.30
0.36
0.34
1.92
0.7-4.3
0.7-3.5
1.0-3.1
1.0-2.4
0.7-2.7
0.7-2.4
0.7-16.0
Au
Cl
average standard
time of T
loading loading particle deviation
sample contact (C) pH (wt %) (wt %) size (nm) (nm)
AA1 15 h
25 2.5
1.0
0.16
5.7
1.38
AA2 15 min 80 2
1.3
0.16
3.7
1.30
AA3 1 h
80 2
1.0
0.07
5.6
1.50
AA4 15 h
80 2
1.5
0.15
4.4
1.29
particle size
distribution
(nm)
5.0-7.0
(4 particles)
1.7-6.8
(67 particles)
2.0-8.3
(23 particles)
2.0-7.5
(60 particles)
results
time of
Au
Cl
average standard
contact
loading loading particle deviation
sample (h)
pH (wt %) (wt %) size (nm) (nm)
CA1
9.4
1.1
2.1
0.66
CA2
16
9.4
6.1
0.03
4.1
1.01
CA3
10.3
1.7
0.04
1.8
0.33
CA4
16
10.3
6.4
0.08
4.6a
2.74
particle size
distribution
(nm)
1.0-3.5
(134 particles)
1.7-6.4
(140 particles)
1.0-2.5
(88 particles)
1.7-15.8
(157 particles)
a Plus some very large particles (80-150 nm) not taken into account
in the calculation of the average size.
sample
Imp1
Imp2
Imp3
ImpW2a
ImpW3a
a
results
theor Au
Au
Cl
average standard
loading loading loading particle deviation
(wt %) (wt %) (wt %) size (nm) (nm)
1
2
4
2
4
0.9
0.6
0.09
0.08
>10
>10
>10
4.9
2.7
1.36
1.52
particle size
distribution
(nm)
Zanella et al.
sample
DP
time
(h)
T
(C)
DPU1
DPU2
DPU3
DPU4
DPU5
DPU6
DPU7c
DPU8d
DPU9
DPU10
1
2
4
16
90
4
4
4
4
4
80
80
80
80
80
90
80
80
80
80
results
pHa
theor Au
loading
(wt %)
Au
loading
(wt %)
Cl
loading
(wt %)
average
particle
size (nm)
standard
deviation
(nm)
particle size
distribution
(nm)
2.99
6.26
7.04
7.35
7.84
7.27
7.21
6.3
7.1
7.0
8b
8
8
8
8
8
8
8
2
3
7.8
6.5
7.7
6.8
7.4
7.1
7.1
7.7
2.0
3.4
0.041
0.122
<0.03
<0.03
<0.03
0.045
<0.03
0.04
<0.03
0.079
5.6
5.2
2.7
2.5
2.4
1.7
2.0
1.5
2.0
2.3
1.66
1.10
0.90
0.74
0.70
0.35
0.60
0.29
0.52
0.61
2.3-10.2
2.0-7.5 (135 particles)
0.7-5.5
1.0-5.1
0.7-5.0
0.7-3.7
0.7-4.1
0.7-2.4
1.0-4.0 (85 particles)
1.0-4.4
a pH at the end of the preparation. b The theoretical Au loading corresponds to the Au loading that could be reached if all of the gold in solution
was deposited on TiO2 (100% yield of DP); it is in fact comprised between 7.4 and 7.7 wt %. c Twice higher [urea] ) 0.84 M. d Addition of
magnesium citrate (6.9 10-3 M).
Zanella et al.
identified two forms of gold species on iron oxides (ferrihydrite
and goethite) after coprecipitation: metallic gold colloids and
Au(III) species, which corresponded to 1-5% of all the
deposited gold). The formation of gold colloids was attributed
to oxidation-reduction reactions between Au(III) and Fe(II)
present as traces: adsorption of gold on oxidizable mineral
surfaces induces the reduction of Au(III) to elemental gold,
which is subsequently sorbed on oxides. Indeed, colloidal gold
particles are negatively surface-charged,48,49 so they can react
with positively charged iron oxides by electrostatic interaction
(IEP ferrihydrite and goethite ) 8-9).
It is highly probable that TiO2 can also reduce gold because
it usually contains defects of Ti3+ ions. Let us then form the
hypothesis that gold colloids can form. The difference in gold
loading between DP NaOH samples and DP urea samples can
be explained by the differences in solution pHs. Because gold
colloids are negatively charged on the surface48,49 and because
the TiO2 surface is also negatively charged during DP NaOH
preparations because the solution pH (8 or 7) is higher than
IEPTiO2, gold colloids could not interact with the TiO2 surface
but would be released into the solution. Thus, only the Au(III)
surface complex would be present on TiO2. This interpretation
is consistent with the low Au loading of the samples and with
Harutas XANES results,12 which show that the gold is not
metallic.
For DP urea, all of the gold is deposited on the TiO2 during
the first hour (Table 5). It can be inferred that gold colloids
can interact with the TiO2 surface, which is positively charged
before the pH reaches IEPTiO2. In consequence, gold species in
the DP urea samples would be a mixture of Au(III) surface
complexes and Au(0) colloids. UV-visible spectroscopy of the
samples gathered after centrifugation and washing (before drying
to avoid possible decomposition of Au(III) into Au(0)) should
allow us to check these hypotheses. Detection of gold colloids
should also be attempted in the solution of DP NaOH gathered
after centrifugation.
Table 5 also shows that as the pH increases, the average
particle size becomes smaller; this is observed when (i) the DP
time increases (DPU1 to DPU5), (ii) the DP temperature
increases from 80 to 90 C (DPU2 and DPU6), and (iii) the
urea concentration is twice higher (DPU2 and DPU7). If we
suppose that the particle size measured after calcination reflects
the size of gold colloids before calcination, it can be inferred
that the increase in pH as the DP time increases and the fact
that urea dissociates faster at 90 than at 80 C and that more
urea dissociates when the urea concentration is higher have an
influence on the kinetics of redispersion of gold colloids
(because all of the gold is deposited within the first hour of
DP). Such a phenomenon of redispersion of gold colloids was
reported in a study on the formation of gold colloids in solution
by reduction of gold chloride by sodium citrate.50 It showed
that the first particles formed were large and had a fluffy
morphology, then they shrink over the course of the reaction.
The authors proposed that particles may nucleate in a short burst,
agglomerate weakly, and continue to grow within the agglomerates. As the reaction proceeds, the large agglomerates fall apart,
giving rise to a continual increase in the number of small
particles. To the light of this interpretation, the mechanism of
DP urea can be revisited. It is proposed that the formation of
gold surface complexes and colloids takes place simultaneously.
At the beginning of the DP, the pH is low (Figure 6) and there
are few OH sites for the formation of gold surface complex
and therefore few nucleation sites for colloid growth. As DP
proceeds and pH increases, more and more surface OH sites
Zanella et al.
(46) Puddephatt, R. J. The chemistry of gold; Elsevier Scientific
Publishing Company: Amsterdam, 1978.
(47) Baes, C. F., Jr.; Mesmer, R. R. The hydrolysis of cations; John
Wiley & Sons: New York, 1986.
(48) Enzweiler, J.; Joekes, I. J. Geochem. Explor. 1991, 40, 133.
(49) van Olphen, H. An Introduction to Clay Colloid Chemistry;
Interscience Publishers-John Wiley: New York, 1977.
(50) Chow, M. K.; Zukoski, C. F. J. Colloid Interface Sci. 1994, 165,
97.