Application of Introduction

Pollution originating from cars has become one of the major

Heterogeneous issues for public authorities for both health and
environmental protection. As a result, automotive regulations

Gold Catalysis with have been adopted in Europe, USA and Japan. As a
consequence, the solution to meet them is the catalytic
oxidation and reduction of several harmful pollutants found
Increased Durability: in automotive exhaust gas streams. However, new emissions
control regulation technologies are still being developed to
meet ever more stringent mobile source emissions (1).
Oxidation of CO Gasoline is a mixture of hydrocarbons which is oxidized in
air, to produce energy. However, a number of incomplete

and Hydrocarbons combustion products are formed, mainly unburned

hydrocarbons and CO. Nitrogen oxides (NOx) result from the
thermal fixation of the nitrogen by reaction with oxygen from
at Low Temperature the air at high temperature. The transformation of these
pollutants into harmless CO2, H2O and N2 is achieved by
means of a three-way catalyst (TWC) located in the exhaust
pipe. A TWC is able to reduce the deleterious emissions by up
S. Ivanova, C. Petit, V. Pitchon* to 95% when it is fully warmed up by the exhaust gas, i.e. at
LMSPC, Laboratoire des Matériaux, Surfaces et a temperature higher than 450°C. But state-of-the-art
Procédés pour la Catalyse, UMR 7515 du CNRS – technology gasoline fuelled vehicles emit 90% of such
ECPM, 25, rue Becquerel, 67087 Strasbourg Cedex 2, exhaust emissions within the first minutes of operation
FRANCE. *e-mail: [email protected] following a cold start. These initial high emissions are mainly
due to the inefficient oxidation of hydrocarbons when the
Abstract operating temperature of the catalytic converter is below
2% Au/Al2O3 catalysts were prepared by a novel 300ºC. Therefore, catalysts which are active at low
method involving Direct Anionic Exchange (DAE). The temperature for oxidation of cold-start emissions and which
method produces strong bonding of the gold complex can also withstand high temperature during the normal
(HAuCl4) to the alumina support with no loss of gold operating conditions are required.
during the subsequent steps of preparation. The The activity of gold in the form of nanoparticles for
complete removal of chloride from the catalyst was catalytic oxidation of CO below room temperature no longer
achieved by washing with concentrated ammonia. needs to be proven. Some studies have revealed the good
This procedure ensures a better activity and prevents behaviour of gold catalysts towards the oxidation of
sintering during calcination as shown by TEM. hydrocarbons which compare fairly well with Pt and Pd, the
The catalysts were tested for the oxidation of CO precious metals usually used for TWC (2,3). But the major
and of saturated and unsaturated hydrocarbons (C1 to drawback to gold lies in its thermal stability. It is usually
C3). The catalysts showed high activities over a range accepted that above 400°C, gold catalysts undergo severe
of concentrations and temperatures relevant to sintering and the remaining activity is no longer sufficient for
applications in automotive exhaust cleaning. an application.
Furthermore, a remarkable resistance to thermal Therefore, the main objectives of the work reported in this
ageing at 600°C in the absence or presence of water paper were to prepare a gold catalyst on alumina and ceria,
was observed, due to the presence of the strongly which are common supports used in catalytic exhaust
anchored nanosized gold particles obtained during devices, and to characterise the gold catalyst in terms of
the preparation step. activity and resistance to ageing for the oxidation of carbon
monoxide and hydrocarbons for low temperature
applications.

Gold Bulletin 2006 • 39/1 3

Experimental gold loading was found to be 2wt% for a water-washed
sample and 1.37 wt% for an ammonia-washed sample. The
Preparation of gold catalysts and ageing procedures level of chlorine was found to be 0.33wt% for water-washed
A novel method of preparation has been developed, based sample and below 150 ppm for ammonia-washed sample.
upon the direct anionic exchange (DAE) of the gold species Caution/safety note: The contact of ammonia with gold
with the hydroxyl groups of the support (4). Aqueous solution can result in the formation of gold ammonia
solutions of HAuCl4 of concentration 1.44x10-4 mol l-1 (pH 3.5) complexes (“fulminating gold”) which are explosive (7).
were used in order to obtain a final Au loading of 2 wt. %. Using this washing procedure may not be dangerous as the
Belevantsev et al. (5) reported that the gold precursor, gold complexes are strongly attached to the support by
tetrachlorauric acid, hydrolyses in aqueous solution to yield a DAE. However, it is necessary to be certain that there is no
variety of gold complexes formed as a function of gold in the solution before the addition of ammonia, as
temperature and pH. The principal reaction at room Cosumo (20) reported that “supported metal catalysts which
temperature is the formation of the aquo complex contain gold should never be prepared by impregnation of a
[AuCl3(H2O)]0 by replacement of one ligand Cl- by a water support with solutions which contain both gold salts and
molecule. This reaction is followed by a complex NH4OH. The dried catalysts contain extremely shock sensitive
deprotonation and leads to the formation of the charged gold-nitrogen compounds which might explode with the
complex: [AuCl3(OH)]-. This stage is reported as being the lightest touch”.
limiting step of hydrolysis and is promoted by heating. The
concentration of [AuCl4]- decreases as pH increases and a
variety of hydrolysed species result (6). The relative quantity Catalytic testing and ageing procedures
of each species: [AuCl3(OH)]-, [AuCl2(OH)2]-, [AuCl(OH)3]- and
[Au(OH)4]- depends upon the pH value and on the Various unburned hydrocarbon species may be emitted from
concentration of the gold precursor as described by the hydrocarbon flames. In general, there are two classes of
following chemical equations: unburned hydrocarbons: 1) small molecules that are the
intermediate products of combustion resulting from the
[AuCl4]- + H2O AuCl3(H2O) + Cl- } pH ~ 3 breaking of the C-C chain and 2) larger molecules that are
AuCl3(H2O) [AuCl3(OH)]- + H+ } T°C = 70°C formed by pyro-synthesis in hot, fuel-rich zones within
flames, (e.g. benzene, toluene, xylene, and various polycyclic
[AuCl3(OH)]- + H2O AuCl2(H2O)(OH) + Cl- } pH ~ 4 aromatic hydrocarbons). Small unsaturated molecules are
AuCl2(H2O)(OH) [AuCl2(OH)2]- + H+ } T°C = 70°C usually difficult to oxidise. Therefore, the study was focused
on this type of molecule and the catalysts were evaluated for
[AuCl2(OH)2]- + H2O [AuCl(H2O)(OH)2] + Cl- } pH ~ 5-6 the oxidation of several hydrocarbons (CH4, C2H6, C2H4, C2H2,
[AuCl(H2O)(OH)2] [AuCl(OH)3]- + H+ } T°C = 70°C C3H6 and C3H8). A study of the activity for CO oxidation was
also undertaken, as this reaction is a probe reaction for the
[AuCl(OH)3]- + H2O [Au(H2O)(OH)3] + Cl- + H+ } pH ≥ 7 particle size, as there is general agreement that the activity
[Au(H2O)(OH)3] [Au(OH)4]-+ H+ } T°C = 70°C increases as particle size decreases (8,9). The reaction is
structure-sensitive and therefore a difference in the activity
The support, ␥-Al2O3 powder with a BET surface of 90 m2 reflects a change of the particle size. The CO oxidation was
g-1, was sieved with the fraction 125-250 μm retained. The performed at atmospheric pressure using a fixed bed quartz
gold solution was heated to 70°C and the support added. micro-reactor packed with 50 mg catalyst and a gas mixture
After 20 min, 50 ml concentrated (25 mol l-1) ammonia of 1.5% CO and 4% O2 in helium with a flow rate of 50 cm3
solution was added in order to completely remove the min-1 (GHSV in CO oxidation 23,000 h-1). The oxidation of
chloride ions. The slurry was aged 20 min, filtered and hydrocarbons was performed using 200 mg of catalyst and a
washed with warm water. The slurry was then dried in an mixture containing 1500 ppm hydrocarbon and 4% O2 in
oven at 120°C overnight and calcined in air at 300°C for 4 h. helium with a flow rate of 75 cm3 min-1 (GHSV 15000 h-1).
~
The same catalyst was also made as described without The flow was adjusted by means of Tylan flow controllers. The
washing with ammonia. The ammonia treatment successfully temperature was monitored and controlled by a Eurotherm
removes the chloride ligands from the gold chlorohydroxy system. The analysis was performed by Rosemount Infrared
complexes and chloride simply attached on the support. analysers for both CO and CO2, and by gas chromatography
Chemical analysis of Au and Cl in the samples was performed for hydrocarbon (DB-Wax column, 2m. long, 2.5mm of
by inductively coupled plasma atom emission spectroscopy interior diameter). The experiment was repeated several
at the CNRS Center of Chemical Analysis (Vernaison, France). times in order to measure the reproducibility. The catalyst
The detection limit is 150 ppm for Cl. Chemical analysis was performance was assessed in terms of the T50 temperature,
performed after sample calcination. The Au weight loading defined as the temperature at which 50% conversion was
of the samples is expressed in gram of Au per grams of obtained. Before each test, the catalyst was treated at 300°C
calcined sample: wt % Au = [mAu/(mAu + mAl2O3)] x100. The in air for 2 hours to removed physi-sorbed water and CO2.

Gold Bulletin 2006 • 39/1 4

 Two ageing procedures were used, i.e. heating in situ in air 300
at 600°C for 12 hours or heating ex situ at 600°C in air a
250
containing 5%H2O at a flow rate 200 cm3 min-1 for 12 hours.
200
All the catalysts were systematically characterised by Number of
150
Transmission Electron Microscopy and X-Ray Diffraction. The particles
100
procedure of ageing in air was used at laboratory scale as it
usually mimics quite well real ageing on an engine bench 50

(10). Although this temperature is lower than the one 0

1-5 5-10 10-20 20-30 30-40 40-50 50-60 60-70
generally used, i.e. 900 to 1100°C, it is considerably higher Size (nm)
than the temperature at which gold sintering occurs, as
reported in the literature (11,12).
600
b
500

Results and Discussion 400

Number of
300
particles
1. CO oxidation 200
Effect of chloride 100
Chloride is known to have a sintering effect during thermal 0
< 1nm 1-3 nm 3-5 nm
treatments. This is due to the ease with which gold and
Size (nm)
chloride ions combine to form bridges, favouring the growth
of the particles upon heating (13). Furthermore, chlorine also Figure 2
has a poisoning effect on the CO oxidation reaction by Particles size distribution obtained by TEM a) DAE washed with water,
blocking the active sites (14). Therefore, removing chloride is b) DAE washed with ammonia solution
an essential step to produce an active catalyst. To achieve
this, the catalyst was washed with concentrated (25 mol.l-1) particle size, as shown in Figure 2. The average particle size
NH4OH. After filtration, the sample was calcined and the from the distribution obtained by TEM is ca. 16 nm
activity measured in CO oxidation. This type of washing (measured over 338 particles) for the water-washed sample
prevents the particle size growing during the thermal and decreases to 1.9 nm (measured over 569 particles) for
treatment and hence gold nanoparticles strongly anchored ammonia-washed sample. This latter sample presents a very
to the support are obtained. The very positive effect of such narrow particle size distribution and high degree of metal
a washing procedure can be seen in Figure 1, with a gain of dispersion. The achievement of such a low size for gold
95°C in T50, i.e. a decrease from 163°C for the H2O-washed particles on an alumina support is remarkable as dispersing
catalyst to 68°C for the ammonia-washed sample. gold on such a support is not possible by the current
However, for ammonia-washed samples, a change in the “deposition-precipitation” method, although Datye et al (21)
shape of the conversion curve is observed. There is a plateau observed a similar Au particle size, 2.1–2.4 nm, on an
in activity between 50 and 150°C and full activity is restored Au/Al2O3 catalyst after ammonia washing.
above 150°C. This plateau could be attributed to temporary
deactivation of active sites caused by formation of 2. Oxidation of Hydrocarbons
bicarbonate species on the surface, observed by IR (results Effect of carbon number
not shown). When the temperature is increased, the The oxidation of alkanes from C1 to C3 was studied with the
concentration of these species decreases and the access to ammonia-washed catalyst and the results are presented in
the active sites is restored. Figure 3. The activity sequence is act(C2H6) > act(C3H8) >
The improvement of catalytic activity is related to the act(CH4). The activity of the gold catalyst is lower than that

100 100

80 80
CO conversion (%)

Conversion (%)

60 60

40 40

20 20

0 0
0 50 100 150 200 250 300 300 350 400 450 500 550 600 650 700
Temperature (°C) Temperature (°C)

Figure 1 Figure 3
Effect of the washing procedure: washed with NH3 solution 4M at 25°C Conversion of alkanes on 2% Au/Al2O3 : ( 䡺) C2H6, (O) C3H8, ( 왕) CH4
(O), washed with water at 70°C ( 䡺)

Gold Bulletin 2006 • 39/1 5

Table 1 100
C-C and C-H bonding energies in hydrocarbons
80
Hydrocarbon C-C bond energy C-H bond energy
(kJ mol-1) (kJ mol-1)

Conversion (%)
60

CH4 – 438 40
C2H6 330 410
20
C3H8 334 401
C2H2 836 522 0
100 200 300 400 500 600 700
C2H4 611 430 Temperature (°C)

C3H6 351 410

Figure 4
Activity of 2% Au/A2O3 on HC oxidation, ( 䡺) C2H2, ( 왕) C2H4,
obtained from other noble metals such as Pt or Pd (15) where
( 䡬) C2H6, ( 䊱) C3H6, ( ●) C3H8
the activity increases as the number of carbons increases in
the chain. This is explained by the fact that the governing Ageing effect
factor for the rate of reaction is the rupture of the C-H bond Two ageing procedures were used, i.e. heating in situ in air at
during the sorption process and that the energy of this bond 600°C for 12 hours or heating ex situ at 600°C in air with
decreases from methane to propane, the values being given 5%H2O (200 cm3 min-1) for 12 hours. The effects for CO, C2H2,
in Table 1 (16). C2H4 and C2H6 are shown in figures 5, 6, 7 and 8 respectively.
On gold catalysts, the sequence of activity is unusual, For the 3 hydrocarbon molecules, there is a limited
therefore a factor other than the dissociation energy of the deactivation. These results are very unusual for a gold
C-H bond should be taken into consideration. The small size catalyst since it usually sinters very easily, even at
of gold clusters confers special electronic properties which temperatures as low as 400°C (17,18). This is generally
could lead to marked variations in the bonding energies of considered as the major drawback for an application in
the adsorbate to the metal atoms of the lattice. Therefore, automotive emission control. This observed behaviour is due
there is probably a fraction of oxygen poor surface which is to the fact that sintering does not occur, as confirmed by
readily poisoned by the hydrocarbon residue which occurs XRD in Figure 9. After the thermal ageing at 600°C in the
more rapidly for propane than for ethane. absence or presence of water, the diffraction peak for gold
remains unobservable, confirming the presence of small
Effect of carbon unsaturation
Exhaust gas contains a large proportion of unsaturated small 100
molecules, such as C2H4, C2H2 and C3H6. In this study, the 90

activities for C2 and C3 oxidation were evaluated. In Table 2, 80

Conversion CO (%)

70
the C2H2, C2H4 and C2H6 temperatures at 10% / 50% / 100% 60
conversion (T10, T50 and T100) are reported, whereas an 50
40
evaluation of conversions with reaction temperature is shown
30
in Figure 4. The conversion of C3 (C3H6 and C3H8) is also 20

displayed for comparison. For C2 oxidation, the sequence of 10

0
activity is: act(C2H2) ≈ act(C2H4) > act(C2H6). For C3 oxidation, 0 50 100 150 200 250 300 350
T (°C)
the sequence activity follows the same trend, i.e. the
oxidation of the unsaturated hydrocarbon is easier than for Figure 5
the saturated one. Conversely, there is no influence of Ageing effect on CO oxidation, ( 앳) Fresh, ( 왕) aged in air at 600°C for
the degree of unsaturation between C2H2 and C2H4. The fact 12 hours, ( 䡺) aged in air + 5% H2O at 600°C for 12 hours
that the C-C energy is quite different for these two molecules
(see Table 1), suggests that it is the π-bonding adsorption
100
which controls the reaction rate rather than the rupture of
the C-C bond. 80
Conversion (%)

60

40

Table 2
20
Activity of 2%Au/Al2O3 for C2 hydrocarbons
expressed by T10, T50 and T100. 0
0 100 200 300 400 500 600
C2H2 C2H4 C2H6 Temperature (°C)

T10(°C) 242 243 255

T 50(°C) 280 283 318 Figure 6
C2H2 oxidation on 2% Au/A2O3 catalyst, ( 왕) Fresh, ( 䡺) aged in air at
T100(°C) 360 360 450
600°C for 12 hours, ( 앳) aged in air + 5% H2O at 600°C for 12 hours

Gold Bulletin 2006 • 39/1 6

 100

400
80
a
350
300
Conversion (%)

60
250
Number of
40 200
particles
150
20 100
50
0
0 100 200 300 400 500 600 0
Temperature (°C) 1-3 nm 3-5 nm 5-7nm 7-9 nm > 9 nm
Size (nm)

Figure 7
C2H4 oxidation on 2% Au/A2O3 catalyst, ( 왕) Fresh, ( 䡺) aged in air at
400
600°C for 12 hours, ( 앳) aged in air + 5% H2O at 600°C for 12 hours b
350
300
250
100 Number of
200
particles
80 150
100
Conversion (%)

60 50
0
40 1-3 nm 3-5 nm 5-7nm > 7 nm
Size (nm)
20

0
Figure 10
200 300 400 500 600 Particles size distribution of 2% Au/Al2O3 washed with ammonia
Temperature (°C)
obtained by TEM a) aged in air 600°C, 12 hours b) aged in air + 5%
H2O 600°C, 12 hours
Figure 8
C2H6 oxidation on 2% Au/A2O3 catalyst, ( 왕) Fresh, ( 䡺) aged in air at
complete removal of chloride by ammonia washing restricts
600°C for 12 hours, ( 앳) aged in air + 5% H2O at 600°C for 12 hours
the mobility of the gold species during the thermal
treatment. Such results are very promising, as thermal
resistance has always been the principal handicap to an
3 application in automotive catalysis. In the case of the Al2O3
Intensity, a.u.

support, the activities obtained for molecules previously

proving difficult to oxidise, such as C2H2, are already within a
2
range of temperature suitable for an application. The same
preparation method could easily be applied to supports with
which even lower temperatures were obtained rendering
gold catalysis even more attractive for the low light-off
1 application (19).
20 30 40 50 60 70 80
2 theta, degree

Conclusions
Figure 9
XRD pattern of: 1) Al2O3, 2) 2% Au/Al2O3 as prepared washed with It is possible to prepare highly dispersed gold on alumina
ammonia, 3) 2% Au/Al2O3 washed with ammonia after test in HC using the Direct Anionic Exchange preparation technique.
oxidation with calcination at 600°C + 5% H2O
The catalyst obtained by this method contained nanosized
particles. The most surprising result is probably the total particles which are active in the oxidation of CO. The activity
absence of particle growth after the exposure to 600°C, as can be strongly improved by the complete removal of
proven by the TEM distribution in Figure 10. The particle size, chloride using an ammonia washing procedure. The catalyst,
which was 1.9 nm after preparation with ammonia washing tested in various reactions of saturated and unsaturated
(Fig. 2), increases slightly to 2.6 nm (measured over 534 hydrocarbons from C1 to C3, reveals an activity which is in an
particles) after ageing at 600°C. The presence of 5% H2O at appropriate range of temperature for automotive exhaust
the same temperature does not affect the average particle emission control applications. Furthermore, the catalyst is
size, which remains small with an even slightly lower value of almost perfectly resistant to oxidative ageing treatments to
2.3 nm (measured over 425 particles). temperatures as high as 600°C and the loss of activity
The reason lies in the fact that the method of preparation remains minor. The average gold particle size increase is very
by direct anionic exchange (DAE) leads to the formation of limited. The presence of water during the ageing treatment
small particles strongly anchored to the support. The does not provoke a further deactivation. This is due to the

Gold Bulletin 2006 • 39/1 7

strong bonding of the gold precursor during the preparation References
step which, along with the removal of chloride, inhibits
sintering. 1 J. Kašpar, P. Fornasiero, N. Hickey, Catal. Today, 2003, 77, 419
The choice of ageing procedure has been made according 2 M. Haruta, Now and Future, 1992, 7, 13
to our experience in the field on TWC. Indeed, the use of air 3 J. R. Mellor, A. N. Palazov, B. S. Grigorova, J. F. Greyling, K. Reddy, M. P.
is justified in the sense that it usually mimics fairly well the Letsoalo, J. H. Marsh, Catal. Today, 2002, 72, 145
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Gold Bulletin 2006 • 39/1 8