Topics in Catalysis Vol. 38, No.

4, August 2006 (
2006) 223

DOI: 10.1007/s11244-006-0020-y

Research Article

New approaches to designing selective oxidation catalysts:

Au/C a versatile catalyst
Graham J. Hutchings*, Silvio Carrettin, Philip Landon, Jennifer K. Edwards, Dan Enache,
David W. Knight, Yi-Jin Xu, and Albert F. Carley
School of Chemistry, Main College, Cardi University, Cardi CF10 3AT, UK

Selective oxidation is of key importance in the synthesis of chemical intermediates. For many years a number of oxides and
supported metal catalysts have been used. The key questions involved in the design of selective oxidation catalysts are discussed in
the initial part of this paper. One of the most exciting recent developments in the eld of selective oxidation has been the discovery
that supported gold catalysts are active. The second part of the paper discusses Au/C catalysts, which are shown to be particularly
versatile for oxidation reactions. Four examples of selective oxidation are described using molecular oxygen as oxidant: (a) selective
oxidation of glycerol to glycerate in the presence of base; (b) the oxidation of cyclohexane to cyclohexanol and cyclohexanane in the
presence of a radical initiator; (c) the oxidation of hydrogen to hydrogen peroxide, and (d) the oxidation of benzyl alcohol to
benzaldehyde under solvent free conditions. In contrast, the Au/C catalysts are not active for oxidation of carbon monoxide at
ambient temperature. These examples demonstrate that there exists a rich potential for Au/C as a selective oxidation catalyst and
that research efforts should now be focussed on selective oxidation using supported gold catalysts.
KEY WORDS: selective oxidation; gold; hydrogen peroxide; glycerol; cyclohexane; benzyl alcohol.

1. Introduction examples of selective oxidation that are of commercial

Selective and total oxidation processes have fasci-
nated scientists interested in catalysis for decades. At the
heart of this interest is the never quenched thirst to
design a catalyst that is better than the preceding can-
didates. Anyone who is active in this eld will know this
is a dicult task. Selective oxidation requires the exer-
cise of kinetic rather than thermodynamic control if CO2
and H2O are not to be the only products. Sadly for
many formulations tested for alkane activation this is
the inevitable result. Of course for non-selective oxida-
tion reactions involved in pollution control these kinetic
constraints do not present an immediate problem, but in
this case total oxidation is required, and trace levels of
non-converted pollutants cannot be tolerated. In this
paper some initial thoughts will be given to the factors
that are currently considered to be important in the
design of selective oxidation catalysts. In the second part
attention will be focussed on the use of gold as a new
selective oxidation catalyst and examples will be given of
its versatility.
2. Designing oxidation catalysts
Oxidation lies at the heart of many important
chemical processes. Examples of important reactions are
given in table 1 [1] and it is clear that there are many
* To whom correspondence should be addressed.
E-mail: hutch@cf.ac.uk
importance. Many of these were designed using trial and
error methods, but more recently the advent of high
throughput testing has opened up the possibilities of
generic methodology in the design of catalysts. It is
important that we embrace new approaches in the
selection and design of suitable catalysts. For example it
has been reported that Mittasch, Haber and Bosch tes-
ted ca. 6500 formulations in their quest for the ammonia
synthesis catalysts [2], and as we know now they were
very successful and the design has only been marginally
changed since. However, it is essential that we are e-
cient and if one considers the number of potentially
active elements for oxidation reactions, it rapidly
becomes clear that we have to be very selective indeed.
This has been well recognised in the eld of organic
synthesis as Scheidtmann et al. [2] showed the magni-
tude of the task of covering all the potential bases. He
considered the task of synthesising all possible molecules
with just ve elements: C, H, O, S, N. Preparation of
1 mg of the possible 1063 compounds would exceed the
mass of the known universe by two orders of magnitude,
not to mention that the time required would exceed the
known age of our universe by ca. 1050 years if each
synthesis could be completed in a microsecond.
Recently, an evolutionary approach to the discovery
and optimisation of catalysts has been suggested by
Wolf et al. [3]. In their studies they showed by selecting
catalysts that exceeded set performance limits they were
able to design a catalyst (V0.22Mg0.47Mo0.11Ga0.20Ox
selected from testing formulations comprising 4 out of a

1022-5528/06/08000223/0
2006 Springer Science+Business Media, Inc.

224 G.J. Hutchings et al./Au/C a versatile catalyst

Table 1 precisely, what is the nature of the active site? This is a

Common oxidation processes [1] far more complex system than it appears at rst site.
Reaction Catalyst
Model studies can be instructive based on surface sci-
ence approaches or using well-dened mesoporous or
Total oxidation microporous materials, but typically oxides or sup-
carbon monoxide carbon CuMnO4, Au/MOx at 25 C ported metal catalysts comprise a range of potential
dioxide Pt/MOx > 200 C
sulfur dioxide sulfur Pt, V2O5
active sites. For example, at the present time, there is an
trioxide immense debate concerning the nature of the active site in
hydrocarbons, carbon Three way car exhaust supported gold catalysts [7] and it is possible that cationic
monoxide catalyst Pt, Pd gold may play a valuable role in the oxidation of CO
and nitrogen oxides using nanocrystalline gold. Another area of controversy
carbon dioxide
water and nitrogen
concerns the nature of the active surface in vanadium
CO, VOCs CO2, H2O Pt, Pd/Al2O3 phosphates that are active catalysts for the oxidation of
Selective oxidation butane to maleic anhydride. In this case it is possible that
butane maleic anhydride Vanadium phosphates the active surface may be an amorphous overlayer, and if
propene acrolein MoOBi2O, USb3O10, FeSbO4 this is the case dierent approaches are required to ensure
propene acrylonitrile MoBi2O6, USb3O10, FeSbO4
o-xylene phthalic anhydride V2O5
more eective catalysts are designed [1].
methanol formaldehyde Iron molybdate, Ag It is clear that progress is being made in the design of
ethane ethylene oxide Ag selective oxidation catalysts and one are that has fasci-
ethyl benzene styrene V2O5/TiO2 nated researchers lately is the use of nanocrystalline gold
butene butadiene BiMo2O6 and this is discussed in the next section.
benzene phenol Fe-ZSM-5
propene propene oxide TS-1
toluene benzaldehyde Vanadium phosphates
isobutene methacrylic acid Molybdophosphoric
heteropolyacids
3. Gold catalysis: Au/C a versatile oxidation catalyst
ethane acetic acid Pd-silicotungstic Since the mid 1990s, there has been a dramatic
heteropolyacid
increase in research attention focussed on the use of
supported gold catalysts for redox reactions. Initial
possible total of 8 elements) for the oxidative dehydro- interest in gold catalysts involved two observations.
genation of propane that gave a yield of 9% (selectivity First, and foremost, Haruta and co-workers [8] identi-
57.4%). This was achieved using only 6001000 experi- ed that nanocrystals of Au supported on oxides were
ments out of a total of 20,900 tests theoretically required. highly eective as a catalyst for Co oxidation at sub-
Having found a suitable formulation on which to ambient temperature. Second, Hutchings [9] predicted
base future design strategies there are two questions that that cationic gold would be the most eective catalyst
should be addressed as the whole process of catalyst for the hydrochlorination of acetylene, and this predic-
optimisation and development takes place. First, one tion was subsequently experimentally veried [10]. In the
should consider is the reaction a heterogeneously last few years, the number of publications appearing on
catalysed process? There exist two possible problem gold catalysis involving both homogeneously and het-
areas here. One concerns the possible initiation of the erogeneously catalysed reactions has risen exponen-
reaction on the catalyst surface with the bulk of the tially, and these publication statistics have recently been
reactions occurring in the gas or liquid phase. This is published by Hashmi [11]. With respect to heteroge-
typical of radical reactions, e.g. the oxidation of meth- neously catalysed reactions, most of the publications
ane [4]. In cases such as this the control of the selectivity concern the oxidation of CO at ambient temperature,
often lies in controlling these radical processes and and these data have been reviewed by Bond and
often-marked changes in catalyst formulation have little Thompson [12,13] and by Haruta [7]. Much less atten-
or no eect [5]. The second aspect concerns catalyst tion has focussed on selective oxidation, and yet sup-
stability, since the catalyst loaded to the reactor may be ported gold catalysts have been found to be very
unstable under the reaction conditions. This can be a eective for a broad range of selective oxidation
major problem with liquid phase reactants as demon- reactions. Haruta and co-workers [14] and Moulijn and
strated by Sheldon et al. [6]. If these two factors are co-workers [15] have shown that Au supported on
overlooked it can be dicult to make any progress with microporous or mesoporous titanium silicate structures
the design of selective oxidation catalysts, since if either is very eective for the oxidation of propene to propene
of these factors operate with the reaction of interest then oxide with O2/H2 mixtures, and there is currently sig-
it is clear that the key reactions and intermediates will nicant industrial interest in this reaction. The seminal
probably not be occurring at the solid/gas or solid/liquid studies of Rossi and Prati [1619] have shown that
interface. The second question that should be addressed supported Au catalysts are eective for the oxidation of
is what is the active surface of the catalyst or, more alcohols in the liquid phase with O2 to form monoacids
 G.J. Hutchings et al./Au/C a versatile catalyst
when a base is present. Biella and Rossi [20] extended
this to show that the same catalysts can be used with gas
phase reactants and aldehydes could be formed in high
selectivity. Subsequently, we showed [21,22] that Au/C
catalysts could be very selective for glycerol oxidation to
glycerate. More recently, we have shown that Au/Al2O3
catalysts are selective for the oxidation of H2 with
molecular oxygen to form hydrogen peroxide [23,24].
These examples demonstrate the immense potential of
gold catalysts for selective oxidation reactions.
In this paper, we demonstrate that Au/C can be very
versatile as heterogeneous oxidation catalysts and
demonstrate that this catalyst is useful for four reac-
tions, namely (a) selective oxidation of glycerol to gly-
cerate; (b) the oxidation of cyclohexane to
cyclohexanone and cyclohexanol; (c) the oxidation of
H2/O2 mixtures to hydrogen peroxide, and (d) the oxi-
dation of benzyl alcohol to benzaldehyde.
3.1. Experimental methods
3.1.1. Preparation of Au/C catalysts
Two methods were used to prepare catalysts.
Reductionprecipitation method 1 wt% gold catalysts
supported on activated carbon and graphite were pre-
pared using this method as follows. The carbon support
(graphite or activated carbon, Johnson Matthey,
113.2 g) was stirred in demineralised water (1 L) for
15 min. An aqueous solution of HAuCl4 (41.94% Au,
Johnson Matthey, 2.38 g) in water (70 mL) was slowly
added drop-wise over a period of 30 min. The slurry was
then reuxed for 30 min, cooled and reduced with
formaldehyde over a period of 30 min. The slurry was
then reuxed for 30 min and, following cooling, the
catalyst was recovered by ltration and washed with
water until the washings contained no chloride. The
catalyst was dried for 16 h at 105 C. This method was
also used to prepare 0.25 wt% Au/C and 0.5 wt% Au/C
catalyst samples using smaller amounts of chloroauric
acid.
Impregnation method Catalysts were prepared using
incipient wetness impregnation of activated carbon with
aqueous solutions of HAuCl4 3H2O (STREM 99.9%).
Following impregnation, the catalysts were calcined at
400 C for 3 h (in a ow of 5% H2/argon 100 mL/min).
3.1.2. Catalyst testing
Alcohol oxidation For glycerol oxidation these reac-
tions were carried out using a 50 mL Parr autoclave.
The catalyst was suspended in an aqueous solution of
glycerol (0.6 mol/L, 20 mL). The autoclave was pres-
surised to the required pressure with oxygen and heated
to 60 C. The reaction mixture was stirred (1500 rpm)
for 3 h, following which the reaction mixture was
analysed. Products were analysed using HPLC with
ultraviolet and reective index detectors. Reactant and
products were separated on an ion exclusion column
225
(Alltech QA-1000) heated at 70 C. The eluent was a
solution of H2SO4 (4 10)4 mol/L). Reaction mixture
samples (10 lL) were diluted with a solution of an
internal standard (100 lL, 0.2 mol/L isobutanol) and
20 lL of this solution was analysed. It is essential that a
standard is added so that the carbon mass balance can
be determined. Attempts to nd a suitable internal
standard that could be added prior to reaction were
found to be unsuccessful as they were readily oxidised
under the reaction conditions. Hence, it was found
necessary to add the standard immediately following the
reaction as described.
The oxidation of benzyl alcohol was carried out in a
stirred reactor (100 mL, Autoclave Engineers Inline
MagneDrive III). The vessel was charged with alcohol
(40 mL) and catalyst (0.2 g). The autoclave was then
purged 5 times with oxygen leaving the vessel at 2 bar
gauge. The stirrer was set at 1500 rpm and the reaction
mixture was raised to the required temperature. Samples
from the reactor were taken periodically, via a sampling
system, ensuring that the volume purged before sam-
pling was higher than the tube volume, and analysed by
gas chromatography. The identication of the products
was made by combined use of gas chromatography and
mass spectrometry.
Cyclohexane oxidation Reactions were carried out
in a stirred glass reactor using equal quantities of
catalyst, cyclohexane and radical initiator in a 50 mL
round-bottomed ask with reux condenser connected.
Experiments were carried out in an oil bath heated to
70 C, with reaction mixtures stirred for the time as
required. Analysis of products in reactions was carried
out using GC (Varian Star 3400 CX) tted with DB-5
column and FID. Samples (200 lL) were added to a
standard (20 lL, 3-pentanone, 98% Aldrich) and 0.5 lL
of this sample was analysed using gas chromatography.
Hydrogen peroxide synthesis The catalysts were eval-
uated for the direct synthesis of hydrogen peroxide in a
Parr stainless steel autoclave with a nominal volume of
50 mL. Typically the autoclave was charged with cata-
lyst (10 mg), solvent (CH3OH, 5.6 g; H2O, 2.9 g),
purged three times with CO2 (3 MPa) and then lled
with 5% H2/CO2 and 25% O2/CO2 to give the required
O2/H2 ratio (H2/O2/CO2 = 3.7/6.6/89.7, total pressure
3.7 MPa). The reaction mixture was stirred (1200 rpm)
at 2 C for 30 min. H2 and O2 were analysed by on-line
gas chromatography and H2O2 was determined at the
end of the experiment using a titration method with
Ce(SO4)2.
CO oxidation The catalytic activity for CO oxidation
was determined in a xed bed quartz micro reactor,
operated at atmospheric pressure. The feed consisted of
CO/O2/N2 with a molar ratio of 0.5/19.9/79.6. The
combined ow rate was maintained at 22.5 mL min)1
and a constant catalyst loading of 50 mg was
employed. The catalyst temperature was maintained at
25 C by immersing the quartz bed in a thermostati-
226 G.J. Hutchings et al./Au/C a versatile catalyst
OH
HO
OH
GLYA O
HO OH
GLY O
HO
DHA
cally controlled water bath. Catalysts were tested for a
minimum of 500 min and analysis of the reaction
product was carried out on-line using gas chromatog-
raphy. Conversion was calculated on the basis of CO2
concentration in the euent and carbon balances were
100 2%.
3.2. Oxidation of glycerol
The oxidation of polyols to chemical intermediates
represents a demanding target and is of immense
importance for the production of ne chemicals. Glyc-
erol is a highly functionalised molecule that is readily
available from biosustainable sources, for example it can
be obtained as a by-product of the utilisation of rape-
seed and sunower crops. The ready bioavailability of
glycerol makes it a particularly attractive starting point
for the synthesis of intermediates and a large number of
products can be obtained from glycerol oxidation
(scheme 1). One of the key problems is the potential
complexity of the products that can be formed and so
control of the reaction selectivity by careful design of the
catalyst is required. Glycerol oxidation, in aqueous
solution, using Pd and Pt catalysts tends to produce a
vast array of products and it has been noted that formic
acid, probably resulting from the formation of oxalic
acid, was also formed and under most conditions this is
the major product.
In our studies [21,22] we have studied the oxidation of
glycerol with dioxygen was also investigated using
1 wt% Au/C catalysts in an autoclave and the results
are given in table 2. NaOH was added as a base since, in
the absence of NaOH, no glycerol conversion was
observed. The role of NaOH in this reaction is worthy of
comment. It is considered that the rate-determining step
is the initial deprotonation of the primary alcohol group
and this is facilitated by the presence of base. In addi-
tion, as noted earlier, the carbon supports were also
inactive for glycerol oxidation under these conditions,
HO
OH
O
OH
OH HO OH
TARAC
O O
O
O
HO OH
HO OH
OH
O O
O
HYPAC MESAC
CO2
Scheme 1.
even when NaOH was present, hence the presence of
gold is essential. For all the data presented in table 2,
the carbon mass balance was 100% indicating that,
under these conditions, supported Au/C catalysts are
extremely selective for this reaction and no C1 or C2
by-products were detected. In addition, it is apparent
that the selectivity to glyceric acid and the glycerol
conversion are very dependent upon the glycerol/NaOH
ratio. In general, with high concentrations of NaOH,
exceptionally high selectivities to glyceric acid can be
observed. However, decreasing the concentration of
glycerol, and increasing the mass of the catalyst and the
concentration of oxygen, leads to the formation of tar-
tronic acid via consecutive oxidation of glyceric acid.
Interestingly, this product is stable with these catalysts.
It is apparent that, with careful control of the reaction
conditions, 100% selectivity to glyceric acid can be
obtained with 1 wt% Au/C. For comparison, the sup-
ported Pd/C and Pt/C always gave other C3 and C2
products in addition to glyceric acid and, in particular,
also gave some C1 by-products. In a nal set of experi-
ments, catalysts with lower Au concentrations were
investigated. For catalysts containing 0.25 or 0.5 wt%
Au supported on graphite, lower glycerol conversions
were observed (18 and 26%, respectively as compared to
54% for 1 wt% Au/graphite under the same conditions)
and lower selectivities to glyceric acid were also
observed.
3.3. Oxidation of cyclohexane
Activation of CH bonds in alkanes is known to be
very dicult to achieve selectively at temperatures below
100 C. To date, the lowest temperature for selective
oxidation of the alkane CH bond has been achieved by
Thomas et al. using transitional metal ions substituted
molecular sieve catalysts at 100 C [2527]. We therefore
wished to investigate the activation of CH bonds at
temperatures below this, and in particular we have
 G.J. Hutchings et al./Au/C a versatile catalyst 227

Table 2
Oxidation of glycerol using 1 wt% Au/C catalystsa

Catalyst Glycerol Po2 bar Glycerol/metal NaOH Glycerol Selectivity (%)

(mmol) mol ratio (mmol) conversion
(%) Glyceric acid Glyceraldehyde Tartronic acid

1 wt% Au/activated carbon 12 3 538b 12 56 100 0 0

1 wt% Au/graphite 12 3 538b 12 54 100 0 0
12 6 538b 12 72 86 2 12
12 6 538b 24 58 97 0 3
6 3 540c 12 56 93 0 7
6 3 540c 6 43 80 0 20
6 3 214d 6 59 63 0 12
6 3 214d 12 69 82 0 18
6 6 214d 6 58 67 0 33
6 6 214d 12 91 92 0 6
6 6 214d 0 0
a
60 C, 3 h, H2O (and 20 mL), stirring speed 1500 rpm; b220 mg catalyst; c217 mg catalyst; d450 mg catalyst.

examined the use of supported gold catalysts and we
have found that they can be eective at temperature as
low as 70 C.
The oxidation of cyclohexane to cyclohexanol and
cyclohexanone, which in a recent review has been
acknowledged to be a reaction that continues to be a
signicant challenge. The aerobic oxidation of cyclo-
hexane is central to the production of nylon-6 and
nylon-6,6 and the worldwide production exceeds
106 tonnes per annum. Commercially, the process is
operated at 150160 C with cobalt naphthenate as an
initiator for the radical oxidation process that gives 70
85% selectivity at 4% conversion. Operation at high
conversions leads to total oxidation and consequently
this large-scale commercial process has been designed to
operate at low conversion. There is clearly scope to
produce a more ecient process but given the current
focus on green chemistry the main scope is to design a
system that gives 100% specicity. One approach has
been to use hydrogen peroxide as oxidant, and promis-
ing results have been obtained. However, it is recognised
that the desired ideal oxidant is air (or its reactive
component dioxygen, O2) and the observation of high
selectivity with air has been more elusive which can be
attributed to the fact that air oxidations are intrinsically
non-selective and dicult to control.
Most recently, Zhao et al. [28,29] have shown that
gold can be active for the activation of cyclohexane at
150 C and selectivities of ca. 90% can be achieved for
the Au/ZSM-5 catalyst, and >90% for a Au/MCM-41
catalyst although an initial induction period was
apparent with these catalysts. It was also shown that
these gold catalysts can be reused but the activity
gradually declines and the selectivity shifts from cyclo-
hexanone to cyclohexanol. These studies show that
supported gold catalysts are indeed active for the acti-
vation of CH bonds but the temperature used for these
studies was 140160 C, which is signicantly higher
than the temperature range we wished to explore.
We have concentrated on attempting to activate
cyclohexane at temperatures well below 100 C, using
oxygen as oxidant, and in this paper we explore this for
a range of supported gold catalyst.
Our initial experiments [30] were carried out using a
range of polar and apolar solvents either using a glass
reactor at ambient pressure or using an autoclave at
0.3 MPa both using air as oxidant and with a range of
radical initiators with 1% Au/graphite as catalyst. Radi-
cal initiators were added since the industrial process is
known to be a radical chain reaction, and using our
reaction conditions and catalysts in the absence of radical
initiators no reaction was observed. We had previously
shown that this catalyst was very selective for the oxida-
tion of glycerol in the presence of base [21,22]. Although
cyclohexane conversion was observed, particularly with
methanol and water as solvents, no partial oxidation
products were observed. However, at 70 C when no
solvent was used selective products were observed in small
amounts when tertiary butyl hydroperoxide was used as
an initiator (table 3). Only cyclohexanol and cyclohex-
ananone were observed as products. The addition of 1,4-
diuorobenzene improves the observed selectivity but this
is by virtue of the relationship between selectivity and
conversion that is apparent for this reaction (gure 1). No
conversion was observed in the absence of gold, i.e. using
graphite alone or in the absence of catalyst but with all
other reaction components present, conrming that the
catalysis is intimately involved with the gold. In addition,
no conversion was observed in the absence of tertiary
butyl hydroperoxide indicating that the supported gold
nanocrystals alone could not activate dioxygen at this low
temperature. No conversion was observed in the absence
of dioxygen but with the gold catalyst and tertiary butyl
hydroperoxide being present, showing that the hydro-
peroxide alone is not involved in the oxidation chemistry.
3.4. Direct synthesis of hydrogen peroxide
In previous studies, the oxidation of propene to
propene oxide using O2/H2 has been shown to be
228 G.J. Hutchings et al./Au/C a versatile catalyst

Table 3
Cyclohexane oxidation without solventa

Catalystb Time (h) Additive Conv. (%) Selectivity (%)

Cyclohexanol Cyclohexanone Total

0.5% Au 17 6.0 11.0 6.2 17.2

0.5% Au 17 1,4-diuorobenzene 1.0 64.5 35.5 100
0.25% Au 17 4.7 9.5 5.8 15.3
0.25% Au 17 1,4-diuorobenzene 1.2 20.9 12.7 33.6
1% Au 17 3.7 14.4 8.7 23.1
1% Au 17 1,4-diuorobenzene 0.7 33.4 22.7 56.0
2% Au 17 7.3 5.9 4.0 9.9
2% Au 17 1,4-diuorobenzene 1.0 35.1 23.1 58.2
a
Reaction conditions: 70 C, 10 mL cyclohexane, 0.05 g additive, 0.12 g catalyst, 0.08 g tertiary butyl hydroperoxide.
b
All catalysts supported on carbon.

alloys there had been almost no academic interest in this

Figure 1. Time dependence of the conversion of cyclohexane and the
selectivity for cyclohexanol and cyclohexanone using 0.5% Au/
graphite catalyst at 70 C. Key: n: the conversion of cyclohexane
with 1,4-diuorobenzene; d: the conversion of cyclohexane without
1,4-diuorobenzene; m: the selectivity of cyclohexanol for reaction
with 1,4-diuorobenzene; : the selectivity of cyclohexanone for
reaction with 1,4-diuorobenzene; n: the selectivity of cyclohexanol
for reaction without additive; e: the selectivity of cyclohexanone for
reaction without additive.
possible, and very high selectivities to propene oxide
have been reported [14,15]. In this reaction the selective
oxidation is considered to occur via a surface hydro-
peroxy species formed in situ from O2/H2. This has
prompted us to study the formation of hydrogen per-
oxide by the direct oxidation of H2/O2 mixtures. We
have shown that AuPd alloys supported on alumina
can be very eective for the direct synthesis of hydrogen
peroxide and the addition of PdAu exerts a signicant
promotion eect in the observed rate of hydrogen per-
oxide synthesis [23,24]. As noted in our earlier papers,
the direct synthesis of hydrogen peroxide from the oxi-
dation of H2 with O2 has been a subject of intense
commercial interest for almost 100 years and all the
earlier eort concentrated on using Pd catalysts. In
contrast, until our recent study with supported AuPd
reaction.
At present, hydrogen peroxide is produced by the
sequential hydrogenation and oxidation of an alkyl
anthraquinone. This process is only economically viable
on a relatively large scale (46 104 tpa) and this
necessitates the transportation and storage of concen-
trated solutions of hydrogen peroxide since the reagent
is used as an oxidant, bleach or disinfectant on a rela-
tively small scale at any one time. The identication of a
direct route for the synthesis of hydrogen peroxide from
the reaction of dioxygen and hydrogen would be highly
benecial. For example, this presents the possibility of
small-scale distributed synthesis. At present, no com-
mercial process exists for the direct process, but interest
in this possibility is now apparent.
In our preceding papers concerning the direct syn-
thesis of H2O2 we have shown that catalysts based on
AuPd alloys supported on alumina can give signi-
cantly improvements in the rate of hydrogen peroxide
formation when compared with the Pd only catalyst
[23,24]. We have started to investigate the eect of
supports other than alumina, and in this paper report
the initial results using activated carbon as support. The
results are shown in table 4 and the results for the alu-
mina-supported catalysts are shown for comparison. It
is apparent that at 2 C the support is inactive for the
direct synthesis reaction, and the addition of gold alone
does not signicantly improve the rate of synthesis of
hydrogen peroxide. Indeed, the rate for the gold only
catalyst is much lower than when alumina is used as
support. The two Pd catalysts display very similar
activities, indicating that the role of the support in this
case is not a dominant feature. However, the addition of
AuPd induces a marked increase in the rate of hydro-
gen peroxide synthesis. This is more signicant for the
carbon support catalysts and the rate is almost double
that recorded for the alumina-supported catalyst. The
catalysts reported in this study have all been prepared by
calcination at 400 C and no leaching of Au or Pd is
observed under these experimental conditions. All these
 G.J. Hutchings et al./Au/C a versatile catalyst 229

Table 4 the presence of excess base. Against this background we

Catalytic performance of Au, AuPd and Pd catalystsa
Catalyst Productivity/
mol-H2O2/h/kgcat
5% Au/ C 0.5
2.5% Au2.5% Pd/C 34
5% Pd/C 12
5% Au/Al2O3 3.1
2.5% Au2.5% Pd/Al2O3 18
5% Pd/Al2O3 12
a
All catalysts calcined in air at 400 C for 3 h, all reactions 2 C in
methanol/water solvent.
catalysts are inactive for the oxidation of CO at ambient
temperature indicating that the active sites for selective
oxidation are dierent from those required for total
oxidation. The low activity of these Au/Al2O3 catalysts
is considered to be the size of the Au nanocrystals,
which is found to be ca. 25 nm with many larger parti-
cles, which are signicantly larger than the preferred Au
particle sizes in active CO oxidation catalysts of ca.
25 nm.
3.5. Oxidation of primary alcohols
The oxidation of primary alcohols to aldehydes is
widely recognised as a fundamental laboratory and
commercial procedure. The process is of immense
industrial synthetic interest as aldehydes are both valu-
able intermediates as well as being high value compo-
nents for the perfumery industry. At present many
oxidations of this type are carried out using stoichiom-
etric oxygen donors, e.g. chromate or permanganate,
that are expensive to operate and have toxicity issues.
Consequently, there has been signicant interest in the
development of catalytic approaches to this problem,
and in particular in the design of suitable heterogeneous
catalysts, many of which use H2O2 as the oxidant. Pd
catalysts have also been used but until recently these
catalysts have shown relatively low activity. Kaneda and
co-workers [31] have, however, shown that hydroxyap-
atite-supported Pd nanoclusters are highly eective and
give very high turnover frequencies in the oxidation of
benzyl alcohol. As noted earlier supported gold catalysts
are eective for the oxidation of polyols to monoacids in
Oxidation of alcohols using Au/Ca
decided to study the oxidation of primary alcohols using
CO conv./%
supported Au catalysts under solvent free conditions
and in the absence of base. In this paper we present our
initial observations showing that Au/C catalysts have
<1 signicant potential for the selective oxidation of pri-
<1
<1
mary alcohols to aldehydes.
<1 The results for the oxidation of benzyl alcohol, octan-
<1 1-ol and geraniol using oxygen are shown in table 5.
<1 Although the Au/C catalyst is inactive with octan-1-ol,
we have observed some activity with benzyl alcohol and
geraniol for reaction under solvent free conditions at
100 C. With benzyl alcohol we observe very high
selectivities for the aldehydes and we consider these
results demonstrate that gold catalysts have signicant
potential and we now are attempting to improve the
activity of supported gold catalysts. The results for
geraniol show much higher activity. At low conversion,
cis- and trans-citral were the main products, but at
higher conversions, we identied many products such as
b-pinene, limonene, c-terpinene, linalool, nerol and
some traces of geranic acid. For high conversions some
condensation products with M 2
MGeraniol  18
were detected. These products were likely formed by
acid-catalysed isomerisation. A key nding in our study
is that no gold is lost from the catalysts during use under
solvent free conditions. Previously Biella and Rossi [20]
have shown that supported gold catalysts can oxidise
alcohols in the gas phase at >200 C, and again alde-
hydes are observed in very high selectivity. Most
recently Corma and co-workers [32] have shown that
Au/CeO2 where the CeO2 is nanocrystalline can give
very high rates and selectivities for the oxidation of
alcohols, mainly secondary alcohols, to their corre-
sponding keto compound. Hence, we consider that the
use of gold catalysts for selective oxidation of alcohols
to aldehydes and ketones, or in the presence of base to
acids, will be a growth area for gold catalysis.
4. Concluding comments
The design of selective oxidation catalysts requires
attention to a number of details. These include how the
Table 5

Alcohol 3 h reaction data S0.5b S1.0 S1.5 [Au] %c

Conv. (%) Sel. (%)b

Benzyl alcohol 2.3 90.4 88.6 88.9 88.7 0

Octan-1-ol 0 0
Geraniol 17.5 d 0
a
Reaction conditions: alcohol (40 mL), catalyst (0.2 g), 1500 rpm, 100 C, Po2 2 bar.
b
Selectivity to the aldehydes, the ester being the only other observed product, Sx selectivity to the aldehyde at x% benzyl alcohol conversion.
c
Percentage of gold leached from the catalyst.
d
Selectivity: trans-citral 12.1%, cis-citral 65.2%, nerol 6.2%.
230 G.J. Hutchings et al./Au/C a versatile catalyst
discovery programme will be structured, for example
can high throughput methodology or evolutionary
design programmes be utilised? Once catalysis has been
observed it is essential to consider the role of homoge-
neous reactions versus the desired heterogeneously ca-
talysed reactions. Homogeneous chemistry, occurring
either as a result of radical processes or catalyst insta-
bility, can mask genuine heterogeneously catalysed
processes and lead to non-fruitful research lines being
investigated. Against this background we have shown
that Au/C is a very versatile oxidation catalyst and can
selective oxidise alcohols, alkanes and hydrogen using
molecular oxygen and high selectivities can be observed.
Consequently, we anticipate further discoveries for
catalysis by gold, particularly for selective oxidation of
alkenes and alcohols.
Acknowledgments
This work formed part of the EU AURICAT project
(Contract HPRN-CT-2002-00174) and the ATHENA
project sponsored by the EPSRC and Johnson Matthey
and we thank them for funding this research. In addition
we thank the World Gold Council who have provided
sponsorship for the studentship of JE under the GROW
scheme.
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