Applied Catalysis B: Environmental 40 (2003) 43–49

Catalytic combustion of volatile organic compounds on

gold/cerium oxide catalysts
Salvatore Scirè a,∗ , Simona Minicò a , Carmelo Crisafulli a ,
Cristina Satriano a , Alessandro Pistone b
a Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, 95125 Catania, Italy
b Dipartimento di Chimica Industriale ed Ingegneria dei Materiali, Università di Messina,

Salita Sperone 31, 98166 Messina, Italy

Received 3 March 2002; received in revised form 29 May 2002; accepted 29 May 2002

Abstract
Catalytic combustion of some representative volatile organic compounds (VOCs) (2-propanol, methanol and toluene) was
investigated on gold/cerium oxide catalysts prepared by coprecipitation (CP) and deposition–precipitation (DP). The presence
of gold has been found to enhance the activity of cerium oxide towards the oxidation of the selected volatile organic compounds,
the extent of this effect depending on the preparation method of gold catalysts. On the basis of characterisation data (H2 -TPR,
X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), BET surface area) it has been suggested that the
catalytic activity of the Au/CeO2 system is related to the capacity of gold nanoparticles to weaken the surface Ce–O bonds
adjacent to Au atoms, thus enhancing the reactivity of the CeO2 surface capping oxygen which is involved in the volatile
organic compounds oxidation through a Mars-van Krevelen reaction mechanism.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Volatile organic compounds; Catalytic combustion; Gold catalysts; Cerium oxide; Methanol; 2-Propanol; Toluene

1. Introduction
Volatile organic compounds (VOCs), which are
emitted from many industrial processes and trans-
portation activities, are considered as an important
class of air pollutants [1]. Catalytic combustion is
one of the most promising technology for VOCs
abatement, due to its definitive character and save of
energy [1]. The major advantages of this approach are
that it can operate with dilute effluent streams (<1%
VOCs) and at lower temperatures than thermal oxi-
dation. Supported noble metals (Pt, Pd, Rh) or metal
∗ Corresponding author.
E-mail address: sscire@dipchi.unict.it (S. Scirè).
oxides (Cu, Cr, Mn) are typical catalysts for such an
application [1].
Recently, some of us have shown that Au/iron
oxide catalysts present a high activity towards the
catalytic oxidation of VOCs [2]. The catalytic be-
haviour of this system has been found to be de-
pendent on preparation method and pre-treatment
conditions used [3]. The high activity of Au/Fe2 O3
catalysts has been explained on the basis of the ca-
pacity of gold to increase the mobility of the iron
oxide lattice oxygen which is involved in the VOCs
oxidation through a Mars-van Krevelen mechanism
[2,4].
Ceria (CeO2 ) is a crucial component in the automo-
bile three-way catalysts primarily for its role in oxygen

0926-3373/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 0 2 ) 0 0 1 2 7 - 3
44 S. Scirè et al. / Applied Catalysis B: Environmental 40 (2003) 43–49
storage, taking up oxygen under oxidising conditions
and releasing it under reducing ones [5]. Nowadays,
the importance of ceria in catalysis is rapidly growing
with new applications in different fields [6]. Potential
uses of CeO2 for the removal of soot from diesel en-
gine exhaust, for the removal of organics from wastew-
aters and as an additive for combustion processes have
been described [6].
Noble metal-modified (Pt, Pd, Rh) cerium oxide
catalysts have been reported [5–8] to exhibit a higher
oxygen storage capacity and reducibility than pure ce-
ria, thus resulting in better catalytic performance. Gold
supported on ceria has been also described as a very
good catalyst for redox reactions, such as CO [9,10]
and CH4 oxidation [10]. More recently, Au/CeO2 was
found to be very active for low temperature water–gas
shift reaction [11].
Following these considerations in this paper, we
report a study on the catalytic oxidation of some
representative VOCs (2-propanol, methanol and tolu-
ene) on Au/cerium oxide catalysts. The influence
of two different preparation methods (coprecipita-
tion (CP) and deposition–precipitation (DP)) on the
performance of Au/CeO2 catalysts has been investi-
gated.
2. Experimental
Au/cerium oxide catalysts were prepared by copre-
cipitation or deposition–precipitation, using HAuCl4
(Fluka) and Ce(NO3 )3 ·6H2 O (Aldrich) as precursors.
In the case of the CP method, an aqueous mixture of
the precursors was poured at 7.5 ml/min rate into an
aqueous solution of Na2 CO3 (1 M and pH = 11.9)
maintained at 70 ◦ C under vigorous stirring (500 rpm).
In the DP method, after the pH of the aqueous solution
of HAuCl4 was adjusted to the value of 8 using 0.1 M
NaOH, cerium oxide, prepared as later described, was
added under vigorous stirring (500 rpm) to the gold so-
lution, keeping the slurry at 70 ◦ C for 2 h. Both in CP
and DP methods the obtained slurries were kept digest-
ing for 24 h, washed several times (until disappearance
of nitrates and chlorides), then dried under vacuum
at 70 ◦ C and finally ground before use. Cerium oxide
was prepared by precipitation from Ce(NO3 )3 ·6H2 O
following preparation conditions similar to those
employed for the coprecipitated Au/CeO2 catalyst.
Before catalytic activity tests and characterisation
measurements, all samples were calcined at 450 ◦ C
for 1 h by flowing a 10% O2 stream diluted in He.
Samples were coded as follows: AuCeCP for the cat-
alyst prepared by coprecipitation, AuCeDP for that
prepared by deposition–precipitation and CeO2 for the
pure cerium oxide. The gold content of the Au/cerium
oxide catalysts used in this work, measured by atomic
absorption, was 5.0 wt.% for AuCeDP and 4.7 wt.%
for AuCeCP.
Catalytic activity tests were performed in a conti-
nuous-flow fixed-bed microreactor, using 0.1 g of
catalyst (80–140 mesh) diluted with an inert glass
powder. The reactant mixture was fed to the reactor
by flowing a part of the He stream through a satu-
rator containing the VOC and then mixing with O2
and He before reaching the catalyst. The reactant
mixture was 0.7 vol.% VOC and 10 vol.% O2 , the
remainder being helium. A space velocity (GHSV) of
7.6 × 10−3 mol/(h gcat ) was always used. The effluent
gases were analysed on-line by a gas chromatograph,
equipped with a packed column with 10% FFAP on
Chromosorb W and FID detector, and by a quadrupole
mass spectrometer (VG quadrupoles). The carbon
balance was always higher than 95%.
Surface area measurements were carried out us-
ing the BET nitrogen adsorption method with a Sorp-
tomatic series 1990 (Thermo Quest). Before the tests
all samples were outgassed (10−3 Torr) at 120 ◦ C.
X-ray photoelectron spectroscopy (XPS) measure-
ments were performed with a Perkin-Elmer PHI
5600 ESCA/SAM spectrophotometer equipped with
a hemispherical analyser both a dual Al/Mg anode
and monochromatic Al source. The operating condi-
tions were kept constant at 13 keV and 300 W. Spec-
tra were obtained by using the Mg K␣1,2 radiation
(1253.6 eV) with a pass energy of 23.5 eV. The pres-
sure in the analysis chamber was about 10−8 Pa during
the analysis. In order to subtract the surface charging
effect, the C 1s hydrocarbon peak has been fixed,
in agreement with the literature, at a binding energy
of 285 eV.
X-ray powder diffraction (XRD) analysis of the
samples was performed with an APD 2000 (Italstruc-
ture) diffractometer using a Cu K␣ radiation. Diffrac-
tion peaks of crystalline phases were compared with
those of standard compounds reported in the JCPDS
Data File.
 S. Scirè et al. / Applied Catalysis B: Environmental 40 (2003) 43–49
Fig. 1. Conversion of 2-propanol and products distribution on
CeO2 (A), AuCeCP (B) and AuCeDP (C) catalysts.
3. Results and discussion
Fig. 1 shows the conversion of 2-propanol and the
yields to CO2 and acetone as a function of reaction
temperature, on Au/cerium oxide catalysts prepared by
coprecipitation (AuCeCP) or deposition–precipitation
45
(AuCeDP) and for comparison on the Au-free cerium
oxide (CeO2 ). It is possible to observe that on the
CeO2 sample (Fig. 1A), the oxidation of 2-propanol
starts at 160 ◦ C, reaching a total conversion at about
340 ◦ C. It must be reminded that CO2 , water and
acetone were the only products formed under the ex-
perimental conditions used. Acetone is formed at low
temperature with a nearly 100% selectivity, which
falls quickly to zero at higher temperatures with a cor-
responding increase of the selectivity to CO2 . Accord-
ing to the literature [2,12], it seems likely that acetone
is the first oxidation product and it is intermediate in
2-propanol combustion. However, our experimental
results do not allow to rule out that CO2 is also formed
by direct oxidation of the alcohol. It must be noted
that the formation of other products (acetaldehyde,
acetic acid and propene) has been reported in the
2-propanol oxidation on several metal oxides (Mn3 O4 ,
TiO2 , V2 O5 ) [12–14]. Analogously to that reported
in the case of the Au/Fe2 O3 system [2,4], also on the
cerium oxide based catalysts considered in the present
work, the lack of formation of these compounds is
probably due to the basic character of the oxide used.
The activity of the AuCeCP catalyst (Fig. 1B) is
slightly higher than that exhibited by CeO2 (Fig. 1A).
In fact, on AuCeCP, both the light-off temperature and
the temperature at which the CO2 formation arises are
shifted about 40 ◦ C lower than on the pure ceria. In
the case of the AuCeDP sample (Fig. 1C), the light-off
temperature is sensibly lower (about 80 ◦ C). Moreover,
on this sample CO2 begins to be formed at 100 ◦ C, i.e.
80 and 120 ◦ C lower compared to AuCeCP and CeO2 ,
respectively.
The conversion of methanol, as a function of reac-
tion temperature, on cerium oxide based catalysts is
reported in Fig. 2. It must be underlined that CO2 is
the only product revealed. The absence of intermediate
compounds in the case of methanol oxidation can be
probably explained considering that formic aldehyde
(which should be the intermediate oxidation product)
is a very reactive species which evolves easily to CO2
[2,14]. The figure shows that the presence of gold im-
proves the catalytic activity of pure cerium oxide to-
wards the combustion of methanol. Analogously to
that found in the 2-propanol oxidation, also in the ox-
idation of methanol, the sample prepared by DP is
more active than that prepared by CP. The same trend
is also observed in the toluene oxidation (Fig. 3). In
46 S. Scirè et al. / Applied Catalysis B: Environmental 40 (2003) 43–49

Fig. 2. Conversion of methanol on Au/CeO2 catalysts.

this latter case, the difference between the catalytic be-
haviour of AuCeDP and that of AuCeCP is more rel-
evant than that observed in the oxidation of alcohols.
In fact, on the AuCeDP catalyst, toluene conversion
starts at about 200 ◦ C approaching 100% at ca. 360 ◦ C,
whereas on AuCeCP and CeO2 catalysts the light-off
temperatures are, respectively, 200 and 300 ◦ C higher.
The catalytic activity results previously discussed
clearly indicate that gold enhances the combustion
activity of ceria. The presence of gold is more effec-
tive in improving the catalytic behaviour of cerium
oxide based catalysts when gold is added to ceria
by deposition–precipitation. In order to understand
the influence of the preparation method on the ac-
tivity of Au/CeO2 catalysts towards VOC oxida-
tion several characterisations (XRD, XPS, H2 -TPR
and surface area measurements) have been carried
out.

Fig. 3. Conversion of toluene on Au/CeO2 catalysts.

 S. Scirè et al. / Applied Catalysis B: Environmental 40 (2003) 43–49 47

Fig. 4. XRD profiles of Au/CeO2 catalysts.

XRD spectra of CeO2 , AuCeCP and AuCeDP are of gold on the surface compared to AuCeCP. This is
reported in Fig. 4. The XRD profile of the Au-free in accordance with literature data which report that
cerium oxide sample reveals the presence of diffrac- deposition–precipitation has the advantage over copre-
tion peaks related to CeO2 phase. On both gold cipitation to favour the location of gold on the surface,
containing catalysts, together with the characteristic thus avoiding that active species are buried within the
pattern of CeO2 , a small broad peak at about 38◦ , support [16].
attributed to metallic gold, can be also observed. The Fig. 6 reports temperature programmed reduc-
average size of gold particles, estimated from the tion (H2 -TPR) profiles carried out on cerium oxide
line-width of this peak by using the Sherrer equation, based catalysts. In the examined temperature range
was 6 nm for AuCeDP and 8 nm for AuCeCP. The (30–600 ◦ C), the CeO2 sample showed one reduction
formation of smaller gold particles by deposition–
precipitation compared to coprecipitation has been
reported on several Au/metal oxides catalysts [11,
15,16].
Fig. 5 reports XPS spectra, in the Au 4f region,
of the AuCeDP and AuCeCP samples. In this region,
each gold species shows two peaks due to the Au 4f7/2
and Au 4f5/2 transitions. On both samples, these peaks
are centred at 83.5 ± 0.2 and 87.0 ± 0.2 eV, respec-
tively, indicating the presence of gold in the metal-
lic state [3,15,17]. This is quite reasonable consider-
ing that gold samples have been calcined at 450 ◦ C. It
has been in fact reported that at calcination tempera-
tures higher than 300 ◦ C gold is present just as Au0
[3,18]. The quantitative XPS analysis of AuCeCP and
AuCeDP samples evidences that the atomic content
of gold on the surface of both samples is less than
1%. However, as shown in Fig. 5, the intensity ratio
of Au 4f peaks between DP and CP samples is about
3, indicating that AuCeDP contains a higher amount Fig. 5. XPS spectra of Au/CeO2 catalysts.
48 S. Scirè et al. / Applied Catalysis B: Environmental 40 (2003) 43–49
Fig. 6. H2 -TPR profiles of Au/CeO2 catalysts.
peak with a maximum at 520 ◦ C, which can be at-
tributed to the reduction of the surface capping oxygen
of ceria [19,20]. It must be reminded that the reduc-
tion of bulk oxygen of ceria has been reported to occur
at T > 700 ◦ C [19,20] and therefore it does not ap-
pear in TPR profiles of Fig. 6. On gold/cerium oxide
catalysts, the peak related to the reduction of surface
oxygen of ceria resulted to be shifted down to 240 and
140 ◦ C on AuCeCP and AuCeDP, respectively. This
indicates that the presence of gold facilitates the re-
duction of ceria surface oxygen species, with an effect
which is more relevant in the case of the DP sample.
Similar promotion effects on the CeO2 reducibility are
well known for noble metals (Pt, Rh, Pd) supported
on ceria [19,20]. A higher oxygen reducibility of ceria
has been also observed by Fu et al. on Au/CeO2 cat-
alysts and related to a weakening of the Ce–O bond
induced by gold [11]. An analogous effect of gold in
enhancing the reducibility of a metal oxide has been
reported on Au/Fe2 O3 catalysts [2]. Considering that
the reducibility of the lattice oxygen of a metal oxide
reflects the reactivity of this oxygen [2,21], H2 -TPR
results of Fig. 6 clearly indicates that the surface cap-
ping oxygen reactivity of investigated catalysts is in
the order: AuCeDP > AuCeCP > CeO2 . From Fig. 6
it can be also inferred that H2 consumption measured
on the AuCeDP sample is considerably higher than
that of AuCeCP and CeO2 catalysts. According to
the literature [22] this result can be explained con-
sidering that AuCeDP presents a higher surface area
(105 m2 /g) compared to AuCeCP (50 m2 /g) and CeO2
(45 m2 /g). This is confirmed by the fact that a cerium
oxide sample (HSACeO2 ) with a higher surface area
(95 m2 /g) showed an H2 -TPR profile (Fig. 6) with the
same reduction temperature of surface oxygens, but
with a higher H2 consumption compared to the CeO2
sample (45 m2 /g) used as catalyst in this work.
On the basis of these H2 -TPR results, it can be in-
ferred that the amount of reducible surface oxygen
species in the Au/CeO2 system is mainly controlled by
the specific area of ceria. The role of gold appears to be
that of modifying the properties of ceria, enhancing the
reducibility of CeO2 surface oxygen. It is highly prob-
able that the presence of gold causes a decrease in the
strength of the surface Ce–O bonds adjacent to gold
atoms [11,23], thus leading to a higher surface lattice
oxygen mobility and therefore to a higher reactivity
of these oxygens. In this context, in order that Au can
perform its positive function, it is essential that gold
particles are located on the surface of ceria. This ac-
counts for the higher oxygen reducibility observed in
the case of the DP sample (Fig. 6), for which a higher
amount of gold on the surface has been found (Fig. 5).
Accordingly, catalytic activity data showed that the
sample prepared by deposition–precipitation is sensi-
bly more active than that prepared by coprecipitation,
thus pointing out that there is a direct relationship be-
tween surface oxygen mobility of the gold/oxide sys-
tem and its catalytic activity towards the oxidation of
VOCs. This is quite reasonable considering that the
VOCs oxidation occurs through a Mars-van Krevelen
mechanism implying surface lattice oxide ions as the
active oxygen species [2,12]. Nevertheless, it must be
reminded that DP and CP samples exhibited slightly
different gold particle sizes, and this could somehow
affect the catalytic activity of these samples. It has
been, in fact, reported that the activity of gold catalysts
towards several reactions increases as the Au particle
size decreases [16]. Even though, with our data, it is
not possible to rule out this hypothesis, however, it
must be noted that, in the present case, the difference
in the particle dimensions of DP and CP samples is
 S. Scirè et al. / Applied Catalysis B: Environmental 40 (2003) 43–49
too small and, in our opinion, not sufficient to justify
the remarkably different catalytic behaviour observed.
Moreover, it is plausible that Au particle size is not
a crucial factor in the combustion of VOCs, since the
reactive oxygen for this reaction is provided by ce-
ria. A similar conclusion has been also reported in the
water gas shift reaction on Au/CeO2 catalysts [11].
A detailed investigation on the effect of gold size on
the catalytic combustion of VOCs on several Au/metal
oxide catalysts is currently in progress.
4. Conclusions
Au/CeO2 catalysts appear to be promising for ap-
plications in the field of the combustion of volatile
organic compounds. The high activity of the Au/CeO2
system might be related to the capacity of gold
nanoparticles to weaken the Ce–O bond, thus increas-
ing the mobility/reactivity of the surface lattice oxygen
which is involved in the volatile organic compounds
oxidation through a Mars-van Krevelen reaction mech-
anism. In this context, deposition–precipitation has
been found to be more suitable than coprecipitation
to obtain highly active Au/CeO2 catalysts, because
deposition–precipitation leads to gold nanoparticles
which are preferentially located on the surface of ceria.
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