Catal Lett (2011) 141:198–206

DOI 10.1007/s10562-010-0470-5

The Catalytic Use of Supported Gold Nanoparticles for Styrene

Synthesis Via Oxidative Dehydrogenation of Ethylbenzene
Jie Xu • Jun Huang • Yong-Mei Liu •
Yong Cao • Yong-Xin Li • Kang-Nian Fan

Received: 16 August 2010 / Accepted: 8 October 2010 / Published online: 26 October 2010
Ó Springer Science+Business Media, LLC 2010

Abstract A series of supported gold catalysts have been 1 Introduction

prepared and tested as a new type of catalyst for the oxi-
dative dehydrogenation of ethylbenzene to styrene. The In the past decade, catalysis by gold has emerged as one of
effects of the supports (a-Mn2O3, Fe2O3, TiO2, Al2O3, and the most intensively studied topics in chemistry. Au was
CeO2), preparation methods, gold loadings, and reaction historically considered to be chemically inert and hence a
conditions have been investigated. Among the catalysts poor catalyst [1, 2]. However, when finely divided as small
tested, the Au/CeO2 sample containing a 6.0 wt% gold particles (B5 nm) and suitably deposited onto an oxide
content prepared via a routine deposition–precipitation support [3, 4], Au could become a highly active and
method exhibited the highest ethylbenzene conversion selective catalyst in many reactions including oxidation
(66.9%) and remarkable styrene selectivity (91.0%). The [5–7], hydrogenation [8], selective isomerization [9] and
superior catalytic performance of the Au/CeO2 catalysts one-pot multistep reactions [10–12]. The outstanding cat-
can be attributed to a dramatic increase in the oxygen alytic ability of Au is related to the size and shape of the
mobility and storage capacity of the parent CeO2 material nanoparticles (NPs), the degree of coordinative unsatura-
in association with the closely contacted Au nanoparticles, tion of the Au atoms, and the interactions between Au and
which is confirmed by the TPR, total OSC, and XPS the oxide support [2–4]. Of particular interest to the current
measurements. chemical community is the Au-catalyzed selective oxida-
tion, which is believed to be essential for the development
Keywords Gold
Ceria
Oxidative dehydrogenation of new alternative and greener routes toward sustainability
(ODH)
Ethylbenzene [7, 13]. One recent focus in this area is to expand the scope
of the selective aerobic oxidations [5–7] that can be effi-
ciently catalyzed by supported Au NPs. In this context,
several liquid phase aerobic oxidations, including the
selective oxidation of alcohols [13–16], aldehydes [17],
amines [12, 18, 19], oximes [20] and olefinic hydrocarbons
Electronic supplementary material The online version of this [7, 13] have been developed. Despite significant research
article (doi:10.1007/s10562-010-0470-5) contains supplementary
material, which is available to authorized users. effort, there have been few studies on the selective oxi-
dation of less reactive hydrocarbons in the gas phase over
J. Xu
Y.-X. Li (&) the supported Au NPs [21, 22], probably due to the fact that
College of Chemistry and Chemical Engineering, Changzhou
both the reactants and products are prone to undesired
University, Gehu Road 1, Changzhou, Jiangsu 213164,
People’s Republic of China combustion in the presence of molecular oxygen at high
e-mail: liyx@em.jpu.edu.cn temperatures [23–25].
Styrene (ST) is one of the most important monomers
J. Huang
Y.-M. Liu
Y. Cao
K.-N. Fan
extensively used in the chemical industry for the manu-
Shanghai Key Laboratory of Molecular Catalysis and Innovative
Materials, Department of Chemistry, Fudan University, facture of polymers, copolymers and reinforced plastics
Shanghai 200433, People’s Republic of China [26]. In 2009, the worldwide production of ST was more

123
Catalytic Use of Supported Gold Nanoparticles 199

than 23 megatons (http://www.sriconsulting.com/WP/Pub DP-derived materials at 450 °C for 4 h in 5 vol%H2/Ar

lic/Reports/styrene/). Most of the ST monomer is com- gas. The final catalyst is denoted as nAu/CeO2-DP here-
mercially produced by means of the direct catalytic dehy- inafter where DP denotes the routine NaOH-mediated DP
drogenation (DH) of ethylbenzene (EB) at high reaction method, n represents the nominal Au loading.
temperatures (600–650 °C), with multi-promoted potas- To investigate the effect of preparation method on Au
sium-iron oxide as a catalyst [27, 28]. Due to its highly ODH activity, two additional 4 wt% Au/CeO2 samples
endothermic nature, this traditional route suffers from were prepared by urea-mediated deposition–precipitation
several pronounced disadvantages such as intensive energy (UDP) and conventional wet impregnation (IMP) methods.
consumption and rapid coking. In the last few years, con- In addition, a Au/a-Mn2O3 catalyst was prepared, as
siderable research efforts have been directed toward the Au/a-Mn2O3 catalysts had been reported to show good low
development of less energy-intensive processes for the temperature CO activity [37]. Au was deposited to the
production of ST [26]. The catalytic oxidative dehydro- a-Mn2O3 support by the UDP method. A further series of
genation (ODH) of EB in the presence of air or molecular gold catalysts including Au/TiO2 (Type A, Lot no.
oxygen (O2) is an attractive alternative to the traditional Au/TiO2 #02-1), and Au/Fe2O3 (Type C, Lot no. Au/Fe2O3
DH process [29–31], which is thermodynamically favored #02-5) were supplied by the World Gold Council,
at much lower temperatures and usually does not lead to Au/Al2O3 (catalogue no. 79-0160) was provided by Mintek.
the formation of coke. However, this selective oxidation is
particularly challenging, given the high reactivity of ST 2.2 Characterization of Catalysts
toward further oxidation.
To date, the most promising catalysts suggested for this Structural analysis of the various Au/CeO2 catalysts was
process have been confined to several carbon nanostruc- carried out on a Bruker D8 Advance X-ray diffractometer
tures including onion like carbon (OLC) [30, 32] or carbon equipped with a graphite monochromator, operating at
nanofibers (CNF) [33, 34]. Nevertheless, the fine powdered 40 kV and 40 mA and employing nickel-filtered Cu-Ka
nature, and intrinsically low resistance to combustion of the radiation (k = 1.5406 Å). The morphologies of all
carbon-based nanomaterials have greatly hindered their Au/CeO2 catalysts were studied by JEOL 2010 electron
practical applications [35]. Very recently, we have reported microscope. The bulk loading amount of Au in all
that high surface area (180 m2 g-1) mesostructured ceria Au/CeO2 catalysts were measured by inductively coupled
material featuring superior low temperature redox proper- plasma atomic emission spectroscopy (ICP-AES). Tem-
ties can catalyze the ODH of EB at temperatures around perature programmed reduction (TPR) profiles were
450 °C [36]. In the present work, we report the develop- obtained on a homemade apparatus. The samples were
ment of new efficient ceria supported gold catalyst system pretreated in a mixed gas (O2/N2 = 1/8) at 450 °C for
exhibiting significantly enhanced activity and stability for 30 min and cooled to room temperature. Subsequently, the
the ODH of EB. Our results have shown that the intro- samples were reduced with 5 vol% H2/Ar at 40 mL min-1
duction of gold nanoparticles can lead to a dramatic with a ramping rate of 5 °C min-1 to ca. 900 °C. The H2
increase in the oxygen mobility and oxygen storage consumption was monitored by an on-line thermal con-
capacity of the parent CeO2 material, which makes the ductivity detector (TCD). X-ray photoelectron spectra
catalysts highly active and stable for the reaction. (XPS) analysis was performed on a Perkin Elmer PHI
5000C spectrometer using Mg Ka radiation (1253.6 eV,
pass energy of 20.0 eV). The carbonaceous C 1s line
2 Experimental (284.6 eV) was used as the reference to calibrate the
binding energies (BE).
2.1 Catalyst Preparation
2.3 Catalytic Activity Measurements
A series of Au/CeO2 catalysts were prepared via a routine
deposition–precipitation (DP) method with NaOH as the The activity of the catalysts for ODH of EB was measured
precipitation agent [1]. Briefly, 1 g CeO2 (Evonic, Adnano in the temperature range of 350–500 °C at atmospheric
90, surface area: 90 m2 g-1) was added to an aqueous pressure using a fix-bed, down-flow, tubular quartz reactor
solution with desired amount of HAuCl4 and NaOH (i.d. 4 mm, length 400 mm). Each run used approximately
(NaOH/Au = 100, molar ratio). The suspension was then 50 mg of catalyst in the form of 60–80-mesh particles,
heated to 80 °C and stirred for 4 h, followed by filtering mixed with 300 mg of silicon carbide grains of similar size
and washing for several times with distilled water. The for best temperature control. EB was evaporated at 35 °C
resulting solid product was dried overnight and finally a in flowing N2 and subsequently mixed with O2. Unless
purple colored catalyst was obtained by reduction of the otherwise stated, the corresponding flow rate of EB, O2,

123
200 J. Xu et al.

and N2 is fixed at 0.5, 0.25 and 20 mL min-1 2.0Au/CeO2-DP (Table 1, entry 5) prepared by the routine
(GHSV = 19,972 h-1), respectively. Prior to testing, the DP method showed the highest activity in terms of the
catalysts were pretreated in a mixed gas (O2/N2 = 1/8) at selective formation of ST. The steady-state ST selectivity
450 °C for 30 min. The products were analyzed by an on- obtained was as high as 90.0% which indicated the success
line gas chromatograph (Agilent GC 6820). Permanent in depressing secondary oxidation, in sharp contrast to what
gases (O2, CO, CO2) were separated using a TDX-01 was observed for most of the other supported Au catalysts
column connected to a TCD detector and other reaction (Table 1, entries 1–4). A clear advantage of the Au/CeO2-
products were analyzed employing a FFAP column con- DP catalyst over other noble metals was also noticed when
nected to a FID detector. The catalytic data were acquired the reaction was performed using Pt/CeO2 or Ru/CeO2
after 1 h on stream of the reaction. The carbon balance under otherwise identical conditions (Table 1, entries 6, 7).
closed to 100 ± 5% and was additionally monitored by the It is important to remark that in the presence of small
COx content after catalytic combustion of organic species amount of O2 (nO2/nEB = 0.5), the performances of
in a final total oxidation reactor. Au/CeO2 were comparable to or even higher than those of
the typical iron catalysts (Supporting Information, Table
2.4 Total OSC Measurement S1), noting that we did not introduce any steam in the ODH
tests. However, for the commercial DH process, steam (with
The total oxygen storage capacity (OSC) measurement was high steam/oil ratio (S/O)) as an inert diluent is always
tested at 450 °C. 25 mg ceria-supported Au catalyst diluted required to provide heat, to regenerate the iron-based active
with 300 mg silicon carbide grains of similar size was sites from coking and to shift the equilibrium conversion of
placed in a quartz U-shape reactor. The concentration of EB, which results in large energy consumption.
the three components (H2, H2O, and He) in the outlet gas Further detailed studies were carried out using the
was monitored by an on-line mass spectrometer (Balzers 2.0Au/CeO2-DP catalyst to gain insights into the catalytic
OmniStar, QMS 200). A sample was exposed to alternating requirements for the ODH of EB. First, the effect of the
H2 (40 mL min-1 for 10 s) and He (40 mL min-1 for 80 s) reaction temperature was investigated and is illustrated in
pulses, and the alternating pulsation lasted until the signal Fig. 1. The EB conversion increased rapidly as the reaction
intensity of H2 reached a balance (100 ± 5%). Total OSC temperature was raised from 350 to 450 °C but leveled off
was calculated by integrating the consumption of H2 [lmol at 500 °C, with the selectivity of ST decreases gradually
[O] g-1]. from ca. 97% to 85%. In all cases, ST was obtained as the
major product, accompanied by appreciable amounts of
COx and very small amount of other byproducts such as
3 Results and Discussion benzaldehyde or methyl benzyl alcohol. Presumably,
higher temperature should give rise to better catalytic
3.1 Catalytic Tests activity for the ODH reaction. However, as is well known
in the literature [2], higher reaction temperature (well
Initially, a range of Au catalysts supported on various above the Tammann temperature of bulk gold, see below)
inorganic supports were applied to the ODH of EB under a may also lead to the sintering or growth of Au NPs, which
previously established reaction condition at 450 °C [36]. As can greatly compromised the performance of 2.0Au/CeO2-
can be seen from Table 1, the chemical nature of the sup- DP under these conditions. Moreover, studies on the effect
port has a strong influence on the catalytic performance of of the oxygen concentration revealed that the stoichiome-
the Au NPs. Of the various Au-based catalysts tested, tric O2/EB ratio (nO2/nEB = 0.5) was the ratio of choice

Table 1 Catalytic performance

Entry Catalysts Au loading Conv. Selec. Yield
of various catalysts for ODH of
(wt%) (%) (%) (%)
EB
1 Au/a-Mn2O3 2.0 7.9 12.6 1.0
2 Au/Fe2O3 4.5 10.1 40.8 4.1
3 Au/TiO2 1.5 15.2 59.1 9.0
4 Au/Al2O3 1.5 12.1 44.3 5.4
a
Pt/CeO2, Ru/CeO2 prepared 5 2.0Au/CeO2-DP 2.0 32.7 90.0 29.4
by wet impregnation (IMP), see 6 Pt/CeOa2 2.0 8.4 17.5 1.5
supporting information for the 7 Ru/CeOa2 2.0 9.5 24.2 2.3
detailed preparation methods

123
Catalytic Use of Supported Gold Nanoparticles 201

60 100 To gain further insights into the function of Au, we have

90 investigated the effect of Au loading on the catalytic per-
50
80
formance. As shown in Table 2, EB could only be poorly
Conversion of EB (%)

converted over the parent ceria support [36], whereas the

Selectivity to ST (%)
40 70
introduction of Au remarkably enhanced EB conversion
60 and selectivity for the partial oxidation products. High
30
50 selectivity to ST was obtained over the Au/CeO2 catalysts
with higher Au content (Table 2, entries 2–4) and the ST
20 40
formation increased with the gold loading up to 6.0 wt%
30
10
Au. However, an even higher Au loading amount with
20 8.0 wt% would compromise the catalytic activity. As will
0 10
be discussed later, the undesired formation of larger Au
350 400 450 500 particles ([5 nm) may account for such activity deterio-
Temperature ( °C) ration. The best performance was observed for the catalyst
containing 6.0 wt% Au (Table 2, entry 4), which was
Fig. 1 Catalytic behavior of the 2.0Au/CeO2 at different reaction
temperatures characterized by high selectivity comparable to the best yet
reported for EB ODH [29, 34, 38]. Moreover, in a com-
parison of three different preparation methods (Table 2,
80 100
entries 3, 6, 7), it is observed that the Au/CeO2 catalyst
con. prepared by DP method is more effective. The evolution of
90
70
sel. the catalytic performance at 450 °C as a function of reac-
80
tion time for the Au/CeO2-DP catalysts is shown in Fig. 3.
Conversion of EB (%)

60
Selectivity to ST (%)

70
Remarkably, the 6.0 wt% Au/CeO2 was found to be stable
50
60 during the reaction, and the ST yield did not undergo
40 50 appreciable changes with the time on stream.
40
30
30 3.2 Catalyst Characterization
20
20
10 The ICP-AES analysis (Table 2) shows that the real
10
amount of gold deposited on CeO2 is ca. 10–25% lower
0 0
0.25 0.5 1.0 2.0 than the nominal Au loading, consistent with the known
O2:EB fact that only limited amount of gold contained in the
solution can be deposited onto an oxide support via the
Fig. 2 Effect of molar ratio of O2 to EB on the catalytic ODH routine DP method [3]. The specific surface areas for
performance of the 2.0 Au/CeO2-DP catalyst
the various Au/CeO2-DP catalysts were similar to those for
the parent support (Table 2). The XRD pattern of the
parent ceria (Fig. 4) show well-defined diffraction feature
(Fig. 2). It was clarified that both lower and higher O2/EB characteristics of the cubic fluorite structure of CeO2
ratios would lead to a great reduction in the reaction rate (JCPDS card no. 34-0394). After the deposition of Au NPs
for the selective formation of ST. onto the ceria support, an almost identical XRD pattern

Table 2 Catalytic performance

Entry Catalysts Actual Au Surface Conv. Selec. (%) Yield
of the Au/CeO2 catalysts for
loading area (%) a (%)
ODH of EB ST COx Others
(wt%) (m2 g)

1 CeO2 – 88 19.5 80.2 17.2 2.6 15.6

2 2.0Au/CeO2-DP 1.5 78 32.7 90.0 6.6 3.4 29.4
3 4.0Au/CeO2-DP 2.8 75 50.6 92.4 3.7 3.9 46.8
4 6.0Au/CeO2-DP 4.0 70 66.9 91.0 0.3 8.7 60.9
5 8.0Au/CeO2-DP 6.2 68 65.4 88.1 3.4 8.5 57.6
a
Benzene, benzaldehyde, and 6 4.0Au/CeO2-IMP 3.8 65 40.2 57.2 10.4 32.4 23.0
methylbenzyl alcohol based on 7 4.0Au/CeO2-UDP 3.2 70 47.0 57.4 8.5 34.1 26.9
GC analysis

123
202 J. Xu et al.

100 100 TEM was used as a complementary technique to

90 examine the structures of gold particles. Representative
80 80 TEM images for the various catalysts are shown in Fig. 5.
Conversion of EB (%)

Selectivity to ST (%)
70 In the case of the Au/CeO2-DP samples, the Au NPs were
60 60 small and evenly dispersed over the 2.0Au/CeO2-DP with
50 an average particle size of ca. 3.6 nm. With increasing gold
40 40 loading, a progressive increase in the Au particle size can
Conversion
30 Selectivity
be observed. A considerable fraction of Au particles with
20 20 particle size larger than 5.0 nm was detected over the
10
catalyst containing 8.0 wt% Au. The TEM analysis of the
0 0
4.0Au/CeO2-IMP as well as 4.0Au/CeO2-UDP also showed
0 30 60 90 120 150 180 210 240 270 300 the presence of appreciable fraction of Au particles larger
Time on stream (min) than 5 nm over the support, in good agreement with the
XRD data as described above. All these results strongly
Fig. 3 Time on stream of EB ODH on 6.0Au/CeO2-DP
suggest that the NaOH DP method is more suitable to
achieve a high dispersion of Au NPs with small Au particle
size (\5 nm) over the ceria support. Additionally, it is
interesting to point out that after 5 h on stream of the
4.0Au/CeO2-UDP
reaction at 450 °C, the size of Au NPs has not undergone
4.0Au/CeO2-IMP noticeable changes, which could partly explain the stability
of the catalyst. We note that this lack of agglomeration
indicates that, when properly prepared and in association
Intensity (a.u.)

8.0%Au/CeO2-DP
with a suitable support, supported gold NPs can serve as a
6.0Au/CeO2-DP
stable catalyst for high temperature applications, although
it is known that gold has a relatively low Tammann tem-
4.0Au/CeO2-DP perature (395 °C) [39]. Presumably, the presence of a
strong metal-support interaction (SMSI) between the gold
2.0Au/CeO2-DP particles and the underlying CeO2 support may play a key
role in stabilizing the Au particles [40, 41].
CeO2 TPR experiments were carried out to gain an insight into
20 30 40 50 60 70 80 90
the redox properties of the various catalysts. As shown in
Fig. 6, two main peaks at low (peak a) and high temper-
2 θ (°
ature (peak b) are observed for all samples, assignable to
Fig. 4 XRD patterns of Au/CeO2-DP, 4.0Au/CeO2-IMP and 4.0Au/ the reduction of surface- capping oxygen and bulk oxygen
CeO2-UDP samples species, respectively. While the blank ceria showed a broad
low temperature reduction profile in the range 250–500 °C,
the introduction of Au species drastically decreases the
was obtained for Au/CeO2-DP comparing with CeO2, temperature of the peak a. The lowest temperature (ca.
indicating that the crystalline structure and the average size 77 °C) was observed over 6.0Au/CeO2-DP, a feature sig-
of the crystalline domain of the CeO2 support are well nifying superior low temperature reducibility. In addition,
maintained in the gold samples. Moreover, no peaks due to OSC measurements at 450 °C revealed a limited OSC of
gold species were detected, except in the case of the 8.0Au/ ca. 140 lmol [O] g-1 over the parent ceria material
CeO2-DP sample, where a distinct metallic Au reflection (Fig. 7). This value is consistent with the broad literature
line at 2h = 38.2° appears. Figure 4 also compared the [42–44] showing that the reduction of ceria surface layers
effect of the preparation methods on the size of the Au is limited to 5.0%. When Au NPs were deposited onto the
NPs. It is revealed that the UDP- and IMP-derived 4.0Au/ ceria, the XP spectrum of the Au 4f7/2 core level shows a
CeO2 catalysts already show distinct metallic Au diffrac- predominant contribution from metallic Au0 at a binding
tion lines, in sharp contrast to the absence of any Au fea- energy of 84.0 eV [45] (Fig. 8). Notably, it was found that
tures as observed for the 4.0Au/CeO2-DP sample with a the loading of Au caused a significant modification in the
similar gold content. The average gold crystalline size, oxygen storage behavior of the ceria materials. These
calculated by Scherrer equation, was 5.3, 6.2 and 10.3 nm results can be rationalized by assuming that the presence of
for the 8.0Au/CeO2-DP, 4.0 Au/CeO2-UDP and 4.0Au/ small Au NPs can result in the favorable enhanced oxygen
CeO2-IMP samples, respectively. mobility in the surface layers of ceria, mostly due to the

123
Catalytic Use of Supported Gold Nanoparticles 203

(a)

45

40 (A)
35

Frequency (%)
30

25

20

15

10

0
2 3 4 5 6 7 8
Mean size (nm)

(b)

45

40 (B)
35
Frequency (%)

30

25

20

15

10

0
2 3 4 5 6 7 8
Mean size (nm)

(c)

40
(C)
35

30
Frequency (%)

25

20

15

10

0
2 3 4 5 6 7 8
Mean size (nm)

Fig. 5 TEM images of 2.0Au/CeO2-DP (a), 4.0Au/CeO2-DP (b), 6.0Au/CeO2-DP (c), 8.0Au/CeO2-DP (d), 4.0Au/CeO2-IMP (e), 4.0Au/CeO2-
UDP (f), and the spent 6.0Au/CeO2-DP (g) samples

creation of a high abundance of oxygen vacancies in ceria Bearing in the mind that the catalytic behaviors of ceria-
lattice, which are responsible for the considerably based materials is highly sensitive to the mobility or
enhanced reduction degrees as observed for the Au/CeO2 amount of the lattice oxygen, to gain further insight into the
catalysts. nature of the DP derived Au/CeO2 catalysts in relation to

123
204 J. Xu et al.

(d)

40 (D)

Frequency (%)
30

20

10

0
2 3 4 5 6 7 8

Mean size (nm)

(e) (F)

(g)

40 (G)
Frequency (%)

30

20

10

0
2 3 4 5 6 7 8
Mean size (nm)

Fig. 5 continued

their ODH activity, the total OSC of the various catalysts permitting a rational explanation for the positive effect of
are plotted against with the corresponding reaction rate. As Au loading on the performance of the catalyst. We there-
shown in Fig. 7, the amount of available lattice oxygen fore infer that the present ODH of EB over the Au/CeO2-
species in the Au/CeO2 material directly correlates the based catalysts may proceed via a simple redox mechanism
catalytic activity of CeO2 in the ODH of EB reaction, involving the Ce4?/Ce3? couple, in which the catalyst

123
Catalytic Use of Supported Gold Nanoparticles 205

77
undergoes reduction (by EB) and reoxidation (by O2)
cycles. In this sense, the overall reaction pathway can be
envisaged to involve a delicate redox interplay between Au
6.0Au/CeO2-DP
clusters and the CeO2 matrix during the EB ODH process,
i.e., the reaction proceeds via a facile Au-mediated oxygen-
Intensity (a.u.)

85
transfer mechanism in which the consumption and
4.0Au/CeO2-DP replenishment of the ceria lattice surface oxygen species
88 vicinal to Au NPs play a key role in the reaction process.
To testify this hypothesis, XPS studies on Au/CeO2 sub-
2.0Au/CeO2-DP
351 jected to sequential EB/O2 exposures were carried out. The
results show that the consumption and replenishment of the
CeO2 lattice oxygen, as reflected by the distinct atmospheric-
dependent variation of the ratio of Ce4?/Ce3? (Fig. S1) is
100 200 300 400 500 600 700 800 900
essential for this reaction.
Temperature ( °C)

Fig. 6 TPR profiles of the Au/CeO2-DP and CeO2 samples

4 Conclusions

20
In summary, a novel Au-decorated ceria catalyst, featured
Reaction rate 0.6 with superior low temperature catalytic performance, has
Reaction rate (mmol-ST g catal. h )

Total OSC
-1

been developed for the oxidative dehydrogenation of eth-

-1

Total OSC (mmol O g )

15 ylbenzene to styrene. Compare to other noble metal-oxide

0.5
support combinations, the Au/CeO2-DP catalysts prepared
0.4
via a routine deposition–precipitation method exhibited a
10 high activity and selectivity toward the reaction. In the
presence of small amount of O2 (nO2/nEB = 0.5), a stable
0.3
styrene yield over 60% can be obtained over the 6.0Au/
CeO2-DP catalyst at temperatures around 450 °C. Based on
-1

5
0.2
the TPR profiles and total OSC results, it was clarified that
the introduction of Au nanoparticles (B5 nm) has drasti-
0
0 2.0 4.0 6.0 8.0
0.1 cally enhanced the oxygen mobility and storage capacity of
the ceria, thus leading to the significant improvement of its
Au-loading amount (%)
catalytic activity. Furthermore, the XPS results implied that
Fig. 7 Correlation between the reaction rates of the Au/CeO2 the ODH of ethylbenzene over the Au/CeO2 catalyst may
catalysts with their corresponding total OSC at 450 °C proceed via a simple surface redox mechanism involving
the Ce4?/Ce3? couple.

0
Au 4f5/2
3+
Au 4f7/2 Au 4f7/2
0 Acknowledgments This work was financially supported by the
National Natural Science Foundation of China (20633030, 20721063,
87.7 eV 85.9 eV 84.0 eV
20803012, and 20873026), the National High Technology Research and
Development Program of China (2006AA03Z336), and the National
Basic Research Program of China (2009CB623506), Science & Tech-
nology Commission of Shanghai Municipality (08DZ2270500).
Intensity (a.u.)

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