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Fuel Processing Technology 137 (2015) 164169

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Fuel Processing Technology


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Uranium oxide-supported gold catalyst for watergas shift reaction


Yuan-Yuan Dong, Wei-Ping Liao, Zhang-Huai Suo
Institute of Applied Catalysis, Yantai University, 30 Qingquan Road, Yantai, 264005 Shangdong, China

a r t i c l e

i n f o

Article history:
Received 11 May 2014
Received in revised form 4 April 2015
Accepted 4 April 2015
Available online xxxx
Keywords:
Uranium oxide
Gold catalyst
Watergas shift reaction
Activity
Structure characterization

a b s t r a c t
The orange yellow UO3 and bottle green U3O8 phases were prepared by thermal decomposition of uranyl nitrate
hexahydrate at 400 C and 500 C, respectively. Gold catalysts supported on two oxides were prepared by
incipient wetness impregnation for watergas shift reaction. The gold catalysts were characterized by the techniques such as nitrogen physical adsorption, X-ray diffraction, temperature-programmed reduction, and X-ray
photoelectron spectroscopy. The Au/UO3 catalyst has both microporous and mesoporous structures while the
Au/U3O8 catalyst has only microporous structure. The presence of gold on the oxide surface greatly facilitates
the reduction of uranium oxide support. The active sites for watergas shift reaction are likely dominant metallic
gold with a small portion of oxidized gold species due to UO2+/U4+ redox property. The Au/UO3 catalyst shows
higher activity with 55% conversion of CO in comparison with Au/U3O8. High activity on Au/UO3 catalyst is attributed to facile the reducibility of UO3 and its high surface gold atomic concentration.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Watergas shift reaction (WGSR) is one of the most important
industrial processes for removing carbon monoxide impurity in
hydrogen feedstock in ammonia synthesis, stream reforming of
methanol and glycerol, and for adjusting the CO/H2 ratio in syngas
feeds [1,2]. Two types of industrial catalysts have been commercially
available for this reaction: a high-temperature iron-based catalyst
and a low-temperature copper-based catalyst. In recent years,
many attentions have been paid to using supported gold catalysts
for WGSR. Most of them makes great struggle to improve its catalytic
activity and understand the fundamental aspects related to the natures of active gold sites, role of support, and reaction mechanism
[38]. It is known that the catalytic performance of gold catalyst
depends highly on size and shape of gold nanoparticles, reducible
property of oxide support, gold-oxide interface interactions, and so
on. Andreeva et al. rst used Au/-Fe2 O3 catalyst for WGSR and
found that its activity is comparable with that of a conventional copper catalyst [9,10]. Fu et al. reported subsequently that Au/CeO2 catalyst had higher activity than other oxides-supported gold catalysts
[1113]. The good reducibility of and high oxygen storage of ceria
as well as a perturbation of the lattice constant of ceria caused by
the diffusion of Au ions into ceria were considered to be responsible
for its high activity [1416]. Obviously, the selection of an efcient
support is a decisive factor to provide good catalytic performance.
Uranium is an actinide element with six valence electrons. The ability
to attain high coordination numbers makes it as a promising catalytic
Corresponding author. Tel.: +86 535 6902514; fax: +86 535 6902233.
E-mail addresses: zhsuo@ytu.edu.cn, ytzhsuo@sina.com (Z.-H. Suo).

http://dx.doi.org/10.1016/j.fuproc.2015.04.018
0378-3820/ 2015 Elsevier B.V. All rights reserved.

material. Some studies have focused on uranium oxide as a catalyst or a


catalyst support [1722]. Many chemical processes can proceed efciently due to participation of the catalysts containing uranium oxides. For example, Collette et al. [17] prepared uranium oxides supported on SiO2,
TiO2, Al2O3, and MgO carriers for destructive reaction of volatile organic
compounds and suggested strong oxideoxide interaction. Pollington
et al. [18] and Campbell et al. [19] reported that UOx/Al2O3 catalyst exhibited comparable activity and selectivity to that of conventional supported
Pt catalysts in the catalytic reduction of NO. Berry et al. [20] found that
uranium oxide component could maintain a high dispersion of metallic
nickel in Ni/UOx catalyst and inhibit its sintering. Gordeeva et al.
[21] used porous U3O8 as a support to prepare very active Ni- and
Ru-catalysts for stream reforming of methane. Taylor et al. [22,23]
studied the activity and mechanism of uranium oxide catalysts for
the oxidative destruction of volatile organic compounds and of short
chain alkanes. Choudhary et al. [24,25] demonstrated that Au/U3O8 catalyst had higher selectivity and yield than other oxides-supported gold catalysts for selective oxidation of benzyl alcohols by molecular oxygen.
Recently Ismagilov et al. [26] reviewed the synthesis and characterization
of uranium-containing catalysts. The benet of uranium oxide-based catalyst is high activity, thermal stability, and resistance to poisoning by coke.
The facile uranium redox couple is responsible for high activity of uranium oxide catalyst. Therefore, uranium compounds form a notable class
of efcient catalysts and further studies of this catalytic system can open
a new vista.
In this study, we reported the preparation of uranium oxides and supported gold catalysts for the rst time in watergas shift reaction. The
techniques such as nitrogen adsorption, X-ray diffraction (XRD),
temperature-programmed reduction (TPR) and X-ray photoelectron
spectroscopy (XPS) were employed to understand the structure and

Y.-Y. Dong et al. / Fuel Processing Technology 137 (2015) 164169

the catalytic performance of gold nanoparticles supported on uranium


oxides.
2. Experimental procedure
2.1. Catalyst preparation
The most common uranium salt is uranyl nitrate hexahydrate
UO2(NO3)26H2O. In this study a series of uranium oxides were obtained through thermal decomposition of the salt in static air at the range of
300800 C. The obtained uranium oxides were denoted as UO3-T, in
which T expresses the calcination temperature of uranium salt.
Gold catalysts supported on UO3T were prepared by the impregnation method as the following procedures [27,28]. The solid UO3T was
rst impregnated with a basic solution of HAuCl4 overnight at room
temperature. The pH value of the solution was controlled to be 78
with a 2 mol/L NaOH solution. The obtained wet sample was immersed
in 6 mol/L NH3H2O solution and thereafter washed with distilled water
several times to remove residual chloride ions on the surface. After dried
in a vacuum at 80 C for 12 h, the sample was calcined in air at 300 C for
3 h. For each sample, the theoretic Au loading is 1.0 wt.% and the actual
loading was determined by atomic absorption spectroscopy to be
0.98 wt.%.
2.2. Catalytic activity testing
The watergas shift reaction was carried out in a xed-bed ow reactor at atmospheric pressure, as described in previous work [29]. The
feed gases consisted of 99.99% CO at 10 mL/min and water vapor with
31.1 kPa partial pressure. Reaction temperature was controlled at the
range of 150350 C. Prior to the reaction, 0.5 g gold catalyst was reduced in situ in pure H2 at 200 C for 2 h. The components in feed and
efuent gases were analyzed by gas chromatography and then a QIC20 quadruple mass spectrometer (Hiden Analytical Ltd.). The following
gas chromatography analysis conditions used: pure Ar as carrier gas,
column temperature 50 C, vaporization temperature 120 C, detector
temperature 120 C, a thermal conductivity detector with carbon
black molecular sieve as packed column (internal diameter 3 mm and
length 2 m). The catalytic activity was expressed as CO conversion and
calculated through the amount of H2 in the efuent gas according to
the following expression: CO conversion = n(H2)/n(CO)in in where
n(H2) is the amount of H2 produced by watergas shift reaction and
n(CO)in is the initial amount of CO.

165

800 C at 10 C/min. The 5A molecular sieve was mounted in the gas


line to remove water formed during the reduction prior to going into
the thermal conductivity detector.
XPS analyses of Au/UO3 and Au/U3O8 samples were nished on a
VG ESCA 210 X-ray photoelectron spectrometer using Mg K radiation with an energy of 1253.6 eV and a residual gas pressure of
2.7 10 6 Pa in the analysis chamber. The binding energy reference
of Au 4f, U 4f, and O 1s was taken at 285.0 eV for the C 1s peak arising
from adventitious carbon. The analyzer was operated in constant analyzer energy mode. The surface gold atomic concentration of each
sample was derived from corresponding peak area.
3. Results and discussion
3.1. Phase analyses of uranium oxide and supported gold catalyst
The oxides of uranium including a few species in which UO2
(brown), U3O8 (bottle green), and UO3 (orange-yellow) have been
well-characterized. The oxides readily interconvert at elevated temperatures. According to Heynen and Van der Baan [30], Mckee [31], the uranium salts such as uranyl nitrate and uranyl acetate can decompose to
form hexagonal UO3 phase at above 400 C. Heating UO3 in air to
650 C and higher obtains orthorhombic U3O8 phase. It will obtain
cubic face-centered UO2 and intermediate phases with heating U3O8
or UO3 in hydrogen stream at 700 C and higher. In this experiment, uranium oxides were prepared by thermal decomposition of uranyl nitrate
in air at 300800 C.
As shown in Fig. 1, the diffraction peaks at 2 = 18.4, 24.8, and
29.1 are assigned to monoclinic -UO3 phase (JCPDS 18-1428) and
the diffraction peaks at 2 = 21.4, 26.0, 26.5, 33.9, and 34.3 come
from orthorhombic -U3O8 phase (JCPDS 47-1493). Therefore, an orange yellow phase (UO3) is observed between 300 and 400 C. At
above 400 C, UO3 begins to lose oxygen via the following reaction [32]:
3UO3 (s) -U3O8 (s) + 1/2O2 (g). A bottle green phase (U3O8) was
obtained between 500 and 800 C. However, the diffraction peaks of
UO2 phase (JCPDS 41-1422), i.e., 2 = 28.4, 32.9, 46.9, 55.7, and
58.3, are not observed due to using calcination in air procedure during
the preparation [21,26,32]. In addition to the phase transition from UO3
to U3O8, the increase of calcination temperature also causes the increase
of the crystallization and particle size of uranium oxide.
The diffraction peaks of metallic gold (JCPDS 04-0784), i.e., 2 =
38.2, 44.4, and 64.6, are not obviously observed in Fig. 2 for all supported gold catalysts, indicating the gold particles are probably either
with small average size or highly dispersed on uranium oxide supports.

2.3. Catalyst characterizations


x:

UO3 ; o:

U3 O8

O
X

Intensity

The phase analyses of uranium oxides and supported gold catalysts


were performed on a Shimadzu-6100 X-ray powder diffractometer
with a monochromatic copper K radiation operated at 40 kV and
30 mA. The crystalline phase was identied according to the JCPDS powder diffraction le cards.
The textural property of each sample was measured by isothermal
adsorptiondesorption of nitrogen using a Quantachrome NOVA
3000e automated surface area and pore size analyzer. The specic surface area was determined by using nitrogen adsorption data from the
relative equilibrium pressure interval of 0.03 b P/P0 b 0.3, where P is
the equilibrium nitrogen pressure and P0 is the saturation nitrogen
pressure, according to BrunauerEmmettTeller method. The average
pore radius and the pore size distribution were calculated from the corresponding nitrogen isotherm using BarretJoynerHalenda method.
The H2 TPR proles of UO3, Au/UO3 and AuU3O8 samples were
obtained in TP-5000 multifunction adsorption instrument. Prior to the
reduction, 50 mg sample was baked at 60 C for 2 h and then cooled
down to room temperature in pure nitrogen and subsequently switched
in the reducing gas of 10% hydrogen in argon at 20 mL/min. After the
baseline became smooth, the temperature was linearly raised to

800
700
600
500
400
300

16

18

20

22

24

26

28

30

32

2 (o)
Fig. 1. XRD patterns of uranium oxides obtained at different temperatures (oC).

166

Y.-Y. Dong et al. / Fuel Processing Technology 137 (2015) 164169

x:
O

UO3 ; o:

0.5

U3O8

X
O
O

0.4
O

Pore volume (cm3/g)

Intensity

500
450
400

0.3

0.2

0.1

350
300

0.0

10

20

30

40

50

60

70

80

10

20

30

40

50

60

Pore diameter (nm)


Fig. 2. XRD patterns of gold catalysts supported on uranium oxides obtained at different
temperatures (oC).

When gold was supported on UO3-300, UO3-350, and UO3-400, respectively, only broad and weak diffraction peaks of -UO3 phase are observed. The -UO3 and -U3O8 phases coexist in Au/UO3-450 whereas
-U3O8 phase could only be observed in Au/UO3-500.

Fig. 4. Pore size distributions of Au/UO3 () and Au/U3O8 ().

higher temperature likely results in sintering of uranium oxide and consequently decrease of its intrinsic properties including average pore
size, total pore volume and specic surface area.
3.3. Reducible behaviors of uranium oxide and supported gold catalyst

3.2. Textual properties of uranium oxide and supported gold catalyst


The nitrogen adsorptiondesorption isotherms of Au/UO3 and
Au/U3O8 were shown in Fig. 3. According to the original IUPAC classication, both isotherms are similar to III type isotherm in shape.
Therefore, the interaction between the sorption agent and the catalyst surface is probably weak. The Au/U3O8 does not show a distinct
pore distribution of larger than 1 nm, corresponding to a microporous structure as shown in Fig. 4. However, the Au/UO3 shows both
a small pore of 2 nm and a large pore of 57 nm, which respectively
corresponds to a microporous and a mesoporous structure.
As Table 1 lists, raising calcination temperature from 300 to 800 C
can cause a decrease of the total pore volume from 0.04 to 0.01 cm3/g,
the average pore radius from 1.9 to 1.7 nm, and the specic surface
area from 6.0 to 2.8 m2/g. Kumar et al. reported that U3O8 on the outer
surface has fewer pores than UO3 [33]. Similar results were also reported [20,22,23,30]. So we believe that heat treatment of uranium oxide at
16

Volume adsorbed (cm3/g)

14

3.4. Surface analysis of supported gold catalyst

12

As demonstrated in Fig. 6, there is the Au 4f7/2 and Au 4f5/2 binding


energies of 84.3 and 88.2 eV for Au/UO3, respectively, and 84.7 and
88.8 eV for Au/U3O8. This veries that gold particles should be as metallic gold species with partially oxidized gold species, in agreement with

10
8
6

Table 1
Textural properties of Au catalysts supported on uranium oxides obtained at different
calcination temperatures.

4
2
0

The H2 TPR analysis was often used to study the redox behaviors of
reducible oxide and supported catalyst. For UO3 sample, two reduction
peaks were observed (Fig. 5). The low-temperature peak at 561 C is
assigned to the reduction of oxygen species adsorbed on the surface
and the high-temperature peak at 629 C is from the reduction of the
bulk lattice oxygen species. The addition of gold nanoparticles to UO3
enhances the reducibility of UO3 because the two reduction peaks of
UO3 shift to lower temperature, i.e., 392 C and 458 C. This is in agreement with the results on Ni/UO3 by Berry et al. [20]. For Au/U3O8 sample, there were also two reduction peaks appeared at 424 C and
592 C, respectively. Taylor et al. [22,23] reported that U3O8 has a single
reduction peak at 700 C. Therefore, the addition of gold nanoparticles
to U3O8 also enhances the reducibility of U3O8. However, the two reduction peaks in Au/U3O8 appear at higher temperatures in comparing with
Au/UO3, indicating Au/U3O8 is more difcult to be reduced. Consequently, Au/UO3 should have higher oxygen storage capacity. It can be seen
from the H2-TPR proles of them that the total hydrogen consumption
in Au/U3O8 is larger than in Au/UO3, which might be due to the different
structures formed during the calcination of uranium oxide.

0.0

0.2

0.4

0.6

0.8

1.0

Relative pressure (p/p0)


Fig. 3. Nitrogen adsorptiondesorption isotherms of Au/UO3 () and Au/U3O8 ().

Sample

Total pore volume


(cm3/g)

Average pore radius


(nm)

Specic surface area


(m2/g)

Au/UO3-300
Au/UO3-400
Au/U3O8
Au/U3O8-600
Au/U3O8-700
Au/U3O8-800

0.04
0.03
0.02
0.02
0.02
0.01

1.9
1.9
1.7
1.7
1.7
1.7

6.1
5.9
4.7
4.5
3.6
2.8

Y.-Y. Dong et al. / Fuel Processing Technology 137 (2015) 164169

167

Au/U 3O8
Au4f 7/2

Intensity

Hydrogen TCD signal

Au4f 7/2

(c)

Au/UO 3
(b)

80

(a)

82

100 200 300 400 500 600 700 800

84

86

88

U4f 7/2

90

92

U4f 5/2

Temperature (oC)

3.5. Activity of supported gold catalyst


This blank experiment shows that the Au-free uranium oxide itself is inactive at 350 C below. When gold nanoparticles are induced into inorganic oxide, the activity is affected greatly by the
oxide supports. The authors prepared SiO2 , Al2 O3 , UO 3, and CeO 2supported gold catalysts by the impregnation method and
compared their WGSR activities. The following activity order is

Au/U 3O8

Au/UO 3
376

380

384

388

392

396

O1s

O1s a
Intensity

our previous results [29,34]. The oxidized gold species might be Au+OH or AuOU. The interaction between gold and U3O8 support was
probably stronger because Au/U3O8 has higher Au 4f7/2 and Au 4f5/2
binding energies than Au/UO3. In addition, Au/U3O8 has a broader
Au 4f5/2 spectrum, indicating Au/U3O8 has different gold species from
Au/UO3. As listed in Table 2, Au/U3O8 has lower surface gold atomic concentration, i.e., 0.02%, and most gold particles go into the crystal phase of
Au/U3O8. A higher surface gold atomic concentration of Au/UO3,
i.e., 0.84%, conrms that the active metallic gold species are mainly on
the surface of Au/UO3.
The U 4f7/2 and U 4f5/2 binding energy of Au/UO3 are 381.5 and
392.3 eV, respectively, assigning to U6 + species [22,23,35,36]. The U
4f7/2 and U 4f5/2 binding energies of Au/U3O8 are 0.1 eV lower than
that of Au/UO3, indicating that the uranium species are in lower oxidized states than U4+ species. It may be because some loosely bounded
surface oxygen atoms are desorbed at higher calcination temperatures.
The O 1s XPS spectrum of Au/UO3 is tted into two peaks at 530.8
and 532.7 eV, as shown in Fig. 6. Schindler et al. [37] conrmed that
the resolved bands in the O 1s spectrum occur at distinct ranges in binding energy: bands for U\\O\\U occur at 529.6530.4 eV, bands for
O_U_O at 530.6531.4 eV, bands for O2 in the equatorial plane of
the uranyl polyhedra at 530.9532.2 eV; bands for OH groups in the
equatorial plane of the uranyl polyhedra at 532.0532.5 eV, bands of
H2O groups in the interstitial complex of the uranyl minerals H2Ointerst
at 533.0533.8 eV and bands of physisorbed H2O groups on the surface
of uranyl minerals H2Oadsorb at 534.8535.2 eV. So the present O 1s
spectrum in Au/UO3 assigned to O2 species and OH groups in the equatorial plane of the uranyl polyhedra, respectively. In comparison with
Au/UO3, the two O 1s spectra in Au/U3O8 shift to higher energy at
530.8 and 532.7 eV, respectively. It shows relatively higher U/O atomic
ratio (Table 2), possibly due to relative small oxygen vacancies in
U3O8. The concentrations of surface lattice oxygen are respectively
60% and 50% for Au/UO3 and Au/U3O8. More surface oxygen concentrations should be in favor of WGSR.

Intensity

Fig. 5. H2 TPR proles of (a) UO3, (b) Au/UO3, and (c) Au/U3O8.

Au/U 3O 8
Au/UO 3
524

526

528

530

532

534

536

538

Binding energy (eV)


Fig. 6. Au 4f, U 4f and O 1s XPS spectra of Au/UO3 and Au/U3O8.

obtained: Au/CeO 2 N Au/UO 3 N Au/Al 2 O 3 N Au/SiO 2 , as shown in


Fig. 7. In agreement with the reported results [3,4,1116], Au/CeO2
catalyst gives the highest WGSR activity.
Table 2
Binding energies of Au, U, and O elements and relative surface Au concentrations in Au/
UO3 and Au/U3O8.
Sample

Au/UO3
Au/U3O8
a

Binding energy (eV)


Au
4f7/2

Au
4f5/2

U
4f7/2

U
4f5/2

O 1s

O 1sa

84.4
84.6

88.2
88.7

381.6
381.5

392.3
392.5

530.8
530.9

532.7
532.8

Data were derived from corresponding XPS spectra.

U/O
atom
ratio

Surface Au
concentration
(%)a

0.25
0.26

0.84
0.02

168

Y.-Y. Dong et al. / Fuel Processing Technology 137 (2015) 164169

70

(d)

60

(c)

CO conversion (%)

50
40
30
20
10
0
100

(b)
(a)
150

200

250

300

350

400

Reaction temperature (oC)


Fig. 7. Watergas shift reaction activities of (a) Au/SiO2, (b) Au/Al2O3, (c) Au/UO3-300, and
(d) Au/CeO2.

The optimized reaction conditions (gas space velocity: 1200 h1,


water ow: 0.08 mL/min, catalyst activation: calcined at 300 C for 3 h
and then reduced at 200 C for 2 h) were obtained on Au/CeO2 catalyst.
Many studies on Au/CeO2 catalyst have been reported [3,4,1116] and
our attentions will focus on uranium oxide-supported gold catalysts.
The activity of Au/UO3T is as a function of calcination temperature (T) of uranium oxide. The highest activity with 54.6% CO conversion at 350 C was found in Au/UO 3 catalyst, as shown by Fig. 8.
However, gold catalyst with uranium oxide obtained at 500 C or
higher, i.e., Au/U 3O8 , shows very low activity (b 5% CO conversion
at 350 C). Mckee [31] also found that U3O8 had lower activity than
UO3 for oxidation of carbon. The activity order at reaction temperature of 350 C is summarized as follows: Au/UO 3 N Au/UO3 350 N Au/UO3-400 N Au/UO3-450 N Au/U3O8.
The activity order is easily correlated to the phase transition from
UO3 to U3O8 phases as well as its textual property. Smaller pore size
and specic surface area can make the transportation of the reactant
molecules to active reaction sites more difcult. Larger gold particles
could cause a blockage of the adsorption and spillover of the reactant
molecules, resulting in the decreasing of catalytic activity. Wang et al.
[38] demonstrated that the catalytic activity of porous U3O8 is distinctly
60

(a)
50

CO conversion (%)

(b)
40

(c)

30

(d)

superior to that of U3O8 nanorods for benzyl alcohol oxidation, although


two materials possess similar BET surface areas. In present experiment
each gold catalyst has very small specic surface area, as shown in
Table 1. So the difference in activity is likely caused by other factors
but not its textual property.
Ceria-supported gold catalysts have been reported to be good WGSR
active by many researchers [3,4,1116,3945]. However, there is no
generally accepted picture for the role of ceria and gold. Karpenko
et al. [39,40] found that there is no clear correlation among the three
properties Au3 + content, Ce3 + content and Au0 particle size and
WGSR activity. Deng et al. [41,42] considered that the diffusion of Au
ions into the ceria could cause a perturbation of the lattice constant of
the support during the heating step in the preparation process or thermal treatment. They considered that nonmetallic gold associated with
surface CeO groups, i.e., cationic metal centers (Au+), are responsible
for the activity. The existence and role of reduced metal nanoparticles
are debated. However, Rodriguez et al. [4345] thought that oxidized
gold species are not stable under the typical conditions of WGSR. The
active phase under the reaction conditions of WGSR should consist of
metallic gold nanoparticles on a partially reduced oxide support. The
rate determining steps of the reaction seem to occur at the goldceria
interface, with the active sites involving small gold clusters and O vacancies. The present results on Au/UOx shown there is a small fraction of
oxidized gold species, together with the most abundant metallic gold
particles, on the surfaces of both Au/UO3 and Au/U3O8. But the activities
of the two catalysts are very different.
Comparing with ceria-supported gold catalyst, less information on
uranium oxide and relevant gold catalyst were found. Uranium oxide
is a kind of reducible oxide. There is a UO2+/U4+ redox couple (E =
0.27 V). When gold is induced to uranium oxide, the reduction process
becomes facile, as indicated by Fig. 5. More oxygen vacancies are formed
due to the reducibility of uranium oxide. The oxygen vacancies can alter
the dispersion and chemical state of active gold species. The better reducibility and high oxygen storage capacity of UO3 with respect to
U3O8 are probably the driving force leading to the comparative high catalytic behavior. In addition to the facile UO2+/U4+ redox couple, goldenriched surface is also generated in Au/UO3. More active gold species
on the surface is in favor of WGSR. Our results support the view in
that the action of UO3 in Au/UO3 is same as ceria in Au/CeO2. The intrinsic nature of UO3 plays a key role in WGSR.
Some researchers [1,2,7,10,4347] have proposed WGSR mechanism
on Au/CeO2 catalyst in which involves (i) direct CO adsorption on Au
nanoparticles, as well as adsorption on an adjacent support area (capture zone) and subsequent reverse spillover on the Au particles; (ii)
formation and decomposition of surface formates at active sites, such
as the interface between Au particles and CeO2 support (adlineation
sites), by reaction of COad and OHad, and their subsequent decomposition to CO2 and H2; and (iii) the spillover and reversible spillover of
these species on the support and back. Based on the present results,
the authors inferred that the present Au/UO3 catalyst abides by the
mechanism, where CO molecular adsorbs on metallic gold sites, the adsorption and dissociation of water takes place on oxide defects, and all
subsequent reaction steps occur at oxidemetal interfaces. The goldsupport interaction seems to be a determining factor contributing to
the catalytic activity of gold catalyst.

20

4. Conclusions
10

(e)
0
100

150

200

250

300

350

400

Reaction temperature (oC)


Fig. 8. Watergas shift reaction activities of (a) Au/UO3-300, (b) Au/UO3-350, (c) Au/UO3400, (d) Au/UO3-450, and (e) Au/U3O8.

The authors contribute a novel gold catalyst supported on the facilely reducible uranium oxide for WGSR. Gold catalysts supported on
uranium oxides obtained at different calcination temperatures in the
range from 300 to 500 C were prepared. Their catalytic activities
show obvious dependence on the phase of uranium oxides. At a reaction
temperature of 350 C, the following activity order is obtained: Au/UO3300 N Au/UO3-350 N Au/UO3-400 N Au/UO3-450 N Au/U3O8. Au/UO3 catalyst demonstrates good activity while Au/U3O8 shows very low activity

Y.-Y. Dong et al. / Fuel Processing Technology 137 (2015) 164169

under the same conditions. Only a small portion of gold is oxidized on


the surfaces of both Au/UO3 and Au/U3O8, as shown by XPS results.
Dominant metallic gold with a small portion of oxidized gold species
is thought to be responsible for the activity. Furthermore, the better
WGSR activity on Au/UO3 than on Au/U3O8 is also correlated to facile
intrinsic reducibility of UO3 and surface gold atomic concentration in
Au/UO3 catalyst. The interface between metallic gold particles and uranium oxide is likely the active sites for WGSR.
Acknowledgments
The work was supported by the National Natural Science Foundation
of China (Grant 21273193 and 20973148) and by the Natural Science
Foundation of Shandong Province, China (Grant ZR2011BM024). The
authors also gratefully thank Mrs. Ling Gao from Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences, for XPS analysis
and Prof. Li-Guo Song from department of chemistry, University of
Tennessee-Knoxville, for improving language level of the manuscript.
References
[1] R. Burch, Gold catalysts for pure hydrogen production in the watergas shift reaction: activity, structure and reaction mechanism, Phys. Chem. Chem. Phys. 8
(2006) 54835500.
[2] C. Ratnasamy, J.P. Wagner, Water gas shift catalysis, Catal. Rev. Sci. Eng. 51 (2009)
325440.
[3] C.H. Kim, L.T. Thompson, Deactivation of Au/CeOx water gas shift catalysts, J. Catal.
230 (2005) 6674.
[4] I. Vindigni, M. Manzoli, A. Damin, T. Tabakova, A. Zecchina, Surface and inner defects
in Au/CeO2 WGS catalysts: relation between Raman properties, reactivity and morphology, Chem. Eur. J. 17 (2011) 43564361.
[5] M. Shekhar, J. Wang, W.-S. Lee, W.D. Williams, S.M. Kim, E.A. Stach, J.T. Miller, W.N.
Delgass, F.H. Ribeiro, Size and support effects for the watergas shift catalysis over
gold nanoparticles supported on model Al2O3 and TiO2, J. Am. Chem. Soc. 134
(2012) 47004708.
[6] F. Tao, Z. Ma, Watergas shift on gold catalysts: catalyst systems and fundamental
studies, Phys. Chem. Chem. Phys. 15 (2013) 1526015270.
[7] . Odaba, M.E. Gnay, R. Yldrm, Knowledge extraction for water gas shift reaction over noble metal catalysts from publications in the literature between 2002
and 2012, Int. J. Hydrog. Energy 39 (2014) 57335746.
[8] M. Hinojosa-Reyes, V. Rodrguez-Gonzlez, R. Zanella, Gold nanoparticles supported
on TiO2Ni as catalysts for hydrogen purication via watergas shift reaction, RSC
Adv. 4 (2014) 43084316.
[9] D. Andreeva, V. Idakiev, T. Tabakova, A. Andreev, R. Giovanoli, Low-temperature
watergas shift reaction on Au/-Fe2O3 catalyst, Appl. Catal. A Gen. 134 (1996)
275283.
[10] D. Andreeva, Low temperature water gas shift over gold catalysts, Gold Bull. 35
(2002) 8288.
[11] Q. Fu, S. Kudriavtseva, H. Saltsburg, M. Flytzani-Stephanopoulos, Goldceria catalysts for low-temperature watergas shift reaction, Chem. Eng. J. 93 (2003) 4153.
[12] Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Active nonmetallic Au and Pt species on ceria-based watergas shift catalysts, Science 301 (2003) 935938.
[13] Q. Fu, W. Deng, H. Saltsburg, M. Flytzani-Stephanopoulos, Activity and stability of
low-content goldcerium oxide catalysts for the watergas shift reaction, Appl.
Catal. B Environ. 56 (2005) 5768.
[14] X. Wang, J.A. Rodriguez, J.C. Hanson, M. Prez, J. Evans, In situ time-resolved characterization of AuCeO2 and AuOxCeO2 catalysts during the watergas shift reaction:
presence of Au and O vacancies in the active phase, J. Chem. Phys. 123 (2005)
(221101-1-5).
[15] D. Widmann, R. Leppelt, R.J. Behm, Activation of an Au/CeO2 catalyst for the CO oxidation reaction by surface oxygen removal/oxygen vacancy formation, J. Catal. 251
(2007) 437442.
[16] R. Si, M. Flytzani-Stephanopoulos, Shape and crystal-plane effects of nanoscale ceria
on the activity of AuCeO2 catalysts for the watergas shift reaction, Angew. Chem.
Int. Ed. 47 (2008) 28842887.
[17] H. Collette, S. Maroie, J. Riga, J.J. Verbist, Z. Gabelica, J.B. Nagy, E.G. Derouane, Supported uranium oxides as oxidation catalysts I. synthesis and characterization of
uranium oxides on A12O3, SiO2, TiO2, and MgO supports, J. Catal. 98 (1986)
326334.
[18] S.D. Pollington, A.F. Lee, T.L. Overton, P.J. Sears, P.B. Wells, S.E. Hawley, I.D. Hudson,
D.F. Lee, V.R. Ruddock, Novel supported uranium oxide catalysts for NOx abatement,
Chem. Commun. 8 (1999) 725726.
[19] T. Campbell, M.A. Newton, V. Boyd, D.F. Lee, J. Evans, Effects of precursor and support variation in the genesis of uranium oxide catalysts for CO oxidation and selective reduction of NO: synthesis and characterization, J. Phys. Chem. B 109 (2005)
28852893.

169

[20] F.J. Berry, A. Murray, N.D. Parkyns, Nickeluranium oxide catalysts: characterisation
and evaluation for methanation, Appl. Catal. A Gen. 100 (1993) 131143.
[21] L.G. Gordeeva, Y.I. Aristov, E.M. Moroz, N.A. Rudina, V.I. Zaikovskii, Y.Y. Tanashev,
V.N. Parmon, Preparation and study of porous uranium oxides as supports for
new catalysts of steam reforming of methane, J. Nucl. Mater. 218 (1995) 202209.
[22] S.H. Taylor, C.S. Heneghan, G.J. Hutchings, I.D. Hudson, The activity and mechanism
of uranium oxide catalysts for the oxidative destruction of volatile organic compounds, Catal. Today 59 (2000) 249259.
[23] S.H. Taylor, S.R. O'Leary, A study of uranium oxide based catalysts for the oxidative
destruction of short chain alkanes, Appl. Catal. B Environ. 25 (2000) 137149.
[24] V.R. Choudhary, A. Dhar, P. Jana, R. Jha, B.S. Uphade, A green process for chlorine-free
benzaldehyde from the solvent-free oxidation of benzyl alcohol with molecular oxygen over a supported nano-size gold catalyst, Green Chem. 7 (2005) 768770.
[25] V.R. Choudhary, R. Jha, P. Jana, Solvent-free selective oxidation of benzyl alcohol by
molecular oxygen over uranium oxide supported nano-gold catalyst for the production of chlorine-free benzaldehyde, Green Chem. 9 (2007) 267272.
[26] Z.R. Ismagilov, S.V. Lazareva, Synthesis and characterization of uranium-containing
catalysts, Catal. Rev. Sci. Eng. 55 (2013) 135209.
[27] L. Delannoy, N. El Hassan, A. Musi, N.N. LeTo, J.M. Krafft, C. Louis, Preparation of supported gold nanoparticles by a modied incipient wetness impregnation method, J.
Phys. Chem. B 110 (2006) 2247122478.
[28] Z. Suo, Y. Weng, M. Jin, A. Lv, J. Xu, L. An, Inuence of gold solution pH value and
steeping treatment on CO oxidation reactivity over Au/Al2O3 catalyst, Chin. J.
Catal. 26 (2005) 10221026 (in Chinese).
[29] Q. Yu, W. Chen, Y. Li, M. Jin, Z. Suo, The action of Pt in bimetallic AuPt/CeO2 catalyst
for watergas shift reaction, Catal. Today 158 (2010) 324328.
[30] H.W.G. Heynen, H.S. Van der Baan, The catalytic dehydrogenation of ethylbenzene
and cumene over catalysts containing uranium oxide, J. Catal. 34 (1974) 167174.
[31] D.W. McKee, The catalytic effects of uranium oxides and salts in carbon oxidation, J.
Catal. 97 (1986) 264268.
[32] L.W. Gray, W.J. Kerrigan, A DTA, TGA, and metallurgical study of the exothermic reactions between aluminum and uranium compounds: the solid state reactions of
uranium oxides and uranates with aluminum, J. Inorg. Nucl. Chem. 38 (1976)
16411644.
[33] N. Kumar, Y.R. Bamankar, K.T. Pillai, S.K. Mukerjee, V.N. Vaidya, V. Venugopal, Effect
of feed solution composition and heat treatment conditions on the morphology of
uranium oxide microspheres prepared by solgel process, J. Nucl. Mater. 359
(2006) 8092.
[34] Z. Suo, C. Ma, W. Liao, M. Jin, H. Lv, Structure and activity of AuPd/SiO2 bimetallic
catalyst for thiophene hydrodesulfurization, Fuel Process. Technol. 92 (2011)
15491553.
[35] R.A. Schueneman, A.I. Khaskelis, D. Eastwood, W.J. van Ooij, L.W. Burggraf, Uranium
oxide weathering: spectroscopy and kinetics, J. Nucl. Mater. 323 (2003) 817.
[36] G.C. Allen, P.M. Tucker, J.W. Tyler, The behaviour of uranium oxides in low partial
pressures of O2 studied using X-ray photoelectron spectroscopy, Vacuum 32
(1982) 481486.
[37] M. Schindler, F.C. Hawthorne, M.S. Freund, P.C. Burns, XPS spectra of uranyl minerals
and synthetic uranyl compounds. II: the O 1s spectrum, Geochim. Cosmochim. Acta
73 (2009) 24882509.
[38] Q. Wang, G.-D. Li, S. Xu, J.-X. Li, J.-S. Chen, Synthesis of uranium oxide nanoparticles
and their catalytic performance for benzyl alcohol conversion to benzaldehyde, J.
Mater. Chem. 18 (2008) 11461152.
[39] A. Karpenko, R. Leppelt, J. Cai, V. Plzak, A. Chuvilin, U. Kaiser, R.J. Behm, Deactivation
of a Au/CeO2 catalyst during the low-temperature watergas shift reaction and its
reactivation: a combined TEM, XRD, XPS, DRIFTS, and activity study, J. Catal. 250
(2007) 139150.
[40] A. Karpenko, R. Leppelt, V. Plzak, R.J. Behm, The role of cationic Au3+ and nonionic
Au0 species in the low-temperature watergas shift reaction on Au/CeO2 catalysts,
J. Catal. 252 (2007) 231242.
[41] W. Deng, M. Flytzani-Stephanopoulos, On the issue of the deactivation of Auceria
and Ptceria watergas shift catalysts in practical fuel-cell applications, Angew.
Chem. 118 (2006) 23432347.
[42] W. Deng, C. Carpenter, N. Yi, M. Flytzani-Stephanopoulos, Comparison of the activity
of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the watergas shift reactions, Top. Catal. 44 (2007) 199208.
[43] J.A. Rodriguez, P. Liu, J. Hrbek, J. Evans, M. Prez, Water gas shift reaction on Cu and
Au nanoparticles supported on CeO2(111) and ZnO(0001): intrinsic activity and importance of support interactions, Angew. Chem. Int. Ed. 46 (2007) 13291332.
[44] J.A. Rodriguez, S. Ma, P. Liu, J. Hrbek, J. Evans, M. Prez, Activity of CeOx and TiOx
nanoparticles grown on Au(111) in the watergas shift reaction, Science 318
(2007) 17571760.
[45] J.A. Rodriguez, Gold-based catalysts for the watergas shift reaction: active sites and
reaction mechanism, Catal. Today 160 (2011) 310.
[46] H. Sakurai, T. Akita, S. Tsubota, M. Kiuchi, M. Haruta, Low-temperature activity of
Au/CeO2 for water gas shift reaction, and characterization by ADF-STEM, temperature-programmed reaction, and pulse reaction, Appl. Catal. A Gen. 291 (2005)
179187.
[47] R. Leppelt, B. Schumacher, V. Plzak, M. Kinne, R.J. Behm, Kinetics and mechanism of
the low-temperature watergas shift reaction on Au/CeO2 catalysts in an idealized
reaction atmosphere, J. Catal. 244 (2006) 137152.

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