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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.
165
UO3 ; o:
U3 O8
O
X
Intensity
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
x:
O
UO3 ; o:
0.5
U3O8
X
O
O
0.4
O
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
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.
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
14
12
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
Sample
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
167
Au/U 3O8
Au4f 7/2
Intensity
Au4f 7/2
(c)
Au/UO 3
(b)
80
(a)
82
84
86
88
U4f 7/2
90
92
U4f 5/2
Temperature (oC)
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
Au/UO3
Au/U3O8
a
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
U/O
atom
ratio
Surface Au
concentration
(%)a
0.25
0.26
0.84
0.02
168
70
(d)
60
(c)
CO conversion (%)
50
40
30
20
10
0
100
(b)
(a)
150
200
250
300
350
400
(a)
50
CO conversion (%)
(b)
40
(c)
30
(d)
20
4. Conclusions
10
(e)
0
100
150
200
250
300
350
400
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
169
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