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DOI: 10.1002/cctc.201300709
mance of Pt/CeO2 catalysts in both CO oxidation and the COPROX reaction follows the order Pt/r-CeO2 > Pt/c-CeO2 >
Pt/o-CeO2. The Pt0-CeO2 ensemble is more active than the Pt2 +
-CeO2 ensemble in the catalysis of CO oxidation in excess O2.
H2-assisted CO oxidation catalyzed by the Pt/CeO2 catalysts
was observed in the CO-PROX reaction, and the Pt2 + species
and CeO2 with a large concentration of oxygen vacancies constitute the active structure of the Pt/CeO2 catalyst for the COPROX reaction. The effect of the morphology of the CeO2 support in the preparation, metalsupport interaction, and catalytic performance of Pt/CeO2 catalysts can be correlated the exposed crystal planes and surface composition/structure of the
CeO2 support with different morphologies. These results not
only demonstrate that the structure and catalytic performance
of oxide-supported catalysts can be tuned by controlling the
morphology of the oxide support but also deepens the fundamental understanding of CO oxidation reactions catalyzed by
Pt/CeO2 catalysts.
Introduction
Oxides are widely employed as catalyst supports. The surface
composition and surface structure of the oxide support greatly
affects the structure and catalytic performance of oxide-supported catalysts. Crystal planes exposed on the surface of an
oxide particle determine both the surface composition and the
surface structure. According to Wulffs rule,[1] crystal planes exposed on the surface of a crystalline material are determined
by its morphology. Thus the morphology of an oxide support
is an important macroscopic structural factor that affects the
catalyst structure and catalytic performance of oxide-supported catalysts. However, oxide particles in an oxide-supported
powder catalyst usually exhibit uneven and irregular morphologies and expose various types of crystal planes. Such morphological complexity and inhomogeneity of oxide particles
make it difficult to investigate and understand the effect of the
morphology of the oxide support in oxide-supported catalysts.
In the last decade, the controlled synthesis of oxide nanocrys[a] Y. Gao, Prof. Dr. W. Wang, S. Chang, Prof. Dr. W. Huang
Hefei National Laboratory for Physical Sciences at the Microscale
CAS Key Laboratory of Materials for Energy Conversion
Department of Chemical Physics
University of Science and Technology of China
Jinzhai Road 96, Hefei 230026 (China)
E-mail: huangwx@ustc.edu.cn
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catalyzing the preferential oxidation of CO in a H2-rich gas (COPROX) than Au/CeO2-polyhedra and Au/CeO2-cubes.[32, 33] We recently proposed a morphology-dependent interplay between
oxygen vacancies and Ag-CeO2 in Ag/CeO2 catalysts that controls their structure and catalytic performance.[40]
Pt/CeO2 catalysts are promising catalysts for low-temperature CO-PROX and WGS reactions and thus have attracted
great interest.[4348] Feng et al. deposited Pt clusters on CeO2
octahedra and rods by employing electron-beam evaporation
and observed the morphology-dependent structure of the deposited Pt clusters and catalytic performance in CO oxidation
and dehydrogenation reactions.[34] As far as we know, no study
of Pt/CeO2 catalysts prepared by conventional methods for
powder catalyst preparation, such as depositionprecipitation
and incipient wetness impregnation that employs CeO2 nanocrystals as the support, has been reported. Meanwhile, the
effect of metal loading on the structure and catalytic performance of metal/CeO2 catalysts that employ CeO2 nanocrystals
as the support has been seldom addressed in previous studies.
In this study, we prepared Pt/CeO2 catalysts with various Pt
loadings by a conventional incipient wetness impregnation
method that employed CeO2 cubes (c-CeO2), rods (r-CeO2), and
octahedra (o-CeO2) as the support. Their structures and catalytic activities in CO oxidation in excess O2 and the CO-PROX reaction were studied in detail. Strong morphology effects of the
CeO2 support were observed in the preparation, metalsupport
interaction, and catalytic performance of the Pt/CeO2 catalysts
and could be correlated the exposed crystal planes and surface
composition/structure of the CeO2 nanocrystals. The different
catalytic behaviors of Pt0-CeO2 and Pt2 + -CeO2 ensembles in the
catalysis of CO oxidation and the CO-PROX reaction were also
observed.
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Figure 1. TEM and HRTEM images of CeO2 rods (a, b), cubes (c, d), and octahedra (e, f). The insets schematically illustrate the crystal planes exposed on
the CeO2 rods, cubes, and octahedra.
Figure 2. XRD patterns of A) c-CeO2 and the Pt/c-CeO2 catalysts, B) r-CeO2 and the Pt/r-CeO2 catalysts, and C) o-CeO2 and the Pt/o-CeO2 catalysts.
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For each type of CeO2 nanoTable 1. Pt loading, Pt0/Pt2 + ratio, and specific reaction rate of various Pt/CeO2 catalysts.
crystal, three Pt/CeO2 catalysts
Specific reaction rate of
Specific reaction rate of
Catalyst
Pt loading
Pt0/Pt2 +
with calculated Pt loadings of
ratio
CO oxidation (40 8C)
the PROX reaction (60 8C)
0.2, 0.5, and 1 % were prepared
[wt %]
[mmolCO molPt1 s1]
[mmolCO molPt1 s1]
by a conventional incipient wet0.2 %-Pt/r-CeO2
0.12
0
68
38
ness impregnation method that
0.33
0
118
95
0.5 %-Pt/r-CeO2
employed Pt(NH3)4(NO3)2 as the
1 %-Pt/r-CeO2
0.87
0.53
147
32
precursor followed by subse0.14
0
very low
9
0.2 %-Pt/c-CeO2
quent H2 reduction at 200 8C for
0.39
0
23
19
0.5 %-Pt/c-CeO2
0.88
0.22
40
13
1 %-Pt/c-CeO2
3 h. If we take the Pt/CeO2 cata0.14
0.35
very low
3
0.2 %-Pt/o-CeO2
lyst with a calculated Pt loading
0.32
0.4
18
7
0.5 %-Pt/o-CeO2
of 0.2 % that employs c-CeO2 as
0.72
1.58
8
very low
1 %-Pt/o-CeO2
the support as an example, the
catalyst is denoted as 0.2 %-Pt/cCeO2. The H2 reduction treatment of the catalyst precursors
was monitored by MS, and the
results (not shown) demonstrate
the complete reduction of NO3
to gaseous NH3. It was reported
previously that the reduction
temperature of NO3 can be lowered significantly from 460 to
220 8C by Rh.[50] Thus no N-containing species exist in our Pt/
CeO2 catalysts. The actual Pt
loading in Pt/CeO2 catalysts was
analyzed by using inductively
coupled plasma atomic emission
spectroscopy (ICP-AES), and the
results are summarized in
Table 1. The Pt loadings in Pt/cCeO2, Pt/r-CeO2, and Pt/o-CeO2
are similar for low Pt loadings
but the Pt loading in 1 %-Pt/oCeO2 is a little smaller than that
in 1 %-Pt/c-CeO2 and 1 %-Pt/rCeO2. The XRD patterns of the Figure 3. Representative TEM and HRTEM images and the particle size distribution of 1 %-Pt/r-CeO2 (A1, A2, A3),
1 %-Pt/c-CeO2 (B1, B2, B3), and 1 %-Pt/o-CeO2 (C1, C2, C3).
Pt/CeO2 catalysts are shown in
Figure 2. No diffraction pattern
that arises from Pt could be observed in all of the Pt/CeO2 catsupported on the faces of CeO2 nanocrystals rather than on
alysts except 1 %-Pt/o-CeO2, which exhibits a weak Pt(111) diftheir edges and truncated corners.
fraction peak at 39.88 in its XRD pattern. The morphologies
The surface compositions of Pt/CeO2 catalysts were studied
and structures of Pt/CeO2 were examined by TEM. Pt nanoparby X-ray photoelectron spectroscopy (XPS). No N signal was
detected, which also demonstrates the absence of N-containticles were only clearly identified in 1 %-Pt/r-CeO2, 1 %-Pt/cing species in the catalysts. PO43 was employed in the syntheCeO2, and 1 %-Pt/o-CeO2, the TEM and HRTEM images of which
are shown in Figure 3. The original morphology of the CeO2
sis of o-CeO2 nanocrystals, and our XPS analysis results demonstrate that the P/Ce ratio is 0.06 in o-CeO2 and the Pt/o-CeO2
supports is well preserved after the loading of Pt. By counting
more than 100 Pt nanoparticles for each catalyst, we acquired
catalysts. The Pt 4f XPS spectra of various Pt/CeO2 catalysts are
the size distributions of the supported Pt nanoparticles in 1 %shown in Figure 4. The Pt 4f XPS spectra can be adequately
Pt/r-CeO2, 1 %-Pt/c-CeO2 and 1 %-Pt/o-CeO2. The mean sizes of
fitted with two components with the Pt 4f7/2 binding energy at
the Pt nanoparticles in 1 %-Pt/r-CeO2, 1 %-Pt/c-CeO2, and 1 % 72.6 and 71.5 eV. The former can be assigned to Pt2 + spePt/o-CeO2 do not differ much and are 2.0, 1.5, and 1.7 nm, recies and the latter can be assigned to Pt0 (Pt nanoparticles).[47]
2+
0
spectively. As shown below, the Pt /Pt ratios in 1 %-Pt/rIt can be seen that the Pt species in the Pt/CeO2 catalysts
CeO2, 1 %-Pt/c-CeO2, and 1 %-Pt/o-CeO2 differ significantly,
depend on the Pt loading and the morphology of the CeO2
which will affect the sizes of the supported Pt nanoparticles.
support. The Pt0/Pt2 + ratios in the Pt/CeO2 catalysts estimated
Almost all of the counted Pt nanoparticles in the catalysts are
from the Pt 4f XPS results are summarized in Table 1. For the
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Figure 5. H2-TPR profiles of the catalyst precursors of A) Pt/c-CeO2, B) Pt/r-CeO2, and C) Pt/o-CeO2 catalysts.
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Figure 6. H2-TPR profiles of A) c-CeO2 and as-prepared Pt/c-CeO2, B) r-CeO2 and as-prepared Pt/r-CeO2, and C) o-CeO2 and as-prepared Pt/o-CeO2 catalysts subjected to reoxidation treatment at 300 8C in 20 % O2-Ar for 2 h.
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does not vary much, whereas that in the UV Raman spectra increases slowly with the Pt loading. This could be associated
with both the weak Pto-CeO2 interaction and the stability of
the CeO2(111) surface. The ID/IF2g ratio in the UV Raman spectra
increases from 0.39 for 0.2 %-Pt/c-CeO2 to 0.64 for 0.5 %-Pt/cCeO2, whereas that in the visible Raman spectra does not
change. Meanwhile, the ID/IF2g ratio in the visible Raman spectra
increases from 0.04 for 0.2 %-Pt/r-CeO2 to 0.18 for 0.5 %-Pt/rCeO2, whereas that in the UV Raman spectra does not increase
much. These observations again indicate that defects in the
surface region are more stable in c-CeO2 than in r-CeO2. With
the increase of Pt loading to 1 %, the ID/IF2g ratios in both the
UV and visible Raman spectra increase significantly for Pt/cCeO2, which implies that the Pt nanoparticles are stronger to
create oxygen vacancies within c-CeO2 than the Pt2 + species;
however, the ID/IF2g ratio in the UV Raman spectra does not
change much for Pt/r-CeO2 but that in the visible Raman spectra decreases to 0.07 from 0.18 for 0.5 %-Pt/r-CeO2, which suggests a decrease of the concentration of oxygen vacancies. As
discussed above, in the 0.2 %-Pt/r-CeO2 and 0.5 %-Pt/r-CeO2
catalysts, Pt mainly interacts with the (1 0 0) surface exposed
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Figure 9. Catalytic performance of Pt/CeO2 catalysts in CO oxidation. The reactants consist of 1 % CO balanced with dry air.
Figure 10. CO conversion (A1C1) and O2 conversion and selectivity (A2C2) of the CO-PROX reaction catalyzed by Pt/CeO2 catalysts. The reactants consist of
1 % CO, 1 % O2, and 50 % H2 balanced with N2.
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action temperatures below 80 8C. This order is consistent with
the order of reducibility of the various CeO2 supports. In CO
oxidation reactions catalyzed by CeO2-involved catalysts, the
surface lattice oxygen of CeO2 is an active oxygen species.[18]
Thus, the easier the reduction of the employed CeO2 support,
the weaker the surface CeO bond, and the more active the
catalyst. Therefore, among the CeO2 nanocrystals investigated
herein, as a result of its strong reducibility and large specific
surface area, r-CeO2 is the best support to prepare efficient Pt/
CeO2 catalysts for CO oxidation and the CO-PROX reaction. At
high reaction temperatures in the CO-PROX reaction at which
the O2 conversion approaches 100 %, the CO conversion and
O2 selectivity of Pt/CeO2 catalysts do not depend much on the
Pt loading and CeO2 morphology and decrease with the reaction temperature. This is because high reaction temperatures
increase the surface coverage of H(a) (chemisorbed H adatoms)
on Pt surfaces at the expense of the surface coverage of CO(a)
(chemisorbed CO) on Pt surfaces.[48]
Interestingly, Pt/CeO2 catalysts with the same type of CeO2
support exhibit a morphology-dependent catalytic behavior on
the Pt loading in CO oxidation and the CO-PROX reaction at
low temperatures. In CO oxidation, the CO conversions of the
Pt/c-CeO2 and Pt/r-CeO2 catalysts increase with the Pt loading,
whereas those of the Pt/o-CeO2 catalysts follow the order
0.5 %-Pt/o-CeO2 > 1 %-Pt/o-CeO2 > 0.2 %-Pt/o-CeO2. In the COPROX reaction, the CO and O2 conversion of the Pt/c-CeO2 and
Pt/o-CeO2 catalysts follow the same orders as in CO oxidation
but those of Pt/r-CeO2 do not. The CO conversion in CO oxidation follows the order 1 %-Pt/r-CeO2 > 0.5 %-Pt/r-CeO2 > 0.2 %Pt/r-CeO2 but the CO and O2 conversion in the CO-PROX reaction follow the order 0.5 %-Pt/r-CeO2 > 1 %-Pt/r-CeO2 > 0.2 %-Pt/
r-CeO2. We further compared the specific reaction rates of various Pt/CeO2 catalysts normalized to the Pt loading in CO oxidation (40 8C) and the CO-PROX reaction (60 8C) at low temperatures, and the results are summarized in Table 1. The active
structure of Pt/CeO2 catalysts in CO oxidation reactions is generally believed to be the PtCeO2 interface, but it is still argued
about whether Pt0 or Pt2 + is more active.[4449] 0.2 %-Pt/c-CeO2
(0.2 %-Pt/r-CeO2) and 0.5 %-Pt/c-CeO2 (0.5 %-Pt/r-CeO2) only
contain Pt2 + species, whereas 1 %-Pt/c-CeO2 (1 %-Pt/r-CeO2)
contains both Pt2 + species and Pt nanoparticles. In CO oxidation, the specific reaction rate of 1 %-Pt/c-CeO2 (1 %-Pt/r-CeO2)
is higher than those of 0.2 %-Pt/c-CeO2 (0.2 %-Pt/r-CeO2) and
0.5 %-Pt/c-CeO2 (0.5 %-Pt/r-CeO2). This suggests that the Pt0CeO2 ensemble is more active than the Pt2 + -CeO2 ensemble in
the catalysis of CO oxidation in excess O2. In Pt/o-CeO2 catalysts, which contains both Pt2 + and Pt0 species, the reduced
catalytic activity of 1 %-Pt/o-CeO2 than 0.5 %-Pt/o-CeO2 can be
attributed to the aggregation of supported Pt nanoparticles, as
evidenced by both XRD and TEM results. This reduces the
number of active Pt-CeO2 ensemble sites and thus the catalytic
activity.
In the CO-PROX reaction, the specific reaction rate of 0.5 %Pt/c-CeO2 (0.5 %-Pt/r-CeO2) is higher than that of 1 %-Pt/c-CeO2
(1 %-Pt/r-CeO2), which is in contrast to the case in CO oxidation. This suggests that CO oxidation in the CO-PROX reaction
does not follow the same reaction mechanism as CO oxidation
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in excess O2. It has been established that H2-assisted CO oxidation occurs in the CO-PROX reaction catalyzed by Pt/CeO2 catalysts.[4446] In the presence of H2, H(a) formed on Pt surface
spills over to the CeO2 support to form oxygen vacancies in
CeO2 as well as to hydroxylate and hydrate the CeO2 surface.
The presence of oxygen vacancies in CeO2 promotes its ability
to activate O2, meanwhile, the hydroxylated and hydrated
CeO2 surface supplies additional oxidizing species to oxidize
CO to CO2. It was also found that the presence of a significant
density of oxygen vacancies in CeO2 is beneficial for the H2-assisted CO oxidation mechanism. Recently model catalyst studies have also revealed that hydroxyl groups on an oxide surface can react with CO(a) on the neighboring Pt surface to
form CO2 at 300 K and this reaction is favored by the presence of oxygen vacancies in oxides if a large amount of H(a)
coexists with CO(a) on a Pt surface.[5658] Therefore, both reaction mechanisms of CO oxidation in excess O2 and H2-assisted
CO oxidation should coexist in the CO-PROX reaction catalyzed
by Pt/CeO2 catalysts. Moreover, as the Pt0-CeO2 ensemble is
more active than the Pt2 + -CeO2 ensemble in the catalysis of
CO oxidation following the CO oxidation mechanism in excess
O2, the higher specific reaction rate of 0.5 %-Pt/c-CeO2 (0.5 %Pt/r-CeO2) over 1 %-Pt/c-CeO2 (1 %-Pt/r-CeO2) in the CO-PROX
reaction indicates that the Pt2 + -CeO2 ensemble should be
more active than the Pt0-CeO2 ensemble in the catalysis of CO
oxidation following the H2-assisted CO oxidation mechanism.
Notably, the CO conversion of 0.5 %-Pt/r-CeO2 with a lower Pt
loading is higher that of 1 %-Pt/r-CeO2. This cannot be merely
attributed to the Pt2 + species because 1 %-Pt/r-CeO2 contains
both Pt2 + and Pt0, but can be reasonably associated with the
large concentration of oxygen vacancies in CeO2 of 0.5 %-Pt/rCeO2 that benefits the H2-assisted CO oxidation. The ID/IF2g ratio
in the visible Raman spectra is 0.18 for 0.5 %-Pt/r-CeO2 and
0.07 for 1 %-Pt/r-CeO2. Thus the Pt2 + species and CeO2 with
large concentration of oxygen vacancies constitute the active
structure of the Pt/CeO2 catalyst for the CO-PROX reaction.
The above results provide solid experimental evidence for
the effect of the morphology of the CeO2 support in Pt/CeO2
catalysts from the catalyst preparation process to the catalytic
performance. The effect of the morphology of the CeO2 support can be reasonably correlated with different exposed crystal planes on the CeO2 supports with different morphologies
and their surface composition/structure. c-CeO2 has selectively
exposed {1 0 0} crystal planes, r-CeO2 has exposed {1 0 0} and
{11 0} crystal planes, and o-CeO2 has selectively exposed {111}
crystal planes. DFT calculations show that the surface energy of
low-indexed CeO2 surfaces follows the order (111) < (11 0) <
(1 0 0)[49] but the oxygen vacancy formation energy follows the
order (11 0) < (1 0 0) < (111) because of the restructuring of the
(11 0) surface.[5154] During the Pt/CeO2 catalyst preparation process, the least stable CeO2(1 0 0) surface (c-CeO2) interacts most
strongly with the Pt2 + precursor, followed by CeO2(11 0)
(r-CeO2) and CeO2(111) (o-CeO2). Reduced at the same temperature, Pt/o-CeO2 catalysts with the weakest Pt2 + precursor
CeO2 interaction contain the largest fraction of metallic Pt,
whereas Pt/c-CeO2 catalysts with the strongest Pt2 + precursor
CeO2 interaction contain the largest fraction of Pt2 + species.
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The reducibility and concentration of oxygen vacancies of
CeO2 in the Pt/CeO2 catalysts vary with the CeO2 morphology
and the PtCeO2 interaction. Thus, prepared by the same
method, Pt/CeO2 catalysts with the same Pt loading that
employ CeO2 cubes, rods, and octahedra as the supports have
different structures and exhibit different catalytic activities. On
one hand, the effect of the morphology of the CeO2 support in
the Pt/CeO2 catalysts adequately reveals the structural complexity of oxide-supported catalysts. Different crystal planes exposed on the catalyst nanoparticle surface exhibit different surface reactivities and catalytic activities, thus their contributions
to the observed overall catalytic activity must be unequal. It
has been reported that the coupling between adjacent crystal
planes with different catalytic activities can occur by the migration of surface species during the catalytic reaction.[13, 59, 60] The
structural complexity at the level of the crystal plane and morphology is a major hindrance for the correlation between the
structure and catalytic activity of powder catalysts. On the
other hand, the effect of the morphology of the CeO2 support
in the Pt/CeO2 catalysts proves that the structure and catalytic
performance of Pt/CeO2 catalysts for CO oxidation and the COPROX reaction can be tuned by controlling the morphology of
the CeO2 support. Among the various morphologies of the
CeO2 support investigated in this study, CeO2 rods are the best
support for the preparation of active Pt/CeO2 catalysts. Therefore, the morphology-controlled strategy of oxides will contribute significantly not only to the fundamental understanding of
heterogeneous catalysis by oxide-involved catalysts but also to
the innovation of efficient oxide-involved catalysts.[5]
Conclusions
We have comprehensively studied the structures and catalytic
performances of Pt/CeO2 catalysts with different Pt loadings
and different morphologies of the CeO2 support (cubes, rods,
and octahedra) in CO oxidation and the preferential oxidation
of CO in a H2-rich gas (CO-PROX) reaction. The effect of the
morphology of the CeO2 support exists in Pt/CeO2 catalysts
from the catalyst preparation process to the catalytic performance. The impregnated Pt precursor interacts more strongly
with CeO2 rods and cubes than with CeO2 octahedra and its reduction/decomposition is easier on CeO2 octahedra than on
CeO2 rods and cubes. The Pt/CeO2-octahedra catalyst contains
the largest fraction of metallic Pt, whereas the Pt/CeO2-cubes
catalyst contains the largest fraction of Pt2 + species. The reducibility of pure CeO2 and CeO2 in the Pt/CeO2 catalysts follows the order CeO2-rods > CeO2-cubes > CeO2-octahedra, and
the promotion effect of Pt on the reducibility of CeO2 is stronger in Pt/CeO2-rods and Pt/CeO2-cubes than in Pt/CeO2-octahedra. The concentration of oxygen vacancies of CeO2 in Pt/CeO2
catalysts varies with the CeO2 morphology and the PtCeO2 interaction. The catalytic performance of the Pt/CeO2 catalysts in
both CO oxidation and the CO-PROX reaction follows the order
Pt/CeO2-rods > Pt/CeO2-cubes > Pt/CeO2-octahedra. The Pt0CeO2 ensemble is more active than the Pt2 + -CeO2 ensemble in
the catalysis of CO oxidation in excess O2. H2-assisted CO oxidation catalyzed by the Pt/CeO2 catalysts was observed in the
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CO-PROX reaction, and the Pt2 + species and CeO2 with a large
concentration of oxygen vacancies constitute the active structure of the Pt/CeO2 catalyst for this reaction. These results not
only demonstrate that the structure and catalytic performance
of oxide-supported catalysts can be tuned by controlling the
morphology of the oxide support but also greatly deepens the
fundamental understanding of CO oxidation reactions catalyzed by Pt/CeO2 catalysts.
Experimental Section
All the chemicals were analytical grade reagents and were purchased from Sinopharm Chemical Reagent Co., Ltd. and used as received in our experiments. The synthesis of CeO2 cubes and rods
followed the procedure of Mai et al.[14] Typically, Ce(NO3)36 H2O
(1.96 g) was dissolved in ultrapure water (40 mL; resistance >
18 MW), and NaOH (16.88 g) was dissolved in ultrapure water
(30 mL). The NaOH solution was added dropwise into the Ce(NO3)3
solution under stirring at RT. The solution was stirred for an additional 30 min at RT and then transferred into a 100 mL Teflon
bottle. The Teflon bottle was tightly sealed and hydrothermally
treated in a stainless-steel autoclave at 180 8C for 24 h. After cooling, the obtained white precipitate was collected, washed with ultrapure water, and dried in vacuo at 80 8C for 16 h. Then the acquired yellow powder was calcined in a muffle oven at 500 8C for
4 h to synthesize CeO2 cubes. The synthesis procedure for CeO2
rods was the same as that for CeO2 cubes except that the hydrothermal treatment temperature was 100 8C. The synthesis of CeO2
octahedra followed the procedure of Yan et al.[15] Typically, Ce(NO3)36 H2O (2 mmol) was dissolved in ultrapure water (79 mL),
and then Na3PO4 (1 mL, 0.02 m) was added. The mixed solution
was stirred for 1 h at RT and then transferred into a 100 mL Teflon
bottle. The Teflon bottle was tightly sealed and hydrothermally
treated in a stainless-steel autoclave at 170 8C for 10 h. After cooling, the obtained white precipitate was collected, washed with ultrapure water and ethanol several times, and dried in vacuo at
80 8C for 16 h. Then, the acquired white powder was calcined in
a muffle oven at 500 8C for 4 h to synthesize CeO2 octahedra.
The Pt/CeO2 catalysts were prepared by a conventional incipient
wetness impregnation method. Typically, the desired amount of Pt(NH3)4(NO3)2 solution was added dropwise to CeO2 nanocrystals
(0.3 g) and ultrasonicated for 10 min. After the impregnation, the
sample was kept at RT for 24 h and then dried at 80 8C for 12 h to
prepare the catalyst precursor. The catalyst precursors were reduced in pure H2 at 200 8C for 3 h to prepare the Pt/CeO2 catalysts.
Three Pt/CeO2 catalysts with calculated Pt loadings of 0.2, 0.5, and
1 % (Pt/CeO2 weight ratio) were prepared.
The loading of Pt in the Pt/CeO2 catalysts was determined by using
an Optima 7300 DV inductively coupled plasma atomic emission
spectrometer (ICP-AES). BET specific surface areas were acquired by
using a Beckman Coulter SA3100 surface area analyzer, and the
sample was degassed at 300 8C for 5 h in a N2 atmosphere before
the measurement. XRD patterns were recorded by using a Philips
XPert PRO diffractometer using a Ni-filtered CuKa (wavelength =
0.15418 nm) radiation source with the operation voltage and operation current of 40 kV and 40 mA, respectively. XPS measurements
were performed by using an ESCALAB 250 high-performance electron spectrometer using monochromatized AlKa (hn = 1486.7 eV) as
the excitation source. The likely charging of samples was corrected
by setting the binding energy of the adventitious carbon (C 1s) to
284.8 eV. Laser Raman spectra were obtained in back-scattering
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configuration by using a LABRAM-HR Confocal Laser Raman spectrometer. Ar + (514.5 nm) and HeCd (325 nm) lasers were employed as the excitation source to obtain visible Raman and UV
Raman spectra, respectively. TEM and HRTEM images were acquired by using Jeol-2010 and Jeol-2100F high-resolution transmission electron microscopes with the electron acceleration energy of
200 kV.
H2-TPR experiments were performed by using a Micromeritics
ChemiSorb 2750 instrument, in which the sample (50 mg) was
heated at a rate of 10 8C min1 in a 5 % H2-Ar mixture with a flow
rate of 20 mL min1. During the TPR measurements of the Pt/CeO2
catalysts, the catalyst precursors were reduced at 200 8C with pure
H2 for 3 h, reoxidized at 300 8C in 20 % O2-Ar for 2 h, and then
cooled to RT in Ar prior to the measurements.
The catalytic activity of the Pt/CeO2 catalysts in CO oxidation and
the CO-PROX reaction were evaluated by using a fixed-bed flow reactor. In CO oxidation, Pt/CeO2 (25 mg) diluted with SiO2 (50 mg)
was used, and the reaction gas that consisted of 1 % CO balanced
with dry air was fed at a rate of 30 mL min1. In the CO-PROX reaction, Pt/CeO2 (100 mg) diluted with SiO2 (100 mg) was used, and
the feed gas stream that consisted of 1 % CO, 1 % O2, and 50 % H2
balanced with N2 was fed at a total flow rate of 100 mL min1. The
catalyst was heated to the desired reaction temperature at a rate
of 2 8C min1 and then kept for 35 min until the catalytic reaction
reached the steady state. Then the composition of the effluent gas
was analyzed by using an online GC-14 gas chromatograph. The
conversion of CO and O2 were calculated from the change in their
concentrations of the inlet and outlet gases. O2 selectivity to CO2
was as calculated according to Equation (1):
SO2
X CO
100 %
2 X O2
Acknowledgements
This work was financially supported by the National Basic Research Program of China (2013CB933104, 2010CB923301), the
National Natural Science Foundation of China (21173204), and
the Fundamental Research Funds for the Central Universities.
Keywords: cerium metal-support interaction oxidation
platinum supported catalysts structureactivity relationships
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FULL PAPERS
[51] M. Nolan, S. C. Parker, G. W. Watson, Surf. Sci. 2005, 595, 223 232.
[52] M. Nolan, Chem. Phys. Lett. 2010, 499, 126 130.
[53] D. O. Scanlon, N. M. Galea, B. J. Morgan, G. W. Watson, J. Phys. Chem. C
2009, 113, 11095 11103.
[54] M. V. Ganduglia-Pirovano, J. L. F. Da Silva, J. Sauer, Phys. Rev. Lett. 2009,
102, 026101.
[55] W. H. Weber, K. C. Hass, J. R. McBride, Phys. Rev. B 1993, 48, 178 185.
[56] L. Xu, Y. Ma, Y. Zhang, Z. Jiang, W. Huang, J. Am. Chem. Soc. 2009, 131,
16366 16367.
[57] L. Xu, Z. Wu, Y. Zhang, B. Chen, Z. Jiang, Y. Ma, W. Huang, J. Phys. Chem.
C 2011, 115, 14290 14299.
www.chemcatchem.org
[58] L. Xu, Z. Wu, Y. Jin, Y. Ma, W. Huang, Phys. Chem. Chem. Phys. 2013, 15,
12068 12074.
[59] V. Gorodetskii, J. Lauterbach, H. H. Rotermund, J. H. Block, G. Ertl, Nature
1994, 370, 276 279.
[60] W. X. Huang, R. S. Zhai, X. H. Bao, Langmuir 2001, 17, 3629 3634.
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