Journal of Catalysis 344 (2016) 365–377

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Structure dependence and reaction mechanism of CO oxidation: A model

study on macroporous CeO2 and CeO2-ZrO2 catalysts
Yane Zheng a,b, Kongzhai Li a,b,⇑, Hua Wang a, Yuhao Wang a,b, Dong Tian a,b, Yonggang Wei a,b, Xing Zhu a,b,
Chunhua Zeng a, Yongming Luo c
a
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China
b
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
c
Faculty of Environmental Engineering, Kunming University of Science and Technology, Kunming 650093, China

a r t i c l e i n f o a b s t r a c t

Article history: Three-dimensionally ordered macroporous (3DOM) CeO2 and CeO2-ZrO2 oxides with different particle
Received 1 July 2016 sizes, oxygen vacancy concentrations, oxygen mobility and preferentially exposed surface planes were
Revised 24 September 2016 synthesized, which, as model catalysts, give a new approach for understanding the structural dependence
Accepted 12 October 2016
and reaction mechanism of CO oxidation over CeO2-based catalysts. The prepared 3DOM CeO2 and CeO2-
ZrO2 catalysts exhibited much higher catalytic activity for CO oxidation than the nonporous samples.
Although the textural and reducible features of catalysts could affect the catalytic performance, the pref-
Keywords:
erentially exposed surface plane is crucial for determining the catalytic activity. The {1 1 0} plane of CeO2
3DOM CeO2-ZrO2
CO oxidation
could create more active sites for CO adsorption, resulting in relatively high activity for CO oxidation.
Oxygen vacancy Higher concentration of oxygen vacancy would also enhance the reactivity for CO oxidation. Langmuir-
In situ DRIFTs Hinshelwood mechanism should be the crucial reaction pathway for CO oxidation over the 3DOM
Reaction mechanism CeO2-based catalysts, although the Mars-van Krevelen mechanism cannot be ignored.
Ó 2016 Elsevier Inc. All rights reserved.

1. Introduction peratures, which leads to the production of large numbers of oxy-

Catalytic oxidation of carbon monoxide (CO), one of the most
important prototype reactions in heterogeneous catalysis, has
attracted considerable attention due to its extensive application
in environmental and energy areas (such as stationary and vehicle
exhaust control, air purification and CO removal in H2-rich feed)
[1]. Among various heterogeneous catalysts involved, supported
metals and reducible oxides show prominent properties. Currently,
noble metals, especially Au and platinum group metals, with the
presence of supports present high activity for CO oxidation at
low temperature [2]. Metallic oxides used as supports can be clas-
sified as inert or active according to their redox properties. Thus,
Al2O3 and SiO2 fit within the inert supports [3,4], while reducible
transition metal oxides such as, MnO2, Fe2O3, Co3O4 and CeO2 have
to be considered as active supports [5–8]. Liu et al. [6] prepared Pt-
group metals on both the inert supports and reducible supports,
such as Al2O3- or Fe2O3-supported Pt or Pd. It was found that Pt
or Pd on Fe2O3 can facilitate Fe3+ reduction at relatively low tem-
⇑ Corresponding author at: State Key Laboratory of Complex Nonferrous Metal
Resources Clean Utilization, Kunming University of Science and Technology,
Kunming 650093, China.
E-mail addresses: kongzhai.li@aliyun.com, kongzhai.li@foxmail.com (K. Li).
gen vacancies. The partly reduced FeOx is involved in the CO
oxidation, acting as an oxygen donor. On the other hand, the inter-
face sites between Al2O3 and Pt/Pd are insignificant. Ceria-based
supports as reducible oxides owned higher redox capacity, and
the high dispersion of Pt on ceria-based oxides plays an important
role for its superior catalytic activity [9]. The interaction between
Pt and ceria-based oxides can inhibit the Pt growth and sintering
at high temperature, which is absent on the Pt/Al2O3 or Pt/ZrO2
catalyst.
For the Au on inert supports system, such as Au/Al2O3 [3], the
noble metals are the only active sites, which determined the activ-
ity for CO oxidation. As for the Au-reducible supports system, the
support plays an important role in the catalytic process, particu-
larly for CeO2 and other transition metal oxides [10–14]. CeO2
was proposed to enhance the dispersion and stability of metal
components which behave as active sites [12–14]. More impor-
tantly, since CO oxidation usually takes place at the metal-
support interface, the ‘‘active” support CeO2 is also involved in
the reaction owing to the abundant active oxygen species present
on the surface [15]. Kim et al. [8] reported that, for Au/CeO2 cata-
lysts, the chemical modification on the CeO2 support is promising
for the optimization of oxidation catalysis.

http://dx.doi.org/10.1016/j.jcat.2016.10.008
0021-9517/Ó 2016 Elsevier Inc. All rights reserved.
366 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377
As for the independent reducible oxide catalysts, Venkatas-
wamy et al. [5] suggested that the mixed reducible CeO2-MnOx
oxides showed remarkable enhancement on the activity for CO oxi-
dation at lower temperatures, which can be attributed to a highly
dispersed state of Mn2+/Mn3+ in the ceria matrix, facile redox beha-
viour, and a synergistic Mn-Ce interaction. Luo et al. [7] found that
in Co3O4-CeO2 catalyst, Co3O4 crystallites are considered to be
encapsulated by nanosized CeO2, with only a small fraction of Co
ions exposing on the surface and strongly interacting with CeO2.
They proposed that the CO oxidation over Co3O4-CeO2 should take
place preferentially at the interface of Co3O4-CeO2 instead of the
surface of Co3O4. Experimental results also reveal that CeO2 and
CeO2-ZrO2 oxides show prominent catalytic activity for CO oxida-
tion [16–18]. CeO2-ZrO2 mixed oxides with better oxygen storage
capacity have been considered as an outstanding material in
three-way catalysts (TWCs), which aim at the simultaneous purifi-
cation of CO, HC and NOx in automotive exhaust. The introduction
of Zr could retard the sintering of oxide particles and improve the
thermal stability, which are required for highly active TWCs.
Currently, the interaction between CO and CeO2 during the
reaction has emerged as one of the most important issues to
understand the catalytic mechanism. The reaction models include
rapid adsorption of CO molecules on low-coordination surface
noble metal sites and its subsequent oxidation at the perimeter
of metal nano-particles where oxygen is activated [19–21]. For
the independent ceria based catalysts, CO oxidation is believed to
proceed via Mars-van Krevelen mechanism over ceria [22–24]. It
involves a complex series of redox reactions: the removal of sur-
face oxygen by CO with formation of oxygen vacancies and conse-
quent annihilation of vacancies by gas-phase oxygen. Since the
oxidation of reduced cerium oxides is very fast, the reduction pro-
cess, i.e., removal of surface oxygen, is the rate determination step.
Moreover, it is also found that CO interaction with ceria is structure
dependent and oxygen vacancy formation energy is sensitive to the
exposing crystal planes of CeO2 nano particles [24–27]. The activity
of CeO2 can be improved through predominantly exposing their
{1 0 0} and {1 1 0} planes [24,25,27]. Further investigation suggests
that the interaction of CeO2 with CO also involves the formation of
carbonate-like complexes on the {1 0 0} and {1 1 0} surfaces [28].
The carbonate species is competitive to CO2 formation and desorp-
tion, although CO could directly react with the surface active oxy-
gen on CeO2 [29]. This is similar with the characteristics of CO
oxidation over noble metal catalysts. Despite the intensive studies
of CO oxidation on ceria based catalysts, there is still a lack of clear
recognition as to the relationship among different factors (i.e., CO
adsorption, formation/concentration of oxygen vacancies, oxygen
mobility and the crystal planes of CeO2 exposed) in the catalytic
process.
Strategy for investigating the catalytic mechanism usually
involves preparing a series of catalysts with variable characteristics
(e.g., particle size, morphology, externally-exposed facets, or defect
concentration) and observing their catalytic behaviours using
in situ instruments. Three-dimensionally ordered macroporous
(3DOM) materials, which possess periodic features with uniform
large pore size (>50 nm), are proposed to benefit the catalytic
activity resulting from the more abundant active sites on the acces-
sibly macroporous wall surface [30]. The effect of catalyst features
on the catalytic behaviour may be magnified over the 3DOM cata-
lysts, which would make the processes able to respond to nuances
in its physicochemical properties. It is therefore reasonable to
believe that the 3DOM CeO2-based catalysts would be ideal candi-
dates to thoroughly investigate the relationship between their tex-
tural/reducible properties and catalytic activity.
In the present work, two series of 3DOM CeO2 and CeO2-ZrO2
solid solutions were prepared, which present different characteris-
tics in CeO2 particle size, oxygen vacancy concentration, reducibil-
ity, oxygen mobility and preferential exposed crystal planes of
CeO2. Investigations on the physicochemical properties of these
catalysts were performed, which were associated with their cat-
alytic activity for CO oxidation. Particularly, the nature of the inter-
action of CO with 3DOM catalysts using in situ infrared technology
was also studied. Based on the experimental data, the possible
reaction mechanisms are discussed in detail. The results showed
that the crystal plane of CeO2 preferentially exposed and oxygen
vacancy concentration are the critical factors for catalytic CO oxi-
dation over 3DOM CeO2-based oxide catalysts. These results will
bring new insights into the determinant factors and reaction
mechanisms.
2. Experimental
2.1. Catalyst preparation
The 3DOM CeO2 and CeO2-ZrO2 solid solutions were fabricated
via PMMA-templating route. The precursor solutions of catalysts
were obtained by mixing stoichiometric amounts of Ce(NO3)3
6H2-
O and ZrOCl2
8H2O with deionized water at room temperature
(RT). The atomic ratio of Ce:Zr was 8:2. And then citric acid was
added into the precursor and dissolved at 60 °C for 1 h under stir-
ring. After that, dried PMMA colloidal crystal templates were
added in the solutions for 4 h. The precursors were then dried at
60 °C for 24 h. Finally, the CeO2 and CeO2-ZrO2 samples were
obtained by calcination at 350 °C for 2 h with a ramp rate of
2 °C/min. The obtained powders were then heated at 2 °C/min up
to 450 °C with a dwell time of 2 h. These as-synthesized CeO2
and CeO2-ZrO2 samples were abbreviated accordingly as C450
and CZ450, respectively. Both the C450 and CZ450 samples were
further calcined at 600 and 800 °C in air for 2 h, respectively,
labelled as C600, C800, CZ600 and CZ800.
The nonporous CeO2-ZrO2 sample was prepared via a co-
precipitation method. The stoichiometric amounts of Ce(NO3)3-

6H2O and ZrOCl2
8H2O were dissolved in deionized water under
stirring at RT. The atomic ratio of Ce:Zr was also 8:2. The hydrox-
ides were precipitated by adding drops of ammonia solution. The
mixtures were stirred for one hour, when the pH increased to
8.0. The precipitates were dried at 60 °C for 24 h, and then calcined
at 350 °C for 2 h with a ramp rate of 2 °C/min. The obtained solids
were then heated at 2 °C/min up to 450 °C with a dwell time of 2 h.
The as-synthesized nonporous CeO2-ZrO2 sample was labelled as
N-CZ450. Similarly with the 3DOM samples, the N-CZ450 was also
calcined at 600 and 800 °C in air for 2 h, respectively, named as N-
CZ600 and N-CZ800.
2.2. Physical and chemical characterizations
Specific surface area of samples was performed on a Quan-
tachrome Autosorb-iQ instrument. The data were calculated
according to the BET method by the N2 adsorption isotherm at liq-
uid N2 temperature (77 K).
X-ray powder diffraction (XRD) patterns of the catalysts were
measured by a Rigaku diffractometer using Cu Ka radiation
(k = 0.15406 nm). The operating voltage and current were 40 kV
and 200 mA. The scanning rate is 5°/min.
Raman spectra of the catalysts were recorded at RT in a Ren-
ishaw Invia Raman imaging microscope. The exciting wavelength
was 514.5 nm from an Ar ion laser with a powder of ca. 10 mW
on the catalysts.
The morphology of the catalysts was observed by a scanning
electron microscopy (SEM) by a Hitachi S4800 instrument with
accelerating voltages of 3 kV.
 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377
The morphology of the catalysts was observed by transmission
electron microscopy (TEM) characterization, using a JEOL-2100
microscope operating at 200 kV.
The X-ray photoelectron spectroscopy (XPS) analysis was per-
formed on a PHI 5000 Versaprobe II system using a monochromatic
Al-Ka X-rays source. Spectra were recorded at RT in vacuum
(<107 Pa). The C 1s signal at 284.8 eV was used for calibration of
the XP-signals.
Temperature-programmed reduction (TPR) and temperature-
programmed desorption (TPD) profiles were obtained from RT to
900 °C. Experimental data were collected from Quantachrome
Instruments. The amount of catalyst either for TPR or for TPD test-
ing was 100 mg using a heating rate 10 °C/min in all cases. After a
standard cleaning pretreatment, TPR was carried out in a flow of
10% H2/Ar (25 mL/min) up to 900 °C. For TPD testing, the pre-
treated sample was exposed to 5% O2/N2 (25 mL/min) at 100 °C
for 30 min and then purged with N2 for 30 min. Then the sample
was heated up to 900 °C using a heating rate of 10 °C/min in all
cases.
CO-TPR over different catalysts (100 mg) was also conducted on
the CATLAB catalyst characterization system (produced by Hiden
Analytical Co., England). Before each of the experiments, the sam-
ple was pretreated in flowing 10% O2/Ar (25 mL/min) at 400 °C for
1 h, cooled down to RT and then switched to argon purging for
30 min. After that, the pretreated sample was exposed to 1%CO/
Ar (25 mL/min) at RT for 30 min and then ramped (10 °C/min) up
to 600 °C. The gas was analysed by an online mass spectrometer
(MS).
Diffuse reflectance infrared Fourier transform spectroscopy
(DRIFTS) analysis was used to evaluate the adsorbed species on
the catalyst under reaction conditions. Infrared spectra were
recorded by an FTIR spectrometer (vertex 70, Bruker, Germany)
equipped with a liquid N2 cooled Mercury-Cadmium-Telluride
(MCT) detector. A Pike Technologies HC-900 DRIFTS cell with nom-
inal cell volume of 6 cm3 was used. Scans were collected from 4000
to 1000 cm1 at a resolution of 4 cm1. Catalyst samples were
placed in a DRIFTS cell equipped with SeZn windows. Before each
of the following in situ DRIFTS experiments, the sample was pre-
treated in the DRIFTS cell in flowing 10%O2/Ar (25 mL/min) at
400 °C for 1 h and then cooled to RT before switching to Ar. In
CO adsorption experiments, the pretreated sample was purged
with Ar at RT before switching to 1%CO/Ar (25 mL/min) flow for
30 min.
For the In situ DRIFTS CO-TPR experiments, the pretreated sam-
ple was exposed to 1%CO/Ar (25 mL/min) at RT for 30 min and then
purged with argon at RT for 30 min. Then the sample was heated
(10 °C/min) up to 600 °C in flowing argon (50 mL/min).
100
A B
T90
80
CO conversion%
60
T50
40
20
T10
0 0
200 300 400
Temperature (oC)
Fig. 1. CO conversion as a function of reaction temperature over macroporous (A) and nonporous (B) samples.
367
2.3. Catalytic activity testing
Catalytic activity evaluation was performed in a plug-flow,
temperature-controlled microreactor system. The sample
(100 mg), loaded into the quartz tube with inner diameter of
6 mm, was pretreated in flowing 10%O2/Ar (25 mL/min) at 400 °C
for 1 h. And then, it was cooled down to RT in O2/Ar atmosphere
and switched to argon purging for 30 min thereafter. After that,
the gas mixture (1% of CO, 10 vol% O2 balance Ar) was introduced
into the reactor with a flow of 50 mL/min at RT, and the system
was ramped up to 600 °C and cooled back to RT at a rate of
10 °C/min. The outlet gaseous products were analysed by a gas
chromatograph (Agilent 7890A GC System, produced by Agilent
Co.), which is equipped with HP-Plot 5A and HP-Plot-Q column.
3. Results
3.1. Catalytic activity
Fig. 1 exhibits the CO oxidation activity over 3DOM CeO2 and
CeO2-ZrO2 and nonporous CeO2-ZrO2 samples. It is convenient to
compare the catalytic activities of the samples by adopting the
reaction temperatures T10, T50, and T90 (corresponding to CO con-
version of 10%, 50% and 90%, respectively), as summarized in
Table 1. For the series of 3DOM CeO2 samples, C450 is the most
active, followed by C600 and C800. For example, the temperature
for T50 is 300 °C over C450, 340 °C over C600, and 366 °C over
C800. For the series of 3DOM CeO2-ZrO2 samples, CZ450 shows a
very low catalytic activity, while a drastic increase in the activity
occurs over the CeO2-ZrO2 sample preheated at 600 °C (CZ600
sample). Further increasing the ageing temperature to 800 °C
would reduce the activity. It can be seen that a T50 is achieved at
255 °C for CZ600, while only 4% and 13% CO conversion is obtained
at the same temperature for CZ450 and CZ800 samples, respec-
tively. The macroporous CeO2-ZrO2 samples present totally differ-
ent phenomenon compared with the 3DOM CeO2-ZrO2 samples, as
shown in Fig. 1B. Their activity for CO oxidation linearly decreases
with increasing the calcination temperature. The N-CZ450 catalyst
oxidizes 50% of CO at a temperature of 345 °C, while the T50 values
for N-CZ600 and N-CZ800 catalysts are 370 and 420 °C, respec-
tively. This is a usual case for the CeO2-ZrO2 catalyst, because cal-
cination at high temperature may result in sintering of the catalyst,
reducing the catalytic activity.
It should be stressed that the CZ450 sample exhibits the lowest
catalytic activity, while the CZ600 sample shows the best catalytic
performance among the six samples. This suggests that some evo-
lution of the structural and/or surface properties of the material
100
T90
80
CO conversion%
60
T50
C450 40
C600
C800 N-CZ450
CZ450 20 N-CZ600
CZ600 T10 N-CZ800
CZ800
500 600 200 300 400 500 600
Temperature (oC)
368 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377

Table 1
Catalytic activities, activation energies (Ea) and BET specific surface areas (SBET) of different samples.

Samples T10 (°C) T50 (°C) T90 (°C) Ea (kJ/mol) SBET (m2/g)
C450 240 300 355 62 42
C600 260 340 425 92 40
C800 300 366 473 112 38
CZ450 308 445 534 137 50
CZ600 200 255 343 57 46
CZ800 225 310 394 83 43
N-CZ450 270 345 445 73 87
N-CZ600 295 370 545 75 70
N-CZ800 325 420 600 94 50

-4 -4
C450
A C600
B CZ450
CZ600
-5 C800 -5
CZ800
CZ450
CZ600
-6 CZ800 -6
ln k

ln k
-7 -7

-8 -8

-9 -9
1.4 1.6 1.8 2.0 2.2 2.4 1.5 1.6 1.7 1.8 1.9 2.0
1000/T (K -1) 1000/T (K -1)

Fig. 2. Arrhenius plots for CO oxidation over macroporous (A) and nonporous (B) catalysts under the conditions of CO concentration = 1 vol%, CO/O2 molar ratio = 1/10, and
SV = 30,000 mL/(g h).

may occur when increasing the calcination temperature from 450
to 600 °C. On the other hand, it is an exceptional phenomenon that
the CeO2-ZrO2 solid solutions (i.e., CZ450 sample) possess much
lower catalytic activity than single CeO2 (i.e., C450 sample),
because CeO2-ZrO2 solid solutions prepared in the same conditions
usually have smaller particle size and a higher oxygen vacancy
concentration which prove to be beneficial to improving catalytic
activity. Further investigation of the difference among the above
different samples may lead to a better understanding of the CO oxi-
dation mechanism (involving the key factor to determine the activ-
ity and the reaction path) over CeO2-based catalysts.
The apparent activation energy (Ea) over different samples was
also obtained based on the catalytic activity. It is reported that the
reaction order was related to the concentration of CO and O2.
When the CO concentration is relatively low, the CO should be
first-order [31,32]. Jia et al. [33] also claimed that the oxidation
of CO obeys a reaction mechanism of first order towards CO con-
CeO2-ZrO2 samples. In addition, the stability of the CZ600 catalyst
is examined at 300 °C with a CO conversion at ca. 80%, and the
results shown in Fig. S1. As can be seen, the CZ600 catalyst main-
tained its activity during 100 h testing.
3.2. Structural properties of catalysts
X-ray diffraction patterns of the different 3DOM CeO2 and CeO2-
ZrO2 catalysts are shown in Fig. 3. In the case of the bare CeO2, all
the diffraction peaks can be indexed to (1 1 1), (2 0 0), (2 2 0), (3 1 1),
(4 0 0), (3 1 1) and (4 2 0) crystal faces, corresponding to a face-
centred cubic (fcc) fluorite structure of CeO2 [37]. No ZrO2 crystal
phase was detected in the XRD profiles of all the CeO2-ZrO2
samples, which indicates the formation of solid solutions. For
(111)

centration. Some works suppose that the oxidation of CO in the

presence of excess oxygen (CO/O2 molar ratio P1/2) would obey
(220)

(311)
(200)

a first-order reaction [34–36]. In the present work, the amount of

(331)
(420)
(222)

(400)

O2 is excess (CO/O2 molar ratio = 1/10). Therefore, it is reasonable

CZ600
Intensity (a.u.)

to propose that the oxidation of CO should obey a first-order reac-

tion with respect to CO concentration(c). r = kc = (A exp(Ea/ CZ450
RT))c, where r, k, A, and Ea are the reaction rate (mol/s), rate con-
stant (s1), pre-exponential factor, and apparent activation energy
(kJ/mol), respectively.
The Arrhenius plots for CO oxidation over the macroporous and
C600
nonporous samples are shown in Fig. 2, and their apparent activa-
tion energies are summarized in Table 1. It can be observed that
C450
the Ea value for CO oxidation decreased in the sequence CZ450
(137 kJ/mol) > C800 (112 kJ/mol) > N-CZ800 (94 kJ/mol) > C600 10 20 30 40 50 60 70 80
(92 kJ/mol) > CZ800 (83 kJ/mol) > N-CZ600 (75 kJ/mol) > N-CZ450 2 Theta (deg.)
(73 kJ/mol) > C450 (62 kJ/mol) > CZ600 (57 kJ/mol). This suggests
that CO oxidation proceeds more readily over the macroporous Fig. 3. XRD patterns of different 3DOM CeO2 and CeO2-ZrO2 samples.
 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377 369

Table 2 tions. This explanation should be that some isolated Zr species

Average crystal parameters of different 3DOM CeO2 and CeO2-ZrO2 samples. may exist in an amorphous state on the sample heated at low tem-
Samples Phase Crystallite size (nm) Lattice constant (nm) peratures, which could be incorporated into CeO2 lattice after ther-
CeO2 CeO2 mal treatment at relatively high temperatures.
C450 Cubic 15.2 0.5401 Raman spectra of the 3DOM CeO2 and CeO2-ZrO2 samples are
C600 Cubic 23.5 0.5410 shown in Fig. 4. The pure CeO2 sample exhibits a strong peak cen-
CZ450 Cubic 5.9 0.5365 tred at 462 cm1 corresponding to F2g Raman active mode in metal
CZ600 Cubic 7.8 0.5347
oxides with fluorite-like structure [39]. This peak broadens and
slightly shifts to 470 cm1 for the CeO2-ZrO2 samples. It has been
CeO2, the diffraction peaks become sharper and stronger after ther- reported that the broadening of the ceria main line is related either
mal treatment at 600 °C. This is a consequence of the better to a decrease of ceria crystallite size or to the presence of defects
arrangement of the atoms into the framework of pure CeO2 and such as oxygen vacancies [37]. For the CeO2-ZrO2 samples, a broad
the decreased number of lattice defects [38]. However, for the band centred at 601 cm1 can be observed. This band could be
CeO2-ZrO2, these changes are less remarkable, indicating a good linked to oxygen vacancies due to the substitution of Zr4+ into
thermal stability. the ceria lattice [40]. The appearance of a very weak band at
The average crystal parameters of the samples are listed in 300 cm1 could be related to the displacement of the oxygen atoms
Table 2. It is obvious that both the two CeO2-ZrO2 samples show from their ideal fluorite lattice positions [41]. To make a quantita-
much lower lattice constants for CeO2 compared with pure CeO2. tive analysis of the concentration of oxygen vacancies, the I601/I462
This lattice shrinkage should result from the smaller Zr4+ ion enter- ratios were calculated from the Raman spectra, as shown in Fig. 4B.
ing into the fluorite-type lattice of CeO2. It is also noted that the The I601/I462 ratio is only 0.04 and 0.02 for the C450 and C600
lattice constant for CeO2-ZrO2 samples (CZ450 vs CZ600) further respectively, while it is 0.24 for the CZ600 sample.
decreases when increasing the calcination temperature from 450 Fig. 5 shows the SEM images of the 3DOM CeO2 and CeO2-ZrO2
to 600 °C, suggesting greater formation of CeO2-ZrO2 solid solu- samples. It can be seen that the C450 and CZ450 samples have

0.25
A B
601
0.20
CZ600
Intensity (a.u.)

I 601 /I 462

CZ450 0.15
462
0.10

C600 0.05

C450
0.00
200 300 400 500 600 700 800 900 C450 C600 CZ450 CZ600
-1
Raman shift (cm ) Samples

Fig. 4. Raman spectra (A) and the I601/I462 ratios calculated from Raman spectra (B) of different 3DOM CeO2 and CeO2-ZrO2 samples.

Fig. 5. SEM images of 3DOM C450 (a1), CZ450 (b1), C600 (a2) and CZ600 (b2) samples.
370 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377

open, periodic and interconnected three-dimensionally (3D)
frameworks. The pore sizes estimated from the SEM images are
in the range of 100–150 nm. When the samples were further pre-
heated at 600 °C, there is no great difference in the morphologies
and textural structure among the two samples (C600 and CZ600).
It indicates that the 3DOM ceria-based materials have higher ther-
mal and structural stability, which are required for the further
development of durable, highly active and versatile catalysts for
CO oxidation.
Fig. 6 shows the TEM and HRTEM images of different 3DOM
CeO2 and CeO2-ZrO2 samples. The macroporous structure with
overlapped pores can be clearly observed in the TEM images. The
pore sizes of macroporous samples are 100 ± 20 nm, and the voids
are interconnected through open windows which agrees with the
observed by SEM images. The CeO2 particle size of C450 is in the
range of 4–10 nm with a narrow distribution (Fig. 6-a2) and a
mean diameter of 6.0 nm by statistical analysis of more than 300
CeO2 particles. The 3DOM C600, CZ450 and CZ600 samples reveal
a mean particle diameter of 8.0, 5.1 and 5.9 nm, respectively (see
Fig. 6-b2, c2, d2). In addition, the macroporous walls are composed
of closely packed particles with limited microporous or meso-
porous. The lattice fringes with a width of 3.1 Å and 1.9 Å indexed
as {1 1 1} and {1 1 0} planes of CeO2, respectively, can be found in all
the samples (see Fig. 6-a3, b3, c3, d3). To identify the percentage of

Fig. 6. TEM and HRTEM images of 3DOM C450 (a1-3), C600 (b1-3), CZ450 (c1-3) and CZ600 (d1-3).
 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377
the exposed {1 1 0} plane, the ratio of {1 1 0}/{1 1 0 + 1 1 1} was
obtained by statistical analysis of more than 300 CeO2 particles
for each sample. Parts of the TEM images used for statistical anal-
ysis were plotted in Fig. S2. The ratio of {1 1 0}/{1 1 0 + 1 1 1} for
C450, C600, CZ450 and CZ600 samples is 23%, 20%, 8% and 45%,
respectively. This suggests that there are more {1 1 0} planes on
the surface of CZ600 sample.
Fig. 7 shows the N2 adsorption-desorption isotherms of differ-
ent 3DOM CeO2 and CeO2-ZrO2 samples. The CZ450 sample dis-
plays a type II isotherm and a type H2 hysteresis loop in the
relative pressure (P/P0) range of 0.2–0.85, which could be linked
to capillary condensation taking place in mesopores, indicating
that textural mesopores existed within the skeletons. However,
some of the mesopores are lost after calcination at higher temper-
atures, which can be explained by grain growth. The two 3DOM
CeO2 samples presented a nonporous model, indicating that there
is almost no mesopores existing within the macroporous walls.
Compared with the CeO2 samples (surface area = 40–42 m2/g),
the macroporous CeO2-ZrO2 samples showed a slightly higher sur-
face area (46–50 m2/g).
XPS was performed to determine the chemical state of Ce and O
species on the surface of different samples. The oxidation states of
Ce were analysed by fitting the curves of Ce 3d XPS bands, as
shown in Fig. 8. Table 3 presents the relative percentages of the
C450
C600
Volume Adsorbed(cm3/g)
CZ450
CZ600
0.0 0.2 0.4 0.6 0.8
Relative Pressure (P/P0)
Fig. 7. Nitrogen adsorption-desorption isotherms of different 3DOM CeO2 and
CeO2-ZrO2 samples.
Fig. 8. Ce 3d and O 1s XPS patterns of different 3DOM CeO2 and CeO2-ZrO2 samples.
371
cerium species calculated by the area ratios of the Ce3+/(Ce + Zr)
and two oxygen species. The peaks labelled as V correspond to
Ce 3d5/2 contributions, and those of labelled as U represents the
Ce 3d3/2 contributions. The peaks labelled as V, V0 0 and V000 are
assigned to Ce(IV) final states, and the peak V0 is denoted as Ce
(III) final states. The same assignment can be applied to the U
structures, which correspond to the Ce 3d3/2: the line U0 is assigned
to Ce(III) final state coordinated to oxygen vacancies and the other
lines indicative of the presence of Ce4+ ions [42–44].
The quantitative analysis (see Table 3) shows that the atom
ratio of Ce/Zr for CZ450 is lower than that for the CZ600 sample
(2.34 vs. 3.25), indicating that the CZ450 sample is enriched with
ZrO2 on the surface. Since CeO2 is the active component for CO oxi-
dation, this can be used to explain the relatively lower activity of
CZ450 sample. In addition, it is also found that the average ratios
of Ce3+/(Ce + Zr) decreased (see Table 3) in the order of
CZ600 > C450 > C600 > CZ450 (which ranges from 0.13 to 0.18),
which is completely consistent with the order of the catalytic
activity over different samples. This indicates that Ce3+ concentra-
tion plays a very important role for determining the catalytic
property.
To further confirm the importance of the oxygen mobility, oxy-
gen storage capacity (OSC) measurements were also performed by
the successive CO pulse mode (see Fig. S3). The quantitative data
on the TOSC for different samples are shown in Table 3. The TOSC
values decrease in the order of CZ600 > C450 > C600 > CZ450
which is completely agreement with the order of catalytic activity.
The O 1s spectra of pure CeO2 samples (C450 and C600) can be
fitted with three peaks at ca. 529.6 eV (main band, labelled as OIII),
531.1 eV (labelled as OII) and 532.2 eV (labelled as OI), respec-
tively. It is generally accepted that the 529.6 eV peak is character-
istic of the lattice oxygen (O2) in cerium oxide with the peak at
531.1 and 532.2 eV attributed to surface oxygen (Os) and/or surface
hydroxyl species OHs, respectively [45]. However, the O 1s spectra
of CeO2-ZrO2 samples (CZ450 and CZ600) can only be fitted with
two peaks (OII and OIII), as indicated by the disappearance of the
surface hydroxyl species (OI). It is noted that the lattice oxygen
(OIII) is the most abundant species for each sample. Since surface
oxygen species usually play a very important role in the catalytic
process, the surface-Oads.(OI + OII)/bulk-Olatt.(OIII) molar ratios
1.0 are calculated based on the XPS data. As shown in Table 3, the ratio
decreases in the order of C450 > CZ600 > C600 > CZ450. However,
by ignoring the effect of surface hydroxyl species (OI), the
sequence of the Oads./Olatt. ratios among the four samples would
be as follows: CZ600 > C450 > CZ450 > C600.
372 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377

Table 3
XPS-derived characteristics for different 3DOM CeO2 and CeO2-ZrO2 samples.

Samples Ce3+ Ce4+ Ce3+/Ce4+ Atom ratio of Ce/Zr Ce3+/(Ce+Zr) OI OII OIII (OI + OII)/OIII TOSCa mmol/g
C450 17 83 0.20 – 0.17 10 19 71 0.41 1.01
C600 15 85 0.18 – 0.15 7 13 80 0.25 0.93
CZ450 19 81 0.23 2.34 0.13 – 16 84 0.19 0.77
CZ600 24 76 0.32 3.25 0.18 – 22 78 0.28 1.12
a
TOSC is determined by summarizing OSC of 20 CO pulses at T = 400 °C.

Fig. 9. H2-TPR profiles (A) and cumulative H2 uptake (B) and initial H2 consumption rate (C) of different 3DOM CeO2 and CeO2-ZrO2 samples.

3.3. Reducibility and oxygen mobility

Fig. 9A shows the H2-TPR profiles of the four samples, and O2-TPD
Fig. 9B exhibits the cumulative hydrogen uptake associated with
the phases present in the samples as a function of reduction tem- CZ600
perature. For pure CeO2, two reduction peaks are detected in the
H2-TPR profile: a low temperature peak at 580 °C and a high tem- CZ450
perature peak in a range higher than 800 °C corresponding to the
TCDsignal (a.u.)

reduction of surface and bulk ceria, respectively. The CeO2-ZrO2

samples only show one obvious reduction peak, centred at about
656 °C, and the intensity of this peak is much higher than either
of the two peaks over the pure CeO2 sample. This suggests that
oxygen located within the subsurface or bulk of CeO2-ZrO2 samples
could migrate to the surface immediately as surface oxygen is con-
sumed, indicative of relatively high lattice oxygen mobility [38].
The total hydrogen consumption of CeO2-ZrO2 samples
(123 mmol/g for CZ450 and 134 mmol/g for CZ600) is much higher
than that of CeO2 (68 mmol/g for C450 and 42 mmol/g for C600). It
is generally accepted that the low-temperature reducibility of a
catalyst can be conveniently evaluated using the initial H2 con-
sumption rate where less than 25% oxygen in the sample is
removed for the first reduction peak [46]. As shown in Fig. 9C,
CZ600 presents the highest H2 consumption rate among the four
samples.
To further investigate the adsorption and activation of oxygen
on CeO2 and CeO2-ZrO2, O2-TPD measurements were carried out,
as shown in Fig. 10. The O2 desorption peaks of the pure CeO2
samples (C450 and C600) can be divided into three parts in the
temperature ranges of 80–250 °C (low-temperature), 250–500 °C
(middle-temperature), and 500–900 °C (high-temperature),
respectively. The low-temperature peak is assigned to the
desorption of physically adsorbed oxygen (O2), and the middle-
temperature peak can be associated with the consumption of che-
misorbed surface-active oxygen species [47]. The high temperature
must be related to the release of lattice oxygen. For the CeO2-ZrO2
samples, the peaks at temperatures lower than 300 °C are very
weak and only one main peak in the range of 300–900 °C is
observed. This is similar to the phenomena observed in the TPR
C600
C450
100 200 300 400 500 600 700 800 900
Temperature (οC)
Fig. 10. O2-TPD profiles of different 3DOM CeO2 and CeO2-ZrO2 samples.
profiles, which indicates that there was no clear distinction
between the desorption of surface and bulk oxygen. Because the
oxygen in the subsurface can quickly migrate to the surface as
the surface oxygen is released indicates a relatively high lattice
oxygen mobility [38].
Fig. 11A shows the CO2 profiles evolved during CO-TPR over dif-
ferent 3DOM CeO2 and CeO2-ZrO2 samples. Both the two CeO2
samples exhibit three weak reduction peaks with the increase of
the temperature. For the two CeO2-ZrO2 samples, only a strong
band is observed in the range of 240–600 °C. The production tem-
perature of CO2 in the CO-TPR is in general alignment with the
trend of the catalytic activity (Fig. 1A), which is an indication that
the lattice oxygen participates in CO oxidation on 3DOM CeO2 and
CeO2-ZrO2 samples. H2, as a byproduct, is also observed during
CO-TPR over the four samples, as shown in Fig. 11B. This is similar
to the observation by Wu et al. [24]. It is proposed that the forma-
 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377 373

Fig. 11. CO2 (A) and H2 (B) evolution during CO-TPR over different 3DOM CeO2 and CeO2-ZrO2 samples. (C) In situ DRIFT spectra collected during CO-TPR of C450 at different
temperature.

Fig. 12. In situ DRIFT spectra of CO adsorption on different 3DOM CeO2 and CeO2-ZrO2 samples at RT.

tion of H2 is mainly due to the reaction between adsorbed surface
OH groups and CO via water-gas shift type reactions [48]:
CO þ OH ! 1=2H2 þ CO2
CO þ 2OH ! H2 þ CO2 þ OL
To investigate the evolution of surface OH groups during CO-
TPR of the samples up to 600 °C, the in situ DRIFT spectra of C450
were employed, as shown in Fig. 11C. It can be seen that, bands
characteristic of formate (2842 cm1) derived from reaction
between CO and surface OH groups start to appear at 300 °C. For-
mate species is an intermediate in water-gas shift type reactions.
With the temperature increase, the formate decomposes to H2
and CO2.
It should be noted that the intensity of H2 peaks over pure CeO2
is much higher than that over CeO2-ZrO2 samples, indicating more
OH groups on the surface of CeO2. On the other hand, the 3DOM
CeO2-ZrO2 samples (CZ450 and CZ600) produce much more CO2
than the pure CeO2 in the CO-TPR testing. This suggests that the
ð1Þ
CO2 formation over the 3DOM CeO2-ZrO2 samples should be due
to direct CO reaction with reactive lattice oxygen instead of the
ð2Þ
water-gas shift reaction between CO and hydroxyl groups. This
must be associated with relatively high reducibility and oxygen
mobility of the 3DOM CeO2-ZrO2 samples.
3.4. Interaction with CO
DRIFT spectroscopy technology was used to investigate CO
adsorption and oxidation behaviour on these 3DOM CeO2 and
CeO2-ZrO2 samples. Fig. 12 shows the in situ DRIFT spectra from
CO adsorption on different samples at RT as a function of time after
switching in the CO feed. Based on the investigations of CO and CO2
374 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377
Table 4
Assignments of in situ DRIFT spectra observed in the CO adsorption at room temperature over the 3DOM CeO2 and CeO2-ZrO2 samples.
Species v(CO3)
Bicarbonate 1420, 1626
Unidentate carbonate 1420, 1360
Bidentate carbonate 1036, 1270, 1560
Bridged carbonate 1036, 1310, 1695
adsorption on ceria [24,48–51], CO interacts strongly with the sur-
face oxygen and forms a variety of carbonate species in the range
from 800 to 1800 cm1, and the assignments of the observed vibra-
tional bands are summarized in Table 4. Bicarbonate species,
unidentate carbonate species, bidentate carbonate species, bridged
carbonate species are formed upon the interaction of CO with the
surface oxygen of CeO2. Similar carbonate species are also observed
on the surface of the two CeO2-ZrO2 samples, while the corre-
sponding peaks are stronger for the CZ600 sample. It indicates that
CZ600 possesses more CO active sites [10].
In addition to the carbonate species (wave numbers in the range
from 800 to 1800 cm1), the bands at 2000–2200 cm1 were also
distinguished. Bands in the 2000–2200 cm1 region can be associ-
ated with linear or bridge-bonded CO interacting with sites on the
surfaces. A bridged carbonyl species will adsorb at lower wave
numbers than a linear carbonyl species [52]. The vibrational peaks
at ca. 2172 and 2117 cm1 are ascribed to CO adsorbed on the Ce
sites [53].
The bands with a wave number lower than 2100 cm1 are often
detected on noble metal catalysts (Au or Pt catalysts), which can be
assigned to negatively charged metal clusters or metal atoms [54].
The presence of the band at 2007 cm1 should be part of the wave
number at 2117 cm1 shifted to the lower wave number. The shift
of CO vibrational frequency is determined by the d and p-back
bonds orbitals [55–57]. When only a d bond is formed, the stability
of the carbonyls increases with the effective positive charge of the
cations, and, correspondingly, the CO vibrational frequency is
Fig. 13. In situ DRIFT spectra of CO oxidation on different 3DOM CeO2 and CeO2-ZrO2 samples.
p(CO3) d(OH) v(OH)
864 1216 3619
– – –
864 – –
– – –
shifted towards higher frequencies. However, the p-back bond is
formed at the expense of electron transfer from the d electrons
of the metal cation to the 2p⁄ antibonding orbitals of the CO mole-
cule [58,59]. As a result, the metalAC bond becomes stronger (i.e.
the carbonyls are more stable), which reflects in a red shift of the
CAO stretching vibrations [57]. Therefore, the lower band at
2007 cm1 can be attributed to the enhanced CeACO bond, indicat-
ing a stronger interaction between CeO2 and CO. It can be seen in
Fig. 12 that the CZ600 sample shows relatively high intensity of
peaks in the ranges of both 800–1800 cm1 and 2007 cm1, which
indicates that this sample could strongly interact with the CO
molecules.
Fig. 13 shows the in situ DRIFT spectra obtained as the samples
are heated in the reactant mixture. Three major types of carbonate
species were detected over the samples: bicarbonate species (864,
1440, 1626 and 3619 cm1), unidentate carbonate species (1440–
1360 cm1), and bidentate carbonate species (864, 1036, 1260–
1290 and 1563 cm1). The bicarbonate species (major peak at
1626 cm1) gradually disappeared, while the bidentate carbonate
(major peak at 1523–1563 cm1) species began to increase to a
great extent when the reaction temperature increased to 200 °C.
On the other hand, gaseous CO2 peaks (2293 and 2356 cm1)
started to appear at 200 °C and kept increasing in the intensity
with temperature. This is consistent with the increasing of CO con-
version (see Fig. 1A). These phenomena can be summarized as fol-
lows: bicarbonate species first transformed into bidentate
carbonate species (below 200 °C), followed by the decomposition
 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377 375

120 50 120 100

A B

Relative intensity (a.u.)

CO conversion at 673 K

Relative intensity (a.u.)

CO conversion at 673 K surface areas
ratio of (110) oxygen vacancy Crystallite Size

CO conversion / %
CO conversion / %
100 40 100 80

80 30 80 60

60 20 60 40

40 10 40 20

20 0 20 0
C450 C600 CZ450 CZ600 C450 C600 CZ450 CZ600
Samples Samples

Fig. 14. The relationship between the catalytic activities of CO oxidation and physicochemical properties of different catalysts (the relative intensity is calculated from that
amplify the same multiple on the original data).

of bidentate carbonate species into gaseous CO2 with increasing showed that the TOF (converted CO per surface O per second) of CO
temperature. The band intensity of carbonate species over CeO2 oxidation follows the order of {1 1 0} > {1 0 0}  {1 1 1}. The TEM
samples, especially C600, is much higher than that over CeO2- images show that all the 3DOM CeO2 and CeO2-ZrO2 samples
ZrO2 samples in the range of 200–400 °C. It is reported that the expose both {1 1 0} and {1 1 1} surfaces (see Fig. 6). The statistical
accumulation of carbonate species could cover the CO active sites, analysis based on the HRTEM images suggests that the ratios of
leading to a reversible deactivation [10,60]. Therefore the C600 and {1 1 0}/{1 1 0 + 1 1 1} decrease in the order of CZ600 > C450 >
C450 samples show lower activity than CZ600. C600 > CZ450 (see Figs. 6 and S2). This order is consistent with
the sequence of catalytic activity (see Fig. 1).
The relationship between the catalytic activities (CO conver-
4. Discussion sion) for CO oxidation and physicochemical properties of different
catalysts is summarized in Fig. 14. It can be seen that, for pure CeO2
4.1. Dominant factors for CO oxidation over CeO2-based catalysts samples (C450 and C600), the increase in particle size and the
decrease in oxygen vacancy concentration would reduce the cat-
It is generally accepted that the importance of ceria in catalysis alytic activity. We also note that this influence occurs with the pre-
originates from its extraordinary efficiency for reversible oxygen condition that there are no changes of the preferentially exposed
release via the rapid formation and elimination of oxygen vacan- surface plane over the two pure CeO2 samples (ratios of {1 1 0}/
cies [61]. The presence of oxygen vacancies provides relative free- {1 1 0 + 1 1 1} for C450 and C600 are 23% and 20%, respectively, as
dom for the movement of lattice oxygen and thus increases the shown in Fig. 6). For the two CeO2-ZrO2 samples (CZ450 and
mobility of oxygen [62]. O2 can adsorb on the vacancies, which CZ600), the sample heated at 600 °C (CZ600 sample) showed more
could reduce surface Gibbs energy, balance surface charge, and abundant oxygen vacancy and higher catalytic activity. This can be
form surface active oxygen species [11]. This would promote oxy- ascribed to the relatively higher ratios of {1 1 0}/{1 1 0 + 1 1 1} over
gen reactivity to CO in the catalytic process [15]. The results in the the CZ600 sample. CZ600 also revealed lower activation energies
present work reveal a similar phenomenon. The XRD, Raman spec- for CO oxidation (see Table 1), which should be linked to the bind-
tra and XPS results (see Figs. 3, 4 and 8 and Tables 2 and 3) indicate ing energies of CO or O (O2) with the exposed surface plane. Chen
that more oxygen vacancies are detected on the surface of CZ600 et al. [29] suggested that the barrier for the CO to react with a sur-
compared with the other samples, resulting in relatively high face O at CeO2 {1 1 0} is 0.25 eV, while it is 0.61 eV for the CO to
reducibility and oxygen mobility (observed by H2-TPR and react with a surface O at CeO2 {1 1 1}. In other words, the O at
O2-TPD, as shown in Figs. 9 and 10, respectively). The CZ600 shows CeO2 {1 1 0} is more active compared to that at CeO2 {1 1 1}. The fact
much higher catalytic activity for CO oxidation than the other three that the {1 1 0} surface is more reactive for promoting CO oxidation
samples (see Fig. 1). This suggests that both the oxygen vacancies can also be seen from the overall CO oxidation energy, which was
and oxygen mobility are important for catalytic CO oxidation. calculated to be exothermic by 1.1 eV at the {1 1 0} surface and
The textural properties such as the crystallite size and specific only 0.4 eV at the {1 1 1} surface (with respect to the noninteract-
surface area also influence the catalytic performance for CO oxida- ing CO-CeO2 systems). Nolan and Watson [28] reported that the
tion. Fan et al. [18] reported that the higher specific surface area interaction with CO molecule on the CeO2 {1 1 1} surface leads to
and smaller crystallite size of the catalyst can enhance the catalytic a weak adsorption, with an adsorption energy of 6 kcal/mol.
performance for CO oxidation. The CZ450 is also an exception in However, for the {1 1 0} surfaces, the adsorption energy is much
this respect. It can be seen in Table 1 that the specific surface areas higher (45 kcal/mol), indicating a relatively strong interaction
of 3DOM CZ450 are higher than or equal to those of the other between adsorbed CO and CeO2 {1 1 0} surface. Fig. 14A also
3DOM CeO2 or CeO2-ZrO2 samples. In addition, it also possesses a showed that the ratios of {1 1 0}/{1 1 0 + 1 1 1} and oxygen vacancy
smaller crystallite size of CeO2, as shown in Table 2. However, concentration over different samples followed the same trend as in
the CZ450 sample shows the worst catalytic performance for CO the values of CO conversion for CO oxidation. This phenomenon
oxidation among all the samples. demonstrates that the preferentially exposed surface plane and
Surface structure dependence of CeO2 catalysts for CO oxidation oxygen vacancy concentration are crucial factor in determining
is also confirmed by intensive experimental and theoretical studies catalytic activity.
[63–66]. To get a greater understanding of the nature of different
CeO2 surface planes in the catalytic process, Wu et al. [24] system- 4.2. CO adsorption and reaction mechanism
atically investigated CO oxidation over a series of ceria nanocrys-
tals with defined surface planes (nanoshapes) including rods As observed in the CO-TPR process (Fig. 11), surface water-gas
({1 1 0} + {1 0 0}), cubes ({1 0 0}), and octahedra ({1 1 1}). The results shift reaction between CO and surface OH groups was detected.
376 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377
Scheme 1. Reaction mechanism model of CO oxidation over 3DOM CeO2-ZrO2 catalysts.
The results of in situ DRIFTS during CO-TPR (Fig. 11C) show the
presence of formate species, which is indentified as an intermedi-
ate from CO to carbonate [48]. Jardim et al. [53] also reported that
the presence of surface OH groups on the catalyst could enhance
the catalytic activity for CO oxidation. In our results, there are
abundant OH groups on the surface of 3DOM CeO2 sample (Figs. 8
and 11), while low catalytic activity for CO oxidation observed over
the CZ600 sample. By contrast, the CZ600 shows the best catalytic
performance, although limited OH groups can be detected on the
surface of CeO2-ZrO2 samples. In addition, Fig. S5 shows the curves
of CO conversion over the C450 catalyst both in the heating and
cooling processes in CO oxidation. As seen, there are no obvious
differences between the heating and cooling processes. Since the
fresh catalyst has abundant OH groups, these phenomena indicate
that the surface OH groups should not be a crucial factor in deter-
mining the catalytic activity.
The results of in situ DRIFTS during CO adsorption (Fig. 12) show
the presence of two types of CO species: adsorbed CO on surface Ce
sites (the band at ca. 2007 cm1) and CO chemically bonded to sur-
face oxygen forming carbonate species. The former species were
often detected on the supported noble metal catalysts, indicating
a strong interaction between CO and catalysts [54]. The high inten-
sity of the band at 2007 cm1 on the CZ600 sample suggests strong
interaction between CO and CZ600. This can be related to the fact
that there are more {1 1 0} surfaces exposed on this sample,
because Ce is more active on {1 1 0} surface than on {1 1 1} [67].
On the other hand, the Raman (Fig. 4) and XPS (Fig. 8) results
indicate that the CZ600 sample also possesses abundant oxygen
vacancies, which can adsorb O2 molecules. In this case, a
Langmuir-Hinshelwood (L-H) mechanism should occur over the
CZ600 catalyst. According to this mechanism, the CO molecules
firstly adsorb on the catalyst surface and react with the adsorbed
oxygen thereafter, followed by the formed CO2 desorbing into the
gas phases (see Scheme 1). It should be noted that large amounts
of carbonate species were detected on the C600 sample during
the CO catalytic oxidation (see Fig. 13), indicating the accumula-
tion of carbonate species. The accumulation should be related to
the relatively low concentration of oxygen vacancy on this sample,
because less O2 can be adsorbed on the vacancies to form active
oxygen to remove the adsorbed CO species. This results in rela-
tively lower catalytic activity of this sample.
On the other hand, the CO-TPR result (see Fig. 11A) reveals that,
in the absence of O2, the 3DOM CeO2 or CeO2-ZrO2 can be reduced
by CO during the similar temperature region with the catalytic CO
oxidation. This indicates that a Mars-van Krevelen (M-K) mecha-
nism based on the redox property of CeO2 or CeO2-ZrO2 catalysts
also cannot be ignored. In a Mars-van Krevelen process, CO reacts
with lattice oxygen of ceria to form CO2 and leave an oxygen
vacancy, and then the replenishing of the vacancy by gas-phase
oxygen completes the cycle (see Scheme 1). However, it should
not be crucial compared with the L-H mechanism, because there
is no obvious relationship between the reducibility and the cat-
alytic activity among the different samples.
5. Conclusions
A series of 3DOM CeO2 and CeO2-ZrO2 catalysts with varying
particle sizes, oxygen vacancy concentrations, oxygen mobility
and preferentially exposed surface planes were synthesized by a
colloidal crystal template method. Their physicochemical proper-
ties were associated with the catalytic performances to identify
the most crucial factor in determining catalytic activity. The inter-
actions of catalysts with CO and reaction mechanism were further
investigated in detail. The prepared 3DOM CeO2 and CeO2-ZrO2
materials were highly ordered and interconnected with each other
by small pore windows, and the good macroscopic order still
retained even after ageing at 800 °C, indicating a high thermal sta-
bility of the macroporous structure. Such 3DOM framework is ben-
eficial for CO oxidation. One of the most important phenomena is
that CZ450 sample, which possesses higher surface area and smal-
ler particle size compared with the pure CeO2, showed much
poorer catalytic activity for CO oxidation. By contrast, the CZ600
sample presented the highest catalytic activity among all the cata-
lysts due to the highest ratio of {1 1 0}/{1 1 0 + 1 1 1} and oxygen
vacancy concentration. The ratios of {1 1 0}/{1 1 0 + 1 1 1} and oxy-
gen vacancy concentration over different samples follow the same
trend as the CO conversion. These results suggest that the prefer-
entially exposed surface plane and oxygen vacancy concentration
are more crucial for determining the catalytic activity of CeO2-
based catalysts when compared with the other parameters (e.g.,
crystallite size and surface area).
 Y. Zheng et al. / Journal of Catalysis 344 (2016) 365–377 377

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