Chemical Engineering Journal 247 (2014) 4249

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Redox behavior of active PdOx species on (Ce,Zr)xO2Al2O3 mixed oxides

and its inuence on the three-way catalytic performance
Siyu Lin, Linyan Yang, Xue Yang, Renxian Zhou
Institute of Catalysis, Zhejiang University, Hangzhou 310028, PR China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 PdOx species are mainly dispersed on

Al2O3-rich grains surface in fresh

catalysts.
 PdOx species migrate to (Ce,Zr)xO2rich grains surface after aging
treatment due to Pd-(Ce,Zr)xO2
interaction.
 Interaction between PdOx species and
(Ce,Zr)xO2 promotes the thermal
stability.
 Co-precipitation preparation method
improves catalysts thermal stability.

a r t i c l e

i n f o

Article history:
Received 25 December 2013
Received in revised form 3 March 2014
Accepted 7 March 2014
Available online 15 March 2014
Keywords:
(Ce,Zr)xO2Al2O3
Pd-only three-way catalysts
Thermal stability
PdOx species
Redox behavior

a b s t r a c t
Two kinds of (Ce,Zr)xO2Al2O3 mixed oxides (designated as CZA-m and CZA-c) were prepared through
mechanically mixed and co-precipitation method, and the corresponding supported Pd-only three-way
catalysts calcined at different temperatures were investigated by XRD, N2 adsorption, in situ DRIFTS,
HRTEM, H2-TPR and O2-TPSR. The results show that PdOx species are mainly dispersed on Al2O3-rich
grains surface in fresh catalyst, after thermal aging treatment, some PdOx species would migrate to
(Ce,Zr)xO2-rich grains surface due to the strong interaction of PdOx-(Ce,Zr)xO2 and the sintering of alumina with loss of surface area. When thermally treated at 9001000 C, the interaction of both Al2O3(Ce,Zr)xO2 and PdOx-(Ce,Zr)xO2-rich grains would be promoted, which enhances the thermal stability of
PdO species and the reoxidation ability of Pd0 to PdO under high temperature reaction conditions, especially for Pd/CZA-c catalyst. Meanwhile, more stable PdOx species which have strong interaction with
support are formed and their reducibility is improved. Therefore, Pd/CZA-c catalyst exhibits better thermal stability than that of Pd/CZA-m.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Three-way catalysts (TWCs) have been extensively used to remove pollution gases from gasoline automotive [13]. They can
work efciently to convert hydrocarbons (HC), CO and NOx into
CO2, H2O and N2 by redox reaction in a narrow window of air/fuel
(A/F) ratio [1,4]. Typical TWCs are composed of three parts, includ Corresponding author. Tel.: +86 571 88273290; fax: +86 571 88273283.
E-mail address: zhourenxian@zju.edu.cn (R. Zhou).
http://dx.doi.org/10.1016/j.cej.2014.03.015
1385-8947/ 2014 Elsevier B.V. All rights reserved.

ing precious metals such as Rh, Pt and Pd, ceriazirconia mixed

oxides as promoters, and alumina as support [57]. Pd-only TWCs
have received considerable attention due to its better resistance to
thermal sintering, lower cost and higher activity for removing HC
and CO than other precious metals [814]. The interaction between
PdOx and support has a great effect on the properties of PdOx species. The chemical state and stability of PdOx species on the support
surface plays an important role on the low temperature light-off
performance of Pd-only TWCs and their thermal stability under
high temperature conditions. Wang et al. [15,16] studied the effect

S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

of rare earth elements (La, Nd, Pr, Sm and Y) doping on three-way

catalytic performance of Pd/CexZr1 xO2, and showed that the
addition of La or Pr promoted the interaction between PdOx species
and CexZr1 xO2, resulting in an increase of thermal stability and
oxygen storage capacity. Li et al. [17] reported that the introduction of 3% Ni into Ce0.67Zr0.33O2 improved the dispersion of PdOx
species on the surface of support and the catalytic performance
of Pd/Ce0.67Zr0.33O2 before/after aging treatment due to the formation of homogeneous CeZrNiO ternary solid solution which was
in favor of the interaction between PdOx species and support.
However, the interaction between PdOx and CeZr support would
be weakened under high temperature conditions because of the
sintering and encapsulation of PdOx, in which leads to a gradual
decrease of catalytic activities [5,18]. In order to maintain a ne
dispersion of precious metals to get a good thermal stability,
c-Al2O3 is introduced into CeO2ZrO2 as a diffusion barrier
[19]. A great diversity of the distribution and chemical state of
PdOx species on the supports is caused by different interaction between PdOx species and supports, especially for low precious metal
loading. In addition, the stability and redox behavior of active PdOx
species on the supports would also be affected under high temperature conditions, and further affects catalytic performances of
three-way catalysts. But there is a lack of related research in the
inuence of the physicochemical properties of active PdOx species
on the catalytic performances of (Ce,Zr)xO2Al2O3 mixed oxides
supported Pd-only TWCs.
In this work, two kinds of (Ce,Zr)xO2Al2O3 mixed oxides with
different interaction between (Ce,Zr)xO2 and Al2O3, and the corresponding supported Pd-only catalysts calcined at different temperatures were prepared. Their textural and structural properties,
redox behavior, dispersion state and stability of PdOx species on
(Ce,Zr)xO2Al2O3 supports were characterized by X-ray diffraction
(XRD), N2 adsorption, in situ DRIFTS, high resolution transmission
electron
microscopy
(HRTEM),
hydrogen
temperatureprogrammed reduction (H2-TPR) and oxygen temperatureprogrammed surface reaction (O2-TPSR). And the three-way
catalytic performances of the catalysts were evaluated under the
simulated automobile exhaust.

2. Experimental
2.1. Catalyst preparation
(Ce,Zr)xO2 sample (designated as CZ, Ce0.67Zr0.33O2) was prepared by co-precipitation method [11]. Pure c-Al2O3 (supplied by
Rhodia Company) was mechanically mixed with CZ powder to
prepare (Ce,Zr)xO2Al2O3-m sample (designated as CZA-m).
(Ce,Zr)xO2Al2O3-c sample (designated as CZA-c) was prepared by
co-precipitation method. The ammonia solution was added
dropwise to the quantitative mixed aqueous solution of Ce(NO3)3
 6H2O, ZrO(NO3)2  6H2O and Al(NO3)3  9H2O under continuous
stirring until pH = 9.5. After aging at room temperature for 12 h,
the obtained precipitate was supercritical dried in the medium of
ethanol (241 C, 6.14 MPa) for 2 h. Then, the dried sample was
calcined at 500 C in air for 4 h. In the CZA-m and CZA-c samples,
the weight ratio of CZ to Al2O3 is 1:1. All the supports were
pressed into pellets, crushed and sieved to 4060 meshes
(0.30.45 mm).
The corresponding supported Pd-only catalysts with Pd content
of 1.0 wt.% were prepared by conventional wet impregnation
method with an aqueous of H2PdCl4 as reported before [15,17],
and designated as Pd/CZ, Pd/CZA-m, Pd/CZA-c and Pd/Al2O3,
respectively. Then the catalysts were calcined at 900, 1000 or
1100 C for 4 h in order to investigate the thermal stability
property.

43

2.2. Catalytic performance test

The three-way catalytic performance tests were carried out in a
quartz xed-bed micro-reactor (i.d. = 6 mm) at atmospheric pressure [1517]. The catalyst (0.2 ml, sieved fraction from 0.3 to
0.45 mm) was held in the quartz tube by packing quartz wool at
both ends of the catalysts bed. The simulated exhaust gas including
NO (0.1%)NO2 (0.03%)C3H6 (0.067%)C3H8 (0.033%)CO (0.75%)
O2 (0.745%, the oxygen needed for full conversion to CO2, H2O and
N2) and Ar (balance) was fed to catalyst bed at a space velocity of
43,000 h 1. The concentration of CO, NOx (NO and NO2) and total
HC (C3H6 and C3H8) was analyzed by on-line Fourier transform
infrared spectrophotometer (BRUKER EQ55) equipped with a multiple reection transmission cell (Infrared Analysis Inc.; path
length 10.0 m). All spectra were taken at a resolution of 2 cm 1
for 128 scans.
2.3. Physicochemical characterization
Powder X-ray diffraction (XRD) patterns were recorded on an
ARL XTRA diffractometer operating at 40 kV and 40 mA with nickel-ltered Cu Ka radiation and ranging from 20 to 80 with a 0.02
step size. The textural properties were determined by N2 physisorption using Tristar II 3020 (Micromeritics Inc.) at 77 K. Samples
were degassed under vacuum at 200 C for 3 h before testing. Diffuse reectance infrared Fourier transform spectroscopy (DRIFTS)
studies were conducted on a Nicolet 6700 FTIR tted with an
MCT detector. The DRIFTS cell was tted with CaF2 windows and
a heating cartridge that allowed samples to be heated to 500 C.
Spectra were collected at the resolution of 4 cm 1 and 32 scans.
Prior to infrared experiment, the sample was pretreated with 10%
O2 at 450 C for 0.5 h and then cooled down to 30 C in order to remove the contaminants. The composition of feed stream was same
to the catalytic performance test. HRTEM studies were performed
with a TECNAI G220 instrument operated at 200 kV. The samples
for the HRTEM studies were previously dispersed in ethanol and
deposited onto a perforated carbon lm supported on a copper
grid. H2-TPR experiments were carried out on a GC-1690 chromatography to estimate the redox behavior of the catalysts. The samples (50 mg) were rst purged under pure N2 (30 ml min 1) at
200 C for 30 min and then cooled down to 50 C in liquid nitrogen. A ow of 5% H2/Ar (40 ml min 1) was switched into the system, and the temperature was raised to 900 C at a rate of 10 C
min 1. The consumption of H2 was measured online over a gas
chromatograph (GC, KX100) with thermal conductivity detector
(TCD), and the water formed during the program was absorbed
with 5A molecular sieve. Thermal stability of the active PdOx species on the support was measured by means of O2-TPSR. A 100 mg
catalyst was used for each measurement. Prior to TPSR experiments, the samples were rst pretreated under pure N2
(40 ml min 1) atmosphere at 500 C for 0.5 h and then cooled
down to room temperature. A ow of 2% O2 /He (40 ml min 1)
was switched into the system, and the temperature was raised to
1100 C at a heating rate of 20 C min 1. After reaching 1100 C,
the reaction temperature was cooled down to 300 C at a cold rate
of 20 C min 1 again. The outlet gases were analyzed online over a
gas chromatograph (GC, KX100) with thermal conductivity
detector.
3. Results and discussion
3.1. Catalytic performance
The three-way catalytic performance of the catalysts was evaluated under the simulated automobile exhaust. The conversions of

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S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

(A) HC, (B) CO, (C) NO and (D) NO2 over Pd/CZA-m and Pd/CZA-c
catalysts calcined at different temperatures are shown in Figs. 1
and 2. For fresh catalysts, Pd/CZA-m catalyst shows higher catalytic
performance than that of Pd/CZA-c. But the catalytic performance
of Pd/CZA-m obviously decreases with the increasing calcination
temperature, after Pd/CZA-m catalyst calcined at 1100 C, T90%
(the temperature required to attain 90% conversion) of HC, CO,
NO and NO2 is 320, 245, 328 and 273 C. While the catalytic performance of Pd/CZA-c does not decrease obviously except for NO2
conversion, T90% of HC, CO, NO and NO2 is 314, 211, 317 and
304 C, which increase 25, 5, 13 and 41 C compared with the fresh
catalyst. The results indicate that Pd/CZA-c catalyst exhibits better
thermal stability than that of Pd/CZA-m. In order to get further
information about the effect of textural and structural properties,
redox behavior, chemical state and stability of active PdOx species
on three-way catalytic performance under different thermal treatment conditions, the physicochemical properties of the catalysts
are characterized below.
3.2. Physicochemical characterization
3.2.1. Textural and structural properties
Textural and structural properties of the catalysts were investigated by XRD and N2 adsorption, and the results are shown in Fig. 3
and Table 1. For all the catalysts, the diffraction peaks correspond
to a mainly cubic uorite structure of CeO2. No splitting peaks referred to PdOx phase can be discovered because of the detection
limit of the XRD technique, indicating that PdOx particles are too
small to be detected. The diffraction peaks become greatly narrower with the increasing calcination temperature on account of

the growth and sintering. As compared with Pd/CZA-m catalyst,

Pd/CZA-c exhibits more symmetrical peak shape and wider diffraction line, validating the small crystallites and high homogeneity.
While for the Pd/CZA-m catalyst calcined at 1100 C, h-Al2O3 and
a-Al2O3 phase is observed. It suggests that the thermal stability
of Pd/CZA-c catalyst is better than that of Pd/CZA-m. As listed in
Table 1, the lattice parameter and crystallite size of the catalysts
are calculated from the (1 1 1) plane (2h = 28.7) by Scherrers
equation. Pd/CZA-c shows smaller lattice parameter and crystallite
size than Pd/CZA-m. As the ion radius of Al3+ (0.057 nm) is smaller
than that of Ce4+ (0.097 nm)/Ce3+ (0.114 nm) and Zr4+ (0.084 nm),
incorporation some Al3+ into the (Ce,Zr)xO2 lattice by replacing of
Ce4+/Ce3+ or Zr4+ may lead to the shrinkage of the lattice parameter.
Interestingly, the lattice parameter of CeO2 in Pd/CZA-m becomes
also smaller with increasing of the calcination temperature, which
shows more Al3+ incorporation into the (Ce,Zr)xO2 lattice during
thermal aging treatment. From Table 1, we can also see that the
BET surface area of fresh Pd/CZA-m is much larger than that of
Pd/CZA-c catalyst. However, Pd/CZA-c catalyst still maintains large
surface area obviously higher than that of Pd/CZA-m after calcination at high temperature, which is in agreement with the results of
XRD. The crystallite size becomes large with the increase of the calcination temperature due to the sintering of catalysts. And the
smaller crystallite size in Pd/CZA-c catalyst than that in Pd/CZAm catalyst calcined at the same temperature indicates that Pd/
CZA-c catalyst is more thermal stable than Pd/CZA-m catalyst.
The results show that CZA-c prepared by co-precipitation method
exhibits better thermal stability than CZA-m because of the stronger interaction between (Ce,Zr)xO2 and Al2O3, which keeps large
surface area, small crystallite size and restrains from the formation

Fig. 1. Conversion of (A) HC, (B) CO, (C) NO and (D) NO2 as a function of reaction temperature under stoichiometric HC + CO + NO + NO2 over Pd/CZA-m catalysts.

S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

45

Fig. 2. Conversion of (A) HC, (B) CO, (C) NO and (D) NO2 as a function of reaction temperature under stoichiometric HC + CO + NO + NO2 over Pd/CZA-c catalysts.

Fig. 3. XRD patterns of the Pd/CZA-m and Pd/CZA-c catalysts.

of a-alumina phase under high temperature condition, nally improves the thermal stability of Pd/CZA-c catalyst.

3.2.2. H2-TPR studies

The reducibility of the catalysts is characterized by H2-TPR technique. As illustrated in Fig. 4, PdOx species supported on Al2O3 is
more easily reduced and the hydrogen consumption peak between
5 and 15 C represents the reduction of PdOx species highly dispersed on the surface of Al2O3. The H2 consumption is 68 lmol g 1cat which is approaching the theoretical value (82 lmol g 1cat,
theoretical for PdO reduction alone). And a negative peak at about

70 C is generally assigned to the decomposition of PdHx phase

[16,20]. Except for the negative peak, the H2-TPR proles of Pd/
CZ catalyst exhibits another two peaks (a and b) of hydrogen consumption at 18 C and 93 C. The peak a between 10 and 50 C
should be assigned to the reduction of highly dispersed PdOx species, and the peak b between 80 and 150 C may be attributed to
the reduction of stable PdOx species having strong interaction with
(Ce,Zr)xO2 oxides which would promote the reduction of Ce4+ to
Ce3+ [21]. However, the H2 consumption over Pd/CZ catalyst is
too large to be reasonably attributed to the reduction of noble
metal oxides, 491 for peak a and 84 lmol g 1cat for peak b. As
known to all that H2 molecules will split into H atoms by precious
metal, these active H atoms can easily reduce oxides at relatively
low temperature [22,23]. We suggest that PdOx species promote
the adsorption and spillover of hydrogen from noble metal particles to the (Ce,Zr)xO2 oxides support, leading to the interfacial
Ce4+ reduction at relatively low temperature.
H2-TPR proles of the all Pd/CZA-m and Pd/CZA-c catalysts also
exhibit two peaks of hydrogen consumption, and the total H2 consumption over the catalysts is also much larger than the theoretical
value. The results indicate that some PdOx species may disperse on
(Ce,Zr)xO2-rich grains surface in the catalysts, resulting in the interfacial Ce4+ reduction. For the fresh catalysts, peak a between 4 and
20 C shifts to lower temperature in comparison with that of Pd/CZ
catalyst, which means that more PdOx species are dispersed on
Al2O3-rich grains surface. The H2 consumption for peak b over
Pd/CZA-m (99 lmol g 1cat) is larger than that over Pd/CZA-c,
which may be that more stable PdOx species exist in Pd/CZA-m
compared with that of Pd/CZA-c catalyst. Therefore, Pd/CZA-m catalyst shows a better catalytic performance.

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S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

Table 1
Textural and structural properties of the Pd/CZA-m and Pd/CZA-c catalysts.

Catalysts

Calcination temperature (C)

SBET (m2 g

Pd/CZA-m

500
900
1000
1100

Pd/CZA-c

500
900
1000
1100

Lattice parametera (nm)

Crystallite size (nm)

163.0
56.0
35.8
15.9

0.5420
0.5405
0.5379
0.5357

5.4
7.9
10.3
23.7

135.0
73.7
52.0
23.5

0.5351
0.5334
0.5340
0.5343

3.9
6.8
8.2
17.0

Lattice constants are calculated by JADE 7.

Fig. 4. H2-TPR traces for the indicated catalysts.

However, the changes of redox behavior of the catalysts are

more obvious after thermal aging treatment. For Pd/CZA-m catalyst, the reduction peaks (a and b) of PdOx species and the decomposition peak of palladium hydride shift to higher temperature
with the increase of calcination temperature. Moreover, the intensity of the decomposition peak of palladium hydride is obviously
increased. As reported in literature [24], the existence of large palladium particles is in favor of the formation of PdHx phase, it implied that Pd is partly sintered after aging treatment. Therefore,
the catalytic performance of Pd/CZA-m obviously decreases with
the increase of calcination temperature. And for the Pd/CZA-m catalyst calcined at 9001000 C, the H2 consumption of peak a obviously increases, indicating that some PdOx species migrate onto
(Ce,Zr)xO2-rich grains surface that promotes the spilling of hydrogen, which may be caused by the decreasing of Al2O3 surface area.
While for Pd/CZA-c catalyst, the reduction peak b of stable PdOx
species and the decomposition peak of palladium hydride shift to
lower temperature after calcined at higher than 900 C. The H2
consumption of peak b is obviously increased and the intensity
of the decomposition peak of palladium hydride does not increase
much in comparison with that of fresh Pd/CZA-c catalyst, especially for Pd/CZA-c catalysts calcined at 9001000 C. It indicates
that small particle size of PdOx can be still maintained, the interaction between PdOx and support is promoted and more stable PdOx
species having strong interaction with support are formed after
thermal aging treatment, resulting in increasing the reducibility
of the stable PdOx species. Therefore, Pd/CZA-c exhibits better thermal stability than Pd/CZA-m.
3.2.3. O2-TPSR studies
In order to investigate the thermal stability of PdOx species and
the reoxidation properties of Pd0 into PdO dispersed on the support
surface, O2-TPSR experiments were carried out. O2-TPSR proles of

fresh Pd/CZ and Pd/Al2O3 catalysts as well as the Pd/CZA catalysts

before/after calcined at 1000 C are shown in Fig. 5. We can see
that Pd/CZ catalyst exhibits one decomposition peak of PdO at
about 987 C during rising temperature and one reoxidation peak
of Pd0 into PdO at about 659 C during lowering temperature.
While the decomposition peak is at about 800 C and the reoxidation peak is at about 505 C for Pd/Al2O3 catalyst. It suggests that
compared with Pd/Al2O3 catalyst, PdOx species dispersed on
(Ce,Zr)xO2 grains are more stable, which may be due to the stronger
interaction between PdOx species and (Ce,Zr)xO2.
For fresh Pd/CZA-m and Pd/CZA-c catalysts, two decomposition
peaks of PdO during rising the temperature are observed, which
should be attributed to the thermal decomposition of PdOx species
dispersed on Al2O3-rich and (Ce,Zr)xO2-rich grains respectively,
which is in agreement with H2-TPR results. According to calculation, the content of PdOx species dispersed on Al2O3-rich grains
in Pd/CZA-m and Pd/CZA-c catalysts is 71.6% and 51.2%, respectively. Moreover, two peaks attributed to the reoxidation of Pd0
into PdO are also observed during lowering the temperature. The
peaks at about 650 and 510 C can be attributed to the reoxidation
of Pd0 into PdO dispersed on (Ce,Zr)xO2-rich and Al2O3-rich grains,
respectively. However, the intensity of reoxidation peak at about
510 C in Pd/CZA-m catalyst is obviously weakened during lowering the temperature, and Pd/CZA-c catalyst even only exhibits
one reoxidation peak at about 650 C. The results suggest that
some metallic Pd species dispersed on Al2O3-rich grains may migrate onto (Ce,Zr)xO2-rich grains surface during the high temperature test because of having stronger interaction between PdOx
species and (Ce,Zr)xO2-rich grains, especially for Pd/CZA-c catalyst.
And it would promote the thermal stability of PdO species and the
reoxidation ability of Pd0 to PdO under high temperature reaction
conditions.
For the Pd/CZA catalysts calcined at 1000 C, only one decomposition peak of PdOx species during rising temperature and one
reoxidation peak of Pd0 into PdO during lowering temperature is
observed, at about 815 and 640 C, respectively. It suggests that
after calcined at 1000 C, the PdOx species migrate to (Ce,Zr)xO2rich grains surface, which is favor of increasing reoxidation ability
of Pd0 into PdO and thermal stability for the Pd/CZA catalysts.
3.2.4. HRTEM studies
Fig. 6 gives the HRTEM images of different catalysts calcined at
500 and 1000 C. From Fig. 6, it can be seen that for the catalysts
before/after calcined at 1000 C, PdOx particles exhibit a good dispersed state on the support surface, the particle sizes of PdO are 4
5 and 810 nm, respectively. Pd/CZA-c exhibits smaller particle
sizes of PdO in comparison with that of Pd/CZA-m calcined at
1000 C. The interplanar spacing of 0.2650.267 nm is in correspondence with to PdO (1 0 1) lattice fringes, and PdOx species
mainly disperse on the Al2O3-rich grains surface for fresh Pd/
CZA-m catalysts, while for fresh Pd/CZA-c catalyst PdOx species
disperse on both Al2O3-rich and (Ce,Zr)xO2-rich grains surface. In

S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

47

Fig. 5. O2-TPSR proles of the indicated catalysts calcined at 500 C (A) and 1000 C (B).

Fig. 6. HRTEM images of (A) Pd/CZA-m calcined at 500 C, (B) Pd/CZA-c calcined at 500 C, (C) Pd/CZA-m calcined at 1000 C, (D) Pd/CZA-c calcined at 1000 C.

addition, for both the two kinds catalysts calcined at 1000 C, PdOx
species are mainly dispersed on (Ce,Zr)xO2-rich grains surface,
which is in agreement with H2-TPR and O2-TPSR results.
3.2.5. In situ DRIFTS studies
The chemical state of PdOx species on the supports was analyzed by in situ DRIFTS under reaction conditions, and the result
is shown in Fig. 7. Bands in the region of 18002200 cm 1 are
attributed to carbonyls adsorbed on PdOx sites [25,26]. In fresh
Pd/CZA-m catalyst, a band at about 2160 cm 1 is detected from
50 to about 150 C, which is attributed to carbonyls adsorbed on

Pd(2+) sites. While the band at about 21402160 cm 1 is very

weak in fresh Pd/CZA-c catalyst probably due to its larger reducibility (as shown in Fig. 4). Moreover, in the Pd/CZA-c catalyst weak
bands attributed to carbonyls adsorbed on Pd(1+) and Pd(0) sites
are also observed in the region of 19452120 cm 1. After running
the reaction up to 210 C, a band at about 2240 cm 1 is observed
in Pd/CZA-m catalyst, which is attributed to NCO species adsorbed
on Al2O3-rich grains [27,28], and the band in Pd/CZA-m starts to
appear at about 270 C. The formation of NCO species is usually regarded as a useful ngerprint for monitoring the NO dissociation
process [27,28]. The result is in well agreement with onset of NO

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S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

Fig. 7. DRIFTS spectra of (A) Pd/CZA-m calcined at 500 C, (B) Pd/CZA-c calcined at 500 C, (C) Pd/CZA-m calcined at 1000 C, (D) Pd/CZA-c calcined at 1000 C under
stoichiometric CO + NOx + HC + O2 reaction condition. Spectra were taken from 50 C to 400 C.

conversion over the catalysts, as shown in Figs. 1 and 2, and Pd/

CZA-m catalyst exhibits better catalytic performance for NO and
NO2 conversions in comparison with Pd/CZA-c. Moreover, the band
at about 2240 cm 1 displays a signicantly stronger intensity in
Pd/CZA-m catalyst, indicating that more PdOx species are dispersed
on Al2O3-rich grains surface in Pd/CZA-m. As can be seen in Fig. 7,
after thermal aging treatment at 1000 C, the band at about
2240 cm 1 in Pd/CZA-m is weaken while no in Pd/CZA-c probably
due to the CZ-Al2O3 interaction being promoted and less independent alumina phase exiting, especially in Pd/CZA-c catalyst. Meanwhile, more PdOx species dispersed on Al2O3-rich grains surface
may be migrated onto the (Ce,Zr)xO2-rich grains due to the stronger interaction between PdOx species and (Ce,Zr)xO2-rich grains,
which is also the possible reason. In addition, in Pd/CZA-m catalyst
calcined at 1000 C, weak band about 21402160 cm 1 which can
be attributed to carbonyls species adsorbed on Pd(2+) sites is still
present but no in the region of 19452120 cm 1, which may be
caused by the change of Pd particle size and its reducibility due
to aggregation. However, in Pd/CZA-c catalyst calcined at
1000 C, carbonyls assigned to CO (2110 cm 1) adsorbed on
Pd(1+) can be observed at low temperature, simultaneously, another two types of adsorbed carbonyls species attributed to atop
(2090 cm 1) and bridge (1962 cm 1) Pd(0) sites are also obviously
observed. During raising the temperature the intensity of atopbonded CO species is decreased and the bond shifts to lower wave
numbers for carbonyls species adsorbed on Pd(0). The decrease in
intensity and the shift are more pronounced for atop species,
which may be the net effect of a thermal contribution and its lower
energy of adsorption [25]. And raising the temperature also leads
to a continuous increase in intensity of bridge-bonded CO species,
characteristic of an increase in CO coverage probably due to that
more PdOx species having strong interaction with support are
formed and its reducibility is improved after thermal aging treatment (as shown in Fig. 4).

4. Conclusions
Two kinds of (Ce,Zr)xO2Al2O3 mixed oxides were prepared
using mechanically mixed and co-precipitation methods to study
the redox behavior of active PdOx species on (Ce,Zr)xO2Al2O3
mixed oxides and inuence on the three-way catalytic performance. In summary, the following conclusions can be derived from
the results of the present work: (1) CZA-c prepared using co-precipitation method exhibits better thermal stability than CZA-m
due to having stronger interaction between (Ce,Zr)xO2 and Al2O3
in the former, which maintains large surface area, small particle
size and inhibits the formation of a-alumina phase under the high
temperature condition. (2) After being thermally treated at 900
1000 C, the interaction between (Ce,Zr)xO2 and Al2O3 is enhanced,
especially for Pd/CZA-c, which is in favor of increasing thermal stability of the Pd/CZA catalysts. Thus, Pd/CZA-c catalyst exhibits better thermal stability than that of Pd/CZA-m. (3) PdOx species are
mainly dispersed on Al2O3-rich grains surface in fresh catalysts,
after thermal aging treatment, some PdOx species would migrate
to (Ce,Zr)xO2-rich grains surface due to the strong interaction of
PdOx-(Ce,Zr)xO2 and the sintering of alumina with loss of surface
area, and it enhances the thermal stability of PdO species and the
reoxidation ability of Pd0 into PdO under high temperature reaction conditions. (4) For Pd/CZA-c catalyst, more stable PdO species
having strong interaction with (Ce,Zr)xO2-rich grains support are
formed and its reducibility is improved after thermally treated at
9001000 C. Due to these reasons listed above, Pd/CZA-c catalyst
exhibits better thermal stability than Pd/CZA-m catalyst.

Acknowledgements
We gratefully acknowledge the nancial supports from the
Ministry of Science and Technology of China (No.:

S. Lin et al. / Chemical Engineering Journal 247 (2014) 4249

2011AA03A406) and Zhejiang Leading Team of Science and Technology Innovation.

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