JOURNAL OF RARE EARTHS, Vol. 34, No. 3, Mar. 2016, P.

259

Effect of synthesis methods on activity of V2O5/CeO2/WO3-TiO2

catalyst for selective catalytic reduction of NOx with NH3
SHEN Meiqing ()1,2,3, XU Lili ()1, WANG Jianqiang ()1, LI Chenxu ()1,
WANG Wulin ()1, WANG Jun ( )1,*, ZHAI Yanping ()4,*
(1. Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering & Technology, Tianjin University, Tianjin
300072, China; 2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China; 3. State Key Laboratory of Engines,
Tianjin University, Tianjin 300072, China; 4. China Huadian Science and Technology Institute, Beijing 100070, China)
Received 21 August 2015; revised 12 November 2015

Abstract: The effect of synthesis methods on the activity of V/Ce/WTi catalysts was investigated for the selective catalytic reduction
(SCR) of NOx by NH3. V/Ce/WTi-DP (deposition precipitation) catalyst showed excellent NH3-SCR performance, especially the better medium-temperature activity and the less N2O formation than V/Ce/WTi-IMP (impregnation). These catalysts were characterized
by X-ray diffraction (XRD), Brumauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), temperature-programmed
reduction (H2-TPR), and in situ DRIFTS techniques. The XPS and H2-TPR results revealed that V/Ce/WTi-DP exhibited more surface Ce species, higher level of O and higher reducibility of Ce species. Reflected by in situ DRIFTS results, the deposition precipitation method (DP) contributed to a greater amount of weakly adsorbed NO2, monodentate nitrate and NH3 species with better reactive activity. Meanwhile, the cis-N2O22 species, an intermediate for N2O formation, was very limited. As a result, these advantages
brought about the superior SCR activity and N2 selectivity for V/Ce/WTi-DP.
Keywords: V/WTi; Ce-modified; synthesis method; Ce species; NH3-SCR; rare earths

The removal of NOx from the stationary and mobile

sources has been regarded as a major environmental
concern[1]. At present, the selective catalytic reduction
(SCR) is one of the most favored De-NOx technologies.
Generally, V2O5-WO3-TiO2 catalyst has been the most
widely employed commercial catalyst with good activity
and resistance to SO2. Nevertheless, there are some disadvantages. For example, V2O5-WO3-TiO2 catalyst is only
highly efficient in the temperature range of 300400
C[24], and it is circumscribed since the temperatures of
flue and exhaust gas exceed the applicable temperature
range[5]. On the other hand, N2O generation is found
above 400 C[2]. Therefore, it is urgent to develop a novel,
efficient SCR catalyst for a wide temperature range and
low N2O formation.
Recently, Ce-based oxides have attracted much attention for being used as a promoter or an active catalyst,
due to their high oxygen storage capacity and superior
redox properties[6,7]. As a SCR catalyst, ceria supported
on titania seems to be promising for improving medium
temperature activities[810]. Researchers have made great
efforts to introduce Ce to traditional V2O5-WO3-TiO2
catalyst. In our precious research[11], the addition of Ce
greatly enhanced the low temperature activity of the

fresh V2O5-ZrO2/WO3-TiO2 catalyst, and the promotional effect of CeO2 was attributed to the enrichment of
Ce3+, the increased redox properties and more active adsorbed nitrates. Chen et al.[12] improved SCR performance for V2O5-WO3/TiO2 catalyst in the broad temperature range of 200500 C by wet impregnation method,
using CeOx as a promoter. Lee et al.[13] investigated that
the addition of 10% ceria to Sb-V2O5/TiO2 catalyst by
precipitation method significantly enhanced the NOx
conversion and showed high N2 selectivity. Moreover, Li
et al.[14] prepared the V2O5-CeOx/TiO2-carbon nanotube
by sol-gel method and found that the appearance of Ce3+
increased chemisorbed oxygen thus facilitated the SCR
activity. Although the promotional effect of Ce for
V2O5-WO3-TiO2 catalyst in NH3-SCR reaction is generally accepted, there is not any work dealing with the effect of preparation methods on the structure and activity
of V/Ce/WTi catalyst. In this regard, this research would
contribute to developing novel Ce-modified catalyst.
In this work, we systematically investigated Ce-modified V/WTi catalysts, focusing on the effect of synthesis
methods on the catalyst structure and activity in NH3SCR reaction. The V/Ce/WTi catalysts were prepared by
deposition-precipitation method (DP) which has been

Foundation item: Project supported by the Grant from the China Huadian Science and Technology Institute (CHDI.KJ-20) and the National HighTech Research and Development Program of China (863, 2011AA03A405)
* Corresponding author: WANG Jun, ZHAI Yanping (E-mail: wangjun@tju.edu.cn; yanpingzhai@chai.ac.cn; Tel.: +86-22-27892301; +86-10-59216261)
DOI: 10.1016/S1002-0721(16)60023-6

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slightly studied and the conventional impregnation

method (IMP). By means of a series of characterization
methods, it was found that V/Ce/WTi catalyst prepared
by deposition-precipitation method showed higher NOx
conversion and less N2O production. And this result was
mainly attributed to the status of Ce species influenced
by preparation method.

1 Experimental

JOURNAL OF RARE EARTHS, Vol. 34, No. 3, Mar. 2016

Table 1 Synthesis methods and chemical composition of all
the catalysts
Composition/
Samples

Preparation process

Ce/WTi-IMP

Ce impregnation

V2O5 CeO2
Ce/WTi-DP

Ce deposition precipitation

V/Ce/WTi-IMP

Ce impregnation/V impregnation

V/Ce/WTi-DP
V/WTi

1.1 Catalysts preparation

Impregnation and deposition precipitation methods
were applied to prepare the CeO2/WO3-TiO2 catalyst first.
The commercial support, 10 wt.%WO3-90 wt.%TiO2 (WTi),
was obtained from Millennium Inorganic Chemicals Inc.
In the impregnation method, the catalyst was prepared by
incipient wetness impregnation. The calculated quantity
of WTi powder was added slowly into the calculated
amount of cerium nitrate solution, and kept stirring for 2
h. Then the sample was statically dried overnight at 110
C, followed by calcination in air at 500 C for 4 h. For
the deposition precipitation method, the catalyst was
synthesized by hydrolysis with ammonium hydroxide.
The calculated amount of cerium nitrate (Ce(NO3)36H2O)
was dissolved in a beaker containing 300 mL de-ionized
water, and the desired quantity of WTi powder was
added into the solution with stirring at the room temperature for 30 min. Subsequently, the dilute aqueous
ammonia as a precipitating agent was added dropwise to
the suspension until the PH value reached about 9.0. After being continuously stirred for 2 h, the resultant precipitate was filtered, dried overnight at 110 C and then
calcined at 500 C for 4 h in air. The CeO2/WO3-TiO2
catalysts obtained via the two methods were denoted as
Ce/WTi-IMP and Ce/WTi-DP respectively.
The V2O5/CeO2/WO3-TiO2 catalysts with 1% V2O5
loading were prepared by incipient wetness impregnation
of V on prepared Ce/WTi-IMP and Ce/WTi-DP catalysts,
which were denoted as V/Ce/WTi-IMP and V/Ce/WTiDP. The complex of VO(CO2)2 was prepared by reacting
V2O5 powder with oxalic acid with continuous stirring at
70 C for 20 min. Subsequently, the desired quantity of
Ce/WTi powder was added into the mixed solution and
stirred for 2 h. The as-synthesized sample was dried
overnight at 110 C and then calcined at 500 C for 4 h in
air. Synthesis methods and chemical composition of all
the catalysts are shown in Table 1.
1.2 Catalytic activity measurement
The activity tests were performed in a quartz reactor at
atmospheric pressure, using 200 mg sample (6080 mesh)
sufficiently mixed with 800 mg quartz (6080 mesh).
The concentrations of NO, NO2, N2O, H2O and NH3
were monitored by a Fourier transform infrared (FTIR)

wt.%*

3.610

3.623

1.015 3.553

Ce deposition precipitation/V impregnation 1.015 3.573

V impregnation

1.025

*The chemical composition were obtained by ICP-AES

spectrometer (MKS-2030). The gas flow rates in all experiments were controlled at 500 mL/min by mass flow
controllers. Prior to the experiments, the catalysts were
pre-treated at 500 C for 30 min under 5% O2/N2. The
NH3-SCR activity tests were performed using the gas
composition of 500 ppm NO, 500 ppm NH3, 5% O2 and
4% H2O with N2 as the balance. The testing temperature
was from 80 C to 550 C at a ramping rate of 10 C/min.
The NOx conversion was calculated using the following
equation:
NO x inlet NO x outlet
NO x conversion =
(1)
100%
NO x inlet
NOx=NO+NO2
(2)
1.3 Catalysts characterization

The Ce and V contents were performed by inductively

coupled plasma atomic emission spectroscopy (ICPAES). BET-surface areas were measured by N2 adsorption at 77 K using an F-Sorb 3400 volumetric adsorption/desorption apparatus. The X-ray powder diffraction
patterns were collected with a step size of 0.02 from 20
to 80 (XRD, Bruker D8 Advance TXS, Cu K radiation). X-ray photoelectron spectroscopy (XPS) experiments were obtained with a PHI-1600 ESCA system.
The base pressure was about 3109 mbar. The binding
energy was calibrated internally by the carbon deposit C
1s binding energy (BE) at 284.8 eV.
Temperature-programmed reduction by hydrogen experiments (H2-TPR) was performed to characterize the
reducibility of V species and Ce species in the V/Ce/WTi
samples. Prior to the reduction, the samples (100 mg)
were pre-treated at 500 C under 2% O2/N2 (30 mL/min)
for 1 h. Then after cooling down to 30 C in N2, the samples were heated at a ramping rate of 10 C/min from 30
to 900 C under a flow of 5% H2/N2 (15 mL/min). The
consumption of H2 was monitored by a thermal conductivity detector (TCD).
In situ diffuse reflectance infrared Fourier transform
spectra (in situ DRIFTS) of adsorption species were performed on Nicolet 6700 FTIR equipped with a MCT detector at a resolution of 4 cm1, averaging 10 scans for
each spectrum. The samples were initially treated with

SHEN Meiqing et al., Effect of synthesis methods on activity of V2O5/CeO2/WO3-TiO2 catalyst for selective

261

10% O2/N2 (50 mL/min) at 500 C for 30 min, and then

the samples were cooled down to the target temperature.
Prior to reactant gas (NH3 or NO) chemisorption, the
background spectra were collected. Then the gas containing 3000 ppm NH3 or 3000 ppm NO+5% O2 in N2
(50 ml/min) passed through the sample at the target temperature for 45 min and the in situ DRIFTS spectra were
recorded after purging the weakly adsorbed gas molecules.

conversion over V/Ce/WTi-IMP is obviously lower than

Ce/WTi-IMP and hence slightly higher than that of
V/WTi. Above 400 C, both V/Ce/WTi catalysts show a
close activity to V/WTi without dramatic decrease as
Ce/WTi presented. These comparison results suggest that
synthesis methods affect the catalytic activity, especially
in the relatively low temperature range, which should be
closely related to the status of Ce species.

2 Results and discussion

2.2 Phase composition and surface area of catalysts

2.1 NH3-SCR catalytic activity

Fig. 1 shows the NOx conversion and N2O formation

curves in SCR activity evaluation. The V/Ce/WTi catalysts prepared by two different methods exhibit better activity than V/WTi catalyst especially below 400 C (Fig.
1(a)). Compared with the V/Ce/WTi-IMP, V/Ce/WTiDP catalyst shows excellent NH3-SCR activity, with over
90% NOx conversion in a wide temperature range from
275 to 500 C. As seen from Fig. 1(b), V/Ce/WTi-DP
produces little N2O, which is also superior to V/Ce/
WTi-IMP and V/WTi. Moreover, Ce/WTi catalysts were
evaluated as a comparison to confirm this result. As displayed in Fig. 1(c), below 400 C, V/Ce/WTi-DP and
Ce/WTi-DP exhibit almost the same NOx conversion,
and that is remarkably higher than the NOx conversion of
V/WTi. In contrast, as illustrated in Fig. 1(d), the NOx

Fig. 2 shows the XRD patterns for the Ce/WTi, V/WTi

and V/Ce/WTi catalysts. The diffraction peaks of all
samples are ascribed to standard anatase-phase TiO2
peaks (PDF-ICDD 655714), but no peaks due to CeO2
and V2O5 are observed. That could be because cerium
and vanadium are well dispersed on the surface of the
commercial support as highly amorphous states or the
formed crystallites are too small to be detected by XRD.
It has been reported that the highly dispersed ceria should
be responsible for the excellent performance of Ce-Ti
based catalysts[10].
The BET surface area and average crystallite size of
TiO2 calculated by Scherrers equation are shown in Table 2. No significant difference has been figured out
among all these catalysts, except for V/Ce/WTi-IMP with
the obviously decreased BET surface area. It is clear that
the deposit precipitation method is in favor of improving

Fig. 1 NH3-SCR performance over various catalysts as a function of temperature

(a), (c), (d) NOx conversion; (b) N2O concentration

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Fig. 2 XRD profiles of different catalysts

Table 2 BET surface area and average TiO2 crystallite size
of samples
Sample

BET surface area/(m2/g)

TiO2 crystallite size/nm*

Ce/WTi-IMP

80.33

18.32

Ce/WTi-DP

83.42

18.23

V/Ce/WTi-IMP

74.83

18.60

V/Ce/WTi-DP

80.81

18.42

V/WTi

80.55

18.10

* Crystallite size was calculated by Scherrer equation from XRD results

the BET surface area of catalysts, which could offer

more active sites for reaction and thus be beneficial to
NH3-SCR activity.
2.3 Valence state and distribution of Ce species

To understand the chemical states of Ce and O on the

catalysts surface, Fig. 3 shows the XPS spectra of Ce 3d,
and O 1s, together with a summary of the atomic surface
concentrations of Ce, O, W and Ti in Table 3.

As presented in Fig. 3, the complex Ce 3d peaks are

fitted into eight peaks. The bands labeled u and v represent the 3d104f1 initial electronic state corresponding to
Ce3+, while the peaks labeled u, u, u, v, v and v represent the 3d104f0 state of Ce4+ ions[15,16]. The surface
mole percentages of Ce3+ in Ce is calculated from the
normalized peak areas of Ce3+ and Ce4+ core level spectra.
It is evident from Table 3 that V/Ce/WTi-DP shows a
higher Ce3+ ratio than V/Ce/WTi-IMP (53.22% vs
44.43%). Furthermore, V/Ce/WTi catalysts both exhibit
lower surface Ce content (at.%) than the corresponding
Ce/WTi, because of the addition of V. And more notably,
the surface Ce concentration over V/Ce/WTi-DP changes
little from 0.91 to 0.75 (down 17.6%), while V/Ce/WTiIMP catalyst displays a significant decrease from 1.19 to
0.70 (down 41.2%). Two possible explanations could be
suggested. Firstly, more Ce species are covered by the
additive V over V/Ce/WTi-IMP than V/Ce/WTi-DP.
Secondly, surface Ce species may migrate into the bulk
phase more easily during the additional calcination process for V impregnated on Ce/WTi-IMP catalyst. The
above results indicate that the status of surface Ce species may be affected by preparation method, and the
deposition precipitation method contributes to more surface Ce species insusceptible to the impregnated V species.
The O 1s peak was fitted into two kinds of peaks. The
sub-bands at 529.5530.0 eV could be attributed to the
lattice oxygen O2 (denoted as O). The shoulder
sub-bands at 531.0531.6 eV are assigned to the surface
adsorbed oxygen (denoted as O) such as O22 or O belonging to defect oxide or hydroxyl-like species[13,16]. As
shown in Table 3, the O ratio of Ce/WTi-DP is 66.50%
which is evidently higher than the 55.22% of Ce/WTi-

Fig. 3 XPS spectra of Ce 3d of V/Ce/WTi catalysts (a), O 1s of Ce/WTi catalysts (b) and O 1s of V/Ce/WTi catalysts (c)
Table 3 XPS surface compositional analysis
Samples

Surface atomic concentration/at.%

Ti

Ce

Surface mole ratio/%

O

Ce3+/(Ce3++Ce4+)

O/(O+O)

Ce/WTi-IMP

18.62

3.58

1.19

76.61

55.22

Ce/WTi-DP

17.52

3.63

0.91

77.94

66.50

V/Ce/WTi-IMP

22.16

4.01

0.70

73.12

44.43

40.44

V/Ce/WTi-DP

21.68

4.11

0.75

73.46

53.22

45.84

V/WTi

22.24

4.09

73.67

36.52

SHEN Meiqing et al., Effect of synthesis methods on activity of V2O5/CeO2/WO3-TiO2 catalyst for selective

IMP. Likewise, through comparing V/Ce/WTi catalysts

with V/WTi, the O ratio follows the sequence:
V/Ce/WTi- DP>V/Ce/WTi-IMP>V/WTi, which is in
good accordance with the activity order below 400 C. It
is well- known that surface adsorbed oxygen (O) is
more reactive in the oxidation reactions due to its higher
mobility than lattice oxygen (O)[17]. In other words, O
can react easily with NO to produce NO2 or nitrate species[18,19], then participating further in the consequent reactions with NH3. Hence, the V/Ce/WTi-DP catalyst
with a higher ratio of O presents better SCR activity
than V/Ce/WTi-IMP catalyst.
2.4 Reducibility of Ce species

The H2-TPR experiment was used to investigate the

presence of reducible species in the prepared catalysts.
Reduction curves of the different catalysts were compared as is shown in Fig. 4. Moreover, the signals have
been fitted with Gaussian lines to assess the H2 consumptions for the individual species, and the results of
quantitative analysis are displayed in Table 4.
As shown in Fig. 4(a), the commercial WTi support
(reference) exhibits two major reduction peaks at 562
and 686 C. They can be assigned to the reduction of
some sulfate species existing on the surface of support[14,20], well dispersed tungsten species and TiO2 sup-

Fig. 4 H2-TPR profiles on the catalysts

(a) Impregnation method; (b) Deposition precipitation method

263

Table 4 H2-temperature programmed reduction

Reduction peaks temperature/C
Samples

4+

3+

Ce -Ce and
V5+-V4+

V/Ce/WTi-IMP

489

sulfate species W6+-W4+

553

630

Total H2
consumption of
Ce and V (a.u.)
1.75

Ce/WTi-IMP

466

533

609

1.81

V/Ce/WTi-DP

480

540

623

1.80

Ce/WTi-DP

484

595

697

1.20

V/WTi

483

537

620

1.00

WTi

562

686

port[20,21]. Both Ce/WTi-IMP and V/WTi-IMP show three

overlapped reduction peaks: the low temperature peaks
around 400500 C are attributed to the reduction of surface Ce4+ to Ce3+ [16,22] and the V5+ to V3+ [13], the other
two peaks are attributed to the reduction of the support.
The addition of V over the Ce/WTi-IMP catalyst causes
some changes of the TPR profiles. The first peak for
V/Ce/WTi-IMP is ascribed to the coreduction of surface
Ce4+ to Ce3+ and V5+ to V3+, which is difficult to be distinguished due to the similar reduction temperatures.
Compared with the reduction peak of surface Ce species
on Ce/WTi-IMP catalyst, it shifts to higher temperature
that is close to the reduction temperature of V species on
V/WTi catalyst. The coreduction of surface Ce4+ and V5+
consumes less H2 than the reduction of Ce species on
Ce/WTi-IMP catalyst by itself. These results indicate that
the changed reduction peak over V/Ce/WTi-IMP is
mainly caused by the changed Ce species rather than V
species, which is also consistent with XPS results. And
the reduction of surface Ce species is inhibited by the
additive V, resulting in the lower activity over
V/Ce/WTi-IMP than that over Ce/WTi-IMP.
Compared with Ce/WTi-IMP, Ce/WTi-DP shows
three distinct peaks with the corresponding reduction of
surface Ce species and the support (Fig. 4(b)). While the
higher reduction temperature and smaller amount of H2
consumption from the reduction of surface Ce4+ to Ce3+
are related with the presence of more Ce3+, according to
XPS results. After adding V on Ce/WTi-DP, the obtained
V/Ce/WTi-DP catalyst presents an overlapped reduction
peak and the first peak is also ascribed to the coreduction
of surface Ce4+ to Ce3+ and V5+ to V3+. More importantly,
the reduction temperature of the first peak over
V/Ce/WTi-DP catalyst is similar with that of Ce species
on Ce/WTi and V species on V/WTi. The H2 consumption of the coreduction is more than that of each reduction alone. Thereby the constant reduction temperature of
surface Ce species may contribute to the almost same activity with Ce/WTi-DP below 400 C.
In addition, the distribution of the active components
and the interaction of metal-support may vary with the
preparation methods. Comparing with commercial WTi
support, the reduction peaks of the support in all im-

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pregnated samples shift to the similar position at the

lower temperature. It is most likely to be a V-O-Ti or
Ce-O-Ti interaction, when the V species or Ce species
are impregnated on TiO2 surface[23]. While, for Ce/WTiDP catalyst, these reduction peaks shift slightly to higher
temperature, implying the different interaction between
Ce species and the WTi support, and hence different distribution of Ce species. Subsequently, after V impregnation (V/Ce/WTi-DP), these reduction peaks shift to the
similar temperature if it is compared to impregnated
samples, suggesting that the V-O-Ti species are formed
at this moment. Consequently, the preparation methods
make a critical effect on the distribution of active species.
Then Ce species and V species may be in the similar
situation due to the same process of addition.
2.5 Surface adsorbed species of catalysts

2.5.1 NH3 adsorption

In situ DRIFTS experiments were conducted to investigate the effect of synthesis methods on the variety and
quantity of Lewis acid sites and Brnsted acid sites. As
shown in Fig. 5(a), after NH3 adsorption on different
V/Ce/WTi catalysts at 50 C, several bands are detected
in the range of 10001800 cm1. The bands observed at
1670 and 1440 are assigned to symmetric and asymmet-

Fig. 5 DRIFTS spectra of V/Ce/WTi (a) and Ce/WTi (b) catalysts during NH3 desorption at different temperatures
(100, 200 and 300 C) after NH3 adsorption at 50 C

JOURNAL OF RARE EARTHS, Vol. 34, No. 3, Mar. 2016

Table 4 Assignments of DRIFTS bands observed during the
NH3 adsorption
Wavenumber/cm1

Assignments

Ref.

Asymmetric and symmetric vibrations of

1440 and 1672

NH bonds in NH4+ coordinately linked to

[24]

Brnsted acid sites

Asymmetric and symmetric vibrations of
1207, 1250 and 1600

the coordinated NH3 linked to Lewis acid

[24]

sites

ric bending vibrations of the NH band in NH4+ linked to

Brnsted acid sites[24], while the bands at 1600 and 1250,
1207 cm1 are assigned to asymmetric and symmetric
bending vibrations of the coordinated NH3 linked to
Lewis acid sites[24]. The assignments of in situ DRIFTS
bands are listed in Table 4. It is worth noting that the two
catalysts exhibit a significant difference on the proportion between both acid sites (L/B). The V/Ce/WTi-DP
catalyst shows less Brnsted acid sites but more Lewis
acid sites especially for that corresponding to the band at
1207 cm1. Parallelly, these differences on acid sites are
also observed between Ce/WTi-DP and Ce/WTi-IMP
(shown in Fig. 5(b)). Therefore, it is most likely that the
distinctions between the two acid sites are mainly caused
by the changed status of Ce species on WTi, as a result of
different synthesis methods. For Ce/WTi catalyst, the
Lewis acid sites are mainly provided by wolframyl species and Ce species and the Brnsted acid sites are assigned to WOH species[25,26]. Thereby, more Lewis acid
sites over Ce/WTi-DP and V/Ce/WTi-DP can be attributed to more Ce species induced by deposition precipitation method, which contributes to more adsorbed NH3
species especially for that at 1207 cm1. Reflected by the
better SCR activity on V/Ce/WTi-DP and Ce/WTi-DP,
the absorbed NH3 species at 1207 cm1 may play the
most crucial role.
2.5.2 Reaction between pre-adsorbed NH3 species and
NO+O2
To investigate the reactivity of adsorbed NH3 species
linked to Lewis acid sites, in situ DRIFTS spectra of the
reaction between pre-adsorbed NH3 species and NO+O2
are shown in Fig. 6. For the two V/Ce/WTi samples, after NH3 are pre-adsorbed and N2 purging for 30 min, the
NH3 species linked to Lewis acid sites (1600 and 1250,
1210 cm1) and Brnsted acid sites (1670 and 1440 cm1)
form on the surface. When NO+O2 are introduced, the
intensities of the bands due to NH3 species decrease.
Meanwhile, some new bands attributed to adsorbed nitrate species (1620, 1572 and 1540 cm1) appear. As for
adsorbed NH3 species on V/Ce/WTi-IMP, the intensity
of dominant band at 1250 cm1 decreases slowly and
dose not vanish until 30 min, whereas the inferior band at
1210 cm1 almost disappears after 7 min. As compared to
V/Ce/WTi-IMP, the dominant adsorbed NH3 species on
V/Ce/WTi-DP is corresponding to the band at 1210 cm1.

SHEN Meiqing et al., Effect of synthesis methods on activity of V2O5/CeO2/WO3-TiO2 catalyst for selective

265

Fig. 6 DRIFTS spectra of V/Ce/WTi-IMP (a) and V/Ce/WTi-DP (b) catalysts pretreated with 3000 ppm NH3, followed by being exposed to 3000 ppm NO+4% O2 as a function of time at 200 C

After the catalyst is purged with NO+O2, the band at

1210 cm1 decreases quickly and totally vanishes at 7
min, accompanied by the appearance of nitrate species
(1280 and 1241 cm1). Thereby, the comparison results
indicate that the adsorbed NH3 species at the band of
1210 cm1 shows higher reactive activity than that at
1250 cm1 band. Then the abundant reactive NH3 species
corresponding to 1210 cm1 bring about better activity
for V/Ce/WTi-DP.
2.5.3 NOx adsorption
The DRIFTS spectra of NO+O2 over Ce/WTi and
V/Ce/WTi catalysts at different temperatures are shown
in Fig. 7. Several distinct bands appear at 1625, 1572,
1540, 1280 and 1241 cm1, which are assigned to the
gas-phase or weakly adsorbed NO2 species (1625
cm1)[27,28], bidentate nitrate (1572 cm1)[29], monodentate
nitrate (1540 and 1280 cm1)[30] and bridged nitrate (1241
cm1)[31] respectively. Compared with V/Ce/WTi-IMP,
the V/Ce/WTi-DP catalyst exhibits more adsorbed nitrate
species. As reported in many studies[10,25], the weakly adsorbed NO2 and monodentate nitrate are the major active

nitrate species in SCR reaction. Therefore, more active

nitrate species on V/Ce/WTi-DP catalyst especially
above 200 C could strongly illuminate the better SCR
performance at above 200 C.
Interestingly, a new band at 1372 cm1 appears above
200 C over V/Ce/WTi-IMP catalyst as shown in Fig 7(a).
The DRIFTS spectra from 200350 C of Ce/WTi catalysts are provided to further explain the presence of the
band (Fig. 7(b)). The same band is observed on the
Ce/WTi-IMP and the intensity of the band increases with
the increasing temperature, which is consistent with the
changes on V/Ce/WTi-IMP. Based on the results, we
could conclude that the band at 1372 cm 1 of
V/Ce/WTi-IMP stems from the Ce/WTi-IMP. The band
can be assigned to cis-N2O22 species, which are able to
dissociate easily the NO bond to give N2O[32,33]. The
process was described by precious studies on CeO2. They
have emphasized that an initial disproportionation of NO
into NO2 (with participation of surface O2) and N2O22
occurs, then the generated N2O22- further evolves into
NO3 and gaseous N2O at high temperature, respect-

Fig. 7 DRIFTS spectra of V/Ce/WTi (a) and Ce/WTi (b) catalysts during NOx desorption at different temperatures after NO and O2
co-adsorption at 50 C

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JOURNAL OF RARE EARTHS, Vol. 34, No. 3, Mar. 2016

tively[34]. Therefore, the absence of cis-N2O22 on the

Ce/WTi-DP leaves very limited possibility for N2O formation on V/Ce/WTi-DP in NH3 SCR reaction.

the formation of active nitrates species, but also inhibit

producing cis-N2O22 species. The latter as an intermediate for N2O formation are adverse to NH3-SCR reaction.

3 Discussion

4 Conclusions

The effect of synthesis methods on the catalytic activity of catalysts was investigated in detail in this study. It
is obvious that the synthesis methods affect the catalytic
activity, especially in the relatively low temperature
range. V/Ce/WTi prepared by deposition precipitation
method exhibits higher NOx conversion and less N2O
production, which is mainly dependent on the status of
Ce species.
According to BET and XPS results, the deposition precipitation method is beneficial to improving the BET surface area of catalysts and hence V/Ce/WTi-DP displays
more surface Ce species. Meanwhile, the higher amount
of the Ce3+ formed on V/Ce/WTi-DP could create a
charge imbalance, and then contribute to more surface
adsorbed oxygen (O)[21,35], which facilitates NO oxidation and the formation of adsorbed nitrates. H2-TPR results indicate that the distribution of surface Ce species
on the two V/Ce/WTi samples may be different. In the
case of V/Ce/WTi-IMP, Ce species and V species may
be in the similar situation due to the same method of addition. As reported[36], owing to the remarkably close radius ratio (V:Ti=0.063 nm:0.068 nm), the strong interaction between the stabilization of V ions and TiO2 surface
is generated. Therefore, it may affect the distribution of
Ce species negatively and then inhibit the reduction of
surface Ce species, which is supported by the XPS and
H2-TPR results. For deposition precipitation method, on
the contrary, it is more possible that Ce species and V
species are in different situation on the support surface,
which illustrates that the Ce concentration and reducibility are almost unaffected by V impregnation. Thus
V/Ce/WTi-DP shows almost the same activity with
Ce/WTi-DP below 400 C.
In addition, the surface acid sites of a catalyst play an
important role in NH3-SCR reaction, and Lewis acid sites
may be more crucial than Brnsted acid sites for low
temperature SCR activity[37]. V/Ce/WTi-DP can provide
more Lewis acid sites than V/Ce/WTi-IMP. This superiority contributes to more adsorbed NH3 species, especially for that at 1210 cm1. Meanwhile, the adsorbed
NH3 species at the band of 1210 cm1 shows higher reactive activity than that at 1250 cm1 band, which is one of
the reasons for the better medium temperature activity
over V/Ce/WTi-DP than V/Ce/WTi-IMP. Furthermore,
V/Ce/WTi-DP exhibits more adsorbed nitrates, of which
the major active nitrate species are adsorbed NO2 and
monodentate nitrate. And this can be attributed to the
higher O percentage of V/Ce/WTi-DP as described
above. The O could not only facilitate NO oxidation and

V/Ce/WTi-DP exhibited the excellent NH3-SCR performance, especially the superior medium-temperature
activity and the less N2O formation comparing to the
V/Ce/WTi-IMP, which was mainly dependent on the
status of Ce species influenced by synthesis methods.
V/Ce/WTi-DP not only possessed more surface Ce species, the increased number of Ce3+, but also presented
higher reducibility of Ce species. In this situation, the
number of reactive intermediates for NH3-SCR increased
on V/Ce/WTi-DP, including more active NH3 species
linked to Lewis acid sites, the weakly adsorbed NO2 and
monodentate nitrate. And these were responsible for the
higher NOx conversion. Additionally, little cis-N2O22
intermediate species for N2O formation were produced
on V/Ce/WTi-DP, contributing to the higher N2 selectivity in NH3-SCR reaction.

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