JOURNAL OF RARE EARTHS, Vol. 34, No. 10, Oct. 2016, P.

1004

Modification of Cu/ZSM-5 catalyst with CeO2 for selective catalytic

reduction of NOx with ammonia
LIU Xuesong (刘雪松)1,2, WU Xiaodong (吴晓东)1,2,*, WENG Duan (翁 端)1,2,*, SHI Lei (石 磊)3
(1. Key Laboratory of Advanced Materials of Ministry of Education, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China; 2.
Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China; 3. Redbud Innovation Institute, Longyan 364000, China)

Received 15 February 2016; revised 5 April 2016

Abstract: Cu/ZSM-5 and CeO2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of
CeO2 was found to enhance the NOx selective catalytic reduction (SCR) activity of the catalyst at low temperatures, but the
high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, induc-
tively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectroscopy (XPS), electron paramagnetic
resonance (EPR), H2 temperature-programmed reduction (TPR) and NH3 temperature-programmed desorption (TPD). The results
showed that more CuO clusters instead of isolated Cu2+ species were obtained on the modified catalyst. These active CuO clusters, as
well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the
oxidation of NO to NO2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxi-
dation of NH3 by O2 and decreased surface acidity of the catalyst.

Keywords: Cu/ZSM-5; CeO2 modification; NH3-SCR; CuO clusters; surface acid sites; rare earths

Vehicle exhaust emission standards have recently be-
come stricter, due to the hazardous nature of exhaust
emissions and increasingly serious haze weather in
China[1]. However, due to the intrinsic characteristics of
diesel combustion, nitrogen oxides (NOx) are generated
in the localized high-temperature reaction zone and par-
ticular matters (PM) are formed in the diffusion combus-
tion zones. Several technologies are being implemented
to reduce these harmful pollutants. One of the promising
technologies for reducing NOx is known as urea-selective
catalytic reduction (SCR)[2,3]. The SCR is a means of
converting NOx with the aid of a catalyst into N2 and
H2O. The aqueous urea solution which is injected into
the hot exhaust stream, generates ammonia (NH3) during
H2O decomposition, thermal urea decomposition, and
hydrolysis. Vanadia (V2O5) is generally used as an SCR
catalyst[4–7], but zeolite catalysts such as Cu-zeolite and
Fe-zeolite have been researched and commercialized be-
cause of the toxicity of vanadium. The Cu-based zeolite
catalysts have higher SCR activity than Fe-based zeolite
catalysts in low temperature range[8].
In recent years, the de-NOx performance of Cu-zeolite
catalysts with superior low-temperature activity has been
improved in many studies[9–12]. Moreover, the effects of
additive addition on catalytic activity have been stud-
ied[13–15]. Seo et al.[16] modified the Cu-ZSM-5 catalyst
with ZrO2. They found that the addition of ZrO2 im-
proved the low-temperature activity of the SCR catalyst.
Ceria has been applied as a promoter in a number of
catalysts[17–20]. Nevertheless, the modification mecha-
nisms of additives on Cu/ZSM-5 catalyst for NH3-SCR
reaction have been rarely reported. In this work, a CeO2
doped Cu/ZSM-5 catalyst was prepared and the role of
ceria was discussed.
1 Experimental
1.1 Catalyst preparation
Cu/ZSM-5 and CeO2-modified Cu/ZSM-5 (SiO2:Al2O3=
25:1) catalysts were synthesized by wetness impregna-
tion[21] using Cu(NO3)2·3H2O and Ce(NO3)3·6H2O
(Shanghai Ling Feng Chemical Reagent, China) and
ZSM-5 (Nankai Catalyst Company, China) powders as
the precursors, and the obtained catalysts were denoted
as CuZ and CuCeZ, respectively. The nominal contents
of Cu and CeO2 in the catalysts was 2 wt.% and 5 wt.%,
respectively.
1.2 Activity measurement
The NH3-SCR activity was evaluated in a fixed bed
quartz reactor, and the effluent gases were monitored by

Foundation item: Project supported by the the National Natural Science Foundation of China (51372137) and Ministry of Science and Technology,
China (2015AA034603)
* Corresponding author: WU Xiaoding, WENG Duan (E-mail: wuxiaodong@tsinghua.edu.cn, duanweng@tsinghua.edu.cn; Tel.: +86-10-62792375, +86-10-62785986)
DOI: 10.1016/S1002-0721(16)60127-8
LIU Xuesong et al., Modification of Cu/ZSM-5 catalyst with CeO2 for selective catalytic reduction of NOx with ammonia 1005

infrared spectroscopy (Thermo Nicolet 380). The reac- perature and flushed with He for 10 min. The atmosphere
tion gas consisted of 500 ppm NO, 500 ppm NH3, 5% O2, was then changed to 10% H2/Ar (50 mL/min), and the
10% H2O, and N2 in balance. The flow rate of the reac- reactor temperature was raised to 600 ºC at a heating rate
tion gas was 1000 mL/min, the amount of catalyst of 10 ºC/min. H2 consumption during the experiment was
(sieved to 50–80 mesh) used was 300 mg, and the gas monitored with a thermal conductivity detector.
hourly space velocity (GHSV) was kept at 100000 h−1. Ammonia temperature-programmed desorption (NH3-
The concentration of NOx (NO, N2O, and NO2) was de- TPD) analysis was performed using a TP 5000-II multi-
tected at the ppm level. The NOx conversion of the cata- ple adsorption apparatus (Xianquan, China). The samples
lysts was calculated using Eq. (1): (~50 mg) were pretreated in He at 500 ºC for 30 min.
NO x conversion (%) = When the temperature decreased to 50 ºC, NH3 was in-
troduced until adsorption on the samples was saturated.
NO in − NO − NO − 2N 2 O out
out 2 out (1) The samples were then purged with He to remove resid-
× 100
NO in ual NH3 from the surface of the samples. The samples
The NH3/NO oxidation tests were performed for the were then heated in He from 100 to 500 ºC at a rate of 10
catalysts using a feed gas composition of 500 ppm ºC/min for subsequent NH3 desorption.
NH3/NO, 5% O2, 10% H2O and N2 in balance. The NH3
and NO conversion were calculated by Eqs. (2) and (3), 2 Results and discussion
respectively:
NH 3in − NH 3out 2.1 Structural properties
NH 3 conversion (%)= × 100 (2) The modification of CeO2 on the structure of the cata-
NH 3in
lysts was investigated by XRD, and the results are shown
NO 2out in Fig. 1. For comparison, the diffraction pattern of
NO conversion (%) = × 100 (3) ZSM-5 zeolite was included. All the catalysts exhibit the
NO in
typical peaks corresponding to ZSM-5 zeolite, which
1.3 Catalyst characterization implied that the original zeolite structure remains in-
tact[22]. After copper impregnation, the diffraction peaks
X-ray powder diffraction (XRD) patterns were re-
of CuO are identified, indicating that the copper species
corded on a diffractometer (D8 ADVANCE, Bruker,
aggregate on the surface of the ZSM-5 support due to the
Germany) employing Cu Kα radiation (λ=0.15418 nm).
impregnation method adopted. For the CeO2 modified
Data were collected in the range of 5°≤2θ≤50° with a
catalyst, the diffraction peaks of CuO almost disappear,
scanning velocity of 6 (°)/min.
while ceria can be detected by XRD[23], indicating the
Textural properties were determined by nitrogen phy-
improved dispersion of CuO by the CeO2 addition.
sisorption at −196 °C using a JW-BK122F (Beijing
The specific surface areas and micropore volumes of
JWGB, China) instrument. Prior to the measurements,
the catalysts are summarized in Table 1. The SBET and
the samples were degassed at 0.01 Pa at 220 °C. The spe-
pore volume of the catalysts are lower than those of the
cific surface area and desorption pore volume were as-
ZSM-5 support, owing to coverage of CuO and CeO2 on
sessed using the Brunauer-Emmett-Teller (BET) and
the external surface and pore structure of the zeolite. In-
Barrett-Joyner-Halenda methods, respectively.
terestingly, the textural data of the CeO2 modified
The actual contents of Cu, Ce, Al and Si were deter-
Cu/ZSM-5 catalyst are higher than those of Cu/ZSM-5
mined on an Agilent 5100 inductively coupled plasma
optical emission spectrometry (ICP-OES) instrument.
Electron paramagnetic resonance (EPR) spectra in the
X-band were recorded on a CW spectrometer JES-
FA200 (JEOL) at microwave power of 1 mW, modula-
tion frequency of 100 kHz, and central field of 300 mT.
Before the measurements, the samples were heated in
vacuum from room temperature to 100 ºC for 30 min.
The samples were then cooled to –150 ºC. Mn2+ was
used as an external reference sample, and the g value and
EPR spectral intensity of Cu2+ were determined.
Hydrogen temperature-programmed reduction (H2-
TPR) was performed on a Micromeritics Auto Chem II.
Prior to the H2-TPR experiment, the test sample (50 mg)
Fig. 1 XRD patterns of the support and catalysts as well as the
was treated with He at a total flow rate of 50 mL/min at
standard data of CuO and CeO2
300 ºC for 30 min and subsequently cooled to room tem-
1006 JOURNAL OF RARE EARTHS, Vol. 34, No. 10, Oct. 2016

Table 1 Textural properties and chemical composition of

the samples
SBET/ Pore volume/ Concentration/(wt.%)a
Sample 2 3
(m /g) (cm /g) Al Si Cu Ce
ZSM-5 411 0.227 2.67 40 – –
CuZ 252 0.139 2.58 39 2.05 –
CuCeZ 302 0.167 2.41 36 1.98 4.22
a
Obtained by ICP-OES

catalyst. It may be related to the improved dispersion of

CuO on the ZSM-5[24], which is consistent with the XRD
results.
As indicated by the ICP-OES results in Table 1, the
obtained Cu and Ce contents in the catalysts are close to
the nominal values. Thus, the Cu content should not be
responsible for the different catalytic behaviors of the
catalysts.

2.2 Catalytic activity

The temperature dependency of NOx conversion dur-
ing the NH3-SCR reaction over the catalysts is shown in
Fig. 2. The CeO2 modified catalyst shows superior SCR
activity at low temperatures (175–300 ºC), but experi-
ences a loss at high temperatures (300–550 ºC).
The oxidation of NO to produce NO2 and that of NH3 Fig. 3 (a) NH3 oxidation and (b) NO oxidation curves of the
catalysts (Reaction conditions: 500 ppm NO or 500 ppm
by O2 to consume the reductant are important for the
NH3, 5% O2, 10% H2O and N2 in balance. GHSV=
low- and high-temperature SCR activities of the catalysts,
100000 h–1)
respectively, and the results are shown in Fig. 3. Obvi-
ously, both the conversions of NH3 and NO increase with 2.3 EPR studies
the CeO2 addition. The accelerated competitive reactions
The hyperfine structure of isolated Cu2+ species was
between NH3-SCR and NH3 oxidation would lead to a
characterized by EPR analysis[26]. Fig. 4 shows the EPR
loss in high-temperature SCR activity. It has been sug-
spectra of the catalysts. Four adsorption peaks are de-
gested that CuO catalyzes the oxidation of NO to NO2, tected in the parallel region, and a sharp peak is observed
which favors the reduction of NOx at low temperatures in the vertical region. The EPR signals at g∥=2.386, A∥=
via the so-called fast SCR reaction[25]. CuCeZ shows 12.899, and g⊥=2.082 mT are ascribed to Cu2+ species
higher catalytic activity for NO oxidation to NO2 than
CuZ, which improves the low-temperature SCR activity
of the CeO2 modified catalyst.

Fig. 2 NH3-SCR curves of the catalysts (Reaction conditions:

500 ppm NO, 500 ppm NH3, 5% O2, 10% H2O and N2 in
balance. GHSV=100000 h–1)
Fig. 4 EPR spectra of the catalysts measured at –150 ºC
LIU Xuesong et al., Modification of Cu/ZSM-5 catalyst with CeO2 for selective catalytic reduction of NOx with ammonia
on the site (I) displaced from the six-ring structure into
the ellipsoidal cavity of the ZSM-5 zeolite[27,28]. It can be
seen that the hyperfine splitting peaks of the CeO2-
modified Cu/ZSM-5 are lower in intensity, indicating a
reduction in the number of isolated Cu2+ active species.
The decrease in the amount of Cu2+ species would lead to
a drop in the high-temperature SCR activity, because the
isolated Cu2+ species are the active sites for the NH3-
SCR reaction within the whole temperature range, espe-
cially in the high temperature range (300–550 ºC)[28,29].
2.4 H2-TPR studies
H2-TPR is commonly used for determining types of
copper species and the redox properties of catalysts. Fig.
5 shows the TPR curves of the samples. The copper-free
H-zeolites do not contain any reducible species and al-
most no H2 consumption is found, while three reduction
peaks are observed for the CuZ catalyst. The first peak at
210 ºC is attributed to the reduction of surface CuO clus-
ters on the external surface of the zeolite framework,
proceeding via a one-step reduction with the stoichiome-
try of one mole of H2 for one mole of CuO clusters[30].
The second peak at 250 ºC is attributed to the reduction
of isolated Cu2+ in the zeolite framework to Cu+. The
third peak at 330 ºC is attributed to the reduction of CuO
crystallites from CuO to Cu0. The peak attributed to re-
duction of stable Cu+ to Cu0 is not detected in this tem-
perature range.
After the addition of CeO2, a sharp co-reduction peak
attributed to surface CuO clusters, isolated Cu2+ and
CeO2 is observed at 218 ºC, and it shifts to lower tem-
peratures. The reduction peak is suggested to arise
mainly from the reduction of surface CuO clusters based
on its similar position to that of the first reduction peak
for CuZ. Surface CuO clusters favor low-temperature
reactions via the stronger catalytic activity for NO oxida-
tion and hereby the so-called fast SCR reaction[21,31].
Meanwhile, these clusters inhibit high-temperature SCR
Fig. 5 H2-TPR curves of the catalysts and support
1007
activity owing to their high catalytic activity toward NH3
oxidation[21]. This is consistent with the activity of the
CeO2 modified catalyst.
2.5 NH3-TPD studies
The catalyst surface acidity plays an important role for
the NH3-SCR reaction[32–35], and the acid properties of
ZSM-5, Cu/ZSM-5 and CeO2-modified Cu/ZSM-5 were
studied by NH3-TPD. Fig. 6 shows the NH3-TPD profiles
of the samples. Three overlapped peaks (A, B, and C)
can be deconvoluted[36]. For the ZSM-5 support, the peak
(A) at the lowest temperature is related to the weak
Brønsted acid sites at surface hydroxyls. The two peaks
(B and C) at higher temperatures are possibly assigned to
the structural Brønsted acid sites referred to moderate
and strong acidity[36–40]. After the copper loading, the
peaks A, B and C over Cu/ZSM-5 catalyst change a lot
in the position and intensity. The peak A of the catalysts
represents the adsorbed NH3 molecules at weak Brønsted
acid sites on the zeolite and weak Lewis acid sites related
to Cu species. The peak B is ascribed to the residual
structural Brønsted acid sites on the zeolite and moderate
Lewis acid sites related to Cu species. The peak C stands
for the adsorbed NH3 molecules at both strong Brønsted
acid sites on the ZSM-5 support and new Lewis acid sites
created by Cu species[40]. Table 2 lists the amounts of dif-
ferent acid sites calculated from the NH3-TPD results. It
can be seen that the loading of Cu reduces the weak and
strong acid sites of ZSM-5 mainly because of the substi-
tution of the support proton (–Si–OH–Al) by Cu2+ ions,
although Cu species themselves also create some Lewis
acid sites[41]. Meanwhile, more moderate Lewis acid sites
are created by Cu species, resulting in an increase in the
amount of total moderate acid sites. Upon introduction of
CeO2, the ammonia uptake of both moderate and strong
acid sites decreases considerably, while the amount of
weak acid sites changes slightly. This may be due to the
coverage of both Cu species and support by Ce species.
Combined with the NOx conversion in Fig. 2, the low
NH3 adsorption capacity of CuCeZ at high temperatures
would inhibit the SCR reaction. The observation is
Fig. 6 NH3-TPD profiles of the catalysts and support
1008
Table 2 Acidity of the catalysts and support obtained from
NH3-TPD
Acidity/(μmol/g)
Sample
Weak Moderate Strong Total
CuCeZ 76.2 36.6 0.3 113.1
CuZ 74.2 78.2 5.4 157.8
ZSM-5 115.3 51.9 34.7 201.9
in good agreement with the conclusions of the previous
study, in which it was observed that the moderate and
strong acid sites are the source of NH3 for the SCR reac-
tion at high temperatures[42].
3 Conclusions
In this work, the effects of ceria impregnation on the
structure and SCR activity of the Cu/ZSM-5 catalyst
were investigated. The interactions of ceria with copper
species and the zeolite support improved the dispersion
of copper species mainly in the form of surface CuO
clusters. These surface CuO clusters, as well as the
Cu-Ce synergistic effect, facilitated the fast NH3-SCR
reaction at low temperatures via enhanced oxidation abil-
ity of NO to NO2. However, these surface CuO clusters
also made against the high-temperature SCR reaction due
to the reduced supply of the reductant via catalyzing NH3
oxidation. The inhibition was also attributed to the de-
crease in the amounts of isolated Cu2+ and acid sites after
the addition of Ce.
References:
[1] Seo C K, Kim H N, Choi B C, Lim M T, Lee C H, Lee C
B. De-NOx characteristics of a combined system of LNT
and SCR catalysts according to hydrothermal aging and
sulfur poisoning. Catal. Today, 2011, 164: 507.
[2] Schuler A, Vostmeier M, Kiwic P, Gieshoff J, Hautpmann
W, Drochner A, Vogel H. NH3-SCR on Fe zeolite cata-
lysts—From model setup to NH3 dosing. Chem. Eng. J.,
2009, 154: 333.
[3] Grossale A, Nova I, Tronconi E. Study of a Fe-zeolite-
based system as NH3-SCR catalyst for diesel exhaust af-
tertreatment. Catal. Today, 2008, 136: 18.
[4] Choo S T, Yim S D, Nam I S, Ham S W, Lee J B. Effect of
promoters including WO3 and BaO on the activity and du-
rability of V2O5/sulfated TiO2 catalyst for NO reduction by
NH3. Appl. Catal. B, 2003, 44: 237.
[5] Kobayashi M, Kuma R, Masaki S, Sugishima N. TiO2-
SiO2 and V2O5/TiO2-SiO2 catalyst: Physico-chemical
characteristics and catalytic behavior in selective catalytic
reduction of NO by NH3. Appl. Catal. B, 2005, 60: 173.
[6] Ciardelli C, Nova I, Tronconi E, Chatterjee D, Konrad B B,
Weibel M, Krutzsch B. Reactivity of NO/NO2-NH3 SCR
system for diesel exhaust aftertreatment: Identification of
the reaction network as a function of temperature and NO2
feed content. Appl. Catal. B, 2007, 70: 80.
JOURNAL OF RARE EARTHS, Vol. 34, No. 10, Oct. 2016
[7] Jung K Y, Jung Y R, Jeon J K, Kim J H, Park Y K, Kim S.
Preparation of mesoporous V2O5/TiO2 via spray pyrolysis
and its application to the catalytic conversion of 1,2-di-
chlorobenzene. J. Ind. Eng. Chem., 2011, 17: 144.
[8] Baik J H, Yim S D, Nam I S, Mok Y S, Lee J H, Cho B K,
Oh S H. Control of NOx emissions from diesel engine by
selective catalytic reduction (SCR) with urea. Top. Catal.,
2004, 30-31: 37.
[9] Park J H, Park H J, Nam I S, Shin C H, Lee J H, Cho B K,
Oh S H. Hydrothermal stability of CuZSM5 catalyst in
reducing NO by NH3 for the urea selective catalytic reduc-
tion process. J. Catal., 2006, 240: 47.
[10] Cheng Y, Hoard J, Lambert C, Kwak J H, Peden C H F.
NMR studies of Cu/zeolite SCR catalysts hydrothermally
aged with urea. Catal. Today, 2008, 136: 34.
[11] Lisi L, Pirone R, Russo G, Stanzione V. Cu-ZSM5 based
monolith reactors for NO decomposition. Chem. Eng. J.,
2009, 154: 341.
[12] Moura de Oliveira M L, Silva C M, Tost R M, Farias T L,
Lopez A J, Castellon E R. A study of copper-exchanged
mordenite natural and ZSM-5 zeolites as SCR-NOx cata-
lysts for diesel road vehicles: Simulation by neural net-
works approach. Appl. Catal. B, 2009, 88: 420.
[13] Xia Q H, Hidajat K, Kawi S. Effect of ZrO2 loading on the
structure, acidity, and catalytic activity of the SO42–/ZrO2/
MCM-41 acid catalyst. J. Catal., 2002, 205: 318.
[14] Das D, Mishra H K, Pradhan N C, Dalai A K, Parida K M.
Studies on structural properties, surface acidity and ben-
zene isopropylation activity of sulphated ZrO2-TiO2 mixed
oxide catalysts. Micropor. Mesopor. Mat., 2005, 80: 327.
[15] Si Z C, Weng D, Wu X D, Li J, Li G. Structure, acidity
and activity of CuOx/WOx-ZrO2 catalyst for selective
catalytic reduction of NO by NH3. J. Catal., 2010, 271: 43.
[16] Seo C K, Choi B, Kim H, Lee C H, Lee C B. Effect of
ZrO2 addition on de-NOx performance of Cu-ZSM-5 for
SCR catalyst. Chem. Eng. J., 2012, 191: 331.
[17] Long R Q, Yang R T. Superior Fe-ZSM-5 catalyst for se-
lective catalytic reduction of nitric oxide by ammonia. J.
Am. Chem. Soc., 1999, 121: 5595.
[18] Carja G, Delahay G, Signorile C, Coq B. Fe-Ce-ZSM-5 a
new catalyst of outstanding properties in the selective
catalytic reduction of NO with NH3. Chem. Commun.,
2004, 12: 1404.
[19] Chen L, Li J H, Ge M F. Promotional effect of Ce-doped
V2O5-WO3/TiO2 with low vanadium loadings for selective
catalytic reduction of NOx by NH3. J. Phys. Chem. C, 2009,
113: 21177.
[20] Chen L, Si Z C, Wu X D, Weng D, Ran R, Yu J. Rare
earth containing catalysts for selective catalytic reduction
of NOx with ammonia: A Review. J. Rare Earths, 2014,
32: 907.
[21] Liu X S, Wu X D, Weng D, Si Z C. Durability of Cu/
SAPO-34 catalyst for NOx reduction by ammonia: Potas-
sium and sulfur poisoning. Catal. Commun., 2015, 59: 35.
[22] Yan Y, Sachtler W M H, Kung H H. Effect of Cu loading
and addition of modifiers on the stability of Cu/ZSM-5 in
lean NOx reduction catalysis. Catal. Today, 1997, 33: 279.
[23] Priya N S, Somayaji C, Kanagaraj S. Synthesis and char-
acterization of Nd3+-doped Ce0.6Zr0.4O2 and its doping sig-
LIU Xuesong et al., Modification of Cu/ZSM-5 catalyst with CeO2 for selective catalytic reduction of NOx with ammonia
nificance on oxygen storage capacity. Rare Met., 2016.
doi:10.1007/s12598-016-0698-3.
[24] Pang L, Fan C, Shao L N, Song K P, Yi J X, Cai X, Wang
J, Kang M, Li T. The Ce doping Cu/ZSM-5 as a new su-
perior catalyst to remove NO from diesel engine exhaust.
Chem. Eng. J., 2014, 253: 394.
[25] Pereda-Ayo B, Torre U D L, Illán-Gómez M J, Bueno-
López A, González-Velasco J R. Role of the different
copper species on the activity of Cu/zeolite catalysts for
SCR of NOx with NH3. Appl. Catal. B, 2014, 147: 420.
[26] Soria J, Martínez-Arias A, Martínez-Chaparro A, Conesa
J C, Schay Z. Influence of the preparation method, out-
gassing treatment, and adsorption of NO and/or O2 on the
Cu2+ species in Cu-ZSM-5: An EPR study. J. Catal., 2000,
190: 352.
[27] Gómez S A, Campero A, Martínez-Hernández A, Fuentes
G A. Changes in Cu2+ environment upon wet deactivation
of Cu-ZSM-5 deNOx catalysts. Appl. Catal. A, 2000, 197:
157.
[28] Ma L, Cheng Y S, Cavataio G V, McCabe R W, Fu L X,
Li J H. Characterization of commercial Cu-SSZ-13 and
Cu-SAPO-34 catalysts with hydrothermal treatment for
NH3-SCR of NOx in diesel exhaust. Chem. Eng. J., 2013,
225: 323.
[29] Bin F, Song C L, Lü G, Song J O, Wu S H, Li X D. Selec-
tive catalytic reduction of nitric oxide with ammonia over
zirconium-doped copper/ZSM-5 catalysts. Appl. Catal. B,
2014, 150-151: 532.
[30] Calligaris M, Nardin G. Cation site location in hydrated
chabazites. Crystal structure of barium-and cad-
mium-exchanged chabazites. Zeolites, 1982, 2: 200.
[31] Liu F, He H. Structure-activity relationship of iron titanate
catalysts in the selective catalytic reduction of NOx with
NH3. J. Phys. Chem. C, 2010, 114: 16929.
[32] Brandenberger S, Kröcher O, Wokaun A, Tissler A, Alt-
hoff R. The role of Brøsted acidity in the selective catalytic
reduction of NO with ammonia over Fe-ZSM-5. J. Catal.,
2009, 268: 297.
[33] Schwidder M, Kumar M S, Bentrup U, Pérez-Ramírez J,
Brückner A, Grünert W. The role of Brønsted acidity in
1009
the SCR of NO over Fe-MFI catalysts. Micropor. Mesopor.
Mat., 2008, 111: 124.
[34] Long R Q, Yang R T. Temperature-programmed desorp-
tion/surface reaction (TPD/TPSR) study of Fe-exchanged
ZSM-5 for selective catalytic reduction of nitric oxide by
ammonia. J. Catal., 2001, 198: 20.
[35] Li J Y, Song Z X, Ning P, Zhang Q L, Liu X, Li H, Huang
Z Z. Influence of calcination temperature on selective cata-
lytic reduction of NOx with NH3 over CeO2-ZrO2-WO3
catalyst. J. Rare Earths, 2015, 33: 726.
[36] Zhang D Z, Wei Y X, Xu L, Chang F X, Liu Z Y, Meng S
H, Su B L, Liu Z M. MgAPSO-34 molecular sieves with
various Mg stoichiometries: Synthesis, characterization
and catalytic behavior in the direct transformation of
chloromethane into light olefins. Micropor. Mesopor. Mat.,
2008, 116: 684.
[37] Izadbakhsh A, Farhadi F, Khorasheh F, Sahebdelfar S,
Asadi M, Feng Y Z. Effect of SAPO-34’s composition on
its physico-chemical properties and deactivation in MTO
process. Appl. Catal. A, 2009, 364: 48.
[38] Martins G A V, Berlier G, Coluccia S, Pastore H O, Su-
perti G B, Gatti G, Marchese L. Revisiting the nature of
the acidity in chabazite-related silicoaluminophosphates:
combined FTIR and 29Si MAS NMR study. J. Phys. Chem.
C, 2007, 111: 330.
[39] Martins G V A, Berlier G, Bisio C, Coluccia S, Pastore H
O, Marchese L. Quantification of Brønsted acid sites in
microporous catalysts by a combined FTIR and NH3-TPD
study. J. Phys. Chem. C, 2008, 112: 7193.
[40] Kieger S, Delahay G, Coq B, Neveu B. Selective catalytic
reduction of nitric oxide by ammonia over Cu-FAU cata-
lysts in oxygen-rich atmosphere. J. Catal., 1999, 183: 267.
[41] Wang J, Yu T, Wang X Q, Qi G S, Xue J J, Shen M Q, Li
W. The influence of silicon on the catalytic properties of
Cu/SAPO-34 for NOx reduction by ammonia-SCR. Appl.
Catal. B, 2012, 127: 137.
[42] Wang L, Li W, Schmieg S J, Weng D. Role of Brøsted
acidity in NH3 selective catalytic reduction reaction on
Cu/SAPO-34 catalysts. J. Catal., 2015, 324: 98.