Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240

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Journal of Molecular Catalysis A: Chemical

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

Performance of Fe-ZSM-5 for selective catalytic reduction of NOx with

NH3 : Effect of the atmosphere during the preparation of catalysts
Shuangshuang Lai, Yong She, Wangcheng Zhan ∗ , Yun Guo, Yanglong Guo, Li Wang,
Guanzhong Lu ∗
Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai, 200237,
PR China

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

Article history: Fe-ZSM-5 catalysts for selective catalytic reduction (SCR) of NOx with ammonia were prepared by ion
Received 20 March 2015 exchange under different atmospheres and characterized by X-ray diffraction (XRD), X-ray photoelec-
Received in revised form 26 August 2016 tron spectroscopy (XPS), Temperature-programmed desorption of NH3 and NO (NH3 -TPD and NO-TPD),
Accepted 27 August 2016
Ultraviolet–visible (UV–vis) spectroscopy and in situ diffuse reflectance Fourier transform infrared spec-
Available online 28 August 2016
troscopy (DRIFT). The results show that the atmosphere during ion exchange and calcination significantly
affects the cation exchange capacity and the nature of the Fe species in Fe-ZSM-5 catalysts. An air atmo-
Keywords:
sphere was conducive to improving the ability of ZSM-5 zeolites for Fe ionic exchange. However, isolated
Fe-ZSM-5
Selective catalytic reduction
Fe3+ sites were dominant in Fe-ZSM-5 catalyst (Fe-Z(N2 )) prepared under a N2 atmosphere, and small
Nitrogen oxide oligomeric Fex Oy clusters and Fex Oy nano-particles were markedly increased in Fe-ZSM-5 catalyst pre-
Preparation of catalyst pared in air, resulting in the higher SCR activity and wide temperature window of Fe-Z(N2 ). Moreover,
Atmosphere effect Fe-Z(N2 ) catalyst possessed more Brønsted acid sites and could adsorb more NH3 species, promoting its
SCR activity. In situ DRIFT studies showed that NH3 can be adsorbed on both Brønsted and Lewis acid
sites on Fe-ZSM-5 catalyst, and this adsorbed NH3 can react with gaseous NOx . Additionally, NOx can be
adsorbed on Fe-ZSM-5 catalyst, mainly as a bidentate nitrate, but these nitrate species cannot be con-
firmed to react with gaseous NH3 because of the overlap with the strong absorption band of adsorbed NH3
species. Based on the IR results and weak adsorption of NOx over Fe-ZSM-5 catalysts, it was concluded
that NH3 -SCR over this Fe-ZSM-5 catalyst predominantly follows the Eley-Rideal reaction mechanism.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction of novel, highly efficient, stable and environmentally friendly NH3 -

Nitrogen oxides (NOx ) and particulate matter (PM) emitted from
diesel vehicles are major atmospheric pollutants. Selective catalytic
reduction of NOx with NH3 (NH3 -SCR) is one of the most promising
techniques for NOx elimination from diesel exhaust under oxygen-
rich conditions. A great variety of catalysts have been developed
for this process, such as V2 O5 /TiO2 [1,2], zeolite-based catalysts
[3,4], mesoporous materials-based catalysts [5,6] and oxide cat-
alysts [7–9]. Among them, V2 O5 /TiO2 catalysts possess excellent
H2 O/SO2 durability and are the most widely used in industry. How-
ever, V2 O5 /TiO2 catalysts exhibit some inevitable disadvantages,
such as a narrow temperature window and volatility of the active
component (V2 O5 ) at high temperatures. The latter is likely harm-
ful for the ecology and human health. Therefore, the development
∗ Corresponding authors.
E-mail addresses: zhanwc@eust.edu.cn (W. Zhan), gzhlu@ecust.edu.cn (G. Lu).
SCR catalysts has attracted extensive attention.
Among different NH3 -SCR catalysts, zeolite-based catalysts
generally have high activity and selectivity over a wider temper-
ature range, as well as good thermal stability, which has aroused
wide interest in researchers developing zeolite-based catalysts. At
present, the zeolites ZSM-5 [3,10,11], ␤ [12,13], USY [14,15] and
SSZ-13 [16–18] are mainly used as matrices for NH3 -SCR cata-
lysts. Transition metals and rare earth metals are usually used
as the active components of zeolite-based SCR catalysts, e.g., Cu
[11,16,19], Fe [3,10,20], Mn [21] and Ce [22]. On the whole, Cu- and
Fe-modified ZSM-5 are the most widely studied among zeolite-
based SCR catalysts. In general, Cu-modified ZSM-5 exhibits high
SCR activity, particularly at low reaction temperatures, while Fe-
modified ZSM-5 exhibits high SCR activity at high temperatures
with a wide temperature window.
Several studies have focused on the effect of different prepara-
tion methods, such as chemical vapour deposition [23], hydrother-
mal synthesis [24], impregnation [25,26] and liquid/solid-state ion

http://dx.doi.org/10.1016/j.molcata.2016.08.026
1381-1169/© 2016 Elsevier B.V. All rights reserved.
 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240
exchange [3,10,27], on the SCR activity of Fe-modified ZSM-5 cat-
alysts. It was proposed that preparation methods have a marked
effect on the location of Fe in the ZSM-5 matrix, leading to differ-
ent activities for NH3 -SCR [28]. Among the preparation methods
mentioned above, liquid ion exchange is most commonly used
for preparing metal-exchanged zeolites [3,26,29,30]. However, it is
well known that synthesis conditions generally have a significant
influence on the structure, physico-chemical properties and reac-
tive activity of Fe-modified ZSM-5 catalysts. For example, thermal
treatment significantly affected the catalytic activity of Fe-ZSM-5
catalysts prepared by chemical vapour deposition [31–33]. Fe-ZSM-
5 catalysts exhibited a slightly higher activity when a slow heating
rate (0.5 ◦ C/min) was applied during calcination [31]. When the
thermal treatment was carried out in helium rather than in oxygen,
partial auto-reduction of iron from Fe3+ to Fe2+ occurred together
with the formation of Fe3 O4 clusters [32]. In the liquid ion exchange
method, only Fe precursors have been investigated to study their
effect on the activity and hydrothermal stability of NH3 -SCR in
Fe-ZSM-5 [34,35]. Other synthesis conditions, such as the atmo-
sphere during ion exchange and calcination processes, have not
attracted attention. To the best of our knowledge, related work
has only reported by Brandenberger and co-authors. They synthe-
sized Fe-ZSM-5 samples by liquid ion exchange of NH4 -ZSM-5 with
FeCl2 ·4H2 O under nitrogen instead of air, followed by calcination of
the obtained sample under nitrogen [36]. Unfortunately, although
a more detailed picture of the role of Brønsted acidity in the SCR of
NO by ammonia in Fe-ZSM-5 catalysts has been obtained, the role
of the N2 atmosphere in the preparation of Fe-ZSM-5 samples has
not been described. As mentioned above, although some effort has
been made to study the effect of the calcination process on the SCR
activity of Fe-modified ZSM-5 catalysts, it is very necessary to thor-
oughly study the nature of the Fe species and NH3 -SCR activity of
Fe-ZSM-5 catalyst as a function of preparation parameters of liquid
ion exchange.
Herein, Fe-ZSM-5 zeolite catalysts were prepared by liquid ion
exchange under atmospheres of air and N2 , respectively, and their
physicochemical and catalytic properties for the SCR reaction with
ammonia were investigated. It is interesting that different atmo-
spheres during ion exchange and calcination processes can affect
the degree of ionic exchange, the nature of the Fe species and the
SCR activity of Fe-ZSM-5 catalysts. At the same time, the NH3 -SCR
reaction pathway over prepared Fe-ZSM-5 catalysts was explored
and discussed here on the basis of DRIFTS studies.
2. Experimental
2.1. Preparation of catalysts
Fe-ZSM-5 samples were prepared by ion exchange method. Typ-
ically, 3 g of NH4 -ZSM-5 (purchased from Nankai University, Si/Al
atomic ratio = 25) was added to 300 mL of 0.05 M FeSO4 ·7H2 O aque-
ous solution. The pH value of the synthesis solution was adjusted
to approximately 3.2 using dilute H2 SO4 , and the suspension was
stirred under continuous flow of N2 at 80 ◦ C for a certain time.
Then, the solid was filtered and washed with deionized water, dried
overnight at 120 ◦ C and finally calcined at 600 ◦ C for 5 h in N2 . The
obtained samples were labelled as Fe-Z(N2 -x), where x is the time of
ion exchange. The samples exposed to the air atmosphere during
ion exchange and calcination were labelled as Fe-Z(Air-x). Addi-
tionally, if NH4 -ZSM-5 was calcined at 600 ◦ C for 5 h in air, the
obtained sample was labelled as H-ZSM-5.
2.2. Catalyst characterization
Powder X-ray diffraction (XRD) patterns of samples were
acquired on a D/MAX 2550 VB/PC X-ray diffractometer (Japan,
233
RIGAKU). The Fe content in the samples was analysed using an
inductively coupled plasma optical emission spectrometer (ICP-
OES, Thermo Elemental, IRIS 1000). The N2 adsorption-desorption
isotherms were measured on a Quantachrome NOVA1200 surface
area analyser at −196 ◦ C. Prior to the measurements, all samples
were degassed at 180 ◦ C until a stable vacuum of approximately
5 mTorr was reached. The specific surface area of the sample
was calculated using the Brunauer-Emmett-Teller (BET) method.
Ultraviolet–visible (UV–vis) spectra were recorded on a Varian Cary
500 UV–vis-NIR spectrophotometer at 200–800 nm with BaSO4 as
a reference, and the spectra were converted with the Kubelka-
Munk (K-M) function F(R) for comparison. X-ray photoelectron
spectroscopy (XPS) was conducted on a Thermo Fisher ESCALAB
250Xi spectrometer with Mg K␣ radiation at room temperature
under 5.0 × 10−10 mbar. Fe 2p binding energy was calibrated with
a C1s band at 285.4 eV from carbon impurity. Peak fitting was per-
formed using XPSPEAK 4.1 with a linear background and 20:80
Lorentzian:Gaussian convolution product shapes.
Temperature-programmed desorption of NH3 adsorbed on the
catalyst (NH3 -TPD) was carried out in a conventional flow system
equipped with a thermal conductivity detector (TCD). After 50 mg
of the sample was pre-treated at 600 ◦ C for 30 min and cooled to
room temperature in N2 , it was allowed to adsorb NH3 for 1 h from
the mixed gas 10% NH3 /N2 . After purging the sample in N2 for 1.5 h
at 90 ◦ C, NH3 -TPD was carried out at 90–600 ◦ C in a flow of N2
(50 mL/min). The rate of heating was 10 ◦ C/min.
NO-TPD was carried out in a conventional flow system equipped
with a NOx analyser (Thermo Fisher Model 42i-HL NO-NOx -
chemiluminescence analyser) as the detector. 50 mg of the sample
was pre-treated in Ar (450 mL/min) at 500 ◦ C for 1 h and cooled
to room temperature. Then, the sample was exposed to a flow of
500 ppm NO/Ar (300 mL/min) for 1 h. After purging the sample in
Ar (300 mL/min) for 1 h, NO-TPD was carried out at RT ∼500 ◦ C in a
flow of Ar (300 mL/min). The rate of heating was 10 ◦ C/min.
In situ diffuse reflectance infrared Fourier transform spec-
troscopy (DRIFTS) was conducted on a Nicolet NEXUS 670-FTIR
spectrometer equipped with a MCT detector. The diffuse
reflectance FT-IR experiments were carried out in situ in a high-
temperature IR cell. Prior to each experiment, the sample was
pre-treated in situ in the IR cell at 550 ◦ C in a flow of Ar (50 mL/min)
for 60 min and then cooled to 50 ◦ C. The background spectrum was
recorded in flowing Ar and was subtracted from the sample spec-
trum obtained. The IR spectra were recorded by accumulating 128
scans at a resolution of 4 cm−1 .
2.3. Catalytic activity testing
The SCR activity of the catalyst was measured in a fixed-bed
quartz reactor. Fe-ZSM-5 catalysts were powdered and sieved to
20–40 mesh. 200 mg of Fe-ZSM-5 catalysts was used in each run.
The reactant gas consisted of 500 ppm NO, 500 ppm NH3 , 5%O2 and
balance Ar. The total flow rate was 300 mL/min (under ambient con-
dition) and the gas hourly space velocity (GHSV) was 58,000 h−1 .
The concentrations of NO and NO2 were continually monitored by
a chemiluminescent NO/NOx analyser (Thermo-Scientific, Model
42i-HL). NOx conversion (XNOx ) was calculated as follows:
XNOx = (1-([NO] + [NO2 ])out /([NO] + [NO2 ])in ) × 100%
3. Results and discussion
3.1. Catalytic performance
Fig. 1 shows the NOx conversions of the NH3 -SCR reaction as
a function of reaction temperature over different Fe-ZSM-5 cata-
234 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240

100 Fe-Z(N2-60)

80
NOx Conversion (%)

Fe-Z(N2-36)

Intensity (a.u.)
60
ZSM-5 Fe-Z(Air-6)
Fe-Z(N2-12)
40
Fe-Z(N2-24)
Fe-Z(N2-36) Fe-Z(Air-2)
Fe-Z(N2-60)
20
Fe-Z(air-2)
Fe-Z(air-6) ZSM-5
0
100 200 300 400 500 600 700
o
10 20 30 40 50 60
Temperature ( C)
2 Theta ( )
o

Fig. 1. Catalytic performance of Fe-ZSM-5 and H-ZSM-5 catalysts for NH3 -SCR.
Fig. 2. XRD patterns of ZSM-5, Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and Fe-Z(Air-2)
catalysts.
lysts. The NOx conversion over the H-ZSM-5 catalyst was very low
(no more than 50%) at <300 ◦ C. Only when the reaction tempera-
ture was raised >525 ◦ C did the NOx conversion over the H-ZSM-5 724.3
catalyst increase to 95%. Compared with the H-ZSM-5 catalyst, the 710.6
718.6
SCR activity was markedly improved after introducing Fe into the Fe-Z(N2-36)

H-ZSM-5 catalyst. As shown in Fig. 1, the NOx conversion over
the Fe-Z(N2 -12) catalyst was >95% over a wide temperature win-
dow (320–575 ◦ C). Furthermore, the SCR activities of the Fe-Z(N2 -x)
catalysts at low temperature increased with the increase in Fe con-
tent, while its activities at high temperature decreased slightly. In
other words, more than 90% NOx conversion was still obtained over
a wide temperature window over different Fe-Z(N2 -x) catalysts.
The SCR activity of the Fe-Z(Air-x) catalyst was lower than that of
the Fe-Z(N2 -x) catalyst with equivalent Fe contents, especially at
high reaction temperatures. Over the Fe-Z(Air-2) catalyst, the NOx
conversion sharply decreased at >455 ◦ C, showing a narrow tem-
perature window. When the Fe content was continually increased
to 1.8 wt%, there was a further decrease in the SCR activity of the
Fe-Z(Air-6) catalyst at high reaction temperatures.
The turnover frequency (TOF) values of different catalysts for
the SCR reaction were estimated at 100 ◦ C on the basis of their BET
surface area (Table 2), and the GHSV was changed to keep the NOx
conversion less than 20% over all catalysts. The TOF values were
4.4 × 10−7 , 3.6 × 10−7 , 1.5 × 10−7 and 1.8 × 10−7 mol h−1 m2 g−1 for
Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and Fe-Z(Air-2) catalysts,
respectively, which clearly shows that a N2 atmosphere during the
ion exchange process can effectively improve the catalytic perfor-
mance of Fe-ZSM-5 catalyst. Since an equivalent Fe content was
incorporated in the corresponding catalysts, such as Fe-Z(N2 -36)
and Fe-Z(Air-2), the difference of NH3 -SCR activity between Fe-
Z(N2 -x) and Fe-Z(Air-x) catalysts could be attributed to the different
nature of Fe species in Fe-ZSM-5 catalysts. This is discussed in fur-
ther detail below.
3.2. Structural characterization of catalysts
3.2.1. ICP
The Fe contents of the samples were determined by inductively
coupled plasma (ICP) analysis and are shown in Table 1. The Fe con-
tent in the Fe-Z(N2 -x) samples increased with the increase in ion
exchange time. For example, under an atmosphere of N2 during ion
exchange, the Fe content of the Fe-Z(N2 -x) samples increased from
0.9 wt% to 1.9 wt% when the time for ion exchange was increased
from 12 h to 60 h. Similarly, under an atmosphere of air during ion
exchange, the Fe contents of the Fe-Z(Air-2) and Fe-Z(Air-6) sam-
ples were 1.4 wt% and 1.8 wt%, respectively, after 2 h and 6 h of ion
exchange. Conversely, to load similar Fe contents, the time of ion
Intensity (a.u.)
Fe-Z(Air-2)
735 730 725 720 715 710 705 700
Binding energy (eV)
Fig. 3. XPS spectra of Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts.
exchange under an air atmosphere is much shorter than that under
a N2 atmosphere, indicating that the capacity for Fe cation exchange
under an air atmosphere is better than that under a N2 atmosphere.
3.2.2. XRD
The XRD patterns of Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and
Fe-Z(Air-2) catalysts are shown in Fig. 2. All Fe-ZSM-5 catalysts
exhibited typical diffraction peaks of the ZSM-5 zeolite, indicat-
ing that the structure of the ZSM-5 zeolite was retained after Fe
exchange. No diffraction peaks belonging to Fe2 O3 were observed at
2␪ = 33.1, 35.6, 40.9 and 49.5◦ in the XRD patterns of all the catalysts,
indicating that the Fe species are highly dispersed in all Fe-ZSM-5
catalysts.
3.2.3. XPS
Fig. 3 shows the XPS spectra of Fe 2p3/2 and Fe 2p1/2 for Fe-
Z(N2 -36) and Fe-Z(Air-2) catalysts. Two peaks centred at 710.6 and
724.3 eV were observed in the spectra of both samples, which were
assigned to Fe 2p3/2 and 2p1/2 , respectively [37], and a satellite peak
of Fe 2p3/2 was located at 718.6 eV [38]. The peak at BE = 710.6 eV
of Fe 2p3/2 was close to the binding energy of Fe 2p3/2 of Fe2 O3
(BE = 710.4–711 eV) [39,40], indicating that Fe in Fe-ZSM-5 cata-
lysts was mainly present as the +3 form.
The deconvolution of Fe 2p3/2 peak was very difficult because
there is a large difference in the BE values of FeO and/or Fe2 O3
obtained by different researchers, and the FWHM of every peak
at deconvolution was not unambiguous. Even the deconvolution of
the Fe 2p3/2 peak for both FeO and Fe2 O3 consisted of several peaks,
 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240 235

Table 1
Percentage of the area of the sub-bands and wt% Fe of the corresponding species by numerical analysis of UV–vis spectra (Fig. 4) for Fe-ZSM-5 catalysts.

Catalyst Total Fe content d (wt%) Fe1 a Fe2 b Fe3 c

I1 (%) (wt%) I2 (%) (wt%) I3 (%) (wt%)

Fe-Z(N2 -12) 0.9

Fe-Z(N2 -24) 1.1
Fe-Z(N2 -36) 1.3 78.2 1.02 17.8 0.23 4.0 0.05
Fe-Z(N2 -60) 1.9 58.8 1.12 25.9 0.49 15.3 0.29
Fe-Z(Air-2) 1.4 57.4 0.80 24.1 0.34 18.5 0.26
Fe-Z(Air-6) 1.8 35.8 0.65 28.0 0.50 36.2 0.65
a
Isolated Fe ion in tetrahedral and octahedral coordination.
b
Small oligomeric Fex Oy clusters.
c
Fex Oy nano-particles on zeolite surface.
d
detected by ICP.

Table 2
BET surface area (SBET ) and the total area of the two desorption peaks (Area) of
NH3 -TPD curves (Fig. 5A) for different ZSM-5 samples.
Fe-Z(Air-6)
Sample SBET (m2 /g) Area Area/SBET

ZSM-5 334 / /
Fe Z(N2 -60) 276 2834 10.3
Fe-Z(N2 -36) 275 2664 9.7 Fe-Z(N2-60)
Fe-Z(Air-6) 265 2261 8.5

F(R)
Fe-Z(Air-2) 272 1731 6.4

and there was a small overlap between the deconvolution peaks
for FeO and Fe2 O3 [39,41]. To approximately compare the differ-
ence in FeO/Fe2 O3 (mol) between the Fe-Z(N2 -36) and Fe-Z(Air-2)
catalysts, the Fe 2p3/2 peaks in Fig. 3 were fitted with a linear back-
ground and 20:80 Lorentzian:Gaussian convolution product shapes
[38,39,42]. The peaks at 707.5 and 714.6 eV were assigned to FeO
and Fe(OH)O, respectively, while the other five peaks were due to
the overlap of FeO, Fe2 O3 and Fe(OH)O. Therefore, these results
clearly reveal that a small quantity of Fe2+ also existed on the sur-
face of the Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts. Conversely, the
area of every deconvolution peak for the Fe-Z(N2 -36) catalyst was
close to that of the corresponding peaks for the Fe-Z(Air-2) catalyst,
indicating that the ratio of Fe2+ /Fe3+ on Fe-Z(N2 -36) was close to
that on Fe-Z(Air-2). This is mainly due to the easy oxidation of FeO
to Fe2 O3 even at low temperature. Therefore, in the preparation
process of the Fe-Z(N2 -36) catalyst, which included steps such as
filtering under an air atmosphere, Fe2+ ions on the surface of the
Fe-Z(N2 -36) catalyst were easily oxidized to Fe3+ .
3.2.4. UV–vis spectroscopy
The UV–vis spectra of Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and
Fe-Z(Air-2) catalysts are shown in Fig. 4. It has been reported that
UV–vis spectra can distinguish between different Fe species on Fe-
ZSM-5 catalysts to isolated Fe3+ species (bands below 300 nm),
small oligomeric Fex Oy clusters (between 300 and 400 nm) and
Fex Oy nano-particles on the zeolite surface (above 400 nm) [31,43].
The percentage areas of the sub-bands and wt% Fe of the corre-
sponding species, obtained by numerical analysis of UV–vis spectra
for Fe-ZSM-5 catalysts (Fig. 4), are shown in Table 1. I1 , I2 and I3
represent the area (%) of sub-bands at ␭ ≤ 300 nm, ␭ = 300–400 nm
and ␭ > 400 nm, respectively. The results indicate that I1 for the Fe-
Z(N2 -x) catalyst was higher than that for the Fe-Z(Air-x) catalyst
with equivalent Fe contents, whereas I2 and I3 presented a con-
trary result, especially I3 . For example, I1 , I2 and I3 are 78.2%, 17.8%
and 4.0% for the Fe-Z(N2 -36) catalyst with 1.3 wt% Fe content, while
they are 57.5%, 24.1% and 18.5% for the Fe-Z(Air-2) catalyst with
1.4 wt% Fe content. However, with increasing Fe content of catalysts
(1.8 wt% and 1.9 wt%), I1 decreased markedly, while I3 dramatically
increased and I2 increased slightly, regardless of the atmosphere
during the preparation process. The results mentioned above sug-
Fe-Z(Air-2)
Fe-Z(N2-36)
200 300 400 500 600 700
Wavelength (nm)
Fig. 4. UV–vis spectra of Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and Fe-Z(Air-2) cat-
alysts.
gest that the atmosphere during the preparation process has a great
influence on the nature of Fe species in Fe-ZSM-5 catalysts.
Brandenberger et al. [44] suggested that different Fe species on
Fe-ZSM-5 catalyst may act as active sites at different temperatures:
at <300 ◦ C, the SCR activity of Fe-ZSM-5 catalyst is primarily caused
by isolated iron sites; at >300 ◦ C, small oligomeric iron species are
involved in the SCR reaction; at ≥500 ◦ C, Fex Oy nano-particles catal-
yse the SCR reaction. Furthermore, surface iron particles not only
contributed to the SCR reaction but also caused nonselective oxida-
tion of NH3 at ≥350 ◦ C, while oligomeric iron species also exhibited
catalytic activity for NH3 oxidation up to 500 ◦ C. As shown in Fig. 4
and Table 1, the Fe-Z(N2 -36) catalyst possessed more isolated Fe3+
sites than the Fe-Z(Air-2) catalyst, leading to its higher SCR activity
at <300 ◦ C. On the contrary, compared with the Fe-Z(N2 -36) cata-
lyst, more Fex Oy oligomers and nano-particles on the Fe-Z(Air-2)
catalyst brought on the more serious nonselective oxidation of NH3 ,
resulting in the lower SCR activity of Fe-Z(Air-2) at high temper-
ature (≥450 ◦ C). When the Fe content was increased from 1.3 wt%
for the Fe-Z(N2 -36) catalyst to 1.9 wt% for the Fe-Z(N2 -60) catalyst,
the amount of isolated Fe3+ sites and Fex Oy oligomers increased
from 1.02 wt% and 0.23 wt% to 1.12 wt% and 0.49 wt%, respectively,
leading to further increase in the SCR activity of the Fe-Z(N2 -60)
catalyst at low temperature compared with the Fe-Z(N2 -36) cat-
alyst. At the same time, because of the increase in the amount of
Fex Oy nano-particles from 0.05 wt% to 0.29 wt%, the SCR activity
of the Fe-Z(N2 -60) catalyst at high temperature decreased slightly
compared with the Fe-Z(N2 -36) catalyst. On the contrary, for the Fe-
Z(Air-x) catalysts, when the Fe content was increased from 1.4 wt%
for the Fe-Z(Air-2) catalyst to 1.8 wt% for the Fe-Z(Air-6) catalyst,
236 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240

A B
Fe-Z(N2-60)
Fe-Z(Air-2)

0.01
Intensity (a.u.)

Aborbance
Fe-Z(Air-6)
Fe-Z(N2-36)

Fe-Z(N2-36) 3660

Fe-Z(Air-2)

3610

100 200 300 400 500 600 700 3800 3750 3700 3650 3600 3550 3500
Temperature ( C)
o -1
Wavenumber (cm )

Fig. 5. (A) NH3 -TPD curves of Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and Fe-Z(Air-2) catalysts and (B) their DRIFT spectra after being exposed under 500 ppm NH3 /Ar
(50 mL/min) at 50 ◦ C for 90 min.

the amount of isolated Fe3+ sites sharply decreased from 0.80 wt% 800
to 0.65 wt%, accompanied by the increase in the amount of Fex Oy
oligomers from 0.34 wt% to 0.50 wt%, leading to the same SCR activ-

NOx Concentration (ppm)

ity for Fe-Z(Air-2) and Fe-Z(Air-6) catalysts at low temperatures. 600
However, the amount of Fex Oy nano-particles rapidly increased
from 0.26 wt% to 0.65 wt%, leading to a marked decline in the SCR
activity at high temperature over Fe-Z(Air-6) catalysts. The above 400
Fe-Z(N2-60)
results indicate that to obtain a high SCR activity, Fe-ZSM-5 catalyst
should be designed and prepared to enhance the concentration of
isolated Fe3+ species. 200 Fe-Z(N2-36)

3.3. The absorption properties for NH3 and NO
Fig. 5A shows the NH3 -TPD curves of Fe-Z(N2 -60), Fe-Z(N2 -
36), Fe-Z(Air-6) and Fe-Z(Air-2) catalysts, in which there are two
NH3 desorption peaks. The peak located at 200 ◦ C can be ascribed
to physisorbed NH3 , and the peak at 400 ◦ C can be ascribed to
NH3 strongly adsorbed on Brønsted hydroxyl groups and strong
Lewis iron sites [45,46]. The ratios between the total area of the
two desorption peaks and the BET surface areas for different cat-
alysts (Area/SBET ) were calculated, and the results are shown in
Table 2. It was found that Area/SBET for the Fe-Z(N2 -x) catalysts
were larger than those for the Fe-Z(Air-x) catalysts with equivalent
Fe content, indicating that Fe-Z(N2 -x) catalysts possess a higher
adsorption capacity for NH3 . Furthermore, for both Fe-Z(N2 -x) and
Fe-Z(Air-x) catalysts, Area/SBET increased with the increase in the
Fe content. The ratio between the areas of the desorption peaks
at approximately 400 ◦ C and 200 ◦ C for the Fe-Z(N2 -x) catalyst
was remarkably higher than that for the Fe-Z(Air-x) catalysts with
equivalent Fe content, indicating that the Fe-Z(N2 -x) catalysts pos-
sessed more Brønsted acid sites and Lewis iron sites that can adsorb
NH3 . This high ability of Fe-Z(N2 -x) catalysts for NH3 adsorption can
prompt their SCR activity. The detailed relationship between NH3
species adsorbed on the catalyst surface and SCR activity will be
discussed in the DRIFTS measurements section.
The relative concentration of Brønsted acid sites over Fe-ZSM-5
catalysts was also measured by FTIR spectroscopy. The sample was
pre-treated as follows: it was dried in an IR cell under a flow of
Ar at 550 ◦ C for 1 h and then cooled to 50 ◦ C; after recording the
background spectrum in Ar, the sample was exposed to a flow of
500 ppm NH3 /Ar (50 mL/min) at 50 ◦ C for 90 min, and the DRIFT
spectra of Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts after NH3 adsorp-
tion are shown in Fig. 5B. When NH3 was fed into the IR cell, the
OH- groups on the catalyst surface were consumed by the inter-
action of NH3 with OH-, thereby creating negative peaks at the
corresponding wavenumbers. The negative peak at 3610 cm−1 was
assigned to the OH stretch of the Brønsted acidic sites, and the neg-
ative peak at 3660 cm−1 arose from the OH groups associated with
extra-framework Al [47,48]. Compared with the Fe-Z(Air-2) cata-
Fe-Z(Air-6)
Fe-Z(Air-2)
0
0 100 200 300 400 500
o
Temperature ( C)
Fig. 6. TPD curves of NO adsorbed over Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and
Fe-Z(Air-2) catalysts.
lyst, the peak at 3610 cm−1 for the Fe-Z(N2 -36) catalyst showed a
much higher intensity, and the peak at 3660 cm−1 showed similar
intensities for the two catalysts. Since the relative concentration of
Brønsted acidic sites can be determined using the intensities of the
peaks at 3610 cm−1 [48], it was clear that the Fe-Z(N2 -36) catalysts
possessed more Brønsted acid sites than the Fe-Z(Air-2) catalyst.
The NO-TPD profiles of Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6)
and Fe-Z(Air-2) catalysts are shown in Fig. 6. As shown in Fig. 6, all
the catalysts exhibited two NO desorption peaks at approximately
126 ◦ C and 325 ◦ C. The former can be ascribed to physisorbed NO
species, and the latter can be ascribed to the decomposition of
nitrate species with higher thermal stability. Although the positions
of the two desorption peaks were very close for different catalysts,
the areas of the desorption peaks were very different. The areas
of both desorption peaks were larger for the Fe-Z(N2 -x) catalysts
than for the Fe-Z(Air-x) catalysts with equivalent BET surface areas,
indicating that the Fe-Z(N2 -x) catalysts possessed a higher capac-
ity for NO adsorption. In other words, more nitrate species could
be adsorbed over the surface of the Fe-Z(N2 -x) catalysts, which was
beneficial to the SCR activity of Fe-Z(N2 -x) catalysts. However, with
increasing content of Fe in the Fe-Z(Air-x) catalysts, the areas of
both desorption peaks in the NO-TPD curves of the Fe-Z(Air-6) and
Fe-Z(Air-2) catalysts hardly changed. On the contrary, the areas of
both desorption peaks in the NO-TPD curves of the Fe-Z(N2 -60)
catalyst were slightly higher than those of the Fe-Z(N2 -36) cata-
lyst, which promoted the SCR activity of the Fe-Z(N2 -60) catalyst
at low temperatures, compared with the Fe-Z(N2 -36) catalyst.
 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240 237

Fe-Z(Air-2) Fe-Z(N2-36)
1165 1165

0.02
1517
0.01 1268
1268 1592 1517
1592 1947 1740 70 min
70 min 1463

Absorbance
1740 1463
Absorbance
1947

60

60
40

40
20

20
10
10
2 2

2000 1800 1600 1400 1200 1000 2000 1800 1600 1400 1200 1000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 7. In situ DRIFT spectra of Fe-Z(Air-2) and Fe-Z(N2 -36) catalysts exposed in a flow of 500 ppm NH3 /Ar (50 mL/min) at 150 ◦ C for different times.

Fe-Z(Air-2) Fe-Z(N2-36)
1165 1165
0.01
0.02 1668 1562
1668 15621517 1517 1268
1268 1592
1592
1463 30 min
1463
Absorbance

Absorbance

30 min
10
10
5

NH3 NH3

2000 1800 1600 1400 1200 1000 2000 1800 1600 1400 1200 1000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 8. In situ DRIFT spectra of Fe-Z(Air-2) and Fe-Z(N2 -36) catalysts after adsorbing NH3 , followed by introduction of 500 ppm NO + 5 vol.% O2 /Ar at 150 ◦ C for different times.

3.4. In situ DRIFTS absorption spectroscopy
3.4.1. NH3 adsorption and the surface reaction of NO + O2
Fig. 7 shows in situ DRIFTS spectra of the Fe-Z(Air-2) and Fe-
Z(N2 -36) catalysts during the adsorption of NH3 at 150 ◦ C. Prior to
NH3 adsorption, the catalyst was pre-treated at 550 ◦ C in Ar for 1 h
and then cooled to 150 ◦ C. The pre-treated catalyst was exposed
to a flow of 500 ppm NH3 /Ar (50 mL/min) at 150 ◦ C, and IR spectra
were taken at different times. As shown in Fig. 7, after being exposed
to NH3 at 150 ◦ C, many bands appeared at 1947, 1740, 1592, 1517,
1463, 1268 and 1165 cm−1 . The bands at 1947, 1740 and 1463 cm−1
were attributed to NH4 + species chemisorbed on the Brønsted acid
sites, and the bands at 1592, 1268 and 1165 cm−1 were assigned
to coordinated NH3 bound to Lewis acid sites [49–51]. The band at
1517 cm−1 might be attributed to amide (-NH2 ) species [52]. The
intensities of all bands increased significantly in the initial 60 min
and then remained stable, and the types of NH3 species adsorbed
on the Fe-Z(Air-2) and Fe-Z(N2 -36) catalysts were identical. How-
ever, the intensities of the corresponding bands for the Fe-Z(N2 -36)
catalyst were stronger than those for the Fe-Z(Air-2) catalyst, indi-
cating that the Fe-Z(N2 -36) catalyst possessed a higher adsorption
capacity for NH3 , in accordance with the NH3 -TPD results.
At the end of the experiment corresponding to Fig. 7, the IR
cell was purged with Ar for 30 min at 150 ◦ C. Then, the mixed gas
NO + O2 /Ar was introduced into the IR cell at 150 ◦ C, and in situ
DRIFT spectra were recorded at different times. As shown in Fig. 8,
after NO + O2 was introduced into the cell, the intensities of the
bands at 1740, 1592, 1268 and 1165 cm−1 first decreased and
then became stable, indicating that some of the NH4 + species on
Brønsted acid sites and coordinated NH3 bound to Lewis acid sites
participated in the SCR process. The band assigned to amide (-NH2 )
species at 1517 cm−1 was unchanged after 30 min, while many new
bands were detected at 1668 and 1562 cm−1 , which were attributed
to NOx species. It is noticeable from Fig. 8 that the intensities of the
238 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240

Fe-Z(N2-36) Fe-Z(Air-2)

1574 1630
1630 0.005 1570
0.005
1688
1688 60 min
60 min

Absorbance

Absorbance
50
50

40 40

30 30

20 20

10 10

4 4

2000 1800 1600 1400 1200 2000 1800 1600 1400 1200
-1
Wavenumber (cm ) Wavenumber (cm-1)

Fig. 9. In situ DRIFT spectra of Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts in a flow of 500 ppm NO + 5% O2 /Ar (50 mL/min) at 150 ◦ C for different times.

Fe-Z(N2-36) Fe-Z(Air-2)
1169 1169
0.01
0.02 1574 1268 1570
1630 1268
1630
60min
1947 1947
60min
Absorbance

Absorbance

50 50

30 30

20
20
4
4
NO+O2 NO+O2

2000 1800 1600 1400 1200 1000 2000 1800 1600 1400 1200 1000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 10. In situ DRIFT spectra of (A) Fe-Z(N2 -36) and (B) Fe-Z(Air-2) catalysts pre-treated by exposure to 500 ppm NO + 5 vol.% O2 /Ar, followed by exposure to 500 ppm NH3
at 150 ◦ C for different times.

corresponding bands decreased more markedly for the Fe-Z(N2 -36) for the Fe-Z(N2 -36) catalyst was remarkably stronger than that for
catalyst compared with the Fe-Z(Air-2) catalyst due to the higher the Fe-Z(Air-2) catalyst. It was reported that the amount of biden-
SCR activity of the Fe-Z(N2 -36) catalyst at low temperatures (Fig. 1). tate nitrate on the catalyst can affect its activity in the SCR reaction
[56]. Therefore, the higher amount of bidentate nitrate on the sur-
face of the Fe-Z(N2 -36) catalyst may possibly be responsible for its
3.4.2. NO + O2 adsorption and the reaction with NH3
higher SCR activity, compared with the Fe-Z(Air-2) catalyst.
In situ DRIFTS spectra for the co-adsorption of NO and O2 are
At the end of the experiment corresponding to Fig. 9, the IR cell
shown in Fig. 9. Prior to adsorption, the catalyst was pre-treated at
was purged with Ar for 30 min at 150 ◦ C. After this, the mixed gas
550 ◦ C in Ar for 1 h and then cooled to 150 ◦ C. The pre-treated cata-
of 500 ppm NH3 /Ar was introduced into the IR cell at 150 ◦ C, and
lysts were exposed to a flow of 500 ppm NO + 5%O2 /Ar (50 mL/min)
in situ DRIFT spectra were recorded at different times. As shown
at 150 ◦ C, and IR spectra were taken at different times. As shown
in Fig. 10, after NH3 was introduced into the system, the inten-
in Fig. 9, the intensities of bands were lower due to the weak
sity of the band at 1630 cm−1 (assigned to gaseous NO2 ) decreased
adsorption of NOx on the surface of the Fe-Z(N2 -36) and Fe-Z(Air-
quickly, but the change in the band at 1574 cm−1 (correspond-
2) catalysts. There were two relatively strong bands at 1574 and
ing to bidentate nitrate) was unclear because of overlap with the
1630 cm−1 , which can be attributed to bidentate nitrate [51,53] and
band from the strongly adsorbed NH3 species. These results reveal
the asymmetric stretching frequency of gaseous NO2 , respectively
that the gaseous NO2 can react with adsorbed NH3 species, but it
[49,54,55]. The intensities of these bands increased gradually with
was uncertain whether nitrate species adsorbed on the surface of
increasing time, and the relative intensity of the band at 1574 cm−1
 S. Lai et al. / Journal of Molecular Catalysis A: Chemical 424 (2016) 232–240
Fe-ZSM-5 catalysts were active in the SCR reaction. However, the 21333003), Science and Technology Commission of Shanghai
intensities of the bands at 1169, 1268, 1516, 1593 and 1947 cm−1 Municipality (16ZR1407900) and Fundamental Research Funds for
increased markedly due to the adsorption of NH3 on the catalyst the Central Universities (WJ1514020).
surface. Further, the intensities of these bands for the Fe-Z(N2 -36)
catalyst were stronger than those for Fe-Z(Air-2) catalyst, coincid-
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[17]
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[19]
In summary, the atmosphere during ion exchange and calcina- [20]
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of the Fe species in Fe-ZSM-5 catalysts. An air atmosphere can [21]
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[24]
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[38]
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[45]
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