Documente Academic
Documente Profesional
Documente Cultură
a r t i c l e
i n f o
Article history:
Received 20 March 2015
Received in revised form 26 August 2016
Accepted 27 August 2016
Available online 28 August 2016
Keywords:
Fe-ZSM-5
Selective catalytic reduction
Nitrogen oxide
Preparation of catalyst
Atmosphere effect
a b s t r a c t
Fe-ZSM-5 catalysts for selective catalytic reduction (SCR) of NOx with ammonia were prepared by ion
exchange under different atmospheres and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature-programmed desorption of NH3 and NO (NH3 -TPD and NO-TPD),
Ultravioletvisible (UVvis) spectroscopy and in situ diffuse reectance Fourier transform infrared spectroscopy (DRIFT). The results show that the atmosphere during ion exchange and calcination signicantly
affects the cation exchange capacity and the nature of the Fe species in Fe-ZSM-5 catalysts. An air atmosphere was conducive to improving the ability of ZSM-5 zeolites for Fe ionic exchange. However, isolated
Fe3+ sites were dominant in Fe-ZSM-5 catalyst (Fe-Z(N2 )) prepared under a N2 atmosphere, and small
oligomeric Fex Oy clusters and Fex Oy nano-particles were markedly increased in Fe-ZSM-5 catalyst prepared in air, resulting in the higher SCR activity and wide temperature window of Fe-Z(N2 ). Moreover,
Fe-Z(N2 ) catalyst possessed more Brnsted acid sites and could adsorb more NH3 species, promoting its
SCR activity. In situ DRIFT studies showed that NH3 can be adsorbed on both Brnsted 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 conrmed 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
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 oxygenrich 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 catalysts [79]. Among them, V2 O5 /TiO2 catalysts possess excellent
H2 O/SO2 durability and are the most widely used in industry. However, 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 harmful 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).
http://dx.doi.org/10.1016/j.molcata.2016.08.026
1381-1169/ 2016 Elsevier B.V. All rights reserved.
of novel, highly efcient, stable and environmentally friendly NH3 SCR catalysts has attracted extensive attention.
Among different NH3 -SCR catalysts, zeolite-based catalysts
generally have high activity and selectivity over a wider temperature 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 [1618] are mainly used as matrices for NH3 -SCR catalysts. 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-modied ZSM-5 are the most widely studied among zeolitebased SCR catalysts. In general, Cu-modied ZSM-5 exhibits high
SCR activity, particularly at low reaction temperatures, while Femodied ZSM-5 exhibits high SCR activity at high temperatures
with a wide temperature window.
Several studies have focused on the effect of different preparation methods, such as chemical vapour deposition [23], hydrothermal synthesis [24], impregnation [25,26] and liquid/solid-state ion
exchange [3,10,27], on the SCR activity of Fe-modied ZSM-5 catalysts. It was proposed that preparation methods have a marked
effect on the location of Fe in the ZSM-5 matrix, leading to different 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 signicant
inuence on the structure, physico-chemical properties and reactive activity of Fe-modied ZSM-5 catalysts. For example, thermal
treatment signicantly affected the catalytic activity of Fe-ZSM-5
catalysts prepared by chemical vapour deposition [3133]. Fe-ZSM5 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 atmosphere 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 synthesized 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 Brnsted 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-modied ZSM-5 catalysts, it is very necessary to thoroughly 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 atmospheres 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.
233
2. Experimental
2.1. Preparation of catalysts
Fe-ZSM-5 samples were prepared by ion exchange method. Typically, 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 aqueous 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 ow of N2 at 80 C for a certain time.
Then, the solid was ltered and washed with deionized water, dried
overnight at 120 C and nally 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). Additionally, if NH4 -ZSM-5 was calcined at 600 C for 5 h in air, the
obtained sample was labelled as H-ZSM-5.
234
Fe-Z(N2-60)
80
60
ZSM-5
Fe-Z(N2-12)
Fe-Z(N2-24)
Fe-Z(N2-36)
Fe-Z(N2-60)
Fe-Z(air-2)
Fe-Z(air-6)
40
20
Fe-Z(N2-36)
Intensity (a.u.)
100
Fe-Z(Air-6)
Fe-Z(Air-2)
ZSM-5
0
100
200
300
400
500
600
700
10
20
30
Temperature ( C)
40
50
60
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.
724.3
710.6
718.6
Fe-Z(N2-36)
Intensity (a.u.)
lysts. The NOx conversion over the H-ZSM-5 catalyst was very low
(no more than 50%) at <300 C. Only when the reaction temperature was raised >525 C did the NOx conversion over the H-ZSM-5
catalyst increase to 95%. Compared with the H-ZSM-5 catalyst, the
SCR activity was markedly improved after introducing Fe into the
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 window (320575 C). Furthermore, the SCR activities of the Fe-Z(N2 -x)
catalysts at low temperature increased with the increase in Fe content, 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 temperature 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
4.4 107 , 3.6 107 , 1.5 107 and 1.8 107 mol h1 m2 g1 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 performance 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 FeZ(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 further detail below.
Fe-Z(Air-2)
735
730
725
720
715
710
705
700
235
Table 1
Percentage of the area of the sub-bands and wt% Fe of the corresponding species by numerical analysis of UVvis spectra (Fig. 4) for Fe-ZSM-5 catalysts.
Catalyst
Fe-Z(N2 -12)
Fe-Z(N2 -24)
Fe-Z(N2 -36)
Fe-Z(N2 -60)
Fe-Z(Air-2)
Fe-Z(Air-6)
0.9
1.1
1.3
1.9
1.4
1.8
a
b
c
d
Fe1 a
Fe2 b
Fe3 c
I1 (%)
(wt%)
I2 (%)
(wt%)
I3 (%)
(wt%)
78.2
58.8
57.4
35.8
1.02
1.12
0.80
0.65
17.8
25.9
24.1
28.0
0.23
0.49
0.34
0.50
4.0
15.3
18.5
36.2
0.05
0.29
0.26
0.65
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.
SBET (m2 /g)
Area
Area/SBET
ZSM-5
Fe Z(N2 -60)
Fe-Z(N2 -36)
Fe-Z(Air-6)
Fe-Z(Air-2)
334
276
275
265
272
/
2834
2664
2261
1731
/
10.3
9.7
8.5
6.4
Fe-Z(Air-6)
Fe-Z(N2-60)
F(R)
Sample
Fe-Z(Air-2)
Fe-Z(N2-36)
200
300
400
500
600
700
Wavelength (nm)
Fig. 4. UVvis spectra of Fe-Z(N2 -60), Fe-Z(N2 -36), Fe-Z(Air-6) and Fe-Z(Air-2) catalysts.
gest that the atmosphere during the preparation process has a great
inuence 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 catalyse the SCR reaction. Furthermore, surface iron particles not only
contributed to the SCR reaction but also caused nonselective oxidation 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) catalyst, 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 temperature (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) catalyst. 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 FeZ(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
A
Fe-Z(Air-6)
Fe-Z(N2-36)
0.01
Fe-Z(Air-2)
Aborbance
Intensity (a.u.)
Fe-Z(N2-60)
Fe-Z(N2-36)
3660
Fe-Z(Air-2)
3610
100
200
300
400
500
600
700
3800
3750
3700
Temperature ( C)
o
3650
3600
3550
3500
-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.
800
NOx Concentration (ppm)
the amount of isolated Fe3+ sites sharply decreased from 0.80 wt%
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 activity for Fe-Z(Air-2) and Fe-Z(Air-6) catalysts at low temperatures.
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
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.
600
400
Fe-Z(N2-60)
200
Fe-Z(N2-36)
Fe-Z(Air-6)
Fe-Z(Air-2)
0
0
100
200
300
400
500
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 cm1 for the Fe-Z(N2 -36) catalyst showed a
much higher intensity, and the peak at 3660 cm1 showed similar
intensities for the two catalysts. Since the relative concentration of
Brnsted acidic sites can be determined using the intensities of the
peaks at 3610 cm1 [48], it was clear that the Fe-Z(N2 -36) catalysts
possessed more Brnsted acid sites than the Fe-Z(Air-2) catalyst.
The NO-TPD proles 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 capacity for NO adsorption. In other words, more nitrate species could
be adsorbed over the surface of the Fe-Z(N2 -x) catalysts, which was
benecial 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) catalyst, which promoted the SCR activity of the Fe-Z(N2 -60) catalyst
at low temperatures, compared with the Fe-Z(N2 -36) catalyst.
237
Fe-Z(N2-36)
Fe-Z(Air-2)
1165
1165
0.02
Absorbance
0.01
1592
1740
1947
1268
1463
70 min
Absorbance
1517
1947
1740
1592 1517
1463
1268
70 min
60
60
40
40
20
20
10
10
2000
1800
1600
1400
-1
1200
1000
2000
1800
1600
1400
-1
1200
1000
Wavenumber (cm )
Wavenumber (cm )
Fig. 7. In situ DRIFT spectra of Fe-Z(Air-2) and Fe-Z(N2 -36) catalysts exposed in a ow 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
1668 15621517
1463
Absorbance
Absorbance
1592
0.02
1268
30 min
10
30 min
1668 1562
1517
1268
1592
1463
10
5
NH3
2000
NH3
1800
1600
1400
-1
1200
1000
Wavenumber (cm )
2000
1800
1600
1400
-1
1200
1000
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.
on the Fe-Z(Air-2) and Fe-Z(N2 -36) catalysts were identical. However, the intensities of the corresponding bands for the Fe-Z(N2 -36)
catalyst were stronger than those for the Fe-Z(Air-2) catalyst, indicating 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 cm1 rst decreased and
then became stable, indicating that some of the NH4 + species on
Brnsted acid sites and coordinated NH3 bound to Lewis acid sites
participated in the SCR process. The band assigned to amide (-NH2 )
species at 1517 cm1 was unchanged after 30 min, while many new
bands were detected at 1668 and 1562 cm1 , which were attributed
to NOx species. It is noticeable from Fig. 8 that the intensities of the
238
Fe-Z(Air-2)
Fe-Z(N2-36)
1630
0.005
1688
Absorbance
60 min
50
40
50
40
30
30
20
20
10
10
2000
1800
1630
1570
0.005
1688
60 min
Absorbance
1574
1600
1400
1200
-1
2000
1800
1600
1400
1200
Wavenumber (cm-1)
Wavenumber (cm )
Fig. 9. In situ DRIFT spectra of Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts in a ow of 500 ppm NO + 5% O2 /Ar (50 mL/min) at 150 C for different times.
Fe-Z(N2-36)
0.02
1574
Fe-Z(Air-2)
1169
1268
1630
1630
1947
50
1570
1268
60min
1947
Absorbance
60min
Absorbance
1169
0.01
50
30
30
20
20
4
NO+O2
NO+O2
2000
1800
1600
1400
-1
1200
1000
Wavenumber (cm )
2000
1800
1600
1400
1200
1000
-1
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.
for the Fe-Z(N2 -36) catalyst was remarkably stronger than that for
the Fe-Z(Air-2) catalyst. It was reported that the amount of bidentate nitrate on the catalyst can affect its activity in the SCR reaction
[56]. Therefore, the higher amount of bidentate nitrate on the surface of the Fe-Z(N2 -36) catalyst may possibly be responsible for its
higher SCR activity, compared with the Fe-Z(Air-2) catalyst.
At the end of the experiment corresponding to Fig. 9, the IR cell
was purged with Ar for 30 min at 150 C. After this, the mixed gas
of 500 ppm NH3 /Ar was introduced into the IR cell at 150 C, and
in situ DRIFT spectra were recorded at different times. As shown
in Fig. 10, after NH3 was introduced into the system, the intensity of the band at 1630 cm1 (assigned to gaseous NO2 ) decreased
quickly, but the change in the band at 1574 cm1 (corresponding to bidentate nitrate) was unclear because of overlap with the
band from the strongly adsorbed NH3 species. These results reveal
that the gaseous NO2 can react with adsorbed NH3 species, but it
was uncertain whether nitrate species adsorbed on the surface of
4. Conclusions
In summary, the atmosphere during ion exchange and calcination remarkably affects the cation exchange capacity and the nature
of the Fe species in Fe-ZSM-5 catalysts. An air atmosphere can
improve the ability of ZSM-5 zeolites for Fe ionic exchange. There
are three types of Fe species in Fe-ZSM-5 catalysts, i.e., isolated Fe3+
sites, small oligomeric Fex Oy clusters and Fex Oy nano-particles, and
their distribution depends on the atmosphere during the preparation process. Isolated Fe3+ sites and oligomeric Fex Oy are dominant
in the Fe-Z(N2 -x) catalysts, whereas the amount of Fex Oy nanoparticles is markedly increased in the Fe-Z(Air-x) catalysts.
Since the isolated Fe3+ sites possess high SCR activity at low temperatures and Fex Oy particles show high activity for non-selective
oxidation of NH3 , Fe-Z(N2 -x) catalysts exhibit a higher SCR activity
at low temperatures and a wide temperature window. Additionally, Fe-Z(N2 -x) catalysts possess more Brnsted acid sites than
Fe-Z(Air-x) catalysts. These can adsorb more NH3 species on the
catalyst surface, thus promoting its SCR activity. Similarly, the FeZ(N2 -x) catalyst has a higher adsorption capacity for nitrate species,
which is also benecial to its SCR activity.
In situ DRIFTS was applied to investigate NH3 /NOx adsorption
and the surface reaction of NH3 with NOx . The results show that
NH3 can be adsorbed on both Brnsted acid sites and Lewis acid
sites on the Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts and participates
in the SCR process. Additionally, NOx can be adsorbed on Fe-ZSM5 catalyst mainly as a bidentate nitrate, but these nitrate species
cannot be conrmed to react with gaseous NH3 . Based on the weak
adsorption of NOx over the Fe-Z(N2 -36) and Fe-Z(Air-2) catalysts, it
was proposed that NH3 -SCR over the prepared Fe-ZSM-5 catalysts
mainly follows the Eley-Rideal reaction mechanism.
Acknowledgements
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
239
[45]
[46]
[47]
M.D. Amiridis, R.V. Duevel, I.E. Wachs, Appl. Catal. B 20 (1999) 111122.
S.L. Zhang, Q. Zhong, J. Mol. Catal. A 373 (2013) 108113.
R.Q. Long, R.T. Yang, J. Catal. 188 (1999) 332339.
Y. Cao, S. Zou, L. Lan, Z.Z. Yang, H.D. Xu, T. Lin, M.C. Gong, Y.Q. Chen, J. Mol.
Catal. A 398 (2015) 304311.
H.L. Zhang, C.J. Tang, C.Z. Sun, L. Qi, F. Gao, L. Dong, Y. Chen, Micropor.
Mesopor. Mater. 151 (2012) 4455.
R. Zukerman, L. Vradman, L. Titelman, C. Weidenthaler, M.V. Landau, M.
Herskowitz, Micropor. Mesopor. Mater. 116 (2008) 237245.
L. Xu, X.S. Li, M. Crocker, Z.S. Zhang, A.M. Zhu, C. Shi, J. Mol. Catal. A 378 (2013)
8290.
W.P. Shan, F.D. Liu, H. He, X.Y. Shi, C.B. Zhang, Chem. Commun. 47 (2011)
80468048.
D.M. Meng, W.C. Zhan, Y. Guo, Y.L. Guo, L. Wang, G.Z. Lu, ACS Catal. 5 (2015)
59735983.
R.Q. Long, R.T. Yang, J. Am. Chem. Soc. 121 (1999) 55955596.
L. Olsson, H. Sjvall, R.J. Blint, Appl. Catal. B 81 (2008) 203217.
N. Wilken, K. Kamasamudram, N.W. Currier, J. Li, A. Yezerets, L. Olsson, Catal.
Today 151 (2010) 237243.
A.V. Kucherov, D.E. Doronkin, A.Y. Stakheev, A.L. Kustov, M. Grill, J. Mol. Catal.
A 325 (2010) 7378.
G. Qi, R.T. Yang, R. Chang, Catal. Lett. 87 (2003) 6771.
J. Prez-Ramrez, J.M. Garca-Corts, F. Kapteijn, G. Mul, J.A. Moulijn, C.
Salinas-Martnez de Lecea, Appl. Catal. B 29 (2001) 285298.
J.H. Kwak, D. Tran, J. Szanyi, C.H.F. Peden, J.H. Lee, Catal. lett. 142 (2012)
295301.
L. Ren, L. Zhu, C. Yang, Y. Chen, Q. Sun, H. Zhang, C. Li, F. Nawaz, X. Meng, F.
Xiao, Chem. Commun. 47 (2011) 97899791.
U. Deka, A. Juhin, E.A. Eilertsen, H. Emerich, M.A. Green, S.T. Korhonen, B.M.
Weckhuysen, A.M. Beale, J. Phys. Chem. C 116 (2012) 48094818.
I.M. Saaid, A.R. Mohamed, S. Bhatia, J. Mol. Catal. A 189 (2002) 241250.
P. Boron, L. Chmielarz, J. Gurgul, K. Latka, B. Gil, B. Marszalek, S. Dzwigaj,
Micropor. Mesopor. Mater. 203 (2015) 7385.
M. Richter, A. Trunschke, U. Bentrup, K.W. Brzezinka, E. Schreier, M.
Schneider, M.M. Pohl, R. Fricke, J. Catal. 206 (2002) 98113.
K. Krishna, G.B.F. Seijger, C.M. van den Bleek, M. Makkee, H.P.A. Calis, Top.
Catal. 30 (2004) 115121.
S. Brandenberger, O. Krcher, A. Tissler, R. Althoff, Ind. Eng. Chem. Res. 50
(2011) 43084319.
J. Prez-Ramrez, G. Mul, F. Kapteijn, J.A. Moulijn, A.R. Overweg, A. Domnech,
A. Ribera, I.W.C.E. Arends, J. Catal. 207 (2002) 113126.
L. Zhu, L. Zhang, H.X. Qu, Q. Zhong, J. Mol. Catal. A 409 (2015) 207215.
A. Shishkin, P.A. Carlsson, H. Harelind, M. Skoglundh, Topic in Catal. 56 (2013)
567575.
R.Q. Long, R.T. Yang, Catal. Lett. 74 (2001) 201205.
S. Brandenberger, O. Krocher, A. Tissler, R. Althoff, Catal. Rev. Sci. Eng. 50
(2008) 492531.
J.A.Z. Pieterse, S. Booneveld, R.W. van den Brink, Appl. Catal. B 51 (2004)
215228.
L. Ma, J.H. Li, Y.S. Cheng, C.K. Lambert, L.X. Fu, Environ. Sci. Technol. 46 (2012)
17471754.
M.S. Kumar, M. Schwidder, W. Grnert, A. Brckner, J. Catal. 227 (2004)
384397.
P. Marturano, L. Drozdova, G.D. Pirngruber, A. Kogelbauer, R. Prins, Phys.
Chem. Chem. Phys. 3 (2001) 55855595.
A.A. Battiston, J.H. Bitter, D.C. Koningsberger, Catal. Lett. 66 (2000) 7579.
S. Brandenberger, O. Krcher, A. Tissler, R. Althoff, Ind. Eng. Chem. Res. 50
(2011) 43084319.
M. Rivallan, G. Berlier, G. Ricchiardi, A. Zecchina, M.T. Nechita, U. Olsbye, Appl.
Catal. B 84 (2008) 204213.
S. Brandenberger, O. Krchera, A. Wokaun, A. Tissler, R. Althoff, J. Catal. 268
(2009) 297306.
Handbook of X-Ray Photoelectron Spectroscopy, in: W.M. Wagner, L.E. Riggs,
J.F. Davis, G.E. Moulder (Eds.), Perkin-Elmer Corp., Eden Prairie, 1979.
H. Den Daas, M. Passacantando, L. Lozzi, S. Santucci, P. Picozzi, Surf. Sci. 317
(1994) 295302.
N.S. McIntyre, D.G. Zetaruk, Anal. Chem. 49 (1977) 15211529.
H. Seyama, M. Soma, J. Electron Spectrosc. Relat. Phenom. 42 (1987) 97101.
C.L. Corkhill, D.J. Vaughan, Appl. Geochem. 24 (2009) 23422361.
P. Mills, J.L. Sullivan, J. Phys. D: Appl. Phys. 16 (1983) 723.
S. Brandenberger, O. Krcher, A. Tissler, R. Althoff, Appl. Catal. A 373 (2010)
168175.
S. Brandenberger, O. Krcher, A. Tissler, R. Althoff, Appl. Catal. B 95 (2010)
348357.
L.J. Lobree, I.C. Hwang, J.A. Reimer, J. Catal. 186 (1999) 242253.
K. Krishna, M. Makkee, Catal. Today 114 (2006) 2330.
M.S. Kumar, M. Schwidder, W. Grnert, U. Bentrup, A. Brckner, J. Catal. 239
(2006) 173186.
240
[52] W.S. Kijlstra, D.S. Brands, H.I. Smit, E.K. Poels, A. Bliek, J. Catal. 171 (1997)
219230.
[53] A. Boix, R. Mariscal, J.L.G. Fierro, Catal. Lett. 68 (2000) 169174.
[54] H.Y. Chen, T. Voskoboinikov, W.M.H. Sachtler, J. Catal. 180 (1998) 171183.
[55] R.Q. Long, R.T. Yang, J. Catal. 190 (2000) 2231.
[56] Z.C. Si, D. Weng, X.D. Wu, J. Li, G. Li, J. Catal. 271 (2010) 4351.