Applied Catalysis B: Environmental 62 (2006) 104–114

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Selective catalytic reduction of nitrogen oxides by

ammonia on iron oxide catalysts
N. Apostolescu a, B. Geiger a, K. Hizbullah b, M.T. Jan c, S. Kureti a,*,
D. Reichert a, F. Schott a, W. Weisweiler a
a
Institut für Technische Chemie und Polymerchemie, Universität Karlsruhe, Kaiserstr. 12, 76128 Karlsruhe, Germany
b
Department of Environmental Sciences, University of Peshawar, 25120 Peshawar, Pakistan
c
Department of Chemistry, Islamia College, University of Peshawar, 25120 Peshawar, Pakistan
Received 11 April 2005; received in revised form 17 June 2005; accepted 4 July 2005
Available online 26 August 2005

Abstract

In this study, new Fe2O3 based materials are developed for the selective catalytic reduction (SCR) of NOx by NH3 in diesel exhaust. As a
result of the catalyst screening, performed in a synthetic model exhaust, ZrO2 is considered to be the most effective carrier for Fe2O3. The
modification of the Fe2O3/ZrO2 system with tungsten leads to drastic increase of SCR performance as well as pronounced thermal stability.
These results show that tungsten acts as bifunctional component. The highest catalytic activity is observed for ZrO2 that is coated with
1.4 mol% Fe2O3 and 7.0 mol% WO3 (1.4Fe/7.0W/Zr). By the use of this catalyst quantitative conversion of NOx is obtained between 285 and
430 8C with selective formation of N2. Here, the turnover frequency of NOx per Fe atom is found to be 35
105 s1 that indicates a high
catalytic performance. The SCR activity of the 1.4Fe/7.0W/Zr material is decreased in the presence of H2O and CO2, whereas it is increased
by NO2.
Temperature programmed reduction by H2 (HTPR) analyses show that the Fe sites of the 1.4Fe/7.0W/Zr catalyst are mainly in the form of
crystalline Fe2O3, whereby relatively small oxide entities are also present. The strongly aggregated Fe2O3 species are associated with the
presence of the promoter tungsten. Based upon stationary catalytic examinations as well as diffuse reflectance infrared fourier transform
spectroscopy (DRIFTS) studies we postulate an Eley Rideal type mechanism for SCR on 1.4Fe/7.0W/Zr catalyst. The mechanistic model
includes a redox cycle of the active Fe sites. As first reaction step, we assume dissociative adsorption of NH3 that leads to partial reduction of
the iron as well as to production of very reactive amide surface species. These amide intermediates are supposed to react with gaseous NO to
form N2 and H2O. In the final step, the reduced Fe sites be regenerated by oxidation with O2. As a side reaction of SCR, imide species,
originated from decomposition of amide, are oxidized by NO2 or O2 into NO.
# 2005 Elsevier B.V. All rights reserved.

Keywords: SCR; Diesel exhaust; NOx; NH3; Fe2O3; ZrO2; WO3; Reaction mechanism

1. Introduction basic adsorbents, for instance Al2O3 and Ba(OH)2/BaCO3.

Selective catalytic reduction (SCR) and NOx storage
reduction catalyst (NSR) are the most favoured catalytic
procedures to reduce the emission of nitrogen oxides
exhausted from diesel engines. The NSR technology is
based upon periodic adsorption and reduction of NOx [1].
The storage reduction catalysts consist of platinum as well as
* Corresponding author. Tel.: +49 721 608 8090; fax: +49 721 608 2816.
E-mail address: kureti@ict.uni-karlsruhe.de (S. Kureti).
The platinum component supports the oxidation of NO into
NO2 that is subsequently stored by the adsorbents. When the
storage capacity is reached, rich exhaust conditions are
established momentarily by engine management systems.
Hereby, NOx desorbs from the substrate and is reduced by
H2, CO and hydrocarbons on the precious metal. However, a
serious constraint of NSR is the susceptibility of the basic
adsorbents to sulfur poisoning.
In SCR technique, NOx is continuously reduced by
ammonia over TiO2 supported V2O5/WO3 catalysts resulting

0926-3373/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2005.07.004
 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114
c(i)in, c(i)out inlet or outlet concentration of
component i
c(j) concentration of component j formed
in SCR
X(i) conversion of component i
S(j) selectivity of component j formed in SCR
r(NOx) rate of NOx reduction
F volume flow rate at standard conditions
Tr, Ts reaction or standard temperature
nFe2 O3 molar amount of Fe2O3 used in the
measurement
in selective formation of nitrogen [2]. The ammonia required
can be produced ‘‘on board’’ by decomposition of urea.
Nevertheless, a disadvantage of SCR is the toxicological
concern of V2O5 and its rather low melting point (ca.
650 8C) that could lead to discharge of catalyst mass. Hence,
the target of the present work has been to develop a non-
hazardous SCR catalyst that shows high performance as well
as physical stability even at elevated temperature. It has been
reported that Fe2O3 [3–9], Fe containing mixed oxides
[10–13] and Fe-exchanged materials [14–18], especially
Fe-ZSM5 zeolite [19–33], exhibit remarkable SCR activity.
Additionally, as Fe2O3 reveals high thermal stability [34,35],
iron oxide has been used as catalytic component in this
study. Furthermore, we have aimed to examine the technical
potential as well as the active sites of the best catalyst.
Moreover, mechanistic investigations have been carried out
to provide a better understanding of the surface reactions
occurring in SCR.
2. Synthesis
In this work several carrier oxides, i.e. MgAl2O4, SiO2,
TiO2 and ZrO2, were used to evaluate the most effective
support for Fe2O3 in SCR. TiO2 (<325 mesh, Sigma–Aldrich)
was commercially available, whereas MgAl2O4 was synthe-
sized by polyvinyl alcohol (PVA) technique as we have
published recently [36]. In this synthesis, an aqueous PVA
solution (9 wt.% PVA) was mixed with the appropriate
amount of metal nitrate, whereby the molar ratio of metal
cation/VA monomer was 2. The solution was evaporated,
dried at 250 8C and subsequently ground to powder;
calcination was carried out at 750 8C for 5 h. The preparation
of ZrO2 was performed based upon the literature using
hydrazine as pH stabilizer [37]. ZrO(NO3)2 (Fluka) was added
to an aqueous solution of hydrazine (Fluka), whereby the pH
was kept higher than 9. The mixture was digested for 72 h at
100 8C. Finally, the precursor was annealed for 6 h at 750 8C
in air. SiO2 was synthesized by sol–gel method (40 8C) using a
mixture of 14 cm3 TEOS (Fluka), 8 cm3 ethylene glycol
(Fluka) and 25 cm3 water. The coagulated gel was heated at
600 8C for 2 h in air.
105
All the supports were impregnated at room temperature
by a solution of Fe(NO3)3 (Merck) with known concentra-
tion. For impregnation incipient wetness method was used,
i.e. a defined volume of the solution was taken such that it
was completely absorbed. With this technique the load of
iron oxide can be calculated in a simple way. The content of
Fe2O3 was established to be 2.6 mol% for all the catalysts to
employ the same molar amounts in the catalytic studies.
For ZrO2 based system a Fe2O3 loading of 1.4 mol% as
well as different tungsten contents (0.78–10 mol%) were
also taken. Tungsten oxide was used to examine its effect on
catalytic activity and aging susceptibility. For preparation
(NH4)6H2W12O41 (Fluka) was added to the Fe(NO3)3
solution and then impregnation was performed as described
above. The different loads of Fe and W were established by
varying the corresponding concentration of Fe(NO3)3 and
(NH4)6H2W12O41.
For comparison pure a-Fe2O3 was also employed. This
sample was prepared by PVA technique in the same way
mentioned above. Moreover, the a-Fe2O3 was doped with
2 wt.% phosphate and sulfate, respectively, to increase its
catalytic activity [38,39]. Doping was conducted by using a
solution of (NH4)3PO4 or (NH4)2SO4 (Fluka).
After drying at 100 8C, all the impregnated samples
were finally calcined in air at 500 8C for 2 h. Furthermore,
selected systems were also annealed in air for 72 h at 600 8C
to investigate the effect of thermal aging on SCR activity.
For simplicity the prepared catalysts are denoted as follows:
2.6Fe/MgAl (2.6 mol% Fe2O3 on MgAl2O4), 2.6Fe/Si
(2.6 mol% Fe2O3 on SiO2), 2.6Fe/Ti (2.6 mol% Fe2O3 on
TiO2) 2.6Fe/Zr (2.6 mol% Fe2O3 on ZrO2), Fe (pure
a-Fe2O3), P/Fe (a-Fe2O3 doped by 2 wt.% phosphate), S/
Fe (a-Fe2O3 doped by 2 wt.% sulfate), 1.4Fe/Zr (1.4 mol%
Fe2O3 on ZrO2), 1.4Fe/0.78W/Zr (1.4 mol% Fe2O3 and
0.78 mol% WO3 on ZrO2) and 1.4Fe/7.0W/Zr (1.4 mol%
Fe2O3 and 7.0 mol% WO3 on ZrO2).
3. Characterization
Crystalline phase of the pure and coated supports were
investigated by powder X-ray diffraction (PXRD). PXRD
patterns were recorded at room temperature on a Siemens D
501 employing Ni filtered Cu Ka radiation. A 2u step-size of
0.028 was used with an integration time of 1 s. The samples
were measured with a rotation velocity of 120 rpm. BET
surface area was examined by single-point Areameter II
Table 1
Crystalline phase and BET surface area of pure supports and Fe2O3
Support Phase BET (m2 g1)
MgAl2O4 Spinel 70
SiO2 Amorphous 950
TiO2 Anatase 14
ZrO2 Tetragonal 70
Fe2O3 Hematite 4
106 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114
from Ströhlein Instruments employing N2 as adsorbate. The
crystalline phase and BET surface area of the carriers as well
as pure Fe2O3 are summarized in Table 1. After modification
of these materials with dopants, i.e. Fe2O3, WO3, phosphate
or sulfate, both PXRD and BET give the same results as that
demonstrated in Table 1.
4. Catalytic studies
Catalytic examinations are performed on a laboratory
bench with the use of temperature programmed reaction
(TPR). Before the measurement the sample is pressed to
pellet with a pressure of 40 MPa, granulated and sieved in a
mesh size of 250–500 mm. The catalyst, i.e. 40 mmol
support impregnated by iron oxide and tungsten oxide,
respectively, is then charged into a quartz glass tube (i.d.
22 mm). For the materials that are coated with 2.6 mol%
iron oxide the mass of Fe2O3 is 0.166 g, while for the
systems with 1.4 mol% Fe2O3 it is 0.089 g. The catalyst is
fixed with quartz wool and pretreated in nitrogen flow at
500 8C for 15 min to remove possible impurities. After
cooling down to 150 8C, the model exhaust is passed over
the sample with a total flow of 2000 scm3 min1. Since the
supports show different molar weights, the reaction
conditions result in specific weight/flow ratios (W/F) that
are demonstrated in Table 2. The standard feed gas consists
of 500 ppm NO, 500 ppm NH3, 5 vol.% O2 and N2 as
balance. To evaluate the best catalyst, further components of
real exhaust, i.e. H2O (5 and 10 vol.%) and CO2 (5 and
10 vol.%), are dosed to the exhaust gas. Furthermore, the
molar ratio of NO/NO2 and NOx/NH3 as well as the
concentration of O2 is varied. The model exhaust is a blend
of synthetic air and pure gases (Messer Griesheim) that are
fed from independent flow controllers (MKS Instruments).
Water is added to the gas stream with a liquid flow controller
(Bronkhorst). NO2 is optionally dosed by the use of a pre-
reactor that contains a Pt catalyst. NO and synthetic air
(460 scm3 min1) pass the Pt catalyst heated to 200 8C and
are then mixed with the other components of the feed. By
this method a NO/NO2 ratio of 1 is obtained (referred to SCR
reactor temperature of 150 8C). Temperature of the reactor
as well as pre-reactor is monitored by a K type thermocouple
directly placed in front of the catalyst bed. In TPR, the
catalyst is treated with the feed for 30 min and then
temperature is linearly increased from 150 to 500 8C at the
rate of 1.7 K min1. Furthermore, for the best catalytic
material stationary measurements at selected temperatures
are also performed to balance the mass of nitrogen and to
determine the selectivity of N2. Here, the reactor effluents
are recorded after they reach steady state.
The analysis of NH3, CO and CO2 is conducted by means
of hot measuring non-dispersive infrared spectroscopy
(NDIR, Binos 5, Fisher-Rosemount). NOx is monitored
by chemilumiscence technique (El-ht, Eco Physics), while
N2O is detected with the use of NDIR (Ultramat 5E,
Siemens). After passing the Binos 5 analyser H2O and NH3
are removed from the gas stream by a condenser unit (3 8C)
and liquid H3PO4, respectively, to avoid cross sensitivity in
the NOx and N2O analysis.
The performance of the catalysts is in terms of percentual
conversion of NOx (X(NOx)), Eq. (1); for the most active
material the percentual conversion of NH3 (X(NH3)), Eq. (1)
and the percentual selectivity of N2O (S(N2O)), Eq. (2) are
also shown.
cðiÞin  cðiÞout
XðiÞ ¼
100; i ¼ NOx or NH3 (1)
cðiÞin
2cðN2 OÞout
SðN2 OÞ ¼
100 (2)
cðNOx Þin  cðNOx Þout
5. TPD studies
Temperature programmed desorption (TPD) of ammonia
is carried out for the most effective catalyst to determine the
uptake of NH3. For TPD the same laboratory bench is used
as for catalytic investigations. The solid (40 mmol support
with additional dopant) is pre-treated in nitrogen flow at
600 8C for 15 min, cooled down to room temperature and
treated with a gas mixture of 1000 ppm NH3 in N2. After
saturation, the sample is flushed with nitrogen and then TPD
is started, with N2 as carrier gas (2000 scm3 min1). The
material is heated to 600 8C at the rate of 16 K min1,
whereby reactor effluents are continuously monitored.
6. DRIFTS studies
Diffuse reflectance infrared fourier transform spectro-
scopy (DRIFTS) analyses are performed for the best
catalytic system to provide a better understanding of the
surface reactions occurring in SCR. The spectra are recorded
on an ATI Mattson Galaxy 5020 FTIR spectrometer
equipped with a MCT detector and DRIFTS optics from
Graseby Specac. The stainless steel IR cell contains a ZnSe
window and is connected to a gas-handling system. The
spectra are recorded in the range from 500 to 4000 cm1
with an instrument resolution of 4 cm1. Fifteen thousand
scans are accumulated to a spectrum. The temperature is
monitored by a K type thermocouple placed 5 mm under-
neath the sample surface. During the measurements,
spectrometer as well as DRIFTS optics are purged with
nitrogen to avoid diffusion of air into the system.
Before the spectra are collected, the catalyst pellets are
charged in the sample holder of the cell, heated for 60 min at
500 8C in nitrogen (500 scm3 min1) and cooled down to
200 8C in the N2 flow. The catalyst is then exposed to a gas
mixture that consists of 500 ppm NH3 in N2 or 500 ppm NO
in N2 (500 scm3 min1). After 10 min of adsorption the cell
 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114 107

is purged with N2 and the spectra are recorded. Furthermore, Table 2

the sample treated with NH3 is exposed at 200 8C to one of SCR activity data of fresh and aged Fe2O3 catalystsa,b,c
the following mixtures for 5, 10, 15, 20 and 25 min: (a) Catalyst X(NOx)max Tmax TOFd W/F
(%) (8C) (105 s1) (g s scm3)
20 vol.% NO in N2, (b) 20 vol.% O2 in N2, (c) 500 ppm NO2
and 20 vol.% O2 in N2. After respective exposures, the cell is 2.6Fe/Ti 32 305 6.7 0.10
2.6Fe/MgAl 42 285 8.8 0.18
flushed with N2 and the analyses are made. Furthermore, the
Fe 43 255 9.0 0.19
catalyst is also exposed to NH3 at 50 8C with subsequent P/Fe 46 275 9.6 0.20
heating at 200 8C in N2 flow in order to examine the thermal S/Fe 61 300 13 0.20
behaviour of the formed ammonium species. 2.6Fe/Si 74 330 15 0.077
For all the spectra the unreacted sample is used as 2.6Fe/Zr 91 335 19 0.15
1.4Fe/Zr 90 335 32 0.15
reference, whereby the background scans are conducted in
1.4Fe/0.78W/Zr 100 335 35 0.15
N2 (500 scm3 min1) at 50 and 200 8C, respectively. The 2.6Fe/Zr (aged) 64 395 13 0.15
DRIFTS data are only displayed in the spectral region from 1.4Fe/Zr (aged) 65 395 22 0.15
1000 to 1800 cm1 as in this range the most prominent 1.4Fe/0.78W/Zr (aged) 90 420 31 0.15
bands are observed. 1.4Fe/7.0W/Zr (aged) 100 285 35 0.18
a
The sample codes are explained in Section 2.
b
Aging conditions: 72 h at 600 8C in air.
c
Reaction conditions: 40 mmol support coated with 1.4 mol% (0.089 g)
7. HTPR studies Fe2O3, 2.6 mol% Fe2O3 (0.166 g), 2 wt.% phosphate or sulfate; c(NO) =
c(NH3) = 500 ppm, c(O2) = 5 vol.%, N2 balance, F = 2000 scm3 min1, DT/
From the literature it is known that temperature Dt = 1.7 K min1.
d
programmed reduction by H2 (HTPR) is a suitable technique TOF is the number of NOx molecules converted per Fe per second.
to characterize oxide systems [40]. HTPR is performed for
the most prominent catalyst, whereby the same bench is TPR data recorded in absence of a catalyst reveal no
employed as in SCR studies. For the analysis the sample is change in NOx and NH3 concentration. This evidences that
not pressed to pellet because only a relatively low gas flow gas phase reactions play no role under the conditions
(100 scm3 min1) is dosed. The mass of Fe taken in each established in our study.
HTPR run is 10 mg. The powder is pre-treated in nitrogen
flow at 300 8C for 15 min to eliminate adsorbed species, e.g. 8.2. Effect of W on the SCR activity and thermal
H2O. After cooling down to 150 8C, the reaction mixture stability of the 1.4Fe/Zr catalyst
consisting of 5 vol.% H2 and 95 vol.% N2 is added and then
the temperature is linearly increased to 850 8C at the rate of Table 2 displays that a complete conversion of NOx is
20 K min1. The final temperature is hold for 10 min. The obtained over 1.4Fe/Zr modified by 0.78 mol% W. However,
concentration of H2 is continuously measured by TCD the thermal treatment in air for 72 h at 600 8C results in
(Shimadzu). For the specific detection of H2 the water significant decrease of SCR performance of 1.4Fe/Zr as well
formed during HTPR is removed by passing the reactor as 1.4Fe/0.78W/Zr, whereby the W containing system is less
effluents through a cold trap (196 8C). deactivated (Table 2). From these data, we conclude that
tungsten oxide acts as a bifunctional component. On one
hand, it promotes the catalytic activity of Fe2O3, while
8. Results and discussion on the other hand, it reduces the suceptibility of thermal
aging.
8.1. SCR performance of the W free catalysts Fig. 1 shows that the SCR performance as well as thermal
stability of the 1.4Fe/W/Zr system appreciably depends on
In order to compare the performance of all the catalysts the load of tungsten oxide. To discuss the results of TPR the
the maximum NOx conversion (X(NOx)max) as well as the temperature, at which the NOx conversion reaches 90%, is
corresponding temperature (Tmax) and turnover frequency taken. In case of fresh catalysts, the activity follows no clear
(TOF) are used (Table 2). The turnover frequency is defined trend for W contents below 6.2 mol%, whereas at higher
as the number of NOx molecules converted per Fe per second loadings the SCR activity does not change markedly. The
(based on total Fe content). Table 2 demonstrates that among aged catalysts show peak performance at a W content of
the W free materials with 2.6 mol% Fe2O3 the 2.6Fe/Zr 7.0 mol%. If the load of tungsten is smaller than 2.3 mol%
catalyst exhibits the highest SCR activity and therefore ZrO2 the catalyst exhibits strong thermal deactivation, but at
is considered to be the most effective carrier. By employing contents being higher than 6.2 mol% fresh and aged material
the 1.4Fe/Zr catalyst the same activity is obtained as for reveal the same activity. Hence, for the latter W loads the
2.6Fe/Zr. However, from the TOF values we deduce that catalyst is considered to be thermally stable. Furthermore, a
1.4Fe/Zr reveals a significant higher SCR performance. For prolonged heat treatment of the exhausted 1.4Fe/7.0W/Zr
this reason, the 1.4Fe/Zr catalyst is used for the further material for further 24 h at 600 8C does not lead to any
investigations. change in SCR activity any more.
108 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114

Fig. 1. Effect of the W load on the temperature with 90% NOx conversion in
SCR on fresh (*) and aged (&) 1.4Fe/W/Zr catalysts. Reaction conditions:
m(catalyst) = 5.9 g, c(NO) = c(NH3) = 500 ppm, c(O2) = 5 vol.%, N2 bal-
ance, W/F = 0.18 g s scm3 and DT/Dt = 1.7 K min1. Aging conditions:
72 h at 600 8C in air.
Fig. 2. PXRD patterns of the fresh (a) and aged (b) 1.4Fe/7.0W/Zr catalyst.
The reflexes indicated by arrows are referred to WO3, while all the other
peaks are assigned to tetragonal ZrO2. For simplicity the ZrO2 reflexes are
only labelled for pattern (b).

As the 1.4Fe/7.0W/Zr catalyst exhibits the highest SCR
performance among all the materials tested (Table 2) as well
as good thermal stability this sample is employed in the
following examinations. If not mentioned otherwise the
catalyst is thermally pretreated as described above (72 h at
600 8C).
The BET surface area of the 1.4Fe/7.0W/Zr catalyst
(60 m2 g1) is not affected by the thermal treatment.
Furthermore, the PXRD pattern of fresh 1.4Fe/7.0W/Zr
shows the typical reflexes of tetragonal ZrO2, while in the
diffractogram of the aged sample signals of WO3 are also
observed (Fig. 2). These additional reflexes are attributed to
agglomeration of WO3 species that leads to the formation of
crystalline domains.
8.3. Comparison of TPR with stationary data and mass
balance of nitrogen
The TPR data of the 1.4Fe/7.0W/Zr catalyst recorded
under the standard reaction conditions show that the SCR
reaction begins at 150 8C (Fig. 3) and leads to entire
conversion of NOx in the temperature range from 285 to
430 8C. The complete conversion of NOx corresponds to a
TOF value of 35
105 s1 (Table 2). This turnover
frequency indicates that the 1.4Fe/7.0W/Zr sample is very
active in the selective catalytic reduction of NOx. However,
the TOF value is two orders of magnitude smaller than for
Fe-ZSM-5 zeolite [26]. At higher temperature the 1.4Fe/
7.0W/Zr catalyst shows a slight decrease of NOx conversion.
The SCR reaction also results in the formation of N2O as by-
product, whereby the evolution of N2O starts at 250 8C; the
maximum N2O selectivity of 6% is reached at 500 8C. The
SCR data measured under stationary conditions at 200, 250,
350 and 450 8C are listed in Table 3 together with the
corresponding results of TPR. The comparison shows that
the difference of X(NOx) as well as S(N2O) is rather small,
whereas for X(NH3) there is a large distinction between
stationary and dynamic data. This proves that stationary
conditions are not yet attained in TPR. The rather low
conversion of NH3 observed in dynamic measurement is
associated with its thermal desorption from the catalyst.
Contrary, there is no significant release of NH3 from the
reactor and the stainless steel pipes of the bench. This is
proven by NH3 TPD performed in the absence of a catalyst.
The TPD spectrum of the 1.4Fe/7.0W/Zr material shows
NH3 desorption between 85 and 550 8C with two broad
peaks at 155 and 295 8C and a shoulder at about 425 8C (not
depicted). The NH3 uptake of the 1.4Fe/7.0W/Zr catalyst is
108 mmol/gcat. The fresh and aged material as well as the
pure ZrO2 support exhibit the same NH3 TPD profile.
Based upon the stationary data the N2 concentration is
calculated from the balance of nitrogen (Eq. (3)) in order to

Table 3
Comparison of the SCR performance of the aged 1.4Fe/7.0W/Zr catalyst under dynamic (TPR) and stationary conditionsa
T (8C) X(NOx)TPR (%) X(NOx)stat (%) S(N2O)TPR (%) S(N2O)stat (%) X(NH3)TPR (%) X(NH3)stat (%)
200 36 44 0 0 21 43
250 90 96 0 0 74 96
350 100 100 2 0 93 100
450 98 94 5 2 99 97
a
Reaction conditions: m(catalyst) = 5.9 g, c(NO) = c(NH3) = 500 ppm, c(O2) = 5 vol.%, N2 balance, W/F = 0.18 g s scm3, in TPR: DT/Dt = 1.7 K min1.
 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114
Fig. 3. SCR performance of aged 1.4Fe/7.0W/Zr catalyst. Reaction con-
ditions: m(catalyst) = 5.9 g, c(NO) = c(NH3) = 500 ppm, c(O2) = 5 vol.%,
N2 balance, W/F = 0.18 g s scm3 and DT/Dt = 1.7 K min1.
determine the N2 selectivity (Eq. (4)). The result indicates a
selective formation of N2 between 200 and 350 8C. At
450 8C, where N2O forms, the selectivity of N2 is negligibly
reduced to 0.98.
ðcðNOx Þin  cðNOx Þout Þ þ ðcðNH3 Þin
 cðNH3 Þout Þ  2cðN2 OÞ
cðN2 Þ ¼ (3)
2 Zr catalyst
2cðN2 Þ
SðN2 Þ ¼ (4)
cðNOx Þin  cðNOx Þout
Furthermore, the stationary results show a molar NOx:NH3
stoichiometry of 1. In agreement with literature [12] and the
mass balance of nitrogen this ratio is referred to the overall
reaction given in Eq. (5).
4NO þ 4NH3 þ O2 ! 4N2 þ 6H2 O (5)
8.4. Effect of O2 on oxidation of NH3 on the
1.4Fe/7.0W/Zr catalyst
The catalytic oxidation of NH3 by O2 is examined as SCR
can principally be limited by competitive NH3/O2 reaction.
The oxidation of NH3 is carried out in the absence of NOx,
whereby different concentrations of O2, i.e. 5, 10 and
15 vol.%, are used. In these TPR experiments X(NH3) first
shows negative values due to thermal desorption and later on it
starts increasing (Fig. 4). With 5 vol.% oxygen in the feed
NH3 conversion starts increasing at 305 8C, whereby a
conversion of 50% is reached at 370 8C. Complete NH3
oxidation is observed at 450 8C (Fig. 4). As compared to TPR
with 5 vol.% O2 the oxidation of NH3 is accelerated if 10 and
15 vol.% O2 are dosed. However, the measurements, in which
10 and 15 vol.% O2 is added, show very similar results. The
conversion of NH3 increases already at 250 8C and reaches
109
Fig. 4. Effect of O2 on NH3 oxidation performance of aged 1.4Fe/7.0W/Zr
catalyst. Reaction conditions: m(catalyst) = 5.9 g, c(NH3) = 500 ppm,
c(O2) = 5, 10 or 15 vol.%, N2 balance, W/F = 0.18 g s scm3 and DT/
Dt = 1.7 K min1.
50% at about 325 8C. Since the evolution of both NOx and
N2O is not observed, it is very likely that the NH3/O2 reaction
on 1.4Fe/7.0W/Zr results in formation of N2 (Eq. (6)).
4NH3 þ 3O2 ! 2N2 þ 6H2 O (6)
8.5. Effect of O2 on the SCR activity of the 1.4Fe/7.0W/
As ammonia is strongly oxidized by O2 on the 1.4Fe/
7.0W/Zr catalyst (Section 8.4) the effect of oxygen on SCR
activity is examined. For this purpose the concentration of
O2 is varied from 0 to 15 vol.%. Fig. 5 evidences that the
SCR reaction is drastically suppressed at temperatures above
300 8C if the O2 concentration increases to 10 or 15 vol.%.
NH3 is then completely oxidized above 340 8C, while N2O is
only formed in negligible concentrations being smaller than
12 ppm (not depicted). This observation is in good agreement
with the NH3 oxidation data that show an enhanced
conversion of ammonia with increasing concentration of
O2. Hence, we conclude that at elevated temperatures SCR is
restricted by the competitive consumption of ammonia by
catalytic NH3/O2 reaction. However, Fig. 5 also shows that O2
is an essential component for SCR because in the absence of
O2 only a small amount of NOx is converted.
8.6. Effect of CO2, H2O and NO2 on the SCR activity of
the 1.4Fe/7.0W/Zr catalyst
The effect of carbon dioxide is examined by increasing
the concentration to 5 and 10 vol.% in the feed. The TPR
data (not depicted) show that the temperature at which NOx
conversion reaches 90% does not change in comparison
to the measurement performed in the absence of CO2.
However, the temperature region exhibiting complete NOx
110 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114

Fig. 5. Effect of O2 on SCR performance of aged 1.4Fe/7.0W/Zr catalyst. Fig. 6. Effect of H2O on SCR performance of aged 1.4Fe/7.0W/Zr catalyst.
Reaction conditions: m(catalyst) = 5.9 g, c(NO) = c(NH3) = 500 ppm, Reaction conditions: m(catalyst) = 5.9 g, c(NO) = c(NH3) = 500 ppm,
c(O2) = 0, 5, 10 or 15 (—) vol.%, N2 balance, W/F = 0.18 g s scm3 and c(O2) = 5 vol.%, c(H2O) = 5 vol.%, N2 balance, W/F = 0.18 g s scm3
DT/Dt = 1.7 K min1. and DT/Dt = 1.7 K min1.

reduction is diminished. Entire conversion of NOx is only The high selectivity of N2O increasing to 90% is
observed between 285 and 390 8C with 5 vol.% CO2, while attributed to the pre-treatment procedure. In TPR the
in the presence of 10 vol.% it occurs from 285 to 360 8C. catalyst is exposed to the feed gas for 30 min at 150 8C
From these results we deduce that CO2 leads to a slight before the measurement is started. In case of NO2 dosage
diminution of the SCR activity of 1.4Fe/7.0W/Zr catalyst. this treatment obviously leads to the formation of a
A stronger deactivation is observed when water is added substantial amount of NH4NO3. This interpretation is
to the feed (Fig. 6), whereby the same results are obtained supported by stationary SCR data that are recorded without
for 5 and 10 vol.% H2O. In both measurements, NOx corresponding pre-treatment. These results (not illustrated)
conversion of 90% is only attained at 275 8C, while total show a maximum N2O selectivity of 10% only that ranges
removal of NOx occurs between 320 and 365 8C. However, from 220 to 225 8C.
in the presence of H2O nitrous oxide is not formed. The Ammonium nitrate is not formed if the standard TPR
deactivation of the catalyst by CO2 and especially by H2O is conditions are used because no NO2 is dosed here.
very likely associated with the competitive adsorption on the Furthermore, the 1.4Fe/7.0W/Zr catalyst exhibits a rather
active Fe sites of 1.4Fe/7.0W/Zr. low NO oxidation activity as compared to the highly active
In contrast to H2O, the dosage of 250 ppm NO2 (c(NO)in/
c(NO2)in = 1) results in clear increase of catalytic perfor-
mance (Fig. 7) as a strong diminution of nitrogen oxides is
observed in the whole temperature range. After the start of
TPR the conversion of NOx first decreases and then it goes
through a minimum of 42% at 180 8C. A detailed analysis
shows that only the concentration of NO2 increases in this
region, while NO decreases continuously. Complete con-
version of NOx is found at 260 8C, whereas the conversion
restarts decreasing at 350 8C. Furthermore, the TPR data
indicate the formation of nitrous oxide at low temperature
showing peak selectivity at 190 8C.
The maximum of NOx conversion observed at 150 8C is
referred to the reaction of NO2 with NH3 to form NH4NO3. It
is well known in SCR that ammonium nitrate is produced
below 200 8C if a relatively high concentration of NO2 is
present [41]. With rising temperature the thermal decom-
position of NH4NO3 prevails that results in the production of
Fig. 7. Effect of NO2 on SCR performance of aged 1.4Fe/7.0W/Zr catalyst.
N2O and H2O [41]. Hence, the evolution of N2O observed in Reaction conditions: m(catalyst) = 5.9 g, c(NO) = c(NO2) = 250 ppm,
the low temperature region is associated with the thermal c(NH3) = 500 ppm, c(O2) = 5 vol.%, N2 balance, W/F = 0.18 g s scm3
decomposition of the formed ammonium nitrate. and DT/Dt = 1.7 K min1.
 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114
Pt systems [42]. The stationary data show a NO2 yield of 5%
at 150 8C, while the maximum yield amounts to 10%
(340 8C). With 10 and 15 vol.% O2 the peak yield of NO2 is
also found at 340 8C being 15 and 20%, respectively.
8.7. Fe sites of the 1.4Fe/7.0W/Zr catalyst
The nature of the iron sites of the 1.4Fe/7.0W/Zr catalyst
is studied by the use of HTPR. For reference purposes
corresponding examinations are also performed with 7.0W/
Zr, 1.4Fe/Zr and a a-Fe2O3 sample. The a-Fe2O3 pattern is
prepared by PVA technique, whereby the final calcination is
carried out at 600 8C for 5 h; the crystalline phase is
confirmed by PXRD.
The pure iron oxide sample indicates a HTPR pattern
(Fig. 8(a)) that is typical for a-Fe2O3, i.e. a low temperature
(LT) and a high temperature (HT) signal is observed with a
HT/LT peak ratio very close to 8. The total consumption of
H2 that is expressed as molar ratio of H2/Fe amounts to 1.5.
Moreover, the PXRD pattern of the iron oxide removed after
the first HTPR peak shows exclusively reflexes that are
referred to Fe3O4. These results confirm literature data that
prove the reduction of Fe2O3 by H2 to be a two-step
mechanism according to the sequence Fe2O3 ! Fe3O4 ! Fe
[43–46].
The HTPR curve of the 1.4Fe/7.0W/Zr sample reveals a
broad LT peak, that is shifted to higher temperature (540 8C)
as referred to a-Fe2O3, and two overlapped HT signals located
at 730 and 840 8C (Fig. 8(b)). The latter HT feature also
appears in case of 7.0W/Zr (Fig. 8(c)) and is therefore
assigned to the reduction of WO3 species. Furthermore, it is
obvious that the relative intensity of the LT peak is much more
pronounced as compared to a-Fe2O3. To estimate the HT/LT
ratio as well as the H2 consumption of the 1.4Fe/7.0W/Zr
catalyst we subtract the HTPR pattern of 7.0W/Zr from that of
1.4Fe/7.0W/Zr. However, it must be noted here that this
procedure does not imply possible interactions between Fe
Fig. 8. HTPR patterns of: (a) a-Fe2O3 prepared by PVA technique,
(b) 1.4Fe/7.0W/Zr, (c) 7.0W/Zr and (d) 1.4Fe/Zr.
111
and W species and hence a careful conclusion should be
drawn from this simplification. The modified HTPR curve
(not illustrated) shows a H2/Fe ratio of 1.3 that points to the
predominant existence of crystalline Fe2O3; for a-Fe2O3 the
H2/Fe ratio is 1.5 as already mentioned above. Moreover, the
HT/LT ratio is estimated to be 1 indicating that in addition to
the crystalline aggregates other Fe3+ containing species are
also present. Based upon the estimated ratios of LT/HT and
H2/Fe as well as the respective values for a-Fe2O3 we
carefully deduce that about one half of the Fe3+ sites exists as
crystalline entities, while the second half is in the form of
other structures. It has been shown that iron-exchanged ZSM-
5 zeolites reveal different Fe3+ oxo species, i.e. isolated,
oligomeric or strongly aggregated structures [24,47]. In
HTPR, such sites exhibit a H2 consumption peak at ca. 420 8C
[20,48] that is in the range of the LT peak of 1.4Fe/7.0W/Zr.
This feature at 420 8C is generally associated with the
reduction of Fe3+ to Fe2+ species, while the further conversion
to elemental Fe occurs at very high temperatures (>900 8C).
These temperatures are not considered in our HTPR
experiments; thus, this potential reduction step is not possible
to ascertain. Moreover, Chen and Sachtler [28] have observed
in their HTPR study of Fe-ZSM-5 a H2 consumption peak that
appears at 430 8C. The authors associate this feature with the
existence of an oxygen bridged binuclear Fe complex.
Additionally, for an overexchanged Fe-ZSM-5 sample
Grünert and co-workers have reported the coexistence of
crystalline Fe2O3 and Fe3+ oxo sites [48]. This material
reveals a HT/LT ratio of 3.5 and a H2/Fe ratio of 1.4. Taking
into account the literature data mentioned above we interpret
the HTPR profile of the 1.4Fe/7.0W/Zr catalyst with the pre-
dominant existence of crystalline Fe2O3 (ca. 50%), whereby a
significant amount of relatively small oxide entities is also
present. However, the detailed structures of the latter species
can hardly be explained by the use of HTPR only.
Contrary, the 1.4Fe/Zr catalyst shows a completely
different HTPR profile as compared to 1.4Fe/7.0W/Zr. Here,
a single HTPR peak is observed that appears at 480 8C. In
agreement with our HTPR analysis of a-Fe2O3 (Fig. 8(a)) as
well as reference data from Grünert and co-workers [48]
this result evidences the absence of a- and g-Fe2O3. As
discussed for the 1.4Fe/7.0W/Zr catalyst we relate this
single peak to the exclusive presence of small Fe3+
containing oxide structures. Furthermore, the H2/Fe ratio
found to be 0.85 leads to the conclusion that in HTPR some
Fe3+ species are reduced to a lower valency than 2+; for
comparison the reduction of Fe3+ to Fe2+ species corre-
sponds to a H2/Fe ratio of 0.5. A very similar interpretation
has been proposed by Chen and Sachtler for the HTPR of a
Fe-ZSM-5 type catalyst [28]. In PXRD analysis performed
after the HTPR analysis of 1.4Fe/Zr no reflexes attributable
to Fe or iron oxides are detected.
The different HTPR data obtained for 1.4Fe/Zr and
1.4Fe/7.0W/Zr provide evidence that the promoter markedly
causes the formation of larger oxide units, i.e. crystalline
Fe2O3. This effect might be related to the presence of
112 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114

crystalline WO3 (Fig. 2) that covers the surface area and

leads to the formation of larger Fe aggregates. Grünert and
co-workers have recently reported that in SCR on Fe-ZSM-5
zeolite isolated Fe3+ species exhibit the highest efficiency,
while oligomeric and strongly aggregated sites are less
active [24]. This seems to be in contradiction to our catalytic
data that show 1.4Fe/7.0W/Zr to be significantly more active
than 1.4Fe/Zr. However, as will be shown in Section 8.8, the
mechanism of SCR on 1.4Fe/7.0W/Zr catalyst is different
from that postulated for Fe-ZSM-5. Hence, it is not clear if in
1.4Fe/7.0W/Zr the potentially different Fe sites follow the
same trend in activity as for Fe-ZSM-5. Furthermore, the
performance, even that of the highly aggregated entities,
might be significantly enhanced by the interaction with the
W species.
Fig. 10. DRIFT spectrum of the 1.4Fe/7.0W/Zr catalyst after NH3 exposure
at 200 8C.
8.8. Mechanism of the SCR reaction

Fig. 9 shows the rate of NOx reduction versus the
concentration of NH3 at 300 8C. The rate is defined by
Eq. (7) and refers to the steady state. In these measurements
the standard feed gas is taken, whereby ammonia
concentration ranges from 90 to 1050 ppm. First, r(NOx)
increases linearly, while at NH3 concentrations above
500 ppm it changes no more. These data exclude a Langmuir
Hinshelwood type mechanism that should result in decrease
of SCR rate if one reactant is dosed in excess. However, the
curve is typical for the Eley Rideal type mechanism, i.e. one
educt adsorbs on active sites and the second one reacts from
gas phase. This type of mechanism is also discussed by
Ramis et al. for SCR on Fe2O3 [4].
FTr
rðNOx Þ ¼ ðcðNOx Þin  cðNOx Þout Þ
Ts nFe2 O3
The DRIFT spectrum of the 1.4Fe/7.0W/Zr catalyst recorded
during NH3 exposure at 200 8C evidences three bands at 1245,
1440 and 1610 cm1 (Fig. 10). Furthermore, two broad
features are observed at higher wavenumbers, i.e. at 3265
and 3355 cm1. Contrary, the catalyst exposed to NO instead
of NH3 does not show any DRIFTS bands. From these results
we deduce that ammonia is the species that adsorbs on the
catalyst surface, while NO reacts from the gas phase.
The DRIFT spectrum of the Fe free 7.0W/Zr system,
recorded after NH3 treatment, shows bands at 1200 and
1610 cm1 only, whereas no feature is detected at
1440 cm1. Moreover, same peaks as for 1.4Fe/7.0W/Zr
are found in the spectral range above 3000 cm1.
The peaks observed at ca. 1220 and 1610 cm1 are
referred to the das(NH3) and ds(NH3) vibrations of ammonia
molecularly adsorbed on Lewis acid sites [49]. Furthermore,
(7) the band located at 1440 cm1 is associated with the d(NH)
vibration of imide species [4,50]. This feature is not
interpreted as the ds(NH4) vibration of ammonium species
that might be originated from the reaction of NH3 with
Brønsted acid OH groups [49,51]. Such species are formed
on 1.4Fe/7.0W/Zr catalyst by NH3 treatment at 50 8C that is

Fig. 9. Rate of NOx reduction vs. NH3 concentration on aged 1.4Fe/7.0W/

Zr catalyst. SCR is carried out under stationary conditions. Reaction
conditions: T = 300 8C, m(catalyst) = 5.9 g, c(NO) = 500 ppm, c(NH3) = Fig. 11. DRIFT spectrum of the 1.4Fe/7.0W/Zr catalyst after NH3 exposure
140–1050 ppm, c(O2) = 5 vol.%, N2 balance and W/F = 0.18 g s scm3. at 50 8C (a) and subsequent heating at 200 8C in N2 (b).
 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114
performed after heating at 500 8C in N2. The band of the
ds(NH4) vibration, depicted in Fig. 11(a), is located at
1465 cm1 that is very close to the frequency of the d(NH)
vibration. Subsequent treatment at 200 8C in N2 leads to
complete disappearance of the 1465 cm1 band, while a new
feature is detected at 1440 cm1 (Fig. 11(b)). For
comparison, the same experiments are carried out with
the 7.0W/Zr catalyst. The DRIFT spectrum recorded at
50 8C also shows the 1465 cm1 band. This peak is totally
removed at 200 8C, whereas no signal appears at 1440 cm1.
These results prove that the bands at 1440 and 1465 cm1
are associated with different surface species, i.e. imide and
ammonium. Furthermore, the DRIFTS data indicate
formation of imide species by heating the catalyst to
200 8C after exposure to NH3 at 50 8C. We assume that the
production of imide is referred to the thermal decomposition
of NH3 adsorbed on catalytically active iron sites. A more
detailed mechanism is presented below.
The DRIFTS bands at 3265 and 3355 cm1, found after
NH3 exposure at 50 and 200 8C, are ascribed to the
symmetric and asymmetric stretching vibrations of the
coordinated ammonia [49,52].
The DRIFTS results of 7.0W/Zr and 1.4Fe/7.0W/Zr
provide evidence that the imide species are exclusively
formed on the Fe2O3 component of the 1.4Fe/7.0W/Zr
catalyst. On the other hand, it is obvious that the molecular
NH3 is principally coordinated to all available Lewis acid
sites, e.g. Zr4+, W6+ and Fe3+. As the NH3 TPD pattern of
1.4Fe/7.0W/Zr and pure ZrO2 is the same, it is very likely
that that the main part of NH3 adsorbs on the Zr4+ sites.
After the NH3 exposure at 200 8C and purging with N2,
the 1.4Fe/7.0W/Zr catalyst is treated with NO/N2, O2/N2 or
NO2/O2/N2 as described in Section 6. Fig. 12 shows the
development of the DRIFTS band of the imide species
(1440 cm1) with time and also in dependence of the type of
Fig. 12. Development of the DRIFTS band of the d(NH) vibration of imide,
located at 1440 cm1, in the presence of 20 vol.% NO (^), 20 vol.% O2
(&) and 500 ppm NO2/20 vol.% O2 (~). In these gas mixtures, N2 is used
as balance and T = 200 8C.
113
oxidant. The measurements show the fastest rate of imide
conversion if NO2 is present, whereas no reaction occurs in
NO/N2 atmosphere. As imide does not react with NO it is
deduced that this surface species plays no role in SCR, i.e.
N2 formation. However, the DRIFTS data indicate complete
conversion of imide by O2 and NO2. Since N2O is not
formed in SCR at 200 8C (Table 3) we conclude that imide is
oxidized here into NO according to Eqs. (8) and (9). In
contrast to our conclusion, Ramis et al. [4] speculate amide
to be involved in the production of N2O.
4ðNHÞ þ 3O2 ! 4NO þ 2H2 O (8)
4ðNHÞ þ 6NO2 ! 10NO þ 2H2 O (9)
However, we agree with Ramis et al. [4] that imide is
originated from amide species. Following this route we
assume that first NH3 is molecularly coordinated to the
Fe sites of the catalyst resulting in partial reduction of
the iron. The amide species might then be formed by H+
abstraction. However, our DRIFTS study does not evidence
the existence of amide, probably due to its thermal instabil-
ity. We therefore postulate that amide rapidly undergoes
decomposition into imide, whereby a H+ is abstracted. Since
imide is obviously not involved in SCR, we suppose that the
amide intermediate is the key component for SCR, i.e. the
reaction of amide with gaseous NO might lead to N2
formation. This supposition is consistent with the mechan-
ism proposed by Ramis et al. [4].
In the final reaction step, the reduced Fe sites have to be
regenerated. We assume that this regeneration occurs by
oxidation with O2 as, in addition to NO and NH3, the oxygen
is also essential for SCR reaction (Fig. 5). Summarizing the
single steps of our proposed catalytic cycle (Fig. 13) the
stoichiometry of the overall reaction includes the consump-
tion of 2NH3, 2NO and 0.5O2, while 2N2 and 3H2O are
produced. This stoichiometry is in agreement with Eq. (5)
that is deduced from stationary SCR data (Table 3).
The reaction mechanism that we propose for 1.4Fe/7.0W/
Zr catalyst is quite different from that postulated in the
literature for Fe-ZSM-5 zeolite [53–57]. By the use of Fe-
ZSM-5 material NH3 is protonated by the Brønsted acid sites
of the zeolite to form NH4+. Then, two ammonium ions react
with one NO2 molecule that results in the production of
NO2(NH4+)2 species. This ionic intermediate is subse-
quently converted with another NO leading to the formation
Fig. 13. Postulated reaction mechanism for SCR on the 1.4Fe/7.0W/Zr
catalyst.
114 N. Apostolescu et al. / Applied Catalysis B: Environmental 62 (2006) 104–114

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