Journal of Colloid and Interface Science 478 (2016) 11–21

Contents lists available at ScienceDirect

Journal of Colloid and Interface Science

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

Regular Article

Comparison study of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts for selective

catalytic reduction of NO with NH3 at low temperature
Lin Zhu a, Zhaoping Zhong a,⇑, Han Yang a, Chunhua Wang b
a
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, PR China
b
College of Energy and Power Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, PR China

g r a p h i c a l a b s t r a c t

SCR activity was inhibited seriously.

10 vol.%H2O
NH3
Coordinated NH3
Cu-Fe/TiO2
Nitrate species
N2+H2O
Coordinated NH3
Co-Fe/TiO2
Nitrate species
NO+O2
10 vol.%H2O

Temperature window shifted towards higher temperature.

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

Article history: In this paper, a series of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts were prepared by sol gel method. Cu-Fe-Ti
Received 30 March 2016 and Co-Fe-Ti oxide catalysts showed the moderate catalytic activity for selective catalytic reduction (SCR)
Revised 25 May 2016 of NO with NH3 at low temperature. The catalysts with the molar ratio as 4:1:10 (M:Fe:Ti) were selected
Accepted 27 May 2016
as the representatives for comparison of reaction properties and H2O resistance, which were denoted as
Available online 27 May 2016
Cu-Fe/TiO2 and Co-Fe/TiO2 respectively. The characterization results manifested Co-Fe/TiO2 owned more
adsorption capacity of the reactants and Cu-Fe/TiO2 had better redox ability. The in situ DRIFTS experi-
Keywords:
ments indicated that adsorbed NH3 species and nitrate species both exhibited reaction activity for Co-
Cu-Fe/TiO2
Co-Fe/TiO2
Fe/TiO2, while nitric oxide was only be reduced by adsorbed NH3 species through Eley-Rideal mechanism
SCR for Cu-Fe/TiO2 at 150 °C. Co-Fe/TiO2 exhibited the better resistance to H2O and its temperature window
Low temperature shifted towards the higher temperature in presence of 10 vol% H2O, while the SCR activity of Cu-Fe/TiO2
H2O was inhibited significantly in the whole temperature range investigated. The suppression of adsorption
and activation for NH3 and NOx might be the reasons for the reversible inactivation, which was confirmed
by the inhibitation of catalytic activities for separation NH3 and NO oxidation under the wet condition.
We speculated that different thermal stability of adsorbed species and redox capacity of catalysts leaded
to the different SCR behavior in absence and presence of H2O.
Ó 2016 Elsevier Inc. All rights reserved.

⇑ Corresponding author at: School of Energy and Environment, Southeast

University, Nanjing, PR China.
E-mail address: zzhong@seu.edu.cn (Z. Zhong).

http://dx.doi.org/10.1016/j.jcis.2016.05.052
0021-9797/Ó 2016 Elsevier Inc. All rights reserved.
12 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
1. Introduction
Nitrogen oxides generated by the stationary source as industrial
boilers and mobile source like automobiles, have been a major
atmospheric pollutant for many years that contribute to the forma-
tion of photochemical smog and acid rain [1,2]. Selective catalytic
reduction (SCR) of NO with NH3 is the well-known economic and
efficient technology for the removal of nitrogen oxides and the
industrial V2O5-WO3(MoO3)/TiO2 catalyst has been widely
employed for NOx abatement of coal-fired power plants [3]. Due
to the relatively high reaction temperature (300–400 °C), the SCR
unit is usually located upstream of the desulfurizer and electro-
static precipitator in order to avoid reheating the flue gas. How-
ever, the temperature of flue gas could not satisfy the
requirement of vanadium-based catalysts in many industrial occa-
sions. Meanwhile, the catalysts installed before the dust remover
are easy to be blocked or poisoned by the dust in the flue gas.
Therefore, a lot of researches have been performed to find a new
catalyst with good low temperature activity that can substitute
the conventional vanadium-based catalyst.
The transition metal elements such as manganese, copper, iron
and rare earth element like cerium were all selected as the active
elements for low temperature SCR catalysts [4–6]. According to
the abundant literatures, it is general accepted that NO could be
reduced by NH3 through the Langmuir-Hinshelwood (L-H) mecha-
nism and Eley-Rideal (E-R) mechanism [7–10]. The redox reaction
takes place between the activated ammonia and gaseous NO for
the E-R mechanism and the adsorption and activation of ammonia
is the key step for this pathway. The adsorbed ammonia species
react with the adsorbed NOx species in the L-H mechanism. The
formation of active nitrate species is recognized as the important
step for the L-H mechanism.
Copper based catalysts have been widely investigated as the cat-
alysts for the selective catalytic ammonia oxidation (SCO) [11] due
to the excellent redox capacity. Cui et al. [12] synthesized the meso-
porous CuO/RuO2 via co-nanocasting-replication method and the
series of catalysts showed the good activity and high N2 selectivity
for ammonia oxidation at low temperature. He et al. [13] used the
Cu/TiO2 catalysts for selective catalytic oxidation of ammonia and
found that TiO2 was a more suitable support than Al2O3 for copper
based catalysts in the SCO of NH3. Although the copper oxides
exhibited the good ability for adsorption and activation of ammo-
nia, only limited researches for copper oxide catalysts [14–16] were
reported for selective catalytic reduction of NO with NH3.
Cobalt element has been used as the importance active species
for catalytic oxidation of NO recently. As reported, the addition of
NO2 could promote the NO conversion at low temperature and the
pathway for NH3-NO/NO2 mixtures is called the Fast SCR reaction
[17–19]. At the same time, the active nitrate species on the surface
of catalysts contribute to the reduction of NO through L-H mecha-
nism. Zhong et al. [20] prepared a series of Ni-Co perovskite cata-
lysts used for catalytic oxidation of NO and found that
LaNi0.7Co0.3O3 showed the best catalytic activity. Wang et al. [21]
synthesized the different ceria substrate composite catalysts
through sol gel method and the activity tests indicated that Ce-
Co composite catalyst exhibited the best catalytic activity. The
strong interaction between Ce and Co was also reported by Shang
et al. [22] for the Ce-Co-Ti catalysts. Zhong et al. [23] discussed the
influence of preparation methods on the catalytic activity of Co/
Zr1
xCexO2 for NO oxidation and they thought the citrate complex-
ation method was better than the impregnation method. Previous
published works suggested that the addition of cobalt element
contributed to the improvement of NO oxidation efficiency. How-
ever, the reactivity of cobalt oxide catalyst for NO removal through
NH3-SCR technology was seldom reported.
Based on the discussion of mechanism for selective catalytic
reduction of NO with NH3 at low temperature, we attempt to
investigate the novel low temperature SCR catalysts through intro-
ducing the different active elements to Fe-Ti oxide catalyst. In this
work, Cu-Fe-Ti and Co-Fe-Ti oxide catalysts synthesized by sol gel
method were used for the selective catalytic reduction (SCR) of NO
with NH3. The two typical catalysts were characterized by N2
physisorption, NH3/NO-TPD, H2-TPR and in situ DRIFTS (in situ dif-
fuse reflectance infrared Fourier transform spectroscopy). The cat-
alytic activities for SCR reaction of the catalysts were compared
under the dry and wet conditions. The NH3/NO oxidation activities
were performed in absence and presence of water in order to clar-
ify the influence on the SCR activity brought by high concentration
water vapor.
2. Experimental
2.1. Catalyst preparation
A series of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts were prepared
by sol-gel method. The molar ratio of M:Fe:Ti is x:1:10 (M = Cu, Co;
x = 2, 3, 4, 5). The butyl titanate was the titanium precursor and
transition metal nitrates were the precursors of other metal oxides.
Butyl titanate (20 mL) was well mixed with 10 mL ethanol to form
solution A. The stoichiometric transition metal nitrates were dis-
solved in mixed solution of 5 mL ethanol, 5 mL acetic acid and
5 mL deionized water forming solution B. Solution B was added
into solution A dropwise under vigorous stirring at room tempera-
ture. The transparent sols transformed to the gels gradually. The
gels were kept at room temperature for several days. The gel sam-
ples were dried at 105 °C overnight. Then the samples were cal-
cined at 350 °C for 1 h (heating rate 5 °C/min) and then 500 °C
for 3 h (heating rate 2 °C/min) in muffle furnace. The calcined
power samples were pelleted, crushed and sieved to 40–60 mesh
for performance evaluation. The catalysts with the molar ratio of
4:1:10 (M:Fe:Ti) were selected for the comparative study and
denoted as Cu-Fe/TiO2 and Co-Fe/TiO2, respectively.
2.2. Catalyst characterization
The N2 adsorption-desorption isotherms were obtained at

196 °C using a V-Sorb 2800P instrument (GOLD APP instruments,
China). Prior to N2 adsorption, the catalysts were degassed at
250 °C for 5 h. The surface areas were determined by BET equation
in 0.05–0.35 partial pressure range and the average pore sizes were
determined by BJH method from the adsorption branches of the
isotherms.
NH3-TPD and NO-TPD were carried out using FineSorb 3010D
chemisorption analyzer (FINETEC instruments, China). Prior to
TPD experiments, the samples (100 mg, 40–60 mesh) were pre-
treated at 400 °C in a flow of high-purify helium (20 mL/min) for
1 h and cooled down to 80 °C. Then the samples were exposed to
a flow of 5 vol% NH3/N2 or 5 vol% NO/N2 (20 mL/min) for 30 min,
followed by He purge for another 1 h. Finally, the temperature
was raised to 600 °C in He flow at the rate of 10 °C/min. The
amount of ammonia or NOx species desorbed from the catalysts
was monitored by a thermal conductivity detector (TCD).
H2-TPR was also performed using the same instrument. Before
the experiment, the catalysts (50 mg, 40–60 mesh) were pre-
treated at 400 °C in a flow of high purify Ar (20 mL/min) for 1 h
and cooled down to 50 °C. Then the temperature was raised lin-
early to 700 °C at the rate of 10 °C/min in a flow of 10 vol% H2/Ar
(20 mL/min). The H2 consumption was monitored by TCD.
In situ DRIFTS spectra were measured by an FTIR spectrometer
(Thermo Nicolet 6700) equipped with a diffuse reflectance optics
 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
accessory (DRP-NI8). An in situ DRIFTS reactor cell with the KBr
windows connected to a purging/adsorption gas control system
was used for the in situ DRIFTS experiments. Prior to NH3/NO
+ O2 adsorption, the catalysts were pretreated at 450 °C in a flow
of 5 vol% O2/N2 for 0.5 h and cooled down to 150 °C. Thereafter,
the background spectra were recorded, which were automatically
subtracted from the final spectra during the dynamic experiment
process. The total flow rate was 30 mL/min and the inlet gas con-
centrations were kept at 1000 ppm NH3 or 1000 ppm NO with
5 vol% O2. All spectra were recorded by accumulating 32 scans with
a resolution of 4 cm
1.
2.3. Activity test
The steady-state SCR activity test was carried out in a fixed-bed
stainless steel reactor (i.d 10 mm) containing 1.5 mL of catalyst.
The typical composition of the reactant gas was: 500 ppm NO,
500 ppm NH3, 3.5 vol% O2, 10 vol% H2O (when used) and N2 as
the balance gas. The deionized water was injected into the preheat-
ing section by the micro syringe pump, which was vaporized and
mixed with other gas components. The total flow rate was 1.5 L/
min (refers to 1 atm and 298 K) which corresponded to a gas
hourly space velocity (GHSV) of 60,000 h
1. The NO, NO2, and O2
concentration were measured online by the flue gas analyzer
(MRU 600, Germany) while the N2O concentration was measured
by NGA 2000 analyzer (Rosemont, Germany). The analysis of the
product was performed when the reaction system reached a steady
state for at least 0.5 h. The NOx conversion was calculated as
follows.
 
½NOx out
NOx conversion ¼ 1
 100%
½NOx in
The separate NH3 oxidation and NO oxidation activity tests were
carried out using the method similar to that for NH3-SCR activity
with 500 ppm NH3 for NH3 oxidation (500 ppm NO for NO oxida-
tion), 3.5 vol% O2 and 10 vol% H2O (when used) in N2 balance. For
NH3 oxidation test, the outlet concentration of NH3 was measured
by ULTRAMAT6 analyzer (Siemens, Germany).
3. Results and discussion
3.1. Catalytic activity in absence of H2O
The SCR activity and N2O concentration in exhaust gas for a ser-
ies of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts in absence of water are
shown in Fig. 1. The Cu-Fe-Ti oxide catalysts exhibited the moder-
ate NOx conversion efficiency in the temperature range from
150 °C to 250 °C. The increase of Cu addition improved the SCR
activity for Cu-Fe-Ti oxide catalysts slightly. When the molar ratio
(Cu:Fe:Ti) reached 5:1:10, the NOx conversion at higher tempera-
ture started to decrease. The SCR activities of Co-Fe-Ti oxide cata-
lysts increased with the elevation of temperature below 225 °C and
the NOx conversions were over 80% between 200 °C and 250 °C. As
the molar ratio (Co:Fe:Ti) was above 4:1:10, the improvement of
SCR activity was not obvious any more. The NOx conversion
decreased for the two kinds of catalysts to some degree at
250 °C, which was caused by the over oxidation of ammonia.
The formation of by-product N2O increased monotonically as
the reaction temperature rose for Cu-Fe-Ti oxide catalysts, while
the concentration of N2O in exhaust gas became obvious only
above 200 °C for Co-Fe-Ti oxide catalysts. The concentration of
N2O in the outlet was highest for the catalyst with the maximum
addition. The production for N2O of the Cu-Fe-Ti oxide catalysts
was more than that of the Co-Fe-Ti oxide catalysts at low
temperature. According to the published literatures [8,17], over
13
dehydrogenation for adsorbed ammonia species and decomposi-
tion of ammonium nitrate intermediate species both could lead
to the formation of by-product N2O.
Considering the SCR activity and N2O formation for the series of
catalysts, the catalysts with the molar ratio (M:Fe:Ti = 4:1:10)
exhibited the representativeness for the different kinds of catalytic
materials, which was in line with the composition of manganese
based catalyst reported by Wu et al. [24]. Therefore, the corre-
sponding catalysts were selected for the deep comparative study
and denoted as Cu-Fe/TiO2 and Co-Fe/TiO2, respectively.
3.2. Characterization
3.2.1. N2-physisorption and XRD
The structural parameters of catalysts derived from N2-
physisorption are summarized in Table 1. There was not the obvi-
ous difference between the two catalysts in the structural param-
eters. Although the total pore volume was smaller for Co-Fe/TiO2,
the BET surface area was slightly bigger than that for Cu-Fe/TiO2
due to the smaller size of average pore diameter. It could be con-
cluded that the structural parameters were not the main reason
for the difference on the reaction characteristic.
X-ray diffraction (XRD) technology was applied to investigate
the crystallographic structure of the prepared catalysts. The XRD
patterns for Cu-Fe/TiO2 and Co-Fe/TiO2 are shown in Fig. 2. The
patterns both exhibited peaks at 25.28°, 36.94°, 37.80°, 38.35°,
48.05°, 53.89°, 55.06°, 62.68°, 68.76°, 70.31° and 75.03°, corre-
sponding to the (1 0 1), (1 0 3), (0 0 4), (1 1 2), (2 0 0), (1 0 5),
(2 1 1), (2 0 4), (1 1 6), (2 2 0) and (2 1 5) planes of TiO2 (anatase,
JCPDS 21-1272). The higher diffraction peak signal intensity for
Cu-Fe/TiO2 catalyst indicated the higher crystallization degree
ð1Þ
and the bigger grain size of TiO2 compared with Co-Fe/TiO2 sample,
which was in accordance with the result of pore size from N2
physisorption. Apart from the diffraction peaks for anatase TiO2,
the peak signals for CuO (tenorite, JCPDS 45-0937) and CoTi2O5
(JCPDS 35-0793) were detected for the two catalysts, respectively.
The existence of CoTi2O5 indicated the strong interaction between
cobalt and titanium might account for the low crystallization
degree of TiO2.
3.2.2. NH3/NO-TPD and IR spectra analysis
It is well-known that the adsorption of reactants is important
for different reaction mechanisms. Fig. 3 shows the result of
NH3/NO-TPD profiles and corresponding IR spectra at 150 °C for
Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts. There were three ammonia
desorption peaks for Co-Fe/TiO2 catalyst, while only two desorp-
tion peaks were observed for Cu-Fe/TiO2 catalyst. The weak acid
sites were on the surface of Cu-Fe/TiO2 catalyst mainly, while more
strong acid sites existed on the surface Co-Fe/TiO2 catalyst. The
integral area of desorption signals for Co-Fe/TiO2 catalyst was
1.54 times that of Cu-Fe/TiO2 catalyst and the thermal stability of
ammonia adsorbed species for Co-Fe/TiO2 catalyst was much
stronger. According to the corresponding IR spectra, the coordi-
nated NH3 bound to Lewis acid sites was main adsorbed species
on the surface of catalysts (1211, 1232 and 1195 cm
1 for dsNH3;
1604 and 1608 cm
1 for dasNH3) at 150 °C [7–10,25]. Only weak
symmetric bending vibration of ionic NH+4 at 1695 cm
1 was
observed, which was due to the weak thermal stability for
Brønsted acid sites. The intensity of IR spectra also indicated that
more surface acid sites were for Co-Fe/TiO2 catalyst.
The NO-TPD profiles for Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts
were similar with the NH3-TPD profiles. The integral area ratio dis-
played in Fig. 3 manifested that the amount of adsorbed NOx spe-
cies for Co-Fe/TiO2 was more than that for Co-Fe/TiO2 catalyst. The
IR bands at 1602, 1604, 1243 cm
1 could be attributed to bridging
nitrate and the bands at 1575 cm
1 corresponded to the vibration
14 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21

Fig. 1. NOx conversion and N2O concentration in NH3-SCR reaction for a series of Cu-Fe-Ti (A) and Co-Fe-Ti (B) oxide catalysts in absence of water. Reaction condition: [NO] =
[NH3] = 500 ppm, [O2] = 3.5 vol%, N2 as balance and GHSV = 60,000 h
1.

Table 1
Structural parameters of Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts.

Sample BET surface area Total pore volume Average pore diameter
(m2/g) (cm3/g) (nm)
Cu-Fe/TiO2 76.19 0.121 5.7
Co-Fe/TiO2 80.78 0.114 5.0

of bidentate nitrate. The IR bands at 1548, 1530, 1276 cm
1 were

assigned to the monodentate nitrate [7–10,25]. Based on the iden-
tification of different adsorbed nitrate species by the IR spectra, it
could be concluded that the intensities for all kinds of adsorbed
nitrate species for Co-Fe/TiO2 catalyst were higher. The higher des-
orption temperature in NO-TPD profile of Co-Fe/TiO2 catalyst indi-
cated the stronger thermal stability for adsorbed nitrate species.

3.2.3. H2-TPR analysis

Temperature programmed reduction technique was employed
to investigate the reducibility of Cu-Fe/TiO2 and Co-Fe/TiO2 cata-
lysts as depicted in Fig. 4. The Cu-Fe/TiO2 catalyst possessed two Fig. 2. XRD profiles for Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts.
 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
Fig. 3. NH3/NO-TPD profiles (A) and IR spectra at 150 °C (B) for Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts.
distinct reduction peaks at 161 °C and 202 °C. The reduction profile
of pure CuO was characterized by a single reduction peak at 392 °C
[26]. The separation and shift toward low temperature of reduction
peak indicated the interaction existed between the support and
copper oxide. The low temperature peak at 161 °C was due to the
reduction of well dispersed CuO on TiO2 support and the reduction
peak at 202 °C corresponded to the reduction of crystalline CuO
[27,28]. There were two broad reduction peaks between 310 °C
and 550 °C, which was attributed to the consecutive reduction of
Fe2O3-Fe3O4-FeO [19]. The reduction peak above 610 °C could be
regarded as the reduction of Fe2+ to Fe0 [19]. Three broad reduction
peaks were observed distinctly for Co-Fe/TiO2 catalyst and the H2-
TPR profile was similar with the curve of sol-gel 10% Co/TiO2 cata-
lyst reported by Yung et al. [29]. The broad reduction features indi-
cated heterogeneity in the oxidation states for the cobalt species
[29]. The sol-gel preparation method provided a strong linkage
between Ti and Co species resulting in this phenomenon partially.
The emergence of CoTi2O5 in XRD pattern could confirm this
Fig. 4. H2-TPR profiles for Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts.
15
speculation. Base on the reduction temperature, we deduced that
the reduction peak at 367 °C was caused by the superimposed
reduction of Co3+ or Co3O4 to Co2+ [20,22] and Fe2O3 to Fe3O4
[19]. The board reduction peak at 557 °C was correlated to the
reduction of Fe3O4 to FeO and Co2+ to Co0 [23,29]. The reduction
of bulk cobalt species might account for the emergence of reduc-
tion peak at 650 °C. According to the H2-TPR profiles, it could be
concluded that the redox ability of Cu-Fe/TiO2 catalyst was better
than that of Co-Fe/TiO2 sample. The weaker thermal stability of
adsorbed species for Cu-Fe/TiO2 catalyst in the temperature pro-
grammed desorption profile might be in related with the reducibil-
ity of catalyst surface. The excellent redox capacity of Cu-Fe/TiO2
catalyst accelerated the activation of reactants and redox cycle
resulting in the good SCR activity at low temperature.
3.2.4. In situ DRIFTS analysis
To investigate the reaction mechanism of SCR over the Cu-Fe/
TiO2 and Co-Fe/TiO2 catalyst at low temperature, the catalysts
were exposed to NH3 or NO + O2 at 150 °C firstly until adsorptions
were saturated. The catalysts were then purged with N2 and subse-
quently exposed to the reverse gases. IR spectra were recorded as a
function of time.
3.2.4.1. Reaction between NO + O2 and pre-adsorbed NH3. The in situ
DRIFTS experiments of reaction between NO + O2 and pre-
adsorbed NH3 species at 150 °C were carried out, and the results
are shown in Fig. 5. Apart from the IR bands (1211, 1232 cm
1
for dsNH3 and 1608 cm
1 for dasNH3) discussed in Section 3.2.2,
after NH3 + O2 adsorption and N2 purge the bands at 3100–
3400 cm
1 (3157, 3201, 3253, 3347 and 3386 cm
1) attributed to
NAH stretching vibration modes of coordinated NH3 also showed
up (as shown in Fig. 5A) [7–10]. The negative band around
3641 cm
1 was due to the surface OAH stretching [30]. After NO
+ O2 passed over the NH3-pretreated Cu-Fe/TiO2 catalyst, the IR
bands attributed to coordinated NH3 (1211, 1232 and 1608 cm
1)
showed an obvious decline in intensity and disappeared after
40 min, and then the nitrate species began to form on the catalyst
surface, including bridging nitrate (1602 and 1240 cm
1),
16 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21

Fig. 5. In situ DRIFTS spectra of the catalysts for the reaction between NO + O2 and pre-adsorbed NH3 species at 150 °C: (A) Cu-Fe/TiO2 and (B) Co-Fe/TiO2.

monodentate nitrate (1506 and 1276 cm
1) and bidentate nitrate
(1560 cm
1) [7–10,31].
Similar with Cu-Fe/TiO2 catalyst, the coordinated NH3 bound to
Lewis acid sites (1195 cm
1 for dsNH3 and 1604 cm
1 for dasNH3)
was the main adsorbed species on the Co-Fe/TiO2 surface [7,10].
Meanwhile, a weak IR band at 1695 cm
1 assigned to symmetric
deformation of NH+4 bound to Brønsted acid sites was observed
after the NH3 pretreatment [8] (as shown in Fig. 5B). After NO
+ O2 passed over the NH3-pretreated Co-Fe/TiO2 catalyst, the IR
bands attributed to coordinate NH3 (1195 and 1604 cm
1) showed
the dramatic decline in intensity. After 40 min, the nitrate species
corresponding to bridging nitrate (1623 cm
1) and monodentate
nitrate (1530 cm
1) were observed dramatically on the catalyst
surface [7,10]. These results indicated that coordinated NH3 on
the surface of Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts both could react
with NO + O2 at 150 °C.
3.2.4.2. Reaction between NH3 and pre-adsorbed NOx species. Fig. 6
shows the in situ DRIFTS of reaction between NH3 and pre-
adsorbed NOx species over Cu-Fe/TiO2 and Co-Fe/TiO2. After the
pretreatment of Cu-Fe/TiO2 with NO + O2, the catalyst surface
was mainly covered by bridging nitrate (1602 and 1243 cm
1),
bidentate nitrate (1575 cm
1) and monodentate nitrate (1530
and 1276 cm
1) [7,10,25] (as shown in Fig. 6A). After the injection
of NH3, the IR band at 1602 cm
1 showed a little decrease in the
first 10 min and the IR band at 1575 cm
1 increased slightly. At
30 min, the IR bands at 1565, 1504, 1276 and 1243 cm
1 showed
the obvious increases and the bands in the region of 3100–
3400 cm
1 (3162, 3209, 3255 and 3347 cm
1) attributed to NAH
stretching vibration for coordinated NH3 were detected obviously
[9,30]. The IR bands at 1602 and 1243 cm
1 might be caused by
overlap of IR bands from bridging nitrate and coordinated NH3.
The bands at 1575 cm
1 and 1530 cm
1 shifted to 1565 cm
1 and
 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21 17

Fig. 6. In situ DRIFTS spectra of the catalysts for the reaction between NH3 + O2 and adsorbed NOx species at 150 °C. (A) Cu-Fe/TiO2 and (B) Co-Fe/TiO2.

1504 cm
1 respectively, which could be ascribed to the deforma-
tion nitrate species when the catalyst surface was exposed to
NH3. It was interesting that the intensity of IR band at 1565 cm
1
reached the maximum at 30 min and then decreased gradually,
while the IR band at 1504 cm
1 became obvious at 30 min and
then increased during the later 20 min. We deduced that the
adsorption of NH3 leaded to the transformation of different nitrate
species on the surface. Meanwhile, the nitrate species enhanced
the adsorption of ammonia species in contrast to the IR spectrum
in Fig. 5A. After the catalyst was exposed in NH3 for 60 min,
adsorbed NH3 and nitrate species can be observed on the Cu-Fe/
TiO2 surface at the same time. The total intensity for different
nitrate species did not change obviously and the broad banks at
3200–3600 cm
1 still existed after 60 min. These results indicated
that the reaction between ammonia and nitrate species was unli-
kely to take place at 150 °C for Cu-Fe/TiO2 catalyst.
After N2 + O2 adsorption and N2 purge, different kinds of nitrate
species were formed on the surface of Co-Fe/TiO2, including biden-
tate nitrate (1575 cm
1), monodentate nitrate (1548 cm
1), bridg-
ing nitrate (1604 and 1243 cm
1) [7,10,25,30]. During the first
30 min after NH3 introduction, the bands of monodentate nitrate
(1548 cm
1) and bridging nitrate (1604 cm
1) decreased gradually,
implying the reaction with NH3 took place. At 40 min, the bands in
the region of 3100–3400 cm
1 assigned to NAH stretching vibra-
tion for coordinated NH3 were observed and the board bands at
3200–3600 cm
1 corresponding to nitrate species decreased obvi-
ously. After 30 min, the intensity of bridging nitrate (1602 cm
1)
decreased gradually and the bidentate nitrate (1575 cm
1)
18 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
increased inversely, suggesting the transformation or deformation
for nitrate species occurred due to the influence of coordinated
NH3. The IR band at 1602 cm
1 might be caused by overlap of IR
bands for bridging nitrate and coordinated NH3. The increase of
intensity of IR band at 1243 cm
1 was caused by the adsorption
of NH3, which was verified by the emergence of 1218 cm
1 IR band
at 60 min. Different with the phenomenon of Cu-Fe/TiO2 catalyst,
the bridging and monodentate nitrate species on the surface of
Co-Fe/TiO2 exhibited the reaction activity with NH3 at 150 °C.
Comparing the change of IR spectra for the two catalysts during
the transient conditions, it could be concluded that the NOx can be
removed through E-R mechanism and L-H mechanism for Co-Fe/
TiO2 catalyst, while nitric oxide was only be reduced through E-R
mechanism for Cu-Fe/TiO2 sample at 150 °C.
3.3. Effect of water on SCR activity
3.3.1. SCR activity in presence of H2O
The influence of H2O on the SCR activity is important for a novel
low temperature SCR catalyst. The NOx conversion and N2O forma-
tion of Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts in absence and pres-
ence of water vapor are illustrated in Fig. 7. It was obvious that
the SCR activities at low temperature for the two catalysts were
inhibited seriously by 10 vol% water vapor. In accordance with
published reports [32,33], the inactivation brought by water vapor
was reversible and the activity could recover after cutting off the
supply of water vapor. This indicated that the decrease of NOx con-
version caused by H2O resulted from the competitive adsorption
between H2O and NH3/NOx for active sites instead of the perma-
nent deactivation of active sites for SCR reaction.
Comparing the test results under dry and wet conditions in
Fig. 7, the inhibition of water vapor on different catalysts varied
in the inactivation degree. The temperature window for Co-Fe/
TiO2 catalyst shifted towards the higher temperature range. As
the temperature rose, the SCR activity recovered gradually. The
maximum efficiency for NOx removal was 93.8% at 300 °C in pres-
ence of H2O, while the 96.2% NOx conversion was obtained at
225 °C in absence of H2O. The SCR activity of Cu-Fe/TiO2 catalyst
was suppressed dramatically in the whole temperature range
investigated. The maximum NOx conversion under the wet condi-
tion was only 65.8% that was much lower than that under the dry
condition. In addition to the decrease of NOx conversion, the for-
mation of by-product N2O was inhibited at the same time, which
was beneficial for the application in real industrial environment.
Fig. 7. NOx conversion and N2O concentration in NH3-SCR reaction for Cu-Fe/TiO2
and Co-Fe/TiO2 catalysts in absence and presence of water vapor. Reaction
condition: [NO] = [NH3] = 500 ppm, [O2] = 3.5 vol%, [H2O] = 10 vol% (when used),
N2 balance and GHSV = 60,000 h
1.
The concentration of N2O for Co-Fe/TiO2 became obvious above
250 °C and increased with the elevation of reaction temperature.
The amount of N2O in the exhaust for Cu-Fe/TiO2 catalyst was more
than that for Co-Fe/TiO2 catalyst, which was in line with the result
in absence of H2O.
3.3.2. Effect of H2O on NH3 and NO oxidation
In order to understand the reason for the influence on SCR activ-
ity brought by H2O on the two catalysts, the separation NH3 and
NO oxidation tests were performed in absence and presence of
H2O. The NH3 conversion, N2O and NO concentration in the pro-
duct under the dry and wet conditions are showed in Fig. 8. The
Cu-Fe/TiO2 and Co-Fe/TiO2 catalysts showed the similar NH3 con-
version without water vapor. The NH3 conversion and N2O concen-
tration both increased with temperature rising. However, the
composition of products and the trend for N2O formation were dif-
ferent. The N2O concentration in the outlet for Cu-Fe/TiO2 catalyst
was higher than that for Co-Fe/TiO2 catalyst, especially at low tem-
peratures. A small amount of NO was detected for Cu-Fe/TiO2 cat-
alyst above 250 °C, while no NO was observed for Co-Fe/TiO2
catalyst in the whole temperature range investigated.
The different mechanisms for ammonia catalytic oxidation
(SCO) have been summarized and reported in the scientific litera-
ture [11]. Curtin et al. [34] found the CuO/Al2O3 system was active
for ammonia oxidation to nitrogen and water. They proposed a
hypothesis about a pool of monoatomic surface nitrogen species
with varying oxidation states and whether N2 or N2O formed
depended upon the average oxidation state of this pool. The
reduced lability of surface lattice oxygen species favored a lower
average oxidation state for the monoatomic surface nitrogen pool
and leaded to N2 formation. Some researchers considered that
the subsequent dehydrogenation of ammonia (ANH3 ? ANH2 ?
NH ? N) [35] took place until the Nads species was formed which
could interact with Oads to produce NO [36], while the formation
of N2 occurred by interaction of two Nads species [12]. According
to the number of oxygen atom in reaction products, we deduced
that the type of products was directly related with the lability of
surface active oxygen species. As the temperature increased, more
oxygen species were activated on the surface of catalyst and then
desorbed with the Nads species forming the N2O and NO in the
exhaust. In contrast with Cu-Fe/TiO2 catalyst, the combining capac-
ity of active oxygen species with the catalyst surface for Co-Fe/TiO2
catalyst was stronger leading to the results that less N2O was
detected at the temperature below 250 °C and NO was not
observed even at 300 °C. The weaker thermal stability for adsorbed
ammonia in NH3-TPD and the lower reduction temperature in H2-
TPR profile were the embodiments for the higher lability of active
oxygen species on the surface of Cu-Fe/TiO2 catalyst.
The ammonia oxidation activity and formation of N2O were
inhibited significantly in presence of 10 vol% H2O. Almost no N2O
was formed at low temperature and N2 was the main product for
NH3 oxidation under the wet condition. Although the catalytic per-
formance at low temperature decreased, the N2 selectivity of cata-
lysts was improved by producing more environmental-friendly N2
and H2O. Combining the experiment results and opinions in litera-
tures [16,29,33], it could be deduced that the existence of water
vapor inhibited the process for adsorption and activation of ammo-
nia at low temperature. When the temperature was over 250 °C,
the influence of water vapor became weaker and there was
30 ppm N2O detected for Co-Fe/TiO2 catalyst at 300 °C. For Cu-Fe/
TiO2 catalyst, the percentage of NO in the reaction product
exceeded the share of N2O, suggesting that the pathway for NH3
oxidation reaction changed due to the addition of water vapor.
The ‘‘internal” selective catalytic reduction (i-SCR) might be the
reason explaining that NO was not found in the exhaust at the tem-
perature below 250 °C. The formed NO could be reduced by the
 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
Fig. 8. NH3 conversion, N2O and NO concentration in NH3-SCO reaction for different catalysts. Reaction conditions: [NH3] = 500 ppm, [O2] = 3.5 vol%, [H2O] = 10 vol% (when
used), N2 balance and GHSV = 60,000 h
1:(A) Cu-Fe/TiO2; (B) Co-Fe/TiO2.
unoxidized ammonia with the excess oxygen through SCR route.
The inhibitation brought by H2O decreased and the percentage of
oxidized ammonia increased with the temperature rising. Due to
lack of enough reductant, more direct oxidation product emerged
in the exhaust at higher temperature.
As we can see in Section 3.3.1, water vapor not only inhibited
the SCR activity of Cu-Fe/TiO2 catalyst at low temperature, but
decreased the NO conversion at 300 °C. Combining with the effect
of H2O on NH3 oxidation activity, we proposed a hypothesis that
under the wet condition the elevation for NH3 oxidation activity
by temperature was more remarkable than SCR activity, resulting
in more ammonia being oxidized to N2O and NO. Therefore, the
NOx conversion decreased even at higher temperature for Cu-Fe/
TiO2 catalyst in presence of H2O. The speculation was confirmed
by the fact that the temperature point for transition of SCR activity
was in agreement with that for distinct NO concentration detected
in NH3-SCO reaction under the wet condition. Compared with Cu-
Fe/TiO2 catalyst, the thermal stability of adsorbed ammonia for Co-
Fe/TiO2 catalyst was stronger according to the NH3-TPD profile.
These coordinated ammonia on medium strong and strong acid
sites of Co-Fe/TiO2 catalyst were stabilized at the higher tempera-
19
ture. The elevated temperature weakened the inhibitation of H2O
on the adsorption and activation of NH3. So the SCR activity for
Co-Fe/TiO2 catalyst recovered gradually in the high temperature
range.
The NO oxidation activities for Cu-Fe/TiO2 and Co-Fe/TiO2 cata-
lysts in absence and presence of H2O are revealed in Fig. 9. The NO
oxidation efficiency for Co-Fe/TiO2 catalyst was higher than that
for Cu-Fe/TiO2 sample in absence of H2O, especially at higher tem-
peratures. The NO conversion in separation oxidation test reached
56.33% for Co-Fe/TiO2 catalyst at 300 °C. This result was in line
with the majority of related researches, confirming the excellent
NO oxidation activity for cobalt based catalysts [20–23]. The
in situ DRIFTS experiment exhibited the reaction activity of
adsorbed nitrate species at low temperature. The abundant
adsorbed nitrate species could account for the good catalytic per-
formance of Co-Fe/TiO2 catalyst. The NO oxidation activity for cat-
alysts both decreased with the addition of water vapor in the feed
gas. It was indicated that the inhibition for NO oxidation might be
another reason for loss of SCR activity for Co-Fe/TiO2 catalyst at
low temperature. Due to the nonreactivity of nitrate species
adsorbed on Cu-Fe/TiO2 catalyst at 150 °C, it was difficult to judge
20 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
Fig. 9. NO conversion in NO catalytic oxidation reaction for Cu-Fe/TiO2 and Co-Fe/
TiO2 catalysts. Reaction conditions: [NO] = 500 ppm, [O2] = 3.5 vol%, [H2O] = 10 vol%
(when used), N2 balance and GHSV = 60,000 h
1.
whether the inhibition of NO oxidation in presence of H2O influ-
enced its SCR activity in the investigated temperature range.
4. Conclusions
A series of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts prepared by sol
gel method were used for selective catalytic reduction (SCR) of NO
with NH3 and showed the moderate catalytic activity at low tem-
perature. The denitration efficiency improved with the increase
of the amount of active elements and reaction temperature below
225 °C. The catalysts with the molar ratio as 4:1:10 (M:Fe:Ti) were
selected as the representatives for comparison of reaction proper-
ties and H2O resistance, which were denoted as Cu-Fe/TiO2 and Co-
Fe/TiO2 respectively. The characterization results manifested Co-
Fe/TiO2 owned more adsorption capacity of the reactants and the
excellent redox ability accounted for the better SCR activity at
low temperature for Cu-Fe/TiO2. The in situ DRIFTS experiments
indicated that adsorbed NH3 species and nitrate species both
exhibited reaction activity for Co-Fe/TiO2, while nitric oxide was
only be reduced by adsorbed NH3 species through Eley-Rideal
mechanism for Cu-Fe/TiO2 at 150 °C. Co-Fe/TiO2 exhibited the bet-
ter resistance to H2O and its temperature window shifted towards
the higher temperature in presence of 10 vol% H2O, while the SCR
activity of Cu-Fe/TiO2 was inhibited significantly in the whole tem-
perature range investigated. The amount of N2O decreased in pres-
ence of H2O at the same time. The suppression of adsorption and
activation for NH3 and NOx might be the reasons for the reversible
inactivation of H2O, which was confirmed by the inhibitation of
catalytic activities for separation NH3 and NO oxidation under
the wet condition. We speculated that the lability of active oxygen
species was stronger for Cu-Fe/TiO2 and different thermal stability
of adsorbed species and redox ability of catalysts leaded to the dif-
ferent SCR behavior in absence and presence of H2O.
Acknowledgements
This research was financially supported by the Policy-induced
Project of Jiangsu Province for the Industry-University-Research
Cooperation (BY2015070-21) and the Natural Science Fund Pro-
gram of Jiangsu Province (BK20150749).
References
[1] V.I. Pârvulescu, P. Grange, B. Delmon, Catalytic removal of NO, Catal. Today 46
(1998) 233–316.
[2] S. Roy, M.S. Hegde, G. Madras, Catalysis for NOx abatement, Appl. Energy 86
(2009) 2283–2297.
[3] G. Busca, L. Lietti, G. Ramis, F. Berti, Chemical and mechanistic aspects of the
selective catalytic reduction of NOx by ammonia over oxide catalysts: a
review, Appl. Catal., B: Environ. 18 (1998) 1–36.
[4] J.H. Li, H.Z. Chang, L. Ma, J.M. Hao, R.T. Yang, Low-temperature selective
catalytic reduction of NOx with NH3 over metal oxide and zeolite catalysts—a
review, Catal. Today 175 (2011) 147–156.
[5] M.F. Fu, C.T. Li, P. Lu, L. Qu, M.Y. Zhang, Y. Zhou, M.G. Yu, Y. Fang, A review on
selective catalytic reduction of NOx by supported catalysts at 100–300°°C—
catalysts, mechanism, kinetics, Catal. Sci. Technol. 4 (2014) 14–25.
[6] C. Lei, S. Zhichun, W. Xiaodong, W. Duan, R. Rui, Y. Jun, Rare earth containing
catalysts for selective catalytic reduction of NOx with ammonia: a review, J.
Rare Earth. 32 (2014) 907–917.
[7] F.D. Liu, H. He, C.B. Zhang, W.P. Shan, X.Y. Shi, Mechanism of the selective
catalytic reduction of NOx with NH3 over environmental-friendly iron titanate
catalyst, Catal. Today 175 (2011) 18–25.
[8] S.J. Yang, C.Z. Wang, J.H. Li, N.Q. Yan, L. Ma, H.Z. Chang, Low temperature
selective catalytic reduction of NO with NH3 over Mn–Fe spinel: performance,
mechanism and kinetic study, Appl. Catal., B: Environ. 110 (2011) 71–80.
[9] L. Chen, J.H. Li, M. Ge, DRIFT study on Cerium
Tungsten/Titiania catalyst for
selective catalytic reduction of NOx with NH3, Environ. Sci. Technol. 44 (2010)
9590–9596.
[10] T. Chen, B. Guan, H. Lin, L. Zhu, In situ DRIFTS study of the mechanism of low
temperature selective catalytic reduction over manganese-iron oxides, Chin. J.
Catal. 35 (2014) 294–301.
[11] M. Jabłońska, R. Palkovits, Copper based catalysts for the selective ammonia
oxidation into nitrogen and water vapour—recent trends and open challenges,
Appl. Catal., B: Environ. 181 (2016) 332–351.
[12] X.Z. Cui, J. Zhou, Z.Q. Ye, H.R. Chen, L. Li, M.L. Ruan, J.L. Shi, Selective catalytic
oxidation of ammonia to nitrogen over mesoporous CuO/RuO2 synthesized by
co-nanocasting-replication method, J. Catal. 270 (2010) 310–317.
[13] S.L. He, C.B. Zhang, M. Yang, Y. Zhang, W.Q. Xu, N. Cao, H. He, Selective catalytic
oxidation of ammonia from MAP decomposition, Sep. Purif. Technol. 58 (2007)
173–178.
[14] Z.C. Si, D. Weng, X.D. Wu, Y. Jiang, B. Wang, Synergistic effects between copper
and tungsten on the structural and acidic properties of CuOx/WOx-ZrO2
catalyst, Catal. Sci. Technol. 1 (2011) 453–461.
[15] X. Gao, X.S. Du, L.W. Cui, Y.C. Fu, Z.Y. Luo, K.F. Cen, A Ce–Cu–Ti oxide catalyst
for the selective catalytic reduction of NO with NH3, Catal. Commun. 12 (2010)
255–258.
[16] X.S. Du, X. Gao, L.W. Cui, Z.Z. Zheng, P.D. Ji, Z.Y. Luo, K.F. Cen, Experimental and
theoretical studies on the influence of water vapor on the performance of a Ce-
Cu-Ti oxide SCR catalyst, Appl. Surf. Sci. 270 (2013) 370–376.
[17] I. Nova, C. Ciardelli, E. Tronconi, D. Chatterjee, B. Bandl-Konrad, NH3–NO/NO2
chemistry over V-based catalysts and its role in the mechanism of the Fast SCR
reaction, Catal. Today 114 (2006) 3–12.
[18] M. Iwasaki, H. Shinjoh, A comparative study of ‘‘standard”, ‘‘fast” and ‘‘NO2”
SCR reactions over Fe/zeolite catalyst, Appl. Catal., A: Gen. 390 (2010) 71–77.
[19] F.D. Liu, H. He, C.B. Zhang, Z.C. Feng, L.R. Zheng, Y.N. Xie, T. D Hu, Selective
catalytic reduction of NO with NH3 over iron titanate catalyst: catalytic
performance and characterization, Appl. Catal., B: Environ. 96 (2010) 408–420.
[20] S.F. Zhong, Y.Y. Sun, H.C. Xin, C.P. Yang, L. Chen, X.B. Li, NO oxidation over Ni–
Co perovskite catalysts, Chem. Eng. J. 275 (2015) 351–356.
[21] Z.H. Wang, F.W. Lin, S.D. Jiang, K.Z. Qiu, M. Kuang, R. Whiddon, K.F. Cen, Ceria
substrate–oxide composites as catalyst for highly efficient catalytic oxidation
of NO by O2, Fuel 166 (2016) 352–360.
[22] D.H. Shang, Q. Zhong, W. Cai, High performance of NO oxidation over Ce–Co–Ti
catalyst: the interaction between Ce and Co, Appl. Surf. Sci. 325 (2015) 211–
216.
[23] D.H. Shang, Q. Zhong, W. Cai, Influence of the preparation method on the
catalytic activity of Co/Zr1
xCexO2 for NO oxidation, J. Mol. Catal. A: Chem. 399
(2015) 18–24.
[24] Z.B. Wu, B.Q. Jiang, Y. Liu, Effect of transition metals addition on the catalyst of
manganese/Titania for low-temperature selective catalytic reduction of nitric
oxide with ammonia, Appl. Catal., B: Environ. 79 (2008) 347–355.
[25] B.Q. Jiang, Z.G. Li, S.C. Lee, Mechanism study of the promotional effect of O2 on
low-temperature SCR reaction on Fe–Mn/TiO2 by DRIFT, Chem. Eng. J. 225
(2013) 52–58.
[26] X.Y. Jiang, G.H. Ding, L.P. Luo, Y.X. Chen, X.M. Zheng, Catalytic activities of CuO/
TiO2 and CuO-ZrO2/TiO2 in NO+ CO reaction, J. Mol. Catal. A: Chem. 218 (2004)
187–195.
[27] P.M. Sreekanth, P.G. Smirniotis, Selective reduction of NO with CO over Titania
supported transition metal oxide catalysts, Catal Lett 122 (2008) 37–42.
[28] H.Y. Zhu, Y. Wu, X. Zhao, H.Q. Wan, L.J. Yang, J.M. Hong, Q. Yu, L. Dong, Y. Chen,
C. Jian, J. Wei, P.H. Xu, Influence of impregnation times on the dispersion of
CuO on anatase, J. Mol. Catal. A: Chem. 243 (2006) 24–30.
[29] M.M. Yung, E.M. Holmgreen, U.S. Ozkan, Cobalt-based catalysts supported on
Titania and zirconia for the oxidation of nitric oxide to nitrogen dioxide, J.
Catal. 247 (2007) 356–367.
 L. Zhu et al. / Journal of Colloid and Interface Science 478 (2016) 11–21
[30] Y. Shu, H. Sun, X. Quan, S. Chen, Enhancement of catalytic activity over the
iron-modified Ce/TiO2 catalyst for selective catalytic reduction of NOx with
ammonia, J. Phys. Chem. C 116 (2012) 25319–25327.
[31] M.P. Ruggeri, I. Nova, E. Tronconi, J.A. Pihl, T.J. Toops, W.P. Partridge, In-situ
DRIFTS measurements for the mechanistic study of NO oxidation over a
commercial Cu-CHA catalyst, Appl. Catal., B: Environ. 166–167 (2015) 181–
192.
[32] Z.H. Lian, F.D. Liu, H. He, X.Y. Shi, J.S. Mo, Z.B. Wu, Manganese–niobium mixed
oxide catalyst for the selective catalytic reduction of NOx with NH3 at low
temperatures, Chem. Eng. J. 250 (2014) 390–398.
[33] B.X. Shen, X.P. Zhang, H.Q. Ma, Y. Yao, T. Liu, A comparative study of Mn/CeO2,
Mn/ZrO2 and Mn/Ce-ZrO2 for low temperature selective catalytic reduction of
21
NO with NH3 in the presence of SO2 and H2O, J. Environ. Sci. 25 (2013) 791–
800.
[34] T. Curtin, F. O’Regan, C. Deconinck, N. Knüttle, B.K. Hodnett, The catalytic
oxidation of ammonia: influence of water and sulfur on selectivity to nitrogen
over promoted copper oxide/alumina catalysts, Catal. Today 55 (2000) 189–
195.
[35] W.D. Mieher, W. Ho, Thermally activated oxidation of NH3 on Pt(1 1 1):
intermediate species and reaction mechanisms, Surf. Sci. 322 (1995) 151–167.
[36] A.P. Seitsonen, D. Crihan, M. Knapp, A. Resta, E. Lundgren, J.N. Andersen, H.
Over, Reaction mechanism of ammonia oxidation over RuO2(1 1 0): a
combined theory/experiment approach, Surf. Sci. 603 (2009) L113–L116.