Journal of the Energy Institute 112 (2024) 101458

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Journal of the Energy Institute

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The facilitating effect of sulfide treatment coupled sol-gel method on

NH3-SCR activity of Fe–Mn/TiO2 catalysts
Junqiang Xu a, Tao Zheng a, Xianlin Zou a, Hong Shen a, Fang Guo a, *, Qiang Zhang a,
Minghua Duan b
a
School of Chemistry & Chemical Engineering, Chongqing University of Technology, Chongqing, 400054, China
b
SPIC Yuanda Environmental Protection of Catalyst Co., Ltd, Chongqing, 401336, China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Paul Williams The 5Fe–3Mn–S/TiO2-SG catalysts were synthesized by sulfide treatment coupled sol-gel method to develop new
NH3-SCR catalysts with wide temperature window, good low-temperature activity and environment-friendly.
Keywords: The evolution of catalyst surface chemical state, morphology, structure, acidity and interaction forces were
NH3-SCR systematically investigated by XPS, BET, XRD, SEM, H2-TPR, NH3-TPD, UV, IR and steady-state kinetic tests. The
Fe–Mn/TiO2 catalyst
influence of sulfide treatment coupled sol-gel method on NO conversion was explored. XRD, BET and SEM
Sulfide treatment
characterization revealed that sulfide treatment resulted in smaller catalyst particles and higher dispersion,
DFT
which increased the specific surface area. XPS, NH3-TPD and steady-state kinetic tests results demonstrated that
the sulfide treatment catalysts had a higher surface adsorbed oxygen (Oα) content, which could produce more
oxygen vacancies on the catalyst surface, thus increasing the number of acid sites. H2-TPR and UV results
demonstrated that the 5Fe–3Mn–S/TiO2-SG catalysts exhibited the strongest contact between the carrier and the
active component. The 5Fe–3Mn–S/TiO2-SG catalyst obtained more than 80% NO conversion in the operational
temperature range of 220–420 ◦ C, according to the NH3-SCR reaction data. The temperature window was
expanded by 120 ◦ C compared to conventional Fe–Mn/TiO2 catalysts, and 98% conversion was achieved at
300 ◦ C. Meanwhile, DFT calculations of the SO2- 4 -MnFe2O4(311) crystalline surface of the 5Fe–3Mn–S/TiO2-SG
catalysts revealed that it could form stronger chemisorption for both NH3 and NO, which promoted the NH3-SCR
reaction more effectively. The DFT calculation results and the experimental findings agreed well.

1. Introduction environmental friendliness, Fe-based catalysts have received a lot of

NO is a significant class of atmospheric pollutants that have a
negative impact on human health, plant and animal growth, and cause
serious environmental issues like haze and photochemical smog [1,2].
One of the best solutions for reducing NO emissions is NH3-SCR, which
has been used extensively in industry. Currently, V2O5-WO3/TiO2 is the
main high-efficiency SCR catalyst on the market. It’s a pity, this catalytic
system does have significant drawbacks, though, including a very small
operating temperature range of 300–400 ◦ C, toxic and challenging va­
nadium material recovery, low N2 selectivity at high temperatures, and
astronomical cost of use [3]. Therefore, the development of green and
new NH3-SCR catalysts with wide temperature window and good low
temperature activity has received important attention in denitrification.
Due to their strong medium and high temperature activity and
attention. However, the narrow working temperature window and low
activity of single Fe-based catalysts cannot meet the requirements of
practical applications. Therefore, elemental doping and other methods
are usually used to improve the catalytic activity and N2 selectivity of
iron-based oxide catalysts. As an illustration, Sun et al. [4] enhanced the
surface acidity of Fe2O3 catalyst by Sm doping, which strengthened the
adsorption of NH3 while lowering the activation energy of NH3,
increasing denitrification efficiency by an 11 times factor. Chen et al. [5]
doped Ti4+ onto the octahedral active site of γ-Fe2O3, which reduced the
entropy of the crystal and thus improved the thermal stability. Current
literatures [6–8] about modified Fe-based catalysts have focused on
metal element doping. However, relatively few studies have been con­
ducted on the effect of sulfate on the SCR performance of denitrification
catalysts, and most of them focus on the introduction of sulfate to

* Corresponding author. School of Chemistry & Chemical Engineering, Chongqing University of Technology No.66 Hongguang Rd., Banan, Chongqing, 400054,
China.
E-mail address: guofang@cqut.edu.cn (F. Guo).

https://doi.org/10.1016/j.joei.2023.101458
Received 18 August 2023; Received in revised form 2 November 2023; Accepted 3 November 2023
Available online 10 November 2023
1743-9671/© 2023 Published by Elsevier Ltd on behalf of Energy Institute.
J. Xu et al.
enhance the sulfur resistance of the catalysts. Yu et al. [9] introduced
CuSO4 as a sulfur source to make the catalyst exhibit higher sulfur
resistance. Qi et al. [10] effectively enhanced the SO2 resistance by
ferrying an atomic layer deposition (ALD) film of Fe2O3 over the surface
of the catalyst, followed by sulfation. Wang et al. [11] Sulfate modifi­
cation could significantly broaden the SCR reaction temperature win­
dow while improving N2 selectivity.
According to the above reports, the modification of the surface
structure and NH3-SCR performance of Fe–Mn/TiO2 catalysts by sulfide
treatment is not clear. In this study, Fe–Mn–S/TiO2-SG catalysts were
synthesized by sulfide treatment coupled sol-gel method, and the XPS,
BET, XRD and H2-TPR techniques were used to thoroughly examine the
Fe–Mn–S/TiO2-SG catalysts. By combining the activity assessment of
NH3-SCR with density generalization theory (DFT) calculations, the
impact of sulfide treatment on the functionality of NH3-SCR was further
studied.
2. Experimental
2.1. Preparation of the catalyst
2.1.1. Impregnation process
By using the impregnation process, 5Fe–3Mn–S/TiO2 catalysts were
created. Deionized water was used to dissolve the appropriate amounts
of (NH4)2SO4 (99%, AR), Mn(NO3)2⋅4H2O (98%, AR), and Fe
(NO3)3⋅9H2O (98.5%, AR) at a molar ratio of S:Mn:Fe = 1:3:5. The
combined solution was then given 2.0 g of TiO2. After impregnation, the
solution was continuously magnetically stirred at 80 ◦ C for 4 h. The
samples were dried in a 110 ◦ C oven for 12 h, and then kept at 500 ◦ C
with a 5 ◦ C/min gradient for 5 h in an air-conditioned muffle furnace.
The same process was used to create catalysts with various sulfur con­
centrations, identified as 5Fe–3Mn-xS/TiO2, where x stands for the
molar proportion of sulfur to iron. For activity assessment, all catalysts
were crushed and sieved to a 20–40 mesh size. The catalyst without the
addition of (NH4)2SO4 was named as 5Fe–3Mn/TiO2.
2.1.2. Sol-gel process
By using the sol-gel process, the 5Fe–3Mn–S/TiO2-SG catalyst was
created. Firstly, 10 mL of C16H36O4Ti (98.5%, AR) was added to 10 mL
of anhydrous ethanol and dispersed to prepare A solution. Then,
appropriate amounts of (NH4)2SO4 (99%, AR), Mn(NO3)2⋅4H2O (98%,
AR), Fe(NO3)3⋅9H2O (98.5%, AR) were dissolved in a mixture of 5 mL of
anhydrous ethanol, 5 mL of acetic acid and 1 mL of water to prepare
solution B, where the molar ratio of S:Mn:Fe was 1:3:5. Drop by drop,
solution B was poured into solution A while being sufficiently stirred to
create a sol, and the gel was formed after aging for 3 h. The catalyst was
dried at 110 ◦ C for 12 h and calcined at 500 ◦ C for 5 h. The 5Fe–3Mn–S/
TiO2-SG catalyst was obtained.
2.2. Catalysts characterization
X-rays were obtained with Cu-Kα radiation on a Shimadzu (MPD)
instrument in Japan, and the diffraction pattern was measured at a scan
rate of 2o/min from 10o to 80o.
The pore structures of the catalysts were determined by a low tem­
perature liquid nitrogen adsorption and desorption apparatus (JW-
BK132, JWGB SCI. &TECH, China). Additionally, the samples’ specific
surface area and pore size were determined using the BET and BJH
methods, respectively.
The SEM images of all samples were acquired by field emission
scanning electron microscope ((JEOL 7800F, Japan).
Qualitative and semi-quantitative valence distribution of each
element on the catalyst surface by X-ray photoelectron spectroscopy (Al-
Kα radiation, hν = 1486.46 eV). Utilizing the C 1s peak’s (284.8 eV)
calibration of elemental binding energies in catalysts.
H2-programmed temperature reduction analysis was performed
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Journal of the Energy Institute 112 (2024) 101458
using a BSD-C200 automated chemisorption analyzer (BEISHIDE, Bei­
jing, China). A 60 mg sample was placed in a helium atmosphere with
300 ◦ C for 60 min, cooled and then passed through a H2/Ar mixture at
10 ◦ C/min to test the H2-TPR. NH3 programmed temperature desorption
analysis was performed using a BSD-C200 Automatic Chemisorption
Analyzer (BEISHIDE, Beijing, China) to measure the surface acidity and
ammonia adsorption capacity of the catalyst. The SCR catalyst (60 mg)
was incubated at 300 ◦ C for 60 min in a helium (He) atmosphere, cooled
to 50 ◦ C, and then maintained or 60 min with a 5% NH3/He mixture.
Finally, NH3-TPD was tested by heating the catalyst (10 ◦ C/min) from
50 ◦ C to 800 ◦ C in a helium (He) atmosphere.
The UV–vis of the catalyst was tested in a UV–Vis photometer (model
UV-27001) using BaSO4 as a reference sample. UV–visible spectral
conversion using Kubelka-Munk function. The functional groups of the
catalysts were detected by IRTracer-100 (Shimadzu, Japan) type FTIR
spectrometer for the region of 4000-400 cm− 1.
2.3. Experimental conditions
The NO conversion of the catalyst was measured by a flue gas
analyzer (Vario Plus, MRU GmbH, Germany). Firstly, 200 mg of catalyst
was compressed and crushed and sieved to 20–40 mesh. Then it was
installed in a fixed-bed reactor (XIANKE, Shandong, China) waiting for
testing, and the testing temperature range was 150oC–450 ◦ C. The re­
action gases composed of 400 ppm of NO, 400 ppm of NH3, and 3% of
O2, while an appropriate amount of AR was passed to maintain equi­
librium. The overall volumetric flow rate was 100 mL min− 1, or 30,000
h− 1 of GHSV. Equation (1) is used to determine the conversion rate of
NO.
[NO]in − [NO]out
NO conversion(%) = ×100% (1)
[NO]in
2.4. Kinetic studies
The following circumstances guided the steady-state kinetic studies:
400 ppm NH3 and NO, 3% O2, total gas flow rate of 50–200 mL/min,
using 200 mg 0.18–0.85 mm particle size, in denitrification reaction
efficiency of less than 20%, so it could be regarded as a differential
system. Therefore, the denitrification kinetics of Fe–Mn–S/TiO2 catalyst
could be studied under this reaction condition. Equation (2) was used to
determine the number of reaction stages, and the activation energy
required for the SCR denitrification reaction was calculated from
Arrhenius equation (3):
x
RNO = − kCNO y
CNH 3
COz 2 (2)
k = k0 e− Ea /(Rg T )
(3)
2.5. Computing techniques
The Material Studio 2019 software’s CASTEP module served as the
foundation for all DFT computations, a fundamental quantum me­
chanics program designed for use in solid materials science. PW91 under
the GGA was used in the calculation, using a 1 × 1 × 1 Gamma grid to
sample the Brillouin zone. The plane wave truncation energy is set to
500 eV, and the convergence criterion for the atomic forces was set to
0.05 eV/Å. In order to define the adsorption energy:
Eads = E(adsorbate + surface)-E(adsorbate)-E(surface)
where E(adsorbate + surface) stands for the total energy of reactants
adsorbed onto the model surface, and E(adsorbate) and E(surface)
denote the energy of reactants in the free state and the pure model
surface, respectively, where the larger negative value of Eads indicates
the stronger adsorption performance of the adsorbate.
J. Xu et al. Journal of the Energy Institute 112 (2024) 101458

Fig. 1. Catalytic performance of NH3-SCR with sulfide treatment catalysts: (a) (b) NO conversion, (c) Arrhenius plots for NO reduction.

Table 1
Structural parameters of the catalyst.
catalysts SBET Vp Dp TiO2 crystallite
(m2•g− 1)a (cm3•g− 1)b (nm)c size (nm)

5Fe–3Mn/TiO2 47.8 0.35 17.4 20.7

5Fe–3Mn–S/ 51.7 0.36 15.8 16.5
TiO2
5Fe–3Mn–S/ 52.5 0.38 18.2 16.2
TiO2-SG
a
BET surface areas.
b
BJH desorption pore volume.
c
Average Pore Size.

all catalysts above 300 ◦ C displayed an increasing trend, indicating that

Fig. 2. XRD patterns of the samples.
3. Results
3.1. NH3-SCR activity of the catalysts
Fig. 1(a) illustrates the NO conversions utilizing various catalysts as a
function of temperature at 150–450 ◦ C. With the increase of ammonium
sulfate((NH4)2SO4) content, the high-temperature catalytic activity of
the addition of ammonium sulfate has a positive contribution to the
reaction. When the ratio of sulfate content to active component content
was 0.25, 0.5, and 1, the catalysts showed a significant increase in high-
temperature catalytic activity above 300 ◦ C. However, the catalyst’s
denitrification activity below 300 ◦ C drastically diminished with the
addition of excessive ammonium sulfate. such as the ratio of 1.5, 2.5,
and 3.5, and the addition of too much surface ammonium sulfate sup­
pressed the catalyst’s low-temperature performance. The NO conversion
of Fe–Mn/TiO2 catalyst at 400 ◦ C was 21%, and when the ratio of
ammonium sulfate content was 1, the NO conversion increased to 84%,
while the low-temperature activity was basically maintained. Therefore,
comparing from the activity diagram, the best denitrification perfor­
mance of Fe–Mn/TiO2 catalyst was achieved when the ratio of ammo­
nium sulfate to active component was 1. The highest denitrification

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J. Xu et al.
Fig. 3. N2 adsorption-desorption isotherms of the samples.
activity of 97% was achieved at a reaction temperature of 300 ◦ C. More
than 80% conversion of NO was achieved in the temperature range of
220–420 ◦ C. After determining the optimal ammonium sulfate content,
the catalyst was optimized by the sol-gel method. As shown in Fig. 1(b),
the temperature window of 5Fe–3Mn–S/TiO2 catalyst T80 = 220–420 ◦ C
Fig. 4. SEM images of (a) (b) (c) 5Fe–3Mn/TiO2. (d) (e) (f) 5Fe–3Mn–S/TiO2. (g) (h) (i) 5Fe–3Mn–S/TiO2-SG at different magnifications.
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Journal of the Energy Institute 112 (2024) 101458
was widened by 30 ◦ C.
To clarify the differences in the intrinsic activity on Fe, Fe–Mn/TiO2
and Fe–Mn–S/TiO2 catalysts, the NH3-SCR kinetic experiments were
carried out in the dynamic zone (NO conversion below 20%) [12,13].
The final kinetic model Equation (4) was obtained after measuring three
feed gas reaction stages. The calculated results were presented in Fig. 1
(c). The comparison revealed that sulfide treatment slightly increased
the activation energy (Ea) of the catalyst and shifted the operating
temperature to the high temperature range. It indicated that the surface
acidity of the sulfide treatment catalyst increased significantly, which
would negatively affect the redox performance of the catalyst and
properly suppress the low temperature activity, which agreed with the
information from the activity diagram.
(4)
36435.32
rNO = − kCNO = 39340.11e− RT CNO0 (1 − X)
3.2. Catalyst crystallization, pore size and morphology
The XRD patterns of all samples were shown in Fig. 2. All the iden­
tified peaks were observed to be consistent with anatase TiO2 [14]. The
strong diffraction peaks of 5Fe–3Mn/TiO2 catalyst at 25.3◦ , 37.9◦ , 48.1◦ ,
54.0◦ , 55.1◦ , 62.7◦ , 68.9◦ and 75.2◦ attachments belonged to anatase
(101), (004), (200), (105), (211), (204), (116) and (215) diffractions,
respectively [JCPDS No. 21–1272]. The characteristic diffraction peaks
of rutile TiO2 appeared at 27.45◦ , 36.09◦ and 41.23◦ [JCPDS No.
21–1276] [15]. Faint MnFe2O4 crystalline form appeared at 34.88◦
J. Xu et al. Journal of the Energy Institute 112 (2024) 101458

Fig. 5. XPS spectra of (a) Ti 2p, (b) O 1s, (c)Fe 2p, (d) Mn 2p, (e) S 2p of the catalysts.

(311), 17.99◦ (111) [JCPDS No. 38–0430]. In contrast, the peak in­
tensity of the 5Fe–3Mn–S/TiO2 catalyst showed a significant decrease.
5Fe–3Mn–S/TiO2-SG catalysts were not observed in MnFe2O4 crystalline
form, while no more distinctive peaks were produced, indicating that
the sulfide treatment catalysts possessed better surface dispersion.
Related research has revealed that anatase TiO2 can greatly boost
catalytic performance at low temperatures and that rutile TiO2 only
contributes a modest percentage to the catalytic activity [16].
In addition, the Scherrer equation was used to calculate the crys­
tallites’ sizes, which relied on the characteristic peak at 25◦ for the (101)
reflection. Table 1 revealed that Sulfide treatment reduced the size of
anatase grains. This was because sulfide treatment damaged the lattice

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J. Xu et al. Journal of the Energy Institute 112 (2024) 101458

Table 2 Table 3
Summarize the atomic ratio (%) of each type in different samples. Acidity of the all catalysts determined by NH3-TPD.
Catalysts Oα/ Fe2+/(Fe3++ Mn4+/(Mn4++ Catalysts Surface acidity/μmol NH3 g−cat1
(Oα+Oβ) Fe2+) Mn2+)
Weak Medium strong and strong Total
5Fe–3Mn/TiO2 9.8 55.8 41.5
5Fe–3Mn/TiO2 33.6 80.5 114.1
5Fe–3Mn–S/TiO2 15.5 56.4 49.7
5Fe–3Mn–S/TiO2 39.4 191.8 231.2
5Fe–3Mn–S/TiO2- 20.7 59.6 52.3
5Fe–3Mn–S/TiO2-SG 43.9 131.7 175.6
SG

Ti 2p3/2 of the 5Fe–3Mn–S/TiO2-SG catalyst was slightly shifted toward

of TiO2 and prevented the formation of TiO2 particles. Numerous
research had demonstrated that the stronger the catalytic activity, the the lower binding energy, indicating that sulfide treatment and sol-gel
method optimization resulted in higher electron cloud density of the
better the active component dispersion, and the smaller the catalyst
grain size [17,18]. Therefore, the 5Fe–3Mn–S/TiO2-SG catalyst pre­ catalyst titanium species.
The catalyst’s O 1s energy spectrum was shown in Fig. 5(b). The
pared by sulfide treatment coupled sol-gel method possessed better
NH3-SCR activity. characteristic peak at 529.8 eV was attributed to Oβ, and the charac­
teristic peak at 531.3 eV was attributed to Oα [25]. It was observed that
The N2 adsorption/desorption isotherm of the catalyst was displayed
in Fig. 3. The essential parameters of the samples are listed in Table 1. the electron binding energy of O 1s in sulfide treatment catalysts shifted
to lower binding energy, indicated that sulfide treatment increased the
All three catalysts were discovered to contain type IV isotherms, a
characteristic mesoporous structure, with either H2-type or H1:H2-type electron cloud density of Oβ and Oα. Table 2 showed that the
Oα/(Oα+Oβ) ratio of the 5Fe–3Mn–S/TiO2-SG catalyst was 20.7, which
hysteresis loops, demonstrating that the catalysts possess a full TiO2
mesoporous structure [19,20]. Table 1 showed that the 5Fe–3Mn–­ was higher than the other samples. Studies demonstrated that Oα mi­
grates faster and possesses lower binding energy than Oβ, which could
S/TiO2-SG catalyst had a BET specific surface area of 52.5 m2 g− 1, a
desorption pore volume of 0.38 cm3 g− 1, and a pore width of 18.2 nm. In accelerate the redox reaction in SCR reaction [26], It is suggested that
both sulfide treatment and sol-gel optimization could promote the for­
general, the specific surface area of catalysts was related to the number
of active sites and the dispersion of components. The larger the specific mation of oxygen vacancies, which was a significant factor in the
surface area, the better the catalytic performance of catalyst NH3-SCR
[21,22]. The results of the BET and the activity test were in agreement.
The catalysts’ shape and particle size were assessed, and the findings
were depicted in Fig. 4. Both 5Fe–3Mn/TiO2 catalysts and sulfide
treatment catalysts were composed of irregular particle aggregates,
which contained massive pore structures. The surface morphology of the
5Fe–3Mn–S/TiO2 catalysts did not change significantly compared to the
5Fe–3Mn/TiO2 catalysts, which still showed crystalline particles. The
5Fe–3Mn–S/TiO2-SG catalysts showed significant morphological
changes, showing a larger pore structure on the scale of 1 μm and 500
nm. In Fig. 4(i), the 5Fe–3Mn–S/TiO2-SG catalyst had smaller crystallite
size and more compact position on the 100 nm scale, resulting in larger
pores.

3.3. Surface chemical states of the catalysts

As can be seen in Fig. 5, XPS was used to examine the surface

chemical states of all samples. Fig. 5 (a) showed the Ti 2p energy spectra
of the catalysts. All catalysts exhibited three characteristic peaks around
458.6 eV, 464.4 eV and 471.8 eV corresponding to Ti 2p3/2, Ti 2p1/2
and satellite peaks, which were attributed to the Ti4+ state [23,24]. The Fig. 7. UV–Vis diffuse reflectance spectra of catalysts.

Fig. 6. H2-TPR (a), NH3-TPD (b) diagrams of the samples.

6
J. Xu et al.
Fig. 8. FTIR spectra of industrial catalysts.
catalyst’s outstanding catalytic activity.
Fig. 5(c) showed the Fe 2p energy spectrum of the catalyst. The two
pairs of peaks were Fe3+ (about 712.9 eV and 726.3 eV) and Fe2+ (about
710.2 eV and 723.3 eV), respectively [27]. The ratio of
Fe2+/(Fe3++Fe2+) of the samples was calculated from the peak regions
and presented in Table 2. The results demonstrated that both sulfide
treatment and sol-gel method optimization promoted the formation of
Fe2+. It was shown that the intermediate valence of Fe2+ facilitated the
formation of unsaturated bonds and enhanced electron mobility, which
improved the NH3-SCR activity of the catalyst [27,28]. In summary, the
5Fe–3Mn–S/TiO2-SG catalyst revealed the best catalytic activity, and
the catalyst’s NH3-SCR performance were constant.
The XPS energy spectrum of Mn 2p was shown in Fig. 5(d). It could
be found that two valence states of Mn were present mainly in the
catalyst, located near 641.4 eV, 652.5 eV (Mn2+) and 643.9 eV, 652.2 eV
(Mn4+), respectively [29]. Based on the peak areas, a significant increase
in Mn4+ content was found for the sulfide treatment catalysts. The cat­
alyst’s redox capacity might be improved by more Mn4+, which would
increase conversion efficiency in the low temperature range [30], which
was evident from the NO conversion results.
Fig. 5(e) displayed the S 2p energy spectrum of the catalyst. In order
Fig. 9. Optimized geometric configuration of MnFe2O4.
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Journal of the Energy Institute 112 (2024) 101458
Table 4
Castep Optimize the pattern parameters of the geometric configuration.
Unit Cell symmetry group Lattice constant(Å) lattice angle(degree)
MnFe2O4 FD-3M a=8.16 α=90
b=8.16 β=90
c=8.16 γ=90
to identify the type of sulfur species present in the catalyst after sulfide
treatment, the chemical state of S was examined by XPS. The energy
spectrum peaked at 168.7 eV, with S6+ being responsible for 168.8 eV
[31]. Considering that the sulfate introduced during the preparation
process was thermally stable after calcination, the presence of sulfur
species in the catalyst was considered to be in the form of sulfate SO2− 4
[32], which agreed with the results of the FTIR analysis. The result was
an increase in the catalyst’s acidity, making NH3 easier to adsorb and
activate in the SCR reaction [31].
3.4. Surface acidity and redox properties of the catalysts
The redox properties of catalysts have important impact on the
denitrification reaction because it could act as a mediator of the reaction
[33]. Fig. 6(a) showed the H2-TPR curves of the three catalysts. The
reduction peaks of the 5Fe–3Mn/TiO2 catalysts at 310 ◦ C and 375 ◦ C
were attributed to the reduction of Fe2O3 to Fe3O4 [34], while the
hydrogen consumption peaks at 720–800 ◦ C were attributed to the
reduction of Ti4+→Ti3+ [35,36]. By comparison, it was not difficult to
find that the reduction peaks of the 5Fe–3Mn–S/TiO2 and 5Fe–3Mn–­
S/TiO2-SG catalysts were significantly enhanced compared to the con­
ventional 5Fe–3Mn/TiO2 catalysts, and the increase in the intensity of
the H2 depletion peak could be attributed to the increase in the number
of surface oxygen species due to the increase in the lattice structure
defects on the catalyst surface. These results indicated that sulfide
treatment had accelerated the transfer and transmission of electrons and
promoted the formation of activation molecules, thus reduced the acti­
vation energy of the reaction and accelerating it towards thermody­
namic equilibrium. There were strong reduction peaks at 424 ◦ C and
418 ◦ C, which were thought to be a superimposed reduction of sulfate
ions and Fe species [37–39]. Also the reduction peaks shift to higher
temperatures suggested that sulfide treatment enhanced the interaction
forces between the active ingredient and the carrier. In conclusion,
redox properties were the main influencing factor for SCR reactions at
low temperatures and one of the key reasons for the increased intensity
of the reduction peak of the catalyst due to sulfide treatment.
The surface acidity has a significant impact on the adsorption and
activation of NH3 on the catalyst [40]. Therefore, the NH3-TPD method
was used to investigate the surface acidity of the catalyst (Fig. 6(b)). Low
temperature NH3 desorption peaks belonging to weak acidic sites
desorption were observed for all samples at around 105 ◦ C due to the
breakage of weak hydrogen bonds between NH3 and acidic groups
adsorbed on the catalyst surface [41,42]. The high temperature NH3
desorption peaks at 250–500 ◦ C were attributed to medium to strong,
strong acid sites [43,44]. The platforms corresponding to the attachment
at 600 ◦ C could be labeled as Lewis acid sites [45–47]. Table 3 contains
the numbers of both acid sites determined from the NH3-TPD data,
which was evident that there were much more sulfide treatment cata­
lytic acid sites. It was determined that the weak acidic sites made it
Table 5
Adsorption energy of NH3 and NO at different crystal surfaces.
Crystal Surface Eads/eV
NH3 NO
MnFe2O4(111) − 0.06 − 0.70
MnFe2O4(311) − 0.73 − 2.37
SO2-
4 -MnFe2O4(311) − 1.76 − 3.86
J. Xu et al.
Fig. 10. The structure of NH3 and NO adsorption on Fe atom of MnFe2O4(311) (a) (b) and MnFe2O4 (111) (c) (d) surface.
Fig. 11. The structure of NH3 and NO adsorption on Fe atom of SO2-
4-
MnFe2O4(311) surface.
easier for NH3 to desorb at low temperatures [48]. The comparison in
the figure indicated that the desorption peak of the Lewis acid sites of the
5Fe–3Mn–S/TiO2-SG catalyst was significantly stronger than that of
5Fe–3Mn–S/TiO2. The homogeneous dispersion of active ingredients,
which is essential to the high temperature denitrification process, may
also be promoted by the strong acid site [49–51]. Therefore, these
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Journal of the Energy Institute 112 (2024) 101458
results could explain that the 5Fe–3Mn–S/TiO2-SG catalysts had
exhibited better high-temperature SCR activity.
3.5. Surface interactions
To elucidate the interaction between the S component and the
catalyst, the samples were examined using UV–Vis spectroscopy, and the
findings were shown in Fig. 7. The absorption edge of the unloaded
carrier TiO2 was located at 354 nm [52]. The TiO2 absorption edge of
5Fe–3Mn/TiO2 shifted to 396 nm. Compared with 5Fe–3Mn–S/TiO2
catalyst, the TiO2 absorption edge of the catalyst moved toward the
long-wave direction and the electron energy level on the catalyst surface
became higher. This indicated that electrons move more easily from the
valence band to the conduction band, thus forming electron-hole pairs,
which may account for the better low-temperature activity of the
5Fe–3Mn/TiO2 catalyst compared to the 5Fe–3Mn–S/TiO2 catalyst. It
had been demonstrated that the peaks between 300 and 400 nm were
oligomeric Fe oxide clusters, while the absorption edge of Fe2O3 parti­
cles was above 400 nm, showing that improving the preparation process
may also help the catalyst’s active ingredients be distributed more
evenly.
3.6. FTIR characterization
Infrared spectroscopy could effectively detect the formation of sul­
fides. Fig. 8 showed the IR spectra of each catalyst. The stretching and
bending vibrations of the surface-OH group were found at 3426 and
1627 cm− 1 [53], the Ti–O stretching vibration at 690 cm− 1, and the
bending vibration of the metal oxide (M − OH) hydroxyl group at 1127
cm− 1 [54]. The characteristic peaks appearing at 981 and 985 cm− 1 for
the sulfide treatment catalyst were correspond to SO2−4 [32], while the
5Fe–3Mn/TiO2 catalyst did not had a distinct characteristic absorption
J. Xu et al.
Fig. 12. Partial density of states on the surfaces of MnFe2O4(311) and SO2-
4 -MnFe2O4(311) for (a) N of NH3 molecule, (b) N of NO molecule, (c) Fe on surfaces, (d) N
and Fe when NH3 absorbed, (e)N and Fe when NO absorbed.
Fig. 13. Possible mechanism of NH3-SCR on 5Fe–3Mn–S/TiO2-SG.
peak here, indicating the introduction of SO2−
4 in the sulfide treatment
catalyst material.
3.7. DFT results
The original crystal model MnFe2O4 used in this study was obtained
from the CCDC database. The model was geometrically optimized using
CASTEP to completely relax all atomic and lattice parameters in the
model. Fig. 9 showed the optimized MnFe2O4 crystal model, and the
relevant lattice parameters were listed in Table 4. The crystal faces of
MnFe2O4(311) and MnFe2O4(111) were cut on the crystal model that
reached the steady state after optimization. In addition, a vacuum layer
of 15 Å was established to prevent the interaction forces between the
layers
Fig. 10 showed the structures of (a) (b) MnFe2O4(311) crystalline
surface and (c) (d) MnFe2O4(111) crystalline surface adsorbed with NH3
9
Journal of the Energy Institute 112 (2024) 101458
and NO. The adsorption energy Eads values for NH3 and NO on the
MnFe2O4(311) crystal surfaces were − 0.73ev and − 2.37eV, and on the
MnFe2O4(111) crystal surfaces were − 0.06eV and − 0.70eV as seen in
table 5. The Eads value of NO was smaller than the Eads value of NH3,
which showed that NO adsorption on the catalyst was significantly
stronger than NH3 adsorption. The Eads values of MnFe2O4(311) crystal
surfaces became smaller, which indicated that the adsorption capacity of
MnFe2O4(311) crystal surfaces was stronger and more favorable for the
adsorption behavior of SCR reaction to occur. Therefore, MnFe2O4(311)
crystal surfaces were used in the subsequent study.
The above characterization analysis revealed that the physico­
chemical properties of the sulfide treatment catalyst surface were
changed. Sulfur species in the form of SO2− 4 were produced, which
interacted electronically mainly with Fe and Mn in the catalyst. The
SO2-
4 -MnFe2O4(311) crystal model was developed as shown in Fig. 11.
The adsorption energy Eads values of NH3 and NO on the SO2- 4-
J. Xu et al.
MnFe2O4(311) crystal surface were − 1.76ev and − 3.86eV. Compared
with the MnFe2O4(311) crystalline surface, the adsorption energy Eads
value decreased. It indicated that sulfide treatment enhanced the
adsorption ability and surface acidity of NH3 and NO, and improved the
reaction rate, causing the catalyst’s operating temperature to rise into
the high temperature zone. Also, it agreed with the catalyst’s activity
data.
As a result of the introduction of PDOS, the orbital modifications and
variations of adsorbed molecules and active sites were further investi­
gated as shown in Fig. 12. It was discovered that both 2p and 2s orbitals
of N moved to the deep energy level after adsorption, reducing the
system energy. At the same time, the 3d orbitals of Fe and 2p of N
produce overlap, indicating that both NH3 and NO could be chemisorbed
on the MnFe2O4(311) crystal surface and SO2- 4 -MnFe2O4(311) crystal
surface. Only compared with the adsorption of NH3, the adsorption of
NO was more stable because the orbitals of 2p of N and 3d of Fe in NO
overlapped more and completely overlapped under the action of 1.8 eV,
and the p and d orbitals of N and Fe atoms were hybridized, which has
leaded to stronger electronic interactions.
By comparing the PDOS maps of the two models of MnFe2O4(311)
crystal surface and SO2- 4 -MnFe2O4(311) crystal surface, the peak split­
ting of the d-orbit PDOS of the Fe atoms near the Fermi energy level of
the SO2-4 -MnFe2O4(311) crystal surface was found. The electron inter­
action orbitals in the core of Fe atom were divided from two peaks to
three peaks. Furthermore, the peak positions were moved to higher
energy levels, resulting in enhanced acidity of the catalyst. The results
revealed that the Fe atoms on the crystalline surface of SO2- 4-
MnFe2O4(311) were more favorable for the adsorption of NH3 and NO,
which resulted in a better NH3-SCR activity of the catalyst.
Therefore, it could be determined from the above characterization
and DFT that the sulfide treatment improved the catalyst acidity,
causing the catalyst’s high temperature NH3-SCR activity to significantly
rise. Fig. 13 exhibits the probable SCR mechanism for this catalyst.
Firstly, the redox cycle (Fe3+ + Mn2+ ↔ Fe2+ + Mn4+) increased the
mobility of oxygen, thus generated more oxygen vacancies. The unsat­
urated coordination between Fe3+ and O2− resulted in the formation of
acid sites on Fe2O3, so that NH3 was adsorbed mainly on Fe2O3. How­
ever, Sulfide treatment led to the disruption of the unsaturated coordi­
nation sites on Fe2O3, new acid sites were created by SO2− 4 on the
surface, which pushed NH3 adsorption to SO2− 4 on the catalyst surface.
4. Conclusion
The 5Fe–3Mn–S/TiO2-SG catalysts prepared by sulfide treatment
coupled sol-gel method were characterized by wide temperature win­
dow, good low-temperature activity and environment-friendly. The
Fe–Mn/TiO2 catalysts’ NH3-SCR performance was improved, and the
active temperature window was expanded, thanks to the proper quantity
of sulfide treatment, but an excess of S may result in a rise in operating
temperature into the high temperature region. The catalysts had the best
NH3-SCR activity when the S:Fe molar ratio was 1:5. Compared with the
5Fe–3Mn/TiO2 catalyst, the 5Fe–3Mn–S/TiO2-SG catalyst was more
uniformly distributed and possessed a larger specific surface area, while
the interaction between the active component and the carrier in the
sample was stronger and was able to achieve 80% NO removal over a
wider temperature window (220–420 ◦ C) and 97% conversion at 300 ◦ C.
In addition, the results of steady-state kinetic tests revealed that sulfide
treatment slightly increased the activation energy (Ea) and shifted the
active temperature of the catalyst to a higher temperature, which
significantly increased the surface acidity of the catalyst and slightly
suppressed the low-temperature activity. The (311) crystal surface
adsorption of NH3 and NO on MnFe2O4 and SO2- 4 -MnFe2O4 was calcu­
lated by DFT, and the chemisorption of NO was found to be stronger. The
adsorption energies of NH3 and NO on the MnFe2O4(311) crystal surface
and SO2-4 -MnFe2O4(311) crystal surface were calculated by DFT, and it
was found that the chemisorption of NO was stronger. Meanwhile, PDOS
10
Journal of the Energy Institute 112 (2024) 101458
analysis demonstrated that SO2-
4 -MnFe2O4(311) crystal surface was more
favorable for the adsorption of NH3 and NO, yielding a catalyst with
good NH3-SCR activity.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors thank the National Natural Science Foundation of China
(No.21902017), Key project of science and technology research program
of Chongqing Education Commission of China (No KJZD-M202101101),
the Project of fundamental research and frontier exploration of
Chongqing (cstc2019jcyj-msxmX0052), Youth project of science and
technology research program of Chongqing Education Commission of
China (KJQN20211107), Foundation of technological innovation and
application development of Chongqing (cstc2021jscx-msxmX0308), and
Scientific Research Foundation of Chongqing University of Technology
(2020ZDZ022).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.joei.2023.101458.
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