Chemosphere 274 (2021) 129910

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Chemosphere
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Removal of dimethyl sulfide by post-plasma catalysis over CeO2-MnOx

catalysts and reaction mechanism analysis
Lu Hu a, c, Nan Jiang a, b, c, *, Bangfa Peng b, Zhengyan Liu a, c, Jie Li a, b, c, **, Yan Wu a, b, c
a
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian University of Technology, Dalian, 116024,
China
b
School of Electrical Engineering, Dalian University of Technology, Dalian, 116024, China
c
School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, China

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

Dimethyl sulfide (DMS) decomposi-

tion using a post-plasma catalysis
(PPC) is investigated.

The intermediates and degradation
mechanism of DMS in PPC system are
proposed.

The redox cycle of Mn3þþCe4þ 4
Mn4þþCe3þ on catalyst surface pro-
vide Oa constantly.

The activity decline of CeO2-MnOx
(1:1) catalyst is caused by a large
amount of Ce2(SO4)3.

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

Article history: The combination of a multistage rod plasma reactor and post CeO2-MnOx catalysts is studied to treat
Received 10 September 2020 dimethyl sulfide (DMS). The physicochemical properties of all catalysts and the effect of the catalytic
Received in revised form performance of CeO2-MnOx catalysts on DMS removal efficiency are studied. Placing CeO2-MnOx catalysts
11 January 2021
after the non-thermal plasma system can improve the capability of DMS degradation. The results exhibit
Accepted 5 February 2021
Available online 15 February 2021
that CeO2-MnOx (1:1) catalyst presents a higher catalytic activity than that of CeO2, MnOx, CeO2-MnOx
(1:0.5) and CeO2-MnOx (1:3). At the power of 21.7 W, the combination of dielectric barrier discharge and
Handling Editor: Chang- Ping Yu CeO2-MnOx (1:1) catalyst could improve the DMS removal efficiency and CO2 selectivity by 16.2% and
18.2%, respectively. This result maybe closely related with its specific surface area, redox properties and
Keywords: oxygen mobility. In addition, the degradation mechanism of DMS over CeO2-MnOx catalysts is proposed.
Post-plasma catalysis Finally, the stability of the CeO2-MnOx (1:1) catalyst is investigated, and the reason for the decreased
Dimethyl sulfide removal activity of the used catalyst is analyzed.
CeO2-MnOx catalysts © 2021 Elsevier Ltd. All rights reserved.
Volatile organic sulfur compounds (VOSCs)
Mixed oxides.

1. Introduction

Volatile organic sulfur compounds (VOSCs) are emitted from

* Corresponding author. Key Laboratory of Industrial Ecology and Environmental
Engineering (Ministry of Education, China), Dalian University of Technology, Dalian,
chemical plants, tanneries, sewage treatment plants and waste
116024, China. composting plants (Jo et al., 2011; Zhang et al., 2019a). Some VOSCs
** Corresponding author. School of Electrical Engineering, Dalian University of not only cause global warming, acid deposition and photochemical
Technology, Dalian, 116024, China. smog, but also stimulate to people’s olfactory organs, even make
E-mail addresses: jiangnan@dlut.edu.cn (N. Jiang), lijie@dlut.edu.cn (J. Li).

https://doi.org/10.1016/j.chemosphere.2021.129910
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
L. Hu, N. Jiang, B. Peng et al.
people feel restless and nausea (Jarrige and Vervisch, 2007; Chen
et al., 2012). In order to reduce the harm caused by VOSCs emis-
sion to human health and the environment, it is necessary to study
and develop a high-effective VOSCs abatement technique.
Recently, the methods to remove VOSCs include adsorption,
catalytic oxidation, membrane separation and plasma, etc. (Yan
et al., 2006; Xiao et al., 2014; Wang et al., 2020a). Wherein the
non-thermal plasma (NTP) technology has been inclusive
employed in pollutants removal (Peng et al., 2020) due to its mild
processing condition, short processing time and highly removal
efficiency (Liu et al., 2020a). Dielectric barrier discharge (DBD) is
regarded as a common method to create NTP (Ansari et al., 2020)
for its high plasma density and energy-saving (Guo et al., 2015).
However, DBD is restricted by the low mineralization rate of pol-
lutants, poor energy utilization efficiency, and large ozone pro-
duction (Van Durme et al., 2008; Yao et al., 2018). In recent years,
many researchers have combined DBD with post-catalyst to form a
post-plasma catalysis (PPC) system which contributes to the
improvement of energy yield, the reduction of by-products and the
improvement of oxidation (Quoc An et al., 2011; Li et al., 2014;
Sultana et al., 2019). In PPC, the long-lived species (ozone) gener-
ated by the discharge is decomposed into active oxygen. The high
reactive of active oxygen is beneficial to improve pollutants
removal efficiency and CO2 selectivity (Ruan et al., 2020).
In general, noble metal oxides are efficient catalysts for VOSCs
degradation. However, the disadvantage of these catalysts is obvi-
ously expensive and easy-poisoning tendency (Zhang et al., 2021).
Therefore, many other metal oxides (MnO2, CeO2, Co3O4, NiO, etc.)
have been investigated and used extensively. Among them, the rare
earth metal oxides especially CeO2 catalysts have high oxygen
storage capacity (Liu et al., 2020b; Jampaiah et al., 2019; Huang
et al., 2013) and oxygen transfer performance since the oxidation
reduction cycle (Ce4þ4Ce3þ) at low temperature (Long et al., 2019;
Zhang et al., 2020). Moreover, the reaction between Ce and SO2
generates stable CeSO4 and Ce2(SO4)3, which enhances the SO2
tolerance of composite catalysts (Wang et al., 2018). Wang et al.
reported that combined DBD with CeO2 rod to treat methanol can
make the methanol conversion and CO2 selectivity reach 94.1% and
90.1%, and can suppress ozone concentration (Wang et al., 2019).
Besides, incorporating CeO2 into the SAPO-34 framework can
improve the resistance of MneCe catalyst to SO2 and H2O at low
temperature NH3-SCR, because CeO2 has a certain inhibitory effect
on the sulfated manganese active sites on the surface of sample
(Fan et al., 2017). However, pure CeO2 has the disadvantage of
insufficient oxygen vacancies. One way to improve this deficiency is
to combine another metal oxide with CeO2 (Xiong et al., 2015).
MnOx has high oxygen mobility capacity owing to the existence of
various valence states (Mn2þ, Mn3þ, and Mn4þ) (Jampaiah et al.,
2015). MnOx has various crystal structure (a, b, g, d, etc.) with
different interconnection modes of MnO6 octahedra (Zhu et al.,
2017). Moreover, the weak interaction of MneO facilitates the
generation of oxygen vacancies, the decomposition of ozone and
the catalysis of DMS. The catalytic activity of the catalyst can be
improved when Mn ions are introduced into CeO2, which is prob-
ably related to the BET surface area and the interaction between
CeO2 and MnOx (Zhu et al., 2016; Wang et al., 2013). CeO2-MnOx
catalysts have a potential catalytic effect and higher activity than
single metal oxides, which is beneficial to ozone removal and
pollutant decomposition (Liu et al., 2013). Whereas, the suitable Ce/
Mn ratio of CeO2-MnOx mixed oxides for removing VOSCs in PPC
system is unclear, which need to study the relationship between
the removal efficiency of VOSCs and different CeO2-MnOx mixed
oxides. The most suitable ratio of catalysts can also be obtained by
studying the physicochemical properties of CeO2-MnOx samples.
Furthermore, the degradation mechanism of VOSCs helps to
2
Chemosphere 274 (2021) 129910
understand the interaction between ozone and catalysts, and
clarify the catalytic performance of catalysts in PPC system.
In this work, combination of a multistage rod DBD reactor and
CeO2-MnOx catalysts of different proportions constitutes a PPC
system for the degradation of a typical VOSCs with foul odor,
dimethyl sulfide (DMS). Here, the effects of different catalysts on
DMS conversion and energy yield are studied. The effect of Ce/Mn
proportions on physicochemical properties of CeO2-MnOx catalysts
are deeply investigated by various characterization techniques. At
the same time, the mechanism of catalytic degradation is inferred
from the intermediate products. In addition, the stability of the
CeO2-MnOx (1:1) catalyst has been investigated, and the deactiva-
tion mechanism of used catalyst has been analyzed.
2. Material and methods
The experimental flow chart of processing DMS in the PPC
system is shown in Fig. 1, which incorporates gas distribution, po-
wer supply, DBD reactor and measurement system. Gaseous DMS
with a certain concentration of 400 ppm is acquired by feeding a
nitrogen stream through DMS liquid with an ice bath. The total flow
for the experiments is fixed at 2 L min1. The gaseous DMS passes
through a multistage rod DBD reactor which is surrounded with
recycled water outside. The gas treated by NTP passes through a
tube filled with 3 g catalyst. And the preparation and specific
characterization methods of catalysts are shown in the Supple-
mentary Material S1. Finally, the exhaust gas is absorbed by NaOH
solution.
A multistage rod DBD reactor is used for DMS removal. The high-
voltage electrode is made of three copper-filled quartz tubes with
an inner diameter of 4 mm and an outer diameter of 6 mm. The
ground electrode is two fin rods composed of 17 fins. The thickness,
diameter, and spacing of a fin are 1, 10 and 2 mm, respectively. The
discharge space is designed for 1 mm. In this experiment, the fre-
quency of the AC power is controlled at 5 kHz. The specific mea-
surement methods and calculation formula are provided in the
Supplementary Material S2.
3. Results and discussion
3.1. Catalysts characterization
3.1.1. Structure and pore size of catalysts
Currently, XRD is a mature structural analysis test method. Fig. 2
presents the XRD patterns of different catalysts. And the calculated
average crystallite size is listed in Table S2. The diffraction peaks at
2q ¼ 39.167, 56.160 can be indexed as Mn2O3 (PDF#71-0636). The
strong diffraction at 2q ¼ 28.391, 33.130 , 47.390 , 56.610 corre-
sponds to the cubic fluorite type oxide structure (PDF#65-5923).
No obvious peaks of manganese oxide are obtained in spectrums of
CeO2-MnOx (1:0.5) and CeO2-MnOx (1:1), which is caused by the
uniform distribution of manganese oxides in the SEM results
(Supplementary Material S3) (Zhu et al., 2016). Another possible
reason is that Mn species with a lesser ion radius enters the CeO2
crystal lattice. (Guo et al., 2017). These results are also consistent
with the Raman in Supplementary Material S4. The diffraction
spectrum of CeO2-MnOx (1:3) shows that further increasing the
manganese content in CeO2 will form a large amount of Mn2O3 and
Mn3O4. Similar results are also reported by Arena et al. (2017) and
Wang et al. (2017). Besides, the average crystallite size is calculated
using Scherrer’s equation. The BET surface areas measured by N2
adsorption/desorption are listed in Table S2. It should be noted that
the average crystallite size of CeO2-MnOx mixed oxides decreases
slightly compared with that of pure CeO2 and MnOx. And the BET
surface area of CeO2-MnOx mixed oxides is larger than that of pure
L. Hu, N. Jiang, B. Peng et al.
Fig. 1. Schematic diagram of experimental setup.
Fig. 2. XRD patterns of different catalysts.
CeO2 and MnOx. These results demonstrate that the BET surface
area of catalysts is related to the crystallite size (Lin et al., 2018).
What can be found is that the CeO2-MnOx (1:1) catalyst has the
largest BET surface area among these samples, which facilitates the
generation of active sites (Zhu et al., 2016; Hao et al., 2019). Except
for CeO2-MnOx (1:1) catalyst, the BET surface area of CeO2-MnOx
(1:3) in the mixed catalysts is greater than CeO2-MnOx (1:0.5).
Since the active of catalysts is positively related to its BET surface
area, the performance of mixed oxides decreases in the order of
CeO2-MnOx (1:1) > CeO2-MnOx (1:3) > CeO2-MnOx (1:0.5).
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Chemosphere 274 (2021) 129910
Moreover, the crystallite sizes pore size of these catalysts
(3.353e12.639 nm) is larger than the size of DMS molecules
(0.438 nm), which facilitates the free migration of reaction mole-
cules to the inner surface of catalysts.
3.1.2. The surface properties of catalysts
The elemental composition and its state change on superficial
layer of prepared catalysts are further detected by XPS. Fig. 3 pre-
sents the peaks of Ce 3d, Mn 2p and O 1s in the XPS spectra of CeO2,
MnOx, CeO2-MnOx samples. For the Ce 3d spectra, eight peaks can
be fitted by deconvolution according to the literatures (Zhao et al.,
2019). Six peaks V0 (882.58 eV), V1 (889.24 eV), V2 (898.60 eV), V0ˈ
(901.16 eV), V1ˈ (907.63 eV) and V2ˈ (916.92 eV) refer to three pairs of
spin orbits of Ce4þ, while the other peaks U0 (884.32 eV) and U0ˈ
(902.89 eV) could be assigned to Ce3þ (Fig. 3a). The ratio of Ce3þ/
(Ce4þþ Ce3þ) is calculated according to their peak areas. As shown
in Table S3, it is found that the Ce3þ/(Ce4þþ Ce3þ) ratio of all cat-
alysts range from 12.32% to 15.96%. The concentration of Ce3þ in
CeO2-MnOx (1:1) is higher than that of CeO2-MnOx (1:0.5) and
CeO2-MnOx (1:3). This may be the result of the interaction between
CeO2 and MnOx, in which the Ce3þ from the reduction of Ce4þ is re-
oxidized to Ce4þ.
The band at 641.8 eV represents the initial electronic state of
Mn3þ. The peak at 642.5 eV binding energy is considered to be the
Mn4þ (Fig. 3b) (Long et al., 2019). H2-TPR analyses also indicate the
presence of two kinds of manganese oxide. Moreover, a band at
640.4 eV in the spectrum of CeO2-MnOx (1:3) is attributed to Mn2þ
(Wang et al., 2017). According to the result of XRD, the presence of
Mn2þ in the CeO2-MnOx (1:3) catalyst is also proved. Furthermore,
CeO2-MnOx (1:1) has the highest content of Mn4þ (45.90%), which
contributes to the degradation of DMS. Tang et al. also obtained the
similar conclusion that the modified MnOx-CeO2 catalyst with more
Mn4þ species has higher catalytic oxidation activity for HCHO (Tang
et al., 2006). In addition, it can be observed that the content of
Mn4þ increases with the decrease of Ce4þ, this indicates that there
L. Hu, N. Jiang, B. Peng et al.
Fig. 3. XPS spectra of prepared catalysts (a) Ce 3d; (b) Mn 2p; (c) O 1s.
is an electron transfer between Ce and Mn. Ce4þ captures electrons
released from the oxidation of Mn3þ to Mn4þ and can be reduced to
Ce3þ. Actually, Mn4þ is the activated state of Mn3þ after being
activated by Ce4þ (Leng et al., 2018). In short, it is suggested that the
higher content of Mn4þ, the faster oxidation reduction rate of
Mn3þ þ Ce4þ 4 Mn4þ þ Ce3þ in CeO2-MnOx catalysts (Zhao et al.,
2019).
The XPS of O 1s can be divided into a peak at 529.67 eV and a
peak at 531.69 eV (Fig. 3c). The peak at 529.67 eV is attributed to
lattice oxygen (Ob) and another peak is due to surface adsorbed

oxygen (Oa) such as O22 , O , a part of defect oxide or hydroxyl-like
groups, respectively (Li et al., 2011). The CeO2-MnOx (1:1) catalyst
has the largest Oa/(Oa þ Ob) ratio (42.65%), because the interaction
between Ce and Mn. The oxidation of Mn3þ to Mn4þ would be
realized via the oxygen species generated from the oxygen reser-
voir of CeO2 (Wang et al., 2020b; Tang et al., 2006). The resulting
Ce3þ will be re-oxidized to Ce4þ. There is enhanced oxygen mobility
and availability due to the combined action of Ce3þ and Mn4þ in
CeO2-MnOx (1:1), which promotes the oxidation reduction rate of
Mn3þ þ Ce4þ 4 Mn4þ þ Ce3þ and then promotes the removal of
DMS. Furthermore, Oa has more reactive than Ob because it has a
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Chemosphere 274 (2021) 129910
higher mobility, which would facilitate the degradation of VOSCs
(Leng et al., 2018).
The H2-TPR patterns is used to comprehend the relationship
between the redox property of CeO2, MnOx, CeO2-MnOx samples
and the catalytic performance. According to Fig. S1, a peak appears
at 302  C in the MnOx sample because hydrogen is consumed
during the conversion of MnO2/Mn2O3 to Mn3O4 (Mn4þ/Mn3þ).
The peak at 414  C indicates that Mn3O4 is reduced to MnO
(Mn3þ/Mn2þ) (Liu et al., 2013). The reduction peak of pure CeO2 at
482  C is attributed to easily reducible surface Ce4þ species. For
CeO2, an incomplete reduction peak is observed at higher tem-
perature, which implies the bulk reduction of CeO2. The reduction
temperature of the CeO2-MnOx catalysts is lower than that of pure
MnOx or pure CeO2. Because the manganese species enters the
cerium lattice to improve the redox ability at low temperature. The
XRD characterization results are consistent with this. And no
obvious reduction peaks correspond to CeO2 are observed in
cerium-manganese mixed catalysts, which indicates that the
reduction of Ce4þ occurs with the oxidation of Mn3þ (Zhang et al.,
2019b). The hydrogen consumption of CeO2-MnOx (1:0.5), CeO2-
MnOx (1:1) and CeO2-MnOx (1:3) catalyst are shown in Table S2. At
the data of hydrogen consumption, the CeO2-MnOx (1:1) consume
the most hydrogen gas (10.057 mmol/g) among CeO2-MnOx mixed
oxides indicating that CeO2-MnOx (1:1) possesses more oxygen
species, which is beneficial to DMS degradation.
3.2. Plasma-catalytic removal of DMS
Fig. 4 presents the removal efficiency, CO2 selectivity and energy
yield of DMS removal in PPC system over different catalysts under
the power from 3.0 W to 34.4 W. In NTP system, the removal effi-
ciency of DMS is varied from 28.3% to 74.3%, with the discharge
power ranging from 3.0 W to 34.4 W. The DMS removal efficiency
for the plasma combination with the various catalysts is 79.8%,
80.1%, 81.6%, 87.3% and 86.2% over MnOx, CeO2, CeO2-MnOx (1:0.5),
CeO2-MnOx (1:1), CeO2-MnOx (1:3), as the discharge power is
34.4 W. Compared with NTP, the CO2 selectivity is increased by
19.3% at 34.4 W after introduction of CeO2-MnOx (1:1). Fig. 4c
shows that the energy yield of DMS by plasma with catalysts is
higher than that of DMS by plasma alone under the same input
power, which can be attributed to the removal efficiency of DMS
increases after the addition of catalysts. The energy yield of the
plasma-catalysis system over CeO2-MnOx (1:1) catalyst is 17.7 g/
kWh at 3.0 W, which is higher than that of plasma alone (12.6 g/
kWh). The catalytic activity of CeO2-MnOx (1:1) is better than that
of other prepared catalysts. This result can be explained by the
measured datas of BET, XPS, and H2-TPR. The catalytic performance
is determined by many factors. The higher BET surface area facili-
tates the exposure of active sites (Zhu et al., 2017). And through the
analysis of H2-TPR, it has been acquired that the reductions of CeO2-
MnOx catalysts start at the lower temperature compared with pure
CeO2, which may improve the catalytic performance for DMS
oxidation. The high hydrogen consumption of the CeO2-MnOx (1:1)
catalyst may be caused by the more oxygen species of catalyst,
which is beneficial to the removal of DMS. Besides, the interplay
between Ce and Mn species makes Oa content of CeO2-MnOx (1:1)
catalyst higher than CeO2-MnOx (1:0.5) and CeO2-MnOx (1:3) cat-
alysts. Oa is beneficial to the degradation of DMS and intermediate
molecules because the higher mobility than Ob. In addition, Oa can
also replace oxygen vacancies created by electronic compensation,
thereby promoting the redox cycle of Ce and Mn. The redox cycle of
Mn3þ þ Ce4þ 4 Mn4þ þ Ce3þ reduces the energy required for
electron transfer of Ce and Mn, which is conducive to DMS degra-
dation and mineralization.
L. Hu, N. Jiang, B. Peng et al. Chemosphere 274 (2021) 129910

3.3. Reaction by-products identification and degradation

mechanism analysis

3.3.1. By-products
When an oxygen-containing gas is used as a carrier gas, the DBD
reactor will generate a lot of ozone (O3). The generation process of
O3 is shown in (Eqs. (1) and (2)) (Chang et al., 2018). The high-
energy electrons generated by the discharge collide with oxygen
molecules to form oxygen atoms. Oxygen molecules quickly
combine with oxygen atoms to generate O3. In the single NTP
system, the O3 concentration increase from 216.2 ppm at 3.0 W to
1147.6 ppm at 34.4 W (Fig. 5a). In the PPC system, O3 decomposition
is an important factor to promote the oxidation reduction cycle, and
the decomposition process is shown in Eqs (3)e(6). Ozone is
decomposed into atomic oxygen and oxygen molecules at the
active sites of catalysts (Hu et al., 2016). The removal efficiency of
DMS in plasma with catalysts is higher than that without catalysts,
which is related to the generation of atomic oxygen (Fig. 4a).
Compared with the single NTP system, O3 concentration reduces
after adding catalyst. As is shown in Fig. 5a, the O3 concentration
clearly decline to 7.34 ppm in PPC system with CeO2-MnOx (1:1)
catalyst during the power of 3.0 W. The O3 decomposition perfor-
mance is ranked as follows: CeO2-MnOx (1:1) > CeO2-MnOx
(1:3) > CeO2-MnOx (1:0.5) > MnOx > CeO2. It can be ascribed to the
BET surface area of catalysts and interaction of CeO2 and MnOx,
which facilitate the exchange of oxygen. BET results show the CeO2-
MnOx (1:1) catalyst has the highest BET surface area among the four
catalysts. XPS spectrum represents that the CeO2-MnOx (1:1)
catalyst has the higher Oa concentration than other CeO2-MnOx
catalysts. In the view of hydrogen consumption, the same conclu-
sion can be also obtained. The larger hydrogen consumption of
CeO2-MnOx (1:1) indicates that it possesses more oxygen species.

O2 þ e/2O þ e (1)

O þ O2 þ M/O3 þ M (2)

O3 þ */O* þ O2 (3)

O* þ O3 /O2 þ O2 * (4)

2O* / O2 * þ * (5)

O2 * / O2 þ * (6)

Where, * is the surface active site on the catalyst.

Fig. 5b compares the gaseous products for plasma and plasma-
catalytic over the CeO2-MnOx (1:1) catalyst at 7.2 W. There are
many gaseous products in the treatment of DMS with NTP. In
addition to CO2, CO, H2O, O3 and SO2, the N2O, NO2, HCOOH and
HCHO are also detected in gas products. N2O and NO2 in the figure
are the products of oxidation of nitrogen species. DMS react with
active species in the plasma zone is firstly oxidized to HCOOH,
HCHO and other organics, finally to CO, CO2, H2O and SO2. For
processing DMS, the types of gaseous products detected in the PPC
system is consistent with the plasma alone. The intensity of most
Fig. 4. Effect of input power on the plasma-catalytic removal of DMS over CeO2, MnOx,
gas products is decreased, such as O3, HCOOH and HCHO, while
CeO2-MnOx: (a) removal efficiency, (b) CO2 selectivity and (c) energy yield.
CO2, SO2 and CO increase. This may be caused by the reason that

5
L. Hu, N. Jiang, B. Peng et al.
Fig. 5. (a) O3 concentration in the NTP and post-NTP-catalytic system as a function of discharge power; (b) FTIR analysis of gaseous product formed in DMS degradation by plasma
and plasma-catalysis reactor with the discharge power of 7.2 W.
catalyst uses excess ozone to oxidize DMS and intermediates
(HCOOH, HCHO, etc.) to CO2, H2O, SO2 and CO.
In the PPC system, the degradation of DMS is divided into
plasma removal and catalytic treatment. In order to understand the
possible mechanism of DBD treatment and catalytic degradation of
DMS, byproducts at the outlet of the DBD reactor and the surface of
CeO2-MnOx (1:1) catalyst are identified by GC-MS, which are listed
in Table S4 and S5. And the mechanism of DMS degradation is
analyzed based on these byproducts.
3.3.2. Reaction mechanism
In the PPC system, the decomposition of DMS is divided into two
stages, among which the main degradation process of DMS is
through the NTP treatment. According to the analysis above, the
reaction mechanisms of plasma removal DMS is shown in Fig. 6a.
First, high-energy electrons generated by DBD bombard the back-
ground gas to produce active species such as
O,
OH, O3, and
P
N2(A3 þ u ), then active species break the CeH and CeS bonds with
bond energies of 4 eV and 3.3 eV to decompose DMS into CH3S
,

CH , CH SCH
and other groups. Some high-energy electrons with
3 3 2
its energy higher than the chemical bond energy can also directly
collide with DMS to produce a series of small molecule substances.
CH3S
, CH3SCH 2
can collide with oxygen-containing radicals such
as oxygen atoms to generate SO2 and
CH3. The intermediate
products of DMS degradation such as acetaldehyde, methyl alcohol,
acetone and ethanol are produced by the reaction of
CH3 with
O,


OH and other radicals. A small amount of dimethyl disulfide ap-
pears in the intermediate products, which is formed by the com-
bination of two CH3S
radicals. The addition reaction of
formaldehyde and ethanol produces diethoxy methane. One
molecule of acetaldehyde reacts with two molecules of ethanol to
form 1, 1-diethoxyethane. For 2, 2-diethoxy-propan, it may be
formed by the condensation reaction between ethanol and acetone.
Finally, these intermediates are decomposed into formic acid and
methanol, and then continue to be mineralized to produce COx and
H2O.
The second stage is the further degradation of DMS and in-
termediates that occurs on the surface of the catalyst. The possible
degradation pathways are displayed in Fig. 6b, the residual DMS
and some intermediate products (1, 1-diethoxyethane, ethyl ace-
tate, etc.) can react with active oxygen species to be oxidized to
unexpected sulfur-containing organic compounds (dimethyl sul-
fone, dimethyl sulfoxide, S-methyl methanethiosulphonate) and
carbon-containing organics (acetaldehyde, formic acid, etc.). They
6
Chemosphere 274 (2021) 129910
can further react on the catalyst surface to increase the degradation
rate and mineralization rate of DMS. The redox cycle of
Mn3þ þ Ce4þ 4 Mn4þ þ Ce3þ can accelerate the production and
migration of active oxygen species, which can promote DMS and
intermediates oxidation to form CO2, SO2 and H2O. In this part, the
active oxygen species play a major role, which mainly include O*
from ozone decomposition and Oa from oxygen vacancies (Jiang
et al., 2019). The long-lived ozone generated from the NTP stage
will be decomposed into O* which is more active than ozone after
entering the catalytic stage. The oxygen vacancies on the catalyst
surface are formed by the interaction of CeO2 and MnOx which can
be compensated by O*, so as to promote the oxidation reduction
reaction between Mn and Ce. The redox cycle of Mn3þ þ Ce4þ 4
Mn4þ þ Ce3þ on CeO2-MnOx (1:1) catalyst surface can continuously
supply Oa, which can promote DMS and intermediates oxidation to
form CO2, SO2 and H2O.
3.4. Stability and deactivation mechanism of CeO2-MnOx (1:1)
catalyst
The stability of the CeO2-MnOx (1:1) catalyst is tested by pro-
cessing the DMS with the concentration of 400 ppm for a long time
under 8 kV. According to Fig. 7a, the CeO2-MnOx (1:1) catalyst can
maintain the catalyst activity at ambient temperature for 400 min,
when it combines with NTP to process 400 ppm DMS. We can see
the removal efficiency of DMS decline slowly after 400 min, which
is a sign of decreased catalytic activity. The deactivation mechanism
of CeO2-MnOx (1:1) catalyst in PPC system for DMS removal should
be further investigated.
In order to investigate the chemical bonds in fresh and used
CeO2-MnOx (1:1) catalyst, the FTIR spectra of fresh and used CeO2-
MnOx (1:1) is analyzed. The FTIR spectra of the CeO2-MnOx (1:1)
catalyst before and after use are almost similar. The peak at
428 cm1 is the characteristic of CeeO bond of CeO2. The peaks at
513 and 606 cm1 represent MneO bond (Zhong et al., 2019). The
peaks at 1645 and 1382 cm1are corresponded to H2O (Wang et al.,
2020c). The peak at 1382 cm1 is assigned to Mn(NO3)2 (Shen et al.,
2013) which may be formed by the reaction of MnOx with NO2
generated by the plasma. The peak at 3411 cm1 indicates the
stretching mode of the HeO bond in H2O (Zhang et al., 2019a). This
is possible to be caused by the catalyst absorbing moisture in the air
during the PPC process. Compared with the fresh CeO2-MnOx (1:1)
catalyst, the used CeO2-MnOx (1:1) catalyst appears a different peak
at 1138 cm1 which could be assigned to SeO bond (Zhang et al.,
L. Hu, N. Jiang, B. Peng et al.
Fig. 6. (a) The possible degradation pathways of DMS by plasma; (b) The possible degradation pathways of DMS and intermediates on the surface of CeO2-MnOx (1:1) catalyst.
2017). This fact indicates that the poisoning reason of CeO2-MnOx
(1:1) catalyst is the deposition of sulfate or sulfite on the catalyst
surface, which prevents the generation of oxygen vacancies.
The formation of sulfate species is analyzed by TG-DSC curves of
fresh and used CeO2-MnOx (1:1) catalyst. According to Fig. 7c and d,
the weight loss peak below 200  C is corresponded to the loss of
adsorbed water molecules (Li et al., 2020). The weight loss peak
about 705  C in fresh CeO2-MnOx (1:1) catalyst is owing to the
transformation of MnO2 to Mn2O3 (Zhang et al., 2015). Notably, the
curve of used CeO2-MnOx (1:1) catalyst appears a strong peak at
780  C, it may be associated with the decomposition of sulfated
7
Chemosphere 274 (2021) 129910
CeO2 (Ce2(SO4)3 or Ce(SO4)2) (Zhang et al., 2016). The weight loss
peak at 630  C is owing to the loss of the MnSO4 (Zhang et al., 2015).
The deactivation of CeO2-MnOx (1:1) catalyst is due to the depo-
sition of manganese sulfate and cerium sulfate on its surface.
The XPS spectra of fresh and used CeO2-MnOx (1:1) catalyst are
shown in Fig. S2. The corresponding surface element composition
and valence analysis are shown in Table S6. Fig. S2a is the Ce 3d
spectrum, in which the valence states of Ce3þ and Ce4þ corre-
sponding to the eight characteristic peaks are consistent with those
introduced in section 3.1.2. Compared with fresh CeO2-MnOx (1:1)
catalyst, the Ce3þ ratio of used CeO2-MnOx (1:1) catalyst is
L. Hu, N. Jiang, B. Peng et al.
Fig. 7. (a) The stability of CeO2-MnOx (1:1) catalyst; (b) FTIR patterns of fresh and used CeO2-MnOx (1:1) catalyst; (c) TG-DSC curves of fresh CeO2-MnOx (1:1) catalyst; (d) TG-DSC
curves of used CeO2-MnOx (1:1) catalyst.
increased by 1.92%, indicating the presence of Ce2(SO4)3 (Zhang
et al., 2019a). The Ce2(SO4)3 is produced by the reaction of cerium
oxide and sulfur dioxide which is produced by the degradation of
DMS. The Mn 2p spectrum of fresh and used CeO2-MnOx (1:1)
catalyst is shown in Fig. S2b, Mn4þ ratio decreases after CeO2-MnOx
(1:1) catalyst used in PPC system, which proves that there is no
large amount of manganese sulfate after using this catalyst. This
phenomenon due to the fact that Ce has a stronger adsorption ca-
pacity for SO2 than Mn, which protects Mn from being sulfated
(Wang et al., 2018). This is also the reason why CeO2-MnOx catalysts
have higher catalytic active than pure MnOx catalyst. In contrast,
the ratio of Ob has increased from 57.52% to 58.77% after catalyst
used, which may be due to the formation of SO2 4 (Wang et al.,
2020c). Fig. S2d is the spectrum of S 2p. After using the catalyst
in the PPC system, the characteristic peaks of 167.0 eV and 168.8 eV
are appeared, which are ascribed to SO2 2
3 and SO4 , respectively
(Shen et al., 2015). Sulfate species is the main component of S
element which accounts for 77.03% by calculation. This indicates
that the main reason for CeO2-MnOx (1:1) catalyst deactivation is
the large amount of sulfate species on the surface. According to
Table.S5, the S content increase to 5.95% in used CeO2-MnOx (1:1)
catalyst. In summary, there may be a large amount of Ce2(SO4)3 on
the surface of used CeO2-MnOx (1:1) catalyst, which inhibits the
release of Oa.
4. Conclusions
The catalyst characterization shows that CeO2-MnOx mixed
oxides exhibit better catalytic activity than CeO2 or MnOx, while
CeO2-MnOx (1:1) has the highest catalytic performance in DMS
degradation and mineralization. There are probably related to
8
Chemosphere 274 (2021) 129910
larger BET surface area, better redox properties, and more superior
oxygen mobility due to the interaction between CeO2 and MnOx.
With the introduction of CeO2-MnOx (1:1) catalyst, the highest
DMS removal efficiency, CO2 selectivity and O3 decomposition
ability could be achieved. In PPC system, DMS conversion occurs in
the NTP stage and the catalytic stage. In NTP stage, the collision
between high-energy electrons, active species, free radicals and
excited species with DMS molecules can decompose them into
intermediates, and finally degrade them into CO2, SO2 and H2O. In
catalytic stage, the interaction of Ce and Mn accelerates the
oxidation reduction cycle and the production of Oa, which is helpful
for the further oxidation and decomposition of DMS and in-
termediates. Finally, it is analyzed that the decrease in performance
of CeO2-MnOx (1:1) catalyst is due to the deposition of a large
amount of Ce2(SO4)3 on the surface.
CRediT author statement
Lu Hu: Conceptualization; Investigation; Methodology; Writing
- original draft. Nan Jiang: Supervision; Writing - review & editing.
Bangfa Peng: Investigation; Writing - review & editing. Zhengyan
Liu: Investigation; Writing - review & editing. Jie Li: Supervision;
Writing - review & editing. Yan Wu: Supervision; Writing - review
& editing.
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.
L. Hu, N. Jiang, B. Peng et al.
Acknowledgements
We greatly appreciate financial support from National Natural
Science Foundation of China (Grant Nos. 51877028, 51877027),
Science and Technology Development Fund of Xinjiang Production
and Construction (2019BC009), Dalian High-level Talents Innova-
tion and Entrepreneurship Project (2018RQ28), and the Funda-
mental Research Funds for the Central Universities (DUT19JC20).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2021.129910.
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