Applied Surface Science 581 (2022) 152327

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Applied Surface Science

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Full Length Article

Mn doped CeO2-MoO3/γ-Al2O3 catalysts for the enhanced adsorption and

catalytic oxidation of Hg0 in oxygen atmosphere
Pengfei Cao a, b, Yan Zhang c, *, FengJuan Song b, c, Haitao Zhao d, e, Cheng Heng Pang b, e,
Tao Wu b, e, *
a
School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049, China
b
Key Laboratory of Carbonaceous Wastes Processing and Process Intensification of Zhejiang Province, University of Nottingham Ningbo China, Ningbo 315100, China
c
College of Safety and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266000, China
d
Materials Interfaces Center, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, Guangdong, China
e
Municipal Key Laboratory of Clean Energy Conversion Technologies, The University of Nottingham Ningbo China, Ningbo 315100, China

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

Keywords: A series of Mn-doped CeO2-MoO3/γ-Al2O3 catalysts were synthesized for the adsorption and catalytic oxidation
Elemental mercury of Hg0 from coal-fired flue gas using oxygen as the oxidizing agent. The results showed that the addition of Mn
Catalytic oxidation significantly promoted the adsorption and catalytic performances of CeO2-MoO3/γ-Al2O3 catalysts. The 6 wt%
Flue gas
Mn-doped catalysts exhibited the best Hg0 catalytic oxidation efficiency of 86%. The catalysts were characterized
Coal-fired power plant
Adsorption
to illustrate the structure-activity relationship of Mn-doped catalysts. It is found that the addition of Mn to the
CeO2 and MoO3 lattice increases the concentration of oxygen vacancies on the catalyst surface which promotes
the catalytic oxidation of mercury. HRTEM results indicate that the incorporation of Mn cracked CeO2 crystal
plane with an angle of 105◦ and may generate more active sites at the interface. Besides, the in-situ DRIFT
spectra show that the acidic sites on the Mn-doped catalyst surface were dominated by Brønsted acid sites at
lower temperatures which play an essential role in the adsorption of mercury. Overall, This research reveals the
effect of Mn additives on the promotion of adsorption capacity and catalytic oxidation efficiency of Hg0,
providing a promising approach to widen the effective temperature window of the catalyst.

1. Introduction
Elemental mercury (Hg0) is toxic and presents a persistent threat to
the ecosystem and human health [1,2]. The emission of elemental
mercury from coal combustion processes in coal-fired power plants has
gained increasing attention in recent years because it causes a series of
severe environmental issues, one of which is the biomagnification of Hg0
in aquatic food chains [3]. It was reported that coal-fired power plants
contributed to about one-third of anthropogenic mercury emissions
[4,5]. Therefore, the management of mercury emissions from coal-fired
flue gas is crucial in the control of anthropogenic mercury emissions.
Generally, elemental mercury in coal-fired flue gas is hard to be
captured by the existing air pollution control devices because it is vol­
atile and insoluble in water [5–8]. With more strict legislation on Hg0
emission [9,10], many strategies have been investigated for Hg0 cap­
ture, including adsorbent injection [11], catalytic oxidation [12], and
photochemical oxidation [13], etc. Catalytic-oxidation is one of the most
matured methods in the application of Hg0 removal and has been widely
adopted. In terms of this method, the metal oxide catalysts have recently
attracted more attention, and they are mainly divided into selective
catalytic reduction (SCR) catalysts and transition metal oxide catalysts
[14,15]. The traditional SCR catalysts can remove Hg0 and NOx simul­
taneously, but they faced the drawbacks of low mercury oxidation ef­
ficiency without HCl, and high-temperature deactivation [16,17]. The
Hg0 oxidation efficiency of traditional commercial SCR catalysts is only
65% [18]. In power plants, the concentration of HCl or Cl2 in real flue
gas is usually lower than the reaction needs [19]. On the contrary, the O2
content of coal-fired flue gas in power plants is about 5%, which is a
suitable and sufficient oxidant for Hg0 removal. It was reported that
transition metal oxide catalysts could use O2 as the oxidizing agent for
Hg0 removal [20]. Thus, the development of novel environmental-
friendly transition metal oxide catalysts with a wide temperature win­
dow is a promising approach to achieve cost-effective Hg0 removal using
oxygen in flue gas as the oxidizing agent.

* Corresponding authors.
E-mail addresses: tougaoktz@183.com (Y. Zhang), tao.wu@nottingham.edu.cn (T. Wu).

https://doi.org/10.1016/j.apsusc.2021.152327
Received 26 October 2021; Received in revised form 14 December 2021; Accepted 22 December 2021
Available online 27 December 2021
0169-4332/© 2022 Elsevier B.V. All rights reserved.
P. Cao et al.
Recently, various transition metal oxide catalysts such as V2O5[21],
MnOx [22], FeOx [23], CoOx [24], CeOx [25], and CuO [26] have been
widely studied for Hg0 adsorption and oxidation due to their low cost,
high catalytic oxidation reaction activity, and good thermal stability. In
our previous research, a high throughput screen of metal oxide catalysts
was performed by using a dynamic Hg0-TPSR [27]. Among these cata­
lysts, Mn-based catalysts after the modification of rare-earth metal ox­
ides have been tested, showed a better performance in Hg0 adsorption
[22,27,28]. CeO2 was found to have promotion effects on the perfor­
mance of Mn-based catalysts due to its high oxygen storage capacity and
redox activity [29–31]. In addition, the synergy between Mn and Ce may
accelerate the transfer of electrons and oxygen, thus, further increasing
the catalytic activity [16]. It was reported that the Mo additive had a
promotional effect on exposuring CeO2 (1 1 1) surface which boost the
catalytic oxidation of Hg0 [20,32]. Besides, molybdenum (Mo) doping as
a promoter can improve the catalyst’s crystal dispersion and catalytic
Hg0 removal performance [33]. However, no detailed studies were
carried out using MnOx-CeO2-MoO3 as catalysts to enhance the effi­
ciency of removing Hg0. Regarding the cost effective of the catalysts,
γ-Al2O3, which is usually used as a support for Hg0 removal [22,23], is
selected as the catalyst support in this work due to its outstanding me­
chanical properties, good thermal stability, and lower price [34–36].
Hereby, a series of MnOx-CeO2-MoO3/γ-Al2O3 catalysts with
different Mn-doped ratios were synthesized by the incipient wetness
impregnation (IWI) method for Hg0 removal. Comprehensive charac­
terization and performance testing were conducted to investigate the
effects of Mn addition on the adsorption and catalytic oxidation of Hg0.
Also, the structure–activity relationship between Mn-doped CeO2-
MoO3/γ-Al2O3 catalyst and Hg0 removal was elucidated.
2. Material and methods
2.1. Preparation of catalysts
Mn-doped CeO2-MoO3/γ-Al2O3 catalysts with different loading were
synthesized by a three-step IWI method using (NH4)6Mo7O24⋅4H2O, Ce
(NO3)3⋅6H2O, and Mn(NO3)2⋅4H2O (Sino-pharm Chemical Reagent Co,
Ltd) as the precursors. The (NH4)6Mo7O24⋅4H2O was dissolved in
Fig. 1. Schematic diagram of the experimental system.
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Applied Surface Science 581 (2022) 152327
deionized water and then impregnated on γ-Al2O3 support via IWI
method, the well-impregnated solid solution was then dried in an oven
operated at 120 ◦ C for 24 h and calcined in air at 520 ◦ C for 12 h. Ce
(NO3)3⋅6H2O and Mn(NO3)2⋅4H2O precursors were then impregnated
onto the support in the same way. As the loading of Ce and Mo is 2 wt%
and 8 wt%, CeO2-MoO3/γ-Al2O3 catalysts are assigned as 2Ce8Mo/
γ-Al2O3. In this research, the 2Ce8Mo/γ-Al2O3 catalysts with different
Mn weight ratios were prepared, named 2Ce8MoXMn/γ-Al2O3 (X =
0–8). The detailed procedure for sample preparation was described
elsewhere [37].
2.2. Hg0 removal experiments
As shown in the schematic diagram of the experimental system in
Fig. 1, the mercury capture performance of the catalyst was tested on the
designed experimental device. The Hg0 was supplied by a mercury
generator (Tekran 3310, USA), which could generate Hg0 in N2 at an
accurately controlled level. Hg0 (30 µg/m3) was mixed with O2 (5%)
balanced in N2. The catalyst was heated from 25 to 700 ◦ C at a heating
rate of 1oC/min for dynamic-state analysis. The concentration of the
total amount of mercury (HgT), Hg0, and Hg2+ (Hg2+ = [HgT] – [Hg0],
[38]) were recorded continuously by using the mercury analysis system
(Tekran 3300RS, USA). Therefore, the efficiency of Hg0 oxidized to Hg2+
for each prepared catalyst can be determined. The maximum instant
mercury removal efficiency (ΔXmax) and catalytic oxidation ratio could
be obtained by using the following formula:
[Hg0 ]in − [Hg0 ]out
ΔXmax = × 100% (1)
[Hg0 ]in
Hg2+
Catalytic Oxidation Ratio = × 100% (2)
[Hg0 ]in
2.3. Characterization of catalysts
The specific BET surface area, pore volume, and average pore size of
samples prepared were determined N2 adsorption-desorption at − 196 ◦ C
using Micromeritics ASAP 2020 [39]. Before the test, all samples were
degassed at 200 ◦ C for 6 h to remove moisture and adsorbed gases under
P. Cao et al.
a high vacuum. The Brunauer-Emmett-Teller (BET) method was
employed to calculate the surface area, and the pore size distribution
was estimated utilizing the Barret-Joyner-Halenda (BJH) with the
desorption branches. To determine the crystal phase structure of the
samples, X-Ray diffraction (XRD, Bruker D8 A25, Germany) with Cu Kα
radiation (λ = 1.5406 Å) was conducted at 2θ of 20–80◦ at the rate of
0.067◦ /sec [40]. Transmission electron microscope (TEM) and high-
resolution transmission electron microscopy (HRTEM) images were
captured using a JEM 2100 microscope operated at 200 Kv, the sample
was dispersed into ethanol assisted by ultra-sonication, and then drop­
ped on copper grid support and dried in air before analysis [37]. X-Ray
photoelectron spectroscopy (XPS) analysis was carried out using a
Kratos AXIS Ultra DLD spectrometer with a monochromatic Al Kα (hv =
1486.7 eV) radiation source under a vacuum pressure of 10− 7 Pa. The
surface charging was neutralized by using low-energy electrons and the
pass energy of the electron energy analyzer is 20 eV [41]. The binding
energy was calibrated with respect to the C 1s level 284.6 eV of
contaminated carbon. The CasaXPS solftware (Version 2.2.73) was used
for XPS peaks fitting. The samples were firstly dropped onto tin foil
paper with a smooth surface. After that, a copper sheet (around 1 × 1
cm2) with sticky carbon tape was pressed into powders on a foil paper,
which then was loaded into a sample chamber for the test. Raman
spectra were recorded by using a Raman Renishaw RM2000. A 514 nm
diode laser supplied the pump radiation to obtain the spectral range of
1000–2000 cm− 1, and the Raman emission was focused through a 50×
objective [9]. In-situ diffuse reflectance infrared Fourier transform
spectroscopy (In-situ DRIFTS) was employed to study the surface acidic
sites of the catalysts by using NH3 as the alkaline probe molecule [10].
The IR spectra were recorded on a Fourier transform infrared spec­
trometer (Bruker V70, USA) equipped with a Praying Mantis™ reaction
chamber (Harrick, USA). The catalyst was initially heated to 400 ◦ C in
N2 to remove impurities adsorbed by the materials. The background
spectrum was collected in N2 atmosphere (and subtracted from the
Fig. 2. Hg0 and HgT TPSR profiles of (a) 2Ce8MoXMn/γ-Al2O3 catalysts with different loading of Mn doping. HgT and Hg0 are represented by the line with a solid
symbol and a hollow symbol, respectively. (b) Hg2+ profiles of 2Ce8MoXMn/γ-Al2O3 catalysts.
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Applied Surface Science 581 (2022) 152327
catalyst spectra). The adsorption process was carried out until the
adsorption of NH3 reached a steady state, after which a desorption
process with N2 purging was conducted.
3. Results and discussion
3.1. Hg0 adsorption and catalytic oxidation
3.1.1. Qualitative analysis for Hg0 removal performance.
The Hg0 temperature-programmed surface reaction (Hg0-TPSR) was
used to qualitative and quantitatively analyze the mercury adsorption
efficiency and catalytic oxidation characteristics of 2Ce8Mo/γ-Al2O3
catalysts doped with different loading of Mn. The dynamic transient-
state results of Hg0 and Hg2+ are displayed in Fig. 2. Fig. 2(a) shows
the adsorption and oxidation profiles for HgT and Hg0 from 25 ◦ C to
700 ◦ C. Lines with solid and hollow symbols present HgT and Hg0,
respectively. It could be seen that HgT and Hg0 exhibit a similar
changing trend for all 2Ce8MoXMn/γ-Al2O3 catalysts. However, an
appreciable difference between the concentration of HgT and Hg0 was
observed when increasing the Mn loading. The catalyst doped with 6 wt
% of Mn exhibited the most significant distinction, but the difference
decreased as Mn loaded up to 8 wt%. The conversion profiles of Hg2+ are
presented in Fig. 2(b), which were calculated by the difference between
HgT and Hg0. The results reveal that 2Ce8Mo/γ-Al2O3 catalysts with 6
wt% Mn loadings are optimal, generating the highest volume of Hg2+ at
the low-temperature range.
The characteristic temperatures of Hg0 adsorption and desorption
processes were summarized in Table 1, including the initial adsorption
temperature (Ta0), the adsorption rate peak (Tra, peak), the best effective
adsorption range (Ta, region), and the initial desorption temperature (Td0).
As shown in Table 1, when Mn composition increased from 0 wt% to 8
wt%, Ta0 gradually decreased from 58.8 ◦ C to 27.8 ◦ C. The results
indicate that the addition of Mn contributed to lowering the Ta0. Also,
P. Cao et al. Applied Surface Science 581 (2022) 152327

Table 1
Characteristic temperatures of CeMo-catalyst promoted by Mn.
Sample Ta0 Tra,peak Ta,region Td0
(◦ C) (◦ C) (◦ C) (◦ C)
2Ce8Mo 58.8 104.3 342.2 479.4
2Ce8Mo2Mn 31.8 61.8 209.2 458.7
2Ce8Mo4Mn 29.2 52.6 203.1 452.7
2Ce8Mo6Mn 30.3 57.2 191 443.8
2Ce8Mo8Mn 27.8 60.1 183.6 432.8
Tra peak decreased with an increase of manganese composition. The
adsorption rate of 2Ce8Mo/γ-Al2O3 catalysts reached its maximum at
104.3 ◦ C. After adding Mn, the maximum rate of adsorption was at
60 ◦ C. This indicates that the addition of Mn could lower the tempera­
ture peaks of Ta0 and Tra. Thus, the addition of Mn leads to the
adsorption of catalysts starting at a lower temperature, which widens
the effective temperature range. The adsorption rate and optimal
effective adsorption range are criteria of the adsorption capacity of
catalysts. Although the adsorption rate peak was not spotted earliest for
the catalysts doped with 6 wt% of Mn, it can reach the maximum
instantaneous adsorption rate (in Fig. 2(a)).
Besides, the removal efficiency is the key parameter indicating its
effective adsorption range. It is defined to be the best effective adsorp­
tion range when the removal efficiency is over 80%. Both Hg0 adsorp­
tion and desorption for samples without doping manganese begin at
higher temperatures. The optimal effective adsorption range gradually
shifts toward lower temperatures as the manganese content increases.
The results show that the adsorption amount of 6 wt% manganese is the
largest and starts at a lower temperature, while the amount of Hg0
adsorption for 0 wt% manganese is the lowest. This suggests that the
incorporation of Mn broadens the effective temperature window for
adsorption and catalysis and moves to a lower temperature.
3.1.2. Quantitative analysis of Hg0 catalytic oxidation
The characteristic of mercury catalytic oxidation with respect to
catalysts were quantitatively analyzed according to The Hg0-TPSR re­
sults of the 2Ce8Mo/γ-Al2O3 catalysts promoted by various composi­
tions of Mn. The catalytic capacity study of these catalyst samples had
been implemented by integrating the TPSR results to compute the
amount of Hg2+. The result is shown in Table 2. The adsorption area (Sa)
and desorption area (Sd) were calculated by integrating results in Fig. 2
(a), representing the amount of Hg0 adsorbed and desorbed, respec­
tively. From Table 2, it is clear that the adsorption amount of Hg in
2Ce8Mo6Mn/γ-Al2O3 is more than twice that in 2Ce8Mo/γ-Al2O3. When
the experimental temperature increased to about 700 ◦ C, the residual
Hg0 in the samples was negligible because of its total desorption.
Therefore, the significant difference between Sa and Sd was considered
as Hg2+ formation by catalytic oxidation. Another alternative calcula­
tion of Hg2+ was to integrate the results from Fig. 2(b) directly. Two sets
of results have shown the same trend, where the sample with 6 wt% Mn
showed the best catalytic capacity, followed by the catalyst with 8 wt%
Mn. Sa and SHg2+ have significantly increased after the addition of Mn.
Furthermore, 2Ce8Mo6Mn/γ-Al2O3 catalysts show the highest effi­
ciency of Hg adsorption and catalytic oxidation. In particular, the cat­
alytic oxidation efficiency reached 86% when the Mn doping rate was 6
wt%. It shows that the addition of Mn improves the adsorption and
catalytic oxidation effect, which is probably related to the synergy be­
tween CeO2 and Mn additives.
Furthermore, a steady-state experiment over the 2Ce8Mo6Mn/
γ-Al2O3 catalyst was conducted to investigate the effect of the operating
temperatures on Hg0 total removal efficiency and the catalytic oxidation
efficiency, and the results are shown in Fig. 3. The operating tempera­
tures are within the range of 100–400 ◦ C that is below the initial Hg0
desorption temperature. The total removal efficiency of Hg0 was higher
than 80% at the temperature range of 150–350 ◦ C, with the highest
efficiency of 93% at 225 ◦ C. Regarding the catalytic oxidation efficiency
of Hg0, it is lower than 34% at temperatures below 225 ◦ C. However, it is
significantly improved above 80% between 250 and 350 ◦ C. Both Hg0
adsorption and catalytic oxidation contribute to the total removal effi­
ciency of Hg0. On the contrary, the capacity of Hg0 adsorption increases
with the temperature rise to 225 ◦ C, and then it decreases at a higher
temperature. A possible explanation is that surface active acidic sites are
not stable at higher temperatures, which is further confirmed by the in
situ DRIFTS characterization. It can be concluded that Hg0 adsorption
prefers at a lower temperature, while catalytic Hg0 oxidation always
occurs at a higher temperature. The results show a good agreement with
the observation from the dynamic-state analysis.
3.2. Structure characterization
3.2.1. XRD crystallographic analysis
As shown in Fig. 4(a), the XRD patterns of 2Ce8Mo/γ-Al2O3 catalyst
with different Mn doping were investigated to understand each cata­
lyst’s crystallization and monolayer coverage. The XRD spectra indicate
that two main components in the sample are assigned as γ-Al2O3 and
CeO2. For all the samples, no peaks of Mn and Mo were observed,
implying their good dispersion in γ-Al2O3 or their existence in the
amorphous or low crystalline state. The diffraction peaks at 37◦ , 46◦ ,
and 67◦ are correspond to the phase of γ-Al2O3. As the amount of Mn
increases, the peak of γ-Al2O3 gradually decreases. It could be attributed
to the strong interaction between the support and the active metal oxide.
Ce peaks were detected at 28.6◦ , 47.5◦ , and 56.3◦ , corresponding to
(1 1 1), (2 0 0), and (3 1 1) planes of CeO2 (JCPDS No. 34-0394), respec­
tively. It is found that the diffraction peak of CeO2 gradually decreases
and shifts to a higher Bragg angle when increases the manganese
loading. Due to the interaction between the two metal oxides, the
incorporated Mnx+ cations into the CeO2 lattice leads to a decrease in

Table 2
Characteristic areas of CeMo-catalyst promoted by Mn.
Sample Sa Sd Sa-Sd SHg2+
(min μg/m3) (min μg/m3) (min μg/m3) (min μg/m3)

2Ce8Mo 1748.9 318.9 1430.7 1424.6

2Ce8Mo2Mn 2807.6 375.79 2431.9 2424.5
2Ce8Mo4Mn 3030.8 590.6 2440.3 2436.2
2Ce8Mo6Mn 3898.6 514.9 3383.6 3374.8
Fig. 3. Steady-state analysis of total removal efficiency and catalytic oxidation
2Ce8Mo8Mn 3642.9 574.8 3068.1 3067.0
efficiency of Hg0 on the 2Ce8Mo6Mn/γ-Al2O3 catalyst.

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P. Cao et al. Applied Surface Science 581 (2022) 152327

Fig. 4. (a) XRD patterns of 2Ce8MoXMn/γ-Al2O3 catalysts with ranges of Mn loadings. (b) XRD semi-quantitative analysis of 2Ce8Mo/γ-Al2O3 and 2Ce8MoXMn/
γ-Al2O3 and catalysts.

lattice parameters [42]. Additionally, the synergistic effect between Mn

Table 3
and Mo increases the diffusion effect, resulting in higher single layer
The surface properties of Ce-Mo catalysts with different ratios of Mn.
coverage [38]. Fig. 4(b) shows the semi-quantitative analysis of CeO2
(1 1 1) crystallites modified by different Mn loadings. As we can see that Catalysts Surface area(m2/ Total pore volume Average pore width
g) (cm3/g) (Å)
the peak intensity of CeO2 gradually decreases with the introduction of
MnOx. This indicates that the doping of MnOx reduces the crystallinity of γ-Al2O3 242.2 0.48 79.7
2Ce8Mo 173.6 0.43 100.1
CeO2 but improves its dispersibility.
2Ce8Mo2Mn 180.9 0.42 93.8
2Ce8Mo4Mn 178.3 0.42 94.2
3.2.2. BET surface area and pore structure 2Ce8Mo6Mn 165.2 0.39 94.7
The effect of modified Mo-based catalysts with different Mn ratios on 2Ce8Mo8Mn 162.2 0.39 95.8
the surface area, pore volumes, and pore width of catalysts was further
evaluated. The results for the 2Ce8Mo/γ-Al2O3 and 2Ce8MoXMn/
γ-Al2O3 catalysts are displayed in Table 3. Obviously, pure γ-Al2O3 has

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the largest specific surface area and pore volume. As shown in Table 3, a
slight rise was found when 2 wt% Mn was added to the 2Ce8Mo/γ-Al2O3
catalysts. However, when the loading of Mn was further increased, the
surface area of BET began to decrease gradually. This may be due to the
phase separation of massive MnOx when more Mn was doped into CeO2
[43]. A similar trend was observed on the specific surface area and pore
volume of the sample prepared by the impregnation process. This phe­
nomenon is mainly because the metal oxide is impregnated onto the
γ-Al2O3 surface and blocks its pores resulting in a decrease in surface
area and total pore volume. Moreover, the average pore width shifted to
slightly higher values indicating that the small pores are filled. Also, this
phenomenon demonstrates that the growth and agglomeration of
nanoparticles lead to the formation of a crystal with a high loading of
manganese. Moreover, the specific surface area of the crystalline
structure is usually smaller than that of the amorphous structure.
Although the BET of the sample decreased with the addition of man­
ganese, the activity of the catalyst increased. It suggests that surface area
is not a key factor affecting mercury catalysis.

3.2.3. XPS valence states analysis

The elemental valence state of the surface of the 2Ce8Mo6Mn/
γ-Al2O3 catalyst was verified by XPS spectral analysis. Fig. 5 shows the
distracted XPS spectra of Ce 3d, Mn 2p, and Mo 3d. The XPS map of the
tested and fitted Ce 3d is displayed in Fig. 5(a). Two sets of spin–orbit
multiples u(u-u′′′ ) and v(v-v′′′ ) are observed corresponding to Ce 3d3/2
and Ce 3d5/2, respectively. Among them, u’ and v’ peaks were attributed
to Ce3+, while the remaining six peaks refer to Ce4+. It is obvious that the
proportion of Ce3+ in the catalyst with added Mn is significantly
enhanced. As a result, the redox performance of catalysts is enhanced as
the ratio of Ce3+ is proportional to oxygen vacancy [42]. It indicated
that Mnx+ had been incorporated into the CeO2 lattice resulting in a
change in the Ce3+ ratio. This is consistent with the XRD results. Ce3+
could create an unbalanced charge, vacancy, and unsaturated chemical
bond on the catalyst surface, which is conducive to the attachment of
chemical adsorption oxygen on the catalyst surface. Thus, the redox
conversion between Ce3+ and Ce4+ could improve the removal rate of
mercury [44].
Fig. 5(b) shows the XPS spectrum of the Mn 2p. The two prominent
peaks’ positions were approximately 654 eV and 643 eV, corresponding
to Mn2p1/2 and Mn2p3/2, respectively. As shown in Fig. 5(b), both Mn
2p1/2 and 2p3/2 spectra could be divided into two sub-peaks. The peaks
of 641.5 eV and 653.1 eV are attributed to Mn3+, the peaks of 642.7 eV
and 654.1 eV are assigned to Mn4+. The fitted results show that the
valence state of manganese in catalyst 2Ce8Mo6Mn/γ-Al2O3 is mainly
Mn4+. Previous studies [16] reported that Mn4+ promotes the adsorp­
tion and oxidation of Hg0 as it adsorbs electrons in the oxygen vacancy
to form Mn3+. Fig. 5(c) also shows the two prominent Mo peaks corre­
sponding to the photoelectron lines of Mo3d3/2 and 3d5/2. For the
catalyst 2Ce8M/γ-Al2O3, peaks centred on 235.6 eV and 232.5 eV [45]
refer to Mo6+. The peaks of 236.1 eV [46] and 233.1 eV [47] for catalyst
2Ce8Mo6Mn/γ-Al2O3 are attributed to Mo6+ as well. All peaks attrib­
Fig. 5. The XPS spectra of (a) Ce3d, (b) Mn2p and (c) Mo3d of 2Ce8Mo/
uted to Mo6+ indicate that the high oxygen concentration on the catalyst
γ-Al2O3 and 2Ce8Mo6Mn/γ-Al2O3 catalysts.
surface may be beneficial to the oxidation of mercury. In Fig. 5(c), after
the addition of Mn, there is a shift for Mo6+ peaks of the photoelectron
lines of Mo3d3/2 and 3d5/2 toward higher binding energy. It can be nanoparticles are observed, which formed layer structure (in Fig. 6(b)).
explained that Mn doped into the lattice of MoO3 resulting in the for­ The HRTEM images of Fig. 6(c) clearly show a well-crystallized (1 1 1)
mation of Mn-Mo-O [48,49]. Meanwhile, the lattice distortion induces lattice plane with a lattice spacing of 0.31 nm, demonstrating that the
the oxygen vacancies [50,51], which enhances the catalytic oxidation of crystal structure of CeO2 is fluorite-type in the samples [42]. The results
Hg0 [52]. are consistent with our previous research [46]. After the incorporation
of MnOx, the lattice spacing of (1 1 1) plane in Fig. 6(d) slightly reduced
3.2.4. TEM and high-resolution TEM (HRTEM) morphology study from 0.31 nm to 0.30 nm. This indicates that Mnx+ cations with a smaller
To investigate the morphology and structural characteristics of the ion radius have been incorporated into the cerium lattice to cause lattice
catalyst, 2Ce8Mo/γ-Al2O3 and 2Ce8Mo6Mn/γ-Al2O3 catalysts were distortion. No molybdenum oxides with a clear lattice spacing were
characterized by TEM and HRTEM. Without Mn additives, the 2Ce8Mo/ found in the HRTEM image, it might be because MoO3 exists mainly in
γ-Al2O3 catalyst is consists of nanoparticles that formed a porous an amorphous structure. Furthermore, compared with the complete
structure (in Fig. 6(a)). While for Mn-doped catalyst, flakes instead of CeO2 crystal plane in Fig. 4(c) and (d) CeO2 crystal plane has cracked,

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P. Cao et al. Applied Surface Science 581 (2022) 152327

Fig. 6. TEM image of (a) 2Ce8Mo/γ-Al2O3 catalyst, (b) 2Ce8Mo6Mn/γ-Al2O3 catalyst; HRTEM image of (c) 2Ce8Mo/γ-Al2O3 and (d) 2Ce8Mo6Mn/γ-Al2O3; top view
of structural configuration of the CeO2 (1 1 1) surface of (e) 2Ce8Mo/γ-Al2O3 and (f) 2Ce8Mo6Mn/γ-Al2O3.

which may generate more active sites at the interface to improve the
catalytic oxidation effect of Hg0 [53]. Fig. 6(e) and (f) are simulated
microstructures diagrams of the (1 1 1) plane of Ce. It gives evidence that
the cracking angle of CeO2 crystal planes of 2Ce8Mo6Mn/γ-Al2O3 is
105◦ .

3.3. Raman spectroscopy surface study

Raman spectrum is an effective way to examine the variations in

vibrational and rotational modes associated with 2Ce8Mo/γ-Al2O3 and
2Ce8Mo6Mn/γ-Al2O3 catalyst, of which the results presented in Fig. 7.
When there is no MnOx is incorporated, the Raman spectrum of the
2Ce8Mo/γ-Al2O3 catalyst displays a weak peak and a strong peak at
positions of about 300 cm− 1 and 950 cm− 1, respectively. Both peaks
refer to MoO3, which corresponds to the stretching vibration of the
Mo–– O bond. When doped 6 wt% of MnOx on the catalysts, the peak
intensity of MoO3 decreased significantly, but a new peak appeared
around 600 cm− 1 attributed to MnOx [38]. Additionally, two peaks Fig. 7. The Raman spectra of 2Ce8Mo/γ-Al2O3 and 2Ce8Mo6Mn/
located at 920 cm− 1 and 990 cm− 1 were detected, indicating that the Mn γ-Al2O3 catalysts.
cations dope into the lattice of MoO3 to form Mo-Mn-O solid solution
scattered on the alumina carrier [42]. This result shows an agreement

7
P. Cao et al. Applied Surface Science 581 (2022) 152327

with XPS results. The incorporation of Mnx+ in MoO3 lattice leads to the
formation of oxygen vacancy, promoting the catalytic oxidation of Hg0.
Even though the peaks corresponding to manganese and molybdenum
are weak and not apparent in XRD patterns, they are detected by Raman
spectrum analysis. It suggests that MnOx and MoO3 components are well
dispersed on the surface of the catalyst. There are also no CeO2 and
Al2O3 peaks detected here which is consistent with XRD results.

3.4. In situ DRIFT characterization of surface acid sites

The properties of the surface acidic sites on the catalysts were

analyzed by in situ DRIFT analysis using NH3 as a molecular probe.
Previous literature has shown that the removal efficiency of Hg0 posi­
tively correlated with the number of Brønsted acid sites on the catalyst
surface [37,54]. To further understand the effect of acidic sites on Hg0
adsorption and catalytic oxidation, the in-situ NH3-DRIFT on
2Ce8Mo6Mn/γ-Al2O3 catalyst was performed at different temperatures.
As shown in Fig. 8 (a), the peaks located around 1680 and 1460 cm− 1
were attributed to the coordinated NH4+ on the Brønsted acid sites,
while the peaks at 1600 and 1230 cm− 1 were attributed to the adsorp­
tion of NH3 on the Lewis acid sites. As the temperature increase, the
amount of both Brønsted acid and Lewis acid sites perform an apparent
decrease, but the decline rate of Brønsted acid is more significant. It
reveals that Brønsted acid sites are not thermal stability at high tem­
peratures. Hg0-TPSR results show that Hg0 adsorption mainly occurs at
temperatures below 200℃, and catalytic oxidation starts at higher
temperatures. Moreover, the capacity of Hg0 adsorption decreases when
increases the temperatures, which performs a similar trend to the in-situ
NH3-DRIFT results. This result indicates that Brønsted acid on the
catalyst surface significantly affects Hg0 adsorption other than catalytic
oxidation. More Brønsted acid on the catalyst surface, higher capacity of
Hg0 adsorption. Fig. 8(b) presents a semi-quantitative analysis of
Brønsted acid and Lewis acid, including the integrated area of Fig. 8(a)
and the ratio of Brønsted acid and Lewis acid (B/L). The Brønsted acid Fig. 8. In suit DRIFT study of surface acid sites of 2Ce8Mo6Mn/
accounts for a large proportion at temperatures below 200 ◦ C, the value γ-Al2O3 catalysts.
of B/L gradually decreases with the temperature rising. It confirms that
Hg0 adsorption is positively correlated with the amount of Brønsted acid CRediT authorship contribution statement
sites more than Lewis acid sites on the catalyst surface. Additionally, Mn
additives increase the amount of Brønsted acid, which lowers the tem­ Pengfei Cao: Conceptualization, Methodology, Software, Formal
perature of Hg0 absorption during the Hg0-TPSR analysis. analysis, Investigation, Data curation, Writing – original draft. Yan
Zhang: Data curation, Validation, Writing – review & editing. Feng­
4. Conclusions Juan Song: Methodology, Investigation, Data curation. Haitao Zhao:
Data curation, Validation, Writing – review & editing. Cheng Heng
The 2Ce8MoXMn/γ-Al2O3 catalysts exhibited an excellent capacity Pang: Validation, Writing – review & editing. Wu Tao: Supervision,
for Hg0 removal at lower temperatures under O2 atmosphere. Among Resources, Writing – review & editing, Project administration.
them, 2Ce8Mo6Mn/γ-Al2O3 was found as the most efficient one (around
86% Hg0 oxidation efficiency under 5% O2). Mn incorporated catalysts Declaration of Competing Interest
perform better Hg0 removal performances, of which the efficiency is
more than twice of the 2Ce8Mo/γ-Al2O3 catalyst. It is found that Mnx+ The authors declare that they have no known competing financial
cations doped into CeO2 lattice resulted in lattice distortion. The higher interests or personal relationships that could have appeared to influence
oxidation efficiency is attributed to the increased concentration of ox­ the work reported in this paper.
ygen vacancies and the strong interaction between CeO2 and Mn. The
reason is that when a manganese ion substitutes the Ce4+ ion, an oxygen Acknowledgments
vacancy is generated to maintain the charge balance. It demonstrated
that the addition of manganese widens the effective temperature win­ Following funding bodies are acknowledged for partially sponsoring
dow and lowers the Hg0 removal temperature. In general, Mn-doped this research: National Key R&D Program of China (2017YFB0602602
2Ce8Mo/γ-Al2O3 catalysts have greatly improved on adsorption and and 2017YFC0210400) and National Natural Science Foundation of
catalytic oxidation performance. Specifically, the catalytic oxidation China (51606106, 52074176, 52173234 and 22008191), Shandong
efficiency reached 86% and the total adsorption capacity also increased Society for Environmental Science (202017), Ningbo Natural Science
significantly. This is mainly due to the synergistic effect between CeO2 Foundation (2017A610233) and Shaanxi Natural Science Foundation
and Mn. It is concluded that the doping of manganese leads to an in­ (2020JQ-014). Authors 1 and 2 contributed equally to this work.
crease in the concentration of oxygen vacancies and an increase in the
number of surface active sites, thereby improving the efficiency of the
catalytic oxidation and adsorption of mercury.

8
P. Cao et al. Applied Surface Science 581 (2022) 152327

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