molecules

Article
Dy-Modified Mn/TiO2 Catalyst Used for the Selective Catalytic
Reduction of NO in Ammonia at Low Temperatures
Bing Xu *, Zhen Wang, Jie Hu, Lei Zhang , Zhipeng Zhang, Hongtan Liang, Yong Zhang and Guozhi Fan

Hubei Provincial Engineering Technology Research Center of Agricultural and Sideline Resources, Chemical
Engineering and Utilization, School of Chemistry and Environmental Engineering, Wuhan Polytechnic University,
Wuhan 430023, China; wz45151204@163.com (Z.W.); hujie9231@126.com (J.H.); zhanglei@whpu.edu.cn (L.Z.);
m17663252107@163.com (Z.Z.); 18883632995@163.com (H.L.); yongzhang@whpu.edu.cn (Y.Z.);
fgzcch@whpu.edu.cn (G.F.)
* Correspondence: xubing200806@163.com

Abstract: A novel Mn/TiO2 catalyst, prepared through modification with the rare-earth metal Dy, has
been employed for low-temperature selective catalytic reduction (SCR) denitrification. Anatase TiO2 ,
with its large specific surface area, serves as the carrier. The active component MnOx on the TiO2
carrier is modified using Dy. Dyx Mn/TiO2 , prepared via the impregnation method, exhibited remark-
able catalytic performance in the SCR of NO with NH3 as the reducing agent at low temperatures.
Experiments and characterization revealed that the introduction of a suitable amount of the rare-earth
metal Dy can effectively enhance the catalyst’s specific surface area and the gas–solid contact area
in catalytic reactions. It also significantly increases the concentration of Mn4+ , chemisorbed oxygen,
and weak acid sites on the catalyst surface. This leads to a notable improvement in the reduction
performance of the DyMn/TiO2 catalyst, ultimately contributing to the improvement of the NH3 -SCR
denitrification performance at low temperatures. At 100 ◦ C and a space velocity of 24,000 h−1 , the
Dy0.1 Mn/TiO2 catalyst can achieve a 98% conversion rate of NOx . Furthermore, its active tempera-
ture point decreases by 60 ◦ C after the modification, highlighting exceptional catalytic efficacy at low
temperatures. By doubling the space velocity, the NOx conversion rate of the catalyst can still reach
96% at 130 ◦ C, indicating significant operational flexibility. The selectivity of N2 remained stable at
over 95% before reaching 240 ◦ C.
Citation: Xu, B.; Wang, Z.; Hu, J.;
Zhang, L.; Zhang, Z.; Liang, H.;
Zhang, Y.; Fan, G. Dy-Modified Keywords: NH3 -SCR de-NOx ; Dy; Mn/TiO2 catalyst; low-temperature catalysis
Mn/TiO2 Catalyst Used for the
Selective Catalytic Reduction of NO in
Ammonia at Low Temperatures.
Molecules 2024, 29, 277. https:// 1. Introduction
doi.org/10.3390/molecules29010277 Due to the swift advancement of the industrial economy, the issue of environmen-
Academic Editor: Jonathan Albo tal pollution has become progressively more pronounced and has gradually garnered
widespread concern within society [1–3]. Nitrogen oxides (primarily NO), as a crucial
Received: 1 December 2023 air pollutant, significantly affect the chemical composition of the troposphere and are
Revised: 23 December 2023
responsible for producing well-known phenomena such as the greenhouse effect, acid
Accepted: 3 January 2024
rain, PM2.5, and photochemical smog [4–9]. As a result, the emission of nitrogen oxides
Published: 4 January 2024
has garnered widespread concern. Countries worldwide have successively established
stringent emission standards for nitrogen oxides in response to air pollution. Strict rules
and regulations promote the rapid development of technology for treating NOx [10–15].
Copyright: © 2024 by the authors.
Currently, there are three primary methods of controlling nitrogen oxides, which
Licensee MDPI, Basel, Switzerland. include raw material control technology prior to combustion, combustion process control
This article is an open access article technology, and post-combustion control technology. Currently, the initial two techniques
distributed under the terms and can effectively decrease the overall volume of nitrogen oxides, yet meeting the rigorous
conditions of the Creative Commons emission norms proves to be a challenge. The post-combustion control technology has
Attribution (CC BY) license (https:// emerged as the cornerstone for complying with emission standards [16–20]. Currently, the
creativecommons.org/licenses/by/ most feasible methods for reducing NOx emissions primarily involve selective non-catalytic
4.0/). reduction (SNCR) and selective catalytic reduction (SCR). Of these, selective catalytic

Molecules 2024, 29, 277. https://doi.org/10.3390/molecules29010277 https://www.mdpi.com/journal/molecules

Molecules 2024, 29, 277 2 of 13

reduction of NOx using ammonia as the reductant (NH3 -SCR) is the most widely used and
effective technology in the flue gas denitrification industry. Currently, the V2 O5 -WO3 /TiO2
catalyst, the most frequently employed in NH3 -SCR technology, exhibits outstanding
denitrification performance within the temperature range of 280 ◦ C to 400 ◦ C. However,
V2 O5 -WO3 /TiO2 catalysts have activity at high temperatures and a narrow temperature
window. According to the characteristics of high flue gas and sulfur content, the catalyst is
prone to poisoning failure and high denitration cost [21–26]. The V2 O5 contained in the
spent catalyst after use exhibits biological toxicity, posing a threat to both the ecological
environment and human health. Regulations have been issued by various countries globally
to dispose of invalid V2 O5 -WO3 /TiO2 catalysts as hazardous wastes, resulting in increased
disposal costs. Therefore, the development of new low-temperature and harmless catalysts
provides the NH3 -SCR process with advantages such as low energy consumption, low
investment cost, and long catalyst life. Simultaneously, it is imperative that the non-toxic
nature of the failed catalyst toward the environment is emphasized [27–37].
Zhang et al. [17] successfully prepared Cu-SAPO-34 and Mn/SAPO-34 catalysts
through hydrothermal synthesis. Through the study of the low-temperature NH3 -SCR
denitrification activity of the two catalysts, it was discovered that Mn had a more significant
role in enhancing the catalyst’s activity at low temperatures. The analysis of characteriza-
tion revealed that MnO2 exhibits a remarkable catalytic function in the oxidation of NO,
thereby significantly enhancing the rapid progress of the SCR reaction.
In their study, Qi et al. [31] examined the SCR reaction mechanism of the MnOx -CeO2
catalyst system, which contains rare-earth elements, at low temperatures. The findings
revealed that NH3 , when adsorbed on the Lewis acid sites on the catalyst surface, reacts
with gaseous NO upon activation, resulting in the conversion of all intermediate products
to NH2 NO, which subsequently decomposes to produce N2 and water. Among them,
Ce possesses a specific alkalinity, which facilitates the interaction of oxygen ions in the
surrounding environment with NOx , thereby oxidizing NOx .
Niu et al. [38] were the first to modify Mn/TiO2 with Tm, leading to a significant
enhancement of the catalyst’s selective catalytic activity at low temperatures. Upon addition
of an appropriate amount of Tm, it was discovered that the concentration of Mn4+ on the
catalyst’s surface, the chemisorption of oxygen, NO, and NH3 , as well as the reduction
performance of the Tm-Mn/TiO2 catalyst, were significantly improved. This enhancement
is beneficial for improving the NH3 -SCR reaction’s effectiveness on NOx .
To enhance the study of NOx conversion activity at low temperatures, identify addi-
tional elements that can modify the catalyst, boost the selectivity for industrial application,
and reduce the cost of implementation, our group has conducted extensive research on
the modification of the conventional V2 O5 -WO3 /TiO2 catalyst system, including the mod-
ification of transition metals such as copper, cadmium, and iron. The findings revealed
that the reactive temperatures for the catalytic reactions were all above 240 ◦ C, which is
unsatisfactory for the current industrial optimization objectives. Therefore, we continue
to choose the Mn/TiO2 catalytic system for doping modification and utilize Dy from the
rare-earth elements as the modifying element to enhance the conversion rate of NO at low
temperatures. The results indicate that the inclusion of an adequate quantity of Dy can
considerably enhance the conversion activity of Mn/TiO2 to NO via NH3 -SCR technology,
specifically at low temperatures ranging from 100 ◦ C to 180 ◦ C.
Rare-earth metals are primarily used as raw materials for rare-earth permanent magnet
materials, making them one of the most significant applications of these metals. Rare-
earth metals are extensively utilized in new energy batteries. In recent years, the field of
denitration catalysts has gradually incorporated the rare-earth metals Tm and Ce, resulting
in impressive research outcomes. In our research group, Dy was tasked with modifying
the Mn/TiO2 catalytic system. The prepared DyMn/TiO2 catalyst exhibited outstanding
catalytic performance at space velocities of 24,000 and 48,000 h−1 below 180 ◦ C; this
will greatly reduce the operating cost of SCR denitration. By successfully modifying the
MnOx /TiO2 catalyst with dysprosium, the application scope of rare-earth resources can
Molecules 2024, 29, 277 3 of 13

be expanded. Additionally, these findings will serve as a valuable guide and reference for
the widespread adoption of low-temperature catalysts in industrial SCR denitrification
processes.

2. Results and Discussion

2.1. SCR Performance
Figure 1 shows the SCR performance test curve of the catalyst sample. At a space
velocity of 24,000 h−1 , Figure 1a illustrates the variation of NOx conversion for Dyx Mn/TiO2
catalysts with varying molar ratios. Figure 1a reveals that all catalysts exhibit a tendency to
initially rise and then decline within the temperature range of 70–340 ◦ C. At 160 ◦ C, the
Mn/Ti catalyst achieved a 98% conversion of NOx . After the introduction of the rare-earth
metal Dy, the NOx conversion of the Dyx Mn/TiO2 catalyst improved significantly below
160 ◦ C, demonstrating outstanding low-temperature catalytic activity. The conversion of
NOx for the Dy0.05 Mn/TiO2 and Dy0.15 Mn/TiO2 catalysts reached 98% at 130 ◦ C, while
the Dy0.1 Mn/TiO2 catalyst even achieved a 98% NOx conversion at 100 ◦ C. Additionally,
the activity temperature point decreased by 60 ◦ C compared to its pre-modification state,
demonstrating outstanding catalytic performance at low temperatures. At a space velocity
of 48,000 h−1 , Figure 1b illustrates the variation of NOx conversion for Dyx Mn/TiO2
catalysts with varying molar ratios. Upon examination of Figure 1b, it is apparent that the
catalytic capacity of all catalysts has diminished. However, the NOx conversion efficiency
of the Dy0.1 Mn/TiO2 catalyst surpasses that of other catalysts, attaining a remarkable
96% at 130 ◦ C. The results indicate that the introduction of the rare-earth metal Dy can
significantly enhance the NOx conversion of the Mn/Ti catalyst, and when the molar ratio
of Dy/Ti is 0.1, the catalyst exhibits outstanding denitration performance.
Simultaneously, the series of prepared catalysts demonstrate notable catalytic activity
within the Space velocity range of 24,000 h−1 to 48,000 h−1 , indicating their broad op-
erational flexibility in catalytic reactions and making them highly suitable for industrial
application. Figure 1c,d display the N2 selectivity of Dyx Mn/TiO2 catalyst samples when
the space velocity is 24,000 h−1 and 48,000 h−1 , respectively, ensuring an N2 selectivity of
over 95% below 240 ◦ C. At elevated space velocities, when the temperature exceeds 260 ◦ C,
the selectivity decreases due to an increased likelihood of side reactions and a reduced
contact time and chance between gas and catalyst, primarily attributed to the excessive
space velocity. In summary, when the molar ratio of Dy/Ti is 0.1, the Dyx Mn/TiO2 catalyst
sample exhibits the best low-temperature SCR denitrification performance and outstanding
N2 selectivity. Lastly, the stability of the Dy0.1 Mn/TiO2 catalyst sample was tested at
150 ◦ C. As shown in Figure 1e, the catalytic efficiency of the Dy0.1 Mn/TiO2 catalyst sample
consistently remained above 98% throughout the entire test period, demonstrating the
catalyst’s exceptional stability.

2.2. SEM, Crystallinity, and Porous Property Analyses

Figure 2 displays the SEM images of the Mn/TiO2 catalyst and the Dyx Mn/TiO2
catalyst. As the molar ratio of Dy increases, the active components on the catalyst surface
gradually increase, as evident from Figure 2. However, the surface of the Dy0.15 Mn/TiO2
catalyst exhibited noticeable agglomeration, leading to a decrease in the catalyst’s specific
surface area. Concurrently, this phenomenon obscured the active sites on the surface to
some extent, ultimately diminishing the catalyst’s SCR catalytic activity. As shown in
Figure 2c, the Dy0.1 Mn/TiO2 catalyst boasts a considerable amount of active components
uniformly distributed across its surface, thereby manifesting commendable catalytic activity
in SCR catalytic performance experiments.
Figure 3 displays the XRD patterns of the Dyx Mn/TiO2 catalyst. All catalysts exhibited
comparable XRD diffraction peaks, suggesting that the addition of the rare-earth metal Dy
did not alter the crystal structure of the catalyst. Characteristic peaks of anatase TiO2 were
observed at 25.8◦ , 38.0◦ , 47.6◦ , 54.5◦ , 62.8◦ , 69.5◦ , and 75.2◦ . Anatase TiO2 is more beneficial
for enhancing the catalytic performance of SCR [35]. As shown in Figure 3, no characteristic
 Molecules 2024, 29, 277 4 of 13

peaks of Mn and Dy oxides were observed on the surface of the catalyst sample. This
suggests that the oxides of Mn and Dy are either highly dispersed on the surface of the
catalyst or exist in an amorphous form, which cannot be detected by XRD [39]. Upon the
introduction of the rare-earth metal Dy, as the Dy/Ti molar ratio increases, the diffraction
peak intensity exhibits a trend of initial decrease, subsequent increase, and subsequent
decrease. The introduction of Dy into the system indicates a reduction in the crystallinity of
the TiO2 support. Table 1 presents the ICP–OES analysis of catalysts. The results indicate
that the actual loading mass of Dy in each catalyst essentially aligns with the theoretical
Molecules 2024, 29, x FOR PEER REVIEW 4 of 13
value. It also demonstrates that the prepared catalyst does indeed contain a specific amount
of Mn and Dy oxides, which to some extent corroborates the XRD data analysis.

Figure
Figure1.1. Effect
Effect of
of Dy/Mn
Dy/Mn molar
molar ratio on NO
ratio on NOx conversion
conversion(a,b)
(a,b)and
andNN2selectivity
selectivityatatdifferent
different space
space
x 2
velocities (24,000 h−1−,1 48,000 h−1−) 1(c,d); results of Dy0.1Mn/TiO2 catalyst stability testing (e).
velocities (24,000 h , 48,000 h ) (c,d); results of Dy0.1 Mn/TiO2 catalyst stability testing (e).

2.2. SEM, Crystallinity, and Porous Property Analyses

Figure 2 displays the SEM images of the Mn/TiO2 catalyst and the DyxMn/TiO2
catalyst. As the molar ratio of Dy increases, the active components on the catalyst surface
gradually increase, as evident from Figure 2. However, the surface of the Dy0.15Mn/TiO2
catalyst exhibited noticeable agglomeration, leading to a decrease in the catalyst’s specific
surface area. Concurrently, this phenomenon obscured the active sites on the surface to
Molecules 2024, 29, x FOR PEER REVIEW 5 of 1
Molecules 2024, 29, 277 5 of 13

Figure 2. SEM
Figure microstructures
2. SEM microstructuresofofthe
the different catalysts.(a)(a)Surface
different catalysts. Surface morphology
morphology of Mn/TiO
of Mn/TiO 2. (b
2 . 6 of 13
Molecules 2024, 29, x FOR PEER REVIEW
Surface morphology
(b) Surface of of
morphology DyDy
0.5Mn/TiO 2. (c) Surface morphology of Dy0.1Mn/TiO2. (d) Surfac
0.5 Mn/TiO2 . (c) Surface morphology of Dy0.1 Mn/TiO2 . (d) Surface
morphology of Dy0.15 Mn/TiO 2.
morphology of Dy0.15 Mn/TiO2 .

Figure 3 displays the XRD patterns of the DyxMn/TiO2 catalyst. All catalysts exhibited
comparable XRD diffraction peaks, suggesting that the addition of the rare-earth meta
Dy did not alter the crystal structure of the catalyst. Characteristic peaks of anatase TiO
were observed at 25.8°, 38.0°, 47.6°, 54.5°, 62.8°, 69.5°, and 75.2°. Anatase TiO2 is more
beneficial for enhancing the catalytic performance of SCR [35]. As shown in Figure 3, no
characteristic peaks of Mn and Dy oxides were observed on the surface of the catalys
sample. This suggests that the oxides of Mn and Dy are either highly dispersed on the
surface of the catalyst or exist in an amorphous form, which cannot be detected by XRD
[39]. Upon the introduction of the rare-earth metal Dy, as the Dy/Ti molar ratio increases
the diffraction peak intensity exhibits a trend of initial decrease, subsequent increase, and
subsequent decrease. The introduction of Dy into the system indicates a reduction in the
crystallinity of the TiO2 support. Table 1 presents the ICP–OES analysis of catalysts. Th
results indicate that the actual loading mass of Dy in each catalyst essentially aligns with
the theoretical value. It also demonstrates that the prepared catalyst does indeed contain
a specific amount of Mn and Dy oxides, which to some extent corroborates the XRD data
analysis.
Figure 3.
Figure XRD patterns
3. XRD patternsofofthe different
the catalysts.
different catalysts.

Table 1. Mass fraction

Figure of the
4 depicts theDyadsorption–desorption
xMn/TiO2 catalysts measured with ICP–OES.
isotherms of all catalysts. The catalysts
exhibit type IV isotherms and type H2 hysteresis loops, which are hallmarks of
Catalyst Sample Theoretical Load Capacity Actual Load Capacity
mesoporous materials. The measurement and calculation of specific surface area, pore
volume,Mn/TiO 2
and pore diameter are based15.55%
on BETMnand BJH equations, as14.41%
detailedMnin Table 2
Dy 0.05Mn/TiO 2 14.29% Mn, 7.03% Dy 13.07% Mn, 6.70%
below. The specific surface area of the Mn/TiO2 catalyst is only 7.94 m /g. With
2 Dythe
Molecules 2024, 29, 277 6 of 13

Table 1. Mass fraction of the Dyx Mn/TiO2 catalysts measured with ICP–OES.

Catalyst Sample Theoretical Load Capacity Actual Load Capacity

Mn/TiO 15.55% Mn
2 of the different catalysts. 14.41% Mn
Figure 3. XRD patterns
Dy0.05 Mn/TiO2 14.29% Mn, 7.03% Dy 13.07% Mn, 6.70% Dy
Dy0.1 Mn/TiO2 13.22% Mn, 13.02% Dy 12.18% Mn, 13.20% Dy
Figure 4 depicts
Dy0.15 Mn/TiO2the adsorption–desorption
12.30% Mn 18.18%isotherms
Dy of13.02%
all catalysts. The
Mn, 18.85% Dycatalysts
exhibit type IV isotherms and type H2 hysteresis loops, which are hallmarks of
mesoporous materials. The measurement and calculation of specific surface area, pore
Figure 4 depicts the adsorption–desorption isotherms of all catalysts. The catalysts
volume, andIV
exhibit type pore diameter
isotherms andaretypebased on BET loops,
H2 hysteresis and BJH equations,
which as detailed
are hallmarks in Table 2
of mesoporous
below. The specific surface area of the Mn/TiO 2 catalyst is only 7.94
materials. The measurement and calculation of specific surface area, pore volume, and pore m 2/g. With the

introduction
diameter areof Dy, on
based theBET
specific
and BJHsurface area initially
equations, increases
as detailed in Tableand then The
2 below. decreases.
specificThe
pore volume
surface area becomes
of the Mn/TiOlarger2 catalyst
but the pore
is onlysize
7.94 2
becomes
m /g. Withsmaller. The specificofsurface
the introduction Dy, thearea
ofspecific
the Dysurface
0.1Mn/TiO area2 catalyst is as highand
initially increases as 49.47 m2/g, which
then decreases. Theisporehigher thanbecomes
volume 37.01 mlarger
2/g in the

but the pore size becomes smaller. The specific surface

literature [39]. The large surface area of the catalyst facilitates thearea of the Dy Mn/TiO catalyst
0.1 rapid adsorption
2 of
is as highand
reactants as 49.47 m2 /g, which
the desorption ofisproducts
higher thanon 37.01 m2 /g insurface,
the catalyst the literature
thereby[39]. The large the
enhancing
surface area of theSCR
low-temperature catalyst facilitates
catalytic the rapid of
performance adsorption of reactants
the catalyst [38]. Theand the desorption
results indicate that
of products on the catalyst surface, thereby enhancing the low-temperature
the specific surface area of the catalyst and the gas–solid contact area of the SCR catalytic
catalytic
performance of the catalyst [38]. The results indicate that the specific surface area of the
reaction can be significantly increased when an appropriate amount of the rare-earth
catalyst and the gas–solid contact area of the catalytic reaction can be significantly increased
metal Dy is introduced, which also enhances the SCR denitrification activity of the
when an appropriate amount of the rare-earth metal Dy is introduced, which also enhances
catalyst.
the SCR denitrification activity of the catalyst.

Figure
Figure4.4.(a)
(a)Nitrogen
Nitrogenadsorption-esorption curveofofthe
adsorption-esorption curve thedifferent
different catalysts.
catalysts. (b)(b) Pore
Pore sizesize distribution
distribution
curve
curveofofthe
thedifferent
different catalysts.
catalysts.

Table 2. The pore analysis data of the different catalysts.

BET Surface Area Pore Volume Average Pore

Catalyst Sample
(m2 /g) (cm3 /g) Diameter (nm)
Mn/TiO2 7.94 0.044 26.78
Dy0.05 Mn/TiO2 21.00 0.071 13.62
Dy0.1 Mn/TiO2 49.47 0.086 7.53
Dy0.15 Mn/TiO2 35.91 0.087 9.88

2.3. XPS Analysis

Figure 5 displays the X-ray photoelectron spectroscopy (XPS) characterization of the
Dyx Mn/TiO2 catalyst, aiming to investigate the variations in elemental valence on the
surface of various catalysts. It involves the separation and fitting of characteristic peaks for
Mn, O, and Dy elements in each catalyst, and the computation of the relative concentrations
of Mn, O, and Dy elements in varying valence states on the surface of each catalyst. As
 2.3. XPS Analysis
Figure 5 displays the X-ray photoelectron spectroscopy (XPS) characterization of the
DyxMn/TiO2 catalyst, aiming to investigate the variations in elemental valence on the
Molecules 2024, 29, 277 surface of various catalysts. It involves the separation and fitting of characteristic peaks
7 of 13
for Mn, O, and Dy elements in each catalyst, and the computation of the relative
concentrations of Mn, O, and Dy elements in varying valence states on the surface of each
catalyst.
illustratedAsinillustrated
Figure 5a,in theFigure 5a, the photoelectron
photoelectron peaks for Mn peaks
2p3/2 forandMnMn2p3/2
2p1/2and are Mn 2p1/2
situated
are situated around 642.0 eV and 653.5 eV, respectively. Mn 2p3/2
around 642.0 eV and 653.5 eV, respectively. Mn 2p3/2 was categorized into three electronicwas categorized into
three electronic peaks,
2+ namely Mn 2+ (641.2
3+ ± 0.1 eV), Mn 3+ (642.3 ± 0.1
peaks, namely Mn (641.2 ± 0.1 eV), Mn (642.3 ± 0.1 eV), and Mn (643.8 ± 0.1 eV) [38]. 4+ eV), and Mn 4+ (643.8

±According
0.1 eV) [38]. According
to relevant to relevant
literature [39], literature
high levels[39], high
of Mn levels of the
4+ promote Mn4+NH promote the NH3-
3 -SCR catalytic
SCR catalytic
reduction reduction
reaction. Tablereaction.
2 showsTable 2 shows
that with that with
the addition ofthe
the addition
rare-earthofmetal
the rare-earth
Dy, the
Mn4+ /(Mn
metal 2+ +Mn
Dy, the Mn4+3+
/(Mn
+ Mn2+ 4+
+ )Mn 3+ + Mn4+) ratio first increases and then decreases. The
ratio first increases and then decreases. The Dy0.1 Mn/TiO2
Dy 0.1Mn/TiO
catalyst 2 catalyst
exhibits exhibits
the highest ratio,the highest
aligning withratio, aligning
the results of thewith
SCRthe results oftest.
performance theThis
SCR
4+
performance
aligns with the test. This aligns
literature’s with the
conclusion: Mnliterature’s conclusion:
concentration Mn
is a crucial concentration
factor
4+ in determining is a
the catalyst’s
crucial factor inlow-temperature
determining the catalytic activity.
catalyst’s low-temperature catalytic activity.

Figure
Figure5.5.XPS
XPSof
ofthe
the different
different catalysts: (a) Mn
catalysts: (a) Mn 2p,
2p,(b)
(b)OO1s,
1s,(c)
(c)Dy
Dy4d.
4d.

AsAsshown
shown in in Figure
Figure 5b, all catalysts
catalysts exhibit
exhibittwo
twooverlapping
overlappingpeaks peaksaround
around529.8529.8eVeV
and
and531.5
531.5eV eV [38].
[38]. The peak at at 529.8
529.8 eV
eVbelongs
belongstotolattice
latticeoxygen
oxygen(denoted
(denoted asas
OβO),β),while
while
thepeak
the peakat at531.5
531.5 eV
eV belongs
belongs to adsorbed
adsorbedoxygen
oxygen(denoted
(denotedasasOO αα).).According
Accordingtotoa aliterature
literature
report [39],
report [39], O
Oαα has
has aa higher mobility
mobility than
than OOββ. It can bebe converted
convertedtotolattice
latticeoxygen
oxygenatat
oxygen vacancies
oxygen vacancies on the catalyst surface, thereby enhancing the oxidation
the catalyst surface, thereby enhancing the oxidation ability ability of NO at
of NO
low temperatures and promoting the rapid progress of the SCR reaction.
at low temperatures and promoting the rapid progress of the SCR reaction. Table 2 reveals Table 2 reveals
thatwith
that with the
the addition
addition of ofthe
therare-earth
rare-earthmetal Dy,
metal thethe
Dy, ratio of O
ratio /(O
ofαO α+
α/(O
Oβ )β)on
α + O onthe
thecatalyst
catalyst
surface gradually increases. This suggests that the amount of adsorbed oxygen
surface gradually increases. This suggests that the amount of adsorbed oxygen is a pivotal is a pivotal
factor influencing
factor influencing thethecatalyst’s
catalyst’slow-temperature
low-temperature catalytic performance.
catalytic performance. The The
location of Dyof
location
4d is indicated to be around 1294 eV, as depicted in Figure 5c, which corresponds to the
Dy 4d is indicated to be around 1294 eV, as depicted in Figure 5c, which corresponds to
Dy3+ on the catalyst surface.
the Dy on the catalyst surface.
3+

2.4. H2 -TPR, NH3 -TPD Analysis

The H2-TPR experiment is conducted to investigate the redox behavior of the DyxMn/TiO2
catalyst. The redox properties of catalysts significantly determine their catalytic properties.
As illustrated in Figure 6, all catalysts exhibit two broad, overlapping reduction peaks
within the temperature range of 150–550 ◦ C. For the Mn/Ti catalyst, the reduction peak
around 359 ◦ C is attributed to the reduction process of MnO2 → Mn2 O3 [31,38]. The
reduction peak within the temperature range of 420–520 ◦ C is attributed to the reduction
process of Mn2 O3 → Mn3 O4 → MnO [39]. Compared to the peak of Mn/TiO2 , the re-
duction peak of the Dy–Mn/Ti catalyst shifted towards lower temperatures due to the
synergistic effect between Dy and Mn/TiO2 . Among them, the Dy0.1 Mn/TiO2 catalyst
and the Dy0.15 Mn/TiO2 catalyst exhibit the lowest reduction peak temperatures. The peak
performance of the Dy0.1 Mn/TiO2 catalyst is notably broader and encompasses regions of
lower temperature. Upon calculating the peak area, it is observed that the Dy0.1 Mn/TiO2
catalyst boasts the largest peak area, as illustrated in Table 3. The H2 -TPR results indicate
that the Dy0.1 Mn/TiO2 catalyst exhibits the optimal reduction behavior at low temperatures
 the reduction peak of the Dy–Mn/Ti catalyst shifted towards lower temperatures due to
the synergistic effect between Dy and Mn/TiO2. Among them, the Dy0.1Mn/TiO2 catalyst
and the Dy0.15Mn/TiO2 catalyst exhibit the lowest reduction peak temperatures. The peak
performance of the Dy0.1Mn/TiO2 catalyst is notably broader and encompasses regions of
Molecules 2024, 29, 277 lower temperature. Upon calculating the peak area, it is observed that the Dy0.1 8 Mn/TiO
of 13 2

catalyst boasts the largest peak area, as illustrated in Table 3. The H2-TPR results indicate
that the Dy0.1Mn/TiO2 catalyst exhibits the optimal reduction behavior at low
temperatures andthe
and demonstrates demonstrates theactivity
highest catalytic highestamong
catalytic activity
the SCR among
catalysts, the SCR catalysts,
corroborating the
findings from the
corroborating theprior SCR catalytic
findings from theperformance tests. performance tests.
prior SCR catalytic

Figure 6. H
Figure 6. H22-TPR
-TPRanalysis
analysisofofthe
thedifferent
different catalysts.
catalysts.

TableIn
3. the
TheNH 3-SCR
valence reaction, the
concentration adsorption
of elements capacity
on the surface of thedifferent
of the catalystcatalysts
for NHand3 is H
crucial.
2
Figure 7 peak
reduction shows the NH3-TPD characterization results for all DyxMn/TiO2 catalysts. Three
area.
weak desorption peaks can be observed for the Mn/TiO2 catalyst. The peak around 118 °C
4+ /Mnn+ (%) Oα /(Oα + Oβ ) H2 Reduction NH3 -TPD Peak
isCatalyst Sample
attributed to theMn physical adsorption of(%) NH3 on thePeakcatalyst,
Area (%) the peak Areaaround(%) 266 °C is
attributed to the desorption peak of NH3 adsorbed on the Bronsted acid site (weak acid),
Mn/TiO2 31.75 39.59 76.91 7.28
and theMn/TiO
Dy0.05 peak around
2
351 °C is attributed
33.64 to the desorption
49.36 73.29 peak of NH3 adsorbed
44.37 on the
Lewis acid site
Dy0.1 Mn/TiO 2 (strong35.06 acid) [38]. Upon introduction 100.00
60.21 of the rare-earth100.00 metal Dy, the
Dy0.15 Mn/TiO
desorption peak2 on weak 33.02
acid significantly61.32intensified. As 77.64 the Dy content78.88 increased, the
Note: The peak area of H reduction and NH -TPD are normalized with Dy Mn/TiO
area of the desorption peak initially expanded and then diminished. As illustrated in
2 3 0.1 2 as the standard.

Table 3, it is observed that the peak area of NH3 desorption for the Dy0.1Mn/TiO2 catalyst
is theInlargest
the NH 3 -SCR all
among reaction, the adsorption
catalysts, suggesting capacity of the
the highest catalyst
number of for
weak NHacid
3 is crucial.
sites on the
catalyst surface. According to literature reports [38], weak acids are crucial toThree
Figure 7 shows the NH 3 -TPD characterization results for all Dy x Mn/TiO 2 catalysts. the low-
weak desorption peaks can be observed for the Mn/TiO2 catalyst. The peak around 118 ◦ C
temperature catalytic activity of catalysts. Consequently, the moderate incorporation of
is attributed to the physical adsorption of NH3 on the catalyst, the peak around 266 ◦ C is
Dy notably enhances the adsorption capacity of NH3 on the catalyst surface, substantially
attributed to the desorption peak of NH3 adsorbed on the Bronsted acid site (weak acid),
increases the number of weak acid sites on the catalyst surface, and consequently boosts
and the peak around 351 ◦ C is attributed to the desorption peak of NH3 adsorbed on
the
the Lewis acidactivity
catalyst’s at low
site (strong temperatures.
acid) The resultsofofthe
[38]. Upon introduction therare-earth
NH3-TPDmetal characterization
Dy, the
desorption peak on weak acid significantly intensified. As the Dy content increased, the area
of the desorption peak initially expanded and then diminished. As illustrated in Table 3,
it is observed that the peak area of NH3 desorption for the Dy0.1 Mn/TiO2 catalyst is the
largest among all catalysts, suggesting the highest number of weak acid sites on the catalyst
surface. According to literature reports [38], weak acids are crucial to the low-temperature
catalytic activity of catalysts. Consequently, the moderate incorporation of Dy notably
enhances the adsorption capacity of NH3 on the catalyst surface, substantially increases the
number of weak acid sites on the catalyst surface, and consequently boosts the catalyst’s
activity at low temperatures. The results of the NH3 -TPD characterization experiments
further corroborate and validate the previous results of the NH3 -SCR performance tests.
Molecules 2024, 29, x FOR PEER REVIEW 9 of 13

Molecules 2024, 29, 277 experiments further corroborate and validate the previous results of the NH3-SCR
9 of 13
performance tests.

Figure
Figure7.7.NH
NH3-TPD analysis of the different catalysts.
3 -TPD analysis of the different catalysts.

3. Experiment
Table 3. The valence concentration of elements on the surface of the different catalysts and H2
reduction peak area.
3.1. Synthesis Catalyst
A series of DyMn/TiO2 catalysts with varying Dy/Mn molar ratios
H2 Reduction NHwere
3-TPD prepared
Peak
Catalyst
using theSample
impregnationMn4+/Mn n+(%) Oα/(Oα + Oβ) (%)
method. The detailed synthesis procedure is as follows: Weigh
Peak Area (%) Area (%)
an appropriate
Mn/TiO2 amount of Dysprosium
31.75 Nitrate
39.59 (AR, purchased
76.91 from Shanghai7.28 Mcleam
Biochemical Technology Co., Ltd., Shanghai, China) and manganese acetate (AR, purchased
Dy0.05Mn/TiO2 33.64 49.36 73.29 44.37
from Alddin Reagent Co., Ltd., Shanghai, China) into a beaker that holds 50 mL of deionized
Dy0.1Mn/TiO2 35.06 60.21 100.00 100.00
water. To facilitate dissolution, place the beaker into a magnetic water bath stirring pot and
Dy0.15Mn/TiO2 33.02 61.32 77.64
stir thoroughly. Weigh an appropriate amount of titanium dioxide powder (AR, purchased
78.88
Note: The peak area of H2 reduction and NH3-TPD are normalized with Dy0.1Mn/TiO2 as the
from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China) and add it gradually to the
standard.
beaker. Stir at room temperature for 2 h, and then raise the temperature to 90 ◦ C using the
water bath. Continue stirring until the water evaporates to a viscous state. Then, remove
3. Experiment
the beaker and dry it in a 110 ◦ C drying oven for 15 h to obtain a dry, block-like solid.
3.1. Synthesis Catalyst
Subsequently, transfer the block-shaped solid to a quartz crucible and roast it in a muffle
furnace ◦
at 400of C (with a heating rate of 6 ◦ C/min)
A series DyMn/TiO 2 catalysts with varying for four hours
Dy/Mn molarin an airwere
ratios atmosphere
preparedto
yield the
using the impregnation
calcined solid method.
particles.The
Finally, make
detailed a catalyst
synthesis powder with
procedure a particleWeigh
is as follows: diameter
an
ranging from
appropriate 0.25 to 0.45
amount mm throughNitrate
of Dysprosium tablet pressing, grinding,from
(AR, purchased and sieving
Shanghaito achieve
Mcleama
mesh size of 40–60.
Biochemical TechnologyThe synthesized
Co., Ltd.,catalyst
Shanghai,seriesChina)
is denoted
andbymanganese
the symbol acetate
Dyx Mn/TiO(AR,2 ,
purchased from Alddin Reagent Co., Ltd., Shanghai, China) into a beaker that holdswas
where x represents the molar ratio of Dy to Ti (Mn:Ti = 0.3:1; the mass fraction of Dy 50
7.02%,
mL 13%, andwater.
of deionized 18.13%, Torespectively). Additionally,
facilitate dissolution, place when x is 0,into
the beaker it corresponds to the
a magnetic water
Molecules 2024, 29, x FOR PEER REVIEW
Mn/TiO 10 of is
13
bath 2 catalyst,
stirring pot and also
stirprepared via the
thoroughly. impregnation
Weigh method.The
an appropriate amountreaction mechanism
of titanium dioxide
shown in
powder Figure
(AR, 8.
purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China)
and add it gradually to the beaker. Stir at room temperature for 2 h, and then raise the
temperature to 90 °C using the water bath. Continue stirring until the water evaporates to
a viscous state. Then, remove the beaker and dry it in a 110 °C drying oven for 15 h to
obtain a dry, block-like solid. Subsequently, transfer the block-shaped solid to a quartz
crucible and roast it in a muffle furnace at 400 °C (with a heating rate of 6 °C/min) for four
hours in an air atmosphere to yield the calcined solid particles. Finally, make a catalyst
powder with a particle diameter ranging from 0.25 to 0.45 mm through tablet pressing,
grinding, and sieving to achieve a mesh size of 40–60. The synthesized catalyst series is
denoted by the symbol DyxMn/TiO2, where x represents the molar ratio of Dy to Ti (Mn:Ti
= 0.3:1; the mass fraction of Dy was 7.02%, 13%, and 18.13%, respectively). Additionally,
when x is 0, it corresponds to the Mn/TiO2 catalyst, also prepared via the impregnation
method.The reaction mechanism is shown in Figure 8.

Figure 8.
Figure 8. Main
Main schematic
schematic diagram
diagram of
of NH
NH33-SCR denitration.

3.2. Characterization of Catalysts

The phase composition and crystal phase composition of the catalyst were analyzed
using an X-ray diffractometer (D8ADVANCE, Bruker Corporation, Bremen, Germany),
with cu-k α serving as the radiation source. The tube voltage was set to 40 kV, the tube
Molecules 2024, 29, 277 10 of 13

3.2. Characterization of Catalysts

The phase composition and crystal phase composition of the catalyst were analyzed
using an X-ray diffractometer (D8ADVANCE, Bruker Corporation, Bremen, Germany),
with cu-k α serving as the radiation source. The tube voltage was set to 40 kV, the tube
current to 30 mA, the XRD scanning range to 10–80◦ , and the step size to 0.02◦ . A scanning
electron microscope (JSM-7610FPlus, JEOL Co., Ltd., Tokyo, Japan) was used to observe
the morphology of aerogel under an accelerating voltage of 15 kV. The specific surface area
and pore structure of the samples were determined using a specific surface area and pore
volume aperture analyzer (ASAP2460, Micromeritics, Norcross, GA, USA). The calculation
of test data was performed according to BET analysis. The X-ray photoelectron spectrometer
(Escalab 250xi, Thermo Fisher Scientific, Waltham, MA, USA) was employed for the XPS
test, with the aim of investigating the valence state of atoms present on the surface of the
catalyst. The binding energies of the measured elements were corrected using the C 1s
peak (284.6 eV). An analysis was conducted using an Al Kα X-ray with a tube voltage of
1486.6 eV. The content of metal elements in the catalyst was determined by inductively
coupled plasma atomic emission spectrometry (ICPOES 730, Aglient Technology Co., Ltd.,
Santa Clara, CA, USA).
The H2 -TPR experiment employed the BELCAT-A system (BELCAT-A, Bayer, Tokyo,
Japan) for temperature-programmed reduction, aimed at examining the impact of the
catalyst’s redox property on its catalytic performance. Test procedure: Weigh 100 mg of
sample and transfer it into a reaction tube. Dry it at a rate of 10 ◦ C/min, increasing from
room temperature to 300 ◦ C. Use a high-purity nitrogen flow rate (30 mL/min) to purge it
for 1 h, and then allow it to cool down to 50 ◦ C. Convert N2 to a reducing gas (10% H2 /N2 )
for purge purposes, remove any residual N2 on the sample surface and within the pipeline,
maintaining a flow rate of 30 mL/min, then increase the temperature from 50 ◦ C to 700 ◦ C
at a rate of 10 ◦ C/min. Record the TCD signal value.
The NH3 -TPD analysis was also conducted using the BELCAT-A system (BELCAT-A,
Bayer, Japan) to investigate the impact of acidity on the catalytic performance of the catalyst.
Test procedure: Weigh 50–200 mg of sample and transfer it into a reaction tube. Program
the temperature to rise to 300 ◦ C at a rate of 10 ◦ C/min for drying pretreatment. Purge it
with a N2 flow of 30 mL/min for 1 h and cool it to 50 ◦ C. Subsequently, introduce a 10%
NH3 /N2 mixture (30 mL/min) and leave it to saturate for an hour. Afterward, switch
on the flow of N2 (30 mL/min) to purge for an hour and remove any weakly physically
adsorbed NH3 on the surface. Finally, under an N2 atmosphere, raise the temperature at a
rate of 10 ◦ C/minute until it reaches 600 ◦ C for desorption. The desorbed gas is detected
using a thermal conductivity detector (TCD).

3.3. Characterization of Catalysts

The laboratory self-made denitration activity evaluation equipment is the experimental
device employed for the NH3 -SCR performance test of the experimental catalyst (Figure 9).
The reactor has an inner diameter of 1 cm and a length of 50 cm. The center of the reaction
tube is filled with 0.096 g of catalyst, and the temperature of the reactor is monitored
using a thermocouple. During the reaction process, the temperature is maintained between
100–400 ◦ C. For every 30 ◦ C increase, the temperature is held for approximately 20 min
to stabilize the concentration of each tail gas component. Real-time data are recorded
sequentially. Rotor flowmeters and volume flowmeters are utilized to harmoniously
regulate the flow of gases from each pathway, stabilizing the overall flow rate of the
simulated flue gas atmosphere. Additionally, the gas volume space velocity is adjusted
to 24,000 h−1 (Flow rate is 300 mL/min) and 48,000 h−1 , respectively. An online flue gas
analyzer (GW-2000) is employed to monitor the NOx content in the reactor’s exhaust, a
nitrous oxide detector (FGD2-C-N2 O) is utilized to measure the N2 O level in the reaction’s
 center of the reaction tube is filled with 0.096 g of catalyst, and the temperature of the
reactor is monitored using a thermocouple. During the reaction process, the temperature
is maintained between 100–400 °C. For every 30 °C increase, the temperature is held for
approximately
Molecules 2024, 29, 277 20 min to stabilize the concentration of each tail gas component. Real-time11 of 13
data are recorded sequentially. Rotor flowmeters and volume flowmeters are utilized to
harmoniously regulate the flow of gases from each pathway, stabilizing the overall flow
exhaust, and a specific length gas detection tube is used to determine the concentration of
rate of the simulatedammonia
flue gas in atmosphere.
both the intake Additionally,
air and the exhaust. the gas volume space velocity is
adjusted to 24,000 h (Flow rate is 300 mL/min) and 48,000 h−1, respectively. An online
−1
[ NO x ] − [ NO x ]out
flue gas analyzer (GW-2000) is employed (%) = the in
to monitor
NO x conversion NOx content × 100%
in the reactor’s (1)
[ NO x ]in
exhaust, a nitrous oxide detector (FGD2-C-N2O) is utilized to measure the N2O level in the
reaction’s exhaust, and a specific ]in + detection
[ NO xgas [ NH 3 ]in − [ NO x ]outis− used to −determine
[ NH 3 ]out [ N2 O]out
N2 selectivity (%)length
= tube the (2)
× 100%
[ NO x ]in + [ NH 3 ]in − [ NO x ]out − [ NH 3 ]out
concentration of ammonia in both the intake air and the exhaust.

Figure 9. Flow chart ofFigure

catalyst performance
9. Flow testperformance
chart of catalyst device. test device.
4. Conclusions
An 𝑁𝑂 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛
efficient Mn/TiO2%catalyst, prepared through 100%modification with the rare-earth
(1)
metal Dy, has been employed for low-temperature selective catalytic reduction (SCR) deni-
trification. The Dyx Mn/TiO2 catalyst, prepared by the impregnation method, exhibited
𝑁 𝑠𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 %
outstanding catalytic performance. Experiments and characterization 100% revealed (2) that the
introduction of a suitable amount of the rare-earth metal Dy can effectively enhance the
specific surface area of the catalyst and increase the contact area for gas–solid reactions.
4. Conclusions Concurrently, the incorporation of the rare-earth metal Dy significantly enhances the con-
centration of Mn4+ on the catalyst surface and the chemisorption of oxygen, significantly
An efficient Mn/TiO 2 catalyst,
contributing prepared through
to the improvement modification
of the catalyst’s withthethe
activity. Lastly, SCR rare-earth
catalytic perfor-
metal Dy, has been employed for low-temperature
mance was confirmed through NH 3 -TPD selective
and H 2 -TPR catalytic reduction (SCR)
experiments. The findings indicate
denitrification. ThethatDy the incorporation of a suitable amount of the metal Dy significantly enhances the
xMn/TiO2 catalyst, prepared by the impregnation method,
adsorption capacity of NH3 on the catalyst surface and effectively augments the number
exhibited outstanding catalytic performance. Experiments and characterization revealed
of weak acid sites on the catalyst surface, thereby enhancing the catalyst’s activity at low
that the introduction of a suitable
temperatures, amount
ameliorating theof the rare-earth
reduction performance metal
of theDy can effectively
DyMn/TiO 2 catalyst, and
enhance the specificultimately
surface area of thethe
bolstering catalyst and increase
performance of NH3 -SCR thedenitration
contact area for
at low gas–solid The
temperatures.
Dy0.1 Mn/TiO ◦ C under a space
reactions. Concurrently, 2 catalyst can achieve
the incorporation of a 98%rare-earth
the NOx conversion metal rateDy
at 100
significantly
velocity of 24,000 h−4+1 . Additionally, its active temperature point is 60 ◦ C lower than before
enhances the concentration of Mn on the catalyst surface and the chemisorption of
modification, demonstrating an outstanding catalytic performance at low temperatures.
oxygen, significantlyAfter
contributing
doubling thetospacethe improvement
velocity, the NOxof the catalyst’s
conversion activity.
of the catalyst Lastly,
remains the even
at 96%
SCR catalytic performance ◦
at 130 C, was confirmed
demonstrating through
substantial NH3-TPD
operational and HThe
flexibility. 2-TPR experiments.
selectivity to N2 remains
above 95% up to 240 ◦ C.
The findings indicate that the incorporation of a suitable amount of the metal Dy
significantly enhances the adsorption capacity of NH3 on the catalyst surface and
Author Contributions: Investigation: B.X., Z.W., J.H., L.Z., Z.Z., H.L., Y.Z. and G.F.; original
effectively augments the number
manuscript of and
writing: B.X. weakZ.W.;acid sitesreview:
manuscript on the B.X.,catalyst surface,
J.H. and L.Z. thereby
All authors have read and
agreed to the
enhancing the catalyst’s published
activity atversion
low oftemperatures,
the manuscript. ameliorating the reduction
performance of theFunding:
DyMn/TiO 2 catalyst,
This research and ultimately
was supported bolstering
by the financial the performance
assistance provided ofof the
by the Key Project
Scientific Research Program of the Hubei Provincial Department
NH3-SCR denitration at low temperatures. The Dy0.1Mn/TiO2 catalyst can achieve a 98% of Education (D20201602) and the
Hubei Natural Science Foundation (2023AFB385).
NOx conversion rate at 100 °C under a space velocity of 24,000 h−1. Additionally, its active
Molecules 2024, 29, 277 12 of 13

Institutional Review Board Statement: The study was conducted in the laboratory of the Hubei
Provincial Engineering Technology Research Center of Agricultural and Sideline Resources Chem-
ical Engineering and Utilization, School of Chemistry and Environmental Engineering, Wuhan
Polytechnic University and approved by the Institutional Review Board, 2023.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors express their gratitude to the laboratory of the Hubei Provincial En-
gineering Technology Research Center of Agricultural and Sideline Resources Chemical Engineering
and Utilization, School of Chemistry and Environmental Engineering, Wuhan Polytechnic University,
in whose laboratories the study was carried out.
Conflicts of Interest: The authors declare no conflict of interest.

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