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One-step hydrothermal synthesis of MnOx-CeO2/reduced graphene oxide

composite aerogels for low temperature selective catalytic reduction of NOx

Kunmeng Zhu, Wenqian Yan, Sijia Liu, Xiaodong Wu, Sheng Cui, Xiaodong
Shen

PII: S0169-4332(19)33841-3
DOI: https://doi.org/10.1016/j.apsusc.2019.145024
Reference: APSUSC 145024

To appear in: Applied Surface Science

Received Date: 6 September 2019

Revised Date: 6 December 2019
Accepted Date: 9 December 2019

Please cite this article as: K. Zhu, W. Yan, S. Liu, X. Wu, S. Cui, X. Shen, One-step hydrothermal synthesis of
MnOx-CeO2/reduced graphene oxide composite aerogels for low temperature selective catalytic reduction of
NOx, Applied Surface Science (2019), doi: https://doi.org/10.1016/j.apsusc.2019.145024

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One-step hydrothermal synthesis of MnOx-CeO2/reduced
graphene oxide composite aerogels for low temperature selective
catalytic reduction of NOx
Kunmeng Zhu a,b, Wenqian Yan a,b, Sijia Liu a,b, Xiaodong Wu a,b, Sheng Cui a,b,*, Xiaodong Shen a,b,*
a
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science
and Engineering, Nanjing Tech University, Nanjing 210009, China
b
Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Nanjing
Tech University, Nanjing 210009, China

*Corresponding Authors
Tel.: +86 25 83587234; fax: +86 25 83221690
E-mail address: xdshen@njtech.edu.cn (X. Shen)
Tel.: +86 25 83587234; fax: +86 25 83221690
E–mail address: scui@njtech.edu.cn (S. Cui)

Abstract
In response to the problem of air pollution caused by nitrogen oxides (NOx), we synthesized a three-
dimensional (3D) MnOx-CeO2 nanoparticles /reduced graphene aerogel for low-temperature selective
catalytic reduction (SCR) of NOx with NH3 by a facile one-step hydrothermal treatment. During the
hydrothermal reaction, the graphene nanosheets and MnOx-CeO2 nanoparticles self-assembled into
3D interconnected networks, in which the nanoparticles MnOx-CeO2 with uniform size were densely
anchored onto the graphene nanosheets. Besides, the MnOx-CeO2/reduced graphene oxide(RGA)
exhibited unique properties such as high specific surface area, and numerous catalytically active sites
in comparison with pure MnOx-CeO2 nanoparticles. Evidences have shown that the chemical bonding
between MnOx-CeO2 and GO achieved high selective catalytic reduction efficiency. The MnOx-
CeO2/RGA composites displayed highly enhanced catalytic activity in comparison to bare MnOx-
CeO2 nanoparticles which achieved 99 % NOx conversion at 220 °C. This work provided a versatile
approach to induce the combination of reduced graphene oxide sheets and other oxide nanoparticles,
which opened up new avenues for the design and manufacture of catalysts used for low temperature
SCR of NOx with NH3.
Keywords: Reduced graphene oxide; Mn-Ce mixed oxide; Hydrothermal synthesis; Low temperature
catalysis; Selective catalytic reduction

1. Introduction
Nitrogen oxides (NO, NO2 and N2O) produced by combustion have remained a major source of
air pollution during the last few decades[1]. They are the main cause of acid rain and photochemical
smog, and contribute to the greenhouse effect. As the focus and difficulty of current atmospheric
environmental protection, researchers have attracted more attention on NOx pollution and elimination
[2, 3]. The selective catalytic reduction (SCR) method is the most mature flue gas denitration
technology at present [4-6]. Its reaction mechanism is mainly summarized to selectively reduce the
NOx in the flue gas and then transfer into H2 and H2O by using a catalyst and a reducing agent
(generally NH3) at a certain temperature. As the key of SCR technology in flue gas treatment, the
development of highly selective catalysts has become the focus of current research.

1
 The most commonly used catalyst in industrial NH3-SCR production is V2O5/TiO2 and
WO3(MoO3) modified V2O5/TiO2[7-9]. Vogt et al.[10] studied the catalytic performance of supported
and unsupported V2O5 based catalysts for the SCR of NOx with NH3. Chen et al.[11] prepared TiO2-
supported V2O5 and V2O5 + WO3 catalysts, the introduction of WO3 to V2O5/TiO2 increased the active
site of SCR and broadened the temperature range of SCR. But they have some disadvantages such as
biotoxicity, high activity temperature window (300-400 °C), low operating temperature range, and
poor thermal stability at high temperatures. It is desirable to prepare environmentally friendly and low
temperature active catalysts that are installed downstream of the particulate trap and flue gas
desulfurization to allow the catalyst to operate in a cleaner environment and extend catalyst life.
CeO2 is a widely used catalyst material because of its cost efficiency and innocuity[12]. It has
excellent oxygen storage capacity, and in particular, the Ce3+ and Ce4+ can be converted to each other
under oxidation and reduction conditions[13]. The transition metal is capable of supplying electrons at
a low temperature because the d electron orbit is not filled[14-16]. The researchers[17] found that
among the oxides of transition metals such as Cr, Mn, Cu, and V, Mn oxides have the best low-
temperature catalytic activity. Several valence states of MnOx can be converted into each other, which
contributes to the progress of the redox reaction[18-20]. Therefore, CeO2 and MnOx are often
compounded and used as new catalyst material[21, 22]. Qi et al.[23] prepared a manganese-cerium
oxide catalyst by co-precipitation method. The results showed that the best Mn-Ce mixed-oxide
catalyst (Mn / (Mn+Ce)=0.4㸧yielded 95% NO conversion at 150 °C at a space velocity of 42,000 h-1.
Gao et al.[24] prepared a metal-doped MnOx-CeO2 catalyst by coprecipitation. The results show that
the Co/Ni doped MnOx-CeO2 catalyst has high SCR performance and good tolerance to SO2.
Composite metal oxide materials have the disadvantages of easy agglomeration, poor adsorption
capacity, and poor conductivity. Hence, functional materials need to be used as a carrier for such
materials to further enhance their catalytic activity. Graphene is a lamellar two-dimensional material
composed of carbon atoms, which has been widely studied in the fields of nanoelectronics, sensors,
catalysis and energy since it was discovered in 2004[25, 26]. However, the π-π interaction between
the graphene sheets tends to result in a stack of graphene sheets, which makes some properties of the
composites lower than theoretical predictions. In recent years, graphene aerogel composite materials
have attracted more and more researchers’ attention[27, 28]. The introduction of graphene can
effectively solve the shortcomings of single-component materials, and provides many catalytically
active sites and large specific surface areas, which makes it have great potential in the field of
catalysis. Several studies[29, 30] have shown that during the formation of graphene aerogel network,
nanoparticles can be captured into the network structure of graphene aerogel in some way. By loading
CeO2-MnOx nanoparticles in a graphene aerogel, the nano-oxide particles lead to good catalytic
activity, and avoid the agglomeration between the graphene sheets. As a carrier, graphene aerogel has
a large number of catalytically active sites and high specific surface area[31, 32], so that the active
component can be dispersed to contact the reactants sufficiently .
In this work, a self-assembled MnOx-CeO2/reduced graphene oxide aerogel (RGA) material was
successfully synthesized by hydrothermal method for SCR of NOx at low temperatures. The as-
prepared MnOx-CeO2/RGA has high NO reduction efficiency by NH3 in the low temperature range of
120–240 °C. The catalyst maintained high N2 selectivity and nearly complete NOx conversion at low
temperatures of 220 °C and GHSV=30,000 h−1.

2
2. Experimental section

2.1. Synthesis of MnOx-CeO2/reduced graphene oxide aerogels

Self-assembled MnOx-CeO2/RGA nanocomposites were prepared by one-step hydrothermal

method and freeze-drying technique. In the typical synthesis process, 12 ml uniform aqueous GO
dispersion (5 mg/ml) was dissolved in 9 ml deionized water, adjust the pH value of the diluted GO
dispersion to 11.5 by using ammonia solution (28 wt%), a mixed A solution was formed after stirred
at room temperature for 1 h. 0.082 ml 50% Mn(NO3)2 aqueous solution and 38 mg Ce(NO3)3·6H2O
were dissolved in 9 ml deionized water and stirred at room temperature for 1 h to form a mixed
solution B. The B solution was added dropwise to the A solution, and the mixture was vigorously
stirred for 2 h and then sonicated for 15 min. Then, the resulting suspension was transferred to a
Teflon-lined autoclave and reacted in an oven at 180 °C for 12 h. After the autoclave was naturally
cooled to room temperature, the composite wet gel was taken out and washed several times with
deionized water and then freeze dried at -45 °C for 48 h. For comparison, RGA, MnOx/RGA,
CeO2/RGA, MnOx, CeO2 and MnOx-CeO2 were also prepared by a similar preparation method. At the
same time, MnOx-CeO2/RGA was heat treated at 350 °C for 3h to verify that the material still has
excellent performance as a catalyst at higher temperatures.

2.2. Materials characterization

The morphology of the products was characterized by Scanning electron microscope (SEM)
equipped with an energy dispersive X-ray (EDS) fluorescence analysis (JSM-7600F). Transmission
electron microscope (TEM) images and High Resolution Transmission Electron Microscopy
(HRTEM) images were recorded on a JEOL JEM 2100F microscope at 200 kV. X-ray diffraction
(XRD) patterns were obtained using a Rigaku Ultimate Type IV (Japan) with Cu Kα irradiation
source (λ=1.5418 Å) through the 2θ range from 10° to 80°. The thermo-gravimetric (TG) was
obtained using a TGA5500 to study the structural thermal stability and composition of samples. The
specific surface area was measured with Quantachrome Surface Area and Porosity Analyzer and
calculated using the Brunauer–Emmett–Teller (BET) equation. Raman spectra were recorded on a
thermo fischer DXR multichannel confocal microspectrometer with 532 nm laser excitation. X-Ray
photoelectron spectroscopy (XPS) was obtained using a ThermoFisher ESCALAB 250Xi to study the
surface composition of samples by recording Mn 2p, Ce 3d, O 1s and C 1s XPS spectra.
Hydrogen temperature-programmed reduction (H2-TPR) was conducted with a AutoChem II
2920 auto-adsorption apparatus to analyze the temperature reducibility of the catalysts. First, the
catalysts (0.10 g) were pretreated at 300 °C for 30 min in a flowing stream of high-purity nitrogen and
then cooled to room temperature. The flowing gas was switched to 5% H2/N2, and the sample was
heated to 600 °C at a ramping rate of 10 °C·min−1. The consumption of H2 was measured by a thermal
conductivity detector (TCD).

2.3. Catalytic Activity Measurements

The selective catalytic reduction (SCR) activity measurement and the stability test were carried
out in a fixed-bed quartz microreactor (i.d.=8 mm) operating in a steady state flow mode. The test
system of the catalyst activity is shown in Fig.1. The simulated gas system uses a mixture of cylinder
gas to simulate industrial furnace flue gas. The simulated flue gas includes NO, O2, N2, and reducing

3
agent NH3. A 200 mg sample was used in each run. The reactant gas composition was typically 500
ppm NO, 500 ppm NH3, 3 vol% O2 and balance gas N2. The total flow rate of the feed gas was 500
ml·min–1, corresponding to a gas hourly space velocity (GHSV) of 30000 h–1. Before the start of the
experimental analysis, the simulated flue gas was passed into the reactor for 2 hours to saturate the
catalyst adsorption and avoid the reduction of NO caused by the physical adsorption of the catalyst.
Each temperature was stable for more than 20 minutes before analysis was started. The reaction
temperature was increased from 80 to 240 °C in steps of 20 °C/min. The NO/NO2/NOx concentrations
at the inlet and outlet of the reactor were monitored online by a flue gas analyzer (MRU VarioPlus,
Germany). NOx conversion and N2 selectivity were calculated as follows:
out
‫׋‬in
NOx െ ‫׋‬NOx
NOx conversion(%) ൌ 100 ൈ
‫׋‬in
NOx

out
‫׋‬in in
NO ൅ ‫׋‬NH3 െ ‫׋‬NO2 െ 2‫׋‬N2 O
N2 selectivity(%) ൌ 100 ൈ
‫׋‬in in
NO ൅ ‫׋‬NH3

3. Results and discussion

3.1. Morphological analysis

Morphological analysis of MnOx-CeO2/RGA was performed by using SEM and TEM. As shown
in Fig.2(a), the rich pore structure formed by the cross-linking between graphene sheets, which
resulted in a high specific surface area of MnOx-CeO2/RGA. As can be seen from the TEM image in
Fig. 2(b), the sheet of graphene of the composite aerogel has light transmissivity. MnOx-CeO2
nanoparticles with an average diameter of about 5 nm were uniformly distributed on both sides of the
RGO sheets, which can efficiently avoid the aggregation of particles. In more detail, the HRTEM
image in Fig. 2(c, d) shows that the interplanar spacings of the sample are 0.308 nm, 0.312 nm and
0.27 nm, corresponding to the (112) crystal plane of Mn3O4 and the (111), (200) crystal planes of
CeO2, respectively. Elemental mapping under EDS mode was also employed to further investigate the
microstructure and compositional distribution of the composite aerogels. The elemental analysis result
(Fig.2 e) shows that the MnOx-CeO2/RGA nanocomposite only contained Mn, Ce, O and C elements,
which indicated the material had high purity. The uniform distribution of MnOx and CeO2 in the
composites was also observed in elemental mapping (Fig.2 f), further confirming that the MnOx and
CeO2 nanoparticles had good dispersibility in the 3D structure of graphene aerogel.

3.2. XRD analysis

The crystalline phase of the samples were analyzed by powder XRD[33, 34]. Fig.3 shows the
XRD patterns of RGA, MnOx/RGA, CeO2/RGA, MnOx-CeO2 and MnOx-CeO2/RGA samples with 2θ
angles ranging from 10 ° to 80 °. A new RGO diffraction peak appeared at 23.9 ° after hydrothermal
reaction, confirming the elimination of oxidized functional groups in RGO. The RGO broad
diffraction peaks indicated that the graphene sheets were poorly ordered along their stacking direction
and there was a strong π-π stacking interaction between the sheets, which proved the formation of
graphene aerogels[35]. The sharp diffraction peak at 2θ = 17.9 ° (d = 4.94 Å) and 32.23 ° (d = 2.76 Å)
belonged to the (101) and (103) diffractive plane of Mn3O4. The sharp peak at about 2θ = 44.3° was
attributed to the (204) reflection of Mn2O3, corresponding to an interlayer spacing of 2.03 nm. The
characteristic diffraction peaks of MnO2 were 2θ = 37.9 ° (d = 2.367 Å), 59.8 ° (d = 1.545 Å), which
could be ascribed to (011) and (220) planes. The diffraction peak at 33.1°, 47.5° could be attributed to

4
the (200) and (220) crystal faces of the face-centered cubic fluorite structure CeO2. The peak at 28.78
° was attributed to the (112) plane of Mn3O4 (2θ = 28.9 °, d = 3.08 Å) and the (111) plane of CeO2 (2θ
=28.5 °, d = 3.12 Å). Since the weak diffraction intensity of graphene, no characteristic diffraction
peak of RGA was observed. It was confirmed by XRD analysis that the MnOx-CeO2/RGA composite
was successfully prepared via hydrothermal reaction.
3.3. TG analysis
To evaluate the mass ratio of MnOx-CeO2 to GA, a thermogravimetric analysis (TGA) was
performed. The temperature increased to 180 ° C and the weight loss of 2.4% was attributed to the
composite material removed the physically adsorbed water during the heating process. Continue to
increase the temperature, the quality of the composite material began to decline significantly after 250
Ԩ, which is caused by the pyrolysis of graphene. Fig. 4 shows that the mass ratio of graphene in the
composite material is about 38.9%, and the mass ratio of MnOx-CeO2 is about 58.6%.
3.4. BET analysis
The Brunauer-Emmett-Teller (BET) surface area, pore size and porous properties of the MnOx-
CeO2/RGA nanocomposite were evaluated by nitrogen adsorption-desorption isotherms[36]. As
shown in Fig.5, the adsorption-desorption isotherms of MnOx-CeO2/RGA indicated that the sample
was a mesoporous material and had a multi-level pore structure. Table.1 shows that the specific
surface area of the composite oxide prepared by hydrothermal method is much higher than that of
conventional nano-oxide, which proved the material prepared by this experimental method was easier
to obtain the sample with high porosity. As shown in the inset pictures, the average pore diameter was
9.4 nm. The specific surface area of MnOx-CeO2/RGA was 169.8 m2/g, which was much higher than
MnOx-CeO2 and MnOx-CeO2 powder. This result indicated that the agglomeration of the
nanoparticles can be strongly avoided by loading them onto the graphene sheets. The large specific
surface area can provide more contact opportunity between catalyst material and reaction gaseous,
thereby increasing the utilization of the active material. Due to the different drying methods, the
specific surface area (<200 m2/g) obtained by freeze drying or oven drying was lower than the
specific surface area of the sample obtained by CO2 supercritical drying (500-1200 m2/g)[37].
Compared with pure graphene aerogel, MnOx-CeO2/RGA nanocomposite had a lower specific surface
area, but it was proved that MnOx and CeO2 nanoparticles were effectively combined with graphene
sheets.
3.5. Raman analysis
The Raman spectra of MnOx, CeO2, RGA and MnOx-CeO2/RGA are shown in Fig. 6. The two
prominent peaks at 1340 cm-1 and 1590 cm-1 belonged to the D band and the G band of the Raman
spectrum of MnOx-CeO2/RGA. The characteristic Raman peak D band was related to the defects
existing in the graphene, and the G band was the vibration peak of the sp2 hybrid carbon atom[38].
The ID/IG (the intensity ratio of the D-band to the G-band) can judge the disorder of the material. In
general, the more defect were generated, the intensity of the D-band peak would be stronger. By
calculating, the ID/IG was 1.07, which was much higher than that of graphene oxide[39], indicating
GO was successfully reduced by hydrothermal process. Compared with RGA, the shifting of the D
band and the G band of MnOx-CeO2/RGA was observed, and the G band was moved from 1580 cm-1
to 1590 cm-1. These changes indicated the significant interaction and charge transfer between
graphene nanosheets and MnOx-CeO2 nanoparticles, which contributed to the redox reaction[40]. Due
to the strong interaction between MnOx and CeO2, more MnOx-CeO2 solid solution and oxygen
vacancies were formed [41] , which resulted in the movement of vibrational peak of CeO2(462 cm-1)
in MnOx-CeO2/RGA, compared with pure CeO2(458 cm-1). These results further indicated a good
combination of MnOx-CeO2 nanoparticles and graphene. At the same time, more oxygen vacancies
formed on the surface of the catalyst, which facilitated oxygen migration.

5
3.6. XPS analysis
The chemical composition, elemental valence and atomic concentration of the material were
further studied by XPS[42, 43], as shown in Fig. 7 and Fig. 8. Fig. 8(a) shows the Mn2p spectrum of
MnOx-CeO2/RGA composite. Three peaks at 641.5 eV, 642.5 eV and 643.3 eV were observed in
Mn2p3/2, which related to Mn2+, Mn3+ and Mn4+. The peak at 653.8 eV in the Mn2p1/2 spectrum
belonged to Mn4+[44]. Multivalent manganese oxide facilitated the transfer of electrons and promoted
the redox reaction. Fig. 8(b) shows that Ce existed in the mixed valence state of Ce4+ and Ce3+, and
the d orbital splitting resulted in the Ce 3d orbital consisting of two spin-orbit states of 3d3/2 and 3d5/2,
due to its non-stoichiometric nature[45]. The Ce4+ ion belonged to the 3d104f0 electronic state, and the
Ce3+ ion belonged to the 3d104f1 electronic state. The characteristic peaks of Ce4+ 3d3/2 were located at
901.5, 907.9 and 917.2 eV, and the characteristic peaks at 882.9, 889.1, and 898.8 eV were designated
as Ce4+ 3d5/2[46]. The two satellite peaks were located at 884.6 eV (Ce3+ 3d5/2) and 903.6 eV (Ce3+
3d3/2). In the redox environment, the oxygen vacancies can be rapidly formed or eliminated by the
mutual conversion of Ce4+ and Ce3+[47], thereby enhancing the activity of the catalyst SCR-NOx. The
XPS plot of O1s in Fig. 8(c) shows that there were two types of oxygen on surface, the peak at 529.9
eV belonged to lattice oxygen (Oβ), the peaks at 531.1 eV and 532.4 eV belonged to chemisorbed
oxygen (Oα, surface adsorbed oxygen). Chemically adsorbed oxygen (Oα) has a higher mobility than
lattice oxygen (Oβ) , and a higher concentration of chemically adsorbed oxygen Oα is beneficial to
promote NOx reduction and rapid “SCR” reaction[48]. The C1s peak of MnOx-CeO2/RGA (Fig. 8(d))
shows that the main peak near 284.8 eV was attributed to the C-C bond of the graphite structure, and
the peaks at 285.9 eV and 288.8 eV belonged to C-O and O-C=O. The weak intensity peaks of C-O
and O-C = O indicated that GO was reduced to RGO[49], only a small amount of residual oxygen-
containing groups were presented to provide an active site for attachment of the MnOx-CeO2 particles.
Fig. 7(e)~(h) shows the XPS of the heat treated sample. The heat-treated MnOx-CeO2/RGA still has
various valence states of MnOx and a higher concentration of chemically adsorbed oxygen Oα, which
is the reason why the material has better catalytic performance at higher temperatures.
3.7. H2-TPR Analysis
Redox performance is a key feature for catalyst materials, which is usually directly related to the
catalytic performance of the catalysts. The redox properties of MnOx-CeO2/RGA and heat-treated
MnOx-CeO2/RGA catalysts were investigated by H2-TPR characterization. As shown in Fig. 9, two
different reduction peaks at around 220 °C and 375 °C were shown in the curve of MnOx-CeO2,
respectively. As for the MnOx-CeO2/RGA catalyst, there were three different reduction peaks at 220
°C, 375 °C and 530 °C. The reduction peak near 220 °C was attributed to the reduction of MnO2 to
Mn2O3, and the reduction peak near 375 °C was attributed to the further reduction of Mn2O3 to
Mn3O4[50, 51]. The addition of graphene component led to an increase in oxygen mobility, which
promoted the reduction of Ce4+ to Ce3+, resulting in a broad and weak reduction peak at 530 ° C.[52].
The H2-TPR result reveals that MnOx-CeO2 has synergistic effect with RGA, which can effectively
improve the redox ability of MnOx-CeO2/RGA catalyst.
3.8. Catalytic activity
Fig.10 shows the schematic diagram of the catalytic mechanism of MnOx-CeO2/RGA. The
reaction mechanism is that under certain temperature and catalyst action, NH3 selectively reduces NOx
in the flue gas to N2 while generating water. Graphene aerogel provides high specific surface area and
a large number of catalytic sites, and the mutual conversion of different valence oxides can promote
the redox reactions, which is the key to achieving high efficient catalytic perfermence of the catalysts.
Fig.11(a) shows the catalytic efficiency of the prepared catalysts as a function of temperature. Both
catalysts exhibited lower SCR activity at temperatures below 100 °C, especially for MnOx-CeO2.
When the temperature raised to 220 °C, MnOx-CeO2 obtained 91% NOx conversion rate, while MnOx-
CeO2/RGA catalyst reached 99% NOx conversion rate, which indicated the catalyst prepared by this

6
method had a certain catalytic activity in the low temperature range, and the catalytic performance of
MnOx-CeO2/RGA was more superior. The result shows that MnOx-CeO2/RGA had excellent catalytic
performance in a lower temperature region, which was attributed to the high specific surface area of
graphene aerogel and provided a large number of catalytic active sites. The catalyst versus N2
selectivity curve is shown in Fig.11(b). Both catalysts achieved near 100% N2 selectivity below 100
°C. However, since NH3 was easily oxidized to form N2O at high temperature, the N2 selectivity of
the two materials tended to decrease with increasing temperature. Compared with MnOx-CeO2,
MnOx-CeO2/RGA had better selectivity. As shown in Fig. 11, MnOx-CeO2/RGA had excellent
activity and selectivity for the low-temperature NH3-SCR of NOx.
3.9. Stability test
The long time stability test of MnOx–CeO2/RGA catalyst at 220 °C is shown in Fig.12. Initially, the
NOx conversion can almost reach 99%. The conversion decreased slightly in the next 5 h and still
stabilized above 95% after 5 h. Fig.12 clearly shows that the high conversion can be consistently
stable for mMore than 18 h in the stability test.

4. Conclusion
In summary, we synthesized a 3D-structured MnOx-CeO2/RGA composites wrapping
nanoparticles inside the network by one-step hydrothermal method. The obtained material exhibited a
3D mesoporous structure, and the MnOx-CeO2 nanoparticles were uniformly anchored onto the RGO
sheet. The high specific surface area made the MnOx-CeO2 active component evenly distributed and
better contact with NOx. Various valence states of MnOx and oxygen vacancies can work as key redox
sites that facilitated NOx reduction.Catalytic activity tests demonstrate that MnOx-CeO2/RGA
exhibited excellent SCR activity and stability in a broad temperature window and the maximal NOx
conversion (‫׽‬99%) could be attained at 220 °C. Comparing oxide catalysts, composites can achieve
higher catalytic efficiency with less quality. We believe that the as-obtained composite materials have
great prospects in the field of low temperature SCR of NOx.

Acknowledgments
This work was financially supported by the Key Research and Development Project of Jiangsu
Province (BE2019734, BE2017151,BE2016171), the Major Program of Natural Science Fund in
Colleges and Universities of Jiangsu Province (15KJA430005), the Program of Science and
Technology of Suqian City (M201704, H201801, H201803), the National Natural Science Foundation
of China (51702156, 81471183), the Program for Changjiang Scholars and Innovative Research Team
in University (IRT_15R35), the Postgraduate Research & Practice Innovation Program of Jiangsu
Province (SJCX18_0342), the Priority Academic Program Development of Jiangsu Higher Education
Institutions and the Brand Major Program Development of Jiangsu Higher Education Institutions
(PPZY2015B128), the General Program of Natural Science Fund in Colleges and Universities of
Jiangsu Province (19KJB430023), Science and technology innovation project for overseas of Nanjing
City, Postdoctoral Science Foundation of Jiangsu Province (2019K005), China Postdoctoral Science
Foundation (2019M661781). Any opinions, findings, and conclusions or recommendations expressed
in this paper are those of the authors and do not necessarily reflect the views of these programs.

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Fig. 1 Test System of the catalyst activity

11
Fig. 2. SEM images of (a) MnOx-CeO2/RGA; TEM images of (b) MnOx-CeO2/RGA; HRTEM images
of (c, d) MnOx-CeO2/RGA; STEM of (e) EDX and (f) Elemental maps of MnOx-CeO2/RGA

12
Fig. 3. X-ray diffraction patterns of the RGA, MnOx/RGA, CeO2/RGA, MnOx-CeO2 and MnOx-
CeO2/RGA nanocomposites.

Fig. 4. TGA curves of the MnOx-CeO2 and MnOx-CeO2/RGA.

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Fig. 5. Nitrogen adsorption–desorption isotherms of (a) MnOx-CeO2/RGA,
(b) MnOx-CeO2

Fig. 6. Raman spectra of MnOx, CeO2, RGA and MnOx-CeO2/RGA

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 Fig. 7. XPS survey spectra of MnOx-CeO2/RGA

Fig. 8. High resolution XPS scans of (a). Mn 2p, (b). Ce 3d, (c). O 1s, (d).C 1s of MnOx-CeO2/RGA
and (e). Mn 2p, (f). Ce 3d, (g). O 1s, (h).C 1s of MnOx-CeO2/RGA heat treatment at 350 °C

15
 Fig. 9. H2-TPR profiles of (a). MnOx-CeO2 nanostructures, (b). MnOx-CeO2/RGA (c), MnOx-
CeO2/RGA heat treatment at 350 °C

Fig. 10. Schematic diagram of the catalytic mechanism of MnOx-CeO2/RGA

Fig. 11. (a) NH3-SCR performance of the catalysts. (b) N2 selectivity over the MnOx–CeO2 and
MnOx–CeO2/RGA catalysts. Reaction conditions: 500 ppm NO, 500 ppm NH3, 5% O2, balance N2,
and GHSV = 30000 h−1.

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Fig. 12. Stability test of the MnOx–CeO2/RGA catalyst. Reaction conditions: 500 ppm NO, 500 ppm
NH3, 5% O2, balance N2, and GHSV = 30000 h−1.

17
Table. 1 Pore structure of MnOx-CeO2 powder, MnOx-CeO2 and MnOx-CeO2/RGA

Average pore size

Sample BET surface area (m2/g)
(nm)

MnOx-CeO2 powder 10.8 1.5

MnOx-CeO2 60.7 1.7

MnOx-CeO2/RGA 169.8 9.4

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Highlights
1. MnOx-CeO2 nanoparticle reduction graphene oxide composite aerogel (MnOx-CeO2/RGA)
were synthesized.

2. In-situ MnOx-CeO2/RGA composite exhibited excellent SCR activity.

3. High specific surface area contribute to the enhanced SCR activity.

4. The maximum NOx conversion (99%) of composite aerogel could be attained at 220 °C.

Graphical Abstract

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 Author contributions section

Kunmeng Zhu completed the experimental conception, performed the data analyses and wrote a
manuscript;
Wenqian Yan contributed to the conception of the study;
Sijia Liu contributed significantly to analysis and manuscript preparation;
Xiaodong Wu helped perform the analysis with constructive discussions;
Sheng Cui and Xiaodong Shen gave instructive comments on the research and guided the
completion of the experiment

Declaration of Interest Statement

We declare that we do not have any commercial or associative interest that represents a
conflict of interest in connection with the work submitted

Xiaodong Shen, PhD

Professor

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