Spinel Mangane-Based Catalysts with High Oxygen Vacancy Used for NH3-SCR Reaction at Low Temperature

doi:10.19894/j.issn.1000-0518.220315

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (5): 697-707.DOI: 10.19894/j.issn.1000-0518.220315

• Full Papers • Previous Articles Next Articles

Spinel Mangane-Based Catalysts with High Oxygen Vacancy Used for NH₃-SCR Reaction at Low Temperature

Fan WU¹^,², He-Yuan TIAN¹^,², Peng LIU¹^,², Li-Wei SUN¹(), Yi-Bo ZHANG²^,³(), Xiang-Guang YANG¹^,²^,³()

^1.State Key Laboratory of Rare Earth Resource Utilization，Jilin Province Key Laboratory of Green Chemistry and Process，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.University of Science and Technology of China，Hefei 230026，China
^3.Ganjiang Innovation Academy，Chinese Academy of Sciences，Ganzhou 341000，China

Received:2022-09-27 Accepted:2023-03-27 Published:2023-05-01 Online:2023-05-26
Contact: Li-Wei SUN,Yi-Bo ZHANG,Xiang-Guang YANG
About author:xgyang@gia.cas.cn
yibozhang@gia.cas.cn
liweisun@ciac.ac.cn
Supported by:
the National Natural Science Foundation of China(22072141);the Youth Innovation Promotion Association of Chinese Academy of Sciences(2018263);Jiangxi Province “Double Thousand Plan”(jxsq2020101047);the Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3);the Self-deployed Projects of Ganjiang Innovation Academy, Chinese Academy of Sciences(E055C003)

Abstract

Abstract:

Different spinel composite oxide catalysts， LiMn₂O₄， ZnMn₂O₄ and CrMn₂O₄ are prepared and activities of the catalysts for selective catalytic reduction of NO _x by NH₃ （NH₃-SCR） are tested at 50~450 ℃. The effects of catalyst structure， metal elements and valence states on NH₃-SCR activity are investigated. The catalysts are characterized by physical adsorption instrument （BET）， X-ray diffractometer （XRD）， transmission electron microscope （TEM）， scanning electron microscope （SEM）， X-ray photoelectron spectroscopy （XPS）， NH₃ temperature-programmed desorption （NH₃-TPD） and H₂ temperature-programmed reduction （H₂-TPR），etc. The structure-activity relationship of spinel catalyst is also studied. The results show that： The LiMn₂O₄ spinel catalyst has the best activity with more than 90% NO conversion at the space velocity of 6×10⁴ mL/（g?h） at 150 ℃， and it shows more than 80% NO conversion at 100~400 ℃， demonstrating good low temperature activity and wide temperature range. However， the denitrification activity of ZnMn₂O₄ and CrMn₂O₄ is relative poor， and the two have similar activities. In the presence of water， the activity of LiMn₂O₄ decreased greatly， while the activities of ZnMn₂O₄ and CrMn₂O₄ decreases slightly， showing better water resistance. The conversion rate of ZnMn₂O₄ reach 90% at 150 ℃， which is better than that of CrMn₂O₄ in the presence of water. Spinel ZnMn₂O₄ has a good NO conversion rate in a wide temperature range and strong water resistance.

Key words: Selective catalytic reduction, Ammonia, Nitrogen oxide, Spinel oxide, Low temperature denitrification, Waste gas treatment

CLC Number:

O643.3

Fan WU, He-Yuan TIAN, Peng LIU, Li-Wei SUN, Yi-Bo ZHANG, Xiang-Guang YANG. Spinel Mangane-Based Catalysts with High Oxygen Vacancy Used for NH₃-SCR Reaction at Low Temperature[J]. Chinese Journal of Applied Chemistry, 2023, 40(5): 697-707.

Figures/Tables 12

Fig.1 XRD patterns of LiMn2O4 （A）， ZnMn2O4 （B）， CrMn2O4 （C） and MnO2 （D）

Table 1 Cell parameters （a） and particle size （D） values of each sample

Catalyst	a/nm	D/nm
LiMn₂O₄	0.296 0	28.0
ZnMn₂O₄	0.537 7	12.3
CrMn₂O₄	0.678 1	39.6
MnO₂	0.390 0	19.3

Fig.2 SEM images of LiMn2O4 （A）， ZnMn2O4 （B）， CrMn2O4 （C） and MnO2 （D）

Fig.3 TEM images of LiMn2O4 （A， B），ZnMn2O4 （C， D）， CrMn2O4 （E， F） and MnO2 （G， H）

Table 2 Structural characteristic parameters of different catalysts

Sample	Surface area/（m²?g^-1）	Pore diameter/nm	Pore volume/（cm³?g^-1）
LiMn₂O₄	22.01	3.05	0.14
ZnMn₂O₄	86.51	3.06	0.41
CrMn₂O₄	66.79	3.83	0.27
MnO₂	110.601	3.82	0.34

Fig.4 Catalytic reduction conversion rate （A） and NH3 conversion rate （B） with different NO catalysts

Fig.5 Mn2p （A） and O1s （B） XPS profiles of different catalysts

Table 3 The atomic concentration on the surface of different catalysts

Sample	x（Metal）/%	x（Mn）/%	x（O）/%	x（O₁）/%	x（O₂）/%	x（O₃）/%	x（Mn⁴⁺）/%
LiMn₂O₄	21.02	21.21	57.77	30.99	47.05	21.96	43.78
ZnMn₂O₄	15.75	22.06	62.19	36.49	42.73	20.78	57.70
CrMn₂O₄	12.00	23.72	64.28	33.90	45.34	20.76	35.91
MnO₂	-	31.03	68.97	27.12	40.31	32.57	59.55

Table 4 Binding energy （eV） of atoms on different catalysts

Sample	Mn			O
Sample	Mn²⁺	Mn³⁺	Mn⁴⁺	O₁	O₂	O₃
LiMn₂O₄	/	642.3/653.7	643.5/654.7	529.4	530.1	532.1
ZnMn₂O₄	/	641.9/653.5	643.3/654.8	530.1	530.7	531.8
CrMn₂O₄	640.8/652.4	642.1/653.6	643.8/654.8	529.9	530.5	531.6
MnO₂	/	641.8/653.3	643.2/654.4	529.2	529.8	532.1

Fig.6 NH3-TPD diagram on different catalysts

Fig.7 H2-TPR diagram on different catalysts

Fig.8 NO conversion rate of different catalysts in the presence of water

References 28

1	ZHANG N Q， LI L C， GUO Y Z， et al. A MnO₂-based catalyst with H₂O resistance for NH₃-SCR： study of catalytic activity and reactants-H₂O competitive adsorption［J］. Appl Catal B： Environ， 2020， 270： 118860.
2	ZHAN S H， QIU M Y， YANG S S， et al. Facile preparation of MnO₂ doped Fe₂O₃ hollow nanofibers for low temperature SCR of NO with NH₃［J］. J Mater Chem A， 2014， 2（48）： 20486-20493.
3	YU S H， LU Y Y， GAO F， et al. Study on the crystal plane effect of CuO/TiO₂ catalysts in NH₃-SCR reaction［J］. Catal Today， 2020， 339： 265-273.
4	LIETTI L L， ALEMANY J N， FERLAZZO FORZATTI P， et al. Reactivity and physicochemical characterization of V₂O₅-WO₃/TiO₂ De-NOx catalysts［J］. J Catal， 1995， 155： 117-130.
5	ZHOU X M， HUANG X Y， XIE A J， et al. V₂O₅-decorated Mn-Fe/attapulgite catalyst with high SO₂ tolerance for SCR of NOx with NH₃ at low temperature［J］. Chem Eng J， 2017， 326： 1074-1085.
6	ZHANG R D， LUO N， YANG W， et al. Low-temperature selective catalytic reduction of NO with NH₃ using perovskite-type oxides as the novel catalysts［J］. J Mol Catal A： Chem， 2013， 371： 86-93.
7	LYUMENG Y， LU P， CHEN X B， et al. The deactivation mechanism of toluene on MnOx-CeO₂ SCR catalyst ［J］. Appl Catal B： Environ， 2020， 277： 119257.
8	YANG B， JIN Q J， HUANG Q， et al. Synergetic catalytic removal of chlorobenzene and NO from waste incineration exhaust over MnNb_0.4Ce_0.2O catalysts： performance and mechanism study［J］. J Rare Earths， 2020， 38（11）： 1178-1189.
9	WANG X Y， LAN Z X， ZHANG K， et al. Structure-activity relationships of AMn₂O₄ （A=Cu and Co） spinels in selective catalytic reduction of NOx： experimental and theoretical study［J］. J Phys Chem C， 2017， 121（6）： 3339-3349.
10	ZHANG Q L， ZHANG Y Q， ZHANG T X， et al. Influence of preparation methods on iron-tungsten composite catalyst for NH₃-SCR of NO： the active sites and reaction mechanism［J］. Appl Surf Sci， 2020， 503： 190-202.
11	YU C， HOU D， HUANG B， et al. A MnOx@Eu-CeOx nanorod catalyst with multiple protective effects： strong SO₂-tolerance for low temperature DeNOx processes［J］. J Hazard Mater， 2020， 399： 123011.
12	YOU X C， SHENG Z Y， YU D Q， et al. Influence of Mn/Ce ratio on the physicochemical properties and catalytic performance of graphene supported MnOx-CeO₂ oxides for NH₃-SCR at low temperature［J］. Appl Surf Sci， 2017， 423： 845-854.
13	DONOVAN A P， UPHADE B S， SMIRNIOTIS P G. TiO₂-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH₃. evaluation and characterization of first row transition metals［J］. J Catal， 2004， 221（2）： 421-431.
14	LIU L， WANG B D， YAO X J， et al. Highly efficient MnOx/biochar catalysts obtained by air oxidation for low-temperature NH₃-SCR of NO［J］. Fuel， 2021， 283： 119336.
15	SINGH P P， THATIKONDA T， KUMAR K A， et al. Cu-Mn spinel oxide catalyzed regioselective halogenation of phenols and N-heteroarenes［J］. Org Chem， 2012， 77： 5823-5828.
16	GAO F Y， TANG X L， SANI Z D， et al. Spinel-structured Mn-Ni nanosheets for NH₃-SCR of NO with good H₂O and SO₂ resistance at low temperature［J］. Catal Sci Technol， 2020， 10（22）： 7486-7501.
17	KANG M， YEON T H， PARK E D， et al. Novel MnOx catalysts for NO reduction at low temperature with ammonia［J］. Catal Lett， 2006， 106（1/2）： 77-80.
18	LIU C， SHI J W， GAO C， et al. Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NOx with NH₃： a review［J］. Appl Catal B： General， 2016， 522： 54-69.
19	KIM K J， LEE J H， KOH T Y， et al. Improved cyclic stability by octahedral Co³⁺ substitution in spinel lithium manganese oxide thin-film cathode for rechargeable microbattery［J］. Electrochim Acta， 2016， 200： 84-89.
20	QI F H， XIONG S C， LIAO Y， et al. A novel dual layer SCR catalyst with a broad temperature window for the control of NO emission from diesel bus［J］. Catal Commun， 2015， 65： 108-112.
21	QI G S， YANG R T， et al. Performance and kinetics study for low-temperature SCR of NO with NH₃ over MnOx-CeO₂ catalyst［J］. J Catal， 2003， 217（2）： 434-441.
22	JONG H L， SCHMIEG S J， OH SE H. Improved NOx reduction over the staged Ag/Al₂O₃ catalyst system［J］. Appl Catal A： General， 2008， 342（1/2）： 78-86.
23	HAN L， CAI S， GAO M， et al. Selective catalytic reduction of NOx with NH₃ by using novel catalysts： state of the art and future prospects［J］. Chem Rev， 2019， 119（19）： 10916-10976.
24	GAO F Y， TANG X L， YI H H， et al. Improvement of activity， selectivity and H₂O&SO₂-tolerance of micro-mesoporous CrMn₂O₄ spinel catalyst for low-temperature NH₃-SCR of NOx［J］. Appl Surf Sci， 2019， 466： 411-424.
25	GAO F Y， TANG X L， YI H H， et al. In-situ DRIFTS for the mechanistic studies of NO oxidation over α-MnO₂， β-MnO₂ and γ-MnO₂ catalysts［J］. Chem Eng J， 2017， 322： 525-537.
26	LIAM J F， YANG Q， LI W， et al. Ceria modified FeMnO—enhanced performance and sulphur resistance for low-temperature SCR of NOx［J］. Appl Catal B： Environ， 2017， 206： 203-215.
27	YI T， LI J W， ZHANG Y B， et al. A novel nano-sized catalyst CeO₂-CuO/hollow ZSM-5 for NOx reduction with NH₃［J］. Chem Res Chin Univ， 2018， 34（4）： 661-664.
28	JIANG B， DENG B， ZHANG Z， et al. Effect of Zr addition on the low-temperature SCR activity and SO₂ tolerance of Fe-Mn/Ti catalysts［J］. J Phys Chem C， 2014， 118： 14866-14875.

[1]	Hui-Hui LI, Kai-Sheng YAO, Ya-Nan ZHAO, Li-Na FAN, Yu-Lin TIAN, Wei-Wei LU. Ionic Liquid-Modulated Synthesis of Pt-Pd Bimetallic Nanomaterials and Their Catalytic Performance for Ammonia Borane Hydrolysis to Generate Hydrogen [J]. Chinese Journal of Applied Chemistry, 2023, 40(4): 597-609.
[2]	Bing LI, Jun-Hui LIU, Ya-Kun SONG, Xiang LI, Xu-Ming GUO, Jian XIONG. Recent Advances in Application of Metal-Organic Frameworks for Hydrogen Generation by Catalytic Hydrolysis of Ammonia Borane [J]. Chinese Journal of Applied Chemistry, 2023, 40(3): 329-340.
[3]	Yang LIU, Hai-Bao ZHANG, Qiang CHEN. Optimization of Process Parameters for Ammonia Synthesis by Nanosecond Pulsed Dielectric Barrier Discharge Plasma [J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 268-276.
[4]	Rong CAO, Jie-Zhen XIA, Man-Hua LIAO, Lu-Chao ZHAO, Chen ZHAO, Qi WU. Theoretical Research Progress of Single Atom Catalysts in Electrochemical Synthesis of Ammonia [J]. Chinese Journal of Applied Chemistry, 2023, 40(1): 9-23.
[5]	LIU Yang, ZHANG Hai-Bao, CHEN Qiang. Research Progress on Ammonia Synthesis Using Low Temperature Plasma [J]. Chinese Journal of Applied Chemistry, 2021, 38(6): 622-636.
[6]	LIU Jun-Hui, GUO Xu-Ming, SONG Ya-Kun, GUO Xin-Wen. Recent Advances in Hydrogen Generation by Catalytic Hydrolysis of Ammonia Borane [J]. Chinese Journal of Applied Chemistry, 2021, 38(2): 157-169.
[7]	LIU Lin-Chang, GUO Ya-Jun, ZHU Hong-Lin, MA Jing-Jing, LI Zhong-Yi, SHUI Miao, ZHENG Yue-Qing. Research Progress on Supported Ultrafine Nano-catalysts for Hydrolytic Dehydrogenation of Ammonia Borane [J]. Chinese Journal of Applied Chemistry, 2021, 38(11): 1405-1422.
[8]	BI Yipiao, GONG Xue, YANG Fa, RUAN Mingbo, SONG Ping, XU Weilin. Polyvalent MnO_x/C Electrocatalyst for Highly Efficient Nitrogen Reduction Reaction [J]. Chinese Journal of Applied Chemistry, 2020, 37(9): 1048-1055.
[9]	PENG Bingxian, WANG Xiaoli, LIU Ruihan, ZHOU Aihong. Degradation of Ammonia-Nitrogen in Wastewater by TiO₂/Pumice Photocatalyst under Solar Light [J]. Chinese Journal of Applied Chemistry, 2017, 34(8): 946-954.
[10]	LI Yuhe, HU Hailong. Hydrothermal Synthesis of an Approximate Two-Dimensional Hexgonal Nickel Nanoplatelets [J]. Chinese Journal of Applied Chemistry, 2017, 34(8): 918-927.
[11]	DING Ding, WANG Qi, JIN Fang, CHEN Yazhong, CUI Peng, LIU Rong, SHEN Hao. Influences of the Ammonia Evaporation Pressure on the Structure of Cu/SiO₂ Catalysts and Catalytic Performances for Dimethyl Oxalate Hydrogenation to Ethylene Glycol [J]. Chinese Journal of Applied Chemistry, 2016, 33(4): 466-472.
[12]	HUANG Lu1, YANG Yao1, PAN Daodong1,2*. Electrocatalytic Oxidation of Ammonia with Ir Catalysts Supported on TiO₂ [J]. Chinese Journal of Applied Chemistry, 2013, 30(05): 584-589.
[13]	YU Mingzhu1, LI linru1, LU Tianhong1, CHEN Zhaoyang2, MA Chunan2, DU Jiangyan1*. Electrocatalytic Performanace of Ir Catalyst Supported on Mixture of WC and Vulcan XC-72 Carbon for Ammonia Oxidation [J]. Chinese Journal of Applied Chemistry, 2013, 30(04): 448-452.
[14]	LI Linru1, CHEN Chong1, XU Bin2, CAO Gaoping2, YANG Yusheng2, LU Tianhong1,3*. Electrocatalytic Performance of Ir Catalyst Supported on Macropore Carbon for Ammonia Oxidation [J]. Chinese Journal of Applied Chemistry, 2012, 29(01): 95-99.
[15]	TANG Yawen1,2, XIE Guofang2, KONG Qingmei2, CHEN Yu2, LU Lude1, LU Tianhong2*. Preparation of Carbon Supported Ir-Co Catalyst and Its Electrocatalytic Performance for Ammonia Oxidation [J]. Chinese Journal of Applied Chemistry, 2011, 28(08): 931-935.

Spinel Mangane-Based Catalysts with High Oxygen Vacancy Used for NH₃-SCR Reaction at Low Temperature

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 28

Related Articles 15

Recommended Articles

Metrics

Comments