稀土改性锰基低温NH3-SCR催化剂的理性设计:机理、策略与展望

doi:10.1016/S1872-2067(26)65163-7

催化学报 ›› 2026, Vol. 89: 40-75.DOI: 10.1016/S1872-2067(26)65163-7

稀土改性锰基低温NH₃-SCR催化剂的理性设计:机理、策略与展望

姚悦洋^a^,^b, 张楠^b, 焦睿谦^b, 刘盼盼^b, 冯祥波^a^,^*(), 马丹丹^b, 李俊^b, 陈玉^b, 石建稳^b^,^*()

^a西京学院,西安市先进光电子材料与能源转换器件重点实验室, 材料与能源科学技术研究院,陕西西安 710123
^b西安交通大学电气工程学院,电工材料电气绝缘全国重点实验室,陕西西安 710049

收稿日期:2026-01-13 接受日期:2026-03-16 出版日期:2026-10-18 发布日期:2026-09-01
通讯作者: *电子信箱: fengxiangbo@xjtu.edu.cn (冯祥波),
jianwen.shi@mail.xjtu.edu.cn (石建稳).
基金资助:
国家自然科学基金(52470127);国家自然科学基金(52306165);中央高校基础研究经费(xtr062023001);中央高校基础研究经费(xtr052024009);陕西省创新能力支持计划项目(2024RS-CXTD-22);西安市科学技术局社会科技发展创新示范项目(2024JH-CXSF-0020);陕西秦创园“科学家+工程师”团队建设项目(2025QCY-KXJ-097)

Rational design of rare earth-modified Mn-based catalysts for low-temperature NH₃-SCR: Mechanisms, strategies, and prospects

Yueyang Yao^a^,^b, Nan Zhang^b, Ruiqian Jiao^b, Panpan Liu^b, Xiangbo Feng^a^,^*(), Dandan Ma^b, Jun Li^b, Yu Chen^b, Jian-Wen Shi^b^,^*()

^aTechnological Institute of Materials & Energy Science (TIMES), Xi’an Key Laboratory of Advanced Photo-electronics Materials and Energy Conversion Device, School of Materials and New Energy, Xijing University, Xi’an 710123, Shaanxi, China
^bState Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China

Received:2026-01-13 Accepted:2026-03-16 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:fengxiangbo@xjtu.edu.cn(X. Feng),jianwen.shi@mail.xjtu.edu.cn(J.-W. Shi).
About author:Xiangbo Feng (Technological Institute of Materials & Energy Science, Xijing University) received his Ph.D. degree and conducted postdoctoral research at Xi'an Jiaotong University. He currently serves as a Professor, Associate Dean at Xijing University, and holds several concurrent positions including specially-appointed researcher at Xi'an Jiaotong University. He is a (youth) editorial board member for Journal of Rare Earths and Frontiers in Thermal Engineering. His research focuses on green energy and low-carbon conversion, efficient control of atmospheric pollution, and the development of novel nanoporous catalytic materials. He has presided over multiple research projects, including grants from the National Natural Science Foundation of China. He has published over 60 SCI papers as the first or corresponding author, with 17 papers recognized as ESI Highly Cited Papers and 15 as ESI Hot Papers. He is a recipient of several awards, including the Shaanxi and Chongqing Natural Science Awards. He has been selected as a Wiley China High-Contribution Author and listed among the World's Top 2% Scientists, and was honored as a "Young Science and Technology Star" in the Shaanxi Innovation Talent Climbing Project, among multiple other talent honors.
Jian-Wen Shi (School of Electrical Engineering, Xi‘an Jiaotong University) is a professor and doctoral supervisor at Xi’an Jiaotong University. He received his B.S. in 2000 and Ph.D degree in 2007 from China University of Petroleum (East China). He joined the faculty of the Institute of Urban Environment, Chinese Academy of Sciences, in 2007 as an assistant researcher, and was promoted to associate researcher in 2009. From 2010 to 2011, he conducted research as a visiting scholar at The University of Queensland (Australia). Since the end of 2013, he has been working at the School of Electrical Engineering, Xi‘an Jiaotong University, and was promoted to professor in 2022. He has been recognized as a Distinguished Teacher of Shaanxi Provincial Excellent Doctoral Dissertation and the Chief Scientist of the “Scientists + Engineers” team in the Qinchuangyuan innovation platform of Shaanxi Province. His research interests focus on energy and environmental catalysis, including the conversion of solar energy to chemical energy, conversion of electrical energy to chemical energy (such as direct seawater splitting and CO₂ electrocatalytic reduction), and catalytic purification of flue gas from coal-fired power plants. He has published more than 170 peer-reviewed SCI papers in journals such as Nat. Commun., Angew. Chem. Int. Ed., ACS Nano, Appl. Catal. B, and Chin. J. Catal with 35 ESI Highly Cited Papers. His work has been cited over 11000 times, with an H-index of 67 (Web of Science). He has been consecutively named in Stanford University‘s World’s Top 2% Scientists List for six years (2020-2025).
Supported by:
National Natural Science Foundation of China(52470127);National Natural Science Foundation of China(52306165);Fundamental Research Funds for the Central Universities(xtr062023001);Fundamental Research Funds for the Central Universities(xtr052024009);Innovation Capability Support Plan Project in Shaanxi Province(2024RS-CXTD-22);Scientific and Technical Innovation Demonstration Project for Social Development of Xi'an Municipal Bureau of Science and Technology(2024JH-CXSF-0020);Shaanxi Province Qinchuangyuan "Scientists+Engineers" Team Construction Project(2025QCY-KXJ-097)

摘要/Abstract

摘要：

燃煤、钢铁及水泥等行业排放的氮氧化物(NO_x)是造成区域灰霾、酸雨和臭氧污染的重要前体物. 以NH₃为还原剂的选择性催化还原(NH₃-SCR)技术是目前最高效的烟气脱硝手段之一. 商用V₂O₅-WO₃/TiO₂催化剂在中高温段(300-400 °C)活性优异, 但低温活性差, 且钒具有生物毒性. 锰基(MnO_x)催化剂因其多变的价态和优异的氧化还原性, 在低温(< 250 °C) SCR领域展现出巨大潜力, 但面临N₂选择性差、易受SO₂和H₂O中毒失活以及操作窗口窄等关键挑战. 稀土(RE)元素改性被证明是优化锰基催化剂性能的有效策略, 但目前缺乏对其构效关系和反应机理的系统性认识.

本文梳理和总结了稀土改性锰基催化剂在低温NH₃-SCR领域的最新研究进展, 探讨其构效关系、反应机理及抗中毒机制. 首先从本征结构出发, 建立了纯MnO_x催化剂的价态、晶相、形貌及制备方法与SCR性能的关联, 为理解RE改性带来的增益提供了基准. 随后, 将RE-Mn催化剂分为三大类: RE改性MnO_x, RE-Mn复合氧化物以及负载型RE-Mn催化剂, 重点剖析了不同稀土元素(如Ce, Sm, Gd, Er, Eu等)在提升低温活性、拓宽温度窗口、提高N₂选择性以及构建多层次H₂O/SO₂抗中毒机制中的作用. 研究发现, RE的引入主要通过电子调控优化Mn³⁺/Mn⁴⁺循环, 增加表面化学吸附氧浓度, 并调变Lewis酸位与Brönsted酸位的数量与强度. 例如, Ce通过其优异的储氧能力和Ce³⁺/Ce⁴⁺氧化还原对, 促进“快速SCR”反应路径, 同时通过优先硫酸化形成动态沉积-分解平衡, 有效保护Mn活性位点; Sm和Gd通过降低反应活化能、稳定晶相结构, 显著提升低温活性和N₂选择性; Er和Eu则能有效拓宽活性温度窗口. 进一步阐述了在Mn-RE-M三元复合氧化物体系中, 引入第三金属(如Fe, Co, Ni, Nb等)如何通过功能互补, 构建多电子转移循环(如Mn³⁺ + Co³⁺ ⇌ Mn⁴⁺ + Co²⁺)或调变表面酸性与吸附选择性, 从而在更宽的温度范围内实现活性、选择性与稳定性的协同优化. 在负载型催化剂部分, 对比了TiO₂, Al₂O₃, 碳材料及分子筛等载体的作用, 指出载体不仅能通过金属-载体相互作用稳定活性组分, 还能通过特定晶面暴露、限域效应或构建疏水表面等方式, 进一步增强抗中毒能力和稳定性. 最后, 从反应机理层面深度解析了RE改性的本质: RE元素通过调变电子结构, 优化了Langmuir-Hinshelwood (L-H)和Eley-Rideal (E-R)反应路径随温度的动态切换, 并通过对中间体的调控抑制了N₂O等副产物的生成, 从而实现了高活性和高N₂选择性的统一.

未来研究应聚焦真实工况下催化剂的长期稳定性与抗中毒机制, 探索低成本、高原子利用率的稀土设计, 并推进实验室成果的工程化应用. 本综述为开发面向复杂烟气条件的高效稀土-锰基低温SCR催化剂提供了设计原则和理论指导.

关键词: 选择性催化还原, 锰基催化剂, 稀土改性, 低温活性, 反应机理, 抗中毒策略

Abstract:

Nitrogen oxides (NO_x) emitted from industrial processes pose severe environmental threats, necessitating efficient abatement technologies. Selective catalytic reduction with NH₃ (NH₃-SCR) at low temperatures represents a promising route, with Mn-based oxides being among the most active candidates. However, their practical application is hindered by insufficient N₂ selectivity, susceptibility to SO₂ and H₂O poisoning, and a narrow operational window. Rare earth (RE) modification has emerged as a highly effective strategy for optimizing Mn-based catalysts in low-temperature NH₃-SCR of NO_x, yet a systematic understanding of the structure-activity relationships and reaction mechanisms remains lacking. This review provides a systematic and mechanistic overview of recent advances in RE-modified Mn-based catalysts for low-temperature NH₃-SCR. We first establish the structural-performance relationships of pure MnO_x, focusing on valence states, crystal phases, morphologies, and synthesis methods. Subsequently, we classify and discuss three major catalyst families: RE-modified MnO_x, RE-Mn composite oxides, and supported RE-Mn systems. Special emphasis is placed on the roles of RE elements in enhancing low-temperature activity, broadening the temperature window, improving N₂ selectivity, and constructing multi-level anti-poisoning mechanisms against H₂O and SO₂. We further elucidate the underlying reaction pathways and how RE doping modulates the electronic structure, active site distribution, and intermediate transformation. Finally, we identify key challenges for industrial deployment, such as long-term stability under complex flue gas, scalability, and cost-effectiveness, and propose future research directions toward the rational design of robust, high-performance SCR catalysts. This work provides a mechanistic framework and design principles for developing high-performance RE-Mn catalysts under practical flue-gas conditions.

Key words: Selective catalytic reduction, Mn-based catalysts, Rare earth modification, Low-temperature activity, Reaction mechanism, Anti-poisoning strategies

姚悦洋, 张楠, 焦睿谦, 刘盼盼, 冯祥波, 马丹丹, 李俊, 陈玉, 石建稳. 稀土改性锰基低温NH₃-SCR催化剂的理性设计:机理、策略与展望[J]. 催化学报, 2026, 89: 40-75.

Yueyang Yao, Nan Zhang, Ruiqian Jiao, Panpan Liu, Xiangbo Feng, Dandan Ma, Jun Li, Yu Chen, Jian-Wen Shi. Rational design of rare earth-modified Mn-based catalysts for low-temperature NH₃-SCR: Mechanisms, strategies, and prospects[J]. Chinese Journal of Catalysis, 2026, 89: 40-75.

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参考文献

[1]	M. P. Heap, S. L. Chen, J. C. Kramlich, J. M. McCarthy, D. W. Pershing, Nature, 1988, 335, 620-622.
[2]	M. G. Schultz, T. Diehl, G. P. Brasseur, W. Zittel, Science, 2003, 302, 624-627.
[3]	B. Gu, L. Zhang, R. Van Dingenen, M. Vieno, H. J. Van Grinsven, X. Zhang, S. Zhang, Y. Chen, S. Wang, C. Ren, S. Rao, M. Holland, W. Winiwarter, D. Chen, J. Xu, M. A. Sutton, Science, 2021, 374, 758-762.
[4]	K. Song, J.-W. Shi, X. Zhou, Y. Gui, J. Li, D. Ma, Y. Chen, C. He, Y. Jia, B. Qin, L. Liang, Y. Zhang, Y. Cheng, S. Wang, Appl. Catal. B, 2024, 354, 124131.
[5]	K. Song, X. Zhou, D. Ma, X. Guo, J. Li, S. Yang, P. Xiao, R. Chen, J.-W. Shi, Process. Saf. Environ. Prot., 2024, 191, 897-906.
[6]	L. Han, S. Cai, M. Gao, J.-Y. Hasegawa, P. Wang, J. Zhang, L. Shi, D. Zhang, Chem. Rev., 2019, 119, 10916-10976.
[7]	R. Chen, T. Zhang, Y. Guo, J. Wang, J. Wei, Q. Yu, Chem. Eng. J., 2021, 420, 127588.
[8]	W. Dong, Y. Zhu, H. Chang, C. Wang, J. Yang, J. Shi, J. Gao, W. Yang, L. Lan, Y. Wang, X. Zhang, H. Dai, Y. Miao, L. Xu, Z. He, C. Song, S. Wu, D. Wang, N. Yu, E. Wang, Nature, 2021, 589, 586-590.
[9]	F. Gholami, M. Tomas, Z. Gholami, M. Vakili, Sci. Total Environ., 2020, 714, 136712.
[10]	R. Jiao, N. Zhang, D. Ma, P. Liu, Y. Yao, X. Feng, K. Lin, J. Li, Y. Chen, J.-W. Shi, Coord. Chem. Rev., 2026, 558, 217804.
[11]	Y. Pan, S. Sanati, R. Abazari, A. Jankowska, J. Goscianska, V. Srivastava, U. Lassi, J. Gao, Coord. Chem. Rev., 2025, 522, 216231.
[12]	J.-K. Lai, I. E. Wachs, ACS Catal., 2018, 8, 6537-6551.
[13]	S. W. Byun, S. J. Lee, M. Kim, W.-B. Bae, H. Shin, M. J. Hazlett, D. Kang, B. Tesfaye, P. W. Park, S. B. Kang, Chem. Eng. J., 2022, 444, 136517.
[14]	F. Liu, W. Shan, X. Shi, C. Zhang, H. He, Chin. J. Catal., 2013, 32, 1113-1128.
[15]	A. Shi, X. Wang, T. Yu, M. Shen, Appl. Catal. B, 2011, 106, 359-369.
[16]	J. Huang, H. Huang, L. Liu, H. Jiang, Mol. Catal., 2018, 446, 49-57.
[17]	C. Chen, H. Xie, P. He, X. Liu, C. Yang, N. Wang, C. Ge, Appl. Surf. Sci., 2022, 571, 151285.
[18]	D. An, S. Yang, W. Zou, J. Sun, W. Tan, J. Ji, Q. Tong, C. Sun, D. Li, L. Dong, J. Phys. Chem. C, 2022, 126, 12168-12177.
[19]	F. Eigenmann, M. Maciejewski, A. Baiker, Appl. Catal. B, 2006, 62, 311-318.
[20]	H. Kang, J. Wang, J. Zheng, W. Chu, C. Tang, J. Ji, R. Ren, M. Wu, F. Jing, Mol. Catal., 2021, 501, 111376.
[21]	N. Zhang, L. Li, Y. Guo, J. He, R. Wu, L. Song, G. Zhang, J. Zhao, D. Wang, H. He, Appl. Catal. B, 2020, 270, 118860.
[22]	G. Gao, J.-W. Shi, Z. Fan, C. Gao, C. Niu, Chem. Eng. J., 2017, 325, 91-100.
[23]	X. Tang, J. Li, L. Sun, J. Hao, Appl. Catal. B, 2010, 99, 156-162.
[24]	L. Zhang, L. Li, Y. Cao, X. Yao, C. Ge, F. Gao, Y. Deng, C. Tang, L. Dong, Appl. Catal. B, 2015, 165, 589-598.
[25]	D. Meng, W. Zhan, Y. Guo, Y. Guo, L. Wang, G. Lu, ACS Catal., 2015, 5, 5973-5983.
[26]	B. Wang, M. Wang, L. Han, Y. Hou, W. Bao, C. Zhang, G. Feng, L. Chang, Z. Huang, J. Wang, ACS Catal., 2020, 10, 9034-9045.
[27]	G. Qi, R. T. Yang, R. Chang, Appl. Catal. B, 2004, 51, 93-106.
[28]	Z. Fan, J.-W. Shi, C. Gao, G. Gao, B. Wang, Y. Wang, C. He, C. Niu, Chem. Eng. J., 2018, 348, 820-830.
[29]	G. Gao, J.-W. Shi, C. Liu, C. Gao, Z. Fan, C. Niu, Appl. Surf. Sci., 2017, 411, 338-346.
[30]	Z. Fang, S. Zhang, A. Wang, Y. Guo, Y. Guo, L. Wang, W. Zhan, J. Rare Earths, 2023, 41, 917-925.
[31]	C. Gao, J.-W. Shi, Z. Fan, G. Gao, C. Niu, Catalysts, 2018, 8, 11.
[32]	X. Feng, J. Zhu, K. Song, J. Zeng, X. Zhou, X. Guo, K. Lin, C. Zhang, C. Xie, J.-W. Shi, Sep. Purif. Technol., 2024, 336, 126285.
[33]	X. Tang, C. Wang, F. Gao, Y. Ma, H. Yi, S. Zhao, Y. Zhou, J. Environ. Chem. Eng., 2020, 8, 104399.
[34]	X. Yao, J. Cao, L. Chen, K. Kang, Y. Chen, M. Tian, F. Yang, Chin. J. Catal., 2019, 40, 733-743.
[35]	S. Zhao, K. Song, J. Zhu, D. Ma, J.-W. Shi, Sep. Purif. Technol., 2022, 302, 122119.
[36]	L. J. France, Q. Yang, W. Li, Z. Chen, J. Guang, D. Guo, L. Wang, X. Li, Appl. Catal. B, 2017, 206, 203-215.
[37]	T. V. W. Janssens, H. Falsig, L. F. Lundegaard, P. N. R. Vennestrøm, S. B. Rasmussen, P. G. Moses, F. Giordanino, E. Borfecchia, K. A. Lomachenko, C. Lamberti, S. Bordiga, A. Godiksen, S. Mossin, P. Beato, ACS Catal., 2015, 5, 2832-2845.
[38]	N. Tang, Y. Liu, H. Wang, Z. Wu, J. Phys. Chem. C, 2011, 115, 8214-8220.
[39]	L. Yao, Q. Liu, S. Mossin, D. Nielsen, M. Kong, L. Jiang, J. Yang, S. Ren, J. Wen, J. Hazard. Mater., 2020, 387, 121704.
[40]	N.-Y. Topsøe, Science, 1994, 265, 1217-1219.
[41]	K. Song, K. Guo, Y. Lv, D. Ma, Y. Cheng, J.-W. Shi, ACS Appl. Mater. Interfaces, 2023, 15, 4132-4143.
[42]	K. Song, J. Hu, P. Lu, D. Ma, X. Zhou, J. Li, T. Jiang, L. Li, S. Wu, J.-W. Shi, Appl. Catal. B, 2024, 343, 123548.
[43]	H. Yuan, N. Sun, J. Chen, J. Jin, H. Wang, P. Hu, ACS Catal., 2018, 8, 9269-9279.
[44]	J. Yang, Y. Huang, J. Su, L. Chen, M. Zhang, M. Gao, M. Yang, F. Wang, X. Zhang, B. Shen, Sep. Purif. Technol., 2022, 297, 121544.
[45]	M. Wang, S. Ren, X. Xing, Y. Zhou, J. Yang, L. Chen, X. Li, J. Energy Inst., 2022, 103, 54-59.
[46]	D. H. Kim, Y. J. Park, K.-Y. Lee, H. P. Ha, D. W. Kwon, Appl. Catal. A, 2022, 643, 118770.
[47]	D. Wang, Q. Yao, S. Hui, Y. Niu, Fuel, 2019, 251, 23-29.
[48]	S. Yang, S. Xiong, Y. Liao, X. Xiao, F. Qi, Y. Peng, Y. Fu, W. Shan, J. Li, Environ. Sci. Technol., 2014, 48, 10354-10362.
[49]	J. Yang, S. Ren, B. Su, Y. zhou, G. Hu, L. Jiang, J. Cao, W. Liu, L. Yao, M. Kong, J. Yang, Q. Liu, Catal. Lett., 2021, 151, 2964-2971.
[50]	S. Yang, Y. Fu, Y. Liao, S. Xiong, Z. Qu, N. Yan, J. Li, Catal. Sci. Technol., 2014, 4, 224-232.
[51]	L. Zhang, X. Wen, Z. Lei, L. Gao, X. Sha, Z. Ma, H. He, Y. Wang, Y. Jia, Y. Li, AIP Adv., 2018, 8, 045004.
[52]	S. Feng, Z. Li, B. Shen, P. Yuan, J. Ma, Z. Wang, W. Kong, J. Environ. Manag., 2022, 317, 115457.
[53]	N. Zhang, X. Ju, X. Feng, K. Song, Y. Chen, J.-W. Shi, Mater. Today, 2025, 89, 312-343.
[54]	W. Chen, R. Zou, X. Wang, ACS Catal., 2022, 12, 14347-14375.
[55]	F. Lin, Q. Wang, J. Zhang, J. Jin, S. Lu, J. Yan, Ind. Eng. Chem. Res., 2019, 58, 22763-22770.
[56]	Y. Qi, X. Shan, M. Wang, D. Hu, Y. Song, P. Ge, J. Wu, Water Air Soil Pollut., 2020, 231, 289.
[57]	F. Gao, X. Tang, H. Yi, C. Chu, N. Li, J. Li, S. Zhao, Chem. Eng. J., 2017, 322, 525-537.
[58]	X. Liu, F. Liu, J. Li, Y. Lan, J. Yang, A. Murali, C. Chen, W. Zhang, Inorg. Chem. Commun., 2023, 155, 111093.
[59]	B. Zhao, R. Ran, X. Wu, D. Weng, Appl. Catal. A, 2016, 514, 24-34.
[60]	P. Gong, J. Xie, D. Fang, D. Han, F. He, F. Li, K. Qi, Chin. J. Catal., 2017, 38, 1925-1934.
[61]	L. Chen, S. Ren, X. Xing, J. Yang, J. Li, J. Yang, Q. Liu, J. Environ. Chem. Eng., 2022, 10, 108239.
[62]	S. S. Rao, S. Sharma, Can. J. Chem. Eng., 2023, 101, 6521-6533.
[63]	Y. Li, Y. Li, Y. Wan, S. Zhan, Q. Guan, Y. Tian, RSC Adv., 2016, 6, 54926-54937.
[64]	J.-W. Shi, C. Gao, C. Liu, Z. Fan, G. Gao, C. Niu, J. Nanopart. Res., 2017, 19, 194.
[65]	X. Feng, B. Wang, G. Gao, S. Gao, C. Xie, J.-W. Shi, Fuel, 2023, 352, 129159.
[66]	X. Yao, K. Ma, W. Zou, S. He, J. An, F. Yang, L. Dong, Chin. J. Catal., 2017, 38, 146-159.
[67]	J. Ji, N. Gao, W. Song, Y. Tang, Y. Cai, L. Han, L. Cheng, J. Sun, S. Ma, Y. Chu, C. Tang, L. Dong, Appl. Catal. B, 2023, 324, 122263.
[68]	X. Fang, Y. Liu, Y. Cheng, W. Cen, ACS Catal., 2021, 11, 4125-4135.
[69]	L. Wang, X. Li, S. Ren, M. Liu, X. Wang, W. Wang, C. He, S. Chai, C. Zheng, X. Li, Y. Chai, Sep. Purif. Technol., 2025, 379, 135179.
[70]	L. Wang, S. Ren, X. Li, C. He, C. Zheng, X. Li, S. Chai, K. Li, C. C. Xu, J. Environ. Chem. Eng., 2025, 13, 116933.
[71]	K. Song, S. Zhao, Z. Li, K. Li, Y. Xu, Y. Zhang, Y. Cheng, J.-W. Shi, J. Colloid Interface Sci., 2023, 629, 243-255.
[72]	X. Xiao, J. Wang, X. Jia, C. Ma, W. Qiao, L. Ling, ACS Omega, 2021, 6, 12801-12812.
[73]	J. Wang, H. Xie, D. Shu, T. Chen, H. Liu, X. Zou, D. Chen, Fuel, 2024, 356, 129604.
[74]	P. Sun, R.-T. Guo, S.-M. Liu, S.-X. Wang, W.-G. Pan, M.-Y. Li, Appl. Catal. A, 2017, 531, 129-138.
[75]	Y. Zhang, P. Wu, G. Li, K. Zhuang, K. Shen, S. Wang, T. Huang, Environ. Sci. Pollut. Res., 2020, 27, 26954-26964.
[76]	C. Gao, J.-W. Shi, Z. Fan, Y. Yu, J. Chen, Z. Li, C. Niu, Fuel Process. Technol., 2017, 167, 322-333.
[77]	C. Niu, B. Wang, Y. Xing, W. Su, C. He, L. Xiao, Y. Xu, S. Zhao, Y. Cheng, J.-W. Shi, J. Clean. Prod., 2021, 290, 125858.
[78]	Q. Zhu, A. Wang, J. Zhang, Y. Guo, Y. Guo, L. Wang, W. Zhan, Catalysts, 2022, 12, 471.
[79]	B. Qin, R.-T. Guo, J. Zhou, L.-G. Wei, T.-Y. Yin, W.-G. Pan, Appl. Surf. Sci., 2022, 598, 153823.
[80]	H. Xie, P. He, C. Chen, C. Yang, S. Chai, N. Wang, C. Ge, Catal. Lett., 2023, 153, 850-862.
[81]	Y. Yang, F. Zhu, S. Li, D. Zhao, S. Ding, S. Wang, S. Shi, C. Chen, Appl. Surf. Sci., 2024, 669, 160514.
[82]	L. Song, C. Liu, C. Bian, X. Cheng, X. Li, Y. Cheng, S. Li, X. Fan, H. He, Catal. Today, 2024, 437, 114768.
[83]	X. Zhang, S. Lv, X. Zhang, K. Xiao, X. Wu, J. Environ. Sci., 2021, 101, 1-15.
[84]	J. Chen, P. Fu, D. Lv, Y. Chen, M. Fan, J. Wu, A. Meshram, B. Mu, X. Li, Q. Xia, Chem. Eng. J., 2021, 407, 127071.
[85]	K.-M. Zhu, W.-Q. Yan, S.-J. Liu, X.-D. Wu, S. Cui, X.-D. Shen, Appl. Surf. Sci., 2020, 508, 145024.
[86]	L. Ye, P. Lu, X. Chen, P. Fang, Y. Peng, J. Li, H. Huang, Appl. Catal. B, 2020, 277, 119257.
[87]	C. Yang, J. Yang, Q. Jiao, D. Zhao, Y. Zhang, L. Liu, G. Hu, J. Li, Ceram. Int., 2020, 46, 4394-4401.
[88]	L. Gan, K. Li, W. Yang, J. Chen, Y. Peng, J. Li, Chem. Eng. J., 2020, 391, 123473.
[89]	H. Jiang, J. Wang, J. Zhou, Y. Chen, M. Zhang, Ind. Eng. Chem. Res., 2019, 58, 1760-1768.
[90]	C. Li, X. Tang, H. Yi, L. Wang, X. Cui, C. Chu, J. Li, R. Zhang, Q. Yu, Appl. Surf. Sci., 2018, 428, 924-932.
[91]	X. Yao, T. Kong, L. Chen, S. Ding, F. Yang, L. Dong, Appl. Surf. Sci., 2017, 420, 407-415.
[92]	Z. Liu, Y. Yi, S. Zhang, T. Zhu, J. Zhu, J. Wang, Catal. Today, 2013, 216, 76-81.
[93]	Z. Ma, L. Sheng, X. Wang, W. Yuan, S. Chen, W. Xue, G. Han, Z. Zhang, H. Yang, Y. Lu, Y. Wang, Adv. Mater., 2020, 32, 1907806.
[94]	K. Song, K. Guo, S. Mao, D. Ma, Y. Lv, C. He, H. Wang, Y. Cheng, J.-W. Shi, ACS Catal., 2023, 13, 5020-5032.
[95]	J. Tang, X. Wang, H. Li, L. Xing, M. Liu, ACS Omega, 2023, 8, 7262-7278.
[96]	R. Yang, Z. Gao, M. Sun, G. Fu, G. Cheng, W. Liu, X. Yang, X. Zhao, L. Yu, J. Rare Earths, 2021, 39, 1370-1381.
[97]	L.-G. Wei, R.-T. Guo, J. Zhou, B. Qin, X. Chen, Z.-X. Bi, W.-G. Pan, Fuel, 2022, 316, 123438.
[98]	Z. He, Y. Wang, Y. Liu, L. Lian, D. Kong, Y. Zhao, Fuel, 2024, 365, 131126.
[99]	M. Liu, X. Li, S. Ren, L. Wang, F. Li, C. He, S. Chai, C. Zheng, X. Li, C. C. Xu, Chem. Eng. J., 2025, 524, 169007.
[100]	D. Ren, K. Gui, S. Gu, Appl. Surf. Sci., 2021, 561, 149847.
[101]	J. Rong, W. Zhao, W. Luo, K. Kang, L. Long, Y. Chen, X. Yao, J. Rare Earths, 2023, 41, 1323-1335.
[102]	G. Zhai, Z. Han, H. Du, Y. Gao, X. Pan, Environ. Sci. Pollut. Res., 2022, 29, 17295-17308.
[103]	Y. Geng, W. Shan, F. Liu, S. Yang, J. Hazard. Mater., 2021, 405, 124223.
[104]	L. Long, S. Tian, Y. Zhao, X. Zhang, W. Luo, X. Yao, J. Colloid Interface Sci., 2023, 648, 876-888.
[105]	X. Wang, R. Duan, W. Liu, D. Wang, B. Wang, Y. Xu, C. Niu, J.-W. Shi, Appl. Surf. Sci., 2020, 510, 145517.
[106]	X. Wu, X. Yu, Z. Huang, H. Shen, G. Jing, Appl. Catal. B, 2020, 268, 118419.
[107]	X. Li, Y. Niu, J. Li, M. Yang, R. Chen, D. Shao, X. Zheng, C. Zhang, Y. Qi, Chem. Eng. J., 2023, 454, 140180.
[108]	Q. Zhang, S. Zhang, X. Hu, Y. Huang, Chin. J. Chem. Eng., 2024, 71, 272-282.
[109]	T. Wu, S. Ren, R.-T. Guo, C.-F. Li, Y.-H. You, S.-Y. Guo, W.-G. Pan, Fuel, 2024, 357, 129917.
[110]	K. Song, C. Gao, P. Lu, D. Ma, Y. Cheng, J.-W. Shi, Fuel, 2023, 331, 125861.
[111]	X. Feng, J. Zeng, J. Zhu, K. Song, X. Zhou, X. Guo, C. Xie, J.-W. Shi, J. Colloid Interface Sci., 2024, 659, 1063-1071.
[112]	L.-A. Sun, Y.-J. Xu, Q.-Q. Cao, B.-Q. Hu, C. Wang, G.-H. Jing, Prog. Chem., 2010, 22, 1882-1891.
[113]	Q. Zhao, B. Chen, J. Li, X. Wang, M. Crocker, C. Shi, Appl. Catal. B, 2020, 277, 119215.
[114]	G. Qi, R. T. Yang, J. Catal., 2003, 217, 434-441.
[115]	L. Chen, Q. Wang, X. Wang, Q. Cong, H. Ma, T. Guo, S. Li, W. Li, Chem. Eng. J., 2020, 390, 124251.
[116]	S. Li, B. Huang, C. Yu, Catal. Commun., 2017, 98, 47-51.
[117]	G. Qi, R. T. Yang, J. Phys. Chem. B, 2004, 108, 15738-15747.
[118]	F. Wang, S. Li, R. You, Z. Han, W. Yuan, B. Zhu, Y. Gao, H. Yang, Y. Wang, Appl. Surf. Sci., 2023, 638, 158124.
[119]	S. Hao, Y. Cai, C. Sun, J. Sun, C. Tang, L. Dong, Catalysts, 2020, 10, 1329.
[120]	Y. Zeng, F. Lyu, Y. Wang, S. Zhang, Q. Zhong, Z. Zhong, Mol. Catal., 2022, 525, 112356.
[121]	Z. Chen, S. Ren, M. Wang, J. Yang, L. Chen, W. Liu, Q. Liu, B. Su, Fuel, 2022, 321, 124113.
[122]	L. Liu, K. Xu, S. Su, L. He, M. Qing, H. Chi, T. Liu, S. Hu, Y. Wang, J. Xiang, Appl. Catal. A, 2020, 592, 117413.
[123]	Y. Chen, H. Li, J. Zhang, Y. Cao, J. Li, J. Yang, F. Li, C. Liu, Y. Wang, Y. Long, J. Hu, Fuel Process. Technol., 2022, 227, 107136.
[124]	X. Shi, J. Guo, T. Shen, A. Fan, S. Yuan, J. Li, Chem. Eng. J., 2021, 421, 129995.
[125]	X. Hou, H. Chen, Y. Liang, X. Yang, Y. Wei, Catal. Lett., 2020, 150, 1041-1048.
[126]	F. Gao, X. Tang, H. Yi, J. Li, S. Zhao, J. Wang, C. Chu, C. Li, Chem. Eng. J., 2017, 317, 20-31.
[127]	R. Chen, X. Fang, J. Li, Y. Zhang, Z. Liu, Chem. Eng. J., 2023, 452, 139207.
[128]	W. Yoon, Y. Kim, G. Jong Kim, J.-R. Kim, S. Lee, H. Han, G. Hyeon Park, H.-J. Chae, W. Bae Kim, Chem. Eng. J., 2022, 434, 134676.
[129]	H. Chang, X. Chen, J. Li, L. Ma, C. Wang, C. Liu, J. W. Schwank, J. Hao, Environ. Sci. Technol., 2013, 47, 5294-5301.
[130]	C. Yu, D. Hou, B. Huang, M. Lu, R. Peng, Z. Zhong, J. Hazard. Mater., 2020, 399, 123011.
[131]	M. Fu, C. Li, P. Lu, L. Qu, M. Zhang, Y. Zhou, M. Yu, Y. Fang, Catal. Sci. Technol., 2014, 4, 14-25.
[132]	L. Li, B. Sun, J. Sun, S. Yu, C. Ge, C. Tang, L. Dong, Catal. Commun., 2017, 100, 98-102.
[133]	L. Chen, X. Yao, J. Cao, F. Yang, C. Tang, L. Dong, Appl. Surf. Sci., 2019, 476, 283-292.
[134]	Y. Teng, X. Guo, H. Xue, T. Meng, L. Han, Catal. Lett., 2024, 154, 3645-3653.
[135]	S. Zhao, K. Song, R. Jiang, D. Ma, H. Long, J.-W. Shi, Catal. Today, 2023, 423, 113966.
[136]	D. Yan, J. Zhao, J. Li, G. Abbas, Z. Chen, T. Guo, Catal. Lett., 2023, 153, 2838-2852.
[137]	F. Gao, Y. Niu, Y. Cui, Y. Liu, N. Luo, J. Wen, E. Duan, C. Wang, H. Yi, Y. Zhou, X. Tang, J. Environ. Chem. Eng., 2024, 12, 113849.
[138]	J. Li, C. Zhang, Q. Li, T. Gao, S. Yu, P. Tan, Q. Fang, G. Chen, Chem. Eng. Sci., 2022, 251, 117438.
[139]	Z. Yang, P. Tang, C. Xu, B. Zhu, Y. He, T. Duan, J. He, G. Zhang, P. Cui, J. Energy Inst., 2023, 108, 101201.
[140]	P. Wu, Y. Zhang, K. Zhuang, K. Shen, S. Wang, T. Huang, J. Rare Earths, 2020, 38, 1215-1223.
[141]	X. Hou, H. Chen, Y. Liang, Y. Wei, Z. Li, Catal. Surv. Asia, 2020, 24, 291-299.
[142]	X. Bian, J. Wang, Y. Bai, Y. Li, W. Wu, Y. Yang, Catalysts, 2024, 14, 558.
[143]	C. Hu, C. Liu, K. Du, C. Pang, Z. Zhuo, Q. Gao, J. Environ. Chem. Eng., 2023, 11, 110440.
[144]	H. Hu, S. Cai, H. Li, L. Huang, L. Shi, D. Zhang, ACS Catal., 2015, 5, 6069-6077.
[145]	C. Xie, S. Yang, J. Shi, B. Li, C. Gao, C. Niu, Chem. Eng. J., 2017, 327, 1-8.
[146]	M.-J. Kim, J.-R. Youn, S.-J. Lee, I.-S. Ryu, S. Chan Nam, S. Kwan Jeong, S. Goo Jeon, J. Ind. Eng. Chem., 2022, 108, 438-448.
[147]	S. M. Lee, K. H. Park, S. C. Hong, Chem. Eng. J., 2012, 195-196, 323-331.
[148]	G. Li, D. Mao, M. Chao, G. Li, J. Yu, X. Guo, J. Rare Earths, 2021, 39, 805-816.
[149]	C. Gao, J.-W. Shi, Z. Fan, B. Wang, Y. Wang, C. He, X. Wang, J. Li, C. Niu, Appl. Catal. A, 2018, 564, 102-112.
[150]	Z. Fan, Z. Wang, J.-W. Shi, C. Gao, G. Gao, B. Wang, Y. Wang, X. Chen, C. He, C. Niu, J. Catal., 2019, 370, 30-37.
[151]	R.-J. Cui, X.-S. Huang, G.-D. Zhang, Z.-C. Tang, Ind. Eng. Chem. Res., 2024, 63, 7003-7017.
[152]	H. Liu, Z. Yan, H. Mu, L. Liu, H. Wang, J. Luan, X. Ke, Energy Fuels, 2022, 36, 965-977.
[153]	Z. Fan, J.-W. Shi, C. Niu, B. Wang, C. He, Y. Cheng, Chem. Eng. J., 2020, 398, 125572.
[154]	Y. Liang, W. Liu, H. Wu, Q. Liu, L. Yao, Fuel, 2024, 355, 129478.
[155]	N. Li, T. Wang, Y. Zhao, L. Hou, Z. Zhang, W. Wu, Mol. Catal., 2024, 552, 113691.
[156]	G. Huang, J. Yang, C. Lv, D. Li, D. Fang, J. Environ. Chem. Eng., 2023, 11, 110966.
[157]	S. Raja, M. S. Alphin, L. Sivachandiran, Catal. Sci. Technol., 2020, 10, 7795-7813.
[158]	X. Lu, C. Song, S. Jia, Z. Tong, X. Tang, Y. Teng, Chem. Eng. J., 2015, 260, 776-784.
[159]	L. Wang, Y. Ren, X. Yu, C. Peng, D. Yu, C. Zhong, J. Hou, C. Yin, X. Fan, Z. Zhao, J. Liu, Y. Wei, J. Catal., 2023, 417, 226-247.
[160]	L. Chen, S. Ren, Y. Jiang, L. Liu, M. Wang, J. Yang, Z. Chen, W. Liu, Q. Liu, Fuel, 2022, 320, 123969.
[161]	Y. Li, Y. Hou, Y. Zhang, Y. Yang, Z. Huang, J. Colloid Interface Sci., 2022, 608, 2224-2234.
[162]	L. Qiu, D. Li, H. Li, Z. Ren, Z. Zhu, F. Ouyang, M. Guo, Chemosphere, 2022, 302, 134740.
[163]	Y. Zhu, Y. Zhang, R. Xiao, T. Huang, K. Shen, Catal. Commun., 2017, 88, 64-67.
[164]	K. Song, X. Feng, N. Zhang, D. Ma, L. Shi, Y. Chen, J. Li, J.-W. Shi, Coord. Chem. Rev., 2025, 535, 216615.
[165]	K. Niu, Q. Liu, C. Liu, Z. Yu, Y. Zheng, Y. Su, Y. Zhao, B. Liu, S. Cui, G. Zang, M. Guo, Chem. Eng. J., 2024, 487, 150714.
[166]	Z. Shi, Q. Peng, J. E, B. Xie, J. Wei, R. Yin, G. Fu, Fuel, 2023, 331, 125885.
[167]	M. Li, M. Gao, G. He, Y. Yu, H. He, Environ. Sci. Technol., 2023, 57, 3875-3882.
[168]	L.-Y. Lin, T.-T. Hsieh, J.-C. Hsu, Y.-C. Wang, Appl. Surf. Sci., 2023, 614, 156139.
[169]	D. Wang, Q. Yao, C. Mou, S. Hui, Y. Niu, Fuel, 2019, 254, 115719.
[170]	K. Zhang, N. Luo, Z. Huang, G. Zhao, F. Chu, R. Yang, X. Tang, G. Wang, F. Gao, X. Huang, Chem. Eng. J., 2023, 476, 146889.
[171]	T. Wu, R.-T. Guo, C.-F. Li, Y.-H. You, W.-G. Pan, Chemosphere, 2023, 333, 138942.

Catalyst	Synthesis	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_x conversion	N₂ selectivity	Year/Ref.
MnO₂	All MnO_x (analytical grade, Aladdin) were used as received	500; 500; 3.0; 27,000; N₂	> 90% (100-250 °C)	—	2018/[16]
Mn₂O₃			∼90% (150-200 °C)	—
Mn₃O₄			> 80% (225-250 °C)	—
MnO			∼60% (300 °C)	—
MnO₂@CeO₂	thermal decomposition	500; 500; 5.0; 60,000; N₂	> 90% (100-275 °C)	—	2023/[58]
Mn₂O₃@CeO₂			> 80% (100-250 °C)	—
Mn₃O₄@CeO₂			> 80% (175-250 °C)	—
MnO/CeO₂-NR	hydrothermal	1000; 1000; 6.0; 13000; Ar	∼50% (350 °C)	∼80% (150-450 °C)	2023/[62]
Mn₂O₃/CeO₂-NR			∼60% (350 °C)	∼85% (150-450 °C)
MnO₂/CeO₂-NR			∼70% (350 °C)	∼90% (150-450 °C)
α-MnO₂	hydrothermal + wet impregnation	500; 500; 11.0; 36,000; N₂	> 80% (90-120 °C)	—	2022/[61]
β-MnO₂			> 70% (90-120 °C)	—
γ-MnO₂			∼20% (90-110 °C)	—
CeO₂ @α-MnO₂			> 95% (75-250 °C)	—
CeO₂ @ β-MnO₂			> 95% (75-250 °C)	—
CeO₂ @ γ-MnO₂			> 95% (75-250 °C)	—
α-MnO₂	redox hydrothermal	500; 500; 19.0; 36,000; N₂	> 70% (90-120 °C)	> 70% (50-120 °C)	2021/[49]
β-MnO₂			∼30% (50-120 °C)	∼40% (50-120 °C)
γ-MnO₂			> 80% (90-120 °C)	∼60% (50-120 °C)
δ-MnO₂			∼50% (50-120 °C)	> 70% (50-100 °C)

Catalyst	Synthesis	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_x conversion	N₂ selectivity	Year/Ref.
MnO₂	All MnO_x (analytical grade, Aladdin) were used as received	500; 500; 3.0; 27,000; N₂	> 90% (100-250 °C)	—	2018/[16]
Mn₂O₃			∼90% (150-200 °C)	—
Mn₃O₄			> 80% (225-250 °C)	—
MnO			∼60% (300 °C)	—
MnO₂@CeO₂	thermal decomposition	500; 500; 5.0; 60,000; N₂	> 90% (100-275 °C)	—	2023/[58]
Mn₂O₃@CeO₂			> 80% (100-250 °C)	—
Mn₃O₄@CeO₂			> 80% (175-250 °C)	—
MnO/CeO₂-NR	hydrothermal	1000; 1000; 6.0; 13000; Ar	∼50% (350 °C)	∼80% (150-450 °C)	2023/[62]
Mn₂O₃/CeO₂-NR			∼60% (350 °C)	∼85% (150-450 °C)
MnO₂/CeO₂-NR			∼70% (350 °C)	∼90% (150-450 °C)
α-MnO₂	hydrothermal + wet impregnation	500; 500; 11.0; 36,000; N₂	> 80% (90-120 °C)	—	2022/[61]
β-MnO₂			> 70% (90-120 °C)	—
γ-MnO₂			∼20% (90-110 °C)	—
CeO₂ @α-MnO₂			> 95% (75-250 °C)	—
CeO₂ @ β-MnO₂			> 95% (75-250 °C)	—
CeO₂ @ γ-MnO₂			> 95% (75-250 °C)	—
α-MnO₂	redox hydrothermal	500; 500; 19.0; 36,000; N₂	> 70% (90-120 °C)	> 70% (50-120 °C)	2021/[49]
β-MnO₂			∼30% (50-120 °C)	∼40% (50-120 °C)
γ-MnO₂			> 80% (90-120 °C)	∼60% (50-120 °C)
δ-MnO₂			∼50% (50-120 °C)	> 70% (50-100 °C)

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV; balance gas	NO_x conversion	N₂ selectivity	Year/[Ref.]
MnO_x	thermal decomposition	500 ppm; 500 ppm; 5.0 vol%; 60000 h^-1; N₂	< 60% (50-350 °C)	> 50% (50-200 °C)	2017/[66]
CeO₂	thermal decompositions		< 30% (50-350 °C)	> 90% (50-350 °C)
MnCe-MMM	mechanical mixing		< 30% (50-350 °C)	> 50% (50-350 °C)
MnCe-IM	impregnation		< 80% (50-350 °C)	> 70% (50-175 °C)
MnCe-HTM	hydrothermal treatment		∼100% (100-325 °C)	> 70% (50-200 °C)
MnCe-CPM	Co-precipitation		> 80% (125-350 °C)	> 70% (50-200 °C)
MnCe-SGM	sol-gel		> 80% (125-350 °C)	> 70% (50-200 °C)

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV; balance gas	NO_x conversion	N₂ selectivity	Year/[Ref.]
MnO_x	thermal decomposition	500 ppm; 500 ppm; 5.0 vol%; 60000 h^-1; N₂	< 60% (50-350 °C)	> 50% (50-200 °C)	2017/[66]
CeO₂	thermal decompositions		< 30% (50-350 °C)	> 90% (50-350 °C)
MnCe-MMM	mechanical mixing		< 30% (50-350 °C)	> 50% (50-350 °C)
MnCe-IM	impregnation		< 80% (50-350 °C)	> 70% (50-175 °C)
MnCe-HTM	hydrothermal treatment		∼100% (100-325 °C)	> 70% (50-200 °C)
MnCe-CPM	Co-precipitation		> 80% (125-350 °C)	> 70% (50-200 °C)
MnCe-SGM	sol-gel		> 80% (125-350 °C)	> 70% (50-200 °C)

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_x conversion	N₂ selectivity	Year/Ref.
MnO_x	Co-precipitation	500; 500; 3.0; 60,000; N₂	∼90% (150-225 °C)	—	2024/[81]
Mn-Ce (Ce:Mn=0.05)	Co-precipitation	500; 500; 3.0; 60,000; N₂	∼100% (100-225 °C)	> 80% (50-350 °C)	2024/[81]
MnO_x	methanol reduction	500; 500; 3.0; 60,000; N₂	∼50% (100-150 °C)	> 70% (0-125 °C)	2024/[73]
Mn-Sm (Sm:Mn=0.05)	methanol reduction	500; 500; 3.0; 60,000; N₂	100% (25-200 °C)	> 80% (0-150 °C)	2024/[73]
MnO_x	Co-precipitation	700; 700; 5.0; 30,000; N₂	> 80% (100-180 °C)	—	2024/[82]
Mn-Ce (Ce:Mn=1)	Co-precipitation	700; 700; 5.0; 30,000; N₂	> 80% (100-200 °C)	—	2024/[82]
Mn-Ce (Ce:Mn=1.5)	Co-precipitation	500; 500; 5.0; 60,000; Ar	100% (100-200 °C)	> 60% (50-200 °C)	2023/[67]
MnO_x	Co-precipitation	500; 500; 5.0; 48,600; Ar	∼80% (∼200 °C)	> 90% (50-300 °C)	2023/[30]
Mn-Er (Er:Mn=0.1)	Co-precipitation	500; 500; 5.0; 48,600; Ar	> 80% (52-250 °C)	> 90% (50-300 °C)	2023/[30]
Mn-Ce (Ce:Mn=0.25)	hydrothermal + impregnation	500; 500; 11.0; 36,000; N₂	> 90% (150-250 °C)	> 70% (75-150 °C)	2022/[45]
Mn-La (La:Mn=0.022)	Co-impregnation	600; 600; 3.0; 54,000; Ar	> 80% (200-300 °C)	—	2021/[83]
MnO_x	polymer-assisted deposition	500; 500; 5.0; 38, 000; N₂	> 50% (200-255 °C)	—	2021/[72]
Mn-Ce (Ce:Mn=1)	polymer-assisted deposition	500; 500; 5.0; 38, 000; N₂	> 90% (150-250 °C)	> 80% (60-220 °C)	2021/[72]
MnO₂	hydrothermal	500; 500; 5.0; 30,000; N₂	∼100% (90-150 °C)	> 90% (50-110 °C)	2021/[68]
Mn-Ce (Ce:Mn=0.25)	hydrothermal	500; 500; 5.0; 30,000; N₂	∼100% (105-150 °C)	> 90% (50-130 °C)	2021/[68]
Mn-Ce	solvothermal	500; 500; 3.0; 52,500; N₂	> 90% (150-310 °C)	—	2021/[84]
Mn-Ce	hydrothermal	500; 500; 5.0; 30,000; N₂	> 80% (160-240 °C)	> 90% (80-140 °C)	2020/[85]
Mn-Ce (Ce:Mn=1)	Co-precipitation	500; 500; 10.0; 60,000; N₂	> 90% (200-300 °C)	—	2020/[86]
Mn-Ce nanorods	hydrothermal	500; 500; 6.0; 200,000; N₂	> 70% (200-300 °C)	> 80% (0-300 °C)	2020/[87]
α-MnO₂	hydrothermal	500; 500; 3.0; 100,000; N₂	> 60% (175-300 °C)	—	2020/[88]
Mn-Ce	hydrothermal	500; 500; 3.0; 100,000; N₂	> 80% (125-275 °C)	—	2020/[88]
Mn-Ce	hydrothermal	500; 500; 5.0; 50,000; Ar	> 90% (200-320 °C)	—	2019/[89]
Mn-Ce	sacrificial template	1000; 1000; 5.0; 30,000; N₂	> 90% (100-180 °C)	> 70% (60-180 °C)	2019/[90]
MnO_x	Co-precipitation	500; 500; 5.0; 36,000; N₂	∼100% (150-300 °C)	∼100% (90-300 °C)	2018/[28]
Mn-Gd (Gd:Mn = 0.1)	Co-precipitation	500; 500; 5.0; 36,000; N₂	∼100% (120-330 °C)	∼100% (150-300 °C)	2018/[28]
Mn-Ce	impregnation	500; 500; 5.0; 60,000; N₂	> 80% (100-250 °C)	—	2017/[91]
Mn-Eu (Eu:Mn = 0.1)	Co-precipitation	600; 600; 5.0; 108,000; Ar	100% (150-400 °C)	> 95% (100-400 °C)	2017/[74]
Mn-Ce (Ce:Mn = 0.2)			100% (150-250 °C)	—
Mn-Sm (Sm:Mn = 0.1)			100% (150-300 °C)	—
Mn-Ce (Ce:Mn = 1)	surfactant-template	500; 500; 5.0; 64000; He	100% (100-200 °C)	> 70% (150-200 °C)	2013/[92]

稀土改性锰基低温NH₃-SCR催化剂的理性设计:机理、策略与展望

Rational design of rare earth-modified Mn-based catalysts for low-temperature NH₃-SCR: Mechanisms, strategies, and prospects

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Metrics

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_x conversion	SO₂ resistance	H₂O resistance	Combined H₂O + SO₂ tolerance	Year/Ref.
MnO_x	methanol reduction	500; 500; 3.0; 60000; N₂	∼ 50% (100-150 °C)	25 ppm SO₂, ∼45% to ∼40% after ∼3 h at 150 °C	3% H₂O, 100% to ~20% after ∼3 h at 150 °C	25 ppm SO₂, 3% H₂O, ~40% to ~20% after 3 h at 150 °C	2024/[73]
Mn-Sm	methanol reduction	500; 500; 3.0; 60000; N₂	100% (25-200 °C)	25 ppm SO₂, ∼90% to ~40% after ∼3 h at 150 °C	3% H₂O, 100% to ∼60% after ∼3 h at 150 °C	25 ppm SO₂, 3% H₂O, ~90% to ~40% after 3 h at 150 °C	2024/[73]
Mn-Ce	Co-precipitation	500; 500; 5.0; 60000; Ar	100% (100-200 °C)	100 ppm SO₂, 100% to ∼75% after ∼9 h at 200 °C	10% H₂O, 100% to ~90% after 2 h at 200 °C	100 ppm SO₂, 10% H₂O, 100% to ~35% after 4 h at 200 °C	2023/[67]
Mn-Er	Co-precipitation	500; 500; 5.0; 48600; Ar	> 80% (52-250 °C)	—	5% H₂O, 100% to ~95% after 10 h at 150 °C	50 ppm SO₂, 5% H₂O, ∼ 95% to ∼ 90% after 10 h at 150 °C	2023/[30]
MnO_x	Co-precipitation	500; 500; 5.0; 30000; N₂	> 90% (160-260 °C)	100 ppm SO₂, 100% to ∼20% after 2 h (dropping to ∼0% after 4 h) at 200 °C	5% H₂O, ~100% to ~60% after 4 h at 200 °C	100 ppm SO₂, 5% H₂O, 100% to ~0% after 2 h at 200 °C	2022/[102]
Mn-Pr	Co-precipitation	500; 500; 5.0; 30000; N₂	∼100% (120-220 °C)	100 ppm SO₂, 100% to ∼ 90% after 2 h (and to ~20% after 4 h) at 200 °C	5% H₂O, ~100%, no deactivation after 4 h at 200 °C	100 ppm SO₂, 5% H₂O, 100% to ~90% after 4 h at 200 °C	2022/[102]
Mn-Ce	hydrothermal	500; 500; 5.0; 30000; N₂	∼ 100% (90-150 °C)	250 ppm SO₂, 100% to ∼70% after 6 h at 150 °C	—	—	2021/[68]
Mn-Ce	solvothermal	500; 500; 3.0; 52500; N₂	> 90% (150-310 °C)	200 ppm SO₂, 100% to ∼ 0% after 4 h at 150 °C	5% H₂O, ~90% to ~75% after 4 h at 150 °C	—	2021/[84]
Mn-Ce	sacrificial template	1000; 1000; 5.0; 30000; N₂	> 90% (100-180 °C)	100 ppm SO₂, ~100% to ~80% after 12 h at 180 °C	10% H₂O, ~100%, no deactivation after 8 h at 180 °C	—	2018/[90]
MnO_x	Co-precipitation	500; 500; 5.0; 36000; N₂	∼100% (150-300 °C)	100 ppm SO₂, ~100% to ~10% after 4 h at 200 °C	5% H₂O, ~100% to ~70% after 6 h 200 °C	100 ppm SO₂, 5% H₂O, ~100% to ~30% after 8 h at 200 °C	2018/[28]
Mn-Gd	Co-precipitation	500; 500; 5.0; 36000; N₂	∼100% (120-330 °C)	100 ppm SO₂, ~100% to ~90% after 4 h at 200 °C	5% H₂O, no deactivation after 6 h 200 °C	100 ppm SO₂, 5% H₂O, ~100% to ~60% after 8 h at 200 °C	2018/[28]
Mn-Ce	impregnation	500; 500; 5.0; 60000; N₂	> 80% (100-250 °C)	—	—	100 ppm SO₂, 5% H₂O, ~90% to ~70% after 10 h at 200 °C	2017/[91]
Mn-Eu	Co-precipitation	600; 600; 5.0; 108,000; Ar	100% (150-400 °C)	—	—	100 ppm SO₂, 5% H₂O, 100% to ~90% after 4h at 350 °C	2017/[74]
Mn-Sm	Co-precipitation	500; 500; 5.0; 49000; Ar	∼90% (250 °C)	100 ppm SO₂, 100% to 96% after 14 h at 100 °C	2% H₂O, no deactivation after 14 h 100 °C	100 ppm SO₂, 2% H₂O, 96% to ~90% after 16 h at 100 °C	2015/[25]

RE element	Primary focus	Key mechanistic highlight	Main advantage	Ref.
Ce	redox hub and SO₂ trap	Ce³⁺/Ce⁴⁺-Mn³⁺/Mn⁴⁺ shuttle; higher surface Mn⁴⁺ and chemisorbed oxygen; preferential sulfation and core-shell protection; promotes (NH₄)₂SO₄ decomposition; sulfate-derived B-sites	high activity and strong H₂O/SO₂ tolerance	[67-72 93]
Sm	electronic/kinetic promoter	lowers apparent activation energy; strengthens the nitrate route; less N₂O	improved low-temperature activity and N₂ selectivity	[25,73]
Gd	phase and structure stabilizer	stabilizes texture and inhibits crystallization; maintains Mn⁴⁺ and chemisorbed oxygen at high GHSV and long time-on-stream	structural durability	[28]
Eu	electronic protection + sacrificial sulfation	preferential Eu sulfation protects Mn sites	SO₂ resistance	[74]
Pr	SO₂-affinity modifier	preferential sulfation (sacrificial layer); supports redox cycling	SO₂ tolerance with activity retention	[109]
Er	defect/oxygen-vacancy promoter	More oxygen vacancies; maintains higher Mn⁴⁺; broadens the activity window	wide operation window	[30]
Tm	acidity tuning	induces B-sites via Tm-OH groups; enhances NH₃ adsorption/activation and NH₃ migration	acidity-driven low-temperature activity	[77]
Ho	mechanism/pathway tuning	promotes dual L-H and E-R routes;	mechanistic flexibility	[75]

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_x conversion	N₂ selectivity	Year/Ref.
Mn-Ce-Co	two-step hydrothermal	500; 500; 5.0; 24000; N₂	∼100% (90-270 °C)	∼100% (60-240 °C)	2020/[105]
Mn-V-Ce	hydrothermal	500; 500; 6.0; 160000; N₂	> 90% (200-350 °C)	> 90% (75-300 °C)	2020/[106]
Mn-Ce-Co	one-step redox precipitation	300; 300; 5.0; 30,000; N₂	> 80% (87-277 °C)	> 90% (50-175 °C)	2023/[107]
Mn-Ce-Fe	impregnation	500; 500; 5.0, 50000; N₂	> 90% (125-225 °C)	> 80% (0-150 °C)	2024/[108]
Mn-Ce-Sm-Fe	impregnation	500; 500; 5.0, 50000; N₂	> 90% (100-275 °C)	> 80% (0-200 °C)	2024/[108]
Mn-Ce	hydrothermal	600; 600; 5.0; 108000; Ar	> 70% (200-350 °C)	> 95% (100-400 °C)	2024/[109]
Mn-Ce-Pr	one-step impregnation	600; 600; 5.0; 108000; Ar	> 90% (180-345 °C)	> 95% (100-400 °C)	2024/[109]
Mn-Nb-Fe	electrospinning	500; 500; 5.0; 36000; N₂	∼100% (180-300 °C)	> 90% (60-300 °C)	2023/[110]
Mn-Nd-Nb-Fe	electrospinning	500; 500; 5.0; 36000; N₂	∼100% (160-300 °C)	> 90% (60-360 °C)	2023/[110]
Mn-Ce	wetness Impregnation	600; 600; 6.5; 84000; Ar	> 90% (150-350 °C)	> 80% (50-250 °C)	2021/[96]
Mn-V-Ce	wetness Impregnation	600; 600; 6.5; 84000; Ar	> 90% (150-400 °C)	> 85% (50-400 °C)	2021/[96]
Mn-Gd-Co	one-step synthesis	500; 500; 5.0; 100000; N₂	∼100% (100-250 °C)	> 90% (50-300 °C)	2024/[111]
Mn-Ce	Co-precipitation	500; 500; 5.0; 30000; N₂	> 80% (100-300 °C)	> 80% (100-150 °C)	2020/[33]
Mn-Fe			> 80% (100-300 °C)	> 80% (100-150 °C)
Mn-Ce-Fe			> 95% (150-200 °C)	> 90% (100-150 °C)

Catalyst system	Synergistic effects and performance enhancement	Ref.
Mn-Ce-W	W moderately weakens the redox strength of the Mn-Ce system. It slightly reduces NO oxidation at low temperatures but strongly suppresses over oxidation of NH₃ at higher temperature, which decreases N₂O formation and improves resistance to water	[103]
Mn-Ce-Fe	Ce and Fe build an electron transfer cycle involving Mn³⁺ and Fe³⁺ that markedly enhances low-temperature activity. CeO₂ reacts preferentially with SO₂, protects Mn active sites and improves sulfur resistance.	[33]
Mn-Ce-Sn	Sn doping strengthens the Ce³⁺/Ce⁴⁺ redox cycle and increases the concentration of oxygen vacancies, which promotes oxidation of NO to NO₂ and activates the fast SCR route. It also greatly increases the amount of surface acid sites, so low-temperature de-NO_x activity is significantly enhanced.	[129]
Mn-Ce-Sm	Ce captures SO₂ through chemisorption and preferential sulfation. Sm increases the number of L-sites, stabilizes the structure and enhances hydrophobicity, and its electronic effects suppress over oxidation of NH₃. These contributions together improve N₂ selectivity and sulfur resistance.	[105]
Mn-Ce-La	In LaMnO₃ perovskite, the lattice position of Ce doping precisely controls performance. Substitution at the A site enhances SO₂ tolerance, whereas substitution at the B site effectively improves N₂ selectivity. La forms the perovskite framework and influences the surface area and thermal stability of the catalyst.	[124]
Mn-Ce-Pr	Pr induces a broom like morphology and increases the specific surface area. It also acts as an SO₂ trap that reacts preferentially and forms sulfates with a relatively high decomposition temperature, which effectively protects Mn active centers.	[109]
Mn-Ce-Si	Among Si⁴⁺, Zr⁴⁺ and Al³⁺ dopants, Si⁴⁺ gives the best overall effect. It provides the richest oxygen vacancies and acid sites, the highest Mn⁴⁺ content and an appropriate redox strength, and these features combine to enhance activity, selectivity and resistance to poisoning.	[34]
Mn-Ce-Cr	Cr establishes Mn-Cr redox cycles and effectively suppresses formation of MnSO₄, so catalysts poisoned by H₂O and SO₂ can fully recover their activity through simple thermal regeneration.	[128]
Mn-Ce-Co	Co introduction creates a new Mn³⁺/Co³⁺ redox cycle that works together with the Mn⁴⁺/Ce³⁺ cycle. This cooperation promotes oxygen migration and oxygen vacancy formation and suppresses MnSO₄ formation.	[107] [126]
Mn-Sm-Fe	Sm increases the number of L-sites and builds Sm²⁺/Mn⁴⁺ and Sm²⁺/Fe³⁺ electron transfer cycles, which enhance NO activation and N₂ selectivity. Fe acts as a sacrificial site that reacts preferentially with SO₂, and this sacrificial behavior works together with Sm to improve sulfur resistance.	[121]
Mn-Ce-Ni	Ni enhances the overall oxidation ability, promotes oxidation of NO to NO₂ and activates the fast SCR route. It also effectively suppresses N₂O formation and improves selectivity.	[126]
Mn-Ce-Eu MnO_x@Eu-CeO_x	The Eu-CeO_x shell physically isolates the MnO_x core and minimizes SO₂ poisoning while enhancing surface acidity, which builds a core-shell cooperative protection mechanism.	[130]
Gd-Mn-Co	Gd stabilizes the layered structure and significantly increases the specific surface area. Together with Co, it raises the contents of Mn⁴⁺ and Co³⁺, strengthens redox ability and acidity and results in high activity over a wide temperature window.	[111]
Mn-Ce-Nb-Fe	Nb⁵⁺ and Fe³⁺ strengthen electronic interactions and surface acidity. Nb reacts preferentially with SO₂ and promotes decomposition of surface NH₄HSO₄, which protects Mn and Ce active sites in a cooperative way.	[104]
Mn-Nb-Fe-Nd	Nb and Nd form Nb-O-Nd bridges. Their electronic effects enhance adsorption of NH₃ and NO while suppressing adsorption of SO₂ and thus provide precise and simultaneous promotion of reactants and inhibition of poisons.	[110]

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_xconversion	SO₂ resistance	H₂O resistance	Combined H₂O + SO₂ tolerance	Year/ [Ref.]
Mn-V- Ce	hydrothermal	500; 500; 6.0; 160000; N₂	> 90% (200-350 °C)	100 ppm SO₂, ~100% to ~80% after 12 h at 220 °C	5.5% H₂O, ~100% to ~80% after 12 h at 220 °C	100 ppm SO₂, 5.5% H₂O, ~100% to ~60% after 12 h at 220 °C	2020/[106]
Mn-Ce-Fe	Co- precipitation	500; 500; 5.0; 30000; N₂	> 95% (150-200 °C)	200 ppm SO₂, ~100% to ~60% after 8 h at 175 °C	10% H₂O, ~100% to ~90% after 8 h at 175 °C	200 ppm SO₂, 5.5% H₂O, ~100% to ~60% after 8 h at 175 °C	2020/[33]
Mn-Ce-Fe	impregnation	500; 500; 5.0; 50000; N₂	> 90% (125-225 °C)	100 ppm SO₂, ~100% to ~30% after 10 h at 180 °C	—	—	2024/[108]
Mn-Ce-Sm-Fe	impregnation	500; 500; 5.0; 50000; N₂	> 90% (100-275 °C)	100 ppm SO₂, ~100% to ~95% after 10 h at 180 °C	—	—	2024/[108]
Mn-Ce	hydrothermal	600; 600; 5.0; 108000; Ar	> 70% (200-350 °C)	100 ppm SO₂, ~80% to ~60% after 10 h at 250 °C	—	100 ppm SO₂, 5% H₂O, ~80% to ~50% after 24 h at 250 °C	2024/[109]
Mn-Ce-Pr	one-step impregnation	600; 600; 5.0; 108000; Ar	> 90% (180-345 °C)	100 ppm SO₂, ~100% to ~90% after 10 h at 250 °C	—	100 ppm SO₂, 5% H₂O, ~100% to ~80% after 24 h at 250 °C	2024/[109]
Mn-Gd-Co	one-step synthesis	500; 500; 5.0; 100000; N₂	∼100% (100-250 °C)	—	—	100 ppm SO₂, 5% H₂O, ~100% to ~90% after 14 h at 240 °C	2024/[111]
Mn-Nb-Fe	electrospinning	500; 500; 5.0; 36000; N₂	∼100% (180-300 °C)	100 ppm SO₂, ~90% to ~30% after 8 h at 120 °C	10% H₂O, ~90% to ~70% after 7 h at 120 °C	100 ppm SO₂, 10% H₂O, ~50% to ~20% after 3 h at 120 °C	2023/[110]
Mn-Nd-Nb-Fe	electrospinning	500; 500; 5.0; 36000; N₂	∼ 100% (160-300 °C)	100 ppm SO₂, ~95% to ~50% after 8 h at 120 °C	10% H₂O, ~95% to ~90% after 7 h at 120 °C	100 ppm SO₂, 10% H₂O, ~70% to ~30% after 3 h at 120 °C	2023/[110]
Mn-Ce	Co- precipitation	500; 500; 5.0; 60000; N₂	> 70% (150-250 °C)	—	—	100 ppm SO₂, 5% H₂O, ~60% to ~30% after 10 h at 250 °C	2023/[104]
Mn-Ce-Nb			> 90% (175-275 °C)	—	—	100 ppm SO₂, 5% H₂O, ~60% to ~30% after 10 h at 250 °C
Mn-Ce-Fe			> 70% (150-275 °C)	—	—	100 ppm SO₂, 5% H₂O, ~90% to ~60% after 10 h at 250 °C
Mn-Ce-Nb-Fe			> 90% (150-250 °C)	—	—	100 ppm SO₂, 5% H₂O, ~90% to ~60% after 10 h at 250 °C
Mn-V- Ce	Wetness impregnation	600; 600; 6.5; 84,000; Ar	> 90% (150-400 °C)	100 ppm SO₂, 100% to ∼70% after 12 h at 200 °C	5% H₂O, ~100% to ~80% after 12 h at 200 °C	100 ppm SO₂, 5% H₂O, 100% to ~60% after 12 h at 200 °C	2021/[96]
Mn-Ce-Co	one-step redox precipitation	300; 300; 5.0; 30000; N₂	> 80% (87-277 °C)	100 ppm SO₂, ~95% to ~60% after 10 h at 210 °C	10% H₂O, ~95% to ~90% after 15 h at 210 °C	100 ppm SO₂, 10% H₂O, ~90% to ~60% after 10 h at 250 °C	2023/[107]
Mn-Ce-Sn	ultrasonication-assisted coprecipitation	1000; 1000; 2.0; 35000; N₂	∼100% (110-230 °C)	100 ppm SO₂, ~100% to ~95% at 220 °C	—	100 ppm SO₂, 10% H₂O, ~100% to ~90% at 220 °C	2013/[129]
Mn-V- Ce	hydrothermal	500; 500; 6.0; 160000; N₂	> 90% (200-350 °C)	100 ppm SO₂, ~100% to ~80% after 12 h at 220 °C	5.5% H₂O, ~100% to ~80% after 12 h at 220 °C	100 ppm SO₂, 5.5% H₂O, ~100% to ~60% after 12 h at 220 °C	2020/[106]
Mn-Sm-Fe	PEG-assisted co-precipitation	500; 500; 5.0; 60000; N₂	∼100% (75-200 °C)	100 ppm SO₂, ~100% to ~55% after 3 h at 200 °C	5% H₂O, 100%, no deactivation after 1 h at 200 °C	100 ppm SO₂, 5% H₂O, ~55% to ~40% after 3 h at 200 °C	2022/[121]
Mn-Fe-Ce-Al	Co- precipitation	200; 200; 5.0; 1667; N₂	> 80% (100-130 °C)	100 ppm SO₂, ~80% to ~75% after 8 h at 100 °C	4% H₂O, ~80% to ~75% after 8 h at 100 °C	100 ppm SO₂, 4% H₂O, 83% to ~60% after 120 h at 100 °C	2020/[119]
Mn-Ce-Co	Co- precipitation	500; 500; 5.0; 48000; N₂	~90% (75-200 °C)	150 ppm SO₂, 90% to ~70% after 4 h at 175 °C	—	150 ppm SO₂, 10% H₂O, 85% to >70% after 6 h at 175 °C	2017/[126]
Mn-Ce-Ni	Co- precipitation	500; 500; 5.0; 48000; N₂	~90% (125-200 °C)	150 ppm SO₂, 90% to ~70% after 4 h at 175 °C	—	150 ppm SO₂, 10% H₂O, 85% to ~70% after 6 h at 175 °C	2017/[126]
Mn-Ce-Cr	Co- precipitation	500; 500; 5.0; 90000; N₂	> 90% (150-220 °C)	—	—	100 ppm SO₂, 5% H₂O, 91% to ~60% after 4 h at 240 °C	2022/[128]
Mn-Ce-Eu	chemical precipitation	600; 600; 2.5; 90000; Ar	> 90% (100-200 °C)	100 ppm SO₂, ~95% to ~90% after 33 h at 200 °C	—	—	2020/[130]
Mn-Ce-Zr	hydrothermal	500; 500; 5.0; 60000; N₂	< 80% (200 °C)	—	—	100 ppm SO₂, 5% H₂O, 80% to ~60% after 8 h at 200 °C	2019/[34]
Mn-Ce-Al			> 80% (200 °C)	—	—	100 ppm SO₂, 5% H₂O, 80% to <60% after 8 h at 200 °C
Mn-Ce-Si			~80% (200 °C)	—	—	100 ppm SO₂, 5% H₂O, 80% to <60% after 8 h at 200 °C

Catalyst	Preparation method	Reaction conditions: [NO_x]; [NH₃]; [O₂]; GHSV (ppm, ppm, vol%, h^-1); balance gas	NO_x conversion	N₂ selectivity	Year/Ref.
Mn/TiO₂(Ac)	wet impregnation	500; 500; 3.0; 27000; N₂	> 90% (175-300 °C)	—	2018/[16]
Mn/TiO₂(N)	wet impregnation	500; 500; 3.0; 27000; N₂	> 90% (125-275 °C)	—	2018/[16]
Mn-Ce-Sn	inverse co-precipitation	500; 500; 5.0; 60000; N₂	~70% (225 °C)	—	2019/[133]
Mn-Ce-Sn/TiO₂	inverse co-precipitation	500; 500; 5.0; 60000; N₂	~80% (225 °C)	—	2019/[133]
Mn/Al₂O₃	impregnation	500; 500; 5.0; 80000; N₂	> 80% (200-250 °C)	> 70% (100-350 °C)	2024/[134]
Mn-Ce/Al₂O₃			> 80% (125-300 °C)	> 70% (100-350 °C)
Mn-Nd/Al₂O₃			> 80% (150-275 °C)	> 70% (100-350 °C)
Mn-La/Al₂O₃			> 80% (150-275 °C)	> 70% (100-350 °C)
Mn-Y/Al₂O₃			> 80% (175-275 °C)	> 70% (100-350 °C)
Mn-Ce/CC	incipient-wetness impregnation	500; 500; 5.0; 20000; N₂	> 90% (90-240 °C)	> 60% (90-240 °C)	2023/[135]
Mn-Ce/TiO₂	impregnation	600; 600; 5.0; 20000; N₂	> 90% (120-220 °C)	> 80% (90-150 °C)	2023/[136]
Mn-Ce-Sb/TiO₂	impregnation	600; 600; 5.0; 20000; N₂	> 90% (120-220 °C)	> 80% (90-200 °C)	2023/[136]
Mn-Ce-Co/TiO₂	Sol-gel	500; 500; 8.0; 32000; N₂	> 90% (125-250 °C)	> 80% (75-225 °C)	2024/[137]
Mn-Ce/TiO₂	Co-precipitation	500; 500; 3.0; 75000; N₂	> 90% (120-220 °C)	> 80% (90-240 °C)	2023/[80]
Mn-Ce-Sm/TiO₂	Co-precipitation	500; 500; 3.0; 75000; N₂	> 90% (130-220 °C)	> 80% (90-240 °C)	2023/[80]
Mn-Ce/TiO₂ with 001 facets	hydrothermal	800; 800; 8.0; 10000; N₂	91.2% (180 °C)	> 85% (80-220 °C)	2022/[138]
Mn-Ce/TiO₂ with 001facets	hydrothermal	800; 800; 8.0; 10000; N₂	68.1% (180 °C)	> 75% (80-220 °C)	2022/[138]
Mn-Ce/C₃N₄	ultrasonic-assisted deposition-precipitation	1000; 1000; 3.0; 24000; N₂	> 90% (125-300 °C)	> 90% (100-275 °C)	2023/[139]
Mn-Ce/γ-Al₂O₃			> 90% (175-275 °C)	> 90% (100-300 °C)
Mn-Ce/ MNT			> 90% (175-275 °C)	> 90% (100-275 °C)
Mn-Ce/TiO₂			> 90% (150-275 °C)	> 90% (100-300 °C)
Mn-Ce	coprecipitation	500; 500; 5.0; 100000; Ar	> 90% (150-200 °C)	> 90% (50-325 °C)	2022/[78]
Mn-Ce/TiO₂	coprecipitation	500; 500; 5.0; 100000; Ar	> 90% (125-225 °C)	> 90% (50-325 °C)	2022/[78]
Mn-Ce-Ti/CFA	physical separations + chemical activation + calcination	500; 500; 5.0; 54000; N₂	> 90% (120-360 °C)	> 90% (60-330 °C)	2022/[35]
Mn-Sm/TiO₂	coprecipitation + wet impregnation	500; 500; 8.0; 60000; N₂	> 90% (150-250 °C)	> 80% (100-225 °C)	2022/[46]
Mn-Gd/TiO₂	Co-precipitation	500; 500; 5.0; 100000; N₂	100% (120-350 °C)	100% (90-300 °C)	2018/[28]
Mn-Nd/TiO₂	impregnation	500; 500; 5.0; 20000; N₂	100% (140-220 °C)	> 90% (60-200 °C)	2020/[140]
Mn-Tm/TiO₂	impregnation	500; 500; 5.0; 36000; N₂	> 90% (120-300 °C)	> 90% (60-270 °C)	2021/[77]
Mn-Ho/TiO₂	impregnation + drying + calcination	800; 800; 5.0; 20000; N₂	> 90% (100-200 °C)	> 90% (60-180 °C)	2020/[75]
Mn-La/TiO₂	sol-gel	1000; 1000; 7.0; 30000; N₂	> 90% (130-260 °C)	> 90% (120-260 °C)	2020/[141]¹
Mn-Eu/TiO₂	inverse co-precipitation	500; 500; 5.0; 36000; N₂	100% (180-390 °C)	> 90% (100-460 °C)	2017/[76]

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