Research progress in catalytic oxidation of toluene over Mn-based catalysts

doi:10.16085/j.issn.1000-6613.2023-0896

Abstract

Abstract:

Toluene is an aromatic pollutant coming from a wide range of sources, which causes strong harm to human health and environment. Manganese oxide is considered as the most potential catalyst for oxidation of toluene due to its controllable morphology, diverse crystal structure and variable valence state. In this paper, the research progress of catalytic oxidation of toluene by manganese-based catalysts in recent years was reviewed, including single manganese oxide and composite manganese oxide. The effects of morphology, crystal structure, oxygen vacancy, metal-carrier interaction and other factors on the catalytic oxidation performance of toluene were discussed. The catalytic reaction mechanisms of toluene oxidation were also summarized. Finally, it is suggested that developing a simple synthesis process to construct MnO _x or Mn-based composite nano-catalyst, and studying the actual factors affecting the catalyst behavior for industrial exhaust are the future research directions in this field.

Key words: toluene catalytic oxidation, manganese oxide, activity, oxygen species

摘要：

甲苯是一种来源广泛的芳香族化合污染物，对人体健康及环境都产生强烈的危害。锰氧化物具有形貌可控、晶体结构多样、价态可变等特点，被认为是最具有应用潜力的甲苯氧化催化剂。本文综述了近年来锰基催化剂催化氧化甲苯的研究进展，主要介绍了单一锰氧化物和复合锰氧化物，讨论了形貌、晶型结构、氧空位、金属-载体相互作用等因素对甲苯催化氧化性能的影响，并归纳了一部分甲苯催化氧化的反应机理。最后，提出开发简单的合成工艺以构建MnO _x 纳米催化剂或Mn基复合纳米催化剂，研究实际的工业尾气影响催化剂行为的因素等是该领域未来的研究方向。

关键词: 甲苯催化氧化, 锰氧化物, 活性, 氧物种

CLC Number:

TQ426

CUI Weiyi, TAN Naidi, HUO Qilei, LI Wei. Research progress in catalytic oxidation of toluene over Mn-based catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6129-6139.

崔维怡, 谭乃迪, 霍其雷, 李伟. 锰基催化剂催化氧化甲苯的研究进展[J]. 化工进展, 2024, 43(11): 6129-6139.

Figures/Tables 8

References 67

1	MELLOUKI A, WALLINGTON T J, CHEN J. Atmospheric chemistry of oxygenated volatile organic compounds: Impacts on air quality and climate[J]. Chemical Reviews, 2015, 115(10): 3984-4014.
2	HE Chi, CHENG Jie, ZHANG Xin, et al. Recent advances in the catalytic oxidation of volatile organic compounds: A review based on pollutant sorts and sources[J]. Chemical Reviews, 2019, 119 (7): 4471-4568.
3	Yue LYU, LI Caiting, DU Xueyu, et al. Catalytic removal of toluene over manganese oxide-based catalysts: A review[J]. Environmental Science and Pollution Research, 2020, 27(3): 2482-2501.
4	CHEN Jinfeng, ZHANG Xiaodong, SHI Xiaoyu, et al. Synergistic effects of octahedral TiO₂-MIL-101(Cr) with two heterojunctions for enhancing visible-light photocatalytic degradation of liquid tetracycline and gaseous toluene[J]. Journal of Colloid and Interface Science, 2020, 579: 37-49.
5	YANG Cuiting, MIAO Guang, PI Yunhong, et al. Abatement of various types of VOCs by adsorption/ catalytic oxidation: A review[J]. Chemical Engineering Journal, 2019, 370: 1128-1153.
6	ZHANG Shihan, YOU Juping, KENNES C, et al. Current advances of VOCs degradation by bioelectrochemical systems: A review[J]. Chemical engineering journal, 2018, 334: 2625-2637.
7	KAMAL M S, RAZZAK S A, HOSSAIN M M. Catalytic oxidation of volatile organic compounds (VOCs)‍—A review[J]. Atmospheric Environment, 2016, 140: 117-134.
8	GUO Yunlong, WEN Meicheng, LI Guiying, et al. Recent advances in VOC elimination by catalytic oxidation technology onto various nanoparticles catalysts: a critical review[J]. Applied Catalysis B: Environmental, 2021, 281: 119447.
9	秦媛. 锰基催化剂催化氧化甲苯性能及其氧物种循环过程的研究[D]. 大连: 大连理工大学, 2020.
	QIN Yuan. Study of the performance of toluene catalytic oxidation and the cycle of oxygen species over Mn-based catalysts[D]. Dalian: Dalian University of Technology, 2020.
10	XU Haomiao, YAN Naiqiang, QU Zan, et al. Gaseous heterogeneous catalytic reactions over Mn-based oxides for environmental applications: A critical review[J]. Environmental Science & Technology, 2017, 51(16): 8879-8892.
11	GU Wenxiu, LI Chenqi, QIU Jianhao, et al. Facile fabrication of flower-like MnO₂ hollow microspheres as high-performance catalysts for toluene oxidation[J]. Journal of Hazardous Materials, 2021, 408(15): 124458.
12	ZENG Xiaohong, CHENG Gao, LIU Qi, et al. Novel ordered mesoporous γ-MnO₂ catalyst for high-performance catalytic oxidation of toluene and o-Xylene[J]. industrial & engineering chemistry research, 2019, 58(31): 13926-13934.
13	NGUYEN DINH Minh Tuan, NGUYEN Chinh Chien, TRUONG VU Tan Linh, et al. Tailoring porous structure, reducibility and Mn⁴⁺ fraction of ε-MnO₂ microcubes for the complete oxidation of toluene[J]. Applied Catalysis A: General, 2020, 595: 117473.
14	PULLERI J K, SINGH S K, YEARWAR D, et al. Morphology dependent catalytic activity of Mn₃O₄ for complete oxidation of toluene and carbon monoxide[J]. Catalysis Letters, 2021, 151(1): 172-183.
15	ZHAO Baohuai, RAN Ran, WU Xiaodong, et al. Phase structures, morphologies, and NO catalytic oxidation activities of single-phase MnO₂ catalysts[J]. Applied Catalysis A: General, 2016, 514: 24-34.
16	ZHOU Jing, QIN Lifan, XIAO Wei, et al. Oriented growth of layered MnO₂ nanosheets over α-MnO₂ nanotubes for enhanced room-temperature HCHO oxidation[J]. Applied Catalysis B: Environmental, 2017, 207: 233-243.
17	LI Kan, CHEN Chen, ZHANG Hongbo, et al. Effects of phase structure of MnO₂ and morphology of δ-MnO₂ on toluene catalytic oxidation[J]. Applied Surface Science, 2019, 496(1): 143662.
18	YANG Wenhao, SU Ziang, XU Zhenghao, et al. Comparative study of α-, β-, γ- and δ-MnO₂ on toluene oxidation: Oxygen vacancies and reaction intermediates[J]. Applied Catalysis B: Environmental, 2020, 260: 118150.
19	HUANG Na, QU Zhenping, DONG Cui, et al. Superior performance of α@β‍-MnO₂ for the toluene oxidation: Active interface and oxygen vacancy[J]. Applied Catalysis A: General, 2018, 560: 195-205.
20	MO Shengpeng, ZHANG Qi, LI Jiaqi, et al. Highly efficient mesoporous MnO₂ catalysts for the total toluene oxidation: Oxygen-vacancy defect engineering and involved intermediates using in situ DRIFTS[J]. Applied Catalysis, B. Environmental, 2020, 264: 118464.
21	ZENG Jia, XIE Hongmei, LIU Zhao, et al. Oxygen vacancy induced MnO₂ catalysts for efficient toluene catalytic oxidation[J]. Catalysis Science & Technology, 2021, 11(20): 6708-6723.
22	ZHANG Xiaodong, Xutian LYU, BI Fukun, et al. Highly efficient Mn₂O₃ catalysts derived from Mn-MOFs for toluene oxidation: The influence of MOFs precursors[J]. Molecular Catalysis, 2020, 482: 110701.
23	YANG Xueqin, YU Xiaolin, LIN Mengya, et al. Enhancement effect of acid treatment on Mn₂O₃ catalyst for toluene oxidation[J]. Catalysis Today, 2019, 327: 254-261.
24	Yue LYU, LI Caiting, DU Xueyu, et al. Catalytic oxidation of toluene over MnO₂ catalysts with different Mn(Ⅱ)precursors and the study of reaction pathway[J]. Fuel, 2020, 262: 116610.
25	YANG Wenhao, PENG Yue, WANG Ya, et al. Controllable redox-induced in-situ growth of MnO₂ over Mn₂O₃ for toluene oxidation: Active heterostructure interfaces[J]. Applied Catalysis B: Environmental, 2020, 278: 119279.
26	WANG Feng, DENG Jiang, IMPENG S, et al. Unraveling the effects of the coordination number of Mn over α‍-MnO₂ catalysts for toluene oxidation[J]. Chemical Engineering Journal, 2020, 396: 125192.
27	CHEN Jin, CHEN Xi, CHEN Xi, et al. Homogeneous introduction of CeO _y into MnO _x -based catalyst for oxidation of aromatic VOCs[J]. Applied Catalysis B: Environmental, 2018, 224: 825-835.
28	ZHAO Lele, ZHANG Zhiping, LI Yushi, et al. Synthesis of Ce _a MnO _x hollow microsphere with hierarchical structure and its excellent catalytic performance for toluene combustion[J]. Applied Catalysis B: Environmental, 2019, 245: 502-512.
29	LUO Yongjin, LIN Daifeng, ZHENG Yingbin, et al. MnO₂ nanoparticles encapsuled in spheres of Ce-Mn solid solution: Efficient catalyst and good water tolerance for low-temperature toluene oxidation[J]. Applied Surface Science, 2020, 504: 144481.
30	ZHANG Xiaodong, BI Fukun, ZHU Ziqiao, et al. The promoting effect of H₂O on rod-like MnCeO _x derived from MOFs for toluene oxidation: A combined experimental and theoretical investigation[J]. Applied Catalysis B: Environmental, 2021, 297: 120393.
31	LUO Yongjin, ZHENG Yingbin, ZUO Jiachang, et al. Insights into the high performance of Mn-Co oxides derived from metal organic frameworks for total toluene oxidation[J]. Journal of Hazardous Materials, 2018, 349: 119-127.
32	WANG Peifen, WANG Jing, AN Xiaowei, et al. Generation of abundant defects in Mn-Co mixed oxides by a facile agar-gel method for highly efficient catalysis of total toluene oxidation[J]. Applied Catalysis B: Environmental, 2021, 282: 119560.
33	DONG Cui, QU Zhenping, JIANG Xiao, et al. Tuning oxygen vacancy concentration of MnO₂ through metal doping for improved toluene oxidation[J]. Journal of Hazardous Materials, 2020, 391: 122181.
34	XIONG Shangchao, HUANG Nan, PENG Yue, et al. Balance of activation and ring-breaking for toluene oxidation over CuO-MnO _x bimetallic oxides[J]. Journal of Hazardous Materials, 2021, 415: 125637.
35	XU Yue, QU Zhenping, REN Yewei, et al. Enhancement of toluene oxidation performance over Cu-Mn composite oxides by regulating oxygen vacancy[J]. Applied Surface Science, 2021, 560: 149983.
36	LI Jianrong, ZHANG WanPeng, LI Chang, et al. Efficient catalytic degradation of toluene at a readily prepared Mn-Cu catalyst: Catalytic performance and reaction pathway[J]. Journal of Colloid and Interface Science, 2021, 591: 396-408.
37	LUO Mengmeng, CHENG Yan, PENG Xuzhe, et al. Copper modified manganese oxide with tunnel structure as efficient catalyst for low-temperature catalytic combustion of toluene[J]. Chemical Engineering Journal, 2019, 369: 758-765.
38	LI Mingyang, ZHANG Cheng, FAN Liman, et al. Enhanced catalytic oxidation of toluene over manganese oxide modified by lanthanum with a coral-like hierarchical structure nanosphere[J]. ACS Applied Materials & Interfaces, 2021, 13(8): 10089-10100.
39	CHEN Jie, CHEN Xi, XU Wenjian, et al. Hydrolysis driving redox reaction to synthesize Mn-Fe binary oxides as highly active catalysts for the removal of toluene[J]. Chemical Engineering Journal, 2017, 330: 281-293.
40	SOLTAN W BEN, SUN Jing, WANG Wenlong, et al. Discovering the key role of MnO₂ and CeO₂ particles in the Fe₂O₃ catalysts for enhancing the catalytic oxidation of VOC: Synergistic effect of the lattice oxygen species and surface-adsorbed oxygen[J]. Science of the Total Environment, 2022, 819: 152844.
41	LU Hanfeng, KONG Xianxian, HUANG Haifeng, et al. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene[J]. Journal of Environmental Sciences, 2015, 32: 102-107.
42	GONG Pijun, FANG De, HE Feng, et al. In situ construction of MnO₂@CeO₂ catalyst with a cake-like hierarchical nanosheets structure for efficient toluene oxidation[J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107665.
43	REN Quanming, MO Shengpeng, FAN Jie, et al. Enhancing catalytic toluene oxidation over MnO₂@Co₃O₄ by constructing a coupled interface[J]. Chinese Journal of Catalysis, 2020, 41: 1873-1883.
44	ZHANG Qi, MO Shengpeng, LI Jiaqi, et al. In situ DRIFT spectroscopy insights into the reaction mechanism of CO and toluene co-oxidation over Pt-based catalysts[J]. Catalysis Science & Technology, 2019, 9(17): 4538-4551.
45	MO Shengpeng, ZHANG Qi, ZHANG Mingyuan, et al. Elucidating the special role of strong metal-support interactions in Pt/MnO₂ catalysts for total toluene oxidation[J]. Nanoscale Horizons, 2019, 4(6): 1425-1433.
46	XIE Shaohua, DAI Hongxing, DENG Jiguang, et al. Preparation and high catalytic performance of Au/3DOM Mn₂O₃ for the oxidation of carbon monoxide and toluene[J]. Journal of Hazardous Materials, 2014, 279: 392-401.
47	LI Jiamin, QU Zhenping, QIN Yuan, et al. Effect of MnO₂ morphology on the catalytic oxidation of toluene over Ag/MnO₂ catalysts[J]. Applied Surface Science, 2016, 385(1): 234-240.
48	WANG Shihao, LIU Qi, ZHAO Ziqi, et al. Enhanced low-temperature activity of toluene oxidation over the rod-like MnO₂/LaMnO₃ perovskites with alkaline hydrothermal and acid-etching treatment[J]. Industrial & Engineering Chemistry Research, 2020, 59 (14): 6556-6564.
49	CHEN Xi, CHEN Xi, CAI Songcai, et al. MnO _x /Cr₂O₃ composites prepared by pyrolysis of Cr-MOF precursors containing in situ assembly of MnO _x as high stable catalyst for toluene oxidation[J]. Applied Surface Science, 2019, 475: 312-324.
50	ZHANG Chuanhui, WANG Chao, HUANG He, et al. Insights into the size and structural effects of zeolitic supports on gaseous toluene oxidation over MnO _x /HZSM-5 catalysts[J]. Applied Surface Science, 2019, 486: 108-120.
51	REDDY K H P, KIM Beom-Sik, LAM Su Shiung, et al. Effective toluene oxidation under ozone over mesoporous MnO _x /γ-Al₂O₃ catalyst prepared by solvent deficient method: Effect of Mn precursors on catalytic activity[J]. Environmental Research, 2021, 195: 110876.
52	YANG Jingsi, LI Luming, YANG Xiushan, et al. Enhanced catalytic performances of in situ-assembled LaMnO₃/δ-MnO₂ hetero-structures for toluene combustion[J]. Catalysis Today, 2019, 327: 19-27.
53	LIU Wei, XIANG Wenjie, GUAN Nana, et al. Enhanced catalytic performance for toluene purification over Co₃O₄/MnO₂ catalyst through the construction of different Co₃O₄-MnO₂ interface[J]. Separation and Purification Technology, 2021, 278: 119590.
54	LIU Wei, XIANG Wenjie, CHEN Xi, et al. A novel strategy to adjust the oxygen vacancy of CuO/MnO₂ catalysts toward the catalytic oxidation of toluene[J]. Fuel, 2022, 312: 122975.
55	WANG Yazhou, XIE Shaohua, DENG Jiguang, et al. Morphologically controlled synthesis of porous spherical and cubic LaMnO₃ with high activity for the catalytic removal of toluene[J]. ACS Applied Materials & Interfaces, 2014, 6(20): 17394-17401.
56	WANG Yuan, ARANDIYAN H, LIU Yuxi, et al. Template-free scalable synthesis of flower-like Co₃ _-x Mn _x O₄ spinel catalysts for toluene oxidation[J]. ChemCatChem, 2018, 10(16): 3429-3434.
57	DONG Cui, QU Zhenping, QIN Yuan, et al. Revealing the highly catalytic performance of spinel CoMn₂O₄ for toluene oxidation: Involvement and replenishment of oxygen species using in situ designed-TP techniques[J]. ACS Catalysis, 2019, 9(8): 6698-6710.
58	HOU Zhongyan, FENG Jie, LIN Tao, et al. The performance of manganese-based catalysts with Ce_0.65Zr_0.35O₂ as support for catalytic oxidation of toluene[J]. Applied Surface Science, 2018, 434: 82-90.
59	QI Meijuan, LI Zhe, ZHANG Zhang, et al. Controllable synthesis of MnO₂/iron mesh monolithic catalyst and its significant enhancement for toluene oxidation[J]. Chinese Chemical Letters, 2023, 34(2): 107437.
60	ZHOU Xiaoying, SHANG Yingnan, WEI Wei, et al. Effect of a mixed precursor over monolith MnO _x /La-Al₂O₃ catalyst for toluene oxidation[J]. New Journal of Chemistry, 2020, 44(26): 10859-10869.
61	项文杰. 锰基双金属催化剂催化氧化甲苯性能研究[D]. 沈阳: 沈阳化工大学, 2022.
	XIANG Wenjie. Study on catalytic oxidation of toluene with manganese-based bimetallic catalyst[D]. Shenyang: Shenyang University of Chemical Technology, 2022.
62	GONG Pijun Gong, HE Feng, XIE Junlin, et al. Catalytic removal of toluene using MnO₂-based catalysts: A review[J]. Chemosphere, 2023, 318: 137938.
63	CHEN Linzhu, LIU Yongjun, FANG Xue, et al. Simple strategy for the construction of oxygen vacancies on α-MnO₂ catalyst to improve toluene catalytic oxidation[J]. Journal of Hazardous Materials, 2021, 409: 125020.
64	LI Renzhu, ZHANG Long, ZHU Simin, et al. Layered δ-MnO₂ as an active catalyst for toluene catalytic combustion[J]. Applied Catalysis A： General, 2020, 602: 117715.
65	HUANG Jing, FANG Ruimei, SUN Yanjuan, et al. Efficient α-MnO₂ with (2 1 0) facet exposed for catalytic oxidation of toluene at low temperature: A combined in-situ DRIFTS and theoretical investigation[J]. Chemosphere, 2021, 263: 128103.
66	YANG Wenhao, ZHAO Xiaoguang, WANG Ya, et al. Atomically dispersed Ag on δ‍-MnO₂ via cation vacancy trapping for toluene catalytic oxidation[J]. Catalysis Science & Technology, 2022, 12(19): 5932-5941.
67	LI Luming, WAHAB Md Abdul, LI Hongmei, et al. Pt-Modulated CuMnO _x nanosheets as catalysts for toluene oxidation[J]. ACS Applied Nano Materials, 2021, 4(7): 6637-6647.

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