非均相催化臭氧氧化作用机理研究进展

doi:10.16085/j.issn.1000-6613.2023-0507

摘要/Abstract

摘要：

高级氧化技术作为治理难降解污染物、污水提标改造的有效处理技术发展迅速。非均相催化臭氧氧化因氧化效率高、使用便捷等优势受到广泛关注。当前研究主要集中于对高效催化剂制备及其降解效能方面，而对非均相催化臭氧氧化机理方面的探索和总结尚不完善。本文根据非均相催化剂类型差异系统综述了催化臭氧氧化体系中重要的吸附作用机理以及催化氧化作用机理，讨论了金属氧化物材料的表面羟基、路易斯活性位点、氧化还原电偶，非金属材料的电子来源差异、表面官能团，复合材料的复合特性对臭氧的吸附与活性氧物种产生的影响。同时总结了非均相催化氧化过程中活性氧物种之间的产生、转化与鉴定以及详细的羟基自由基和超氧自由基的相互转化过程，为后续发展非均相催化臭氧氧化技术提供参考。

关键词: 非均相催化臭氧氧化, 氧化还原电偶, 电子来源, 活性氧物种

Abstract:

Advanced oxidation has developed rapidly as an effective technology for the treatment of refractory pollutants and sewage upgrading. Heterogeneous catalytic ozone oxidation has attracted wide attention due to its advantages of high oxidation efficiency and convenient use. The current research mainly focuses on the preparation of highly efficient catalyst and its degradation efficiency, while the exploration and summary of the mechanism of heterogeneous catalytic ozone oxidation are not perfect. In this paper, the important adsorption mechanism and the catalytic oxidation mechanism in the catalytic ozone oxidation system were summarized according to the type difference of heterogeneous catalysts. The effects of surface hydroxyl group, Lewis active site and redox coupling of metal oxide materials, electronic source differences and surface functional groups of non-metallic materials, and composite characteristics of composite materials on the adsorption of ozone and reactive oxygen species production were discussed. At the same time, the generation, transformation and identification among reactive oxygen species and the detailed interconversion process of hydroxyl radicals and superoxide radicals in the heterogeneous catalytic oxidation process were also summarized to provide a reference for the subsequent development of heterogeneous catalytic ozone oxidation technology.

Key words: heterogeneous catalytic ozone oxidation, redox coupling, electronic source, reactive oxygen species

中图分类号:

高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.

GAO Yufei, LU Jinfeng. Mechanism of heterogeneous catalytic ozone oxidation:A review[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 430-438.

图/表 4

图1 HCO技术中常用催化剂

图2 O3与金属氧化物表面羟基吸附作用机理

图3 HCO过程

表1 非均相催化臭氧氧化作用机制

催化剂类型	催化剂	模型污染物	催化机理	活性物种	参考文献
金属氧化物	α-MnO₂	4-氯苯酚	Mn³⁺缺陷、氧空位	·OH、· $O 2 -$ 、 $1 O 2$ 、 $* O$	[16]
金属氧化物	CeO₂	4-硝基酚	Ce³⁺/Ce⁴⁺、氧空位	·OH、 $1 O 2$ 、 $* O$	[17]
非金属材料	g-C₃N₄	4-氯苯甲酸/苯甲醛	氮空位、含氧官能团	·OH、· $O 2 -$	[18]
非金属材料	无定形B	阿特拉津	B—B键、B²⁺/B³⁺	· $O 2 -$ 、 $1 O 2$	[9]
复合材料	MnO _x /CeO _x /γ-Al₂O₃	土霉素	Mn³⁺/Mn⁴⁺、Ce³⁺/Ce⁴⁺	·OH	[13]
	Fe₃O₄/Co₃O₄	磺胺甲唑	Fe²⁺/Fe³⁺、Co²⁺/Co³⁺	·OH、· $O 2 -$	[22]
	Cu _x O/ Fe₃O₄	邻苯二甲酸二甲酯	Fe²⁺/Fe³⁺、Cu⁺/Cu²⁺	·OH、· $O 2 -$	[23]
	CeO _x /TiO₂-ZrO₂	草酸	Ce³⁺/Ce⁴⁺	·OH	[24]
	LaCoO₃/g-C₃N₄	苯并三唑	氮空位、—C—O—Co、Co²⁺/Co³⁺	·OH、· $O 2 -$ 、 $1 O 2$	[14]
	MnO/g-C₃N₄	阿特拉津	—C—N—Mn、—C—O—Mn、Mn²⁺/Mn³⁺	·OH	[25]
	CuO/g-C₃N₄	草酸	—	·OH、· $O 2 -$	[26]
	ZnO/g-C₃N₄	阿特拉津	—	·OH、· $O 2 -$ 、 $1 O 2$	[27]
	Ce(Ⅲ) / g-C₃N₄	草酸	Ce(Ⅲ)位、表面羟基	·OH	[28]

表1 非均相催化臭氧氧化作用机制

催化剂类型	催化剂	模型污染物	催化机理	活性物种	参考文献
金属氧化物	α-MnO₂	4-氯苯酚	Mn³⁺缺陷、氧空位	·OH、· $O 2 -$ 、 $1 O 2$ 、 $* O$	[16]
金属氧化物	CeO₂	4-硝基酚	Ce³⁺/Ce⁴⁺、氧空位	·OH、 $1 O 2$ 、 $* O$	[17]
非金属材料	g-C₃N₄	4-氯苯甲酸/苯甲醛	氮空位、含氧官能团	·OH、· $O 2 -$	[18]
非金属材料	无定形B	阿特拉津	B—B键、B²⁺/B³⁺	· $O 2 -$ 、 $1 O 2$	[9]
复合材料	MnO _x /CeO _x /γ-Al₂O₃	土霉素	Mn³⁺/Mn⁴⁺、Ce³⁺/Ce⁴⁺	·OH	[13]
	Fe₃O₄/Co₃O₄	磺胺甲唑	Fe²⁺/Fe³⁺、Co²⁺/Co³⁺	·OH、· $O 2 -$	[22]
	Cu _x O/ Fe₃O₄	邻苯二甲酸二甲酯	Fe²⁺/Fe³⁺、Cu⁺/Cu²⁺	·OH、· $O 2 -$	[23]
	CeO _x /TiO₂-ZrO₂	草酸	Ce³⁺/Ce⁴⁺	·OH	[24]
	LaCoO₃/g-C₃N₄	苯并三唑	氮空位、—C—O—Co、Co²⁺/Co³⁺	·OH、· $O 2 -$ 、 $1 O 2$	[14]
	MnO/g-C₃N₄	阿特拉津	—C—N—Mn、—C—O—Mn、Mn²⁺/Mn³⁺	·OH	[25]
	CuO/g-C₃N₄	草酸	—	·OH、· $O 2 -$	[26]
	ZnO/g-C₃N₄	阿特拉津	—	·OH、· $O 2 -$ 、 $1 O 2$	[27]
	Ce(Ⅲ) / g-C₃N₄	草酸	Ce(Ⅲ)位、表面羟基	·OH	[28]

参考文献 32

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