金属基催化剂非均相催化臭氧氧化机理与研究进展

doi:10.19965/j.cnki.iwt.2025-0345

摘要/Abstract

摘要：

非均相催化臭氧氧化（HCO）技术因其具有高效矿化有机污染物的能力而在水处理领域受到广泛关注。该技术通过催化剂表面活性位点高效活化臭氧并生成羟基自由基（·OH）、超氧自由基（O₂ ^·-）等活性氧物种（ROS），显著提高了有机污染物降解和矿化效率。金属基催化剂因具有优异的催化活性、结构稳定性和可调控性而成为研究重点。系统阐述了金属氧化物（如Al₂O₃、MgO、MnO₂、FeOOH等）、多金属氧化物和新型金属基催化剂的结构特性、催化效能及其在水处理中的应用现状；探讨了催化剂表面羟基、氧空位及金属离子等活性位点在臭氧活化过程中的关键作用机制及调控策略，并对比分析了自由基路径与非自由基路径的生成机理，为开发低成本、高稳定性的臭氧催化材料及自由基-非自由基协同氧化工艺提供了理论支撑与技术路径。

关键词: 金属基催化剂, 非均相催化臭氧氧化, 活性位点, 自由基/非自由基机制

Abstract:

Heterogeneous catalytic ozonation(HCO) has garnered significant attention in the field of water treatment due to its exceptional capability to mineralize organic pollutants. This technology enhances the degradation and mineralization efficiency of organic contaminants by activating ozone through catalytic surface-active sites, thereby generating reactive oxygen species(ROS) such as hydroxyl radicals(·OH) and superoxide radicals(O₂ ^·-). Metal-based catalysts have become a research focus due to their superior catalytic activity, structural stability, and tunability. This review systematically elaborated on the structural characteristics, catalytic performance, and application status of metal oxides(e.g., Al₂O₃, MgO, MnO₂, FeOOH), multimetal oxides, and novel metal-based catalysts in water treatment. The critical roles and regulatory strategies of active sites(e.g., surface hydroxyl groups, oxygen vacancies, and metal ions) in ozone activation mechanisms were explored, while the formation pathways of radical-dominated and non-radical processes were comparatively analyzed. The findings provided theoretical foundations and technical pathways for developing cost-effective, highly stable ozone catalytic materials and synergistic oxidation processes integrating radical and non-radical mechanisms.

Key words: metal-based catalysts, heterogeneous catalytic ozonation, active sites, radical/non-radical mechanism

中图分类号:

X703

杨宇婷, 张立, 秦志峰, 吴丽杰, 翟志强. 金属基催化剂非均相催化臭氧氧化机理与研究进展[J]. 工业水处理, 2026, 46(4): 35-45.

Yuting YANG, Li ZHANG, Zhifeng QIN, Lijie WU, Zhiqiang ZHAI. Advances in the application and mechanism of metal-based catalysts in catalytic ozonation[J]. Industrial Water Treatment, 2026, 46(4): 35-45.

https://gyscl.magtechjournal.com/CN/Y2026/V46/I4/35

图/表 5

图1 CF/O₃系统的可能机制

Fig.1 Probable mechanism of CF/O₃ system

表1 不同催化剂在污染物去除中的最佳pH条件及羟基状态

Table 1 Optimal pH conditions and hydroxyl group states of various catalysts in pollutant removal

催化剂	污染物	pH_pzc	最佳pH	羟基状态	去除率/%	参考文献
MgO	喹啉	7.2	7.2	Mg—OH	94.8	〔9〕
Si-nZVI	喹啉	5.4	5.4	Fe—O^-	91.9	〔28〕
Ce/海泡石（SEP）	对硝基苯酚（PNP）	6.38	7	Ce—OH	74	〔37〕
Mn-Ce/Al₂O₃	阿拉特津（ATZ）	7.03	9.2	Mn $̿$ Ce—O^-	100	〔47〕
介孔Fe₃O₄（Om-Fe₃O₄）	ATZ	5.65	9.5	Fe—O^-	100	〔48〕
CaO	四羟基磷硫酸盐（THPS）废水	11.9	12.38	Ca—O^-	100	〔49〕
Co₃O₄@Co-NCMK3	ATZ	6.96	5	Co—OH₂ ⁺	96.2	〔50〕
CaMn₄O₈	苯酚	5.58	5.58	Mn—OH	100	〔51〕
NC-LaMnO₃	2-氯苯酚	8.98	9.0	Mn—OH	80	〔52〕
Ca₂Fe₂O₅	喹啉	9.5	12	Fe—O^-	90.63	〔53〕

表1 不同催化剂在污染物去除中的最佳pH条件及羟基状态

Table 1 Optimal pH conditions and hydroxyl group states of various catalysts in pollutant removal

催化剂	污染物	pH_pzc	最佳pH	羟基状态	去除率/%	参考文献
MgO	喹啉	7.2	7.2	Mg—OH	94.8	〔9〕
Si-nZVI	喹啉	5.4	5.4	Fe—O^-	91.9	〔28〕
Ce/海泡石（SEP）	对硝基苯酚（PNP）	6.38	7	Ce—OH	74	〔37〕
Mn-Ce/Al₂O₃	阿拉特津（ATZ）	7.03	9.2	Mn $̿$ Ce—O^-	100	〔47〕
介孔Fe₃O₄（Om-Fe₃O₄）	ATZ	5.65	9.5	Fe—O^-	100	〔48〕
CaO	四羟基磷硫酸盐（THPS）废水	11.9	12.38	Ca—O^-	100	〔49〕
Co₃O₄@Co-NCMK3	ATZ	6.96	5	Co—OH₂ ⁺	96.2	〔50〕
CaMn₄O₈	苯酚	5.58	5.58	Mn—OH	100	〔51〕
NC-LaMnO₃	2-氯苯酚	8.98	9.0	Mn—OH	80	〔52〕
Ca₂Fe₂O₅	喹啉	9.5	12	Fe—O^-	90.63	〔53〕

图2 α-Fe₂O₃复合金属氧化物催化臭氧化的合理机制

Fig.2 Plausible mechanism for α-Fe₂O₃ composite metal oxides catalytic ozonation

图3 CaMn₄O₈催化臭氧化降解苯酚的机理示意

Fig.3 Schematic illustration of the catalytic ozonation mechanism for phenol degradation over the mixed-valence CaMn₄O₈ catalyst

表2 非均相催化臭氧氧化中自由基与非自由基路径对比

Table 2 Comparison of radical and non-radical pathways in heterogeneous catalytic ozonation

类别	自由基路径	非自由基路径
主要活性物种	·OH、O₂ ^·-	¹O₂、O^* _ad
生成机制	臭氧通过催化剂表面活性位点（如表面羟基、Fe²⁺/Fe³⁺）分解，引发链式反应	臭氧在氧空位直接解离生成¹O₂或O^*；表面电子转移生成非自由基活性氧
氧化特性	氧化能力强，反应快速	氧化能力较弱，依赖催化剂表面的直接氧化或电子转移
反应选择性	无选择性攻击所有污染物	优先攻击含供电子基团的污染物（如芳香族、氨基化合物）
适应性	易受水质（pH、共存离子）干扰	抗环境干扰能力强，较宽的pH适应性；稳定性高，适用于复杂水质
副产物风险	可能产生有毒副产物	副产物生成风险低
适用场景	简单水质；需快速去除污染物	复杂工业废水、需选择性降解
典型催化剂	FeOOH、Fe-Mn/γ-Al₂O₃	Fe-N₄、碳基材料

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