多金属氧化物催化臭氧氧化有机污染物的研究进展

doi:10.19965/j.cnki.iwt.2021-0005

摘要/Abstract

摘要：

水中难降解有机污染物对环境安全和人类健康造成严重的威胁，作为高级氧化技术的一种，非均相催化臭氧氧化技术，被证明是降解有机污染物有效的处理技术。在非均相催化臭氧氧化技术中，多金属氧化物因其制备方法较为简便且多金属的复合促进氧化还原循环和电子传递，常被开发用于高效催化臭氧氧化的催化剂。综述了多金属氧化物，包括钙钛矿氧化物、尖晶石氧化物、天然矿石、羟基氧化物等多金属氧化物的制备方法、性质及作为催化剂在催化臭氧降解药物分子、染料、酚类、个人护理用品等多种有机污染物中的应用，总结多金属氧化物催化臭氧氧化有机污染物过程中的作用机理，为今后多金属氧化物的制备、应用及反应机理探究提供理论借鉴。

关键词: 多金属氧化物, 非均相催化臭氧氧化, 活性位点, 反应机理

Abstract:

Refractory organic pollutants in water threaten both environmental safety and human health. As one of the advanced oxidation processes(AOPs), heterogeneous catalytic ozonation has been proved to be effective for degradation these pollutants. Due to the simple preparation method and the function with promoting the redox cycle and electron transfer by combination of multi metals, poly-metallic oxides are extensively employed as catalysts for heterogenous catalytic ozonation. The preparation methods and catalytic activities of poly-metallic oxides, including perovskite oxides, spinel oxides, natural minerals, oxyhydroxides and other metallic oxides composite were discussed, their applications for degradation of various organic contaminants, such as pharmaceuticals, dyes, phenolic compounds and personal care products were summarized. The corresponding catalytic ozonation mechanisms by utilizing these poly-metallic oxides were analyzed, which provided theoretical foundation and strategies for preparation, application and catalytic mechanistic research of poly-metallic oxides.

Key words: poly-metallic oxide, heterogenous catalytic ozonation, active sites, reaction mechanism

中图分类号:

X703

孔涛,任诺,陈春茂,王郁现. 多金属氧化物催化臭氧氧化有机污染物的研究进展[J]. 工业水处理, 2021, 41(7): 1-18.

Tao Kong,Nuo Ren,Chunmao Chen,Yuxian Wang. Research progress of catalytic ozonation of organic contaminants by poly-metallic oxides[J]. Industrial Water Treatment, 2021, 41(7): 1-18.

https://www.iwt.cn/CN/Y2021/V41/I7/1

图/表 21

参考文献 103

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有机物	pH	k_O₃/(L·mol^-1·s^-1)	pH	k_·OH/(L·mol^-1·s^-1)
苯	1.7~3	2±0.4	7	7.8×10⁹
硝基苯	2	0.09±0.02	7	3.2×10⁹
氯苯	2	0.75±0.2	9	4.5×10⁹
苯酚	8	1.8×10⁷	7.4~7.7	1.4×10¹⁰
4-氯苯酚	8	3.4×10⁷	9	7.6×10¹⁰
2-氯苯酚	8	6.6×10⁷	6.5~7.7	1.2×10¹⁰
4-硝基苯酚	8	1.4×10⁷	7	3.8×10⁹
苯甲酸盐	5	1.2±0.2	≤3	4.3×10⁹
草酸	8	< 4×10²	0.5	1.4×10⁶
草酸根离子	5~6	< 4×10²	6	7.7×10⁶
甲酸	2~4	5±5	1	1.4×10⁸
乙酸	2.5、5	1.8×10^-5	1	1.6×10⁷
丁二酸	4~6	< 3	1.5~10	3.1×10⁸
水杨酸	1.5~7	< 500	2	2.2×10¹⁰

有机物	pH	k_O₃/(L·mol^-1·s^-1)	pH	k_·OH/(L·mol^-1·s^-1)
苯	1.7~3	2±0.4	7	7.8×10⁹
硝基苯	2	0.09±0.02	7	3.2×10⁹
氯苯	2	0.75±0.2	9	4.5×10⁹
苯酚	8	1.8×10⁷	7.4~7.7	1.4×10¹⁰
4-氯苯酚	8	3.4×10⁷	9	7.6×10¹⁰
2-氯苯酚	8	6.6×10⁷	6.5~7.7	1.2×10¹⁰
4-硝基苯酚	8	1.4×10⁷	7	3.8×10⁹
苯甲酸盐	5	1.2±0.2	≤3	4.3×10⁹
草酸	8	< 4×10²	0.5	1.4×10⁶
草酸根离子	5~6	< 4×10²	6	7.7×10⁶
甲酸	2~4	5±5	1	1.4×10⁸
乙酸	2.5、5	1.8×10^-5	1	1.6×10⁷
丁二酸	4~6	< 3	1.5~10	3.1×10⁸
水杨酸	1.5~7	< 500	2	2.2×10¹⁰

氧化剂	电化学氧化电位(EOP)/V
·OH	+1.90~+2.70
O₃	+2.08
过氧化氢(H₂O₂)	+1.78
O₂^·-	+1.44
¹O₂	+0.81
O₂	+0.4

氧化剂	电化学氧化电位(EOP)/V
·OH	+1.90~+2.70
O₃	+2.08
过氧化氢(H₂O₂)	+1.78
O₂^·-	+1.44
¹O₂	+0.81
O₂	+0.4

催化剂	污染物	处理效率	反应条件	活性位点	文献
LaCoO₃	苯并三唑(BZA)	BZA：100%(CO或SO，15 min)；TOC：67%(CO，60 min)，60%(SO，60 min)	O₃ 2 mg/L；BZA 10 mg/L；催化剂0.5 g/L	表面羟基，Co²⁺/Co³⁺加速O₃分解	〔60〕
NC-LaMnO₃	2-氯苯酚(2-CP)	TOC：80%(CO，75 min)，25%(SO，75 min)	O₃ 20 mg/L，4 mg/min；2-CP 50 mg/L；催化剂0.3 g/L；pH 5.56	表面羟基(pH=或 < pH_pzc时活性最高)为O₃提供吸附位点，Mn³⁺/Mn⁴⁺之间的电子传递驱动O₃分解产生ROS	〔51〕
NC-LaCoO₃	2-氯苯酚(2-CP)	TOC：68%(CO，75 min)，25%(SO，75 min)		—
LaMn₄O_x	草酸(OA)；苯并三唑(BTA)	OA：100%(CO，45 min)，10%(SO，45 min)；BTA：100%(CO，30 min)，100%(SO，60 min)；TOC：95%(CO，90 min)，50%(SO，90 min)	O₃ 20 mg/L，100 mL/min；OA 50 mg/L；BTA 50 mg/L；催化剂0.2 g/L；pH 6.8	表面氧空位，表面羟基及Lewis酸性位点	〔37〕
SrTiO₃	草酸(OA)	OA：45.8%(CO，60 min)，9.3%(SO，60 min)	O₃：20 mg/(L·min)；OA 100 mg/L；催化剂1.25 g/L；pH 3	未探究	〔59〕
LaTi_0.15Cu_0.85O₃	丙酮酸	丙酮酸：75%(CO，200 min)，5%(SO，200 min)	O₃ 50 mg/L，40 L/h；丙酮酸5 mmol/L；catalyst 1 g/L；pH 6	未探究	〔43, 44〕
LaTi_0.15Cu_0.85O₃	没食子酸	没食子酸：100%(CO，120 min)，100%(SO，180 min)；TOC：50%(CO，180 min)，35%(SO，180 min)	O₃ 5 mg/L，40 L/h；没食子酸1 mmol/L；催化剂1 g/L；pH 3.5	未探究	〔45〕
LaTi_0.15Cu_0.85O₃	磺胺甲唑(SMX)	SMX：100%(CO或SO，10 min)；TOC：28%(SO，2 h)，85%(CO，2 h)	O₃ 20 mg/L，40 L/h；SMX 30 mg/L；催化剂1 g/L；pH 7；TOC 15 mg/L	未探究	〔48〕
LaTi_0.15Cu_0.85O₃	双氯芬酸(DCF)；17α-乙炔基二醇(EST)	DCF：100%(CO或SO，10 min)；TOC：95%(CO，120 min)，40%(SO，120 min)；EST-TOC：90%(CO，120 min)，65%(SO，120 min)	O₃ 20 mg/L；EST 9 mg/L；DCF 30 mg/L；催化剂0.1 g/L；pH 7	未探究	〔47〕
LaTi_0.15Cu_0.85O₃	双氯芬酸(DCF)；17α-乙炔基二醇(EST)	COD：40%(SO，320 min)，70%(CO，320 min)	O₃ 50 mg/L，40 L/h；COD 1 100 mg/L；催化剂1 g/L；pH 5.8	未探究	〔46〕
LaTi_0.15Co_0.85O₃	双氯芬酸(DCF)；17α-乙炔基二醇(EST)	DCF：100%(CO或SO，10 min)；TOC：78%(CO，120 min)，40%(SO，120 min)；EST-TOC：80%(CO，120 min)，65%(SO，120 min)；	O₃ 20 mg/L；EST 9 mg/L；DCF 30 mg/L；催化剂0.1 g/L；pH 7	未探究	〔47〕
LaTi_0.15Co_0.85O₃	磺胺甲唑(SMX)	SMX：100%(CO或SO，10 min)；TOC：28%(SO，2 h)，60%(CO，2 h)	O₃ 20 mg/L；SMX 30 mg/L；催化剂1 g/L；pH 7；TOC 15 mg/L	未探究	〔48〕

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