金属材料协同VB12催化卤代有机物降解研究进展

doi:10.16085/j.issn.1000-6613.2021-0481

摘要/Abstract

摘要：

卤代有机物（HOCs）是环境领域的主要污染物类型之一，因其高持久性、毒性和生物累积性而受到广泛关注。还原脱卤技术是一种高效、低耗、易行的HOCs处理方式，而生物辅酶因子维生素B₁₂（VB₁₂）对HOCs的还原脱卤有很高的催化活性。本文总结了单金属、双金属、金属矿物及半导体等金属材料协同VB₁₂催化降解HOCs的研究进展，讨论了每种金属材料与VB₁₂的协同催化机制、降解HOCs机理特性、实际应用情况及局限性等。结果表明，金属材料协同VB₁₂对HOCs还原脱卤具有加速电子转移、金属表面介导催化、活化碳-卤键等独特的优势和广阔的应用前景。最后，结合最新研究，指明目前该体系在机理研究、材料设计、实际应用、技术等方面所面临的挑战及未来的研究方向。

关键词: 卤代有机物, 维生素B₁₂, 还原脱卤, 金属材料, 协同催化

Abstract:

Halogenated organic compounds (HOCs) are a class of primary pollutants. Because of their high persistence, toxicity, bioaccumulation and strong resistance to natural degradations, HOCs have aroused great concerns. Reductive dehalogenation is an effective, low-cost and feasible approach for the degradation of HOCs. Vitamin B₁₂ (VB₁₂) is a biological cofactor that can efficiently catalyze the reductive dehalogenation reaction of HOCs. In this review, we summarized the synergistic systems of mono-metal, bimetallic materials, metal mineral compounds, and semiconductor materials in combination with VB₁₂ for the catalytic reductive degradation of HOCs. The synergistic catalytic mechanism, HOCs degradation mechanism and their practical applications are discussed. Results indicated that the synergistic system of metal material and VB₁₂ has unique advantages on catalyzing the reductive dehalogenation of HOCs such as accelerating electron transfer, mediating surface catalysis and activation carbon-halogen bond, and therefore is promising for future application. Finally, based on the latest researches, challenges and future research directions were proposed including mechanism investigation, material design, practical application, and technology development.

Key words: halogenated organic compounds, vitamin B₁₂, reductive dehalogenation, metal materials, synergistic catalysis

中图分类号:

X523

巫秀玲, 赵晓祥, 孙铸宇. 金属材料协同VB₁₂催化卤代有机物降解研究进展[J]. 化工进展, 2022, 41(2): 708-720.

WU Xiuling, ZHAO Xiaoxiang, SUN Zhuyu. Catalytic degradation of halogenated organic compounds by synergistic system of metal materials and VB₁₂: a review[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 708-720.

图/表 9

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HOCs	反应体系	反应条件	反应时间及降解率	一级反应动力学常数k_obs	降解产物	参考文献
四氯乙烯（PCE） 900μmol/L	Zn⁰	1g/L Zn⁰	—	（0.186±0.028）d^-1?m^-2	—	［67］
	Zn⁰-VB₁₂	1g/L Zn⁰，45μmol/L VB₁₂	—	（1.44±0.23）d^-1?m^-2	三氯乙烯（TCE）
	Fe⁰	1g/L Fe⁰	—	（2.47±0.49）×10^-3d^-1?m^-2	—
	Fe⁰-VB₁₂	1g/L Fe⁰，45μmol/L VB₁₂	—	（3.00±0.21）×10^-2d^-1?m^-2	三氯乙烯（TCE）
三氯乙烯（TCE） 900μmol/L	Zn⁰	0.75g/L Zn⁰	—	（1.15±0.8）×10^-3d^-1?m^-2	—	［67］
三氯乙烯（TCE） 900μmol/L	Zn⁰-VB₁₂	0.75g/L Zn⁰，45μmol/L VB₁₂	—	（0.645±0.035）d^-1?m^-2	1，2-二氯乙烯（1，2-DCE）	［67］
十氯酮（CLD） 10mg/L	DTT-VB₁₂	25mL乙醇，13.56mg VB₁₂，231mg DTT	40min，76.0%	—	—	［68］
十氯酮（CLD） 10mg/L	Zn⁰-VB₁₂	25mL乙醇，13.56mg VB₁₂，65.9mg Zn⁰	20min，90.0%	—	五氯茚	［68］
2，2'，4，4'-四溴二苯（BDE47） 25mg/L	BM Al	2g/L BM Al ，甲醇/水=40/60（体积比），pH=4	2h，15.6%	—	—	［69］
2，2'，4，4'-四溴二苯（BDE47） 25mg/L	BM Al-VB₁₂	2g/L BM Al ，0.3mmol/L VB₁₂，甲醇/水=40/60（体积比），pH=4	2h，97.6%	2.94h^-1	二苯醚	［69］
1，2，3-三氯丙烷（1，2，3-TCP）12.27mg/L	μZVI	0.5g/L μZVI	未降解	—	—	［70］
1，2，3-三氯丙烷（1，2，3-TCP）12.27mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	7d，90.0%	（0.287±0.012）d^-1	丙烯
1，2-二氯丙烷（1，2-DCP）9.48mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1，2-二氯丙烷（1，2-DCP）9.48mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	21d，70.0%	（0.0594±0.0060）d^-1	丙烯
1，3-二氯丙烷（1，3-DCP）24.79mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1，3-二氯丙烷（1，3-DCP）24.79mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	28d，90.0%	（0.0503±0.0038）d^-1	环丙烷
1-氯丙烷（1-CP） 20.89mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1-氯丙烷（1-CP） 20.89mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	28d，40.0%	（0.0182±0.0044）d^-1	丙烷
1，2-二氯乙烷（1，2-DCA）13.52mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1，2-二氯乙烷（1，2-DCA）13.52mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	28d，90.0%	0.0847d^-1	乙烯（未测到，基于计算）
四氯乙烯（PCE） 0.1mmol/L	nZVI	2g/L nFe⁰，pH= 8.2	未降解	—	—	［74］
四氯乙烯（PCE） 0.1mmol/L	nZVI-VB₁₂	2g/L nZVI，0.5mmol/LVB₁₂，pH=8.2	6h，80.0%	（0.25±0.01）h^-1	TCE和顺-DCE	［74］
二氯甲烷（DCM） 26mg/L	TC	0.177mmol/L TC，pH=9.6	未降解	—	—	［75］
	TC-VB₁₂	0.177mmol/L TC，0.004mmol/L VB₁₂，pH=9.6	8h，80.0%	0.24h^-1	—
	TC-VB₁₂-nCu⁰	0.177mmol/L TC，0.004mmol/L VB₁₂，0.5g/L nCu⁰，pH=9.6	2h，99.0%	1.35h^-1	甲烷
全氟辛酸（PFOA） 50mg/L	NaBH₄	11.25mmol/L NaBH₄，pH=4.0，T=70℃	18h，3.1%	—	—	［76］
	NaBH₄-nCu⁰-VB₁₂	11.25mmol/L NaBH₄，0.2mmol/L VB₁₂，2g/L nCu⁰，pH=4.0，T=70oC	18h，15.5%	—	—
	nZVI-nCu⁰-VB₁₂	25g/L nZVI，2g/L nCu⁰，0.2mmol/L VB₁₂ ，pH=4.0，T=70oC	18h，29.9%	—	—
	TC	45mmol/L TC，pH=4.0，T=70oC	18h，34.5%	—	—
	TC-nCu⁰-VB₁₂	45mmol/L TC，2g/L nCu⁰，0.2mmol/L VB₁₂，pH=4.0，T=70oC	18h，65.0%	—	—
全氟辛磺酸（PFOS） 200μmol/L	nZVI	2g/L nZVI，T=70oC	未降解	—	—	［33］
全氟辛磺酸（PFOS） 200μmol/L	nZVI-VB₁₂	2g/L nZVI，200μmol/L VB₁₂，T=70oC	10d，53.8%	6.4×10^-2d^-1	PFHxS、PFHpS、PFHxA、PFOA、PFUdA	［33］

HOCs	反应体系	反应条件	反应时间及降解率	一级反应动力学常数k_obs	降解产物	参考文献
四氯乙烯（PCE） 900μmol/L	Zn⁰	1g/L Zn⁰	—	（0.186±0.028）d^-1?m^-2	—	［67］
	Zn⁰-VB₁₂	1g/L Zn⁰，45μmol/L VB₁₂	—	（1.44±0.23）d^-1?m^-2	三氯乙烯（TCE）
	Fe⁰	1g/L Fe⁰	—	（2.47±0.49）×10^-3d^-1?m^-2	—
	Fe⁰-VB₁₂	1g/L Fe⁰，45μmol/L VB₁₂	—	（3.00±0.21）×10^-2d^-1?m^-2	三氯乙烯（TCE）
三氯乙烯（TCE） 900μmol/L	Zn⁰	0.75g/L Zn⁰	—	（1.15±0.8）×10^-3d^-1?m^-2	—	［67］
三氯乙烯（TCE） 900μmol/L	Zn⁰-VB₁₂	0.75g/L Zn⁰，45μmol/L VB₁₂	—	（0.645±0.035）d^-1?m^-2	1，2-二氯乙烯（1，2-DCE）	［67］
十氯酮（CLD） 10mg/L	DTT-VB₁₂	25mL乙醇，13.56mg VB₁₂，231mg DTT	40min，76.0%	—	—	［68］
十氯酮（CLD） 10mg/L	Zn⁰-VB₁₂	25mL乙醇，13.56mg VB₁₂，65.9mg Zn⁰	20min，90.0%	—	五氯茚	［68］
2，2'，4，4'-四溴二苯（BDE47） 25mg/L	BM Al	2g/L BM Al ，甲醇/水=40/60（体积比），pH=4	2h，15.6%	—	—	［69］
2，2'，4，4'-四溴二苯（BDE47） 25mg/L	BM Al-VB₁₂	2g/L BM Al ，0.3mmol/L VB₁₂，甲醇/水=40/60（体积比），pH=4	2h，97.6%	2.94h^-1	二苯醚	［69］
1，2，3-三氯丙烷（1，2，3-TCP）12.27mg/L	μZVI	0.5g/L μZVI	未降解	—	—	［70］
1，2，3-三氯丙烷（1，2，3-TCP）12.27mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	7d，90.0%	（0.287±0.012）d^-1	丙烯
1，2-二氯丙烷（1，2-DCP）9.48mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1，2-二氯丙烷（1，2-DCP）9.48mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	21d，70.0%	（0.0594±0.0060）d^-1	丙烯
1，3-二氯丙烷（1，3-DCP）24.79mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1，3-二氯丙烷（1，3-DCP）24.79mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	28d，90.0%	（0.0503±0.0038）d^-1	环丙烷
1-氯丙烷（1-CP） 20.89mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1-氯丙烷（1-CP） 20.89mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	28d，40.0%	（0.0182±0.0044）d^-1	丙烷
1，2-二氯乙烷（1，2-DCA）13.52mg/L	μZVI	0.5g/L μZVI	未降解	—	—
1，2-二氯乙烷（1，2-DCA）13.52mg/L	μZVI-VB₁₂	0.5g/L μZVI，1mmol/L VB₁₂	28d，90.0%	0.0847d^-1	乙烯（未测到，基于计算）
四氯乙烯（PCE） 0.1mmol/L	nZVI	2g/L nFe⁰，pH= 8.2	未降解	—	—	［74］
四氯乙烯（PCE） 0.1mmol/L	nZVI-VB₁₂	2g/L nZVI，0.5mmol/LVB₁₂，pH=8.2	6h，80.0%	（0.25±0.01）h^-1	TCE和顺-DCE	［74］
二氯甲烷（DCM） 26mg/L	TC	0.177mmol/L TC，pH=9.6	未降解	—	—	［75］
	TC-VB₁₂	0.177mmol/L TC，0.004mmol/L VB₁₂，pH=9.6	8h，80.0%	0.24h^-1	—
	TC-VB₁₂-nCu⁰	0.177mmol/L TC，0.004mmol/L VB₁₂，0.5g/L nCu⁰，pH=9.6	2h，99.0%	1.35h^-1	甲烷
全氟辛酸（PFOA） 50mg/L	NaBH₄	11.25mmol/L NaBH₄，pH=4.0，T=70℃	18h，3.1%	—	—	［76］
	NaBH₄-nCu⁰-VB₁₂	11.25mmol/L NaBH₄，0.2mmol/L VB₁₂，2g/L nCu⁰，pH=4.0，T=70oC	18h，15.5%	—	—
	nZVI-nCu⁰-VB₁₂	25g/L nZVI，2g/L nCu⁰，0.2mmol/L VB₁₂ ，pH=4.0，T=70oC	18h，29.9%	—	—
	TC	45mmol/L TC，pH=4.0，T=70oC	18h，34.5%	—	—
	TC-nCu⁰-VB₁₂	45mmol/L TC，2g/L nCu⁰，0.2mmol/L VB₁₂，pH=4.0，T=70oC	18h，65.0%	—	—
全氟辛磺酸（PFOS） 200μmol/L	nZVI	2g/L nZVI，T=70oC	未降解	—	—	［33］
全氟辛磺酸（PFOS） 200μmol/L	nZVI-VB₁₂	2g/L nZVI，200μmol/L VB₁₂，T=70oC	10d，53.8%	6.4×10^-2d^-1	PFHxS、PFHpS、PFHxA、PFOA、PFUdA	［33］

HOCs	反应体系	反应条件	反应时间及降解率	一级反应动力学常数k_obs/h^-1	降解产物	参考文献
二氯甲烷（DCM） 10mg/L	VB₁₂	20mg/L VB₁₂，pH=8.2	—	0.005	—	［96］
	Fe⁰	20g/L Fe⁰，pH=8.2	—	0.006	—
	Fe/Cu	20g/L Cu/Fe［5%（质量分数）Cu］，pH=8.2	—	0.018	—
	Fe⁰-VB₁₂	20g/L Fe⁰，20mg/L VB₁₂，pH=8.2	—	0.030	—
	Fe/Cu-VB₁₂	20g/L Cu/Fe［5%（质量分数）Cu］，20mg/L VB₁₂，pH=8.2	8h，100.0%	0.444	一氯甲烷、甲烷
二氯甲烷（DCM） 26mg/L	Al⁰	50g/L Al⁰，pH=10	未降解	—	—	［55］
	Cu/Al⁰	60g/L Cu/Al⁰ ［20%（质量分数）Cu］，pH=10	4h，42.0%	0.11	—
	Al⁰-VB₁₂	50g/L Al⁰，1mmol/L VB₁₂，pH=10	—	0.07	—
	Cu/Al⁰-VB₁₂	60g/L Cu/Al⁰ ［20%（质量分数）Cu］，1mmol/L VB₁₂，pH=10	2h，98.0%	1.46	一氯甲烷、甲烷
五氯酚（PCP） 20mg/L	nFe⁰	5g/L nFe⁰，pH=8.5	8h，75.0%	0.564	四氯酚	［57］
	nFe/Cu	5g/L nFe/Cu［10%（质量分数）Cu］，pH=8.5	4h，100.0%	2.375	四氯酚和三氯酚
	nFe/Cu-VB₁₂	5g/L nFe/Cu［10%（质量分数）Cu］，20mg/LVB₁₂，pH=8.5	3h，100.0%	3.272	二氯酚、氯酚和苯酚

HOCs	反应体系	反应条件	反应时间及降解率	一级反应动力学常数k_obs/h^-1	降解产物	参考文献
二氯甲烷（DCM） 10mg/L	VB₁₂	20mg/L VB₁₂，pH=8.2	—	0.005	—	［96］
	Fe⁰	20g/L Fe⁰，pH=8.2	—	0.006	—
	Fe/Cu	20g/L Cu/Fe［5%（质量分数）Cu］，pH=8.2	—	0.018	—
	Fe⁰-VB₁₂	20g/L Fe⁰，20mg/L VB₁₂，pH=8.2	—	0.030	—
	Fe/Cu-VB₁₂	20g/L Cu/Fe［5%（质量分数）Cu］，20mg/L VB₁₂，pH=8.2	8h，100.0%	0.444	一氯甲烷、甲烷
二氯甲烷（DCM） 26mg/L	Al⁰	50g/L Al⁰，pH=10	未降解	—	—	［55］
	Cu/Al⁰	60g/L Cu/Al⁰ ［20%（质量分数）Cu］，pH=10	4h，42.0%	0.11	—
	Al⁰-VB₁₂	50g/L Al⁰，1mmol/L VB₁₂，pH=10	—	0.07	—
	Cu/Al⁰-VB₁₂	60g/L Cu/Al⁰ ［20%（质量分数）Cu］，1mmol/L VB₁₂，pH=10	2h，98.0%	1.46	一氯甲烷、甲烷
五氯酚（PCP） 20mg/L	nFe⁰	5g/L nFe⁰，pH=8.5	8h，75.0%	0.564	四氯酚	［57］
	nFe/Cu	5g/L nFe/Cu［10%（质量分数）Cu］，pH=8.5	4h，100.0%	2.375	四氯酚和三氯酚
	nFe/Cu-VB₁₂	5g/L nFe/Cu［10%（质量分数）Cu］，20mg/LVB₁₂，pH=8.5	3h，100.0%	3.272	二氯酚、氯酚和苯酚

HOCs	反应体系	反应条件	反应时间及降解率	一级反应动力学常数k_obs/h^-1	降解产物	参考文献
四氯化碳（CT） 5mmol/L	FeS	200mmol/L FeS，pH=8	30min，70.0%	—	—	［113］
四氯化碳（CT） 5mmol/L	FeS-VB₁₂	200mmol/L FeS，4mmol/L VB₁₂，pH=8	30min，95.0%	1.91	氯仿，二氯甲烷	［113］
四氯乙烯（PCE） 0.1mmol/L	mFeS	4.17g/L mFeS，pH=8.3	120h，10.0%	—	—	［36］
	nFeS	4.17g/L nFeS，pH=8.3	120h，20.0%	0.0013±0.001	—
	mFeS-VB₁₂	4.17g/L mFeS，0.1mmol/L VB₁₂，pH=8.3	120h，60.0%	—	—
	nFeS-VB₁₂	4.17g/L nFeS，0.1mmol/L VB₁₂，pH=8.3	120h，100.0%	0.188±0.003	乙炔，1，3-丁二烯
PCE 0.035mmol/L	nFeS	4.17g/L nFeS，pH=12	120h，25.0%	—	—	［59］
PCE 0.035mmol/L	nFeS-VB₁₂	4.17g/L nFeS，0.1mmol/L VB₁₂ ，pH=12	15h，95.0%	0.2036	乙炔，三氯乙烯，乙烯	［59］
PCE 0.1mmol/L	S^2-	0.1mmol/LS^2-，pH=8.3	未降解	—	—	［114］
	nFeS	4.17g/L nFeS，pH=8.3	220h，10.0%	—	—
	nFeS-S^2-	0.1mmol/L S^2-，4.17g/L nFeS，pH=8.3	220h，12.0%	—	—
	VB₁₂-S^2-	1mmol/L VB₁₂，0.1mmol/L S^2-，pH=8.3	220h，18.0%	—	—
	nFeS-VB₁₂	4.17g/L nFeS，1mmol/L VB₁₂，pH=8.3	220h，32.0%	—	—
	nFeS-VB₁₂-S^2-	0.1mmol/L S^2-，4.17g/L nFeS，1.0mmol/L VB₁₂，pH=8.3	220h，82.0%	0.008±0.001	乙炔，乙烯，1，3-丁二烯，三氯乙烯
PCE 0.25mmol/L	nFeS	4.17g/L nFeS，pH=12	5h，15.0%	—	—	［115］
	nFeS-水泥浆	4.17g/L nFeS，水泥与溶液的质量比为0.1，pH=12	5h，40.0%	—	—
	nFeS-VB₁₂	4.17g/L nFeS，0.1mmol/L VB₁₂，pH=12	5h，40.0%	0.10	—
	nFeS-VB₁₂-水泥浆	4.17g/L nFeS，0.1mmol/LVB₁₂，水泥与溶液的质量比为0.1，pH=12	5h，99.0%	0.57	乙烯，乙炔和C₃~C₄烃

金属材料协同VB₁₂催化卤代有机物降解研究进展

Catalytic degradation of halogenated organic compounds by synergistic system of metal materials and VB₁₂: a review

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HOCs	反应体系	反应条件	反应时间及降解率	降解产物	参考文献
苯乙基溴（PhCH₂CH₂Br） 3mmol/L	TiO₂	0.67g/L TiO₂，λ=365nm，30mL EtOH ，N₂氛围	微量	微量	［127］
苯乙基溴（PhCH₂CH₂Br） 3mmol/L	TiO₂-VB₁₂	0.67g/L TiO₂-VB₁₂，λ=365nm，30mL EtOH ，N₂氛围	24h，95.0%	乙苯，2，3-二苯基丁烷
苄基溴（PhCH₂Br） 3mmol/L	TiO₂-VB₁₂	0.67g/L TiO₂-VB₁₂，λ=365nm，30mL EtOH ，N₂氛围	24h，99.0%	甲苯，二芳基乙烷
1，1-双（4-氯苯基）-2，2，2- 三氯乙烷（DDT）3mmol/L	TiO₂-VB₁₂	0.67g/L TiO₂-VB₁₂，λ=365nm，30mL EtOH ，N₂氛围	24h，99.0%	DDD、TTDB、DDA乙酯
1，1-双（4-氯苯基）-2，2- 二氯乙烷（DDD）3mmol/L	TiO₂-VB₁₂	0.67g/L TiO₂-VB₁₂，λ=365nm，30mL EtOH ，N₂氛围	24h，82.0%	DDMU、DDMS、DCS
三氯甲苯（PhCCl₃） 3mmol/L	TiO₂	0.167g/L TiO₂，λ=365nm，6mL MeOH，UV，空气	3h，3.0%	苯甲酸甲酯	［122］
	Pt-TiO₂	0.167g/L Pt-TiO₂［0.15%（质量分数）Pt］，λ=365nm，6mL MeOH ，UV，空气	3h，10.0%	苯甲酸甲酯
	TiO₂-VB₁₂	0.167g/L TiO₂，0.0228mmol/L VB₁₂，λ=365nm，6mL MeOH，UV，空气	3h，99.0%	苯甲酸甲酯
	TiO₂-VB₁₂	0.167g/L TiO₂，0.0228mmol/L VB₁₂，λ=365nm，6mL MeOH，UV，O₂	3h，91.0%	苯甲酸甲酯
DDT 2.4mmol/L	TiO₂	0.6g/L TiO₂，λ=420nm，0.2mmol/L TEOA，5mL MeOH	未降解	—	［129］
	TiO₂-VB₁₂	0.6g/L TiO₂-VB₁₂，λ=420nm，0.2mmol/L TEOA，5mL MeOH	30min，24.0%	DDD
	Ru^Ⅱ-TiO₂	0.6g/L Ru^Ⅱ-TiO₂，λ=420nm，0.2mmol/L TEOA，5mL MeOH	30min，13.0%	DDD
	VB₁₂-Ru^Ⅱ-TiO₂	0.6g/L VB₁₂-Ru^Ⅱ-TiO₂，λ=420nm，0.2mmol/L TEOA，5mL MeOH	30min，100%	DDMU、DDMS、TTDB、DDA甲酯

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[3]	徐伟, 李凯军, 宋林烨, 张兴惠, 姚舜华. 光催化及其协同电化学降解VOCs的研究进展[J]. 化工进展, 2023, 42(7): 3520-3531.
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[5]	陈瑛，宋存义，张建祺. 协同催化臭氧化工艺对水中微量有机污染物的降解 [J]. 化工进展, 2006, 25(9): 1069-.