Catalytic mechanism and strategies for enhancing performance of heterogeneous Fenton catalysts: A review

doi:10.19965/j.cnki.iwt.2022-0871

Abstract

Abstract:

Heterogeneous Fenton catalyst can react with hydrogen peroxide to produce highly reactive oxygen species, which has the advantages of fast degradation of pollutants, easy recovery of catalyst and wide applicable pH range. It has broad application prospects in the removal of organic pollutants. Based on the comprehensive investigation of previous studies, this paper reviewed the main mechanisms involved in the catalytic reactions of heterogeneous Fenton catalysts, including positive and negative center reaction mechanism, accelerated electron transfer catalytic mechanism and oxygen vacancy mechanism. The research on kinetic modeling of heterogeneous Fenton process in recent years was summarized. According to the catalytic mechanism, aiming at the bottleneck problems such as low Fe²⁺ generation rate, low hydrogen peroxide utilization rate and poor catalyst stability in the existing heterogeneous Fenton catalytic system, the methods to improve the catalytic performance of heterogeneous Fenton catalysts from three aspects including doping elements, changing catalyst structure and introducing external energy were summarized. Finally, the future research direction of heterogeneous Fenton catalyst was pointed out.

Key words: heterogeneous Fenton catalysts, catalytic mechanism, catalyst modification, dynamic simulation calculation

摘要：

非均相Fenton催化剂与过氧化氢反应可以产生高活性氧物种，具有对污染物降解速度快、催化剂易回收、适用pH范围广等优点，在去除有机污染物方面有广泛的应用前景。基于对以往研究的综合调查，综述了非均相Fenton催化剂在催化反应过程中涉及的主要机理，包括正负电中心类原电池机理、加速电子转移催化机理和氧空位作用机制，总结了近年来非均相Fenton工艺在动力学建模方面的最新研究，之后针对现有非均相Fenton催化体系中Fe²⁺生成速率低、过氧化氢利用率低、催化剂稳定性差等瓶颈问题，分别从掺杂元素、改变催化剂结构、引入外部能量3个方面总结了提升非均相Fenton催化剂催化性能的策略方法，最后，指出了未来非均相Fenton催化剂的研究方向。

关键词: 非均相Fenton催化剂, 催化机理, 催化剂改性, 动力学模拟计算

CLC Number:

X703

Huiling LI, Fan CHENG, Dongni SHI, Ran TENG, Jinyuan JIANG, Ming CHEN, Wei TAN. Catalytic mechanism and strategies for enhancing performance of heterogeneous Fenton catalysts: A review[J]. Industrial Water Treatment, 2023, 43(11): 78-92.

李慧玲, 程凡, 石冬妮, 滕然, 蒋进元, 陈明, 谭伟. 非均相Fenton催化剂催化机理及性能提升策略综述[J]. 工业水处理, 2023, 43(11): 78-92.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2022-0871

https://www.iwt.cn/EN/Y2023/V43/I11/78

Figures/Tables 6

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目标污染物	催化体系/反应器	操作条件	降解性能	建模技术	实验验证	参考文献
亚甲基蓝（MB）	Fe₃O₄-多壁碳纳米管	pH=3~5，H₂O₂ 2 g/L，催化剂1 g/L，MB初始质量浓度25 mg/L	70 min时降解率94%	ANN	R ²=0.993 4	〔59〕
甲硝唑（MTZ）	以富勒土-废铸造砂-TiO₂为载体/固定床分批原位降解	pH=3.5，H₂O₂ 1.05 g/L，催化剂1 675 kg/m³，MTZ初始质量浓度25 mg/L	120 min时降解率91%	ANN-GA遗传算法	RMSE=0.91%，R ²=0.993 3	〔60〕
酸性蓝5（AB5）	马铁矿纳米颗粒	pH=3，H₂O₂ 2 mmol/L，催化剂2.5 g/L，AB5初始质量浓度10 mg/L	70 min时降解率100%	ANN	R ²=0.995	〔61〕
酸性黄36（AY36）	黄铁矿/硫化床、搅拌釜	pH=3，H₂O₂=2 mmol/L，催化剂1 g/L，AY36初始质量浓度10 mg/L	70 min时降解率93.7%	CFD	—	〔62〕
双酚A（BPA）	电Fenton	电流53.59 mA，pH=3.0，BPA初始质量浓度20 mg/L	60 min时降解率99.9%	CFD	R² =0.968	〔63〕

目标污染物	催化体系/反应器	操作条件	降解性能	建模技术	实验验证	参考文献
亚甲基蓝（MB）	Fe₃O₄-多壁碳纳米管	pH=3~5，H₂O₂ 2 g/L，催化剂1 g/L，MB初始质量浓度25 mg/L	70 min时降解率94%	ANN	R ²=0.993 4	〔59〕
甲硝唑（MTZ）	以富勒土-废铸造砂-TiO₂为载体/固定床分批原位降解	pH=3.5，H₂O₂ 1.05 g/L，催化剂1 675 kg/m³，MTZ初始质量浓度25 mg/L	120 min时降解率91%	ANN-GA遗传算法	RMSE=0.91%，R ²=0.993 3	〔60〕
酸性蓝5（AB5）	马铁矿纳米颗粒	pH=3，H₂O₂ 2 mmol/L，催化剂2.5 g/L，AB5初始质量浓度10 mg/L	70 min时降解率100%	ANN	R ²=0.995	〔61〕
酸性黄36（AY36）	黄铁矿/硫化床、搅拌釜	pH=3，H₂O₂=2 mmol/L，催化剂1 g/L，AY36初始质量浓度10 mg/L	70 min时降解率93.7%	CFD	—	〔62〕
双酚A（BPA）	电Fenton	电流53.59 mA，pH=3.0，BPA初始质量浓度20 mg/L	60 min时降解率99.9%	CFD	R² =0.968	〔63〕

策略	催化剂	目标污染物	操作条件				降解性能		参考文献
策略	催化剂	目标污染物	催化剂投加质量浓度/（g·L^-1）	H₂O₂投加浓度/（mmol·L^-1）	pH	污染物初始质量浓度/（mg·L^-1）	反应时间/min	降解率/%	参考文献
掺杂金属元素	Pb-Fe/Ni	二氯甲烷	0.4	10	2	5	180	95.33	〔66〕
	Ag/Fe₃O₄	苯甲酸	0.2	300	3	122	90	90	〔67〕
	Co-FeS-10%Co	罗丹明B	0.2	1	3	50	35	99.90	〔68〕
	Cu_0.68Zn_0.32Fe₂O₄	罗丹明B	1	0.5	6.78	10	150	90	〔69〕
	Fe_0.7Zn_0.3S	苯酚	0.1	1	3.5	0.2	30	95.70	〔70〕
	Fe₃O₄/CeO₂	酸性橙G	2	26	2.5	50	120	98.20	〔71〕
	Fe₃O₄-Ce	头孢氨苄	0.125	1	3.5	0.9	150	58	〔72〕
	Fe₃O₄-CeO₂	儿茶酚	1	30	2.4	10	90	89.20	〔73〕
	MCO（Mn²⁺掺杂 CeO₂）	碱性蓝17	0.5	1.5	8	100	60	100	〔74〕
	MnO₂-Fe₃O₄/CuO	亚甲基蓝	1.6	16	7	10	150	98	〔75〕
	Fe₃O₄-Zn	罗丹明B	1	10	4	10	60	97	〔76〕
掺杂非金属元素	α-FeOOH/RGO-N	四环素	5	500	4	100	120	100	〔77〕
	FeCoN₆	双酚A	0.1	PMS 0.2 g/L*	6.5	20	6	100	〔78〕
	Fe₃O₄@B-rGO	双酚A	0.4	6	5	20	180	94.20	〔79〕
引入载体进行负载	2，5-DBQ@ECDP-Fe₃O₄	4-硝基苯酚	2	5	3	20	120	99	〔80〕
	2Fe6Cu/HMS	酸性橙Ⅱ	1	27.4	7	100	120	93	〔81〕
	CuFeO₂/BC	四环素	0.5	50	5	20	300	88.40	〔82〕
	Fe/OMC	4-氯苯酚	0.2	6.6	3	100	270	96	〔83〕
	Fe⁰-Fe₂O₃/OMC	酸性橙Ⅱ	0.5	109.6	—	100	30	98	〔84〕
	Fe-200	邻苯二甲酸二甲酯	2	20	6.7	20	60	100	〔85〕
	Fe₃O₄@B. subtilis SPMC	强力霉素	0.5	20	7	25	30	100	〔86〕
	Fe₃O₄@C	亚甲基蓝	0.25	25	3	20	120	99	〔87〕
	MeSAPO-44	活性红X-3B	0.5	10	4	50	60	99	〔88〕
	NZVI/累托石	4-氯苯酚	0.1	60	3	100	210	98	〔89〕
	Sch@BC	磺胺甲硝唑	1	2	3	100	60	100	〔90〕
与有机配体进行复合	Fe₃O₄@β-CD	4-氯苯酚	2	30	3	100	90	100	〔91〕
与有机配体进行复合	Fe₃O₄@ZIF-67	四溴双酚A	0.1	PMS 0.1 g/L*	—	40	7	100	〔92〕

策略	催化剂	目标污染物	操作条件				降解性能		参考文献
策略	催化剂	目标污染物	催化剂投加质量浓度/（g·L^-1）	H₂O₂投加浓度/（mmol·L^-1）	pH	污染物初始质量浓度/（mg·L^-1）	反应时间/min	降解率/%	参考文献
掺杂金属元素	Pb-Fe/Ni	二氯甲烷	0.4	10	2	5	180	95.33	〔66〕
	Ag/Fe₃O₄	苯甲酸	0.2	300	3	122	90	90	〔67〕
	Co-FeS-10%Co	罗丹明B	0.2	1	3	50	35	99.90	〔68〕
	Cu_0.68Zn_0.32Fe₂O₄	罗丹明B	1	0.5	6.78	10	150	90	〔69〕
	Fe_0.7Zn_0.3S	苯酚	0.1	1	3.5	0.2	30	95.70	〔70〕
	Fe₃O₄/CeO₂	酸性橙G	2	26	2.5	50	120	98.20	〔71〕
	Fe₃O₄-Ce	头孢氨苄	0.125	1	3.5	0.9	150	58	〔72〕
	Fe₃O₄-CeO₂	儿茶酚	1	30	2.4	10	90	89.20	〔73〕
	MCO（Mn²⁺掺杂 CeO₂）	碱性蓝17	0.5	1.5	8	100	60	100	〔74〕
	MnO₂-Fe₃O₄/CuO	亚甲基蓝	1.6	16	7	10	150	98	〔75〕
	Fe₃O₄-Zn	罗丹明B	1	10	4	10	60	97	〔76〕
掺杂非金属元素	α-FeOOH/RGO-N	四环素	5	500	4	100	120	100	〔77〕
	FeCoN₆	双酚A	0.1	PMS 0.2 g/L*	6.5	20	6	100	〔78〕
	Fe₃O₄@B-rGO	双酚A	0.4	6	5	20	180	94.20	〔79〕
引入载体进行负载	2，5-DBQ@ECDP-Fe₃O₄	4-硝基苯酚	2	5	3	20	120	99	〔80〕
	2Fe6Cu/HMS	酸性橙Ⅱ	1	27.4	7	100	120	93	〔81〕
	CuFeO₂/BC	四环素	0.5	50	5	20	300	88.40	〔82〕
	Fe/OMC	4-氯苯酚	0.2	6.6	3	100	270	96	〔83〕
	Fe⁰-Fe₂O₃/OMC	酸性橙Ⅱ	0.5	109.6	—	100	30	98	〔84〕
	Fe-200	邻苯二甲酸二甲酯	2	20	6.7	20	60	100	〔85〕
	Fe₃O₄@B. subtilis SPMC	强力霉素	0.5	20	7	25	30	100	〔86〕
	Fe₃O₄@C	亚甲基蓝	0.25	25	3	20	120	99	〔87〕
	MeSAPO-44	活性红X-3B	0.5	10	4	50	60	99	〔88〕
	NZVI/累托石	4-氯苯酚	0.1	60	3	100	210	98	〔89〕
	Sch@BC	磺胺甲硝唑	1	2	3	100	60	100	〔90〕
与有机配体进行复合	Fe₃O₄@β-CD	4-氯苯酚	2	30	3	100	90	100	〔91〕
与有机配体进行复合	Fe₃O₄@ZIF-67	四溴双酚A	0.1	PMS 0.1 g/L*	—	40	7	100	〔92〕

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