不同电极活化过硫酸盐处理污染物的研究进展

doi:10.11894/iwt.2020-0655

摘要/Abstract

摘要：

近些年来活化过硫酸盐在处理水体有机污染物方面得到广泛应用。电化学活化过硫酸盐是一种新型、高效、环境友好且具有良好前景的活化方式。该活化方式能够使目标污染物得到有效降解，而且对pH的适应范围很广。电极材料是影响电化学活化最重要的因素之一。综述了金属电极、金属氧化物电极和碳材料电极在电活化过硫酸盐降解水中有机污染物方面的应用，并讨论了不同电极的活化机理。最后总结了不同材料电极在应用中存在的一些问题，并提出了未来的发展方向。

关键词: 活化过硫酸盐, 电极材料, 电化学, 自由基, 水处理

Abstract:

In recent years, activated persulfate has been widely used in the treatment of organic pollutants in water. Electrochemical activated persulfate is a novel, efficient, environmentally friendly and promising activation method. This activation method can degrade target pollutants well, and has a wide range of adaptability to pH. Electrode material is one of the most important factors affecting electrochemical activation. The application of metal electrode, metal oxide electrode and carbon electrode in electro activated persulfate degradation of organic pollutants in water is reviewed. The activation mechanism of different electrodes is discussed. Finally, some problems existing in the application of electrodes with different materials are summarized, and the development direction of electrochemical activation in the future is proposed.

Key words: activated persulfate, electrode material, electrochemistry, free radicals, water treatment

中图分类号:

X703

陈永盛,廖德祥,魏福强,胡超,琚佳琪,刘泊洋. 不同电极活化过硫酸盐处理污染物的研究进展[J]. 工业水处理, 2021, 41(6): 141-148.

Yongsheng Chen,Dexiang Liao,Fuqiang Wei,Chao Hu,Jiaqi Ju,Boyang Liu. Research progress in the treatment of pollutants by electro activated persulfate with different electrodes[J]. Industrial Water Treatment, 2021, 41(6): 141-148.

https://www.iwt.cn/CN/Y2021/V41/I6/141

图/表 2

参考文献 60

1	Glaze W H . Drinking-water treatment with ozone[J]. Environmental Science & Technology, 1987, 21 (3): 224- 230.
2	米记茹, 田立平, 刘丽丽, 等. 过硫酸盐活化方法的研究进展[J]. 工业水处理, 2020, 40 (7): 12- 17. URL
3	蒲嘉懿. 金属有机骨架材料衍生物活化过一硫酸氢钾降解水体中污染物[D]. 广州: 华南理工大学, 2017.
4	Furman O S , Teel A L , Watts R J . Mechanism of base activation of persulfate[J]. Environmental Science & Technology, 2010, 44 (16): 6423- 6428. URL
5	Fan Yan , Ji Yuefei , Kong Deyang , et al. Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process[J]. Journal of Hazardous Materials, 2015, 300, 39- 47. doi: 10.1016/j.jhazmat.2015.06.058
6	Zhu Linli , Ai Zhihui , Ho Wingkai , et al. Core-shell Fe-Fe₂O₃ nanostructures as effective persulfate activator for degradation of methyl orange[J]. Separation & Purification Technology, 2013, 108, 159- 165. URL
7	Zhang Mi , Chen Xiaoqing , Zhou He , et al. Degradation of p-nitrophenol by heat and metal ions co-activated persulfate[J]. Chemical Engineering Journal, 2015, 264, 39- 47. doi: 10.1016/j.cej.2014.11.060
8	Xie Pengchao , Ma Jun , Liu Wei , et al. Removal of 2-MIB and geosmin using UV/persulfate: Contributions of hydroxyl and sulfate radicals[J]. Water Research, 2015, 69, 223- 233. doi: 10.1016/j.watres.2014.11.029
9	Tang Lin , Liu Yani , Wang Jiajia , et al. Enhanced activation process of persulfate by mesoporous carbon for degradation of aqueous organic pollutants: Electron transfer mechanism[J]. Applied Catalysis B: Environmental, 2018, 231, 1- 10. doi: 10.1016/j.apcatb.2018.02.059
10	Ren Wei , Xiong Liangliang , Yuan Xuehong , et al. Activation of peroxydisulfate on carbon nanotubes: Electron-transfer mechanism[J]. Environmental Science & Technology, 2019, 53 (24): 14595- 14603. URL
11	Govindan K , Raja M , Noel M , et al. Degradation of pentachlorophenol by hydroxyl radicals and sulfate radicals using electrochemical activation of peroxomonosulfate, peroxodisulfate and hydrogen peroxide[J]. Journal of Hazardous Materials, 2014, 272, 42- 51. doi: 10.1016/j.jhazmat.2014.02.036
12	Wu Simiao , Liang Guannan , Guan Xiaohong , et al. Precise control of iron activating persulfate by current generation in an electrochemical membrane reactor[J]. Environment International, 2019, 131, 105024. doi: 10.1016/j.envint.2019.105024
13	Zhang L , Ding W , Qiu J , et al. Modeling and optimization study on sulfamethoxazole degradation by electrochemically activated persulfate process[J]. Journal of Cleaner Production, 2018, 197 (1): 297- 305. URL
14	Xu Xiangrong , Li Xiangzhong . Degradation of azo dye orange G in aqueous solutions by persulfate with ferrous ion[J]. Separation and Purification Technology, 2010, 72 (1): 105- 111. doi: 10.1016/j.seppur.2010.01.012
15	De Laat J , Le T G . Kinetics and modeling of the Fe(Ⅲ)/H₂O₂ system in the presence of sulfate in acidic aqueous solutions[J]. Environmental Science & Technology, 2005, 39 (6): 1811- 1818. URL
16	Ramos M A V , Yan Weile , Li Xiaoqin , et al. Simultaneous oxidation and reduction of arsenic by zero-valent iron nanoparticles: Understanding the significance of the core-shell structure[J]. Journal of Physical Chemistry C, 2009, 113 (33): 14591- 14594. doi: 10.1021/jp9051837
17	Liang Chenju , Su H W . Identification of sulfate and hydroxyl radicals in thermally activated persulfate[J]. Industrial & Engineering Chemistry Research, 2009, 48 (11): 5558- 5562. URL
18	Miao Dongtian , Liu Guoshuai , Wei Qiuping , et al. Electro-activated persulfate oxidation of malachite green by boron-doped diamond (BDD) anode: Effect of degradation process parameters[J]. Water Science & Technology, 2020, 81 (5): 925- 935. URL
19	Bu Lingjun , Zhu Shumin , Zhou Shiqing , et al. Degradation of atrazine by electrochemically activated persulfate using BDD anode: Role of radicals and influencing factors[J]. Chemosphere, 2018, 195, 236- 244. doi: 10.1016/j.chemosphere.2017.12.088
20	Silveira J E , Garciacosta A L , Cardoso T O , et al. Indirect decolorization of azo dye Disperse Blue 3 by electro-activated persulfate[J]. Electrochimica Acta, 2017, 258 (20): 927- 932. URL
21	Chen W S , Huang C P . Mineralization of aniline in aqueous solution by electrochemical activation of persulfate[J]. Chemosphere, 2015, 125, 175- 181. doi: 10.1016/j.chemosphere.2014.12.053
22	Song Haoran , Yan Linxia , Jiang Jin , et al. Electrochemical activation of persulfates at BDD anode: Radical or nonradical oxidation?[J]. Water Research, 2018, 128 (1): 393- 401. URL
23	Tsitonaki A , Petri B G , Crimi M , et al. In situ chemical oxidation of contaminated soil and groundwater using persulfate: A review[J]. Critical Reviews in Environmental Science and Technology, 2010, 40 (1): 55- 91. doi: 10.1080/10643380802039303
24	Mousset E , Oturan N , Oturan M A , et al. An unprecedented route of·OH radical reactivity evidenced by an electrocatalytical process: Ipso-substitution with perhalogenocarbon compounds[J]. Applied Catalysis B: Environmental, 2018, 226, 135- 146. doi: 10.1016/j.apcatb.2017.12.028
25	Padmaja S , Alfassi Z B , Neta P , et al. Rate constants for reactions of SO₄^·-radicals in acetonitrile[J]. International Journal of Chemical Kinetics, 1993, 25 (3): 193- 198. doi: 10.1002/kin.550250307
26	Sharma S B , Mudallar M , Rao B S , et al. Radiation chemical oxidation of benzaldehyde, acetophenone, and benzophenone[J]. Journal of Physical Chemistry A, 1997, 101 (45): 8402- 8408. doi: 10.1021/jp9718717
27	George C H , El Rassy H , Chovelon J M . Reactivity of selected volatile organic compounds(VOCs) toward the sulfate radical(SO₄^·-)[J]. International Journal of Chemical Kinetics, 2001, 33 (9): 539- 547. doi: 10.1002/kin.1049
28	李小娟, 廖凤珍, 叶兰妹, 等. 金属有机骨架及其衍生材料活化过硫酸盐在水处理中的应用进展[J]. 化工进展, 2019, 38 (10): 4712- 4721. URL
29	Yuan Songhu , Liao Peng , Alshawabkeh A N . Electrolytic manipulation of persulfate reactivity by iron electrodes for trichloroethylene degradation in groundwater[J]. Environmental Science & Technology, 2014, 48 (1): 656- 663. URL
30	Jeon P , Park S , Baek K , et al. Controlled release of iron for activation of persulfate to oxidize orange G using iron anode[J]. Korean Journal of Chemical Engineering, 2017, 34 (5): 1305- 1309. doi: 10.1007/s11814-017-0062-9
31	Zheng Lei , Jin Hui , Yu Men , et al. Degradation of sulfamethoxazole by electrochemically activated persulfate using iron anode[J]. International Journal of Chemical Reactor Engineering, 2019, 17 (2): 20180160. URL
32	Yu Yanghai , Zhou Shiqing , Bu Lingjun , et al. Degradation of diuron by electrochemically activated persulfate[J]. Water, Air, and Soil Pollution, 2016, 227 (8): 279. doi: 10.1007/s11270-016-2978-9
33	Li Xue , Tang Shoufeng , Yuan Deling , et al. Improved degradation of anthraquinone dye by electrochemical activation of PDS[J]. Ecotoxicology and Environmental Safety, 2019, 177, 77- 85. doi: 10.1016/j.ecoenv.2019.04.015
34	Song Haoran , Yan Linxia , Ma Jun , et al. Nonradical oxidation from electrochemical activation of peroxydisulfate at Ti/Pt anode: Efficiency, mechanism and influencing factors[J]. Water Research, 2017, 116, 182- 193. doi: 10.1016/j.watres.2017.03.035
35	Cai Chun , Zhang Zhuoyue , Zhang Hui , et al. Electro-assisted heterogeneous activation of persulfate by Fe/SBA-15 for the degradation of OrangeⅡ[J]. Journal of Hazardous Materials, 2016, 313, 209- 218. doi: 10.1016/j.jhazmat.2016.04.007
36	Li Jun , Yan Jianfei , Yao Gang , et al. Improving the degradation of atrazine in the three-dimensional (3D) electrochemical process using CuFe₂O₄ as both particle electrode and catalyst for persulfate activation[J]. Chemical Engineering Journal, 2019, 361, 1317- 1332. doi: 10.1016/j.cej.2018.12.144
37	Lin H , Wu J , Zhang H , et al. Degradation of clofibric acid in aqueous solution by an EC/Fe³⁺/PMS process[J]. Chemical Engineering Journal, 2014, 244 (15): 514- 521. URL
38	Matzek L W , Tipton M , Faemer A T , et al. Understanding electrochemically activated persulfate and its application to ciprofloxacin abatement[J]. Environmental Science & Technology, 2018, 52 (10): 5875- 5883. URL
39	Liu Zhen , Ding Haojie , Zhao Chun , et al. Electrochemical activation of peroxymonosulfate with ACF cathode: Kinetics, influencing factors, mechanism, and application potential[J]. Water Research, 2019, 159, 111- 121. doi: 10.1016/j.watres.2019.04.052
40	Nie Chunyang , Ao Zhimin , Duan Xiaoguang , et al. Degradation of aniline by electrochemical activation of peroxydisulfate at MWCNT cathode: The proofed concept of nonradical oxidation process[J]. Chemosphere, 2018, 206, 432- 438. doi: 10.1016/j.chemosphere.2018.04.173
41	Yuan Songhu , Liao Peng . Response to comment on "Electrolytic manipulation of persulfate reactivity by iron electrodes for TCE degradation in groundwater"[J]. Environmental Science & Technology, 2014, 48 (8): 4632- 4633.
42	Bu Lingjun , Zhou Shiqing , Shi Zhou , et al. Iron electrode as efficient persulfate activator for oxcarbazepine degradation: Performance, mechanism, and kinetic modeling[J]. Separation and Purification Technology, 2017, 178, 66- 74. doi: 10.1016/j.seppur.2017.01.007
43	Li Jun , Ren Yi , Lai Leiduo , et al. Electrolysis assisted persulfate with annular iron sheet as anode for the enhanced degradation of 2, 4-dinitrophenol in aqueous solution[J]. Journal of Hazardous Materials, 2018, 344, 778- 787. doi: 10.1016/j.jhazmat.2017.11.007
44	Chen W , Jhou Y , Huang C , et al. Mineralization of dinitrotoluenes in industrial wastewater by electro-activated persulfate oxidation[J]. Chemical Engineering Journal, 2014, 252, 166- 172. doi: 10.1016/j.cej.2014.05.033
45	Li Lianghao , Huang Zhuangpeng , Fan Xiaoxiao , et al. Preparation and characterization of a Pd modified Ti/SnO₂-Sb anode and its electrochemical degradation of Ni-EDTA[J]. Electrochemical Acta, 2017, 231, 354- 362. doi: 10.1016/j.electacta.2017.02.072
46	Xie Ruzhen , Meng Xiaoyang , Sun Peizhe , et al. Electrochemical oxidation of ofloxacin using a TiO₂-based SnO₂-Sb/polytetrafluoroethylene resin-PbO₂ electrode: Reaction kinetics and mass transfer impact[J]. Applied Catalysis B: Environmental, 2017, 203, 515- 525. doi: 10.1016/j.apcatb.2016.10.057
47	Wang Kaixuan , Huang Dahong , Wang Weilai , et al. Enhanced perfluorooctanoic acid degradation by electrochemical activation of peroxymonosulfate in aqueous solution[J]. Environment International, 2020, 137, 105562. doi: 10.1016/j.envint.2020.105562
48	Li Jing , Lin Heng , Zhu Kangmeng , et al. Degradation of Acid Orange 7 using peroxymonosulfate catalyzed by granulated activated carbon and enhanced by electrolysis[J]. Chemosphere, 2017, 188, 139- 147. doi: 10.1016/j.chemosphere.2017.08.137
49	Evseev A K , Khubutiya M S , Goldin M M , et al. Electrochemical synthesis of peroxodisulfates from dilute sulfate solutions for detoxification of biological media[J]. Russian Journal of Electrochemistry, 2008, 44 (8): 901- 909. doi: 10.1134/S1023193508080041
50	Goldin M M , Khubutiya M S , Kolesnikov V A , et al. Indirect electrochemical synthesis of active oxygen in dilute sulfate solutions[J]. Journal of Applied Electrochemistry, 2009, 39 (2): 185- 189. doi: 10.1007/s10800-008-9652-x
51	Zhuo Qiongfang , Wang Jinbao , Niu Junfeng , et al. Electrochemical oxidation of perfluorooctane sulfonate(PFOS) substitute by modified boron doped diamond(BDD) anodes[J]. Chemical Engineering Journal, 2020, 379, 122280. doi: 10.1016/j.cej.2019.122280
52	Davila O O , Bergeron L L , Gutierrez P R , et al. Electrochemical oxidation of dibenzothiophene compounds on BDD electrode in acetonitrile-water medium[J]. Journal of Electroanalytical Chemistry, 2019, 847 (15): 113172. URL
53	Radjenovic J , Sedlak D L . Challenges and opportunities for electrochemical processes as next-generation technologies for the treatment of contaminated water[J]. Environmental Science & Technology, 2015, 49 (19): 11292- 11302. URL
54	Farhat A , Keller J , Tait S , et al. Removal of persistent organic contaminants by electrochemically activated sulfate[J]. Environmental Science & Technology, 2015, 49 (24): 14326- 14333. URL
55	Zhang Tao , Chen Yin , Wang Yuru , et al. Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation[J]. Environmental Science & Technology, 2014, 48 (10): 5868- 5875. URL
56	Duan Xiaoguang , Ao Zhimin , Zhou Li , et al. Occurrence of radical and nonradical pathways from carbocatalysts for aqueous and nonaqueous catalytic oxidation[J]. Applied Catalysis B: Environmental, 2016, 188, 98- 105. doi: 10.1016/j.apcatb.2016.01.059
57	Ding Jing , Bu Lingjun , Zhao Qingliang , et al. Electrochemical activation of persulfate on BDD and DSA anodes: Electrolyte influence, kinetics and mechanisms in the degradation of bisphenol A[J]. Journal of Hazardous Materials, 2020, 388, 121789. doi: 10.1016/j.jhazmat.2019.121789
58	Bu Lingjun , Ding Jing , Zhu Ningyuan , et al. Unraveling different mechanisms of persulfate activation by graphite felt anode and cathode to destruct contaminants of emerging concern[J]. Applied Catalysis B: Environmental, 2019, 253, 140- 148. doi: 10.1016/j.apcatb.2019.04.030
59	Song Haoran , Yan Linxia , Jiang Jin , et al. Enhanced degradation of antibiotic sulfamethoxazole by electrochemical activation of PDS using carbon anodes[J]. Chemical Engineering Journal, 2018, 344, 12- 20. doi: 10.1016/j.cej.2018.03.050
60	Song Haoran , Yan Linxia , Wang Yuwei , et al. Electrochemically activated PMS and PDS: Radical oxidation versus nonradical oxidation[J]. Chemical Engineering Journal, 2020, 391, 123560. doi: 10.1016/j.cej.2019.123560

污染物	阳极	阴极	氧化剂及投加量	时间/min	去除率/%	文献
三氯乙烯	铁	MMO	PDS，2 mmol/L	30	100	〔29〕
橙黄G	铁	Ti	PDS，5 mmol/L	240	100	〔30〕
磺胺甲恶唑	铁	石墨	PDS，3.5 mmol/L	60	>80	〔31〕
敌草隆	铁	铁	PDS，1 mmol/L	15	>60	〔32〕
苯胺	Pt	Pt	PDS，质量分数3%	420	>70	〔21〕
蒽醌染料	Pt	石墨	PDS，10 mmol/L	60	93.75	〔33〕
卡马西平	Ti/Pt	不锈钢	PDS，5 mmol/L	30	>80	〔34〕
酸性橙（Orange Ⅱ）	Ti/RuO₂-IrO₂	不锈钢	PDS，4.2 mmol/L	60	89	〔35〕
阿特拉津	Ti/RuO₂-IrO₂	不锈钢	PDS，4 mmol/L	60	>99	〔36〕
氯贝酸（clofibric acid）	Ti/RuO₂-IrO₂	不锈钢	PMS，10 mmol/L	60	82	〔37〕
卡马西平	BDD	不锈钢	PDS，5 mmol/L	30	>80	〔22〕
阿特拉津	BDD	不锈钢	PDS，1 mmol/L	30	78.2	〔19〕
环丙沙星	BDD	石墨	PDS，22 mmol/L	120	84	〔38〕
卡马西平	Ti/Pt	活性碳毡	PMS，50 mmol/L	40	100	〔39〕
苯胺	石墨	碳纳米管	PDS，5.55 mmol/L	150	>90	〔40〕

污染物	阳极	阴极	氧化剂及投加量	时间/min	去除率/%	文献
三氯乙烯	铁	MMO	PDS，2 mmol/L	30	100	〔29〕
橙黄G	铁	Ti	PDS，5 mmol/L	240	100	〔30〕
磺胺甲恶唑	铁	石墨	PDS，3.5 mmol/L	60	>80	〔31〕
敌草隆	铁	铁	PDS，1 mmol/L	15	>60	〔32〕
苯胺	Pt	Pt	PDS，质量分数3%	420	>70	〔21〕
蒽醌染料	Pt	石墨	PDS，10 mmol/L	60	93.75	〔33〕
卡马西平	Ti/Pt	不锈钢	PDS，5 mmol/L	30	>80	〔34〕
酸性橙（Orange Ⅱ）	Ti/RuO₂-IrO₂	不锈钢	PDS，4.2 mmol/L	60	89	〔35〕
阿特拉津	Ti/RuO₂-IrO₂	不锈钢	PDS，4 mmol/L	60	>99	〔36〕
氯贝酸（clofibric acid）	Ti/RuO₂-IrO₂	不锈钢	PMS，10 mmol/L	60	82	〔37〕
卡马西平	BDD	不锈钢	PDS，5 mmol/L	30	>80	〔22〕
阿特拉津	BDD	不锈钢	PDS，1 mmol/L	30	78.2	〔19〕
环丙沙星	BDD	石墨	PDS，22 mmol/L	120	84	〔38〕
卡马西平	Ti/Pt	活性碳毡	PMS，50 mmol/L	40	100	〔39〕
苯胺	石墨	碳纳米管	PDS，5.55 mmol/L	150	>90	〔40〕

[1]	江晶, 崔兆伦, 张楚燕, 黄楠. 硼掺杂金刚石薄膜电化学氧化处理对硝基苯酚[J]. 工业水处理, 2025, 45(3): 157-164.
[2]	刘会媛, 柳鑫华, 关俊霞, 王瀛, 舒世立, 王磊, 李雨龙, 闫子萱, 夏雨博, 杜嘉瑞, 周鑫, 向和琼, 张心媛. 聚环氧琥珀酸衍生物在酸介质中的缓蚀性能[J]. 工业水处理, 2025, 45(3): 137-143.
[3]	李金, 仇璐, 刘锐, 李军, 李瀚屹, 颜兵, 何江, 梁贤金, 易彪. 垃圾渗滤液处理系统方案评价模型研究[J]. 工业水处理, 2025, 45(3): 121-128.
[4]	张晓, 张立杰, 王渤, 陈俊任, 任子安, 齐悦君. 基于微藻技术的减污降碳协同增效研究进展[J]. 工业水处理, 2025, 45(3): 34-43.
[5]	蒲梦晗, 黎人铖, 肖伟龙, 高铭, 陈文清. 电容去离子技术电极抗腐蚀性能研究进展[J]. 工业水处理, 2025, 45(3): 44-54.
[6]	杨雄强, 王浩宇. 污水处理厂低碳运行策略与案例[J]. 工业水处理, 2025, 45(2): 36-45.
[7]	安余梁, 祁峰, 母锐敏, 马桂霞. 微藻除磷机理及其工艺模式的研究进展[J]. 工业水处理, 2025, 45(2): 10-17.
[8]	唐安中, 邸雪梅, 陈佳明. 低碳约束下石化污水污染物溯源分析与过程减排[J]. 工业水处理, 2025, 45(2): 197-202.
[9]	赵璇, 刘涛, 杨蒙, 乔森. IFFAS-ESMBR一体式复合工艺处理低C/N石化废水[J]. 工业水处理, 2025, 45(1): 32-40.
[10]	李守彪, 吴亚品, 徐凤麒, 郭宇, 颜薇, 江波. ClO _x ^-产物对电氧化去除COD性能评价及水体毒性影响[J]. 工业水处理, 2024, 44(9): 143-150.
[11]	张毅豪, 侯保林, 王佳欣, 张婷, 任志文. Fe₃O₄掺杂改性电极电化学去除Pb²⁺的效能研究[J]. 工业水处理, 2024, 44(8): 107-113.
[12]	王渤, 张立杰, 陈俊任, 任子安, 齐悦君. 微藻处理含抗生素类废水研究进展[J]. 工业水处理, 2024, 44(8): 44-52.
[13]	陈娟娟, 李伟斌, 黄鸥, 晁伟翔, 张典典, 任南琪, 路璐. 基于降本增效目标的污水处理厂低碳运行调控策略[J]. 工业水处理, 2024, 44(8): 53-60.
[14]	郎明娇, 杨朝美, 曾广勇. 光催化膜的构筑及其在废水处理中的研究进展[J]. 工业水处理, 2024, 44(7): 47-56.
[15]	夏凡, 仲伟豪, 毛伟, 于洪涛. 促进 CaCO3在溶液中成核的高效电化学水软化器[J]. 工业水处理, 2024, 44(7): 83-88.

选择文件类型/文献管理软件名称

选择包含的内容