光电催化降解农药的研究进展

doi:10.11924/j.issn.1000-6850.casb2023-0646

中国农学通报 ›› 2024, Vol. 40 ›› Issue (4): 140-147.doi: 10.11924/j.issn.1000-6850.casb2023-0646

光电催化降解农药的研究进展

姜炳杉¹(), 李曦¹^,²(), 周芹¹()

¹ 黑龙江大学现代农业与生态环境学院，哈尔滨 150080
² 黑龙江大学财务处，哈尔滨 150080

收稿日期:2023-09-12 修回日期:2023-11-17 出版日期:2024-02-05 发布日期:2024-01-29
通讯作者:
周芹，女，1971年出生，黑龙江海伦人，副研究员，博士研究生，研究方向：食品安全检测及农药产品分析。通信地址：150080 哈尔滨市南岗区学府路74号黑龙江大学农学楼225，Tel：0451-86609502，E-mail：zhouqin@hlju.edu.cn。
李曦，女，1990年出生，黑龙江哈尔滨人，中级会计师，硕士研究生，研究方向：食品安全检测及农药产品分析。通信地址：150080 哈尔滨市南岗区学府路74号黑龙江大学主楼209，Tel：0451-86609502，E-mail：2020073@hlju.edu.cn。
作者简介:
姜炳杉，男，2000年出生，黑龙江哈尔滨人，硕士研究生，主要研究方向：农药降解。通信地址：150080 哈尔滨市南岗区学府路74号黑龙江大学农学楼223，Tel：0451-86609342，E-mail：jiangbingshan1@163.com。
基金资助:
现代农业产业技术体系建设项目“质量安全与营养品质评价”(CARS-170503)

Research Progress in Photoelectrocatalytic Degradation of Pesticides

JIANG Bingshan¹(), LI Xi¹^,²(), ZHOU Qin¹()

¹ College of Advanced Agriculture and Ecological Environment, Heilongjiang University, Harbin 150080
² Financial Department of Heilongjiang University, Harbin 150080

Received:2023-09-12 Revised:2023-11-17 Published-:2024-02-05 Online:2024-01-29

摘要/Abstract

摘要：

化学农药是一种危害高、难降解的环境污染物，农药残留对生态环境造成严重破坏并危害人体健康。光电催化具有安全环保、氧化能力强、易操作等优势，已成为降解农药残留最具前景的高级氧化技术之一。笔者综述了光电催化降解农药的基本原理、常用电极材料及制备方法，重点总结了光电催化降解农药的最新应用，评估了光源、pH等影响因素对农药降解的影响，这些为其短期内的实际应用提供了基础。目前涉及农药污水降解的研究较少，未来除针对电极材料改良外更应当侧重于实际农药废水的降解研究。

关键词: 光电催化, 农药, 有机污染物, 降解

Abstract:

Pesticide is a kind of environmental pollutant with high hazards and difficult to degrade, and pesticide residues cause serious damage to the ecological environment and jeopardize human health. Photoelectrocatalysis has become one of the most promising advanced oxidation technologies for degrading pesticide residues due to its advantages of safety, environmental protection, strong oxidizing ability and easy operation. The basic principle of photoelectrocatalytic degradation of pesticides, commonly used electrode materials and preparation methods are reported in this study, with emphasis on summarizing the latest applications of photoelectrocatalytic degradation of pesticides. And the effects of light source, pH and other influencing factors on pesticide degradation are evaluated, which provide the basis for short-term practical applications. However, there are fewer research studies on actual pesticide wastewater degradation, and the degradation of actual pesticide wastewater in the future should be emphasized in addition to the electrode material improvement.

Key words: photoelectrocatalysis, pesticide, organic pollutant, degradation

姜炳杉, 李曦, 周芹. 光电催化降解农药的研究进展[J]. 中国农学通报, 2024, 40(4): 140-147.

JIANG Bingshan, LI Xi, ZHOU Qin. Research Progress in Photoelectrocatalytic Degradation of Pesticides[J]. Chinese Agricultural Science Bulletin, 2024, 40(4): 140-147.

图/表 2

参考文献 38

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农药	浓度/ (mg/L)	基质	照射源	单元配置	操作条件	最佳去除效率	文献
阿特拉津	2	农药废水	300 W高压灯	石英水套电池，FTO/ MI-TiO₂，001光阳极(7.5 cm²)，铂片阴极(1.5 cm× 6.0 cm)	Na₂SO₄=0.1 mol/L，E=0.6 V vs SCE	5 h可降解96.5%，TOC去除率9.8%，水体毒性降低99.6%	[30]
阿特拉津	2	水	氙灯(200 mW/cm²)	半圆形石英降解电池(80 mL)，TiO₂NT光阳极(15 cm²)铂丝阴极	E=0.2 V，于0.1 mol/L Na₂SO₄中	降解率为96.8%，k=0.478×10^-3/s	[44]
敌草隆+ 阿特拉津	60	模拟雨水	300 W氙气灯， AM 1.5G(4410 W/m²)	置于80 mL烧杯中，采用BDD/TiO₂光阳极，Pt阴极	E=9 V，采用模拟雨水电解质	两种农药在120 min内降解超过90%	[45]
二氯吡啶酸	100	超纯水	UVC紫外线灯(9 W)	单室电化学电池150 mL，MMO-Ti/TiO₂RuO₂光阳极，Pt阴极	j=30 mA/cm²， Na₂SO₄ 3.0 g/L或 NaCl 3.7 g/L	Na₂SO₄中降解率为18.8%，TOC去除率为6.95%，NaCl中降解率为58.4%，TOC去除率为53.6%	[11]
二氯吡啶酸	20	水	UVC紫外线灯	150 mL电化学电池Ti/MMO/ZnO，光电阳极，Pt板阴极	E=0.5 V vs Ag/AgCl，Na₂SO₄ 0.1 mol/L	降解率为77%，K_app=6.4×10^-3/s	[13]
西玛津	100	水	1000 W太阳光模拟器	三电极石英光电解池，FTO/BiMoVO₄光电阳极，碳布阴极(2.0 cm×2.5 cm)	E=2.5 V， K₂SO₄ 50 mmol/L， Fe²⁺ 0.2 mmol/L，空气流量0.2 mmol/L	0.75 min降解率为100%， K_app=0.08 /s，2 h TOC降解率达到100%	[46]
草甘膦	50	水	紫外线照射(9 W)	单室压滤式流动反应器，1.5 L溶液，BDD和DSA(R)光阳极(78 cm²)，不锈钢(AISI 304)阴极	j=10 mA/cm²， NaCl 2 g/L， pH 4.5~5.0	1 h后，使用BDD矿化率达到70%能耗为2.0 kWh/g，使用DSA(R)矿化率达到100%，能耗为1.25 kWh/g	[29]
甲磺隆	15	水	500 W氙灯（紫外截断）	置于反应管中以FTO/ABGCN-2为光阳极，Pt丝阳极	Na₂SO₄ 0.5 mol/L	57 min后降解率为100%	[47]
苯线磷	20	水	模拟太阳光照	14 mL石英反应器，W/WO₃光阳极，Pt网状阴极	E=1 V vs Ag/AgCl 于H₂SO₄(pH 1)中	2 h后降解率达到100%	[48]
苯线磷	20	水	模拟太阳光 AM 1.5G(100 mW/cm²)	光电催化石英反应器，W/WO₃光阳极(0.5 cm²)，Pt箔阴极	E=1 V vs Ag/AgCl 于H₂SO₄中	3 h后降解80%，k=0.14510^-3/s	[9]
毒虫畏、亚胺硫磷、苯线磷	各20	水	500 W氙灯可见光光照强度为100 mW/cm²	石英反应器，W/WO₃光阳极，Pt丝阴极	E=1 V vs Ag/AgCl 于H₂SO₄中	毒虫畏降解率为95%，亚胺硫磷降解率为99.9%，苯线磷降解率为100%	[49]
二嗪农	20	水	500 W氙灯可见光光照强度(100 mW/cm²)	石英反应器，W/WO₃光阳极，Pt丝阴极	E=1 V vs Ag/AgCl 于H₂SO₄中	2 h后降解率达到90%	[50]
西维因	0.2	水	35 W汞灯	Au-RGO/TiO₂ NT光阳极，Pt薄片阴极	E=15 V，pH=10	8 h降解率达到96.5%	[39]
2,4-二氯苯酚	5-25	水	14 W紫外线灯 (5500 mW/cm²)	三电极电化学电池，TiO₂纳米管涂层圆盘（电极面积为32 cm²）光电催化流动反应器，阴极采用铂丝阴极，电解质溶液1 L	j=1.5 mA/cm²， Na₂SO₄ 50 mmol/L	在浓度为10 mg/L时达到最佳去除率为90%，矿化率为20%	[4]
4-氯苯酚	10	水	AM 1.5G光源	80 mL立方石英电池，FTO/WO_3-x光阳极(2.0 cm×4.0 cm)，不锈钢阴极(2.0 cm×4.0 cm)	E=1.5 V， Na₂SO₄0.1 mol/L	降解率为84.5%，二氯化率为48%，k=0.262×10^-3/s	[43]
4-氯苯酚	20	水	300 W氙灯	TiO2纳米锥(7.5 cm²)光电阳极，石墨板(15 cm²)阴极	E=2.2 V vs RHE in 0.1 mol/L Na₂SO₄,	3 h后降解率为99%，矿化率为55%	[51]
4-氟-3- 甲基苯酚	50	水	300 W氙灯，420 nm 紫外滤波器(100 mW/cm²)	标准三室电池(100 mL)，In₂O₃/In₂S₃/CdS光阳极，Pt薄片阴极	E=0.6 V vs Ag/AgCl， H₂SO₄ 0.1 mol/L	3 h后降解率为87.3%，矿化率为71%	[31]
三苯基氯化锡	0.1	水	紫外线灯	三电极石英光电解池(50 mL)，FTO-TiO₂光阳极，碳毡阴极	E=2.5 V vs Ag/AgCl， K₂SO₄ 50 mmol/L， Fe²⁺ 0.2 mmol/L	2 h后矿化率达到100%	[42]

农药	浓度/ (mg/L)	基质	照射源	单元配置	操作条件	最佳去除效率	文献
阿特拉津	2	农药废水	300 W高压灯	石英水套电池，FTO/ MI-TiO₂，001光阳极(7.5 cm²)，铂片阴极(1.5 cm× 6.0 cm)	Na₂SO₄=0.1 mol/L，E=0.6 V vs SCE	5 h可降解96.5%，TOC去除率9.8%，水体毒性降低99.6%	[30]
阿特拉津	2	水	氙灯(200 mW/cm²)	半圆形石英降解电池(80 mL)，TiO₂NT光阳极(15 cm²)铂丝阴极	E=0.2 V，于0.1 mol/L Na₂SO₄中	降解率为96.8%，k=0.478×10^-3/s	[44]
敌草隆+ 阿特拉津	60	模拟雨水	300 W氙气灯， AM 1.5G(4410 W/m²)	置于80 mL烧杯中，采用BDD/TiO₂光阳极，Pt阴极	E=9 V，采用模拟雨水电解质	两种农药在120 min内降解超过90%	[45]
二氯吡啶酸	100	超纯水	UVC紫外线灯(9 W)	单室电化学电池150 mL，MMO-Ti/TiO₂RuO₂光阳极，Pt阴极	j=30 mA/cm²， Na₂SO₄ 3.0 g/L或 NaCl 3.7 g/L	Na₂SO₄中降解率为18.8%，TOC去除率为6.95%，NaCl中降解率为58.4%，TOC去除率为53.6%	[11]
二氯吡啶酸	20	水	UVC紫外线灯	150 mL电化学电池Ti/MMO/ZnO，光电阳极，Pt板阴极	E=0.5 V vs Ag/AgCl，Na₂SO₄ 0.1 mol/L	降解率为77%，K_app=6.4×10^-3/s	[13]
西玛津	100	水	1000 W太阳光模拟器	三电极石英光电解池，FTO/BiMoVO₄光电阳极，碳布阴极(2.0 cm×2.5 cm)	E=2.5 V， K₂SO₄ 50 mmol/L， Fe²⁺ 0.2 mmol/L，空气流量0.2 mmol/L	0.75 min降解率为100%， K_app=0.08 /s，2 h TOC降解率达到100%	[46]
草甘膦	50	水	紫外线照射(9 W)	单室压滤式流动反应器，1.5 L溶液，BDD和DSA(R)光阳极(78 cm²)，不锈钢(AISI 304)阴极	j=10 mA/cm²， NaCl 2 g/L， pH 4.5~5.0	1 h后，使用BDD矿化率达到70%能耗为2.0 kWh/g，使用DSA(R)矿化率达到100%，能耗为1.25 kWh/g	[29]
甲磺隆	15	水	500 W氙灯（紫外截断）	置于反应管中以FTO/ABGCN-2为光阳极，Pt丝阳极	Na₂SO₄ 0.5 mol/L	57 min后降解率为100%	[47]
苯线磷	20	水	模拟太阳光照	14 mL石英反应器，W/WO₃光阳极，Pt网状阴极	E=1 V vs Ag/AgCl 于H₂SO₄(pH 1)中	2 h后降解率达到100%	[48]
苯线磷	20	水	模拟太阳光 AM 1.5G(100 mW/cm²)	光电催化石英反应器，W/WO₃光阳极(0.5 cm²)，Pt箔阴极	E=1 V vs Ag/AgCl 于H₂SO₄中	3 h后降解80%，k=0.14510^-3/s	[9]
毒虫畏、亚胺硫磷、苯线磷	各20	水	500 W氙灯可见光光照强度为100 mW/cm²	石英反应器，W/WO₃光阳极，Pt丝阴极	E=1 V vs Ag/AgCl 于H₂SO₄中	毒虫畏降解率为95%，亚胺硫磷降解率为99.9%，苯线磷降解率为100%	[49]
二嗪农	20	水	500 W氙灯可见光光照强度(100 mW/cm²)	石英反应器，W/WO₃光阳极，Pt丝阴极	E=1 V vs Ag/AgCl 于H₂SO₄中	2 h后降解率达到90%	[50]
西维因	0.2	水	35 W汞灯	Au-RGO/TiO₂ NT光阳极，Pt薄片阴极	E=15 V，pH=10	8 h降解率达到96.5%	[39]
2,4-二氯苯酚	5-25	水	14 W紫外线灯 (5500 mW/cm²)	三电极电化学电池，TiO₂纳米管涂层圆盘（电极面积为32 cm²）光电催化流动反应器，阴极采用铂丝阴极，电解质溶液1 L	j=1.5 mA/cm²， Na₂SO₄ 50 mmol/L	在浓度为10 mg/L时达到最佳去除率为90%，矿化率为20%	[4]
4-氯苯酚	10	水	AM 1.5G光源	80 mL立方石英电池，FTO/WO_3-x光阳极(2.0 cm×4.0 cm)，不锈钢阴极(2.0 cm×4.0 cm)	E=1.5 V， Na₂SO₄0.1 mol/L	降解率为84.5%，二氯化率为48%，k=0.262×10^-3/s	[43]
4-氯苯酚	20	水	300 W氙灯	TiO2纳米锥(7.5 cm²)光电阳极，石墨板(15 cm²)阴极	E=2.2 V vs RHE in 0.1 mol/L Na₂SO₄,	3 h后降解率为99%，矿化率为55%	[51]
4-氟-3- 甲基苯酚	50	水	300 W氙灯，420 nm 紫外滤波器(100 mW/cm²)	标准三室电池(100 mL)，In₂O₃/In₂S₃/CdS光阳极，Pt薄片阴极	E=0.6 V vs Ag/AgCl， H₂SO₄ 0.1 mol/L	3 h后降解率为87.3%，矿化率为71%	[31]
三苯基氯化锡	0.1	水	紫外线灯	三电极石英光电解池(50 mL)，FTO-TiO₂光阳极，碳毡阴极	E=2.5 V vs Ag/AgCl， K₂SO₄ 50 mmol/L， Fe²⁺ 0.2 mmol/L	2 h后矿化率达到100%	[42]

光电催化降解农药的研究进展

Research Progress in Photoelectrocatalytic Degradation of Pesticides

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