有机农药光催化降解机理研究进展
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摘要
应用光催化技术降解有机农药来减少农药对农业环境的污染是目前环境领域中的新兴研究课题。对光催化降解的机理以及不同种类农药(有机氯类农药、有机磷类农药、拟除虫菊酯类农药、氨基甲酸酯类农药、其他类农药)的光催化降解研究进展进行了总结。结果表明:在半导体纳米粒子和光催化体系组合作用下,有机农药均可得到有效的降解。本研究提出了光催化降解有机农药的应用前景,并对现行光催化技术的一些缺陷提出建议及展望,以期为有机农药光催化降解的深入研究提供参考。
The application of photocatalytic degradation of organic pesticides to reduce pesticide pollution onagricultural environment is a new research subject in the field of environment at present. In this paper, themechanism of photocatalytic degradation and the research progress of photocatalytic degradation of differentkinds of pesticides(organochlorine pesticides, organophosphorus pesticides, pyrethroid pesticides, carbamatepesticides and other pesticides) were summarized. The results showed that: organic pesticides could beeffectively degraded under the combination effect of semiconductor nanoparticles and photocatalytic system. Inthis study, the authors put forward the application prospect of photocatalytic degradation of organic pesticides,and proposed some suggestions concerning the defects of photocatalytic technology, so as to provide referencefor further research on photocatalytic degradation of organic pesticides.
The application of photocatalytic degradation of organic pesticides to reduce pesticide pollution onagricultural environment is a new research subject in the field of environment at present. In this paper, themechanism of photocatalytic degradation and the research progress of photocatalytic degradation of differentkinds of pesticides(organochlorine pesticides, organophosphorus pesticides, pyrethroid pesticides, carbamatepesticides and other pesticides) were summarized. The results showed that: organic pesticides could beeffectively degraded under the combination effect of semiconductor nanoparticles and photocatalytic system. Inthis study, the authors put forward the application prospect of photocatalytic degradation of organic pesticides,and proposed some suggestions concerning the defects of photocatalytic technology, so as to provide referencefor further research on photocatalytic degradation of organic pesticides.
引文
[1]白博.Cu2+/Ce4+/Ti O2复合纳米微粒光催化降解农药废水的试验研究[J].辽宁化工,2012,41(5):31-32,58.
[2]束放,熊延坤.我国农药生产现状和农药减量使用的重要意义[J].山东农药信息,2016(2):18-20.
[3]陈晓明,王程龙,薄瑞,等.中国农药使用现状及对策建议[J].农药科学与管理,2016,37(2):4-8.
[4]Aragay G,Pino F,Merko?i A.Nanomaterials for sensing and destroying pesticides[J].Chemical reviews,2012,112(10):5317-5338.
[5]江兰,郑飞,冷鹏飞,等.纳米农药的研究进展[J].广东农业科学,2010,37(5):97-100.
[6]陈小军,徐汉虹,胡珊,等.农药光催化降解研究进展[J].农药,2006,45(6):381-384.
[7]刘祥英,邬腊梅,柏连阳,等.Ti O2光催化降解农药研究新进展[J].中国农学通报,2010,26(12):203-208.
[8]Echavia G R M,Matzusawa F,Negishi N.Photocatalytic degradation of organophosphate and phosphonoglycine pesticides using Ti O2immobilized on silica gel[J].Chemosphere,2009,76(5):595-600.
[9]陈士夫,赵梦月,陶跃式,等.光催化降解有机磷农药的研究[J].环境科学,1995,16(5):61-63.
[10]彭延治,徐明芳,曾常军,等.UV-Ti O2-Fenton光催化降解敌百虫农药废水的研究[J].工业水处理,2006,26(6):33-36.
[11]Saien J,Khezrianjoo S.Degradation of the fungicide carbendazim in aqueous solutions with UV/Ti O2process:optimization,kinetics and toxicity studies[J].Journal of Hazardous Materials,2008,157(2):269-276.
[12]陈建秋,王铎,娄红瑞,等.多菌灵和五氯酚钠的光降解和光催化降解初探[J].现代农药,2006,5(2):38.
[13]宋秀兰,姚伟峰,吴一平.半导体光催化的应用研究[J].上海电力学院学报,2012,28(1):81-85.
[14]Byrne J A,Dunlop P S M,Hamilton J W J,et al.A review of heterogeneous photocatalysis for water and surface disinfection[J].Molecules,2015,20(4):5574-5615.
[15]Dong S,Feng J,Fan M,et al.Recent developments in heterogeneous photocatalytic water treatment using visible lightresponsive photocatalysts:a review[J].RSC Advances,2015,5(19):14610-14630.
[16]苏茜,张勇.二氧化钛光催化降解有机磷农药的机理和影响因素[J].广州化学,2005,30(1):52-57.
[17]Wang Y,Sun C,Zhao X,et al.The application of nano-Ti O2photo semiconductors in agriculture[J].Nanoscale Research Letters,2016,11(1):529.
[18]Burrows H D,Santaballa J A,Steenken S.Reaction pathways and mechanisms of photodegradation of pesticides[J].Journal of photochemistry and photobiology B:Biology,2002,67(2):71-108.
[19]Yu B,Zeng J,Gong L,et al.Investigation of the photocatalytic degradation of organochlorine pesticides on a nano-Ti O2coated film[J].Talanta,2007,72(5):1667-1674.
[20]李爽,张兰英,王显胜,等.二氧化钛光催化降解地下水中的六六六[J].吉林大学学报理学版,2007,45(1):153-156.
[21]余彬彬.有机氯农药在纳米Ti O2中的光催化降解研究[D].厦门:厦门大学,2007.
[22]Quan X,Zhao X,Chen S,et al.Enhancement of p,p′-DDT photodegradation on soil surfaces using Ti O2induced by UV-light[J].Chemosphere,2005,60(2):266-273.
[23]Ananpattarachai J,Kajitvichyanukul P.Photocatalytic degradation of p,p′-DDT under UV and visible light using interstitial N-doped Ti O2[J].Journal of Environmental Science and Health,Part B,2015,50(4):247-260.
[24]Ye M,Chen Z,Wang W,et al.Hydrothermal synthesis of Ti O2hollow microspheres for the photocatalytic degradation of 4-chloronitrobenzene[J].Journal of hazardous materials,2010,184(1):612-619.
[25]Affam A C,Chaudhuri M.Degradation of pesticides chlorpyrifos,cypermethrin and chlorothalonil in aqueous solution by Ti O2photocatalysis[J].Journal of environmental management,2013,130:160-165.
[26]Wu M,Deng J,Li J,et al.Simultaneous biological-photocatalytic treatment with strain CDS-8 and Ti O2for chlorothalonil removal from liquid and soil[J].Journal of Hazardous Materials,2016,320:612-619.
[27]Moradas G,Auresenia J,Gallardo S,et al.Biodegradability and toxicity assessment of trans-chlordane photochemical treatment[J].Chemosphere,2008,73(9):1512-1517.
[28]Tapia-Orozco N,Rodríguez Vázquez R.Photoactive Ti O2films formation by drain coating for endosulfan degradation[J].International Journal of Photoenergy,2013.
[29]Thomas J,Kumar K P,Chitra K R.Synthesis of Ag doped nano Ti O2as efficient solar photocatalyst for the degradation of endosulfan[J].Advanced Science Letters,2011,4(1):108-114.
[30]Rani M,Shanker U,Jassal V.Recent strategies for removal and degradation of persistent&toxic organochlorine pesticides using nanoparticles:A review[J].Journal of Environmental Management,2017,190:208-222.
[31]邱常义,马维新.纳米二氧化钛光催化降解有机磷农药的研究[J].江西化工,2008(1):49-51.
[32]殷晓梅,王欣,雷磊,等.有机磷农药纳米Ti O2光催化降解反应器的优化设计[J].农业工程学报,2012,28(12):251-256.
[33]王琰,崔建宇,胡林,等.悬浮态Ti O2静止光催化降解有机磷农药[J].中国农业大学学报,2008,13(2):73-77.
[34]Evgenidou E,Konstantinou I,Fytianos K,et al.Photocatalytic oxidation of methyl parathion over Ti O2and Zn O suspensions[J].Catalysis Today,2007,124(3):156-162.
[35]Evgenidou E,Konstantinou I,Fytianos K,et al.Study of the removal of dichlorvos and dimethoate in a titanium dioxide mediated photocatalytic process through the examination of intermediates and the reaction mechanism[J].Journal of hazardous materials,2006,137(2):1056-1064.
[36]Liu W,Chen S,Zhao W,et al.Study on the photocatalytic degradation of trichlorfon in suspension of titanium dioxide[J].Desalination,2009,249(3):1288-1293.
[37]骆爱兰.拟除虫菊酯类农药残留ELISA检测及消解去除研究[D].扬州:扬州大学,2004.
[38]陈梅兰,陈金缓.Ti O2光催化降解低浓度溴氰菊酯[J].环境污染与防治,2000,22(1):13-14.
[39]李焱.溴氰菊酯在茶叶中的辐照降解研究[D].合肥:安徽农业大学,2007.
[40]Lin L,Xie M,Liang Y,et al.Degradation of cypermethrin,malathion and dichlorovos in water and on tea leaves with O3/UV/Ti O2treatment[J].Food control,2012,28(2):374-379.
[41]Yao B H,Zheng H L,Yang L Q,et al.Studies on preparation of Cd S/Ti O2/Float pearls coupled photocatalyst and degradation of beta-cypermethrin[J].Guang pu xue yu guang pu fen xi=Guang pu,2007,27(5):1010-1014.
[42]Kuo W S,Chiang Y H,Lai L S.Solar photocatalysis of carbaryl rinsate promoted by dye photosensitization[J].Dyes and Pigments,2008,76(1):82-87.
[43]Alalm M G,Ookawara S,Fukushi D,et al.Improved WO3photocatalytic efficiency using Zr O2and Ru for the degradation of carbofuran and ampicillin[J].Journal of hazardous materials,2016,302:225-231.
[44]Fenoll J,Hellín P,Flores P,et al.Degradation intermediates and reaction pathway of carbofuran in leaching water using Ti O2and Zn O as photocatalyst under natural sunlight[J].Journal of Photochemistry and Photobiology A:Chemistry,2013,251:33-40.
[45]Wang Q,Lemley A T.Oxidation of carbaryl in aqueous solution by membrane anodic Fenton treatment[J].Journal of agricultural and food chemistry,2002,50(8):2331-2337.
[46]Kanan M C,Kanan S M,Austin R N,et al.Photodecomposition of carbaryl in the presence of silver-doped zeolite Y and Suwannee River natural organic matter[J].Environmental science&technology,2003,37(10):2280-2285.
[47]Liu X,Kang Y,Luo D.Synthesis of novel Au/Fe VO4/Bi2O3heterojunction for efficient visible-light-driven photocatalysis[J].Materials Letters,2016,185:189-192.
[48]Kiss A,Virág D.Photostability and photodegradation pathways of distinctive pesticides[J].Journal of environmental quality,2009,38(1):157-163.
[49]Sarasidis V C,Plakas K V,Patsios S I,et al.Investigation of diclofenac degradation in a continuous photo-catalytic membrane reactor.Influence of operating parameters[J].Chemical Engineering Journal,2014,239:299-311.
[50]Oller I,Malato S,Sánchez-Pérez J A,et al.Detoxification of wastewater containing five common pesticides by solar AOPsbiological coupled system[J].Catalysis Today,2007,129(1):69-78.
[51]Angthararuk D,Sutthivaiyakit P,Blaise C,et al.Photo-catalysis of bromacil under simulated solar light using Au/Ti O2:evaluation of main degradation products and toxicity implications[J].Environmental Science and Pollution Research,2015,22(2):1468-1479.
[52]Reddy P V L,Kim K H.A review of photochemical approaches for the treatment of a wide range of pesticides[J].Journal of hazardous materials,2015,285:325-335.
[53]燕红芳,王敬国,慕康国,等.镧掺杂纳米Ti O2应用助剂筛选及其对农药残留的光催化降解效果[J].中国稀土学报,2012,30(4):58-63.
[54]梁春华.铒掺杂二氧化钛光催化降解甲胺磷农药的研究[J].吉林农业大学学报,2012,34(5):536-539.
[55]金星海.改性Ti O2光催化降解二苯醚类农药的研究[D].哈尔滨:黑龙江大学,2010.
[2]束放,熊延坤.我国农药生产现状和农药减量使用的重要意义[J].山东农药信息,2016(2):18-20.
[3]陈晓明,王程龙,薄瑞,等.中国农药使用现状及对策建议[J].农药科学与管理,2016,37(2):4-8.
[4]Aragay G,Pino F,Merko?i A.Nanomaterials for sensing and destroying pesticides[J].Chemical reviews,2012,112(10):5317-5338.
[5]江兰,郑飞,冷鹏飞,等.纳米农药的研究进展[J].广东农业科学,2010,37(5):97-100.
[6]陈小军,徐汉虹,胡珊,等.农药光催化降解研究进展[J].农药,2006,45(6):381-384.
[7]刘祥英,邬腊梅,柏连阳,等.Ti O2光催化降解农药研究新进展[J].中国农学通报,2010,26(12):203-208.
[8]Echavia G R M,Matzusawa F,Negishi N.Photocatalytic degradation of organophosphate and phosphonoglycine pesticides using Ti O2immobilized on silica gel[J].Chemosphere,2009,76(5):595-600.
[9]陈士夫,赵梦月,陶跃式,等.光催化降解有机磷农药的研究[J].环境科学,1995,16(5):61-63.
[10]彭延治,徐明芳,曾常军,等.UV-Ti O2-Fenton光催化降解敌百虫农药废水的研究[J].工业水处理,2006,26(6):33-36.
[11]Saien J,Khezrianjoo S.Degradation of the fungicide carbendazim in aqueous solutions with UV/Ti O2process:optimization,kinetics and toxicity studies[J].Journal of Hazardous Materials,2008,157(2):269-276.
[12]陈建秋,王铎,娄红瑞,等.多菌灵和五氯酚钠的光降解和光催化降解初探[J].现代农药,2006,5(2):38.
[13]宋秀兰,姚伟峰,吴一平.半导体光催化的应用研究[J].上海电力学院学报,2012,28(1):81-85.
[14]Byrne J A,Dunlop P S M,Hamilton J W J,et al.A review of heterogeneous photocatalysis for water and surface disinfection[J].Molecules,2015,20(4):5574-5615.
[15]Dong S,Feng J,Fan M,et al.Recent developments in heterogeneous photocatalytic water treatment using visible lightresponsive photocatalysts:a review[J].RSC Advances,2015,5(19):14610-14630.
[16]苏茜,张勇.二氧化钛光催化降解有机磷农药的机理和影响因素[J].广州化学,2005,30(1):52-57.
[17]Wang Y,Sun C,Zhao X,et al.The application of nano-Ti O2photo semiconductors in agriculture[J].Nanoscale Research Letters,2016,11(1):529.
[18]Burrows H D,Santaballa J A,Steenken S.Reaction pathways and mechanisms of photodegradation of pesticides[J].Journal of photochemistry and photobiology B:Biology,2002,67(2):71-108.
[19]Yu B,Zeng J,Gong L,et al.Investigation of the photocatalytic degradation of organochlorine pesticides on a nano-Ti O2coated film[J].Talanta,2007,72(5):1667-1674.
[20]李爽,张兰英,王显胜,等.二氧化钛光催化降解地下水中的六六六[J].吉林大学学报理学版,2007,45(1):153-156.
[21]余彬彬.有机氯农药在纳米Ti O2中的光催化降解研究[D].厦门:厦门大学,2007.
[22]Quan X,Zhao X,Chen S,et al.Enhancement of p,p′-DDT photodegradation on soil surfaces using Ti O2induced by UV-light[J].Chemosphere,2005,60(2):266-273.
[23]Ananpattarachai J,Kajitvichyanukul P.Photocatalytic degradation of p,p′-DDT under UV and visible light using interstitial N-doped Ti O2[J].Journal of Environmental Science and Health,Part B,2015,50(4):247-260.
[24]Ye M,Chen Z,Wang W,et al.Hydrothermal synthesis of Ti O2hollow microspheres for the photocatalytic degradation of 4-chloronitrobenzene[J].Journal of hazardous materials,2010,184(1):612-619.
[25]Affam A C,Chaudhuri M.Degradation of pesticides chlorpyrifos,cypermethrin and chlorothalonil in aqueous solution by Ti O2photocatalysis[J].Journal of environmental management,2013,130:160-165.
[26]Wu M,Deng J,Li J,et al.Simultaneous biological-photocatalytic treatment with strain CDS-8 and Ti O2for chlorothalonil removal from liquid and soil[J].Journal of Hazardous Materials,2016,320:612-619.
[27]Moradas G,Auresenia J,Gallardo S,et al.Biodegradability and toxicity assessment of trans-chlordane photochemical treatment[J].Chemosphere,2008,73(9):1512-1517.
[28]Tapia-Orozco N,Rodríguez Vázquez R.Photoactive Ti O2films formation by drain coating for endosulfan degradation[J].International Journal of Photoenergy,2013.
[29]Thomas J,Kumar K P,Chitra K R.Synthesis of Ag doped nano Ti O2as efficient solar photocatalyst for the degradation of endosulfan[J].Advanced Science Letters,2011,4(1):108-114.
[30]Rani M,Shanker U,Jassal V.Recent strategies for removal and degradation of persistent&toxic organochlorine pesticides using nanoparticles:A review[J].Journal of Environmental Management,2017,190:208-222.
[31]邱常义,马维新.纳米二氧化钛光催化降解有机磷农药的研究[J].江西化工,2008(1):49-51.
[32]殷晓梅,王欣,雷磊,等.有机磷农药纳米Ti O2光催化降解反应器的优化设计[J].农业工程学报,2012,28(12):251-256.
[33]王琰,崔建宇,胡林,等.悬浮态Ti O2静止光催化降解有机磷农药[J].中国农业大学学报,2008,13(2):73-77.
[34]Evgenidou E,Konstantinou I,Fytianos K,et al.Photocatalytic oxidation of methyl parathion over Ti O2and Zn O suspensions[J].Catalysis Today,2007,124(3):156-162.
[35]Evgenidou E,Konstantinou I,Fytianos K,et al.Study of the removal of dichlorvos and dimethoate in a titanium dioxide mediated photocatalytic process through the examination of intermediates and the reaction mechanism[J].Journal of hazardous materials,2006,137(2):1056-1064.
[36]Liu W,Chen S,Zhao W,et al.Study on the photocatalytic degradation of trichlorfon in suspension of titanium dioxide[J].Desalination,2009,249(3):1288-1293.
[37]骆爱兰.拟除虫菊酯类农药残留ELISA检测及消解去除研究[D].扬州:扬州大学,2004.
[38]陈梅兰,陈金缓.Ti O2光催化降解低浓度溴氰菊酯[J].环境污染与防治,2000,22(1):13-14.
[39]李焱.溴氰菊酯在茶叶中的辐照降解研究[D].合肥:安徽农业大学,2007.
[40]Lin L,Xie M,Liang Y,et al.Degradation of cypermethrin,malathion and dichlorovos in water and on tea leaves with O3/UV/Ti O2treatment[J].Food control,2012,28(2):374-379.
[41]Yao B H,Zheng H L,Yang L Q,et al.Studies on preparation of Cd S/Ti O2/Float pearls coupled photocatalyst and degradation of beta-cypermethrin[J].Guang pu xue yu guang pu fen xi=Guang pu,2007,27(5):1010-1014.
[42]Kuo W S,Chiang Y H,Lai L S.Solar photocatalysis of carbaryl rinsate promoted by dye photosensitization[J].Dyes and Pigments,2008,76(1):82-87.
[43]Alalm M G,Ookawara S,Fukushi D,et al.Improved WO3photocatalytic efficiency using Zr O2and Ru for the degradation of carbofuran and ampicillin[J].Journal of hazardous materials,2016,302:225-231.
[44]Fenoll J,Hellín P,Flores P,et al.Degradation intermediates and reaction pathway of carbofuran in leaching water using Ti O2and Zn O as photocatalyst under natural sunlight[J].Journal of Photochemistry and Photobiology A:Chemistry,2013,251:33-40.
[45]Wang Q,Lemley A T.Oxidation of carbaryl in aqueous solution by membrane anodic Fenton treatment[J].Journal of agricultural and food chemistry,2002,50(8):2331-2337.
[46]Kanan M C,Kanan S M,Austin R N,et al.Photodecomposition of carbaryl in the presence of silver-doped zeolite Y and Suwannee River natural organic matter[J].Environmental science&technology,2003,37(10):2280-2285.
[47]Liu X,Kang Y,Luo D.Synthesis of novel Au/Fe VO4/Bi2O3heterojunction for efficient visible-light-driven photocatalysis[J].Materials Letters,2016,185:189-192.
[48]Kiss A,Virág D.Photostability and photodegradation pathways of distinctive pesticides[J].Journal of environmental quality,2009,38(1):157-163.
[49]Sarasidis V C,Plakas K V,Patsios S I,et al.Investigation of diclofenac degradation in a continuous photo-catalytic membrane reactor.Influence of operating parameters[J].Chemical Engineering Journal,2014,239:299-311.
[50]Oller I,Malato S,Sánchez-Pérez J A,et al.Detoxification of wastewater containing five common pesticides by solar AOPsbiological coupled system[J].Catalysis Today,2007,129(1):69-78.
[51]Angthararuk D,Sutthivaiyakit P,Blaise C,et al.Photo-catalysis of bromacil under simulated solar light using Au/Ti O2:evaluation of main degradation products and toxicity implications[J].Environmental Science and Pollution Research,2015,22(2):1468-1479.
[52]Reddy P V L,Kim K H.A review of photochemical approaches for the treatment of a wide range of pesticides[J].Journal of hazardous materials,2015,285:325-335.
[53]燕红芳,王敬国,慕康国,等.镧掺杂纳米Ti O2应用助剂筛选及其对农药残留的光催化降解效果[J].中国稀土学报,2012,30(4):58-63.
[54]梁春华.铒掺杂二氧化钛光催化降解甲胺磷农药的研究[J].吉林农业大学学报,2012,34(5):536-539.
[55]金星海.改性Ti O2光催化降解二苯醚类农药的研究[D].哈尔滨:黑龙江大学,2010.