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综述Photo-Fenton谢银德,陈锋,何建军,赵进才(,100080):Photo-Fenton氧化法是一种近几年来引起极大关注的新的有效的高级氧化技术,并逐渐应用于环境污染物的处理领域.本文简要介绍了这方面的研究进展情况,包括其机理研究和应用研究以及一些新的改进的Photo-Fenton氧化方法.:Fenton;Photo-Fenton;高级氧化技术:1000-3231(2000)04-0357-09:O64:A,.,400,,86%,.,,,,(PCBs).COD.,.1,80,,[1~4].,.1987,Glaze[5](AOP).,[6],.:2000-09-01;:2000-09-13;:,:,,100101:(29877026,29725715,29637010);:(1965-),,,.357184Vo1.18No.4200011PHOTOGRAPHICSCIENCEANDPHOTOCHEMISTRYNov.,2000,Fe2+(Fe3+)/H2O2,Photo-Fenton[7]..2Fenton21Fenton1894Fenton[8]..,Fe2+/H2O2Fenton,Fenton.22FentonFenton,,.[9~11].[12,13]DMPOFenton,,.,Fenton,:Fe2++H2O2Fe3++OH+OH-k1=761.9(mol/L)-1s-1(1)Fe2++OHFe3++OH-(2)OH+H2O2HO2+H2O(3)Fe2++HO2Fe(HO2)2+(4)Fe3++HO2Fe2++O2+H+(5)HO2O2-+H+(6)Fe3++O2-Fe2++O2(7)HO2+HO2H2O2+O2(8)OH+HO2H2O+O2(9)OH+O2-OH-+O2(10)OH+OHH2O2(11)Fenton,(+2.8V),,5693kJ,.Fenton,.,[14~16].,.:,,35818,.Fenton,,,.,Fenton[17~19].3Photo-Fenton31Fenton,.,,.,Kremer[12]..:Fe3++HO-2Fe3+HO2-()(12)Fe3+HO2-()Fe(HO2)2+()(13)Fe(HO2)2+()+H2O2products(Fe2+,OH-,H2O,O2)(14)(),().H2O2/Fe3+=300~10,().(4~02),().,,:Fe3++H2OFe(OH)2++H+(15)Fe3++2H2OFe(OH)2++2H+(16)2Fe3++2H2OFe2(OH)24++2H+(17)Fe3++H2O2Fe(HO2)2++H+(18)Fe(OH)2++H2O2Fe(OH)(HO2)++2H+(19)Fe(HO2)2+Fe2++HO2(20)Fe(OH)(HO2)+Fe2++HO2+OH-(21),FeHO2Fe(HO2)2+Fe(OH)(HO2)+,,.HO2.Fenton,.,[20,21]()Fe=O,.,.[22].4:Photo-Fenton359()()().RushBeilski[23](pH=3.6~10)H3FeO4.pH=0~3FeO2+.Pignatello[24]Photo-FentonPhoto-Fenton:[Fe-OOH]2++h[Fe-OOH]2+*(22)[Fe-OOH]2+*Fe2+*+HO2(23)[Fe-OOH]2+*{Fe-OFe=O}+OH(24)[Fe-OOH]2+*FeO+OH-(25)(24),.(24)(Fe).1998Bossmann[25].311Photo-Fenton1991ZeppFaustHolgneFenton,Fenton2--2-[11].Fenton.,Fenton.,Fenton(Fenton),,,Fenton(k1k2,126).,(),H2O2.Fe3++H2O2Fe2++H++HO2k2=0.002(mol/L)-1s-1(26),Fe3+OH-Fe(OH)2+[26,27].Fe(),Fe3+Fe(OH)2+Fe2(OH)24+FeLn(n-3)-(L=).pH0,Fe(H2O)63+.pH.:Fe3++OH-Fe(OH)2+k3=6.51011(27)Fe(OH)2++OH-Fe(OH)2+k4=3.081010(28)Fe(OH)2++OH-Fe(OH)3(29)pH.-().:Fe(OH)2++hFe2++OH(30)360181Fe()species(nm)Fe(H2O)3+62540.065Fe(OH)+23130.14Fe(OH)4+23500.007Fe(OH)2+3500.017,Fe()Fe(OH)2+.350nm,Fe(OH)2+Fe2(OH)4+2Fe2+00170.007[28](1).Fe(OH)2+Fe2+,H2O2OH,Fe/Fe.,(30)OH,.312Photo-Fenton,3~5%,Fenton.Fe(OH)x(3-x)+(x=0~3),,.,,.,dye*[29~32],Fe3+Fe2+,Fe2+H2O2OH,(31~34),1.1Photo-FentonDyehDye*(31)Dye*+Fe3+Fe2++Dye+(32)Fe2++H2O2Fe3++OH+OH-(33)Dye+(orDye)+OH(34)313Photo-FentonFe(C2O4)3-3/H2O2/h,Fe(),Fe(C2O4)3-3(35~37),,300nmFe()=124.,(~550nm):Fe(C2O4)3-3+hFe2++2C2O42-+C2O4-(35)4:Photo-Fenton361C2O4-CO2-+CO2(36)CO2-+Fe(C2O4)3-3Fe2++CO2+3C2O42-(37),Fenton,(37):Fe2++H2O2+3C2O42-Fe(C2O4)3-3+OH-+OH(38).HustonPignatello[33]C2O4-.,.[34~38].32Photo-Fenton300nm,250nm,350~400nm,,.Photo-FentonFenton,Fenton,,,H2O2,.,,Fe3+/Fe2+.Photo-Fenton,,KiwiFaustHolgne,BoltonCaterAmiri,SedlakOllisRupertPignatello.[39][40][41][42][43][44~46][47][48~50][51][52]Photo-Fenton.4Photo-FentonAOP.,,,OH,.pH3,Fe(OH)3Fe2+Fe3+,.,pH,,Photo-Fenton.,.,.36218:[1]ZhaoJ,WuT,WuK,etal.Photoassisteddegradationofdyepollutants:Evidencefortheneedofsubstratead-sorptiononTiO2particles[J].Environ.Sci.Technol.,1998,32:2394~2400[2]LiuG,WuT,ZhaoJ,etal.Photoassisteddegradationofdyepollutants:IrreversibledegradationofARundervisiblelightirradiationinair-equilibratedaqueousTiO2dispersions[J].Environ.Sci.Technol.,1999,33:2081~2087[3]WuT,LinT,ZhaoJ,etal.TiO2-assistedphotodegradationofdyes:Photooxidationofasquaryliumcyaninedyeinaqueousdispersionsundervisiblelightirradiation[J].Environ.Sci.Technol.,1999,33:1379~1387[4]WuT,LiuG,ZhaoJ,etal.EvidenceforH2O2generationduringtheTiO2assistedphotodegradationofdyesinaque-ousdispersionsundervisiblelightillumination[J].J.Phys.Chem.,1999,103:4862~4867[5]GlazeWH,KangJW,ChapinDH.Thechemistryofwaterandwastewatertreatmentprocessesinvolvingozone,hydrogenperoxideandultravioletradiation[J].Ozone.Sci.Eng.,1987,9:335~341[6]LegriniO,OliverosE,BraunAM.Photochemicalprocessesforwatertreatment[J].Chem.Rev.,1993,93:671~699[7]ZeppRG,FaustBC,HolgneJ.Hydroxylradicalformationinaqueousreactions(pH3~8)ofiron()withhydro-genperoxide:thePhoto-Fentonreaction[J].Environ.Sci.Technol.,1992,26:313~319[8]FentonHJH.Oxidationoftartaricacidinthepresenceofiron[J].J.Chem.Soc.,1894,65:899~910[9]KremerML.ComplexvisasFreeRadicalmechanismforthecatalyticdecompositionofH2O2byFe3+[J].Int.J.Chem.Kinet.,1985,17:1299~1314[10]WinkDA,NimbusRW,DesertersMF,etal.AkineticinvestigationofintermediatesformedduringtheFentonreagentmediateddegradationofN-nitrosodimethylamine:evidenceforanoxidativepathwaynotinvolvinghydroxylradical.Chem.Rev.Toxicol.,1991,4:510~512[11]WallingC,AmarnathK.OxidationofmandelicacidbyFentonsreagent[J].J.Am.Chem.Soc.,1982,104:1085~1089[12]KremerML,SteinG.Thecatalyticdecompositionofhydrogenperoxidebyferricperchlorate[J].Trans.FaradaySoc.,1959,55:959~973[13]BarbWG,BaxendaleJH,GeorgeP,etal.Reactionofferrousandferricionswithhydrogenperoxide.Part.Theferrousionreaction[J].Trans.FaradaySoc.,1951,47:462~500[14]BishopDF,DternG,FleischmannM,etal.Hydrogenperoxidecatalyticoxidationofrefractoryorganicsinmenic-ipalwastewaters,I&ECProcessDesignandDevelopment,1968,7(1):196~201[15]TripathiGNR.Electron-transfercomponentinhydroxylradicalre