多相芬顿催化水处理技术与原理

PＲOGＲESSINCHEMISTＲYDOI10.7536/PC170552http//．progchem．ac．cnProgressinChemistry2017299981～999*123123＊＊1．5100062．1000853．100049。、pH、。、/。、。。。O643.32+2X131.2X52A1005-281X201709-0981-19201752720178172017924*No．51538013No．2016YFA0203200TheworkwassupportedbytheNationalNaturalScienceFoundationofChinaNo．51538013andtheNationalKeyＲesearchandDevelopmentPlanNo．2016YFA0203200．＊＊[e-mail]alyticWaterTreatmentTechnologyandMechanism*LaiLyu123ChunHu123＊＊1．KeyLaboratoryforWaterQualityandConservationofthePearlＲiverDeltaMinistryofEducationSchoolofEnvironmentalScienceandEngineeringGuangzhouUniversityGuangzhou510006China2．KeyLaboratoryofDrinkingWaterScienceandTechnologyＲesearchCenterforEco-EnvironmentalSciencesChineseAcademyofSciencesBeijing100085China3．UniversityofChineseAcademyofSciencesBeijing100049ChinaAbstractHeterogeneousFentoncatalyticwatertreatmenttechnologyisaneffectivemethodfordegradationoforganicpollutantsinwater．ComparedtothehomogeneousFentonreactionithastheadvantagesofrecyclabilitywidepHresponserangeeasysolid-liquidseparationandnon-productionofironsludge．ThisarticlemainlyreviewstheclassicalFentonreactionmechanismtheheterogeneousFentonreactionmechanismandthedevelopedheterogeneousFenton/Fenton-likecatalystsbasedonthebasicmechanism．ThebottleneckproblemsofthepresentheterogeneousFentonsystemincludinglowactivityunderneutralconditionpoorstabilityofthecatalystandlowutilizationefficiencyofH2O2aresummarized．ParticularlytheemphasisistointroducethedevelopednewtypeheterogeneousFentonsystemsincludingtheone-centerCu-basedFenton-likesystemandthedual-centerFenton-likesystemforsolvingthebottleneckproblems．Wethinkthedual-centerＲeview·982·ProgressinChemistry2017299981～999Fenton-likesystemhasactuallybroketheconceptoftheclassicalFentonreactioncreatingtheelectron-richcentersandelectron-deficiencycentersbasedonthepolarizationtheoryofelectrondistributionwhichrealizestheefficientlyselectivereductionofhydrogenperoxideandoxidativedegradationofpollutantssolvingthetechnicalbottleneckproblemsoftheclassicalFentonreactioninwatertreatment．KeywordsHeterogeneousFentoncatalysiswatertreatmentdualreactioncenterhydrogenperoxideThispapersummarizestheclassicalFentonreactionconventionalone-centerheterogeneousFentonsystemandthedevelopeddual-centerheterogeneousFenton-likesystemandtheircharacteristicsandreactionmechanismswith/withoutpollutants．Contents1Introduction2ClassicalFentonreactionmechanism3HeterogeneousFentoncatalyticreactionmechanism3.1HeterogeneousFentonreactionmechanismwithoutconsideringorganicpollutants3.2HeterogeneousFentonreactionmechanisminconsiderationoforganicpollutants4DevelopmentandutilizationofheterogeneousFentoncatalysts4.1Zero-valentmetalcatalyst4.2Transitionmetaloxidecatalyst4.3Metalspecies-supportedcatalysts4.4Metalions-dopedcatalysts5ExistingproblemsofheterogeneousFentoncatalyticsystem6DevelopmentofnovelheterogeneousFentonsystemanditscatalyticmechanismfordegradationoforganicpollutantsinwater6.1One-centerheterogeneousFentonsystem6.2Dual-centerheterogeneousFenton-likesysteminducedbylatticeoxygen6.3Dual-centerheterogeneousFenton-likesysteminducedbysurfaceorganicligand7Conclusionandoutlook1、、、12。3。。。、4。·OH5。pH、、2。、。、H2O246。2017299981～999·983·。。21894H．J．H．FentonpH2～5Fe2+H2O2。H2O2“”Fe2+H2O2。。1964H．Ｒ．Eisenhauer7。8、9、10。11、12、13、14、1516。。HaberWeiss17Fe2+H2O2。18。Fe2+H2O2·OHFe2+Fe3+1。·OH2.7V569.3kJ2、3π4Ｒ·ＲX+·ＲHXOH。·OH。H2O2·OHHO·2/O·－25。Fe3+H2O2Fe2+H2O2HO·26Fe3+HO·2Fe2+O27。Fe2++H2O2→Fe3++OH－+·OH1·OH+ＲX→ＲX+·+OH－2ＲH+·OH→Ｒ·+H2O3ＲHX+·OH→ＲHXOH4H2O2+·OH→H2O+HO·25Fe3++H2O2→Fe2++H++HO·26Fe3++HO·2→Fe2++O2+H+711mol/LpH19Fig．1SpeciationofFeⅡinwaterasafunctionofpHat1mol/Lionicstrength19·OHk=109～1010L·mol－1·s－1·OH。pH·OH。pH119。pH＜3Fe2+1pH。pH3～4Fe2+FeOH+FeOH2。FeOH2Fe2+pHFeOH2·OHpH4。pH＞3。pH3。pH。Fe3+H2O2Fe2+6k≈0.02L·mol－1·s－1·OHk≈76L·mol－1·s－120Fe3+。Fe3+Ｒeview·984·ProgressinChemistry2017299981～999Fe2+。H2O2·OHH2O2Fe3+Fe2+H2O2HO·2O2H2O2。H2O2。·OH。H2O2H2O2。H2O2。H2O2。。H2O2Mostaghim21Co2+/H2O2Mn2+/H2O2。Gabriel22Cu2+/H2O2、180%。Nichela23H2O2Cu2+Fe3+TOC。pH。H2O223～25Cu+Fe2+Haber-WeissH2O2·OH8Cu2+Fe3+H2O2HO·2Cu+910。Cu2+H2O2Fe3+H2O226～32Cu2+H2O2Cu+·O2H11Cu+·O2HH2O2·OH12。Cu++H2O2→Cu2++OH－+·OH8Cu2++H2O2→Cu++H++HO·29Cu2++HO·2→Cu++O2+H+10Cu2++H2O2→Cu+·O2H+H+11Cu+·O2H+H2O2→Cu++O2+·OH+H2O12H2O2。33。、pH23、34、34、353637、3839。25pH、、H2O2。3、pH。、、。。H2O2、、。H2O2H2O2。H2O2。。。3.14041H2O2。H2O22017299981～999·985·H2O2O2。H2O2H2O2·OHHO·2/O·－2。H2O213～1542≡Mn++H2O2→≡Mn+1++OH－+·OH13≡Mn+1++H2O2→≡Mn++H++HO·214HO·2+≡Mn+1+→≡Mn++H++O215H2O2。H2O2·OH。。Yang2H2O2·OHFeOCl。FeOClFeOCl·OH1～3。FeOClH2O2·OH2FeOClH2O2≡FeⅡH2O2HO·2。FeOCl≡FeⅡH2O2·OH≡FeⅢ。·OH。FeOClH2O2·OHO-Fe-Cl·OH。Costa43H2Fe3O4Fe0/Fe3O42FeOCl2Fig．2MechanismoftheFentonreactionovertheFeOCl23Fe0Fe3+Fe0/Fe3O4Fe2+43Fig．3SketchoftheelectrontransferfromFe0toFe3+magnetitetoregenerateFe2+surf43Fe0/Fe3O4。Fe0/Fe3O4H2O23。Fe0/Fe3+Fe2+H2O2·OHFe0Fe3+Fe2+。CoMnH2O24445CoMnH2O2。Co2+Mn2+Fe2+H2O2·OH1617E0Co3+/Co2+=1.81V、E0Mn3+/Mn2+=1.51VE0Fe3+/Fe2+=0.77V1819Co2+Mn2+。≡Co2++H2O2→≡Co3++OH－+·OH16≡Mn2++H2O2→≡Mn3++OH－+·OH17≡