化学需氧量COD快速测定新方法研究进展

Progressinnewmethodsforrapiddeterminationofchemicaloxygendemand(COD)郑青,韩海波,周保学,李金花,白晶and蔡伟民Citation:科学通报54,3241(2009);doi:10.1360/972009-207Viewonline::《中国科学》杂志社ArticlesyoumaybeinterestedinResearchprogressontherapid,realtime,online,insitumonitoringwaterqualitybiochemicaloxygendemandSCIENTIASINICAChimica48,956(2018);RecentprogressonconfinementofpolysulfidesthroughphysicalandchemicalmethodsJournalofEnergyChemistry27,1555(2018);Anewapproachfordeterminationofcomponentnumberinchemicalsystem:SubspacecomparisonChineseScienceBulletin45,1368(2000);NewmethodsandprogressinresearchontheoriginsandevolutionofprehistoricagricultureinChinaSCIENCECHINAEarthSciences60,2141(2017);MethodsofrapidorbitforecastingaftermaneuversforgeostationarysatellitesScienceinChinaSeriesG-Physics,Mechanics&Astronomy52,333(2009);2009年第54卷第21期:3241~3250(COD).,2009,54:3241~3250ZhengQ,HanHB,ZhouBX,etal.Progressinnewmethodsforrapiddeterminationofchemicaloxygendemand(COD)(inChinese).ChineseSciBull(ChineseVer),2009,54:3241―3250,doi:10.1360/972009-207(COD),,*,,,,200240;,200240*,E-mail:[e-mail]2009-02-07,2009-08-17(:2009AA063003)(:20677039)(:05nm05004)(:NCET-04-0406),,.,TiO2,,,.,,.,,,(2006),41127%V,,“”.,,.,,.,“”“”“”.(chemicaloxy-gendemand,COD),,(,mg·L−1).,,[1].,(DO),,.,COD.COD(GB11914-89,EPA410.4)K2Cr2O7KMnO4,COD.K2Cr2O7,,KMnO4.COD,,,2h;,;,[2~4].,,,[5~12]DownloadedtoIP:192.168.0.24On:2019-05-1706:00:48年11月第54卷第21期3242,.,COD,COD,,,.1COD,,,STTPPhoenix-1010COD.(DO)COD,3~15min,20~1500,20~100000mg·L−1,,,.O3/UV,Prengle[13],,O3/UVPeyton[14].32222OHOOHO+⎯⎯→+(1)O3+H2O⎯⎯→O2+2·OH(2)H2O2⎯⎯→2·OH(3)[15]O3/UV,,COD,0.03mg·L−1,.0~50%,COD,KMnO4.[16,17]UV/O3COD,Fe2+,Co2+,Cu2+,H2O2,Br−O3BrO3−,,,.2COD,.,,CO2H2O.COD,,PbO2,Cu(BDD).2.1PbO2Lar,PbO2,[18~22].:,,PbO2,:PbO2[]+H2OWDRk⎯⎯⎯→←⎯⎯⎯PbO2[·OH]+H++e−(4),PbO2[],kWDR.;,.,:PbO2[·OH]+ROTRk⎯⎯⎯→PbO2[]+RO+H++e−(5)R,RO,kOTR.,,,(6).,.PbO2[·OH]+H2OOERk⎯⎯⎯→PbO2[]+O2(aq)+3H++3e−(6)kOER.PopovicJohnson,[23,24].SOTRRtotWDR0SWDROTRR2kCiFAkkkC⎧⎫⎪⎪=⎨⎬+⎪⎪⎩⎭Γ,(7)F,A,Γ0,SRC,()SbtotRR2/iCCFADσ⎛⎞=−⎜⎟⎜⎟⎝⎠,(8)bRC,DσDownloadedtoIP:192.168.0.24On:2019-05-1706:00:48()bRtot2/CiFADσ=.(9)(9),,Li[19]PbO2COD,COD.,,,.Westbroek[20]Pt/PbO2COD,20~25000mg·L−1,,COD,.[25]PbO2COD,,,20~30h,,.,Cl−/COD10,+10.5%.PbO2,200671RoHSWEEE,,PbCdHgCr6+PBDEPBB6,,,.2.2CuSilva[26]Cu0.1mol·L−1NaOH,0.380.11V,CuCu2OCu2OCuO/Cu(OH)2.CuO,,:CuOOHCuOOHe−−++⎯⎯→(10)(red)(oxid)2CuOOHCuOHO+⎯⎯→++有机物有机物(11)Silva53~2801.4mg·L−1,20.3mg·L−1.Lee[27]Cu,.CtC0t,iti0t,:0exp()tCCqt=−,(12)0exp()tiiqt=−,(13)q,(m0),(A)(V),omAqV=.(14)(12)~(14),A/V,,;,A/V,,,,,Q0()()dQtitt∞=∫.(15),Lee[28]COD,1~12mg·L−1,.A/V,Lee,,100μm.,,,30min3~10min,1.Lee,Cu,.,,Cu,.,Lee.Cu,Kim[29]COD,10~10000mg·L−1,3,.CuCOD,K2Cr2O70.99,.DownloadedtoIP:192.168.0.24On:2019-05-1706:00:48年11月第54卷第21期32441(a)Cu(b)[28]2.3(BDD)CuPt,BDD,,.BDD,,Si/BDDNb/BDDTi/BDD.BDDCOD,,PbO2.Quan[30]pH.Ti/BDDCOD,20~9000mg·L−1,7.5mg·L−1.1)Si/BDD-,COD,[31,32],.,BDD.Yu[33]BBD,CODK2Cr2O76%,.3COD,n[34~36],COD,ZnO,SnO2TiO2[37~39].,TiO2,.,TiO2,(e−,h+).TiO2,.+22TiOTiO(eh)−⎯⎯→+(16)+eh−+⎯⎯→辐射能(17)(),,.,,,.OH−+h+⎯⎯→·OH(18)H2O+h+⎯⎯→·OH+H+(19)TiO2e−.,Mx+.,TiO2.+0M(XeMx−+⎯⎯→金属离子）（金属单质）(20)O2+e−⎯⎯→·O2−(21)·O2−+H+⎯⎯→·OOH(22)2·OOH⎯⎯→H2O2+O2(23)H2O2+·O2−⎯⎯→·OH+O−+O2(24),.,TiO21),,,.-COD.().:,2007.12~13UVDownloadedtoIP:192.168.0.24On:2019-05-1706:00:48(DO)COD,TiO2COD.,TiO2,TiO2COD,TiO2COD.3.1Karube[40]TiO2,DOCOD,:2+222TiOUV2CHOX+(+)O4CO+H+X+HO2xyzkykzxyxxkk−⎯⎯⎯→－－－(25)X.TiO2,DO,KMnO4,,0~20mg·L−1,.,Karube[41]-COD,,,,COD.3.2TiO2,[42~44]ZnO-KMnO4,TiO2-K2Cr2O7,TiO2-KMnO4COD,1.5~10,10~100,2~100mg·L−1.Cr6+MnO4−,,,,COD.[45]TiO2-K2Cr2O7COD,,0.1~280mg·L−1.,,[46]TiO2-Ce(SO4)2COD,Ce4+Ce3+,Ce3+,1~12mg·L−1,0.4mg·L−1,,.COD.4COD,.,,,.[47]TiO2,COD,:+2TiOhe−+⎯⎯→(26)h++H2O⎯⎯→·OH(ad)+H+(27)3+2+FeeFe−+⎯⎯→(28)+·OH(ad)⎯⎯→CO2+H2O(29)0.5~235mg·L−1,Cl−,NH4+,NO2−,K2Cr2O7.[48]CdS/TiO2COD,TiO2,COD.Zhao[49]TiO2COD,COD.0~360mg·L−1,0.2mg·L−1,NaNO3,.[50~53],TiO2,[54~58],TiO22.UVDownloadedtoIP:192.168.0.24On:2019-05-1706:00:48年11月第54卷第21期3246220V(0.1mg·L−1KF,1mol·L−1NaHSO40.2mol·L−1)TiO2[55](a);(b),TiO2,,,.,,,[55].,[59,60].,.nettotalbackgroundQQQ=−,(30)Qnet.,,netphdQItnFVC==∫,(31)Iph,n,F,V,C.4,Qnet,COD:+22O4H4e2HO−++→(32)netnet1COD(mgL)320003200044QKQnCFV−⋅=×=×=.(33)(33),COD.TiO2COD3.TiO2,TiO2.,,,.,,,.1~10min,.NaH2PO4[61],.0~850mg·L−1[58],CODK2Cr2O7,,Cl−1000mg·L−1,.TiO2,,,.3[55]1,TiO2;2,AgCl/Ag;3,Pt;4,;5,;6,;7,5,.COD,.COD,4[62~64]:(1)K2Cr2O7DownloadedtoIP:192.168.0.24On:2019-05-1706:00:48(HACH-CODmax5B3FEST2001HB2COD-1XP0105SHZ-4);(2)KMnO4(SHZ-33404COD305CE-COD