北京大学电分析课件液液界面电化学及电分析化学简介

液/液界面电化学及电 分析化学简介邵元华,教授CollegeofChemistryandMolecularEngineering PekingUniversity二00二年十一月液/液界面电化学及电 分析化学简介邵元华,教授Coll11.液/液界面电化学的发展历史2.液/液界面电化学的基本原理3.液/液界面电化学的主要研究方法及仪器设备4.液/液界面电化学的现状5.液/液界面电化学的未来展望主要内容1.液/液界面电化学的发展历史主要内容2参考书和文献：1.液/液界面电化学，P.Vanysek著，罗颖华译，汪尔康审校，吉林大学出版社，1987年2.H.H.GiraultandD.J.Schiffrin,inElectroanalyticalChemistry,A.J.Bard.,Ed.;Vol:15,p.1,MarcelDekker,NewYork,19893.H.H.Girault,inModernAspectsofElectrochemistry,J.O.Bockris,B.E.Conway,R.E.White,Eds.;PlenumPress,NewYork,1993,Vol:25,p.14.J.Koryta,Electrochemicalpolarizationphenomenaattheinterfaceoftwoimmiscibleelectrolytesolutions.ElectrochimicaActa,24(1979)293-3005.J.Koryta,Electrochemicalpolarizationphenomenaattheinterfaceoftwoimmiscibleelectrolytesolutions.II.Progresssince1978.ElectrochimicaActa,29(1984)445-4526.VolkovAG,DeamerDW.Liquid-liquidinterfaces.TheoryandMethods.California:CRCPress,1996.参考书和文献：31.BriefIntroductionofElectrochemistryat Liquid/LiquidInterfaces应用电化学方法研究电荷在液/液界面上的转移反应-液/液界面电化学.它是电化学及电分析化学的一个重要分支，也是生物电化学的一个重要组成部分。Charge(electronandion)transferacrossLiquid/Liquid(L/L)interfaces,orOil/Waterinterfaces,ortheinterfacebetweentwoimmiscibleelectrolyteSolutions(ITIES)isoneofthemostfundamentalphysicochemicalprocesses.1.BriefIntroductionofElect4Briefhistory: 1902,NernstandRiesenfeld1906,Cremerpointedoutthattheanalogybetweenthewater/oil/waterconcentrationcellsandbiologicalmembrane1939,VerweyandNiessen,firsttheoreticalpaperontheelectricaldoublelayerandpotentialdistributionatITIES1970s,Gavachetal.inFrance首先认识到L/L界面在一定的实验条件下可以被极化，并用Chronopotentiometry对一些简单离子在Water/Nitrobenzene(W/NB)的转移行为进行了研究。同时用ModifiedVerwey-Niessen(MVN)对实验结果进行了分析。随后Korytaetal.发展了滴水电极及相应的实验装置，并首先研究了中性载体加速离子转移反应。Samecetal.in1979设计了具有iR降补偿性质的四电极恒电位仪，用来记录离子转移反应的伏安图。这样L/L界面电化学才在世界各地得到普及和蓬勃发展。Briefhistory:51980s,汪尔康先生等是中国第一个从事L/L界面电化学研究的group1986,Giraultetal.第一个将微-L/L界面支持在Micropipettes上 1991,Cornetal.应用SHG研究L/L界面 1995，MirkinandBardetal.应用SECM研究L/L界面1997,Y.Shaoetal.第一个将纳米级-L/L界面支持在Nanopipettes上最近几年各种光谱技术也应用于此领域的研究1980s,汪尔康先生等是中国第一个从事L/L界面电化学6WWElectrodeOilGold，Pt，CNB1,2-DCEThedifferencebetweenL/Linterfaceand Electrode/ElectrolyteinterfaceWWElectrodeOilGold，Pt，CNB7Electrochemistryof

L/LinterfacesO+ e=RRedoxReactionsO+ e=RRedoxReactionsMZ(w)=MZ(o)IonTransfertheconventionalElectrochemistryThedifferencebetweenElectrochemistryatL/Linterface andtheconventionalElectrochemistryElectrochemistryofO+ e8ChemicalsensorsElectrochemistryH+，pHK+,Na+,NH4+Cl-,Ac+O+e=RElectroactivespeciesNonelectroactivespeciesL/LInterfaceElectrochemistryatL/LInterfacesisthebridgebetweentheconventionalelectrochemistryandChemicalsensorsChemicalsensorsElectrochemist9ElectrochemistryatLiquid/LiquidInterfacesisafastwaytoselectreceptorsformakingchemicalsensorsElectrochemistryatLiquid/10ElectrodeOBiologicalMembraneModelL/LInterfaceElectrode/electrolyte

Membrane/solutionArtificial,supportedmembraneandBLMElectrodeOBiologicalMembrane11ElectrochemistryatL/LInterfacesNewBranchofElectrochemistryMechanismofChemicalsensorsPhaseTransfercatalyticreactionsMimickingbiologicalmembranesResearchSignificanceandapplicationsofElectrochemistryatL/LInterfacesExtractionMechanismElectrochemistryNewBranchofM122.液/液界面电化学的基本原理2.1.EquilibriumconditionsandNernstpotentialIngeneralatLiquid/Liquidinterfaces,therearetwotypesofchargepartition: (A)thetransferofanionMwiththechargenumberzfromthephasewtothephaseoandthereverse: MZ(w) =MZ(o)M+(w) +L(o) =ML+(o)(B)theelectrontransferbetweenaredoxcoupleO1/R1inthephasewandaredoxcoupleO2/R2inthephaseo,whichcanberepresentedas:O1(w)+R2(o)=R1(w)+O2(o)

2.液/液界面电化学的基本原理2.1.Equilibrium13NernstEquationsNernstEquations14Liquid/Liquidinterfaceshavebeenclassifiedintotheideal-polarizedinterfaceandno-polarizedinterface.2.2.SingleionGibbsenergyoftransferTATBassumptionLiquid/Liquidinterfaceshave15北京大学电分析课件液液界面电化学及电分析化学简介162.3.SolvationofIonBornequation2.4.Interfacialstructureandtheiontransfermechanism(A)MVNMODEL(B)GSMODEL2.3.SolvationofIon2.4.Interf17北京大学电分析课件液液界面电化学及电分析化学简介18北京大学电分析课件液液界面电化学及电分析化学简介192.5.SolventsandbaseelectrolytesThereareover20organicsolventswhichhavebeentestedintheITIESstudiessofar.AspointedoutbyKorytaet.al.,thefollowingthreerequirementshavebeencommonlyusedtochoosetheorganicsolvent:(1).Thesolubilityofsolventinwaterandwaterinthesolventmustbeverysmall.(2).Thesolventmustbesufficientlypolartopromotesufficientdissociationofthesupportingelectrolyteandthuskeepingenoughconductivityofthesolution.(3).Thedensityofthesolventshoulddiffersignificantlyfromthatofaqueousphaseinordertogetaphysicallystablel/linterface.2.5.Solventsandbaseelectrol20Atpresent,themostcommonlyusedorganicsolventsarenitrobenzene(NB)and1,2-dichloroethane(1,2-DCE).Someothersolventshavebeentriedinthepasttwodecades,forexample,propiophenone,4-isopropyl-1-methyl-2-nitrobenzene,dichloro-methane,nitrotulene,chloroform,anilineetc.Inordertogetmoreflexiblechoice,organicsolventmixtureshavebeenalsoemployed,forexample,nitrobenzene+chlorobenzene,NB+benzonitrileandNB+benzene.Baseelectrolytes:TBATPB(tetrabutylammoniumtetraphenylborate),TBATPBCl,CVTPB,BTPPATPB(Bis[triphenylphosphoranylidene]ammoniumtetraphenylborate)Atpresent,themostcommonly21北京大学电分析课件液液界面电化学及电分析化学简介22北京大学电分析课件液液界面电化学及电分析化学简介233.液/液界面电化学的主要研究方法 及仪器设备Almostalltheinstrumentshavebeenusedtostudyclassicalelectrochemistrycanbeusedtoinvestigatethechargetransferatliquid/Liquidinterfaces.4-electrodepotentiostat--------BigiRdropaqueoussolutiondropping(ascending)electrodetwo-electrodesystem--------microelectrodesRecently,wedevelopedanoveltechniquetostudyITIESwiththree-electrodesetupwiththehelpofthephaseratio.Thus,allelectrochemicallabscandoresearchonthissubjects.3.液/液界面电化学的主要研究方法Almostallth24北京大学电分析课件液液界面电化学及电分析化学简介252-电极系统2-电极系统26应用于液/液界面电化学研究的升水电极-四电极系统应用于液/液界面电化学研究的27北京大学电分析课件液液界面电化学及电分析化学简介28北京大学电分析课件液液界面电化学及电分析化学简介29新的技术，例如:SHG(Secondharmonicgeneration)microelectrodes,micropipettesandnano-pipettesSECMFemto-laserSimulationsThinfilms现已用在L/LInterfaces的研究。各种电化学方法和技术新的技术，例如:各种电化学方法和技术304.液/液界面电化学的现状Structure: MVNModelandGSModelMechanism: FacilitatediontransfermechanismKinetics: Butler-Volmerequation,Marcustheory Nanometeropipettes SECMApplications:

Thinfilms(solarcell,drugdelivery)4.液/液界面电化学的现状31目前国际上液/液界面电化学研究 存在的主要问题1.界面结构未知!MVN模型和混合溶剂层模型(GS)2.可供选择作为有机相的有机溶剂数目有限3.没有很好的获取转移反应动力学的实验手段4.iR(i-电流，R-电阻，iR降是由于溶液中电阻所引起的干扰)降及充电电流较常规电化学更加严重目前国际上液/液界面电化学研究1.界面结构未知!MVN32HowtosolvetheseProblemsMicroelectrodes:SolidandNano-andMicropipettes+ScanningElectrochemicalMicroscopy,SECMHowtosolvetheseProblemsMic33ElectrochemistryatL/LInterfacesArtificialMembrane/ElectrolyteInterfacesBLMArtificialMembraneandBiosensorsModifiedL/LInterfacesMicroelectrodesNano-andMicropipettesSECMElectrochemistryArtificialMe34TheSEMdiagramsofNano-andMicropipettesMicropipettesNanopipettesTheSEMdiagramsofMicropipett35MicropipettesTheta()MicropipetteMicropipettesTheta()Micropip36TheSEMdiagramsofNano-andMicropipettesMicropipettesNanopipettes我们group可以制备内径从几个nm到十几个m的玻璃纳、微米管TheSEMdiagramsofMicropipett37AqueousPhaseOrganicPhaseAqueousPhaseOrganicPhaseAsymmetricDiffusionFieldAqueousPhaseOrganicPhaseAque38TBATPBassupportingelectrolyteinDCETBATPBClassupportingelectrolyteinDCEBTPPATPBassupportingelectrolyteinDCEMicropipetteasatooltodeterminetheionicspecieslimitingthepotentialwindowatL/LInterfacesTBATPB(Tetrabutyalammoniumtetraphenylborate)TBATPBCl(tetrabutyl-ammoniumtetrakis[4-chlorophenyl]borate)BTPPATPB(Bis[triphosphor-anylidene]ammoniumtetraphenyl-borate)1,2-dichloroethane(DCE)TBATPBassupportingTBATPBCl39Ag/AgCl/0.01MTBACl/0.25mMDB18C6+0.01MTBATPBCl//0.01MKCl/AgCl/AgIdentifythedifferentmechanismsAg/AgCl/0.01MTBACl/0.25mMDB18C40ACTTOCTICTIDwowowowoIdentifyofdifferentmechanismsoffacilitatediontransfersACTTOCTICTIDwowowowoIdentifyo41北京大学电分析课件液液界面电化学及电分析化学简介42Idisk=4nFaDCIpip=3.35nFaDCWhyIpipisabout2.63timesbiggerthanIdisk?Silanizationplaysveryimportantrolehere!Anal.Chem.,1998,70,p3155-3161Idisk=4nFaDCIpip=3.35nFaDCW433.4E-93.4E-944北京大学电分析课件液液界面电化学及电分析化学简介45Nanometer-sizedL/LInterface纳米管NanopipetAqueousPhaseNanometer-sized纳米管Aqueous46Nano-ITIESkofrom0.1cm/sto10cm/sA54nmradiusB5nmradiusJ.Am.Chem.Soc.,1997,119,8103K+(w)+DB18C6(DCE)=[K+DB18C6](DCE)

Nano-ITIESJ.Am.Chem.Soc.,199747北京大学电分析课件液液界面电化学及电分析化学简介48J.Am.Chem.Soc.,1998,120,12700科学意义和创新点：第一次在实验上实现了非氧化还原物质的Generation/CollectionMode。对于测量反应中间产物和快速电荷转移反应动力学有重要意义。J.Am.Chem.Soc.,1998,120,12749北京大学电分析课件液液界面电化学及电分析化学简介50Thephotoof-micropipetteundermicroscopeThephotoof-micropipetteun51北京大学电分析课件液液界面电化学及电分析化学简介52“Non-solution”L/LInterfaceElectrochemistry“Non-solution”L/LInterface53Generator(1)andcollector(2)voltammogramsofthetransferofK+betweenwaterandDCEcontainingDB18C6igvs.Egandicvs.Egcurvesobtainedwithanaqueousfilmlinkingtwobarrelsofthe-pipetGenerator(1)andcollectorig54Detectionofammoniaintheair.Cyclicvoltammogamsobtainedwitha-pipetexposedtoair(1)andammoniavaporaboveits2MsolutionDetectionofammoniaintheai55ThepotentialwindowsdependupontheamountofAgar.Scanrateis30mV/s.Theradiusofthemicropipetteis4m，curves1、2、3and4correspondingto25%、10%、1%and0.5%ofAgar,respectivelyAgar-waterMicroelectrodeThepotentialwindowsdependu56CyclicVoltammogramsofK+transferfacilitatedbyDB18C6.KClis0.1M，Scanrate=30mV/s。Theradiusofthemicropipetteis3μm。Curves1,2and3correspondingtotheconcentrationsofDB18C60.25,0.5and1.0mM.123CyclicVoltammogramsofK+tra57(a)r=12µm(b)r=3µm.(a)r=12µm(b)r=3µm.58Planarstructure(a)and3Dstructure(b)ofanewtypeofcrownetherCyclicvoltammogramwithscanrateof10mV/sfora14m-radiusmicropipetteelectrodewith100mMNaClinaqueousphaseand10mMTBATPBinorganicphasePlanarstructure(a)and3DCy59Alkalimetalionstransferacrossthewater/DCEinterfaceFacilitatedbyDB18C6Alkalimetalionstransferacr60Ionradius(r),formaltransferpotentialofrelevantalkalimetalionsandtheassociationconstantsofcomplex(M-DB18C6)+inDCEphaseIonradius(r),formaltransfe61冰/有机相溶液界面研究示意图冰/有机相溶液界面研究示意图62应用常规三电极装置(恒电位仪)研究电荷在液/液界 面上的转移反应实验装置图Aqueousphase应用常规三电极装置(恒电位仪)研究电荷在液/液界Aqueou63异相电子转移反应创新点：用四(二)电极系统所能研究的体系，如离子、加速离子和电子转移反应，均能用常规三电极系统进行研究，这对于普及和发展此领域有重要意义。异相电子转移反应创新点：用四(二)64Ag/AgClAg/AgCl655.液/液界面电化学的未来展望InterfacialstructureApplicationsBiologicalMembranesKineticsandPhaseTransferCatalysisSolarcellsDrugDeliveryandpharmacokinetics5.液/液界面电化学的未来展望66液/液界面电化学及电 分析化学简介邵元华,教授CollegeofChemistryandMolecularEngineering PekingUniversity二00二年十一月液/液界面电化学及电 分析化学简介邵元华,教授Coll671.液/液界面电化学的发展历史2.液/液界面电化学的基本原理3.液/液界面电化学的主要研究方法及仪器设备4.液/液界面电化学的现状5.液/液界面电化学的未来展望主要内容1.液/液界面电化学的发展历史主要内容68参考书和文献：1.液/液界面电化学，P.Vanysek著，罗颖华译，汪尔康审校，吉林大学出版社，1987年2.H.H.GiraultandD.J.Schiffrin,inElectroanalyticalChemistry,A.J.Bard.,Ed.;Vol:15,p.1,MarcelDekker,NewYork,19893.H.H.Girault,inModernAspectsofElectrochemistry,J.O.Bockris,B.E.Conway,R.E.White,Eds.;PlenumPress,NewYork,1993,Vol:25,p.14.J.Koryta,Electrochemicalpolarizationphenomenaattheinterfaceoftwoimmiscibleelectrolytesolutions.ElectrochimicaActa,24(1979)293-3005.J.Koryta,Electrochemicalpolarizationphenomenaattheinterfaceoftwoimmiscibleelectrolytesolutions.II.Progresssince1978.ElectrochimicaActa,29(1984)445-4526.VolkovAG,DeamerDW.Liquid-liquidinterfaces.TheoryandMethods.California:CRCPress,1996.参考书和文献：691.BriefIntroductionofElectrochemistryat Liquid/LiquidInterfaces应用电化学方法研究电荷在液/液界面上的转移反应-液/液界面电化学.它是电化学及电分析化学的一个重要分支，也是生物电化学的一个重要组成部分。Charge(electronandion)transferacrossLiquid/Liquid(L/L)interfaces,orOil/Waterinterfaces,ortheinterfacebetweentwoimmiscibleelectrolyteSolutions(ITIES)isoneofthemostfundamentalphysicochemicalprocesses.1.BriefIntroductionofElect70Briefhistory: 1902,NernstandRiesenfeld1906,Cremerpointedoutthattheanalogybetweenthewater/oil/waterconcentrationcellsandbiologicalmembrane1939,VerweyandNiessen,firsttheoreticalpaperontheelectricaldoublelayerandpotentialdistributionatITIES1970s,Gavachetal.inFrance首先认识到L/L界面在一定的实验条件下可以被极化，并用Chronopotentiometry对一些简单离子在Water/Nitrobenzene(W/NB)的转移行为进行了研究。同时用ModifiedVerwey-Niessen(MVN)对实验结果进行了分析。随后Korytaetal.发展了滴水电极及相应的实验装置，并首先研究了中性载体加速离子转移反应。Samecetal.in1979设计了具有iR降补偿性质的四电极恒电位仪，用来记录离子转移反应的伏安图。这样L/L界面电化学才在世界各地得到普及和蓬勃发展。Briefhistory:711980s,汪尔康先生等是中国第一个从事L/L界面电化学研究的group1986,Giraultetal.第一个将微-L/L界面支持在Micropipettes上 1991,Cornetal.应用SHG研究L/L界面 1995，MirkinandBardetal.应用SECM研究L/L界面1997,Y.Shaoetal.第一个将纳米级-L/L界面支持在Nanopipettes上最近几年各种光谱技术也应用于此领域的研究1980s,汪尔康先生等是中国第一个从事L/L界面电化学72WWElectrodeOilGold，Pt，CNB1,2-DCEThedifferencebetweenL/Linterfaceand Electrode/ElectrolyteinterfaceWWElectrodeOilGold，Pt，CNB73Electrochemistryof

L/LinterfacesO+ e=RRedoxReactionsO+ e=RRedoxReactionsMZ(w)=MZ(o)IonTransfertheconventionalElectrochemistryThedifferencebetweenElectrochemistryatL/Linterface andtheconventionalElectrochemistryElectrochemistryofO+ e74ChemicalsensorsElectrochemistryH+，pHK+,Na+,NH4+Cl-,Ac+O+e=RElectroactivespeciesNonelectroactivespeciesL/LInterfaceElectrochemistryatL/LInterfacesisthebridgebetweentheconventionalelectrochemistryandChemicalsensorsChemicalsensorsElectrochemist75ElectrochemistryatLiquid/LiquidInterfacesisafastwaytoselectreceptorsformakingchemicalsensorsElectrochemistryatLiquid/76ElectrodeOBiologicalMembraneModelL/LInterfaceElectrode/electrolyte

Membrane/solutionArtificial,supportedmembraneandBLMElectrodeOBiologicalMembrane77ElectrochemistryatL/LInterfacesNewBranchofElectrochemistryMechanismofChemicalsensorsPhaseTransfercatalyticreactionsMimickingbiologicalmembranesResearchSignificanceandapplicationsofElectrochemistryatL/LInterfacesExtractionMechanismElectrochemistryNewBranchofM782.液/液界面电化学的基本原理2.1.EquilibriumconditionsandNernstpotentialIngeneralatLiquid/Liquidinterfaces,therearetwotypesofchargepartition: (A)thetransferofanionMwiththechargenumberzfromthephasewtothephaseoandthereverse: MZ(w) =MZ(o)M+(w) +L(o) =ML+(o)(B)theelectrontransferbetweenaredoxcoupleO1/R1inthephasewandaredoxcoupleO2/R2inthephaseo,whichcanberepresentedas:O1(w)+R2(o)=R1(w)+O2(o)

2.液/液界面电化学的基本原理2.1.Equilibrium79NernstEquationsNernstEquations80Liquid/Liquidinterfaceshavebeenclassifiedintotheideal-polarizedinterfaceandno-polarizedinterface.2.2.SingleionGibbsenergyoftransferTATBassumptionLiquid/Liquidinterfaceshave81北京大学电分析课件液液界面电化学及电分析化学简介822.3.SolvationofIonBornequation2.4.Interfacialstructureandtheiontransfermechanism(A)MVNMODEL(B)GSMODEL2.3.SolvationofIon2.4.Interf83北京大学电分析课件液液界面电化学及电分析化学简介84北京大学电分析课件液液界面电化学及电分析化学简介852.5.SolventsandbaseelectrolytesThereareover20organicsolventswhichhavebeentestedintheITIESstudiessofar.AspointedoutbyKorytaet.al.,thefollowingthreerequirementshavebeencommonlyusedtochoosetheorganicsolvent:(1).Thesolubilityofsolventinwaterandwaterinthesolventmustbeverysmall.(2).Thesolventmustbesufficientlypolartopromotesufficientdissociationofthesupportingelectrolyteandthuskeepingenoughconductivityofthesolution.(3).Thedensityofthesolventshoulddiffersignificantlyfromthatofaqueousphaseinordertogetaphysicallystablel/linterface.2.5.Solventsandbaseelectrol86Atpresent,themostcommonlyusedorganicsolventsarenitrobenzene(NB)and1,2-dichloroethane(1,2-DCE).Someothersolventshavebeentriedinthepasttwodecades,forexample,propiophenone,4-isopropyl-1-methyl-2-nitrobenzene,dichloro-methane,nitrotulene,chloroform,anilineetc.Inordertogetmoreflexiblechoice,organicsolventmixtureshavebeenalsoemployed,forexample,nitrobenzene+chlorobenzene,NB+benzonitrileandNB+benzene.Baseelectrolytes:TBATPB(tetrabutylammoniumtetraphenylborate),TBATPBCl,CVTPB,BTPPATPB(Bis[triphenylphosphoranylidene]ammoniumtetraphenylborate)Atpresent,themostcommonly87北京大学电分析课件液液界面电化学及电分析化学简介88北京大学电分析课件液液界面电化学及电分析化学简介893.液/液界面电化学的主要研究方法 及仪器设备Almostalltheinstrumentshavebeenusedtostudyclassicalelectrochemistrycanbeusedtoinvestigatethechargetransferatliquid/Liquidinterfaces.4-electrodepotentiostat--------BigiRdropaqueoussolutiondropping(ascending)electrodetwo-electrodesystem--------microelectrodesRecently,wedevelopedanoveltechniquetostudyITIESwiththree-electrodesetupwiththehelpofthephaseratio.Thus,allelectrochemicallabscandoresearchonthissubjects.3.液/液界面电化学的主要研究方法Almostallth90北京大学电分析课件液液界面电化学及电分析化学简介912-电极系统2-电极系统92应用于液/液界面电化学研究的升水电极-四电极系统应用于液/液界面电化学研究的93北京大学电分析课件液液界面电化学及电分析化学简介94北京大学电分析课件液液界面电化学及电分析化学简介95新的技术，例如:SHG(Secondharmonicgeneration)microelectrodes,micropipettesandnano-pipettesSECMFemto-laserSimulationsThinfilms现已用在L/LInterfaces的研究。各种电化学方法和技术新的技术，例如:各种电化学方法和技术964.液/液界面电化学的现状Structure: MVNModelandGSModelMechanism: FacilitatediontransfermechanismKinetics: Butler-Volmerequation,Marcustheory Nanometeropipettes SECMApplications:

Thinfilms(solarcell,drugdelivery)4.液/液界面电化学的现状97目前国际上液/液界面电化学研究 存在的主要问题1.界面结构未知!MVN模型和混合溶剂层模型(GS)2.可供选择作为有机相的有机溶剂数目有限3.没有很好的获取转移反应动力学的实验手段4.iR(i-电流，R-电阻，iR降是由于溶液中电阻所引起的干扰)降及充电电流较常规电化学更加严重目前国际上液/液界面电化学研究1.界面结构未知!MVN98HowtosolvetheseProblemsMicroelectrodes:SolidandNano-andMicropipettes+ScanningElectrochemicalMicroscopy,SECMHowtosolvetheseProblemsMic99ElectrochemistryatL/LInterfacesArtificialMembrane/ElectrolyteInterfacesBLMArtificialMembraneandBiosensorsModifiedL/LInterfacesMicroelectrodesNano-andMicropipettesSECMElectrochemistryArtificialMe100TheSEMdiagramsofNano-andMicropipettesMicropipettesNanopipettesTheSEMdiagramsofMicropipett101MicropipettesTheta()MicropipetteMicropipettesTheta()Micropip102TheSEMdiagramsofNano-andMicropipettesMicropipettesNanopipettes我们group可以制备内径从几个nm到十几个m的玻璃纳、微米管TheSEMdiagramsofMicropipett103AqueousPhaseOrganicPhaseAqueousPhaseOrganicPhaseAsymmetricDiffusionFieldAqueousPhaseOrganicPhaseAque104TBATPBassupportingelectrolyteinDCETBATPBClassupportingelectrolyteinDCEBTPPATPBassupportingelectrolyteinDCEMicropipetteasatooltodeterminetheionicspecieslimitingthepotentialwindowatL/LInterfacesTBATPB(Tetrabutyalammoniumtetraphenylborate)TBATPBCl(tetrabutyl-ammoniumtetrakis[4-chlorophenyl]borate)BTPPATPB(Bis[triphosphor-anylidene]ammoniumtetraphenyl-borate)1,2-dichloroethane(DCE)TBATPBassupportingTBATPBCl105Ag/AgCl/0.01MTBACl/0.25mMDB18C6+0.01MTBATPBCl//0.01MKCl/AgCl/AgIdentifythedifferentmechanismsAg/AgCl/0.01MTBACl/0.25mMDB18C106ACTTOCTICTIDwowowowoIdentifyofdifferentmechanismsoffacilitatediontransfersACTTOCTICTIDwowowowoIdentifyo107北京大学电分析课件液液界面电化学及电分析化学简介108Idisk=4nFaDCIpip=3.35nFaDCWhyIpipisabout2.63timesbiggerthanIdisk?Silanizationplaysveryimportantrolehere!Anal.Chem.,1998,70,p3155-3161Idisk=4nFaDCIpip=3.35nFaDCW1093.4E-93.4E-9110北京大学电分析课件液液界面电化学及电分析化学简介111Nanometer-sizedL/LInterface纳米管NanopipetAqueousPhaseNanometer-sized纳米管Aqueous112Nano-ITIESkofrom0.1cm/sto10cm/sA54nmradiusB5nmradiusJ.Am.Chem.Soc.,1997,119,8103K+(w)+DB18C6(DCE)=[K+DB18C6](DCE)

Nano-ITIESJ.Am.Chem.Soc.,1997113北京大学电分析课