北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用

FundamentalsofElectroanalyticalChemistry

電分析化學(xué)原理、方法和應(yīng)用

YuanhuaShao（邵元華，教授Ph.D.） CollegeofChemistryandMolecularEngineering PekingUniversity Fundamentalsof1Outline:

1.Principles 2.Methods 3.Applications

Outline:2Part1 Principles1. Introduction 2. ElectrochemicalCell:Thermodynamic PropertiesandElectrodePotentials 3. TheInterfacialRegion 4. FundamentalsofKineticsand MechanismofElectrodeReactions 5. MassTransport 6. KineticsandTransportinElectrode Reactions Part2 Methods 1 ElectrochemicalExperiments 2 HydrodynamicElectrodes 主要內(nèi)容Part1 Principles主要內(nèi)容3 Part2 Methods 3 CyclicVoltammetryandLinearSweep Techniques 4 StepandPulseTechniques 5 ImpedanceMethods 6 Non-ElectrochemicalProbesofElectrodes andElectrodeProcesses Part3 Applications 1 PotentiometricSensors 2 AmperometricandVoltammetricSensors 3 ElectrochemistryinIndustry 4 Corrosion 5 Bioelectrochemistry主要內(nèi)容 Part2 Methods主要內(nèi)容4GeneralBooks:1*A.J.BardandL.R.Faulkner,Electrochemicalmethods,fundamentalsandapplications,Wiley,NewYork,1980(2ndEdition,2001)2*C.M.A.BrettandA.M.O.Brett,Electrochemistry,Principles,Methods,andApplications,Oxford,19933*SouthamptonElectrochemistryGroup,NewInstrumentalMethodsinElectrochemistry,EllisHorwood,Chichester,19854A.M.Bond,ModernpolarographicmethodsinAnalyticalChemistry,Dekker,NewYork,19805J.Koryta,PrinciplesofElectrochemistry,Wiley,19876P.Delahay,NewInstrumentalmethodsinElectrochemistry,19547R.N.Adams,Electrochemistryatsolidelectrodes,19698*J.O'M.BockrisandA.N.Reddy,ModernElectrochemistry,Plenum,NewYork,19709電化學(xué)基礎(chǔ)，張祖訓(xùn)，汪爾康，200010生命科學(xué)中的電分析化學(xué)，彭圖治，楊麗菊編著,199911*電極過(guò)程動(dòng)力學(xué)導(dǎo)論，查全性，1976(19872ndEdition)12電化學(xué)研究方法，田昭武，198413*電化學(xué)測(cè)定方法，騰島昭等著，陳震等譯，199514電分析化學(xué)，蒲國(guó)剛，袁倬斌，吳守國(guó)編著，1993GeneralBooks:5Series1.ElectroanalyticalChemistry,ed.A.J.Bard2.ModernAspectsofElectrochemistry,eds.J.O'M.Bockris,B.E.Conway,etal.,

JournalsNature,Science,JACS,Angew.Chem.IntEditAnal.Chem.,(May1,2000)J.Phys.Chem.B.,J.Electroanal.Chem.,ElectrochimicaActa,J.Electrochem.Society.,Electroanalysis,ElectrochemicalandSolidStateLetters,J.AppliedElectrochemistry,ElectrochemistryCommunications,J.SolidStateElectrochemistrySeries6Reviews:AccountsofChemicalResearchAnalyticalChemistryAnnualReviewsofPhysicalChemistryChemicalReviewsWebsites:/estir/Reviews:7ChapterOne(第一章)

Introduction(導(dǎo)言)

1.1 Introduction1.2 ScopeofElectroanalyticalChemistry1.3 BriefHistory1.4 ExamplesChapterOne(第一章)81.1 Introduction(導(dǎo)言)電分析化學(xué)和電化學(xué)：兩者沒(méi)有區(qū)別！基本原理相同，僅研究的側(cè)重點(diǎn)可能不同。電化學(xué)池：

原電池(GalvanicCell)：化學(xué)能電能 電解池(ElectrolyticCell)：電能化學(xué)能一個(gè)簡(jiǎn)單的電分析化學(xué)實(shí)驗(yàn)：組成：工作(研究)電極(W),參比電極(R)，輔助(對(duì))電極(C),電解質(zhì)溶液，恒電位儀(potentiostat),PC計(jì)算機(jī)(接口+軟件)。研究重點(diǎn)研究重點(diǎn)9北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用10ElectroanalyticalChemistry

isthebranchofchemistryconcernedwiththeinterrelationofelectricalandchemicaleffects.Alargepartofthisfielddealswiththestudyofchemicalchangescausedbythepassageofanelectriccurrentandtheproductionofelectricalenergybychemicalreactions.Infact,thefieldofelectrochemistryencompassesahugearrayofdifferentphenomena(e.g.,electrophoresisandcorrosion),devices(electrochromicdisplays,electro-analyticalsensors,batteries,andfuelcells),andtechnologies(theelectroplatingofmetalsandthelarge-scaleproductionofaluminumandchlorine).Whilethebasicprinciplesofelectro-chemistrydiscussedinthistextapplytoallofthese,themainemphasishereisontheapplicationofelectrochemicalmethodstothestudyofchemicalsystems.1.2ScopeofElectroanalyticalChemistryElectroanalyticalChemistryis11Scientistsmakeelectrochemicalmeasurementsonchemicalsystemsforavarietyofreasons.Theymaybeinterestedinobtainingthermodynamicdataaboutareaction.Theymaywanttogenerateanunstableintermediatesuchasaradicalionandstudyitsrateofdecayoritsspectroscopicproperties.Theymayseektoanalyzeasolutionfortraceamountsofmetalionsororganicspecies.Intheseexamples,electro-chemicalmethodsareemployedastoolsinthestudyofchemicalsystemsinjustthewaythatspectroscopicmethodsarefrequentlyapplied.Therearealsoinvestigationsinwhichtheelectrochemicalpropertiesofthesystemsthemselvesareofprimaryinterest,forexample,inthedesignofanewpowersourceorfortheelectrosynthesisofsomeproduct.Manyelectrochemicalmethodshavebeendevised.Theirapplicationrequiresanunderstandingofthefundamentalprinciplesofelectrodereactionsandtheelectricalpropertiesofelectrode-solutioninterfaces.Scientistsmakeelectrochemica12VariablesaffectingtherateofanelectrodereactionVariablesaffectingtherateo131.3電化學(xué)的簡(jiǎn)史：LuigiGalvani(1737-1798):從1786年開(kāi)始，進(jìn)行著名的"animal electricity“實(shí)驗(yàn)－解剖青蛙AlessandroVolta(1745-1827):HumphryDavy(1778-1829):MichaelFaraday(1791-1867):Grove: 燃料電池(1839)Lippmann: 1873Helmholtz: 雙電層(1879)F.G.Cottrell: Cottrell公式1902W.Nernst: Nernst公式1904Tafel: Tafel公式1905Gouy,Chapman: 1905Stern:1924Heyrovsky,Shikata: Polarograph1925(1959NobelPrize Winner)1.1.3電化學(xué)的簡(jiǎn)史：14J.Butler,M.Volmer: Butler-Volmer公式1924-1930P.Delahay,Gerischer,Frumkin,Levich,Bakeretal:1950sto1960s發(fā)展了各種理論，研究方法等R.Marcus: 1950s-1960s,ElectronTransferTheory(NobelPrize Winner,1992)T.Kuwana: 1960s,光譜電化學(xué)Gavach,Korytaetal:1970s開(kāi)始研究液/液界面電化學(xué)MillerandMurray:1975,化學(xué)修飾電極M.Fleischmann,A.Bewicketal:1970sto1980s,insitu光譜、波譜電化學(xué)M.Fleischmann,W.Wightmanetal:ultramicroelectrodes1970s-1980sA.J.Bard: SECM,1989Sagivetal: 1980s,self-assembledmembranesP.Hansmaetal:STM-Electrochemistry,1980sLiorZhangorWang:??????J.Butler,M.Volmer: Butler-Vo15研究方法：穩(wěn)態(tài)和暫態(tài)技術(shù)：光譜、波譜技術(shù)：表面技術(shù)：SPM(ScanningProbe Microscopy)研究方法：16(a)Generalprincipleofstudyingasystembyapplicationofanexcitation(orperturbation)andobservationofresponse.(b)Inaspectrophotometricexperiment,theexcitationislightofdifferentwavelengths(),andtheresponseistheabsorbance(A)curve.(c)Inanelectrochemical(potentialstep)experiment,theexcitationistheapplicationofapotentialstep,andtheresponseistheobservedi-tcurve.(a)Generalprincipleofstudyi17應(yīng)用領(lǐng)域：1.化學(xué)電源(電池,燃料電池)：2.電解電鍍：3.腐蝕：4.電化學(xué)合成：5.電催化：6.生物電分析化學(xué)：7.電化學(xué)傳感器：Ion-SelectiveElectrodes8.TAS9.單細(xì)胞和單分子測(cè)量應(yīng)用領(lǐng)域：18白鼠腦神經(jīng)遞質(zhì)活體伏安分析示意圖白鼠腦神經(jīng)遞質(zhì)活體伏安分析示意圖19北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用20Polarography(極譜)andVoltammetry(伏安法)的區(qū)別？polarographyAclassicalelectroanalyticaltechniquediscoveredin1922byJ.Heyrovsky,forwhichhewasawardedtheNobelPrizeforChemistryin1959.Essentially,itislinear-sweepvoltammetryusingadropping-mercuryelectrodeforworkingelectrodeandalargemercurypoolascounterelectrode.voltammetryAnelectrochemicalmeasuringtechniqueusedforelectrochemicalanalysisorforthedeterminationofthekineticsandmechanismofelectrodereactions."Voltammetry"isafamilyoftechniqueswiththecommoncharacteristicsthatthepotentialoftheworkingelectrodeiscontrolled(typicallywithapotentiostat)andthecurrentflowingthroughtheelectrodeismeasured.Inoneofthemostcommonapplicationsofthetechnique,thepotentialisscannedlinearlyintime;thisiscalledthe"linear-sweepvoltammetry,""LSV,"or"LV.""Cyclicvoltammetry(CV)"isalinear-sweepvoltammetrywiththescancontinuedinthereversedirectionattheendofthefirstscan,thiscyclecanberepeatedanumberoftimes.Polarography(極譜)andVoltamme21Figure1.Basicvoltammetry.(a)Apparatusforvoltammetrywithatwo-electrodecell,appropriateforuseinsolutionsoflowresistanceandmicroelectrodes.(b)Apparatusforvoltammetrywithathree-electrodecell.Inpracticeapotentiostatthatautomaticallycontrolsthepotentialoftheworkingelectrodewithrespecttoareferenceelectrodeisused.Question:兩電極和三電極系統(tǒng)有什么區(qū)別？為什么一般的電化學(xué)研究需用三電極系統(tǒng)？May1,2000;pp.346A-352A(AnalyticalChemistry)VoltammetryRetrospectiveAllenJ.Bard,UniversityofTexas-AustinandCynthiaG.Zoski,UniversityofRhodeIslandFigure1.Basicvoltammetry.Q22北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用23Three-dimensionalvoltammetry.

Representationofthethree-dimensionalI-t-EsurfaceforaNernstianreaction.Thetypicalsteady-statevoltammogramrepresentsacutparalleltotheI-Eplane.(b)Acutrepresentingalinearpotentialsweepacrossthissurface.(AdaptedfromRef.6.)Three-dimensionalvoltammetry.24電分析化學(xué)的特點(diǎn)：

interdisciplinarynatureandversatility異相反應(yīng)，與表面、界面及相關(guān)的區(qū)域有關(guān)，可控催化。電分析化學(xué)的特點(diǎn)：25電化學(xué)及電分析化學(xué)的發(fā)展趨勢(shì)1，與納米技術(shù)相結(jié)合2，與生物、生命科學(xué)相結(jié)合

信息科學(xué)生命科學(xué)能源科學(xué)環(huán)境科學(xué)材料科學(xué)電化學(xué)及電分析化學(xué)的發(fā)展趨勢(shì)1，與納米技術(shù)相結(jié)合信息科學(xué)26

ChapterTwo(第二章)ElectrochemicalCells:Thermodynamic PropertiesandElectrodePotentials2.1 Introduction,Galvanicandelectrolyticcells2.2 Thecellpotentialofanelectrochemicalcell2.3 Calculationofcellpotential:activitiesorconcentrations? ChapterTwo(第二章)272.4 Electrodeclassification2.5 Referenceelectrodes2.6 Themovementofionsinsolution:diffusion and migration2.7 Conductivityandmobility2.8 Liquidjunctionpotentials2.9 Ion-SelectiveElectrodesandBiomembranes北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用282.1 導(dǎo)言，原電池和電解池1.Whyisitthathalf-reactionsinelectrochemicalcellsproceedspontaneouslyinonedirectionandfurnishcurrent?2.Whatistheeffectofthesaltbridge?3.Whatistheeffectofionmigration?4.Whatisabsoluteandrelativepotentialdifferences?Zn/Zn2+(aq),Cu2+(aq)/Cu Hg/Hg2Cl2/Cl-(aq),Zn2+(aq)/ZnAg/AgCl/TBACl(aq)/TBATPB(o)//LiCl(aq)/AgCl/Ag根據(jù)IUPAC的規(guī)定，左邊的半反應(yīng)是氧化反應(yīng)(anode,陽(yáng)極)，右邊的半反應(yīng)是還原反應(yīng)(cathode,陰極)2.1 導(dǎo)言，原電池和電解池29Ecell=Eright-EleftPotential:電位，電勢(shì)但物理學(xué)，“位”與“勢(shì)”的概念是不同的。空間某點(diǎn)的電位，是將單位正電荷從無(wú)窮遠(yuǎn)處(或以無(wú)任何力作用的無(wú)窮遠(yuǎn)的真空為參考點(diǎn))移到該點(diǎn)所做的功，它具有絕對(duì)的意義。電勢(shì)則是空間兩點(diǎn)的電位差(或電位降)，如金屬和其離子溶液所形成的電極電勢(shì)，實(shí)際上是金屬和溶液兩相之間電位差的一種衡量，又是該電極電勢(shì)與標(biāo)準(zhǔn)電極電勢(shì)差的一種衡量。Ecell=Eright-EleftPotentia30電化學(xué)池： anode cathode

原電池(GalvanicCell)：化學(xué)能電能 - +電解池(ElectrolyticCell)：電能化學(xué)能+ -一些電化學(xué)池既可以作為原電池，也可以作為電解池，例如；汽車用的Lead-acid電池，在放電時(shí)是原電池，反應(yīng)為：anode(-ve): Pb+SO42-

→PbSO4 +2ecathode(+ev): PbO2 +4H+ +SO42-+2e→2H2O+PbSO4在充電時(shí)為電解池，上述半反應(yīng)倒過(guò)來(lái)！Question:為什么Lead-acid電池或其它的電池可以充電？電化學(xué)池：312.2 電池的電動(dòng)勢(shì)和電極電勢(shì)界面電勢(shì)(絕對(duì)電勢(shì)及絕對(duì)電勢(shì)差)內(nèi)電勢(shì)(Galvani,),外電勢(shì)(Volta,)和表面電勢(shì)()外電勢(shì)(Volta,):將單位正電荷從無(wú)窮遠(yuǎn)處的真空中移到物體近旁距表面約10-4cm處作的功。(是可測(cè)的)金屬和電解質(zhì)溶液界面外電勢(shì)之差，叫做Volta電勢(shì)：=電極-溶液表面電勢(shì)()：將單位正電荷從物體表面附近的一點(diǎn)移到物體相內(nèi)所做的電功稱之為表面電勢(shì)(涉及到化學(xué)作用，是不可測(cè)的)。= + “電位”與“電勢(shì)”的區(qū)別！=+2.2 電池的電動(dòng)勢(shì)和電極電勢(shì)32=ze=ze=ze+ze+=ze+(電化學(xué)勢(shì))=ze=ze=ze+ze+=ze+33Figure.Aschematicdiagramtoillustratethat,intheinterphaseregion(indicatedbyshading),theregenerallyisnetdipoleorientationandnet,orexcess,chargedensityAnelectrodeislikeagiantcentralionElectrode/electrolyteDoublelayerFigure.Aschematicdiagramto34Doublelayersarecharacteristicofallphaseboundaries1V,1nm,thefieldstrength(gradientofpotential)isenormous-itisoftheorder107V/cm.Theeffectofthisenormousfieldattheelectrode-electrolyteinterfaceis,inasense,theessenceofelectrochemistry!Doublelayersarecharacterist35A(a)物質(zhì)相的內(nèi)電勢(shì)、外電勢(shì)和表面電勢(shì)(b)電極與溶液間的內(nèi)電位差和外電位差A(yù)(a)物質(zhì)相的內(nèi)電勢(shì)、外電勢(shì)和表面電勢(shì)36Tomeasurethepotentialdifferenceacrossametal-solutionelectrifiedinterface(seeexplodedview),oneterminalofthepotential-measuringinstrumentisconnectedtothemetalelectrode.Whatistobedonewiththesecondterminal?Tomeasurethepotential37Allonecanmeasure,inpractice,isthepotentialdifferenceacrossasystemofinterfaces,orcell,notthepotentialdifferenceacrossoneelectrode-electrolyteinterface.Allonecanmeasure,38TheabsolutepotentialDifferenceacrossasingleelectrifiedinterfacecannotbemeasured!Itisnotnecessarytoknowexactvalueofitbutthedifferenceofabsolutepotentialdifferenceisimportantforelectrochemists!Theabsolutepotential39J.O'M.BockrisandA.N.Reddy,ModernElectrochemistry,Plenum,NewYork,1970,p623J.O'M.BockrisandA.N.Reddy,M40電池電動(dòng)勢(shì)和電極電勢(shì)電池電動(dòng)勢(shì)：將電位差計(jì)接在電池的兩個(gè)電極之間而直接測(cè)得的電勢(shì)值習(xí)慣上稱之為電池的電動(dòng)勢(shì)電極電勢(shì)：當(dāng)采用相對(duì)電勢(shì)法時(shí)，系用一定的參比電極與研究電極組成電池，這一電池的電動(dòng)勢(shì)稱為相對(duì)于給定參比電極而確定的研究電極電勢(shì)。(金屬和溶液相接觸的內(nèi)電位差即為金屬電極和溶液間的電極電勢(shì))所謂“電極/溶液”之間的絕對(duì)電勢(shì)不但無(wú)法直接測(cè)量，在處理電極過(guò)程動(dòng)力學(xué)問(wèn)題時(shí)也不需要用到它！在計(jì)算電池電動(dòng)勢(shì)時(shí)，也完全可以采用相對(duì)電極電勢(shì)來(lái)代替絕對(duì)電極電勢(shì)！電池電動(dòng)勢(shì)和電極電勢(shì)所謂“電極/溶液”之間的絕對(duì)電勢(shì)不但無(wú)法412.3 計(jì)算電極電勢(shì)(E)：活度or濃度？eq=eqo+RT/(zF)lnaMz+=E=Eo+RT/(zF)lnaMz+Nernst公式(方程)O+ze=RE=Eo+RT/(zF)lnaO/aR(A.J.BardandL.R.Faulkner,Electrochemicalmethods,1980,中譯本，p61-71，查全性，電極過(guò)程動(dòng)力學(xué)導(dǎo)論，第二版，第二章)

a=C2.3 計(jì)算電極電勢(shì)(E)：422.4 電極的分類一般來(lái)說(shuō)，電極可以分為如下四類：(1). A.一個(gè)金屬電極與它的水溶液中的離子相接觸,e.g. Cu/Cu2+ E=Eo+RT/(F)lnaMz+半反應(yīng)：Mz+ +ze=M B.一個(gè)非金屬它的離子相接觸，e.g.H2/H+或 Cl2/Cl-在一個(gè)惰性導(dǎo)電物質(zhì)表面上E=Eo+RT/(F)lnPH21/2/aH+(2)一個(gè)金屬電極與一個(gè)水溶液中的陰離子相接觸，此陰離子可與金屬電極的離子形成難溶物。例如：Hg/Hg2Cl2/Cl-，thecalomelelectrode(甘汞電極)(3)惰性電極，Pt,Au,C,Hgetc(4)上述不能包括的電極，例如：化學(xué)修飾電極等2.4 電極的分類432.5 參比電極顧名思義，參比電極是給出一個(gè)固定的值，其它的電極電勢(shì)的測(cè)量以此為基礎(chǔ)。一個(gè)好的參比電極應(yīng)該不受溫度、時(shí)間和通過(guò)小電流而變化,應(yīng)遵守Nernst方程！Type1:thehydrogenelectrodeType2:thecalomelelectrodeType3:glasselectrode,ion-selectiveelectrodes各種參比電極的制備和鹽橋的制備(電化學(xué)測(cè)定方法，騰島昭等著，陳震等譯，1995。P87-99)2.5 參比電極44ThehydrogenelectrodeThesaturatedcalomelelectrodeThehydrogenelectrodeThesatu45北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用462.7 電導(dǎo)和淌度(mobility)i=ziuiF(ui是離子淌度子)(i是一種離子的摩爾導(dǎo)電率)=ii=zi2F2Di/RT Nernst-EinsteinrelationDi=kBT/(6r) Stokes-Einsteinrelationti=i/ transportnumber2.7 電導(dǎo)和淌度(mobility)472.8 液接電勢(shì)Liquidjunctionpotentialsaretheresultofdifferencecationandanionmobilitiesundertheinfluenceofanelectricfield.Liquidjunctionpotentialcanbeclassifiedintothreetypes:(1)Twosolutionsofthesameelectrolytebutwithdifferentconcentrations(2)Twosulotionsofthesameconcentrationofoneoftheions,buttheotheriondiffers(3)Othercases.Ecell=ENernst+Ej

減小液接電勢(shì)的主要方法是應(yīng)用鹽橋。2.8 液接電勢(shì)482.9 離子選擇性電極和生物膜離子選擇性電極(Ion-SelectiveElectrodes)是一種能在多種離子存在下，用電位法測(cè)量溶液中給定離子活度的分析測(cè)量工具。是電化學(xué)傳感器的基礎(chǔ)。E=E0

2.303RT/(ziF)lgaiNikolsky-Eisenman方程E=K2.303RT/(ziF)lg[ai+Kijpotaiz/z]2.9 離子選擇性電極和生物膜49北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用50北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用51北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用52作業(yè)：1.第一、二章后的習(xí)題(A.J.BardandL.R.Faulkner,Electrochemicalmethods,fundamentalsandapplications,Wiley,NewYork,1980,2001)2.第一章后的習(xí)題(電分析化學(xué)，蒲國(guó)剛，袁倬斌，吳守國(guó)編著,1993)作業(yè)：53作業(yè)：Deviseelectrochemicalcellsinwhichthefollowingreactionscouldbemadetooccur.If liquidjunctionsarenecessary,notetheminthecellschematicappropriately,butneglect theireffects. (a)H2O?H++OH- (b)2H2+O2

?H2O (c)2PbSO4+2H2O?PbO2+Pb+4H++2SO42- (d)2Ce3++2H++BQ?2Ce4++H2Q(aqueous,whereBQisp-benzoquinoneandH2Qis p-hydroquinone) (e)Ag++I-

?AgI(aqueous) (f)Fe3++Fe(CN)64-

?Fe2++Fe(CN)63-(aqueous) (g)Cu2++Pb?Pb2++Cu(aqueous) Whathalf-reactionstakeplaceattheelectrodeineachcell?Whatisthestandardcell potentialineachcase?Whichelectrodeisnegative?Wouldthecelloperateelectrolytically orgalvanicallyincarryingoutanetreactionfromlefttoright?Besureyourdecisions accordwithchemicalintuition.Obtainthedissociationconstantofwaterfromtheparametersofthecellconstructedfor reaction(a)inproblem1(T=298K).作業(yè)：54

FundamentalsofElectroanalyticalChemistry

電分析化學(xué)原理、方法和應(yīng)用

YuanhuaShao（邵元華，教授Ph.D.） CollegeofChemistryandMolecularEngineering PekingUniversity Fundamentalsof55Outline:

1.Principles 2.Methods 3.Applications

Outline:56Part1 Principles1. Introduction 2. ElectrochemicalCell:Thermodynamic PropertiesandElectrodePotentials 3. TheInterfacialRegion 4. FundamentalsofKineticsand MechanismofElectrodeReactions 5. MassTransport 6. KineticsandTransportinElectrode Reactions Part2 Methods 1 ElectrochemicalExperiments 2 HydrodynamicElectrodes 主要內(nèi)容Part1 Principles主要內(nèi)容57 Part2 Methods 3 CyclicVoltammetryandLinearSweep Techniques 4 StepandPulseTechniques 5 ImpedanceMethods 6 Non-ElectrochemicalProbesofElectrodes andElectrodeProcesses Part3 Applications 1 PotentiometricSensors 2 AmperometricandVoltammetricSensors 3 ElectrochemistryinIndustry 4 Corrosion 5 Bioelectrochemistry主要內(nèi)容 Part2 Methods主要內(nèi)容58GeneralBooks:1*A.J.BardandL.R.Faulkner,Electrochemicalmethods,fundamentalsandapplications,Wiley,NewYork,1980(2ndEdition,2001)2*C.M.A.BrettandA.M.O.Brett,Electrochemistry,Principles,Methods,andApplications,Oxford,19933*SouthamptonElectrochemistryGroup,NewInstrumentalMethodsinElectrochemistry,EllisHorwood,Chichester,19854A.M.Bond,ModernpolarographicmethodsinAnalyticalChemistry,Dekker,NewYork,19805J.Koryta,PrinciplesofElectrochemistry,Wiley,19876P.Delahay,NewInstrumentalmethodsinElectrochemistry,19547R.N.Adams,Electrochemistryatsolidelectrodes,19698*J.O'M.BockrisandA.N.Reddy,ModernElectrochemistry,Plenum,NewYork,19709電化學(xué)基礎(chǔ)，張祖訓(xùn)，汪爾康，200010生命科學(xué)中的電分析化學(xué)，彭圖治，楊麗菊編著,199911*電極過(guò)程動(dòng)力學(xué)導(dǎo)論，查全性，1976(19872ndEdition)12電化學(xué)研究方法，田昭武，198413*電化學(xué)測(cè)定方法，騰島昭等著，陳震等譯，199514電分析化學(xué)，蒲國(guó)剛，袁倬斌，吳守國(guó)編著，1993GeneralBooks:59Series1.ElectroanalyticalChemistry,ed.A.J.Bard2.ModernAspectsofElectrochemistry,eds.J.O'M.Bockris,B.E.Conway,etal.,

JournalsNature,Science,JACS,Angew.Chem.IntEditAnal.Chem.,(May1,2000)J.Phys.Chem.B.,J.Electroanal.Chem.,ElectrochimicaActa,J.Electrochem.Society.,Electroanalysis,ElectrochemicalandSolidStateLetters,J.AppliedElectrochemistry,ElectrochemistryCommunications,J.SolidStateElectrochemistrySeries60Reviews:AccountsofChemicalResearchAnalyticalChemistryAnnualReviewsofPhysicalChemistryChemicalReviewsWebsites:/estir/Reviews:61ChapterOne(第一章)

Introduction(導(dǎo)言)

1.1 Introduction1.2 ScopeofElectroanalyticalChemistry1.3 BriefHistory1.4 ExamplesChapterOne(第一章)621.1 Introduction(導(dǎo)言)電分析化學(xué)和電化學(xué)：兩者沒(méi)有區(qū)別！基本原理相同，僅研究的側(cè)重點(diǎn)可能不同。電化學(xué)池：

原電池(GalvanicCell)：化學(xué)能電能 電解池(ElectrolyticCell)：電能化學(xué)能一個(gè)簡(jiǎn)單的電分析化學(xué)實(shí)驗(yàn)：組成：工作(研究)電極(W),參比電極(R)，輔助(對(duì))電極(C),電解質(zhì)溶液，恒電位儀(potentiostat),PC計(jì)算機(jī)(接口+軟件)。研究重點(diǎn)研究重點(diǎn)63北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用64ElectroanalyticalChemistry

isthebranchofchemistryconcernedwiththeinterrelationofelectricalandchemicaleffects.Alargepartofthisfielddealswiththestudyofchemicalchangescausedbythepassageofanelectriccurrentandtheproductionofelectricalenergybychemicalreactions.Infact,thefieldofelectrochemistryencompassesahugearrayofdifferentphenomena(e.g.,electrophoresisandcorrosion),devices(electrochromicdisplays,electro-analyticalsensors,batteries,andfuelcells),andtechnologies(theelectroplatingofmetalsandthelarge-scaleproductionofaluminumandchlorine).Whilethebasicprinciplesofelectro-chemistrydiscussedinthistextapplytoallofthese,themainemphasishereisontheapplicationofelectrochemicalmethodstothestudyofchemicalsystems.1.2ScopeofElectroanalyticalChemistryElectroanalyticalChemistryis65Scientistsmakeelectrochemicalmeasurementsonchemicalsystemsforavarietyofreasons.Theymaybeinterestedinobtainingthermodynamicdataaboutareaction.Theymaywanttogenerateanunstableintermediatesuchasaradicalionandstudyitsrateofdecayoritsspectroscopicproperties.Theymayseektoanalyzeasolutionfortraceamountsofmetalionsororganicspecies.Intheseexamples,electro-chemicalmethodsareemployedastoolsinthestudyofchemicalsystemsinjustthewaythatspectroscopicmethodsarefrequentlyapplied.Therearealsoinvestigationsinwhichtheelectrochemicalpropertiesofthesystemsthemselvesareofprimaryinterest,forexample,inthedesignofanewpowersourceorfortheelectrosynthesisofsomeproduct.Manyelectrochemicalmethodshavebeendevised.Theirapplicationrequiresanunderstandingofthefundamentalprinciplesofelectrodereactionsandtheelectricalpropertiesofelectrode-solutioninterfaces.Scientistsmakeelectrochemica66VariablesaffectingtherateofanelectrodereactionVariablesaffectingtherateo671.3電化學(xué)的簡(jiǎn)史：LuigiGalvani(1737-1798):從1786年開(kāi)始，進(jìn)行著名的"animal electricity“實(shí)驗(yàn)－解剖青蛙AlessandroVolta(1745-1827):HumphryDavy(1778-1829):MichaelFaraday(1791-1867):Grove: 燃料電池(1839)Lippmann: 1873Helmholtz: 雙電層(1879)F.G.Cottrell: Cottrell公式1902W.Nernst: Nernst公式1904Tafel: Tafel公式1905Gouy,Chapman: 1905Stern:1924Heyrovsky,Shikata: Polarograph1925(1959NobelPrize Winner)1.1.3電化學(xué)的簡(jiǎn)史：68J.Butler,M.Volmer: Butler-Volmer公式1924-1930P.Delahay,Gerischer,Frumkin,Levich,Bakeretal:1950sto1960s發(fā)展了各種理論，研究方法等R.Marcus: 1950s-1960s,ElectronTransferTheory(NobelPrize Winner,1992)T.Kuwana: 1960s,光譜電化學(xué)Gavach,Korytaetal:1970s開(kāi)始研究液/液界面電化學(xué)MillerandMurray:1975,化學(xué)修飾電極M.Fleischmann,A.Bewicketal:1970sto1980s,insitu光譜、波譜電化學(xué)M.Fleischmann,W.Wightmanetal:ultramicroelectrodes1970s-1980sA.J.Bard: SECM,1989Sagivetal: 1980s,self-assembledmembranesP.Hansmaetal:STM-Electrochemistry,1980sLiorZhangorWang:??????J.Butler,M.Volmer: Butler-Vo69研究方法：穩(wěn)態(tài)和暫態(tài)技術(shù)：光譜、波譜技術(shù)：表面技術(shù)：SPM(ScanningProbe Microscopy)研究方法：70(a)Generalprincipleofstudyingasystembyapplicationofanexcitation(orperturbation)andobservationofresponse.(b)Inaspectrophotometricexperiment,theexcitationislightofdifferentwavelengths(),andtheresponseistheabsorbance(A)curve.(c)Inanelectrochemical(potentialstep)experiment,theexcitationistheapplicationofapotentialstep,andtheresponseistheobservedi-tcurve.(a)Generalprincipleofstudyi71應(yīng)用領(lǐng)域：1.化學(xué)電源(電池,燃料電池)：2.電解電鍍：3.腐蝕：4.電化學(xué)合成：5.電催化：6.生物電分析化學(xué)：7.電化學(xué)傳感器：Ion-SelectiveElectrodes8.TAS9.單細(xì)胞和單分子測(cè)量應(yīng)用領(lǐng)域：72白鼠腦神經(jīng)遞質(zhì)活體伏安分析示意圖白鼠腦神經(jīng)遞質(zhì)活體伏安分析示意圖73北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用74Polarography(極譜)andVoltammetry(伏安法)的區(qū)別？polarographyAclassicalelectroanalyticaltechniquediscoveredin1922byJ.Heyrovsky,forwhichhewasawardedtheNobelPrizeforChemistryin1959.Essentially,itislinear-sweepvoltammetryusingadropping-mercuryelectrodeforworkingelectrodeandalargemercurypoolascounterelectrode.voltammetryAnelectrochemicalmeasuringtechniqueusedforelectrochemicalanalysisorforthedeterminationofthekineticsandmechanismofelectrodereactions."Voltammetry"isafamilyoftechniqueswiththecommoncharacteristicsthatthepotentialoftheworkingelectrodeiscontrolled(typicallywithapotentiostat)andthecurrentflowingthroughtheelectrodeismeasured.Inoneofthemostcommonapplicationsofthetechnique,thepotentialisscannedlinearlyintime;thisiscalledthe"linear-sweepvoltammetry,""LSV,"or"LV.""Cyclicvoltammetry(CV)"isalinear-sweepvoltammetrywiththescancontinuedinthereversedirectionattheendofthefirstscan,thiscyclecanberepeatedanumberoftimes.Polarography(極譜)andVoltamme75Figure1.Basicvoltammetry.(a)Apparatusforvoltammetrywithatwo-electrodecell,appropriateforuseinsolutionsoflowresistanceandmicroelectrodes.(b)Apparatusforvoltammetrywithathree-electrodecell.Inpracticeapotentiostatthatautomaticallycontrolsthepotentialoftheworkingelectrodewithrespecttoareferenceelectrodeisused.Question:兩電極和三電極系統(tǒng)有什么區(qū)別？為什么一般的電化學(xué)研究需用三電極系統(tǒng)？May1,2000;pp.346A-352A(AnalyticalChemistry)VoltammetryRetrospectiveAllenJ.Bard,UniversityofTexas-AustinandCynthiaG.Zoski,UniversityofRhodeIslandFigure1.Basicvoltammetry.Q76北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用77Three-dimensionalvoltammetry.

Representationofthethree-dimensionalI-t-EsurfaceforaNernstianreaction.Thetypicalsteady-statevoltammogramrepresentsacutparalleltotheI-Eplane.(b)Acutrepresentingalinearpotentialsweepacrossthissurface.(AdaptedfromRef.6.)Three-dimensionalvoltammetry.78電分析化學(xué)的特點(diǎn)：

interdisciplinarynatureandversatility異相反應(yīng)，與表面、界面及相關(guān)的區(qū)域有關(guān)，可控催化。電分析化學(xué)的特點(diǎn)：79電化學(xué)及電分析化學(xué)的發(fā)展趨勢(shì)1，與納米技術(shù)相結(jié)合2，與生物、生命科學(xué)相結(jié)合

信息科學(xué)生命科學(xué)能源科學(xué)環(huán)境科學(xué)材料科學(xué)電化學(xué)及電分析化學(xué)的發(fā)展趨勢(shì)1，與納米技術(shù)相結(jié)合信息科學(xué)80

ChapterTwo(第二章)ElectrochemicalCells:Thermodynamic PropertiesandElectrodePotentials2.1 Introduction,Galvanicandelectrolyticcells2.2 Thecellpotentialofanelectrochemicalcell2.3 Calculationofcellpotential:activitiesorconcentrations? ChapterTwo(第二章)812.4 Electrodeclassification2.5 Referenceelectrodes2.6 Themovementofionsinsolution:diffusion and migration2.7 Conductivityandmobility2.8 Liquidjunctionpotentials2.9 Ion-SelectiveElectrodesandBiomembranes北京大學(xué)電分析課件電分析化學(xué)原理、方法和應(yīng)用822.1 導(dǎo)言，原電池和電解池1.Whyisitthathalf-reactionsinelectrochemicalcellsproceedspontaneouslyinonedirectionandfurnishcurrent?2.Whatistheeffectofthesaltbridge?3.Whatistheeffectofionmigration?4.Whatisabsoluteandrelativepotentialdifferences?Zn/Zn2+(aq),Cu2+(aq)/Cu Hg/Hg2Cl2/Cl-(aq),Zn2+(aq)/ZnAg/AgCl/TBACl(aq)/TBATPB(o)//LiCl(aq)/AgCl/Ag根據(jù)IUPAC的規(guī)定，左邊的半反應(yīng)是氧化反應(yīng)(anode,陽(yáng)極)，右邊的半反應(yīng)是還原反應(yīng)(cathode,陰極)2.1 導(dǎo)言，原電池和電解池83Ecell=Eright-EleftPotential:電位，電勢(shì)但物理學(xué)，“位”與“勢(shì)”的概念是不同的。空間某點(diǎn)的電位，是將單位正電荷從無(wú)窮遠(yuǎn)處(或以無(wú)任何力作用的無(wú)窮遠(yuǎn)的真空為參考點(diǎn))移到該點(diǎn)所做的功，它具有絕對(duì)的意義。電勢(shì)則是空間兩點(diǎn)的電位差(或電位降)，如金屬和其離子溶液所形成的電極電勢(shì)，實(shí)際上是金屬和溶液兩相之間電位差的一種衡量，又是該電極電勢(shì)與標(biāo)準(zhǔn)電極電勢(shì)差的一種衡量。Ecell=Eright-EleftPotentia84電化學(xué)池： anode cathode

原電池(GalvanicCell)：化學(xué)能電能 - +電解池(ElectrolyticCell)：電能化學(xué)能+ -一些電化學(xué)池既可以作為原電池，也可以作為電解池，例如；汽車用的Lead-acid電池，在放電時(shí)是原電池，反應(yīng)為：anode(-ve): Pb+SO42-

→PbSO4 +2ecathode(+ev): PbO2 +4H+ +SO42-+2e→2H2O+PbSO4在充電時(shí)為電解池，上述半反應(yīng)倒過(guò)來(lái)！Question:為什么Lead-acid電池或其它的電池可以充電？電化學(xué)池：852.2 電池的電動(dòng)勢(shì)和電極電勢(shì)界面電勢(shì)(絕對(duì)電勢(shì)及絕對(duì)電勢(shì)差)內(nèi)電勢(shì)(Galvani,),外電勢(shì)(Volta,)和表面電勢(shì)(