本文报道了一种适用于同轴微波腔的新型ESR—电化学池的设计。工作电极的长度可调节,部分屏蔽微波辐射的功能由上下两个屏蔽套承担。除了传统的螺线管,工作电极还可由打孔的金属筒、金属网、甚至复合材料制成。对电极可根据需要置于共振腔的外面或里面。总之,新设计灵活实用,适合更多的研究场合。本文列举了一些应用实例。
New cell designs for simultaneous electrochemical(EC) and electron spin resonance (ESR) measurements are reported for coaxial microwave cavity. Adjustable shieldings are introduced so that the working electrode can be much shorter than the full height of the cavity. Besides the traditional helical electrode, the working electrode can be cylinders made from metal plates, metallic meshes or even composite materials. The counter electrode can be placed either inside or outside the cavity. These features make the new designs more flexible than that previously reported. With a nonperforated cylindrical electrode, this cell can be used to determine the standard potential and the number of electrons of electrode reactions involving radicals. Other possible applications are also briefed.
McKinneyTM.ElectronSpinResonanceandElectrochmistry.ElectroanalyticalChemistry,Vol.10,ed.BardAJ.DekkerM.NewYork,1965,chap.22KasteningB.ElectronSpinResonance.ComprehensiveTreatiseofElectrochemistry,vol.8,ed.WhiteRE,BockrisJO’M,ConwayBE.NewYork:PlenumPres,1984,chap.73GoldgergIB,McKinneyTM.PrinciplesandTechniquesofElectrochemicalElectronParamagneticResonanceExperiments.LaboratoryTechniquesinElectroanalyticalChemistry,ed.KisingerPT,HeinemanWR,DekkerM.NewYork:1996,chap.294AlendoerferRD,MartinchekGA,BruckensteinS.SimultaneousElectrochemicalElectronSpinResonanceMeasurementswithaCoaxialMicrowaveCavity.Anal.Chem.,1975,47:8905GoldgergIB,BardAJ.SimultaneousElectrochemicalElectronSpinResonanceMeasurements.Ⅰ.CelDesignandPreliminaryResults.J.Phys.Chem.,1971,75:32816HawkridgeFM,KuwanaT.IndirectCoulometricTitrationofBiologicalElectronTransportcomponents.Anal.Chem.,1973,45:10217BirdCL,KuhnAT.ElectrochemistryoftheViologens.Chem.Soc.Rev.,1981,10:498ZhuangL,LuJ.DevelopmentinpotentialmodulatedESRtechnique.J.Electroanal.Chem.,1997,429:1159MuS,KanJ,ZhuangL,LuJ.Interconversionofpolaronandbipolaronofpolyanilineduringtheelectrochemicalpolymerizationofaniline.J.Electroanal.Chem.,inpres10ZhuangL,LuJ,AiX,YangH.InsituESRstudyonelectrochemicallithiumintercalationintopetroleumcoke.J.Electroanal.Chem.,1995,397:31511GerischerH,DeckerF,ScrosatiB.TheElectronicandtheIonicContributiontotheFreEnergyofAlkaliMetalsintheIntercalationCompounds.J.Electrochem.Soc.,1994,141:2297