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1、物理化學(xué)學(xué)~(WuliHuaxueXuebao1JanuaryActaPhys.一Chim.Sin.,2011,27(1):149—155149【Article]www.whxb.pku.edu.cn離子液體添加劑【BMlM】HSO4對鋅電積過程析氧反應(yīng)動力學(xué)的影響張啟波華一新(離子液體冶金重點實驗室,昆明理工大學(xué)冶金與能源工程學(xué)院,昆明650093)摘要:研究了1-丁基-3-甲基咪唑硫酸氫鹽([BMIMIHSO)離子液體對鋅電積過程析氧反應(yīng)的影響.研究工作借助于動電位極化,電化學(xué)阻抗譜,掃描電
2、鏡和X射線衍射等測試技術(shù).動電位極化曲線及對應(yīng)的動力學(xué)參數(shù)分析表明,[BMIM]HSO對陽極析氧反應(yīng)具有催化作用,可提高析氧反應(yīng)速率常數(shù).電化學(xué)阻抗譜數(shù)據(jù)表明,【BMIM]HSO能顯著降低陽極析氧電荷傳遞電阻,在所研究的1.85—2.10V電位范圍內(nèi)添加5mg.L?!綛MIM】HSO,電阻值至少降低50%.此外,添加劑對陽極表面二次反應(yīng)具有抑制作用,其在陽極表面的吸附,阻礙了陰離子的陽極活化位點吸附過程.電化學(xué)測試結(jié)果與長時間(120h)陽極極化后所得陽極表面形貌和結(jié)晶取向分析結(jié)果相一致.[B
3、MIM]HSO的添加能有效抑制中間產(chǎn)物盧一PbO的形成,促進鉛銀電極表面大塊且疏松多孔a-PbO:的生成,加速陽極析氧的進行.關(guān)鍵詞:電化學(xué)阻抗譜:鋅電積:析氧:離子液體添加劑:表面形貌中圖分類號:0646EffectoftheIonicLiquidAdditive一[BMIM]HSO4ontheKineticsofOxygenEvolutionduringZincElectrowinningZHANGQI.BoHUAY._Xin(KeyLaboratoryofIonicLiquidsMetal
4、lurgy,FacultyofMetallurgicalandEnergyEngineering,KunmingUniversityofScienceandTechnology,Kunming650093,PR.China)Abstract:Theefectoflheionicliquidadditive1-butyl-3一methylimidazoliumhydrogensulfate([BMlM】HSO4)onthekineticsofoxygenevolutionduringzincele
5、ctrowinningfr0manacidicsulfatesolutionwasinvestigated.Weusedpotentiodynamicpolarization,electrochemicalimpedancespectroscopy,scanningelectronmicroscopy,andX—raydiffractionforthisstudy.Potentiodynamicpolarizationcurvesandthecorresp0ndingkineticparamet
6、eranalysisshowthat【BMIM]HSO4hasacatalyticefectonoxygenevolutionbystimulatingthereactionrateconstant.ImpedancedatareveaIthat『BMlM]HSO4canmarkedlyreducetheoxygenevolutionchargetransferresistance.Theadditionof5mg·L『BMIM]HSO4obviouslydecreasedtheresistan
7、cevaluebyatIeast50%overthestudiedpotentiaIrangefr0m1.85tO2.1OInaddition,theresultsoftheimpedancemeasurementsalsosuggestaninhibitioneffectof『BMlM]HSO4onthesecondaryreactionsandthisiSduetotheadsorptionoftheadditiveontheanodeSUrface,whichdecreasedtheamo
8、untofactivesitesforanionadsorption.AlIelectrochemicaIresultswerecorroboratedwithamorphologicalandorientationanalysisoftheanodicsurfaceafter120hofanodicpolarization.Theadditionof【BMlM]HSO4inhibitedthegenerationoftheintermediateproduct/3.PbO2anditpromo