物理化学学报(WuliHuaxueXuebao)OctoberActaPhys.鄄Chim.Sin.,2007,23(10)：1515-15191515[Article]www.whxb.pku.edu.cnPbO2阳极在硫酸溶液中的析氧失活行为11,23,4曹江林吴祖成鄢李红霞张鉴清(1浙江大学环境工程系,杭州310027;2天津大学环境科学与工程学院,天津300072;3浙江大学化学系,杭州310027;4中国科学院金属研究所,金属腐蚀与防护国家重点实验室,沈阳110016)摘要：采用热分解鄄电镀法制备了以Sb掺杂SnO2(Sb鄄SnO2)为底层的Ti基PbO2阳极(Ti/PbO2).采用加速电解寿命测试、电化学阻抗谱、XRD、SEM鄄EDX等技术,研究了Ti/PbO2阳极在硫酸溶液中的电解失效行为和机制.结果表明,在新制备的PbO2镀层中,由于氧空位的存在,PbO2镀层的内应力表现为拉应力,随着电解的进行,阳极表面生成的活性氧原子在向基底扩散的过程中,将Pb3+态氧化为Pb4+态,逐渐占据镀层内作为自由电子施主的氧空位,这不仅导致镀层的导电性能下降,同时使镀层的应力逐渐由拉应力转变为压应力,镀层性质逐渐劣化.这一过程基本结束时,活性氧原子才大量扩散至Ti基底导致基底的钝化,在Ti基底和镀层界面出现显著的界面应力,在界面应力和镀层内压应力的共同作用下,阳极出现鼓泡、脱落,迅速进入失活阶段.关键词：失活;PbO2阳极;内应力中图分类号：O646InactivationofPbO2AnodesduringOxygenEvolutioninSulfuricAcidSolution11,23,4CAOJiang鄄LinWUZu鄄Cheng鄢LIHong鄄XiaZHANGJian鄄Qing(1DepartmentofEnvironmentalEngineering,ZhejiangUniversity,Hangzhou310027,P.R.China;2SchoolofEnvironmentalScienceandEngineering,TianjinUniversity,Tianjin300072,P.R.China;3DepartmentofChemistry,ZhejiangUniversity,Hangzhou310027,P.R.China;4StateKeyLaboratoryforCorrosionandProtectionofMetals,InstituteofMetalResearch,ChineseAcademyofSciences,Shenyang110016,P.R.China)Abstract：Ti鄄substratePbO2(Ti/PbO2)anodeswithSb鄄dopedSnO2interlayerwerepreparedbythermaldecomposition鄄electroplatingtechnique.ThebehaviorandmechanismoftheinactivationofTi/PbO2anodeswerestudiedbytheacceleratedlifetest,electrochemicalimpedancespectrum,XRDandSEM鄄EDX.TheresultsshowedthattheinactivationofTi/PbO2anodeswasadevelopingprocess.Duringoxygenevolution,partialactiveoxygenatoms3+4+producedasintermediateproductdiffusetowardTisubstrate,andtheyoxidizePbtoPbinthePbO2coatingtooccupygraduallytheoxygenvacanciesasfreeelectrondonors.Thisresultedinnotonlythedecreaseofconductivitybutalsoachangeofintrinsicstressesfromtensilestressestocompressivestresses.Whentheprocesswasfinishedonthewhole,largenumbersofactiveoxygenatomsbegantodiffusetoTisubstrate.TheoxidationofTisubstrateledtotheproductionofaninterfacialstresses.Undertheeffectsofc