含胱氨酸的硫酸溶液中铅及铅-锡合金电氧化时新的电势振荡.pdfVIP

2007年12月 湖南师范大学自然科学学报 Vo1．30 No．4 第30卷第4期 Journal of Natural Science of Hunan Normal University Dec．，2007 含胱氨酸的硫酸溶液中铅及铅一锡合金电 氧化时新的电势振荡 彭 斌，李则林 (湖南师范大学化学化工学院，化学生物学及中药分析教育部重点实验室，中国长沙 410081) 摘 要 利用循环伏安交叉环判据，发现Pb及Pb-0．23％Sn合金电极在含胱氨酸(Cys)的硫酸溶液中电氧化 时，涉及周期性析氧的新的电势振荡．阳极极化时电极表面经PbS04氧化生成PbO 膜，Cys在覆盖PbO 膜的电极 表面上的电氧化过程由扩散传质步骤所控制．振荡可归因于电极表面Cys浓度的周期性变化，即扩散控制下的氧 化耗尽与析氧导致的对流恢复．通过比较发现，微量sn的加人不仅显著地减小了电势振荡出现的下限电流值，还 缩短了振荡发生的电流区间． 关键词 铅；铅·锡合金；胱氨酸；电氧化；电势振荡 中图分类号 G236 文献标识码 A 文章编号 1000-2537(2007)04-0081-04 New Potential Oscillations during the Electrooxidation of Lead and Lead-Tin Alloy in H2 SO4 with Cystine PENG Bin，LIZe—lin (College of Chemistry and Chemical Engineering，Hunan Normal University Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research(Ministry of Education)，Changsha 410081，China) Abstract New potential oscillations with periodic oxygen evolution have been observed during the electrooxi— dation of lead and lead—tin alloy in H2SO4 with cystine based on the CV criterion．The electrode surface could be oxidized to PbO2 via PbSO4 during the anodic polarization，and mass transfer plays the key role in the oscillations for the electrooxidation of cystine on the PbO2-covered surface．The oscillations can be ascribed to the periodic ch~ge of cystine concentration on the surface，namely，the consumption by oxidation under diffusion and the re— sumpfion by convection through oxygen evolution．Moreover，it has been found that the oscillations begin at a lower current and occur within a narrower region by doping lead with small proportion of tin． Key words Pb；Pb—Sn alloy；cystine；electro—oxidation；potential oscillations 迄今为止，人们已