电解质溶液对聚吡咯电聚合中过氧化行为的影响  

Effects of Electrolyte Solutions on Overoxidation of Polypyrrole During Its Electrochemical Polymerization

作　　者：李美超[1] 朱婉霞[1] 朱静娜[1] 莫卫民[1] 

机构地区：[1]浙江工业大学分析测试中心,化学工程与材料学院,绿色化学合成技术国家重点实验室培育基地,杭州310032

出　　处：《高等学校化学学报》2012年第1期128-132,共5页Chemical Journal of Chinese Universities

基　　金：浙江省自然科学基金(批准号:Y4100647);浙江省分析测试科技计划(批准号:2011C37060)资助

摘　　要：分别以硫酸/水和高氯酸锂/乙腈为电解质溶液,采用循环伏安法在铂基底电极上电聚合制备了聚吡咯,研究了电解质溶液对聚吡咯电聚合过程中过氧化行为的影响.与硫酸/水溶液相比,在高氯酸锂/乙腈溶液中电聚合制备的聚吡咯发生过氧化的峰电位正移了0.42 V.采用原位傅里叶变换红外(in situ FTIR)光谱技术检测,结果表明,电聚合制备的聚吡咯在2种电解质溶液中均发生了过氧化反应,其β-C经氧化生成C—OH或C O.在硫酸/水溶液中,部分聚吡咯发生电氧化降解生成CO2,致使其共轭结构被破坏,电导率迅速下降.而在高氯酸锂/乙腈溶液中,在更高的电位范围内,聚吡咯并没有氧化降解成CO2.Polypyrrole（PPy） was prepared by cyclic voltammetry on a platinum electrode in H2SO4/H2O and LiClO4/CH3CN solutions,respectively.The effects of electrolyte solutions on overoxidation of polypyrrole during its electrochemical polymerization were studied by in situ spectroelectrochemical measurements.Compared with the solution of H2SO4/H2O,the overoxidative peak potential of polypyrrole in LiClO4/CH3CN was positively shifted by 0.42 V.The results show that the β-C of the pentacycle is oxidized to oxygen-containing groups such as C—OH and C-O during the overoxidation of polypyrrole at high potentials.Polypyrrole partially degraded with the formation of CO2 in H2SO4/H2O solutions,which resulted in loss of conductivity,and did not obviously degrade during overoxidation in the solution LiClO4/CH3CN at the higher potentials.

关 键 词：聚吡咯 电聚合 过氧化 电解质溶液 原位红外光谱 

分 类 号：O646.542[理学—物理化学] O631.23[理学—化学]