应用EQCM研究含有二苯基联苯胺和二亚酰胺官能团的电活性聚合物的氧化还原过程

运用电化学石英晶体微天平技术(EQCM)联合循环伏安法(CV)和计时安培分析法对3种含有二苯基联苯胺和二亚酰胺的电活性聚合物薄膜进行了研究.这些聚合物薄膜具有多个氧化和还原状态.中性聚合物薄膜可以在二苯基联苯胺连接处被电化学氧化或在二亚酰胺处被电化学还原.在氧化还原转化过程期间,聚合物薄膜的电子转移、离子补偿和溶剂运输的动力学取决于聚合物的类型、其所处的氧化还原状态、电位扫描速率和氧化还原转换的方向.确定了包含二苯基联苯胺聚合物在不同电化学条件的氧化还原转化的机理.动力学控制步骤也许与聚合物薄膜在每个氧化还原状态的特定几何结构有关,并受到不同电解质和溶剂的影响.研究了含有二苯基联苯胺和二亚酰胺的电活性聚合物薄膜电子转移反应的级数、反离子补偿和溶剂传输,并定量地测定了氧化还原过程中离子和溶剂进出电活性膜的流量.

EQCM study of redox processes of electroactive polymers with diphenylbenzidine and diimide groups

Three different electroactive polymer films containing diphenylbenzidine and diimide functional groups were investigated by Electrochemical Quartz Crystal Microgravimetry （EQCM） combined with Cyclic Voltammetry（CV） and Chronoamperometry. These polymer films have multiple oxidative and reductive states. The neutral polymer films can be electrochemically oxidized at their diphenylbenzidine linkage or reduced at their diimide sites. The kinetics of electron transfer, ion com- pensation, and solvent transport during redox switching of such polymer films depend on the type of polymer, its specific redox state, the voltage scan rate, and the direction of redox switching or poten- tial step. The mechanism of redox switching under different electrochemical conditions has been de- termined. The controlling kinetic step may be related to the specific geometrical structure of polymer films at each redox state, and is influenced by different electrolytes and solvents. The order of elec- tron transfer, counter ion compensation, and solvent transport are identified, and the fluxes of ions and solvent are quantitatively determined.