Abstract: The combination of electrochemistry with surface plasmon resonance (SPR) has been used to in situ investigate the kinetic growth process of polyaniline (PAn) at a gold surface. Sequential oscillations of SPR kinetic curve with a periodicity equal to that of cyclic potential were observed during the film growth. Such a drastic effect is attributed to a larger electronic density at PAn/Au electrode with respect to the bare gold electrode. Evidence from the SPR kinetic curve confirmed that there were three distinct kinetic stages for PAn film growth. In initial fast increase stage, the growth rate of the film was dependant linearly on aniline concentration and the square root of film thickness. A slower kinetic growth was observed in the second stage due to the three dimensional growth and the film degradation. In the third stage, The degradation of PAn film dominates. Different polymerization modes have different growth rate, and thus lead to different structures and properties of the film.

Key words: surface plasmon resonance, polyaniline, in situ electrochemistry, kinetic analysis

摘要： 将电化学与表面等离子体激元共振(SPR)光谱技术结合起来，首次应用于研究金电极上聚苯胺(PAn)的动力学增长过程。在PAn膜的形成过程中，发现SPR的动力学曲线随电位的变化而发生连续的振荡。这种电位调制的SPR动力学曲线的振荡归因于电极表面电子密度的变化。SPR动力学曲线的变化趋势表明，PAn膜的增长过程经历了3个不同的动力学阶段。在膜增长的第1阶段，膜增长速度与苯胺浓度的一次方和膜厚的平方根成正比。在膜增长的第2阶段，由于三维增长、膜降解等因素，增长速度明显减小。在第3阶段，膜的降解处于主要地位，PAn膜呈现负增长。不同电聚合方式具有不同的增长速度，并且产生了不同的膜结构和性质。

关键词: 表面等离子体激元共振光谱, 聚苯胺, 现场电化学, 动力学分析