电化学联用表面等离子体共振光谱法对苯胺电化学聚合过程的研究

In Situ Investigation on Electrochemical Polymerization and Properties of Polyaniline Thin Films by Electrochemical Surface Plasmon Resonance

采用双光电池传感器作为检测器件,设计并构建了新型表面等离子体共振(SPR)光谱仪,在一定范围内实现了SPR角度的快速测量。将此SPR光谱仪与电化学工作站联用,构建了电化学联用-时间分辨SPR(EC-TR-SPR)光谱仪,以聚苯胺电化学制备过程为研究体系,验证了此EC-TR-SPR光谱仪的特性。同时通过对聚苯胺膜的暂态电化学方法测试(计时电流法和差分脉冲法),考察了仪器的时间分辨能力及其响应速度,验证了此仪器系统在小分子反应动力学以及稳态和暂态电化学联用方法研究中的应用价值。实验结果表明,此SPR光谱仪具有高的时间分辨能力,其时间分辨率可达0.1 ms;对聚苯胺膜的暂态电化学测试结果表明,此联用技术可实时监测SO2"4在聚苯胺膜中的掺杂和去掺杂过程,而单纯的电化学电流-时间曲线无法区分。

A new type of surface plasmon resonance（ SPR） spectroscopy system was designed and built.Here,a kind of dual photocell sensor was developed as a detection device to achieve a rapid measurement of SPR angle within a certain range. This SPR system was combined and integrated with electrochemical workstation to obtain a new type of electrochemistry-time-resolved SPR（ EC-TR-SPR） instrument via instrumental technique. This EC-TR-SPR instrument was used to characterize the electrochemical polymerization process of aniline to validate the spectroscopic characteristics. Applications of transient electrochemical characterization methods,including chronoamperometry and differential pulse voltammetry,confirmed the time resolution and the applicability of this instrument system toward the steady state and transient electrochemical methods upon small molecular reactions. The experiment results showed that this ECTR-SPR possessed the time resolution up to 10000 times per second（ 0. 1 ms）,and could be used to real-time investigate the doping and de-doping of polymerization process of aniline monomer as well as the prepared polyaniline film,which could not be discriminated on a conventional electrochemical current-time curve..