邻苯二胺导电聚合物膜的光谱电化学

Spectroelectrochemical Studies of the Conducting Polymer of o-Phenylenediamine

运用循环伏安法、电化学现场共振拉曼光谱技术和紫外一可见反射光谱技术研究了邻苯二胺导电聚合物（P－o－PD）膜在酸性溶液中的氧化还原过程．循环伏安实验结果表明：聚邻苯二胺的氧化还原过程受表面过程控制，并且在该过程中存在3种稳定的氧化还原态．现场共振拉曼光谱结果证实存在具有不同的结构和稳定性的3种稳定态，并明确指出聚邻苯二胺是一种以吩嗪环为主要结构单元的梯形聚合物．3种状态的P－o-PD表现出不同的紫外-可见光谱特点．进一步用现场时间分辨紫外可见光谱技术研究聚邻苯二胺氧化还原的动态过程，提出了聚邻苯二胺可能的氧化还原机理．

The redox mechanism of the conducting polymer film of poly-o-phenylenediamine(P-o-PD) in acid solution has been studied by cyclic voltammetry(CV), electrochemicalinsitu resonance Raman spectroscopy and UV-Vis subtractive reflectance spectroscopy. Theresults of the CV show that the redox process of P-o-PD is controlled by the surfaceprocesses and three steady redox states are formed in the redox process. The in-situ resonanceRaman spectra not only verify the existence of the three steady states of P-o-PD, but alsoindicate that the structure of P-o-PD is dominated by a ladder polymer with phenazine rings. Thethree kinds of P-o-PD display different stabilities and UV-Vis aborption spectra.Furthermore, the in-situ time--resolved UV-Vis reflectance spectroscopy is used to study the dynamicredox process of P-o-PD, and a possible reaction mechanism is proposed at last.