Raman and Spatially Resolved Spectroelectrochemistry

该项目涉及分析化学和表面化学的一般领域，以及电化学和光谱学的子领域。将使用两种光谱技术来探测电极表面和附近的溶液。空间分辨吸收光谱将被用来研究电化学生成的物种的反应，特别是那些正在进行催化氧化还原反应的物种。此外，这项技术还将被用于研究圆柱形微电极和非常规几何结构的电极的扩散。将尝试在电化学发光系统中产生光学增益。拉曼光谱将被用来获得关于电生物种的结构信息，并探测碳电极的表面。碳表面光谱将与材料的电化学行为相关联。还将研究修饰碳电极上表面氧化物的结构。对电极-溶液界面的光谱电化学研究将使电极的分子表面态与其电子转移特性相关联，从而在分子水平上更好地理解非均相电子转移反应。空间分辨光谱电化学研究将为复杂电化学反应机制的计算机模拟和具有不寻常几何结构的电极上的扩散提供实验测试。

This project is in the general field of analytical and surface chemistry and in the subfields of electrochemistry and spectroscopy. Two spectroscopic techniques will be employed to probe electrode surfaces and nearby solutions. Spatially resolved absorption spectroscopy will be employed to examine reactions of electrochemically generated species, particularly those undergoing catalytic oxidation-reduction reactions. In addition, this technique will be employed to study diffusion to cylindrical microelectrodes and to electrodes of unusual geometry. Generation of optical gain in electro- chemiluminescent systems will be attempted. Raman spectroscopy will be employed to obtain structural information about electrogenerated species and to probe the surface of carbon electrodes. The carbon surface spectrum will be correlated with the electrochemical behavior of the material. The structure of surface oxides on modified carbon electrodes also will be examined. Spectroelectrochemical investigations of the electrode-solution interface will enable correlation of the molecular surface states of electrodes with their electron transfer characteristics and thereby lead to a better understanding of heterogeneous electron transfer reactions at the molecular level. Spatially resolved spectroelectrochemical studies will provide an experimental test of computer simulations of complex electrochemical reaction mechanisms and of diffusion at electrodes with unusual geometries.