The Electrochemistry of Nitrogen and Sulfur Oxides: In situ Spectroelectrochemical Studies

本研究项目研究了控制水溶液中氮硫氧化物和含氧阴离子非均相氧化和还原的界面结构和动力学。在分析和表面化学计划的支持下，凯斯西储大学化学系的Daniel Scherson教授使用了能够直接探测金属-溶液界面上的化学过程的光学技术，包括共振和表面增强拉曼光谱、紫外-可见反射光谱、X射线吸收方法和二次谐波产生。研究了含氮、硫小分子在有序金属表面和过渡金属大环化合物修饰的金属表面上的结合和反应活性。该项目的一项重要内容涉及制定战略，以便在亚微秒尺度上实现这些测量的时间分辨率。从这个项目中获得的信息提高了我们对涉及氮氧化物和硫氧化物的分子和离子形式的化学反应的理解。对这类化合物的兴趣跨越了广泛的学科，从大气科学和毒理学到催化剂和神经生物学。通过这些研究，对氮氧化物和硫氧化物化合物中化学键的形成和解离有了基本的认识。

This research project investigates aspects of interfacial structure and dynamics that control the heterogeneous oxidation and reduction of nitrogen and sulfur oxides and oxyanions in aqueous solution. With the support of the Analytical and Surface Chemistry Program, Professor Daniel Scherson in the Department of Chemistry at Case Western Reserve University, uses optical techniques that enable direct probing of chemical processes at metal-solution interfaces, including resonance and surface enhanced Raman spectroscopies, ultraviolet-visible reflectance spectroscopy, X-ray absorption methods, and second harmonic generation. The binding and reactivity of small nitrogen and sulfur containing molecules to ordered metal surfaces and metal surfaces modified by transition metal macrocyclic compounds are studied. An important thrust of the project involves the development of strategies for achieving temporal resolution in these measurements on the sub-microsecond scale. Information obtained from this project improves our understanding of chemical reactions involving molecular and ionic forms of nitrogen and sulfur oxides. Interest in this class of compounds spans a wide variety of disciplines, ranging from atmospheric sciences and toxicology to catalysts and neurobiology. Fundamental insight into the formation and dissociation of chemical bonds in nitrogen oxide and sulfur oxide compounds is obtained from these studies.