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

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教授和他的团队探索了控制水溶液中氮、硫氧化物和氧阴离子非均相氧化和还原动力学的界面结构方面。他们开发和实施原位光谱技术，使直接探测金属-溶液界面的化学过程成为可能。方法包括共振和表面增强拉曼、紫外可见归一化差分反射和二次谐波产生。人们的注意力集中在含氮和含硫的小分子与金属表面的结合和反应性上，这些金属表面具有明确的微地形，无论是裸露的还是被过渡金属大环修饰的。该项目的一项重要内容涉及制定高空间分辨率和低至亚微秒量级的时间分辨率监测界面动力学的战略。双光束符合策略的实施为检测吸附在单一表面上的两个或多个物种提供了特异性。从这个项目中获得的信息提高了我们对化学反应的基本理解，包括涉及氮氧化物和硫氧化物的分子和离子形式的化学键的形成和解离。对这类化合物的兴趣横跨多个学科，从大气科学和毒理学到催化和神经生物学。因此，参与这项研究的学生接触到了广泛的基础和应用学科，并很好地适应了许多尚未解决的高度跨学科问题领域带来的挑战，特别是与纳米科学、医学和生物技术相关的领域。与克利夫兰地区的私立K-12女子机构Hathaway Brown的密切联系，使这些研究机会扩大到高中生。

ABSTRACT CHE-0616800Scherson/Case Western ReserveWith the support from the Analytical and Surface Chemistry Program, Professor Daniel Scherson and his group in the Department of Chemistry at Case Western Reserve University explore aspects of interfacial structure that control the dynamics of heterogeneous oxidation and reduction of nitrogen and sulfur oxides and oxyanions in aqueous electrolytes. They develop and implement in situ spectroscopic techniques that enable direct probing of chemical processes at metal-solution interfaces. Methods include resonance and surface enhanced Raman, ultraviolet-visible normalized differential reflectance, and second harmonic generation. Attention is focused on the binding and reactivity of small nitrogen- and sulfur-containing molecules to metal surfaces of well defined microtopography, either bare or modified by transition metal macrocycles. An important thrust of the project involves the development of strategies for monitoring interfacial dynamics with high spatial resolution and temporal resolution down to the sub-microsecond scale. Implementation of dual beam coincidence tactics provides specificity for detection of two or more species adsorbed on single surface. Information obtained from this project improves our fundamental understanding of chemical reactions, including formation and dissociation of chemical bonds 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 catalysis and neurobiology. As a result, students involved in this research are exposed to a broad range of both fundamental and applied disciplines, and become well suited to face the challenges posed by a multitude of yet unresolved highly interdisciplinary problem areas, particularly those related to nanoscience, medicine and biotechnology. Close links with Hathaway Brown, a private women's K-12 institution in the Cleveland area, allows extension of these research opportunities to high school students.