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

在凯斯西储大学分析和表面化学项目的支持下，凯斯西储大学化学系的Daniel Scherson教授及其团队探索了控制水性电解质中氮、硫氧化物和氧离子非均相氧化和还原动力学的界面结构方面。他们开发并实施了原位光谱技术，可以直接探测金属-溶液界面的化学过程。方法包括共振和表面增强拉曼，紫外-可见光归一化微分反射和二次谐波产生。关注的重点是含氮和含硫小分子与明确微形貌的金属表面的结合和反应性，无论是裸露的还是被过渡金属大环修饰的。该项目的一个重要推力涉及开发监测界面动力学的策略，具有高空间分辨率和低至亚微秒尺度的时间分辨率。双光束重合策略的实现为检测吸附在单个表面的两种或多种物质提供了特异性。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，包括氮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跨越了各种学科，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将接触到广泛的基础和应用学科，并非常适合面对众多尚未解决的高度跨学科问题领域所带来的挑战，特别是与纳米科学，医学和生物技术相关的问题。该校与位于克利夫兰地区的私立女子K-12教育机构海瑟薇·布朗（Hathaway Brown）有着密切的联系，可以将这些研究机会扩展到高中生。

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.