Structure and Dynamics in Heterogeneous Reactions

本项目支持的研究重点是对表面和界面的原子和分子结构、组成以及这些界面的化学性质和反应性之间的联系有一个基本的了解。许多重要的技术，从在化学品和燃料的生产中使用催化，到电子元件的加工，再到防止腐蚀和结构恶化，都取决于对表面和界面的结构和反应性的理解。这个项目包含四个特定的研究课题。第一部分详细探讨了在污染控制和化学生产中重要的催化氧化反应的分子动力学。第二部分是关于结构金属表面氧化和腐蚀的机制及其预防策略。第三部分探讨了表面自组装过程的微观机制，与下一代电子设备的生产和对生物膜和膜的理解有关。第四个主题旨在开发方法，以详细分析复杂的表面和界面，这是本研究项目的主题。这些研究课题中的每一个都有助于培养学生的研究方法，同时提供支持广泛技术的基础知识。本研究项目重点研究表面和界面的详细原子、分子和电子结构及其化学性质和反应性之间的联系。这些表面结构和反应性的基本问题在四个相互关联的领域得到解决。催化氧化的研究主要集中在纳米等离子体传感器的实现上，以评估非均相催化氧化反应中催化剂表面中间体的覆盖和存在。从这些测量中获得的机理信息将与二极管激光吸收光谱获得的产物内部状态分布信息相结合，以提供更完整的催化氧化反应动力学图像。第二个领域是利用光电子能谱和电化学表面分析，研究极端环境下合金结构氧化，以及混合分子缓蚀剂的协同效应。第三个领域涉及大型有机分子在液固界面的自组装机制，重点是化学吸附自组装单层（SAMs）的合成，以及石墨上物理吸附SAMs形成的能量学的定量评估。第四个领域的工作开发了在x射线光电子能谱中使用静态和动态差分电荷的方法，以实现复杂复合表面材料的化学和电子特性分析，这是先前研究主题的重点。

NON-TECHNICAL SUMMARYThe focus of the research supported in this project is to gain a fundamental understanding of the connection between the atomic and molecular structure and composition of surfaces and interfaces, and the chemical properties and reactivity of these interfaces. A large number of important technologies, ranging from the use of catalysis in the production of chemicals and fuels, to the processing of electronic components, to the prevention of corrosion and structural deterioration, depend on an understanding of the structure and reactivity of surfaces and interfaces. Four particular research topics are contained in this project. The first explores the detailed molecular dynamics of catalytic oxidation reactions important in pollution control and chemical production. The second is concerned with mechanisms of surface oxidation and corrosion of structural metals and strategies for its prevention. The third explores the microscopic mechanism of the process of self-assembly at surfaces, relevant to the production of next generation electronic devices and the understanding of bio-films and membranes. The fourth topic seeks to develop methods for the detailed analysis of the complex surfaces and interfaces that are the subject of this research project. Each of these research topics serves to train students in research methods while providing the fundamental knowledge to support a wide array of technologies. TECHNICAL SUMMARYThis research project focuses on the connection between the detailed atomic, molecular, and electronic structure of surfaces and interfaces, and their chemical properties and reactivity. These fundamental questions of surface structure and reactivity are addressed in four interrelated areas. Studies of catalytic oxidation focus on the implementation of nanoplasmonic sensors to evaluate the coverage and presence of intermediates on the catalyst surface during heterogeneous catalytic oxidation reactions. Mechanistic information obtained from these measurements will be coupled with product internal state distribution information obtained by diode laser absorption spectroscopy, to provide a more complete picture of the catalytic oxidation reaction dynamics. The second area addresses structural alloy oxidation in extreme environments, and synergistic effects in mixed molecular corrosion inhibitors, using photoelectron spectroscopy and electrochemical analysis of the surfaces. The third area concerns the mechanisms of self-assembly of large organic molecules at the liquid-solid interface, with a focus on the synthesis of fundamentally interesting chemisorbed self-assembled monolayers (SAMs), and the quantitative evaluation of the energetics of formation of physisorbed SAMs on graphite. Work in the fourth area develops methods to use both static and dynamic differential charging in X-ray photoelectron spectroscopy to enable the chemical and electronic property analysis of complex composite surface materials that are the focus of the previous research topics.