Reaction of Carbon with Nitric and Unified Mechanism for Oxidation Carbon Gasification

摘要CTS-9523801 这是碳和一氧化氮之间的反应（形成氮和碳的氧化物）的研究，包括一个假设的表面氧复合物的检查，这可能是一个统一的机制，为所有的碳的氧化气化反应的基础。 在本研究的第一部分中，使用电子显微镜和单晶石墨测量碳和一氧化氮之间的反应速率，用于非催化和催化反应。 对于未催化的系统，测量包括氧和一氧化氮与碳的反应的相对速率，活化能对温度的依赖性，抽象的基面原子的动力学，水和一氧化碳的动力学效应，和表面氮物种。 对于催化反应，周转频率由石墨基面上的单层沟道速率数据确定;催化剂选自过渡金属、碱金属和碱土金属。 本研究的第二部分旨在更好地理解由分子轨道理论提出的氧中间体;该物种是统一机制的关键。 用程序升温脱附法（TPD）研究了四种气体（氧气、一氧化氮、水和二氧化碳）对四种石墨的吸附。 在各种温度下中断TPD实验后，对石墨样品进行光谱分析（傅里叶变换红外、X射线光电子和碳-13核磁共振），以确定表面氧物质和一氧化碳解吸能之间的相关性（如果存在）。 碳的“气化”是大量能源、化学和环境过程中的关键要素。 这个项目研究了一个反应（在这个系列中要研究的第四个）在家庭的碳酸气化反应，并试图减少收集到的知识，以统一的机制的过程。 ***

ABSTRACT CTS-9523801 This is a study of the reaction between carbon and nitric oxide (forming nitrogen and carbon oxides), including an examination of a hypothetical surface oxygen complex which could be the basis for a unified mechanism for all oxidative gasification reactions of carbon. In the first part of this study, rates are measured for the reaction between carbon and nitric oxide using electron microscopy and single-crystal graphite for both uncatalyzed and catalyzed reactions. For the uncatalyzed system, measurements include the relative rates of reaction of oxygen and nitric oxide with carbon, the dependence of activation energy on temperature, the kinetics of abstraction of basal-plane atoms, kinetic effects of water and carbon monoxide, and surface nitrogen species. For catalyzed reactions, turnover frequency is determined from the monolayer channeling rate data on the basal plane of graphite; catalysts are selected from the transition metals, alkali metals, and alkaline earths. The second part of this study seeks better understanding of the oxygen intermediate suggested by molecular orbital theory; this species is the key to a unified mechanism. Four graphites with four gases (oxygen, nitric oxide, water, and carbon dioxide) are studied by temperature-programmed desorption (TPD). Spectroscopic analyses (Fourier-transform infrared, X-ray photoelectron, and carbon-13 nuclear magnetic resonance) are performed on graphite samples after interrupting TPD experiments at various temperatures to determine, if it exists, a correlation between surface oxygen species and carbon - monoxide desorption energies. The "gasification" of carbon is a key element in a large number of energy, chemical, and environmental processes. This, project examines one reaction (the fourth to be studied in this series) in the family of carbol gasification reactions and attempts to reduce the collected knowledge to a unified mechanism for the process. ***