Matrix Isolation and Theoretical Study of the Mechanisms of Oxidation Processes

基质分离和氧化过程机理的理论研究

• 批准号: 9877076
• 负责人: Bruce Ault
• 金额: --
• 依托单位: University of Cincinnati Main Campus
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-07-01 至 2003-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9877076&HistoricalAwards=false
• 关键词: Matrix; Isolation; Theoretical; Study; Mechanisms

In this project supported by the Experimental Physical Chemistry Program of the Chemistry Division, Bruce Ault of the University of Cincinnati and Janet Del Bene of Youngstown State University will study two classes of oxidation-reduction reactions using matrix-isolation spectroscopy. The first class consists of high-valent transition metal oxo compounds, specifically chromyl chloride and methyltrioxorhenium, and the second involves organic peroxides, with hydrogen peroxide as a prototype. The goals of this project include identification of key intermediates in the reaction pathways, spectroscopic and structural characterization of these intermediates, comparison of experimental results to high-level theoretical calculations, and deduction of the reaction mechanism for these reactions. The reactive intermediates will be trapped and preserved in cryogenic inert matrices using a range of deposition techniques and different forms of energy input to initiate reaction. Trapped species will be characterized by infrared, Raman, and visible/ultraviolet spectroscopy.This project will aid in understanding the mechanisms of oxidation reactions that are at the heart of current research into catalysis. Oxidation of organics constitutes one of the most important reactions in industry, but environmental waste needs to be decreased and raw materials to be conserved better. Other areas impacted by this work include atmospheric chemistry and air pollution, waste water treatment, the production of fine chemicals, and synthetic organic methodology.

在这个由化学系实验物理化学计划支持的项目中，辛辛那提的布鲁斯奥尔特和扬斯敦州立大学的珍妮特德尔贝内将使用基质隔离光谱学研究两类氧化还原反应。 第一类由高价过渡金属含氧化合物组成，特别是铬酰氯和甲基三氧化铼，第二类涉及有机过氧化物，过氧化氢作为原型。 该项目的目标包括鉴定反应途径中的关键中间体、这些中间体的光谱和结构表征、实验结果与高级理论计算的比较以及推导这些反应的反应机理。 使用一系列沉积技术和不同形式的能量输入来引发反应，将活性中间体捕获并保存在低温惰性基质中。 捕获的物种将通过红外、拉曼和可见/紫外光谱来表征。这个项目将有助于理解氧化反应的机制，这是目前催化研究的核心。 有机物的氧化是工业中最重要的反应之一，但需要减少环境废物并更好地保护原材料。 受这项工作影响的其他领域包括大气化学和空气污染，废水处理，精细化学品生产和合成有机方法。