CAREER: Rational Design of Green Catalysts for Chemical Oxidations

化学催化项目支持北卡罗莱纳州立大学的Elon A. Ison教授，他将开发利用过渡金属催化的新方法，以实现碳氢化合物的清洁高效氧化。所提出的工作将合理设计新的催化系统，用于通过化学氧化将碳氢化合物原料转化为有价值的材料。传统上，氧化是用强化学计量氧化剂进行的，包括Mn(VII), Cr(VI), Os（VIII）和氯基氧阴离子盐。这些试剂除了成本高昂外，还会导致环境污染。解决选择性氧化这一关键问题的方法是开发过渡金属催化剂，这种催化剂可以介导产生所需氧化产物的反应，并最大限度地减少不良副产物。在自然界中，酶被用作有氧氧化的催化剂，根据其催化机制分为氧化酶和加氧酶。氧化酶通过双氧作为氢受体催化底物氧化，而加氧酶通过氧原子转移催化底物氧化。氧原子转移氧化反应，即模拟加氧酶，是众所周知的，也是不对称催化中最成功的方法之一。这些过程突出了本研究计划中将采用的两种主要策略，这两种策略将设计用于有机基质催化氧化的系统。底物氧化（氧化酶）过程中不涉及氧原子转移的过程。系统)，将利用氧作为终端氧化剂，以及涉及将氧原子转移到底物的过程(加氧酶？系统)，将利用一氧化二氮作为氧化剂。更广泛的影响将涉及在催化和绿色化学领域的本科和研究生水平的新课程和实验室的发展。此外，一个新的研究生研讨会系列叫做？无机研究系列讲座？，以及一个名为？无机催化与能源（ICE）？旨在建立北卡罗莱纳州立大学的无机团体和三角研究区域内的研究机构之间的合作。扩大参与将包括指导、发展和招募来自不同背景的新一代科学家（高中生、本科生、研究生和博士后助理），以探索利用催化作为技术的STEM领域的职业。

The Chemical Catalysis Program supports Professor Elon A. Ison at North Carolina State University who will develop new methodologies using transition metal catalysis to accomplish the clean and efficient oxidation of hydrocarbons. The proposed work will rationally design new catalytic systems for use in the conversion of hydrocarbon feed stocks into valuable materials via chemical oxidation. Traditionally, oxidations are performed with strong stoichiometric oxidants, including salts of Mn(VII), Cr(VI), Os(VIII), and chlorine-based oxoanions. These reagents, in addition to their significant costs, lead to environmental contaminants. The solution to the critical problem of selective oxidation is the development of transition metal catalysts that can mediate reactions that result in desired oxidized products and minimize undesirable by-products. In nature, enzymes are employed as catalysts for aerobic oxidations and are characterized as oxidases and oxygenases depending on their catalytic mechanisms. Oxidases catalyze the oxidation of substrates by employing dioxygen as a hydrogen acceptor, while oxygenases oxidize substrates by oxygen atom transfer. Oxygen atom-transfer oxidation reactions, that is, oxygenase mimics, are well-known and are among the most successful methods in asymmetric catalysis. These processes highlight the two main strategies that will be employed in this research program that will design systems for the catalytic oxidation of organic substrates. Processes that do not involve oxygen atom transfer in substrate oxidation (?oxidase? systems), will utilize oxygen as a terminal oxidant, and processes that involve the transfer of an oxygen atom to a substrate (?oxygenase? systems), will utilize nitrous oxide as an oxidant.Broader impacts will involve the development of new courses and labs on the undergraduate and graduate levels in the area of catalysis and green chemistry. Additionally, a new graduate seminar series called ?Inorganic Research Seminar Series?, and an annual symposium entitled ?Inorganic Catalysis and Energy (ICE)? aimed at establishing collaborations among the inorganic groups at North Carolina State University and the research institutions within the Research Triangle area will be developed. Broadening participation will include the mentorship, development, and recruitment of a new generation of scientists (high-school, undergraduate, graduate students, and postdoctoral associates) from diverse backgrounds to explore careers in STEM fields that utilize catalysis as a technology.