Rational Design of Fluorinated Environments for Aerobic "Green" Catalysis

有氧“绿色”催化氟化环境的合理设计

• 批准号: 0967934
• 负责人: Robert Barat
• 金额: $ 30.16万
• 依托单位: New Jersey Institute of Technology
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-05-01 至 2014-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0967934&HistoricalAwards=false
• 关键词: Rational; Design; Fluorinated; Environments; Aerobic

0967934BaratThe work which will be conducted by Profs. Barat and Gorun at New Jersey Institute of Technology is to design active catalyst species which are in essence miniature reaction vessels. This feature makes them similar to enzyme catalyst sites. The PIs intend to use perfluorinated phthalocyanines as hydrophobic vessels surrounding hydrophilic metal centers for the aerobic oxidation of mercaptans to disulfides. These perfluorinated phthalocyanines should be more resistant to damage by catalytically-produced oxygen radicals than other oxidation catalysts, which is another feature in common with enzymes. The work proposed is a straightforward study of the influence of ligand structure on catalyst activity, and stability. The authors propose to study the kinetics of the homogeneous radical-based oxidation, as well as evaluating heterogenized versions of the catalyst (Cobalt-based phthalocyanines coordinated to SiO2 through imidazolyl groups).The project aims to provide catalysts for oxidation of molecules which are more "green" than previous catalysts by allowing the use of air for the reaction without the catalyst being destroyed by the oxygen. This is done by replacing reactive C-H bonds with unreactive C-F bonds in the catalyst species. Further fine tuning of the catalyst is possible by using organic chemistry modifications of the catalyst. The investigators have chosen mercaptan oxidation, now used to remove sulfur from gasoline, as the first reaction for study. This is a useful benchmark, and success will allow projection of the concept to other catalysts and reactions. These studies will be of interest to the community enrolling at NJIT, and the PIs will involve undergraduates in the research program.

0967934Barat这项工作将由教授进行。新泽西理工学院的 Barat 和 Gorun 将设计活性催化剂物质，其本质上是微型反应容器。这一特征使它们类似于酶的催化剂位点。 PI 打算使用全氟化酞菁作为亲水金属中心周围的疏水容器，将硫醇有氧氧化成二硫化物。这些全氟化酞菁应该比其他氧化催化剂更能抵抗催化产生的氧自由基的损害，这是与酶的另一个共同特征。 所提出的工作是对配体结构对催化剂活性和稳定性影响的直接研究。作者提议研究均相自由基氧化的动力学，并评估催化剂的异质化版本（钴基酞菁通过咪唑基与 SiO2 配位）。该项目旨在提供比以前的催化剂更“绿色”的分子氧化催化剂，允许使用空气进行反应，而无需催化剂 被氧气破坏。这是通过用催化剂物质中的非反应性 C-F 键替换反应性 C-H 键来实现的。通过使用催化剂的有机化学改性可以进一步微调催化剂。研究人员选择硫醇氧化（目前用于去除汽油中的硫）作为第一个研究反应。这是一个有用的基准，成功将允许将该概念投射到其他催化剂和反应中。这些研究将引起 NJIT 入学社区的兴趣，PI 将让本科生参与研究项目。