CAREER: CAS: Understanding the Chemistry of Palladium and Silyl Compounds to Design Catalyst Active Sites

职业：CAS：了解钯和甲硅烷基化合物的化学性质以设计催化剂活性位点

• 批准号: 2238379
• 负责人: Amanda Cook-Sneathen
• 金额: $ 77万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2028-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2238379&HistoricalAwards=false
• 关键词: CAREER; CAS; Understanding; Chemistry; Palladium

In this CAREER project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Amanda Cook-Sneathen of the Department of Chemistry and Biochemistry at the University of Oregon is developing new catalysts by understanding the interactions of molecules at a liquid-solid interface. The ultimate goal of this research program is to develop solid catalysts that have an active site – the location of chemical reactions on a catalyst – that is structurally understood. Solid catalysts are used ubiquitously in the chemical industry but understanding how they function is significantly challenging. Only with knowledge of the active site structure on a molecular level can one develop hypotheses on how to improve reactions. In this project, active sites made of palladium will be installed on the surface of silica (the primary component of sand and glass) to synthesize solid catalysts, and their activities and mechanisms of action will be investigated. This research program sits at the interface of organic and inorganic chemistry and homogeneous and heterogeneous catalysis and has the potential to contribute to a more sustainable future. Students working on this project will benefit intellectually and practically because of the interdisciplinary nature of the research. Mentorship, immersion of high-school students in chemistry labs, and increasing diversity, equity, and inclusion through outreach are also parts of the project. Heterogeneous catalysis is vital in the chemical industry, where it is used in 90% of chemical processes. These catalysts are integral to sustainable practices, since they are robust and recyclable. Improvement of heterogeneous catalysts is often empirical and is hindered by a lack of structural understanding of the active site, precluding informative mechanistic studies. This project utilizes surface organometallic chemistry to control the structure and reactivity of metal sites on surfaces, specifically palladium sites supported on silica. There are three Aims: 1) Surface-supported (silyl)Pd(H) species will be formed and their reactivity as catalysts for alkene isomerization will be tested; 2) Oxidative addition of silyl halides to palladium complexes will be investigated; 3) Cationic, surface-supported palladium sites will be synthesized, and their catalytic activity in the Diels-Alder reaction will be demonstrated. In addition to the research goals, there are several complementary educational goals: 1) educate through effective mentorship, 2) increase representation in STEM, and 3) increase awareness of contributions of chemists from underrepresented and marginalized groups.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在这个由化学系化学结构、动力学和机制 B 项目资助的职业项目中，俄勒冈大学化学与生物化学系的 Amanda Cook-Sneathen 正在通过了解液体中分子的相互作用来开发新的催化剂-固体界面。该研究计划的最终目标是开发具有活性位点（催化剂上化学反应的位置）的固体催化剂，该活性位点在结构上已被广泛使用。但了解它们的功能有多重要是一项挑战，只有了解分子水平上的活性位点结构，才能提出如何改进反应的假设，在该项目中，由钯制成的活性位点将安装在二氧化硅的表面上。 （沙子和玻璃的主要成分）合成固体催化剂，其活性和作用机制将被研究，该研究项目位于有机和无机化学以及均相和非均相催化的界面，有可能为以下领域做出贡献。更可持续的未来。由于该研究的跨学科性质、让高中生沉浸在化学实验室中以及通过外展增加多样性、公平性和包容性，从事该项目将在智力和实践上受益。这些催化剂在化学工业中至关重要，90% 的化学过程都使用这些催化剂，因为它们坚固且可回收，因此多相催化剂的改进通常是凭经验进行的，并且因缺乏催化剂而受到阻碍。该项目利用表面有机金属化学来控制表面金属位点的结构和反应性，特别是二氧化硅负载的钯位点。将形成 Pd(H) 物种并测试其作为烯烃异构化催化剂的反应性 2) 将卤化硅氧化加成至钯络合物； 3) 将合成表面负载的阳离子钯位点，并展示其在 Diels-Alder 反应中的催化活性 除了研究目标外，还有几个补充性的教育目标：1) 通过有效的指导进行教育， 2) 增加 STEM 中的代表性，3) 提高对代表性不足和边缘化群体的化学家贡献的认识。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力评估进行评估，认为值得支持优点和更广泛的影响审查标准。