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

俄勒冈大学化学与生物化学系的Amanda Cook-Sneathen通过了解液体-固体界面上分子的相互作用，正在开发新的催化剂。该项目由化学部门化学结构、动力学与机制B项目资助。这项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，这种活性位点在结构上是可以理解的。固体催化剂在化学工业中广泛使用，但了解它们的功能是非常具有挑战性的。只有在分子水平上了解活性位点结构，才能对如何改进反应提出假设。在本项目中，将钯制成的活性位点安装在二氧化硅（沙子和玻璃的主要成分）表面，合成固体催化剂，并研究其活性和作用机理。这个研究项目位于有机和无机化学、均相和多相催化的界面，有潜力为更可持续的未来做出贡献。由于研究的跨学科性质，从事该项目的学生将在智力和实践上受益。指导、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，也是该项目的一部分。多相催化在化学工业中至关重要，90%的化学过程都使用多相催化。这些催化剂是可持续实践的组成部分，因为它们坚固耐用，可回收利用。多相催化剂的改进往往是经验的，并且由于缺乏对活性位点的结构理解而受到阻碍，从而妨碍了信息机制的研究。该项目利用表面有机金属化学来控制表面上金属位点的结构和反应性，特别是二氧化硅支撑的钯位点。目的：1)形成表面负载的（硅基）钯(H)，并测试其作为烯烃异构化催化剂的反应活性；2)研究硅卤化物与钯配合物的氧化加成反应；3)将合成表面负载的阳离子钯位，并证明其在Diels-Alder反应中的催化活性。除了研究目标之外，还有几个互补的教育目标：1)通过有效的指导进行教育，2)增加STEM的代表性，以及3)提高对代表性不足和边缘化群体的化学家贡献的认识。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.