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.

在这个职业项目中，由化学结构，动力学和机制B计划资助，俄勒冈大学化学和生物化学系的Amanda Cook-Sneathen正在通过了解液态固体界面上分子的相互作用，从而开发新的催化剂。该研究计划的最终目的是开发具有活性位点的固体催化剂 - 在结构上是催化剂上化学反应的位置。固体催化剂在化学工业中普遍使用，但了解它们的功能是显着挑战的。只有了解分子水平上的主动位点结构的知识才能提高如何改善反应的假设。在这个项目中，将在二氧化硅表面（沙子和玻璃的主要成分）中安装由钯制成的活性位点，以合成固体催化剂，并将研究其活性和作用机制。该研究计划位于有机和无机化学以及同质和异质催化的界面，并有可能为更可持续的未来做出贡献。从事该项目的学生将由于研究的跨学科性质而受益于智力和实际上。该项目的一部分也是该项目的一部分，指导，沉浸在化学实验室中的高中生以及通过外展的多样性，公平和包容性的增加也是该项目的一部分。异质性催化在化学工业中至关重要，在化学工业中，它用于90％的化学过程。这些催化剂是可持续实践不可或缺的，因为它们是可靠的且可回收的。异质催化剂的改善通常是经验的，并且由于缺乏对活性部位的结构理解而阻碍，从而排除了信息性的机械研究。该项目利用表面有机化学来控制表面上金属位点的结构和反应性，特别是在二氧化硅上支撑的钯位点。有三个目的：1）将形成表面支持的（Silyl）Pd（H）物种，并将测试它们作为烯烃异构化催化剂的反应性； 2）将研究向钯络合物氧化添加甲硅烷基卤化物； 3）将合成阳离子，表面支撑的钯位点，并将证明它们在Diels-Alder反应中的催化活性。除了研究目标外，还有几个完整的教育目标：1）通过有效的心态进行教育，2）增加STEM的代表性，3）提高对代表性不足和边缘化群体的化学家的贡献的认识。这项奖项反映了NSF的法定任务，并认为通过基金会的知识优点和更广泛的cribitia cripitia cripitia cripitia criperia cripitia reception the Apportaution aweartia奖。