CAREER: Bifunctional and Bimetallic Single-Site Catalysts for Sustainable Synthesis

职业：用于可持续合成的双功能和双金属单中心催化剂

• 批准号: 2142798
• 负责人: Dianne Xiao
• 金额: $ 69.95万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-02-01 至 2027-01-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2142798&HistoricalAwards=false
• 关键词: CAREER; Bifunctional; Bimetallic; Single; Site

With funding from both the Chemical Catalysis program in the Division of Chemistry (CHE) and the Solid State and Materials Chemistry program in the Division of Materials Research (DMR), Dr. Dianne Xiao and her research group at the University of Washington will design new heterogeneous catalysts that will enable more sustainable chemical synthesis, including the use of renewable feedstocks and the replacement of hazardous reagents. Her group will explore how multiple metal centers and organic functional groups can work together to catalyze transformations not achievable by a single component in isolation. Dr. Xiao will also be engaged in multiple outreach and educational activities aimed at broadening STEM participation and enhancing public scientific literacy. These will include developing outreach activities in partnership with local museums and organizations, designing new inquiry-based labs and educational resources at the college level, and creating a series of science lectures aimed at informing the public on energy and environmental issues.In enzymes, multiple organic and inorganic functional groups work together to lower activation barriers and enhance reaction rates. Applying these bioinspired concepts to the design of new heterogeneous catalysts, this project will explore a simple yet versatile templating strategy for precisely positioning multiple functional groups within metal–organic framework pores. Current approaches for tethering bimetallic and bifunctional sites to solid surfaces suffer from active site non-uniformity, low structural precision, and poor chemical tunability. These synthetic limitations have, in turn, greatly limited our knowledge of how these structural motifs behave and react in a heterogeneous catalysis context. Our proposed templating strategy provides an opportunity to explore the chemistry of bimetallic and bifunctional active sites and identify nuanced catalyst structure–activity relationships. For example, how do acid-base distance, pKa, and structural flexibility influence the activity and stability of bifunctional aldol condensation catalysts? Similarly, what roles do metal identity, nuclearity, and ligand environment play in facilitating bimetallic O2 activation and transfer? Answers to these questions will help inform the development of future condensation and oxidation catalysts that enable waste valorization and promote green chemistry principles. Using these new synthetic tools, Dr. Xiao will interrogate sophisticated surface-supported active sites, including bifunctional acid–base sites for biomass utilization and bimetallic species for aerobic oxidation catalysis. Dr. Xiao will also be actively engaged in STEM outreach programs across multiple age demographics, from K–12 to college and the older adult population.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.

在化学部（CHE）化学催化计划和材料研究部（DMR）固态和材料化学计划的资助下，华盛顿大学的Dianne Xiao博士和她的研究小组将设计新的多相催化剂，以实现更可持续的化学合成，包括使用可再生原料和替换危险试剂。她的团队将探索多个金属中心和有机官能团如何协同工作，催化单一组分无法实现的转化。肖博士还将参与多项旨在扩大STEM参与和提高公众科学素养的外联和教育活动。这些措施包括与当地博物馆和组织合作开展外展活动，在大学层面设计新的基于探究的实验室和教育资源，以及创建一系列旨在向公众宣传能源和环境问题的科学讲座。在酶中，多种有机和无机官能团共同作用，降低活化障碍，提高反应速率。将这些生物启发的概念应用于新型多相催化剂的设计，该项目将探索一种简单而通用的模板策略，用于在金属有机框架孔内精确定位多个官能团。目前用于将双功能位点和双功能位点束缚到固体表面的方法遭受活性位点不均匀性、低结构精度和差的化学可调谐性。这些合成的限制，反过来，大大限制了我们的知识，这些结构基序的行为和反应中的多相催化背景。我们提出的模板策略提供了一个机会，探索化学的双功能活性位点，并确定微妙的催化剂的结构-活性关系。例如，酸碱距离、pKa和结构灵活性如何影响双功能羟醛缩合催化剂的活性和稳定性？同样，金属身份，核性和配体环境在促进CO_2活化和转移中起什么作用？对这些问题的回答将有助于为未来冷凝和氧化催化剂的开发提供信息，这些催化剂能够实现废物的价值化并促进绿色化学原理。利用这些新的合成工具，肖博士将研究复杂的表面支撑活性位点，包括用于生物质利用的双功能酸碱位点和用于有氧氧化催化的生物物种。肖博士还将积极参与STEM外展项目，涵盖从K-12到大学和老年人口的多个年龄段。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。