CAS: Collaborative Research: Macrocyclic and Supramolecular Pincer Catalysts Using Ruthenium and First Row Metals for Carbon Dioxide Reduction

CAS：合作研究：使用钌和第一排金属还原二氧化碳的大环和超分子钳式催化剂

• 批准号: 2102416
• 负责人: Elizabeth Papish
• 金额: $ 35.63万
• 依托单位: University of Alabama Tuscaloosa
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102416&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; Macrocyclic; Supramolecular

With the support of the Chemical Catalysis program in the Division of Chemistry, Elizabeth T. Papish of The University of Alabama, Jared H. Delcamp of The University of Mississippi, and Charles Edwin Webster of Mississippi State University will study the transformation of the greenhouse gas carbon dioxide into synthetic fuels with new metal catalysts of novel structure. Envisioning a sunlight-driven energy infrastructure in our future requires efficient and robust catalysts that can power artificial photochemically driven reactions for fuel production. Using sunlight to create fuels as stored chemical energy available on demand is attractive relative to our current fossil fuel-reliant infrastructure. Nonetheless, this vision requires fast, durable, and selective catalysts that would ideally utilize readily available and affordable metals where feasible. The current lack of such catalysts represents a significant gap in the current knowledge base. The investigators will design new catalysts for carbon dioxide reduction to fuels with innovative structures previously untested. They will work on controlling and understanding carbon dioxide reduction through design of robust and highly active catalysts via synthetic, mechanistic, and computational studies. These studies can elucidate the factors that impact catalysis and eventually lead to the production of solar fuels from a greenhouse gas in a carbon neutral fashion. The results of this research are to be shared broadly, and this project is expected to help train a diverse group of 10-15 undergraduate and graduate students over the project period. The investigators will visit local schools for outreach events and host high school students in their research laboratories. In addition, undergraduate students will perform catalytic reactions in a teaching lab setting, and the results will be shared with the community, to offer educational experiences along with experiment verification.With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Elizabeth T. Papish of The University of Alabama, and her collaborators, Jared H. Delcamp of The University of Mississippi, and Charles Edwin Webster of Mississippi State University, will study carbon dioxide reduction with new metal catalysts containing first row transition metals and macrocyclic ligands. More efficient, robust, and selective catalysts are needed for artificial photochemical schemes aimed at converting carbon dioxide to fuels or fuel precursors. Using prior experience in the synthesis and testing of efficient self-sensitized catalysts that retain activity in water, the collaborative team will work on designing new robust catalysts using two strategies: active site isolation via use of a macrocyclic pincer ligand, and low-coordinate metal complexes via the use of low-valent metals. Synthetic, mechanistic, and computational studies will be directed toward three goals: (1) to increase the understanding of CNC-pincer ligated first-row metal catalysts, (2) to expand the knowledge of under-explored supramolecular catalysts with iridium photosensitizers, and (3) to understand the behavior of homogeneous catalysts linked to semiconductor electrodes. The long-term goal is to move the field of molecular catalyst design closer to a durable, earth-abundant metal-based catalyst system for the photocatalytic reduction of carbon dioxide coupled to water splitting in a solar powered photo-electrochemical cell using the knowledge gained in the above tasks. Applying these ideas systematically to first-row metals is still largely uncharted territory, with the potential payoff being understanding how to make solar fuels with first row-metal complexes. The scientific results will be communicated through publications, presentations, and patents; the broader impacts will include outreach events and catalysis research experiments in an undergraduate teaching laboratory setting.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.

在化学系化学催化项目的支持下，伊丽莎白·T。亚拉巴马大学的帕皮斯，贾里德H。密西西比大学的Delcamp和密西西比州立大学的Charles Edwin韦伯斯特将研究用新型结构的金属催化剂将温室气体二氧化碳转化为合成燃料。展望未来太阳能驱动的能源基础设施，需要高效和强大的催化剂，可以为人工光化学驱动的燃料生产反应提供动力。相对于我们目前依赖化石燃料的基础设施，利用阳光来制造燃料作为储存的化学能是有吸引力的。尽管如此，这一愿景需要快速，耐用和选择性的催化剂，在可行的情况下，理想地利用容易获得和负担得起的金属。目前缺乏这类催化剂，这是目前知识基础的一个重大缺口。研究人员将设计新的催化剂，用于将二氧化碳还原为具有以前未经测试的创新结构的燃料。他们将致力于通过合成，机械和计算研究设计鲁棒和高活性的催化剂来控制和理解二氧化碳的减少。这些研究可以阐明影响催化作用的因素，并最终导致以碳中和的方式从温室气体生产太阳能燃料。这项研究的结果将被广泛分享，预计该项目将有助于在项目期间培训10-15名本科生和研究生。调查人员将访问当地学校开展外联活动，并在他们的研究实验室接待高中生。此外，本科生将在教学实验室环境中进行催化反应，并将结果与社区共享，以提供沿着实验验证的教育经验。亚拉巴马大学的帕皮什和她的合作者贾里德·H.密西西比大学的Delcamp和密西西比州立大学的Charles Edwin韦伯斯特将研究用含有第一行过渡金属和大环配体的新金属催化剂减少二氧化碳。为了将二氧化碳转化为燃料或燃料前体，人工光化学方案需要更有效、更耐用和更有选择性的催化剂。利用之前在合成和测试在水中保持活性的高效自敏化催化剂方面的经验，合作团队将使用两种策略设计新的稳健催化剂：通过使用大环钳形配体进行活性位点分离，以及通过使用低价金属进行低配位金属络合物。合成、机理和计算研究将针对三个目标：（1）增加对CNC-钳形连接的第一排金属催化剂的理解，（2）扩展对具有铱光敏剂的未开发的超分子催化剂的知识，以及（3）理解连接到半导体电极的均相催化剂的行为。长期目标是将分子催化剂设计领域更接近于使用在上述任务中获得的知识在太阳能光电化学电池中用于二氧化碳的光催化还原耦合到水裂解的耐用的、地球丰富的金属基催化剂系统。将这些想法系统地应用于第一行金属仍然是一个未知的领域，潜在的回报是了解如何用第一行金属络合物制造太阳能燃料。科学成果将通过出版物、演讲和专利进行交流;更广泛的影响将包括在本科教学实验室环境中的推广活动和催化研究实验。该奖项反映了NSF的法定使命，并被认为值得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来支持。

项目成果

Low-Valent Cobalt(I) CNC Pincer Complexes as Catalysts for Light-Driven Carbon Dioxide Reduction

低价钴 (I) CNC Pincer 配合物作为光驱动二氧化碳还原的催化剂

• DOI: 10.1021/acscatal.2c01281
• 发表时间: 2022
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Boudreaux, Chance M.;Nugegoda, Dinesh;Yao, Wenzhi;Le, Nghia;Frey, Nathan C.;Li, Qing;Qu, Fengrui;Zeller, Matthias;Webster, Charles Edwin;Delcamp, Jared H.
• 通讯作者: Delcamp, Jared H.

Sensitized and Self‐Sensitized Photocatalytic Carbon Dioxide Reduction Under Visible Light with Ruthenium Catalysts Shows Enhancements with More Conjugated Pincer Ligands

钌催化剂在可见光下的敏化和自敏化光催化二氧化碳还原显示出更多共轭钳配体的增强

• DOI: 10.1002/ejic.202101016
• 发表时间: 2022
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Das, Sanjit;Nugegoda, Dinesh;Yao, Wenzhi;Qu, Fengrui;Figgins, Matthew T.;Lamb, Robert W.;Webster, Charles Edwin;Delcamp, Jared H.;Papish, Elizabeth T.
• 通讯作者: Papish, Elizabeth T.