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: 2102552
• 负责人: Charles Edwin Webster
• 金额: $ 18.29万
• 依托单位: Mississippi State University
• 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 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102552&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.

在化学催化计划的支持下，阿拉巴马大学的伊丽莎白·T·帕普什（Elizabeth T. Papish），密西西比大学的贾里德·H·德尔坎普（Jared H. Delcamp）和密西西比州立大学的查尔斯·埃德温·韦伯斯特（Charles Edwin Webster）将研究与新型金属型结构的合成型二氧化碳二氧化碳碳二氧化碳碳二氧化碳碳二氧化碳碳质含量的转变。在我们的未来，设想阳光驱动的能源基础设施需要有效，可靠的催化剂，这可以为人工光化学驱动的反应提供燃料生产的反应。相对于我们当前的化石燃料稳态基础设施，使用阳光作为可按需使用的储存的化学能来创建燃料。尽管如此，这种愿景需要快速，耐用和选择性的催化剂，理想情况下可以利用可行的可用金属。当前缺乏这种催化剂代表了当前知识库中的显着差距。研究人员将设计新的催化剂，以减少二氧化碳的碳，以具有以前未经测试的创新结构的燃料。他们将通过合成，机械和计算研究来设计和高度活跃的催化剂来控制和理解二氧化碳还原。这些研究可以阐明影响催化的因素，并最终导致以碳中性方式从温室气体产生太阳能燃料。这项研究的结果将广泛分享，预计该项目将在整个项目期间帮助培训一个由10至15名本科生和研究生组成的多样化小组。调查人员将访问当地学校进行外展活动，并在其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执行催化反应，结果将与社区共享，提供教育经验，并提供实验验证。在化学分校的化学催化计划中，伊丽莎白·帕皮斯（Elizabeth T.将使用含有第一行过渡金属和大环配体的新金属催化剂研究二氧化碳还原。对于旨在将二氧化碳转换为燃料或燃料前体的人工光化学方案需要更有效，健壮和选择性催化剂。利用在保留水中活性的有效自敏催化剂的合成和测试方面的先前经验，协作团队将使用两种策略来设计新的健壮催化剂：通过使用巨型晶状体配体进行主动隔离，并通过使用低价属于低价属的巨型金属配合物。 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.长期的目标是将分子催化剂设计的领域移动到更接近耐用的，富含地球的金属催化剂系统，以使用上述任务中获得的知识在太阳能光电动化学细胞中脱氧二氧化碳的光催化还原。系统地将这些想法系统地应用于第一行金属仍然是未知的领域，潜在的回报是了解如何用第一排金属配合物制造太阳能燃料。科学结果将通过出版物，演示和专利进行传达；更广泛的影响将包括在本科教学实验室环境中进行的外展活动和催化研究实验。该奖项反映了NSF的法定任务，并且使用基金会的知识分子优点和更广泛的审查标准，被认为值得通过评估来提供支持。

项目成果

Carbene–Calcium Silylamides and Amidoboranes

• DOI: 10.1021/acs.organomet.2c00464
• 发表时间: 2022-10
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Akachukwu D. Obi;Lucas A. Freeman;Samuel J. Coates;Andrew J. H. Alexis;Nathan C. Frey;D. Dickie;C. E. Webster;Robert J. Gilliard

N‐Heterocyclic Carbene‐Assisted Reversible Migratory Coupling of Aminoborane at Magnesium

N—杂环卡宾—镁下氨基硼烷的辅助可逆迁移偶联

• DOI: 10.1002/anie.202211496
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Obi, Akachukwu D.;Frey, Nathan C.;Dickie, Diane A.;Webster, Charles Edwin;Gilliard, Jr, Robert J.
• 通讯作者: Gilliard, Jr, Robert J.

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.

Triphenylene containing blue-light emitting semi-fluorinated aryl ether polymers with excellent thermal and photostability

含苯并菲的蓝光发射半氟化芳基醚聚合物，具有优异的热稳定性和光稳定性

• DOI: 10.1039/d2qm00099g
• 发表时间: 2022
• 期刊: Materials Chemistry Frontiers
• 影响因子: 7
• 作者: Shelar, Ketki Eknath;Le, Nghia;Mukeba, Karl M.;Dey, Sriloy;Farajidizaji, Behzad;Athukorale, Sumudu;Pittman, Charles U.;Webster, Charles Edwin;Donnadieu, Bruno;Caldona, Eugene
• 通讯作者: Caldona, Eugene

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.