Collaborative Research: Atomistic Switches on Pyridinol Based Pincer Ligated Catalysts for Carbon Dioxide Reduction

合作研究：基于吡啶醇的钳式连接催化剂的原子开关用于二氧化碳还原

• 批准号: 1800281
• 负责人: Jared Delcamp
• 金额: $ 15.05万
• 依托单位: University of Mississippi
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-15 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800281&HistoricalAwards=false
• 关键词: Collaborative; Research; Atomistic; Switches; Pyridinol

With funding from the Catalysis Program of the Chemistry Division, Dr. Elizabeth Papish of the University of Alabama at Tuscaloosa, Dr. Jared Delcamp of the University of Mississippi, and Dr. Charles Edwin Webster of Mississippi State University are engaged in collaborative research designing new catalysts that can harness sunlight to convert carbon dioxide, a greenhouse gas leftover from fuel combustion, into carbon monoxide, a fuel precursor. The ability to convert carbon dioxide to carbon monoxide is challenging, and is an important step in a strategy to harness sunlight to make diesel fuel from carbon dioxide. This conversion may become useful for securing the energy future of the US, as it can provide a means to replace oil reserves as are they are depleted. Furthermore, solar fuel formation coupled with fuel combustion can be considered carbon neutral, as this process does not add carbon dioxide to the atmosphere. The research team is using synthetic chemistry to make new catalysts, test those catalysts, and computationally optimize and understand the critical steps in this process. The key innovation has been understanding how changes to small, remote groups on the catalyst can influence the course of the reaction. This project uses metals that are earth abundant and non-toxic making the chemical reactions more sustainable and environmentally friendly. This project is training a diverse group of graduate and undergraduate students at universities in Alabama and Mississippi. This synergistic collaboration enhances the learning experience for the students in these groups. The Papish group is conducting outreach events, including "Careers in Chemistry" seminars at the University of Alabama and science demonstrations at a nearby elementary school to engage students in STEM education. Drs. Papish, Delcamp, and Webster combine a wide variety of expertise in organometallic synthesis and mechanistic studies, light driven catalysis and harnessing solar energy, and organometallic computational chemistry. Their groups are designing, testing, and studying new catalysts bearing pincer ligands with oxygenated substituents on the periphery that are bound to both precious and earth abundant metals. The groups are elucidating how the protonation state of the remote oxygenated substituents on the ligands alters catalyst lifetime, reaction rate, and selectivity with these complexes. By understanding how electron donor groups influence proton coupled electron transfer (PCET) and reduces the energy requirements for catalytic processes, the groups are designing highly durable and active catalysts. This team is taking an iterative, mechanistic approach with feedback between the synthesis, catalysis, and computational studies that is leading to the development of highly active, durable catalysts. These catalysts are also being integrated into a complete photoelectrochemical cell where carbon dioxide reduction is coupled with water oxidation. This project is training a diverse group of undergraduate and graduate students over the project period. Dr. Papish is hosting "Careers in Chemistry" seminars at the University of Alabama each year. She and her group are also visiting local elementary schools to perform demonstrations and discuss opportunities in science with the students. New experiments are also being developed for undergraduate chemistry labs to introduce catalytic chemistry research to the teaching lab.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.

With funding from the Catalysis Program of the Chemistry Division, Dr. Elizabeth Papish of the University of Alabama at Tuscaloosa, Dr. Jared Delcamp of the University of Mississippi, and Dr. Charles Edwin Webster of Mississippi State University are engaged in collaborative research designing new catalysts that can harness sunlight to convert carbon dioxide, a greenhouse gas leftover from fuel combustion, into carbon monoxide,燃料前体。将二氧化碳转换为一氧化碳的能力是具有挑战性的，并且是利用阳光以从二氧化碳制造柴油燃料的策略的重要一步。这种转换对于确保美国的能源未来可能有用，因为它可以提供一种替代石油储量的方法，因为它们被耗尽。此外，太阳能燃料形成和燃料燃烧可以被视为中性碳，因为此过程不会在大气中添加二氧化碳。研究团队正在使用合成化学来制造新的催化剂，测试这些催化剂，并在此过程中优化并理解关键步骤。关键的创新是了解催化剂上小型偏远群体的变化如何影响反应的过程。 该项目使用的是地球丰富且无毒的金属，从而使化学反应更加可持续和环保。该项目正在阿拉巴马州和密西西比大学的大学培训一群不同的研究生和本科生。这种协同的合作增强了这些小组学生的学习经验。教皇小组正在进行宣传活动，包括阿拉巴马大学和科学示范的“化学职业”研讨会，以吸引学生参加STEM教育。博士。 Papish，Delcamp和Webster在有机金属合成和机理研究，轻驱动催化和利用太阳能以及有机金属计算化学方面结合了多种专业知识。他们的小组正在设计，测试和研究带有钳子配体的新催化剂，并在外围带有氧化取代基，并与珍贵和地球丰富的金属结合。两组正在阐明配体上远程氧化取代基的质子化状态如何改变催化剂的寿命，反应速率和这些复合物的选择性。通过了解电子供体组如何影响质子耦合的电子转移（PCET）并减少催化过程的能量需求，这些组正在设计高度耐用和活性的催化剂。该团队正在采用一种迭代，机械方法，并在合成，催化和计算研究之间进行反馈，这导致了高度活跃，耐用的催化剂的发展。这些催化剂也集成到完整的光电化学细胞中，其中二氧化碳还原与水氧化结合。该项目正在项目期间培训一组多样化的本科生和研究生。 Papish博士每年在阿拉巴马大学举办“化学职业”研讨会。她和她的小组还访问当地小学，与学生进行演示并讨论科学的机会。还为本科化学实验室开发了新的实验，以将催化化学研究引入教学实验室。该奖项反映了NSF的法定任务，并使用基金会的智力优点和更广泛的影响评估审查标准，认为值得通过评估来获得支持。

项目成果

Impact of the Dissolved Anion on the Electrocatalytic Reduction of CO2 to CO with Ruthenium CNC Pincer Complexes

• DOI: 10.1002/cctc.202000742
• 发表时间: 2020-10
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: Hunter Shirley;Matthew T. Figgins;Chance M. Boudreaux;Nalaka P. Liyanage;R. W. Lamb;C. E. Webster;Elizabeth T. Papish;J. Delcamp

Structure Function Relationships in Ruthenium Carbon Dioxide Reduction Catalysts with CNC Pincers Containing Donor Groups

• DOI: 10.1002/ejic.202000444
• 发表时间: 2020-07
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Sanjita Das;Dinesh Nugegoda;Fengrui Qu;Chance M. Boudreaux;Phillip E. Burrow;Matthew T. Figgins;R. W. Lamb;C. E. Webster;J. Delcamp;Elizabeth T. Papish

Photoinduced Generation of a Durable Thermal Proton Reduction Catalyst with in Situ Conversion of Mn(bpy)(CO)3Br to Mn(bpy)2Br2

通过 Mn(bpy)(CO)3Br 原位转化为 Mn(bpy)2Br2 光诱导生成耐用热质子还原催化剂

• DOI: 10.1021/acs.inorgchem.0c00480
• 发表时间: 2020
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Shirley, Hunter;Parkin, Sean;Delcamp, Jared H.
• 通讯作者: Delcamp, Jared H.

Cover Feature: Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes (Eur. J. Inorg. Chem. 19/2020)

封面专题：-X-配体对 Re(pyridylNHC-CF 3 )(CO) 3 X 配合物光催化还原 CO 2 为 CO 的影响 (Eur. J. Inorg. Chem. 19/2020)

• DOI: 10.1002/ejic.202000421
• 发表时间: 2020
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Shirley, Hunter;Sexton, Thomas More;Liyanage, Nalaka P.;Palmer, C. Zachary;McNamara, Louis E.;Hammer, Nathan I.;Tschumper, Gregory S.;Delcamp, Jared H.
• 通讯作者: Delcamp, Jared H.

Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes: Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC-CF 3 )(CO) 3 X Complexes

❀X 配体对 Re(pyridylNHC-CF 3 )(CO) 3 X 配合物光催化还原 CO 2 为 CO 的影响：❀X 配体对 CO 2 光催化还原为 CO 的影响

• DOI: 10.1002/ejic.202000283
• 发表时间: 2020
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Shirley, Hunter;Sexton, Thomas More;Liyanage, Nalaka P.;Palmer, C. Zachary;McNamara, Louis E.;Hammer, Nathan I.;Tschumper, Gregory S.;Delcamp, Jared H.
• 通讯作者: Delcamp, Jared H.