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: 1800214
• 负责人: Elizabeth Papish
• 金额: $ 35.79万
• 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: 2018
• 资助国家: 美国
• 起止时间: 2018-07-15 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800214&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.

在化学系催化项目的资助下，阿拉巴马大学塔斯卡卢萨分校的伊丽莎白·帕皮什博士、密西西比大学的贾里德·德尔坎普博士和密西西比州立大学的查尔斯·埃德温·韦伯斯特博士正在合作研究设计新的催化剂，这种催化剂可以利用阳光将二氧化碳--一种燃料燃烧产生的温室气体--转化为燃料前体一氧化碳。将二氧化碳转化为一氧化碳的能力具有挑战性，这是利用阳光从二氧化碳制造柴油的战略中的重要一步。这种转换可能对确保美国的能源未来有用，因为它可以提供一种手段，在石油储备枯竭的情况下取代石油储备。此外，太阳能燃料的形成与燃料燃烧相结合可以被认为是碳中性的，因为这个过程不会向大气中添加二氧化碳。研究小组正在使用合成化学来制造新的催化剂，测试这些催化剂，并通过计算优化和了解这一过程中的关键步骤。关键的创新是了解催化剂上较小、较远的基团的变化如何影响反应过程。该项目使用地球上丰富的无毒金属，使化学反应更可持续和环保。该项目正在阿拉巴马州和密西西比州的大学培养不同类型的研究生和本科生。这种协同协作增强了这些小组中的学生的学习体验。Papish小组正在开展外联活动，包括在阿拉巴马大学举行的“化学职业”研讨会，以及在附近一所小学举行的科学示范活动，以吸引学生参与STEM教育。帕皮什、德尔坎普和韦伯斯特博士结合了金属有机合成和机械研究、光驱动催化和利用太阳能以及有机金属计算化学方面的广泛专业知识。他们的团队正在设计、测试和研究新型催化剂，这些催化剂的外围带有含氧取代基的钳形配体，可以与贵金属和富含稀土的金属结合。这些基团正在阐明配体上远程含氧取代基的质子化状态如何改变催化剂的寿命、反应速度和与这些络合物的选择性。通过了解电子给体基团如何影响质子耦合电子转移(PCET)和降低催化过程的能量需求，这些小组正在设计高度耐用和活性的催化剂。这个团队正在采取一种迭代的机械方法，在合成、催化和计算研究之间进行反馈，从而开发出高活性、耐用的催化剂。这些催化剂还被集成到一个完整的光电化学电池中，在那里二氧化碳还原和水氧化相结合。该项目在项目期间培养了一批不同的本科生和研究生。帕皮什博士每年都会在阿拉巴马大学主持“化学职业”研讨会。她和她的团队还访问了当地的小学，进行示范，并与学生讨论科学机会。本科生化学实验室也正在开发新的实验，以将催化化学研究引入教学实验室。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

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

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.

Reinvestigating Catalytic Alcohol Dehydrogenation with an Iridium Dihydroxybipyridine Catalyst

重新研究铱二羟基联吡啶催化剂催化酒精脱氢

• DOI: 10.1021/acs.organomet.0c00398
• 发表时间: 2020
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Yao, Wenzhi;DeRegnaucourt, Alexa R.;Shrewsbury, Emily D.;Loadholt, Kylie H.;Silprakob, Weerachai;Qu, Fengrui;Brewster, Timothy P.;Papish, Elizabeth T.
• 通讯作者: Papish, Elizabeth T.

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