CAS: Principles of Cooperativity for the Electrocatalytic Reduction of Carbon Dioxide

化学系的化学催化项目支持路易斯维尔大学的克雷格·格拉珀豪斯教授和约书亚·司布真博士的研究项目。该项目的重点是二氧化碳的捕获和反应性。使用电力生产燃料和化学品是使用风能和太阳能等间歇性可再生能源的最有利方法之一。此外，利用电力制造商业化学品也可能比使用目前涉及加热的方法更节能。该项目开发更可持续的系统，以捕获二氧化碳并将其转化为燃料或其他化学产品。新的反应使用了丰富的金属，如锌，在一个支持的分子框架合成廉价的起始材料。基础研究可以提供一种途径，通过这种途径，可再生电力和化石燃料燃烧产生的高浓度二氧化碳可以用于形成商业上有用的材料。该研究为本科生和研究生提供了可再生能源研究的跨学科实践经验，为他们在科学，技术，工程和数学方面的职业生涯做好准备。参加路易斯维尔大学年度可再生能源研讨会的高中生有机会参与研究和开发独立的科学博览会项目。在化学系化学催化计划的资助下，路易斯维尔大学的克雷格·格拉珀豪斯教授和约书亚·斯布真博士正在开发混合氨基硫脲-吡啶腙金属配合物，用于二氧化碳捕获和还原的催化剂。助催化剂通过引入相邻的刘易斯酸和刘易斯碱位点来利用金属-配体协同性。还原将在包括Cu-Ni合金在内的各种电极上进行。本计画将探讨影响产物分布的因素、反应机制、以及助触媒与电极间的反应性。预计的结果包括量化刘易斯酸度和刘易斯碱度对二氧化碳与金属助催化剂的结合和催化反应性的影响。 研究团队将确定Cu-Ni合金中二氧化碳还原的独特C-C耦合产物，并对C-C耦合过程进行机理分析。 该小组将增加具有不同成分的Cu-Ni合金的反应性的基础知识。参加路易斯维尔大学年度可再生能源研讨会的高中生有机会参与研究和开发独立的科学展览项目。该奖项反映了NSF的法定使命，并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，被认为值得支持。

The Chemical Catalysis Program of the Division of Chemistry supports the research program of Professor Craig Grapperhaus and Dr. Joshua Spurgeon of the University of Louisville. This project focuses on the capture and reactivity of carbon dioxide. Generating fuels and chemicals using electricity is one of the most favorable approaches for using intermittent renewables such as wind and solar. Also, making commercial chemicals from electricity may also be more energetically efficient than using current methods which involve heating. This project develops more sustainable systems to capture carbon dioxide and convert it to fuels or other chemical products. The new reactions employ an abundant metal, such as zinc, within a supporting molecular framework synthesized from inexpensive starting materials. The fundamental research could provide a pathway by which renewable electricity and high concentrations carbon dioxide from fossil fuel combustion could be used to form commercially useful materials. The research provides undergraduate and graduate students hands-on interdisciplinary experience in renewable energy research preparing them for careers in science, technology, engineering, and mathematics. High-school student participants in the annual renewable energy workshop at the University of Louisville have the opportunity to participate in the research and develop independent science fair projects.With funding from the Chemical Catalysis Program of the Division of Chemistry, Professor Craig Grapperhaus and Dr. Joshua Spurgeon of the University of Louisville are developing hybrid thiosemicarbazone-pyridylhydrazone metal complexes as co-catalysts for carbon dioxide capture and reduction. The co-catalysts utilize metal-ligand cooperativity through the incorporation of neighboring Lewis acid and Lewis base sites. Reductions will be performed at a variety of electrodes including Cu-Ni alloys. The project will investigate the factors influencing product distribution, reaction mechanism, and reactivity between the co-catalyst and electrode. Projected outcomes include the quantification of the effect of Lewis acidity and Lewis basicity on the binding and catalytic reactivity of carbon dioxide with the metal co-catalyst. The research team will identify of unique C-C coupled products from carbon dioxide reduction at the Cu-Ni alloy and draw mechanistic insights into the C-C coupling process. The group will increase fundamental knowledge of the reactivity of Cu-Ni alloys with varying compositions. High-school student participants in the annual renewable energy workshop at the University of Louisville have the opportunity to participate in the research and develop independent science fair projects.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.