Synthesis of CO Dehydrogenase Model Complexes for Catalytic Reductions of CO2

用于催化还原 CO2 的 CO 脱氢酶模型复合物的合成

• 批准号: 8652194
• 负责人: David Charles Lacy
• 金额: $ 5.15万
• 依托单位: CALIFORNIA INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-04-01 至 2016-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8652194
• 关键词: Acids; Active Sites; Address; Affect; Area; Binding; Binding Sites; Carbon; Carbon Dioxide; Carbon monoxide dehydrogenase; Catalysis; Cells; Chemistry; Collection; Communities; Complex; Copper; Custom; Data; Development; Electrochemistry; Electronics; Ensure; Environment; Enzymes; Equilibrium; Evolution; Gases; Goals; Hydrogen; Imines; Inorganic Chemistry; Institutes; Ions; Lasers; Lead; Life; Ligands; Literature; Mediating; Metabolism; Metals; Methods; Modeling; Molecular; Motivation; Nature; Nickel; Organometallic Chemistry; Oxidation-Reduction; Oximes; Planets; Play; Preparation; Production; Protocols documentation; Protons; Reducing Agents; Relative (related person); Research; Resources; Role; Site; Solutions; Spectrum Analysis; Structure; Sulfur; Synthesis Chemistry; System; Techniques; Technology; Temperature; Water; Work; anthropogenesis; catalyst; cofactor; design; experience; improved; interest; microbial; oxidation; pressure; public health relevance; research study; response; sample fixation; stem; success; uptake

DESCRIPTION (provided by applicant): The nickel enzyme CODH (carbon monoxide dehydrogenase) plays a critical role in carbon cycling via microbial metabolism that converts CO2 to cellular carbon and, as such, is essential to life on this planet. Functional model complexes are lacking and thus this proposal aims to prepare heterobimetallic complexes with Ni/Fe centers resembling CODH with the goal to answer questions regarding the enzyme function and ultimately design systems for selective and efficient CO2 reduction. Purely functional models, those that are electrocatalysts for CO2 reduction, contain only one type of metal ion and operate at large overpotentials. New synthetic CODH model complexes are needed to illuminate the details necessary for producing a structurally faithful functional model. Our strategy involves the synthesis of heterobimetallic Ni/Fe complexes for CO2 reduction, a first in synthetic chemistry. We will utilize functionalized diimineo-dioxime ligands that allow sie-selective incorporation of two distinct metal ions. Questions to be addressed with these model complexes include: how does CO2 bind to heterobimetallic Ni/Fe centers? How does the Lewis acidic metal ion affect CO2 binding? What is the binding equilibria and extent of activation at reduced Ni/Fe centers? What conditions favor electrocatalytic reduction of CO2? Can the presence of a Lewis acidic metal improve Faradaic efficiencies and/or lower the overpotential necessary for catalysis? The Peters lab is suited to conduct these studies. Prof. Jonas Peters is an expert in synthetic organometallic and inorganic chemistry. Additionally, he is knowledgeable in the field of electrochemistry and electrocatalytic methods. Finally, the academic environment and facilities available at Caltech encourages rich collaborative discussions that will ensure the success of the proposed studies.

描述（由申请人提供）：镍酶 CODH（一氧化碳脱氢酶）通过微生物代谢将二氧化碳转化为细胞碳，在碳循环中发挥着关键作用，因此对于地球上的生命至关重要。由于缺乏功能模型复合物，因此该提案旨在制备具有类似于 CODH 的 Ni/Fe 中心的异双金属复合物，目的是回答有关酶功能的问题，并最终设计用于选择性和高效 CO2 还原的系统。纯功能模型是用于二氧化碳还原的电催化剂，仅包含一种类型的金属离子并在较大的过电势下运行。需要新的合成 CODH 模型复合体来阐明生成结构可靠的功能模型所需的细节。我们的策略涉及合成异质双金属镍/铁络合物以减少二氧化碳，这在合成化学中尚属首次。我们将利用功能化的二亚胺二肟配体，它可以选择性地结合两种不同的金属离子。这些模型复合物需要解决的问题包括：CO2 如何与异双金属 Ni/Fe 中心结合？路易斯酸性金属离子如何影响 CO2 结合？还原 Ni/Fe 中心的结合平衡和激活程度是多少？什么条件有利于电催化还原CO2？路易斯酸性金属的存在能否提高法拉第效率和/或降低催化所需的过电势？彼得斯实验室适合进行这些研究。 Jonas Peters 教授是合成有机金属和无机化学方面的专家。此外，他在电化学和电催化方法领域也拥有丰富的知识。最后，加州理工学院的学术环境和设施鼓励丰富的合作讨论，这将确保拟议研究的成功。