Modeling Product Selectivity in Electrocatalytic Carbon Dioxide Reduction Using Scaling Relationships

使用比例关系对电催化二氧化碳还原中的产物选择性进行建模

• 批准号: 10312421
• 负责人: Adam J Pearce
• 金额: $ 6.6万
• 依托单位: YALE UNIVERSITY
• 依托单位国家: 美国
• 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://reporter.nih.gov/project-details/10312421
• 关键词: Acetyl Coenzyme A; Acids; Active Sites; Address; Affect; Alkanesulfonates; Archaea; Area; Bacteria; Bioinorganic Chemistry; Biological Models; Biology; Biomass; Carbon Dioxide; Carbon Monoxide; Carbon monoxide dehydrogenase; Catalysis; Charge; Chemical Industry; Complex; Development; Electrodes; Electronics; Electrons; Electrostatics; Environment; Enzymatic Biochemistry; Enzymes; Faculty; Frequencies; Goals; Hybrids; Hydrogen Bonding; In Situ; Iron; Kinetics; Knowledge; Lead; Leadership; Ligands; Mentorship; Metals; Methanol; Mind; Modeling; Molecular; Monitor; Outcome; Oxalates; Oxidoreductase; Oxygen; Pathway interactions; Pharmacologic Substance; Phenanthrolines; Property; Reaction; Reporting; Research; Resources; Role; Route; Scientist; Structural Models; Structure; Surface; System; Thermodynamics; Universities; Variant; Wood material; Work; Writing; career; catalyst; comparative; design; electric field; enzyme model; infrared spectroscopy; insight; next generation; pressure; reaction rate; sample fixation; skills; student mentoring; theories

Project Summary The Wood-Ljungdahl (WL) pathway is a CO2 fixation pathway that relies on two different CO2 reducing enzymes — formate dehydrogenase (FDH) and carbon monoxide dehydrogenase (CODH) — to ultimately convert CO2 to biomass through formate and carbon monoxide. Biology has successfully evolved catalysts for the reactions in the WL-pathway that feature remarkable activity and selectivity that is envied by the pharmaceutical and commodity chemicals industries, where the efficient utilization of CO2 as a C1 building block is desirable. Despite this, attempts to design structural models of these enzymes for homogenous electrocatalytic CO2 reduction have been unsuccessful. A more comprehensive understanding of the enzymes found in the WL- pathway and the design of better CO2 reduction catalysts will require a better understanding of how the intrinsic properties — reduction potential (E1/2) of the catalyst , pKa and concentration of acid, and degree of intermediate stabilization by secondary sphere effects — direct product selectivity. In order to better understand how the properties of these enzymes lead to disparate selectivity, molecular “thermodynamic-kinetic scaling relationships” for the electrochemical CO2 reduction reaction (CO2RR) will be developed. “Scaling relationships” are defined as a correlation between thermodynamic variables with kinetic outcomes such as turnover frequency or selectivity. These scaling relationships will be used to determine how perturbations to tunable thermodynamic variables (catalyst E1/2, acid pKa, etc.) affect selectivity outcomes. Monitoring the selectivity as a function of these variables will enable the building of a selectivity model. In addition, we will determine how secondary sphere effects alter the selectivity through hydrogen bonding and electrostatic interactions in analogy to similar effects found in enzyme active sites. Last, we aim to address how electric fields — which are increasingly implicated in enzymatic mechanisms of action — alter the selectivity of CO2RR through the study of hybrid electrodes featuring an anchored molecular CO2 reduction catalyst. Prof. Mayer and Yale University have provided an excellent environment to not only conduct my proposed research but to grow as a scientist. The research I am proposing to conduct under the mentorship of Prof. Mayer will give me the knowledge to address a wide range of complex problems. During my burgeoning postdoctoral tenure, I am continuing to develop my professional skills by communicating my work through presentations and writing, and to continue mentoring students as I've done throughout my career but with a new perspective. Additionally, Yale University has surrounded me with faculty that are knowledgeable in many of the areas I aim to be. For example, Prof. Patrick Holland's incredible reputation for ligand design and Prof. Sharon Hammes– Schiffer's leadership in PCET theory will undoubtedly be beneficial resources for my proposed molecular CO2 electroreduction. Under the guidance of Prof. Mayer and Yale University, I will continue to develop my identity as an independent scientist.

项目概要 Wood-Ljungdahl (WL) 途径是一种二氧化碳固定途径，依赖于两种不同的二氧化碳还原途径 酶——甲酸脱氢酶（FDH）和一氧化碳脱氢酶（CODH）——最终 通过甲酸盐和一氧化碳将二氧化碳转化为生物质的生物学已经成功地开发出催化剂。 WL 途径中的反应具有显着的活性和选择性，这是由 制药和日用化学品行业，其中有效利用二氧化碳作为 C1 组成部分 尽管如此，仍需要尝试设计这些酶的均质电催化结构模型。 对 WL- 中发现的酶的更全面的了解尚未成功。 途径和更好的二氧化碳还原催化剂的设计将需要更好地理解内在的机制 性质——催化剂的还原电位（E1/2）、pKa和酸浓度、中间体程度 通过二次球效应实现稳定——直接产物选择性。 为了更好地了解这些酶的特性如何导致不同的选择性，分子 电化学 CO2 还原反应 (CO2RR) 的“热力学-动力学模型关系”将是 开发的“标度关系”被定义为热力学变量与动力学之间的相关性。 这些结果（例如周转频率或选择性）将用于确定如何进行。 对可调热力学变量（催化剂 E1/2、酸 pKa 等）的扰动会影响选择性结果。 监测选择性作为这些变量的函数将能够建立选择性模型。 此外，我们将确定二次球体效应如何通过氢键和改变选择性 静电相互作用与酶活性位点中发现的类似效应类似，最后，我们的目标是解决如何解决这一问题。 电场——越来越多地涉及酶的作用机制——改变了酶的选择性 CO2RR 通过研究具有锚定分子 CO2 还原催化剂的混合电极。 梅耶尔教授和耶鲁大学提供了一个极好的环境，不仅使我能够开展我的提议 我建议在梅耶尔教授的指导下进行研究，但要成长为一名科学家。 在我的博士后生涯中，它将为我提供解决各种复杂问题的知识。 在任期内，我将通过演示和交流我的工作来继续发展我的专业技能 写作，并继续以新的视角指导学生，就像我在整个职业生涯中所做的那样。 此外，耶鲁大学为我提供了在我目标的许多领域知识渊博的教师 例如，Patrick Holland 教授在配体设计方面享有盛誉，而 Sharon Hammes 教授则– Schiffer 在 PCET 理论方面的领导地位无疑将为我提出的分子 CO2 提供有益的资源 在Mayer教授和耶鲁大学的指导下，我将继续发展我的身份。 作为一名独立科学家。