EAGER: Project for Preliminary Studies of Electrochemical Reduction of Carbon Dioxide: Nano-Particle and Mechanistic Studies

利用可再生电能或直接光电催化还原二氧化碳，可为未来提供一种化学原料和高价值化学品的来源。光电催化还原过程的基础是电化学途径。过去的研究表明，电化学还原二氧化碳的效率较低，但在碳氢化合物和C-C键的形成方面取得了一些成功。这项研究表明，电化学还原的机理是复杂的，并且只有粗略的了解。尽管二氧化碳还原为高价值产品和燃料的机理尚不确定，但很明显，它需要在CO吸附、氢的有效性和促进C-C键偶联的中间体之间取得平衡。因此，催化剂的选择和性质是一个因素，凯斯西储大学的Pi Robert Savinell建议在选定的金属和复合金属的模型表面上进行初步实验，这将提供证据，证明定制用于二氧化碳还原的电催化剂是一种可行的方法。电催化剂对二氧化碳的电化学还原活性不能仅通过比较伏安法来测量。因此，对电化学数据本身的解释可能是模棱两可和误导性的。因此，电化学二氧化碳还原必须与直接产物分析相结合。Pi Savinell建议使用一种新的方法--微分电化学质谱来捕获和分析从电极表面析出的挥发性产物作为电位的函数。电流与m/e信号同时记录，因此可以估计产品的效率和选择性，从而提供详细的信息，从而从机理上了解反应。这些实验和电催化剂的制备是开发的一个挑战，需要有重点的努力，这是这一热切获奖的基础。这项研究旨在证明所提出的电催化途径和方法是可行的，并能对理解二氧化碳的电化学还原产生重大影响。本研究获得的初步数据将为化学工程/材料科学研究生的博士论文研究提供实验研究计划的基础。此外，参与此项目的本科生将学习实验电池设计和DEM校准。这个渴望的项目可能有助于吸引这些本科生继续研究生学习，因为他们直接参与了令人兴奋的实验和与社会相关的科学。

1047563SavinellThe electrochemical reduction of carbon dioxide with renewable electrical energy sources, or by direct photoelectrocatalytic reduction, could provide a source of chemical feedstocks and high value chemicals of the future. Fundamental to photoelectrocatalytic reduction processes are electrochemical pathways. Past research on electrochemical reduction of CO2 showed low efficiency but demonstrated some success at forming hydrocarbons and C-C bonds. This research made clear that the electrochemical reduction mechanisms are complex and only sketchily understood.Although the mechanism of CO2 reduction to high value products and fuels isuncertain, it is apparent that it requires a balance between CO adsorption, H availability, and intermediates that facilitate C-C bond coupling. Thus, catalyst selection and properties are factors, and the PI Robert Savinell of Case Western Reserve University proposes preliminary experiments on model surfaces of selected metals and composite metals that would provide evidence that tailoring electrocatalysts for CO2 reduction is a feasible approach.The activity of an electrocatalyst towards electrochemical reduction of CO2cannot be measured through comparative voltammetry alone. Consequently, the interpretation of electrochemical data by itself can be ambiguous and misleading. Therefore, electrochemical CO2 reduction must be combined with direct product analysis. PI Savinell proposes to use a new approach, Differential Electrochemical Mass Spectrometry, for the capture and analysis of the volatile products evolving from an electrode surface as a function of potential. The current is recorded simultaneously with m/e signals so product efficiencies and selectivity can be estimated, thus providing detailed information leading to mechanistic understanding of the reactions. These experiments and the preparation of the electrocatalysts are a challenge to develop and require a focused effort, which is the basis of this EAGER award. The proposed research is designed to show that the electrocatalytic approaches and methodologies proposed are feasible and can have a major impact in understanding of electrochemical reduction of carbon dioxide.The preliminary data obtained from this research will provide the foundation of the experimental research program for the PhD dissertation studies of a chemical engineering/materials science graduate student. In addition, undergraduate students participating in this project will address experimental cell design and DEMS calibration. This EAGER project is likely to be helpful to attracting these undergraduate students to pursue graduate study because of their direct involvement in exciting experiments and socially relevant science.