Interrelated Photo and Electrocatalytic Processes for the Reduction of CO2: Controlling Multiproton/Multielectron Events

去除大气中有害二氧化碳的一个重要方法是将其转化为有用的化学物质。这种化学可以在电化学池中进行，但最近的一些进展表明，可以用光进行二氧化碳转化。因此，一个目标是使二氧化碳和水与阳光反应，产生既作为燃料又作为原材料的重要化学物质。无论这种化学是通过电化学还是光化学进行的，反应都需要能量。实际的二氧化碳转化过程要求能量输入尽可能少。为此，需要催化剂来最小化这种能量输入，同时还能提供所需的反应产物。目前，人们对构建实现这种效率的电催化剂和光催化剂所需的化学知识知之甚少。BCarsly研究小组正在推进对基础化学的理解，这是开发实用二氧化碳催化剂所必需的。他们正在利用这一知识来构建具有更高的化学活性、产品选择性和能源消耗的新催化剂。催化剂设计方面的这种以知识为基础的进步对于产生对环境负责和有益于社会的二氧化碳利用新途径至关重要。博卡斯莱博士积极参与与他的研究工作相关的外展活动，包括对下一代化学研究人员的教育，以及根据普林斯顿大学暑期实验室学习计划开展的K-12外展活动。他的活动包括一项特别计划，鼓励未被充分代表的群体中的本科生考虑接受科学方面的研究生教育。国家科学基金会的资助使博卡斯莱博士能够在普林斯顿大学研究用于电化学和光化学二氧化碳利用的催化剂。电催化研究的重点是使用金属合金体系来解决材料科学(即电极组成)和理解水中二氧化碳还原为有机氧化物所必需的机理问题。目前，人们正在寻求对二氧化碳还原过程中电子和质子转移耦合的详细机制的理解。特别令人感兴趣的是二氧化碳的还原形成碳-碳键。目前正在进行三种类型的研究：1)亚稳定的表面氧化物在二氧化碳还原中的作用；2)以羰基锰络合物为均相催化剂将CO2光化学和电催化还原为CO；3)混合金属电极作为多碳产物形成的PCET催化剂。就基础化学及其在新燃料资源和环境保护领域带来的能力而言，理解所有这些系统所依据的统一化学主题具有变革性。博卡斯利博士积极参与下一代电化学研究人员的教育，他们是环境敏感型替代能源未来的关键。此外，博卡斯莱博士还通过普林斯顿大学材料项目和普林斯顿大学暑期实验室学习项目开展社区外展和K-12教育领域的活动。Bcarsly的研究项目还与普林斯顿大学化学系面向未被充分代表的未成年人的外联计划合作，将不同选择的国家本科生带到普林斯顿研究实验室进行为期10周的夏季研究体验。该奖项反映了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。

One important approach to remove undesirable CO2 in the atmosphere is to convert it to useful chemicals. This chemistry can be carried out in an electrochemical cell, but there are also recent advances showing that it is possible to do CO2 conversion with light. Thus, one goal is to react CO2 and water with sunlight to generate chemicals that are important both as fuels and as raw materials. Whether this chemistry is carried out electrochemically or photochemically, the reactions require energy. Practical CO2 conversion processes require that the energy input be as small as possible. To that end, catalysts are needed that minimize this energy input while also providing desirable reaction products. Presently, there is only limited understanding of the chemistry needed to build both electrocatalysts and photocatalysts that achieve such efficiency. The Bocarsly research group is advancing the understanding of the fundamental underlying chemistry necessary to develop practical CO2 catalysts. They are using this knowledge to construct new catalysts with improved chemical activity, product selectivity, and energy consumption. This knowledge-based advancement in catalyst design is critical to produce new routes to CO2 utilization that are environmentally responsible and socially beneficial. Dr. Bocarsly is actively engaging in outreach activities related to his research efforts including the education of next generation chemical researchers and K-12 outreach activities carried out under Princeton's Summer Laboratory Learning Program. His activities include a special program to encourage undergraduates in underrepresented groups to consider graduate education in the sciences.Funding from the National Science Foundation makes possible Dr. Bocarsly's studies at Princeton University on catalysts for electrochemical and photochemical CO2 utilization. Electrocatalytic studies focus on the use of metal alloy systems to address both materials science (i.e. electrode composition) and mechanistic question necessary to understand the reduction of aqueous CO2 to organic oxygenates. Presently, an understanding of the detailed mechanisms that allow the coupling of electron and proton transfer in the reduction of CO2 is being sought. Of particular interest is the reduction of CO2 to form carbon-carbon bonds. Three types of studies are underway: 1) The role of meta-stable surface oxides in the reduction of CO2; 2) The photochemical and electrocatalytic reduction of CO2 to CO using manganese carbonyl complexes as homogeneous catalysts; 3) Mixed metal electrodes as PCET catalysts for the formation of multiple carbon products. Understanding unifying chemical themes that underlie all these systems is transformative in terms of fundamental chemistry and the capability it brings in the areas of new fuel resources and environmental protection. Dr. Bocarsly is heavily involved in the education of next generation electrochemical researchers, who are key to an environmentally sensitive alternate energy future. In addition, Dr. Bocarsly carries out activities in the areas of community outreach and K-12 education through Princeton's Materials Program and Princeton's Summer Laboratory Learning Program. Bocarsly's research program also partners with Princeton's Department of Chemistry Outreach to Underrepresented Minors Program, to bring a diverse selection of the national undergraduate population into Princeton research labs for a 10-week summer research experience.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.