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

去除大气中不需要的二氧化碳的一个重要方法是将其转化为有用的化学物质。这种化学反应可以在电化学电池中进行，但最近的进展也表明，用光进行二氧化碳转化是可能的。因此，其中一个目标是让二氧化碳和水与阳光发生反应，产生对燃料和原材料都很重要的化学物质。无论这种化学反应是电化学的还是光化学的，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小。为此，需要将这种能量输入最小化，同时提供理想反应产物的催化剂。目前，人们对制造达到这种效率的电催化剂和光催化剂所需的化学知识了解有限。Bocarsly研究小组正在推进对开发实用二氧化碳催化剂所必需的基本潜在化学的理解。他们正在利用这些知识来构建具有更好的化学活性、产物选择性和能耗的新催化剂。这种基于知识的催化剂设计进步对于产生对环境负责、对社会有益的二氧化碳利用新途径至关重要。Bocarsly博士积极参与与他的研究工作相关的外展活动，包括下一代化学研究人员的教育和普林斯顿大学夏季实验室学习计划下的K-12外展活动。他的活动包括一个特别项目，鼓励代表性不足群体的本科生考虑在科学领域接受研究生教育。美国国家科学基金会（National Science Foundation）的资助使Bocarsly博士在普林斯顿大学对电化学和光化学二氧化碳利用催化剂的研究成为可能。电催化研究的重点是使用金属合金系统来解决材料科学（即电极组成）和机制问题，这些问题是理解水相二氧化碳还原为有机氧合物所必需的。目前，正在寻求对减少二氧化碳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)亚稳定表面氧化物在CO2还原中的作用；2)以羰基锰配合物为均相催化剂，光化学和电催化还原CO2为CO；3)混合金属电极作为PCET催化剂，形成多种碳产物。理解所有这些系统背后统一的化学主题，对于基础化学及其在新燃料资源和环境保护领域带来的能力来说是革命性的。Bocarsly博士积极参与下一代电化学研究人员的教育，他们是环境敏感的替代能源未来的关键。此外，Bocarsly博士还通过普林斯顿大学的材料计划和普林斯顿大学的夏季实验室学习计划在社区外展和K-12教育领域开展活动。Bocarsly的研究项目还与普林斯顿大学化学系合作，向未被充分代表的未成年人推广项目，将全国不同的本科生带到普林斯顿大学的研究实验室，进行为期10周的暑期研究体验。该奖项反映了美国国家科学基金会的法定使命，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。

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.