SusChEM: A Mechanistic Approach to Understanding and Lowering the Overpotential for CO2 Reduction to C1 Organic Products

SusChEM：一种理解和降低 CO2 还原为 C1 有机产品的过电势的机械方法

• 批准号: 1308652
• 负责人: Andrew Bocarsly
• 金额: $ 42万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-15 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1308652&HistoricalAwards=false
• 关键词: SusChEM; Mechanistic; Approach; Understanding; Lowering

The NSF Chemical Catalysis Program supports the efforts of Professor Andrew B. Bocarsly of Princeton University to investigate the mechanisms of carbon dioxide (CO2) reduction to one carbon (C1) organic products: formic acid, formaldedhyde or methanol. In the case of methanol, a 6-electron, 6-proton reaction is required which can be undertaken using either a one-electron redox mediator or in some cases can be observed to occur via a direct CO2-surface interaction. In all cases, a complex reaction mechanism is implicated. The research group examines the rate limiting step(s) associated with the formation of formate, one of the major reaction products. Heterogeneous CO2 reduction at post-transition metal oxide interfaces, interface-free CO2 reduction using transition metal based molecular systems, and cyanogel systems for CO2 electroreduction are under study. The first two topics explore the critical question of the role of a reactive surface in the reaction pathway. To consider this question under kinetically limiting conditions leading to formate formation, the team examines anodized post transition metal electrodes. These materials are catalytic in the absence of an additional dissolved catalyst, allowing the research group to look specifically at the range of heterogeneous processes occurring directly at the electrode interface during CO2 reduction. The study is organized using periodic trends, with zinc, cadmium, indium, bismuth and lead selected as key systems. The second study attacks the problem from the opposite direction. In this study, aromatic amine catalysts are used to carry-out the reduction of CO2 in the absence of a surface. Here, advantage is taken of the photoexcited ruthenium(bipyridyl) systems, charge transfer quenched by an aromatic amine to generate CO2 reduction absent an electrode interface. The team also explores manganese complexes containing bisphosphinine (L2) ligands, in this regard. The final study uses cyanogel chemistry to both generate alloy materials that will facilitate the electrode-based studies, and to produce novel electrolytes that are known to have a high CO2 capacity. Understanding CO2 activation is a critical chemical challenge as it contributes to the development of new fuel resources and as well as potentially lowering greenhouse gases in the environment. In addition to its pivotal role in the education of next generation electrochemical researchers, who are key to an alternate energy future, this program impacts K-12 education by providing an excellent tool for teaching both students and teachers fundamental chemical concepts using the currently topical problem of greenhouse gas control as a motivating principle. Another important aspect of the proposed program is its close affiliation with an aggressive startup company that is focused on taking this research out of the laboratory and into the real world. Demonstration scale systems that will convert CO2 into commercial chemicals are planned.

NSF化学催化计划支持普林斯顿大学的Andrew B. Bocarsly教授，以研究二氧化碳（CO2）还原为一种碳（C1）有机产品的机理：甲酸，甲基甲醛或甲醇。 在甲醇的情况下，需要使用单电子氧化还原介质或在某些情况下可以通过直接的CO2表面相互作用进行6电子，6-蛋白反应。 在所有情况下，都涉及复杂的反应机制。研究小组研究了与甲酸形成相关的速率限制步骤，甲酸的形成是主要的反应产物之一。正在研究中，使用基于过渡金属的分子系统的过渡后金属氧化金属界面，无界面CO2还原以及用于CO2电源的Cyanogel系统的异质二氧化碳减少。前两个主题探讨了反应表面在反应途径中的作用的关键问题。 为了在动力学上限制构造形成的情况下考虑这个问题，该团队检查了阳极氧化后的过渡金属电极。在没有附加溶解的催化剂的情况下，这些材料是催化性的，使研究组可以专门研究在二氧化碳还原过程中直接在电极界面直接发生的异质过程范围。该研究是使用周期性趋势进行组织的，锌，镉，ins，二氮和铅被选为关键系统。第二项研究从相反的方向攻击了问题。在这项研究中，芳香胺催化剂用于在没有表面的情况下降低二氧化碳。在这里，利用光激发唯一（Bipyridyl）系统的优势，由芳香胺淬灭的电荷转移，以生成不存在电极界面的CO2还原。在这方面，该小组还探索了含有双膦氨酸（L2）配体的锰配合物。最终研究使用氰凝结化学来生成合金材料，这些合金材料将促进基于电极的研究，并产生新的电解质，已知具有较高的二氧化碳能力。了解CO2激活是一个关键的化学挑战，因为它有助于开发新的燃料资源，并有可能降低环境中的温室气体。除了它在下一代电化学研究人员的教育中的关键作用（这是替代能源未来的关键）外，该计划还通过提供了一种出色的工具来教授学生和老师的基本化学概念，从而影响K-12教育温室气体控制是一种激励原则。拟议计划的另一个重要方面是它与一家激进的创业公司的密切联系，该公司致力于将这项研究带出实验室和现实世界。计划将CO2转换为商业化学品的演示量表系统。