CAREER: Iminium Salts as Potential Water Oxidation Catalysts

职业：亚胺盐作为潜在的水氧化催化剂

• 批准号: 1055397
• 负责人: Ksenija Glusac
• 金额: $ 55万
• 依托单位: Bowling Green State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-06-15 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1055397&HistoricalAwards=false
• 关键词: CAREER; Iminium; Salts; Potential; Water

Professor Ksenija Glusac of Bowling Green State University is supported by the Chemical Catalysis (CAT) Program in the Division of Chemistry to explore iminium ions and their pseudobase derivatives as potential catalysts for the oxidation of water to molecular oxygen. The proposed water-oxidation catalytic cycle consists of four steps. Iminium ions are first reacted with water to form the pseudobases. This is followed with the conversion of the pseudobases to the corresponding alkoxyl radicals via proton-coupled electron transfer (PCET). The alkoxyl radicals are then combined in pairs to produce peroxide derivatives, which subsequently undergo two-electron oxidation to release oxygen and recover the iminium ions. Each step will be studied with appropriately selected model compounds. Cyclic voltammetry, femtosecond pump-probe measurements, as well as electron paramagnetic resonance (EPR) spectroscopy will be used to follow the steps of the scheme, and density functional theory (DFT) calculations will be conducted to inform the proposed experiments. The overarching goal of the proposal is to develop a purely organic catalyst to facilitate the splitting of water to produce oxygen and hydrogen fuel in a solar fuel cell setup. If successful it will contribute significantly to the development of renewable energy sources and hence to energy sustainability. In addition to several teaching and training activities, the educational broader impacts include the development of a summer program that covers lectures, discussions, seminars and student presentations. The emphasis of the program is on mentoring of female and minority undergraduate students to encourage them to consider graduate education and help them achieve academic excellence.

鲍灵格林州立大学的Ksenija Glusac教授在化学系化学催化（CAT）项目的支持下，探索了作为水氧化为分子氧的潜在催化剂的铝离子及其假碱衍生物。所提出的水-氧化催化循环包括四个步骤。微量离子首先与水反应形成假碱。接下来是通过质子耦合电子转移（PCET）将假碱转化为相应的烷氧基自由基。然后，烷氧基自由基成对结合产生过氧化物衍生物，其随后经过双电子氧化以释放氧气并回收胺离子。每个步骤都将使用适当选择的模型化合物进行研究。循环伏安法、飞秒泵探测测量以及电子顺磁共振（EPR）光谱将用于遵循该方案的步骤，密度泛函理论（DFT）计算将进行，以告知拟议的实验。该提案的首要目标是开发一种纯有机催化剂，以促进水的分解，从而在太阳能燃料电池装置中产生氧气和氢燃料。如果成功，它将对可再生能源的发展，从而对能源的可持续性作出重大贡献。除了几项教学和培训活动外，更广泛的教育影响还包括制定一个涵盖讲座、讨论、研讨会和学生演讲的暑期项目。该计划的重点是指导女性和少数民族本科生，鼓励他们考虑研究生教育，帮助他们取得学术成就。