CAREER: Iminium Salts as Potential Water Oxidation Catalysts

鲍灵绿色州立大学的Ksenija Glusac教授得到化学系化学催化（CAT）项目的支持，以探索亚胺离子及其假碱衍生物作为水氧化为分子氧的潜在催化剂。所提出的水氧化催化循环包括四个步骤。碘离子首先与水反应形成假碱。随后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以产生过氧化物衍生物，其随后经历双电子氧化以释放氧并回收亚胺离子。将使用适当选择的模型化合物研究每个步骤。循环伏安法，飞秒泵浦探测测量，以及电子顺磁共振（EPR）光谱将用于遵循该计划的步骤，并将进行密度泛函理论（DFT）计算，以通知拟议的实验。该提案的总体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气燃料。如果成功，它将大大促进可再生能源的发展，从而促进能源的可持续性。除了几个教学和培训活动，教育更广泛的影响包括暑期课程，包括讲座，讨论，研讨会和学生演讲的发展。 该方案的重点是指导女性和少数民族本科生，鼓励她们考虑研究生教育，并帮助她们实现学业卓越。

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.