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.
