Elucidating the Proton-Coupled Electron Transfer Pathways Underpinning the Electrocatalytic Generation of Fuels

Multi-electron, multi-proton processes underpin catalytic transformations that convert energy-poor feedstocks like carbon dioxide and water into fuels. The specific proton-coupled electron transfer reaction mechanisms that a catalyst navigates in a fuel production reaction can dramatically impact the efficiency, durability, and selectivity of the system. The goal of this research program is to access deep mechanistic insight to the proton-coupled electron transfer processes in fuel-forming catalysis, and to learn how catalyst and system parameters can be used to direct fuel production through energy efficient pathways that maximize catalyst selectivity and durability.The proposed research will employ mechanistic studies and reaction kinetics analysis to elucidate the proton-coupled electron transfer reaction pathways through which metal hydride reaction intermediates are generated. Studies will evaluate how structural and electronic factors dictate both available pathways and competition between pathways. Links between reaction pathway and catalyst efficiency, selectivity, and durability will be identified. Finally, previously unexplored mechanisms to form metal hydride complexes that leverage acid–base functionality to circumvent high kinetic barriers will be investigated. Collectively, this research will provide a blueprint for interpreting and controlling proton-coupled electron transfer reactivity in fuel producing catalysts with the goal of accessing next generation catalysts that operate with optimum efficiency, selectivity, and durability.