Progress towards creating more efficient systems in which metal oxide materials perform the conversion of energy-poor substrates to energy-dense fuels requires an in depth understanding of the surface chemistry of these compounds. Historically, the reactivity of metal oxides has been described primarily in terms of the electron; however, recent studies have exposed the impact charge compensating cations impart on the ability for charge transfer reactions to occur, suggesting that these materials are capable of performing proton-coupled electron transfer. Mechanistic insight into these PCET reactions at the surface of these materials remains limited, despite advances in spectroscopic methods. Our group uses polyoxometalates as models for the surfaces of extended state metal oxides due to their resemblance both morphologically and electronically to their bulk congeners. In addition, POMs possess solubility into organic solvents, enabling the use of molecular characterization otherwise not available to heterogeneous systems. These analytical tools allow our group to perform various kinetic analyses, such as temperature dependance studies or kinetic isotope effects, to develop a thorough understanding of the mechanisms by which small molecule activation reactions occur. These studies aim to build on the knowledge of PCET at the surface of metal oxide compounds in order to improve the design of heterogeneous catalysts for the conversion of energy-poor substrates to energy-rich chemical fuels.

Mechanistic analysis of proton-coupled electron transfer at metal oxides using polyoxovanadate-alkoxide clusters as models

ACS Spring 2022

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