Heterogeneous metal oxides have been widely used in order to produce energy dense fuels from relatively inert substrates. However, continued improvement to these systems depends critically on understanding the surface reactivity of these compounds towards charge transfer reactions. Recent studies have demonstrated metal oxides are capable of acting as proton-coupled electron transfer reagents, suggesting that describing reactions at metal oxides strictly in terms of the energetics of electron transfer does not accurately depict the reactivity of the materials. Rather, thermochemical parameters such as bond dissociation free energy of O-H bonds at the surface of the materials are able to accurately express the driving force of these types of reactions. Despite these results, constraints in the spectroscopic techniques available to heterogeneous materials has limited the ability to study these reactions. As a result, our lab has turned to utilizing polyoxometalate clusters as atomically precise analogues for bulk metal oxide materials. A wide range of analytical techniques become available to study these reactions as a result of POMs ability to dissolve in organic solvents, enabling the study of these reactions both energetically and mechanistically through the establishment of thermochemical and kinetic parameters. This work aims to improve the understanding of how the surface of metal oxide materials are capable of performing PCET, in order to build on the design of heterogeneous metal oxide catalysts that perform energy conversion processes in order to form energy-dense fuels.

Modelling proton-coupled electron transfer at metal oxide surfaces using polyoxovanadate-alkoxide clusters

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.