Connecting Thermodynamics and Kinetics of Proton Coupled Electron Transfer at Polyoxovanadate Surfaces Using the Marcus Cross Relation.

ABSTRACT: Here, we evaluate the efficacy of multiple methods for elucidating the average bond dissociation free energy (BDFE) of two surface hydroxide moieties in a reduced polyoxovanadate cluster, [V₆O₁₁(OH)₂(TRIOL^NO2)₂]^-2. Through cyclic voltammetry, individual thermochemical parameters describing proton coupled electron transfer (PCET) are obtained, without the need for synthetic isolation of intermediates. Further, we demonstrate that a method involving a series of open circuit potential measurements with varying ratios of reduced to oxidized clusters is most attractive for the direct measurement of BDFE(O-H) for polyoxovanadate clusters as this approach also determines the stoichiometry of PCET. We subsequently connect the drivin

SUBMITTER: Fertig AA 

PROVIDER: S-EPMC9906739 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature