Activation by oxidation and ligand exchange in a molecular manganese vanadium oxide water oxidation catalyst.

ABSTRACT: Despite their technological importance for water splitting, the reaction mechanisms of most water oxidation catalysts (WOCs) are poorly understood. This paper combines theoretical and experimental methods to reveal mechanistic insights into the reactivity of the highly active molecular manganese vanadium oxide WOC [Mn₄V₄O₁₇(OAc)₃]^3- in aqueous acetonitrile solutions. Using density functional theory together with electrochemistry and IR-spectroscopy, we propose a sequential three-step activation mechanism including a one-electron oxidation of the catalyst from [Mn₂ ³⁺Mn₂ ⁴⁺] to [Mn³⁺Mn₃ ⁴⁺], acetate-to-water ligand exchange, and a second one-electron oxidation

SUBMITTER: Cardenas G 

PROVIDER: S-EPMC8513927 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature