Open AccessOxygen-Atom Defect Formation in Polyoxovanadate Clusters via Proton-Coupled Electron Transfer
Author(s) -
Eric Schreiber,
Alex A Fertig,
William W. Brennessel,
Ellen M. Matson
Publication year - 2022
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c13432
Subject(s) - chemistry , electron transfer , proton coupled electron transfer , reactivity (psychology) , metal , redox , cluster (spacecraft) , proton , oxide , ligand (biochemistry) , catalysis , molecule , oxygen , moiety , photochemistry , chemical physics , crystallography , inorganic chemistry , stereochemistry , medicine , biochemistry , physics , alternative medicine , receptor , organic chemistry , pathology , quantum mechanics , computer science , programming language
The uptake of hydrogen atoms (H-atoms) into reducible metal oxides has implications in catalysis and energy storage. However, outside of computational modeling, it is difficult to obtain insight into the physicochemical factors that govern H-atom uptake at the atomic level. Here, we describe oxygen-atom vacancy formation in a series of hexavanadate assemblies via proton-coupled electron transfer, presenting a novel pathway for the formation of defect sites at the surface of redox-active metal oxides. Kinetic investigations reveal that H-atom transfer to the metal oxide surface occurs through concerted proton-electron transfer, resulting in the formation of a transient V III -OH 2 moiety that, upon displacement of the water ligand with an acetonitrile molecule, forms the oxygen-deficient polyoxovanadate-alkoxide cluster. Oxidation state distribution of the cluster core dictates the affinity of surface oxido ligands for H-atoms, mirroring the behavior of reducible metal oxide nanocrystals. Ultimately, atomistic insights from this work provide new design criteria for predictive proton-coupled electron-transfer reactivity of terminal M═O moieties at the surface of nanoscopic metal oxides.