Oxygen-Atom Defect Formation in Polyoxovanadate Clusters via Proton-Coupled Electron Transfer.
J Am Chem Soc
; 144(11): 5029-5041, 2022 03 23.
Article
en En
| MEDLINE
| ID: mdl-35275632
ABSTRACT
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 VIII-OH2 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 MâO moieties at the surface of nanoscopic metal oxides.
Texto completo:
1
Bases de datos:
MEDLINE
Asunto principal:
Oxígeno
/
Protones
Tipo de estudio:
Prognostic_studies
Idioma:
En
Revista:
J Am Chem Soc
Año:
2022
Tipo del documento:
Article
País de afiliación:
Estados Unidos