O reduction proton-coupled electron transfer by a V() aquo on a polyoxovanadate-alkoxide cluster

We report the transfer of H-atoms from a reduced polyoxovanadate alkoxide [ n Oct 4 N][V 6 O 6 (OH 2 )(OMe) 12 ] via concerted proton-electron transfer. Oxygen reduction is compared between bridging and terminal O-H bonds revealing similar mechanisms, providing new insight to design criteria for metal-oxide electrocatalysts that faciliate oxygen reduction by concerted-proton electron transfer. We report the reduction of O 2 to H 2 O 2 via concerted proton-electron transfer from the terminal V( iii )-OH 2 moiety of a reduced polyoxovanadate-alkoxide cluster.