Issue 6, 2023

Regioselectivity of concerted proton–electron transfer at the surface of a polyoxovanadate cluster

Abstract

Proton-coupled electron transfer (PCET) is an important process in the activation and reactivity of metal oxide surfaces. In this work, we study the electronic structure of a reduced polyoxovanadate-alkoxide cluster bearing a single bridging oxide moiety. The structural and electronic implications of the incorporation of bridging oxide sites are revealed, most notably resulting in the quenching of cluster-wide electron delocalization in the most reduced state of the molecule. We correlate this attribute to a change in regioselectivity of PCET to the cluster surface (e.g. reactivity at terminal vs. bridging oxide groups). Reactivity localized at the bridging oxide site enables reversible storage of a single H-atom equivalent, changing the stoichiometry of PCET from a 2e/2H+ process. Kinetic investigations indicate that the change in site of reactivity translates to an accelerated rate of e/H+ transfer to the cluster surface. Our work summarizes the role which electronic occupancy and ligand density play in the uptake of e/H+ pairs at metal oxide surfaces, providing design criteria for functional materials for energy storage and conversion processes.

Graphical abstract: Regioselectivity of concerted proton–electron transfer at the surface of a polyoxovanadate cluster

Supplementary files

Article information

Article type
Edge Article
Submitted
26 אוק 2022
Accepted
19 דצמ 2022
First published
20 דצמ 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 1386-1396

Regioselectivity of concerted proton–electron transfer at the surface of a polyoxovanadate cluster

E. Schreiber, W. W. Brennessel and E. M. Matson, Chem. Sci., 2023, 14, 1386 DOI: 10.1039/D2SC05928B

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