Constructing an Adaptive Heterojunction as a Highly Active Catalyst for the Oxygen Evolution Reaction

Adv Mater. 2020 Jul;32(30):e2001292. doi: 10.1002/adma.202001292. Epub 2020 Jun 21.

Abstract

Electrochemical water splitting is of prime importance to green energy technology. Particularly, the reaction at the anode side, namely the oxygen evolution reaction (OER), requires a high overpotential associated with OO bond formation, which dominates the energy-efficiency of the whole process. Activating the anionic redox chemistry of oxygen in metal oxides, which involves the formation of superoxo/peroxo-like (O2 )n - , commonly occurs in most highly active catalysts during the OER process. In this study, a highly active catalyst is designed: electrochemically delithiated LiNiO2 , which facilitates the formation of superoxo/peroxo-like (O2 )n - species, i.e., NiOO*, for enhancing OER activity. The OER-induced surface reconstruction builds an adaptive heterojunction, where NiOOH grows on delithiated LiNiO2 (delithiated-LiNiO2 /NiOOH). At this junction, the lithium vacancies within the delithiated LiNiO2 optimize the electronic structure of the surface NiOOH to form stable NiOO* species, which enables better OER activity. This finding provides new insight for designing highly active catalysts with stable superoxo-like/peroxo-like (O2 )n - for water oxidation.

Keywords: adaptive junctions; cycling; delithiation; oxygen evolution; reconstruction.