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

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. Electrochemical delithiation and surface reconstruction of LiNiO2 lead to the formation of an adaptive heterojunction between delithiated‐LiNiO2 and the surface NiOOH layer. Such a process facilitates the formation of NiOO* species within the reconstructed NiOOH surface and the OER activity is boosted significantly.