Tuning of lattice oxygen reactivity and scaling relation to construct better oxygen evolution electrocatalyst

Abstract

Developing efficient and low-cost electrocatalysts for oxygen evolution reaction is crucial in realizing practical energy systems for sustainable fuel production and energy storage from renewable energy sources. However, the inherent linear scaling relation for most catalytic materials imposes a theoretical overpotential ceiling, limiting the development of efficient electrocatalysts. Herein, using modeled Na_xMn₃O₇ materials, we report an effective strategy to construct better oxygen evolution electrocatalyst through tuning both lattice oxygen reactivity and scaling relation via alkali metal ion mediation. Specifically, the number of Na⁺ is linked with lattice oxygen reactivity, which is determined by the number of oxygen hole in oxygen lone-pair states formed by native Mn vacancies, governing the barrier symmetry between O–H bond cleavage and O–O bond formation. On the other hand, the presence of Na⁺ could have specific noncovalent interaction with pendant oxygen in *OOH to overcome the limitation from linear scaling relation, reducing the overpotential ceiling. Combining in situ spectroscopy-based characterization with first-principles calculations, we demonstrate that an intermediate level of Na⁺ mediation (NaMn₃O₇) exhibits the optimum oxygen evolution activity. This work provides a new rational recipe to develop highly efficient catalyst towards water oxidation or other oxidative reactions through tuning lattice oxygen reactivity and scaling relation.

While water-splitting provides a renewable means to generate fuel, the water-oxidation half-reaction is considered a bottleneck process. Here, authors tune lattice oxygen reactivity and scaling relations via alkali metal ion mediation in NaMn₃O₇ for oxygen evolution electrocatalysis.