Construction of “Metal Defect/Oxygen Defect Junction” in ZnFe2O4–NiCo2O4 Heterostructures for Enhancing Electrocatalytic Oxygen Evolution

Abstract Defect engineering is a promising approach to improve the conductivity and increase the active sites of transition metal oxides used as catalysts for the oxygen evolution reaction (OER). However, when metal defects and oxygen defects coexist closely within the same crystal, their compensating charges can diminish the benefits of both defect structures on the catalyst's local electronic structure. To address this limitation, a novel strategy that employs the heterostructure interface of ZnFe 2 O 4 –NiCo 2 O 4 to spatially separate the metal defects from the oxygen defects is proposed. This configuration positions the two types of defects on opposite sides of the heterojunction interface, creating a unique structure termed the “metal‐defect/oxygen‐defect junction”. Physical characterization and simulations reveal that this configuration enhances electron transfer at the heterostructure interface, increases the oxidation state of Fe on the catalyst surface, and boosts bulk charge carrier concentration. These improvements enhance active site performance, facilitating hydroxyl adsorption and deprotonation, thereby reducing the overpotential required for the OER.