Dynamically Stabilized Electronic Regulation and Electrochemical Reconstruction in Co and S Atomic Pair Doped Fe3O4 for Water Oxidation

The electronic regulation and surface reconstruction of earth‐abundant electrocatalysts are essential to efficient oxygen evolution reaction (OER). Here, an inverse‐spinel Co,S atomic pair codoped Fe3O4 grown on iron foam (Co,S‐Fe3O4/IF) is fabricated as a cost‐effective electrocatalyst for OER. This strategy of Co and S atomic pair directional codoping features accelerates surface reconstruction and dynamically stabilizes electronic regulation. CoS atomic pairs doped in the Fe3O4 crystal favor controllable surface reconstruction via sulfur leaching, forming oxygen vacancies and Co doping on the surface of reconstructed FeOOH (Co‐FeOOH‐Ov/IF). Before and after surface reconstruction via in situ electrochemical process, the Fe sites with octahedral field dynamically maintains an appropriate electronic structure for OER intermediates, thus exhibiting consistently excellent OER performance. The electrochemically tuned Fe‐based electrodes exhibit a low overpotential of 349 mV at a current density of 1000 mA cm−2, a slight Tafel slope of 43.3 mV dec−1, and exceptional long‐term electrolysis stability of 200 h in an alkaline medium. Density functional theory calculations illustrate the electronic regulation of Fe sites, changes in Gibbs free energies, and the breaking of the restrictive scaling relation between OER intermediates. This work provides a promising directional codoping strategy for developing precatalysts for large‐scale water‐splitting systems. CoS atomic pair directional co‐doped Fe3O4 as an oxygen evolution reaction precatalyst that display a facile in situ electrochemical reconstruction process to finally achieve a Co‐doped FeOOH with oxygen vacancies is designed. CoS atomic pairs doped in the Fe3O4 crystal favour controllable surface reconstruction via sulphur leaching, forming oxygen vacancies and Co doping on the surface of reconstructed FeOOH.