Dual Electronic and Structural Engineering of Ni–Fe Alloys via Molten Salt Electrodeposition for Enhanced Oxygen Evolution Reaction

Abstract Accurate modulation of electronic configurations and rational design of surface morphologies in catalytic materials are crucial for enhancing oxygen evolution reaction (OER) performance. However, integrating these complementary strategies remains a significant challenge due to their divergent modulation mechanisms and scales. Herein, an innovative molten salt electrodeposition methodology is presented that simultaneously regulates electronic configuration and microstructural morphology in a unified synthesis framework, successfully fabricating a defect‐enriched porous Ni–Fe alloy electrode. Specifically, the porous channels are formed by controlling the in situ electrochemical growth of Ni–Fe alloys, whereas the defects comprising dislocations and twins are deliberately incorporated via a strain‐mediated release mechanism. The strategically distributed porous channels provide abundant active sites and facilitate the timely release of bubbles. Simultaneously, the defects induce localized lattice strain that optimizes the d‐band center of Ni, balancing the adsorption/desorption energetics of intermediates. The fabricated alloy electrode consequently demonstrates exceptional OER performance with an overpotential of 265 mV at 10 mA·cm −2 and remarkable durability sustaining 500 mA·cm −2 for 120 h. This work establishes that Ni–Fe alloy electrodes with dual optimization of morphological architecture and defect configuration can rival noble metal‐based catalysts, proposing a streamlined synthesis protocol for designing self‐supporting OER electrodes with enhanced activity and durability.