Triggered Directed Electron Redistribution Endowed by Efficient Ohmic Contacts of NiMoN/Ni₃S₂ for Boosting Large Current‐Density Overall Seawater Splitting

Abstract The rational construction of interfacial nanostructures of metal/semiconductor (MS) contacted electrocatalysts has a significant impact on improving their intrinsic activities. However, MS contacts are often plagued by a strong Fermi‐level pinning effect, resulting in the formation of the Schottky barrier that affects the adsorption of hydrogen/oxygen intermediates. Herein, an Ohmic contact between metallic Ni₃S₂ and semiconducting NiMoN is well‐designed, which effectively reduces the electron conduction barriers. The as‐obtained NiMoN/Ni₃S₂ has remarkable bifunctional water electrolysis performance. At 10 mA·cm⁻², the overpotential of hydrogen evolution and oxygen evolution reaction is 70 and 154 mV, respectively. Impressively, the formation of hydroxide during surface reconstruction can avoid the chlorine evolution on the catalyst surface. At an industrial process temperature of 85 °C, it takes only 340 mV for the overall seawater splitting of 500 mA·cm⁻². UPS and UV‐VIS diffuse spectra combined with theoretical calculation results confirm that the self‐driven directed electron transfer derived from the Ohmic contact can induce local electron enrichment at the interface region, thus promoting the formation of *O to *OOH. This study provides important insights into the coordinated modulation of built‐in electric fields and the preparation of efficient multifunctional catalysts with a high abundance of active sites.