Electrolyte‐Mediated Selective Interfacial H‐Bond Network for Durable Seawater Electrolysis

ABSTRACT Ni‐based catalysts, the most popular candidates for anodes in seawater electrolysis, are severely hampered by the corrosion‐induced degradation under high‐current‐density operation. Here, a minimalist electrolyte engineering was proposed to construct an interfacial H‐bond network for highly selective penetration, which effectively suppresses Cl ⁻ corrosion while facilitating OH ⁻ transfer. Through the introduction of trace sodium tungstate and sodium benzoate into alkaline seawater electrolyte, NiFe‐LDH anode exhibits exceptional stability exceeding 5000 h at 1.2 A cm ⁻² . In situ spectroscopic analyses and computational simulations of MD, and AIMD reveal that the oxyanions promote the surface reconstruction into active NiFeOOH and induce reorientation of interfacial water molecules. It leads to a reversed O‐down configuration that strengthens catalyst‐network interaction and promotes Grotthuss‐type proton transfer. The resulting H‐bond network enhances redox kinetics, enriches interfacial OH ⁻ concentration, and establishes a Cl ⁻ lean microenvironment. This approach demonstrates across various nickel‐based catalysts and maintains performance under intermittent power supply conditions. Furthermore, it achieves a H ₂ production rate of 161 mL min ⁻¹ with an energy consumption of 4.3 kWh/Nm ³ H ₂ on seawater electrolyzer. Our work provides a generalized electrolyte‐mediated strategy for seawater splitting, highlighting the critical role of interfacial hydrogen‐bond engineering in catalyst design and industrial application.