Amphiphilic Bonding Intercalation Reshapes Active Sites and Interlayer Microenvironment for Selective and Stable Seawater Oxidation

Direct seawater electrolysis is severely constrained by the activity‐durability trade‐off and chloride‐induced corrosion. Herein, we design corrosion‐resistant, highly selective layered double hydroxide (LDH) catalysts by transitioning interlayer bonding from weak electrostatic attraction to strong coordination. Amphiphilic dodecylbenzenesulfonate (SDBS) coordinates with Fe active centers, forming robust Fe─O─S bonds that establish a securely locked microenvironment. Density functional theory reveals this coordination upshifts the Fe d‐band center and enhances Fe─O covalency, lowering the thermodynamic oxygen evolution barrier. Simultaneously, molecular dynamics simulations show that hydrophobic alkyl tails reorganize the interfacial hydrogen‐bond network. This creates a kinetic barrier against chloride, enabling high hydroxide‐to‐chloride diffusion selectivity (D OH − /D Cl − ≈ 1.94). Consequently, the NiFe‐SDBS electrode decouples stability from activity, delivering an ultralow overpotential of 239 mV at 10 mA cm −2 and sustaining 1000 mA cm −2 for >1000 h with negligible degradation. In a zero‐gap anion exchange membrane (AEM) electrolyzer, it achieves 1000 mA cm −2 at ∼4.64 kWh Nm −3 and maintains robust stability (>600 h at 500 mA cm −2 ) with an ultra‐low degradation rate of 0.18 mV h −1 . This work establishes coordination‐driven microenvironment engineering as a generalizable paradigm for durable electrocatalyst design.