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

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.