Phosphoryl‐Engineered MOFs Promote Interfacial Reconstruction for Efficient Seawater Ethanol Electrooxidation

The hydrogen production efficiency of hybrid seawater electrolysis devices hinges on high‐performance catalytic materials with superior activity and chlorine corrosion resistance under the alkaline seawater conditions. However, the controllable modulation of catalyst structures to construct an effective anti‐chlorine protective layer, one that simultaneously enhances both Cl corrosion resistance and anodic oxidation reaction activity, remains a formidable challenge. Herein, we report a phosphonyl‐ligand engineering strategy that promotes the transformation of metal–organic frameworks (MOFs) into metal oxyhydroxides containing oxygen‐anions during alkaline seawater ethanol oxidation reaction (EOR) with enhanced activity and Cl – corrosion resistance. Leveraging the tunable nature of organic ligands in MOFs provides a versatile platform for the in situ formation of oxygen anion layers with robust chlorine corrosion resistance. A phosphorus‐containing MOF (P a ‐Ni‐TPA) was synthesized by partially substituting terephthalic acid (TPA) with 4‐phosphonobenzoic acid (P a ). In contrast to the conventional MOF (Ni‐TPA), the in situ generated metal oxyhydroxide from P a ‐Ni‐TPA incorporates PO 4 3– . PO 4 3– promotes the adsorption of ethanol and its intermediates onto nickel centers while inhibiting Cl adsorption, thereby significantly boosting both EOR activity and Cl corrosion resistance. These findings establish a detailed structure‐performance correlation between MOF structural evolution and both catalytic activity toward alkaline seawater EOR and resistance to chlorine corrosion.