Engineered PW12-polyoxometalate docked Fe sites on CoFe hydroxide anode for durable seawater electrolysis

Abstract Seawater electrolysis driven by offshore renewable energy is a promising avenue for large-scale hydrogen production but faces challenges in designing robust anodes that suppress surface chlorine reactions and corrosion at high current densities. Here we report a strategy by selectively docking PW12-polyoxometalate (PW12-POM) onto Fe sites of CoFe hydroxide anode to modulate the electronic structure of adjacent Co active centers and regulate Cl⁻/OH⁻ adsorption for efficient alkaline seawater oxidation. Our CoFe-based anode achieves low overpotentials, high catalytic selectivity, and notable durability, with continuous operation at 1 A cm⁻² for over 1300 hours and at 2 A cm⁻² more than 600 hours. Theoretical calculations and ex situ/in situ analyses reveal that PW12-POM coordination at Fe sites stabilizes Fe, suppresses its leaching, modulates Co acidity, promotes OH⁻ adsorption, and protects metal sites from Cl⁻ corrosion.