Operando-reconstructed polyatomic ion layers boost the activity and stability of industrial current–density water splitting

Metal–organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction (OER). Current structure–activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis. Herein, modeling based on NiFe Prussian blue analogs (NiFe-PBAs) show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions (ammonium and carbonate) that re-adsorb onto the surface of NiFe OOH during the OER process. Interestingly, the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen–mediated mechanism, thus contributing to the high activity. In addition, this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions, thus breaking the activity–stability trade-off. Consequently, our constructed NiFe-PBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm⁻². The scale-up NiFe-PBAs operated with a low energy consumption of ∼4.18 kWh m⁻³ H₂ in industrial water electrolysis equipment. The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59 $k{g^{-1}}_{H_2}$, meeting global targets (<US$2.5 $k{g^{-1}}_{H_2}$).