Surface Cladding Engineering via Oxygen Sulfur Distribution for Stable Electrocatalytic Oxygen Production

Abstract Inevitable leaching and corrosion under anodic oxidative environment greatly restrict the lifespan of most catalysts with excellent primitive activity for oxygen production. Here, based on Fick’ s Law, we present a surface cladding strategy to mitigate Ni dissolution and stabilize lattice oxygen triggering by directional flow of interfacial electrons and strong electronic interactions via constructing elaborately cladding‐type NiO/NiS heterostructure with controlled surface thickness. Multiple in situ characterization technologies indicated that this strategy can effectively prevent the irreversible Ni ions leaching and inhibit lattice oxygen from participating in anodic reaction. Combined with density functional theory calculations, we reveal that the stable interfacial O−Ni−S arrangement can facilitate the accumulation of electrons on surficial NiO side and weaken its Ni−O covalency. This would suppress the overoxidation of Ni and simultaneously fixing the lattice oxygen, thus enabling catalysts with boosted corrosion resistance without sacrificing its activity. Consequently, this cladding‐type NiO/NiS heterostructure exhibits excellent performance with a low overpotential of 256 mV after 500 h. Based on Fick's law, this work demonstrates the positive effect of surface modification through precisely adjusting of the oxygen‐sulfur exchange process, which has paved an innovative and effective way to solve the instability problem of anodic oxidation.