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

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.

Surface Reconstruction of Covellite CuS Nanocrystals for Enhanced OER Catalytic Performance in Alkaline Solution.

Oxygen evolution reaction (OER) is one of the important half-reactions in energy conversion equipment such as water-spitting devices, rechargeable metal-air batteries, and so on. It is beneficial to develop efficient and low-cost catalysts that understand the reaction mechanism of OER and analyze the reconstruction phenomenon of transition metal sulfide. Interestingly, copper sulfide and cuprous sulfide with the same components possess different reconstruction behaviors due to their different metal ion valence states and different atomic arrangement modes. Because of a unique atomic arrangement sequence and certain cationic defects, the reconstruction phenomenon of CuS nanomaterials are that S2- is firstly oxidized to SO4 2- and then Cux + is converted into CuO via Cu(OH)2 . In addition, the specific "modified hourglass structure" of CuS with excellent conductivity is easier to produce intermediates. Compared with Cu2 S, CuS exhibits excellent OER activity with a lower overpotential of 192 mV at 10 mA cm-2 and remarkable electrochemical stability in 1.0 m KOH for 120 h. Herein, this study elucidates the reconstruction modes of CuS and Cu2 S in the OER process and reveals that CuS has a stronger CuS bond and a faster electronic transmission efficiency due to "modified hourglass structure," resulting in faster reconstruction of CuS than Cu2 S.