| Abstract: | Fabricating cost‐effective, bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in basic media is critical for renewable energy generation. Here, NiSe/CP, Ni0.85Se/CP, and NiSe‐Ni0.85Se/CP heterostructure catalysts with different phase constitutions are successfully prepared through in situ selenylation of a NiO nanoflake array oriented on carbon paper (CP) by tuning the original Ni/Se molar ratio of the raw materials. The relationship between the crystal phase component and electrocatalytic activity is systematically studied. Benefiting from the synergetic effect of the intrinsic metallic state, facile charge transport, abundant catalytic active sites, and multiple electrolyte transmission paths, the optimized NiSe‐Ni0.85Se/CP exhibits a remarkably higher catalytic activity for both the HER and OER than single‐phase NiSe/CP and Ni0.85Se/CP. A current density of 10 mA cm−2 at 1.62 V and a high stability can be obtained by using NiSe‐Ni0.85Se/CP as both the cathode and anode for overall water splitting under alkaline conditions. Density functional theory calculations confirm that H and OH− can be more easily adsorbed on NiSe‐Ni0.85Se than on NiSe and Ni0.85Se. This study paves the way for enhancing the overall water splitting performance of nickel selenides by fabricating heterophase junctions using nickel selenides with different phases. |
