\u3cem\u3eIn Situ\u3c/em\u3e Activated Co\u3csub\u3e3–x\u3c/sub\u3eNi\u3csub\u3ex\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e as a Highly Active and Ultrastable Electrocatalyst for Hydrogen Generation

Abstract

The spinel Co3O4 has emerged as a promising alternative to noble-metal-based electrocatalysts for electrochemical water electrolysis in alkaline medium. However, pure Co3O4, despite having high activity in anodic water oxidation, remains inactive toward the hydrogen evolution reaction (HER). Here, a Ni-doped Co3O4(Co3–xNixO4) prepared by a simple method exhibits favorable HER activity and stability (\u3e300 h, whether in 1 M KOH or the realistic 30 wt % KOH solution) after in situ electrochemical activation, outperforming almost all of the oxide-based electrocatalysts. More importantly, using the combination of in situ Raman spectroscopy and multiple high-resolution electron microscopy techniques, it is identified that the surface of Co3–xNixO4 crystals is reduced into intertwined CoyNi1–yO nanoparticles with highly exposed {110} reactive planes. Density functional theory calculations further prove that the Ni-doped CoO component in CoyNi1–yO plays a major role during the alkaline HER, because the introduction of Ni atoms into Co–O octahedra can optimize the electrical conductivity and tailor the adsorption/desorption free energies of Had and OHad intermediates