NiCu alloys anchored Co3O4 nanowire arrays as efficient hydrogen evolution electrocatalysts in alkaline and neutral media

The introduction of the NiCu alloy altered the inherent electronic structure of Co3O4, resulting in increased exposure of the active sites and improved endogenous electrocatalytic activity, leading to enhanced reaction kinetics and long-term stability in both neutral and alkaline HER catalysis. [Display omitted] •The Co3O4@NiCu catalysts with abundant active sites and large electrochemical surface area was successfully prepared.•The easy penetration of valence electrons from Co3O4 to NiCu, favored the improvement of HER performance.•Co3O4@NiCu produces more catalytic active sites, facilitating the rapid release of hydrogen during the reaction.•The anchoring of NiCu alloy contributes to both improved HER activity and stability. Robust and long-lasting non-precious metal electrocatalysts are essential to achieve sustainable hydrogen production. In this work, we synthesized Co3O4@NiCu by electrodepositing NiCu nanoclusters onto Co3O4 nanowire arrays that were formed in situ on nickel foam. The introduction of NiCu nanoclusters altered the inherent electronic structure of Co3O4, significantly increasing the exposure of active sites and enhancing endogenous electrocatalytic activity. Co3O4@NiCu exhibited overpotentials of only 20 and 73 mV, respectively, at 10 mA cm−2 current densities in alkaline and neutral media. These values were equivalent to those of commercial Pt catalysts. Finally, the electron accumulation effect at the Co3O4@NiCu, along with a negative shift in the d-band center, is finally revealed by theoretical calculations. Hydrogen adsorption on consequent electron-rich Cu sites was effectively weakened, leading to a robust catalytic activity for the hydrogen evolution reaction (HER). Overall, this study proposes a practical strategy for creating efficient HER electrocatalysts in both alkaline and neutral media.