Synergistic Nanotubular Copper‐Doped Nickel Catalysts for Hydrogen Evolution Reactions

Developing highly active electrocatalysts with low cost and high efficiency for hydrogen evolution reactions (HERs) is of great significance for industrial water electrolysis. Herein, a 3D hierarchically structured nanotubular copper‐doped nickel catalyst on nickel foam (NF) for HER is reported, denoted as Ni(Cu), via facile electrodeposition and selective electrochemical dealloying. The as‐prepared Ni(Cu)/NF electrode holds superlarge electrochemical active surface area and exhibits Pt‐like electrocatalytic activity for HER, displaying an overpotential of merely 27 mV to achieve a current density of 10 mA cm^?2 and an extremely small Tafel slope of 33.3 mV dec^?1 in 1 m KOH solution. The Ni(Cu)/NF electrode also shows excellent durability and robustness in both continuous and intermittent bulk water electrolysis. Density functional theory calculations suggest that Cu substitution and the formation of NiO on the surface leads to more optimal free energy for hydrogen adsorption. The lattice distortion of Ni caused by Cu substitution, the increased interfacial activity induced by surface oxidation of nanoporous Ni, and numerous active sites at Ni atom offered by the 3D hierarchical porous structure, all contribute to the dramatically enhanced catalytic performance. Benefiting from the facile, scalable preparation method, this highly efficient and robust Ni(Cu)/NF electrocatalyst holds great promise for industrial water–alkali electrolysis.