Exploiting highly efficient, cost-effective and stable electrocatalysts is key to decreasing hydrogen evolution reaction (HER) kinetics energy barrier. Herein, the alkaline HER kinetics energy barrier can greatly reduce by the joint strategies of the cation vacancy and heterostructure engineering, which is seldom explored and remains ambiguous. In this study, an efficient and stable copper foam-supported Cu3P-CoP heterostructure electrocatalyst with cation vacancy defects (defined as Cu3P-CoP-VAl/CF) was designed for HER via the successive coprecipitation, electrodeposition, alkali etching and phosphorization treatments. As anticipated, the as-obtained Cu3PCoP-VAl/CF electrocatalyst reveals a remarkable catalytic activity for HER with a low overpotential of 205 mV at a current density of 100 mA center dot cm(-2), a high turnover frequency value of 1.05 s(-1) at an overpotential of 200 mV and a small apparent activation energy (Ea) of 9 kJ center dot mol(-1), while shows superior long-term stability at large current densities of 100 and 240 mA center dot cm(-2). Systematic experiment and characterization data demonstrate that the formed cation vacancy could optimize the Ea, leading to the decrease of the kinetic barriers of Cu3P-CoP/CF heterostructure, as well as the established heterogeneous interface induced a synergistic effect between biphasic components on boosting the kinetics toward HER. The results of density functional theory disclose that the synergistic effect of Cu3P-CoP heterostructure could decrease the energy barrier and optimize Gibbs free energy of hydrogen adsorption, resulting in the enhancement of intrinsic catalytic activity of Cu3P-CoP-VAl/CF. More significantly, the alkali-cell assembled by Cu3P-CoP-VAl/CF (cathode) and RuO2/CF (anode) behaves outstanding water splitting performance, delivering a current density of 10 mA center dot cm(-2) at a relatively small applied voltage of 1.58 V, along with encouraging long-term durability. In addition, the alkaline Zn-H2O battery with Cu3P-CoPVAl/CF as the cathode has been fabricated for the simultaneous generation of electricity and hydrogen, which displays a large power density of up to 4.1 mW center dot cm(-2). The work demonstrates that rational strategy for the design of competent electrocatalysts can effectively accelerate the kinetics of HER, which supplies valuable insights for practical applications in overall water splitting.
