The sluggish charge transfer and poor intrinsic activity are the obstacles that limit the development for electrocatalysts on hydrogen evolution. A novel core-shell heterostructure composed of CuP nanowires with supported CoO nanosheets was synthesized. Owing to numerous active sites and synergistic effect, the as-prepared CuP@CoO was highly efficient for hydrogen evolution and outperformed the single component. The theoretical calculations demonstrate that CuP@CoO had a zero bandgap for the incorporation of metallic CuP, which can greatly accelerate the charge transfer. Besides, the adsorption free energy of intermediates on CuP@CoO can also be optimized, leading to a small energy barrier in the reaction pathway, and thereby an increased intrinsic activity. This work highlights the significance of exploiting the synergistic effect of the heterostructure on the charge transfer and intrinsic activity when designing highly efficient electrocatalysts for hydrogen evolution.
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