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As one of the most sustainable, efficient, and cleanest ways for hydrogen production, electrochemical water splitting relies heavily on cost-efficient and stable electrocatalysts. Herein, a self-supported and nitrogen-doped hybrid CoP/Ni2P was synthesized through a simple two-step hydrothermal process followed by low-temperature phosphorization and nitridation (N-CoP/Ni2P@NF). Both experimental and density functional theory calculation results suggest that nitrogen doping can tune the electrical structure of the CoP/Ni2P heterostructure