Precious metals (Pt, Ir, Ru, and so on) and related compounds usually demonstrate superb catalytic activity for electrochemical hydrogen production. However, scarcity and stability are still challenges for hydrogen evolution reaction, even for single-atomic-site electrocatalysts. Herein, a fluorine (F) doping strategy is proposed to enhance the strong metal–support interaction between the F-doped Ni3N support and the loaded ruthenium (Ru) species. Via synergistically modulating both the Ru loading amount and F doping concentration, outstanding HER activity was achieved in Ru@F–Ni3N with an overpotential (η) of 115 mV at 100 mA cm–2, superior to the benchmark Pt/C (η = 201 mV). Density functional theory simulation in combination with X-ray photoelectron spectra and X-ray absorption spectroscopy characterizations convincingly demonstrate that, with the strongest electronegativity, F doping could effectively stabilize Ru atoms doped in the F–Ni3N substrate and simultaneously reduce the H bonding strength, which accelerated the desorption of H2. These findings provide a facile strategy to modulate both catalytic activities and stabilities of heteroatom-loaded catalytic materials.

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