Vanadium -mediated ultrafine Co/Co9S8 nanoparticles anchored on Co-N-doped porous carbon enable efficient hydrogen evolution and oxygen reduction reactions.

Developing cost-effective, highly-active and robust electrocatalysts is of vital importance to supersede noble-metal ones for both hydrogen evolution reactions (HERs) and oxygen reduction reactions (ORRs). Herein, a unique vanadium-mediated space confined strategy is reported to construct a composite structure involving Co/Co9S8 nanoparticles anchored on Co-N-doped porous carbon (VCS@NC) as bifunctional electrocatalysts toward HER and ORR. Benefitting from the ultrafine nanostructure, abundant Co-Nx active sites, large specific surface area and defect-rich carbon framework, the resultant VCS@NC exhibits unexceptionable HER catalytic activity, needing extremely low HER overpotentials in pH-universal media (alkaline: 117 mV, acid: 178 mV, neutral: 210 mV) at a current density of 10 mA cm-2, paralleling at least 100 h catalytic durability. Notably, the VCS@NC catalyst delivers high-efficiency ORR performance in alkaline solution, accompanied with a quite high half wave potential of 0.901 V, far overmatching the commercial Pt/C catalyst. Our research opens up novel insight into engineering highly-efficient multifunctional non-precious metal electrocatalysts by a metal-mediated space-confined strategy in energy storage and conversion system.