A novel hybrid electrocatalyst of Co2B and Co nanoparticles immobilized on N–B-doped carbon derived from nano-B4C (Co2B/Co/N–B–C/B4C) is in situ synthesized by pyrolysis of nano-B4C supporting Co­(OH)2 nanoparticles with melamine. The Co2B and Co nanoparticles are formed and anchored on the generated N and B codoped carbon and undecomposed B4C. The hybrid exhibits remarkable catalytic performances toward the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR)a very small potential of 1.53 V at 10 mA cm–2 for the OER and a high catalytic kinetics and superior durability for the ORRwhich are superior to the RuO2 and Pt/C catalyst, respectively. Most impressively, the hybrid delivers a very small potential gap of 710 mV, which is lower than those of most bifunctional electrocatalysts reported. In addition, the hybrid also shows a satisfying hydrogen evolution reaction performance offering a small overpotential of 220 mV at 10 mA cm–2 and wonderful stability. The excellent trifunctional catalytic performances issue from synergetic effects of Co2B, metal Co, Co/N-doped carbon, and B self-doped carbon coexisting in the hybrid with good interaction mutually. This work provides a new-type efficient multifunctional catalyst for regenerative fuel cell and overall water-splitting technologies.

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