Facile electrospinning preparation of phosphorus and nitrogen dual-doped cobalt-based carbon nanofibers as bifunctional electrocatalyst

•Novel Co-based CNFs catalysts were prepared by the electrospinning technique.•The CoNP-CNFs catalyst exhibits the excellent ORR and HER catalytic activity.•Synergy of N/P is responsible for the excellent catalytic performance.•Pyridinic-N and Co-Nx clusters of CoNP-CNFs were as catalytic active sites.

A novel electrochemical catalyst of phosphorus and nitrogen dual-doped cobalt-based carbon nanofibers (CoNP-CNFs) is prepared by a facile and cost-effective electrospinning technique. Excellent features of the porous carbon nanofibers with large amounts of Co atoms, N/P-doping effect, abundant pyridinic-N and CoNx clusters as catalytic active sites, and the advantages of the structure and composition result in a high catalytic efficiency. In alkaline or acidic media, CoNP-CNFs exhibits remarkable electrocatalytic activities and kinetics for oxygen reduction reaction (ORR), superior methanol tolerance and stability, and a similar four-electron pathway. In addition, CoNP-CNFs also shows excellent performance for hydrogen evolution reaction (HER), offering a low onset potential of −0.216 V and a stable current density of 10 mA cm−2 at potential of −0.248 V. The mechanism of ORR and HER catalytic active site arises from the doping of N/P atoms in the Co-based CNFs, which is responsible for the excellent electrocatalytic performance. Due to the excellent catalytic efficiencies, CoNP-CNFs act as a promising catalyst material for fuel cells and water splitting technologies.

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