Defective porous carbon microrods derived from fullerenes (C) as high-performance electrocatalysts for the oxygen reduction reaction.

Disrupting the integrity of the sp-carbon skeleton offers an effective strategy to create active sites for the oxygen reduction reaction (ORR). In this work, fullerene (C) molecules, composed of 12 pentagons and 25 hexagons all bonded by sp-C atoms, are assembled into microrods (C70MRs) at the liquid-liquid interface and then broken down by calcination to generate metal-free fullerene-derived ORR electrocatalysts. The effect of the pyrolysis temperature on C70MRs is investigated, and it is found that pyrolysis at 900 °C effectively unfolds the C cages and converts them into a highly porous, defect-rich carbon material (C70MRs-900) with the rod-shaped morphology well-retained. These structural features endow C70MRs-900 with outstanding ORR activity and stability together with remarkable methanol tolerance, better than C70MRs annealed at either lower (800 °C) or higher (1000 °C) temperatures. Furthermore, nitrogen atoms are successfully incorporated into the defective carbon skeleton by annealing C70MRs at 900 °C in the presence of NHCl. The resultant N-doped C70MRs-900 exhibits remarkable ORR performance with a half-wave potential of 0.836 V, comparable to that of the commercial 20% Pt/C catalyst. This work presents a simple and effective route of utilizing fullerene molecules as starting materials to develop high-performance metal-free, carbon-based electrocatalysts toward the ORR and even beyond.