Coordinated regulation of phosphorus/nitrogen doping in fullerene-derived hollow carbon spheres and their synergistic effect for the oxygen reduction reaction

Fullerene-derived carbons have been demonstrated as effective electrode materials for electrocatalytic reactions. The heteroatoms in the carbon matrix are essential to enhance their electrocatalytic performance but are still challenging for effective doping strategies and understanding their synergistic effect. Herein, we regulate the phosphorus/nitrogen (P/N) doping in the carbon structure based on the control mixing of pyritic acid (PA) with the assembled diamine-C₆₀ hollow spheres (N@FHS). After pyrolysis, the carbon spheres are shown to have a homogenous distribution of N and P (NP@CHS). The structural and molecular analysis reveals that the doping of P may facilitate the formation of graphitic N in the carbon framework. When used as electrocatalysts for the oxygen reduction reaction (ORR), NP@CHSs exhibit superior oxygen reduction reaction (ORR) performance in contrast to those of fullerene-derived carbon with single N doping and the commercial Pt/C (20 wt%) catalyst. Density functional theory (DFT) studies indicate that P/N-doping promotes the charge transfer in the carbon structure owing to its strong electronegativity. The enhanced ORR activity should be mainly due to the P- and N-coordinated neighboring C sites with the defective fullerene pentagon ring.