Nitrogen-doping hollow carbon nanospheres derived from conjugated microporous polymers toward oxygen reduction reaction.

The exploitation non-precious or metal-free electrocatalysts of oxygen reduction reaction (ORR) is of significance for construction of next-generation fuel cells. In this work, hollow-spherical conjugated microporous polymers (CMPs) comprising porphyrin units were synthesized as precursors to prepare N-doping porous carbon spheres (CMP-NP-x) by a direct pyrolysis method. The as-resulted CMP-NP-x exhibited spherical morphology with hollow structure similar to that of CMPs precursors. The BET surface area of CMP-NP-x can be tailored by the pyrolysis temperature varying from 868 m g to 1118 m g. According to XPS analysis, the pyrrolic N content in the sample decreased but the graphitic N and pyridinic N increased with increasing of the pyrolysis temperature from 800 °C to 1000 °C. Taking advantages of porous structure with large accessible surface areas and N species active sites, the resulting CMP-NP-x showed superior ORR activity and methanol tolerance to commercial Pt/C catalyst. In particular, CMP-NP-900 possesses the highest onset potential (0.930 V), half-wave potential (0.857 V) and limiting current density of 4.45 mA cm, compared with Pt/C catalyst and other samples, making it a promising metal-free catalyst superior to commercial Pt/C catalyst in alkalic condition.