▎ 摘　　要

The metal-free nitrogen-doped graphitic-carbon@graphene (Ng-C@G) is prepared from a composite of polyaniline and graphene by a facile polymerization following by pyrolysis for electrochemical oxygen reduction reaction (ORR). Pyrolysis creates a sponge-like with ant-cave-architecture in the polyaniline derived nitrogenous graphitic-carbon on graphene. The nitrogenous carbon is highly graphitized and most of the nitrogen atoms are in graphitic and pyridinic forms with less oxygenated is found when pyrolyzed at 800 degrees C. The electrocatalytic activity of Ng-C@G-800 is even better than the benchmarked Pt/C catalyst resulting in the higher half-wave potential (8 mV) and limiting current density (0.74 mA cm(-2)) for ORR in alkaline medium. Higher catalytic performance is originated from the special porous structure at microscale level and the abundant graphitic- and pyridinic-N active sites at the nanoscale level on carbon-graphene matrix which are beneficial to the high O-2-mass transportation to those accessible sites. Also, it possesses a higher cycle stability resulting in the negligible potential shift and slight oxidation of pyridinic-N with better tolerance to the methanol.