LAUSR

Pore engineering has been recognized as a power methodology to fabricate carbon‐based catalysts with highly efficient electrocatalytic performance for oxygen reduction reaction. This paper reports an interfacial self‐assembly engineering for the growth of mesoporous N‐doped carbon with spherical or cylindrical pores on graphene nanosheets. The resulting 2D porous nanocomposites templated from Pluronic block copolymers possess similar N doping contents of ≈2.6 wt%, average pore sizes of ≈8 nm in diameter, and specific surface areas of ≈420 m2 g−1. Due to the faster in‐plane ion diffusion offered by the continuous cylindrical channels, the porous carbon nanosheets with cylindrical pores exhibit superior oxygen reduction reaction (ORR) electrocatalytic performance in 0.1 m KOH, with a half‐wave‐potential (E1/2) of +0.74 V and a limiting current density (JL) of 4.8 mA cm−2, comparable to those of the commercial Pt/C catalysts. This study sheds light on the influence of pore structure on the ORR catalytic performance of 2D carbon materials, and also provides clues for the fabrication of porous materials with tailorable pore structures for high‐performance electrocatalysts.