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Herein,we develop a novel method to synthesize evenly dispersed fine Co nanoparticles(NPs)(particle size of ~42 nm) encapsulated in N-doped porous carbon matrix(NPCM) with superficial N-doped porous carbon nanofibers(NPCNF)(denoted as Co@NPCM/CNF-850) as an oxygen reduction reaction(ORR) electrocatalyst.