A high-performance doped carbon catalyst with highly porous structures was prepared through a simple one-step pyrolysis process using polyacrylonitrile, melamine and iron chloride as precursors. The catalysts were characterized intensively by scanning electron microscope (SEM), high resolution transmission microscope (HRTEM), X-ray photoelectron spectroscopy (XPS), and liner sweeping voltammetry (LSV) , etc. The characterization results confirm the fluffy porous structures of the as-prepared catalyst, and reveals that the melamine addition can not only endow the catalysts with fluffy structures and high surface areas, but also modify the N contents and the distribution of N species in the catalysts.

 The catalysts exhibit excellent oxygen reduction reaction (ORR) performance, outstanding methanol tolerance, remarkable stability and nearly 100% selectivity for the four-electron ORR process. Remarkably, for sample PAC50M with ratio of PA/ melamine of 1:50, its ORR catalytic activity can be even superior to that of commercial Pt/C catalyst in alkaline media, with half-wave potential 27 mV more positive. To our knowledge, it is also one of the most active ORR catalysts in alkaline media to date.