Heteroatoms doping is able to produce catalytic sites in carbon materials for oxygen reduction reaction (ORR); while hierarchically porous structure is necessary for efficient exposure and accessibility of the usually limited catalytic sites in such activated carbon catalysts. This work reports an in situ generated dual-template method to synthesize the Fe/N/S co-doped hierarchically porous carbon (FeNS/HPC), with NaCl crystallites formed during the precursor lyophilization process as the primary template to generate ∼500 nm macropores with ultrathin graphene-like carbon-layer walls, and Fe3O4 nanoparticles formed during the high-temperature carbonization process as the secondary template to produce mesopores on the walls of macropores. As well as the coexistence of graphitic-N, pyridinic-N, and thiophene-S which are beneficial to ORR, the as prepared FeNS/HPC possesses a highly graphitized and interconnected hierarchical porous structure, giving a specific surface area as high as 938 m2 g-1. As a consequence, it exhibits excellent four-electron oxygen reduction performance in both alkaline and acid electrolytes. The in situ generation and facile solution removal make the present template method a promising way for scale-up preparation of active porous carbon materials for various applications.
Keywords: NaCl crystal template; dual template method; hierarchically porous carbon; nitrogen doping; oxygen reduction reaction; sulfur doping.