Herein, we reported a special Fe-N-doped double-shelled hollow carbon microsphere (Fe-N-DSC) which was prepared by a facile, in situ polymerization followed by pyrolysis. With porous ferroferric oxide (FeO) hollow microspheres as the templates, where pyrrole monomers were dispersed around the outer surface and prefilled the interior space. By adding hydrochloric acid, Fe ions were released to initiate polymerization of pyrrole on both the outer and inner surfaces of FeO microspheres until they were completely dissolved, resulting in the Fe-containing polypyrrole double-shelled hollow carbon microspheres (Fe-PPY-DSC). The Fe-PPY-DSC was then pyrolyzed to generate the Fe-N-DSC. The FeO hollow microspheres played trifunctional roles, i.e., the template to prepare a double-shelled hollow spherical structure, the initiator (i.e., Fe ions) for the polymerization of pyrrole, and the Fe source for doping. The Fe-N-DSC exhibited a superior catalytic activity for oxygen reduction as comparable to commercial Pt/C catalysts in both alkaline and acidic media. The high catalytic performance was ascribed to the special porous double-shelled hollow spherical structure, which provided more active sites and was beneficial to a high-flux mass transportation.
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