N-Doped Carbon Electrocatalyst: Marked ORR Activity in Acidic Media without the Contribution from Metal Sites?

Fe−N−C electrocatalysts have been demonstrated to be the most promising substitutes for benchmark Pt/C catalysts for the oxygen reduction reaction (ORR). Herein, we report that N-doped carbon materials with trace amounts of iron (0–0.08 wt. %) show excellent ORR activity and durability comparable and even superior to those of Pt/C in both alkaline and acidic media without significant contribution by the metal sites. Such an N-doped carbon (denoted as N-HPCs) features a hollow and hierarchically porous architecture, and more importantly, a noncovalently bonded N-deficient/N-rich heterostructure providing the active sites for oxygen adsorption and activation owing to the efficient electron transfer between the layers. The primary Zn-air battery using N-HPCs as the cathode delivers a much higher power density of 158 mW cm⁻², and the maximum power density in the H₂−O₂ fuel cell reaches 486 mW cm⁻², which is comparable to and even better than those using conventional Fe−N−C catalysts at cathodes.