Order of Activity of Nitrogen, Iron Oxide, and FeNx Complexes towards Oxygen Reduction in Alkaline Medium

Abstract In alkaline medium, it seems that both metal‐free and iron‐containing carbon‐based catalysts, such as nitrogen‐doped nanocarbon materials, FeO x ‐doped carbon, and Fe/N/C catalysts, are active for the oxygen reduction reaction (ORR). However, the order of activity of these different active compositions has not been clearly determined. Herein, we synthesized nitrogen‐doped carbon black (NCB), Fe 3 O 4 /CB, Fe 3 O 4 /NCB, and FeN 4 /CB. Through the systematic study of the ORR catalytic activity of these four catalysts in alkaline solution, we confirmed the difference in the catalytic activity and catalytic mechanism for nitrogen, iron oxides, and Fe–N complexes, respectively. In metal‐free NCB, nitrogen can improve the ORR catalytic activity with a four‐electron pathway. Fe 3 O 4 /CB catalyst did not exhibit improved activity over that of NCB owing to the poor conductivity and spinel structure of Fe 3 O 4 . However, FeN 4 coordination compounds as the active sites showed excellent ORR catalytic activity.