Nitrogen-containing electrocatalysts, such as metal–nitrogen–carbon (M–N–C) composites and nitrogen-doped carbons, are known to exhibit high activities for an oxygen reduction reaction (ORR). Moreover, even if the mechanism by which nitrogen improves the activities is not completely understood, a strong electronic interaction between nitrogen and active sites has been found in these composites. Herein, we demonstrate a case in which nitrogen improves the electroactivity, but in the absence of a strong interaction with other components. The overpotentials of the ORR and oxygen evolution reaction (OER) on perovskite oxide catalysts were significantly reduced simply by mixing the catalyst particles with polypyrrole/carbon composites (pPy/C). Any strong interactions between pPy (a nitrogen-containing compound) and active sites of the catalysts are not confirmed. A scenario based on the sequential task allocation between pPy and oxide catalysts for the ORR was proposed: (1) molecular oxygen is incorporated into pPy as a form of superoxide (pPy+O2−), (2) the superoxide is transferred to the active sites of perovskite catalysts, and (3) the superoxide is completely reduced along the 4e ORR process.
