Use of Cobalt Polyphthalocyanine and Graphene as Precursors to Construct an Efficient Co 9 S 8 /N,S‐G Electrocatalyst for the Oxygen Electrode Reaction in Harsh Media

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are fundamental reactions connected with energy conversion and/or storage devices. However, the sluggish kinetics of the ORR and OER reduce the efficiency. To address these issues, the development of efficient and robust electrode catalysts is required desperately. Herein, a new Co 9 S 8 nanocrystal hybrid anchored on a N‐ and S‐dual‐doped graphene (Co 9 S 8 /N,S‐G) was prepared by a two‐step method, namely, a π–π assembly process of p ‐phenyl‐bis(3,4‐dicyanophenyl)thioether cobalt polyphthalocyanine (PTCoPPc) and graphene oxide and a pyrolysis procedure. Electrochemical studies demonstrated that Co 9 S 8 (800)/N,S‐G exhibited a comparable ORR performance with 20 wt % Pt/C, such as an onset potential and a half‐wave potential of 0.931 and 0.811 V vs. the reversible hydrogen electrode, respectively, a limiting current density of 5.207 mA cm −2 , and a good long‐term stability with a current retention of 92.6 % after 10 000 s continuous measurements. Co 9 S 8 (900)/N,S‐G displayed an excellent OER activity, which was ascribed to the presence of pyridinic N, graphitic N, and the occupation of Co−N to catalyze the ORR; and the oxygen adsorption on the surface of Co 9 S 8 (900)/N,S‐G contributed significantly to the OER activity. The approach developed here offered a new strategy to construct efficient oxygen electrode catalysts.