Experimental and Theoretical Elucidation of Metal‐Free Sulfur and Nitrogen Co‐Doped Porous Carbon Materials with an Efficient Synergistic Effect on the Oxygen Reduction Reaction

Abstract Metal‐free carbon‐based catalysts have attracted significant attention owing to their unique electronic structure and excellent catalytic activity for the oxygen reduction reaction (ORR). Recently, several heteroatom‐doped carbon catalysts with ORR performances comparable with those of state‐of‐the‐art Pt‐based catalysts have been reported. However, the intrinsic influence of heteroatoms on the catalytic activity has not been thoroughly investigated to date. This paper reports porous carbons co‐doped with N and S, prepared using an ion‐exchange resin and tetramethylammonium cations, with an onset potential of 0.93 V versus reversible hydrogen electrode (RHE) and a half‐wave potential of 0.79 V versus RHE. First‐principles calculations reveal that the change in the atomic charge caused by the co‐doping of N and S is important for inducing a high ORR activity. This paper presents a rational synthetic strategy for metal‐free catalysts and provides fundamental insights into their electrocatalysis.