Owing to the difficulty in controlling the dopant or defect types and their homogeneity in carbon materials, it is still a controversial issue to identify the active sites of carbon-based metal-free catalysts. Herein, we report a proof of concept study on the active-site evaluation for a highly oriented pyrolytic graphite catalyst with specific pentagon carbon defective patterns (D-HOPG).It is demonstrated that specific carbon defect types (edged pentagon in this work) could be selectively created via controllable N-doping. Work function analyses coupled with macro/microelectrochemical performance measurements suggest that the pentagon defects in D-HOPG served as major active sites for acidic oxygen reduction reaction (ORR), even much superior to the pyridinic nitrogen sites in N-doped highly oriented pyrolytic graphite (N-HOPG). This work enables us to elucidate the relative importance of the specific carbon defects vs N-dopant species and their respective contributions to the observed overall acidic ORR activity.
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Newly N-S-C coordination-structured active sites, originating from the integrity of edged thiophene S, graphitic N, and pentagon defects, were reconstructed by N-modified S defects in carbon aerogel with a 3D hierarchical macro-mesomicroporous structure. This metal-free material exhibited outstanding oxygen reduction reaction (ORR) activity (e.g., half-wave potentials of 0.76 V in 0.5 M H 2 SO 4 and 0.1 M HClO 4 ; 0.85 V in 0.1 M KOH) with good stability and high current density in both acidic and alkaline electrolytes. The experimental and computational results reveal that the pentagon S defect is essential for the ORR in acidic electrolytes because it provides a remarkable increase in reactivity. One graphitic-type N in the meta-position of the pentagon defect further significantly improves the reactivity as a result of locally precise control of the electronic structure, thus forming highly active sites for ORR in acid.
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