Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes

Co-N-C catalysts are promising candidates for substituting platinum in electrocatalysis and organic transformations. The heterogeneity of the Co species resulting from high-temperature pyrolysis, however, encumbers the structural identification of active sites. Herein, we report a self-supporting Co-N-C catalyst wherein cobalt is dispersed exclusively as single atoms. By using sub-Ångström-resolution HAADF-STEM in combination with XAFS and DFT calculation, the exact structure of the Co-N-C is identified to be CoN₄C₈-1-2O₂, where the Co center atom is coordinated with four pyridinic N atoms in the graphitic layer, while two oxygen molecules are weakly adsorbed on Co atoms in perpendicular to the Co-N₄ plane. This single-atom dispersed Co-N-C catalyst presents excellent performance for the chemoselective hydrogenation of nitroarenes to produce azo compounds under mild reaction conditions.