▎ 摘　　要

This work demonstrates the molecular engineering of active sites on a graphene scaffold. It was found that the N-doped graphene nanosheets prepared by a high-temperature nitridation procedure represent a novel chemical function of efficiently catalyzing aerobic alcohol oxidation. Among three types of nitrogen species doped into the graphene lattice-pyridinic N, pyrrolic N, and graphitic N- the graphitic sp(2) N species were established to be catalytically active centers for the aerobic oxidation reaction based on good linear correlation with the activity results. Kinetic analysis showed that the N-doped graphene-catalyzed aerobic alcohol oxidation proceeds via a Langmuir-Hinshelwood pathway and has moderate activation energy (56.1 +/- 3.5 kJ.mol(-1) for the benzyl alcohol oxidation) close to that (51.4 kJ.mol(-1)) proceeding on the catalyst Ru/Al2O3 reported in literature. An mechanism was proposed to be different remarkably from that occurring on the noble metal catalyst. The possible formation of a sp(2) N-O-2 adduct transition state, which can oxidize alcohols directly to aldehydes without any byproduct, including H2O2 and carboxylic acids, may be a key element step. Our results advance graphene chemistry and open a window to study the graphitic sp(2) nitrogen catalysis.