Nitrogen-doped graphene stabilized gold nanoparticles for aerobic selective oxidation of benzylic alcohols

Increasing efforts have been made to fabricate Au/graphene composites due to the fascinating properties of both graphene and gold. Some Au nanoparticles with an average size of tens of nanometers were directly deposited on reduced graphene oxide (RGO), utilizing the residual oxy-functional groups as the "hitching post'' of the nanoparticles. Some functional groups, such as amino and thiol, were attached to the surface of the graphene in order to stabilize gold nanoparticles with a smaller particle size (<5 nm in general). Unfortunately, most of these strategies result in Au particles with limited exposed atoms, which is certainly a disadvantage for their application, such as catalysis. Introduction of nitrogen heteroatoms into the framework of graphene can not only modulate the electronic structure, but also change the surface properties of the graphene. In this work, naked Au nanoparticles with an average size of about 2-4 nm were fabricated on nitrogen-doped graphene nanosheets (NG) via the direct simple reduction method. The Au/NG nanocomposites were characterized by XRD, XPS, TEM, AFM and Raman. It was revealed that the nitrogen atoms doped in NG, rather than defects or oxygen moieties, play an essential role in stabilizing Au NPs. It was also found that the initial reaction rate of benzyl alcohol oxidation over the Au/NG catalyst is about ten fold higher than that over Au/graphene catalysts. Our findings may provide a clue of nitrogen incorporation to stabilize uncapped noble metal nanoparticles on graphene or other inorganic oxide supports, such as TiO2.