Biomass-Derived N-doped Carbon Materials with Silica-Supported Ultrasmall ZnO Nanoparticles: Robust Catalysts for the Green Synthesis of Benzimidazoles

Graphical Extra support : Ultrasmall ZnO nanoparticles anchored on N-doped carbon atoms with a silica support (ZnO/SiO 2 -NC) have been fabricated by using a self-assembly strategy with chitosan as a precursor. An average size of 2.55 nm for the ZnO nanoparticles was obtained, helped by the interaction between the zinc ions and the hybrid support (see the figure). Ultrasmall ZnO nanoparticles anchored on N-doped carbon materials with a silica support (ZnO/SiO 2 -NC) were fabricated from chitosan and metal ions by using a one-pot self-assembly strategy and were successfully applied to the synthesis of 2-arylbenzimidazoles under mild conditions. These catalysts showed excellent stability and could be used six times without any loss of conversion and selectivity. The use of silica gel and the biomass chitosan as a source of hydrophilic N-doped carbon materials facilitated the uniform dispersion of the ZnO nanoparticles in methanol and therefore the contact of these nanoparticles with reactants, thus contributing to a high catalytic performance. TEM analysis showed that the ZnO nanoparticles were around 2.55 nm in diameter and uniformly distributed on the support surface. The binding behavior of ZnO and N-doped carbon materials affected the catalytic activity. Interestingly, temperature-programmed NH 3 desorption indicated that the interactions between ZnO and N-doped carbon materials might induce the presence of more acidic sites in these catalysts, thus resulting in enhanced activity and hence promoting this transformation.