Janus N-Doped Carbon@Silica Hollow Spheres as Multifunctional Amphiphilic Nanoreactors for Base-Free Aerobic Oxidation of Alcohols in Water

Abstract

The hydrophobicity/hydrophilicity of nanocatalysts has a significant impact on their performances via modulating the adsorption, transfer, and desorption of reactants/products. In this work, we reported a novel multifunctional amphiphilic nanoreactor composed of Janus nitrogen-doped carbon@silica hollow nanostructure and ultrasmall Pt nanoparticles. The core/shell polybenzoxazine@mesosilica spheres were used as the precursor for pyrolysis. It was found that the internal polybenzoxazine was decomposed from interior to exterior and transformed into a nitrogen-doped carbon hollow shell that partly embedded into the mesosilica layer, forming the Janus hollow spheres. The obtained nanoreactor showed remarkable activity and selectivity for base-free aerobic oxidation of alcohols in water using air as the oxidant. A one-pot oxidation-condensation cascade reaction was also successfully demonstrated to synthesize imines from alcohols and amines with good yields. The sorption analyses revealed that the superior hydrophilicity/hydrophobicity strengthened both adsorption of hydrophobic alcohols from water and desorption of byproduct water molecules from the active sites. The doped nitrogen atoms in the carbon matrix were used not only as anchoring sites for stabilizing ultrasmall Pt nanoparticles but also as basic active sites for accelerating the deprotonation process. Moreover, due to the anchoring effect of nitrogen and the extremely stable amphiphilicity, this nanoreactor exhibited excellent catalytic stability.