Selective Allylic Oxidation of Cyclohexene Catalyzed by Nitrogen-Doped Carbon Nanotubes

Carbon nanotubes (CNTs) and nitrogen-doped CNTs (NCNTs) were systematically investigated as metal-free catalysts in the selective allylic oxidation of cyclohexene using molecular oxygen as oxidant in the liquid phase. High cyclohexene conversion (up to 59.0%) and 620.1 mmol g(-1) h(-1) mass-normalized activity were obtained for NCNTs, competing with the state-of-the-art metal catalysts. The positive effect of nitrogen dopant on the performance of CNTs was demonstrated, with respect to the aspects of enhancing activity and increasing selectivity of 2-cyclohexen-1-one, allowing for a ketone/alcohol ratio of 3.7 at 59% conversion. The unique catalytic role of NCNTs was attributed to their capability to promote the radical chain propagation via stabilizing peroxyl and cycloxyl radicals, which boosted the further conversion of 2-cyclohexen-1-ol toward 2-cyclohexen-1-one as well.