Semi-closed synthesis of nitrogen and oxygen Co-doped mesoporous carbon for selective aqueous oxidation

Abstract

Heteroatom-doped meso/micro-porous carbon materials are conventionally produced by harsh carbonization under an inert atmosphere involving specific precursors, hard/soft templates, and heteroatom-containing agents. Herein, we report a facile synthesis of N and O co-doped meso/micro-porous carbon (NOMC) by template-free carbonization of a small-molecule precursor in a semi-closed system. The semi-closed carbonizaiton process yields hydrophilic NOMCs with large surface area in a high yield. The porous structure as well as the elemental composition of NOMCs can be modulated by changing the holding time at a particular temperature. NOMCs as metal-free heterogeneous catalysts can selectively oxidize benzyl alcohol and its derivatives into aldehydes/ketones with > 85% conversion in aqueous solution, which is much higher than that of the control sample obtained in tube furnace (21% conversion), mainly due to their high N content, high percentage of pyridinic N, and large surface area. The presence of O-containing moieties also helps to improve the hydrophilicity and dispersion ability of catalysts and thus facilitates the mass transfer process during aqueous oxidation. The NOMC catalysts also dispayed excellent activity for a wide range of substrates with a selectivity of > 99%.