Base-free catalytic aerobic oxidation of mercaptans over MOF-derived Co/CN catalyst with controllable composition and structure

Abstract

The oxidation of mercaptans under mild and base-free conditions is of vital importance in terms of economy and environment for petroleum processing industry. Here, we developed a series of MOF-derived cobalt-based nitrogen-doped (N-doped) carbon (Co/CN-x) catalysts for the base-free catalytic oxidation of mercaptans. The optimal Co/CN-900 showed excellent catalytic activity for the oxidation of mercaptans under base-free conditions, yielding complete conversion of various mercaptans and > 99.0% selectivity of disulfides. The high performance can be contributed to the advantages of hierarchical pore structure for the diffusion and migration of substrates, self-carrying alkalinity for the formation of mercaptide anion, abundant active Co sites for catalytic oxidation of mercaptans as well as the synergistic effects between the Co nanoparticles (NPs) and N-doped carbon supports. Furthermore, a possible mechanism for base-free catalytic oxidation of mercaptans over Co/CN-x catalysts is proposed based on a set of control experiments and density functional theory (DFT) calculations.