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

Canyang Zhang; Hongyi Gao; Guangtong Hai; Yaojun Zeng; Xingqi Wang; Liwen Xing; Jie Zhao; Ge Wang; Xingtian Shu

doi:10.1016/j.jcis.2021.10.013

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

J Colloid Interface Sci. 2022 Feb;607(Pt 2):1836-1848. doi: 10.1016/j.jcis.2021.10.013. Epub 2021 Oct 6.

Authors

Canyang Zhang¹, Hongyi Gao², Guangtong Hai¹, Yaojun Zeng¹, Xingqi Wang¹, Liwen Xing³, Jie Zhao⁴, Ge Wang⁵, Xingtian Shu⁶

Affiliations

¹ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, PR China.
² Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, PR China; Shunde Graduate School, University of Science and Technology Beijing, Shunde 528399, PR China.
³ Department of Materials Science and Engineering, College of Chemistry and Materials Engineering, Beijing Technology and Business University, Beijing 100048, PR China.
⁴ Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, PR China. Electronic address: [email protected].
⁵ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, PR China. Electronic address: [email protected].
⁶ Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, PR China.

PMID: 34695736
DOI: 10.1016/j.jcis.2021.10.013

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.

Keywords: Base-free oxidation; Co-based catalyst; MOF; Mercaptan oxidation; Nitrogen doped carbon.