Zeolitic Imidazolate Framework-Mediated Synthesis of Co3O4 Nanoparticles Encapsulated in N-Doped Graphitic Carbon as an Efficient Catalyst for Selective Oxidation of Hydrocarbons

Abstract

The aerobic solvent-free selective oxidation of the C-H bonds of hydrocarbons to the corresponding ketones by earth-abundant catalysts would provide high added value both from economy and environment points of view. In this respect herein, Co3O4 nanocrystals embedded into N-doped graphitic carbon nanohybrids (Co3O4@GNC) are prepared by uniform seed-mediated growth and deposition of Co-based zeolitic imidazolate framework-9 (ZIF-9) nanocrystals on graphene oxide (GO) nanosheets followed by facile carbonization of the ZIF-GO composite under inert atmosphere at high temperature. The specific textural and chemical characteristics of as-synthesized nanohybrids at different pyrolysis temperatures were comprehensively investigated by performing various spectroscopic tools. N-Doped graphitic carbon wrapped Co3O4 nanocrystals is demonstrated to be an efficient oxidation catalyst of arylalkanes. Under the optimized reaction conditions, Co3O4@GNC-B catalyst (as-synthesized at 700 °C carbonization temperature) was found to exhibit superior catalytic performance with improved stability (reproducible conversion values upon six cycles) in ethylbenzene oxidation, providing 65.8% conversion of ethylbenzene with an exclusive selectivity of 72.6% for acetophenone. With the help of combined catalytic studies and the different characterization methods including X-ray photoelectron spectroscopy and X-ray absorption fine structure analysis we can emphasis that the presence of Co-Nx active site and the synergistic effect between Co3O4 nanocrystals and unique N-containing interconnected carbonaceous framework is responsible for the superior catalytic activity and stability of Co3O4@GNC. Moreover, the Co3O4@GNC catalyst could also be explored for a variety of arylalkane substrates in oxidation reaction with high catalytic activity. Furthermore, future studies could be extended on the design of precious-metal-free robust catalysts as-derived from ZIFs for advanced applications in fine-chemical production.