Cobalt-nitrogen co-doped porous carbon sphere as highly efficient catalyst for liquid-phase cyclohexane oxidation with molecular oxygen and the active sites investigation

Abstract

The selective oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) is a challenging issue in the chemical industry. At present the industrial conversion of cyclohexane to cyclohexanone and cyclohexanol is normally controlled at less than 5% selectivity. Thus, the development of highly active and stable catalysts for the aerobic oxidation of cyclohexane is necessary to overcome this low-efficiency process. Therefore, we have developed a cobalt-nitrogen co-doped porous sphere catalyst, Co-NC-x (x is the Zn/Co molar ratio, where x = 0, 0.5, 1, 2, and 4) by pyrolyzing resorcinol-formaldehyde resin microspheres. It achieved 88.28% cyclohexanone and cyclohexanol selectivity and a cyclohexane conversion of 8.88% under Co-NC-2. The results showed that the introduction of zinc effectively alleviated the aggregation of Co nanoparticles and optimized the structural properties of the material. In addition, Co⁰ and pyridinic-N are proposed to be the possible active species, and their proportion efficiently increased in the presence of Zn²⁺ species. In this study, we developed a novel strategy to design highly active catalysts for cyclohexane oxidation.

Key words： KA oil production; cyclohexane selective oxidation; cobalt-nitrogen co-doped porous carbon spheres; metal-organic framework

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by National Natural Science Foundation of China (Grant No. 22178294), Science and Technology Innovation Program of Hunan Province (Grant No. 2022RC1117), Project of Hunan Provincial Education Department (Grant No. 22A0125), Hunan Provincial Natural Science Foundation of China (Grant No. 2021JJ30663), Postgraduates Scientific Research Innovation Project of Xiangtan University (Grant No. QL20220146), Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization, and Environment-friendly Chemical Process Integration Technology Hunan Province Key laboratory. In addition, we would like to thank KetengEdit for its linguistic assistance during the preparation of this manuscript.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2395-3 and is accessible for authorized users.

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