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

doi:10.1007/s11705-024-2395-3

2024, Vol. 18

Issue (3) : 33 https://doi.org/10.1007/s11705-024-2395-3

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

Lei Chen, Yuan Sun, Jinshan Chi, Wei Xiong(

), Pingle Liu, Fang Hao(

)

College of Chemical Engineering, National & Local United Engineering Research Centre for Chemical Process Simulation and Intensification, Xiangtan University, Xiangtan 411105, China

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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.

Keywords KA oil production cyclohexane selective oxidation cobalt-nitrogen co-doped porous carbon spheres metal-organic framework

Corresponding Author(s): Wei Xiong,Fang Hao

Just Accepted Date: 28 December 2023 Issue Date: 07 February 2024

Cite this article:

Lei Chen,Yuan Sun,Jinshan Chi, et al. Cobalt-nitrogen co-doped porous carbon sphere as highly efficient catalyst for liquid-phase cyclohexane oxidation with molecular oxygen and the active sites investigation[J]. Front. Chem. Sci. Eng., 2024, 18(3): 33.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2395-3
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I3/33

Fig.1 The preparation process of the Co-NC-x catalysts from its precursor RF@Zn-Co-ZIF-x.

Fig.2 XRD patterns of catalysts: (a) the different precursors of RF@Zn-Co-ZIF-x (at different Zn/Co ratios), and (b) their derived Co-NC-x catalysts.

Fig.3 Raman spectra of Co-NC-0, Co-NC-0.5, Co-NC-1, Co-NC-2 and Co-NC-4, respectively.

Fig.4 (a) N₂ adsorption-desorption isotherms and (b) pore size distribution of different catalysts with different metal ratios in preparation of RF@Zn-Co-ZIF-x precursor.

Fig.5 SEM images of (a, b) RF resin microspheres, (c) RF@Zn-Co-ZIF-2, and (d) the Co-NC-2.

Fig.6 (a, b) TEM and (c) HRTEM, (d) HAADF-STEM image and (e–i) corresponding elemental EDS mapping images of the Co-NC-2.

Fig.7 XPS spectra of (a) Co 2p and (b) N 1s of Co-NC-0 and Co-NC-2.

Tab.1 The catalytic activity of the different catalysts in the liquid phase selective oxidation of cyclohexane^a)

Fig.8 (a) Effects of Zn/Co molar ratios on the catalytic performance of Co-NC catalysts and (b) the effect of different pyrolysis temperatures on the catalytic performance of Co-NC-2. Reaction conditions: cyclohexane 15 g, catalyst 20 mg, reaction temperature = 155 °C, O₂ pressure = 0.8 MPa, and reaction time = 90 min.

Fig.9 Effect of the reaction factors: (a) reaction temperature, (b) reaction time, (c) O₂ pressure, and (d) the recyclability on the catalytic performance of Co-NC-2 in cyclohexane selective oxidation. Reaction conditions: cyclohexane 15 g, catalyst 20 mg; (a) O₂ pressure = 0.8 MPa, reaction time = 90 min; (b) O₂ pressure = 0.8 MPa, reaction temperature = 155 °C; (c) reaction temperature = 155 °C, reaction time = 90 min; (d) reaction temperature = 155 °C, O₂ pressure = 0.8 MPa, reaction time = 90 min.

Tab.2 The adsorption energies of CHHP, Q=O, Cy–OH on the models of different active sites

Fig.10 Potential energy diagrams for (a) the synthesis and (b) decomposition of the CHHP into cyclohexanone and (c) cyclohexanol on the different reaction active sites.

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