Ultrasound-assisted co-precipitation synthesis of mesoporous Co3O4–CeO2 composite oxides for highly selective catalytic oxidation of cyclohexane

doi:10.1007/s11705-022-2145-3

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (8) : 1211-1223 https://doi.org/10.1007/s11705-022-2145-3

RESEARCH ARTICLE

Ultrasound-assisted co-precipitation synthesis of mesoporous Co₃O₄–CeO₂ composite oxides for highly selective catalytic oxidation of cyclohexane

Shangjun Fu¹, Kuiyi You^1,²(

), Zhenpan Chen¹(

), Taobo Liu¹, Qiong Wang¹, Fangfang Zhao¹, Qiuhong Ai^1,², Pingle Liu^1,², He’an Luo^1,²

¹. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China
². National & Local United Engineering Research Center for Chemical Process Simulation and Intensification, Xiangtan University, Xiangtan 411105, China

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Abstract

The one-step highly selective oxidation of cyclohexane into cyclohexanone and cyclohexanol as the essential intermediates of nylon-6 and nylon-66 is considerably challenging. Therefore, an efficient and low-cost catalyst must be urgently developed to improve the efficiency of this process. In this study, a Co₃O₄–CeO₂ composite oxide catalyst was successfully prepared through ultrasound-assisted co-precipitation. This catalyst exhibited a higher selectivity to KA-oil, which was benefited from the synergistic effects between Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ redox pairs, than bulk CeO₂ and/or Co₃O₄. Under the optimum reaction conditions, 89.6% selectivity to KA-oil with a cyclohexane conversion of 5.8% was achieved over Co₃O₄–CeO₂. Its catalytic performance remained unchanged after five runs. Using the synergistic effects between the redox pairs of different transition metals, this study provides a feasible strategy to design high-performance catalysts for the selective oxidation of alkanes.

Keywords Co₃O₄–CeO₂ composite oxides cyclohexanone cyclohexanol ultrasonic-assisted co-precipitation selective oxidation solvent-free

Corresponding Author(s): Kuiyi You,Zhenpan Chen

Online First Date: 24 April 2022 Issue Date: 02 August 2022

Cite this article:

Shangjun Fu,Kuiyi You,Zhenpan Chen, et al. Ultrasound-assisted co-precipitation synthesis of mesoporous Co₃O₄–CeO₂ composite oxides for highly selective catalytic oxidation of cyclohexane[J]. Front. Chem. Sci. Eng., 2022, 16(8): 1211-1223.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2145-3
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I8/1211

Tab.1 Catalytic properties of different catalysts ^a)

Tab.2 Effects of Ce/Co molar ratio on the oxidation reaction ^a)

Fig.1 Results of selective aerobic oxidation of cyclohexane under different reaction conditions: (a) 60 g cyclohexane, 0.1 g Co₃O₄–CeO₂ catalyst (Ce/Co = 2∶1), 150 °C, 1.5 h; (b) 60 g cyclohexane, 0.1 g Co₃O₄–CeO₂ catalyst (Ce/Co = 2∶1), 150 °C, 0.6 MPa; (c) 60 g cyclohexane, 0.1 g Co₃O₄–CeO₂ catalyst (Ce/Co = 2∶1), 0.6 MPa, 1.5 h; (d) 60 g cyclohexane, 0.6 MPa, 150 °C, 0.6 MPa, 1.5 h.

Fig.2 Cyclic performance of Co₃O₄–CeO₂ catalyst used in selective oxidation of cyclohexane. Reaction conditions: 60 g cyclohexane, 0.1 g Co₃O₄–CeO₂ catalyst (Ce/Co = 2∶1), 150 °C, 0.6 MPa and 1.5 h.

Fig.3 XRD profiles of (a) Co₃O₄, (b) CeO₂, (c) fresh, and (d) used Co₃O₄–CeO₂ catalysts. Crystalline phases detected: (♦) Co₃O₄, (●) CeO₂.

Fig.4 The 532 nm Raman spectra of (a) Co₃O₄, (b) CeO₂, (c) fresh and (d) used Co₃O₄–CeO₂ catalysts. The enlarged image in the inset shows the appearance of oxygen vacancy (defect oxygen) for the Co₃O₄–CeO₂ catalyst.

Fig.5 XPS spectra of (a, d) Co 2p, (b, e) Ce 3d, and (c, f) O 1s of fresh and used Co₃O₄–CeO₂ samples (O_C: chemisorbed oxygen; O_V: oxygen vacancy; O_L: lattice oxygen).

Tab.3 The Ce 3d binding energies and contents of Ce³⁺ or Ce⁴⁺ species for fresh and used Co₃O₄–CeO₂ samples

Tab.4 The O 1s binding energies and contents of O_L, O_V or O_C species for fresh and used Co₃O₄–CeO₂ samples.

Fig.6 EPR characterization of fresh and used Co₃O₄–CeO₂ samples.

Fig.7 H₂-TPR characterization of (a) CeO₂, (b) Co₃O₄, (c) fresh Co₃O₄–CeO₂, and (d) used Co₃O₄–CeO₂ catalysts.

Tab.5 ICP-AES and N₂ adsorption-desorption results of different samples

Fig.8 N₂ adsorption-desorption isotherm and pore diameter distribution diagram of fresh and used Co₃O₄–CeO₂ samples.

Fig.9 (a) TEM, (b) HRTEM images, and (c) histogram of particle diameter distribution of fresh Co₃O₄–CeO₂ catalyst.

Fig.10 Elemental mapping images and EDS results of fresh Co₃O₄–CeO₂.

Fig.11 Possible mechanism for the synergistic catalytic oxidation of cyclohexane to KA-oil with molecular oxygen over Co₃O₄–CeO₂ composite oxides: (a) oxygen activation, (b) formation of CHHP, and (c) decomposition/reduction of CHHP.

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