Magnetically recyclable high-entropy metal oxide catalyst for aerobic catalytic oxidative desulfurization

doi:10.1016/S1872-2067(23)64541-3

Abstract

Abstract:

High-entropy metal oxide catalysts have demonstrated exceptional performance in activating oxygen for catalytic oxidation reactions. However, ensuring their ease of cyclic usage is crucial to broadening their applications. To address this challenge, a magnetic and recyclable high-entropy metal oxide catalyst is designed and its potential in catalytic oxidative desulfurization of fuel oils with oxygen as the oxidant is also investigated. Through a mechanochemical-assisted calcination method, the magnetic high-entropy metal oxide catalyst (HEMO-900) is successfully synthesized, and the structure of the HEMO-900 catalyst is comprehensively characterized. In addition, it is found that the high-entropy structure facilitates charge modulation of the active components, thereby enhancing the oxygen activation performance. The HEMO-900 catalyst exhibits exceptional oxygen activation ability and catalytic oxidative desulfurization performance, and 96.9% of sulfur removal is achieved under optimal conditions. In addition, it achieves profound desulfurization of various fuel samples by efficiently oxidizing and eliminating diverse aromatic sulfur compounds. Additionally, the catalyst demonstrates outstanding magnetically recyclable properties, enabling rapid separation and recovery from the fuel oil phase through the application of an external magnetic field, making the HEMO-900 catalyst maintained a remarkable sulfur removal efficiency of 91.1% even in the 5^th cycle. Therefore, this magnetically recyclable HEMO-900 catalyst possesses significantly promising research and application prospects in the field of catalytic oxidative desulfurization of fuel oils with oxygen as the oxidant, as well as some other heterogeneous catalysis.

Key words: High entropy, Transition metal oxide, Magnetic separation, Catalytic oxidation, Desulfurization

Peiwen Wu, Chang Deng, Feng Liu, Haonan Zhu, Linlin Chen, Ruoyu Liu, Wenshuai Zhu, Chunming Xu. Magnetically recyclable high-entropy metal oxide catalyst for aerobic catalytic oxidative desulfurization[J]. Chinese Journal of Catalysis, 2023, 54: 238-249.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64541-3

https://www.cjcatal.com/EN/Y2023/V54/I11/238

Figures/Tables 10

Fig. 1. Synthesis process diagram for the preparation of HEMO catalysts.

Fig. 2. XRD patterns of HEMO obtained at different temperatures.

Fig. 3. XRD patterns of samples obtained with and without ball milling pretreatment.

Fig. 4. SEM images of HEMO-900. (a,b) SEM images of HEMO-900. (c) Selected area for EDS mapping. (d-h) elemental EDS mapping images of Fig. 4(c) for Co, Cr, Mn, Fe, and Ni, respectively.

Fig. 5. TEM and HRTEM characterizations of HEMO-900. (a) Low magnification TEM image of HEMO-900. (b) Magnified TEM image of HEMO-900. (c) HRTEM image of HEMO-900. (d) Magnified HRTEM image of HEMO-900. (e) HRTEM image of HEMO-900. (f) Magnified HRTEM image of HEMO-900. (g) Selected section of TEM image of HEMO-900 for EDS mapping. (h-l) Elemental EDS mapping images of Fig. 5(g) for Mn, Cr, Co, Ni, and Fe, respectively.

Fig. 6. XPS results for HEMO-900. (a) Co 2p XPS spectrum of HEMO-900. (b) Cr 2p XPS spectrum of HEMO-900. (c) Fe 2p XPS spectrum of HEMO-900. (d) Mn 2p XPS spectrum of HEMO-900. (e) Ni 2p XPS spectrum of HEMO-900. (f) O 1s XPS spectrum of HEMO-900.

Fig. 7. Catalytic oxidative desulfurization performances with O2 as the oxidant. (a) ODS performance of different HEMO catalysts. (b) The effect of reaction temperature on ODS performance of HEMO-900. (c) ODS performance of HEMO-900 to different aromatic sulfides. (d) The effect of initial sulfur concentrations on ODS performance of HEMO-900. (e) The effect of oxygen flow rate on ODS performance of HEMO-900. (f) Investigation of catalytic active sites by control experiments. Experimental conditions: T = 120 °C, m (catalyst) = 0.02 g, V (model oil) = 20 mL, v (O2) = 150 mL min-1.

Fig. 8. GC-MS analysis of the oil phase before and after the ODS process and catalyst phase after ODS.

Fig. 9. Magnetic hysteresis curve and recycling performance of HEMO-900. (a) Magnetic hysteresis curve of HEMO-900. (b) Recycling performance of HEMO-900. Inset in Fig. 9(a) is the optical photograph of the distribution of catalyst in oil and magnetic recovery performance test.

Fig. 10. ESR spectra of HEMO-900 ODS system characterization for superoxide radical.

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