Citation: ZHANG Han, WANG Jun-Er, DONG Hao, YANG Ni-Ni, PAN Lin-Yun, SHEN Hao-Yu, HU Mei-Qin, CHENG Jin-Jin. Heteropoly Acid Grafted-MOFs Functionalized Magnetic Composite Material for Catalytic Oxidative Desulfurization[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(8): 1475-1484. doi: 10.11862/CJIC.2020.153 shu

Heteropoly Acid Grafted-MOFs Functionalized Magnetic Composite Material for Catalytic Oxidative Desulfurization

Zhejiang University Ningbo Institute of Technology, Ningbo, Zhejiang 315100, China

Corresponding author: SHEN Hao-Yu, hyshen@nit.zju.edu.cn
Received Date: 15 February 2020
Revised Date: 15 April 2020

Figures(14)

Carboxylated magnetic microsphere Fe₃O₄-COOH was firstly synthesized by solvothermal method. MIL-101(Cr) functionalized magnetic composite Fe₃O₄-COOH@MIL-101(Cr) was obtained next by one-pot method. Phosphotungstic acid was finally grafted on the Fe₃O₄-COOH@MIL-101(Cr) by ultrasonic impregnation method to obtain HPW@Fe₃O₄-COOH@MIL-101(Cr). Its composition and morphology were characterized by Fourier transform infrared spectrum (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), Vibrating sample magnetometer (VSM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It was used as catalyst with hydrogen peroxide as oxidant to catalyze the oxidation of n-octane simulated oil sample with dibenzothiophene as sulfur source. The effects of ultrasonic reaction time, oxidant dosage, reaction temperature, dosage of the phase transfer agent and the catalyst amount on the desulfurization rate were investigated by using single factor method. The presumed mechanism was discussed. The results showed that the optimized catalytic degradation rate reached when the reaction time was at 60℃, 5 mins, n_H₂O₂/n_S of 4, usage amount of the phase transfer agent CTAB at 0.2%(w/w), with the catalyst amount of 8 g·L^-1. The catalytic degradation rate reached 73.15%. After used for 5 times, the catalytic degradation rate decreased by 7.8%, indicating that the material has good catalytic desulfurization performance and can be reused. Primary mechanism study showed that the active center for the catalytic desulfurization might be the heteropoly acid anion of the HPW@Fe₃O₄-COOH@MIL-101(Cr), in which the Fe₃O₄-COOH@MIL-101(Cr) may act as a supporter and cooperative absorbent.
- heteropoly acid,
- MOFs functionalized,
- magnetic composite material,
- oxidative desulfurization,
- phase transfer agent
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