Nano-SnO2 as Highly Efficient Catalyst for Epoxidation of Cyclic Olefins with Aqueous H2O2†

doi:10.7503/cjcu20180534

Abstract

Abstract:

A green catalytic reaction system with characteristic of high efficiency for the synthesis of epoxides by catalytic epoxidation of functionalized olefins with hydrogen peroxide was constructed. SnO₂ nanoparticles were prepared by hydrothermal synthesis method and calcined at 320 ℃. Subsequently, all catalysts were characterized by X-ray diffraction(XRD), UV-Vis diffuse reflectance spectroscopy(UV-Vis), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). Then, these catalysts were used to catalyze the epoxidation of various functionalized olefins, including cyclic olefins, styrene and linear olefins, using H₂O₂ aqueous solutions as oxidants, with high conversion for olefins and high selectivity to epoxides. Under similar reaction conditions, thus-synthesized nano-SnO₂-170 catalyst was found to be the most active one in the epoxidation of 1-methyl cyclohexene with H₂O₂, for which 100% of conversion and 100% selectivity were achieved within 2 h.

Key words: SnO₂ nanoparticle, H₂O₂, Catalytic epoxidation, Cyclic olefin, Linear olefin

CLC Number:

O643

TrendMD:

LU Xinhuan,TAO Peipei,HUANG Fengfeng,ZHANG Xianggui,LIN Zhicheng,PAN Haijun,ZHANG Haifu,ZHOU Dan,XIA Qinghua. Nano-SnO₂ as Highly Efficient Catalyst for Epoxidation of Cyclic Olefins with Aqueous H₂ $O 2 †$ [J]. Chem. J. Chinese Universities, 2019, 40(3): 528.

Figures/Tables 10

Scheme 1 Synthetic process of nano-SnO2

Fig.1 XRD patterns(A), Fourier transform infrared spectrum(B) and UV-Vis diffuse reflectance spectra(C) of SnO2 samples

Fig.2 SEM images of SnO2-130(A), SnO2-150(B), SnO2-170(C) and SnO2-190(D)

Fig.3 TEM images(A, B) and particle size distributions(C, D) of SnO2-130(A, C) and SnO2-170(B, D) of SnO2 catalysts

Table 1 Effect of different catalysts on epoxidation of cyclohexenea

Entry	Catalyst	Conversion(%)	Selectivity to epoxy cyclohexene^b(%)
1	None	35.7	96.0
2	Nano-Bi₂O₃	37.4	70.4
3	GeO₂	75.5	90.1
4	ZrO₂	81.5	91.2
5	Nano-ZnO	69.5	93.4
6	Al₂O₃	69.8	95.2
7	SnO₂	92.0	95.1
8	Nano-SnO₂-170	99.9	98.1

Fig.4 Effect of synthesis temperature on the epoxidation over nano-SnO2Reaction conditions:nano-SnO2(100 mg), CH3CN(4 mL), acetone(4 mL), 0.2 mol/L NaHCO3(4 mL), cyclohexene(10 mmol), H2O2(12 mmol), 50 ℃, 2.0 h.

Fig.5 Effect of catalyst amount(A), cyclohexene amount(B), solvent(C) and reaction time(D) on epoxidation of cyclohexene Reaction conditions: nano-SnO2-170(100 mg), solvent(4 mL), acetone(4 mL), 0.2 mol/L NaHCO3(4 mL), cyclohexene(10 mmol), H2O2(12 mmol), 50 °C, 0.5—2.5 h. (C) Solvent: a. acetonitrile; b. benzonitrile;c. DMF; d. 1,4-dioxane; e. ethylacetate; f. ethanol; g. butanone; h. cyclohexanone.

Table 2 Epoxidation of various olefins with H2O2 over nano-SnO2*

Fig.6 Recycling results of nano-SnO2 catalystReaction conditions:nano-SnO2-170(100 mg), CH3CN(4 mL), acetone(4 mL), 0.2 mol/L NaHCO3(4 mL), H2O2(12 mmol), 50 ℃, 2.0 h.

Fig.7 TEM image(A), particle size distribution(B) and XRD pattern(C) of nano-SnO2 catalyst after being reused 5 times

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Nano-SnO₂ as Highly Efficient Catalyst for Epoxidation of Cyclic Olefins with Aqueous H₂ $O 2 †$

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