纳米SnO2高效催化烯烃与H2O2环氧化反应研究

doi:10.7503/cjcu20180534

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (3): 528.doi: 10.7503/cjcu20180534

纳米SnO₂高效催化烯烃与H₂O₂环氧化反应研究

鲁新环, 陶佩佩, 黄锋锋, 张香归, 林志成, 潘海军, 张海福, 周丹(), 夏清华()

湖北大学有机化工新材料湖北省协同创新中心,有机功能分子合成与应用教育部重点实验室, 武汉 430062

收稿日期:2019-07-27 出版日期:2019-01-24 发布日期:2019-01-24
作者简介:
联系人简介: 周丹, 女, 博士, 教授, 博士生导师, 主要从事分子筛类孔材料的合成、表征及应用研究. E-mail: d.zhou@hubu.edu.cn; 夏清华, 男, 博士, 教授, 博士生导师, 主要从事多孔材料的开发及有机催化研究. E-mail: xiaqh518@aliyun.com
基金资助:
国家自然科学基金(批准号: 21503074, 21673069, 21571055)、湖北省自然科学基金杰青项目(批准号: 2016CFA040)和湖北省大学生创新创业训练计划项目(批准号: 201710512045)资助.

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

LU Xinhuan, TAO Peipei, HUANG Fengfeng, ZHANG Xianggui, LIN Zhicheng, PAN Haijun, ZHANG Haifu, ZHOU Dan^*(), XIA Qinghua^*()

Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials,Key Laboratory for the Synthesis and Application of Organic Functional Molecules,Ministry of Education, Hubei University, Wuhan 430062, China

Received:2019-07-27 Online:2019-01-24 Published:2019-01-24
Contact: ZHOU Dan,XIA Qinghua E-mail:d.zhou@hubu.edu.cn;xiaqh518@aliyun.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21503074, 21673069, 21571055), the Hubei Province Outstanding Youth Project of Natural Science, China(No.2016CFA040) and the Hubei Province Students Innovation and Entrepreneurship Training Foundation, China(No.201710512045).

摘要/Abstract

摘要：

构建了用于催化烯烃与过氧化氢环氧化反应的高效、绿色催化反应体系. 首先, 通过水热合成法制备了纳米SnO₂, 并在320 ℃下煅烧. 随后, 对所有催化剂进行X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征. 进一步将催化剂用于以H₂O₂水溶液为氧化剂环氧化各种官能化烯烃(包括环烯烃, 苯乙烯和直链烯烃)的反应, 以高转化率和高选择性得到了环氧化物. 在相似的反应条件下, 发现合成的纳米SnO₂-170催化剂在催化1-甲基环己烯与H₂O₂的环氧化反应中的活性最佳, 在2 h内1-甲基环己烯的转化率达到100%, 环氧化物选择性达到100%.

关键词: SnO₂纳米粒子, H₂O₂, 催化环氧化, 环状烯烃, 直链烯烃

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

中图分类号:

O643

TrendMD:

鲁新环, 陶佩佩, 黄锋锋, 张香归, 林志成, 潘海军, 张海福, 周丹, 夏清华. 纳米SnO₂高效催化烯烃与H₂O₂环氧化反应研究. 高等学校化学学报, 2019, 40(3): 528.

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 $O 2 †$ . Chem. J. Chinese Universities, 2019, 40(3): 528.

图/表 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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纳米SnO₂高效催化烯烃与H₂O₂环氧化反应研究

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

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