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Received: 2015-12-09

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Citations:  Bibtex RefMan EndNote GB/T7714

 ORCID:

Umsa Jameel

http://orcid.org/0000-0002-3700-5433

Ming-qiao Zhu

http://orcid.org/0000-0001-7318-4793

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Journal of Zhejiang University SCIENCE A 2016 Vol.17 No.12 P.1000-1012

http://doi.org/10.1631/jzus.A1500332


Green epoxidation of cyclooctene with molecular oxygen over an ecofriendly heterogeneous polyoxometalate-gold catalyst Au/BW11/Al2O3


Author(s):  Umsa Jameel, Ming-qiao Zhu, Xin-zhi Chen, Yi Liu, Zhang-fa Tong

Affiliation(s):  Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China; more

Corresponding email(s):   zhumingqiao@zju.edu.cn

Key Words:  Nano gold, Polyoxometalates (POMs), POM-gold catalyst, Cyclooctene epoxidation, Molecular oxygen


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Umsa Jameel, Ming-qiao Zhu, Xin-zhi Chen, Yi Liu, Zhang-fa Tong. Green epoxidation of cyclooctene with molecular oxygen over an ecofriendly heterogeneous polyoxometalate-gold catalyst Au/BW11/Al2O3[J]. Journal of Zhejiang University Science A, 2016, 17(12): 1000-1012.

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journal="Journal of Zhejiang University Science A",
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pages="1000-1012",
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publisher="Zhejiang University Press & Springer",
doi="10.1631/jzus.A1500332"
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%T Green epoxidation of cyclooctene with molecular oxygen over an ecofriendly heterogeneous polyoxometalate-gold catalyst Au/BW11/Al2O3
%A Umsa Jameel
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%A Xin-zhi Chen
%A Yi Liu
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A1 - Umsa Jameel
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A1 - Yi Liu
A1 - Zhang-fa Tong
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DOI - 10.1631/jzus.A1500332


Abstract: 
An ecofriendly heterogeneous polyoxometalate (POM)-gold catalyst Au/BW11/Al2O3 was synthesized and used for solvent-free epoxidation of cyclooctene under mild reaction conditions using molecular oxygen as an oxidant and t-butyl hydroperoxide (TBHP) as an initiator. The catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), induced coupled plasma optical emission spectrometry (ICP-OES), and Brunauer-Emmett-Teller (BET). The catalyst showed good conversion and high selectivity without use of solvents or environmentally harmful oxidants. Moreover, the catalyst is recyclable up to three cycles with no significant loss in selectivity towards epoxide.

This manuscript describes the synthesis of catalytic system which consisting with nano gold-polyoxometalate catalyst supported on the surface of neutral alumina. The resulting Au/BW11/Al2O3 was very effective for solvent-free epoxidation of cyclooctene under mild reaction conditions using molecular oxygen as an oxidant and TBHP as an initiator.

环境友好非均相多金属氧酸盐-金催化剂Au/BW11/Al2O3上环辛烯分子氧绿色环氧化研究

目的:环氧化物是多种有机合成反应的重要中间体,也可作为环氧树脂、染料和表面活性剂的原料。传统的环氧化存在催化剂分离难、氧化剂成本高和过程含有溶剂等缺点。本文旨在探讨纳米金和多金属氧酸盐负载非均相催化剂用于无溶剂条件下环辛烯环氧化的反应条件对催化性能的影响。
创新点:1. 把纳米金颗粒和多金属氧酸盐(即BW11)结合并负载在固体载体上制备出了一种新型复合催化剂材料;2. 采用分子氧作为氧化剂而不是传统的有机酸或者过氧酸;3. 在温和条件下可获得良好的转化率和较高的环氧化物选择性;4. 催化反应体系未使用有机溶剂;5. 催化剂稳定并可循环使用。
方法:1. 根据文献中所述方法制备BW11;2. 采用标准沉积沉淀法合成Au/Al2O3;3. 采用湿式浸渍法制备催化剂Au/BW11/Al2O3;4. 环辛烯环氧化使用叔丁基过氧化氢(TBHP)作为引发剂,氧气作为氧化剂,在高压反应釜中进行反应;5. 采用扫描电镜和X射线衍射等对催化剂进行表征。
结论:1. 提高焙烧温度可改善催化反应性能;2. 随着催化剂量增加到0.2 g,转化率也随之增加(图8);3. 反应的最佳温度为80 °C(表1);4. 随着反应时间的增加直到24 h,转化率逐渐增加,环氧化物选择性也增加到约87%(图9);5. 催化剂可适用于多种氧化剂(表2);6. 无溶剂下转化率和选择性相对较大(表3);7. 催化剂可以有效活化分子氧和环辛烯;8. 催化剂可以再生,在使用三次后,其活性损失不大。

关键词:纳米金;多金属氧酸盐;环辛烯;环氧化;分子氧

Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article

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