分子氧为氧化剂的Au-Ag/TS-1光催化剂协同光催化丙烯气相环氧化

doi:10.1016/S1872-2067(17)62832-8

催化学报 ›› 2017, Vol. 38 ›› Issue (5): 831-844.DOI: 10.1016/S1872-2067(17)62832-8

分子氧为氧化剂的Au-Ag/TS-1光催化剂协同光催化丙烯气相环氧化

李乃旭^a, 杨斌^a, 刘明^a, 陈勇^a, 周建成^a,b,c

a. 东南大学化学化工学院, 江苏南京 211189;
b. 东南大学成贤学院制药与化学工程学院, 江苏南京 210088;
c. 东南大学江苏省生物药物高技术研究重点实验室, 江苏南京 211189

收稿日期:2017-01-02 修回日期:2017-04-01 出版日期:2017-05-18 发布日期:2017-05-10
通讯作者: Jiancheng Zhou
基金资助:
国家自然科学基金（21576050）；江苏省自然科学基金（BK20150604）.

Synergetic photo-epoxidation of propylene with molecular oxygen over bimetallic Au–Ag/TS-1 photocatalysts

Naixu Li^a, Bin Yang^a, Ming Liu^a, Yong Chen^a, Jiancheng Zhou^a,b,c

a. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, Jiangsu, China;
b. Department of Chemical and Pharmaceutical Engineering, Southeast University Chengxian College, Nanjing 210088, Jiangsu, China;
c. Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189, Jiangsu, China

Received:2017-01-02 Revised:2017-04-01 Online:2017-05-18 Published:2017-05-10
Supported by:
This work was supported by the National Natural Science Foundation of China (21576050) and the Natural Science Foundation of Jiangsu Province (BK20150604).

摘要/Abstract

摘要：

近年来，丙烯环氧化已引起人们广泛的兴趣；然而，大多数过程仍面临分离困难等问题.此外，丙烯转化率和环氧丙烷（PO）的选择性仍然非常低.从环境和经济观点来看，分子氧是丙烯选择性环氧化的理想氧化剂.开发一种气相光催化环氧化方法，即在光能和多相光催化剂存在的情况下，用于化学品生产.因此，本文探讨了通过光催化O₂选择氧化丙烯环氧化.传统的制备方法存在环境污染及能耗大等缺点，而利用氧气直接进行光催化丙烯环氧化制备环氧丙烷是相当具有前景的化学品生产途径.
本文采用水热法制备了微球状TS-1载体，再通过浸渍还原法制备了不同Au/Ag质量比的Au-Ag/TS-1双金属催化剂.通过X射线衍射、扫描电镜、紫外-可见吸收光谱、透射电镜、X射线光电能谱、荧光光谱和N₂吸脱附法等手段对合成的催化剂的组成、形貌和性质进行了研究，通过气相色谱在线分析得到光催化反应结果.
结果表明，通过浸渍还原法可以很好的将贵金属分散到载体表面上.对于Au-Ag/TS-1双金属催化剂，当Au/Ag质量比为4/1时，反应温度为443 K时，环氧丙烷生成速率最大（68.3 μmol/（g·h）），其选择性达52.3%.对于Au-Ag/TS-1光催化剂，双金属负载有利于O₂吸附活化，同时促进了电子的传递，从而抑制电子空穴的复合，有利于氧自由基的形成.结果表明，Au，Ag双金属之间存在协同催化作用，根据实验现象提出了一种可能的反应机理.

关键词: 金, 银, 钛硅分子筛, 光催化, 丙烯环氧化, 协同作用

Abstract:

Au–Ag bimetallic nanoparticle-supported microporous titanium silicalite-1 catalysts were prepared via a hydrothermal-immersion method, and their structures were examined. These materials serve as efficient catalysts for the photosynthesis of propylene oxide via the epoxidation of propene. The Au/Ag mass ratio and reaction temperature were demonstrated to have significant effects on the catalytic activity and selectivity of propylene oxide. The optimal formation rate (68.3 μmol/g·h) and selectivity (52.3%) toward propylene oxide were achieved with an Au:Ag mass ratio of 4:1. Notably, the strong synergistic effect between Au and Ag resulted in superior photocatalysis of the bimetallic systems compared with those of the individual systems. A probable reaction mechanism was proposed based on the theoretical and experimental results.

Key words: Gold, Silver, Titanium silicalite-1, Photocatalysis, Propene epoxidation, Synergetic effect

李乃旭, 杨斌, 刘明, 陈勇, 周建成. 分子氧为氧化剂的Au-Ag/TS-1光催化剂协同光催化丙烯气相环氧化[J]. 催化学报, 2017, 38(5): 831-844.

Naixu Li, Bin Yang, Ming Liu, Yong Chen, Jiancheng Zhou. Synergetic photo-epoxidation of propylene with molecular oxygen over bimetallic Au–Ag/TS-1 photocatalysts[J]. Chinese Journal of Catalysis, 2017, 38(5): 831-844.

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分子氧为氧化剂的Au-Ag/TS-1光催化剂协同光催化丙烯气相环氧化

Synergetic photo-epoxidation of propylene with molecular oxygen over bimetallic Au–Ag/TS-1 photocatalysts

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