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(68.3μmol/(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.
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 pro-posed based on the theoretical and experimental results.
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