Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Gava Zang, Zanjan 45137-6731, Iran.
Org Biomol Chem. 2011 Nov 7;9(21):7420-6. doi: 10.1039/c1ob05752a. Epub 2011 Sep 8.
The application of a novel palladium containing ionic liquid based periodic mesoporous organosilica (Pd@PMO-IL) catalyst in the aerobic oxidation of primary and secondary alcohols under molecular oxygen and air atmospheres is investigated. It was found that the catalyst is quite effective for the selective oxidation of several activated and non-activated alcoholic substrates. The catalyst system could be successfully recovered and reused several times without any significant decrease in activity and selectivity. Moreover, the hot filtration test, atomic absorption spectroscopy (AA) and kinetic study with and without selective catalyst poisons showed that the catalyst works in a heterogeneous pathway without any palladium leaching in reaction solution. Furthermore, nitrogen-sorption experiment and transmission electron microscopy (TEM) image proved the superior stability of high-ordered PMO-IL mesostructure during reaction process. TEM image also confirmed the presence of well-distributed Pd-nanoparticles in the uniform mesochannels of the material. These observations can be attributed to the ionic liquid nature of PMO-IL mesostructure which facilitates the reaction through production, chemical immobilization and stabilization of active palladium nanoparticles, as well as preventing Pd-agglomeration during overall process.
研究了一种新型含钯离子液体的有序介孔有机硅(Pd@PMO-IL)催化剂在分子氧和空气气氛下伯醇和仲醇的有氧氧化中的应用。结果表明,该催化剂对几种活化和非活化醇类底物的选择性氧化非常有效。该催化剂体系可以成功地回收和重复使用多次,而活性和选择性没有明显下降。此外,通过热过滤试验、原子吸收光谱(AA)和有/无选择性催化剂毒物的动力学研究表明,该催化剂在非均相途径中起作用,反应溶液中没有钯浸出。此外,氮气吸附实验和透射电子显微镜(TEM)图像证明了高有序 PMO-IL 介孔结构在反应过程中的优越稳定性。TEM 图像还证实了均匀介孔道中存在分布均匀的 Pd 纳米颗粒。这些观察结果可以归因于 PMO-IL 介孔结构的离子液体性质,它通过产生、化学固定和稳定活性钯纳米颗粒,以及在整个过程中防止 Pd 聚集,促进了反应。