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一锅法通过有机硅烷辅助法合成 M(M = Ag、Au)@SiO2 核壳结构:制备、形成机理及其在多相催化中的应用。

One-pot synthesis of M (M = Ag, Au)@SiO2 yolk-shell structures via an organosilane-assisted method: preparation, formation mechanism and application in heterogeneous catalysis.

机构信息

State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China.

出版信息

Dalton Trans. 2015 May 21;44(19):8867-75. doi: 10.1039/c5dt00925a.

Abstract

We demonstrate the fabrication of yolk-shell catalysts consisting of a single M (M = Ag, Au) nanoparticle encapsulated within a hollow mesoporous organosilica shell via an organosilane-assisted strategy. The advantages of our method lie in its good controllability of the void space as well as the thickness of the mesoporous shell. The M@CTAB/SiO2 synthesized through a modified Stöber method can transform to yolk-shell structures after adding (3-aminopropyl)trimethoxysilane (APTMS)/TEOS or (3-aminopropyl)triethoxysilane (APTES)/TEOS into the synthetic medium. We give unambiguous evidence that the middle CTAB/SiO2 layer transforms into a less dense APTMS-rich organic-inorganic layer which was selectively removed in alkaline aqueous solution, while the amino-functionalized hybrid shells remain intact. Moreover, we discuss the role of alkylamino groups in the shell in the transformation from Ag@SiO2 nanorattles to hollow structures when impregnating the as-synthesized Ag@SiO2 nanorattles in HAuCl4 aqueous solution. The nanorattles also exhibit high catalytic activity for the catalytic reduction of p-nitrophenol.

摘要

我们通过一种有机硅烷辅助的策略,展示了由单个 M(M=Ag、Au)纳米颗粒封装在中空介孔有机硅壳内的蛋黄壳催化剂的制备。我们的方法的优点在于其对空隙空间以及介孔壳的厚度具有良好的可控性。通过改良的 Stöber 法合成的 M@CTAB/SiO2 在添加(3-氨丙基)三甲氧基硅烷(APTMS)/TEOS 或(3-氨丙基)三乙氧基硅烷(APTES)/TEOS 到合成介质后可以转化为蛋黄壳结构。我们明确证明了中间的 CTAB/SiO2 层转化为密度较低的 APTMS 丰富的有机-无机层,该层在碱性水溶液中被选择性去除,而氨基功能化的混合壳保持完整。此外,我们讨论了当将合成的 Ag@SiO2 纳米棒浸渍在 HAuCl4 水溶液中时,壳中的烷基氨基在从 Ag@SiO2 纳米棒到空心结构的转化中所起的作用。纳米棒还表现出对 p-硝基苯酚的催化还原的高催化活性。

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