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在液/液界面处制造具有高催化活性的嵌段共聚物/金属纳米粒子微结构。

Fabricating highly catalytically active block copolymer/metal nanoparticle microstructures at the liquid/liquid interface.

机构信息

Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Jinan 250100, PR China.

Anastro Laboratory, Department of Chemistry, Changwon National University, Changwon 641-773, Republic of Korea.

出版信息

J Colloid Interface Sci. 2018 Jul 15;522:272-282. doi: 10.1016/j.jcis.2018.03.071. Epub 2018 Mar 22.

Abstract

HYPOTHESIS

Our previous studies have shown that the metal nanoparticle/polymer composite structures fabricated at the liquid/liquid interface have good reusability but lower catalytic activity for heterogeneous reactions in aqueous solutions. This should be attributed to the poor water wettability and more compact structure of the polymer matrices. Therefore, it should be possible to improve the catalytic activity through designing and fabricating a porous composite structure with good water wettability.

EXPERIMENTS

A modified liquid/liquid interface adsorption and fabrication method was used. An aqueous solution of copper acetate and a chloroform/DMF mixed solution of PS-b-PAA acted as the two phases. Through spontaneous emulsification, self-assembly of the polymer molecules with Cu ions in the droplets, and adsorption of the formed spherical micelles and nanofibers to the planar liquid/liquid interface, a porous composite microstructure was formed.

FINDINGS

This structure consisted of nanofiber-connected nanospheres which have a PS core and a PAA corona. Tiny and well-dispersed Cu nanoparticles were embedded in the hydrophilic corona and were adsorbed on the nanofibers surface as well. After physical cross-linking with 1,6-diaminohexane, the composite material exhibited high catalytic activity and good reusability for the reactions in aqueous solutions. For example, the rate constant for the reduction of p-nitroaniline reached 1965 s g.

摘要

假设

我们之前的研究表明,在液/液界面上制造的金属纳米粒子/聚合物复合材料结构具有良好的可重复使用性,但在水溶液中的多相反应中的催化活性较低。这应该归因于聚合物基质较差的润湿性和更紧凑的结构。因此,通过设计和制造具有良好润湿性的多孔复合结构,应该有可能提高催化活性。

实验

使用了改进的液/液界面吸附和制造方法。醋酸铜的水溶液和 PS-b-PAA 的氯仿/DMF 混合溶液作为两相。通过自发乳化,聚合物分子与液滴中的 Cu 离子自组装,以及形成的球形胶束和纳米纤维吸附到平面液/液界面上,形成了多孔复合微结构。

结果

该结构由纳米纤维连接的纳米球组成,具有 PS 核和 PAA 冠。微小且分散良好的 Cu 纳米粒子嵌入亲水性冠中,并吸附在纳米纤维表面上。用 1,6-二氨基己烷进行物理交联后,复合材料在水溶液中的反应表现出高催化活性和良好的可重复使用性。例如,对 p-硝基苯胺的还原反应的速率常数达到 1965 s·g。

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