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在聚二甲基硅氧烷-聚氧化乙烯嵌段共聚物模板定向合成 Linde 型 A 沸石中的自组装。

Self-assembly in poly(dimethylsiloxane)-poly(ethylene oxide) block copolymer template directed synthesis of Linde type A zeolite.

机构信息

Dipartimento di Chimica Industriale e Ingegneria dei Materiali, Università di Messina , Salita Sperone 31, I-98166 Sant'Agata (Messina), Italy.

出版信息

Langmuir. 2013 Jun 11;29(23):7079-86. doi: 10.1021/la400951s. Epub 2013 May 24.

DOI:10.1021/la400951s
PMID:23651236
Abstract

We describe the hydrothermal synthesis of zeolite Linde type A (LTA) submicrometer particles using a water-soluble amphiphilic block copolymer of poly(dimethylsiloxane)-b-poly(ethylene oxide) as a template. The formation and growth of the intermediate aggregates in the presence of the diblock copolymer have been monitored by small-angle X-ray scattering (SAXS) above the critical micellar concentration at a constant temperature of 45 °C. The early stage of the growth process was characterized by the incorporation of the zeolite LTA components into the surface of the block copolymer micellar aggregates with the formation of primary units of 4.8 nm with a core-shell morphology. During this period, restricted to an initial time of 1-3 h, the core-shell structure of the particles does not show significant changes, while a subsequent aggregation process among these primary units takes place. A shape transition of the SAXS profile at the late stage of the synthesis has been connected with an aggregation process among primary units that leads to the formation of large clusters with fractal characteristics. The formation of large supramolecular assemblies was finally verified by scanning electron microscopy, which evidenced the presence of submicrometer aggregates with size ranging between 100 and 300 nm, while X-ray diffraction confirmed the presence of crystalline zeolite LTA. The main finding of our results gives novel insight into the mechanism of formation of organic-inorganic mesoporous materials based on the use of a soft interacting nanotemplate as well as stimulates the investigation of alternative protocols for the synthesis of novel hybrid materials with new characteristics and properties.

摘要

我们描述了使用水溶性两亲嵌段共聚物聚(二甲基硅氧烷)-b-聚(氧化乙烯)作为模板合成沸石 Linde 型 A(LTA)亚微米颗粒的水热合成方法。在 45°C 的恒温下,在临界胶束浓度以上,通过小角 X 射线散射(SAXS)监测了嵌段共聚物存在时中间团聚体的形成和生长。生长过程的早期阶段的特征是沸石 LTA 成分掺入嵌段共聚物胶束团聚体的表面,形成具有核壳形态的 4.8nm 的初级单元。在此期间,受限于初始时间 1-3 小时,颗粒的核壳结构没有明显变化,而这些初级单元之间随后发生聚集过程。在合成的后期,SAXS 谱图的形状转变与初级单元之间的聚集过程有关,导致具有分形特征的大团簇的形成。扫描电子显微镜最终证实了大超分子组装体的形成,证明了存在尺寸在 100-300nm 之间的亚微米级聚集体,而 X 射线衍射则证实了结晶沸石 LTA 的存在。我们研究结果的主要发现为基于使用软相互作用纳米模板形成有机-无机介孔材料的机制提供了新的见解,并激发了对具有新特性和性能的新型杂化材料的替代合成方案的研究。

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