Synthesis of hollow inorganic nano-particles templated by polymeric micelles with core-shell-corona structure and their applications

核壳冠结构聚合物胶束模板空心无机纳米粒子的合成及其应用

基本信息

批准号：
17510088
负责人：
NAKASHIMA Kenichi
金额：
$ 2.33万
依托单位：
Saga University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

We tried to synthesize inorganic hollow nano-particles by templating a polymeric micelle with a core-shell-corona structure in aqueous solutions. We started with silica nano-particles. The template micelle was prepared from poly (styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO), and the precursor employed is tetramethoxysilane (TMOS). Silica was deposited in a domain of PVP shell by sol-gel reaction. After removing the template polymer from the polymer-silica hybrid particles by calcinations, we obtained hollow silica nanoparticles. The obtained hollow silica nanoparticles were found to have a spherical structure with narrow distributions of void volume and shell thickness.Furthermore, we tried to control the structural parameters of the hollow silica; i.e., the void volumes by changing the PS chain length, and the wall thickness by changing the amount of the silica precursor. As expected, the void volume of the obtained hollow silica regularly increased with the increase in the PS chain length, and the wall thickness increased with the increase in the concentration of the precursor. To the best of our knowledge, this is the first study in which the cavity size and wall thickness of the hollow silica were successfully fine-tuned on a scale of several nanometers.The significant feature of our method is that each block of the copolymer has its own function during the silica synthesis ; (i) the PS block forms the core of the micelle to be a template of the void space in the hollow silica, (ii) the PVP block forms the shell to be a reaction field of the sol-gel reaction of TMOS, and (iii) PEO forms the corona to stabilize the polymer/silica intermediate hybrids.Our method seems to be a comprehensive one; that is, it can be applied to the other inorganic materials and different triblock copolymer micelles can be used as a template.

我们尝试通过在水溶液中模板化具有核-壳-冠结构的聚合物胶束来合成无机中空纳米粒子。我们从二氧化硅纳米颗粒开始。模板胶束由聚(苯乙烯-b-2-乙烯基吡啶-b-环氧乙烷)(PS-PVP-PEO)制备，所用前驱体是四甲氧基硅烷(TMOS)。通过溶胶-凝胶反应将二氧化硅沉积在 PVP 壳的区域中。通过煅烧从聚合物-二氧化硅杂化颗粒中去除模板聚合物后，我们获得了空心二氧化硅纳米颗粒。发现所获得的空心二氧化硅纳米颗粒具有球形结构，空隙体积和壳厚度分布较窄。此外，我们尝试控制空心二氧化硅的结构参数；即，通过改变 PS 链长度来改变空隙体积，通过改变二氧化硅前体的量来改变壁厚度。正如预期的那样，所得空心二氧化硅的空隙体积随着PS链长的增加而规律性地增加，并且壁厚随着前驱体浓度的增加而增加。据我们所知，这是首次在纳米尺度上成功微调中空二氧化硅的空腔尺寸和壁厚的研究。我们方法的显着特点是共聚物的每个嵌段都具有在二氧化硅合成过程中其自身的功能； (i) PS嵌段形成胶束的核心，作为中空二氧化硅中空隙空间的模板，(ii) PVP嵌段形成壳，作为TMOS溶胶-凝胶反应的反应场，以及( iii) PEO 形成电晕以稳定聚合物/二氧化硅中间杂化物。我们的方法似乎是一种综合方法；也就是说，它可以应用于其他无机材料，并且可以使用不同的三嵌段共聚物胶束作为模板。