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具有独特拓扑结构的单分散介孔二氧化硅纳米颗粒。

Monodisperse mesoporous silica nanoparticles of distinct topology.

作者信息

Luo Leilei, Liang Yucang, Erichsen Egil Sev, Anwander Reiner

机构信息

Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany.

Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany.

出版信息

J Colloid Interface Sci. 2017 Jun 1;495:84-93. doi: 10.1016/j.jcis.2017.01.107. Epub 2017 Jan 31.

DOI:10.1016/j.jcis.2017.01.107
PMID:28189113
Abstract

Monodisperse and uniform high-quality MCM(Mobil Composition of Matter)-48-type CMSNs (Cubic Mesoporous Silica Nanoparticles) are readily prepared by simply optimizing the molar ratio of ethanol and surfactant in the system TEOS-CTAB-NaOH-HO-EtOH (TEOS=tetraethyl orthosilicate, CTAB=cetyltrimethylammonium bromide, EtOH=ethanol). In the absence of ethanol only hexagonal mesoporous silica with ellipsoidal and spherical morphology are obtained. The presence of ethanol drives a mesophase transformation from hexagonal to mixed hexagonal/cubic, further to purely cubic, and finally to a mixed cubic/lamellar. This is accompanied by a morphology evolution involving a mixture of ellipses/spheres, regular rods, uniform spheres, and finally a mixture of spheres/flakes. Preserving the three-dimensional (3D) cubic MCM-48 structure, use of a small amount of ethanol is beneficial to the improvement of the monodispersity of the CMSNs. Moreover, the quality of the CMSNs can also be controlled by changing the surfactant concentration or adjusting the stirring rate. All MSNs were characterized using powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and N physisorption, indicating highly long-range ordered pore arrays, high specific surface areas (max. 1173 mg) as well as high pore volumes (max. 1.14 cmg). The monodispersity of the CMSNs was verified by statistical particle size distribution from SEM (scanning electron microscopy)/TEM (transmission electron microscopy) images and DLS (dynamic light scattering). The mesophase transformation can be rationalized on the basis of an ethanol-driven change of the surfactant packing structure and charge matching at the surfactant/silicate interface. The corresponding morphology evolution can be elucidated by an ethanol-controlled hydrolysis rate of TEOS and degree of condensation of oligomeric silicate species via a nucleation and growth process.

摘要

通过简单优化体系TEOS-CTAB-NaOH-H₂O-EtOH(TEOS=正硅酸四乙酯,CTAB=十六烷基三甲基溴化铵,EtOH=乙醇)中乙醇与表面活性剂的摩尔比,可轻松制备出单分散且均匀的高质量MCM(美孚物质组成)-48型立方介孔二氧化硅纳米颗粒(CMSNs)。在没有乙醇的情况下,仅能得到具有椭圆形和球形形态的六方介孔二氧化硅。乙醇的存在促使介相从六方相转变为六方/立方混合相,进而转变为纯立方相,最终转变为立方/层状混合相。这伴随着形态演变,包括椭圆/球体混合物、规则棒体、均匀球体,最终是球体/薄片混合物。保留三维(3D)立方MCM-48结构,使用少量乙醇有利于提高CMSNs的单分散性。此外,还可通过改变表面活性剂浓度或调节搅拌速率来控制CMSNs的质量。所有介孔二氧化硅纳米颗粒均采用粉末X射线衍射、透射电子显微镜、扫描电子显微镜和N₂物理吸附进行表征,结果表明其具有高度长程有序的孔阵列、高比表面积(最大1173 m²/g)以及高孔容(最大1.14 cm³/g)。通过扫描电子显微镜(SEM)/透射电子显微镜(TEM)图像的统计粒度分布和动态光散射(DLS)验证了CMSNs的单分散性。基于乙醇驱动的表面活性剂堆积结构变化以及表面活性剂/硅酸盐界面处的电荷匹配,可对介相转变做出合理解释。通过乙醇控制的正硅酸四乙酯水解速率以及低聚硅酸盐物种通过成核和生长过程的缩合程度,可阐明相应的形态演变。

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