树枝状介孔氧化硅核/壳复合微球的合成和表征

doi:10.11901/1005.3093.2017.746

材料研究学报

2018, Vol. 32

Issue (10): 791-800 DOI: 10.11901/1005.3093.2017.746

研究论文

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树枝状介孔氧化硅核/壳复合微球的合成和表征

左长智¹, 陈杨¹(

), 陈爱莲²

1 常州大学材料科学与工程学院常州 213164
2 常州大学机械工程学院常州 213164

Synthesis and Characterization of Core/Shell Structured Silica Composite Microspheres with Dendritic Mesoporous Silica Shells

Changzhi ZUO¹, Yang CHEN¹(

), Ailian CHEN²

1 School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China
2 School of Mechanical Engineering, Changzhou University, Changzhou 213164, China

引用本文:

左长智, 陈杨, 陈爱莲. 树枝状介孔氧化硅核/壳复合微球的合成和表征[J]. 材料研究学报, 2018, 32(10): 791-800.
Changzhi ZUO, Yang CHEN, Ailian CHEN. Synthesis and Characterization of Core/Shell Structured Silica Composite Microspheres with Dendritic Mesoporous Silica Shells[J]. Chinese Journal of Materials Research, 2018, 32(10): 791-800.

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摘要:

以阳离子表面活性剂十六烷基三甲基溴化铵为模板、以正硅酸乙酯(TEOS)为前驱体、三乙醇胺为催化剂、正己烷为有机油相,使用油水两相体系实现树枝状介孔氧化硅(Dendritic mesoporous silica, D-mSiO₂)在实心氧化硅(Solid silica, sSiO₂)微球表面的连续均匀包覆,制备出具有核/壳结构的sSiO₂/D-mSiO₂复合微球。使用场发射扫描电子显微镜(FESEM)、高分辨透射电子显微镜(HRTEM)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和氮气吸附/脱附等手段表征了样品的结构。FESEM和TEM结果表明,在复合微球的氧化硅壳层中有大量的放射树枝状开放介孔,其孔道垂直于内核表面呈辐射状,改变TEOS用量可调控包覆层的厚度。小角衍射的结果显示,这种类型的树枝状介孔孔道的有序性比较差,孔道的平均孔径分布在7~9 nm。随着搅拌速率(50~500 r/min)的提高,D-mSiO₂壳层厚度(5~60 nm) 呈先增大后减小趋势。还讨论了树枝状介孔氧化硅核壳复合微球的形成机制及其影响因素。

关键词 ：无机非金属材料, 介孔氧化硅, 树枝状孔道, 核壳结构, 复合微球

Abstract：

Core/shell structured composite microspheres of sSiO₂/D-mSiO₂composed of solid silica (sSiO₂) as core and dendritic mesoporous silica (D-mSiO₂) as shell were synthesized via an oil-water biphase stratification approach with cetyltrimethylammonium bromide (CTAB) as template, tetraethylorthosilicate (TEOS) as precursor, Triethanolamine (TEA) as catalyst and n-hexane as emulsion agent. The synthesized products were characterized by means of field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffractometer (XRD), and nitrogen adsorption/desorption measurements. As revealed by FESEM and TEM that there existed plenty of radiate-dendritic-like open meso-channels, which were perpendicular to the sSiO₂sphere surface.The thicknesses of D-mSiO₂ shell could be controlled by adjusting the TEOS amount. Low-angle XRD analyses suggested that the mesochannles in the shells exhibit poor degree of order, and the average pore diameter was 7~9 nm. Moreover, the D-mSiO₂ shell thicknesses (5~60 nm) increased firstly and then decreased with the increase of stirring rate (50~500 r/min). Finally, the formation mechanism for the mesoporous shells with radiate-dendritic-like open meso-channels of composite microspheres was also discussed.

Key words： inorganic non-metallic materials mesoporous silica dendritic mesoporous channels core/shell structure composite microspheres

收稿日期: 2017-12-18

ZTFLH:

TB332

基金资助:国家自然科学基金(51405038, 51575058, 51875052)

作者简介:

作者简介左长智,男,1991年生,硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2017.746 或 https://www.cjmr.org/CN/Y2018/V32/I10/791

图1 sSiO2/D-mSiO2复合微球样品的红外光谱图

图2 sSiO2和sSiO2/D-mSiO2样品的FESEM照片

图3 sSiO2和sSiO2/D-mSiO2样品的TEM照片

图4 在不同搅拌速度下sSiO2/D-mSiO2复合微球的TEM照片

图5 sSiO2/D-mSiO2复合微球的XRD谱

图6 sSiO2/D-mSiO2复合微球的氮气吸附/脱附等温线及孔径分布曲线

表1 sSiO2/D-mSiO2复合微球的孔结构参数

图7 sSiO2/D-mSiO2复合微球的形成机理图

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