气溶胶辅助自组装制备中空球形二氧化硅材料的机理及应用

doi:10.16085/j.issn.1000-6613.2021-0161

摘要/Abstract

摘要：

以正硅酸乙酯（TEOS）和甲基三乙氧基硅烷（MTES）为混合硅源，不同配比条件下采用气溶胶辅助自组装技术制备高比表面积的中空介孔二氧化硅纳米颗粒（HMSNs），并应用于原花青素（PC）的负载，以期提高其生物利用度。利用扫描电镜（SEM）、透射电镜（TEM）、X射线衍射（XRD）、红外图谱（FTIR）和粒径分析（DLS）等对载体颗粒的形成过程、结构特性以及负载性能进行探究，基于BET分析方法计算HMSNs的比表面积，并对孔径分布进行分析。结果表明，前体溶液水解的活性中间体缩合形成二氧化硅网络结构，同时雾化后的气溶胶液滴在径向浓度梯度自组装成球形结构，水解-缩合与自组装过程协同作用促进了分散性良好的介孔二氧化硅（MSNs）的形成。经退火处理、纯化操作去除模板剂NaCl和表面活性剂十六烷基三甲基溴化铵（CTAB），最终获得具有中空结构的HMSNs。当TEOS/MTES的摩尔比为60/40时，HMSNs具有极大的比表面积（1083m²/g）和较大的孔容积（0.37cm³/g），其孔径主要分布在2~4nm之间，PC在HMSNs上的负载量可达30.7mg/g。

关键词: 中空介孔二氧化硅, 水解-缩合, 气溶胶, 自组装, 载体

Abstract:

Hollow mesoporous silica nanoparticles (HMSNs) with high specific area were prepared by aerosol assisted self-assembly technology using tetraethyl orthosilicate (TEOS) and methyltrimethoxysilane (MTES) in different molar ratio as mixed silicon sources, and applied to proanthocyanidin (PC) loading in order to improve their bioavailability. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (FTIR) and particle size analysis (DLS) were used to investigate the formation process, structural characteristics and loading performance of the carrier particles. The surface area of HMSNs was calculated based on the (BET) analysis and the pore size distribution was also analyzed. The results showed that the active intermediate hydrolyzed by the precursor solution condensed into a silica network structure, and the atomized aerosol droplets self-assembled into a spherical structure at the radial concentration gradient. The synergistic action of the hydrolyzation-condensation process and the self-assembly process led to formation of the mesoporous silica (MSNs) with good dispersive properties. After annealing and purification, the template NaCl and the surfactant hexadecyl trimethyl ammonium bromide (CTAB) were removed, and the HMSNS with hollow structure were finally obtained. When the molar ratio of TEOS/MTES was 60/40, the generated HMSNs had a maximum specific area of 1083m²/g with a large pore volume of 0.37cm³/g, the pore size was distributed between 2—4nm and the loading capacity of PC in HMSNs was as high as 30.7mg/g.

Key words: hollow mesoporous silica, hydrolysis-condensation, aerosol, self-assembly, support

中图分类号:

TQ127.2

付欣, 张玉苍, 李瑞松, 刘群, 郭佳益. 气溶胶辅助自组装制备中空球形二氧化硅材料的机理及应用[J]. 化工进展, 2022, 41(1): 327-335.

FU Xin, ZHANG Yucang, LI Ruisong, LIU Qun, GUO Jiayi. Mechanism and application of aerosol assisted self-assembly to prepare hollow spherical silica materials[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 327-335.

图/表 10

表1 样品的硅源配比及孔结构分析

样品	TEOS/MTES摩尔比	TEOS/g	MTES/g	比表面积/m²·g^-1	孔容积/cm³·g^-1	孔径/nm
HMSNs	—	10.4	—	697	0.38	2.61
HMSNs-1	80/20	8.32	1.36	851	0.32	3.06
HMSNs-2	60/40	6.24	2.72	1083	0.37	2.94
HMSNs-3	40/60	4.16	4.08	977	0.396	3.51

图1 形成过程的SEM图

图2 MSNs、HMSNs的TEM、XRD图

图3 形成过程中N2吸附-脱附等温线和孔径分布图

图4 形成过程的FTIR图

图5 HMSNs、PC@HMSNs的TEM图

图6 不同HMSNs的FTIR图

图7 不同HMSNs的N2吸附-脱附等温线和孔径分布图

图8 粒径和zeta电位分布图

图9 负载率和负载量变化图

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