溶胶-凝胶伴随相分离制备SiO2多孔块体

doi:10.3866/PKU.WHXB201212252

物理化学学报 >> 2013, Vol. 29 >> Issue (03): 646-652.doi: 10.3866/PKU.WHXB201212252

溶胶-凝胶伴随相分离制备SiO₂多孔块体

郭兴忠¹, 李文彦¹, 朱阳², 中西和樹², 金森主祥², 杨辉¹

1 浙江大学材料科学与工程学系, 杭州 310027;
2 日本京都大学大学院理学研究科, 京都, 606-8502

收稿日期:2012-09-15 修回日期:2012-12-24 发布日期:2013-02-25
通讯作者: 杨辉 E-mail:yanghui@zju.edu.cn
基金资助:
浙江省重点创新团队项目(2009R50010)资助

Macroporous SiO₂ Monoliths Prepared via Sol-Gel Process Accompanied by Phase Separation

GUO Xing-Zhong¹, LI Wen-Yan¹, ZHU Yang², NAKANISHI Kazuki², KANAMORI Kazuyoshi², YANG Hui¹

1 Department of Materials Science and Engineering of Zhejiang University, Hangzhou 310027, P. R. China;
2 Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan

Received:2012-09-15 Revised:2012-12-24 Published:2013-02-25
Supported by:
The project was supported by the Key Innovation Team Project of Zhejiang Province, China (2009R50010).

摘要/Abstract

摘要：

以正硅酸甲酯(TMOS)为前驱体, 0.01 mol·L^-1盐酸(HCl)为催化剂, 环氧丙烷(PO)为凝胶促进剂, 粘均分子量(M_v)为10000的聚氧化乙烯(PEO)为相分离诱导剂, 采用溶胶-凝胶伴随相分离制备SiO₂多孔块体材料,利用差热分析(DTA)、傅里叶变换红外(FT-IR)光谱、扫描电镜(SEM)、X射线衍射(XRD)、汞压、N₂吸附/脱附等测试技术对所制得的SiO₂多孔块体进行了表征, 探讨了环氧化物调控溶胶-凝胶以及PEO诱导相分离机理. 结果表明, 加入PEO能诱导SiO₂凝胶发生相分离, 当PEO/TMOS摩尔比为0.0018时, 可以获得共连续多孔结构的SiO₂块体材料, 其大孔孔径分布在1-3 μm之间, 比表面积达719 m²·g^-1, 孔体积为0.48 m³·g^-1. 环氧丙烷因其环氧原子的强亲核性和不可逆的开环反应, 促进溶胶-凝胶转换, 同时借助吸附在SiO₂低聚物上的PEO诱导SiO₂凝胶相分离, 从而制备共连续大孔及骨架结构的多孔块体.

关键词: 多孔块体, SiO₂, 溶胶-凝胶, 相分离, 环氧丙烷, 聚氧化乙烯

Abstract:

Macroporous SiO₂ monoliths were prepared via a sol-gel process accompanied by phase separation using a tetramethoxysilane (TMOS) precursor, 0.01 mol·L^-1 HCl catalyst, propylene oxide (PO) gelation agent, and poly(ethylene oxide) (PEO, viscosity-averaged molecular weight (M_v): 10000) phase separation inducer. Monoliths were characterized by differential thermal analysis/thermogravimetry (DTA/ TG), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), mercury porosimetry, and nitrogen adsorption/desorption analysis (BET). The mechanism of the epoxide-mediated sol-gel reaction and PEO induced phase separation was discussed. The addition of PEO induced phase separation, and monolithic SiO₂ with a cocontinuous macroporous skeletal structure was obtained at PEO/TMOS molar ratio of 0.0018. Monoliths had a narrow pore size distribution of 1-3 μm, surface area as high as 719 m²·g^-1 and pore volume of 0.48 m³·g^-1. This sol-gel transition is mediated by PO because of its strong nucleophilic properties and irreversible ring-opening reaction. Simultaneous phase separation is induced by PEO adsorbed on the SiO₂ oligomers.

Key words: Porous monolith, Silica, Sol-gel, Phase separation, Propylene oxide, Poly(ethylene oxide)

郭兴忠, 李文彦, 朱阳, 中西和樹, 金森主祥, 杨辉. 溶胶-凝胶伴随相分离制备SiO₂多孔块体[J]. 物理化学学报, 2013, 29(03), 646-652. doi: 10.3866/PKU.WHXB201212252

GUO Xing-Zhong, LI Wen-Yan, ZHU Yang, NAKANISHI Kazuki, KANAMORI Kazuyoshi, YANG Hui. Macroporous SiO₂ Monoliths Prepared via Sol-Gel Process Accompanied by Phase Separation[J]. Acta Phys. -Chim. Sin. 2013, 29(03), 646-652. doi: 10.3866/PKU.WHXB201212252

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201212252

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I03/646

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溶胶-凝胶伴随相分离制备SiO₂多孔块体

Macroporous SiO₂ Monoliths Prepared via Sol-Gel Process Accompanied by Phase Separation

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