高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (3): 946.doi: 10.7503/cjcu20200527

• 材料化学 • 上一篇    下一篇

具有不对称孔道结构的小介孔二氧化硅粒子的合成及其高分子杂化膜的构建

童诚1, 吴文韬2, 王挺1()   

  1. 1.浙江工商大学环境科学与工程学院, 杭州 310012
    2.太原科技大学材料科学与工程学院, 太原 030024
  • 收稿日期:2020-08-03 出版日期:2021-03-10 发布日期:2021-03-08
  • 通讯作者: 王挺 E-mail:zjwtwaiting@hotmail.com
  • 基金资助:
    浙江省自然科学基金(LY19B060004)

Preparation of Small Mesoporous SiO2 Particles with Asymmetric Tunnel Structure and Fabrication of the Resulting Hybrid Membranes

TONG Cheng1, WU Wentao2, WANG Ting1()   

  1. 1.School of Environmental Science and Engineering,Zhejiang Gongshang University,Hangzhou 310012,China
    2.School of Materials Science and Engineering,Taiyuan University of Science and Technology,Taiyuan 030024,China
  • Received:2020-08-03 Online:2021-03-10 Published:2021-03-08
  • Contact: WANG Ting E-mail:zjwtwaiting@hotmail.com
  • Supported by:
    ? Supported by the Natural Science Foundation of Zhejiang Province, China(LY19B060004)

摘要:

利用手性阴离子酸表面活性剂, 采用软模板法制备了具有不对称孔道结构的小介孔二氧化硅(SiO2)粒子. 将小介孔SiO2粒子引入聚偏四氟乙烯(PVDF)和聚酰亚胺(PI)中构建了两种有机/无机杂化膜. 利用傅里叶变换红外光谱(FTIR)、 透射电子显微镜(TEM)、 扫描电子显微镜(SEM)和比表面积分析等表征了小介孔SiO2粒子和有机/无机杂化膜的微结构, 并通过超滤实验和气体渗透实验分别考察两种杂化膜的性能. 研究结果表明, 表面含有大量亲水基团的小介孔SiO2粒子具有规则有序排列的孔道结构, 该孔道结构呈现螺旋扭曲和不对称性. 构建的两种有机/无机杂化膜的极性显著提升, 进而有效增强了PVDF杂化膜的膜通量和抗污染性能及PI杂化膜对CO2气体的分离性能, 克服了高分子膜的博弈效应(Trade-off效应). 另外, SiO2的小介孔孔道还可以在PI杂化膜中引入优先通过CO2分子的限域传质通道, 加速了CO2气体在杂化膜中扩散. 但过多小介孔SiO2粒子的加入导致其在高分子基质中团聚, 削弱杂化膜的极性和亲水性, 从而降低了两种杂化膜的分离性能.

关键词: 小介孔二氧化硅粒子, 不对称孔道结构, 有机-无机杂化膜, 气体渗透, 超滤

Abstract:

Through a soft template method using chiral anionic acid as a surfactant, small mesoporous SiO2 particles with asymmetric tunnel structures were firstly prepared. Then, the small mesoporous SiO2 particles were incorporated into polyvinylidene fluoride(PVDF) and polyimide(PI) to fabricate two kinds of organic-inorganic hybrid membranes. Fourier transform infrared spectrometer(FTIR), transmission electron microscope(TEM), Scanning electron microscope(SEM) and Brunner-Emmet-Teller(BET) measurement were employed to characterize the microstructure of the small mesoporous SiO2 and the resulting organic- inorganic hybrid membranes. The performance of the PVDF and PI hybrid membranes were evaluated by ultrafiltration and gas permeation experiments, respectively. The results showed that the small mesoporous SiO2 particles with a lot of hydrophilic groups on its surface had a regular and orderly arranged pore structure, which presented spiral twists and asymmetry. Addition of small mesoporous SiO2 particles would significantly improve the polarity of the two kinds of hybrid membranes, thereby effectively enhancing the anti-pollution performance of the PVDF membranes and the performance of the PI membranes for CO2 separation. Moreover, the tunnel structures of mesoporous SiO2 could also introduce a confined mass transfer channel, which could accelerate the diffusion of CO2 molecule through the PI hybrid membrane. Addition of too many mesoporous SiO2 caused the formation of aggregates in the polymer membranes, which weakened the polarity and hydrophilicity of membranes, thereby depressing the performance of the two kinds of hybrid membranes.

Key words: Small mesoporous SiO2 particles, Asymmetric channel structure, Organic-inorganic hybrid membrane, Gas permeation, Ultrafiltration

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