高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (4): 686-693.doi: 10.7503/cjcu20160678

• 高分子化学 • 上一篇    下一篇

二氧化钛纳米粒子-氧化石墨烯/聚酰亚胺混合基质膜的原位聚合及气体渗透性能

杨彩虹, 满春利, 薛琬蕾, 王挺, 陈迪, 陈潜, 吴礼光()   

  1. 浙江工商大学环境科学与工程学院, 杭州 310012
  • 收稿日期:2016-09-23 出版日期:2017-04-10 发布日期:2019-08-13
  • 作者简介:联系人简介: 吴礼光, 男, 博士, 教授, 博士生导师, 主要从事功能膜材料研究. E-mail: wulg64@zjgsu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21376218, 21076190 )和浙江省膜分离与水处理协同创新中心项目(批准号: 2016YB08)资助

Fabrication of TiO2-GO/PI Mixed Matrix Membranes by In-situ Polymerization and Their Gas Permeation Property

YANG Caihong, MAN Chunli, XUE Wanlei, WANG Ting, CHEN Di, CHEN Qian, WU Liguang*()   

  1. School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China
  • Received:2016-09-23 Online:2017-04-10 Published:2019-08-13
  • Contact: WU Liguang E-mail:wulg64@zjgsu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21376218, 21076190) and the Open Research Fund Program of Collaborative Innovation Center of Membrane Separation and Water Treatment of Zhejiang Province, China(No.2016YB08)

摘要:

以钛酸四丁酯为前驱体, 采用浸渍-沉淀法制备二氧化钛纳米粒子-氧化石墨烯(TiO2-GO)复合物, 再将TiO2-GO复合物与4,4'-(六氟异亚丙基)邻苯二甲酸酐和4,4'-二氨基二苯醚通过原位聚合构建TiO2-GO/TiO2-GO/PI(聚酰亚胺)混合基质膜, 用于CO2的渗透脱除. 采用傅里叶变换红外光谱(FTIR)、 拉曼光谱(Raman)、 透射电子显微镜(TEM)、 扫描电子显微镜(SEM)、 热失重(TG)和Zeta电位等表征了TiO2-GO复合物和TiO2-GO/PI混合基质膜的形貌与结构; 探讨了TiO2掺杂量对TiO2-GO复合物及TiO2-GO/PI混合基质膜的结构和气体渗透性能的影响. 结果表明, TiO2-GO复合物中TiO2纳米粒子较均匀地沉积在GO片层上, TiO2纳米粒子在形成的同时破坏了GO的结构, 使其无序度增加. TiO2的掺杂对TiO2-GO/PI混合基质膜的形貌与结构影响较小, 但提升了TiO2-GO/PI混合基质膜的CO2和N2渗透性能. 但过量的掺杂使TiO2粒子在GO片层上团聚, 从而导致TiO2-GO复合物在混合基质膜中的分散性变差, CO2渗透性及CO2/N2渗透选择性降低. 当TiO2掺杂质量分数为30%时, TiO2-GO/PI混合基质膜的CO2渗透性为360 Barrer[1 Barrer=10-10cm3(STP)·cm/(cm2·s·cm Hg)=7.5×10-14cm3(STP)·cm/(cm2·s·Pa)], CO2/N2的渗透选择性可达31.

关键词: 二氧化钛纳米粒子-氧化石墨烯复合物, 聚酰亚胺, 混合基质膜, 原位聚合, 气体渗透性

Abstract:

Titanium dioxide-graphene oxide(TiO2-GO) nanocomposites were synthesized by impregnation-reduction method using tetrabutyl titanate(C16H36O4Ti) as the source of TiO2, then TiO2-GO/polyimide(TiO2-GO/PI) mixed matrix membranes were fabricated via in-situ polymerization with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)/4,4'-oxydianiline(ODA)/TiO2-GO. The structures of TiO2-GO nanocomposites and TiO2-GO/PI mixed matrix membranes were characterized by Fourier transform infrared spectroscopy(FTIR), Raman spectroscopy and transmission electron microscopy(TEM), scanning electron microscope(SEM), thermo-gravimetric analysis(TGA) and zeta potential instrument. The effects of TiO2-doping on the structure of TiO2-GO nanocomposites and TiO2-GO/PI mixed matrix membranes were discussed, and the gas permeation properties of the mixed matrix membranes were measured. The results reveal that TiO2 nanoparticles are impregnated uniformly in GO nanosheets, the dope of TiO2 would slightly destroy the structure of GO, and the disorder degree of GO structure increased. But the dope of TiO2 which was helpful to improve the dispersion of TiO2-GO nanocomposite in the mixed matrix membrane, thus enhance the gas permeation properties of the mixed matrix membrane. However, the excess of TiO2-doping would lead to the aggregation of TiO2 particles on the GO surface, which depressed the gas permeation properties of the mixed matrix membrane. When the mass fraction of TiO2-doping reached 15% in TiO2-GO nanocomposite, the mixed matrix membrane demonstrated good CO2 permeability and CO2/N2 permeation selectivity, and CO2 permeability was 360 Barrer, and CO2/N2 permeation selectivity reached 31.

Key words: TiO2-graphene oxide nanocomposite, Polyimide, Mixed matrix membrane, In-situ polymerization, Gas permeation property

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