电聚合新型聚间苯二胺薄膜及H_(2)/CO_(2)分离性能研究  

Electropolymerization of Novel Poly-m-phenylenediamine Membrame for H_(2)/CO_(2) Separation

作　　者：张蒙茜 张玉莹 秦家轩 冯霄 李雪艳 畅通 杨海英[1] Mengxi Zhang;Yuying Zhang;Jiaxuan Qin;Xiao Feng;Xueyan Li;Tong Chang;Haiying Yang(Department of Applied Chemistry,Yuncheng University,Yuncheng 044000,China;School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 100081,China;School of Chemical Engineering and Technology,Taiyuan University of Science&Technology,Taiyuan 030024,China)

机构地区：[1]运城学院应用化学系,运城044000 [2]北京理工大学化学与化工学院,北京100081 [3]太原科技大学化学工程与技术学院,太原030024

出　　处：《化学学报》2025年第2期132-138,共7页Acta Chimica Sinica

基　　金：山西省基础研究计划项目(202203021212301,202303021222244,202303021211188,202303021212214);运城市基础研究项目(YCKJ-2023049);运城学院博士科研启动项目(YQ-202414)和运城学院科研创新团队建设计划资助。

摘　　要：膜分离技术由于高能效、操作简便等优势已成为分离纯化氢气的关键技术之一.其中,聚合物膜因其成本低廉、易于加工已大规模商业化,但绝大多数聚合物膜无法突破渗透性和选择性之间的“博弈效应”.对此,本工作合理设计并选用具有多个电化学活性位点的苯胺类衍生物1,3,5-三氨基苯(1,3,5-TAB)、邻苯二胺(OPD)和间苯二胺(MPD)作为构筑单元,通过条件温和可控的电聚合方法将刚性微孔骨架引入聚合物膜中,得到致密无缺陷的自支撑聚间苯二胺(PMPD)膜材料,其H_(2)渗透率为1350 Barrer, H_(2)/CO_(2)选择性为30,分离性能突破了聚合物膜的Robeson上限,且膜材料具有良好的热稳定性和长循环稳定性.实验和分子动力学模拟研究结果均表明,H_(2)在膜材料中的扩散性能远高于CO_(2),占主导分离作用.这种操作简单且普适的电聚合策略为设计其他用于能源气体分离的共轭微孔聚合物膜材料提供了重要的参考价值.Membrane-based gas separations have tremendous potential for hydrogen purification due to high energy efficiency and easy operation, and the separation performance is significantly influenced by membrane materials. Owing to the low cost and processability, polymer membranes have been widely commercialized among these membranes. While, the trade-off between permeability and selectivity is insurmountable for dense polymer membranes. Therefore, introducing rigid porosity into polymer membranes is an urgent issue that needs to be solved. In our study, several aniline-based derivatives with multiple electrochemical active sites (1,3,5-triaminobenzene, o-phenylenediamine and m-phenylenediamine) were rationally designed and electropolymerized to yield novel conjugated microporous networks. Cyclic voltammetry technology was used for electropolymerization, and Ag/Ag+ electrode was selected as the reference electrode, with indium tin oxide (ITO) conductive glass and Ti sheet as the working electrode and counter electrode respectively. Finally, a homogenous and free-standing poly-m-phenylenediamine (PMPD) membrane was obtained after 40-circles electropolymerization. The polymerization reaction was confirmed by Fourier transform infrared spectroscopy (FTIR), solid-state 13C nuclear magnetic resonance spectra (13C NMR) and elemental analysis (EA). The morphology, thermal stability and porosity of PMPD were measured by scanning electron microscopy (SEM), thermogravimetric analysis (TG), and N2-77 K sorption isotherm. The gas separation ability and mechanical performance of PMPD membrane were studied. The H_(2)/CO_(2) separation selectivity reaches 30 with 1350 Barrer of H_(2) permeability, which can exceed the Robeson upper bound. Furthermore, the thermal and 7 d long-term stability tests demonstrate their potential for industrial applications. The resulted H_(2) diffusivity (120×10^(-7) cm^(2)·s^(-1)) of PMPD membrane was superior to CO_(2) (2.4×10^(-7) cm^(2)·s^(-1)), which indicated that the diffusivity of H_(2) playing

关 键 词：电聚合 聚间苯二胺 共轭微孔聚合物 氢气分离 分子动力学模拟 

分 类 号：TQ028.8[化学工程]