电聚合新型聚间苯二胺薄膜及H2/CO2分离性能研究

doi:10.6023/A24120388

化学学报 ›› 2025, Vol. 83 ›› Issue (2): 132-138.DOI: 10.6023/A24120388 上一篇下一篇

研究论文

电聚合新型聚间苯二胺薄膜及H₂/CO₂分离性能研究

张蒙茜^a, 张玉莹^a, 秦家轩^a, 冯霄^b^,^*(), 李雪艳^c, 畅通^a, 杨海英^a^,^*()

a 运城学院应用化学系运城 044000
b 北京理工大学化学与化工学院北京 100081
c 太原科技大学化学工程与技术学院太原 030024

投稿日期:2024-12-31 发布日期:2025-01-26
基金资助:
山西省基础研究计划项目(202203021212301); 山西省基础研究计划项目(202303021222244); 山西省基础研究计划项目(202303021211188); 山西省基础研究计划项目(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); 运城学院科研创新团队建设计划资助

Electropolymerization of Novel Poly-m-phenylenediamine Membrame for H₂/CO₂ Separation

Mengxi Zhang^a, Yuying Zhang^a, Jiaxuan Qin^a, Xiao Feng^b(), Xueyan Li^c, Tong Chang^a, Haiying Yang^a()

a Department of Applied Chemistry, Yuncheng University, Yuncheng 044000, China
b School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
c School of Chemical Engineering and Technology, Taiyuan University of Science & Technology, Taiyuan 030024, China

Received:2024-12-31 Published:2025-01-26
Contact: *E-mail: fengxiao86@bit.edu.cn; hyyang@ycu.edu.cn
Supported by:
Shanxi Provincial Basic Research Program(202203021212301); Shanxi Provincial Basic Research Program(202303021222244); Shanxi Provincial Basic Research Program(202303021211188); Shanxi Provincial Basic Research Program(202303021212214); Yuncheng Basic Research Program(YCKJ-2023049); PhD research Launch project of Yuncheng University(YQ-202414); Scientific Research and Innovation Team Construction Program of Yuncheng University

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摘要/Abstract

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H₂渗透率为1350 Barrer, H₂/CO₂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, H₂在膜材料中的扩散性能远高于CO₂, 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.

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

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 H₂/CO₂ separation selectivity reaches 30 with 1350 Barrer of H₂ 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 H₂ diffusivity (120×10^-7 cm²•s^-1) of PMPD membrane was superior to CO₂ (2.4×10^-7 cm²•s^-1), which indicated that the diffusivity of H₂ playing a dominant role in separation process. Molecular dynamics simulations were subsequently carried out to mimic the adsorption and diffusion behaviors of H₂ and CO₂ in PMPD respectively. The results also demonstrated that H₂ exhibited more outstanding diffusivity than CO₂. This simple, scalable, and cost-effective electropolymerization strategy holds promise for the design of other conjugated microporous polymers for key energy-intensive gas separations.

Key words: electropolymerization, poly-m-phenylenediamine, conjugated microporous polymer, H₂ separation, molecular dynamics simulation

引用此文

张蒙茜, 张玉莹, 秦家轩, 冯霄, 李雪艳, 畅通, 杨海英. 电聚合新型聚间苯二胺薄膜及H₂/CO₂分离性能研究[J]. 化学学报, 2025, 83(2): 132-138.

Mengxi Zhang, Yuying Zhang, Jiaxuan Qin, Xiao Feng, Xueyan Li, Tong Chang, Haiying Yang. Electropolymerization of Novel Poly-m-phenylenediamine Membrame for H₂/CO₂ Separation[J]. Acta Chimica Sinica, 2025, 83(2): 132-138.

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图/表 5

图1. (a) 1,3,5-TAB、OPD和MPD单体结构式及其亲电聚合位点; (b)聚合体系示意图和PMPD无定形晶胞的三维模拟图像, 晶胞大小为3.85 nm×3.85 nm×3.85 nm; (c)相应单体聚合后的ITO基底照片

Figure 1. (a) Structural formulas and active polymeric sites of monomer 1,3,5-TAB, OPD and MPD; (b) Illustration of electropolymerization and three-dimensional view of an amorphous cell network of PMPD. Cell size: 3.85 nm×3.85 nm×3.85 nm; (c) The photographs of ITO glass after electropolymerization

图2. PMPD膜材料及相应单体的(a)红外光谱图和(b)13C固体核磁共振波谱图; PMPD膜材料的(c)平面和(d)截面扫描电子显微镜(SEM)图像

Figure 2. (a) The FTIR-ATR and (b) the solid-state 13C NMR spectra of corresponding precursor MPD and PMPD membrane; The (c) top view and (d) cross-sectional view SEM images of PMPD membrane

图3. 298 K及0.1 MPa条件下(a) PMPD膜材料的H2、CO2、N2和CH4的单组分气体渗透率及气体分子动力学直径关系图; (b)膜材料的H2/CO2单组分气体分离性能与2008年Robeson上限[28](黑色线代表2008年上限图)对比图(详细分离数据见支持信息表S2); (c) PMPD膜材料的H2/CO2混合组分7 d长循环稳定性测试图

Figure 3. (a) The H2, CO2, N2 and CH4 single gas permeability of PMPD membrane at 298 K and 0.1 MPa as a function of the gas kinetic diameter; (b) Comparisons of the H2/CO2 gas separation performance of the membrane to that those of the state-of-the-art polymeric membranes (see Table S2). The black line represent the Robeson upper bound (2008) of polymeric membranes[28]; (c) The 7 d long-term mixed H2/CO2 separation performance of the PMPD membrane

	吸附量/ (cm³•g^-1)	渗透率/ Barrer	溶解度/ (cm³•cm^-3•Pa^-1)	扩散系数/ (×10^-7 cm²•s^-1)
H₂	3.51	1350	0.836	120
CO₂	5.98	45	1.444	2.4

表1. 298 K及0.1 MPa条件下PMPD膜材料的气体吸附量、渗透率、溶解度和扩散系数

Table 1. The gas adsorption capacity, permeability, solubility and diffusivity of PMPD membrane at 298 K and 0.1 MPa

图4. 298 K及0.1 MPa条件下PMPD膜材料的(a) H2吸附密度场分布(蓝色散点区域)和(b) CO2吸附密度场分布(橙色散点区域); (c) H2、CO2模拟吸附等温线; (d) H2、CO2的MSD与模拟时间关系图

Figure 4. The adsorption density field distribution of (a) H2 (blue dots) and (b) CO2 (orange dots); (c) H2 and CO2 simulated adsorption isotherms; (d) The mean square displacement of H2 and CO2 as a function of simulated times at 298 K and 0.1 MPa

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电聚合新型聚间苯二胺薄膜及H₂/CO₂分离性能研究

Electropolymerization of Novel Poly-m-phenylenediamine Membrame for H₂/CO₂ Separation

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