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

doi:10.6023/A24120388

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (2): 132-138.DOI: 10.6023/A24120388 Previous Articles Next Articles

Article

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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Abstract

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

Cite this article

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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Fig. & Tab. 5

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

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

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

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

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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电聚合新型聚间苯二胺薄膜及H2/CO2分离性能研究