In Situ Formation of Tröger’s Base-Derived Porous Organic Polymer Membranes with Greatly Enhanced Ultramicroporosity and Gas Separation Property

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-02-07 DOI:10.1021/acs.macromol.4c02838

Mengtao Wang, Luxin Sun, Chen Luo, Jiachen Chu, Congcong Wu, Kunying Li, Xuepeng Li, Kai Song, Jianxin Li, Xiaohua Ma

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Abstract

Formation of porous organic polymer (POP) membranes is a great challenge due to their highly cross-linked nature that prevents film formability. Here, we reported a series of mechanically strong POP membranes derived from a cross-linked Tröger’s base using 3,3′-dimethylbiphenyl-4,4′-diamine as a linear monomer and 1,3,5-tris(4-aminophenyl)benzene (TPB) as a cross-linking node. As the TPB content increased from 0% (TPB-0) to 75% (TPB-75), these POP membranes show a continuously decreased chain spacing from 7.96 to 6.22 Å, increased Brunauer–Emmet–Teller surface areas from 250 to 531 m² g^–1, and enhanced ultramicropore volumes from 0.046 to 0.143 cm³. Thereby, a huge increase in permeability without sacrificing selectivity was observed for these TPB-based POP membranes. For example, TPB-75 exhibited not only over 19 times larger O₂ permeability (790 vs 50.3 Barrer) but also slightly higher O₂/N₂ selectivity (4.8 vs 4.5) than the linear TPB-0. The overall separation performances quickly improved from below the 2008 trade-off curves for TPB-0 to near the latest 2015 curves for O₂/N₂, H₂/N₂, and H₂/CH₄ as the TPB content increased. These results are attributed to the significantly improved ultramicroporosity that enhanced the molecular sieving effect by the POP structure induced by in situ cross-linking. This design protocol and the POP membranes provide a novel direction for advanced gas separation membranes.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.