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共价有机框架(COF)膜作为一类新型多孔材料，在气体分离领域具有重要应用潜力，但传统COF膜的制备仍面临化学稳定性差、合成工艺复杂及难以规模化等挑战。通过动态共价化学键合取代反应，提出一种制备COF膜的新策略：将无定形共价有机聚合物(COP)膜转化为高结晶度COF膜，从而解决上述COF膜制备面临的问题。以亚胺连接的COP膜为前驱体，均苯四甲酸二酐(PMDA)为替换单体，成功构建三种聚酰亚胺键连接的COF膜(TAPT-PMDA、TAPB-PMDA、TAPA-PMDA)。转化后的COF膜具有高度有序的晶体结构、高比表面积及优异的力学性能，并且TAPT-PMDA和TAPB-PMDA膜具有出色的H2/CO2选择性(1.46和2.24),同时还具有超高的H2渗透性(7.69×10-13和7.06×10-13 mol/(m·s·Pa)),超过2008年Robeson上限。这种无序到有序结构的转化制膜策略为高效、可扩展的COF膜的制备提供了新思路，并推动了气体分离技术的实际应用。
Abstract：Covalent organic framework(COF) membranes, hold significant potential for gas separation. Traditional COF membrane preparation, however, faces challenges like poor chemical stability and complex synthesis. A novel approach converts amorphous covalent organic polymer(COP) membranes into crystalline COF membranes using dynamic covalent chemical bonding substitution. Using imide-linked COP membranes and homophthalic tetracarboxylic dianhydride(PMDA), three polyimide-bonded COF membranes(TAPT-PMDA, TAPB-PMDA, TAPA-PMDA) were developed. These membranes exhibit ordered crystal structures, high surface areas, and robust mechanical properties, with TAPT-PMDA and TAPB-PMDA membranes having excellent H2/CO2 selectivity of 1.46 and 2.24, respectively, as well as ultra-high H2 permeability of 7.69×10-13 and 7.06×10-13 mol/(m·s·Pa), respectively, which exceeded the 2008 Robeson upper limit. This strategy offers a scalable method for efficient COF membrane production, advancing gas separation technology.
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基本信息:
DOI：10.19886/j.cnki.dhdz.2025.0138
中图分类号:TQ051.893
引用信息:
[1]毕静婕,廖耀祖,张卫懿.自支撑共价有机框架的制备及其气体分离性能[J].东华大学学报(自然科学版),2026,52(03):94-101.DOI:10.19886/j.cnki.dhdz.2025.0138.
基金信息:
国家重点研发计划(2023YFB3811100); 国家自然科学基金面上项目(22375037); 中央高校优秀青年团队项目(2232024Y-01)
2026-06-15
2026-06-15