Wang Huijie, Shi Miaomiao, Wang Chong, Chu Zhenyu, Yin Zongyou, Wang Chen
State Key Laboratory of Microbial Technology, Jiangsu Basic Research Center for Synthetic Biology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China.
Nano Lett. 2025 Jun 11;25(23):9353-9361. doi: 10.1021/acs.nanolett.5c01736. Epub 2025 May 28.
High-purity H production accompanied by precise decarbonization paves the way for a carbon-neutral society. Hydrogen-bonded organic frameworks (HOFs) are promising materials for advanced gas separation membranes, but their broad nanoscale pores limit selective separation. High-quality carboxylic acid-based HOF membranes (HOF-S, HOF-M, HOF-L) with pore sizes of 6.2, 16, and 24 Å were synthesized using an innovative pore-tailoring strategy. Under optimized conditions, H can pass through while CO is blocked by the size-exclusion principle. Abundant carboxylic acid groups in pores hinder the mobility of CO via electrostatic interaction, integrating adsorption and molecular sieving to enable excellent H transport and separation. The HOF-S membrane combines size exclusion and HOF-CO interactions, exhibiting excellent selectivity for H/CO (164) and a ternary gas mixture (H/CO selectivity: 154; H/CH selectivity: 201). It also displays long-term stability under both dry and wet conditions. This strategy opens new possibilities for customizing nanofluidic membranes for advanced gas separation technologies.
高纯度氢气生产并伴随着精确脱碳为碳中和社会铺平了道路。氢键有机框架（HOFs）是用于先进气体分离膜的有前景的材料，但其宽泛的纳米级孔径限制了选择性分离。采用创新的孔径定制策略合成了孔径分别为6.2、16和24 Å的高质量羧酸基HOF膜（HOF-S、HOF-M、HOF-L）。在优化条件下，氢气可通过，而一氧化碳则根据尺寸排阻原理被阻挡。孔内丰富的羧酸基团通过静电相互作用阻碍一氧化碳的迁移，将吸附和分子筛作用相结合，实现优异的氢气传输和分离。HOF-S膜结合了尺寸排阻和HOF-CO相互作用，对氢气/一氧化碳表现出优异的选择性（164）以及对三元气体混合物的选择性（氢气/一氧化碳选择性：154；氢气/甲烷选择性：201）。它在干燥和潮湿条件下均表现出长期稳定性。该策略为定制用于先进气体分离技术的纳米流体膜开辟了新的可能性。
