近日，英国谢菲尔德大学Brammer, Lee团队报道了选择性二氧化碳吸收模拟在高氟化无孔晶体材料中的溶解。相关论文发表在2025年10月14日出版的《自然-化学》杂志上。

从混合气体中分离CO₂在CH₄气体净化和蓝氢生产等应用中非常重要。

研究组报道了一系列柔性银配位聚合物（AgCPs），通过类似于氟烷烃溶解的机制，选择性地吸收二氧化碳，这些聚合物表面上是无孔的，但在门压以上对二氧化碳表现出潜在的孔隙。通过改变组成的全氟羧酸配体的全氟烷基链长，合理地改变了CO₂的吸附性能。由于溶解机制失效，AgCPs不吸收CH₄，与烷烃-全氟烷烃不混相一致。

原位单晶和粉末x射线衍射使CO₂分子结合域的直接可视化成为可能。这些技术还揭示了AgCPs的相关结构变化，并证实了CO₂吸收的门控机制。全氟烷基羧酸配体与柔性银(I)配位球的结合产生了高氟化但可移动的晶体区域，这些区域在CO₂对CH₄的选择性吸收中起着不可或缺的作用。

附：英文原文

Title: Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials

Author: Vitrica-Yrezbal, Iigo J., McAnally, Craig A., Snelgrove, Matthew P., Warren, Mark R., Hill, Adrian H., Thompson, Stephen P., Quinn, Martin, Mottley, Sam, Mottley, Stephen, Fletcher, Ashleigh J., Brammer, Lee

Issue&Volume: 2025-10-14

Abstract: Separation of CO2 from gas mixtures is important in applications such as CH4 gas purification and blue hydrogen production. Here we report selective CO2 uptake by a family of flexible silver coordination polymers (AgCPs) that are ostensibly non-porous but exhibit latent porosity to CO2 above a gate pressure, through a mechanism akin to dissolution in fluoroalkanes. The CO2 sorption properties are rationally modified by changing the perfluoroalkyl chain length of the constituent perfluorocarboxylate ligands. The AgCPs do not take up CH4 owing to failure of the dissolution mechanism, consistent with alkane–perfluoroalkane immiscibility. In situ single-crystal and powder X-ray diffraction enable direct visualization of the CO2 molecule binding domains. These techniques also reveal associated structural changes in the AgCPs and confirm the gating mechanism of CO2 uptake. The combination of perfluoroalkylcarboxylate ligands with the flexible silver(I) coordination sphere generates highly fluorinated but mobile regions of the crystals that play an integral role in the selective uptake of CO2 over CH4.

DOI: 10.1038/s41557-025-01943-4

Source: https://www.nature.com/articles/s41557-025-01943-4