中国科学院福建物质结构研究所袁大强团队实现了MOF中高效分离C₂H₂/CO₂/C₂H₄的拓扑定向笼工程。相关论文发表在2025年5月26日出版的《美国化学会杂志》上。

笼式多孔材料利用其独特的“受限窗口-膨胀腔”协同结构，在气体吸附和分离领域显示出显著的优势。研究组提出了一种拓扑导向的原位组装策略，成功构建了具有定制孔结构的金属有机框架。 

以独特的笼通道soc拓扑框架为模板，通过创新性地颠倒传统节点和连接体的作用，研究组采用构象灵活的六吡啶配体作为六个连接节点，利用欠配位的Cu²⁺作为五个连接体，结合卤素阴离子（F^-、Cl^-和Br^-）作为两个连接的拓扑“阻断剂”，成功合成了三种具有前所未有的jcq拓扑网络的MOF材料（LNU-H1、LNU-H2和LNU-H3）。

这些材料表现出独特的“受限窗口-膨胀腔”协同结构，实现了线性通道的完全闭合。值得注意的是，LNU-H1在分离三元C₂H₂/CO₂/C₂H₄气体混合物方面表现出了卓越的性能，这在工业相关条件下的动态突破实验中得到了验证。这项研究不仅证实了拓扑导向孔工程方法的有效性，还为开发用于气体分离应用的先进、节能的功能材料提供了新的见解。

附：英文原文

Title: Topology-Directed Cage Engineering in MOFs for Efficient C2H2/CO2/C2H4 Separation

Author: Yuejiang Han, Chunqing Ji, Yuning Lou, Ran Li, Mingyao He, Daqiang Yuan, Zhengbo Han

Issue&Volume: May 26, 2025

Abstract: Cage-based porous materials, leveraging their unique “confined windows–expanded cavities” synergistic architecture, have demonstrated remarkable advantages in the field of gas adsorption and separation. This study presents a topology-directed in situ assembly strategy that successfully constructs metal–organic frameworks with tailored pore structures. Using the distinctive cage-channel soc topological frameworks as a template, by innovatively reversing the roles of traditional nodes and linkers, we employed the conformationally flexible hexa-pyridine ligands as six-connected nodes and utilized undercoordinated Cu2+ as five-connected linkers, in combination with halogen anions (F–, Cl–, and Br–) as two-connected topological “blockers”, resulting in the successful synthesis of three MOF materials (LNU-H1, LNU-H2, and LNU-H3) featuring an unprecedented jcq topological network. These materials exhibit a unique “confined window–expanded cavity” synergistic structure, achieving complete closure of linear channels. Notably, LNU-H1 demonstrated exceptional performance in the separation of ternary C2H2/CO2/C2H4 gas mixtures, as validated by dynamic breakthrough experiments under industrially relevant conditions. This study not only confirms the effectiveness of the topology-directed pore engineering approach but also provides new insights into the development of advanced, energy-efficient functional materials for gas separation applications.

DOI: 10.1021/jacs.5c05068

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c05068