Yu Liang, Li Shenfang, Zhou Xin, Zhang Bochun, Zhou Kang, Xia Qibin, Wang Sujing, Li Jing, Wang Hao
Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University, Shenzhen, People's Republic of China.
Hefei National Research Center for Physical Sciences at the Microscale, Suzhou Institute for Advanced Research, CAS Key Laboratory of Microscale Magnetic Resonance, Hefei National Laboratory, University of Science and Technology of China, Hefei, People's Republic of China.
Nat Chem. 2025 Jun 4. doi: 10.1038/s41557-025-01836-6.
The rational design and synthesis of ultramicroporous solids featuring uniform pore dimensions remains a notable challenge, yet these materials are critical for the selective discrimination of molecules with similar physicochemical properties. Here we report a family of ten ultramicroporous zirconium-based metal-organic frameworks assembled from isophthalate-based octatopic or hexatopic carboxylate linkers with high coordination density and Zr nodes with relatively low connectivity (4, 6 and 8). The diverse inorganic node geometry, ligand connectivity, structural topology, framework stability and ultramicroporosity of the resultant metal-organic frameworks underscore the pivotal role of linker geometry and functionality in tailoring the adsorptive properties of the material. These ultramicroporous solids hold promise for the separation of industrially relevant hydrocarbons. We show that HIAM-802 and HIAM-601 exhibit high-efficiency separation of hexane isomers based on branching by molecular exclusion. We validated their separation capabilities through breakthrough experiments and further clarified the underlying adsorption mechanisms by density functional theory calculations.
设计和合成具有均匀孔径的超微孔固体仍然是一个显著的挑战，然而这些材料对于选择性区分具有相似物理化学性质的分子至关重要。在此，我们报告了一族由基于间苯二甲酸酯的八齿或六齿羧酸连接体与具有相对低连接性（4、6和8）的Zr节点组装而成的十种超微孔锆基金属有机框架。所得金属有机框架多样的无机节点几何形状、配体连接性、结构拓扑、框架稳定性和超微孔性强调了连接体几何形状和功能在定制材料吸附性能方面的关键作用。这些超微孔固体有望用于分离与工业相关的烃类。我们表明，HIAM - 802和HIAM - 601基于分子排阻的支化作用对己烷异构体表现出高效分离。我们通过突破实验验证了它们的分离能力，并通过密度泛函理论计算进一步阐明了潜在的吸附机制。
