近日，中国科学技术大学汪苏靖团队实现了通过网状方法构建具有高配位密度配体的超微孔锆金属有机框架。2025年6月4日，《自然-化学》杂志发表了这一成果。

具有均匀孔径的超微孔固体的合理设计和合成仍然是一个显著的挑战，但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。研究组报告了一个由十个超微孔锆基金属有机框架组成的家族，这些框架由间苯二甲酸酯基八位或六位羧酸盐连接体组装而成，具有高配位密度和相对较低连接性的Zr6节点（4、6和8）。 

所得金属-有机框架的不同无机节点几何形状、配体连接性、结构拓扑、框架稳定性和超微孔性突显了连接体几何形状和功能在定制材料吸附性能中的关键作用。这些超微孔固体有望分离工业上相关的碳氢化合物。研究组表明，HIAM-802和HIAM-601基于分子排阻支化对己烷异构体表现出高效分离。他们通过突破性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。

附：英文原文

Title: Building ultramicroporous zirconium metalorganic frameworks with ligands of high coordination density through a reticular approach

Author: Yu, Liang, Li, Shenfang, Zhou, Xin, Zhang, Bochun, Zhou, Kang, Xia, Qibin, Wang, Sujing, Li, Jing, Wang, Hao

Issue&Volume: 2025-06-04

Abstract: 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 Zr6 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.

DOI: 10.1038/s41557-025-01836-6

Source: https://www.nature.com/articles/s41557-025-01836-6