近日，浙江师范大学张袁斌团队研究了由一维配位聚合物组装的用于高效气体脱水的三维氢键有机框架。2025年8月26日出版的《德国应用化学》杂志发表了这项成果。

二维（2D）和三维（3D）孔隙配位聚合物因其孔隙性质和气体分离性而被广泛探索，但一维（1D）材料由于依赖于较弱的非共价相互作用来维持永久孔隙度而被探索得很少。近年来，通过协同弱相互作用构建多孔氢键有机框架（HOFs）的研究取得了重大进展，这为人们探索以一维配位聚合物（CPs）为主题的多孔氢键有机框架及其多功能特性提供了前景和动力。

在这项工作中，研究组提出了这样一个HOF， [Cu(bpy)(H₂PO₄)H₂O]_n （ZNU-30）由线性CP通过氢键C─H…π和π -π相互作用。在373 K真空条件下热活化后，ZNU-30发生可逆的单晶到单晶转变，生成具有一维通道的ZNU-30a。值得注意的是，ZNU-30a具有优异的亲水性，在低湿度下具有相当大的吸水性，快速的吸附-脱附动力学，温和的再生条件，以及超过100次吸附-脱附循环的出色循环稳定性。

单组分气体吸附等温线显示出独特的分子筛分行为，在298 K下，通过CO₂和C₁─C₃烯烃/烷烃（CH₄、C₂H₄、C₂H₆、C₃H₆和C₃H₈）优先吸附水(100mg g^-1)。单晶结构分析和DFT计算表明，框架内的多个氢键相互作用促进了水的选择性吸附。突破性实验进一步证实了该材料能够有效地从CH₄和其他气体中分离微量水蒸气的能力。

附：英文原文

Title: 3D Hydrogen-Bonded Organic Framework Assembled From 1D Coordination Polymers for Efficient Gas Dehydration

Author: Yingzhi He, Lingyao Wang, Yunjia Jiang, Guangzu Xiong, Banglin Chen, Yuanbin Zhang

Issue&Volume: 2025-08-26

Abstract: Two -(2D) and three-dimensional (3D) porous coordination polymers have been extensively explored for their porous nature and thus gas separation, but one-dimensional (1D) materials remain much less explored due to their reliance on weaker, non-covalent interactions to sustain the permanent porosity. Recent significant advances on the construction of porous hydrogen-bonded organic frameworks (HOFs) through synergistic weak interactions have provided us with the promise and motivated us to explore porous HOFs using 1D coordination polymers (CPs), and their multifunctional properties. In this work, we present such a HOF, [Cu(bpy)(H2PO4)H2O]n (ZNU-30), constructed from a linear CP via hydrogen bonds, C─Hπ, and π–π interactions. Upon thermal activation at 373 K under vacuum, ZNU-30 undergoes a reversible single-crystal-to-single-crystal transformation, yielding ZNU-30a with 1D channels. Notably, ZNU-30a exhibits exceptional hydrophilicity, featuring considerable water uptake at low humidity, rapid adsorption–desorption kinetics, mild regeneration conditions, and outstanding cycling stability over 100 adsorption–desorption cycles. Single-component gas adsorption isotherms reveal unique molecular sieving behavior, with preferential adsorption of water (100 mg g1) over CO2 and C1─C3 alkene/alkanes (CH4, C2H4, C2H6, C3H6, and C3H8) at 298 K. Single-crystal structural analysis and DFT calculations indicate that the selective adsorption of H2O is facilitated by multiple hydrogen-bonding interactions within the framework. Breakthrough experiments further confirm the material's ability to efficiently separate trace water vapor from CH4 and other gases.

DOI: 10.1002/anie.202515257

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202515257