Cai Youlie, Zheng Yanchun, Chen Yiqi, Wei Runzhi, Xu Hui, Gao Junkuo
School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China.
Institute of Optoelectronic Materials and Devices, China Jiliang University, Hangzhou 310018, China.
Chem Bio Eng. 2024 Feb 1;1(7):615-622. doi: 10.1021/cbe.3c00100. eCollection 2024 Aug 22.
Developing robust microporous hydrogen-bonded organic frameworks (HOFs) is crucial for exploring novel physical adsorbents and revealing the structure-property relationship of hydrogen-bonding pairing behaviors. However, it is still challenging to obtain dense and stable hydrogen-bonded frameworks due to the rigidity and spatial resistance of the tectonic centers. Herein, we report a robust microporous HOF (HOF-ZSTU-4) via 4,4',4',4″-([1,1'-biphenyl]-4,4'-diylbis(azanetriyl))tetrabenzoic acid (HBDATB) with flexible nitrogen nodes composing the tectonic center. Single-crystal X-ray diffraction (SCXRD) analysis shows that the activated framework undergoes a solid-to-solid phase transition because of the torsion of the carboxyl-carboxyl dimer, leading to the switching of the framework from the topology to the topology (HOF-ZSTU-4a). The single-component gas sorption isotherm reveals that HOF-ZSTU-4a has a CH packing density of 0.54 kg L, marking it as the most efficient among reported HOFs. In addition, HOF-ZSTU-4a exhibits promising separation selectivity for several binary gas mixtures, and the dynamic separation performance for CH/CO, CO/N, and CH/N is verified by dynamic breakthrough experiments.
开发坚固的微孔氢键有机框架（HOFs）对于探索新型物理吸附剂和揭示氢键配对行为的结构-性能关系至关重要。然而，由于构造中心的刚性和空间阻力，获得致密且稳定的氢键框架仍然具有挑战性。在此，我们通过具有构成构造中心的柔性氮节点的4,4',4',4″-（[1,1'-联苯]-4,4'-二基双（氮杂三基））四苯甲酸（HBDATB）报道了一种坚固的微孔HOF（HOF-ZSTU-4）。单晶X射线衍射（SCXRD）分析表明，由于羧基-羧基二聚体的扭转，活化后的框架经历了固-固相变，导致框架从拓扑结构转变为拓扑结构（HOF-ZSTU-4a）。单组分气体吸附等温线表明，HOF-ZSTU-4a的CH堆积密度为0.54 kg/L，是已报道的HOFs中效率最高的。此外，HOF-ZSTU-4a对几种二元气体混合物表现出有前景的分离选择性，并且通过动态突破实验验证了其对CH/CO、CO/N₂和CH/N₂的动态分离性能。
