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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Effect of catenation and basicity of pillared ligands on the water stability of MOFs
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Effect of catenation and basicity of pillared ligands on the water stability of MOFs

机译：柱状配体的串联和碱性对MOFs水稳定性的影响

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摘要

Metal-organic frameworks (MOFs) have extremely high surface areas and pore volumes, tunable pore sizes and chemical functionalities and are an interesting addition to the field of porous materials. One of the key challenges that needs to be overcome to elevate MOFs to the applied level is their sensitivity to humid environments. The work reported here seeks to address this critical issue by examining two important contributors to MOF stability or instability: basicity (pK_a value) of the pillar ligand and catenation of the framework. Catenation is the interpenetration or interweaving of two or more identical and independent frameworks. We demonstrate that, using catenation in combination with a pillaring strategy, it is possible to obtain water stable MOFs even when the pillar ligand has lower basicity (pK_a value). This study shows that after 90% relative humidity (RH) exposure, comparing Zn-BDC-DABCO (DMOF) and Zn-BDC-BPY (MOF-508), MOF-508 is stable due to its two-fold interpenetration that prevents significant water adsorption. In contrast, comparing non-catenated isostructural pillared MOFs Zn-TMBDC-DABCO (DMOF-TM) and Zn-TMBDC-BPY (MOF-508-TM), MOF-508-TM is unstable since BPY is less basic (higher pK_a) and less rigid than DABCO.
机译：金属有机骨架（MOF）具有极高的表面积和孔体积，可调节的孔径和化学功能，是多孔材料领域的一个有趣的补充。将MOF提升到应用水平需要克服的关键挑战之一是它们对潮湿环境的敏感性。本文报道的工作旨在通过研究导致MOF稳定性或不稳定性的两个重要因素来解决这个关键问题：支柱配体的碱性（pK_a值）和框架的级联。链接是两个或多个相同且独立的框架的互穿或交织。我们证明，结合使用立柱化策略，即使立柱配体的碱度较低（pK_a值），也可以获得水稳定的MOF。这项研究表明，在暴露于90％的相对湿度（RH）之后，将Zn-BDC-DABCO（DMOF）和Zn-BDC-BPY（MOF-508）进行比较，由于其双重互穿性，MOF-508是稳定的，可防止水吸附。相反，比较未分类的等结构柱状MOF Zn-TMBDC-DABCO（DMOF-TM）和Zn-TMBDC-BPY（MOF-508-TM），由于BPY的碱性较低（pK_a较高），因此MOF-508-TM不稳定。而且比DABCO的刚性要小

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