Chen Shoushun, Zhang Zelin, Chen Wei, Lucier Bryan E G, Chen Mansheng, Zhang Wanli, Zhu Haihong, Hung Ivan, Zheng Anmin, Gan Zhehong, Lei Dongsheng, Huang Yining
Lanzhou Magnetic Resonance Center, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
School of Physical Science and Technology, Electron Microscopy Centre of Lanzhou University, Lanzhou University, Lanzhou, 730000, China.
Nat Commun. 2024 Dec 30;15(1):10776. doi: 10.1038/s41467-024-54493-7.
Metal-organic frameworks (MOFs) are a class of porous materials that are of topical interest for their utility in water-related applications. Nevertheless, molecular-level insight into water-MOF interactions and MOF hydrolytic reactivity remains understudied. Herein, we report two hydrolytic pathways leading to either structural stability or framework decomposition of a MOF (ZnMOF-1). The two distinct ZnMOF-1 water reaction pathways are linked to the diffusion rate of incorporated guest dimethylformamide (DMF) molecules: slow diffusion of DMF triggers evolution of the initial MOF into a water-stable MOF product exhibiting enhanced water adsorption, while fast exchange of DMF with water leads to decomposition. The starting MOF, three intermediates from the water reaction pathways and the final stable MOF have been characterized. The documentation of two distinct pathways counters the stereotype that water exposure always leads to destruction or degradation of water-sensitive MOFs, and demonstrates that water-stable MOFs with improved adsorption properties can be prepared via controlled solvent-triggered structural rearrangement.
金属有机框架材料（MOFs）是一类多孔材料，因其在与水相关的应用中的效用而备受关注。然而，对水与MOF相互作用以及MOF水解反应活性的分子层面的认识仍未得到充分研究。在此，我们报告了导致一种MOF（ZnMOF-1）结构稳定性或框架分解的两条水解途径。这两条不同的ZnMOF-1与水的反应途径与掺入的客体二甲基甲酰胺（DMF）分子的扩散速率有关：DMF的缓慢扩散促使初始MOF演变成具有增强水吸附能力的水稳定MOF产物，而DMF与水的快速交换则导致分解。已对起始MOF、水反应途径中的三种中间体以及最终的稳定MOF进行了表征。这两条不同途径的记录反驳了水暴露总是导致对水敏感的MOFs破坏或降解的刻板印象，并表明可以通过可控的溶剂引发的结构重排制备具有改善吸附性能的水稳定MOFs。
