Song Kunpeng, Bi Xue, Yu Chuang, Pan Ye-Tang, Vahabi Henri, Realinho Vera, He Jiyu, Yang Rongjie
National Engineering Research Center of Flame Retardant Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China.
CentraleSupélec, LMOPS, Université de Lorraine, F-57000 Metz, France.
ACS Appl Mater Interfaces. 2024 Feb 14;16(6):7617-7630. doi: 10.1021/acsami.3c17625. Epub 2024 Feb 5.
Up to now, metal-organic frameworks (MOFs) with open nanostructures have shown outstanding capabilities in trapping smoke particles compared to the original MOFs. However, only a few MOF-based strategies have been reported to synthesize hierarchical porous cages thus far, which are mainly restricted to environmentally unfriendly wet-chemical liquid methods. Herein, as a proof-of-concept, a gas-steamed metal-organic framework approach was designed to fabricate a series of cheeselike open cages with hierarchical porosity. Briefly, zeolitic imidazolate framework-67 (ZIF-67) and phytic acid were employed as precursor and etchant, respectively. Abandoning the conventional wet-chemical method, the coordination bond of ZIF-67 was cleaved by acidic steam, forming an open framework with a high specific surface area and a hierarchical porous structure. The universality of this method was also confirmed by the selection of different etchants. Impressively, they also show outstanding fume-toxic adsorption capability and labyrinth effects based on abundant and complex porous channels. At only 5 wt % loading, CoO@open ZIF-67 cage-2 (CoO@OZC-2) imparted polyurea (PUA) composites with a 21.2% limiting oxygen index, and the peak of heat release rate, total heat release, and total smoke production were reduced by around 37.5, 25.5, and 40.4%, respectively, compared to neat PUA. This work will shed light on the advanced structural design of polymer composites with high fire safety, especially smoke suppression performance, so as to obtain more feasible applications.
到目前为止,与原始金属有机框架(MOF)相比,具有开放纳米结构的MOF在捕获烟雾颗粒方面表现出卓越的能力。然而,迄今为止,仅有少数基于MOF的策略被报道用于合成分级多孔笼,这些策略主要局限于对环境不友好的湿化学液相法。在此,作为概念验证,设计了一种气相蒸镀金属有机框架方法来制备一系列具有分级孔隙率的奶酪状开放笼。简而言之,分别使用沸石咪唑酯框架-67(ZIF-67)和植酸作为前驱体和蚀刻剂。摒弃传统的湿化学方法,ZIF-67的配位键被酸性蒸汽裂解,形成具有高比表面积和分级多孔结构的开放框架。通过选择不同的蚀刻剂也证实了该方法的通用性。令人印象深刻的是,基于丰富且复杂的多孔通道,它们还表现出出色的烟雾毒性吸附能力和迷宫效应。仅在5 wt%的负载量下,CoO@开放ZIF-67笼-2(CoO@OZC-2)赋予聚脲(PUA)复合材料21.2%的极限氧指数,与纯PUA相比,热释放速率峰值、总热释放量和总烟雾生成量分别降低了约37.5%、25.5%和40.4%。这项工作将为具有高消防安全性能,特别是抑烟性能的聚合物复合材料的先进结构设计提供启示,从而获得更可行的应用。