Lee Dennis T, Jamir Jovenal D, Peterson Gregory W, Parsons Gregory N
Department of Chemical and Biomolecular Engineering, North Carolina State University, 911 Partners Way, Raleigh, NC, 27695, USA.
Edgewood Chemical Biological Center, 5183 Blackhawk Road, Aberdeen Proving Ground, MD, 21010, USA.
Small. 2019 Mar;15(10):e1805133. doi: 10.1002/smll.201805133. Epub 2019 Feb 1.
Abatement of chemical hazards using adsorptive metal-organic frameworks (MOFs) attracts substantial attention, but material stability and crystal integration into functional systems remain key challenges. Herein, water-stable, polymer fiber surface-oriented M-TCPP [M = Cu, Zn, and Co; H TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin] 2D MOF crystals are fabricated using a facile hydroxy double salt (HDS) solid-source conversion strategy. For the first time, Cu-TCPP is formed from a solid source and confirmed to be highly adsorptive for NH and 2-chloroethyl ethyl sulfide (CEES), a blistering agent simulant, in humid (80% relative humidity (RH)) conditions. Moreover, the solid HDS source is found as a unique new approach to control MOF thin-film crystal orientation, thereby facilitating radially arranged MOF crystals on fibers. On a per unit mass of MOF basis in humid conditions, the MOF/fiber composite enhances NH adsorptive capacity by a factor of 3 compared to conventionally prepared MOF powders. The synthesis route extends to other MOF/fiber composite systems, therefore providing a new route for chemically protective materials.
使用吸附性金属有机框架（MOF）减轻化学危害引起了广泛关注，但材料稳定性以及晶体与功能系统的整合仍然是关键挑战。在此，通过简便的羟基复盐（HDS）固源转化策略制备了水稳定的、聚合物纤维表面取向的M-TCPP [M = 铜、锌和钴；H TCPP = 5,10,15,20-四（4-羧基苯基）卟啉]二维MOF晶体。首次从固体源形成了Cu-TCPP，并证实其在潮湿（80%相对湿度（RH））条件下对NH和模拟起泡剂2-氯乙基乙基硫醚（CEES）具有高度吸附性。此外，发现固体HDS源是控制MOF薄膜晶体取向的一种独特新方法，从而有利于在纤维上形成径向排列的MOF晶体。在潮湿条件下，以每单位质量的MOF计，与传统制备的MOF粉末相比，MOF/纤维复合材料的NH吸附容量提高了3倍。该合成路线可扩展到其他MOF/纤维复合系统，因此为化学防护材料提供了一条新途径。
