Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14850, United States.
Computational Science Research Center, Korea Institute of Science and Technology (KIST), Seoul 02792, Republic of Korea.
ACS Appl Mater Interfaces. 2022 Dec 7;14(48):53928-53935. doi: 10.1021/acsami.2c17966. Epub 2022 Nov 22.
Chlorine (Cl) is a toxic and corrosive gas that is both an essential reagent in industry and a potent chemical warfare agent. Materials that can strongly bind Cl at low pressures are essential for industrial and civilian personal protective equipment (PPE). Herein, we report the first examples of irreversible Cl capture via the dichlorination of alkene linkages in Zr-based metal-organic frameworks. Frameworks constructed from fumarate (Zr-fum) and stilbene (Zr-stilbene) linkers retain long-range order and accessible porosity after alkene dichlorination. In addition, energy-dispersive X-ray spectroscopy reveals an even distribution of Cl throughout both materials after Cl capture. Cl uptake experiments reveal high irreversible uptake of Cl (>10 wt %) at low partial pressures (<100 mbar), particularly in Zr-fum. In contrast, traditional porous carbons mostly display reversible Cl capture, representing a continued risk to users after exposure. Overall, our results support that alkene dichlorination represents a new pathway for reactive Cl capture, opening new opportunities for binding this gas irreversibly in PPE.
氯（Cl）是一种有毒且具有腐蚀性的气体，既是工业中重要的试剂，也是一种强力的化学战剂。在低压力下能够强烈结合 Cl 的材料，对于工业和民用个人防护设备（PPE）而言至关重要。在此，我们报告了首例通过 Zr 基金属有机骨架中烯烃键的二氯化作用来实现不可逆 Cl 捕获的例子。由富马酸盐（Zr-fum）和联苯（Zr-stilbene）链接构建的骨架在烯烃二氯化后仍保持远程有序和可及的孔隙率。此外，能谱分析揭示了 Cl 在两种材料中的均匀分布。Cl 吸收实验表明，在低分压（<100 毫巴）下，Cl 的不可逆吸收量很高（>10wt%），尤其是在 Zr-fum 中。相比之下，传统的多孔碳主要显示出可逆的 Cl 捕获，这代表着在暴露后对使用者仍存在持续的风险。总的来说，我们的结果表明烯烃二氯化作用代表了一种新的反应性 Cl 捕获途径，为在 PPE 中不可逆地结合这种气体开辟了新的机会。
