Yu Han, David Brooks, Meng He, Yinlin Chen, Wenyuan Huang, Boya Tang, Bing An, Xue Han, Meredydd Kippax-Jones, Mark D. Frogley, Sarah J. Day, Stephen P. Thompson, Svemir Rudić, Yongqiang Cheng, Luke L. Daemen, Anibal J. Ramirez-Cuesta, Catherine Dejoie, Martin Schröder, Sihai Yang
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引用次数: 0
摘要
对金属有机框架(MOFs)进行官能化以增强对痕量苯的吸附仍然是一项重大挑战。在此,我们报告了一系列锆基 MOFs 在氯基功能化后对痕量苯的特殊吸附。值得注意的是,在 298 K 和 0.12 毫巴条件下,由含有氯基的蒽连接体构建的 MFM-68-Cl2 对苯的吸附量高达 4.62 mmol g-1,优于基准材料。原位同步辐射 X 射线衍射、傅立叶变换红外微光谱和非弹性中子散射以及密度泛函理论建模揭示了苯在这些材料中的结合机制。总体而言,MFM-68-Cl2 中的氯基团、优化的孔径、芳香族官能团和连接体的柔韧性之间的空前合作促进了苯吸附性能的提高。这项研究是多孔材料中 -CH-Cl 和 Cl---π 相互作用促进痕量苯吸附增强的首个实例。
Enhanced Benzene Adsorption in Chloro-Functionalized Metal–Organic Frameworks
The functionalization of metal–organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalized with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g–1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy, and inelastic neutron scattering, coupled with density functional theory modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by −CH···Cl and Cl···π interactions in porous materials.
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