Guo Lixia, Han Xue, Li Jiangnan, Li Weiyao, Chen Yinlin, Manuel Pascal, Schröder Martin, Yang Sihai
College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, 100871, China.
Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202417183. doi: 10.1002/anie.202417183. Epub 2024 Dec 27.
Purification and storage of acetylene (CH) are important to many industrial processes. The exploitation of metal-organic framework (MOF) materials to address the balance between selectivity for CH vs carbon dioxide (CO) against maximising uptake of CH has attracted much interest. Herein, we report that the synergy between unsaturated Cu(II) sites and functional groups, fluoro (-F), methyl (-CH), nitro (-NO) in a series of isostructural MOF materials MFM-190(R) that show exceptional adsorption and selectivity of CH. At 298 K, MFM-190(NO) exhibits an CH uptake of 216 cm g (320 cm g at 273 K) at 1.0 bar and a high selectivity for CH/CO (up to ~150 for v/v = 2/1) relevant to that in the industrial cracking stream. Dynamic breakthrough studies validate and confirm the excellent separation of CH/CO by MFM-190(NO) under ambient conditions. In situ neutron powder diffraction reveals the cooperative binding, packing and selectivity of CH by unsaturated Cu(II) sites and free -NO groups.
乙炔（CH）的纯化和储存对许多工业过程都很重要。利用金属有机框架（MOF）材料来解决对CH与二氧化碳（CO₂）的选择性之间的平衡，同时实现CH吸收量最大化，这已引起了广泛关注。在此，我们报告了一系列同构MOF材料MFM-190(R)中不饱和Cu(II)位点与官能团氟（-F）、甲基（-CH₃）、硝基（-NO₂）之间的协同作用，这些材料对CH表现出优异的吸附性能和选择性。在298 K时，MFM-190(NO₂)在1.0 bar下的CH吸收量为216 cm³ g⁻¹（在273 K时为320 cm³ g⁻¹），对CH/CO₂具有高选择性（对于v/v = 2/1，高达约150），与工业裂解流中的情况相关。动态突破研究验证并证实了MFM-190(NO₂)在环境条件下对CH/CO₂的出色分离效果。原位中子粉末衍射揭示了不饱和Cu(II)位点和游离-NO₂基团对CH的协同结合、堆积和选择性。
