A 44.610.8 topology hybrid ultramicroporous material (HUM), {[Cu1.5F(SiF6)(L)2.5]·G}n, (L = 4,4′‐bisimidazolylbiphenyl, G = guest molecules), 1, formed by cross‐linking interpenetrated 3D four‐connected CdSO4‐type nets with hexafluorosilicate anions is synthesized and evaluated in the context of gas sorption and separation herein. 1 is the first HUM functionalized with two different types of fluorinated sites (SiF62− and F− anions) lining along the pore surface. The optimal pore size (≈5 Å) combining mixed and high‐density electronegative fluorinated sites enable 1 to preferentially adsorb C2H2 over CO2 and C2H4 by hydrogen bonding interactions with a high C2H2 isosteric heat of adsorption (Qst) of ≈42.3 kJ mol−1 at zero loading. The pronounced discriminatory sorption behaviors lead to excellent separation performance for C2H2/CO2 and C2H2/C2H4 that surpasses many well‐known sorbents. Dynamic breakthrough experiments are conducted to confirm the practical separation capability of 1, which reveal an impressive separation factor of 6.1 for equimolar C2H2/CO2 mixture. Furthermore, molecular simulation and density functional theory (DFT) calculations validate the strong binding of C2H2 stems from the chelating fix of C2H2 between SiF62− anion and coordinated F− anion.

中文翻译：

---

用六氟硅酸盐阴离子交联 CdSO4 型网络形成超微孔材料，用于有效分离 C2H2/CO2 和 C2H2/C2H4


44.610.8拓扑混合超微孔材料（HUM），{[Cu1.5F(SiF6)(L)2.5]·G}n，（L = 4,4′-双咪唑基联苯，G =客体分子），1，由本文在气体吸附和分离的背景下合成并评估了具有六氟硅酸盐阴离子的交联互穿 3D 四连接 CdSO4 型网络。图 1 是第一个沿孔表面排列的具有两种不同类型氟化位点（SiF62− 和 F− 阴离子）功能化的 HUM。结合混合和高密度电负性氟化位点的最佳孔径 (≈5 Å) 使 1 能够通过氢键相互作用优先吸附 C2H2 而不是 CO2 和 C2H4，且 C2H2 等量吸附热 (Qst) 约为 42.3 kJ mol−1零负载时。明显的区别性吸附行为使 C2H2/CO2 和 C2H2/C2H4 具有优异的分离性能，超越了许多众所周知的吸附剂。进行了动态突破实验来证实 1 的实际分离能力，这表明等摩尔 C2H2/CO2 混合物的分离因子高达 6.1。此外，分子模拟和密度泛函理论 (DFT) 计算验证了 C2H2 的强结合源于 SiF62− 阴离子和配位 F− 阴离子之间 C2H2 的螯合固定。