A Microporous Hydrogen-Bonded Organic Framework with Open Pyrene Sites Isolated by Hydrogen-Bonded Helical Chains for Efficient Separation of Xenon and Krypton

Achieving efficient xenon/krypton (Xe/Kr) separation in emerging hydrogen-bonded organic frameworks (HOFs) is highly challenging because of the lack of gas-binding sites on their pore surfaces. Herein, we report the first microporous HOF (HOF-FJU-168) based on hydrogen-bonded helical chains, which prevent self-aggregation of the pyrene core, thereby preserving open pyrene sites on the pore surfaces. Its activated form, HOF-FJU-168a is capable of separating Xe/Kr under ambient conditions while achieving an excellent balance between adsorption capacity and selectivity. At 296 K and 1 bar, the Xe adsorption capacity of HOF-FJU-168a reached 78.31 cm³/g, with an Xe/Kr IAST selectivity of 22.0; both values surpass those of currently known top-performing HOFs. Breakthrough experiments confirmed its superior separation performance with a separation factor of 8.6 and a yield of high-purity Kr (> 99.5%) of 184 mL/g. Furthermore HOF-FJU-168 exhibits excellent thermal and chemical stability, as well as renewability. Single-crystal X-ray diffraction and molecular modeling revealed that the unique electrostatic surface potential around the open pyrene sites creates a micro-electric field, exerting a stronger polarizing effect on Xe than on Kr, thereby enhancing host-Xe interactions.