Yukun Ye, Lixia Guo, Jiarui Fan, Zhixin Wang, Zhaozhao Hu, Ruohan Li, Siyu Zhou, Lifei Lin, Yiheng Wang, Mark R Warren, Ben Coulson, Pascal Manuel, Sarah J Day, Eamonn T Connolly, Jiangnan Li, Sihai Yang
We report the exceptional propyne (C3H4) storage and propylene (C3H6) purification in a metal-organic framework, PKU-101, controlled via regulation of aromaticity. The pyrene-fused pore interior of PKU-101 provides multiple C─H···π interactions for alkyne, resulting in a record C3H4 adsorption of 250 cm3 cm-3 at 298 K and 1 bar, representing a benchmark sorbent for C3H4. Additionally, the supramolecular interactions enable fine thermodynamic discrimination for alkenes, resulting in excellent separation of C2H4/C3H6 (v/v = 1/1), delivering simultaneously high productivities of C3H6 and C2H4 (267 and 174 L kg-1, respectively; C2H4 purity > 99.9 %). Effective separation of C3H6/C3H8 (v/v = 1/1) and C3H4/C3H6 (v/v = 1/99) with a high C3H6 productivity of 532 L kg-1 (purity of 99.99 %) has also been achieved by PKU-101. In situ crystallographic and spectroscopic studies confirmed the key role of enhanced aromaticity on the discrimination of alkanes/alkenes/alkynes. Importantly, these weak supramolecular interactions enable complete regeneration at only 318 K.