Aromaticity Regulation in Isostructural Metal‐Organic Frameworks for Propyne Storage and Propylene Purification
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 YangABSTRACT
We report the exceptional propyne (C 3 H 4 ) storage and propylene (C 3 H 6 ) 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 C 3 H 4 adsorption of 250 cm 3 cm −3 at 298 K and 1 bar, representing a benchmark sorbent for C 3 H 4 . Additionally, the supramolecular interactions enable fine thermodynamic discrimination for alkenes, resulting in excellent separation of C 2 H 4 /C 3 H 6 ( v / v = 1/1), delivering simultaneously high productivities of C 3 H 6 and C 2 H 4 (267 and 174 L kg −1 , respectively; C 2 H 4 purity > 99.9 %). Effective separation of C 3 H 6 /C 3 H 8 ( v / v = 1/1) and C 3 H 4 /C 3 H 6 ( v / v = 1/99) with a high C 3 H 6 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.