Construction of Fluorinated Propane‐Trap in Metal–Organic Frameworks for Record Polymer‐Grade Propylene Production under High Humidity Conditions
Yong Wang, Tong Li, Libo Li, Rui‐Biao Lin, Xiaoxia Jia, Zeyu Chang, Hui‐Min Wen, Xiao‐Ming Chen, Jinping Li
Abstract
Abstract Propane/propene (C 3 H 8 /C 3 H 6 ) separation is essential in the petrochemical industry but challenging because of their similar physical and chemical properties. Adsorptive separation with C 3 H 8 ‐selective porous materials can energy‐efficiently produce high‐purity C 3 H 6 , which is highly promising for replacing conventional cryogenic distillation but suffers from unsatisfactory performance. Herein, through the precise incorporation of fluorinated functional groups into the confined pore space, a new fluorinated metal–organic framework (FDMOF‐2) featuring the unique and strong C 3 H 8 ‐trap is successfully constructed. FDMOF‐2 exhibits an unprecedented C 3 H 8 capture capacity of 140 cm 3 cm −3 and excellent C 3 H 8 /C 3 H 6 (1:1, v/v) selectivity up to 2.18 (298 K and 1 bar), thus setting new benchmarks for all reported porous materials. Single‐crystal X‐ray diffraction studies reveal that the tailored pore confinement in FDMOF‐2 provides stronger and multiple attractive interactions with C 3 H 8 , enabling excellent binding affinities. Breakthrough experiments demonstrate that C 3 H 8 can be directly extracted from various C 3 H 8 /C 3 H 6 mixtures with FDMOF‐2, affording an outstanding C 3 H 6 production (501 mmol L −1 ) with over 99.99% purity. Benefiting from the robust framework and hydrophobic ligands, the separation performance of FDMOF‐2 can be well maintained even under 70% relative humidity conditions.