Construction of Fluorinated Propane-Trap in Metal-Organic Frameworks for Record Polymer-Grade Propylene Production...

Propane/propene (C₃ H₈ /C₃ H₆ ) separation is essential in the petrochemical industry but challenging because of their similar physical and chemical properties. Adsorptive separation with C₃ H₈ -selective porous materials can energy-efficiently produce high-purity C₃ H₆ , 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 C₃ H₈ -trap is successfully constructed. FDMOF-2 exhibits an unprecedented C₃ H₈ capture capacity of 140 cm³ cm^-3 and excellent C₃ H₈ /C₃ H₆ (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 C₃ H₈ , enabling excellent binding affinities. Breakthrough experiments demonstrate that C₃ H₈ can be directly extracted from various C₃ H₈ /C₃ H₆ mixtures with FDMOF-2, affording an outstanding C₃ H₆ 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.