Construction of Fluorinated Propane‐Trap in Metal–Organic Frameworks for Record Polymer‐Grade Propylene Production under High Humidity Conditions

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.