Metal–Organic Framework with Cylindrical Pore Traps Exhibiting Unprecedented Purification of Octafluoropropane

Although adsorptive separation of hexafluoropropylene/octafluoropropane (C3F6/C3F8) mixture is of great significance for producing C3F8 electronic specialty gas, it remains an extremely challenging task. Here, a metal–organic framework (MOF) of Fe-phth-tpt with optimized pore cages enables selective capture of C3F6, achieving an impressive C3F6 uptake of 3.85 mmol g–1 at 0.1 bar and 298 K. Highly efficient C3F6/C3F8 separation is achieved by Fe-phth-tpt, affording the long breakthrough time of 57.1 min g–1 and high-purity C3F8 gas in one step with a record productivity of 564 cm3 g–1. The pore cages decorated with dense hydrogen atoms and aromatic rings offer multiple adsorption sites for binding C3F6. Additionally, the cylindrical pore cages show shape matching with C3F6 molecules that possess a nearly planar configuration. This work establishes an effective strategy for constructing MOFs with well-matched pores and multiple binding sites for C3F6 recognition, thereby enabling efficient purification of C3F8.