Shape‐Recognition in an Al‐MOF Enables High C 3 F 6 Adsorption and Size‐Sieving Separation of C 3 F 6 /C 3 F 8

ABSTRACT The purification of perfluoropropane (C 3 F 8 ) relies on the selective removal of trace perfluoropropylene (C 3 F 6 ), which remains challenging due to their similar physicochemical properties. Herein, we report a rigid Al‐based MOF, HIAM‐344, featuring nitrate‐regulated narrow pore windows and large cavities that enable simultaneous molecular sieving of C 3 F 6 /C 3 F 8 and high C 3 F 6 adsorption at low pressure. HIAM‐344 exhibits a record‐high C 3 F 6 uptake of 78.8 cm 3 g −1 at 298 K and 1 bar, and maintains a remarkably high capacity of 59.2 cm 3 g −1 at a low pressure of 0.01 bar. Dynamic breakthrough experiments demonstrate complete splitting of C 3 F 6 and C 3 F 8 , and direct production of electronic‐grade C 3 F 8 (>99.999%). Computational studies reveal that the outstanding separation performance originates from the synergistic size and shape recognition, as well as the favorable adsorbate‐adsorbent interactions.