An Unprecedented Pillar‐Cage Fluorinated Hybrid Porous Framework with Highly Efficient Acetylene Storage and Separation

Abstract Despite much intense investigation on the C 2 H 2 /CO 2 separation, the trade‐off between the adsorption capacity and separation selectivity is still tricky. To overcome the dilemma, we have rationally synthesized an ultra‐stable fluorinated hybrid porous material SIFSIX‐Cu‐TPA with the ith‐d topology. Completely differing from the famous pillar‐layer fluorinated materials, SIFSIX‐Cu‐TPA possesses a unique pillar‐cage structure, in which the SiF 6 2− anions cross‐link two adjacent metal nodes as pillars to stabilize the three‐dimensional framework constructed by icosahedral and tetrahedral cages. As anticipated, SIFSIX‐Cu‐TPA has high BET surface area (1330 m 2 g −1 ) as well as high C 2 H 2 uptake (185 cm 3 g −1 at 298 K and 1 bar). At the same time, due to the obvious difference in the adsorption performance of CO 2 and C 2 H 2 especially in the low pressure area, SIFSIX‐Cu‐TPA also exhibits an excellent C 2 H 2 /CO 2 separation performance (breakthrough time up to 68 min g −1 at 298 K and 1 bar).