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

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) as well as high C 2 H 2 uptake (185 cm 3 /g 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 at 298K and 1 bar).