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

Despite much intense investigation on the C2H2/CO2 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 SiF62− 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 m2 g−1) as well as high C2H2 uptake (185 cm3 g−1 at 298 K and 1 bar). At the same time, due to the obvious difference in the adsorption performance of CO2 and C2H2 especially in the low pressure area, SIFSIX‐Cu‐TPA also exhibits an excellent C2H2/CO2 separation performance (breakthrough time up to 68 min g−1 at 298 K and 1 bar). [ABSTRACT FROM AUTHOR]