Adsorption Site Selective Occupation Strategy within a Metal–Organic Framework for Highly Efficient Sieving Acetylene from Carbon Dioxide

Abstract The separation of acetylene and carbon dioxide is an essential but challenging process owing to the similar molecular sizes and physical properties of the two gas molecules. Notably, these molecules usually exhibit different orientations in the pore channel. We report an adsorption site selective occupation strategy by taking advantage of differences in orientation to sieve the C 2 H 2 from CO 2 in a judiciously designed amine‐functionalized metal–organic framework, termed CPL‐1‐NH 2 . In this material, the incorporation of amino groups not only occupies the adsorption sites of CO 2 molecules and shields the interaction of uncoordinated oxygen atom and CO 2 molecules resulting in a negligible adsorption amount and a decrease in enthalpy of adsorption but also strengthened the binding affinity toward C 2 H 2 molecules. This material thus shows an extremely high amount of C 2 H 2 at low pressure and a remarkably high C 2 H 2 /CO 2 IAST selectivity (119) at 1 bar and 298 K.