Molecular Sieving of Acetylene from Ethylene in a Rigid Ultra‐microporous Metal Organic Framework.

Abstract Rigid molecular sieving materials are the ideal candidates for gas separation (e. g., C2H2/C2H4) due to their ultrahigh adsorption selectivity and the absence of gas co‐adsorption. However, the absolute molecular sieving effect for C2H2/C2H4 separation has rarely been realized because of their similar physicochemical properties. Herein, we demonstrate the absolute molecular sieving of C2H2 from C2H4 by a rigid ultra‐microporous metal‐organic framework (F−PYMO−Cu) with 1D regular channels (pore size of ca. 3.4 Å). F−PYMO−Cu exhibited moderate acetylene uptake (35.5 cm3/cm3), but very low ethylene uptake (0.55 cm3/cm3) at 298 K and 1 bar, yielding the second highest C2H2/C2H4 uptake ratio of 63.6 up to now. One‐step C2H4 production from a binary mixture of C2H2/C2H4 and a ternary mixture of C2H2/CO2/C2H4 at 298 K was achieved and verified by dynamic breakthrough experiments. Coupled with excellent thermal and water stability, F−PYMO−Cu could be a promising candidate for industrial C2 separation tasks.