Boosting Ethane/Ethylene Separation by MOFs through the Amino‐Functionalization of Pores

Abstract Adsorption technology based on ethane‐selective materials is a promising alternative to energy‐intensive cryogenic distillation for separating ethane (C 2 H 6 ) and ethylene (C 2 H 4 ). We employed a pore engineering strategy to tune the pore environment of a metal–organic framework (MOF) through organic functional groups and boosted the C 2 H 6 /C 2 H 4 separation of the MOF. Introduction of amino (−NH 2 ) groups into Tb‐MOF‐76 not only decreased pore sizes but also facilitated multiple guest‐host interactions in confined pores. The NH 2 ‐functionalized Tb‐MOF‐76(NH 2 ) has increased C 2 H 6 and C 2 H 4 uptakes and C 2 H 6 /C 2 H 4 selectivity. The results of experimental and simulated transient breakthroughs reveal that Tb‐MOF‐76(NH 2 ) has significantly improved one‐step separation performance for C 2 H 6 /C 2 H 4 mixtures with a high C 2 H 4 (>99.95 %) productivity of 17.66 L kg −1 compared to 7.53 L kg −1 by Tb‐MOF‐76, resulting from the suitable pore confinement and accessible −NH 2 groups on pore surfaces.