Optimizing the Adsorptive Separation of Three‐Component C2 Hydrocarbons by Pore Environment Regulation in Metal–Organic Frameworks

One‐step adsorptive purification of ethylene (C 2 H 4 ) from C2 ternary hydrocarbon mixtures containing acetylene (C 2 H 2 ) and ethane (C 2 H 6 ) remains a fundamental challenge as it involves simultaneously selective adsorption of C 2 H 6 over C 2 H 4 and C 2 H 2 over C 2 H 4 . Here, we report the successful practice of a Nanopore Environment Engineering approach within isoreticular metal–organic frameworks (MOFs) that enables optimal separation of C2 ternary mixtures. Using a pair of pyrimidine‐bridged tetracarboxylate ligands bearing either methyl (─CH 3 ) or amino (─NH 2 ) groups, we synthesized two csq ‐type Zr‐MOFs, HIAM‐411 and HIAM‐412, with modulated nanopore environments. While HIAM‐411 displays selective adsorption of C 2 H 2 and C 2 H 6 over C 2 H 4 , its separation efficiency is largely restricted by the relatively low C 2 H 2 /C 2 H 4 selectivity. In contrast, the amino‐functionalized HIAM‐412 exhibited significantly strengthened hydrogen bonding interactions with C 2 H 2 , achieving an approximately 3‐fold enhancement in the productivity of the high‐purity C 2 H 4 . Our study highlights the critical role of nanopore environment regulation in optimizing the multicomponent separation performance of C2 hydrocarbons.