Tailored Synergistic Binding Environment in Metal‐Organic Frameworks for Record One‐Step Ethylene Purification from Multicomponent Mixtures

Abstract Precise control over pore environments in porous materials remains a long‐standing challenge for efficient ethylene (C 2 H 4 ) purification via physisorption, particularly when targeting impurities with distinct physicochemical properties such as carbon dioxide (CO 2 ) and ethane (C 2 H 6 ). In this study, we report an isoreticular design strategy to fine‐tune the local pore chemistry of metal‐organic frameworks (MOFs), enabling the simultaneous selective adsorption of CO 2 and C 2 H 6 . Through rational organic ligand engineering, the hydroxyl‐functionalized analogue PCP‐TPA‐2OH (also termed as ZU‐925, ZU represents Zhejiang University) breaks the bottleneck of only C 2 H 6 capture exhibited by the parent PCP‐TPA. The tailored synergistic binding environment of ZU‐925 makes it be new benchmark in one‐step C 2 H 4 purification from CO 2 /C 2 H 6 /C 2 H 4 ternary mixtures. Ultra‐purity C 2 H 4 (99.99%) along with high productivity of 17.8 L kg −1 could be realized through only one‐step adsorption. Molecular simulations reveal that the preferential binding of C 2 H 6 arises from a tailored pore environment featuring aligned aromatic units and electronegative oxygen atoms, while Lewis basic hydroxyl groups locally modulate the pore chemistry, contributing to enhanced CO 2 capture. This study provides valuable insights into the design of advanced adsorbents for multiple impurity removal via isoreticular chemistry.