Synergistic C2H2 Binding Sites in Hydrogen-Bonded Supramolecular Framework for One-Step C2H4 Purification from Ternary C2 Mixture

Purification ofC(2)H(4) from the ternary C-2 hydrocarbon mixture in one step is of critical significance but still extremely challenging according to its intermediate physical properties between C2H6 and C2H2. Hydrogen-bonded organic frameworks (HOFs) stabilized by supramolecular interactions are emerging as a new kind of adsorbents that facilitate green separation. However, it remains a problem to efficiently realize the one-step C2H4 purification from C2H6/C2H4/C2H2 mixture because of the low C2H2/C2H4 selectivity. We herein report a robust microporous HOF (termed as HOF-TDCPB) with dense O atoms and aromatic rings distributed on the pore surface which provide C(2)H(6)and C(2)H(2 )preferred environment simultaneously. Dynamic breakthrough experiments indicate that HOF-TDCPB can not only obtain high-purity C(2)H(4)rom binary C-2 mixture, but also firstly realize one-step C(2)H(4 )purification from ternary C2H6/C2H4/C2H2 mixture, with the C2H4 productivity of 3.2 L/kg (>99.999 %) for one breakthrough cycle. Furthermore, HOF-TDCPB displays outstanding stability in air, organic solvents and water, which endow it excellent cycle performance even under high-humidity conditions. Theoretical calculations indicate that multiple O sites on pore channels can create synergistic binding sites for C2H2, thus affording overall stronger multipoint interactions.