Precise Pore Engineering of fcu-Type Y-MOFs for One-Step C2H4 Purification from Ternary C2H6/C2H4/C2H2 Mixtures

The purification of C₂H₄ from C₂H₆/C₂H₄/C₂H₂ mixtures is of great significance in the chemical industry for C₂H₄ production but remains a daunting task. Guided by powerful reticular chemistry principles, herein a systematic study is carried out to engineer pore dimensions and pore functionality of fcu-type Y-based metal–organic frameworks (Y-MOFs) through the construction of a series of eight new structures using linear dicarboxylate linkers with different length and functional groups. This study illustrates how delicate changes in pore size and pore surface chemistry can effectively influence the adsorption preference of C₂H₆, C₂H₄, and C₂H₂ by the MOFs. Importantly, clear relations between pore size/pore surface polarity and C₂ adsorption selectivities of this series of MOFs are established. In particular, HIAM-326 built on a linker decorated with trifluoromethoxy group shows notably preferential adsorption of C₂H₆ and C₂H₂ over C₂H₄, with balanced C₂H₂/C₂H₄ and C₂H₆/C₂H₄ selectivities. This endows the compound with the capability of one-step purification of C₂H₄ from C₂H₆/C₂H₄/C₂H₂ ternary mixtures, which is validated by breakthrough measurements where high purity C₂H₄ (99.9%+) can be obtained directly from the separation column. Its adsorption thermodynamics and underlying selective adsorption mechanisms are further revealed by ab initio calculations.