Ethylene (C₂H₄) and propylene (C₃H₆) are important energy sources and raw materials in the chemical industry. Storage and separation of C₂H₄ and C₃H₆ are vital to their practical application. Metal–organic frameworks (MOFs) having adjustable structures and pore environments are promising candidates for C₃H₆/C₂H₄ separation. Herein, we obtained a Cu-based MOF synthesized by H₃TTCA and pyrazine ligands. By adding different functional groups on the ligands within the MOFs, their pore environments are adjusted, and thus, the C₃H₆ storage capacity and C₃H₆/C₂H₄ separation efficiency are improved. Eventually, the fluoro- and methyl-functionalized iso-MOF-4 exhibits a better gas storage and C₃H₆/C₂H₄ separation performance compared with iso-MOF-1 (nonfunctionalized), iso-MOF-2 (fluoro-functionalized), and iso-MOF-3 (methyl-functionalized). A record-high C₃H₆ uptake of 293.6 ± 2.3 cm³ g^–1 (273 K, 1 atm) is achieved using iso-MOF-4. Moreover, iso-MOF-4 shows excellent repeatability, and only 3.5% of C₃H₆ storage capacities decrease after nine cycles. Employing Grand Canonical Monte Carlo (GCMC) simulations, it is indicated that iso-MOF-4 preferentially adsorbs C₃H₆ rather than C₂H₄ at low pressure. Single-crystal X-ray diffraction on C₃H₆-adsorbed iso-MOF-4 crystals precisely demonstrates the adsorption positions and arrangement of C₃H₆ molecules in the framework, which is consistent with the theoretical simulations. Remarkably, gas sorption isotherms, molecular simulations, and breakthrough experiments comprehensively demonstrate that this unique MOF material exhibits highly efficient C₃H₆/C₂H₄ separation. Additionally, iso-MOF-4 also possesses efficient separation of C₃H₈/CH₄ and C₂H₆/CH₄, indicating its promising potential in storage/separation of light hydrocarbons in industry.

Three versatile amino-functionalized In^III/Al^III/Zr^IV-MOFs with high-physicochemical stability for gas storage/separation, water purification and catalysis.

Dynamic response of flexible MOF for gas storage and separation.