Partial Linker Substitution Strategy to Construct a Quaternary HKUST-like MOF for Efficient Acetylene Storage and...

Multicomponent metal-organic frameworks (MOFs) have received much attention as emerging materials capable of precisely programing exquisite structures and specific functions. Here, we applied a partial linker substitution strategy to compile an HKUST-1-like quaternary MOF by introducing a bifunctional ligand into the well-known HKUST-1 structure. FUT-1, a new HKUST-like topology MOF, was assembled with paddlewheel [Cu₂(COO)₄], triangular metallocycle pyrazole cluster Cu₃(μ₃-OH) (NN)₃ building blocks, and two distinct linkers. FUT-1 exhibited good mechanical stability, water stability, and chemical stability (pH = 3-12) in aqueous solutions. Moreover, the porous environments created by this multicomponent primitive endow FUT-1 with high C₂H₂ storage and significantly selective separation performance of C₂H₂/CO₂. Dynamic breakthrough experiments and ideal adsorbed solution theory calculations further demonstrate that FUT-1 can selectively capture C₂H₂ from C₂H₂/CO₂ mixtures under ambient conditions. Based on grand canonical Monte Carlo simulations, the high C₂H₂ separation performance of FUT-1 is attributed to the π-complex formed between the C₂H₂ molecule and the trinuclear metallocycle clusters on the wall, which provides stronger affinity for C₂H₂ recognition than the CO₂ molecule.