Tetranuclear CuIICluster as the Ten Node Building Unit for the Construction of a Metal–Organic Framework for Efficient C2H2/CO2Separation

Abstract Rational design of high nuclear copper cluster‐based metal–organic frameworks has not been established yet. Herein, we report a novel MOF ( FJU‐112 ) with the ten‐connected tetranuclear copper cluster [Cu 4 (PO 3 ) 2 ( μ 2 ‐H 2 O) 2 (CO 2 ) 4 ] as the node which was capped by the deprotonated organic ligand of H 4 L (3,5‐Dicarboxyphenylphosphonic acid). With BPE (1,2‐Bis(4‐pyridyl)ethane) as the pore partitioner, the pore spaces in the structure of FJU‐112 were divided into several smaller cages and smaller windows for efficient gas adsorption and separation. FJU‐112 exhibits a high separation performance for the C 2 H 2 /CO 2 separation, which were established by the temperature‐dependent sorption isotherms and further confirmed by the lab‐scale dynamic breakthrough experiments. The grand canonical Monte Carlo simulations (GCMC) studies show that its high C 2 H 2 /CO 2 separation performance is contributed to the strong π‐complexation interactions between the C 2 H 2 molecules and framework pore surfaces, leading to its more C 2 H 2 uptakes over CO 2 molecules.