Acetylene Separation by a Ca-MOF Containing Accessible Sites of Open Metal Centers and Organic Groups

Efficient separation of acetylene from a ternary acetylene-containing mixture is an important and vital task in petrochemical industry, which is difficult to achieve using a single material. Herein, a new Ca²⁺-based metal-organic framework (MOF) [Ca(dtztp)_0.5(DMA)]·2H₂O (1) was constructed using the N,O-donor ligand 2,5-di(2H-tetrazol-5-yl)terephthalic acid and the less-studied alkaline earth Ca²⁺ ions. The MOF shows a 3D honeycomb framework based on unique metal-carboxylate-azolate rod secondary building units. Owing to the presence of high-density organic hydrogen-bonding acceptors and open metal sites (OMSs), the activated MOF shows high adsorption capacity for C₂H₂ and selectivity for C₂H₂ over CO₂, C₂H₄, C₂H₆, and CH₄. Dynamic breakthrough experiments indicated the actual C₂H₂ separation potential of the MOF from binary (C₂H₂-C₂H₄ and C₂H₂-CO₂) and ternary (C₂H₂-C₂H₄-CO₂ and C₂H₂-C₂H₄-C₂H₆) mixtures. Simulations revealed that the synergistic interactions between the OMSs and N atoms in MOF and C₂H₂ molecules play an important role in the separation of C₂H₂.