Sustainable Heterogeneous Catalysts for CO₂ Utilization by Using Dual Ligand Zn^II /Cd^II Metal-Organic Frameworks

Two-dimensional Zn^II /Cd^II -based dual ligand metal-organic frameworks (MOFs) {[M(CHDC)(L)]⋅H₂ O}_n involving 4-pyridyl carboxaldehyde isonicotinoylhydrazone (L) in combination with flexible 1,4-cyclohexanedicarboxylic acid (H₂ CHDC) as linkers have been synthesized by adaptable synthetic protocols including a green mechanochemical (grinding) method. Characterization, chemical/thermal stability, phase purity, and solid-state luminescent properties of both MOFs have been established by various analytical methods. Structural analysis revealed dimeric metal clusters composed of [M₂ (CHDC)₂ ]_n loops doubly pillared with L, generating a 2D framework. Both MOFs can be used as highly active solvent-free binary catalysts for CO₂ cycloaddition with epoxides in the presence of the co-catalyst tetrabutylammonium bromide (TBAB) with good catalytic conversion in up to six catalytic cycles without significant loss of activity. The present investigation demonstrates the application of MOFs as efficient heterogeneous catalysts for CO₂ utilization under moderate reaction conditions. Based on the single-crystal X-ray data, a probable mechanism for the cycloaddition reaction has also been proposed.