Ionic‐Liquid‐Functionalized UiO‐66 Framework: An Experimental and Theoretical Study on the Cycloaddition of CO2 and Epoxides

A facile approach for modifying the UiO-66-NH₂ metal-organic framework by incorporating imidazolium-based ionic liquids (ILs) to form bifunctional heterogeneous catalysts for the cycloaddition of epoxides to CO₂ is reported. Methylimidazolium- and methylbenzimidazolium-based IL units (ILA and ILB, respectively) were introduced into the pore walls of the UiO-66-NH₂ framework through a condensation reaction to generate ILA@U6N and ILB@U6N catalysts, respectively. The resultant heterogeneous catalysts, especially ILA@U6N, exhibited excellent CO₂ adsorption capability, which makes them effective for cycloaddition reactions producing cyclic carbonates under mild reaction conditions in the absence of any cocatalyst or solvent. The significantly enhanced activity of ILA@U6N is attributed to the synergism between the coordinately unsaturated Lewis acidic Zr⁴⁺ centers and Br^- ions in the bifunctional heterogeneous catalysts. The size effect of the ILs on coupling between the epoxide and CO₂ was also studied for ILA@U6N and ILB@U6N. A periodic DFT study was performed to provide evidence of possible intermediates, transition states, and pathways, as well as to gain deeper insight into the mechanism of the ILA@U6N-catalyzed cycloaddition reaction between epichlorohydrin and CO₂ .