N‐Heterocyclic Carbene Ag(I)–Based UiO‐67 Metal‐Organic Frameworks for the CO 2 Conversion to Cyclic Carbonates under Mild Conditions

The preparation of cyclic carbonate from CO 2 is one of the effective ways to utilize its resources. Herein, a series of N‐heterocyclic carbenes (NHCs) Ag(I)–based UiO‐67‐type metal‐organic frameworks (MOFs), UiO‐bpdc‐NHC/Ag, UiO‐(bpdc‐NH 2 )‐NHC/Ag, and UiO‐(bpdc‐F 3 )‐NHC/Ag are reported. These MOFs are characterized using powder X‐ray diffraction, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and 19 F NMR (nuclear magnetic resonance), confirming Ag(I) integration. Among them, due to the affinity of trifluorocarbonamide group for CO 2 and the high activity of NHC/Ag, UiO‐(bpdc‐F 3 )‐NHC/Ag possesses the best catalytic performance for the CO 2 conversion to cyclic carbonates. Notably, the catalyst exhibits robust activity under diluted CO 2 akin to flue gas, demonstrating high stability and recyclability. Mechanistic insights implicate Ag(I)‐mediated polarization of propargylic alcohols’ CC bond, facilitating CO 2 insertion and ring‐closure to α‐alkylidene cyclic carbonates. This study underscores MOF‐based catalysts’ potential in sustainable CO 2 utilization, offering a pathway for efficient chemical synthesis in environmentally sensitive contexts.