2D functionalized copper(<scp>ii</scp>)-carboxylate framework for efficient chemical fixation of carbon dioxide: insights from experimental and theoretical analysis

Metal-organic materials are an important class of heterogeneous catalytic materials that offer a variety of organic transformations. A 2D azide functionalized copper(ii)-carboxylate framework (FCCF) was synthesized for catalytic application in the chemical fixation of carbon dioxide. The synthesized MOF was characterized using different techniques, <i>i.e.</i>, FTIR, PXRD, SEM and TGA. Hirshfeld surface analysis was performed to assess intermolecular interactions. The catalytic potential of the FCCF for CO₂ fixation to synthesize organic cyclic carbonates was investigated and optimized under solvent-free conditions and ambient CO₂ pressure at 100 °C within 3-8 hours in the presence of a co-catalyst (tetrabutyl ammonium bromide). The complete conversion of epichlorohydrin into its cyclic carbonate with maximum selectivity was achieved under optimal reaction conditions. The FCCF as a functionalized material exhibited efficient fixation of carbon dioxide. The reaction mechanism for the cycloaddition of CO₂ to epoxide catalyzed by the FCCF was investigated in detail based on experimental inferences and corroborated with the periodic calculations of density functional theory (DFT). Energy calculations depict that the azide-functionalized MOF material (FCCF) efficiently converts CO₂ and epoxides into targeted cyclic carbonates. Therefore, the FCCF is an interesting material for the chemical fixation of CO₂ for developing value-added chemical products.