Facile One-Pot Synthesis of Zn/Mg-MOF-74 with Unsaturated Coordination Metal Centers for Efficient CO Adsorption and Conversion to Cyclic Carbonates.

Bimetallic metal-organic frameworks (MOFs) containing two different inorganic metal nodes exhibited enhanced properties in CO adsorption and catalytic conversion compared with the corresponding monometallic MOFs. In this work, the novel bimetallic Zn/Mg-MOF-74 with different ratios of Zn/Mg was synthesized successfully by a facile one-pot method. Powder X-ray diffraction, Fourier transform infrared, X-ray photoelectron spectroscopy, scanning electron microscopy/transmission electron microscopy, N/CO adsorption/desorption, and CO/NH-temperature-programmed desorption techniques thoroughly characterized the structure, morphology, and physicochemical properties of Zn/Mg-MOF-74. Besides the excellent CO adsorption capacity (128.3 cm/g at 273 K and 1 bar), ZnMg-MOF-74 also showed efficient catalytic activity for the cycloaddition reaction of CO and epoxides to cyclic carbonates with outstanding yield and selectivity all over 99% under solvent-free and mild conditions (60 °C, 0.8 MPa), outperforming the mechanical combination of Zn-MOF-74 and Mg-MOF-74 with the same metal contents, indicating the synergistic effect of two adjacent metals in bimetallic MOF-74. In addition, the ZnMg-MOF-74 catalyst could be recycled for at least five runs and possess good versatility to various substrates. Finally, a feasible mechanism of the catalytic reaction was proposed. Thanks to the high surface area, affinity toward CO, and accessibility of multiple active sites of the unsaturated metal centers as active Lewis acid sites and O atoms from Zn-O and Mg-O as Lewis basic sites, efficient chemical fixation of CO to cyclic carbonates was obtained over the ZnMg-MOF-74 catalyst. The present facile synthesis and application of a robust bimetallic MOF catalyst offered a competitive avenue for the integration of CO adsorption and CO catalytic conversion.