A Facile Method for Preparing UiO-66 Encapsulated Ru Catalyst and its Application in Plasma-Assisted CO2 Methanation.

With increasing applications of metal-organic frameworks (MOFs) in the field of gas separation and catalysis, the preparation and performance research of encapsulating metal nanoparticles (NPs) into MOFs (M@MOF) have attracted extensive attention recently. Herein, an Ru@UiO-66 catalyst is prepared by a one-step method. Ru NPs are encapsulated in situ in the UiO-66 skeleton structure during the synthesis of UiO-66 metal-organic framework via a solvothermal method, and its catalytic activity for CO2 methanation with the synergy of cold plasma is studied. The crystallinity and structural integrity of UiO-66 is maintained after encapsulating Ru NPs according to the X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). As illustrated by X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), and mapping analysis, the Ru species of the hydration ruthenium trichloride precursor are reduced to metallic Ru NPs without additional reducing processes during the synthesis of Ru@UiO-66, and the Ru NPs are uniformly distributed inside the Ru@UiO-66. Thermogravimetric analysis (TGA) and N2 sorption analysis show that the specific surface area and thermal stability of Ru@UiO-66 decrease slightly compared with that of UiO-66 and was ascribed to the encapsulation of Ru NPs in the UiO-66 skeleton. The results of plasma-assisted catalytic CO2 methanation indicate that Ru@UiO-66 exhibits excellent catalytic activity. CO2 conversion and CH4 selectivity over Ru@UiO-66 reached 72.2% and 95.4% under 13.0 W of discharge power and a 30 mL·min-1 gas flow rate ( V H 2 : V C O 2 = 4 : 1 ), respectively. Both values are significantly higher than pure UiO-66 with plasma and Ru/Al2O3 with plasma. The enhanced performance of Ru@UiO-66 is attributed to its unique framework structure and excellent dispersion of Ru NPs.