Plasma-assisted catalytic dry reforming of methane (DRM) over metal-organic frameworks (MOFs)-based catalysts

[Display omitted] •Plasma-assisted dry reforming of methane (DRM) over UiO-67 MOF-based catalyst.•UiO-67 material in the discharge zone improved the plasma generation and gas-phase reactions.•Pt nanoparticles supported on UiO-67 promoted surface reactions, improving DRM.•PtNP@UiO-67 catalysts were robust and stable in the plasma-assisted catalytic DRM. Plasma-assisted dry reforming of methane (DRM) was performed in a dielectric barrier discharge (DBD) reactor. The effect of different packing materials including ZrO2, UiO-67 MOF and PtNP@UiO-67 on plasma discharge was investigated, showing that ZrO2 suppressed the plasma generation while UiO-67 improves it due to its porous nature which favours the formation of filamentary microdischarges and surface discharges. The improved plasma discharge increased the conversion of CH4 and CO2 by about 18% and 10%, respectively, compared to the plasma-alone mode. In addition, the distribution of hydrocarbon products changed from dominant C2H6 in the plasma-alone mode to C2H2 and C2H4 in the UiO-67 promoted plasma-assisted DRM. The UiO-67 MOF was stable in plasma, showing no significant changes in its properties under different treatment times, discharge powers and gases. Pt nanoparticles (NPs) on UiO-67 improved plasma-assisted DRM, especially the selectivity due to the presence of surface reactions. Due to the dehydrogenation of hydrocarbons over Pt NPs, the selectivity to hydrocarbons decreased by 30%, compared to the UiO-67 packing. In situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) was carried out to probe the surface reactions on PtNP@UiO-67 catalyst, showing the decomposition of surface formats to CO and C2H4 dehydrogenation over the metallic Pt. The PtNP@UiO-67 catalyst showed good reusability in the plasma-assisted DRM, and H2 production was improved by high CH4/CO2 molar ratio and low feed flow rate.