Methane dry reforming over Ni catalysts supported on Ce–Zr oxides prepared by a route involving supercritical fluids

Ce0.5Zr0.5O2 mixed oxides were prepared in a flow reactor in supercritical isopropanol with acetylacetone as a complexing agent. Variation of the nature of the Zr salt and the temperature of synthesis affected the phase composition, morphology and specific surface area of oxides. X-ray diffraction and Raman spectroscopy studies revealed formation of metastable t” and t’ phases. Oxides are comprised of agglomerates with sizes depending on the synthesis parameters. Loading NiO decreases the specific surface area without affecting X-ray particle sizes of supports. Such sintering was the most pronounced for a support with the highest specific surface area, which resulted in the lowest surface content of Ni as estimated by X-ray photoelectron spectroscopy and in the formation of flattened NiO particles partially embedded into the support. The catalytic activity and stability of these samples in the dry reforming of methane were determined by the surface concentration of Ni and the morphology of its particle controlled by the metal-support interaction, which also depends on the type of catalyst pretreatment. Samples based on ceria-zirconia oxides prepared under these conditions provide a higher specific catalytic activity as compared with the traditional Pechini route, which makes them promising for the practical application

Ni-loaded nanocrystalline ceria-zirconia solid solutions prepared via modified Pechini route as stable to coking catalysts of CH4 dry reforming

Mixed nanocrystalline Ce-Zr-O oxides (Ce/Zr = 1 or 7/3) were prepared by modified Pechini route using ethylene glycol solutions of metal salts. Detailed characterization of their real structure and surface properties by X-ray diffraction on synchrotron radiation with the full-profile Rietveld analysis, high resolution electron microscopy with elemental analysis, Raman spectroscopy, UV-Vis and X-ray photoelectron spectroscopy revealed a high homogeneity of cations distribution in nanodomains resulting in stabilization of disordered cubic phase. This provides a high dispersion of NiO loaded on these mixed oxides by wet impregnation, a high reactivity and mobility of oxygen in these catalysts and strong interaction of Ni with support in the reduced state. This helps to achieve a high activity and coking stability of developed catalysts in CH4 dry reforming in feeds with CH4 concentration up to 15% and CH4/CO2 ratio =1