Two series of Ni/Ce(Ti/Nb)ZrO₂ catalysts were prepared using citrate route and original solvothermal continuous flow synthesis in supercritical isopropanol and studied in dry reforming of methane (DRM). TEM, XPS and FTIRS of adsorbed CO confirm influence of support composition and preparation method on the catalysts’ morphology and surface features. The oxygen mobility was studied by isotope heteroexchange with C¹⁸O₂. After testing in DRM, carbon deposits after catalysts’ testing in DRM were investigated by temperature-programmed oxidation with thermo-gravimetric analysis. The lowest amounts of carbon deposits were obtained for unmodified Ni-CeZr and Ni-CeNbZr compositions. Ti addition lead to an increased amount of carbon, which was removed at higher temperatures. The use of supercritical supports also resulted in the formation of a higher amount of coke. Catalysts prepared by the supercritical synthesis were tested in DRM for 25 h. The highest activity drop was observed in the first three hours. For all compositions, close values of carbon deposits were revealed.

Nickel-containing mixed ceria-zirconia oxides also doped by Nb and Ti have been prepared by a citrate route and by original solvothermal continuous flow synthesis in supercritical alcohols. Nickel was subsequently deposited by conventional insipient wetness impregnation. The oxides are comprised of ceria-zirconia solid solution with cubic fluorite phase. Negligible amounts of impurities of zirconia are observed for samples prepared by citrate route and doped by Ti. Supports prepared by supercritical synthesis are single-phased. XRD data, Raman, and UV-Vis DR (diffuse reflectance) spectroscopy suggest increasing lattice parameter and amount of oxygen vacancies in fluorite structure after Nb and Ti incorporation despite of the preparation method. These structural changes correlate with the catalytic activity in a methane dry reforming reaction. Catalysts synthesized under supercritical conditions are more active than the catalysts of the same composition prepared by the citrate route. The catalytic activity of samples doped with Ti and Nb is two times higher in terms of TOF (turnover frequency) and increased stability of these catalysts is attributed with the highest oxygen mobility being crucial for gasification of coke precursors.

The Ni-containing catalysts based on ceria–zirconia doped with Ti and Ti+Nb were prepared by the solvothermal method in supercritical fluids. Ni deposition was carried out by incipient wetness impregnation and the one-pot technique. All materials were investigated by a complex of physicochemical methods (XRD, BET, TEM, H₂-TPR). Samples catalytic properties were studied in methane dry reforming in the plug-flow reactor. Conversions of CH₄ and CO₂, H₂/CO ratio, and CO and H₂ yields were measured, and detailed kinetics analysis was carried out. The influence of Ni loading method and support modification on the catalytic behavior in the methane dry reforming process was studied. The preparation method of catalysts affects the textural characteristics. For one-pot samples, pore volume and surface area are lower than for impregnated samples. For catalysts on modified supports, strong metal–support interaction was shown to increase catalytic activity. A reduction pretreatment of samples was shown to have significant influence on their catalytic properties. The kinetic parameters such as reaction rate constant at 700 °C, effective activation energy, and TOF were estimated and analyzed.

To achieve a high activity and coking stability of nickel catalysts in dry reforming of methane, materials comprised of ceria–zirconia doped by Ti were investigated as supports. Ceria–zirconia supports doped with titanium were prepared either via the Pechini method or by synthesis in supercritical alcohol media. Ni-containing catalysts were prepared by two techniques: standard incipient wetness impregnation and one-pot synthesis. The catalytic reaction of DRM to synthesis gas was carried out in the 600–750 °C range over 5% wt. Ni/Ce(Ti)ZrO₂. Dried and calcined supports and catalysts were characterized by physicochemical methods including N₂ adsorption, XRD, Raman, H₂-TPR, and HRTEM. Both preparation methods led to formation of solid solution with cubic fluorite-like structure, as well as after addition of Ti. Introduction of Ti should provide improved oxygen storage capacity and mobility of support oxygen. The highest activity was observed with the catalyst of 5% wt. Ni/Ce_0.75Ti_0.2Zr_0.05O_2−δ composition due to optimized oxide support structure and support oxygen mobility.

Synthesis and study of materials based on bismuth cerates and titanates were carried out. Complex oxides Bi_1.6Y_0.4Ti₂O₇ were synthesized by the citrate route; Bi₂Ce₂O₇ and Bi_1.6Y_0.4Ce₂O₇—by the Pechini method. The structural characteristics of materials after conventional sintering at 500–1300 °C were studied. It is demonstrated that the formation of a pure pyrochlore phase, Bi_1.6Y_0.4Ti₂O₇, occurs after high-temperature calcination. Complex oxides Bi₂Ce₂O₇ and Bi_1.6Y_0.4Ce₂O₇ have a pyrochlore structure formed at low temperatures. Yttrium doping of bismuth cerate lowers the formation temperature of the pyrochlore phase. As a result of calcination at high temperatures, the pyrochlore phase transforms into the CeO₂-like fluorite phase enriched by bismuth oxide. The influence of radiation-thermal sintering (RTS) conditions using e-beams was studied as well. In this case, dense ceramics are formed even at sufficiently low temperatures and short processing times. The transport characteristics of the obtained materials were studied. It has been shown that bismuth cerates have high oxygen conductivity. Conclusions are drawn about the oxygen diffusion mechanism for these systems. The materials studied are promising for use as oxygen-conducting layers in composite membranes.

Catalysts based on perovskite—fluorite nanocomposites with supported nickel 5%Ni/[Pr_0.15Sm_0.15Ce_0.35Zr_0.35O₂ + LaMn_0.9Ru_0.1O₃] were synthesized by three different methods. Structural and surface features of as-prepared samples were elucidated by N₂ adsorption, XRD, HR TEM with EDX; reducibility and reactivity were estimated by H₂-TPR, and catalytic properties were studied in ethanol steam reforming in the 500–700 °C temperature range. The best catalytic activity without coke accumulation was demonstrated for the 5%Ni/[Pr_0.15Sm_0.15Ce_0.35Zr_0.35O₂+ LaMn_0.9Ru_0.1O₃] catalyst with nanocomposite support obtained by a simple sequential polymeric preparation method. Highly dispersed particles of metallic nickel strongly fixed on the support after the reaction were shown by the HR-TEM and H₂ –TPR data. The catalyst provides stable full conversion of ethanol and hydrogen yield above 60% at 600 °C for at least 6 h.