For the development of effective catalysts for the autothermal reforming of methane, the NiPd catalysts were synthesized based on modified aluminum oxide and their physicochemical properties were studied using X-ray diffraction analysis, low-temperature nitrogen adsorption, transmission electron microscopy, and temperature-programmed reduction with hydrogen. It was found that the variation of modifying components (CeO₂, ZrO₂, La₂O₃, Ce_0.5Zr_0.5O₂, and La₂O₃/Ce_0.5Zr_0.5O₂) and their concentrations (10–30 wt %) makes it possible to regulate the particle size of NiO, the composition of a Ni-containing phase (NiO, La₂NiO₄, NiAl₂O₄, or Ni-La-Al-O) and the redox properties of nickel ions. It was shown that the average particle size of NiO increased from 6.7 to 17.5 nm in the following order of supports: La₂O₃/Al₂O₃ < La₂O₃/Ce_0.5Zr_0.5O₂/Al₂O₃ < Al₂O₃ < Ce_0.5Zr_0.5O₂/Al₂O₃ < CeO₂/Al₂O₃ < ZrO₂/Al₂O₃. On the introduction of the modifying oxides CeO₂ and ZrO₂ into aluminum oxide, the fraction of nickel in the composition of NiAl₂O₄ decreased and, therefore, the fraction of difficult-to-reduce Ni²⁺ decreased. The addition of La₂O₃ and La₂O₃/Ce_0.5Zr_0.5O₂ strengthened the interaction of nickel cations with the support up to the formation of Ni-La-Al-O and La₂NiO₄ phases and increased the fraction of difficult-to-reduce Ni²⁺ ions. The resulting NiPd catalysts are promising in the catalysis of the autothermal reforming of methane.

Autothermal reforming of bioethanol (ATR of C₂H₅OH) over promoted Ni/Ce_0.8La_0.2O_1.9 catalysts was studied to develop carbon-neutral technologies for hydrogen production. The regulation of the functional properties of the catalysts was attained by adjusting their nanostructure and reducibility by introducing various types and content of M promoters (M = Pt, Pd, Rh, Re; molar ratio M/Ni = 0.003–0.012). The composition–characteristics–activity correlation was determined using catalyst testing in ATR of C₂H₅OH, thermal analysis, N₂ adsorption, X-ray diffraction, transmission electron microscopy, and EDX analysis. It was shown that the type and content of the promoter, as well as the preparation mode (combined or sequential impregnation methods), determine the redox properties of catalysts and influence the textural and structural characteristics of the samples. The reducibility of catalysts improves in the following sequence of promoters: Re < Rh < Pd < Pt, with an increase in their content, and when using the co-impregnation method. It was found that in ATR of C₂H₅OH over bimetallic Ni-M/Ce_0.8La_0.2O_1.9 catalysts at 600 °C, the hydrogen yield increased in the following row of promoters: Pt < Rh < Pd < Re at 100% conversion of ethanol. The introduction of M leads to the formation of a NiM alloy under reaction conditions and affects the resistance of the catalyst to oxidation, sintering, and coking. It was found that for enhancing Ni catalyst performance in H₂ production through ATR of C₂H₅OH, the most effective promotion is with Re: at 600 °C over the optimum 10Ni-0.4Re/Ce_0.8La_0.2O_1.9 catalyst the highest hydrogen yield 65% was observed.

Hydrogen production through the bi-reforming of methane over exsolution-derived Ni catalysts has been studied. Nickel-based catalysts were prepared through the activation of (CeM)_1−xNi_xO_y (M = Al, La, Mg) solid solutions in a reducing gaseous medium. Their performance and resistance to coking under the reaction conditions were controlled by regulating their textural, structural, morphological, and redox properties through adjustments to the composition of the oxide matrix (M/Ce = 0–4; x = 0.2–0.8; y = 1.0–2.0). The role of the M-dopant type in the genesis and properties of the catalysts was established. The efficiency of the catalysts in the bi-reforming of methane increased in the following series of M: M-free < La < Al < Mg, correlating with the structural behavior of the nickel active component and the anti-coking properties of the support matrix. The preferred M-type and M/Ce ratio determined the best performance of (CeM)_1−xNi_xO_y catalysts. At 800 °C the optimum Ce_0.6Mg_0.2Ni_0.2O_1.6 catalyst provided a stable H₂ yield of 90% at a high level of CO₂ and CH₄ conversions (>85%).

Hydrogen production from biogas over alumina-supported Ce_1−xNi_xO_2−x catalysts was studied in a temperature range of 600–850 °C with an initial gas composition of CH₄/CO₂/H₂O of 1/0.8/0.4. To achieve a high and stable hydrogen yield, highly dispersed Ni catalysts were prepared through the exsolution approach. A solid solution of Ce_1−xNi_xO_2−x was firstly formed on the surface of Al₂O₃ and then activated in H₂/Ar at 800 °C. The genesis and properties of the Ce_1−xNi_xO_2−x/Al₂O₃ catalysts were established using X-ray fluorescence analysis, thermal analysis, N₂ adsorption, ex situ and in situ X-ray diffraction, Raman spectroscopy, electron microscopy, EDX analysis, and temperature-programmed hydrogen reduction. The performance of Ce_1−xNi_xO_2−x/Al₂O₃ catalysts in biogas conversion was tuned by regulation of the dispersion and reducibility of the active component through variation of content (5–20 wt.%) and composition (x = 0.2, 0.5, 0.8) of Ce_1−xNi_xO_2−x as well as the mode of its loading (co-impregnation (CI), citrate sol–gel method (SG)). For the 20 wt.% Ce_1−xNi_xO_2−x/Al₂O₃ catalyst, the rate of the coke formation decreased by a factor of 10 as x increased from 0.2 to 0.8. The optimal catalyst composition (20 wt.% Ce_0.2Ni_0.8O_1.8/80 wt.% Al₂O₃) and preparation mode (citrate sol–gel method) were determined. At 850 °C, the 20 wt.% Ce_0.2Ni_0.8O_1.8/Al₂O₃-SG catalyst provides 100% hydrogen yield at full CH₄ conversion and 85% CO₂ utilization.