Solid solutions Nd2−xSrxNiO4±δ (x = 0, 0.5, 1, 1.2, 1.4) with a K2NiF4 structure can be obtained from freeze-dried precursors. The end members of this series can be obtained at T ≥ 1000 °C only, while complex oxides with x = 1; 1.5 are formed at T ≥ 700 °C. Thermal analysis revealed the two stages of Nd2−xSrxNiO4±δ thermal reduction in a 10%H2/Ar gas mixture that was completed at 900 °C. For x < 0.2, the reduction products demonstrated an exsolution-like morphology with Ni nanoparticles allocated at the surface of oxide grains. As-obtained nanocomposites with x = 0 and x > 1 revealed the outstanding catalytic activity and selectivity in the dry reforming of the methane (DRM) reaction at 800 °C with CH4 conversion close to the thermodynamic values. The appearance of two different maxima of the catalytic properties of Ni/(Nd2O3,SrCO3) nanocomposites could be affiliated with the domination of the positive contributions of Nd2O3 and SrCO3, respectively.

A series of K2NiF4-like complex oxides Nd2-xCaxNiO4 (x = 0-0.4) was obtained by the freeze drying synthesis method. Thermal decomposition of these precursors in H-2 at 900 degrees C resulted in the formation of Ni/(Nd2O3,CaO) composites with different Nd2O3/CaO ratios. Their microstructure was similar to the products of the redox exsolution of perovskites: spherical 30 nm particles of Ni metal were allocated at the surface of dense agglomerates of Nd2O3 and CaO grains. The as-obtained composites demonstrated significant catalytic activity, selectivity, and stability in the reactions of dry reforming and partial oxidation of methane (DRM and POM, respectively) at T >= 800 degrees C.

In order to clarify the role of R2O3 in the metal-oxide catalysts derived from complex oxide precursors, a series of R1.5Ca0.5NiO4 (R = Nd, Sm, Eu) complex oxides was obtained. A significant systematic increase in the orthorhombic distortion of the R1.5Ca0.5NiO4 structure (K2NiF4 type, Cmce) from Nd to Eu correlates with a corresponding decrease in their ionic radii. A reduction of R1.5Ca0.5NiO4 in the Ar/H2 gas mixture at 800 °C causes a formation of dense agglomerates of CaO and R2O3 coated with spherical 25–30 nm particles of Ni metal. The size of metal particles and oxide agglomerates is similar in all Ni/(R2O3,CaO) composites in the study. Their morphology is rather similar to the products of redox exsolution obtained by the partial reduction of complex oxides. All obtained composites demonstrated a significant catalytic activity in the dry reforming (DRM) and partial oxidation (POM) of methane at 700–800 °C. A systematic decrease in the DRM catalytic activity of composites from Nd to Eu could be attributed to the basicity reduction of R2O3 components of the composite catalysts. The maximum CH4 conversion in POM reaction was observed for Ni/(Sm2O3,CaO), while the maximum selectivity was demonstrated by Nd2O3-based composite. The possible reasons for the observed difference are discussed.