LnFeNi(Ru)O₃ perovskites synthesized via a modified Pechini method have been studied as catalyst precursors in CO₂ reforming of methane. The structural and redox properties along with catalytic performance were found to depend upon Ln nature and Ru content in the perovskite. Active and stable catalysts have been formed from perovskite precursors in reaction media at high temperatures due to Fe–Ni–(Ru) alloy particles segregation from the perovskite lattice and their stabilization on the oxide surface. Coking stability of these catalysts in dry reforming of real natural gas containing admixtures of higher hydrocarbons is explained by combined effects of Ni dilution by Ru in alloy nanoparticles and high mobility and reactivity of surface/lattice oxygen in the disordered Ln ferrite support.

Methane oxidative coupling (OCM) is considered a potential direct route to produce C₂ hydrocarbons. Layered perovskite-like Sr₂TiO₄ is a promising OCM catalyst. Mechanochemical activation (MA) is known to be an environmentally friendly method for perovskite synthesis. Sr₂TiO₄ were synthesized using MA of the mixtures containing SrCO₃ or SrO and TiO₂ or TiO(OH)₂ and annealing at 900 and 1100 °C. XRD and FT-IRS showed that MA leads to the starting component disordering and formation of SrTiO₃ only for SrO being pronounced when using TiO(OH)₂. After annealing at 900 °C, Sr₂TiO₄ was mainly produced from the mixtures of SrCO₃ or SrO and TiO(OH)₂. The single-phase Sr₂TiO₄ was only obtained from MA products containing SrCO₃ after calcination at 1100 °C. The surface enrichment with Sr was observed by XPS for all samples annealed at 1100 °C depending on the MA product composition. The OCM activity of the samples correlated with the surface Sr concentration and the ratio of the surface oxygen amount in SrO and perovskite (O_o/O_p). The maximal CH₄ conversion and C₂ yield (25.6 and 15.5% at 900 °C, respectively), and the high long-term stability were observed for the sample obtained from (SrCO₃ + TiO₂), showing the specific surface morphology and optimal values of the surface Sr concentration and O_o/O_p ratio.

Double oxides with the structure of the Ruddlesden–Popper (R-P) layered perovskite A_n+1B_nO_3n+1 attract attention as materials for various electrochemical devices, selective oxygen-permeable ceramic membranes, and catalytic oxidative reactions. In particular, Sr₂TiO₄ layered perovskite is considered a promising catalyst in the oxidative coupling of methane. Our high-resolution transmission electron microscopy (HRTEM) studies of Sr₂TiO₄ samples synthesized using various methods have shown that their structure often contains planar defects disturbing the periodicity of layer alternation. This is due to the crystal-chemical features of the R-P layered perovskite-like oxides whose structure is formed by n consecutive layers of perovskite (ABO₃)_n in alternating with layers of rock-salt type (AO) in various ways along the c crystallographic direction. Planar defects can arise due to a periodicity violation of the layers alternation that also leads to a violation of the synthesized phase stoichiometry. In the present work, a crystallochemical analysis of the possible structure of planar defects is carried out, structures containing defects are modeled, and the effect of such defects on the X-ray diffraction patterns of oxides of the A₂BO₄ type using Sr₂TiO₄ is established as an example. For the calculations, we used the method of constructing probabilistic models of one-dimensionally disordered structures. For the first time, the features of diffraction were established, and an approach was demonstrated for determining the concentration of layer alternation defects applicable to layered perovskite-like oxides of the A₂BO₄ type of any chemical composition. A relation has been established between the concentration of planar defects and the real chemical composition (nonstoichiometry) of the Sr₂TiO₄ phase. The presence of defects leads to the Ti enrichment of particle volume and, consequently, to the enrichment of the surface with Sr. The latter, in turn, according to the data of a number of authors, can serve as an explanation for the catalytic activity of Sr₂TiO₄ in the oxidative coupling of methane.

High-power ball mill activation of the mixture of hydrated zirconium and lanthanum salts (oxonitrates, oxochlorides) with ammonium phosphate followed by hydrothermal treatment at temperatures not exceeding 200�C and a nearly neutral pH was found to yield crystalline dispersed phase of a cubic NH4Zr2(PO4)3 type along with admixtures of disordered orthorhombic compounds of a zirconium orthophosphate type. In the same conditions and at the same Zr/P ratio, hydrothermal treatment of gels obtained by reacting mixed zirconium and lanthanum nitrates solutions with ammonium phosphates yields no crystalline products, and only treatment in acid media generates a phase of the α-ZrPO4(OH) type coexisting with the NH4Zr2(PO4)3 phase if polyethylene oxide is present. X-ray powder diffraction, transmission electron microscopy, 31MAS-NMR, FTIRS and thermal analysis were applied to elucidate factors affecting crystallization of complex zirconium phosphates in the hydrothermal conditions. The most essential factor appears to be generation of some nuclei of zirconium phosphates under high pressures developed in the course of mixed solids mechanical activation. These nuclei are embedded into matrix of such well-crystallized solid products as ammonium nitrate or chloride. Hence, metastable cubic or orthorhombic structure of the phases obtained via mechanical activation route can be assigned to the nuclei-matrix orientation relationship. Due to easily scaled-up synthesis procedure, these results appear to be very promising for manufacturing of dispersed framework zirconium phosphates as acid catalysts or fast proton conductors.

A series of 5%Ni-Ce_xZr_1−xO₂ (x = 0.3, 0.5, 0.7) catalysts has been prepared via one-pot solvothermal continuous synthesis in supercritical isopropanol and incipient wetness impregnation of Ce_xZr_1−xO₂ obtained by the same route. The textural, structural, red-ox, and catalytic properties in methane dry reforming (MDR) of Ni-modified Ce-Zr oxides synthesized by two routes have been compared. It was shown by XRD, TEM, and Raman spectroscopy that the method of Ni introduction does not affect the phase composition of the catalysts, but determines the dispersion of NiO. Despite a high dispersion of NiO and near-uniform distribution of Ni within Ce-Zr particles observed for the one-pot catalysts, they have shown a lower activity and stability in MDR as compared with impregnated ones. This is a result of a low Ni concentration in the surface layer due to segregation of Ce and decoration of nickel nanoparticles with support species.