Double oxides with the structure of the Ruddlesden-Popper (R-P) layered perovskite An+1BnO3n+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.
Keywords: 1D simulation; HRTEM; Ruddlesden–Popper phases; X-ray powder diffraction; defects; nonstoichiometry; oxidative coupling of methane.