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A modified Pechini method involving the formation of carbon shell was proposed and used for the synthesis of the unsubstituted lanthanum and praseodymium hexaaluminates with the magnetoplumbite structure. The peculiarities of the LaAlO 3 and LaAl 11 O 18 phases' formation were studied in a wide temperature range starting from their appearance at 700 °C and finishing at 1300 °C when the complete phase formation occurs. It was found that the size of the formed hexaaluminate's crystallites is a crucial factor affecting the phase purity of the final product. The critical size of the thermodynamic stability of the LaAlO 3 phase is supposed to be 10 nm, which corresponds to the specific surface area of 90 m2/g. The use of a carbon template approach leading to the formation of a core-shell structure during the synthesis procedure allows stabilizing the oxide particles in size and preventing their agglomeration at high temperatures. Depending on the carbon template nature, the carbon content in the samples was found to be 13 wt% (low-carbon-shelled samples) and 40 wt% (high-carbon-shelled samples). In the case of high carbon content, the resulting LaAl 11 O 18 and PrAl 11 O 18 hexaaluminates possess the surface areas as high as 160 m2/g. [ABSTRACT FROM AUTHOR]

Abstract A series of the Rh-containing samples supported on pure γ-Al 2 O 3 , La-doped γ-Al 2 O 3 , LaAl 11 O 18 and LaAlO 3 was prepared and characterized. Diffusion of Rh3+ ions from the surface of the support into its bulk causing the rapid deactivation of the catalyst in a model reaction of CO oxidation under the prompt thermal aging conditions was shown to be accelerated by a presence of lanthanum. The amount of rhodium disappeared from the surface during the high temperature treatment was estimated by a testing reaction of ethane hydrogenolysis and an electron paramagnetic resonance spectroscopy with spin probe. In order to characterize rhodium ions diffused into the bulk of the support at different calcination temperatures, the optical spectroscopic methods (diffuse reflectance UV–vis and photoluminescence spectroscopies) were applied. Rh3+ ions were shown to be applicable as a luminescence probe to follow the process of their bulk diffusion and localization within the matrix of the support, as well as for the structure identification of the La-containing sites responsible for the alumina thermal stabilization. The obtained data on luminescence of Rh3+ ions indicate that already at 800 °C the oxygen octahedrons corresponding to LaAl 11 O 18 structure are being formed in the local coordination surroundings of isolated La ion in the 4%La 2 O 3 -Al 2 O 3 support. It is important to notice that the structures of such kind can be formed in La-doped aluminas only. There are no octahedron positions with sufficient values of the crystal field for the formation of luminescence centers of Rh3+ ions in pure γ-Al 2 O 3. Graphical abstract fx1 [ABSTRACT FROM AUTHOR]