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Synthesis and characterization of spherulite-like nanocrystalline titania with rutile structure (r-TiO2) are described herein. The r-TiO2 particles were synthesized via the convenient and low-cost hydrothermal treatment of TiO(C6H6O7) titanyl citrate. The r-TiO2 spherulites are micron-sized agglomerates of rod-shaped nanocrystals with characteristic sizes of 7(±2) × 43(±10) nm, oriented along (101) crystallographic direction, and separated by micropores, as revealed by SEM and TEM. PXRD and Raman spectroscopy confirmed the nanocrystalline nature of r-TiO2 crystallites. BET analysis showed a high specific surface area of 102.6 m2/g and a pore volume of 6.22 mm3/g. Photocatalytic performances of the r-TiO2 spherulites were investigated for the processes of methyl violet (MV) degradation in water and hydrogen evolution reaction (HER) in aqueous solutions of ethanol. The (MV) degradation kinetics was found to be first-order and the degradation rate coefficient is 2.38 × 10−2 min−1. The HER was performed using pure r-TiO2 spherulites and nanocomposite r-TiO2 spherulites with platinum deposited on the surface (r-TiO2/Pt). It was discovered that the r-TiO2/Pt nanocomposite has a 15-fold higher hydrogen evolution rate than pure r-TiO2; their rates are 161 and 11 nmol/min, respectively. Thus, the facile synthesis route and the high photocatalytic performances of the obtained nanomaterials make them promising for commercial use in such photocatalytic processes as organic contamination degradation and hydrogen evolution.

Nanostructured hexagonal rare-earth orthoferrites (h-RfeO3, R = Sc, Y, Tb-Lu) are well known as a highly effective base for visible-light-driven heterojunction photocatalysts. However, their application is limited by metastability, leading to difficulties in synthesis due to the irreversible transformation to a stable orthorhombic structure. In this work, we report on a simple route to the stabilization of h-YbFeO3 nanocrystals by the synthesis of multiphase nanocomposites with titania additives. The new I-type heterojunction nanocomposites of o-YbFeO3/h-YbFeO3/r-TiO2 were obtained by the glycine–nitrate solution combustion method with subsequent heat treatment of the products. An increase in the mole fraction of the h-YbFeO3 phase in nanocomposites was found with the titanium addition, indicating its stabilizing effect via limiting mass transfer over heat treatment. The complex physicochemical analysis shows multiple contacts of individual nanocrystals of o-YbFeO3 (44.4–50.6 nm), h-YbFeO3 (7.5–17.6 nm), and rutile r-TiO2 (~5 nm), confirming the presence of the heterojunction structure in the obtained nanocomposite. The photocatalytic activity of h-YbFeO3/o-YbFeO3/r-TiO2 nanocomposites was evaluated by the photo-Fenton degradation of the methyl violet under visible light (λ ≥ 400 nm). It was demonstrated that the addition of 5 mol.% of TiO2 stabilizes h-YbFeO3, which allowed us to achieve a 41.5 mol% fraction, followed by a three-time increase in the photodecomposition rate constant up to 0.0160 min−1.

Porous nanocomposites based on PrFeO3-TiO2 were synthesized using the glycine-nitrate combustion method with different values of mass content of TiO2 (0–7.5 %) and subsequent heat treatment in air. The results of X-ray phase analysis and Raman spectroscopy confirmed the presence of ultradispersed TiO2, structurally close to that of anatase. The morphology, specific surface area, and porous structure of the obtained powders were characterized by scanning electron microscopy and adsorption-structural analysis, the results of which showed that the samples had a foam-like mesoporous structure.The specific surface area and the average pore size were in the ranges of 7.6–17.8 m2/g and 7.2–15.2 nm, respectively, and varied depending on the TiO2 content. The optical properties of the nanocomposites were studied by UV-visible diffuse reflection spectroscopy, the energy of the band gap was calculated as 2.11–2.26 eV. The photocatalytic activity of PrFeO3‑TiO2 nanocomposites was investigated in the process of photo-Fenton-like degradation of methyl violet under the action of visible light. It was shown that the maximum reaction rate constant was 0.095 min-1, which is ten times higher than the value for the known orthoferrite-based analogs. The obtained photocatalysts were also characterized by their high cyclic stability. Based on the studies carried out, the obtained porous PrFeO3-TiO2 nanocomposites can be considered to be apromising basis for photocatalysts applied in advanced oxidative processes of aqueous media purification from organic pollutants.