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Abstract
In this work, hydrofluoric acid and ammonium hydrofluoride were used as fluorine precursors, and thiourea and sulfuric acid - as sulfur precursors, and the phase composition, morphology, texture, and electronic structure of non-metals doped TiO2 nanostructures compared, the chemical state of dopants in the obtained materials was examined, and the influence of the specified factors on photocatalytic activity in the processes of photodegradation of complex organic compounds, for example on antibiotic of the tetracycline series – doxycycline, was stadied. It is shown that hydrofluoric acid and thiourea lead to the formation of anatase, while at low ratios of ammonium hydrofluoride to titanium butoxide, anatase heterostructures with brukite are formed, and at high ratios of sulfuric acid to titanium butoxide, the formation of the crystalline phase of titanyl sulfate is observed. It was determined that hydrofluoric acid causes the formation Sheet-like morphology, and the presence of sulfuric acid in the sol-gel reaction mixture leads to the formation of spheroidal particles, which at small ratios of sulfuric acid to titanium butoxide form loosely agglomerated particles of spheroidal morphology, which are formed from anatase crystallites. The photocatalytic activity of codoped TiO2 nanostructures in the doxycycline photodegradation process under UV and visible light irradiation was investigated and it was established that under UV light irradiation the activity mainly depends on the phase composition and crystallite sizes, while under visible light irradiation the activity depends from the interstitual dopants content that increase the materials sensitivity to visible light. It was established that nitrogen, carbon and fluorine co-doped TiO2 nanostructures obtained in the presence of ammonium hydrofluoride are characterized by the presence of surface Ti-F groups and interstitual carbon and surface carbonate, while carbon and sulfur co-doped TiO2 nanostructures obtained in the presence of thiourea after hydrothermal treatment contain Ti-SH groups, which are oxidized as a result of calcination at 450 °C are oxidized with the formation of interstitual sulfur (S6+) and surface sulfate.
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