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Sol–Gel Chemistry of Titanium Alkoxide toward HF: Impacts of Reaction Parameters

Abstract : The sol–gel chemistry of titanium-based oxide prepared in a fluorinated medium leads to an oxy-hydroxyfluorinated framework owing to the occurrence of both hydrolysis and fluorolysis reactions. Here, a systematic study was carried out to investigate the impact of the sol–gel synthesis parameters on the reaction of titanium alkoxides and HF. This study provides comprehensive insights into the sol–gel process in a fluorinated medium. Depending on the extent of fluorination, two types of structures can be stabilized including an anatase Ti1–x–y□x+yO2–4(x+y)F4x(OH)4y and a fluoride-rich hexagonal-tungsten-bronze (HTB) Ti1–x□xO1–4x(F,OH)2+4x phases, where □ refers to titanium vacancies. The reactivity of titanium alkoxide in alcohol toward HF has been shown to mostly depend on the solvent characteristics highlighting an alcohol interchange reaction between the titanium precursor and the solvent. Increasing the fluorine concentration leads to a structural change from the anatase to the fluoride-rich HTB phase, which is rationalized by the preferential linking modes of Ti octahedral subunits in relation to its anionic environment, that is, corner-sharing configuration is favored for Ti4+ in a fluorinated environment. Finally, 19F MAS NMR spectroscopy has allowed identification of the different species involved in the stabilized phases providing spectroscopic signatures to further investigate these complex compounds.
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Wei Li, Monique Body, Christophe Legein, Damien Dambournet. Sol–Gel Chemistry of Titanium Alkoxide toward HF: Impacts of Reaction Parameters. Crystal Growth & Design, American Chemical Society, 2016, 16 (9), pp.5441 - 5447. ⟨10.1021/acs.cgd.6b00910⟩. ⟨hal-01489147⟩

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