American Chemical Society
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Crystallization Mechanism of Gel-Derived SiO2–TiO2 Amorphous Nanobeads Elucidated by High-Temperature In Situ Experiments

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journal contribution
posted on 2023-05-17, 20:30 authored by Alessio Zandonà, Emmanuel Véron, Gundula Helsch, Aurélien Canizarès, Joachim Deubener, Mathieu Allix, Cécile Genevois
SiO2–TiO2 amorphous nanobeads with a TiO2 content up to 50 mol % were synthesized by sol–gel spray drying. Their crystallization during heat treatments was then characterized by in situ high-temperature techniques including X-ray diffraction, Raman spectroscopy, and particularly high-resolution transmission electron microscopy. Intrinsic nanoscale chemical modulations could be identified already in the as-prepared nanobeads and were shown to play a major role for the nonisochemical precipitation of TiO2 nanocrystals during heating experiments: the size and compositional contrast of such fluctuations progressively evolved and increased until the emergence of long-range ordering. The formation of TiO2 polymorphs occurred according to Ostwald’s rule of stages, with the metastable TiO2(B) phase acting as a precursor to stabilize anatase and rutile. The temporary appearance of TiO2(B) nanocrystals at early annealing stages was interpreted as the first direct experimental observation of subcritical crystalline nuclei.