Термодинамический анализ формирования нанокристаллов в системе TiO2-H2O (NaOH, HCl)
https://doi.org/10.17586/2220-8054-2025-16-6-802-811
Аннотация
В работе проведен термодинамический анализ кристаллизации диоксида титана в модификациях анатаза, брукита и рутила из водно-солевых растворов с учетом влияния pH среды, температуры, концентрации реагентов и удельной поверхностной энергии фаз (σ). Показано, что выбор величины σ для термодинамического анализа кристаллизации анатаза является определяющим: при σA = 0.3 Дж/м² минимальный размер частиц определяется кристаллохимическим критерием (lmin~5–7 нм), а при σA = 1.3 Дж/м² -термодинамическими критериями (dcrit ~ 8 нм, deq ~ 12 нм). С использованием значений σ, наиболее приближенных к условиям гидратированной поверхности TiO2 (σR = 1.79, σB = 1.0, σA = 1.13 Дж/м²) определены области возможной кристаллизации каждой модификации. Рутил может кристаллизоваться в относительно широком диапазоне величин pH 0.8-14 (25 °С) и 1.1-10.2 (200 °С), а минимальные размеры частиц рутила в этих условиях определяются термодинамическими критериями – dcrit и deq. Для брукита и анатаза в кислых и щелочных условиях (pH ~1–3 и 9–14) минимальные размеры также, как и для рутила определяются термодинамическими критериями, тогда как в нейтральной области – кристаллохимическим критерием lmin. На основе анализа структурных переходов установлено, что анатаз может трансформироваться в рутил или брукит при размерах частиц более ~16 нм. Рассчитанный размер перехода брукит → рутил составляет ~712 нм.
Об авторах
Д. П. Еловиков
Branch of Petersburg Nuclear Physics Institute named by B. P. Konstantinov of National Research Centre “Kurchatov Institute” – Institute of Silicate Chemistry
Россия
Россия
О. В. Альмяшева
Branch of Petersburg Nuclear Physics Institute named by B. P. Konstantinov of National Research Centre “Kurchatov Institute” – Institute of Silicate Chemistry
Россия
Россия
В. В. Гусаров
Branch of Petersburg Nuclear Physics Institute named by B. P. Konstantinov of National Research Centre “Kurchatov Institute” – Institute of Silicate Chemistry
Россия
Россия
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Рецензия
Для цитирования:
Еловиков Д.П., Альмяшева О.В., Гусаров В.В. Термодинамический анализ формирования нанокристаллов в системе TiO2-H2O (NaOH, HCl). Наносистемы: физика, химия, математика. 2025;16(6):802-811. https://doi.org/10.17586/2220-8054-2025-16-6-802-811
For citation:
Elovikov D.P., Almjasheva O.V., Gusarov V.V. Thermodynamic analysis of nanocrystal formation in the TiO2–H2O (NaOH, HCl) system. Nanosystems: Physics, Chemistry, Mathematics. 2025;16(6):802-811. https://doi.org/10.17586/2220-8054-2025-16-6-802-811
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