ТЕРМОДИНАМИЧЕСКОЕ МОДЕЛИРОВАНИЕ ПРОЦЕССОВ МОЛЕКУЛЯРНОГО НАСЛАИВАНИЯ MoO3 НА β-КРИСТОБАЛИТЕ И МОНОСЛОЯХ MoOX И AlOX МЕТОДОМ DFT: СРАВНИТЕЛЬНАЯ ОЦЕНКА РЕАКЦИЙ MoOCl4 И MoO2Cl2 С H2O
Аннотация
Проведено квантово-химическое моделирование процессов молекулярного наслаивания оксида молибдена (VI) на поверхностях β-кристобалита и аморфных монослоев МоОх и AlOx на β-кристобалите с использованием в качестве реагентов газообразных MoOCl4, MoO2Cl2 и H2O. С помощью метода обобщенного градиентного приближения теории функционала плотности вычислены изменения энергии Гиббса реакций молекулярного наслаивания (ΔG°) в диапазоне температур от 273,15 до 650,15 K. Для газообразных веществ расчеты осуществляли в приближении идеального газа, а для компонентов твердой фазы исключали вклады поступательной и вращательной составляющих движения. Согласно полученным данным, в рассматриваемом температурном диапазоне прогнозируется наиболее высокая реакционная способность поверхности монослоя аморфного оксида алюминия на β-кристобалите. Кроме того, выявлено, что соединение MoOCl4 обладает большей химической активностью по сравнению с MoO2Cl2 в отношении к рассматриваемым подложкам. Дано объяснение отсутствию роста молибденоксидных структур на поверхности β-кристобалита и возможным причинам большей реакционной способности монослоя оксида алюминия по сравнению с поверхностью β-кристобалита и аморфной поверхностью монослоя МоОх. Применяемый нами расчетный подход в целом может помочь в понимании фундаментальных аспектов нуклеации и роста пленок МоО3 и смешанных оксидных материалов типа AlxMoyOz на различных поверхностях. Также были рассчитаны частоты колебательных мод в структурах, содержащих молибден, на поверхности подложек в ангармоническом приближении vSi-O-Mo = 901-1002 см-1, vAl-O-Mo =921-1015 см-1, vMo-O-Mo = 716-889 см-1, vMo=O = 972-1010 см-1.
Для цитирования:
Гаджимурадов С.Г., Сулейманов С.И., Максумова А.М., Дроздов Е.О., Абдулагатов И.М., Абдулагатов А.И. Термодинамическое моделирование процессов молекулярного наслаивания MoO3 на β-кристобалите и монослоях MoOx и AlOx методом DFT: сравнительная оценка реакций MoOCl4 и MoO2Cl2 с H2O. Изв. вузов. Химия и хим. технология. 2025. Т. 68. Вып. 3. С. 50-63. DOI: 10.6060/ivkkt.20256803.7132.
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