Роль pH реакционной среды в образовании нанокристаллических фаз в системе Bi₂O₃-P₂O₅-H₂O

   Показано, что в кислой среде (pH = 2) при температуре 298 K формируется гексагональный BiPO₄, тогда как при pH = 8 и 12 образуются рентгеноаморфные вещества. Показано, что после гидротермальной обработки при 473 K в водно-солевой среде из гексагонального фосфата висмута в кислой среде образуется моноклинная модификация фосфата висмута, а в слабощелочной и щелочной средах из аморфных предшественников образуются наноразмерные частицы кристаллических соединений Bi₃O(OH)(PO₄)₂ (с размером кристаллитов около 62 нм) и Bi₂O₃ (с размером кристаллитов около 70 нм). Методом термодинамического расчета получены зависимости равновесной молярной растворимости этих кристаллических соединений от величины pH водно-солевой суспензии. Термодинамический расчет показал, что соединение BiPO₄ является устойчивым в интервале pH от 0 до 5.8 при температуре 298 и 473 K. Для интервала pH от 5.8 до 9.8 характерно образование соединения Bi₃O(OH)(PO₄)₂ при 298 K, а дальнейшее повышение величины pH приводит к выпадению близких по растворимости Bi₂O₃, BiOOH или Bi(OH)₃ при 298 и 473 K. Полученные путем термодинамического расчета данные согласуются с экспериментальными данными о границах устойчивого существования соединений BiPO₄, Bi₃O(OH)(PO₄)₂ и Bi₂O₃.

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