najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2023-14-2-231-241najo-149Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХColloidal-chemical mechanism of Zn(OH)2–ZnO layer formation at the glass– ammonia solution– Zn(II) interfaceКинетика роста слоёв Zn(OH)2 - ZnO из аммиачных растворов Zn(II) на поверхности стеклаhttps://orcid.org/0000-0001-7432-994XПоляковЕ. В.PolyakovE. V.

Первомайская, 91, Екатеринбург, 620108

Evgeny V. Polyakov

91, Pervomaiskaya str., 620108, Ekaterinburg

polyakov@ihim.uran.ruhttps://orcid.org/0009-0004-2807-2222МаксимоваМ. А.MaksimovaM. A.

Первомайская, 91, Екатеринбург, 620108

Maria A. Maksimova

91, Pervomaiskaya str., 620108, Ekaterinburg

lab515@ihim.uran.ruhttps://orcid.org/0000-0002-1253-8727КузнецоваЮ. В.KuznetsovaJ. V.

Первомайская, 91, Екатеринбург, 620108

Julia V. Kuznetsova

91, Pervomaiskaya str., 620108, Ekaterinburg

jukuznetsova@mail.ruhttps://orcid.org/0000-0003-3642-7121БулдаковаЛ. Ю.BuldakovaL. Yu.

Первомайская, 91, Екатеринбург, 620108

Larisa Yu. Buldakova

91, Pervomaiskaya str., 620108, Ekaterinburg

buldakova@ihim.uran.ruИХТТ УрО РАНInstitute of Solid State Chemistry of Ural Branch of Russian Academy of Sciences202303062025142231241Copyright © Polyakov E.V., Maksimova M.A., Kuznetsova J.V., Buldakova L.Y., 20252025Поляков Е.В., Максимова М.А., Кузнецова Ю.В., Булдакова Л.Ю.Polyakov E.V., Maksimova M.A., Kuznetsova J.V., Buldakova L.Y.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/149

Thermodynamic and experimental studies of Zn(OH)2/ZnO particle formation conditions in the model of closed system Zn2+–NH3,aq–NH3,gas–H+–OH––H2O–N2,gas (1), which often occurs in the process of synthesis of zinc oxide nanoparticles and films by chemical bath deposition (CBD) methods, were carried out. It was shown that the driving force for the formation and growth of Zn(OH)2/ZnO particles in the initially homo geneous system (1) at 25 C is the difference in the chemical potential of particles at the initial temperature (unsaturated system) and the synthesis temperature (supersaturated system). Using vibrational spectroscopy, X-ray phase and chemical analysis, diffuse light scattering and electrophoresis methods, it was found that the phase transformation of Zn(OH)2 into ZnO takes place in the region of 85– 90 C. The colloid-chemical trans formation of Zn(NH3)2+4 ionic particles into colloidal polycrystals of Zn(OH)2/ZnO composition was established for the first time to be a staged process. The first stage of the process in the solution volume is localized at the gas nanobubble-solution interface as a result of rapid formation, growth and removal of gas nanobubbles from the solution. The interaction of positively charged Zn(OH)2 nanoparticles with the surface of larger negatively charged gas nanobubbles creates colloidal aggregates “bubble surface film of hydroxide nanoparticles”. Their adhesion forms an openwork foam-like structure of the colloid in the solution and in the film on the interfaces at the first stage of synthesis. After degassing of the electrolyte solution, the second stage develops, consisting of the nucleation and ionic-molecular growth of Zn(OH)2/ZnO particles from the supersaturated solution, their distribution between the solution and the electrolyte– reactor wall– air interfaces. The film growth at this stage is regulated by the difference in surface charges of the double electric layer of the interface and polycrystalline colloidal particles. In the solution and on the interface, columnar Zn(OH)2/ZnO structures grow as volumetric stars with conical hexagonal spikes.

Проведены термодинамические и экспериментальные исследования условий образования частиц Zn(OH)2/ZnO в модельной замкнутой системе Zn2+ - NH3,aq - NH3gas - H+- OH- - H2O - N2gas (1), которая часто возникает при синтезе наночастиц и плёнок оксида/гидроксида цинка методами химического осаждения в ванне (CBD). Показано, что движущей силой образования и роста частиц Zn(OH)2/ZnO в первоначально однородной системе (1) при 25 °C является разница в химическом потенциале частиц при исходной температуре (ненасыщенная система) и температуре синтеза (пересыщенная система). С помощью колебательной спектроскопии, рентгенофазового и химического анализа, методов диффузного рассеяния света и электрофореза установлено, что фазовое превращение Zn(OH)2 в ZnO происходит при 85 - 90 °C. Впервые установлено, что коллоидно-химическое превращение ионных частиц Zn(NH3)42+ в коллоидные поликристаллы состава  Zn(OH)2/ZnO является стадийным процессом. Первая стадия превращения происходит в объёме раствора. Она локализуется на границе раздела «нанопузырек газа – внешний раствор» в результате быстрого образования, роста и удаления газовых нанопузырьков из раствора. Взаимодействие положительно заряженных наночастиц Zn(OH)2 с поверхностью более крупных отрицательно заряженных газовых нанопузырьков создаёт коллоидные агрегаты «пузырёк||поверхностная плёнка гидроксидных наночастиц».  Их адгезия образует ажурную пеноподобную структуру коллоида Zn(OH)2 в растворе и в плёнке на границах раздела газ-жидкость на первом этапе синтеза. После дегазации раствора электролита развивается вторая стадия, заключающаяся в нуклеации и ионно-молекулярном росте частиц Zn(OH)2/ZnO из пересыщенного раствора, их распределении между раствором и границей раздела электролит - стенка реактора – воздух в виде плёнки. Рост плёнки на этой стадии регулируется разницей в поверхностных зарядах двойного электрического слоя границы раздела и поликристаллических коллоидных частиц. В растворе и на границе раздела столбчатые структуры Zn(OH)2/ZnO растут в форме объёмных звёзд с коническими гексагональными шипами.

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The authors declare that there are no conflicts of interest present.