Mechanism for the Formation of Nanoscale Oxides in a Medium of Supercritical CO2 Fluid

D. V. Golubev; Голубев Д. В.; A. S. Sigov; Сигов А. С.; A. I.  Kolobanov; Колобанов А. И.; V. V. Fomichev; Фомичев В. В.

doi:10.31857/S0044453723070117

Mechanism for the Formation of Nanoscale Oxides in a Medium of Supercritical CO2 Fluid

Autores: Golubev D.¹, Sigov A.¹, Kolobanov A.¹, Fomichev V.¹
Afiliações:
1. Russian Technological University (MIREA)
Edição: Volume 97, Nº 7 (2023)
Páginas: 1038-1044
Seção: ФИЗИЧЕСКАЯ ХИМИЯ НАНОКЛАСТЕРОВ, СУПРАМОЛЕКУЛЯРНЫХ СТРУКТУР И НАНОМАТЕРИАЛОВ
URL: https://journals.rcsi.science/0044-4537/article/view/136638
DOI: https://doi.org/10.31857/S0044453723070117
EDN: https://elibrary.ru/SKRHQM
ID: 136638

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Resumo

A possible mechanism is considered for the formation of nanoscale oxides based on titanium and aluminum isopropoxides in a medium of supercritical CO2 fluid. It is shown that because of intermolecular interactions and high pressure in the system, the supercritical fluid acquires the properties of a condensed medium, the main role of which is to restrain processes of hydrolysis. At the first stage of the hydrolysis of titanium isopropoxide, the water molecule is coordinated in the outer sphere of the central atom due to the formation of intermolecular hydrogen bonds. It is then coordinated into the inner sphere with the formation of a five-coordinate transition state and its destruction, creating a product substituted for the hydroxo group. The next steps proceed in a similar way. The described mechanism agrees with experimental findings and produces nanosized X-ray amorphous titanium oxide. (With aluminum isopropoxide, only the hydrolyzed hydroxo form can be produced.) Results suggest the production of nanosized oxides from isopropoxides in a medium of supercritical CO2 fluid is possible for transitional d-elements.

Palavras-chave

supercritical CO2 fluid, hydrolysis, reaction mechanism, quantum chemical modeling, polarizable continuum model

Bibliografia

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