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

A possible mechanism is considered for the formation of nanoscale oxides based on titanium and aluminum isopropoxides in a medium of supercritical CO 2 fluid. It is shown that because of intermolecular interactions and high pressure in the system, the supercritical fluid acquires the properties of a...

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Bibliographic Details
Published in:Russian Journal of Physical Chemistry A 2023-07, Vol.97 (7), p.1515-1521
Main Authors: Golubev, D. V., Sigov, A. S., Kolobanov, A. I., Fomichev, V. V.
Format: Article
Language:English
Subjects:
Aluminum
Carbon dioxide
Chemistry
Chemistry and Materials Science
Hydrogen bonds
Hydrolysis
Nanomaterials
Physical Chemistry
Physical Chemistry of Nanoclusters
Supercritical fluids
Supramolecular Structures
Titanium
Titanium oxides
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Summary:A possible mechanism is considered for the formation of nanoscale oxides based on titanium and aluminum isopropoxides in a medium of supercritical CO 2 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 CO 2 fluid is possible for transitional d -elements.
ISSN:0036-0244
1531-863X
DOI:10.1134/S0036024423070117