Quantum Chemical Study of the Mechanism of the Catalytic Oxyethylation of Ethylene Glycol on Phosphorus-Doped Titanium Dioxide: The Role of the Surface Phosphoryl and Hydroxyl Groups of the Catalyst Full article
Journal |
Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
||||||||
---|---|---|---|---|---|---|---|---|---|
Output data | Year: 2013, Volume: 54, Number: 2, Pages: 157-167 Pages count : 11 DOI: 10.1134/S002315841302016X | ||||||||
Tags | Apparent Activation Energy; Ethylene Oxide; Quantum Chemical Study; Alkoxyl Group; Density Functional Theory | ||||||||
Authors |
|
||||||||
Affiliations |
|
Abstract:
DFT calculations of the oxyethylation pathways of monoethylene glycol (MEG) and diethylene glycol (DEG) were performed on a model fragment of phosphorus-doped titanium dioxide (anatase). It was shown that the surface hydroxyl group of titanium dioxide, whose proton initiates C-O bond cleavage in the ethylene oxide molecule, plays the key role in the activation of the molecule. At the same time, the phosphoryl group -P(OH)2O activates the reactant molecule R (MEG, DEG, etc.) and carries out the synchronous proton transfer from R to the hydroxyl oxygen atom of titanium dioxide, thus restoring the catalyst structure and closing the catalytic cycle. This restructuring occurs synchronously in one step. The substitution of the catalyst hydroxyl groups by alkoxyl groups can influence oxyethylation occurring via the bimolecular nucleophilic substitution mechanism and can poison the catalyst in some cases.
Cite:
Zavelev D.E.
, Zhidomirov G.M.
, Kozlovskii R.A.
Quantum Chemical Study of the Mechanism of the Catalytic Oxyethylation of Ethylene Glycol on Phosphorus-Doped Titanium Dioxide: The Role of the Surface Phosphoryl and Hydroxyl Groups of the Catalyst
Kinetics and Catalysis. 2013. V.54. N2. P.157-167. DOI: 10.1134/S002315841302016X WOS Scopus РИНЦ
Quantum Chemical Study of the Mechanism of the Catalytic Oxyethylation of Ethylene Glycol on Phosphorus-Doped Titanium Dioxide: The Role of the Surface Phosphoryl and Hydroxyl Groups of the Catalyst
Kinetics and Catalysis. 2013. V.54. N2. P.157-167. DOI: 10.1134/S002315841302016X WOS Scopus РИНЦ
ArticleLinkType.TRANSLATED_TO_ORIGINAL:
Завелев Д.Е.
, Жидомиров Г.М.
, Козловский Р.А.
Квантово-химическое исследование механизма каталитической реакции оксиэтилирования этиленгликоля на модифицированном добавками фосфора оксиде титана. Роль поверхностных фосфорильных и гидроксильных групп катализатора
Кинетика и катализ. 2013. Т.54. №2. С.166-176. DOI: 10.7868/S0453881113020160 РИНЦ
Квантово-химическое исследование механизма каталитической реакции оксиэтилирования этиленгликоля на модифицированном добавками фосфора оксиде титана. Роль поверхностных фосфорильных и гидроксильных групп катализатора
Кинетика и катализ. 2013. Т.54. №2. С.166-176. DOI: 10.7868/S0453881113020160 РИНЦ
Dates:
Submitted: | Jun 25, 2012 |
Published print: | Mar 1, 2013 |
Published online: | Apr 6, 2013 |
Identifiers:
Web of science | WOS:000317351200004 |
Scopus | 2-s2.0-84876196056 |
Elibrary | 20432199 |
Chemical Abstracts | 2013:536705 |
Chemical Abstracts (print) | 158:503517 |
OpenAlex | W2144040755 |