Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Ab Initio Insight into Mechanisms of Ozone Interaction with a Surface of Dehydrated Nanocrystalline TiO2. / Kevorkyants, Ruslan; Chizhov, Yuri V.; Bulanin, Kirill M.
в: Langmuir, Том 36, № 8, 03.03.2020, стр. 1930-1936.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Ab Initio Insight into Mechanisms of Ozone Interaction with a Surface of Dehydrated Nanocrystalline TiO2
AU - Kevorkyants, Ruslan
AU - Chizhov, Yuri V.
AU - Bulanin, Kirill M.
N1 - Publisher Copyright: Copyright © 2020 American Chemical Society.
PY - 2020/3/3
Y1 - 2020/3/3
N2 - Density functional theory (DFT) study of ozone adsorption on dehydrated nanocrystalline TiO2 is presented. Singlet and triplet binding modes of ozone to the oxide's titanium cations are considered. In both the modes, monodentate and bidentate ozone complexes are formed. According to DFT, the triplet monodentates are the most stable species. The formation of monodentate ozone adsorption complexes is in-line with an earlier interpretation of infrared (IR) spectroscopic data on ozone adsorption on an anatase surface. However, the computed difference in the fundamental vibrational frequencies (ν1 - ν3) of ozone in the triplet monodentates is significantly larger than the corresponding IR value. This discrepancy is resolved by demonstrating that the triplet monodentates readily decompose, realizing molecular oxygen that is consistent with published experimental data. The predicted energy barrier of the dissociative adsorption is less than 2 kcal/mol. In contrast, the computed difference in the fundamental vibrational frequencies (ν1 - ν3) of adsorbed ozone in the singlet bidentates perfectly agrees with the experiment.
AB - Density functional theory (DFT) study of ozone adsorption on dehydrated nanocrystalline TiO2 is presented. Singlet and triplet binding modes of ozone to the oxide's titanium cations are considered. In both the modes, monodentate and bidentate ozone complexes are formed. According to DFT, the triplet monodentates are the most stable species. The formation of monodentate ozone adsorption complexes is in-line with an earlier interpretation of infrared (IR) spectroscopic data on ozone adsorption on an anatase surface. However, the computed difference in the fundamental vibrational frequencies (ν1 - ν3) of ozone in the triplet monodentates is significantly larger than the corresponding IR value. This discrepancy is resolved by demonstrating that the triplet monodentates readily decompose, realizing molecular oxygen that is consistent with published experimental data. The predicted energy barrier of the dissociative adsorption is less than 2 kcal/mol. In contrast, the computed difference in the fundamental vibrational frequencies (ν1 - ν3) of adsorbed ozone in the singlet bidentates perfectly agrees with the experiment.
KW - MOLECULAR CALCULATIONS
KW - INFRARED-SPECTRA
KW - IR-SPECTRA
KW - ADSORPTION
KW - WATER
KW - DFT
KW - STABILITY
KW - ORIGIN
KW - ENERGY
KW - BAND
UR - http://www.scopus.com/inward/record.url?scp=85080081615&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/3221f2e6-63f3-3ebc-be3a-fa075007b00d/
U2 - 10.1021/acs.langmuir.9b03879
DO - 10.1021/acs.langmuir.9b03879
M3 - Article
AN - SCOPUS:85080081615
VL - 36
SP - 1930
EP - 1936
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 8
ER -
ID: 52167381