TY - JOUR

T1 - Ozone Activation on TiO2 Studied by IR Spectroscopy and Quantum Chemistry

AU - Aminev, Timur

AU - Krauklis, Irina

AU - Pestsov, Oleg

AU - Tsyganenko, Alexey

N1 - Aminev, T.; Krauklis, I.; Pestsov, O.; Tsyganenko, A. Ozone Activation on TiO2 Studied by IR Spectroscopy and Quantum Chemistry. Appl. Sci. 2021, 11, 7683. https://doi.org/10.3390/app11167683

PY - 2021/8/2

Y1 - 2021/8/2

N2 - The adsorption of different isotopic ozone mixtures on TiO2 at 77K was studied using FTIR spectroscopy and DFT calculations of cluster models. In addition to weakly bound ozone with band positions close to those of free or dissolved molecules, the spectrum of chemisorbed species was observed. The splitting of the 1+3 combination band to eight maxima due to different isotopomers testified to the loss of molecule symmetry. The frequencies of all the isotopic modifications of the ozone molecules which form monodentate or bidentate complexes with four- or five-coordinated titanium atoms were calculated and compared with those of experimentally observed spectra. The four considered complexes adequately reproduced the splitting of the 1+3 vibration band and the lowered anharmonism of chemisorbed O3. The energetically most favorable monodentate complex with four-coordinated titanium atoms showed good agreement with the observed spectra, although a large difference between the frequencies of 1 and 3 modes was found. For better coherence with the experiment, the interaction of the molecule with adjacent cations must be considered.

AB - The adsorption of different isotopic ozone mixtures on TiO2 at 77K was studied using FTIR spectroscopy and DFT calculations of cluster models. In addition to weakly bound ozone with band positions close to those of free or dissolved molecules, the spectrum of chemisorbed species was observed. The splitting of the 1+3 combination band to eight maxima due to different isotopomers testified to the loss of molecule symmetry. The frequencies of all the isotopic modifications of the ozone molecules which form monodentate or bidentate complexes with four- or five-coordinated titanium atoms were calculated and compared with those of experimentally observed spectra. The four considered complexes adequately reproduced the splitting of the 1+3 vibration band and the lowered anharmonism of chemisorbed O3. The energetically most favorable monodentate complex with four-coordinated titanium atoms showed good agreement with the observed spectra, although a large difference between the frequencies of 1 and 3 modes was found. For better coherence with the experiment, the interaction of the molecule with adjacent cations must be considered.

KW - Adsorption

KW - DFT calculation

KW - FTIR

KW - Ozone

KW - TiO2

KW - adsorption

KW - ADSORPTION

KW - SPECTRA

KW - ozone

UR - http://www.scopus.com/inward/record.url?scp=85113354480&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/eb4abd45-b30c-357d-b77f-730594918e1c/

U2 - https://doi.org/10.3390/app11167683

DO - https://doi.org/10.3390/app11167683

M3 - Article

AN - SCOPUS:85113354480

VL - 11

JO - Applied Sciences (Switzerland)

JF - Applied Sciences (Switzerland)

SN - 2076-3417

IS - 16

M1 - 7683

ER -