Electronic-state-driven adsorption of O2 on a nanocrystalline TiO2 under ‘dark’ and UV-irradiation conditions: Ab initio study

[Display omitted] •O2 adsorption on the nanocluster Ti8O16 is modeled using DFT.•Electronic state of the nanocluster determines the nature of adsorption complexes.•The physisorbed O2 is oriented axially, whereas the chemisorbed O2 is oriented laterally.•Axial O2 orientation on a surface of bulk TiO2...

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Bibliographic Details
Published inChemical physics letters Vol. 698; pp. 97 - 101
Main Authors Kevorkyants, R., Sboev, M.N., Chizhov, Yu.V.
Format Journal Article
LanguageEnglish
Published Elsevier B.V 16.04.2018
Subjects
DFT
Nanocrystalline TiO2
O2 adsorption
Photoexcitation
DFT
Nanocrystalline TiO2
O2 adsorption
Photoexcitation
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Summary:[Display omitted] •O2 adsorption on the nanocluster Ti8O16 is modeled using DFT.•Electronic state of the nanocluster determines the nature of adsorption complexes.•The physisorbed O2 is oriented axially, whereas the chemisorbed O2 is oriented laterally.•Axial O2 orientation on a surface of bulk TiO2 is due to the sterical hindrance of Ti3+ centers. DFT study on O2 adsorption on a nanocrystalline titania is presented for the first time. The dioxide’s nanoparticle is modeled via the nanocluster Ti8O16. According to the calculations, O2 physisorbs on the nanocluster Ti8O16 in S0 and T0 states and chemisorbs on the nanocluster in S1 state. The computed adsorption enthalpies, O2 vibrational frequencies, and O2−g-tensor agree well with available data. In contrast to the axial O2 orientation on a surface of titania with oxygen vacancies, in the chemisorption complex O2 is oriented laterally. We explain this by the sterical hindrance of the Ti3+ centers in the former case.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2018.03.012