Effect of aluminum vacancies on the H                         2                         O                         2                          or H                         2                         O interaction with a gamma-AlOOH surface. A solid-state DFT study

Alexander G. Medvedev; Alexey A. Mikhaylov; Ivan Yu Chernyshov; Mikhail V. Vener; Ovadia Lev; Petr V. Prikhodchenko

doi:10.1002/qua.25920

Effect of aluminum vacancies on the H ₂ O ₂ or H ₂ O interaction with a gamma-AlOOH surface. A solid-state DFT study

Alexander G. Medvedev, Alexey A. Mikhaylov, Ivan Yu Chernyshov, Mikhail V. Vener^*, Ovadia Lev, Petr V. Prikhodchenko

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

The adsorption of a single H ₂ O ₂ or H ₂ O molecule on a family of periodic slab models of γ-AlOOH is studied by solid-state DFT. The single H ₂ O ₂ or Н ₂ О molecule interacts with the perfect (010) slab by intermolecular hydrogen bonds (H-bonds). In the models of γ-AlOOH with oxygen and aluminum vacancies, H ₂ O ₂ or Н ₂ О also forms covalent O∙∙∙Al bonds. The energies of covalent O∙∙∙Al and H-bonds are estimated by a combined approach based on simultaneous consideration of the total binding energies with BSSE correction and empirical schemes of the Н-bond energy evaluation. The O∙∙∙Al bond energy ranges from ~75 to ~156 kJ mol ⁻¹ . The total energy of H-bond interactions in the case of H ₂ O ₂ exceeds that of Н ₂ О by ~30 kJ mol ⁻¹ for all considered slab models. In contrast to Н ₂ О, a H ₂ O ₂ molecule always forms two H-bonds as the proton donor. The energy of these bonds noticeably increase on defect γ-AlOOH surfaces in comparison with the perfect slab due to formation of short (strong) H-bonds by adsorbed H ₂ O ₂ .

Original language	American English
Article number	e25920
Journal	International Journal of Quantum Chemistry
Volume	119
Issue number	13
DOIs	https://doi.org/10.1002/qua.25920
State	Published - 5 Jul 2019

Bibliographical note

Funding Information:
This study was supported by the Russian Science Foundation (grant №16-13-00110).

Publisher Copyright:
© 2019 Wiley Periodicals, Inc.

Keywords

catalytic center
intermolecular H-bond energy/enthalpy
oxygen and aluminum vacancies
perfect and defect slab models
the Bader analysis of periodic electron density

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10.1002/qua.25920

Cite this

Medvedev, A. G., Mikhaylov, A. A., Chernyshov, I. Y., Vener, M. V., Lev, O., & Prikhodchenko, P. V. (2019). Effect of aluminum vacancies on the H ₂ O ₂ or H ₂ O interaction with a gamma-AlOOH surface. A solid-state DFT study International Journal of Quantum Chemistry, 119(13), Article e25920. https://doi.org/10.1002/qua.25920

Medvedev, Alexander G. ; Mikhaylov, Alexey A. ; Chernyshov, Ivan Yu et al. / Effect of aluminum vacancies on the H ₂ O ₂ or H ₂ O interaction with a gamma-AlOOH surface. A solid-state DFT study In: International Journal of Quantum Chemistry. 2019 ; Vol. 119, No. 13.

@article{66259fedfb984361bc701e3becb13421,

title = " Effect of aluminum vacancies on the H 2 O 2 or H 2 O interaction with a gamma-AlOOH surface. A solid-state DFT study ",

abstract = " The adsorption of a single H 2 O 2 or H 2 O molecule on a family of periodic slab models of γ-AlOOH is studied by solid-state DFT. The single H 2 O 2 or Н 2 О molecule interacts with the perfect (010) slab by intermolecular hydrogen bonds (H-bonds). In the models of γ-AlOOH with oxygen and aluminum vacancies, H 2 O 2 or Н 2 О also forms covalent O∙∙∙Al bonds. The energies of covalent O∙∙∙Al and H-bonds are estimated by a combined approach based on simultaneous consideration of the total binding energies with BSSE correction and empirical schemes of the Н-bond energy evaluation. The O∙∙∙Al bond energy ranges from ~75 to ~156 kJ mol −1 . The total energy of H-bond interactions in the case of H 2 O 2 exceeds that of Н 2 О by ~30 kJ mol −1 for all considered slab models. In contrast to Н 2 О, a H 2 O 2 molecule always forms two H-bonds as the proton donor. The energy of these bonds noticeably increase on defect γ-AlOOH surfaces in comparison with the perfect slab due to formation of short (strong) H-bonds by adsorbed H 2 O 2 .",

keywords = "catalytic center, intermolecular H-bond energy/enthalpy, oxygen and aluminum vacancies, perfect and defect slab models, the Bader analysis of periodic electron density",

author = "Medvedev, {Alexander G.} and Mikhaylov, {Alexey A.} and Chernyshov, {Ivan Yu} and Vener, {Mikhail V.} and Ovadia Lev and Prikhodchenko, {Petr V.}",

note = "Funding Information: This study was supported by the Russian Science Foundation (grant №16-13-00110). Publisher Copyright: {\textcopyright} 2019 Wiley Periodicals, Inc.",

year = "2019",

month = jul,

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doi = "10.1002/qua.25920",

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Medvedev, AG, Mikhaylov, AA, Chernyshov, IY, Vener, MV, Lev, O & Prikhodchenko, PV 2019, ' Effect of aluminum vacancies on the H ₂ O ₂ or H ₂ O interaction with a gamma-AlOOH surface. A solid-state DFT study ', International Journal of Quantum Chemistry, vol. 119, no. 13, e25920. https://doi.org/10.1002/qua.25920

Effect of aluminum vacancies on the H ₂ O ₂ or H ₂ O interaction with a gamma-AlOOH surface. A solid-state DFT study . / Medvedev, Alexander G.; Mikhaylov, Alexey A.; Chernyshov, Ivan Yu et al.
In: International Journal of Quantum Chemistry, Vol. 119, No. 13, e25920, 05.07.2019.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Effect of aluminum vacancies on the H 2 O 2 or H 2 O interaction with a gamma-AlOOH surface. A solid-state DFT study

AU - Medvedev, Alexander G.

AU - Mikhaylov, Alexey A.

AU - Chernyshov, Ivan Yu

AU - Vener, Mikhail V.

AU - Lev, Ovadia

AU - Prikhodchenko, Petr V.

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N2 - The adsorption of a single H 2 O 2 or H 2 O molecule on a family of periodic slab models of γ-AlOOH is studied by solid-state DFT. The single H 2 O 2 or Н 2 О molecule interacts with the perfect (010) slab by intermolecular hydrogen bonds (H-bonds). In the models of γ-AlOOH with oxygen and aluminum vacancies, H 2 O 2 or Н 2 О also forms covalent O∙∙∙Al bonds. The energies of covalent O∙∙∙Al and H-bonds are estimated by a combined approach based on simultaneous consideration of the total binding energies with BSSE correction and empirical schemes of the Н-bond energy evaluation. The O∙∙∙Al bond energy ranges from ~75 to ~156 kJ mol −1 . The total energy of H-bond interactions in the case of H 2 O 2 exceeds that of Н 2 О by ~30 kJ mol −1 for all considered slab models. In contrast to Н 2 О, a H 2 O 2 molecule always forms two H-bonds as the proton donor. The energy of these bonds noticeably increase on defect γ-AlOOH surfaces in comparison with the perfect slab due to formation of short (strong) H-bonds by adsorbed H 2 O 2 .

AB - The adsorption of a single H 2 O 2 or H 2 O molecule on a family of periodic slab models of γ-AlOOH is studied by solid-state DFT. The single H 2 O 2 or Н 2 О molecule interacts with the perfect (010) slab by intermolecular hydrogen bonds (H-bonds). In the models of γ-AlOOH with oxygen and aluminum vacancies, H 2 O 2 or Н 2 О also forms covalent O∙∙∙Al bonds. The energies of covalent O∙∙∙Al and H-bonds are estimated by a combined approach based on simultaneous consideration of the total binding energies with BSSE correction and empirical schemes of the Н-bond energy evaluation. The O∙∙∙Al bond energy ranges from ~75 to ~156 kJ mol −1 . The total energy of H-bond interactions in the case of H 2 O 2 exceeds that of Н 2 О by ~30 kJ mol −1 for all considered slab models. In contrast to Н 2 О, a H 2 O 2 molecule always forms two H-bonds as the proton donor. The energy of these bonds noticeably increase on defect γ-AlOOH surfaces in comparison with the perfect slab due to formation of short (strong) H-bonds by adsorbed H 2 O 2 .

KW - catalytic center

KW - intermolecular H-bond energy/enthalpy

KW - oxygen and aluminum vacancies

KW - perfect and defect slab models

KW - the Bader analysis of periodic electron density

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JO - International Journal of Quantum Chemistry

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Medvedev AG, Mikhaylov AA, Chernyshov IY, Vener MV, Lev O, Prikhodchenko PV. Effect of aluminum vacancies on the H ₂ O ₂ or H ₂ O interaction with a gamma-AlOOH surface. A solid-state DFT study International Journal of Quantum Chemistry. 2019 Jul 5;119(13):e25920. doi: 10.1002/qua.25920