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.
N1 - Publisher Copyright:
© 2019 Wiley Periodicals, Inc.
PY - 2019/7/5
Y1 - 2019/7/5
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
UR - http://www.scopus.com/inward/record.url?scp=85061822687&partnerID=8YFLogxK
U2 - 10.1002/qua.25920
DO - 10.1002/qua.25920
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AN - SCOPUS:85061822687
SN - 0020-7608
VL - 119
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 13
M1 - e25920
ER -