Free energy of proton transfer at the water–TiO 2 interface from ab initio deep potential molecular dynamics
Abstract
TiO2 is a widely used photocatalyst in science and technology and its interface with water is important in fields ranging from geochemistry to biomedicine. Yet, it is still unclear whether water adsorbs in molecular or dissociated form on TiO2 even for the case of well-defined crystalline surfaces. To address this issue, we simulated the TiO2–water interface using molecular dynamics with an ab initio-based deep neural network potential. Our simulations show a dynamical equilibrium of molecular and dissociative adsorption of water on TiO2. Water dissociates through a solvent-assisted concerted proton transfer to form a pair of short-lived hydroxyl groups on the TiO2 surface. Molecular adsorption of water is ΔF = 8.0 ± 0.9 kJ mol-1 lower in free energy than the dissociative adsorption, giving rise to a 5.6 ± 0.5% equilibrium water dissociation fraction at room temperature. Due to the relevance of surface hydroxyl groups to the surface chemistry of TiO2, our model might be key to understanding phenomena ranging from surface functionalization to photocatalytic mechanisms.
- Authors:
-
[1];
[1];
[1]
- Department of Chemistry, Princeton University, Princeton, USA
- Program in Applied and Computational Mathematics, Princeton University, Princeton, USA
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1597525
- Alternate Identifier(s):
- OSTI ID: 1597245
- Grant/Contract Number:
- SC0007347; SC0019394; AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 9; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Calegari Andrade, Marcos F., Ko, Hsin-Yu, Zhang, Linfeng, Car, Roberto, and Selloni, Annabella. Free energy of proton transfer at the water–TiO 2 interface from ab initio deep potential molecular dynamics. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9SC05116C.
Calegari Andrade, Marcos F., Ko, Hsin-Yu, Zhang, Linfeng, Car, Roberto, & Selloni, Annabella. Free energy of proton transfer at the water–TiO 2 interface from ab initio deep potential molecular dynamics. United Kingdom. https://doi.org/10.1039/C9SC05116C
Calegari Andrade, Marcos F., Ko, Hsin-Yu, Zhang, Linfeng, Car, Roberto, and Selloni, Annabella. Thu .
"Free energy of proton transfer at the water–TiO 2 interface from ab initio deep potential molecular dynamics". United Kingdom. https://doi.org/10.1039/C9SC05116C.
@article{osti_1597525,
title = {Free energy of proton transfer at the water–TiO 2 interface from ab initio deep potential molecular dynamics},
author = {Calegari Andrade, Marcos F. and Ko, Hsin-Yu and Zhang, Linfeng and Car, Roberto and Selloni, Annabella},
abstractNote = {TiO2 is a widely used photocatalyst in science and technology and its interface with water is important in fields ranging from geochemistry to biomedicine. Yet, it is still unclear whether water adsorbs in molecular or dissociated form on TiO2 even for the case of well-defined crystalline surfaces. To address this issue, we simulated the TiO2–water interface using molecular dynamics with an ab initio-based deep neural network potential. Our simulations show a dynamical equilibrium of molecular and dissociative adsorption of water on TiO2. Water dissociates through a solvent-assisted concerted proton transfer to form a pair of short-lived hydroxyl groups on the TiO2 surface. Molecular adsorption of water is ΔF = 8.0 ± 0.9 kJ mol-1 lower in free energy than the dissociative adsorption, giving rise to a 5.6 ± 0.5% equilibrium water dissociation fraction at room temperature. Due to the relevance of surface hydroxyl groups to the surface chemistry of TiO2, our model might be key to understanding phenomena ranging from surface functionalization to photocatalytic mechanisms.},
doi = {10.1039/C9SC05116C},
journal = {Chemical Science},
number = 9,
volume = 11,
place = {United Kingdom},
year = {Thu Mar 05 00:00:00 EST 2020},
month = {Thu Mar 05 00:00:00 EST 2020}
}
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https://doi.org/10.1039/C9SC05116C
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