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Title: 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:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. Department of Chemistry, Princeton University, Princeton, USA
  2. 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. doi: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. doi: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 = {2020},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1039/C9SC05116C

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Cited by: 5 works
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