Elucidating the water–anatase TiO2(101) interface structure using infrared signatures and molecular dynamics

O’Connor, Christopher R.; Calegari Andrade, Marcos F.; Selloni, Annabella; Kimmel, Greg A.

doi:10.1063/5.0161895

Title: Elucidating the water–anatase TiO₂(101) interface structure using infrared signatures and molecular dynamics

Journal Article · 13 September 2023 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0161895 · OSTI ID:2222807

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Princeton University, NJ (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Princeton University, NJ (United States)

The structure and dynamics of water on solid surfaces critically affect the chemistry of materials in ambient and aqueous environments. Here, we investigate the hydrogen bonding network of water adsorbed on the majority (101) surface of anatase TiO₂, a widely used photocatalyst, using polarization- and azimuth-resolved infrared spectroscopy combined with neural network potential molecular dynamics simulations. Our results show that one monolayer of water saturates the undercoordinated titanium (Ti_5c) sites, forming one-dimensional chains of molecule hydrogen bonded to surface undercoordinated bridging oxygen (O_2c) atoms. As the coverage increases, water adsorption on O_2c sites leads to significant restructuring of the water monolayer and the formation of a two-dimensional hydrogen bond network characterized by tightly bound pairs of water molecules on adjacent Ti_5c and O_2c sites. This structural motif likely persists at ambient conditions, influencing the reactions occurring there. In conclusion, the results reported here provide critical details of the structure of the water–anatase (101) interface that were previously hypothesized but unconfirmed experimentally.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830; AC52-07NA27344; FWP 16248; SC0019394

OSTI ID:: 2222807

Report Number(s):: PNNL-SA-189813; TRN: US2407189

Journal Information:: Journal of Chemical Physics, Vol. 159, Issue 10; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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