Origin of hydroxyl pair formation on reduced anatase TiO2(101)

Adamsen, Kræn C.; Petrik, Nikolay G.; Dononelli, Wilke; Kimmel, Greg A.; Xu, Tao; Li, Zheshen; Lammich, Lutz; Hammer, Bjørk; Lauritsen, Jeppe V.; Wendt, Stefan

doi:10.1039/d3cp01051a

Title: Origin of hydroxyl pair formation on reduced anatase TiO₂(101)

Journal Article · 01 May 2023 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d3cp01051a · OSTI ID:1996329

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^[2]; Dononelli, Wilke ^[3];

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Aarhus Univ. (Denmark)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Aarhus Univ. (Denmark); Univ. of Bremen (Germany)

The interaction of water with metal oxide surfaces is of key importance to several research fields and applications. Because of its ability to photo-catalyze water splitting, reducible anatase TiO₂(a-TiO₂) is of particular interest. Here, we combine experiments and theory to study the dissociation of water on bulk-reduced a-TiO₂(101). Following large water exposures at room temperature, point-like protrusions appear on the a-TiO₂(101) surface, as shown by scanning tunneling microscopy (STM). These protrusions originate from hydroxyl pairs, consisting of terminal and bridging OH groups, OH_t/OH_b, as revealed by infrared reflection absorption spectroscopy (IRRAS) and valence band experiments. Utilizing density functional theory (DFT) calculations, we offer a comprehensive model of the water/a-TiO₂(101) interaction. In conclusion, this model also explains why the hydroxyl pairs are thermally stable up to ~480 K.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: Danish National Research Foundation; Innovation Fund Denmark (IFD); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER); Villum Foundation

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1996329

Report Number(s):: PNNL-SA-178908

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 19 Vol. 25; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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