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  Electronic structure of aqueous-phase anatase titanium dioxide nanoparticles probed by liquid jet photoelectron spectroscopy

Ali, H., Seidel, R., Bergmann, A., & Winter, B. (2019). Electronic structure of aqueous-phase anatase titanium dioxide nanoparticles probed by liquid jet photoelectron spectroscopy. Journal of Materials Chemistry A, 7(12), 6665-6675. doi:10.1039/C8TA09414D.

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Ali, Hebatallah1, 2, Author              
Seidel, Robert3, 4, Author
Bergmann, Arno3, Author
Winter, Bernd1, Author              
Affiliations:
1Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
2Fachbereich Physik, Freie Universität Berlin, Arnimallee 14, D-14195 Berlin, Germany, ou_persistent22              
3Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Straße 15, D-12489 Berlin, Germany , ou_persistent22              
4Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany , ou_persistent22              

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 Abstract: We report on the nature of water interactions with anatase TiO2 surfaces. TiO2 nanoparticles (NPs), 3, 6, 10, and 20 nm in diameter, dispersed in different aqueous solutions, were investigated by soft-X-ray photoemission spectroscopy from liquid microjets. One central aspect of this study is the characterization of the electronic structure and identification of the molecular species that exist at the NP–aqueous solution interface as a function of solution pH. Valence and core-level electron binding energies are determined by the respective non-resonant photoelectron spectra. In addition, we report resonant photoemission spectra at the Ti 2p and the O 1s edges, which considerably increases the detection sensitivity of the interfacial species. This also allows us to distinguish between titanium at the surface and inside the aqueous-phase NPs. Furthermore, from the Ti 2p resonant photoelectron spectra, we obtain the so-called partial electron yield X-ray absorption (PEY-XA) spectra, which help here to rule out an anatase-phase transformation or the occurrence of Ti3+ sites due to oxygen defects. However, a more direct spectral feature that allows us to distinguish between molecularly and dissociatively adsorbed water is provided by the actual O 1s resonant photoelectron spectra. This is then exploited to show that water adsorbs molecularly at low pH, and dissociative adsorption at the TiO2 NP (aq) surface is observed at basic pH. Based on our results, we propose a mechanism of the anatase TiO2–H2O interaction that explicitly accounts for the local solution chemical environment. Here, H2O and OH- adsorb at the Ti sites, and no oxygen defects exist.

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Language(s): eng - English
 Dates: 2018-09-282018-12-192018-12-202019-03-28
 Publication Status: Published in print
 Pages: 11
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C8TA09414D
 Degree: -

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Title: Journal of Materials Chemistry A
  Abbreviation : J. Mater. Chem. A
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: 11 Volume / Issue: 7 (12) Sequence Number: - Start / End Page: 6665 - 6675 Identifier: ISSN: 2050-7488
CoNE: https://pure.mpg.de/cone/journals/resource/2050-7488