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Adsorption and Reaction of NH3 on Rutile TiO2(110): An STM Study

  • Hanna Bühlmeyer
    Hanna Bühlmeyer
    Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark
    Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
  • Kræn C. Adamsen
    Kræn C. Adamsen
    Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark
  • Tao Xu
    Tao Xu
    Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark
    Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
    More by Tao Xu
  • Lutz Lammich
    Lutz Lammich
    Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark
    More by Lutz Lammich
  • Jörg Libuda
    Jörg Libuda
    Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
    More by Jörg Libuda
  • Jeppe V. Lauritsen*
    Jeppe V. Lauritsen
    Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark
    *(J.V.L.) Email [email protected]. Phone ++45/23382369.
  • , and 
  • Stefan Wendt*
    Stefan Wendt
    Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark
    *(S.W.) Email [email protected]. Phone ++45/52804185.
    More by Stefan Wendt
Cite this: J. Phys. Chem. C 2022, 126, 15, 6590–6600
Publication Date (Web):April 7, 2022
https://doi.org/10.1021/acs.jpcc.2c01414
Copyright © 2022 American Chemical Society

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    Abstract

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    By means of high-resolution scanning tunneling microscopy (STM), we studied the adsorption and reaction of submonolayer NH3 on rutile TiO2(110) surfaces in different oxidation states. On a clean, reduced TiO2(110) surface with O vacancies, NH3 adsorbs at 120 K exclusively as single molecular species on surface Ti sites. On a TiO2(110) surface with H adatoms, we observed small amounts of NH3 monomers in close proximity to each other and NH3 dimers, in addition to the majority of isolated NH3 monomers. On such a surface, we found that NH3 and H adatoms can diffuse together along the [001] direction and NH3 can diffuse along the [11̅0] direction via “hydroxyl bridges”. On an oxidized TiO2(110) surface with O adatoms (Oot) and O2 molecules, we found dimeric NH3 species and isolated OHt groups. Interestingly, there were also grouped adsorbates of NH2OH stoichiometry (singles and pairs). Following annealing at 330 K, the coverage of paired NH2OH species was much increased. We find a strong affinity of NH3 species to interact with Oot adatoms and Oot adatom pairs and propose dissociation of NH3 species at Oot adatoms. Finally, we discuss the faith of the observed adsorbates at elevated temperature.

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