Adsorption of Water on Reconstructed Rutile TiO(011 )-(2 X 1): Ti=O Double Bonds and Surface Reactivity.

Recent combined experimental and theoretical studies (Beck et al., Phys. Rev. Left. 2004, 93, 036104) have provided evidence for Ti=O double-bonded titanyl groups on the reconstructed rutile TiO- (011)-(2× 1) surface. The adsorption of water on the same surface is now investigated to further probe t...

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Publicado en:Journal of the American Chemical Society Vol. 127; no. 27; pp. 9895 - 9904
Autores principales: Di Valentin, Cristiana, Tilocca, Antonio, Selloni, Annabella, T. J. Beck, Andreas Klust, Matthias Batzill, Losovyj, Yaroslav, Diebold, Ulrike
Formato: Artículo
Publicado: American Chemical Society 7/13/2005
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 7/13/2005
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      pub: American Chemical Society
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        10.1021/ja0511624
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        atl: Adsorption of Water on Reconstructed Rutile TiO(011 )-(2 X 1): Ti=O Double Bonds and Surface Reactivity.
      aug:
        au:
          Di Valentin, Cristiana
          Tilocca, Antonio
          Selloni, Annabella
          T. J. Beck
          Andreas Klust
          Matthias Batzill
          Losovyj, Yaroslav
          Diebold, Ulrike
        affil:
          Dipartimento di Scienza dei Materiali, Universitè degli Studi di Milano-Bicocca, 20125 Milano, Italy.
          Department of Chemistry, Princeton University, Princeton, New Jersey 08540.
          Department of Physics, Tulane University, New Orleans, Louisiana 70118.
          Center for Advanced Microstructures and Devices, Louisiana State University, Baton Rouge, Louisiana 70806.
          Department of Physics and Astronomy and the Center for Material Research and Analysis, University of Nebraska, Lincoln, Nebraska 68588.
      su:
        Titanium compounds
        Adsorption (Chemistry)
        Surface chemistry
        Photoemission
        Ultraviolet radiation
        Hydroxyl group
      sug:
        subj:
          Titanium compounds
          Adsorption (Chemistry)
          Surface chemistry
          Photoemission
          Ultraviolet radiation
          Hydroxyl group
      ab: Recent combined experimental and theoretical studies (Beck et al., Phys. Rev. Left. 2004, 93, 036104) have provided evidence for Ti=O double-bonded titanyl groups on the reconstructed rutile TiO- (011)-(2× 1) surface. The adsorption of water on the same surface is now investigated to further probe the properties of these groups, as well as to confirm their existence. Ultraviolet photoemission experiments show that water is adsorbed in molecular form at a sample temperature of 110 K. At the same time, the presence of a 3σ state in the photoemission spectra and work function measurements indicate a significant amount of hydroxyls within the first monolayer of water. At room temperature, scanning tunneling microscopy (STM) suggests that dissociated water is present, and about 30% of the surface active sites are hydroxylated. These findings are well explained by total energy density functional theory calculations and Car—Parrinello molecular dynamics simulations for water adsorption on the titanyl model of TiO(011)-(2×1). The theoretical results show that a mixed molecular/dissociative layer is the most stable configuration in the monolayer regime at low temperatures, while complete dissociation takes place at 250 K. The arrangement of the protonated mono-coordinated oxygens in the mixed molecular/dissociated layer is consistent with the observed short-range order of the hydroxyls in the STM images.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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