First-Principles Modeling of a Dye-Sensitized TiO/lrO Photoanode for Water Oxidation.

We present a first-principle computational modeling investigation, based on density functional theory (DFT) and time-dependent DFT, on the structural, electronic, optical, and charge generation properties of the semiconductor/dye/catalyst heterointerfaces in a prototypical dye-sensitized photoanode...

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Publicado en:Journal of the American Chemical Society Vol. 137; no. 17; pp. 5798 - 5810
Autores principales: Pastore, Mariachiara, De Angelis, Filippo
Formato: Artículo
Publicado: American Chemical Society 5/6/2015
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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      dt: 5/6/2015
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      pub: American Chemical Society
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        102837737
        10.1021/jacs.5b02128
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        atl: First-Principles Modeling of a Dye-Sensitized TiO/lrO Photoanode for Water Oxidation.
      aug:
        au:
          Pastore, Mariachiara
          De Angelis, Filippo
        affil: Computational Laboratory for Hybrid Organic Photovoltaics (CLHYO), CNR-ISTM, via Elce di Sotto 8, 1-06123 Perugia, Italy
      su:
        Oxidation
        Anodes
        Density functional theory
        Chemical reactions
        Charge exchange
        Catalysts
      sug:
        subj:
          Oxidation
          Anodes
          Density functional theory
          Chemical reactions
          Charge exchange
          Catalysts
      ab: We present a first-principle computational modeling investigation, based on density functional theory (DFT) and time-dependent DFT, on the structural, electronic, optical, and charge generation properties of the semiconductor/dye/catalyst heterointerfaces in a prototypical dye-sensitized photoanode for water oxidation. The investigated architecture comprises a Ru(ll) dye-sensitized TiO substrate tethered to an IrO nanoparticle catalyst. Our realistic modeling strategy and quantitative analysis of the relevant interfacial hole/electron transfer reactions indicates the slow hole injection into IrO and the fast dye excited-state quenching to IrO as the primary sources of the relatively poor cell efficiency experimentally observed. On the basis of this atomistic and electronic structure information, we propose and computationally test, against a prototype dye, a new class of Ru(II) sensitizers, which show potentially improved photoelectrochemical performances. This study constitutes a first step toward the computer-assisted design of new and more efficient materials for solar fuels production through dye-sensitized photoelectrochemical cells.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2015
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