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Electronic origins of photocatalytic activity in d0 metal organic frameworks.
Nasalevich, Maxim A; Hendon, Christopher H; Santaclara, Jara G; Svane, Katrine; van der Linden, Bart; Veber, Sergey L; Fedin, Matvey V; Houtepen, Arjan J; van der Veen, Monique A; Kapteijn, Freek; Walsh, Aron; Gascon, Jorge.
Afiliación
  • Nasalevich MA; Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, Delft, The Netherlands.
  • Hendon CH; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.
  • Santaclara JG; Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, Delft, The Netherlands.
  • Svane K; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.
  • van der Linden B; Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, Delft, The Netherlands.
  • Veber SL; Laboratory of Magnetic Resonance, International Tomography Center, Institutskaya 3A, Novosibirsk 630090, Russia.
  • Fedin MV; Novosibirsk State University, Novosibirsk 630090, Russia.
  • Houtepen AJ; Laboratory of Magnetic Resonance, International Tomography Center, Institutskaya 3A, Novosibirsk 630090, Russia.
  • van der Veen MA; Novosibirsk State University, Novosibirsk 630090, Russia.
  • Kapteijn F; Optoelectronic Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
  • Walsh A; Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, Delft, The Netherlands.
  • Gascon J; Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, Delft, The Netherlands.
Sci Rep ; 6: 23676, 2016 Mar 29.
Article en En | MEDLINE | ID: mdl-27020767
Metal-organic frameworks (MOFs) containing d(0) metals such as NH2-MIL-125(Ti), NH2-UiO-66(Zr) and NH2-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH2-MIL-125(Ti) promote a long lived ligand-to-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π* orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Sci Rep Año: 2016 Tipo del documento: Article País de afiliación: Países Bajos Pais de publicación: Reino Unido
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Sci Rep Año: 2016 Tipo del documento: Article País de afiliación: Países Bajos Pais de publicación: Reino Unido