Ab Initio Study of Hydrogen Adsorption in MOF-5.

Metal-organic frameworks (MOFs) are promising adsorbents for hydrogen storage. Density functional theory and second-order MølIer-Plesset perturbation theory (MP2) are used to calculate the interaction energies between H2 and individual structural elements of the MOF-5 framework. The strongest intera...

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Publicado en:Journal of the American Chemical Society Vol. 131; no. 11; pp. 4143 - 4152
Autores principales: SiIlar, Kaido, Hofmann, Alexander, Sauer, Joachim
Formato: Artículo
Publicado: American Chemical Society 3/25/2009
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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      dt: 3/25/2009
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      pub: American Chemical Society
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        37258149
        10.1021/ja8099079
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        atl: Ab Initio Study of Hydrogen Adsorption in MOF-5.
      aug:
        au:
          SiIlar, Kaido
          Hofmann, Alexander
          Sauer, Joachim
        affil:
          Institut für Cheinie, Humboldt-Uniuersitat zu Berlin, Berlin, Germany
          Cluster of Excellence, UNICAT, Berlin
      su:
        Density functionals
        Dispersion (Chemistry)
        Atmospheric temperature
        Adsorption (Chemistry)
        Hydrogen
        Energy transfer
      sug:
        subj:
          Density functionals
          Dispersion (Chemistry)
          Atmospheric temperature
          Adsorption (Chemistry)
          Hydrogen
          Energy transfer
      ab: Metal-organic frameworks (MOFs) are promising adsorbents for hydrogen storage. Density functional theory and second-order MølIer-Plesset perturbation theory (MP2) are used to calculate the interaction energies between H2 and individual structural elements of the MOF-5 framework. The strongest interaction, ΔH= -7.1 kJ/mol, is found for the α-site of the OZn(OPh) nodes. We show that dispersion interactions and zero-point vibrational energies must be taken into account. Comparison of calculations done under periodic boundary conditions for the complete structure with those done for finite models cut from the MOF-5 framework shows that the interactions with H originate mainly from the local environment around the adsorption site. When used within a Multi-Langmuir model, the MP2 results reproduce measured adsorption isotherms (the predicted amount is 6 wt % at 77 K and 40 bar) if we assume that the H molecules preserve their rotational degrees of freedom in the adsorbed state. This allows to discriminate between different isotherms measured for different MOF-5 samples and to reliably predict isotherms for new MOF structures.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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