Energetics of van der Waals Adsorption on the Metal-Organic Framework NU-1000 with Zr-oxo, Hydroxo, and Aqua Nodes.

We report measurements of adsorption isotherms and the determination of the isosteric heats of adsorption of several small gases (H2, D2, Ne, N2, CO, CH4,C2H6, Ar, Kr, and Xe) on the metal-organic framework (MOF) NU-1000, which is one of the most thermally stable MOFs. It has transition-metal nodes...

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Publicado en:Journal of the American Chemical Society Vol. 140; no. 1; pp. 328 - 339
Autores principales: Zhang, Wei, Ma, Yuanyuan, Santos-Lopez, Iván A., Lownsbury, James M., Yu, Haoyu, Liu, Wei-Guang, Truhlar, Donald G., Campbell, Charles T., Vilches, Oscar E.
Formato: Artículo
Publicado: American Chemical Society 1/10/2018
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Acceso en línea:Ver este registro en EBSCOhost
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      pub: American Chemical Society
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        10.1021/jacs.7b10360
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        atl: Energetics of van der Waals Adsorption on the Metal-Organic Framework NU-1000 with Zr-oxo, Hydroxo, and Aqua Nodes.
      aug:
        au:
          Zhang, Wei
          Ma, Yuanyuan
          Santos-Lopez, Iván A.
          Lownsbury, James M.
          Yu, Haoyu
          Liu, Wei-Guang
          Truhlar, Donald G.
          Campbell, Charles T.
          Vilches, Oscar E.
        affil:
          Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States
          Department of Chemical Engineering, University of Washington, Seattle, Washington 98195-1750, United States
          Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States
          Department of Physics, University of Washington, Seattle, Washington 98195-1560, United States
      su:
        Metal-organic frameworks
        Van der Waals forces
        Adsorption isotherms
        Transition metal catalysts
        Benzoates
      sug:
        subj:
          Metal-organic frameworks
          Van der Waals forces
          Adsorption isotherms
          Transition metal catalysts
          Benzoates
      ab: We report measurements of adsorption isotherms and the determination of the isosteric heats of adsorption of several small gases (H2, D2, Ne, N2, CO, CH4,C2H6, Ar, Kr, and Xe) on the metal-organic framework (MOF) NU-1000, which is one of the most thermally stable MOFs. It has transition-metal nodes of formula Zr6(μ3-OH)4(μ3-O)4(OH)4(OH2)4 that resemble hydrated ZrO2 clusters and can serve as catalysts or catalyst supports. The linkers in this MOF are pyrenes linked to the nodes via the carboxylate groups of benzoates. The broad range of adsorbates studied here allows us to compare trends both with adsorption on other surfaces and with density functional calculations also presented here. The experimental isotherms indicate similar filling of the MOF surface by the di�€erent gases, starting with strong adsorption sites near the Zr atoms, a result corroborated by the density functional calculations. This adsorption is followed by the filling of other adsorption sites on the nodes and organic framework. Capillary condensation occurs in wide pores after completion of a monolayer. The total amount adsorbed for all the gases is the equivalent of two complete monolayers. The experimental isosteric heats of adsorption are nearly proportional to the atom-atom (or molecule- molecule) Lennard-Jones well-depth parameters of the adsorbates but ~13-fold larger. The density functional calculations show a similar trend but with much more scatter and heats that are usually greater (by 30%, on average).
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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