Location, Acid Strength, and Mobility of the Acidic Protons in Keggin 12-HPWO: A Combined Solid-State NMR Spectroscopy and DFT Quantum Chemical Calculation Study.

Solid-state C NMR experiments and quantum chemical Density Functional Theory (DFT) calculations of acetone adsorption were used to study the location of protons in anhydrous 12-tungstophosphoric acid (HPW), the mobility of the isolated and hydrated acidic protons, and the acid strength heterogeneity...

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Publicado en:Journal of the American Chemical Society Vol. 127; no. 51; pp. 18274 - 18281
Autores principales: Jun Yang, Janik, Michael J., Ding Ma, Anmin Zheng, Mingjin Zhang, Neurock, Matthew, Davis, Robert J., Chaohui Ye, Feng Deng
Formato: Artículo
Publicado: American Chemical Society 12/28/2005
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Acceso en línea:Ver este registro en EBSCOhost
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        10.1021/ja055925z
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        atl: Location, Acid Strength, and Mobility of the Acidic Protons in Keggin 12-HPWO: A Combined Solid-State NMR Spectroscopy and DFT Quantum Chemical Calculation Study.
      aug:
        au:
          Jun Yang
          Janik, Michael J.
          Ding Ma
          Anmin Zheng
          Mingjin Zhang
          Neurock, Matthew
          Davis, Robert J.
          Chaohui Ye
          Feng Deng
        affil:
          Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences.
          University of Virginia.
          Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
      su:
        Protons
        Nuclear magnetic resonance spectroscopy
        Density functionals
        Acetone
        Adsorption (Chemistry)
        Hydroxyl group
      sug:
        subj:
          Protons
          Nuclear magnetic resonance spectroscopy
          Density functionals
          Acetone
          Adsorption (Chemistry)
          Hydroxyl group
      ab: Solid-state C NMR experiments and quantum chemical Density Functional Theory (DFT) calculations of acetone adsorption were used to study the location of protons in anhydrous 12-tungstophosphoric acid (HPW), the mobility of the isolated and hydrated acidic protons, and the acid strength heterogeneity of the anhydrous hydroxyl groups. This study presents the first direct NMR experimental evidence that there are two types of isolated protons with different acid strengths in the anhydrous Keggin HPW. Rotational Echo DOuble Resonance (REDOR) NMR experiments combined with quantum chemical DFT calculations demonstrated that acidic protons in anhydrous HPW are localized on both bridging (O) and terminal (O) atoms of the Keggin unit. The CP/MAS NMR experiments revealed that the isolated acidic protons are immobile, but hydrated acidic protons are highly mobile at room temperature. The isotropic chemical shift of the adsorbed acetone suggested that the acid strength of the H(HO) species in partially hydrated HPW is comparable to that of a zeolite, while the acidity of an isolated proton is much stronger than that of a zeolite. Isolated protons on the bridging oxygen atoms of anhydrous HPW are nearly superacidic.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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