Molybdenum Carbide Nanocatalysts at Work in the in Situ Environment: A Density Functional Tight-Binding and Quantum Mechanical/Molecular Mechanical Study.

Heterogeneous reactions catalyzed by transition-metal-containing nanoparticles represent a crucial type of reaction in chemical industry. Because of the existing gap in understanding heterogeneous catalysis between a cluster of a few atoms and a bulk model of periodic slabs, reactions catalyzed by t...

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Publicado en:Journal of the American Chemical Society Vol. 137; no. 12; pp. 4249 - 4260
Autores principales: Xingchen Liu, Salahub, Dennis R.
Formato: Artículo
Publicado: American Chemical Society 4/1/2015
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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      pub: American Chemical Society
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        10.1021/jacs.5b01494
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        atl: Molybdenum Carbide Nanocatalysts at Work in the in Situ Environment: A Density Functional Tight-Binding and Quantum Mechanical/Molecular Mechanical Study.
      aug:
        au:
          Xingchen Liu
          Salahub, Dennis R.
        affil: Department of Chemistry, Institute for Quantum Science and Technology, and Centre for Molecular Simulation, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada
      su:
        Catalysts
        Transition metals
        Nanoparticles
        Chemical industry
        Free energy (Thermodynamics)
      sug:
        subj:
          Catalysts
          Transition metals
          Nanoparticles
          Chemical industry
          Free energy (Thermodynamics)
      ab: Heterogeneous reactions catalyzed by transition-metal-containing nanoparticles represent a crucial type of reaction in chemical industry. Because of the existing gap in understanding heterogeneous catalysis between a cluster of a few atoms and a bulk model of periodic slabs, reactions catalyzed by transition-metal-containing nanoparticles are still not well understood. Herein, we provide a multiscale modeling approach to study the benzene hydrogenation reactions on molybdenum carbide nanoparticles (MCNPs) in the process of in situ heavy oil upgrading. By coupling the quantum mechanical (QM) density functional tight-binding (DFTB) method with a molecular mechanical (MM) force field, a QM/MM model was built to describe the reactants, the nanoparticles and the surroundings. Umbrella sampling (US) was used to calculate the free energy profiles of the benzene hydrogenation reactions in a model aromatic solvent in the in situ heavy oil upgrading conditions. By comparing with the traditional method in computational heterogeneous catalysis, the results reveal new features of the metallic MCNPs. Rather than being rigid, they are very flexible under working condition due to the entropic contributions of the MCNPs and the solvent, which greatly affect the free energy profiles of these nanoscale heterogeneous reactions.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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