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Density functional study of benzene adsorption on the α-Mo2C(0001) surface

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Abstract

Molybdenum carbide (Mo2C) is a valuable industrial catalyst for hydrogenation (HYD) of aromatic compounds—an essential step in in-situ heavy-oil upgrading. Despite the intensive studies on catalytic properties of molybdenum carbides, the basic mechanism of HYD reactions occurring on the surface of Mo2C remains vague. We studied the adsorption of benzene on an α-Mo2C(0001) surface at 0.25-mL coverage with first-principles density functional theory (DFT) calculations to provide further insight into the catalytic mechanism. Five high-symmetry adsorption sites combined with two different orientations of the aromatic ring parallel to the surface were investigated at the GGA-PBE level of DFT. Our results suggest that hollow sites are preferred over bridge sites. For the most favorable adsorption sites, i.e., Hc and Vc, the adsorption energy is ca. −2.5 eV. In addition, DFT-D2 calculations were carried out to incorporate the effect of dispersion. Consequently, the adsorption energies at various sites increased by ca. −1.3 eV in general, while the adsorption geometries were little affected. Analysis of the optimized adsorption geometries and the partial density of states revealed a strong interaction between the aromatic ring of benzene and the Mo2C surface, which leads to the rehybridization of benzene carbon atoms, from sp 2 to sp 3.

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Acknowledgments

We thank Dr. Pedro Pereira’s group at the University of Calgary for useful discussions on the synthesis and characterization of the Mo2C catalyst as well as the catalytic mechanism. We gratefully acknowledge financial support from the Natural Sciences and Engineering Research Council (NSERC) of Canada through a CIAM (InterAmericas Collaboration on Materials) grant as well as the provision of computational resources by Compute Canada/WestGrid.

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Authors and Affiliations

  1. Department of Chemistry and ISSSE (Institute for Sustainable Energy, Environment and Economy), University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada

    Baojing Zhou, Xingchen Liu, Javier Cuervo & Dennis R. Salahub

  2. Department of Chemistry, Computational Institute for Molecules and Materials, Nanjing University of Science and Technology, Nanjing, 210094, China

    Baojing Zhou

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  1. Baojing Zhou
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  2. Xingchen Liu
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  3. Javier Cuervo
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  4. Dennis R. Salahub
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Correspondence to Dennis R. Salahub.

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Zhou, B., Liu, X., Cuervo, J. et al. Density functional study of benzene adsorption on the α-Mo2C(0001) surface. Struct Chem 23, 1459–1466 (2012). https://doi.org/10.1007/s11224-012-0064-5

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  • DOI: https://doi.org/10.1007/s11224-012-0064-5

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