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Evaluating the hydrogen chemisorption and physisorption energies for nitrogen-containing single-walled carbon nanotubes with different chiralities: a density functional theory study

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Abstract

The hydrogen adsorption energies for nitrogen-containing carbon nanotubes (N-CNTs) and for bare carbon nanotubes were calculated using the density functional theory methods at the B3LYP/6–31-G(d) level, including dispersion force corrections. The N-CNTs were finite saturated and non-saturated single-walled carbon nanotubes that contained one or more pyrimidine units, the relative positions of which defined the different configurations of the nanotube. The chemisorption of atomic hydrogen to a full exocyclic monolayer of zigzag, armchair, and chiral N-CNTs was studied as a function of the structural parameters. Zigzag N-CNTs of any configuration, with a larger number of nitrogen atoms, a small diameter and a small length, are more reactive compared to chiral and armchair N-CNTs. The presence of nitrogen in the carbon nanotubes enhances their reactivity to chemisorb atomic hydrogen, showing exothermic energy values. In contrast, the physisorption of molecular hydrogen was endothermic for most of the studied saturated N-CNTs, even when including corrections for van der Waals interactions. The endothermicity was greatest for zigzag nanotubes, then decreased for chiral nanotubes and decreased again for armchair nanotubes. In general, the endothermicity decreased for longer nanotubes, which have larger diameters, and a small number of nitrogen atoms. The results of this study suggest that, with saturated bare carbon nanotubes, saturated, and unsaturated N-CNTs could potentially have a higher capacity as hydrogen-storage media than the corresponding unsaturated carbon nanotubes.

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Acknowledgments

This work was partially supported by the Direction of Scientific and Technological Research DICYT-USACH Project Nr. 061342CF and by the Sociedad de Desarrollo Tecnológico SDT-USACH project Nr. CIA 2981. In addition, the central cluster of the Faculty of Chemistry and Biology and the VRID of the University of Santiago de Chile are acknowledged for allocating computational resources.

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The authors declare that they have no conflict of interest.

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Authors and Affiliations

  1. Laboratorio de Química Computacional y Propiedad Intelectual, Departamento de Ciencias del Ambiente, Facultad de Química y Biología, Universidad de Santiago de Chile, Usach, Casilla 40, Correo 33, Avenida Libertador Bernardo O’Higgins 3363, Estación Central, 71772-K, Santiago, Chile

    M. Leonor Contreras, Diego Cortés-Arriagada & Roberto Rozas

  2. Departamento de Informática, Facultad de Ingeniería, Universidad de Santiago de Chile, Usach, Avenida Ecuador 3659, Estación Central, Santiago, Chile

    Ignacio Villarroel & José Alvarez

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  1. M. Leonor Contreras
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  2. Diego Cortés-Arriagada
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  3. Ignacio Villarroel
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  4. José Alvarez
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  5. Roberto Rozas
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Correspondence to M. Leonor Contreras.

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Contreras, M.L., Cortés-Arriagada, D., Villarroel, I. et al. Evaluating the hydrogen chemisorption and physisorption energies for nitrogen-containing single-walled carbon nanotubes with different chiralities: a density functional theory study. Struct Chem 25, 1045–1056 (2014). https://doi.org/10.1007/s11224-013-0377-z

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