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Thermodynamic study of benzene and hydrogen coadsorption on Pd(111)

(2014) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 16(43). p.23754-23768
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Abstract
Periodic density functional theory (DFT) has been used to study the coadsorption of hydrogen and benzene on Pd(111). The most stable coverages are predicted by constructing the thermodynamic phase diagram as a function of gas-phase temperature and pressure. The common approximation that neglects vibrational contributions to the surface Gibbs free energy, using the PW91 functional, is compared to the one that includes vibrational contributions. Higher coverages are predicted to be thermodynamically the most stable including vibrational frequencies, mainly due to the different entropy contributions. The first approach is also compared to the one using a (optPBE-vdW) vdW-DF functional without vibrational contributions, which predicts higher benzene coverages for benzene adsorption, and lower hydrogen coverages for hydrogen adsorption and coadsorption with a fixed benzene coverage. Inclusion of vibrational contributions using the vdW-DF method has not been implemented due to computational constraints. However, an estimate of the expected result is proposed by adding PW91 vibrational contributions to the optPBE-vdW electronic energies, and under typical hydrogenation conditions high coverages of about theta(H) = 0.89 are expected. Inclusion of vibrational contributions to the surface Gibbs free energy and a proper description of van der Waals interaction are recommended to predict the thermodynamically most stable surface coverage.
Keywords
ENERGY ELECTRON-DIFFRACTION, DENSITY-FUNCTIONAL THEORY, INITIO MOLECULAR-DYNAMICS, GAS-PHASE HYDROGENATION, NICKEL-SILICA CATALYST, AUGMENTED-WAVE METHOD, CARBON-MONOXIDE, METAL-SURFACES, PALLADIUM 111, HETEROGENEOUS CATALYSIS

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MLA
Canduela Rodriguez, Gonzalo et al. “Thermodynamic Study of Benzene and Hydrogen Coadsorption on Pd(111).” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 16.43 (2014): 23754–23768. Print.
APA
Canduela Rodriguez, G., Sabbe, M., Reyniers, M.-F., Joly, J.-F., & Marin, G. (2014). Thermodynamic study of benzene and hydrogen coadsorption on Pd(111). PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 16(43), 23754–23768.
Chicago author-date
Canduela Rodriguez, Gonzalo, Maarten Sabbe, Marie-Françoise Reyniers, Jean-François Joly, and Guy Marin. 2014. “Thermodynamic Study of Benzene and Hydrogen Coadsorption on Pd(111).” Physical Chemistry Chemical Physics 16 (43): 23754–23768.
Chicago author-date (all authors)
Canduela Rodriguez, Gonzalo, Maarten Sabbe, Marie-Françoise Reyniers, Jean-François Joly, and Guy Marin. 2014. “Thermodynamic Study of Benzene and Hydrogen Coadsorption on Pd(111).” Physical Chemistry Chemical Physics 16 (43): 23754–23768.
Vancouver
1.
Canduela Rodriguez G, Sabbe M, Reyniers M-F, Joly J-F, Marin G. Thermodynamic study of benzene and hydrogen coadsorption on Pd(111). PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2014;16(43):23754–68.
IEEE
[1]
G. Canduela Rodriguez, M. Sabbe, M.-F. Reyniers, J.-F. Joly, and G. Marin, “Thermodynamic study of benzene and hydrogen coadsorption on Pd(111),” PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 16, no. 43, pp. 23754–23768, 2014.
@article{5874186,
  abstract     = {Periodic density functional theory (DFT) has been used to study the coadsorption of hydrogen and benzene on Pd(111). The most stable coverages are predicted by constructing the thermodynamic phase diagram as a function of gas-phase temperature and pressure. The common approximation that neglects vibrational contributions to the surface Gibbs free energy, using the PW91 functional, is compared to the one that includes vibrational contributions. Higher coverages are predicted to be thermodynamically the most stable including vibrational frequencies, mainly due to the different entropy contributions. The first approach is also compared to the one using a (optPBE-vdW) vdW-DF functional without vibrational contributions, which predicts higher benzene coverages for benzene adsorption, and lower hydrogen coverages for hydrogen adsorption and coadsorption with a fixed benzene coverage. Inclusion of vibrational contributions using the vdW-DF method has not been implemented due to computational constraints. However, an estimate of the expected result is proposed by adding PW91 vibrational contributions to the optPBE-vdW electronic energies, and under typical hydrogenation conditions high coverages of about theta(H) = 0.89 are expected. Inclusion of vibrational contributions to the surface Gibbs free energy and a proper description of van der Waals interaction are recommended to predict the thermodynamically most stable surface coverage.},
  author       = {Canduela Rodriguez, Gonzalo and Sabbe, Maarten and Reyniers, Marie-Françoise and Joly, Jean-François and Marin, Guy},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keywords     = {ENERGY ELECTRON-DIFFRACTION,DENSITY-FUNCTIONAL THEORY,INITIO MOLECULAR-DYNAMICS,GAS-PHASE HYDROGENATION,NICKEL-SILICA CATALYST,AUGMENTED-WAVE METHOD,CARBON-MONOXIDE,METAL-SURFACES,PALLADIUM 111,HETEROGENEOUS CATALYSIS},
  language     = {eng},
  number       = {43},
  pages        = {23754--23768},
  title        = {Thermodynamic study of benzene and hydrogen coadsorption on Pd(111)},
  url          = {http://dx.doi.org/10.1039/C4CP02991G},
  volume       = {16},
  year         = {2014},
}

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