Reaction of NO on Ni-Pt bimetallic surfaces investigated with theoretical calculations

Shiuan Yau Wu, Yu Chieh Lin, Jia-Jen Ho

Research output: Contribution to journalArticle

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Abstract

We applied periodic density-functional theory to investigate the adsorption and dissociation of NO on bimetallic surfaces, including the xNi@Pt(111), NixPt4-x(111), and (4-x)Pt@Ni(111) surfaces (x = 0-4). For all bimetallic surfaces, NO is preferentially adsorbed on Ni-rich sites, and the adsorption energies increase with an increasing number of top-layer Ni atoms on the surface. When the top-layer compositions are equal (but with varied composition of inner layers), the adsorption energy of NO on these surfaces decreases in the order xNi@Pt(111) > NixPt4-x(111) > (4-x)Pt@Ni(111), whereas the NO dissociation barriers increase in the opposite order; a larger adsorption energy of NO leads to a smaller NO dissociation barrier. We employed the local density of states to investigate the inner-layer effect of the various surfaces; the inner-layer Pt atoms of the 4Ni@Pt(111) surface caused the greatest upshift of the d-band center (of top-layer Ni atoms) toward the Fermi energy, so that the 4Ni@Pt(111) surface exhibited the greatest NO adsorption energy, -2.97 eV, and the smallest NO dissociation barrier, 1.20 eV. In contrast, the inner-layer Ni atoms of the (4-x)Pt@Ni(111) surfaces cause a downshift of the d-band center from the Fermi energy and show much smaller NO adsorption energies and larger NO dissociation barriers. The order of reactivity for dissociation of NO (4Ni@Pt(111) > Ni(111) > NixPt 4-x(111) > Pt(111) > 4Pt@Ni(111)) indicates that various combinations of Ni and Pt would produce varied catalytic effects.

Original languageEnglish
Pages (from-to)7538-7544
Number of pages7
JournalJournal of Physical Chemistry C
Volume115
Issue number15
DOIs
Publication statusPublished - 2011 Apr 21

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dissociation
Adsorption
adsorption
Atoms
energy
Fermi level
atoms
Chemical analysis
Density functional theory
reactivity
density functional theory
causes

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Reaction of NO on Ni-Pt bimetallic surfaces investigated with theoretical calculations. / Wu, Shiuan Yau; Lin, Yu Chieh; Ho, Jia-Jen.

In: Journal of Physical Chemistry C, Vol. 115, No. 15, 21.04.2011, p. 7538-7544.

Research output: Contribution to journalArticle

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AB - We applied periodic density-functional theory to investigate the adsorption and dissociation of NO on bimetallic surfaces, including the xNi@Pt(111), NixPt4-x(111), and (4-x)Pt@Ni(111) surfaces (x = 0-4). For all bimetallic surfaces, NO is preferentially adsorbed on Ni-rich sites, and the adsorption energies increase with an increasing number of top-layer Ni atoms on the surface. When the top-layer compositions are equal (but with varied composition of inner layers), the adsorption energy of NO on these surfaces decreases in the order xNi@Pt(111) > NixPt4-x(111) > (4-x)Pt@Ni(111), whereas the NO dissociation barriers increase in the opposite order; a larger adsorption energy of NO leads to a smaller NO dissociation barrier. We employed the local density of states to investigate the inner-layer effect of the various surfaces; the inner-layer Pt atoms of the 4Ni@Pt(111) surface caused the greatest upshift of the d-band center (of top-layer Ni atoms) toward the Fermi energy, so that the 4Ni@Pt(111) surface exhibited the greatest NO adsorption energy, -2.97 eV, and the smallest NO dissociation barrier, 1.20 eV. In contrast, the inner-layer Ni atoms of the (4-x)Pt@Ni(111) surfaces cause a downshift of the d-band center from the Fermi energy and show much smaller NO adsorption energies and larger NO dissociation barriers. The order of reactivity for dissociation of NO (4Ni@Pt(111) > Ni(111) > NixPt 4-x(111) > Pt(111) > 4Pt@Ni(111)) indicates that various combinations of Ni and Pt would produce varied catalytic effects.

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