Structures, energetics, and reaction barriers for CHx bound to the nickel (111) surface

Jonathan E. Mueller, Adri C.T. Van Duin, William A. Goddard

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Abstract

To provide a basis for understanding and improving such reactive processes on nickel surfaces as the catalytic steam reforming of hydrocarbons, the decomposition of hydrocarbons at fuel cell anodes, and the growth of carbon nanotubes, we report quantum mechanics calculations (PBE flavor of density functional theory, DFT) of the structures, binding energies, and reaction barriers for all CHx species on the Ni(111) surface using periodically infinite slabs. We find that all CHx species prefer binding to μ3 (3-fold) sites leading to bond energies ranging from 42.7 kcal/mol for CH3 to 148.9 kcal/mol for CH (the number of Ni-C bonds is not well-defined). We find reaction barriers of 18.3 kcal/mol for CH 3,ad → CH2,ad + Had (with ΔE ) +1.3 kcal/ mol), 8.2 kcal/mol for CH2,ad → CHad + H ad (with ΔE ) -10.2 kcal/mol) and 32.3 kcal/mol for CH ad → Cad + Had (with ΔE ) 11.6 kcal/mol). Thus, CHad is the stable form of CHx on the surface. These results are in good agreement with the experimental data for the thermodynamic stability of small hydrocarbon species following dissociation of methane on Ni(111) and with the intermediates isolated during the reverse methanation process.

Original languageEnglish (US)
Pages (from-to)20290-20306
Number of pages17
JournalJournal of Physical Chemistry C
Volume113
Issue number47
DOIs
StatePublished - Dec 8 2009

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All Science Journal Classification (ASJC) codes

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

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