Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 114, Issue 47, Pages 20028-20041Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp105513g
Keywords
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Funding
- Intel Components Research
- Intel Corporate Research
- WCU through the National Research Foundation of Korea [31-2008-000-10055-0]
- National Research Foundation of Korea [R31-2008-000-10055-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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Competing, coverage-dependent pathways for ethane (CH3CH3) decomposition on Ni(111) are proposed on the basis of quantum mechanics (QM) calculations, performed by using the PBE flavor of density functional theory (DFT), for all C2H, species adsorbed to a periodically infinite Ni(111) surface. For CH2CH3, CHCH3, and CCH3, we find that the surface C is tetrahedral in each case, with the surface C forming bonds to one, two, or three Ni atoms with bond energies scaling nearly linearly (E-bond = 32.5, 82.7, and 130.8 kcal/mol, respectively). In each of the remaining six C2Hy species, both C atoms are able to form bonds to the surface. Three of these (CH2CH2, CHCH2, and CCH2) adsorb most favorably at a fcc-top site with the methylene C located at an on-top site and the other C at an adjacent fcc site. The bond energies for these species are E-bond = 19.7, 63.2, and 93.6 kcal/mol, respectively. The remaining species (CHCH, CCH, and C-2) all prefer binding at fcc-hcp sites, where the C atoms sit in a pair of adjacent fcc and hcp sites, with binding energies of E-bond = 57.7, 120.4, and 162.8 kcal/mol, respectively. We find that CHCHad is the most stable surface species (Delta H-eth = -18.6), and an important intermediate along the lowest-energy decomposition pathway for ethane on Ni(111). The second most stable species, CCH3, is a close competitor (Delta H-eth = -18.2 kcal/mol), lying along an alternative decomposition pathway that is preferred for high-surface-coverage conditions. The existence of these competing, low- and high-coverage decomposition pathways is consistent with the experiments. The QM results reported here were used as training data in the development of the ReaxFF reactive force field describing hydrocarbon reactions on nickel surfaces [Mueller, J. E.; van Duin, A: C. T.; Goddard, W. A. J. Phys. Chem. C 2010, 114, 4939-4949]. This has enabled Reactive dynamics studying the chemisorption and decomposition of systems far too complex for quantum mechanics. Thus we reported recently, the chemisorption and decomposition of six different hydrocarbon species on a Ni-468 nanoparticle catalysts using this ReaxFF description [Mueller, J. E.; van Duin, A: C. T.; Goddard, W. A. J. Phys. Chem. C 2010, 114, 5675-5685].
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