Competing, Coverage-Dependent Decomposition Pathways for C2Hy Species on Nickel (111)

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 C2Hy 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 (Ebond ) 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 Ebond ) 19.7, 63.2, and 93.6 kcal/mol, respectively. The remaining species (CHCH, CCH, and C2) 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 Ebond ) 57.7, 120.4, and 162.8 kcal/mol, respectively. We find that CHCHad is the most stable surface species (∆Heth ) -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 (∆Heth ) -18.2 kcal/mol), lying along an alternative decomposition pathway that is preferred for high-surface-coverage conditions. The existence of these competing, lowand 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 Ni468 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].