(395al) On the Adsorption of Thiol Molecules On a Nickel Catalyst: A Theoretical Approach

Self-assembled molecules (SAMs) have been studied in literature and shown to modify the surface structure of the substrate on which they are adsorbed [1]. This surface modification results in a modification of the substrate’s properties. Specifically, adsorbed sulfur and thiols have been shown to rearrange the structure of metals including Ni [2-4]. It is expected that this would result in a modification of the electronic and geometric properties of the Ni surface and subsequently enhance (or hinder) its catalytic properties.
Density Functional Theory (DFT) calculations have been performed using Crystal 09 [5] to study the effect of adsorbed thiols molecules on the properties of Ni. Two nickel surfaces were modeled: Ni (1 1 1) and Ni (1 0 0) because it has been reported that adsorption of sulfur causes a reconstruction of (1 1 1) to (1 0 0)[6]. Geometry optimizations and frequency calculations were performed to elucidate the adsorption geometry, adsorbate -- adsorbate interactions, and the electronic properties of the catalyst and these results will be presented at the meeting.

References

[1] S. T. Marshall, M. O'Brien, B. Oetter, A. Corpuz, R. M. Richards, D. K. Schwartz, and J. W. Medlin, "Controlled selectivity for palladium catalysts using self-assembled monolayers," Nature Materials, vol. 9, pp. 853-858, 2010.
[2] G. Somorjai, "Surface Reconstruction and Catalysis," Annual Review of Physical Chemistry, vol. 45, pp. 721-751, 1994.
[3] D. Mullins, D. Huntley, and S. Overbury, "The nature of the sulfur induced surface reconstruction on Ni(1 1 1)," Surface Science, vol. 323, pp. L287-L292, 1995.
[4] D. Alfonso, "Computational Studies of Experimentally Observed Structures of Sulfur on Metal Surfaces," Journal of Physical Chemistry C, vol. 115, pp. 17077-17091, 2011.
[5] R. Dovesi, V. R. Saunders, C. Roetti, R. Orlando, C. M. Zicovich-Wilson, F. Pascale, B. Civalleri, K. Doll, N. M. Harrison, I. J. Bush, P. D'Arco, and M. Llunell, CRYSTAL09 User's Manual. University of Torino, Torino, 2010.
[6] V. Maurice, N. Kitakatsu, M. Siegers, and P. Marcus, "Low-coverage sulfur induced reconstruction of Ni(111)," Surface Science, vol. 373, pp. 307-317, 1997.