title: Investigation of H2 and H2S adsorption on niobium- and copper-doped palladium surfaces.
abstract: Alloying or doping Pd may be an option for overcoming sulfur poisoning. The current investigation probes the mechanism associated with sulfur binding to determine if Nb and Cu are appropriate doping metals. In this study, the effect of doping Pd with Cu or Nb on the binding strength of H(2) and H(2)S was investigated using plane-wave density functional theory-based electronic structure calculations to determine mechanisms of adsorption. Results of this work indicate that for pure Pd and Pd-doped surfaces, H(2) dissociates with the H atoms most stable on the fcc-fcc site. The overall d-band centers calculated for H(2) adsorption at the fcc-fcc site for the pure and doped-Pd surfaces indicate that the H(2) adsorption strength trend is Pd > Cu > Nb. Regarding H(2)S adsorption on Pd and Pd-doped surfaces, it was found that Cu has a lower affinity for H(2)S compared to Pd and Nb. The calculation of the local density of states of the s-, p-, and d-orbitals of the adsorbate-surface complex reveals an increase in the occupation of s-and p-states of the adsorbate and d-states of the dopant metals upon adsorption. In addition, the H(2)S binding trend is found to be Cu < Pd < Nb, with the doped-Cu surfaces exhibiting the weakest binding and doped-Nb surfaces the strongest binding. Geometry comparisons of each H(2)S-adsorbed complex shows that the hydrogen atoms are located closest to the surface in the case of Nb, indicating that the strong H-surface interaction leads to the enhanced adsorption behavior, rather than the S-surface interaction; in fact, the sulfur atom is located furthest from the surface doped with Nb.
authors.affiliation: Department of Energy Resources Engineering, School of Earth Sciences, Stanford University, Green Earth Sciences 065, 367 Panama Street, Stanford, California 94305, USA.
authors.forename: Ekin
authors.initials: E
authors.lastname: Ozdogan
authors.forename: Jennifer
authors.initials: J
authors.lastname: Wilcox