title: Effect of Zn on the adsorption of CO on Pd(111).
abstract: Introduction of a second metal can greatly modify the surface reactivity of a host metal. Recently Jeroro and Vohs found that Pd(111) deposited with 0.03-0.06 monolayer of Zn might possess unique activity to methanol steam reforming reaction. To investigate the distribution of the deposited Zn, we examined the adsorption of CO on two types of model systems. In the first model, Zn is in the top-layer of Pd(111) only, while in the second model Zn is placed in the subsurface exclusively. It is found that Zn atoms in the topmost layer show negligible effect on CO adsorption especially at hollow sites, whereas the second layer Zn atoms affect significantly the interaction of CO with the substrate. It is revealed that the negligible influence of the first layer Zn on CO adsorption is due to the offsetting of the ligand effect by the strain effect. On the other hand, the ligand effect dominates the CO adsorption in the second model where the strain effect is insignificant. It is demonstrated that the d-band centers correlate well with the binding energies of the second model, whereas no such good correlation exists for the first model. Our results show that the subsurface plays a more important role and the observed dramatic modification of surface reactivity of Pd(111) deposited with 0.03-0.06 ML Zn is most likely originated from the subsurface Zn atoms, if the coverage is not underestimated and the deposited Zn atoms are distributed uniformly within a layer.
authors.affiliation: Key Laboratory of Mesoscopic Chemistry of MOE, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China.
authors.forename: Yucheng
authors.initials: Y
authors.lastname: Huang
authors.forename: Weiping
authors.initials: W
authors.lastname: Ding
authors.forename: Zhao-Xu
authors.initials: ZX
authors.lastname: Chen
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry*; D008958:Models, Molecular; D010165:Palladium / Q000737:chemistry*; D011789:Quantum Theory; D013499:Surface Properties; D015032:Zinc / Q000737:chemistry*
chemical_list: D002245:Carbon Dioxide; D010165:Palladium; D015032:Zinc