CO adsorption on nanoislands: Ni on Au(111)

The adsorption behavior of CO on Ni islands grown on Au(111) was studied with a combination of temperature programmed desorption, Fourier transform infrared spectroscopy, and surface resistivity measurements. The Au(111) herringbone reconstruction provides a template for the growth of ordered Ni islands, with evidence for the presence of strain and Au atoms within the islands. The islands grow radially until θ_Ni ≈ 0.3 ML, after which subsequent Ni atoms contribute primarily to a second layer. We study saturated CO adsorption at 227 K over a range of Ni island sizes and find layer-dependent adsorption properties. For single-layer islands at low Ni coverage, CO adsorbs primarily in the atop position and desorbs at lower temperatures than on pure Ni, with a saturation CO coverage of about 0.5 CO/Ni. As second layer Ni grows, saturated CO coverages on the Ni approach unity, with higher desorption temperatures, but still with primarily atop CO. Based on previous studies, we propose that in the first Ni layer, ligand effects from the Au substrate and possibly Au in the islands and strain due to the Ni/Au lattice mismatch affect the Ni-CO bonds. CO adsorption behavior on the two-layer islands is qualitatively explained by a decrease in Au nearest neighbors and the presence of a more expanded/corrugated structure.