关键词: Au/Cu(111), 单原子, 表面合金, CO吸附, 电子性质, 扫描隧道显微镜

Abstract:

Atomic-scale characterization of the atomic structure as well as molecular adsorption on an alloy surface plays a vital role in elucidating the catalytic mechanism of effective catalysts. Au-Cu alloy nanoparticles have important applications in catalyzing CO oxidation and CO₂ reduction. However, the atomic-scale properties of Au-Cu alloy surfaces are rarely investigated. In particular, the physical and chemical properties of singly-dispersed doping atoms, either Au in Cu or vice versa, as well as their influence on the overall surface properties, have not been studied in detail. In response, we first prepared low-coverage bimetallic Au/Cu(111) and Cu/Au(111) films, which were then annealed at high temperature to realize single atomically-dispersed Au/Cu(111) and Cu/Au(111) surface alloys (SA). We characterized the surface structures and adsorption properties by low-temperature scanning tunneling microscopy and spectroscopy (LT-STM/STS). For the SA-Au/Cu(111) system, we found that Au atoms can be incorporated in both the skin and subsurface layer of the Cu(111) substrate. These species can be readily distinguished from the topography contrast in STM. Moreover, STS measurements showed clear differences between the electronic states of doped Au atoms and the Cu host. In particular, we found that Au in the skin layer was strengthened while the subsurface Au showed weakened filled states at approximately −0.5 eV compared with the Cu(111) surface, which corresponds to the characteristic Shockley state of an Au surface. These altered electronic properties at the sites of doped atoms are also reflected by changes in the interactions with probe molecules. Adsorption experiments showed that Au atoms in the top surface prevented the binding of CO molecules, causing various adsorption vacancies in the CO adlayer. In contrast, the subsurface Au atoms had little influence on surface binding with CO molecules. For the SA-Cu/Au(111) system, we found that Cu atoms tend to aggregate into small clusters in the subsurface region of the Au(111) substrate. Only few Cu atoms can be stabilized at the elbow positions of the reconstructed top surface of Au(111). Adsorption experiments showed that only Cu atoms in the skin layer can adsorb CO molecules at liquid nitrogen temperature, while the subsurface Cu atoms cannot. On the other hand, the Au atoms around the doped Cu atoms do not seem to be influenced at all, possibly because of the weak effect of Cu. These experimental results provide details on the atomistic aspects of Au-Cu alloy surfaces, which can improve our understanding of the catalytic mechanism of Au-Cu alloy catalysts.

Key words: Au/Cu(111), Single atom, Surface alloy, CO adsorption, Electronic property, Scanning tunneling microscopy