Atomic-Scale Geometry and Electronic Structure of Catalytically Important Pd/Au Alloys

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• 作者：Ashleigh E. Baber ; Heather L. Tierney ; E. Charles H. Sykes
• 刊名：ACS Nano
• 出版年：2010
• 出版时间：March 23, 2010
• 年：2010
• 卷：4
• 期：3
• 页码：1637-1645
• 全文大小：474K
• 年卷期：0
• ISSN：1936-086X

文摘

Pd/Au bimetallic alloys catalyze many important reactions ranging from the synthesis of vinyl acetate and hydrogen peroxide to the oxidation of carbon monoxide and trimerization of acetylene. It is known that the atomic-scale geometry of these alloys can dramatically affect both their reactivity and selectivity. However, there is a distinct lack of experimental characterization and quantification of ligand and ensemble effects in this system. Low-temperature, ultrahigh vacuum scanning tunneling microscopy is used to investigate the atomic-scale geometry of Pd/Au{111} near-surface alloys and to spectroscopically probe their local electronic structure. The results reveal that the herringbone reconstruction of Au{111} provides entry sites for the incorporation of Pd atoms in the Au surface and that the degree of mixing is dictated by the surface temperature. At catalytically relevant temperatures the distribution of low coverages of Pd in the alloy is random, except for a lack of nearest neighbor pairs in both the surface and subsurface sites. Scanning tunneling spectroscopy is used to examine the electronic structure of the individual Pd atoms in surface and subsurface sites. This work reveals that in both surface and subsurface locations, Pd atoms display a very similar electronic structure to the surrounding Au atoms. However, individual surface and subsurface Pd atoms are depleted of charge in a very narrow region at the band edge of the Au surface state. dI/dV images of the phenomena demonstrate the spatial extent of this electronic perturbation.