Platinum nanofilm formation by EC-ALE via redox replacement of UPD copper: Studies using in-situ scanning tunneling microscopy

被引:117
作者
Kim, Youn-Geun [1 ]
Kim, Jay Y. [1 ]
Vairavapandian, Deepa [1 ]
Stickney, John L. [1 ]
机构
[1] Univ Georgia, Dept Chem, Athens, GA 30602 USA
关键词
D O I
10.1021/jp063766f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The growth of Pt nanofilms on well-defined Au(111) electrode surfaces, using electrochemical atomic layer epitaxy (EC-ALE), is described here. EC-ALE is a deposition method based on surface-limited reactions. This report describes the first use of surface-limited redox replacement reactions (SLR3) in an EC-ALE cycle to form atomically ordered metal nanofilms. The SLR3 consisted of the underpotential deposition (UPD) of a copper atomic layer, subsequently replaced by Pt at open circuit, in a Pt cation solution. This SLR3 was then used a cycle, repeated to grow thicker Pt films. Deposits were studied using a combination of electrochemistry (EC), in-situ scanning tunneling microscopy (STM) using an electrochemical flow cell, and ultrahigh vacuum (UHV) surface studies combined with electrochemistry (UHV-EC). A single redox replacement of upd Cu from a PtCl42- solution yielded an incomplete monolayer, though no preferential deposition was observed at step edges. Use of an iodine adlayer, as a surfactant, facilitated the growth of uniformed films. In-situ STM images revealed ordered Au(111)-(root 3 x root 3)R30 degrees-iodine structure, with areas partially distorted by Pt nanoislands. After the second application, an ordered Moire pattern was observed with a spacing consistent with the lattice mismatch between a Pt monolayer and the Au(111) substrate. After application of three or more cycles, a new adlattice, a (3 x 3)-iodine structure, was observed, previously observed for I atoms adsorbed on Pt(111). In addition, five atom adsorbed Pt-I complexes randomly decorated the surface and showed some mobility. These pinwheels, planar PtI4 complexes, and the ordered (3 x 3)iodine layer all appeared stable during rinsing with blank solution, free of I- and the Pt complex (PtCl42-).
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页码:17998 / 18006
页数:9
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