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Introduction
The chemistry and structure of bi- or multimetallic surfaces
have gained considerable attention because of their importance
in several technical applications, including catalysis, microelectronics, and sensors. In catalysis, the major significance of their
use is that binary systems often exhibit deviations in terms of
catalytic activity and selectivity compared to those of the
individual components1 and are thus suitable to optimize the
performance of catalytic materials. Gold and its combination
with Pd and Pt are used in a range of liquid-phase oxidation2-5
and hydrogenation reactions.6-10
Quasi-planar thin films of two metals or more generally model
catalysts are valuable systems for gaining fundamental insight
into elementary surface processes occurring at real catalytic
surfaces on a molecular level.11 Physically deposited Pd-Au
bimetallic films are often used for electrocatalytic purposes12,13
and are prepared under similar deposition conditions as for the
thin films prepared by us to study the adsorption of large chiral
* Corresponding author. E-mail: baiker@chem.ethz.ch.
ETH Zurich.
Swiss Federal Laboratories for Materials Testing and Research.
(1) Sinfelt, J. H. Acc. Chem. Res. 1977, 10, 15.
(2) Bianchi, C.; Porta, F.; Prati, L.; Rossi, M. Top. Catal. 2000, 13, 231.
(3) Biella, S.; Castiglioni, G. L.; Fumagalli, C.; Prati, L.; Rossi, M. Catal.
Today 2002, 72, 43.
(4) Corma, A.; Domine, M. E. Chem. Commun. 2005, 4042.
(5) Hermans, S.; Devillers, M. Catal. Lett. 2005, 99, 55.
(6) Bond, G. C.; Rawle, A. F. J. Mol. Catal. A: Chem. 1996, 109, 261.
(7) Sarkany, A.; Horvath, A.; Beck, A. Appl. Catal., A 2002, 229, 117.
(8) Venezia, A. M.; LaParola, V.; Pawelec, B.; Fierro, J. L. G. Appl. Catal.,
A 2004, 264, 43.
(9) Claus, P. Appl. Catal., A 2005, 291, 222.
(10) Pawelec, B.; Venezia, A. M.; LaParola, V.; Thomas, S.; Fierro, J. L. G.
Appl. Catal., A 2005, 283, 165.
(11) Gunter, P. L. J.; Niemantsverdriet, J. W.; Ribeiro, F. H.; Somorjai, G. A.
Catal. ReV.sSci. Eng. 1997, 39, 77.
(12) Koel, B. E.; Sellidj, A.; Paffett, M. T. Phys. ReV. B 1992, 46, 7846.
(13) Schmidt, T. J.; Stamenkovic, V.; Markovic, N. M.; Ross, P. N. Electrochim.
Acta 2003, 48, 3823.
Ferri et al.
Figure 2. AFM images (500 500 nm2) of selected Pd, PdAu, Pt,
and PtAu samples together with the Au sample. The images are
referred to as deposited samples. The inset depicts the Au 4f corelevel signals of the Au10 sample.
Ferri et al.
Ferri et al.
following preparation, thus under conditions limiting interdiffusion). Second, the different electronic structures of Pd and Pt,
reflected by the often observed different catalytic properties of
the two metals for identical reactions, certainly play a role. Pd
and Au are miscible in almost all ratios,16,52-54 whereas the
solubility of Pt and Au in solid solutions is limited by a large
miscibility gap between 15 and 100 atom % Pt.17,55 The
immiscibility between Pt and Au together with the fact that
diffusion is not favored by the deposition conditions explains the
absence of differences in the signals of CO on Pt and PtAu
samples and the large discrepancy with the results obtained
with Pd.
Conclusions
Pd-Au and Pt-Au bimetallic surfaces have been prepared by
electron beam deposition, and their structure has been characterized using XPS, AFM, and CO adsorption combined with ATRIR spectroscopy. The changes observed in the infrared frequency
and in the shape of the CO signals upon adsorption from the
liquid phase indicated that morphological changes occur in the
Pd films when decreasing the film thickness from 2 to 0.2 nm
and when introducing a 1 nm Au film. In comparison,
corresponding Pt-Au surfaces were less sensitive toward CO
adsorption, which can be attributed to the large difference in
miscibility among Pd, Pt, and Au. A diffuse Pd/Au interface is
formed when Pd is deposited on Au, which results in the
interdiffusion of Pd into Au and the enrichment of the surface
with Au for very thin Pd films. The overall effect of the formation
of the diffuse interface is a decrease in the metal particle size
induced by Au addition, which cannot be obtained by simply
decreasing the film thickness of vapor-deposited Pd in the
monometallic surfaces.
This study shows that CO adsorption combined with ATR-IR
spectroscopy provides a very sensitive and useful probe for
investigating the mixing of metals at metal/liquid interfaces.
By applying other suitable probe molecules, the method could
be extended to other bimetallic systems that are relevant to
technical devices surrounded by a liquid phase.
Acknowledgment. We kindly acknowledge the financial
support from the Swiss National Science Foundation and the
Foundation Claude and Giuliana.
LA0623477