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Langmuir 2007, 23, 1203-1208

1203

Probing the Interface in Vapor-Deposited Bimetallic Pd-Au and


Pt-Au Films by CO Adsorption from the Liquid Phase
Davide Ferri, Bahar Behzadi,, Peter Kappenberger, Roland Hauert,
Karl-Heinz Ernst, and Alfons Baiker*,
Department of Chemistry and Applied Biosciences, ETH Zurich, HCI, CH - 8093 Zurich, Switzerland,
and Nanoscale Materials Science, Empa, Swiss Federal Laboratories for Materials Testing and Research,
CH - 8600, Dubendorf, Switzerland
ReceiVed August 8, 2006. In Final Form: October 27, 2006
Bimetallic Pd-Au and Pt-Au and monometallic Pd, Pt, and Au films were prepared by physical vapor deposition.
The resulting surfaces were characterized by means of XPS, AFM, and CO adsorption from the liquid phase (CH2Cl2)
monitored by ATR-IR spectroscopy. CO adsorption combined with ATR-IR proved to be a very sensitive method
for probing the degree of interdiffusion occurring at the interfaces whose properties were altered by variation of the
Pd and Pt film thickness from 0.2 to 2 nm. Because no CO adsorption was observed on Au, the evaporation of Pt-group
metals on Au allowed us to study the effect of dilution on the adsorption properties of the surfaces. At equivalent
Pd film thickness, the evaporation of Au reduced the amount of adsorbed CO and caused the formation of 2-fold
bridging CO, which was almost absent in monometallic surfaces. Additionally, the average particle size on Pd-Au
surfaces was smaller than that on monometallic Pd surfaces. The results indicate that a Pd/Au diffuse interface is
formed that affects the Pd particle size even more drastically than the simple decrease in Pd film thickness in monometallic
surfaces. Pt-Au surfaces were less sensitive to CO adsorption, indicating that the two metals do not mix to a significant
extent. The difference in the interfacial behavior of Pd and Pt in the bimetallic gold films is traced to the largely different
Pd-Au and Pt-Au miscibility gaps.

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.

molecules on noble metals.14,15 An important feature of this


deposition method seems to be that alloys are readily obtained
without annealing the pristine films. Annealing is typically
reported in the case of UHV studies and is efficient for studying
and adjusting the surface composition of alloys. Depending on
the annealing temperature, different extents of surface segregation
are obtained.16 Bimetallic films deposited by consecutive electron
beam evaporation of Pd on Au show epitaxial growth at
temperature as low as 150 K with Au interdiffusion increasing
with temperature.12 The formation of a bimetallic film (interdiffusion) or of two distinct films (layer-by-layer epitaxial growth)
represents the two main feasible scenarios (Figure 1) that should
be expected from the preparation of thin films obtained by
sequential evaporation of Au and Pt-group metals without further
treatment. Figure 1a shows the model for a possible bimetallic
film in which the Pt-group metal diffuses through the Au film
upon deposition, thereby forming a corolla of mixed composition around the ideal metal particle that denotes the contact
between the two bulk metal films. It is likely that the occurrence
of one or the other scenario depends on the physical miscibility
between the two metals at the temperature at which deposition
is performed. Because palladium and platinum exhibit vastly
different miscibility phase diagrams with gold,17 it is interesting
to explore the surfaces of Pd-Au and Pt-Au bimetallic films
prepared by physical vapor deposition without controlling the
possible alloy formation by temperature treatment. The films are
potential candidates for studies involving the adsorption of more
complex organic molecules such as chiral modifiers on metal
(14) Ferri, D.; Burgi, T.; Baiker, A. J. Phys. Chem. B 2001, 105, 3187.
(15) Ferri, D.; Burgi, T. J. Am. Chem. Soc. 2001, 123, 12074.
(16) Yi, C. W.; Luo, K.; Wei, T.; Goodman, D. W. J. Phys. Chem. B 2005,
109, 18535.
(17) Okamoto, H.; Massalski, T. B. Phase Diagrams of Binary Gold Alloys;
ASM International: Metals Parks, OH, 1987.

10.1021/la0623477 CCC: $37.00 2007 American Chemical Society


Published on Web 12/09/2006

1204 Langmuir, Vol. 23, No. 3, 2007

Figure 1. Schematic presentation of the formation of mono- and


bimetallic films vapor deposited on Al2O3. (a) Diffusion of the noble
metal into the Au film and (b) layer-by-layer growth of the noble
metal film on Au.

surfaces, whose adsorption will be strongly biased by the


composition of the surface of the as-deposited bimetallic films.18
The characterization of bimetallic surfaces using traditional
methods is complicated by the nature of the metal-metal
interaction and the microscopic range of this interaction. Among
the numerous classic methods available for the characterization
of bimetallic surfaces, the adsorption of carbon monoxide provides
information on the surface structure including both morphological
and electronic aspects.19,20 CO shows a characteristic dependence
of adsorption mode upon coordination, which markedly changes
upon variations in the environment of the metallic atoms (i.e.,
upon changing from metal to metal and from a metal surface to
a composite metal surface). The strong interaction of CO with
catalytic metals can present a drawback for the characterization
of materials whose surfaces are reconstructed upon adsorption.21-23
For bimetallic systems, reconstruction involves the preferential
enrichment of the surface with one component upon interaction
with the adsorbate.
The investigation of metal surfaces in contact with a solution
requires the use of spectroscopic techniques enabling the efficient
subtraction of the large signals of the bulk solvent from the weak
features originating from species populating the surface. In
attenuated total reflection infrared (ATR-IR) spectroscopy,24,25
the infrared radiation propagates through an infrared transparent
material serving as a waveguide (internal reflection element,
IRE) into the absorbing medium in contact with it and reflects
at the interface, thus generating a short-range electric field
decaying from the interface to the bulk medium. The detection
of species residing at the interface and in close proximity to the
IRE/solution contact is enhanced because of this electric field.
Owing to the short path length (up to few micrometers) of the
technique, the contribution from the bulk phase in contact with
the IRE is minimized, and direct information about the solidliquid interface is obtained. The technique becomes highly
surface-sensitive when the right combination of the IRE material
and a pseudoplanar metal surface is chosen. In this respect, ATRIR spectroscopy has been applied to the characterization of mono(18) Behzadi, B.; Vargas, A.; Ferri, D.; Ernst, K. H.; Baiker, A. J. Phys. Chem.
B 2006, 110, 17082.
(19) Ponec, V. AdV. Catal. 1983, 32, 149.
(20) Hollins, P. Surf. Sci. Rep. 1992, 16, 51.
(21) Somorjai, G. A. Catal. Lett. 1992, 12, 17.
(22) Raval, R.; Haq, S.; Harrison, M. A.; Blyholder, G.; King, D. A. Chem.
Phys. Lett. 1990, 167, 391.
(23) Zou, S.; Gomez, R.; Weaver, M. J. Surf. Sci. 1998, 399, 270.
(24) Harrick, N. J. Internal Reflection Spectroscopy; Interscience Publishers:
New York, 1967.
(25) Burgi, T.; Baiker, A. AdV. Catal. 2006, 50, 227.

Ferri et al.

and bimetallic surfaces in contact with solutions14,26-29 with some


emphasis on the electrolyte/metal interfaces,30-37 which take
advantage of remarkable surface enhancement induced by gold
in the so-called Kretschmann configuration.38,39
The aim of this work is to elucidate the surface properties of
bimetallic films prepared using electron beam vapor deposition
of Au, Pt, and Pd. The use of temperature treatments is rather
limited and therefore not applied because serious damage can
occur to the Ge IRE used as a substrate for the films. Surface
composition and morphology have been investigated by X-ray
photoelectron spectroscopy (XPS) and atomic force microscopy
(AFM), respectively. The adsorption properties of the surfaces
are probed by ATR-IR spectroscopy using CO as the adsorbate
in the presence of dichloromethane solvent. CO adsorption should
provide a qualitative measure at a molecular level of the
morphological changes induced by the potential formation of a
true bimetallic interface in comparison with monometallic
surfaces.
Experimental Section
Materials. Dichloromethane solvent (Baker) was stored over 5
molecular sieves. N2 (99.995 vol %) and H2 (99.999 vol %) gases
were purchased from Pangas, and CO (0.5 vol % in argon) was
purchased from Sauerstoffwerk Lenzburg. Pt (99.99%), Pd (99.959%),
and Au (99.99%) wires and Al2O3 (99.3%) tablets used as a target
for electron beam vapor deposition (EB-VD) were supplied by
Umicore.
Thin Film Preparation and Characterization. Thin model films
were prepared by EB-VD onto the trapezoidal Ge internal reflection
element (IRE, 52 20 2 mm3, 45 angle of incidence, Komlas)
used for ATR-IR spectroscopy in a Balzers BAE-370 vacuum system
equipped with a turret allowing the sequential deposition of four
different materials without breaking the vacuum. The methodology
has been described in detail elsewhere.14 Briefly, the materials were
evaporated from a graphite crucible using an electron beam (8 kV,
to 0.15 mA) at a base pressure of about 1.0 10-5 mbar and at
evaporation rates of 0.5 and 1.0 /s for the metals and for Al2O3,
respectively. The IRE was polished with 0.25 m diamond paste
after use and thoroughly cleaned with ethanol. Typically, 100 nm
Al2O3 was deposited on Ge, followed by the metal(s). The film
thickness was measured with a quartz crystal microbalance. Two
series of samples were prepared for both Pt and Pd in which the film
thicknesses were 0.2, 0.5, 1.0, and 2.0 nm. The first series is
represented by the monometallic samples, named M02, M05, M10,
and M20, where M is the metal symbol (Pt or Pd). In the second
series, Pt or Pd was deposited on 1 nm Au in addition to Al2O3
(MAu02, MAu05, MAu10, and MAu20).
The dependence of the composition of the thin films on the
thickness was investigated using XPS. Physical Electronics (PHI)
Quantum 2000 equipment was used with X-rays generated by an Al
source operating at 23.5 W. The spectrometer energy scale was
(26) Zippel, E.; Breiter, M. W.; Kellner, R. J. Chem. Soc., Faraday Trans.
1991, 87, 637.
(27) Ferri, D.; Burgi, T.; Baiker, A. J. Catal. 2002, 210, 160.
(28) Burgener, M.; Ferri, D.; Grunwaldt, J. D.; Mallat, T.; Baiker, A. J. Phys.
Chem. B 2005, 109, 16794.
(29) Ebbesen, S. D.; Mojet, B. L.; Lefferts, L. Langmuir 2006, 22, 1079.
(30) Watanabe, M.; Zhu, Y.; Uchida, H. J. Phys. Chem. B 2000, 104, 1762.
(31) Lu, G. Q.; Sun, S. G.; Cai, L. R.; Chen, S. P.; Tian, Z. W. Langmuir 2000,
16, 778.
(32) Nakamura, R.; Sato, S. Langmuir 2002, 18, 4433.
(33) Pronkin, S.; Wandlowski, T. Surf. Sci. 2004, 573, 109.
(34) Yajima, T.; Uchida, H.; Watanabe, M. J. Phys. Chem. B 2004, 108, 2654.
(35) Shiroishi, H.; Ayato, Y.; Kunimatsu, K.; Okada, T. J. Electroanal. Chem.
2005, 581, 132.
(36) Yan, Y. G.; Li, Q. X.; Huo, S. J.; Ma, M.; Cai, W. B.; Osawa, M. J. Phys.
Chem. B 2005, 109, 790.
(37) Chen, Y. X.; Ye, S.; Heinen, M.; Jusys, Z.; Osawa, M.; Behm, R. J.
J. Phys. Chem. B 2006, 110, 9534.
(38) Hartstein, A.; Kirtley, J. R.; Tsang, J. C. Phys. ReV. Lett. 1980, 45, 201.
(39) Osawa, M. Bull. Chem. Soc. Jpn. 1997, 70, 2861.

Probing the Interface in Vapor-Deposited Films


calibrated using the Au 4f7/2 line (84.0 eV). The beam diameter was
typically 20 mm for survey spectra and 10 mm for line scans. Survey
spectra were obtained over a binding-energy scale of 0-1100 eV
using an analyzer pass energy of 117.4 eV. High-resolution multiplex
data of the patterned samples were obtained at a pass energy of 58.7
eV. The residual vacuum pressure was typically 2 10-9 mbar or
lower during analysis. The binding energies of the photoelectron
peaks were referenced to the C 1s line at 284.6 eV. Data acquisition
and storage were accomplished using PHI-MultiPak software. The
atomic percentages of the elements were calculated using atomic
sensitivity factors included with the instrument data system.
The morphology of mono- and bimetallic films was investigated
by atomic force microscopy (AFM). Measurements were performed
on as-deposited samples at room temperature with a Dimension
3100 from Digital Instruments using tapping mode operation. A
standard cantilever with a resonance frequency of about 284 kHz
and a stiffness of 42 N/m was employed for all measurements.
ATR-IR Spectroscopy. In situ ATR-IR spectra of the solidliquid interface were recorded by co-adding 200 scans at 4 cm-1
resolution on an Equinox 55 spectrometer (Bruker Optics) equipped
with a liquid-nitrogen-cooled MCT detector. After mounting the
coated IRE, the homemade stainless steel flow-through cell was
placed on a dedicated ATR accessory (Optispec), and the sample
compartment was closed to allow the removal of water vapor and
CO2 by dry air overnight. The temperature was maintained at 10 C
throughout the experiments for comparison with previous monometallic Pt14 and Pd27 films.
Measurements were carried out as follows. First, N2-saturated
CH2Cl2 provided from a gas bubble tank was placed into contact
(1 mL/min flow rate) with the coated IRE to reach steady-state
conditions (2 h). Then the gas was changed from N2 to H2 in the
same glass bubble tank without interrupting the liquid flow, and
H2-saturated CH2Cl2 was allowed to flow through the cell for 10 min
to clean the surface. The last spectrum during cleaning served as the
reference spectrum for CO adsorption (ca. 60 min) from CO-saturated
CH2Cl2 provided from a second glass bubble tank. Finally, H2saturated CH2Cl2 was again allowed to flow through the cell following
desorption. All spectra are presented in absorbance units and were
corrected for the contribution of water vapor where required.

Results and Discussion


X-ray photoelectron spectra of the mono- and bimetallic
samples indicated that all metals were in the reduced state (Au
4f core level at 87 and 83.3 eV,40 Figure 2) but no significant
shift was observed in the core-level binding energies of PdAu
and PtAu samples, which would have indicated electronic
modification of either the Au or the Pt-group element.16
Broadening on the high-binding-energy side suggested that a
fraction of the Pt-group metals were in the oxidized state,14,27
likely forming a thin oxide film as confirmed by the slower
attenuation of the concentration of O compared to that of Al at
increasing film thickness. Contamination by adventitious carbon
also increased with film thickness.
XPS was crucial to the estimation of the thickness of the metal
films evaporated on Au/Al2O3.41 The Au 4d5/2, Pt 4f5/2, and Pd
3d core-level lines were used for this purpose. The Pt film
thickness was underestimated in most of the cases, in the worst
case by 16% (PtAu20), but excellent values were obtained for
the thinnest samples. The linear correlation (R ) 0.998) between
the expected (nominal) and the estimated film thickness confirmed
(40) Briggs, D.; Sheah, M. P. Practical Surface Analysis by Auger and X-ray
Photoelectron Spectroscopy; John Wiley & Sons: New York, 1983.
(41) Seah, M. P.; Spencer, S. J.; Bensebaa, F.; Vickridge, I.; Danzebrink, H.;
Krumrey, M.; Gross, T.; Oesterle, W.; Wendler, E.; Rheinlander, B.; Azuma, Y.;
Kojima, I.; Suzuki, N.; Suzuki, M.; Tanuma, S.; Moon, D. W.; Lee, H. J.; Cho,
H. M.; Chen, H. Y.; Wee, A. T. S.; Osipowicz, T.; Pan, J. S.; Jordaan, W. A.;
Hauert, R.; Klotz, U.; vanderMarel, C.; Verheijen, M.; Tamminga, Y.; Jeynes,
C.; Bailey, P.; Biswas, S.; Falke, U.; Nguyen, N. V.; Chandler-Horowitz, D.;
Ehrstein, J. R.; Muller, D.; Dura, J. A. Surf. Interface Anal. 2004, 36, 1269.

Langmuir, Vol. 23, No. 3, 2007 1205

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.

the reliability of the physical vapor deposition technique. On the


contrary, the thickness of Pd in PdAu surfaces was largely
overestimated because of the overlap between the Au 4d and the
Pd 3d signals at all Pd contents.
Figure 2 shows atomic force microscopy images (500 500
nm2) of selected monometallic and bimetallic thin films. The Au
film is composed of a densely packed layer of particles exhibiting
a variable width between about 9 and 30 nm. Comparison with
the morphology of the Al2O3 film14 allows the assignment of
these entities to Au particles. Larger features (up to 65 nm) are
also observed, which might arise from impurities after exposure
to air. The AFM images, which are similar to those of other thin
metal films (Cu,42 Pt,14,26 and Pd27), show the island character
of the electron-beam-deposited films The average particle size
increased when Pt or Pd was evaporated onto the Au film, whereas
the shape of the particles remained largely unaffected. For the
PtAu05 sample, the smallest particles had an approximate
diameter of 10-20 nm. The size of the individual particles
increased to about 30 nm in the PtAu10 sample. However, the
presence of Au did not substantially change the particle size of
the Pt-bimetallic films compared to that of the monometallic
film as demonstrated for the Pt05 and PtAu05 samples. However,
a dramatic difference is observed in the morphology of the Pdcontaining samples. The smallest particles in PdAu10 are about
(42) Ishida, K. P.; Griffiths, P. R. Anal. Chem. 1994, 66, 522.

1206 Langmuir, Vol. 23, No. 3, 2007

Figure 3. ATR-IR spectra of CO adsorption from CH2Cl2 solvent


at 10 C on Pd (bold lines) and PdAu surfaces. Pd film thicknesses:
(b) 0.2, (c) 0.5, (d) 1, and (e) 2 nm. Spectra a have been collected
for CO adsorption on the monometallic Au surface (1 nm) under
equivalent conditions. Spectra b and c have been magnified 3 and
4 times, respectively, for ease of comparison. The inset shows a
magnification of spectra b and c.

15-20 nm, whereas their size is approximately doubled in the


absence of Au (Figure 2).
The adsorption of CO on mono- and bimetallic films is
demonstrated in Figure 3 (Au and Pd) and Figure 4 (Pt) for
experiments carried out under identical conditions and spectra
acquired after 60 min of contact with a CO-saturated solvent.
CO adsorbed on Pd20 and Pt10 exhibited two pairs of signals:
one above 2000 cm-1 (COL; Pt, 2047 cm-1; Pd, 2040 cm-1)
assigned to on-top species and the second below 2000 cm-1
(COB; Pt, 1817 cm-1; Pd, 1905 cm-1) indicating the population
of multicoordinated species.43 The COB species on the Pd film
exhibited a rather broad signal with at least two to three
components, indicating high surface heterogeneity and different
adsorption sites. The CO frequency above and below 1900 cm-1
can be assigned to CO adsorbed predominantly on bridge (2-fold
coordination) and hollow sites (3-fold coordination), respectively.
High intensity for the signal corresponding to 3-fold-bonded
species warrants relatively large domains of reduced metal because
the species occupies more surface atoms than 2-fold-coordinated
species. The assignment agrees with the relatively large size of
the Pd particles determined by STM27 and AFM (Figure 2) and
with the low intensity of the signal of on-top species.
Figure 3a reveals that CO did not adsorb on Au. UHV studies
indicate that CO is completely desorbed at the temperature at
which the present ATR-IR experiments have been performed,44
although a signal at 2109 cm-1 (COL) was observed for a 20nm-thick polycrystalline Au film at ambient temperature under
spectroelectrochemical conditions.33 Owing to the relatively large
particle size, it is likely that the polycrystalline Au film shown
(43) Hoffmann, F. M. Surf. Sci. Rep. 1983, 3, 107.
(44) Rainer, D. R.; Xu, C.; Holmblad, P. M.; Goodman, D. W. J. Vac. Sci.
Technol., A 1997, 153, 1653.

Ferri et al.

Figure 4. ATR-IR spectra of CO adsorption from CH2Cl2 solvent


at 10 C on Pt (bold lines) and PtAu surfaces. Pt film thicknesses:
(a) 0.2, (b) 0.5, (c) 1, and (d) 2 nm. Spectra a and b have been
magnified 5 and 3 times, respectively, for ease of comparison.

in Figure 2 is not corrugated enough to allow CO adsorption.


Despite the ability of CO to bind to gold in different geometries,45
the particle size appears to be a crucial factor for CO adsorption
on Au,46 which occurs preferentially on low-coordinated Au
atoms47 and hence on small clusters or on defects rather than on
extended surfaces. This property makes Au nanoparticles excellent
catalytic materials for CO oxidation compared to bulk Au.48 The
absence of adsorbed CO on the Au film has the benefit that it
allows the investigation of the effect of dilution of Pd and Pt
metals in bimetallic surfaces using infrared spectroscopy and
CO as a probe molecule without the interference from CO
on Au.
In the Pd and Pt monometallic samples, the decrease in film
thickness from 2 to 0.2 nm was accompanied by a decreased CO
adsorption, as expected. The frequency of the CO signals in the
Pd films was perturbed by the decrease in film thickness. Pd10
and Pd05 show signals at 2040 and 1870 cm-1. A shoulder at
ca. 1800 cm-1 is evident in Pd10. A considerable blue shift is
observed in correspondence to Pd02, exhibiting signals at 2068
and 1887 cm-1 for COL and COB, respectively. Similarly, a shift
of 35 cm-1 is observed in the COB signal when changing from
Pd10 to Pd20 (1905 cm-1). Very weak signals were observed
for Pd05 and Pd02. The decrease in film thickness more likely
modifies the distribution of sites available for the adsorption of
COB species and the size of the Pd domains.49 This is best shown
(45) Blizanac, B. B.; Arenz, M.; Ross, P. N.; Markovic, N. M. J. Am. Chem.
Soc. 2004, 126, 10130.
(46) Lemire, C.; Meyer, R.; Shaikhutdinov, S. K.; Freund, H. J. Surf. Sci.
2004, 552, 27.
(47) Boccuzzi, F.; Chiorino, A.; Tsubota, S.; Haruta, M. J. Phys. Chem. 1996,
100, 3625.
(48) Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989, 115,
301.
(49) Wolter, K.; Seiferth, O.; Kuhlenbeck, H.; Baumer, M.; Freund, H. J. Surf.
Sci. 1998, 399, 190.

Probing the Interface in Vapor-Deposited Films

in Figure 3c,d, where the component at ca. 1800 cm-1 completely


disappears from Pd10 to Pd05.
A slight blue shift ( ) 5 cm-1) accompanied by attenuation
of the intensity was observed for the COL signal when the Pt film
thickness was decreased from 2 nm (Pt20, 2045 cm-1) to 1 nm
(Pt10, 2049 cm-1) (Figure 4). Similar to the situation for Pd, the
Pt02 sample exhibits signals for COL and COB at higher frequency
than do the other Pt-containing surfaces (i.e., at 2057 and 1827
cm-1, respectively). The overall intensity of the COL signal for
Pt20 is likely diminished due to the bipolar appearance of the
envelope. As a result, the maximum of the signal also shifts
toward lower frequency. This is likely also occurring for Pd20
but to a lesser extent. The typical second derivative-like shape
associated with the strongest signals of CO on both Pd and Pt
is attributed to the perturbation of the optical properties of the
film probed by the IR radiation propagating through the IRE
upon adsorption of a strong absorber.42,50 The perturbation has
a stronger effect on the appearance of the spectra associated with
thicker films. Further indication of changes in the optical
properties of the metal film was given by the increasing
background absorption on all surfaces on contact with CO owing
to the strong interaction between the CO adsorbate layer and the
metal.33
Evaporation of 1 nm Au on the Al2O3 film prior to the Ptgroup metal induced important changes in the intensity of the
CO signals virtually only in the case of Pd. This reflects important
changes in the adsorption properties of Pd compared to those of
monometallic surfaces. CO adsorption occurred to a large extent
only for PdAu20 and PdAu10, whereas for films thinner than 1
nm extremely weak signals were obtained. The difference with
the corresponding monometallic films and the clear attenuation
of the signals with decreasing film thickness are obvious and
prevent us from discussing possible enhancement effects induced
by Au. The adsorption sites available for CO also appeared to
be modified by the addition of Au. Comparison between Pd10
and PdAu10 reveals that the component of the COB envelope
located at ca. 1800 cm-1 is strongly attenuated or disappears in
the bimetallic surface. Moreover, the maxima of both COL and
COB signals are blue shifted to 2059 ( ) 19 cm-1) and 1908
cm-1 ( ) 38 cm-1), respectively. The shift could be smaller
because of the second derivative shape of the signals in Pd10,
as discussed above, but the value is so large, at least for the
COB signals, that the contribution of this optical effect can be
neglected. To support this argument, it should be noted that the
COB signal is found at the same position in Pd10 and Pd05
despite the band shape observed in Pd10. Figure 3 also clearly
demonstrates that signals due to adsorbed CO are extremely
weak in the PdAu05 and PdAu02 samples, whereas CO is clearly
visible in the corresponding monometallic surfaces.
The increase in frequency of the signal of COB species observed
for the bimetallic surfaces indicates a change in the structure of
the Pd domains induced by the presence of Au, most probably
accompanied by adsorption on 2-fold bridging sites. At very low
Pd content (PdAu02), CO adsorption is inhibited to a larger
extent, and the ratio between on-top and bridging species is close
to 1, indicating the possible diluting effect of Au and the absence
of large Pd domains.
Only minor changes appear in corresponding PtAu surfaces
(Figure 4). Generally, the frequency of the COL signal remains
unchanged with decreasing Pt thickness. However, a blue shift
of ca. 13 cm-1 is observed for the COB signal, which changes
from 1812 to about 1825 cm-1. Additionally, the adsorption
(50) Burgi, T. Phys. Chem. Chem. Phys. 2001, 3, 2124.

Langmuir, Vol. 23, No. 3, 2007 1207

Figure 5. Kinetic of adsorption of CO on Pd and PdAu surfaces.


Pd film thicknesses: () 0.2, () 0.5, (0) 1, and (9) 2 nm.

ability of the bimetallic Pt samples is comparable to that of the


monometallic samples in contrast to that of Pd-containing films.
We note that there are two important differences between the
PdAu and PtAu samples. In contrast to Pd-containing surfaces,
CO adsorption occurs noticeably on all PtAu samples and is still
significant on PtAu02. Moreover, the time at which signal
saturation is achieved is identical for Pt mono- and bimetallic
surfaces (not shown) whereas it is clearly different in Pdcontaining surfaces, the maximum intensity of the CO signal
being achieved at a shorter time on stream on bimetallic samples
(Figure 5). These observations confirm that the extent of
interaction between Au and the two Pt-group metals, as probed
by CO adsorption, is substantially different.
The combination of information obtained from the AFM images
(lower average particle size in bimetallic surfaces compared to
that of Pd films deposited on Al2O3 at identical nominal thickness)
with that obtained from the ATR-IR spectra of CO adsorbed on
Pd indicates that the growth of the Pd film on Au does not follow
a layer-by-layer mechanism (i.e., the Pd-Au bimetallic surface
is not simply composed of two distinct Pd and Au films). The
decrease in the intensity of the CO signals and the disappearance
of some signals with decreasing Pd film thickness on the
monometallic surfaces is interpreted as being the result of a
particle size effect, decreasing the amount of available free metal
for adsorption and affecting the sites to which CO can adsorb
(Figure 1). Figure 3 clearly shows that the decrease in the intensity
of the CO signals is much more significant for the bimetallic
surfaces at equivalent Pd film thickness and that Au induces
strong effects in adsorbed CO at low Pd film thickness (0.2 and
0.5 nm).
The results shown in Figures 3 and 5 indicate the enrichment
of the bimetallic surface with Au and the generation of a diffuse
Pd/Au interface, which can be represented as in the cartoon in
Figure 1a. The diffuse interface can be defined as a bimetallic
slice of undefined extension and composition located at the
boundary between the two monometallic phases, Au and the Pd
domains (likely large particles for thick films) exposed to the
flowing solution. The size of the monometallic Pd domains in
the bimetallic PdAu films decreases with Pd content. The size
and composition of the slice are probably also film thicknessdependent, and it is possible that small Pd domains decorate the
slice, although no indication can be found in the ATR-IR spectra
of CO adsorbed on such features. Although CO-induced surface
reconstruction with consequent surface enrichment with one of
the metals composing the bimetallic material is common, the
intensity decrease with decreasing Pd content observed in Figure

1208 Langmuir, Vol. 23, No. 3, 2007

3 is more consistent with CO adsorption on Pd domains not


influenced by surrounding Au atoms. The ATR-IR spectra rather
indicate that the diffuse interface produces a sort of geometric
effect that influences the adsorption properties of the domains
showing only Pd character. Electronic effects51 often accompanying the formation of true bimetallic interfaces are difficult
to disentangle on the basis of these data from the geometric
effect accounting for our interpretation. Although rather significant, the blue shifts observed in the frequency of the CO
signals on both the PdAu and the PtAu surfaces (Figures 3 and
4) cannot be attributed to electronic effects because similar shifts
have been also found for the monometallic surfaces.
The geometric effect created by the formation of the diffuse
interface is best seen in the formation of prevalently 2-foldadsorbed CO, meaning that more defects are present because of
the reduced size of the metal domains, and in the faster decrease
in the signal of COB compared to that of COL. The reduced size
of the Pd domains is also reflected in the shorter time at which
the maximum in the COL signal intensity is reached in bimetallic
surfaces compared to that in monometallic surfaces. Hence, at
equivalent nominal Pd thickness, the Pd domains in the PdAu
samples are smaller (Figure 1a) than those that would be obtained
hypothetically following layer-by-layer growth (Figure 1b) (no
diffusion of Pd into Au) and those obtained in the monometallic
samples.
AFM and ATR-IR spectroscopy both indicate that the diffusion
of Pt into Au is less probable than in the case of Pd. The only
effect observed on Pt and PtAu surfaces is that the decrease in
the Pt film thickness results in smaller amounts of adsorbed CO.
With the exception of the PtAu10 sample, monometallic and
bimetallic surfaces exhibit approximately the same distribution
of sites for CO adsorption. PtAu02 and Pt02 are significant
examples. Hence, the evaporation of Pt on Au generates two
nearly independent metallic films.
In principle, the differences observed for Pd and Pt in the ease
of formation of the diffuse interface can be associated with the
combination of two factors. First, the present surfaces have been
characterized as prepared (i.e., without thermal treatment
(51) Burch, R. Acc. Chem. Res. 1982, 15, 24.
(52) Jablonski, A.; Overbury, S. H.; Somorjai, G. A. Surf. Sci. 1977, 65, 578.
(53) Shih, H. D.; Bauer, E.; Poppa, H. Thin Solid Films 1982, 88, L21.
(54) Sellidj, A.; Koel, B. E. Phys. ReV. B 1994, 49, 8367.
(55) Bouwman, R.; Sachtler, W. M. H. J. Catal. 1970, 19, 127.

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