12362 J. Phys. Chem.

C 2009, 113, 12362–12372

Comprehensive Study of the Application of a Pb Underpotential Deposition-Assisted

Method for Surface Area Measurement of Metallic Nanoporous Materials

Y. Liu,† S. Bliznakov,‡ and N. Dimitrov*,†,‡

Materials Science and Engineering Program, State UniVersity of New York at Binghamton,
P.O. Box 6000, Binghamton, New York 13902-6000, and Department of Chemistry, State UniVersity of New
York at Binghamton, P.O. Box 6000, Binghamton, New York 13902-6000
ReceiVed: February 19, 2009; ReVised Manuscript ReceiVed: May 15, 2009

An inexpensive, fast, selective, and sensitive technique for surface area measurement of metallic nanoporous
materials (MNPM) is developed, systematically tested, and validated. The approach employed is based on
underpotential deposition (UPD) of metals on foreign substrates. In this work, Pb UPD on Au is chosen to
illustrate the applicability of and reveal the advantages and limitations of the proposed method. Experiments
are designed for surface area measurement of nanoporous gold (NPG) electrodes with pore sizes in the range
of 5-15 nm, prepared by electrochemical dealloying of single phase AupAg1-p (atomic fraction p ) 0.1, 0.2,
and 0.3). Dealloying is performed galvanostatically at a current density of 1 mA cm-2 in a AgClO4 solution,
acidified to pH 1. The experimental results suggest a linearly increasing charge in the Pb UPD layer with
NPG thickness. This finding hints at (i) uniformity of the NPG structure and (ii) the general ability of this
method to work for analysis of bulk materials. The proposed approach is tested by studying the dependence
of the NPG surface area upon the original alloy composition and correlating the results with the NPG structure
and morphology imaged by high-resolution scanning electron microscopy. An anomalously high surface area
is registered in dealloyed Au0.1Ag0.9 samples and is attributed to the lack of a pre-existing percolation backbone.
Unlike the instantaneous Pb UPD process on a flat metal surface, the slow and thickness-dependent kinetics
of Pb layer formation on NPG is associated with hindered mass transport through pores. Further validation
of the Pb UPD method is made by experimental monitoring of heat treatment-enforced coarsening and the
basic modeling of the correlation between surface area and ligament size in NPG. Finally, a critical comparison
with Brunauer-Emmett-Teller (BET) analysis reveals important advantages of the developed method for
surface area measurement in MNPM specimens.

1. Introduction
Metallic nanoporous materials (MNPM) can be described as
metals having a three-dimensional (3D) interconnected solid-void
structure in nanoscale. To date, besides nanoporous Au (NPG)
that can be easily prepared by electrochemical dealloying
(selective Ag dissolution) of single phase AupAg1-p alloys,1-4
successfully synthesized MNPM include nanoporous Pt,5-7 Cu,8,9
Ag,9-11 Pd,12,13 and Ni.14,15 The substantial surface area develop-
ment in MNPM manifested by a several orders of magnitude
increase versus the geometric area of the bulk material renders
these structures attractive for a variety of upcoming technologies
associated with catalysis,16-18 fuel cells,19,20 membranes,21
actuators,22 and electrochemical sensing.23,24 At present, the
characterization of nanoporous metals relies mostly on field
emission scanning electron microscope (FESEM) and/or trans-
mission electron microscope (TEM), when applicable.1-23 When
the determination of surface area is of interest, FESEM and TEM
could provide only a qualitative picture based on measurements
of average pore and ligament sizes and the assumption of a
structural isotropy of the substrate of interest. However, when
a quantitative result is needed, the microscopy techniques fail
to accurately provide details about the actual surface area. Thus,
an inexpensive, fast, accurate, selective, and sensitive technique
* To whom correspondence should be addressed. E-mail: dimitrov@
binghamton.edu. Telephone: +1 607 777 4271.
†
Materials Science and Engineering Program.
‡
Department of Chemistry.
10.1021/jp901536f CCC: $40.75  2009 American Chemical Society
Published on Web 06/19/2009
for surface area measurement of MNPM would not only enable
efficient surface area measurement but would also help to better
understand the kinetics of the structural evolution in MNPM
and to assess the factors and limitations associated with mass
transport through interconnected nanosized channels.
The first choice for the surface area determination of a fine
structure like MNPM would be today’s area characterization
“work horse”, the Brunauer, Emmett and Teller (BET) method.
BET is based on a physical absorption of gas molecules onto
the substrate under characterization. The area can be obtained
on the basis of a pressure measurement of the physically
adsorbed gas isotherms in the chamber.25 It has been widely
used to determine the surface area of hydrogen storage materi-
als,26 nanoparticle assemblies,27 nanotubes,28 nanorods,29 and
nanoporous materials.30 While BET is deemed accurate and
reliable for many of the above listed systems, there are
limitations and shortcomings associated with its efficiency for
characterization of MNPM. For instance, a large amount of
sample is needed (i.e., more than one gram of NPG) for the
BET surface area measurement because the pressure measure-
ment is not sensitive enough. In addition to that, an elevated
temperature treatment ranging between 100 and 350 °C,
recommended generally as an effective way for water/solvent
and contaminant removal, could substantially enhance the
diffusivity of surface atoms and in turn trigger a massive
coarsening of the sample2,21,31,32 due to the Gibbs-Thomson
effect.33 This would ultimately result in a significant decrease
Pb UPD-Assisted Method for Surface Area Measurement
in the surface area of MNPM consisting originally of very fine
ligaments and pores.
A way to address the above limitations is to employ
electrochemical techniques, which can analyze nanosized layers
and do not require heat treatment of the specimens. The double-
layer capacitance and charge of the underpotentially deposited
(UPD) monolayer of metal on foreign substrates are two
electrochemical characteristics that are directly related to the
roughness of the electrode and can thereby be used for sur-
face area measurements of MNPM. The double-layer capaci-
tance could be derived by the analysis of electrochemical
impedance spectroscopy (EIS). The ratio between the double-
layer capacitance measured on porous and flat electrodes from
the same metal correlates directly with the surface area
development. EIS is a powerful technique that also provides
additional information on the shape of the pores,34-38 but as
Cattarin et al.34 reported, the recording of impedance spectra is
complicated with NPG samples. In addition, the EI spectra
analysis is a complex procedure and is often dependent on
critical assumptions (choice of right model, proper fitting
procedures, and sensitive software). Unlike EIS, the UPD
measurement is independent of the shape and uniformity of the
pores, and the charge corresponding to the UPD monolayer
formation or stripping could be easily determined by standard
electrochemical measurements such as chronoamperometry (CA)
and cyclic voltammetry (CV). Thus for MNPM, the UPD
measurement appears to be a more suitable and straightforward
method than EIS for surface area assessment. UPD has been
widely used to characterize the surface area and/or surface
roughness of generally flat single and polycrystalline metal
surfaces.39,40 Most recently, UPD-based protocols have also been
employed in the study of MNPM substrates.7,10,24 The UPD
phenomenon is strictly limited to the formation of one mono-
layer and rarely two complete monolayers perfectly reproducing
the morphology of the underlying substrate.39,40 This way, the
charge of a UPD monolayer is directly proportional to the
substrate surface area. Therefore, measurement of the roughness
factor, Rf, obtained as a ratio of accurately measured UPD layer
charges on developed and flat metal surfaces, would guarantee
an accurate determination of the surface area development.
Applications of UPD as a characterization tool emphasize the
assessment of surface activity of electrochemical sensor
substrates41,42 and the surface area measurement of catalytically
active substrates.43-46 In the second group of applications,
hydrogen UPD on carbon-supported Pt has been used for surface
area assessment of fuel cell catalysts.43-45 Adding to that some
random attempts for surface area characterization of electrodes
including MNPM,7,10,24 one finds no systematic and compre-
hensive study on the kinetics and limitations of the UPD process
in MNPM published so far in the literature. Another missing
piece of information relates to the mechanism of UPD formation
on MNPM. Slow UPD formation onto MNPM substrates lasting
for a couple hundred seconds24 has been reported in contrast
with only a few seconds on a metal surface.39,40 It has been
speculated that the UPD might not be under pure kinetic
control.5,24 If limitations are contributed to by mass transport
(diffusion) control, it is not clear whether these limitations are
due to a narrow pore size and/or to a low UPD metal ion
concentration.
Understanding the UPD process on MNPM is fundamentally
and technologically important. For instance, the UPD process
on MNPM could serve as a model for the faradaic process
operating in typical catalytic and/or sensing scenarios. Also,
surface limited redox replacement (SLRR) of UPD layers that
J. Phys. Chem. C, Vol. 113, No. 28, 2009 12363
has been increasingly used for surface modification47,48 and thin
film growth49,50 on a variety of important substrates would
undoubtedly be affected by limitations considered earlier in this
section. Thus, the work reported herein is aimed at (i) revealing
key details and limitations associated with the mechanism and
kinetics of UPD formation in architectures featuring intercon-
nected porosity metal structures and (ii) developing an inex-
pensive, fast, accurate, selective, and sensitive technique for
surface area measurements of MNPM.
In the present paper, Pb UPD on Au as a well understood
system39,40 is chosen to illustrate the applicability of and reveal
the advantages and limitations of the proposed electrochemical
method. Additional justification for the choice of Pb is provided
by its ability to form a UPD layer on a variety of other noble
metals (Ag,49 Cu,50 Pt,51 and Rh52) that could be processed as
nanoporous substrates. Last but not least, Pb UPD would still
be confined within the limits of a monolayer, even if surface
alloying were to take place as no UPD system with Pb
participation has been shown to feature mixing that goes beyond
a site exchange between the UPD layer and topmost layer of
the substrate.39 Experiments are designed for surface area
measurement of NPG electrodes prepared by electrochemical
dealloying (selective Ag dissolution) of single phase AupAg1-p,
where the atomic fraction p ) 0.1, 0.2, and 0.3. These feature
stable pore and ligament sizes in the range of 5-15 nm and a
controlled dealloying depth to 5 µm. Instead of cyclic voltam-
metry (CV) conventionally used in similar cases,39,40 in this work
UPD measurements were carried out using chronoamperometry
(CA). First, the surface area development is determined by
measuring the roughness factor, Rf, as a function of the alloy
composition and dealloying depth. Second, important aspects
of the UPD mechanism and kinetics are discussed in view of
the duration of UPD at different dealloying depths, the difference
between CA and CV measurements, and the impact of Pb2+
ion concentration on the formation of a UPD layer. Finally,
sample coarsening caused by heat treatment, surface area
modeling, and BET measurements are conducted to ascertain
and validate the applicability of the UPD-assisted method for
surface area measurement in MNPM.
2. Experimental Section
2.1. AupAg1-p Alloy Synthesis. Single phase AupAg1-p
alloys (p ) 0.1, 0.2, and 0.3) were synthesized by high-
temperature melting in inert atmosphere and were characterized
by X-ray diffraction (Philips X’Pert MRD system with Cu KR
radiation) and energy dispersive X-ray spectroscopy (EDXS)
(Zeiss Supra 55 VP system with EDAX detector) to confirm
the mixing and alloy composition. Precalculated amounts of Au
and Ag (both 99.99%, Surepure Chemetals) were placed in a
graphite crucible inside a quartz reactor, deoxygenated by ultra
high purity (UHP) N2 gas (less than 1 ppb oxygen, moisture
content, CO, and CO2) for at least 2 h prior to the melting.
After 20 min melting at 1200 °C, the samples were slowly
cooled to room temperature, rolled into 50 µm thick foil, and
cut into small pieces. This procedure was repeated two more
times to ensure maximum homogeneity and best mixing. Finally,
the alloys were rolled into a 3 mm thick sheet, and cylindrical
samples with a diameter of 6 mm were punched out by a “punch
and die” press (Roper Whitney of Rockford, Inc.). These
samples were then annealed in inert atmosphere at 800 °C for
20 h. Finally, linear scanning voltammetry (LSV) at a scan rate
of 1 mV s-1 (NPG Preparation) was conducted on each alloy
sample in an acidic solution in a three-electrode configuration
to confirm their composition by measuring the dealloying critical
potential.
12364 J. Phys. Chem. C, Vol. 113, No. 28, 2009
2.2. NPG Preparation. For processing of NPG samples the
above-described alloys were first mechanically polished on
alumina slurry (Buehler) to 0.05 µm. The samples were then
rinsed with Barnstead Nanopure water (R > 18.2 Ω cm),
subjected to annealing at 800 °C in N2 atmosphere, and cooled
to room temperature. The dealloying to selectively remove Ag
from the alloys was carried out in a 1 × 10-3 M AgClO4
(99.995+% metal basis, Sigma-Aldrich) and 1 × 10-1 M HClO4
(double distilled, GFS Chemicals) solution at a constant current
density i ) 1 mA cm-2. The selective dissolution was conducted
in a three-electrode cell controlled by a PC-based potentiostat/
galvanostat (EC Epsilon, BASi). Ag wires pretreated by etching
in 8 M HNO3 were used for counter and reference electrodes.
The time, t, required for the penetration of the dissolution front
at a certain depth, d, was calculated by eq 1 represented by the
Faraday law for electrolysis, including the atomic fraction (also
volume fraction in the case of AupAg(1-p)) of Ag, (1-p) to reflect
the complex nature of the dissolving sample (alloy).
(1 - p)zdFAgF
t) (1)
iaAg
Here, z is the number of electrons transferred for the oxidation
of one Ag atom, F is the Faraday’s constant, FAg is the mass
density of Ag and aAg is its atomic weight. The analysis of eq
1 suggests that after dissolving, for instance, 90% of the volume
occupied by Ag atoms in a layer of Au0.1Ag0.9 with thickness
d, 10% will be left as a spongy nanoporous Au. Synthesized
that way, the NPG samples were rinsed with Barnstead
Nanopure water immediately after the dealloying and were then
immersed in water and kept for an hour to make sure all Ag
ions diffused out of the pores.
2.3. UPD Measurements. UPD-assisted surface area mea-
surements were carried out by chronoamperometry and cyclic
voltammetry in a solution containing 1 × 10-2 M Pb(ClO4)2
(99.995+% metal basis, Sigma Aldrich), 1 × 10-1 M NaClO4
(99.99% Sigma Aldrich), and 1 × 10-2 M HClO4 (double
distilled, GFS Chemicals). Background experiments assessing
the charge contribution of side reactions and/or double-layer
charging were performed in the same solution but in the absence
of Pb2+ ions. The reference electrode was Pb wire that was
pretreated by etching in a diluted nitric acid (1:1 ratio) solution
heated to 50 °C. A Pt wire, flame annealed prior to the
experiment, served as counter electrode. All UPD experiments
were carried out in a solution that was deoxygenated for at least
2 h by purging with an UHP N2 gas. CA was used to register
the current transients of UPD formation at a constant potential
20 mV (Pb/Pb2+) and UPD stripping at a constant potential 650
mV (Pb/Pb2+). The surface area of NPG was obtained simply
by dividing either UPD formation or stripping charges by the
charge density of a Pb UPD layer on a flat polycrystalline Au
electrode, prepared by a procedure described elsewhere.49 CV
with a scanning rate 5 mV s-1 was conducted to assess the
kinetic limitations of UPD for the surface area measurement.
In addition to that, regardless of the reference electrode used in
this work, all potentials are reported versus a Pb/Pb2+ pseu-
doreference electrode (except for the dealloying where Ag/Ag+
was quoted as reference), and all solutions used were prepared
with the above listed chemicals as received from the vendors
and Barnstead Nanopure water (R > 18.2 Ω cm).
2.4. SEM and BET Experiments. Alternatively to UPD
measurements, a high-resolution field emission scanning electron
microscope (FESEM) (Zeiss Supra 55 VP) coupled with an in-
Liu et al.
Figure 1. Current density response of AupAg1-p alloys to an anodic
potential scan (sweep rate of 1 mV s-1) using LSV. Inset: Potential
transient of AupAg1-p alloys with a dissolution depth of 1 µm at a
current density of 1 mA cm-2 using chronopotentiometry (CP).
lens detector at an accelerating voltage of 10 kV and a working
distance of 2 mm was used to characterize the NPG samples
after dealloying. Also, BET measurements (Micromeritics ASAP
2020) were conducted to validate the developed UPD-assisted
method and to assess the sensitivity of both approaches to heat-
treated samples. Specific details concerning each of these
experimental procedures are described in Results and Discus-
sion.
3. Results and Discussion
3.1. Dealloying. 3.1.1. Alloy Characterization and Elec-
trochemical Results. Alloy specimens AupAg1-p used as testing
vehicles in this work, were analyzed for homogeneity and
composition. XRD work done on all three compositions (not
shown) ascertained the presence of features characteristic for
the Au-Ag system.53 Given the close structural similarity of
Au and Ag (fcc metals with only 0.4% difference in the lattice
parameters) that limits the quantitative power of XRD, we used
EDXS measurements for compositional analysis. Results from
six point EDXS measurements confirmed the alloy composition
with an error of 0.3% for Au0.1Ag0.9, and 0.4% for Au0.2Ag0.8
and Au0.3Ag0.7. In addition, the alloy composition was verified
by registering the onset of a Ag selective dissolution known as
dealloying critical potential.54 It is known that critical potential
governed by the delicate balance between Ag dissolution and
Au surface diffusion in single-phase AupAg1-p alloys depends
strictly upon alloy composition.1,54 Thus, by analyzing the critical
potential data, one could derive quantitative results for the alloy
composition. Figure 1 shows anodic polarization curves in
perchlorate solution containing Ag ions for all three alloys. The
anodic curves undoubtedly feature increasing critical potentials
with the rise of the Au fraction in the alloys. A comparison of
the results in Figure 1 with data reported earlier in the literature53
clearly confirms the EDXS analysis findings and thereby verifies
the alloy composition. Finally, the absence of features associated
with dissolution of “free” (unalloyed) Ag on the polarization
curves along with the XRD and EDXS results confirms the
homogeneity of the characterized alloys.
3.1.2. SEM Results. Further in this work, selective removal
of Ag from the above-described AupAg1-p alloys (dealloying)
is carried out to leave porous Au with ligaments and pores in
nanodimension. The dealloying is performed at a constant
current of 1 mA cm-2, and the potential transients registered as
a result of each run are presented in the inset of Figure 1. Here,
the main advantage of working at constant current is the precise
control of the dealloying depth enabled by a predefined
Pb UPD-Assisted Method for Surface Area Measurement
Figure 2. Top view FESEM micrographs of dealloyed (a) NPG0.1,
(b) NPG0.2, and (c) NPG0.3 samples.
dissolution rate. The dissolution time calculation for alloys with
different composition is described in the Experimental Section.
It is shown in the inset of Figure 1, that a time of 30-50 s is
needed for the potential to reach steady state. This steady state
then operates for dissolution fronts penetrating to 5 µm, which
is the maximum dealloying depth considered in this work. Also,
the reaching of a steady-state potential for each alloy composi-
tion implies uniformity and isotropy of the substrate structure
developed by dealloying.
Following the dealloying, the NPG layers are first character-
ized using FESEM. An interconnected solid-void 3D structure
typical for dealloyed AupAg1-p alloys is observed with dimen-
sions ranging from 5 to 20 nm for different compositions of
interest (Figure 2). It is also clearly seen that the ligament and
pore size depend upon the original alloy composition. Thus,
NPG prepared by the dealloying of the Au0.3Ag0.7 alloy (NPG0.3)
features the finest pore and ligament size (Figure 2c). At the
same time, while the dimensions generally increase with a
decrease in Au content in the alloy, no clear trend could be
elucidated solely by simple morphology comparison of alloy
samples used in this work. For instance, opposing the above-
mentioned length scale trend, NPG0.1 appears to feature a smaller
pore and ligament size than those of NPG0.2. Also, its structure
is considerably less uniform than that of NPG0.2 and NPG0.3.
Finally, as is shown later in this paper, the surface area of NPG0.1
is almost twice as high compared to that of NPG0.2. Possible
J. Phys. Chem. C, Vol. 113, No. 28, 2009 12365
Figure 3. CV curves of Pb UPD (solid blue) and background (dashed
red) on polycrystalline Au at a sweep rate of 20 mV s-1.
reasons for the discrepancy observed at low Au fractions will
be proposed later in this paper. Another interesting observation
resulting from the analysis of the SEM images presented in
Figure 2 is associated with the similarity between ligament and
pore size. This observation suggests a massive material rear-
rangement during the dealloying process in which pre-existing
percolation ligaments of the more noble metal serve as
nucleation centers for the structuring and growth of the new
interconnected 3D architecture.
3.2. UPD Measurement. Pb UPD on flat polycrystalline Au
is first carried out by CV to investigate the general system
behavior. Then, after determining the formation and stripping
potentials, Pb UPD on NPG is performed using CV and CA.
Further in this section, only results of NPG0.1 are shown as an
illustration of the applicability of the proposed method. Results
featuring identical qualitative and quantitative trends (not shown)
are also obtained for NPG0.2 and NPG0.3.
3.2.1. Pb UPD on Polycrystalline Au. Figure 3 shows the
reversible Pb UPD on a flat polycrystalline Au electrode. The
registered CV allows for determining the formation and stripping
potential and the UPD charge density that is needed as a
normalization factor for the surface area determination of NPG.
The voltammetry presented in Figure 3 shows a solid curve that
is similar to those registered by others on polycrystalline Au.55-57
It is noteworthy that the sharp peak registered at 0.200 V is
typical for Au (111), and the broader wave appearing at 0.450
V is characteristic for the (100) and (110) faces of Au.57 The
CV suggests also that at the potential of 0.020 mV the Au
surface is covered with a monolayer of Pb. Bulk deposition of
Pb becomes apparent at potentials more negative than 0.000 V.
Also, no Pb atoms are expected on the Au surface at potentials
higher than 0.650 mV. Given the fact that the potential of 0.650
mV is negative to the critical potential of Ag dealloying from
AupAg1-p alloys,54 the UPD measurement would not affect the
alloy intactness.
The best choice for “formation” and “stripping” potentials
in further experiments would be 0.020 and 0.650 V, respectively.
The UPD charge density can easily be obtained by simply
integrating the current density over time using either the CV
formation or stripping curves and knowing the potential scan
rate. Similar to other literature sources57 and after taking into
account the correction (∼3.5%) for the background current
(Figure 3, dotted curve), our results suggest a charge density
of 300 ( 10 µC cm-2 for UPD of Pb on a Au polycrystalline
flat surface.
3.2.2. Pb UPD on NPG Using CV. Potential cycling between
0.650 and 0.020 V is applied to determine the charge of Pb
UPD on NPG. As shown in Figure 4a, the formation peaks are
12366 J. Phys. Chem. C, Vol. 113, No. 28, 2009 Liu et al.

Figure 4. (a) Pb UPD CV curves of NPG0.1 samples featuring dealloying depths from 0.5 to 5 µm at the scanning rate of 5 mV s-1. (b) Surface
area development, calculated from the corresponded charges of the formation and stripping CV peaks in Figure 4a, as a function of dealloyed depth.

less distinctive for Pb UPD on NPG0.1 (Figure 4a) as compared

to those for polycrystalline Au (Figure 3). At the same time,
two relatively separate stripping peaks at lower dealloying depths
(less than 1 µm), merge to form a dominant peak at the higher
depths (Figure 4a). Indeed, a careful analysis of the results
presented in Figure 4a reveals many aspects of a typical
diffusion-limited deposition scenario operating for the Pb UPD
process on NPG, when a CV experiment is carried out. For
instance, there is a relatively well-shaped peak registered for
the UPD formation when the dealloying depth is 0.5 µm. For
other depths, the cathodic current density (about -1 mA cm-2)
remains relatively constant upon potential scans from 0.250 to
0.020 V, and no peak could be registered. Then, in the reversed
potential scan (anodic direction), the deposited Pb monolayer
begins stripping off immediately only for the sample dealloyed
to the depth of 0.5 µm.
Unlike the CV run for a 0.5 µm thick layer, the UPD
formation process for the rest of the dealloying depths is still
proceeding even when the reverse potential scan is initiated. A
further manifestation of this behavior is represented by negative
currents registered to higher potentials (as high as 0.220 V) at
which a sharp (anodic) stripping peak would occur if a Pb UPD
layer were stripped from a flat Au electrode (compare Figures
3 and 4). These observations undoubtedly suggest a slow
formation process of the Pb UPD layer that becomes even slower
with an increase in dealloying depth.
Mass transport (diffusion) limitations are also hinted at by Figure 5. FESEM images of mechanically cross-sectioned (a) NPG0.1,
the results in Figure 4b, where the surface area obtained by CV (b) NPG0.2, and (c) NPG0.3 samples after dealloying.
formation and stripping charges is plotted as a function of the
depth of dealloying (Figure 4b). Apparently, the insufficient 5 validate the overall uniformity of the dealloyed layers. Thus,
amount of Pb becomes more and more obvious as the dealloying considering the SEM micrographs in Figures 2 and 5, a rough
depth increases, thereby, leading to a leveling of the roughness estimate suggests ligament and pore sizes of 7-10, 12-15, and
factor Rf, defined as the ratio between the actual and geometric 5-6 nm for NPG0.1, NPG0.2, and NPG0.3, respectively. Overall,
surface area. It is to be noted that no difference in the surface the absence of structural anisotropy in dealloyed layers con-
area measurements done either way is generally observed, sidered in this work confirms mass transport limitations as a
suggesting that the time of formation of a complete Pb compelling reason for saturation of the roughness factor, Rf,
monolayer exceeds substantially the time of registration using with the depth of dealloying in the CV experiment. That is why
CV at the scan rate used in our experiments. To ascertain the an accurate charge-based surface area measurement in any
correlation between the leveling of the Rf and structural aspects MNPM structure would require sufficient time. Thus, a viable
of NPG warranting slow diffusion of Pb2+ ions, we registered way to address this issue would be an infinitely slow CV or
SEM micrographs on cross-sectioned NPGp, where p ) 0.1, even a current measurement at constant potential (CA). The
0.2, and 0.3 atomic fraction. For the sake of clarity, only a second option will be described in detail in the next section.
portion of the cross section of interest is presented in Figure 5. 3.2.3. Pb UPD on NPG Using CA. The main benefit to using
While a careful morphology comparison reveals some length CA instead of CV for studying UPD on NPG is that the process
scale differences (reported also by Cattarin, et al.34 for NPG0.25) can be monitored until a complete Pb monolayer is formed or
between the topmost surface of NPG (thickness less than 50 stripped. In these experiments, the potential is pulsed from the
nm) and the cross-sectioned one, the results presented in Figure open circuit potential (OCP, normally higher than 0.650 V) to
Pb UPD-Assisted Method for Surface Area Measurement J. Phys. Chem. C, Vol. 113, No. 28, 2009 12367

Figure 6. (a) Current density transients of Pb UPD formation on NPG0.1 samples after dealloying to different depths (to 5 µm) at a potential of
0.020 V. (b) Surface area development versus dealloying depth.

Figure 7. (a) Current density transients of Pb UPD stripping on NPG0.1 with dealloying depth (to 5 µm) at the potential of 0.650 V. (b) Surface
area development versus dealloying depth.

0.020 V, and the current transient is registered until the

background current level is reached. In this way, the entire
process of Pb UPD formation on NPG can be precisely
monitored regardless of the time needed for the completion of
the monolayer at different dealloying depths (Figure 6a). By
integrating the current density over time and normalizing by
division to the monolayer charge of UPD Pb on a plain Au
polycrystalline electrode, we obtained a linear relationship of
the Rf versus dealloying depth as shown in Figure 6b.
In another run, a stripping experiment presented in Figure 7
is carried out in the following way. After a full monolayer of
Pb is formed (Figure 6a), the potential is pulsed from 0.020 to
0.650 V for the UPD stripping process to take place. While
taking longer than the stripping from a flat surface, the Pb layer Figure 8. Current transients of Pb UPD stripping on a flat polycrys-
stripping (Figure 7a) is faster than its formation counterpart. talline Au electrode at a potential of 0.650 V. Solid blue and red dashed
The overall stripping time also depends upon the depth of curves represnet Pb UPD stripping carried out at 30 and 630 s after
dealloying. In general, trends for UPD stripping are quite similar the layer formation, respectively. Double-layer charging in a background
to those observed in the UPD formation process. It should be solution is represented by the green dotted curve.
noted that prior to the normalization procedure, the charge
obtained from the results in Figures 6a and 7a is reduced by a 6b and 7b is an anticipated result given the overall uniformity
factor of 0.120. This correction takes into account double-layer and isotropy of the dealloyed samples shown in Figures 2 and
charging effects (∼0.085) manifested by the comparison of 5 and reported numerous times in the literature (see ref 1). That
charges under blue and green curves in Figure 8 and background is why the linearity here is regarded as proof of the applicability
charges (∼0.035) seen best through the comparison of blue and of the proposed approach for surface area measurements. Also,
red curves in Figure 3. Also, the close match between the blue the detailed analysis of the results presented in Figures 6-8
and red curves in Figure 8 clearly rules out any possibility for suggests that the CA procedure successfully addresses issues
additional charge accumulation caused by the possible surface with the incomplete Pb monolayer seen earlier with the CV runs.
alloying known to take place in this system as a site exchange It is now interesting to analyze the effect of the Au content
process strictly confined within the topmost substrate layer.58,59 on the Rf and accuracy of the chronoamperometric data obtained
Continuing the analysis of Figures 6b and 7b one finds an separately using formation and stripping of the UPD layer. The
indisputably linear relationship between the roughness factor relationship of the Rf versus dealloying depth is linear for all
and dealloying depth. The linear dependence shown in Figures alloy compositions considered in this analysis as shown in Figure
12368 J. Phys. Chem. C, Vol. 113, No. 28, 2009
Figure 9. Surface area development at different dealloying thicknesses obtained from (a) UPD formation and (b) UPD stripping using CA.
TABLE 1: Results of Linear Regression Analysis of Data Presented in Figure 9
UPD formation
-1
p% Au slope (µm ) correlation coefficient slope (µm )
10 233 0.993 173
20 157 0.992 116
30 277 0.998 224
9. In general, qualitatively identical trends of the surface area
development are registered regardless of whether formation or
stripping is considered (Figure 9a,b). It can also be seen that
the developed surface area at a given dealloying thickness
decreases in the order of NPG0.3 > NPG0.1 > NPG0.2. Generally,
without considering structural aspects of the alloys prior to
dealloying, the reason for the above trend can be attributed to
the argument that smaller pore size is associated with larger
surface area. This way, the order determined by these measure-
ments is in agreement with the morphology length scale of the
SEM micrographs in Figure 5. In the case of the deep dealloying
considered here, cross-sectioned samples are preferred as more
relevant than top view samples (Figure 2). Indeed, SEM images
(not shown) suggest that the topmost surface morphology is
confined within a layer as thin as 50 nm. While no qualitative
difference in the charge trends is found (Figures 9a,b), there
certainly is a quantitative difference between the area measure-
ments using formation and stripping transients. The fitting slopes
associated with the measurements in Figure 9 are summarized
in Table 1. Theoretically, the charges obtained using the UPD
formation and stripping should be equal as an identical amount
of atoms participate in both processes. Practically, however,
about 22% more surface area is registered on the basis of
formation in comparison with stripping of the UPD layer. In
addition to that, the straight lines obtained from the UPD
stripping data feature better fitting intercepts that are closer to
the theoretical value of 1. One way of realizing the charge
discrepancy in the “formation-stripping” comparison in Table
1 is to attribute the additional charge accumulation to side pro-
cesses taking place concomitantly with the UPD. A side process
taking place in that potential range could be the oxygen
reduction reaction (ORR) on a Au surface.60 Apparently, ORR
would affect the charge accumulated more during the slower
UPD formation process. Because of that argument, UPD
stripping appears to provide more accurate information about
the real surface area development.
The surface area development could also be analyzed through
the surface area density defined as area developed per gram of
Au in the alloy. While this parameter is not in the focus of our
present work, its importance is justified by the immediate
association with general criteria for cost effectiveness. Because
Liu et al.
UPD stripping area development
-1
correlation coefficient surface area density (m2 g-1)
0.999 65-70
0.999 20-25
0.999 30-35
of that and for the sake of accurate data presentation, only ranges
of surface area density are shown in Table 1. Presenting ranges
instead of values is warranted by the fact that the roughness
factor, Rf, is measured for a calculated depth of penetration,
assuming dissolution of the entire Ag during dealloying (eq 1).
At the same time, work of others61 and our own EDS results
suggest that up to a third of that Ag could remain trapped in
the NPG, depending upon the temperature and/or completion
of the dealloying process. Thus, an additional depth that is
unaccounted for in our estimate develops, leading to a reduction
of the surface area density that is not always trivial to quantify.
Taking into account the semiquantitative area density ranges
provided in Table 1, we see that higher surface area does not
necessarily mean a higher area density. Thus, NPG prepared
from a 10% Au alloy has a lower Rf per 1 µm dealloying depth
than NPG0.3, but it has a higher surface area density. The area
density ranges of dealloyed 20% and 30% Au alloys are in
reasonably good agreement with the results of others on NPM
prepared by dealloying. The most recently reported data
measured by BET, impedance, and/or UPD-based approaches
range from 5 to 41 m2 g-1.7,34,62 Values that are well within the
above range could also be indirectly derived by structural
analysis of recently reported NPG structures with stable ligament
and pore sizes on the order of 3-6 nm.61,63 Given the above
comparison, the surface area density obtained for NPG0.1 (Table
1) appears to be unexpectedly high. While no data is available
in the literature for dealloyed 10% Au alloys, we believe that
the lack of a pre-existing percolation Au structure at this low
Au fraction is critical for explanation of this anomaly. Indeed,
the lowest Au fraction at which such structure exists in this
alloy is believed to be 0.198.64,65 The absence of a percolation
Au structure leaves no pre-existing nucleation skeleton for
development of the interconnected porous structure resulting
from the dealloying process in NPG0.1. This, in turn, would lead
to nonuniformity of the structure and to more volume shrinkage
due to the plastic deformation and/or possible collapse of the
finest ligament ensembles.66 As a result, the accordingly
processed material would have poorer mechanical properties
compared to those of a standard bicontinuous solid-void
structure (like NPG0.3) and would rather represent a more open
structure with weakly connected nanoligaments (nanoparticles)
Pb UPD-Assisted Method for Surface Area Measurement
Figure 10. Surface area development at different dealloying depths,
obtained from UPD stripping using CA and CV.
Figure 11. UPD formation time at different dealloying depths, obtained
from UPD stripping using CA. Inset: Effect of Pb concentration on
UPD formation duration. ∆C is the factor of Pb2+ concentration change
with respect to 0.05 M.
and large macro cracks. Structures of that kind that have been
synthesized by agglomeration of supported or unsupported
(mainly) Pt nanoparticles (atomic weight 195 versus 197 for
Au), featuring surface area densities nearing 100 m2 g-1.67,68
Additional analysis of the surface area development and
discussion of the anomalously high surface area density obtained
by dealloying 10% Au alloy will be presented in Validations
of the Proposed Method for Surface Area Measurement as well
as in a more detailed study aiming at further correlating the
alloy composition with the surface area density in the near
future.
3.3. Kinetic Aspects of Pb UPD on NPG Substrates. It
has been demonstrated in the previous section that the UPD
formation is a slow process. Indeed, a comparison between Pb
UPD-assisted surface area measurements at different dealloying
depth of NPG0.1, conducted by CA and CV and shown in Figure
10, visualizes best this conclusion. Identical results (not shown)
are also observed for NPG0.2 and NPG0.3. It is clearly seen that
there is generally no difference in the surface area measurement
using either method at dealloying depths less than 1 µm. At
depths of dealloying exceeding 1 µm, the surface area keeps
increasing linearly in the CA-based protocol, and it eventually
levels when a CV measurement is performed. In addition, the
time of UPD formation increases linearly with dealloying depth
for all three alloy compositions (Figure 11), with the process
being much slower than the one carried out on a flat surface.
Taking into account that the reversibility of Pb UPD on a flat
Au electrode implies fast charge transfer kinetics (Figure 3), it
is apparent that mass transport (diffusion) limitations are a
critical impeding factor that governs the slow Pb UPD formation
J. Phys. Chem. C, Vol. 113, No. 28, 2009 12369
Figure 12. Minimum concentration of Pb2+ required for having
instantaneous UPD formation at different pore sizes.
on NPG. The diffusion limitations are a direct consequence of
the insufficient Pb ion concentration inside the pores for
instantaneous UPD formation. This deficiency can be best
understood by looking into an estimate of the minimum Pb2+
concentration, C, required to form instantaneously a monolayer
in pores with a very high aspect ratio. For this purpose, a simple
model treating the pore of NPG as a cylinder with a radius R
associated with the pore size allows for a derivation of the final
formula for calculating C in the following way. The charge
density, σ, of a Pb UPD monolayer on Au is multiplied by the
area of the cylinder wall to be covered (no bases as the pore is
hollow) and is then divided by the product of a mol of electrons
(z is the state of oxidation of the Pb ions, and F is the Faraday
constant) and the volume of the cylinder (eq 2).
σ × Acyl σ × 2πRh 2σ
C) ) ) (2)
zF × Vcyl zF × πR h
2 zFR
Thus, for R < 8 nm, a Pb concentration higher than 4 M is
needed to provide a sufficient amount of atoms to instanta-
neously cover NPG with one layer of Pb. Apparently, when R
is less than 3 nm, even a solution of Pb(ClO4)2 with the highest
concentration close to its solubility at ambient temperature (∼11
mol/L)69 will be unable to provide ions for instantaneous UPD
formation. To further support this diffusion limitations argument,
the inset in Figure 11 shows a 5-fold faster UPD layer formation
with a 5-fold increase in Pb2+ ion concentration. For a better
idea about the big frame encompassing the mass transport
limitations as a function of pore size, Figure 12 summarizes
data obtained by eq 2. It could be seen that if R is on the order
of 3-4 nm, the concentration needed for instantaneous UPD
formation exceeds 8 - 12 mol/L. The above discussion depicts
quantitatively the reason for slowing the Pb UPD process on
NPG given the fact that solutions no higher than 0.01 M are
most frequently used for studying the UPD systems.39 Appar-
ently, higher concentration solutions could be used to quicken
the UPD-based surface area measurements. It ought to be noted,
however, that other effects of such an approach should not be
discounted. For instance, counterion shielding effects observed
at higher electrolyte concentration could also invoke additional
limitations in the UPD layer formation process. In addition, if
the solution has a concentration close to the maximum elec-
trolyte solubility prior to the UPD stripping process, the peak
amount of dissolved atoms would exceed the solubility limit
and a sudden precipitation before the outward transport manages
12370 J. Phys. Chem. C, Vol. 113, No. 28, 2009
Figure 13. FESEM micrographs of NPG0.2, dealloyed to a depth of 3
µm and annealed for 10 min at (a) 200 °C, (b) 300 °C, and (c) 400 °C.
to lower the local concentration could affect the measurement
quality by introducing noise in the signal.70
3.4. Validations of the Proposed Method for Surface Area
Measurement. 3.4.1. Sample Coarsening by Thermal An-
nealing. The first and most straightforward way to assess the
applicability of UPD measurements for surface area determi-
nation in MNPM is to apply the proposed approach to a system
with well-known and documented behavior. It has been observed
by SEM that the structure of NPG becomes coarser by thermal
annealing.2,21,31,32 Figure 13 shows the FESEM images of
dealloyed NPG0.2 samples that are subjected to annealing for
10 min in N2 atmosphere. In agreement with previous reports
in the literature,31,32 the ligaments and pores become larger as
the annealing temperature increases from ambient (Figure 2b)
to 400 °C (Figure 13 a-c). To register quantitatively the
anticipated reduction in the surface area development, we carried
out an UPD measurement on the samples shown morphologi-
cally in Figure 13 (top view). The respective UPD stripping
curves are presented in Figure 14. A lower stripping current
density and shorter stripping time are observed with the
temperature increase.
The annealing temperature impact on the surface area of NPG
is even better presented in the inset of Figure 14. The reason
for the (nearly) linear relationship of the surface area reduction
with respect to the annealing temperature is not immediately
clear at this point, and no discussion is dedicated to this result.
It is only concluded that the UPD-assisted method could easily
register quantitative trends that have been only qualitatively
studied and documented so far in the literature.31,32
3.4.2. Surface Area Modeling of NPG. A step forward in
testing and qualitatively confirming the results obtained by
Liu et al.
Figure 14. Pb UPD stripping transients of 3 µm thick NPG0.2 samples,
annealed at different temperatures for 10 min. Inset: Surface area change
for the annealed samples.
Figure 15. Dependences of the modeled NPG surface area develop-
ment as a function of the pore size. Inset: “Building block” unit cell of
NPG that is left after dealloying.
the UPD-assisted method proposed herein could be made by
a simple surface area modeling of NPG. The model presented
below is developed by assuming a “lattice” type structure of
the interconnected Au fraction remaining after dealloying as
shown by the “building block” unit cell, depicted in the inset
of Figure 15. As shown in the drawing, a is the “lattice
parameter” of the unit cell, x and 2(a-x) represent the
ligament (Au) and pore (void left from the Ag dissolution)
size of the NPG structure, respectively. Similar modeling,
albeit for cylindrical and not intersecting pores, was reported
previously in the literature.71 While representing a very rough
approximation of the remarkable complexity typical for a
real solid-void interpenetrating structure resulting from
dealloying, the proposed model should still be useful in
providing basic qualitative trends of the surface area evolution
in porous structures. A comparison of the NPG structure as
shown in Figures 3 and 5 with the one assumed by the
simplistic model in Figure 15 undoubtedly reveals limitations
that would most likely lead to underestimation of the
predicted surface area. Noting that the perfection of the
proposed surface area model is not among the top priorities
of this work, one registers qualitatively similar trends
comparing the surface area calculated herein and the one
obtained by a previously reported model.71 While no details
of the presented model have yet been published, the Sup-
porting Information provided with this work reveals sequen-
tial steps in the derivation of eq 3 that links the roughness
factor, Rf, and the ligament size, x of NPG developed by
dealloying of AupAg(1-p) alloy
Pb UPD-Assisted Method for Surface Area Measurement J. Phys. Chem. C, Vol. 113, No. 28, 2009 12371

Rf )
1500
×
[2p-0.5cos ( cos-1(-p0.5)
3 ) ]
-1

[ ( )]
(3)
x -1.5 cos-1(-p0.5) 3
p cos
3

Figure 15 represents the roughness factor, Rf, as calculated

according to eq 3 in 1 µm thick NPGp, where p ) 0.1, 0.2, and
0.3. Generally, key points of interest here are the power law
increase in the surface area clearly seen at pore sizes less than
20 nm and the increase of the surface area developed at a given
dealloying depth with the increase in the original Au fraction
in the alloy. On the basis of data in Figure 15 and the average
pore size determined (to the extent it is possible) by SEM for
each composition (using the cross-sectioned layers in Figure Figure 16. Determination of surface area development (roughness
5), a comparison between experimentally determined and factor) at 1 µm dealloying depth of alloys with different Au fractions
using the UPD-assisted experiments and modeling method.
predicted-by-modeling roughness factors for the alloys studied
is presented in Figure 16. The comparison reveals a clear trend
in the ratio between experimental and modeling results going
from nearly 3.3 to about 1.3 with the increase of the original
Au fraction in the alloy. Interestingly, the analysis of the ratio
between pore and ligament size as determined by the model
suggests also a similar trend, from 4.1 to about 1.6, respectively
(Supplemental Information). Given literature reports on the
similarity between pore and ligament size in dealloyed struc-
tures72 and considering our own experience suggesting ratios
between pore and ligament size not exceeding 1.4 regardless
of the original alloy composition (Figures 2 and 5 and
Supporting Information), one could anticipate the better match
between the model and experiment at higher Au fractions. At
the same time, the calculated value would also be less than the Figure 17. Surface area measured by the Pb UPD-assisted method
experimentally measured one because even for NPG0.3 the model (crossed line-filled bars) and by BET (plain black bars).
portrays a more opened structure in comparison with the real
one. In summary, while the proposed model has a certain value
in revealing qualitative trends that correlate roughness factor, almost identical results are obtained by comparing a BET
ligament size, and the original Au fraction, other approximations measurement done after water removal and degassing on one
that take into account the structural evolution during dealloying hand and a subsequent Pb UPD-assisted area determination on
are needed for quantitatively matching the experimental results. the other hand (Figure 17, 200 °C, 1 h). The latter result
3.4.3. BET Measurement. BET is the most widely used demonstrates clearly the key limitations of a standard BET setup
technique for the surface area measurements of materials with for surface area measurement of NPG. Indeed, when the result
a fine structure. While rather expensive, BET measurements in obtained by BET is deemed reliable, the original NPG archi-
UHV could be done with minimum pretreatment steps. The most tecture would have coarsened to yield at least a five times lesser
standard setup for BET would include two stages: first degassing surface area density. This finding, along with the requirement
and then analysis. The main obstacle encountered for the usage for at least 1 g of sample for running an accurate BET analysis,
of BET specifically for surface area measurement of NPG gives a distinct edge to the Pb UPD-assisted method for surface
samples occurs in the degassing step, when high-temperature area measurement of MNPM with a fast coarsening rate at low
heating for a long period of time is required to remove water to moderate temperatures.
and absorbed gas that affect the accuracy of the measurement.
4. Conclusions
For instance, holding the temperature at 90 °C for 1 h is
recommended for water removal, and treatment at 350 °C for In summary, the present work illustrates systematically the
3 h is dedicated to the removal of absorbed gaseous contami- applicability of and reveals in detail the limitations of a Pb UPD-
nants. The holding temperature and time might be changed assisted method for surface area determination of MNPM
depending upon the sample itself and the accuracy of the exemplified by NPG. A comprehensive comparison between CV
measurement. As shown in Figure 17, without a temperature and CA in the formation and stripping of a Pb UPD layer on
treatment, it is clearly seen that the BET measurement yields a NPG (i) identifies the registration of stripping current transients
much lower surface area density for NPG0.2 than either the UPD- as the best approach for measurement of surface area and (ii)
assisted method measurement or the surface area modeling. No reveals distinct diffusion limitations slowing the UPD process
significant change (or a slight increase) is registered by BET on NPG with a thickness in the single digit micrometer range.
after the sample is heated at 90 °C for 1 h. This result contradicts The diffusion limitations governing the Pb UPD on NPG
findings of others2 and the results in the present work (Sample substrates are attributed to the insufficient bulk concentration
Coarsening by Thermal Annealing), suggesting a significant of Pb2+ ions for the formation of a full monolayer at a high
reduction of the surface area upon heat treatment. This behavior surface to volume aspect ratio. An estimate confirming the latter
could be attributed to a dynamic balance between an area statement suggested that less than 10% of the Pb monolayer
increase caused by the removal of water and thermal treatment could be instantaneously formed when a Pb concentration of
driven coarsening. In the presented validation experiments, 1-50 mM is used. The method developed in this work shows
12372 J. Phys. Chem. C, Vol. 113, No. 28, 2009
an overall trend in the surface area developed by dealloying in
the order of NPG0.3 > NPG0.1 > NPG0.2. While no clear-cut
understanding of the surface area trends with the original Au
fraction has yet been developed, the anomalously high surface
area density registered in NPG0.1 could have important practical
implications in the design and synthesis of low metal loading
catalysts.
A qualitative validation of the Pb UPD-assisted method for
surface area determination by a comparison between the
dealloyed and heat-treated NPG specimens shows reasonable
agreement with literature data. A simple surface modeling
approach provides qualitative trends in surface area development
in NPG and suggests that the closest match with experimental
data could be obtained by model structures featuring similar
pore and ligament size. A coarsening effect taking place during
the removal of water and gaseous contaminations limits the use
of standard BET protocols for surface area determination of
NPG. However, a quantitative agreement is found between BET
and Pb UPD-assisted surface measurements for samples treated
for water and gas removal. Overall, the Pb UPD-assisted method
is proven as an inexpensive, fast, selective, and sensitive
technique for the surface area measurement of MNPM.
Acknowledgment. The authors acknowledge the support of
this work by the National Science Foundation, Division of
Materials Research (DMR-0603019).
Supporting Information Available: Sequential steps in the
derivation of eq 3 and analysis of the ratio between pore and
ligament size. This material is available free of charge via the
Internet at http://pubs.acs.org.
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