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B1029
Fuel cells are attractive power sources for use in portable, stationary, and transportation applications.1,2 Polymer electrolyte
membrane (PEM) fuel cells, among the various types of fuel cells,
are expected to be a high impact technology because they operate at
relatively low temperatures (80 C), have high power density, can
vary their output quickly to meet changes in power demand, and are
suited for automotive applications where quick startup is required.24
However, the high cost of Pt electrocatalysts is one of the major barriers to widespread implementation of fuel cell power sources in a
variety of applications. The oxygen reduction reaction (ORR) at the
cathode is the major contributor to single cell efciency losses due
to the slow kinetics, unlike the anodic hydrogen oxidation reaction
(HOR), necessitating high Pt loadings at the cathode to reduce these
losses. Typical anode and cathode electrocatalysts are comprised of
platinum nanoparticles (35 nm in size) supported on carbon black.3
In addition to the high cost of the typical Pt electrocatalysts, the carbon support causes additional challenges. These challenges include
oxidation of the carbon support resulting in loss of Pt nanoparticles,5
promotion of the formation of peroxide species by the carbon support leading to degradation of the membrane polymer,6 and separation of carbon from the ionomer in the electrode structure leading to
loss of catalyst electrochemically-active surface area.5 Due to these
issues, extensive efforts are underway to develop high-performance,
durable, carbon-free, and low cost (low Pt loading) electrocatalyst
materials.4
Carbon-free unsupported Pt nanoparticles (Pt-black) can avoid
the problems associated with carbon, however, the large particle size
of Pt-black translates to high cathode Pt loadings required to achieve
adequate electrochemically-active surface area (approximately 2 mg
Pt/cm2 compared to < 0.4 mg Pt/cm2 for carbon-supported Pt) and
electronic conductivity.3,4 In recent years, carbon-free catalyst electrode approaches have been proposed, such as coating of Pt lms of
sub-micron thickness directly on the membrane, gas diffusion layer
(GDL),713 columnar Ti and CrN supports,14,15 or on an organic
* Electrochemical Society Student Member.
z
E-mail: wjkhudhayer@ualr.edu
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B1030
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B1031
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B1032
with not only the tips, but also with the high-surface-area nanorod
side walls as well. Therefore, we have investigated the possible
crystal orientations of the Pt nanorod tip facets and side walls by
calculating the angles between the different planes of the Pt nanorods utilizing Crystal-Maker software (CrystalMaker Software
Ltd.). Pt has a face-centered cubic (fcc) crystal structure and has
several equivalent crystal planes due to the symmetry of the fcc lattice. For example, the (100), (010), and (001) planes of Pt are all
identical, and in the following sections we will call them (100)-type
planes (one can also use the notation {100} to represent the family
of (100) planes). Similarly, (110), (101), and (011) planes of Pt have
the same atomic conguration and we will call them (110)-type
planes. Individual single-crystal GLAD Pt nanorods are mainly oriented with the [100] direction perpendicular to the substrate plane
(Fig. 4) and it is possible for (100) planes to make angles of 90, 90,
55, 45, 45, and 90 with the crystal planes (001), (010), (111), (110),
(101), and (011), respectively (Note: This method of crystal orientation calculation cannot be used for a polycrystalline material due to
the randomly oriented nature of crystal grains). This implies that the
nanorod sidewalls are most likely oriented in the [001] and [010]
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B1033
presence of the (100) plane at the tips of the nanorods. This might
be attributed to the presence of some nanorods which are oriented in
the [110] direction perpendicular to the substrate (i.e., weak Pt(220)
peaks observed in XRD results shown in Fig. 4), thus having [100]
planes at the tips of these nanorods. Therefore, especially for long
nanorods (i.e., length > tip diameter), the nanorods are expected to
have a large fraction of Pt(110) planes because these are the dominant planes at the high-surface-area nanorod sidewalls. We believe
that the dominant exposed crystal plane of the nanorods is Pt(110),
the plane that is the most active for the ORR.1822
Electrochemical characterization Electrochemical active surface area measurements and surface area stability CV and RDE
measurements were performed on 50, 200, and 400 nm long Pt
nanorods which correspond to Pt loadings of 0.04, 0.16, and 0.32
mg/cm2, respectively. For comparison, these measurements were
also performed on Pt/C with a Pt loading 0.02 mg/cm2. During CV
measurements, the GLAD Pt nanorod array electrodes were scanned
between 0 and 1.0 V in O2-free 0.1 M HClO4 at a scan rate of 10
mV/s. As shown in the CVs for the Pt nanorods in O2-free electrolyte (Figs. 7a and 7b), the Pt nanorods have an oxide reduction peak
potential of 0.83 V. This potential is 50 mV more positive than the
oxide reduction peak observed for Pt/C (Fig. 7b) indicating that the
GLAD Pt nanorods are less oxophilic than Pt/C.43 As shown in
Fig. 7b, the peak potential for oxide reduction is nearly identical to
that of polycrystalline Pt.
The electrochemically-active surface area (ECSA) of a high surface area catalyst is a critical parameter for dening the Pt loadings
necessary in the fuel cell application. The ECSAs of the Pt/C and
GLAD Pt nanorods were estimated using the charge for hydrogen
adsorption derived from the room temperature CVs. These were
obtained by integrating the charge between the double layer region
and the onset of hydrogen evolution, after subtracting the double
layer charging current, and using the following equation to convert
this charge to ECSAs44)
Figure 3. (a) Bright-eld transmssion electron microscopy (TEM) image of
an individual Pt nanorod and (b) the correspoding selective area electron diffraction (SAED) pattern. Scale bar shown is 50 nm. The single set of diffraction spots in the SAED pattern in (b) shows that the individual Pt nanorod
has a single crystal structure.
the theoretical predictions explained above (Fig. 5). From Figs. 6a,
6b, and 6c, it can be clearly seen that the facets of the nanorod tips
have [111], [100], and [110] orientations as they form rings at about
58, 55, and 44 , respectively. These pole-gure results are also consistent with the simulation results (Fig. 5) with the exception of the
Figure 4. X-ray diffraction (XRD) proles of 50, 200, and 400 nm long
GLAD Pt nanorod arrays. Data is offset for clarity.
ECSAcm2 Pt=gPt
ChargeC=cm2
210C=cm2 PtLoading gPt=cm2
[1]
The results show that the ECSAs of 50, 200, and 400 nm long Pt
nanorods and of Pt/C with Pt loadings of 0.04, 0.16, 0.32 and 0.02
mg/cm2 are 13, 12, 6.7, and 60 m2/g Pt, respectively. The ECSA
value of Pt/C electrocatalyst is in good agreement with values
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B1034
tion thickness at about 300 nm. At these initial stages, the diameters
of nanorods also increase with their length. Therefore, below 300
nm, the total surface area of the Pt nanorods is not expected to linearly depend on their length. However, we can assume that the surface area of the nanorods is dominated by the sidewall area, which
is proportional to the nanorod length, diameter, and number density.
By comparing the length, average diameter, and number density of
200 and 400 nm long rods, we estimated the SAEF of 200 nm Pt
nanorods as 25 [ 32 (200/400) (50/100) (14 109/
3 109)]. Similarly, by comparing 50 and 200 nm long rods, we calculated the SAEF of the 50 nm Pt nanorods to be 7 [ 25 (50/
200) (15/50) (54 109/14 109)]. Dividing these the SAEFs by
the measured Pt loading values, the effective surface areas for the
50, 200, and 400 nm long Pt nanorods were calculated to be approximately 17, 15, and 10 m2/g Pt, respectively. Based on our electrochemical measurements the 50, 200, and 400 nm long Pt nanorods
have ECSAs of 13, 12, and 6.7 m2/g Pt, respectively. Thus, the
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B1035
utilization factor of 50, 200, and 400 nm long Pt nanorods were estimated to be approximately 76% (13/17 100), 80% (12/15 100)
and 67% (6.7/10 100), respectively. Higher utilization of shorter
nanorods is believed to be due to the more complete wetting of the
nanorod sidewalls by the electrolyte solution.
The 50, 200, and 400 nm long Pt nanorods samples were scanned
multiple times in the 0.6 to 1.0 V potential range at a scan rate of 50
mV/s to establish their stability in an acidic environment. Figure 8
shows a series of CVs, taken at room temperature, from 50, 200,
and 400 nm Pt nanorods over 250 and 4500 cycles. For comparison,
the results for the Pt/C are shown in Fig. 9a. ECSA analysis shows
that only 60% of the initial ECSA of the Pt/C sample remained after
1000 potential cycles, while after 4500 cycles the 50, 200, and 400
nm Pt nanorods retained 59, 63, and 82% of their initial ECSAs,
respectively (Fig. 8). These results indicate that the Pt nanorods are
more stable than Pt/C with potential cycling over a potential region
and in an acidic environment relevant to the PEM fuel cell cathode
environment. A shift in the nal Pt/C oxide formation and reduction
peak potentials (Fig.9a) toward those of the Pt nanorods may be
attributed to a decrease in Pt oxophilicity due to an increase in Pt/C
ilim i
ilim i
[2]
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B1036
Figure 8. (Color online) Room temperature CVs of (a) 50, (b) 200, and (c)
400 nm long Pt nanorods over rst cycle, 250, and 4500 cycles (cycling
between 0.6 and 1.0 V at 50 mV/s). Data was recorded in O2-free 0.1 M
HClO4.
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B1037
Figure 10. (Color online) (a) Room temperature CVs of 50, 200, 400 nm long Pt nanorods in oxygen-saturated 0.1 M HClO4 at a scan rate of 10 mV/s and rotation speed of 1600 rpm, (b,c) Calculated ORR area- and mass-specic activities as a function of potential on 50, 200, and 400 nm long Pt nanorods, (d) dependence of area- and mass-specic activities on the ECSA of Pt nanorods of different lengths (different Pt loadings), and comparison of the ORR specic activity
from polycrystalline Pt, Pt/C, NSTF Pt (3M), and Pt nanorods of different lengths. Data are plotted for the positive-going sweep. The data for polycrystalline Pt
and NSTF Pt (3M) catalysts were taken from Mayrhofer et al.47 Based on the current range (0.1 ilim < i < 0.8 ilim) used for extracting kinetic currents, (b) and (c)
were restricted to potential ranges of 0.810.96, 0.890.98, and 0.901.00 V for 50, 200, and 400 nm Pt nanorods, respectively.
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B1038
[3]
where if represents the lm-diffusion-limited current or current density controlled by reactant diffusion within the electrode lm, K is a
constant dependent on oxygen concentration and diffusion coefcient of oxygen in the electrolyte and on its kinematic viscosity, x is
the angular rotation velocity of the RDE, and the other terms have
the same meaning as in Eq. (2). A Koutecky-Levich plot,50 (1/i) vs.
1/x1/2, for a xed potential should show a linear relationship with a
slope of 1/K and a y-intercept of 1/ik 1/if. The Koutecky-Levich
plots for the 400 nm Pt nanorod RDE ORR data at rotation rates of
1600, 2025, and 2500 rpm are shown in Fig. 11b for the diffusionlimited current (current at 0.4 V) and for the currents at 0.90 and
0.95 V. These plots are linear and parallel, as expected. To determine if lm diffusion is affecting the kinetic currents obtained from
RDE measurements and to correct for its effect, the y-intercept of
the Koutecky-Levich plot for i id is subtracted from the y-intercept
for the same plot at the potential of interest (e.g., 0.90 V). Comparison of the kinetic currents derived directly from the y-intercepts of
the Koutecky-Levich plots (ik) to those corrected for lm diffusion
(ik) indicates the extent of the inuence of lm diffusion on the
RDE measurements. This comparison for the 400 nm Pt nanorod
RDE data shows that lm diffusion has minimal effect on the currents at 0.90 and 0.95 V, with <5% difference between ik and ik.
Since all the other lms tested in this study were thinner than the
400 nm lm, it is expected that lm diffusion has minimal inuence
on the kinetic currents at 0.90 and 0.95 V for these lms as well.
Based on the absence of lm diffusion effects at 0.90 and 0.95
V, Eq. (2) was used to extract kinetic currents from the oxygen-saturated electrolyte RDE CVs (Figs. 9b and 10a). The effect of different Pt loadings (i.e., nanorod length and diameter) for GLAD Pt
nanorods is demonstrated in Figs. 10a, 10b and 10c. Based on the
current range (0.1 ilim < i < 0.8 ilim) used for extracting kinetic currents, the polarization curves in Figs. 10b and 10c for 50, 200, and
400 nm long Pt nanorods were restricted to potential ranges of 0.81
0.96, 0.890.98, and 0.901.00 V, respectively. As shown in Fig.
10b, the 200 and 400 nm long nanorods have nearly identical areaspecic ORR activities at 0.90 V, while the 50 nm nanorods have
relatively low activity. Two factors that may contribute to the lower
relative ORR activity of the 50 nm nanorods are: (1) the much lower
Pt loading (0.04 versus 0.16 and 0.32 mg Pt/cm2) leading to reduced
coverage of the glassy carbon disk with nanorods, evident in the
slightly lower diffusion-limited current for this sample (Fig. 10a)
and (2) the 50 nm nanorods do not have well-developed sidewalls
and have almost a particle-like structure as compared to the 200 and
400 nm long nanorods (Fig. 2). This means that the electrolyte is in
contact mainly with the facets at the tips of the nanorods which are
oriented in the [111], [100], and [110] directions (Figs. 4, 5, and 6).
The lower electrochemical activity of the (111) and (100) faces
compared to that of the (110) face will result in lower ORR activity
of the 50 nm long Pt nanorods compared to the activity of the 200
and 400 nm long nanorods that have well-developed (110) sidewalls
in addition to the tip and facet orientations. Figure 10c also shows
that the 400 nm long nanorod sample has lower mass-specic activity at 0.9 V than that of the 50 and 200 nm long nanorod samples
due to larger diameters and incomplete wetting compared to shorter
nanorods. This observation is also supported by the utilization calculation shown in the previous section.
The area- and mass-specic activities for Pt/C and Pt nanorods at
0.9 and 0.95 V are reported in Table I. The reported values of areaand mass-specic activities at 0.9 V taken from the literature4,16,47,49
for polycrystalline Pt and Pt/C are also given in Table I for comparison. Based on the reported area-specic activity and ECSA of 8 m2/
g for NSTF,47 the mass-specic activity was calculated and is also
reported in Table I. The area- and mass-specic activities measured
Figure 11. (Color online) (a) Room temperature positive-going RDE curves
for 400 nm long Pt nanorods in oxygen-saturated 0.1 M HClO4 at scan rate
10 mV/s and different rotation speeds (1600, 2025, and 2500 rpm) and (b)
Koutecky-Levich plots for 400 nm long Pt nanorods extracted from (a) at
0.4, 0.90, and 0.95 V.
for Pt/C in this study are in good agreement with the values reported
by Gasteiger et al.4 and by Paulus et al.48 and slightly lower than
those reported by Garsany et al.34 As discussed by Garsany et al.,34
the higher SA and MA values reported in their study might be attributed to optimization of the catalyst ink formulations. Figure 10d
shows the dependence of area- and mass-specic ORR activity at
0.90 V on the length and ECSA of Pt nanorods. Of the three nanorod
lengths studied, the 200 nm length exhibited the highest mass activity and area-specic activity nearly identical to that of the 400 nm
sample. As discussed above, the 200 nm long nanorods are long
enough to have well-developed sidewalls with the preferred [110]
orientation but, unlike the 400 nm long nanorods, they have smaller
diameters and better wetting. As shown in Table I and Fig. 10e, the
area-specic ORR activity of the 50 nm long Pt nanorods is higher
than that of Pt/C, while the 200 nm and 400 nm long nanorods have
area-specic activities that are higher than the Pt NSTF catalyst and
comparable to that of polycrystalline Pt. As explained in the introduction, electrochemical activity in 0.1 M HClO4 electrolyte follows
the trend Pt(110) > Pt(111) > polycrystalline Pt > Pt(100).18,19
Because the sidewalls of the Pt nanorods are dominated by (110)
planes, one would expect a higher area-specic ORR activity for
GLAD nanorods compared to polycrystalline Pt. Polycrystalline Ptlike ORR activities may be due to the existence of Pt(100) planes at
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B1039
Table I. Summary of the evaluated ORR electrocatalytic activity (area-specic and mass-specic activities at 0.90 and 0.95 V) of Pt-nanorod
array and Pt/C catalysts in 0.1 M HClO4 and comparison to the literature ORR activity values for various Pt catalysts.
Method
Sample
RDE
RDE
RDE
TF-RDE
RDE
TF-RDE
TF-RDE
TF-RDE
TF-RDE
TF-RDE
TF-RDE
50 nm long Pt nanorods
200 nm long Pt nanorods
400 nm long Pt nanorods
20% Pt/C
Bulk Poly-Pt
NSTF Pt
Pt/C (TKK)
Pt/C (TKK)
PT/C (TKK)
46% Pt/HSC (TKK)
20% Pt/C
Pt
loading
(mg/cm2)
ECSA
(m2/g)
0.042
0.014 (d 11.5 nm)
0.014 (d 23 nm)
0.014 (d 5 nm)
0.017
0.014
13
12
6.7
60
8
>60
>60
>60
132
66
0.040
0.160
0.320
0.020
SA(A/cm2)
MA(A/mg)
T
( C)
Scan
rate
(mV/s)
0.90(V)
0.95(V)
0.90(V)
0.95(V)
References
20
20
20
20
20
20
20
20
20
25
30
10
10
10
20
20
20
20
20
20
10
20
632
1080
1194
288
1200
750
100
200
350
292
305
166
250
266
76
0.08
0.13
0.08
0.18
0.06
0.27
0.21
0.02
0.03
0.02
0.05
This work
This work
This work
This work
Ref. 47
Ref. 47
Ref. 47
Ref. 47
Ref. 47
Ref. 51
Ref. 34
the sidewalls and tips of some of the nanorods and to the presence of
low coordination sites at the edges of the low index planes, which
can reduce the electrochemical activity compared to that of ideal
pure Pt(110) in perchloric acid electrolyte. It should be noted that
the existence of Pt(100) planes is expected to improve ORR electrocatalytic activity if adsorbing electrolytes such as sulfuric acid or
peruorosulfonic acid fuel cell electrolyte (e.g., Naon) are used
instead of non-adsorbing perchloric acid electrolyte,21,22 as
explained in the introduction.
The higher area-specic activity of the Pt NSTF catalysts compared to Pt/C catalysts has been attributed to the large Pt crystallite
size resulting in average coordination numbers of surface Pt and
corresponding surface electronic properties approaching those of
polycrystalline Pt.47 As shown in Fig. 2a, the 50 nm long nanorods
have diameters ranging from 5 to 20 nm and thus, due to the singlecrystal nature, their crystallite dimensions are expected to be in the
range of 550 nm (i.e., diameter-length). The comparable area-specic activities of the 50 nm Pt nanorod and the Pt NSTF catalysts is
believed to be due to the similar Pt crystallite dimensions of these
catalysts. In addition to the effects of electrochemically active
Pt(110) planes of Pt nanorods discussed above, the higher area-specic activity of the 200 and 400 nm nanorods can likewise be attributed in part to their larger crystallite dimensions compared to the 50
nm nanorods, Pt/C, and to the Pt NSTF. However, the large crystallite size of the Pt nanorod and the Pt NSTF catalysts result in a
lower ratio of surface to bulk Pt atoms and a concomitantly lower
mass activity than Pt/C, as shown in Fig. 10e and Table I
Temperature-dependence study Hydrodynamic voltammograms of
the Pt nanorods and the Pt/C catalyst were obtained as a function of
temperature between 20 and 60 C in oxygen-saturated 0.1 M HClO4
at 20 mV/s scan rate and 1600 rpm electrode rotation speed. Figure
12 shows an increase in the limiting current in the temperature range
of 2040 C. The increase in current density can be attributed to an
increase in the oxygen diffusion rates with increasing temperature
due to a decrease in electrolyte viscosity. At a temperature of 60 C,
a slight decrease in the limiting current density was observed (Fig.
12), indicating a decrease in both the oxygen concentration and density of the electrolyte at elevated temperature due to a drastic
increase in the vapor pressure of water. This observation was conrmed by Paulus et al.48 who derived an expression which represents the temperature-dependent limiting current density using the
physical-chemical properties of pure water.
Since ik depends on the oxygen concentration in the electrolyte,
which decreases with increasing the operating temperature,48,52,53 it
is most appropriate to dene the kinetics of the reaction in terms of
a concentration-independent apparent rate constant, kapp.52 The
apparent rate constants of ORR can be calculated from Eq. (4) at a
constant overpotential52
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B1040
kapp
ik
nFAreal O2 H
[4]
where kapp is the apparent rate constant, ik is the kinetic current calculated from Eq. (2), n is the number of electrons involved in the
reaction, F is the Faraday constant, Areal is the electrochemicallyactive surface area, [O2] is the oxygen concentration in the bulk of
the electrolyte solution, and [H] is the bulk concentration of protons (0.1 M). The oxygen concentration [O2] values at different
temperatures were taken from the values reported by Wakabayashi
et al.52 in which [O2] values were calculated based on Henrys law.
The apparent rate constants for ORR on Pt/C and Pt nanorods were
calculated at 0.93 and 0.95 V, where the rate of electron transfer is
very slow and clearly the rate-determining step. The apparent rate
constant values were calculated at potentials higher than 0.90 V
because the RDE current of Pt nanorods at 0.90 V and 60 C is in the
diffusion-limited region, as shown in Fig. 12b. Table II shows that
the apparent ORR rate constant on Pt nanorods (5 cm4/mol s) is
higher than that of the conventional catalysts (2 cm4/mol s) indicating that the ORR rate on Pt nanorods is larger than on Pt/C. The
Arrhenius equation48,53 was utilized to calculate the activation energies for ORR on both Pt/C and Pt nanorods
ln kapp
Ea 1
ln A
R T
Figure 13. (Color online) Arrhenius plots for the apparent rate constant kapp
on Pt/C and GLAD Pt nanorods at 0.93 and 0.95 V vs. RHE.
[5]
Table II. Calculated apparent reaction rate constant and activation energy for the ORR on Pt/C and GLAD Pt nanorods at
0.95 V.
Sample
ECSA
(m2/g Pt)
kapp at 0.95 V
and 20 C
(cm4/mol s)
Ea (kJ/mol)
at 0.95 V
20% Pt/C
200 nm long Pt nanorods
60
12
2
5
30.0 6 0.5
25.8 6 0.5
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B1041
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