P78 Journal of The Electrochemical Society, 155 6 P78-P81 2008

0013-4651/2008/1556/P78/4/$23.00 The Electrochemical Society

Analysis of the Impact of Individual Glass Constituents on

Electrocatalysis on Pt Electrodes in Alkaline Solution
K. J. J. Mayrhofer,*,z A. S. Crampton,a G. K. H. Wiberg, and M. Arenzz
Institut fr Physikalische Chemie 1, Technische Universitt Mnchen, Garching, 85748 Deutschland,
Germany

In our previous paper Journal of the Electrochemical Society, 155, P1 2008 we reported on the impact of glass corrosion on
establishing the electrocatalytic activity of fuel cell catalysts. It was shown that the leaching of glass constituents into the
electrolyte is responsible for insufficiently reproducible measurements of the oxygen reduction reaction as well as the hydrogen
oxidation reaction on polycrystalline platinum. In the present report we elucidate which glass constituents are leached into the
electrolyte through the analysis of alkaline electrolytes in contact with Duran glass by inductively coupled plasma optical emission
spectroscopy. By adding these constituents, i.e., silicates, borates, aluminates, and lead, separately to the electrolyte, we evaluate
their individual impact on electrocatalytic measurements. The results presented in this study help to explain the effects seen in
measurements in alkaline electrolyte with glass cells.
2008 The Electrochemical Society. DOI: 10.1149/1.2904882 All rights reserved.

Manuscript submitted January 8, 2008; revised manuscript received March 10, 2008. Available electronically April 23, 2008.

Electrocatalysis in alkaline media has received renewed interest Experimental

in recent years,1 in part due to reports of advances in the preparation
of alkaline membranes for low-temperature fuel cells.2 It is hoped
that with the help of such membranes, the design of alkaline fuel
cells AFCs can be improved considerably. A promising field of
application for an improved direct alcohol AFC technology is low-
power-density devices, where the possibility of utilizing nonplati-
num catalysts1,3-5 is a major advantage over other low-temperature
fuel cells. In order to fully characterize platinum-based catalysts and
their potential alternatives, it is important to use the catalytic activity
of Pt toward the oxygen reduction reaction ORR as a benchmark,6
due to its outstanding activity.7,8 Compared to acidic solutions, how-
ever, studies conducted on well-defined Pt crystal model systems
and polycrystalline Pt in alkaline electrolyte are scarce.9-11 A pos-
sible explanation for this is the experimental difficulties involved in
measurements using conventional setups with liquid alkaline solu-
tions.
Although rarely discussed in the literature, one major issue for
electrocatalytic studies in alkaline media particularly for polycrys-
talline Pt is the reproducibility of the results. In the investigation of
the ORR using a rotating disk electrode setup, even small shifts in
the polarization curves of 510 mV have a profound effect on the
extraction of kinetic parameters of fuel cell reactions. Based on our
previous experience from working in alkaline media,12,13 the elec-
trolyte must be prepared promptly before experiments, in which the
duration of measurement is also kept to a minimum. Only then may
more reproducible measurements to some extent be possible. The
underlying reason for such inconsistencies is that in general, elec-
trochemical experiments have been conducted in glass cells, without
the consideration that in alkaline solutions glass is not stable but
slightly etched over time.14-16 Subsequently, the constituents of typi-
cal laboratory glass, e.g., Duran glass that consists of silicates 70
80%, borates 713%, aluminates 27%, and alkalioxides
48%,17,18 dissolve into the electrolyte and can then interfere with
the reactions occurring at the surface of the working electrode. This
has been demonstrated in our previous work.19 In the present study
we determine in more detail the influence of the individual compo-
nents that are leached out of glass on the electrocatalysis measure-
ments in alkaline media. In particular, we analyze which constitu-
ents have an inhibiting effect on reactions and which constituents
are responsible for the apparent increase in activity of the ORR
observed previously.
* Electrochemical Society Student Member.
a
Permanent address: University of Vermont UVM, Burlington, Vermont 05405,
USA.
z
E-mail: karl.mayrhofer@mytum.de; matthias.arenz@mytum.de
The experimental setup has already been described in a previous
report.19 In short, the electrochemical cell, which was especially
developed for measurements in alkaline electrolytes, consisted ex-
clusively of Teflon components Bohlender, Germany in order to
avoid any influence of glass corrosion on the measurements. Only
the shape of the three-compartment cell was in essence based on a
standard glass cell. The main compartment, in which the rotating
disk Pt working electrode was investigated, had three connections:
one leads to a Teflon side compartment containing the reference
electrode, another connects to a small Teflon compartment contain-
ing the counter electrode, and a third connection is used to purge the
electrolyte with gas via a porous Teflon cork, located at the base of
the main compartment. The porous Teflon was shielded by a small
barrier in order to avoid any gas bubbles reaching and blocking the
surface of the working electrode, while still allowing proper satura-
tion of the electrolyte. The electrolyte itself was prepared using only
a Teflon spatula and a narrow-necked Teflon bottle. Because even
the shaft of the working and the reference electrode were also made
out of Teflon, the electrolyte never came in contact with any glass
components during the whole experiment.
A polycrystalline bulk platinum sample 5 mm diameter,
0.196 cm2 geometrical surface area embedded in a Teflon tip was
used in this study. The crystal was cleaned by washing with concen-
trated perchloric acid for 5 min and then thoroughly rinsed with
Millipore water prior to every measurement. The electrochemical
measurements were conducted in the previously described Teflon
cell using a rotating disk electrode setup Radiometer Analytical,
France with a potentiostat Princeton Applied Research, USA and
rotation controller. The cell was placed in a Faraday cage to sup-
press noise, and the measurements were recorded without applying
any filters. A reversible hydrogen electrode HydroFlex, Gaskatel,
Germany was used as the reference electrode and a Pt mesh as the
counter electrode. The electrolytes were prepared using Millipore
water and KOH pellets Merck, suprapure. For the cyclic voltam-
mograms in argon, ORR, and hydrogen evolution/oxidation reac-
tion, the electrolyte was purged with argon, oxygen, and hydrogen,
respectively Air Liquide. All measurements were conducted at
room temperature without correction for the uncompensated resis-
tance between the surface of the working electrode and the tip of the
Luggin capillary. Although the latter is certainly important for the
determination of absolute activities, in particular in electrolytes with
low conductivity, it is not crucial for the purpose of this study.
For the electrolyte analysis, a simultaneous inductively coupled
plasma optical emission spectroscopy ICP-OES Vista-Pro appara-
tus Varian equipped with a K-style concentric glass nebulizer and
a cinnabar cyclonic spray chamber was used. Typical operation con-
ditions were as follows: plasma gas-flow Ar 12 L/min, nebulizer gas

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 Journal of The Electrochemical Society, 155 6 P78-P81 2008 P79

Table I. Elemental analysis of different alkaline solutions using

ICP-OES. Values below the detection limit for the respective ele-
ment are marked < d.l.

Sample Si ppb Al ppb B ppb Pb ppb

1 0.1 M KOH 5 d.l. d.l. d.l.
Teflon beaker
2 0.1 M KOH 35000 1750 2650 d.l.
glass beaker 50 days
3 Teflon cell 20 d.l. d.l. d.l.
before the addition of glass
4 Teflon cell 420 10 15 13
after the addition of glass
5 Glass cell 1580 40 28 12
working electrode comp.
6 Glass cell 3055 140 42 14
reference electrode comp.

flow 0.9 L/min, radio frequency power of 1.2 kW, and replicates
5 10 s. Each sample was measured four times in a random fash-
ion and the undiluted electrolyte solution was pumped with ca.
400 L/min. For the determination of the Pb concentration a KOH
matrix correction was applied.
Figure 1. CV in Ar-purged 0.1 M KOH electrolyte with 106 M Si2+ at
293 K with a rotation rate of 2500 rpm and a potential scan rate of
100 mV/s. The initial CV dotted line and a CV after scanning for 20 min
between 0.05 and 0.5 V solid line are shown.

Results
in pure 0.1 M KOH solution see Fig. 4, only the Hupd peak at
ICP-OES analysis of the alkaline electrolyte. In order to de- 0.4 V is slightly more pronounced. In the previous report,19 we
termine the corrosion of glass both qualitatively and quantitatively, a showed that the effect of contaminations can be amplified by limit-
series of alkaline electrolyte samples with and without contact to ing the potential window. If in silicate-containing electrolyte the
glass were analyzed by ICP-OES see Table I. The results clearly positive potential limit is decreased to 0.5 V for 20 min, the char-
indicate that after the preparation of the electrolyte in a Teflon bea- acteristic hydrogen adsorption/desorption of hydrogen on Pt is
ker, the alkaline solution is not contaminated by any aluminum, blocked, and no clear double-layer region is any longer observed
boron, or lead, and only tiny amounts of silicon are detected sample Fig. 1. This effect is identical to that which we observed when
1. Moreover, after measurements in the all-Teflon electrochemical adding a piece of Duran glass to the electrolyte.19 The surface is
cell, no decisive amount of these impurities can be detected in the covered by the silicates to such an extent that the properties of Pt are
electrolyte used sample 3. If, however, a piece of Duran glass is clearly modified. The distinct peak at 0.5 V in the negative sweep is
added to the cell, corrosion occurs and the constituents start to dis- due to the reduction of the surface, which is shifted negatively by
solve into the electrolyte. Two hours after the addition of glass to the about 0.3 V. In addition to the voltammetric response to the sili-
electrolyte in the all-Teflon cell it was found that the Si content had cates, we investigated the oxygen reduction on the consequently
increased significantly, while Al, B, and Pb were also detected at modified surface see Fig. 2. Again we followed the protocol of the
concentrations of 10, 15, and 13 ppb, respectively sample 4. If a previous report19 in order to highlight the influence of contamina-
glass cell is used instead of the all-Teflon cell, even higher concen- tions. If the positive potential limit is kept at 0.5 V for 20 min, the
trations of glass constituents are found in the used electrolyte after
2 h measurement time samples 5 and 6. The contaminant concen-
tration in the reference compartment sample 6 is greater than in the
compartment of the working electrode sample 5, due to the in-
creased ratio between the glass/electrolyte contact area and the elec-
trolyte volume. To further demonstrate the importance of prepara-
tion of the electrolyte directly prior to the measurements, a 0.1 M
KOH solution was stored for 50 days in a closed glass beaker before
the ICP-OES analysis sample 2. The concentration of the investi-
gated impurities rises to ppm levels with the exception of lead,
although this is likely due to the different glass brand of the beaker.
Besides the elements shown in Table I, trace amounts of Na, Ca, Ba,
and Sr were also detected in a number of the solutions tested. How-
ever, because these cations were present at such low concentrations,
it is expected that they have no appreciable effect on the electro-
chemical measurements, and consequently these impurities are not
considered further in this report.
The impact of silicate on electrocatalytic reactions. Silicates
are the major constituents dissolved in the electrolyte according to
the ICP-OES measurements. In order to investigate their effect in-
dividually, crystalline SiO2 106 M was added to a 0.1 M KOH
solution. As crystalline SiO2 is harder to dissolve than amorphous Figure 2. Anodic curves of the ORR in 0.1 M KOH with 106 M Si2+. The
SiO2 in glass,14 the solution was placed in a closed Teflon bottle and effect of the positive potential limit after scanning to 0.5 V for 20 min solid
warmed in an oven for 24 h at 60C before use. In Fig. 1, a cyclic line, to 1.0 V for 5 min dotted line, and to 1.5 V for three scans dashed
voltammogramm CV of polycrystalline Pt recorded in this electro- line is shown. For comparison, the ORR in the 0.1 M KOH electrolyte that
lyte is shown. Initially the CV is very similar to the one obtained was stored for 50 days in a glass beaker see Table I sample 2 is also given.

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 P80 Journal of The Electrochemical Society, 155 6 P78-P81 2008

Figure 3. HOR on Pt in a 0.1 M KOH electrolyte with 106 M Si2+. The

positive potential limit was varied by a 100 mV/scan; however, only selected Figure 4. CV in Ar-purged 0.1 M KOH before dotted and after solid the
cathodic sweeps are shown for clarity. addition of 107 M Pb2+, at 293 K with a rotation rate of 2500 rpm and a
potential scan rate of 100 mV/s.

first sweep to 1.0 V indicates a significantly reduced activity toward

oxygen reduction solid line. This inhibiting effect of silicates is
even more severe at higher concentrations chain dotted line. If the
positive potential limit is then kept at 1.0 V for 5 min, the activity
recovers dotted line and a further increase in activity is achieved
by opening the potential window to 1.5 V dashed line due to the
partial removal of the silicate adlayer and thus an increase in the Pt
surface area.
As seen in Fig. 3, silicates dissolved in alkaline electrolyte also
possess an inhibiting effect on the hydrogen oxygen reaction HOR
activity. After limiting the positive potential limit for 30 min to
0.5 V, a strongly inhibited activity is observed solid line. How-
ever, by again increasing the positive potential limit, the HOR ac-
tivity recovers until it almost reaches the impurity-free activity.
Comparing these findings with those of our previous report, the
observed influence of silicates is in agreement with the effect of
glass corrosion on the HOR but in clear contrast with the impact on
the ORR.19 In particular, a limitation in the positive potential limit
leads to an increase in the apparent activity of the ORR. Therefore,
the reported impact of glass corrosion is not solely due to the leach-
ing of silicates into the electrolyte. Furthermore, similar experiments
for aluminates and borates with concentrations at around 106 M
showed no significant impact on the electrocatalytic activity of Pt.
Only at much higher concentrations 104 M did a reduction in
the activity of the HOR and ORR occur to an extent comparable to
the observations for silicates. Consequently, aluminates and borates
exhibit only a minor influence as impurities in electrochemical mea-
surements in alkaline electrolyte when contacted with glass.
formation of an oxide layer on Pt is significantly increased. The
peak potential is slightly shifted to higher potentials in both the
positive and negative sweep. Such behavior has already been re-
ported in earlier studies on the addition of different metals at slightly
higher concentrations.23 It was assumed that the foreign metal ions
are adsorbed by underpotential deposition on the Pt surface.24 It is
interesting to see that even tiny Pb concentrations, as found in the
course of glass corrosion in alkaline solution, could lead to similar
effects.
In Fig. 5 the results for the influence of lead on the ORR are
summarized. For Pt electrodes the catalytic activity of the anodic
sweep is in general less affected by the applied positive potential
limit and the electrode pretreatment, so it is usually used for the
determination of the specific activity of Pt. The Pb-modified Pt elec-
trode, however, behaves quite differently. The anodic sweep in Fig.
5a clearly varies with the pretreatment, i.e., the applied positive
potential limit. After scanning to 0.5 V for 20 min solid line, the Pt

The impact of lead on electrocatalytic reactions. In addition

to Si, Al, and B, we probed the influence of Pb. Although lead was
found only in trace amounts in the ICP-OES analysis of the electro-
lyte see above, even such low concentrations may interfere with
reactions in alkaline solution, as has been demonstrated for Au
electrodes.20-22 In order to analyze the influence of lead on the elec-
trocatalytic properties of Pt, lead oxide was added to the electrolyte
at a concentration comparable to that found in the ICP-OES analysis
107 M. In Fig. 4, the CVs of polycrystalline Pt before and after
the addition of lead are shown. Whereas the initial voltammogram
exhibits the standard features of a polycrystalline Pt electrode in Figure 5. ORR after the addition of 107 M Pb2+ to the alkaline electrolyte.
alkaline electrolyte, the voltammogram after the addition of trace Anodic a and cathodic b curves reveal the effect of the positive potential
amounts of lead already changes drastically. Hydrogen adsorption is limit, i.e., after scanning to 0.5 V for 20 min solid line, to 1.0 V for 5 min
suppressed, as indicated by the disappearance of the Hupd features. dotted line, and to 1.5 V for three scans dashed line. All curves are
In the potential region between 0.8 and 0.9 V the peak due to the background corrected against a CV recorded with the same scan rate.

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 Journal of The Electrochemical Society, 155 6 P78-P81 2008
Figure 6. HOR on Pt in a 0.1 M KOH electrolyte with 107 M Pb2+ added.
The positive potential limit was varied by a 100 mV/scan; however, only
selected cathodic sweeps are shown for clarity.
surface is modified in such a way that the first sweep to 1.0 V
exhibits a much higher activity. After scanning to 1.0 V for an ad-
ditional 5 min, the activity decreases dotted line. This deactivation
is even more pronounced after the positive potential limit is opened
to 1.5 V for three scans dashed line. This change in activity can be
related to the Pb coverage on Pt. Keeping the potential below 0.5 V,
the surface becomes covered to a great extent by Pb, and the activity
is increased following the opening of the potential limit. This behav-
ior is similar to the previous observation of Amadelli et al.23 at
higher Pb concentrations. The stimulating effect of Pb on ORR ac-
tivity might be due to a destabilizing effect of the oxide layer on Pt.
If, however, the positive potential limit is increased, then the equi-
librium coverage of Pb on the Pt surface is reduced. Therefore, the
Pt oxide layer can be formed at lower potentials and the ORR ac-
tivity decreases. Interestingly, the cathodic sweep in Fig. 5b is inde-
pendent of the pretreatment of the electrode and thus not affected by
the adsorption of Pb. In the anodic as well as cathodic sweep, a
distinct decrease of the diffusion-limited current occurs below 0.4 V
when the surface coverage of Pb is high solid line. In this potential
region the modified surface is no longer capable to fully reduce
oxygen to water, and so peroxide is also formed.25 The latter has
also been observed in acid electrolyte,26 however, without any
changes in the ORR kinetic region.
In contrast to the oxygen reduction, an inhibiting effect of a
Pbupd-modified Pt surface is found for the HOR in alkaline electro-
lyte. If traces of Pb2+ are in the electrolyte and the potential is kept
below 0.5 V, the HOR deteriorates immediately and no reaction
takes place up to about 0.4 V solid line, Fig. 6. If the potential is
opened up to 1.0 V, the activity recovers to some extent. This im-
pact of lead is similar to the one described for silicates; however,
even opening up to 1.5 V does not completely avoid the inhibition
by Pb.
In summary, the effect of glass corrosion on the electrocatalysis
reported previously can be explained by a combination of the effects
of the individual constituents of glass, in particular by silicates and
lead. Remarkably, for the ORR the inhibiting effect of silicates
106 M is exceeded by the enhancing effect of Pbupd, even at low
concentrations 107 M in solution.
Conclusion
Previously we reported that glass corrosion in alkaline solution
had a severe impact on the electrocatalytic activity of Pt. In contrast
to studies in glass cells, it was shown that the experiments in an
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P81
all-Teflon cell were reproducible and stable. Here we investigate the
impact of glass corrosion in experiments where the leached compo-
nents are separately added to the electrolyte. It is clearly shown that
an increase in the apparent ORR activity by glass corrosion can be
ascribed to the effect of trace amounts of Pb in the alkaline solution.
However, the ORR activity decreases upon the addition of silicates
to the electrolyte, due to the blockage of active Pt sites. Meanwhile,
the HOR is severely inhibited by both contaminants. In summary,
the observed behavior of a Pt electrode in alkaline electrolyte in
contact with glass is strongly influenced by the constituents that
dissolve into the electrolyte. The effect is dependent on the type of
glass used; however, silicates and trace amounts of lead will always
be present in measurements with glass cells. Stable and reliable
kinetic data in alkaline electrolyte can therefore only be obtained by
avoiding any glass parts and exclusively applying inert materials
such as Teflon while conducting an experiment.
Acknowledgments
This work was supported by the DFG through the Emmy-
Noether project ARE852/1-1. K. J. J. Mayrhofer is grateful to the
Austrian FWF for support through an Erwin-Schrdinger Scholar-
ship. A. S. Crampton is indebted to the German academic exchange
service for a RISE fellowship. Furthermore, Umicore AG & Co. KG
is acknowledged for financial support. We appreciate discussions
with D. Strmcnik, V. R. Stamenkovic, and N. M. Markovic, which
encouraged the ICP measurements. We thank Dr. D. Dautzenberg of
the Technical University Munich for the ICP-OES measurements
and the matrix correction.
Technische Universitt Mnchen assisted in meeting the publication
costs of this article.
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