J Solid State Electrochem (2015) 19:13311340
DOI 10.1007/s10008-014-2470-7
ORIGINAL PAPER
Electroactivity regeneration of sulfur-poisoned platinum
nanoparticle-modified glassy carbon electrode at low
anodic potentials
M. I. Awad & M. M. Saleh & T. Ohsaka
Received: 22 January 2014 / Revised: 20 March 2014 / Accepted: 20 March 2014 / Published online: 15 April 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract This paper focuses on the oxidative regeneration of
the electroactivity of sulfur-poisoned polycrystalline Pt (poly-
Pt) electrode and Pt nanoparticles-modified glassy carbon
(nano-Pt/GC) electrode in O2-saturated 0.1 M HClO4. Recov-
ery of the electroactivity is examined using oxygen reduction
reaction (ORR) as a probing reaction. Recovery of the poi-
soned electrodes is attempted by applying several potential
cycles in the range of 0.06~1.06 V (reversible hydrogen
electrode, RHE) for avoiding the dissolution of platinum when
the potential is excursed to higher positive values. The recov-
ery of the poisoned electrodes is significantly affected by the
dissolved oxygen, i.e., the recovery is more effective under O2
atmosphere than under N2 atmosphere. Moreover, the recov-
ery performance of the nano-Pt/GC electrode is more consid-
erable than that of the poly-Pt electrode. The easier recovery
of the former electrode is attributed to the relative small ratio
of Pt(100) facet as revealed from the facet-dependent
voltammetric behavior for the oxidation of formic acid at the
Pt electrode in HClO4 solution and from the X-ray diffraction
spectrum of the nano-Pt/GC electrode. Interestingly,
controlling the potential range for recovery and the
M. I. Awad : M. M. Saleh : T. Ohsaka (*)
Department of Electronic Chemistry, Interdisciplinary Graduate
School of Science and Engineering, Tokyo Institute of Technology,
4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
e-mail: ohsaka@echem.titech.ac.jp
T. Ohsaka
e-mail: mawad70@yahoo.com
M. I. Awad : M. M. Saleh
Chemistry Department, Faculty of Science, Cairo University, Cairo,
Egypt
M. I. Awad
Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura
University, Makkah Al-Mukarramah 13401, Kingdom of Saudi
Arabia
number of potential cycles was found to lead to a
remarkable electrocatalytic activity of the electrodes for the
ORR. A plausible explanation for the obtained results is given
in view of the voltammetric measurements.
Keywords SO2 tolerance . Platinum nanoparticles . Oxygen
reduction . Adsorption . RRDE
Introduction
The adsorption of sulfur and sulfur-containing compounds on
metal electrodes has received a great interest because of their
potential importance in many fields such as corrosion,
electrocatalysis, and preparation of nanooptoelectronic devices
[15]. Elemental sulfur and sulfur-containing species strongly
adsorb on almost all metals, blocking the active sites and thus
restrict the access of other species that would adsorb or decom-
pose on the electrode surface. Adsorption of sulfur onto metal
electrodes may act as a catalyst for some electrochemical pro-
cesses [69] and as a poison for some other processes [10].
Sulfur poisoning and/or catalysis is often explained based on the
simple blocking of the active sites that would catalyze/inhibit
some reactions and/or changing the electronic effect [11, 12].
Platinum electrode is of outstanding electrocatalytic prop-
erties, and most of the literature regarding SO2 poisoning has
focused on this metal [8, 1316]. However, the recovery of
SO2-poisoned electrode is a complicated issue. It has been
reported that, for example, in H2/Air (O2) polymer electrolyte
membrane (PEM) fuel cell, the total recovery of the cathode
could be partially achieved by the potential scan between 0.06
and 1.26 V (reversible hydrogen electrode, RHE) [17, 18].
Loucka reported that holding the potential at potential values
as high as 1.46 V (RHE) could not completely oxidize the
adsorbed S, and only the periodic potential scan within the
potential range of 0.06~1.66 V (RHE) could be remedial in
1332
the complete removal of adsorbed S by its oxidation to soluble
sulfate according to the following equation [19]:
PtS 4H2 OPt SO4 2 8H 6e 1 ORR was studied in 0.1 M HClO4 using a conventional
Recently, it has been reported that the poisoned platinum
cathode in H2/Air (O2) PEM fuel cell could be completely
recovered when it was flushed with high-humidity (100 %
RH) O2 gas for 2 h at 80 C [20]. In the present paper, we
report on the possible in situ oxidative recovery of sulfur-
poisoned polycrystalline Pt (poly-Pt) electrode and platinum
nanoparticle (of size 20 nm)-modified glassy carbon (nano-Pt/
GC) electrode in O2-saturated 0.1 M HClO4 by few potential
cycles in a narrow potential range (0.06~1.06 V (RHE))
where the possible dissolution of platinum nanoparticles at
high anodic potential is avoided. Nano-Pt of 20 nm used in
this work is quite larger than that cited in the literature.
However, it has been reported that there is a threefold decrease
in the activity of the oxygen reduction reaction (ORR) in
acidic and alkaline media when the size of Pt nanoparticles
decreases from 24 to 2 nm in alkaline media [21, 22]. The
durability of extremely small nanoparticles is another criticism
for such nanoparticles in application to fuel cells [23]. For the
purpose of the present study, we can say that the used size of
the Pt particles is satisfactory. The recovery of the poisoned
electrodes has been examined in N2- and O2-saturated 0.1 M
HClO4 solutions. Rotating ring-disc voltammetry has been
used to probe the impact of the poisoning of these electrodes
on the ORR mechanism.
Experimental
A working electrode of poly-Pt and Pt nanoparticle-
electrodeposited glassy carbon (nano-Pt/GC) electrodes (=
3 mm) was used for the cyclic voltammetric (CV) experi-
ments. The counter and the reference electrodes were, respec-
tively, a spiral Pt wire and an Ag/AgCl/KCl (sat.). The poten-
tials are reported with respect to the RHE. Prior to the elec-
trodeposition of Pt nanoparticles, the GC electrode was polished
first with no. 2000 emery paper and then with aqueous slurries
of successively finer alumina powder (particle size down to
0.06 mm) with the help of a polishing microcloth. The bare
GC electrode was then sonicated for 10 min in Milli-Q water.
Pt nanoparticles were electrodeposited from acidic bath of
0.05 M H2SO4 +20 mM HCl containing 1.0 mM H2PtCl6 by
applying bipotential steps from the open circuit potential
(OCP) to 1.64 V vs. RHE (for 0.1 s) and then to 0.44 V
vs. RHE (for 10 s). Chloride anion was used (20 mM HCl) for
the sake of preparation of small nanoparticles as it adsorbs on
freshly electrodeposited Pt particles, preventing them from their
aggregation. Prior to electrochemical measurements, the thus-
J Solid State Electrochem (2015) 19:13311340
prepared nano-Pt/GC electrodes were subjected to several po-
tential scans in 0.1 M HClO4 solution in the potential range of
01.7 V vs. RHE to remove the adsorbed chloride ions.
two-compartment Pyrex glass container. Milli-Q water
(Millipore, Japan) was used to prepare all the solutions. Per-
chlorate anion has a weak specific adsorption on Pt, and thus,
it was chosen as a suitable electrolyte anion in this study. Prior
to each experiment, O2 gas was bubbled directly into the cell
for 30 min to obtain an O2-saturated solution, and during the
measurements, O2 gas was flushed over the cell solution.
SO2 poisoning solution was prepared by introducing 0.1 M
Na2SO3 in 0.1 M HClO4 solution. In this case, Na2SO3
(Kanto, Japan) was completely converted to SO2 which is
soluble in the aqueous solution. That is to say, a certain
volume of the aforementioned solution was used to prepare
the desired concentration of SO2 in 0.1 M HClO4. Then, SO2
poisoning was done as follows: an irreversibly adsorbed sulfur
dioxide layer was formed on the electrodes from SO2-contain-
ing HClO4 solution by applying a constant potential of 0.66 V
(RHE) for 3 min, and then, the potential cycle was repeated for
several times at 100 mV s1 between 0.66 and 0.06 V in SO2-
free deoxygenated 0.1 M HClO4 solution. Potential cycling
within this potential range ensures the conversion of adsorbed
sulfur species into elemental S [24].
Several scenarios are used for the recovery of the poisoned
electrodes: in scenarios I and II, the potential of poisoned
electrodes was scanned for certain potential cycles at
100 mV s1 in N2- and O2-saturated 0.1 M HClO4 solutions,
respectively, in the potential range of 0.061.06 V (RHE).
Scenario III is similar to scenario II, but each potential cycle
was conducted each time in a fresh HClO4 solution. In sce-
nario IV, the potential of poisoned electrodes was cycled for
several times at 100 mV s1 in O2-saturated 0.1 M HClO4
solution in the potential range of 0.061.56 V (RHE).
A conventional three-electrode cell of around 20 cm3 was
used for the cyclic voltammetric measurements, while in the
case of hydrodynamic voltammetric measurements, the work-
ing electrode compartment was 200 cm3 to eliminate any
possible changes in the O2 concentration during the measure-
ments. Steady-state voltammograms were obtained using a
rotating ring-disk electrode (RRDE) with a GC disk (=
6.0 mm in diameter) and Pt ring using a rotary system from
Nikko Keisoku, Japan. The GC disk-Pt ring RRDE was me-
chanically polished to a mirror surface in the same manner as in
the case of the poly-Pt electrode and then was cleaned ultra-
sonically in Milli-Q water. Then, the platinum nanoparticles
were electrodeposited onto the GC disk as mentioned above.
Electrolyte solutions were, if necessary, deaerated by bubbling
N2 gas for at least 30 min prior to electrochemical measure-
ments. All the measurements were performed at room temper-
ature (251 C). All current densities are calculated on the basis
of the geometric surface area of the relevant working electrode.
J Solid State Electrochem (2015) 19:13311340
Scanning electron microscopy (SEM) analysis of the
Pt nanoparticles electrodeposited onto the GC electrode
was carried out using a JSM-T220 scanning electron
microscope (JEOL Optical Laboratory, Japan) at an ac-
celeration voltage of 20 kV and a working distance of
45 mm.
A computer-controlled X-ray diffraction technique,
PANalytical model XPert PRO Powder, was used to scan
the nano-Pt/GC electrode.
Results and discussion
Figure 1 shows the SEM images of the nano-Pt/GC electrode
at two different magnifications. The platinum nanoparticles,
estimated as about 20 nm in average size, are uniformly
distributed on the entire surface of the GC substrate. This
uniform distribution is probably due to the presence of
chloride ions in the deposition path. It is thought that chlo-
ride ions adsorb on the early electrodeposited Pt particles
and prevent the aggregation of these nanoparticles, as re-
ported previously for the uniform deposition of gold
Fig. 1 SEM images for nano-Pt/GC electrode showing the distribution of
Pt nanoparticles on the GC electrode
1333
nanoparticles with an almost the same size in the presence
of iodide ions [25].
Electrochemical characterization
Figure 2 shows the characteristic CVs obtained at the (a) poly-
Pt and (b) nano-Pt/GC electrodes in N2-saturated 0.1 M
HClO4 solution at 0.1 V s1. It shows clearly the oxidation
of the platinum surface during the positive-going scan in a
broad potential range of 0.71.5 V, which is subsequently
reduced during the negative-going scan in a single broad peak
(centered at ca. 0.74 and 0.70 V for the poly-Pt and nano-Pt/
GC electrodes, respectively). The hydrogen adsorption-
desorption (Hads/des) pattern is also shown at a potential of
<0.36 V. The following remarkable features can be extracted
from this figure:
1. The Hads/des pattern on the Pt electrode is quite surface-
specific and has been considered as a suitable diagnosis
for the crystallographic orientation of the electrode sur-
face [2629]. The Hads/des patterns at the two electrodes
are significantly different, which may suggest the differ-
ence in the relative ratios of the low-index facets of Pt
crystals at these both electrodes. The peak at around
0.30 V observed at the poly-Pt electrode, which has been
reported to correspond to the adsorption of strongly
bounded hydrogen onto Pt(100) facets, is not shown in
the case of the nano-Pt/GC electrode. This reflects the
relative enrichment of the nano-Pt/GC electrode in the
other two low-index facets, i.e., Pt(110) and/or Pt(111)
facets.
10
a
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
E / V vs. RHE
Fig. 2 CVs obtained at (a) poly-Pt and (b) nano-Pt/GC electrodes in N2-
saturated 0.1 M HClO4 solution. Scan rate 100 mV s1
1334
2. The peak potential of the platinum oxide reduction at the
nano-Pt/GC electrode (ca. 0.70 V) is negatively shifted as
compared with that obtained at the poly-Pt electrode (ca.
0.74 V). This negative shift seems to reflect a stronger Pt
O bond as it has been reported that the PtO bond strength
increases with the decrease in the size of Pt nanoparticles
[30, 31].
3. The onset potential of the platinum oxide formation at the
nano-Pt/GC electrode is shifted positively as compared
with that at the poly-Pt electrode. This again confirms the
relative decrease in the Pt(100) facet, because the oxide
growth rate depends on the crystallographic orientation of
the Pt electrode and the oxide formation is much faster at
the Pt(100) facet and occurs at lower positive potentials
compared with the other two facets [26, 32].
4. In the case of the nano-Pt/GC electrode, the so-
called third anodic hydrogen peak is observed at a
potential (ca. 0.21 V) between the strongly and
weakly bonded hydrogen peaks. This peak is con-
sidered to correspond to the oxidation of subsurface
molecular hydrogen formed on Pt(110) sites with
surface structures as reported previously [33, 34].
That is, this observation suggests the relative enrich-
ment of the Pt(110) facet in the present nano-Pt/GC
electrode. A further study regarding the significantly
favorable formation of Pt(110) facet in the electro-
deposition of Pt nanoparticles is currently under
way.
Poisoning of electrodes
The electrodes were poisoned, as mentioned in the
Experimental section, by holding the electrode poten-
tial at 0.66 V (SHE) in 0.5 M HClO4 containing 5 mM
SO2 and then repeating the potential scan for several
times in the potential range between 0.66 and 0.06 V.
Sweeping the potential to 0.06 V reduces the adsorbed
SO2 to the adsorbed SOx species with elemental sulfur
as the main product [24, 35]. It has been also reported
that the sulfide is formed by the reduction of the
adsorbed SO2 at such negative potentials [24, 35]. To
examine this point, the number of electrons per active
site (eps, i.e., the number of electrons required per
adsorption site to oxidize the adsorbed layer) was esti-
mated by measuring the amount of charge passed during
the complete oxidative removal of the adsorbed sulfur
from the poly-Pt (Fig. 3) and nano-Pt/GC electrodes
(data are not shown), which were previously poisoned
by repeating the potential scan in the potential range of
0.06 to 1.56 V (scenario IV); that is, in order to
completely remove the adsorbed sulfur, the potential
scan was repeated in this potential range until the
J Solid State Electrochem (2015) 19:13311340
1st cycle
10
2nd cycle
3rd cycle
4th and 5th cycles
0
i/ A
-10
-20
0.0 0.5 1.0 1.5
E / V vs. Ag/AgCl (KCl sat.)
Fig. 3 Successive voltammograms obtained at the poisoned poly-Pt
electrode (s =0.88) in N2-saturated 0.1 M HClO4 solution. Scan rate
100 mV s1. The cycle number is indicated in the figure
characteristic voltammetric response of a clean Pt was
restored. The eps was calculated using the following
equation [36]:
Qs
eps 2
QH ?s
where Qs is the charge consumed during the completel
oxida-
tive desorption of adsorbed SOx species. Qs (= Qa Qc , n
n1
is the order (first, second,, lth) of potential scan) is calcu-
lated by the summation of the difference between the charge
(Qan) consumed during the oxidation in the entire potential
range of 0.66~1.56 V and the charge (Qcn) consumed in the
reduction of the platinum oxide formed, QH is the charge
consumed during the hydrogen desorption at the clean Pt
electrode, and s is the sulfur surface coverage calculated
according to the established methodology [6, 19, 37], as
Qp
s =1QH , where QpH is the charge consumed during the H
H
desorption at the poisoned electrode. The eps at the poly-Pt
and nano-Pt/GC electrodes was found to equal 7.4 and 7.6,
respectively, which are larger than 6 expected when all of the
adsorbed SOx species are elemental sulfur. Thus, this indicates
that the adsorbed SOx species is a mixture of the elemental
sulfur and sulfide, similarly to the adsorption of sulfur on
smooth and rough Pt electrodes [21].
Recovery of poisoned electrodes
The effect of oxygen on the recovery of the poisoned elec-
trodes was examined, and the results obtained at the poisoned
poly-Pt and nano-Pt/GC electrodes are shown in A and B,
respectively, in Fig. 4, in which the CVs for the ORR are
obtained at the fresh electrodes (curves a), the poisoned elec-
trodes (curves b), and (curves c, d) the electrodes recovered by
scenario I (under N2 atmosphere) and scenario II (under O2
atmosphere) in O2-saturated 0.1 M HClO4 solution. It is
J Solid State Electrochem (2015) 19:13311340 1335

noteworthy to mention that the poisoning of the electrode A

significantly decreases the ORR peak current and shifts the
peak potential in the negative direction (compare curves a 0.0

with curves b). Recovery using scenario I does not signifi-

cantly refresh both electrodes; in the case of the poly-Pt elec- -0.5

i / mA cm-2
trode, the peak current (ip) of the recovered electrode (curve c)
is slightly restored, i.e., ip is equal to 1.05 and 1.25 mA cm2
for the poisoned and recovered electrodes, respectively, -1.0 b

and in the case of the nano-Pt/GC electrode, i p is C d

equal to 1.04 and 1.30 mA cm2 for the poisoned

-1.5
and recovered electrodes, respectively. However, the peak poten-
tial (Ep) shows a significant improvement in the case of the nano- a
Pt/GC electrode (Ep equals 0.56 and 0.67 V for the poisoned and -2.0
0.0 0.2 0.4 0.6 0.8 1.0
recovered nano-Pt/GC electrodes, respectively) as compared E / V vs. RHE
with the poly-Pt electrode (Ep equals 0.56 V for both the poi-
soned and recovered electrodes). On the other hand, the CV B
responses obtained after recovery of the poisoned electrodes
0.0
using scenario II (i.e., in O2-saturated 0.1 M HClO4 (curves d))
are significantly improved; the improvement at the nano-Pt/GC
electrode (ip equals 1.04 and 1.72 mA cm2 for the poisoned -0.5
and recovered electrodes, respectively) is much larger than that at i / mA cm-2
the poly-Pt electrode (ip equals 1.05 and 1.31 mA cm2 for the
b
-1.0
poisoned and recovered electrodes, respectively).
Figure 5 shows the CVs obtained at (A) poly-Pt and (B) nano- C

Pt/GC electrodes ((a) clean electrode and (b, c) electrodes recov- -1.5
ered by scenarios III and IV, respectively) in O2-saturated HClO4 d

solution. The recovery using scenario III results in an almost a

complete recovery of the nano-Pt/GC electrode (curve b) and a
slight recovery of poly-Pt electrode. Scenario IV does not
completely recover the poly-Pt electrode (curve c), and the
oxygen reduction peak potential shifts slightly in the positive
direction of potential, but the nano-Pt/GC electrode is completely
recovered and, interestingly, a significant positive shift (ca.
45 mV) of the oxygen reduction peak potential is observed
(curve a); that is, the nano-Pt/GC electrode recovered by scenario
IV becomes more active for the ORR than the original (non-
poisoned) one. This point is in need for a separate investigation
which is out of the scope of the present study.
RRDE data
Figure 6 shows the steady-state voltammograms for the ORR
obtained at the RRDE with poly-Pt disk and Pt ring in O2-
saturated 0.1 M HClO4 solution. Curves (a) and (b) were
obtained at the clean and poisoned electrodes, respectively.
Curve (c) was obtained at the electrode recovered by scenario
III using three potential cycles, in which each cycle was
conducted each time in a fresh HClO4 solution. Curve (d)
was obtained in a fresh O2-saturated HClO4 solution after the
poisoned electrode was recovered by scenario IV (using one
potential cycle). At the clean electrode (curve a), as expected,
the well-defined voltammograms for the ORR over a wide
potential range are attained and the corresponding ring current
-2.0
0.0 0.2 0.4 0.6 0.8 1.0
E / V vs. RHE
Fig. 4 CVs obtained at (A) poly-Pt and (B) nano-Pt/GC electrodes ((a)
fresh, (b) poisoned, and (c, d) recovered by scenarios I (c) and II (d)).
Voltammograms (c) and (d) were obtained at the tenth potential cycle.
Scan rate 100 mV s1
(curve a) is almost zero, indicating an exclusive four-electron
ORR at the poly-Pt disk electrode [38]. At the poisoned disk
electrode (curve b), the half-wave potential shifted by ca.
300 mV in the negative direction compared with the clean
electrode and the limiting current was reduced to half of that
obtained at the clean disk electrode (curve a) and the ring
current was increased largely, indicating that a two-electron
ORR takes place dominantly (Eq. 3) [3941], which is consis-
tent with the work of Garsany et al. on poisoning and recovery
of commercial carbon-supported Pt nanoparticles [42].
O2 2H 2eH2 O2 3
The formation of hydrogen peroxide is certainly due
to the adsorbed S which inhibits the bond scission of
O2 and thus retards the direct four-electron reduction
of oxygen to water [4346]. Recovery of the electrode
using scenario III (curve c) results in a positive shift of
the onset potential of the ORR and an increase in the
1336 J Solid State Electrochem (2015) 19:13311340

150
A
0.0
b/
100

-0.5
i / mA cm-2

iR / A
c/
-1.0 50

-1.5 d/
c
a/ 2D Graph 1
0
a 0.0 0.2 0.4 0.6 0.8 1.0
-2.0 0.2
0.0 0.2 0.4 0.6 0.8 1.0
b
E / V vs. RHE C
0.0

B a
-0.2

-2
iD / mA cm
0.0
b e
-0.4 d

-0.5
-0.6
i / mA cm-2

-1.0 -0.8
d
a
a
b -1.0
-1.5 0.0 0.2 0.4 0.6 0.8 1.0

-2.0 C Fig. 6 Steady-state voltammograms for the ORR at (a) fresh and (b)
0.0 0.2 0.4 0.6 0.8 1.0
E / V vs. RHE
Fig. 5 CVs obtained at (A) poly-Pt and (B) nano-Pt/GC electrodes in O2-
saturated 0.1 M HClO4: (a) fresh and (b, c) recovered by scenarios III and
IV, respectively. In (b) the fourth cycle is presented and in (c) the second
cycle is presented
disk current along with a decrease in the ring current,
indicating the decrease in the contribution of the two-
electron ORR in the whole process. In this case, the
mass transfer-controlled limiting current is ca. 80 % (at
0.2 V) of that obtained at the clean electrode, but the
kinetics-controlled current in the rising part of the
voltammogram is not significantly recovered. The re-
covery of the electrode using scenario III, in which the
potential is cycled in the range of 0.061.06 V, could
be explained as follows: at potentials of <1.06 V, the
adsorbed sulfur is oxidized to SO2 and SOx along with
the reduction of oxygen to H2O2 (as indicated from
curves b and c). The electrogenerated H2O2 could
react with SO 2 species to produce less adsorbed
HSO 4 - anion according to the following equation
[16], and consequently, the poisoned electrode could
be partially restored.
SO2 H2 O2 HSO4 H 4
E / V vs. RHE
poisoned poly-Pt electrode in O2-saturated 0.1 M HClO4. (c) is the
response obtained at the electrode recovered by four potential cycles in
the potential range of 1.06~0.06 V. The potential cycling for recovery and
the measurement of ORR after that were carried out in different 0.1 M
HClO4 solutions (O2-saturated). (d) is the response obtained after one
potential cycle between 0.06 and 1.56 V in O2-saturated HClO4. (a, b, c,
and d). H2O2 oxidation at the Pt ring electrode in O2-saturated 0.1 M
HClO4 solution. The Pt ring was potentiostated at 1.2 V. Potential scan
rate 10 mV s1. Rotation rate 800 rpm (note that the geometric surface
area of the disk electrodes is 0.28 cm2)
Also, SO2 can be chemically oxidized by the Pt oxide
formed (e.g., PtO) according to the following reaction [1, 19]:
PtO SO2 Pt SO3 5
It has been reported that the amount of the oxide, formed by
dipping the Pt electrode partially covered with adsorbed S in O2-
saturated solution at a disconnected circuit, is similar to that
formed in the case where a potential corresponding to the oxygen
evolution would be applied, i.e., at E>1.56 V (SHE) [47].
Recovery of the electrode using scenario IV results in an
almost complete recovery in the onset potential of the ORR as
well as both mass transfer- and kinetics-controlled currents,
because scanning the potential to 1.56 V in the range of the Pt
oxide formation leads to the oxidation of adsorbed S to soluble
sulfate (Eq. 1).
J Solid State Electrochem (2015) 19:13311340 1337

200
of 0.061.06 V. In this case, the onset potential of the ORR is
completely recovered and even a small positive shift in the
150 onset potential is noticed, being consistent with the recovery
analysis by CV (Fig. 5(B)).
b/ The easier recovery of the nano-Pt/GC electrode compared
iR / A

100 with the poly-Pt electrode (Fig. 6) could be attributed to the

relatively small ratio of the Pt(100) facet in the nano-Pt/GC
electrode, i.e., the enrichment of other two facets, i.e., Pt(111)
50
and Pt(110) as explained above (Fig. 2). This may be under-
c/
stood by the RRDE voltammogram in the potential range of
a/ d/ Hads (i.e., 0.060.26 V) at the nano-Pt/GC electrode, i.e., the
0
0.0 0.2 0.4 0.6 0.8 1.0 decrease in the disc current accompanied by the increase in the
ring current (Fig. 7(a, a)), indicating the formation of H2O2 in
0.0
this potential range, similarly to that reported at Pt(100) single
-0.2
crystalline electrode [48]. Thus, the observation of this unique
RRDE behavior regarding H2O2 regeneration at the nano-Pt
-2

electrode explains why the recovery of this electrode is easier

iD / mA cm

-0.4
than that of the poly-Pt electrode. Consequently, the difference
b in the recovery of the nano-Pt/GC and the poly-Pt electrodes
-0.6
c could be attributed to the difference in the crystallographic
a
-0.8
orientation of both electrodes, i.e., the relative ratio of the low-
d index facets. It is noteworthy to mention that the kinetic
-1.0
current at the partially recovered electrode (Fig. 7(c)) is pos-
0.0 0.2 0.4 0.6 0.8 1.0 itively shifted compared with that obtained at the fresh elec-
E / V vs. RHE trode (curve a), which is consistent with the obtained cyclic
Fig. 7 Steady-state voltammograms for the ORR at (a) fresh, (b) poi- voltammetric measurements shown above (Fig. 5(B)). How-
soned, and (c, d) recovered nano-Pt/GC electrodes in O2-saturated 0.1 M ever, the limiting current is a little smaller, as expected, com-
HClO4. Other experimental conditions and the notation are the same as
those in Fig. 6 pared with the one obtained at the fresh electrode (curve a).
The smaller limiting current at this partially recovered elec-
trode means that the two-electron ORR takes place not a little
Similar results were obtained at the nano-Pt/GC electrode as seen from the difference in the ring currents (a and d).
and are presented in Fig. 7. The main difference in the recov- Garsany et al. have reported that PtCo/VC electrode is recov-
ery behavior of the poisoned poly-Pt and nano-Pt/GC elec- ered more easily compared with Pt/VC even though the for-
trodes is a remarkably efficient recovery of the latter electrode mer has a larger susceptibility for poisoning [42]. They have
using scenario III, i.e., the recovery in a narrow potential range attributed the easier recovery of the former electrode for the
weaker adsorption strength of sulfur species on that electrode.
They reported that the oxygen reduction mechanism is

250

2 mA cm-2
200

b Peak III
idb1
Intensity (a.u.)

150
Peak IV
idb2
ifd Peak II 100
ifin
a
peak I
50

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

E / V vs. RHE
0
40 60 80 100
Fig. 8 CVs obtained at (a) poly-Pt and (b) nano-Pt/GC electrodes in N2-
saturated 0.1 M HClO4 containing 0.13 M formic acid. Potential scan rate 2 (degree)
10 mV s1 Fig. 9 XRD pattern of the nano-Pt/GC electrode
1338
changed from four-electron reduction to two-electron electron
reduction upon poisoning [42].
For further insight into the reason behind the easier recov-
ery of the nano-Pt/GC electrode as compared with the poly-Pt
electrode, the oxidation of formic acid (FA), well known as a
crystallographical facet-dependent electrochemical reaction
[49, 50], was examined at both electrodes and the results are
shown in Fig. 8. The voltammetric behavior at the poly-Pt
electrode is similar to the reported one [51, 52]: FA is oxidized
at poly-Pt electrodes via two pathways [49, 50], i.e., the direct
pathway (dehydrogenation pathway) assigned as peak II at ca.
0.93 V with peak current ifd, and the indirect one (dehydration
pathway) assigned as peak I at 0.63 V with peak current ifin.
The oxidation peaks at 0.73 V (peak III) and 0.44 V (peak IV),
with peak currents denoted as idb1 and idb2, respectively,
during the cathodic scan correspond to the oxidation of FA
after the oxidation of the poisonous intermediate species (CO)
adsorbed on the electrode surface. Generally, it has been
reported that formic acid is oxidized through the above-
mentioned two pathways via the formation of formate as an
intermediate which is further oxidized to either CO or CO2
[52]. The ratio ifd/ifin reflects the preferential oxidation path-
way, i.e., either dehydrogenation or dehydration. Also, it has
been reported that the direct oxidation (peak I) occurs on the
Pt(111) facet, while the indirect oxidation (peak II) occurs at
the Pt(110) and Pt(100) facets [52]. The oxidation peaks (peak
III and peak IV) after the complete removal of a poisonous CO
correspond to the oxidation of FA at the Pt(110) and Pt(100)
facets, respectively [5154]. This means that the dehydroge-
nation pathway prevails on the Pt(111) facet, while the dehy-
dration pathway prevails on the other two facets. At the nano-
Pt/GC electrode, the direct pathway (peak II) is enhanced,
while the oxidation at the Pt(100) facet (peak IV) during the
cathodic scan is completely suppressed, indicating that the
relative ratio of the Pt(100) facet is significantly decreased
compared with that of the poly-Pt electrode, consistently
with the above-mentioned voltammetric results. The heat
of adsorption of SO2 on the Pt(100) facet is larger than
that on the other two facets [55], which could explain the
easier recovery of the nano-Pt/GC electrode with a
relatively small ratio of Pt(100) facet compared with
the poly-Pt electrode.
For further confirmation of the relative small ratio of
Pt(100) facet, as a reason behind the enhancement recovery
of the poisoned nano-Pt/GC electrode, at nano-Pt/GC elec-
trode compared with poly-Pt electrode the XRD spectra of
nano-Pt/GC electrode was taken and shown in Fig. 9. Inter-
estingly, only one peak corresponding to Pt(111) facet is
obtained at 2 of 38.3 in addition to the peaks corresponding
to the underlying glassy carbon substrate at 2 values of ca.
45 and 80 which are attributed to the (011) and (110) planes,
respectively [56, 57]. Again, this confirms the enrichment of
nano-Pt/GC electrode in Pt(111) facet.
J Solid State Electrochem (2015) 19:13311340
From the aforementioned reasons, it becomes clear that
oxygen molecule plays a remarkable role in the recovery of
the poisoned poly-Pt and nano-Pt/GC electrodes and that the
recovery of the poisoned electrodes is critically dependent on
the relative ratio of the low-index facets.
Summary and conclusions
Recovery of the electrocatalytic activities of the poisoned
poly-Pt and nano-Pt/GC electrodes has been conducted in
0.1 M HClO4 using cyclic voltammetry in two potential
ranges, i.e., 0.061.06 V in the short-range recovery and
0.061.56 V in the long-range recovery. ORR has been used
as a probing reaction for the estimation of the extent of
recovery. It has been found that both electrodes are completely
recovered using the long-range recovery approach and that the
short range recovery is remedial only at the nano-Pt/GC
electrode. The enhanced recovery observed at the nano-Pt/
GC electrode has been attributed to a relatively small ratio of
the Pt(100) facet, which is characterized by a large heat of
adsorption of sulfur as compared with other low-index crys-
talline facets, based on the characteristic CV of the nano-Pt/
GC electrode in HClO4 solution and the voltammetric behav-
ior for the oxidation of FA in the same solution.
Acknowledgments This work was financially supported by the Grant-
in-Aid for Scientific Research (A) (no. 19206079) from the Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan and
the New Energy and Industrial Technology Development Organization
(NEDO), Japan.
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