An electrochemical and radiotracer investigation on lead dioxide: Influence of the deposition current and temperature

Article abstract of DOI:10.2298/JSC131022122A

The properties of electrodeposited PbO2 are sensibly influenced by the deposition current and temperature. In particular, tritium radiotracer measurements demonstrated that protons were incorporated into the bulk of an oxide film and on its surface. The d

Full text of DOI:10.2298/JSC131022122A

J. Serb. Chem. Soc. 78 (12) 2099–2114 (2013)
JSCS–4553
UDC 544.6.001.5:546.815–31:66.087+
546.11.027*3:544.032.4
Original scientific paper
An electrochemical and radiotracer investigation on lead
dioxide: influence of the deposition current and temperature
1
1
2
*
ROSSANO AMADELLI , LUCA SAMIOLO and ALEKSANDR B. VELICHENKO
1CNR-ISOF u.o.s. Ferrara c/o Dipartimento di Scienze Chimiche e Farmaceutiche, via
Fossato di Mortara, 17, 44121 Ferrara, Italy and 2Ukrainian State University of Chemical
Technology, Gagarin ave. 8, 49005 Dnipropetrovsk, Ukraine
(Received 22 October 2013)
Abstract: The properties of electrodeposited PbO2 are sensibly influenced by
the deposition current and temperature. In particular, tritium radiotracer mea-
surements demonstrated that protons were incorporated into the bulk of an
oxide film and on its surface. The degree of hydration increased with increas-
ing current and decreased with temperature, and was related to the morpho-
logical characteristics of the oxide, such as roughness measured by changes in
the double layer capacity. Conversely, the amount of hydrogen had negligible
effects on the number of free carriers as evaluated from Mott–Schottky plots.
The hydration degree of the surface seems to be an important factor influencing
electrocatalytic processes at high potentials, such as O2 evolution and O3 for-
mation. On less hydrated, more crystalline PbO2 surfaces, the first process was
inhibited and accordingly, the second was favored.
Keywords: lead dioxide, tritium, electrodeposition, electrocatalysis.
INTRODUCTION
Lead dioxide electrodes have been studied for several years and continue to
attract considerable interest from both practical and theoretical points of view. In
the field of battery applications, research in lead-acid batteries is still very
1
active, and in particular, recent developments of new soluble lead-acid flow
2
3
devices appear rather attractive. A recent review by Li et al. presents very
informative state of the art studies on PbO . Despite the enormous amount of
2
work, there is still a considerable debate on some issues, such as the stoichio-
metry of the oxide (sometimes described as PbO ) and its influence on electro-
x
chemical properties.
The reason of this non-stoichiometry has been attributed to oxygen vacan-
cies, interstitial protons or quasi-free electrons. In the model proposed by Rue-
*Corresponding author. E-mail: amr@unife.it
doi: 10.2298/JSC131022122A
2099
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2100
AMADELLI, SAMIOLO and VELICHENKO
4
tschi and Giovanoli, vacancies are arranged to form layers (named “internal
surfaces”) between crystallographically ordered areas, and the charge due to mis-
4+
–
2+
–
sing Pb would be compensated only by OH or by Pb and OH . Thus, the
formula proposed to describe better the composition of PbO is:
2
4
2
2

4+
Pb
Pb OH
OH
Pb
(1–x–y)
(4x2y)
y
(1xy)
(24x2y)
The model accounts for the fact that experimental studies report evidence for
the presence of Pb(II) and structural water in the PbO lattice. On the one hand,
2
earlier studies remained inconclusive in regards to whether it is fully
3–5
stoichiometric with respect to oxygen
or not; on the other hand, according to
6–8
recent studies based on theoretical calculation,
gen vacancies.
the conductivity is due to oxy-
Different studies agree that electrochemically prepared PbO contains struc-
2
4
tural water (hydrogen) and that there is a correlation between the hydrogen con-
tent and its electrochemical activity. The electrochemical behavior of electro-
9
deposited PbO is very sensitive to the preparation method, and the choice of the
2
electrodeposition parameters of play an important role in the control of the
10–15
morphological characteristics of PbO .
It seems, however, that there has
2
been insufficient systematic investigations on how the control of different para-
meters in the electrodeposition of PbO can affect the amount of structural water
2
in the resulting oxide.
In this work, the influence of parameters such as the deposition temperature
on the inclusion of tritium into electrodeposited PbO films I discussed. Gene-
2
rally, radiochemical studies can provide useful complementary information in the
16–20
study of electrochemical reactions.
In addition, the electrochemical beha-
viors of the obtained films are examined. The starting point was the question
21
raised by Hill several years ago on a possible connection between structural
hydrogen and electrochemical reactions at PbO .
2
EXPERIMENTAL
Chemicals
Ultrapure acids were obtained from Merck and all other chemicals from Sigma–Aldrich
Equipment
The electrochemical experiments were performed employing an EG&G model 273A
potentiostat–galvanostat using EG&G software. Additionally, for impedance measurements,
an EG&G model 5210 lock-in amplifier was used. Simulation calculations of the impedance
data were realized using the B. A. Boukamp Equivalent Circuit simulation program. Measure-
ments were performed in a conventional three-compartment cell. The counter electrode was a
large Pt flag, or a cylindrical Pt gauze surrounding the working electrode in the case of impe-
dance measurements. A saturated calomel electrode (SCE) was used as the reference. This
was in contact with the working electrode compartment through a Luggin tip. X-Ray diffrac-
tion experiments were performed with an Advance Bruker D8 diffractometer.
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ELECTROCHEMICAL AND RADIOTRACER INVESTIGATION ON LEAD DIOXIDE
2101
Methods
Cyclic voltammetry and impedance measurements were performed with PbO2 electro-
deposited on a Pt wire (geometrical area 0.18 cm2). For the radiochemical experiments, PbO2
was galvanostatically deposited onto platinized titanium (geometric area 2 cm2). The experi-
mental conditions were adjusted so that the weight of the deposit was constant, and thickness
was estimated using the reported density of PbO2.4 Both the activity due to tritium incurpo-
rated in the whole films (At) and that due to exchange of tritium at the surface (As) were
measured as described below.
i) For the measurement of At, PbO2 films of different thickness were prepared by electro-
deposition at a constant current from solutions of 1 M HNO3 + 1 M Pb(NO3)2. [3H]water
(tritium water) was added to the solution to give a radiochemical activity of 5×107 d.p.m.
(disintegrations per min). After preparation, the electrodes were washed with dry acetone,
dried in an argon flow, weighed and dissolved in H2O2/aqueous acetate buffer at pH 5.5. A
fixed amount of this solution was added to the scintillating liquid (Insta-gel, Packard), and the
radiochemical activity was counted.
ii) For the determination of As, the amount of tritium exchanged at the oxide surface, the
following procedure was adopted: lead dioxide films having a fixed thickness were prepared
in the absence of [3H]water. They were then immersed in solutions containing [3H]water
(5×107 d.p.m.) for 60 h; this conditioning time was chosen because separate experiments
showed that the uptake of tritium reached a maximum after this period. The samples were
thoroughly washed with dry acetone, dried in an argon flow and immersed in the scintillating
liquid. The release of tritium in the scintillating liquid was measured as a function of time
until the radiochemical activity reached a constant value.
Films of α-PbO2 were prepared from 2 M NaOH solutions saturated with lead acetate.
Ozone analysis was performed mostly by iodometric titration. In some cases, the so-obtained
results were checked by the spectrophotometric method measuring the absorption at 254 nm
and using an extinction coefficient of 3024 L cm-1 mol-1.
RESULTS AND DISCUSSION
X-Ray characterization
The effect of electrodeposition conditions on the XRD spectra of PbO is
2
shown in Fig. 1. At room temperature, an increase in the constant deposition cur-
rent does not result in significant changes in the reflection patterns, except for a
larger contribution of some higher index planes as the current increased (Fig. 1a).
SEM micrographs (Supplementary material) show that at the higher current den-
sities, the films feature crystals without clear crystal edges.
The obtained films consisted of mixture of α- and β-phase PbO , with the
2
14
calculated amount of the former remaining rather constant and less than 10 %
of the total PbO . The size of the crystallites, calculated from the Scherrer
2
Equation:
k
 cos
D 
(1)
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AMADELLI, SAMIOLO and VELICHENKO
14
was also relatively insensitive to current. Using the most intensive β (110)
peak, the calculations yielded particle dimensions of 27 and 30 nm for 5 and 20
–2
mA cm , respectively.
(a)
(b)
Fig. 1. a) Effect of the deposition current on the XRD pattern of PbO2. Peaks marked (*)
correspond to -PbO2 and those marked () to -PbO2. Temperature: 23 °C. b) Effect of the
deposition bath temperature on the XRD pattern of PbO2. Peaks marked with ()
correspond to -PbO2.
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ELECTROCHEMICAL AND RADIOTRACER INVESTIGATION ON LEAD DIOXIDE
2103
The choice of the deposition temperature had a comparatively more pro-
nounced influence. As shown in Fig. 1b, the contribution of the α-PbO poly-
2
morph gradually disappeared as the temperature was increased from 22 to 60 °C.
These results are in agreement with those reported by Sirés et al. for PbO
prepared from methanesulfonic acid.
2
22
Tritium exchange
In the study of electrodeposited PbO under different experimental condi-
2
tions, tritium radiotracer measurements can, in principle, provide a relatively
simple method to obtain information on hydrogen incorporation into the oxide
and at its surface. In fact, according to the disorder model of electrochemically
grown PbO , hydrogen ions on interstitial sites together with quasi-free electrons
2
23
are considered the dominating disorder centers.
The graph displayed in Fig. 2a shows that the total amount of tritium (A )
t
incorporated into the whole PbO film was a linear function of thickness. It also
2
showed that the amount of tritium in the more defective α-PbO film was much
2
larger than that observed with β-PbO for the same deposition current and tempe-
2
rature (cf. plots 1 and 2). The amount of tritium in the bulk decreased signifi-
cantly as the deposition temperature was increased to 60 °C, for the same cons-
tant current (cf. plots 2 and 3). The small amount of the α-polymorph present in
the films obtained at room temperature (vide supra) does not explain the large
decrease in the tritium inclusion brought about by temperature.
In an analogous experiment, the amount of tritium exchanged with the sur-
face (A ) was determined as described in the experimental section. The results
s
reported in Fig. 2b show the release of tritium as a function of time and tempe-
rature from films that had been previously equilibrated in tritiated water for 60 h.
It is possible to note that at there is a rapid initial exchange which may be refer-
red to as surface proton exchange, followed by a slower process, which is thought
17
to evidence the presence of less accessible protons.
The effects of the deposition current and temperature on the radiochemical
activity are summarized in Table I. In principle, a number of correlations are pos-
sible; for example, one may note that both A and A increase as the current
t
s
increased, and that the increase was very pronounced only for samples prepared
at room temperature.
Since it could reasonably be expected that A would depend on the effective
s
surface area, cyclic voltammetry experiments were performed at different scan
rates in the double layer region (1.35–1.45 V) and calculated the capacities as
24
reported in the literature. Then the effective areas were estimated by taking the
–2
25,26
double layer capacity of smooth electrodes (20 μF cm ) as a reference,
Examples are given in Table II. It was observed that there is a direct propor-
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AMADELLI, SAMIOLO and VELICHENKO
tionality between the surface radiochemical activity (A ) and the effective area:
s
both increased with deposition current and decreased with temperature.
(a)
(b)
Fig. 2. a) Overall amount of tritium incorporated into -PbO2, t = 23 °C (1), -PbO2,
t = 23°C (2), and -PbO2, t = 60°C (3), as a function of film thickness; b) amount of tritium
released by -PbO2 in contact with the scintillating medium after a 60-h contact with tritium
water. Samples prepared by electrodeposition at a constant current (10 mA cm-2) onto Pt/Ti
substrates. See experimental section for details.
It was generally observed that high currents favor the formation of PbO
2
films that are less stoichiometric. Additionally, under these conditions, oxygen
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ELECTROCHEMICAL AND RADIOTRACER INVESTIGATION ON LEAD DIOXIDE
2105
evolution could occur and lead to an increase in the microporosity of the coating,
and. as a consequence, the exchange of tritium between the films and the envi-
ronment occur more easily due to the large number of lattice defects and morpho-
17
logical disorder. Conversely, more compact, less defective surfaces are formed
22,27
at high temperature,
which explains why a smaller amount of hydroxyl spe-
cies was present in the surface region as well as across the film.
TABLE I. Amount of tritium incorporated into -PbO2 (t = 23 °C) and -PbO2 (t = 23 and 60
°C) electrochemically grown onto platinized Ti substrates (2 cm2) at a constant current (10
mA cm-2)
t / °C
Deposition current, mA cm-2
23
60
Surface activity (As/100), d.p.m.
5
11.04
18.8
30
35.4
3.82
5.89
7.3
8.2
9.32
10
20
30
40
38
Total activity (At/100), d.p.m.
5
17.8
31.2
47
62
74.2
16.45
30.3
33.3
35
10
20
30
40
33.25
TABLE II. Double layer capacities and roughness factors as a function of PbO2 deposition
current and temperature
Deposition current, mA cm-2
(temperature, °C)
Capacity, mF
Roughness factor Effective area, cm2
5 (23)
5 (60)
20 (23)
5 (23), -PbO2
1.75
0.685
4.6
87.5
34.2
230
15.8
6.15
41.4
270
30
1500
Electrochemical characterization
Electrodeposited PbO is reported to be a narrow band gap semiconductor
2
with high electron conductivity due to non-stoichiometry, which varies with pre-
7,28
parative conditions.
Often the Hall effect is used to determine the number of
free charges. However, reasoning that useful information was obtained from
29
Mott–Schottky analysis for conductive materials, such as Sb–SnO
and boron-
2
30
doped diamond, the capacities of the prepared PbO films were calculate from
2
their impedance and the data was plotted according to:
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AMADELLI, SAMIOLO and VELICHENKO
2






A
C
2
kT
q

E  E 
(2)
fb
2
q N
0
where q is the electron charge, A is the area,  is the vacuum permittivity,  is
0
7
the dielectric constant of PbO , taken as 3.91, and E and E are the applied and
2
fb
2
2
flat-band potentials, respectively. A plot of A /C vs. E should give a straight
line, the slope of which is inversely proportional to the number of carriers N.
Straight lines were indeed observed with a positive slope (n-type conductivity)
for PbO (5 mA, 23 °C) and PbO (5 mA, 60 °C) from which the calculated
2
2
21
21
–3
values of N were 6×10 and 8×10 cm , respectively. The data are the same
within experimental error and so there is no apparent correlation with tritium/
/proton incorporation as a function of temperature. The results are not completely
unexpected, and in fact, Ruetschi and Giovanoli drew attention to this type of
4
experimental findings several years ago. On the other hand, the effect of current
density is more conspicuous as seen in the example of experimental plots of Fig.
3. In the case of PbO (20 mA, 23 °C), The Mott–Schottky plots are non-linear,
2
31
which could be due, for example, to a high number of defects and/or poro-
32
sity. It is noteworthy that hydration was also observed to cause non-linearity in
33
Mott–Schottky plots.
Fig. 3. Mott–Schottky plots for PbO2 electrodeposited at 5 and 20 mA cm-2
at a temperature of 23 °C.
In the literature, reduction of PbO electrodeposited under different condi-
2
tions has been investigated frequently in order to gain insight into activity related
to film morphology. Thus, for example, films with structural characteristics such
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ELECTROCHEMICAL AND RADIOTRACER INVESTIGATION ON LEAD DIOXIDE
2107
as accessibility to species in the electrolyte and fast surface and subsurface
12
exchange of protons are expected to be more easily reduced.
The results reported in Fig. 4a are first scan linear sweep voltammetry curves
for the reduction of different PbO samples in HClO . The scan was started at 1.5
2
4
V, where no faradaic process occurs, and HClO were chosen in order to avoid
4
effects of strong adsorption of the anions. It appears that reduction occurred at
more positive potentials when the films were obtained at relatively high currents;
(a)
Fig. 4. Linear sweep voltammetry
curves for the reduction of PbO2 pre-
pared under different experimental con-
ditions: 1) 5 mA cm-2, 23 °C; 2) 5 mA
cm-2, 60 °C; 3) 20 mA cm-2, 23 °C; a)
first scan experiments after preparation
and b) after polarization of the elec-
trodes at 1.95 V for 1200 s. Scan rate: 5
(b)
mV s-1. Electrolyte: 1 M HClO4.
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AMADELLI, SAMIOLO and VELICHENKO
conversely, an increase in the deposition temperature shifted the reduction pro-
cess to more negative potentials. Films of pure α-PbO were more readily reduced,
2
typically at ≈0.95 V. The lower reduction charge q (Fig. 4a) is likely due to a
3
lower electrodeposition efficiency at high currents, because of the occurrence of
10
O evolution. Qualitatively, the described behavior seemingly parallels the
2
defective structure of films, as also shown by the tritium uptake experiments.
Experiments with films that had previously been used as electrodes for O
2
evolution in HClO at high potentials showed that the only detectable effect was
4
that of temperature (Fig. 4b). A possible explanation is that a gel layer is rapidly
1
formed on PbO in contact with water, which is involved in the reduction pro-
cess:
2
34
PbO + H O  PbO(OH)
2
(3)
2
2
(crystal zone) (gel zone)
+
–
PbO(OH) + 2 H + 2e

Pb(OH) + H O
2+
(4)
(5)
2
2
2
+
Pb(OH) + 2 H
 Pb + 2H O
2
2
The influence of gel formation and its involvement in the cyclic voltammetry
behavior of PbO electrodes in H SO solutions was discussed in a recent EQCM
2
2
4
35
investigation by Pech et al.
One may speculate that the contribution of the crystal zones remains more
pronounced even after polarization at high positive potentials. According to Pav-
36
lov, however, equilibrium (3) is reversible and washing the electrode restores
the crystalline zones
[PbO(OH) ]

nPbO + nH O
(6)
2 n
2
2
and since the present experiment was ex situ, it does not appear likely that gel
formation could explain the observed behavior. Alternatively, following electro-
lysis at high current densities, re-deposition of PbO occurred with the formation
2
37
of small crystallites on the surface, as proposed by Thanos and Wabner.
Thus, experiments were performed in dilute H SO , analogous to those des-
2
4
cribed in Fig. 4 (Supplementary material). The obtained results agreed with those
38
reported earlier in this paper and with the conclusion of Devilliers et al. that
reduction of PbO constituted of larger, more regular crystallites is more difficult.
2
Electrocatalytic behavior
The results presented so far demonstrated that the preparation method deter-
mines the amount of hydrogen incorporated within PbO films and influences the
2
electrochemical behavior. The connection between these experimental aspects is
39
probably the non-stoichiometry of the films.
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Continuing with the characterization, again three types of PbO electrodes,
2
prepared at different temperature and constant current, were examined in order to
assess the effects of these parameters on the O evolution process.
2
Oxygen evolution proceeds in the gel-layer (vide supra) through the follow-
ing elementary steps:
*
…
2
+
–
–
PbO (OH) + H O

PbO (OH) (OH°) + H + e
(7)
2
2
2
*
…
*
+
PbO (OH) (OH°)

2O
PbO (OH) + O + H + e
(8)
(9)
2
2
ads
 O
2
ads

*
where PbO (OH) is an active center located in the hydrous layer and OH is a
2
hydroxyl radical bound to an active center. Thus, it is to be expected that the
thickness of this layer would exert an important influence on this electrochemical
40
process and indeed, it was reported that it lowers the potential of O evolution.
2
Unfortunately, there is presently no convincing evidence of an influence of the
preparation method on the degree of gel-layer formation; the interesting EQCM
35
study by Pech et al. did not explore the effects of varying the electrodeposition
conditions of PbO .
2
In the present study, the O evolution was mainly investigated by impedance
2
spectroscopy, and the results obtained by fitting the data according to the equi-
valent circuit displayed in Fig. 5 are reported in Table III. In this circuit, R is the
ct
electron transfer faradaic resistance; R is the resistance associated to desorption
p
of oxygen radical intermediates; C is the known double layer capacity; C is
dl
p
related to the pseudo-capacitance, i.e., to the potential dependence of the steady
state coverage by reaction intermediates and is hence related in an important way
to electrocatalysis. The number “n” appearing in the tables refers to the behavior
18
of the constant phase element and has a value of 1 for a pure capacity.
A comparison of the data at a fixed potential shows that electrodeposition at
high current or temperature causes a decrease and an increase, respectively, of
both R and R . In all cases R > R , which seemingly indicates to a mechanism
ct
p
p
ct
18
in which desorption of intermediates (reaction (8)) is slow. As reported before:
–1
log (R ) = log (bi°) + bE
(10)
Fig. 5. Scheme of the equivalent cir-
uit used for fitting the impedance
data.
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2110
AMADELLI, SAMIOLO and VELICHENKO
–1
and the Tafel slope b can be obtained from plots of log (R ) vs. potential. In
effect, Fig. 6 shows that there is quite good agreement between the steady-state
–1
polarization plots of E vs. log I (Fig. 6a) and log (R ) plots (Fig. 6b), at least at
p
potentials below 1.9 V. At more positive potentials, R decreases rapidly and
p
41
reaction (8) becomes faster. Indeed, according to MNDO calculations based on
the hydroxylate cluster model Pb (OH) (H O), electron transfer producing OH
3
12
2
radicals and their removal from the surface to give (O) species requires almost
–1
the same energy: 685.3 and 712.5 kJ mol , respectively.
TABLE III. Impedance spectroscopy data for PbO2 prepared under different experimental
conditions. Electrolyte: 1 M HClO4
E / V
Rs / 
Rct / 
Rp / 
Cdl / 10-3 F (n) Cp / 10-3 F (n)
5 mA cm-2, 23 °C
1.65
1.70
1.75
1.80
1.85
1.90
1.95
2.00
2.05
1.12
1.96
1.45
1.13
1.13
1.15
1.12
1.10
1.10
11.25
932.8
443.7
150.2
41.3
18.4
11.4
8.0
1.72 (0.92)
1.92 (0.96)
1.88 (0.94)
1.84 (0.93)
1.62 (0.94)
1.30 (0.96)
0.88 (1.0)
0.83 (1.0)
0.58 (1.0)
1.20 (1.0)
1.17 (1.0)
1.13 (1.0)
1.05 (1.0)
1.10 (1.0)
1.25 (1.0)
1.05 (1.0)
1.69 (0.90)
1.27 (0.90)
10.53
8.90
8.57
6.25
3.80
2.17
1.78
1.68
4.31
2.24
5 mA cm-2, 60 °C
1.75
1.80
1.85
1.90
1.95
2.00
2.05
1.07
1.20
1.18
1.14
1.00
1.00
1.18
17.65
206.4
91.15
47.20
33.15
15.07
4.95
1.45 (0.98)
1.38 (0.96)
1.24 (0.95)
1.03 (0.98)
1.36 (0.98)
1.10 (1.00)
0.77 (1.00)
0.55 (1.00)
0.42 (1.00)
0.50 (0.92)
0.72 (0.85)
0.97 (0.85)
1.41 (0.84)
1.91 (0.84)
15.20
10.17
3.78
1.16
1.06
1.40
2.55
20 mA cm-2, 23 °C
1.70
1.75
1.80
1.85
1.90
1.95
2.00
2.05
0.86
0.86
0.88
0.88
0.87
0.87
0.88
0.90
6.05
111.6
47.15
15.25
8.92
6.10
2.89
3.60 (0.92)
3.50 (0.91)
3.00 (0.92)
1.70 (0.98)
1.42 (1.00)
1.36 (0.97)
1.36 (1.00)
1.30 (1.00)
2.02 (0.98)
2.00(1.00)
2.30 (0.95)
2.92 (0.92)
2.42 (0.93)
3.35 (1.00)
6.40 (0.85)
9.3 (0.83)
5.6
4.15
2.3
1.46
2.29
1.42
1.07
1.36
0.85
Ozone formation is an important reaction occurring on PbO at relatively
2
42
high potentials, in parallel with O evolution (reaction (9)):
2
O + O

O
3
(11)
2
ads
and the efficiency of O generation evidently depends on the coverage and sta-
3
bility of O ; the recombination process (reaction (9)) that forms an oxygen
ads
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ELECTROCHEMICAL AND RADIOTRACER INVESTIGATION ON LEAD DIOXIDE
2111
–1 41
molecule ensures a gain in energy of 891.2 kJ mol . In this context, it is note-
worthy that the stability of O is reported to be higher on less defective oxide sur-
18
faces, which would correspond to the less hydrated PbO (5 mA, 60 °C)
2
samples prepared in the present work.
(a)
(b)
Fig. 6. Effects of PbO2 preparation parameters on: a) E vs. log I from quasi steady-state data;
b) E vs. log(1/Rp) from impedance data. Electrolyte: 1 M HClO4.
The data on the effect of temperature on O formation shown in Fig. 7 con-
3
18
firmed the above reasoning. In addition, it was shown previously that for
E > 1.95 V, the current–potential curves reached a stable profile after relatively
long polarization times. These results were confirmed in the present work for
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2112
AMADELLI, SAMIOLO and VELICHENKO
samples prepared at room temperature, while those deposited at 60 °C did not
exhibit such a time dependence. A tentative explanation might be that in the latter
case, corrosion is less pronounced and the equilibrium in reaction (3) is shifted to
the left; this conclusion would agree with the results of Fig. 4.
Fig. 7. The effect of the PbO2 electrodeposition temperature on the current efficiency of ozone
electrogeneration in 0.5 M H2SO4 as a function of time of operation at 0.5 A cm-2.
CONCLUSIONS
Herein, an investigation into some aspects of the influence of current and
temperature on electrodeposited PbO has been presented. In particular, tritium
2
radiochemical studies provide unequivocal evidence for the presence of structural
water in the bulk of the oxide film and not only on its surface. In battery studies,
the role of the hydrogen content in the PbO lattice has been an issue for years
2
and is still in focus these days.
21
We find, In accordance with the conclusions of Hill, it was found that the
amount of hydrogen in PbO has no direct influence on the electrochemical and
2
electrocatalytic behavior. However, the degree of hydrogen/tritium incorporation
provides information on changes in the chemico-physical characteristics. In parti-
cular, it is related to PbO morphological defects, which in turn influence electro-
2
catalytic processes, such as O and O generation. In this regard, the hydration
2
3
degree of the surface seems to be an important parameter, the control of which
could affect the efficiency of electrocatalytic oxidation processes. Probably, the
question that requires further investigation is a more quantitative analysis of the
relationship between degree of bulk hydration and that of the surface.
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ELECTROCHEMICAL AND RADIOTRACER INVESTIGATION ON LEAD DIOXIDE
2113
SUPPLEMENTARY MATERIAL
Figures S1–S3 are available electronically at http://www.shd.org.rs/JSCS/, or from the
corresponding author on request.
И З В О Д
ИСПИТИВАЊЕ ОЛОВО(IV)-ОКСИДА ЕЛЕКТРОХЕМИЈСКИМ МЕТОДАМА И
МЕТОДОМ ИЗОТОПСКИХ ОБЕЛЕЖИВАЧА: УТИЦАЈ СТРУЈЕ ТАЛОЖЕЊА И
ТЕМПЕРАТУРЕ
1
1
2
ROSSANO AMADELLI , LUCA SAMIOLO и ALEKSANDR B. VELICHENKO
1CNR-ISOF u.o.s. Ferrara c/o Dipartimento di Scienze Chimiche e Farmaceutiche, via Fossato di Mortara,
17, 44121 Ferrara, Italy и 2Ukrainian State University of Chemical Technology, Gagarin ave. 8, 49005
Dnipropetrovsk,Ukraine
На својства електродепонованог PbO2 значајно утичу струја таложења и темпера-
тура. Мерења са трицијумом као изотопским обележивачем показују да су протони
инкорпорирани и у маси оксидног филма и да се налазе на његовој површини. Степен
хидратације се повећава са повећањем струје, а опада са температуром, што је повезано
са морфолошким карактеристикама оксида као што је храпавост која је одређена преко
капацитивности двојног слоја. Супротно, количина водоника занемарљиво утиче на број
слободних преносилаца наелектрисања израчунат из Mott–Schottky дијаграма. Изгледа
да је степен хидрататације површине важан фактор за електрокаталитичке процесе на
високим потенцијалима као што су издвајање О2 и стварање О3. На мање хидратисаним,
више кристалиничним PbO2 површинама први процес је инхибиран, а у складу са тиме,
други фаворизован.
(Примљено 22. октобра 2013)
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