ISSN 1061-9348, Journal of Analytical Chemistry, 2009, Vol. 64, No. 11, pp. 1148–1157. © Pleiades Publishing, Ltd.

, 2009.
Original Russian Text © N.Yu. Stozhko, N.A. Malakhova, I.V. Byzov, Kh.Z. Brainina, 2009, published in Zhurnal Analiticheskoi Khimii, 2009, Vol. 64, No. 11, pp. 1176–1185.

ARTICLES

Electrodes in Stripping Voltammetry:

from a Macro- to a Micro- and Nano-Structured Surface
N. Yu. Stozhko, N. A. Malakhova, I. V. Byzov, and Kh. Z. Brainina
Ural State Economic University, ul. 8 Marta 62, Yekaterinburg, 620219 Russia
Received July 7, 2008; in final form, January 28, 2009

Abstract—A correlation between the morphology of the solid surface and electrochemical response was found
in microscopic and electrochemical investigations. A shift of the oxidation potentials of metals to more negative
values was observed on electrodes with microstructured surface with respect to similar processes on macro-
structured electrodes. The formation of passivating films, causing reverse current and deteriorating the analyt-
ical signal, was not observed, and the performance characteristics of voltammetric procedures were improved.
The experimental data indicated the increased electrochemical activity of modifying metal particles with a
decrease in the particle size. As a result of the deliberate change of the surface composition and the formation
of a micro- and nano-structured surface, a new generation of electrodes was developed with excellent electroan-
alytical characteristics.
DOI: 10.1134/S1061934809110100

The signal in an indicator electrochemical system
forms at the electrode–solution interface and depends
on the state of the electrode surface, which is deter-
mined by the nature, defectiveness, and mechanical
nonuniformity of the material. Using the principles of
surface modification, the material and structure of the
electrodes can be changed in order to obtain a selective
electrochemical response to the change in the analyte
concentration. Over the last decade, extensive experi-
ence has been gained in the design of modified elec-
trodes, the features of immobilizing modifiers on vari-
ous matrices have been studied, and the conditions for
the voltammetric determination of a number of sub-
stances on modified electrodes have been selected
[1−15].
Carbon materials having a broad range of electrical
conductivity and high surface energy and adsorption
and complexing ability are actively used as matrices for
modification [16, 17]. The microgeometry of the car-
bon-containing surface greatly contributes to the total
energy of an electrochemical system and affects the
analytical signal. For example, Compton compared
electrodes with different surface microstructures and
showed that electrodes from edged pyrolytic graphite
with highly nonuniform surface had a wider working
potential range and ensured lower detection limits than
glassy carbon electrodes or electrodes from basal pyro-
lytic graphite with a smooth surface [18, 19]. There are
no clear concepts for the effect of the morphology of a
solid surface on the electrochemical activity of a modi-
fying layer, the character of the electrode processes,
and the analytical signal. Therefore, the next step in the
sophistication of solid-phase electrodes should be a
comprehensive study of the electrode surface, the
development of theoretical concepts predicting the
properties and characteristics of modified electrodes,
and the transition from macro- to micro- and nano-
structures on the electrode surface, drastically changing
electrode properties.
The goal of this work was to study the effect of sur-
face microrelief on the structural organization of the
modifying metal and its electrochemical activity and to
find the peculiarities of electrode processes involving
micro- and nano-size particles (drops) of metals (mer-
cury, gold, and bismuth). To generalize and interpret
the results, we used previously published data [20–27].
EXPERIMENTAL
Reagents and samples. We used ammonium pyrro-
lidine dithiocarbamate (PDTC), sodium acetate
(NaAc), sodium borane, sodium citrate (NaCit), silver
nitrate, chloroauric acid, bismuth(III) nitrate, mer-
cury(II) nitrate, other acids, and Nafion; all reagents
were of high purity or cp grade. All solutions were pre-
pared using triply distilled water. We used Certified
Reference Materials (GSO) of different metal ions in
concentrations of 0.1–10 g/L. Stock solutions with the
concentration 10 mg/L and lower were prepared by
diluting Certified Reference Materials with distilled
water and a supporting electrolyte solution. Stock solu-
tions with the concentration 10 mg/L were prepared
once a month; 1 mg/L, once a week; and 0.1 mg/L and
lower, daily. Colloid silver was synthesized using 1 ×
10–4–1 × 10–3 M solutions of AgNO3 and 3 × 10–4–3 ×
10–3 M solutions of NaCit and NaBH4.
Apparatus and measurement devices. An IVA-5
semiautomatic computerized analyzer for stripping
voltammetry (IVA, Russia) was equipped with a three-

1148
 ELECTRODES IN STRIPPING VOLTAMMETRY
electrode electrochemical cell. A glassy-carbon rod
was an auxiliary electrode, an EVL-1M silver–silver
chloride electrode (Belarus) was a reference electrode,
and modified and nonmodified electrodes made of car-
bon- or gold-containing materials were used as work-
ing electrodes.
Microscopic studies were conducted using optical
microscopes Image-Pro Plus WILD, Nikon LAB-phot-2,
and NU-2 (Karl Zeiss, Germany) and MBS-2 (Russia)
and electron scanning microscopes TESLA BS 300
(Czech Republic) and Philips XL-30 (the United
States).1 X-Ray spectral analysis of the surface of mod-
ified electrodes was performed using an EDAX energy
dispersive analyzer of a Philips XL-30 electron scan-
ning microscope.
The average size of colloid silver particles was eval-
uated by optical spectrophotometry using a KFK-3
spectrophotometer.
Nonmodified working electrodes. We used a
glassy-carbon electrode (GCE), an impregnated graph-
ite electrode (IGE), thick-film electrodes of a graphite-
epoxy paste (TGEs) and carbon-containing inks
(TCEs), and a bulky gold disk electrode (Metrohm,
Switzerland). The electrode named foil electrode was
created by attaching Zl 9999 gold foil 15–20 µm in
thickness to a STEF-0.5 fiberglass material by special
Cementit 3172 glue. The so-called deposited electrode
was prepared by evaporating gold under vacuum onto a
solid support using a VUP-4 facility. For this proce-
dure, a Zl 9999 gold wire (d = 0.2 mm) and polyethyl-
ene terephthalate 0.25 mm in thickness were used. The
thickness of the deposited gold layer was 0.5–1.0 µm.
The electrode named the gold film electrode was
obtained by the electrochemical deposition of a gold
film from a 0.1 g/L solution of Au(III) on an IGE at
−0.2 V for 3 min. The electrode called the compact-
disk electrode was prepared from a compact disk with
a gold coating ~0.1 µm in thickness (CD-R Gold
Ultima, Ireland). The polymer coating applied onto the
gold layer was etched away from the compact disc sur-
face using 0.5 M HNO3. The compact disk was guillo-
tined into strips of certain size (4 × 40 mm). The work-
ing surface of the same area (0.06 cm2) was formed on
all the electrodes using Cementit 3172 glue.
Modified working electrodes. The electrodes were
modified before (ex situ) and in the course of (in situ)
the electrochemical accumulation of the analyte. Ex
situ modification was performed by chemical or elec-
trochemical methods. In the former case, a solution of
a modifier was placed on the working surface of the
electrode. In the latter case, metal films were electrolyt-
ically deposited from salt solutions on the working sur-
face.
1 Microscopic
experiments were conducted in the Institute of Inor-
ganic Chemistry, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, and Yekaterinburg Plant for Processing Nonferrous
Metals.
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 64
1149
As modifiers, we used soluble (HAuCl4) and low-
soluble (Hg2Cl2, Hg(PDTC)Ac, BiPO4, and
Au(PDTC)2Cl) compounds, which were synthesized
just on the electrode surface, and solutions of colloid
silver. To enhance the adhesion and mechanical stabil-
ity of low-soluble modifiers, we added Nafion (cation-
exchange fluor-containing sulfonated polymer) into the
solutions of the modifiers. In the presence of Nafion,
the physical and mechanical properties of the deposit
are improved, because the crystals of low-soluble sub-
stances are intruded into a cross-linked structure of the
polymer regulating the formation and growth of the
deposit crystals. The procedure for preparing and mod-
ifying GCE/Hg and TGE/Hg (in situ) and
TGE/Hg(PDTC)Ac and TGE/Hg2Cl2 (ex situ) was
described in [21–24]; TGE/HAuCl4 in [25, 26]; and
GCE/Bi, TCE/Bi, and TCE/BiPO4 in [27]. The modi-
fied electrodes were regenerated using potential
sweeps; they were used for 5–7 measurements.
Measurements and calculations. To gain the data,
we recorded direct-current and differential-pulse volta-
mmograms. The analytical signals were the maximum
current (I) or the quantity of electricity (Q) correspond-
ing to the amount of substance participating in the elec-
trode process in the integral voltammogram I = f(E) and
the amplitude of the voltammogram derivative di/dE =
f(E) in the potential range of analyte oxidation or reduc-
tion. Additionally, the characteristics of the processes
of metal discharge–ionization were potentials (Ep),
half-width of maximum currents (Ö1/2width), and the
parameter I/Q characterizing the energetic state and
electrochemical activity of a metal on the electrode sur-
face, according to the theory of different energetic
states of a metal on an indifferent electrode proposed by
Kh.Z. Brainina [20].
RESULTS AND DISCUSSION
To estimate the effect of surface microrelief on the
electrochemical characteristics of electrodes, we stud-
ied the processes of metal (mercury, gold, and bismuth)
discharge–ionization on the TGEs with various
microreliefs created using graphite powders differing in
particle shape and dispersity, the composition of graph-
ite-containing pastes, and the methods of surface treat-
ment. Other carbon-containing and metal electrodes
were used for comparison. The energy of the interac-
tion of a deposited metal with the electrode surface can
be characterized by ∆GÓ, that is, the Gibbs free energy.
According to the theory of three energetic states of
a metal deposited on solid electrodes [20], when the
condition ∆GÓ > 0 is obeyed, small nonequilibrum and
energetically active nucleation centers or clusters form
small isles on the surface of indifferent electrodes. The
microgeometry of the electrode surface will affect the
energetic state of the metal; a relief and rough surface
will contribute more to the total energy of the studied
system than a smooth and uniform surface. Based on
this, one can a priori predict that metal will be deposited
No. 11 2009
1150 STOZHKO et al.

Table 1. Electrochemical characteristics of the ionization of mercury reduced from 0.5 M HCl + 0.02 g/L Hg(II) on TGE at –1.1 V
for 180 s, depending on the method of treating the electrode surface, size of graphite particles in the graphite-containing paste, and the
composition of the paste
Treatment Graphite particle Graphite : binder, Reverse
Ep(Hg), V Q(Hg) 10–2, µC I/Q(Hg), s–1
of the TGE surface* size, µm wt % cathodic current
1 80 64 : 36 0.05 0.14 1.40 Not observed
2 80 64 : 36 0.20 1.11 0.75 Not observed
3 80 64 : 36 0.28 2.53 0.30 Observed
1 80 56 : 44 0.06 0.23 1.25 Not observed
1 60 70 : 30 0.05 0.46 1.30 Not observed
1 <50 56 : 44 0.05 0.44 1.20 Not observed
1 <10 50 : 50 0.07 0.86 1.10 Not observed
2 <10 53 : 47 0.19 1.25 0.70 Observed
2 <10 50 : 50 0.22 1.58 0.60 Observed
3 <10 45 : 55 0.30 1.92 0.35 Observed
1 1–2 50 : 50 0.36 2.64 0.30 Observed
* 1, Without treatment; 2, mechanical buffing; and 3, mechanical buffing and polishing.

as a discrete species on a nonuniform nonregular sup-
port.
TGE in situ modified with mercury. The results of
studying the discharge–ionization process of mercury
from the solution containing 0.5 M HCl + 0.02 g/L of
Hg(II) on the TGEs using different methods of surface
treatment, sizes of graphite particles in the graphite–
epoxy paste, and paste composition are presented in
Table 1.
The method of treating the TGE surface greatly
affects the parameter I/Q(Hg). The lowest values of this
parameter were obtained on electrodes with smothered
surfaces, while the highest, on electrodes with a native
untreated surface. The dispersity of the graphite parti-
cles and the concentration of graphite in the graphite-
containing paste affect the value of the parameter
I/Q(Hg). This parameter tends to increase with the
increase in the size of graphite particles and in the con-
centration of graphite in the paste for electrodes with
the native surface. The increase in the size of graphite
particles from 1 to 80 µm leads to the change of I/Q(Hg)
from 0.3 to 1.4. The parameter I/Q(Hg) reached the
highest value at the graphite concentration in the graph-
ite-epoxy paste equal to 64 wt %. When graphite parti-
cles of a large size were present, more relief surface
formed with many apexes of graphite particles. The
structure of this electrode can be considered, to some
approximation, as an ensemble of ultramicroelectrodes
providing the quazispherical diffusion of the iono-
phore. This assumption is confirmed by the fact that the
analytical signal of cadmium can be obtained on the
electrode with a native surface in a nonstirred solution
of a diluted electrolyte, while it is impossible on the
electrode with a buffed surface.
As can be seen in Table 1, the parameter I/Q(Hg)
decreases with an increase in the amount of mercury on
the electrode surface. The metal ionization potential is
shifted to the region of more positive values. The
decrease in the parameter I/Q(Hg) is accompanied by
the abnormal anodic current arising in the anodic volta-
mmograms of mercury, so-called reverse cathodic cur-
rent [28–32]. The reverse current deteriorates the ana-
lytical signals of elements, reduces the sensitivity of the
electrode, and worsens the performance characteristics
of the procedure. It was found by microscopic studies
that reverse current was caused by the formation of a
passivating layer on the electrode surface. To eliminate
the reverse current effect, we ex situ modified the TGE
with low-soluble mercury compounds.
TGE ex situ modified with low-soluble mer-
cury(I) compounds. Electrodes modified with low-
soluble mercury(I) compounds have several consider-
able differences from electrodes modified in situ. First,
the reduction of mercury(I) from a low-soluble com-
pound immobilized on the electrode surface occurs at
potentials 0.3–0.5 V more positive than the reduction of
mercury(I) from the solution to the surface of an
unmodified electrode. Second, smaller and noncoalesc-
ing microdrops of mercury formed in the electrolysis;
these are uniformly arranged on the surface. The third
difference is that there is no reverse cathodic current in
the anodic voltammogram, even after the electrochem-
ical dissolution of mercury from the electrode surface.
The results of the comparison of electrodes modified
with mercury and its compounds applied by different
methods are presented in Table 2. The parameter I/Q(Hg)
increases, the peak of mercury oxidation becomes nar-
rower, and its potential is shifted to more negative poten-
tials in the following order: GCE/Hgin situ–TGE/Hgin situ–
TGE/Hg(PDTC)Acex situ–TGE/Hg2Cl2 + Nafionex situ.

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 ELECTRODES IN STRIPPING VOLTAMMETRY 1151

Table 2. Characteristics of the oxidation peaks of elements recorded in 0.5 M HCl + 10 µg/L of Cu(II), Pb(II), and Cd(II) on
different modified electrodes (for in situ modified electrodes, + 1 × 10–4 M Hg(II)). Eaccum = –0.8 V (Cu) and –1.2 V (Cd and
Pb); τaccum = 120 s; n = 5
Hg Cd Pb Cu
Electrode/modifier,
method of modification I/Q, E , I/Q, E , I/Q, E1/2width, I/Q, E1/2width,
Ep, V 1/2width Ep, V 1/2width Ep, V Ep, V
s–1 mV s–1 mV s–1 mV s–1 mV
GCE/Hg, in situ 1.03 0.24 92 1.79 0.63 63 1.57 0.44 70 0.65 0.18 110
TGE/Hg, in situ 1.15 0.18 88 1.78 0.65 60 1.91 0.46 65 0.77 0.22 100
TGE/Hg(PDTC)Ac, ex situ 1.27 0.12 78 1.85 0.67 57 2.05 0.48 57 0.79 0.20 105
TGE/Hg2Cl2+Nafion, ex situ 1.32 0.12 75 1.87 0.67 55 2.05 0.50 51 0.87 0.26 100

Similar dependences were observed for the analyti-
cal signals of copper, lead, and cadmium. The change
of electrochemical parameters in this order was accom-
panied by the improvement of the resolution ability,
repeatability, and sensitivity of the determination. For
example, the slope of calibration curves for copper,
lead, and cadmium was 0.91, 2.16, and 1.40 using
TGE/Hg(PDTC)Ac and 0.70, 1.0, and 0.67, respec-
tively, with TGE/Hg.
TGE ex situ modified with gold(III) compounds.
Two groups of gold-containing electrodes were com-
pared to determine the effect of surface microrelief on
the electrochemical characteristics [26]. The first group
included bulk or film gold electrodes (disk, film,
annealed, deposited, and compact-disk), while the sec-
ond consisted of electrodes without a visual gold film or
particles on the surface (TGE/HAuCl4 and
TCE/HAuCl4). To prevent the soluble modifier from
washing out from the surface of electrodes of the sec-
ond group, a potential of –1.0 V was applied to the elec-
trodes immediately after their immersion to reduce
HAuCl4 to Au0.
The study of the surface morphology showed that
the microrelief of electrodes of the second group was
considerably less smooth than that of electrodes of the
first group. On such a surface, gold is present as very
small invisible particles. Using energy-dispersive anal-
ysis, we found that gold particles were mainly situated
on the elevated areas of the graphite-containing surface.
Their size varied between 0.05 and 2.00 µm with a pre-
vailing value of 0.15 µm. The distance between the par-
ticles exceeded their sizes by 3–10 times. The differ-
ences in the surface microstructure of electrodes of the
two groups affect their properties. The corresponding
characteristics are presented in Table 3.
In the oxidation of gold from the surface, one peak
was observed; its height and potential differed for dif-
ferent gold and gold-containing electrodes. As can be
seen in Fig. 1a, the lesser the amount of gold on the
electrode surface, the higher the parameter I/Q(Au) and
the activity of gold. The activity of gold manifested
itself as the shift of the potential of the maximum cur-
rent of gold oxidation. The smaller the parameter
I/Q(Au), the more difficult the process of gold electro-
dissolution; the oxidation peak is shifted to more posi-
tive potentials (Fig. 1b). It can be seen in Table 3 that
the oxidation of gold begins earliest on the
TGE/HAuCl4 electrode and latest on the annealed elec-
trode with the lowest parameter I/Q (Au).

2.0 (‡) (b)

1.8

1.6
1.6
I/Q (Au), s–1

1.2
Ö, V

1.4
0.8

0.4 1.2

0 1.0
2.9 9.5 7.7 1.8 0.7 0.5 0.1 0.01 0 0.5 1.0 1.5 2.0
Q(Au), µC I/Q(Au), s–1

Fig. 1. Correlation of the parameter I/Q(Hg) with (a) the amount of gold on the electrode and (b) the potential of the maximum
current of gold oxidation in 0.1 M HCl.

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1152 STOZHKO et al.

Table 3. Electrochemical characteristics of gold transformations on different gold and gold-containing electrodes in 0.1 M HC

Electrode Gold oxidation Gold(III) reduction

Peculiarities
Group No. Type Eox, V Iox, mA Qox, mC I/Q, s–1 Ered*, V Ired*, mA
of voltammogram

1 1 Annealed 1.750 0.289 2.887 0.10 0.850(1) 0.018 Reverse current

0.660(2) 0.016
1 2 Disk 1.300 1.429 9.527 0.15 0.845(1) 0.065 Reverse current
0.605(2) 0.238
1 3 Compact-disk 1.280 1.378 7.660 0.18 0.853(1) 0.105
0.618(2) 0.175
1 4 Deposited 1.275 0.545 1.820 0.20 0.860(1) 0.230
0.655(2) 0.185
1 5 Foil 1.220 0.175 0.700 0.25 0.865(1) 0.024
0.650(2) 0.019
1 6 Film 1.200 0.183 0.522 0.35 0.890 (1) 0.034 Loop
0.665 (2) 0.025
2 7 TCE/HAuCl4 1.175 0.085 0.108 0.70 0.460(1) 0.009
0.288(2) 0.012
2 8 TGE/HAuCl4 1.150 0.013 0.007 1.70 0.395(1) 0.001 Loop
0.275(2) 0.002
* The first (1) and second (2) current maxima of gold(III) reduction and their potentials on the cathode brunch of the cyclic curve.

Gold(III) is reduced stepwise on electrodes of both
groups. The potentials of the first and second peaks of
the reduction of gold(III) are close for electrodes within
one group, the values between the groups differ consid-
erably (Table 3). The peaks of gold(III) reduction are
shifted by 0.3–0.4 V to more negative values for elec-
trodes of the second group.
An interesting feature of the cyclic voltammograms
of gold on the TGE/HAuCl4 and film electrodes, which
are most active in their groups, is the formation of a
loop upon switching the direction of potential sweep.
The appearance of the loop is caused by the increase in
the overvoltage of the cathodic process after gold disso-
lution from the surface and by the increase in the anodic
current upon switching the sweep direction in record-
ing the cyclic curve.
Another peculiarity of cyclic voltammograms
recorded in 0.1 M HCl supporting electrolyte using
electrodes with the lowest activity, that is, annealed
(I/Q(Au) = 0.1) and disk (I/Q(Au) = 0.15), is that an
abnormal anodic current appears at 1.2 V under
cathodic potential sweep [26]. The reason for the
reverse anodic current in this case is the formation of
the low-soluble compound AuCl, causing the passiva-
tion of the electrode and a sharp drop of the oxidation
current of gold. At the cathodic potential sweep in the
region of (1.25 ± 0.05) V, the deposit obviously dis-
solved. At this moment, the oxidation of the gold sur-
face, free from the deposit, begins. The oxidation of
gold at the cathodic potential sweep is terminated at
(0.85 ± 0.05) V, when the reduction of AuC l 2 to Au0
–
begins. The reverse anodic current was not observed on
the other gold electrodes, which is probably because
the amount of gold remaining on the electrode after
its dissolution under anodic potential sweep is not
sufficient. Therefore, one of the conditions for the
appearance of the reverse current in the system Auelectrode
Au+solution, Cl–solution is a certain thickness of gold layer
on the electrode.
Thus, gold is deposited on graphite, mainly, at active
sites like the rough edges, as a three-dimensional
nucleus, from which energetically favored microcrys-
tals are formed. Obviously, the highly developed graph-
ite surface ensures a considerable contribution of the
surface energy to the total energy of the system
(∆G > 0).
It can be seen in Table 4 that the electrochemical
characteristics of the analytical signal of mercury(II)
recorded on gold and gold-containing electrodes
depend on the activity of the gold surface I/Q(Au); that
is, the higher I/Q(Au), the higher I/Q(Hg) (Fig. 2) and
the larger the shift of the anodic peak of mercury to
more negative potentials.
In going form the annealed electrode with a contin-
uous gold coating to TGE/HAuCl4 with the microcrys-

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 ELECTRODES IN STRIPPING VOLTAMMETRY 1153

Table 4. Electrochemical characteristics of the analytical signal of mercury recorded in 0.1 M H2SO4 + 0.004 M HCl + 10.0 µg/L of
Hg(II) on gold and gold-containing electrodes with different parameter I/Q(Au) (n = 7)

Electrode
I/QAu, s–1 EHg, V IHg, nA QHg, nC I/QHg, s–1
Group Type

1 Annealed 0.10 0.82 26 103 0.25

1 Disk 0.15 0.72 102 255 0.40

1 Compact-disk 0.18 0.68 60 133 0.45

1 Deposited 0.20 0.66 25 55 0.45

1 Film 0.35 0.65 43 66 0.65

2 TCE/HAuCl4 0.70 0.65 68 80 0.85

2 TGE/HAuCl4 1.70 0.62 154 81 1.90

tal structure of gold, the analytical signal of mercury(II)
shifted by 0.2 V to more negative potentials (Table 4).
On the more active gold surface, mercury is deposited
in a more active form oxidized at a more positive poten-
tial than mercury deposited on the equilibrium gold sur-
face. The high activity of mercury deposited on
TGE/HAuCl4 considerably facilitates the regeneration
of the electrode. It follows from the data presented that
the value of the analytical signal of mercury(II)
depends on the activity of gold on the electrode surface
rather than on the amount of gold. The highest analyti-
cal signal of mercury(II) was recorded on TGE/HAuCl4
with the lowest amount of gold on its surface but with
the largest parameter I/Q(Au).
The analytical and performance characteristics of
different gold and gold-containing electrodes in the
determination of mercury(II) are presented in Table 5.
The determination limit for mercury(II) (cl) for elec-
trodes of the second group was 0.05–0.01 µg/L, while
for electrodes of the first group, it was 1.0–2.0 µg/L.
The accumulation time of 2.0 µg/L of mercury(II) on
electrodes of the second group was one order of magni-
tude (10–15 s) shorter than that on electrodes of the first
The comparative analysis of electrodes from the two
groups in the determination of arsenic(III) and sele-
nium(IV) is presented in Table 6. It can be seen that the
TGE/HAuCl4 electrode overcomes the other electrodes
by a combination of parameters. With this electrode, no
long anodic activation and surface regeneration are
required.
TCE ex situ modified with bismuth(III) phos-
phate. In the use of electrodes covered with bismuth
particles obtained by reducing bismuth(III) from a
solution or from a low-soluble modifier BiPO4 localized
on the electrode surface, we observed similar regulari-
ties as for electrodes containing gold particles or mer-
cury drops. The smaller the metal particles and the
Au
Hg
2.0
1.8
1.6
1.4
1.2
I/Q, s–1

group. The ratio of useful signals to the residual current 1.0

for electrodes with visible gold coatings varies between 0.8
0.0013 and 0.023, whereas for TCE/HAuCl4 and
TGE/HAuCl4, it is 0.066 and 0.319, respectively, which 0.6
characterizes electrodes of the second group as more 0.4
sensitive than electrodes of the first group. It is charac- 0.2
teristic for electrodes of the first group, except for the 0
film electrode, that the precision of the results is not 1 2 3 4 5 6 7 8
No. of electrode
sufficient and the found concentration of mercury(II)
differs almost twofold from the concentration added to
the model solution. For electrodes of the second group, Fig. 2. Change of parameters I/Q(Au) and I/Q(Hg) for dif-
RSD does not exceed 10%, and the accuracy factor (R) ferent (1–6) gold and (7 and 8) gold-containing electrodes
is close to 100%. (the electrodes are numbered as in Table 3).

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1154 STOZHKO et al.

Table 5. Analytical and performance characteristics of different gold and gold-containing electrodes in the determination of
mercury(II) (P = 0.95, n = 5)

Added 2.0 µg/L of Hg(II)

cl, Hg at Ratio of signal–residual cur-
Group Electrode
τaccum = 60 s, µg/L rent, ×103
Found Hg(II), µg/L RSD, % R, %

1 Annealed 2.0 15 3.9 23 195

1 Disk 2.0 23 4.3 31 215
1 Compact-disk 2.0 11 2.7 20 135
1 Foil 2.0 3 4.1 18 205
1 Deposited 1.0 34 1.2 13 60
1 Film 1.0 13 1.9 15 95
2 TCE/HAuCl4 0.05 66 2.1 4 105
2 TGE/HAuCl4 0.01 319 2.0 5 100

Table 6. Comparative analysis of different types of gold and gold-containing electrodes in the determination of arsenic(III)
and selenium(IV) (n = 5)

Element Group Electrode Added, µg/L Found, µg/L RSD, % R, %

As(III) 1 Annealed 100 46 27 46

1 Disk 5.0 4.6 18 92
1 Foil 10.0 4.2 20 42
1 Deposited 2.0 1.1 22 55
1 Film 2.0 2.3 14 115
2 TGE/HAuCl4-2 0.5 0.5 15 100
Se(IV) 1 Annealed 2.0 3.4 7 170
1 Bulk 20.0 6.5 24 33
1 Foil 10.0 7.6 5 76
1 Deposited 50.0 17.2 5 34
1 Film 2.0 3.0 24 150
2 TGE/HAuCl4 0.1 0.1 10 100

lower their amount on the surface, the more active the
particles and the better the electroanalytical properties
of the electrode [27]. With the decrease of Q(Bi) from
610.5 to 15.5 µC, the values of I/Q(Bi) increased almost
twofold (from 0.48 to 0.91), the potential of the anodic
peak of bismuth shifted by 150 mV to more negative
potentials, and the peak half-width decreased by 40 mV
(Table 7). The most electrochemically active form of
bismuth formed on a nonuniform-micro surface of
TCE/BiPO4 [27]. On this electrode, 63% of the surface
is covered with particles smaller than 0.1 µm, and 2%,
with large particles. The distance between the smallest
particles is from 0.5 to 20 µm, which is 5–20 times
more than their sizes.
As was shown by microscopic and electrochemical
studies, sharp and well-resolved anodic peaks of zinc,
lead, and cadmium were obtained on the electrode with
the smallest (<0.1 µm) and widely-spaced bismuth par-
ticles obtained by reducing BiPO4 [27]. On electrodes
with larger particles (20 and 2 µm), the analytical sig-

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 ELECTRODES IN STRIPPING VOLTAMMETRY 1155

Table 7. Parameters of the oxidation peak of bismuth and the analytical signals of cadmium and lead recorded on electrodes
modified by different procedures (n = 3)

Particle size of Bi,

Bi(III) Pb(II) Cd(II)
Method
Elec-

E1/2width, mV

E1/2width, mV
E1/2width, mV
µm
No. and conditions
trode
of modification

Ep, mV

Ep, mV

Ep, mV
I/Q, s–1

I/Q, s–1

I/Q, s–1
Q, µC

Q, µC

Q, µC
I, µA

I, µA

I, µA
1 TCE Ex situ, 100 mg/L 20 293.02 610.46 0.48 +30 131 0.25 0.33 0.76 –511 72 0.41 0.45 0.92 –753 81
Bi(III), –0.8 V,
4 min

2 GCE In situ, 0.5 mg/L 5–7 30.92 44.17 0.70 –101 109 0.44 0.35 1.25 –524 68 0.66 0.57 1.15 –763 76
Bi(III), –1.4 V,
2 min

3 TCE In situ, 0.5 mg/L 3–4 24.96 31.20 0.80 –109 103 0.50 0.38 1.32 –543 65 1.07 0.75 1.42 –770 60
Bi(III), –1.4 V,
2 min

4 TCE Ex situ, 2.0 g/L 2 15.86 18.02 0.88 –116 96 0.59 0.43 1.38 –551 64 0.75 0.42 1.77 –782 50
BiPO4 + 0.2%
Nafion

5 TCE Ex situ, 2.0 g/L 0.09 14.14 15.54 0.91 –120 90 0.73 0.50 1.46 –563 61 0.95 0.52 1.82 –792 48
BiPO4 + 0.2%
Nafion

The conditions for metal determination are as follows: 0.1 å NaAc + 0.025 å HCl (pH 4.5) + 5.0 µg/L ëd(II), Pb(II); Eaccum = –1.4 Ç; τaccum = 120 s.

nals of these elements either cannot be recorded or are
deteriorated.
The parameters of the oxidation current of bismuth
and the analytical signals of cadmium and lead
recorded on different Bi-modified electrodes are pre-
sented in Table 7. It can be seen that I/Q(Bi) and
I/Q(Me) change in the same direction. On the elec-
trodes with more active bismuth particles, metals are
oxidized at less positive potentials, and their anodic
peaks are narrower, which improves the resolving
power of the method.
TCE ex situ modified with colloid silver. The ini-
tial concentration of a silver salt in the solution for pre-
paring sols considerably affects processes of the
adsorption and aggregation of silver nanoparticles on
the surface of TCE. Using a 10–4 M solution of AgNO3,
we obtained a modifying layer of small silver particles
(10–15 nm), relatively uniformly distributed over the
surface. With the use of a 10–3 M solution of AgNO3,
particles with high polydispersity (particles of
10−15 nm and aggregates of 60–70 nm) were obtained.
The different sizes of silver nanoparticles and aggre-
gates and their distribution over the TCE surface affect
the processes of silver oxidation (Fig. 3a) and reduction
of low-soluble silver compounds, for example, AgI
(Fig. 3b). On the electrode with small monodisperse sil-
ver nanoparticles, well-shaped single peaks of silver
oxidation and silver iodide reduction were recorded. In
the case of electrodes with polydisperse particles, con-
taining large aggregates, characteristically split anodic
and cathodic peaks were observed. Therefore, elec-
trodes with small and uniformly distributed silver nano-
particles (TCE/Agnano) were used to determine iodide
ions. It was found that Òmin = 2 × 10–8 M at an accumu-
lation time of 120 s and that the linearity range is 5 ×
10−8–5 × 10–7 M. The TCE/Agnano compared favorably
with the metallic silver electrode; the determination
limit for iodide ions on the TCE/Agnano electrode was
1.5 times lower than that on the metallic silver elec-
trode.

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1156 STOZHKO et al.

60 (‡) 25 (b)

1
50
20
2

40
15
2

–I, µA
I, µA

30

10
20

5
10

1
0
0.2 0.4 0.6 0 0.2 0.4
E, V –E, V

Fig. 3. (a) Anodic and (b) cathodic voltammograms recorded in 0.1 M KNO3 (a) in the absence and (b) presence of 0.1 M KI using
electrodes with (1) monodisperse (10–15 nm) and (2) polydisperse (10–15 nm) and aggregates (60–70 nm) of silver nanoparticles;
(b) Eaccum = 0.1 V; τaccum = 60 s.

ACKNOWLEDGMENTS
The work was supported by the International Sci-
ence and Technology Center and the Russian Founda-
tion for Basic Research, projects nos. 342, 2897, and
07-03-96070-p_ural_a. The authors are grateful to
N.F. Zakharchuk and V.P. Cheremnykh for their help in
the microscopic studies.
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