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Journal of Electroanalytical Chemistry 498 (2001) 51 57

Behavior of a macrocyclic cobalt complex adsorbed on an

electro-oxidized glassy carbon electrode for the electrocatalytic
reduction of O2
Chan Kang *
Department of Chemistry, Chonbuk National Uni6ersity, Chonju 561 -756, South Korea
Received 22 February 2498; received in revised form 21 June 2000; accepted 23 June 2000
Dedicated to Fred C. Anson for his distinguished contributions to electrochemistry

Abstract
Voltammograms for the catalytic reduction of O2 at an electrochemically oxidized glassy carbon electrode, on which a cobalt
complex with a macrocyclic ligand C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hmc) was adsorbed, were
analyzed. In the presence of O2 in the solution, the reduction of adsorbed (hmc)Co3 + showed two cathodic waves. The catalytic
reduction current of O2 was observed before the second cathodic wave where the (hmc)CoOOH2 + intermediate was reduced. The
(hmc)Co2 + produced from the reduction of the fraction of (hmc)CoOOH2 + at the starting potential of the second cathodic wave
could react with additional O2 and the catalytic wave shifted to the positive direction to appear as the first cathodic wave. The
reactivities for the present system were compared between the edge plane pyrolytic graphite and the electro-oxidized glassy carbon
electrodes. The surfaces of the two electrodes showed almost the same properties as each other for the spontaneous adsorption
of the present cobalt complex and for the electro-reduction of O2 catalyzed by the adsorbed cobalt complex. 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Cobalt complex; Catalytic reduction; Electro-oxidised glassy carbon electrodes

1. Introduction
A cobalt complex with a macrocyclic ligand, C-meso5,7,7,12,14,14 - hexamethyl - 1,4,8,11 - tetraazacyclotetradecane (hmc), was used as a catalyst for the
electroreduction of O2 at glassy carbon (GC) and edge
plane pyrolytic graphite (EPG) electrodes [1,2]. Diffusion controlled redox reactions of the dissolved cobalt
complex were measured at the highly polished GC
electrode [1], but the complex was spontaneously adsorbed on the roughly polished EPG electrode [2]. At
both electrodes, the electroreduction of O2 was catalyzed and the same reaction scheme was suggested to
explain voltammetric responses. Two well separated
cathodic waves were observed during the reduction of
(hmc)Co3 + in the presence of O2. The first wave was
* Tel.: +82-63-2703420; fax: + 82-63-2703408.
E-mail address: chankang@moak.chonbuk.ac.kr (C. Kang).

assigned to the two-electron reduction of (hmc)Co3 +

into (hmc)CoOOH2 + (cobalt hydroperoxide) and the
second wave involved the further reduction of
(hmc)CoOOH2 + to (hmc)Co2 + plus HOOH. The
cobalt hydroperoxide intermediate requires more negative potential for its reduction than that of (hmc)Co3 +
and its reduction is a barrier for the catalytic reduction
of O2. The catalytic current enhancement was observed
as the growth of the second wave when the concentration of O2 was raised.
In another recent study, it was found that the adsorption of the same cobalt complex on the GC electrode was induced by heavily oxidizing the surface [3].
No adsorption of the complex was observed on a
conventionally polished GC surface and the interaction
for the adsorption is still not clear. The GC electrode
with the adsorbed complex was employed for the reduction of O2. Similarly, catalytic reduction of O2 into
HOOH was measured, but voltammetric responses ap-

0022-0728/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 0 ) 0 0 2 2 5 - 4

52

C. Kang / Journal of Electroanalytical Chemistry 498 (2001) 5157

peared to be different from the previous results with the

polished GC and the EPG electrodes. Two cathodic
waves were seen but the catalytic current was measured
as the increase of the first cathodic wave as the O2
concentration increased.
In this report, more experiments were carried out and
detailed explanations are given to understand the
voltammetric behavior of the adsorbed complex on the
electro-oxidized GC electrode. Comparison of the reactivites of the electrode reactions with those in the
previous systems using either the polished GC or the
EPG electrode is the subject of this report to give an
insight about the effects of the different surface states
of carbon electrodes.

2. Experimental

(hmc)Co2 + solution for about 30 s [3]. A smaller

amount of the complex was adsorbed if the electrode
was immersed for a shorter period. The cobalt complex
was presumed to be in its oxidized state if a potential of
several hundred mVs positive of the formal potential
was applied. To obtain a new surface free of surface
redox waves after the electrochemical treatment [8,9], it
was ground with SiC paper and next with 0.3 mm
alumina powder [3]. The polished electrode was sonicated to remove completely any attached powder. A
freshly prepared electrode was used for each new
measurement.
Potentials were measured and quoted with respect to
an Ag  AgCl  3 M NaCl reference electrode with a
potential of 0.22 V versus SHE. 0.1 M CF3COOH
supporting electrolyte was used in all the experiments.
All the experiments were conducted at the ambient
laboratory temperature (22+ 2C).

2.1. Materials
Commercial reagent grade chemicals were used as
received. The macrocyclic ligand, C-meso-5,7,7,12,14,14hexamethyl-1,4,8,11-tetraazacyclotetradecane
(hmc),
and the cobalt complex, [(hmc)Co](CF3SO3)2, were synthesized according to procedures in the literature and
stored under argon in the refrigerator [4 6]. The distilled water was further purified by passage through a
purification train (Milli-Q, Millipore Co.) and used for
the preparation of solutions. The solution of
(hmc)CoOOH2 + was prepared by adding stoichiometric Ru(NH3)26 + to the solution containing (hmc)CoOO2 + immediately after it was produced by the
injection of concentrated (hmc)Co2 + in an O2 saturated
solution [1]. A glassy carbon rod (0.28 cm2, Tokai
carbon Co., GC-20S) as the working electrode was
mounted on a stainless steel shaft with a heat shrinkable polyolefin tube.

2.2. Apparatus and procedures

Electrochemical measurements were conducted in a
two-compartment cell closed with a Teflon cap through
which the electrode and gas bubbling system were
fitted. A GC working electrode and a platinum auxiliary electrode were in one compartment separated by
fritted glass from the other compartment where a reference electrode was held. A Pine Instrument Co. potentiostat (Model RDE 3) and a X-Y recorder (Yokogawa
Co. Model 3025) were used for cyclic voltammetry.
For the electrochemical oxidation of the glassy carbon electrode, the potential was initially scanned to 2.0
V (versus Ag  AgCl), held for 1 or 2 min, and reversed
to 0.5 V [7]. Several repeated scans between 0.5 and
0.5 V after the oxidation treatment gave a stable
background current. To adsorb (hmc)Co2 + on the
pretreated electrode, it was dipped into a 0.5 mM

3. Results and discussion

3.1. Reduction of the adsorbed (hmc)Co 3 + with O2 at

the electro-oxidized GC electrode
Fig. 1 illustrates voltammograms with a (hmc)Co2 +
complex adsorbed on electro-oxidized glassy carbon
(GC) for the catalytic reduction of O2. The cobalt
complex was not adsorbed on the GC electrode polished with alumina powder [1] and the electrochemical
pretreatment induced the adsorption of the complex [3].
Fig. 1(A) is a voltammogram in 0.1 M CF3COOH
supporting electrolyte after the (hmc)Co2 + was adsorbed and it was compared to the dashed background
voltammogram before the adsorption. The formal potential of the (hmc)Co3 + /2 + couple was estimated as
0.09 V. The peak width at half height of the cathodic
peak in Fig. 1(A) was 140 mV at a scan rate of 50 mV
s 1 and thicker than the Nernstian value of 90.6 mV
[10]. This peak shape indicates the presence of repulsive
interactions among the adsorbed molecules [11], which
may originate from positively charged cobalt cations.
With the same complex adsorbed on the roughly polished EPG electrode, a similar formal potential was
measured but the peak width was narrower, for reasons
that cannot be clearly explained [2]. Fig. 1(B and C) are
voltammograms in air saturated and pure O2 saturated
solutions, respectively, with the electrode on which the
(hmc)Co2 + was adsorbed. Two cathodic waves at 0.22
and 0.06 V were observed in Fig. 1(B) and a large
current increase was seen as the first cathodic wave with
increasing the concentration of O2 in Fig. 1(C).
At the initial stage of the potential scanning, the
cobalt complex was in the oxidized state and a reaction
scheme was suggested for its reduction in the presence
of O2 in the previous systems [1,2].

C. Kang / Journal of Electroanalytical Chemistry 498 (2001) 5157

(hmc)Co3 + + e = (hmc)Co2 +

E f1

(hmc)Co2 + + O2 =(hmc)CoOO2 +

(1)
(2)

K2

(hmc)CoOO2 + +e +H+ =(hmc)CoOOH2 +

E f3
(3)

(hmc)CoOOH2 + +e +H+=(hmc)Co2+ +HOOH E f4

(4)
E f and K indicate the formal potential and equilibrium constant, respectively. E f4 was measured at a
more negative potential than E f1 and two cathodic
waves were observed with both the dissolved complex
at the highly polished GC electrode and the adsorbed
one on the roughly polished EPG electrode [1,2]. The

53

reactions of Eqs. (1) (3) were involved in the first

cathodic wave and the reaction of Eq. (4) appeared as
the second cathodic wave. The catalytic reduction of O2
occurred in the second cathodic wave potential region
as the product (hmc)Co2 + complex in Eq. (4) reacts
with another O2 as in Eq. (2) and the product is then
reduced as in Eqs. (3) and (4). Hence the current of the
second peak increased as the concentration of O2
increased.
For the present system, a large increase of the current
appeared as the first wave in Fig. 1(C). In the recent
report, it was explained that the (hmc)CoOOH2 + complex, which is a product of Eq. (3) was reduced at a
more positive potential before the second wave and the
catalytic reduction of O2 occurred in the first cathodic
wave [3]. The second cathodic wave was assigned as the
reduction of (hmc)Co3 + , which did not participate in
the catalytic reaction cycle. However, more careful
studies showed some contradictory results to the suggested explanation.

3.2. Catalytic process for the electroreduction of O2

Fig. 1. (A) Cyclic voltammograms in a pure supporting electrolyte

before (dashed) and after (solid) the adsorption of (hmc)Co2 + on an
electro-oxidized GC. (B) Cyclic voltammogram in an air saturated
solution with the GC electrode on which the (hmc)Co2 + was adsorbed. (C) Repeat of (B), but the solution was saturated with pure
O2. Supporting electrolyte: 0.1 M CF3COOH. Scan rate: 50 mV s 1.

Fig. 2(A) is a voltammogram with the (hmc)Co3 + in

its adsorbed state on the GC electrode in the air
saturated solution as in Fig. 1(B). The potential scan
was reversed at 0.16 V just after the first cathodic wave
and an anodic peak was shown at 0.57 V. A similar
anodic peak was also observed in other experiments at
the polished GC or EPG electrode and it was assigned
as the oxidation of (hmc)CoOOH2 + , which is the reverse reaction of Eqs. (1) (3) [1,2]. This indicates that
the cobalt hydroperoxide intermediate is a product of
the reactions of the first cathodic wave in Fig. 1(B) or
Fig. 2(A). This was further confirmed by employing
(hmc)CoOOH2 + formed by a chemical reaction as
described in the experimental section [1]. The electrooxidized GC electrode was immersed in a solution
containing (hmc)CoOOH2 + . The electrode was then
transferred to 0.1 M CF3COOH pure supporting electrolyte solution and the voltammogram of Fig. 2(B)
was obtained with the initial potential scanning into the
negative direction. The cathodic peak shown at 0.06 V
is quite similar to that for the reduction of (hmc)Co3 +
shown in Fig. 1(A) but the species adsorbed on the
electrode surface was (hmc)CoOOH2 + . If the potential
was initially scanned to the positive direction after the
adsorption of (hmc)CoOOH2 + as in Fig. 2(C), an
anodic peak was shown at 0.58 V, which was the same
potential of the anodic wave shown in Fig. 2(A). Hence
the peak at 0.06 V in Fig. 2(B) can be assigned to the
reduction of the (hmc)CoOOH2 + whose potential is
much more negative than that of the first cathodic wave
in Fig. 1(B). Another point to be noted is that the
height of the first cathodic wave in Fig. 1(B) is almost
twice as high as that for the reduction of (hmc)Co3 +

54

C. Kang / Journal of Electroanalytical Chemistry 498 (2001) 5157

indicates the reduction of (hmc)CoOOH2 + as in Eq.

(4).
Only a small amount of the cobalt complex is required for the catalytic reduction of O2. In Fig. 3,
voltammograms were obtained with the electrode on
which a smaller amount of (hmc)Co2 + was adsorbed
on the electro-oxidized GC surface. The amount of
adsorption was controlled by adjusting the immersion
time of the pretreated electrode in the solution containing (hmc)Co2 + . The dashed and solid voltammograms
in Fig. 3(A) are before and after the adsorption, respectively. The area due to the adsorbed complex is much
smaller than that of Fig. 1(A), which indicates that the
amount of the adsorption was smaller. The voltam-

Fig. 2. (A) Cyclic voltammogram in an air saturated solution with the

GC electrode on which the (hmc)Co2 + was adsorbed. (B) Cyclic
voltammogram in pure supporting electrolyte with the electro-oxidized GC electrode, which was previously immersed in a solution
containing (hmc)CoOOH2 + (see the text). (C) The same as (B), but
the scan direction was reversed. Other conditions were the same as
Fig. 1.

without any O2 in Fig. 1(A). From these results, it can

be concluded that the first cathodic wave, in Fig. 1(B),
is the two-electron reduction of (hmc)Co3 + plus O2
into (hmc)CoOOH2 + , which is further reduced as the
second wave. In this case, the amount of O2 in the
solution seems to be stoichiometric to convert all the
cobalt complex molecules into (hmc)CoOO2 + Eq. (2).
If additional O2 was supplied, in Fig. 1(C), the
catalytic current was observed as the growth of the first
cathodic wave where the (hmc)CoOOH2 + was considered not to be reduced yet. This is probably because the
small amount of (hmc)Co2 + produced from the reduction of (hmc)CoOOH2 + at the starting potential of the
second wave reacted with the additional O2 and the
peak for the catalytic reduction of O2 shifted to the
positive direction to appear as the first wave. In Fig.
1(C), the first wave includes the process of all the
reactions of Eqs. (1) (4) and the second wave also

Fig. 3. (A) Cyclic voltammograms in the pure supporting electrolyte

before (dashed) and after (solid) the adsorption of (hmc)Co2 + on the
electro-oxidized GC. For the adsorption of (hmc)Co2 + , a shorter
immersion time than in Fig. 1(A) was employed (see the text). (B)
Cyclic voltammogram in an air saturated solution with the GC
electrode on which less (hmc)Co2 + was adsorbed as in (A). (C)
Repeat of (B), but the solution was saturated with pure O2. Other
conditions were the same as Fig. 1.

C. Kang / Journal of Electroanalytical Chemistry 498 (2001) 5157

55

Table 1
Effect of solution pH on the peak potentials for the reduction of adsorbed (hmc)Co3+ on the GC electrode in the presence of O2 (air)
[CF3COOH]/M

0.100
0.050
0.010
0.005

[CF3COONa]/M a

Peak potential of the first

cathodic wave/V b

Peak potential of the second

cathodic wave/V b

0.000
0.050
0.090
0.095

0.22
0.20
0.17
0.20

0.06
0.03
0.06
0.10

Formal concentrations.
Voltage versus Ag  AgCl  3 M NaCl. Potentials were measured from the cyclic voltammograms obtained under the conditions employed in
Fig. 1(B) except that the solution pH was changed.
b

mograms of Fig. 3(B and C) were obtained in the air

saturated and pure oxygen saturated solutions, respectively. In Fig. 3(B), the first cathodic wave shown in
Fig. 1(B) almost disappeared with a very small wave at
around 0.2 V because its area is proportional to the
amount of the adsorbed complex. The peak at 0.05 V is
considered as the catalytic reduction wave with a relatively large O2 concentration compared to that of the
catalyst. In Fig. 3(C), the height of the wave increased
as the concentration of O2 increased and it is similar to
that of the assigned catalytic wave in Fig. 1(C). The
peak potential at 0.04 V is more negative than that
of 0.13 V for the same reaction in Fig. 1(C). A much
smaller amount of the adsorbed complex is enough to
obtain a similar catalytic effect and only a fraction of
(hmc)CoOOH2 + in Fig. 1(C) was reduced at the starting potential of the second wave giving the catalytic
wave. From the results of Fig. 1 and Fig. 3, it was
shown that the potential for the catalytic reduction of
O2 varied with the amount of adsorbed cobalt catalyst
or O2 concentration.

3.3. Effect of solution pH and the stability of the

adsorbed complex
It was shown that the reduction potential of
(hmc)CoOOH2 + adsorbed on the EPG electrode was
shifted to the positive direction when the solution pH
was lowered as it involves a protonation step [12]. With
the present system, the effect of the solution pH on the
voltammetric responses was also tested. In the voltammograms under the same conditions as in Fig. 1(B)
except that the solution pH was changed, the peak
potentials of the two cathodic waves were measured
and summarized in Table 1. The solution pH was
controlled with different compositions of CF3COOH
and CF3COONa while the total ionic strength of the
solution was kept constant. As the solution pH was
raised, the peak potential of the first cathodic wave was
not affected (in fact, there were 10 to 20 mV fluctuations for unknown reasons, but this was not from the
pH change) but the second peak potential shifted to the

negative direction. The pH dependence of the second

wave is evident in Table 1, which confirms that the
second wave in Fig. 1(B) is the reduction of
(hmc)CoOOH2 + as was observed on the EPG
electrode.
The stability of the catalyst molecules adsorbed on
the surface was inspected. Fig. 4(A) is a voltammogram
with the bare GC electrode after the electro-oxidation
pretreatment. Fig. 4(B) was obtained in the presence of
O2 (air) in the solution after the cobalt complex was
adsorbed. In Fig. 4(C) repeated scanning of the potential resulted in the gradual disappearance of the second
cathodic wave while the shape of the first cathodic wave
remained the same. After further scanning, the second
wave almost disappeared and a voltammogram of Fig.
4(D) was obtained after the removal of O2 from the
solution. It looks like that of Fig. 4(A), but its current
is a little higher than that of Fig. 4(A). It was reported
that the hydrogen peroxide produced from the reduction of O2 partially oxidized the hmc ligand of the
complex [13]. The higher current in Fig. 4(D) probably
indicates the presence of the deformed product of the
macrocyclic cobalt complex still remaining on the surface as the redox peak shape was lost. The decrease of
the second wave in Fig. 4(C) was considered as the loss
of the wave shape due to such a change of the complex
rather than the dissolution of the adsorbed complex.
The constant shape of the first cathodic wave in Fig.
4(B or C) is still the two-electron reduction of O2 with
the cobalt complex in any deformed form at a constant
amount on the surface. If the complex was lost by its
dissolution into the solution during the repeated scanning, the voltammogram shape should be similar to
that of Fig. 3(B) where only a small amount of the
complex exists on the surface.

3.4. Comparison of the catalytic reduction of O2 by the

adsorbed cobalt complex at the EPG and
electro-oxidized GC electrodes
As the (hmc)Co3 + was adsorbed on the roughly
polished EPG electrode and the electro-oxidized GC

56

C. Kang / Journal of Electroanalytical Chemistry 498 (2001) 5157

electrode, it is interesting to compare how the reactivities

of the various half reactions of the cobalt species during
the catalytic reduction of O2 are different at the two
electrodes and this is summarized in Table 2. All the
cobalt species were in the adsorbed states on the electrode
surfaces. At both electrodes, the reduction potentials of
(hmc)Co3 + into (hmc)Co2 + and those of (hmc)Co3 +
plus O2 into (hmc)CoOOH2 + were quite similar to each
other as is shown in the first two reactions of Table 2.
The reduction of (hmc)CoOOH2 + which is the third half
reaction in Table 2 was also measured at the same
potential of 0.06 V. The last half reaction in Table 2 is
the catalytic reduction of O2 with (hmc)Co2 + as a
catalyst, which is equivalent to Eqs. (2) (4). Its peak
potentials seem to be quite different but it varies as the

Table 2
Comparison of the peak potentials for various half reactions during
the reduction of adsorbed (hmc)Co3+ and O2 at EPG and electro-oxidized GC
Half reactions

Cathodic peak
potentials/V a
At EPG b

(hmc)Co3++e =(hmc)Co2+
(hmc)Co3++O2+H++2e
=(hmc)CoOOH2+
(hmc)CoOOH2++H++e
=(hmc)Co2++HOOH
(hmc)Co2++O2+2H++2e
=(hmc)Co2++HOOH f

At GC

0.08
0.19

0.08 c
0.22 d

0.06

0.06 e

0.11

0.04 g

Voltage versus Ag  AgCl  3 M NaCl.

Ref. [2].
c
From Fig. 1(A).
d
The peak potential of the first cathodic wave in Fig. 1(B).
e
The peak potential of the second cathodic wave in Fig. 1(B).
f
In this half reaction, (hmc)Co2+ is a catalyst.
g
From Fig. 3(C).

Fig. 4. (A) Background voltammogram in the pure supporting electrolyte with the electro-oxidized GC electrode. (B) Cyclic voltammogram in an air saturated solution with the GC electrode on which
the (hmc)Co2 + was adsorbed as in Fig. 1(A). (C) Repeat of (B) after
the several same measurements. (D) Cyclic voltammogram with the
electrode used in (C) after removal of O2 from the solution. Other
conditions were the same as Fig. 1.

oxygen concentration or surface coverage of the catalyst

change as mentioned in the earlier section (compare Figs.
1(C) and 3(C)), which makes a direct comparison
difficult. According to Table 2, the reactivities for the
catalytic reduction of O2 by the present cobalt complex
appeared almost the same at the two electrodes.
It was reported that various oxygen containing functional groups are introduced on the surface during the
oxidation treatment of the GC electrode [7,8,14 17]. The
surface becomes more acidic with some of the newly
formed groups providing protons [7] and some redox
reactions including proton transfer are affected by such
a treatment. As the reduction of (hmc)CoOOH2 + was
affected by the carbon surface states and the solution pH,
the involvement of a proton transfer during its reduction
was proposed [12]. The reduction of (hmc)CoOOH2 +
was more effective in its adsorbed state at the EPG
electrode than in the dissolved state at the highly polished
GC electrode with less surface functional groups. By
oxidizing the GC surface, its reduction potential shifted
to the positive direction [12]. Eventually, the cobalt
complex was adsorbed [3] and the potential of 0.06 V,
the same potential as that with the EPG electrode, was
measured. This potential seems to be the limit of the shift
as the GC surface is oxidized. As the reduction of the
(hmc)CoOOH2 + complex is a barrier for the overall
catalytic reduction of O2, the latter reaction was also
affected by the surface states of the carbon electrodes
[1,2,12]. By oxidizing the GC electrode, its surface
property becomes close to that of the EPG electrode for
the adsorption of the macrocyclic cobalt complex and the
electroreduction of O2 catalyzed by the adsorbed cobalt
complex.

C. Kang / Journal of Electroanalytical Chemistry 498 (2001) 5157

Acknowledgements
This report originated from work carried out in
Professor F.C. Ansons group at the Californial Institute of Technology during the authors stay. The author
wishes to acknowledge the financial support of the
Korea Research Foundation made in the program year
of 1998 (1998-001-D00591).

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