Electrochimica Acta 54 (2009) 1570–1577

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical oxidation of hydrogen peroxide at a bromine

adatom-modified gold electrode in alkaline media
Md. Rezwan Miah 1 , Takeo Ohsaka ∗
Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology,
Mail Box G1-5, 4259 Nagastuta, Midori-ku, Yokohama 226-8502, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Bromine (Br)-adatom (Br(ads) ) was in situ fabricated onto polycrystalline gold (Au (poly)) electrode in Br− -
Received 6 June 2008 containing alkaline media. The surface coverage of Br(ads) ( Br ) varied only in the submonolayer coverage
Received in revised form within the investigated potential window under potentiodynamic condition because of the coadsorption
11 September 2008
of hydroxyl ion (OH− ) in alkaline media. The in situ fabricated Br(ads) -submonolayer-coated Au (poly)
Accepted 18 September 2008
electrode was successfully used for the electrochemical oxidation of hydrogen peroxide (H2 O2 ). About
Available online 30 September 2008
five times higher oxidation current was achieved at the modified electrode as compared with the bare
electrode. The enhancement of the electrode activity towards the electrochemical oxidation of H2 O2 was
Keywords:
Br(ads) -submonolayer
explained based on the enhanced electrostatic attraction between the anionic HO2 − molecules and Br(ads) -
Br(ads) -submonolayer-coated Au (poly) adlayer-induced positively polarized Au (poly) electrode surface.
electrode © 2008 Elsevier Ltd. All rights reserved.
Alkaline media
H2 O2 oxidation reaction
Electrostatic attraction

1. Introduction traditional electrode materials. The high working potentials may

Detection of hydrogen peroxide (H2 O2 ) takes a great part in the
reported amperometric biosensors as H2 O2 is not only an impor-
tant analyte in many fields, including industry, clinical medicine
and the environment, but also important in fabricating biosen-
sors for various substances by combining it with H2 O2 -producing
oxidases such as glucose oxidase, l-lactate oxidase, xanthine oxi-
dase, horseradish peroxidase and carbonic anhydrase, etc. [1–5].
However, the direct electrochemistry of H2 O2 requires a higher
over-potential. Chemical modification of the electrode surface is
a well-established strategy for achieving wider applicability of the
electroanalytical methodology. Accordingly, numerous efforts have
been dedicated to fabricate suitable electrode materials for the
sensitive detection of H2 O2 . Electrochemical sensing of H2 O2 has
been done based on both of its reduction [6–13] and oxidation
[14–22] reactions. However, the electrooxidation of H2 O2 often
requires very high over-potential, particularly at the unmodified
∗ Corresponding author. Tel.: +81 45 9245404; fax: +81 45 9245489.
E-mail addresses: mrmche@yahoo.com (Md.R. Miah),
ohsaka@echem.titech.ac.jp (T. Ohsaka).
1
On leave from the Department of Chemistry, School of Physical Sciences, Shahjalal
University of Science and Technology, Sylhet 3114, Bangladesh.
cause undesired results: (i) the coexisting electroactive substances
can substantially interfere with the H2 O2 oxidation [22], (ii) the
large base-current can result in an uncertainty in the estimation of
H2 O2 oxidation current [22], and (iii) the electrode materials can
undergo a rapid oxidative degradation as H2 O2 is a strong oxidiz-
ing agent [6,7]. Modification of the electrode surface is, therefore,
essentially required to reduce the over-potential of H2 O2 oxidation.
Several strategies have been used to reduce the over-potential
of H2 O2 oxidation reaction. One strategy is to use the redox medi-
ators that help to shuttle electrons between the electrode surface
and H2 O2 molecules [23,24]. Another approach is to make use of
the electrocatalytic effect where a difficult/kinetically slow redox
process is facilitated by electrode modification. In recent years,
there has been a surge of interest in the study of electrocat-
alytic H2 O2 oxidation by inorganic/organic-film coated electrodes
[25–30]. For instance, Khoo et al. [25] have reported the catalytic
ability of a series of oxymetallic films of several elements such
as Co(II), Fe(II), Ni(II), Pb(II), Ce(III), Cr(III), Tl(I) and Mn(III) on
glassy carbon electrodes for the electrocatalytic oxidation of H2 O2 .
Wang and Angnes have described the electrocatalytic behavior of
carbon–fiber electrodes, modified by electrochemical codeposition
of rhodium and glucose oxidase, towards the electrochemical oxi-
dation of H2 O2 and sensing of glucose [26]. A micro-biosensor
was constructed by Li et al. [27] by incorporating the organic con-

0013-4686/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2008.09.041
 Md.R. Miah, T. Ohsaka / Electrochimica Acta 54 (2009) 1570–1577
ducting salt (tetrathiafulvalene–tetracyanoquinodimethane) into a
platinized platinum wire and glucose was sensitively determined
at a low working potential based on the oxidation of H2 O2 .
Halides are the hitherto most extensively studied class of specif-
ically adsorbed anions because of the structural simplicity of these
monatomic, monovalent anions as well as their abundance in the
natural and technological environments. I− adsorption, compared
with other halides, has so far been studied most extensively because
of its highest adsorption affinity [31]. Smooth single crystalline
metallic electrodes and background electrolytes of acidic pH have
received much scientific interest in the arena of halide adsorption
as compared with the polycrystalline rough metallic electrodes and
electrolytes of higher pH [31–41]. This is probably due to the fact
that the voltammetric features of adsorption/desorption of halides
appear as well-defined voltammetric peaks at the single crystalline
electrodes and the acidic electrolytes do not compete with the
adsorption/desorption of the halides, especially with I− and Br− .
In our laboratory, we have been increasingly interested to eval-
uate the effect of chemisorbed halogen (X(ads) )-adlayers, especially
that of iodine (I(ads) ) and bromine (Br(ads) ) at the various metallic
electrodes, on the different electrochemical reactions in alkaline
media. For instance, we recently have reported that I(ads) -modified
polycrystalline gold (Au (poly)) electrode shows a remarkably high
activity towards the electrochemical reduction [6,7] and oxidation
[42] of H2 O2 and oxidation of uric acid [43]. In the present report, we
address a new approach to the electrocatalytic oxidation of H2 O2 at
the Au (poly) electrode in bromide (Br− )-containing alkaline media
based on the voltammetric and amperometric techniques. A tenta-
tive mechanism of the enhanced electrooxidation of H2 O2 in the
presence of Br− is also addressed.
2. Experimental
2.1. Chemicals
Sodium hydroxide (NaOH, 97%) (Kanto Chemical Co. Inc., Japan)
and potassium bromide (KBr, 99.5%), hydrogen peroxide (H2 O2 ,
35.5%) and sulfuric acid (H2 SO4 ) (Wako Pure Chemical Industries,
Japan) were purchased and used as received. Milli-Q water was
used as solvent. The solutions of NaOH and H2 O2 were prepared
by dissolving the required amount of the reagents. The solution
was purged with N2 gas (Nippon Sanso Co. Inc., Japan) before mea-
surements.
2.2. Apparatus and procedures
For cyclic voltammetric measurements, Au (poly) electrodes
( = 1.6 mm sealed in a Teflon jacket) with an exposed surface area
of 2.01 × 10−2 cm2 were used as working electrodes. A spiral Pt
wire and a Ag|AgCl|NaCl (sat.) were the counter and reference elec-
trodes, respectively. A conventional two-compartment Pyrex glass
cell was used. Prior to measurements, N2 gas was bubbled into
the cell for 30 min to obtain a N2 -saturated NaOH solution. The
necessary amount of H2 O2 was added into the solution. All the
measurements were performed at 25 ± 1 ◦ C. The Au (poly) elec-
trodes were polished with aqueous slurries of successively finer
alumina powder (down to 0.06 ␮m), sonicated for 10 min in Milli-Q
water and then electrochemically pretreated in 0.05 M H2 SO4 solu-
tion by repeating the potential scan in the range of −0.2 to 1.5 V vs.
Ag|AgCl|NaCl (sat.) at 0.1 V s−1 for 10 min or until the cyclic voltam-
metric characteristic for a clean Au (poly) electrode was obtained.
The real surface area was obtained from the charge consumed
during the formation of the surface oxide monolayer, considering
482 ␮C charge consumed for the oxide monolayer formation on
1571
1 cm2 surface of the Au (poly) electrode [44]. The roughness fac-
tor (rf), which is defined as the ratio of the real surface area to
the geometric surface area of the electrode, was calculated as 1.2.
The current density was obtained using the geometric surface area
of the electrode. Electrochemical measurements were performed
using an ALS CHI-832A electrochemical analyzer. Chemisorption of
Br− at the electrode was ensured by adding 5 mM KBr into an aque-
ous solution of 0.1 M NaOH. Experiments were always performed
in the presence of added KBr unless otherwise noted.
3. Results and discussion
3.1. Adsorption/desorption of Br− at the Au (poly) electrode
Before proceeding with Br− adsorption, the possibility of the
chemical/electrochemical reaction of Br− in alkaline solution in the
presence of H2 O2 was first clarified. Br− (or I− ) undergoes chemical
oxidation by H2 O2 to produce Br2 (or I2 ) according to reaction (1)
[45,46]:
2Br− (I− ) + 2H+ + H2 O2 = Br2 (I2 ) + 2H2 O (1)
The reaction rate for Br− is slower than that for I− . The reaction
requires strong acidic media. The rate of the reaction decreases
drastically with increasing pH of the solution. Therefore, in highly
alkaline solution (like 0.1 M NaOH which has been used in the
present study) there is actually no possibility of the reaction. In
our previous reports [6,7], it has been demonstrated that a highly
reproducible voltammetric response of H2 O2 to its reduction can
be obtained in I− -containing 0.1 M KOH solution when the solu-
tion is permitted to stand for a while (e.g. 2 h), suggesting that the
reaction (1) is not feasible in alkaline media. The electrochemical
oxidation of Br− to Br2 requires higher potential than that of I− to
I2 [47,48] and does not take place within the potential range used
in this study.
Fig. 1 shows the cyclic voltammograms (CVs) obtained at the Au
(poly) electrode in N2 -saturated 0.1 M NaOH solution containing (a)
0 and (b) 5.0 mM KBr. In the case of the bare electrode, the upper
potential was chosen at 0.2 V to avoid the formation of the surface
oxide. The CV obtained in 0.1 M NaOH solution in the absence of
Br− (CV a) shows three distinct features, namely the (i) so-called
double layer charging, associated to the constant current zone at
E < −0.55 V, (ii) potential-induced reversible adsorption/desorption
of OH− , related to the couple of anodic and cathodic peaks at ca.
−0.22 and −0.19 V, respectively [49] and (iii) irreversible partial oxi-
dation of specifically adsorbed OH− to generate Au(OH)ads species,
associated to the uptake of the anodic current at potential more
positive than ca. 0.1 V [49]. Modifications of the voltammetric fea-
tures of the Au (poly) electrode by the addition of 5.0 mM KBr in the
solution are shown in Fig. 1A (b). Clearly, the presence of Br− gener-
ates quite significant changes in the voltammetric curve obtained
in 0.1 M NaOH: (i) the double layer zone is shifted to more nega-
tive potential, that is, below −0.66 V, (ii) two pairs of well-defined
reversible couples of anodic and cathodic peaks appear at poten-
tials of ca. 0.08 V (designated as PI and PI ) and −0.29 V (designated
as PII and PII ) and (iii) the uptake of the anodic current at E > 0.1 V
is decreased. The changes in the voltammetric features in the pres-
ence of Br− are obviously associated to the adsorption/desorption
of Br− . The voltammetric features in the presence of Br− are consid-
erably similar to those obtained by Markovic et al. in their study of
the adsorption/desorption of Br− at the Au (1 0 0) electrode in 0.1 M
NaOH solution, except that the voltammetric peaks are sharper in
their case [41]. Both of the cathodic peaks (PI and PII ) are assigned
to the desorption of the Br(ads) , while both of the anodic peaks
(PI and PII) are assigned to the adsorption of Br− . In this case, the
1572 Md.R. Miah, T. Ohsaka / Electrochimica Acta 54 (2009) 1570–1577
Fig. 1. (A) CVs obtained at the Au (poly) electrode in N2 -saturated 0.1 M NaOH
solution containing (a) 0 and (b) 5.0 mM KBr. The symbol (*) represents the ini-
tial potential in both cases (a and b) and the upper potentials are (a) 0.2 and (b)
0.3 V. Potential scan rate: 0.1 V s−1 . (B) CVs obtained at various scan rates: (a) 0.05,
(b) 0.1, (c) 0.2, (d) 0.3, (e) 0.4 and (f) 0.5 V s−1 (from inner to outer) keeping other
conditions as the same as those of Fig. 1A (b). Inset shows the change of Eocp of the
Au (poly) electrode in N2 -saturated 0.1 M NaOH solution upon the injection of KBr
(the final concentration of KBr is 5.0 mM) into the solution.
two cathodic (and anodic) peaks result from the different binding
strength of the Br(ads) to the different facets, namely, Au (1 1 1), Au
(1 0 0) and Au (1 1 0) of the Au (poly) electrode. Previous report by
our group on the desorption of self-assembled monolayer of mer-
captoacetic acid (MAA) using the single crystalline Au (1 1 1), Au
(1 0 0) and Au (1 1 0) electrodes in 0.5 M KOH solution showed that
the binding strength of MAA follows the sequence Au (1 1 1) < Au
(1 0 0) < Au (1 1 0) [50]. Similar trend may also be considered for
Br− . Therefore, the couple (PI and PI ) may be assigned to the Au
(1 1 1) facet of the Au (poly) electrode, while the couple (PII and
PII ) to the Au (1 0 0) and Au (1 1 0) facets. The voltammograms in
the presence and absence of Br− are almost the same at poten-
tial more negative than −0.66 V, which implies that Br(ads) -adlayer
undergoes a complete desorption at this potential. Blizanac et al.
[41] also reported that  Br of the Au (1 0 0) electrode in 0.1 M
HClO4 solution became zero at a potential of about −0.4 V vs. SCE.
The two reversible couples in the presence of Br− have slightly
greater intensity as compared with those obtained in the absence of
Br− suggesting the Br− adsorption/desorption along with the OH−
adsorption/desorption in the same potential zone. Decrease of the
uptake of anodic current above 0.1 V also implies the formation of
the Br(ads) -adlayer at the Au (poly) electrode surface. However, the
current above 0.1 V is still prominent, suggesting that the Br(ads) -
adlayer is not compact enough to inhibit fully the chemisorption
of OH− . Our previous study showed that the adsorption of I− onto
the Au (poly) electrode surface in 0.1 M KOH solution significantly
decreased the current above 0 V due to the formation of a com-
pacted monolayer of I(ads) which efficiently blocked the adsorption
of OH− [6,7]. On the contrary, Br-adatom cannot inhibit the coad-
sorption of OH− because of its less adsorption affinity. It has also
been reported by Blizanac et al. that in alkaline media of rela-
tively higher pH, the adsorption of OH− is not fully inhibited by
Br(ads) -adlayer [41]. We will recall the topic later. The peak cur-
rents during the anodic potential sweep are associated with the
progress of adsorption of Br− on the electrode surface.  Br increases
as the electrode potential becomes more and more positive. This
potential-dependent increase of  Br is known as “electrocompres-
sion” [34,35]. The peaks are also attributed to the adlayer structure
transition from one form to other. The adsorption of Br− at potential
of −0.13 > E > −0.66 V (indicated by the anodic peak PII) results in
a disordered Br(ads) -adlayer [41]. According to the results reported
for the adsorption/desorption of Br− at different single crystalline
electrodes in acidic media, it is apparently though that the sec-
ond anodic peak PI is associated with the formation of an ordered
√ √
c( 2 × 2 2)R45◦ -Br(ads) -adlayer structure [34,40,41]. However, a
careful search was made by Blizanac et al. to find the diffraction
√ √
peaks due to the c( 2 × 2 2)R45◦ -Br(ads) -adlayer structure in their
study of adsorption/desorption of Br− at the Au (1 0 0) electrode in
0.1 M NaOH solution [41]. They could not observe such a response
√ √
suggesting that a c( 2 × 2 2)R45◦ -Br(ads) -adlayer structure with
long range order is not formed on the Au (1 0 0) electrode in the
alkaline media. It is apparent that the anodic peak PI is indeed a fin-
√ √
gerprint of the ordering of the Br(ads) -adlayer to c( 2 × 2 2)R45◦
structure. But due to the competitive adsorption of Br− and OH−
√ √
in alkaline solution the domain size of c( 2 × 2 2)R45◦ -Br(ads) -
adlayer structure is probably not large enough to be detected.
Salaita et al. [51] also observed that in Br− -containing alkaline solu-
tions of pH > 10 the adsorption/desorption of OH− gives prominent
reversible couple of anodic and cathodic peaks at the Pt (1 1 1) elec-
trode while Br− was not adsorbed strongly. In the present study,
we also consider that a compact Br(ads) -adlayer on the Au (poly)
electrode surface cannot be formed because of the competitive
adsorption with OH− . Later we will give more evidence in this
regard.
From Fig. 1A (b), we estimated the total charge associated with
the (i) anodic peaks PI and PII for the oxidative adsorption of Br−
and (ii) cathodic peaks PI and PII for the reductive desorption of
Br(ads) -adlayer. Values of 168 and 151 ␮C cm−2 were obtained for
the oxidation and reduction processes, respectively which can be
taken as identical within the experimental error suggesting that
the adsorption/desorption of Br− is a reversible process. The value
of  Br was calculated as 1.74 × 10−9 mol cm−2 using Eq. (2):
Q
Br = (2)
neA
where n is the number of electrons involved in the Br−
adsorption/desorption and in this case n was considered to
be equal to unity (discussed later), e is the charge of an
electron (1.602177 × 10−19 C) and A is the geometric surface
area of Au (poly) electrode. The determined value of  Br is
small as compared to the theoretical value for the mono-
layer of Br(ads) ( Br = 2.3 × 10−9 mol cm−2 ) or our reported value
(2.8 × 10−9 mol cm−2 ) on the adsorption of I− on the Au (poly)
electrode in 0.1 M KOH solution, in which we considered that a
compact I(ads) -adlayer can be fabricated even in the alkaline media
[6,7] because of the strong adsorption affinity of I− . In addition,
the value of  Br should be further small as the estimated charge
also includes the charge associated with the coadsorption of OH− .
Therefore, in the presence case, it might be concluded that a com-
pacted and ordered Br(ads) -adlayer at the Au (poly) electrode in
alkaline media cannot be formed in the potential zone under inves-
tigation because of the coadsorption of OH− . Especially, in the
potential zone of the second couple of the anodic and cathodic
peaks (PII and PII ), the value of  Br is significantly small, and a
√ √
compacted c( 2 × 2 2)R45◦ -Br(ads) -adlayer structure cannot exist.
In other words, the Au (poly) electrode surface is partially covered
with Br(ads) -adlayer. Thus a Br-submonolayer-coated Au (poly) elec-
trode was successfully fabricated in situ in view of investigating the
 Md.R. Miah, T. Ohsaka / Electrochimica Acta 54 (2009) 1570–1577
Fig. 2. Linear plots of the cathodic and anodic peak currents vs. scan rate and the
square root of scan rate. Data were taken from Fig. 1(B).
electrochemical oxidation of H2 O2 in alkaline media (discussed in
the next section).
The Br− adsorption/desorption process was also recorded at
various potential scan rates ranging from 0.05 to 0.5 V s−1 and
the corresponding results are presented in Fig. 1(B). The first and
second peak currents (both anodic and cathodic) were plotted as
function of scan rate () (for PI and PII peak currents) and the
square root of scan rate (for PI and PII peak currents) and the
obtained linear plots are given in Fig. 2. Both of the PI and PII
peak currents vary linearly with  and pass through the origin sug-
gesting a surface-confined process, that is, the cathodic process is
associated with the desorption of Br(ads) -adlayer from the surface
of the electrode. On the other hand, both of the PI and PII peak
currents vary linearly with 1/2 and pass through the origin sug-
gesting a diffusion-controlled process, that is, the anodic process
is associated with the diffusion-controlled adsorption of Br− at the
Au (poly) electrode surface.
Adsorption of Br− was further investigated by monitoring the
open-circuit potential (Eocp ) of the bare Au (poly) electrode upon
the injection of KBr into N2 -saturated 0.1 M NaOH solution in
which the final concentration of KBr was equal to 5.0 mM. Inset
of Fig. 1 clearly shows that the introduction of KBr into the solu-
tion results in a sharp negative shift of Eocp . The negative shift
of Eocp is obviously related to the spontaneous adsorption of Br−
onto the electrode surface. The negative shift of Eocp implies that
the adsorption proceeded through the donation of electron from
anionic Br− species to the electrode surface. The observed change
of Eocp , therefore, further confirms the adsorption of Br− onto the Au
(poly) electrode surface. Details in this regard have been reported
elsewhere by our group [42,43].
The positions of the anodic and cathodic peaks depend on the
concentration of Br− . The dependence of the peak potential (at
a constant scan rate) on the logarithm of the Br− concentration
follows the relation [52]:
2.303RT
 RT   f 
Ep = Ero − log CBr− +
nF F 2
where Ep is the peak potential for equilibrium condition, Ero is the
standard potential for electrosorption of the adsorbed species, n is
1573
Fig. 3. Typical CVs obtained at the Au (poly) electrode in N2 -saturated 0.1 M NaOH
solution containing (a) 5 and (b) 20 mM KBr. Potential scan rate: 0.1 V s−1 . Inset
shows the linear plots of the cathodic peak (PI and PII ) potential vs. log[Br− ].
the number of electrons involved in the electrosorption reaction,
f is the Frumkin interaction parameter and the other parameters
have their usual meanings. The CVs were obtained in N2 -saturated
0.1 M NaOH solution containing 5, 10, 15 and 20 mM Br− . For clarity,
the CVs obtained only in cases of 5 and 20 mM Br− are presented in
Fig. 3. The cathodic peak (PI and PII ) potentials were derived from
the obtained CVs and were plotted as a function of log[Br− ] (inset of
Fig. 3). The linear plots of PI and PII peak potentials have the slopes
of about −64 and −60 mV, respectively. Only the cathodic peak
potentials were considered, as the anodic peak potentials could
not be obtained precisely because of the broad shape of the anodic
peaks. These values of the slopes point out a complete discharge of
Br− to Br(ads) since they are very close to −59 mV for an electrosorp-
tion valency of −1 [52]. Similar values of electrosorption valency of
Br− were obtained by other researchers for the adsorption of Br− at
the Au (1 0 0) electrode surface [41,53]. Based on the obtained value
of the electrosorption valency, the adsorption/desorption process
Br− ion at the Au (poly) electrode surface can be presented by Eq.
(4):
Au + Br(ads) − ⇔ AuBr(ads) + e− (4)
It was also observed that the peak currents (PI, PII, PI and PII )
remain almost unchanged with increasing the concentration of Br−
in the range of 5–20 mM (see Fig. 3), suggesting that no faradic
reaction of Br− takes place within the potential window investi-
gated in this study. In other words, the peak currents are obviously
attributed to the adsorption/desorption of Br− .
3.2. Voltammetric electrooxidation of H2 O2 in Br− -containing
0.1 M NaOH solution
Fig. 4 shows the CVs obtained at the Au (poly) electrode in ini-
tially N2 -saturated 0.1 M NaOH solution containing (a and b) 5.0 and
(c) 0 mM Br− and (a and c) 2.0 and (b) 0 mM H2 O2 . A remarkable
change in the cyclic voltammetric features of H2 O2 was obtained
in the presence of Br− in the solution (compare curves (a) and (c)).
(3) Electrochemical behaviors of H2 O2 at the clean Au (poly) electrode
in alkaline solution have been described in detail in our recent
reports [6,7,42]. The cathodic peak at −0.145 V at the bare Au (poly)
electrode is assigned to the electroreduction of O2 to HO2 − . O2 was
1574 Md.R. Miah, T. Ohsaka / Electrochimica Acta 54 (2009) 1570–1577
Fig. 4. CVs obtained at the Au (poly) electrode in initially N2 -saturated 0.1 M NaOH
solution containing (a and b) 5.0 and (c) 0 mM Br− and (a and c) 2.0 and (b) 0 mM
H2 O2 . The symbol (*) represents the initial potential in all cases. Potential scan rate:
0.1 V s−1 . Inset shows the Eupper dependence of the cathodic peak current at −0.145 V
in the voltammogram (c).
generated by the (i) electrochemical oxidation of H2 O2 at potential
above 0 V and (ii) chemical decomposition of H2 O2 catalyzed by
the bare Au (poly) electrode surface. This peak current was found
to depend strongly on the initial upper potential limit (Eupper ). Inset
of Fig. 4 clearly shows that the peak current diminished gradu-
ally as Eupper shifted to negative direction of potential. As Eupper
became more negative, the electrochemical oxidation reaction of
H2 O2 to generate O2 became less feasible resulting in less con-
Fig. 5. Linear plots of the (a) anodic and (b) cathodic peak currents vs. the square
root of scan rate. Inset shows the linear plots of the (a ) anodic and (b ) cathodic peak
potentials vs. log . Both of the peak currents and peak potentials were derived from
CVs obtained in initially N2 -saturated 0.1 M NaOH solution containing 5.0 mM Br−
and 2.0 mM H2 O2 over scan rate ranging from 0.002 to 1.0 V (not shown).
centration of O2 and consequently the cathodic peak current at
−0.145 V diminished. A small cathodic current was observed even
when Eupper was −0.135 V, where the oxidation of H2 O2 to gener-
ate O2 is not feasible at all. The origin of this small peak current
is the generation of O2 during the previous measurements of the
CVs. Stirring the solution, after recording the previous CVs, almost
completely diminished this peak current. However, small cathodic
current still appeared because of the heterogeneous decomposition
of H2 O2 to O2 at the bare Au (poly) electrode surface. H2 O2 -free
O2 -saturated 0.1 M NaOH solution also gave the cathodic peak at
the same potential for the O2 reduction to HO2 − . Therefore, the
peak current at −0.145 V in the absence of Br− ion is undoubt-
edly assigned to the O2 reduction reaction although N2 -saturated
solution was initially used. A remarkably high peak current for the
oxidation of HO2 − to O2 was achieved in the presence of Br− . Unlike
the bare electrode, the oxidation peak current (jpa ) in the presence
of Br− appeared at −30 mV (Epa ). The oxidation peak current is ca.
five times higher than the potential-independent plateau current at
the bare Au (poly) electrode above 0 V for the same concentration of
H2 O2 . The enhancement of the oxidation current in the presence of
Br− is correlated to the increased electrostatic attraction between
the anionic HO2 − molecules and the Br(ads) -adlayer-induced posi-
tively polarized Au (poly) electrode surface (discussed later). In the
reverse scan, a cathodic peak current (jpc ) assigned to the reduc-
tion of the produced O2 to HO2 − appeared at −0.21 V (Epc ). The
ratio of jpa to jpc is close to 1 indicating a reversible response of the
HO2 − /O2 redox couple in the presence of Br− in 0.1 M NaOH solu-
tion. The formal potential (E◦ ), estimated as the average of Epa and
Epc (i.e., (Epa + Epc )/2) is −120 mV vs. Ag|AgCl|NaCl (sat.) in 0.1 M
NaOH solution. The peak-to-peak separation is 180 mV which is
larger than theoretical value for the 2-electron reversible process.
The larger peak-to-peak separation is associated with the nega-
tive shifting of the cathodic peak current by the Br(ads) -adlayer that
creates an additional activation barrier for the O2 reduction reac-
tion (compare curves a and c). Therefore, the most notable feature
is that the potential-independent HO2 − oxidation at the bare Au
(poly) electrode is transformed into a reversible redox reaction for
Fig. 6. LSVs obtained at the Au (poly) electrode in N2 -saturated 0.1 M NaOH solution
containing 5.0 mM KBr and (a) 0, (b) 2.0, (c) 4.0 and (d) 6.0 mM H2 O2 . Potential scan
rate: 0.1 V s−1 . Inset shows the linear plot of the peak current vs. concentration of
H2 O2 . Data were taken from Fig. 6.
 Md.R. Miah, T. Ohsaka / Electrochimica Acta 54 (2009) 1570–1577 1575

the HO2 − /O2 couple at the Br(ads) -submonolayer-coated Au (poly)

electrode in Br− -containing 0.1 M NaOH solution.
Both of the anodic and cathodic peak currents were recorded at
scan rates () ranging from 0.002 to 1.0 V s−1 and the peak currents
were plotted as a function of 1/2 . The results are shown in Fig. 5.
We can see that both of the peak currents nicely (r2 = 0.999) fall on
their individual straight lines passing through the origin suggesting
that the reactions corresponding to the anodic and cathodic peaks
are solely controlled by diffusion of the analytes, i.e., HO2 − and O2 ,
respectively, to the electrode surface. The peak potentials were also
plotted as a function of log  (inset of Fig. 5). Both of the anodic and
cathodic peak potentials fall on their individual straight lines having
slopes equal to +0.0457 and −0.0636 V decade−1 , respectively. From
these slopes the anodic and cathodic electron transfer coefficients
were calculated as 0.64 and 0.46, respectively [54].
Linear sweep voltammograms (LSVs) were obtained at the Au
(poly) electrode in 0.1 M NaOH solution containing 5.0 mM KBr and
various amounts of H2 O2 in the range of 2.0–6.0 mM. The results
are shown in Fig. 6. The anodic peak current increases with increas-
ing the concentration of H2 O2 . The peak current was plotted as a
function of the concentration of H2 O2 . Inset of Fig. 6 shows that
the points nicely fall on a straight line passing through the origin.
This observation further suggests that the anodic peak current is
associated with the oxidation of H2 O2 .

3.3. Amperometric electrooxidation of H2 O2 in Br− -containing

0.1 M NaOH solution

Fig. 8. (A) Schematic illustration of the induction of positive polarization of Au

Fig. 7 shows the chronoamperograms obtained at the Au (poly)
electrode in N2 -saturated 0.1 M NaOH solution containing (a–d) 2.0
and (e) 0 mM H2 O2 and (a–c and e) 5.0 and (d) 0 mM Br− at various
specified potentials (Esp ): (a) −0.05, (b) 0.05 and (c–e) 0.2 V. In all
cases, the potential was stepped from an initial value of −0.2 V. The
results obtained in the presence of Br− clearly show several fea-
tures: (i) the current at all the examined Esp is relatively higher as
(poly) electrode surface by the Br(ads) -adlayer. (B) Enhanced electrostatic attraction
between the anion HO2 − molecules and Br-adlayer-induced positively polarized Au
(poly) electrode surface for enhancing the oxidation of H2 O2 .
compared with the bare electrode only at the shorter time (t < 10 s),
(ii) the highest current was obtained at the lowest applied Esp and
vise versa, (iii) the current decreased rapidly with time and (iv)
the decrease of current became more pronounced with increas-
ing Esp . The observed current–Esp relationship in Br− -containing
solution could be correlated to the value of  Br at the applied
Esp . The value of  Br increases with the increase of the applied
electrode potential [34,35]. For clarification of the increase of  Br
with Esp , the chronoamperograms were also obtained at (a ) −0.05,
(b ) 0.05 and (c ) 0.2 V in Br− -containing solution in the absence
of H2 O2 and the results are presented in the inset of Fig. 7. Curve
(d ) was obtained in 0.1 M NaOH solution in the absence of both of
Br− and H2 O2 . The higher observed anodic currents (curves a –c )
as compared to the background response (curve d ) are obviously
attributed to the potential-induced adsorption of Br− at the Au
(poly) electrode according to the Eq. (4) as presented in the ear-
lier section. The sequence of the current density clearly implies
that  Br increases with increasing Esp . We assume that the oxida-
tion reaction of H2 O2 takes place at the free space (bare portion)
of the Au (poly) electrode surface (discussed later). At lower Esp ,
higher oxidation current, therefore, was obtained because of lower
 Br . With increasing Esp , the oxidation current decreased owing to
the increase of  Br although H2 O2 oxidation is expected to become
more feasible at higher electrode potential.

3.4. Mechanism of enhanced electrooxidation of H2 O2 in

Fig. 7. Chronoamperograms obtained at the Au (poly) electrode in N2 -saturated
0.1 M NaOH solution containing (a–d) 2.0 and (e) 0 mM H2 O2 and (a–c and e) 5.0
and (d) 0 mM Br− by stepping the potential from an initial value of −0.2 V to var-
ious specified potentials (Esp ): (a) −0.05, (b) 0.05 and (c–e) 0.2 V. Inset shows the
chronoamperograms obtained at (a ) −0.05, (b ) 0.05 and (c and d ) 0.2 V keeping
other conditions the same as Fig. 7 except for the absence of H2 O2 .
Br− -containing solution
Monovalent Br− undergoes an oxidative adsorption by transfer-
ring one electron to the electrode surface, resulting in an adlayer
of neutral Br(ads) -adatoms [41,53]. Br atoms, being more elec-
tronegative than Au atoms, induce a positive polarization of the
1576 Md.R. Miah, T. Ohsaka / Electrochimica Acta 54 (2009) 1570–1577
Fig. 9. CVs obtained at the Au (poly) electrode in N2 -saturated 0.1 M NaOH solution
containing 5.0 mM KBr, 2.0 mM H2 O2 and (a) 0, (b) 100 and (c) 200 mM KF. Potential
scan rate: 0.1 V s−1 .
Au (poly) electrode surface by withdrawing electron density from
the electrode surface. Br(ads) -adlayer-induced positive polariza-
tion of the metallic electrode surfaces has also been considered
elsewhere [42,55]. Shifting of the potential of zero charge to neg-
ative potential by about 300 mV in Br− -containing solution as
compared to the Br− -free solution also indicates such a positive
polarization of the electrode surface [32]. In 0.1 M NaOH solu-
tion, H2 O2 essentially exists as anionic HO2 − species as the pH
of the solution is greater than the pKa value (11.6) of H2 O2 . The
anionic HO2 − species feel an electrostatic attraction to the posi-
tively polarized Au (poly) electrode surface (as schematically shown
in Fig. 8) resulting in a tremendous enhancement of the activity
of the Au (poly) electrode towards the electrochemical oxidation
Fig. 10. CVs obtained at the Au (poly) electrode in N2 -saturated (a) 0.1, (b) 0.04 and
(c) 0.02 M NaOH and (d) 0.1 M H2 SO4 solution containing 5.0 mM KBr and 2.0 mM
H2 O2 . Potential scan rate: 0.1 V s−1 .
reaction of HO2 − . Enhanced electrode activity due to the electro-
static force of attraction between the reactant and the oppositely
charged electrode surface has also been considered for other sys-
tems [42,56–58]. If a non-adsorbing electrolyte is added in excess
into the electrolytic solution, then the degree of the electrostatic
force of attraction between HO2 − molecules and the electrode sur-
face should be decreased as the added anions (being excess) will
mostly be attracted to the positively charged electrode surface and
consequently the oxidation current of HO2 − should be decreased.
Fig. 9 clearly shows that the oxidation current drastically decreased
with increasing the concentration of KF, supporting that the electro-
static force of attraction plays a vital role in the enhanced oxidation
of HO2 − . Similar consideration was also made in our previous report
on the reduction of HO2 − at Pb-modified Au (poly) electrode in
iodide-containing alkaline solution [59]. H2 O2 oxidation current
was found to decrease rapidly with decreasing pH of the solution
as the degree of dissociation of H2 O2 decreases with decreasing pH.
In acidic pH the electrode activity was diminished because in acidic
solution H2 O2 no longer exists as HO2 − (see Fig. 10).
4. Conclusions
Br− undergoes an oxidative chemisorption onto the Au (poly)
electrode surface leading to the formation of adlayer of neutral Br-
adatoms. The value of  Br (1.74 × 10−9 mol cm−2 ) is lower than the
full monolayer coverage because of the coadsorption of OH− . The in
situ prepared Br-submonolayer-coated Au (poly) electrode showed
a substantial enhancement of the activity towards the electrochem-
ical oxidation of H2 O2 in alkaline media. As compared with the bare
Au (poly) electrode, the oxidation current at the modified electrode
was about five times higher and the reaction was solely controlled
by diffusion. Br, being more electronegative than Au, induces a pos-
itive polarization of the Au (poly) electrode surface by withdrawing
electron density from the electrode surface. Increased electrostatic
force of attraction between the anionic HO2 − molecules and the
positively polarized electrode surface was considered as a proba-
ble origin of the enhancement of the electrode activity. Increase of
the ionic strength and decrease of pH of the electrolytic solution
supported the proposed mechanism. A further study of evaluating
the kinetic parameters of the oxidation of H2 O2 at the Br(ads) -
submonolayer-coated Au (poly) electrode is in progress.
Acknowledgments
The present work was supported by the Grant-in-Aid for Scien-
tific Research (A) (No. 19206079) to T. Ohsaka, from the Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan
and also from the New Energy and Industrial Technology Devel-
opment Organization (NEDO), Japan. Md. Rezwan Miah thanks the
Government of Japan for awarding of a MEXT scholarship.
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