Electrochimica Acta 92 (2013) 460–467

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

Electrocatalytic glucose oxidation at binary catalyst of nickel and manganese

oxides nanoparticles modified glassy carbon electrode: Optimization of the
loading level and order of deposition
Sayed M. El-Refaei, M.I. Awad, B.E. El-Anadouli, M.M. Saleh ∗
Department of Chemistry, Faculty of Science, Cairo University, Cairo, Egypt

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

Article history: This work addresses the electrocatalytic activity of a new catalyst composed of nickel and manganese
Received 18 October 2012 binary oxides, prepared by electrodeposition, toward glucose electro-oxidation in alkaline medium. Cyclic
Received in revised form voltammetry, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were
16 December 2012
used to characterize those electrocatalysts. It has been found that the electrocatalytic activity critically
Accepted 5 January 2013
depends on the loading level and the order of deposition of the two oxides; the NiOx /MnOx /GC electrode
Available online 11 January 2013
(MnOx deposited first) showed an excellent electrocatalytic activity and stability toward glucose oxida-
tion compared to NiOx /GC, MnOx /GC or MnOx /NiOx /GC electrodes (NiOx deposited first). At the present
Keywords:
Glucose
work conditions, it has found that, the optimum loading level is 60 cycles of MnOx followed by 10 min
Manganese oxide deposition of nickel. At this loading level, it has been found that, the relation between Ip /v1/2 function and
Nickel oxide scan rate gives the characteristic feature of a catalytic process.
Fuel cell © 2013 Elsevier Ltd. All rights reserved.
Nanoparticles

1. Introduction hydroxide has been extensively employed in many electrocatalytic

Electrocatalytic processes involving the oxidation of sugars are
of great interest in many areas, ranging from medical applica-
tions to wastewater treatment; from the construction of biological
fuel cells to analytical applications in the food industry [1–6].
The investigation of glucose electrochemical oxidation began in
1960s and has remained a very active research area [7]. Subsequent
efforts were devoted to the investigation of electrocatalytic sur-
faces and achieving an understanding of the oxidation mechanism
[8–11]. Several reports regarding the electrocatalysis of glucose
oxidation using transition metal oxides, including both bulk and
nanostructures-based electrodes, such as NiO [12], FeOOH [13],
CuO [14], MnO2 [15], RuO2 [16], Cu2 O and Co3 O4 [17,18] have been
cited. Among these oxides NiOx and MnOx are attractive electrocat-
alysts for glucose oxidation. It is also well-known that nickel and
nickel hydroxide exhibit excellent electrocatalytic performance
in alkaline medium [19–21]. Owing to its unique electrocatalytic
effect arising from the unpaired ‘d’ electrons and vacant d-orbitals
associated with the oxidized form of nickel oxy-hydroxide (NiOOH)
that are readily available to bind any adsorbed species, nickel oxy-
processes [22,23].
On the other hand, it was found that MnOx deposited on Pt
electrode enhances glucose oxidation that was rationalized as a
combined effect of two factors; enhancing glucose adsorption on
MnOx and mediating the electrooxidation of glucose. Thus, MnOx
acting not only as a simple electron sink but also as a catalyst i.e.,
catalytic mediator [15,24].
The purpose of the present work is to fabricate a novel binary
electrocatalyst composed of nanoparticles of NiOx /MnOx modified
glassy carbon electrode (GCE). The binary catalyst is fabricated
electrochemically and is characterized by SEM, EDX and cyclic
voltammetry, aiming to study the effect of loading level, order of
electrodeposition of NiOx and MnOx and stability toward glucose
electrooxidation in alkaline medium.
2. Experimental
All chemicals used in this work were of analytical grade and
were purchased from Merck, Sigma Aldrich and they were used as
received without further purification. All solutions were prepared
using second distilled water.

2.1. Measurements
∗ Corresponding author. Tel.: +20 2 3567 6603; fax: +20 2 3567 7556.
E-mail addresses: mahmoudsaleh90@yahoo.com (M.M. Saleh), Electrochemical measurements were performed using an EG&G
mawad70@yahoo.com (M.I. Awad). potentiostat (model 273A) operated with E-Chem 270 software.

0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.01.024
 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467
An electrochemical cell with a three-electrode configuration was
used in this study. A platinum spiral wire and an Ag/AgCl/KCl (sat.)
were employed as counter and reference electrodes, respectively.
All potentials will be presented with respect to this reference elec-
trode. The working electrode was glassy carbon (d = 3.0 mm). It
was cleaned by mechanical polishing with aqueous slurries of suc-
cessively finer alumina powder (down to 0.06 ␮m) then washed
thoroughly with second distilled water. Scanning electron micro-
scope (SEM) images were taken using field emission scanning
electron microscope, FE-SEM (FEI, QUANTA FEG 250).
2.2. Electrode modification
GCE modification with NiOx was achieved in two sequen-
tial steps. First is the potentiostatic deposition of metallic nickel
on the working electrode (i.e., GCE) from an aqueous solution
of 0.1 M acetate buffer solution (ABS, pH = 4.0) containing 1 mM
Ni(NO3 )2 ·6H2 O by applying a constant potential electrolysis at −1 V
for different time durations. Second is the passivation of the metal-
lic Ni in 0.1 M phosphate buffer solution (PBS, pH = 7) by cycling
the potential between −0.5 and 1 V for 10 cycles at a scan rate
of 200 mV/s [25,26]. Then modification with MnOx was achieved
by cycling the potential from 0 to 0.4 in 0.1 M Na2 SO4 contain-
ing 0.1 M Mn(CH3 COO2 )2 ·5H2 O for 60 cycles, then activation for 5
cycles in 0.5 M NaOH solution in the potential range −0.2 to 0.6 V
[27]. The sequence of the deposition of the two catalysts, i.e., NiOx is
deposited first and then MnOx or vice versa was achieved by keep-
ing the number of MnOx cycles constant at 60 cycles and deposition
time of NiOx is changed.
3. Results and discussion
3.1. Morphological and electrochemical characterizations
Fig. 1 shows SEM images taken for bare GC (A), MnOx /GC (B),
NiOx /GC (C), MnOx /NiOx /GC (D), and NiOx /MnOx /GC (E) electrodes.
In image (A), we can see that the GC substrate is featureless
whereas MnOx is deposited as a porous nanorod-texture (image
B) [27]. The NiOx nanoparticles are uniformly deposited on the
GC substrate with average particle size about 90–100 nm (image
C). In image (D) (MnOx /NiOx /GC sample, NiOx is deposited first)
in which MnOx is deposited on NiOx /GC electrode the microstruc-
ture is significantly different than the image of direct deposition
of MnOx on bare GC (image B), it appears as a combined fea-
ture of the images (B) and (C), where particles of NiOx are
partially covered with MnOx and these result is in accordance
with the electrochemical characterization of the prepared elec-
trodes (cf. Fig. 2d). In image (E) (NiOx /MnOx /GC sample, MnOx
deposited first), NiOx is extensively deposited as compared with
image (C). It seems also that NiOx partially cover the previ-
ously deposited MnOx . This means that the previously deposited
MnOx improves the interface properties in such a way that
enhances the deposition of NiOx . Finally it is clear that the orderly
deposition significantly affect the morphology of the deposited
oxides.
It is well known from literatures that, nickel oxide and not
metallic nickel is the appropriate electrocatalyst for alcohols oxi-
dation in alkaline medium [22,23]. Potentiostatic deposition of
nickel from aqueous Ni(NO3 )2 solutions produces metallic nickel.
So in order to convert metallic nickel to nickel oxide, we perform
nickel passivation process as described in Section 2. The first and
the tenth cycles of ten successive potential scans in PBS (pH = 7)
of the passivation process are shown in Fig. 2. A broad oxidation
wave was observed at the first CV corresponding to the passiv-
ation of metallic nickel with a concurrent transformation between
461
the different phases of nickel oxides. The following successive nine
CVs reveal a negligible anodic current, indicating that a complete
passivation of the surface layer of Ni has been achieved during
the first CV cycle. Interestingly, the absence of any significant
reduction peak in the cathodic scan, within the studied potential
range, indicates that the passive nickel oxide nanoparticles are sta-
ble within the employed potential range and operating pH [28].
There are some beneficial quantities for our work must be defined
here; these quantities are Qpass , QNi , Q(Ni+H2) and QH2 , which repre-
sent the charge consumed respectively, during: passivation of the
deposited metallic nickel, deposition of metallic nickel only, simul-
taneous deposition of Ni and hydrogen evolution reaction (h.e.r.)
and the h.e.r. only. So, QNi can be estimated by subtracting QH2
from Q(Ni+H2) (i.e., QNi = Q(Ni+H2) − QH2 ). Any quantity of charges can
be estimated by integrating the area under curve of I–t relation
of the corresponding process. The values of Q(Ni+H2) and Q(H2) are
listed in Table 1 for the different electrodes. From those values,
the thickness of the deposited nickel film for the NiOx /GC elec-
trode was estimated and found to be; 11, 22, 57, 125, 232, and
482 nm for the deposition time 1, 2, 4, 6, 10, and 20 min, respec-
tively. At NiOx /MnOx /GC electrode the thicknesses were found to
equal 13, 33, 99, 160, 269, and 593 nm at the above mentioned
times.
Fig. 3 compares CVs of the (a) bare and the (b–e) modified GCE in
0.5 M NaOH solutions. The CV of the bare GCE (curve a) is feature-
less, as expected. At the MnOx /GC electrode (curve b); a significant
increase in the charging current is shown as a characteristic fea-
ture of MnOx modified electrodes, this featureless CV corresponds
to the continuous change in the valences of Mn following the
anodic and cathodic potential scanning [29–31]. At the NiOx /GC
electrode (curve c) the well-defined redox waves of the surface con-
fined Ni(II)/Ni(III) transformation is observed [28,32]. It has been
reported that, there are four possible phases produced over the
anodic and the cathodic scan for the nickel hydroxide electrode
substrate, namely, ␤-Ni(OH)2 , ␣-Ni(OH)2 , ␤-NiOOH, and ␥-NiOOH.
The transformations between these four phases can be well identi-
fied using Bode diagram [33,34]. It is well known that the formation
of ␥-NiOOH phase is associated with swelling or volume expansion
of nickel film electrodes with subsequent microcracks and disin-
tegrates. Lower inter electrode spacing results in lower internal
resistance and therefore better efficiency of the electrode toward
electrooxidation processes in alkaline medium [35,36]. Therefore,
␤-NiOOH phase is expected to be a better electroactive material
for high electrochemical performance in alkaline solution [35]. The
Ni(II)/Ni(III) conversions occur via two pathways, by a proton dif-
fusion mechanism in which ␤-NiOOH is likely formed (Eq. (1)), and
Table 1
Values of the electronic charge consumed in the hydrogen evolution reaction and
nickel deposition at GCE and MnOx /GC electrode at different time durations.
Time (min) NiOx /GC NiOx /MnOx /GC
a b
QH2 (mQ) Q(Ni+H2) (mQ) QH2 c (mQ) Q(Ni+H2) d (mQ)
1 0.768 2.942 1.356 4.056
2 1.958 6.486 2.231 8.989
4 3.529 15.120 3.718 24.09
6 5.283 30.96 5.549 38.44
10 8.159 55.7 8.800 64.11
20 15.72 114.5 17.84 139.6
a
As estimated from the integration of I–t curve of hydrogen evolution at GC
electrode, at −1 V, from ABS (pH = 4) at different time durations.
b
As estimated by integration of I–t curve of nickel deposition at GC electrode at
−1 V from ABS (pH = 4) containing 1 mM Ni2 (NO3 ) at different times.
c
As estimated by integration of I–t curve of hydrogen evolution at −1 V from ABS
(pH = 4) at different time durations at MnOx /GC electrode.
d
As estimated by integration of I–t curve of nickel deposition at MnOx /GC elec-
trode at −1 V from ABS (pH = 4) containing 1 mM Ni2 (NO3 ) at different times.
462 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467

Fig. 1. FE-SEM images of GCE (A), MnOx /GC (B), NiOx /GC (C) MnOx /NiOx /GC (D), and NiOx /MnOx /GC (E).

by solvent mechanism in which ␥-NiOOH is formed through the NiOx /GC electrode, this is probably due to the partial deposition of
diffusion of OH− (Eq. (2)) [25,26]. MnOx on the previously deposited NiOx consistently with the SEM
images shown in Fig. 1D.
Ni(OH)2 ↔ NiOOH + H+ + e− (1) At the NiOx /MnOx /GC electrode (curve e), where MnOx is firstly
deposited, several features appears.
Ni(OH)2 + OH− ↔ NiOOH + H2 O + e− (2)

Interestingly in the case of the MnOx /NiOx /GC (i) Firstly, the current of the Ni(II)/Ni(III) redox couple is markedly
electrode (curve d), where NiOx is firstly deposited, the current of enhanced, almost the peak current is doubled as compared
the Ni(II)/Ni(III) couple significantly decreases in comparison with with NiOx /GC (curve c). The amount of the deposited Ni
 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467
120
100
80
1st CV
60
40
I/ A
20
10th CV
0 b
-20
-40
-60
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
E / V vs. Ag/AgCl/KCl (sat.)
Fig. 2. The first and tenth cycles of a 10 successive potential cycles obtained at Ni/GC
in 0.1 M PBS (pH = 7) at a scan rate of 200 mV/s.
(estimated from I–t deposition curves), in the case of the
NiOx /GC and NiOx /MnOx /GC equal to 14.4 and 16.7 ␮g, respec-
tively. However, this increase in the amount of the deposited
nickel in case of the binary catalyst cannot account for the sig-
nificant difference in the current between the single and binary
catalyst modified electrodes. It is likely that the enhancement
in the current of the Ni(II)/Ni(III) couple may be attributed to
the increase of the Ni3+ content by doping the NiOx with MnOx .
According to Das et al. [15,24], Mn(IV) can be converted during
the anodic scan to a powerful and unstable oxidant which is
Mn(V), which can convert some of the Ni2+ to Ni3+ resulting in
an increase in the conductivity of the former according to the
following reaction.
Mn(V) + Ni2+ → Ni3+ + Mn(IV) (3)
(ii) The second feature is the positive shift in Ni(II)/Ni(III) redox
couple potential obtained at NiOx /MnOx /GC electrode as com-
pared with the NiOx /GC electrode (curve c) pointing to the
enhancement of the kinetics of Ni(II)/Ni(III) redox couple.
(iii) The third feature is, the charging current of MnOx /GC electrode
significantly decreases upon the deposition of the NiOx on the
MnOx /GC, almost the response obtained at NiOx /GC (curve c) in
the potential range −0.2 to 0.3 V is restored after the deposition
of NiOx onto MnOx /GC. This is certainly due to the deposition
of NiOx onto the previously deposited MnOx . The significant
enhancement in Ni(II)/Ni(III) couple is consistence with the
heavy deposition of NiOx revealed by SEM (Fig. 1E).
Fig. 4 compares CVs of (A) NiOx /GC and (B) NiOx /MnOx /GC elec-
trodes at different loading levels of NiOx in 0.5 M NaOH solutions.
Note that, the current scale in the two cases is different. In the case
of the NiOx /GC electrode (A), as the loading level of the deposited
NiOx increases, several features appears, firstly, the Ni(II)/Ni(III)
redox couple transformation current increases regularly. Secondly,
the peak potential in general is constant except for the final loading
level (20 min) in which the peak potential is shifted to more positive
values. This could be attributed to the higher energies (potential)
required for NiOOH nucleation at this loading level as the amount of
deposited nickel is significantly large. In the case of NiOx /MnOx /GC
electrode (B), the same behavior occurs, taking into account that the
current for Ni(II)/Ni(III) transformations increases markedly than
that of the NiOx /GC at each relevant loading, and this is attributed
to the crucial role of MnOx as mentioned above. The peak poten-
tial of Ni2+ oxidation (Epa ) shifts to more positive values with the
463
e
100µA
d
c
a
-0.2 0.0 0.2 0.4 0.6
E / V vs. Ag/AgCl/KCl (sat.) (sat.)
Fig. 3. CVs for different electrodes in 0.5 M NaOH solution: bare GC (a), MnOx /GC
(b) NiOx /GC (c), MnOx /NiOx /GC (d) and NiOx /MnOx /GC (e). Scan rate = 100 mV/s.
increase of the loading level. In general, Epa is more positive in the
case of NiOx /MnOx /GC than in the case of NiOx /GC.
3.2. Electrocatalytic oxidation of glucose at the modified
electrodes
The glucose oxidation reaction at the GC and MnOx /GC elec-
trodes has been studied (data note shown). It was found that the
bare GCE is ineffective toward the oxidation of glucose. While at
the MnOx /GC electrode, at the same conditions, the CV is char-
acterized by large charging current as a characteristic feature of
MnOx modified electrode [29–31]. However, on addition of glu-
cose, the oxidation current is enhanced. It has been reported that
glucose oxidation is electrocatalyzed at MnOx modified electrodes
[15,24]. That is to say Mn(IV) is oxidized to Mn(V), then, in a fol-
lowing chemical step, glucose is oxidized according to Eq. (4), i.e.,
EC mechanism.
Mn(V) + glucose → Mn(IV) + products (4)
Fig. 5 shows LSV responses obtained at NiOx /GC (a),
MnOx /NiOx /GC (b) and NiOx /MnOx /GC (c) electrodes in 0.5 M
NaOH solutions containing 20 mM glucose (inset shows the blank
responses). At the NiOx /GC electrode (curve b) glucose oxidation is
markedly enhanced; glucose molecules adsorbed on the surface are
oxidized at higher potentials parallel to the oxidation of Ni(II) oxide.
The later process has the consequence of decreasing the number of
sites for glucose adsorption, along with the poisoning effect of the
products or intermediates of the reaction. This tends to decrease
the overall rate of the glucose oxidation. Thus, the anodic current
passes through a maximum as the potential is anodically swept.
A number of mechanisms have been reported for the electroox-
idation of alcohols on Ni in alkaline solutions. Those mechanisms
can be summed up into two ways; while Fleischmann et al. [37,38]
assumed catalytic/intermediate role for NiOOH, others [39,40]
reported that methanol oxidation takes place after complete con-
version of Ni(OH)2 to NiOOH in the course of an anodic potential
sweep. So we assume that a part of the anodic current is due to glu-
cose oxidation by NiOOH and a part of the current is due to glucose
oxidation on the surface of oxide layer by direct electrooxidation.
The redox transition of nickel species from Ni(II) to Ni(III) occurs,
then in a following step glucose is oxidized on the modified surface
via the following reaction:
Ni(III) + glucose → intermediate + Ni(II) (5)
Ni(III) + intermediate → products + Ni(II) (6)
464 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467

A
100
NiOx/GC

50

I/ A
0

1 min
2 min
4 min
-50 6 min
10 min
20 min
GC
-100
-0.2 0.0 0.2 0.4 0.6

E / V vs. Ag/AgCl/KCl (sat.)

NiOx/MnOx/GC
100

0
I/ A

1 min
2 min
-100 4 min
6 min
10 min
20 min
GC

-200
-0.2 0.0 0.2 0.4 0.6

E / V vs. Ag/AgCl/KCl (sat.)

Fig. 4. CVs of (A) NiOx /GC and (B) NiOx /MnOx /GC, with different NiOx loading level, in 0.5 M NaOH solution at a scan rate 100 mV/s.

Where Ni3+ sites are regenerated by the power source and on the
Ni3+ oxide surface by direct electrooxidation [39,40]:
Ni(III)–glucose → Ni(III)–intermediate
Ni(III)–intermediate → Ni(III)–products
Eqs. (5) and (6) are according to the Fleischmann mechanism
[37,38], and in Eqs. (7) and (8) Ni3+ is used as an active surface for
glucose oxidation. Gluconolactone [41,42] as well as methanoates
and oxalates [4,43] have been reported as the oxidation products
of glucose electrooxidation.
The glucose oxidation at MnOx /NiOx /GC and NiOx /MnOx /GC
electrodes in 0.5 M NaOH is shown as curves b and c, respectively.
It is obvious that the order of the deposition of the nano-MnOx
and NiOx dramatically affects the performance of the binary cata-
lyst. For instance the peak current for glucose oxidation is much
higher in the case of NiOx /MnOx /GC and the onset potential of
glucose oxidation shifted to more positive values in the case
of NiOx /MnOx /GC (c) compared to MnOx /NiOx /GC (a). When the
MnOx /NiOx /GC is used (NiOx is deposited first) (curve b), the
activity significantly decreases. However, the highest response
(7)
is obtained on the NiOx /MnOx /GC electrode, i.e., when MnOx is
(8) firstly deposited followed by the electrodeposition of NiOx . The
larger response at the binary catalyst NiOx /MnOx /GC in compar-
ison with NiOx /GC electrode may be the result of two factors;
firstly, glucose is expected to be adsorbed quite easily on MnOx
due to the possibility of hydrogen bond formation using the
multiple hydroxyl groups present in the molecule [15,24]. Thus
the accessibility of glucose at the electrode surface increases. In
addition, MnOx plays a significant role; Ni2+ can be oxidized to
Ni3+ by the strong oxidant Mn(V), which increases the concen-
tration of Ni3+ in the matrix. As result of this the conductivity
of the matrix increases and this leads to enhancing the glucose
oxidation [15,24].
According to Fig. 3d, the current of the Ni2+ /Ni3+ couple
decreases upon the deposition of MnOx on the NiOx /GC indicating
 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467 465

1200 700
150 A
100 c` 600 1 min NiOx/GC
1000
50
a`c` 2 min
b` a` 4 min
500
I/ A

0 6 min
800
c 10 min
-50 400 20 min 6
600 -100

I/ A
I/ A

300
-150
5
-0.2 0.0 0.2 0.4 0.6 a
400 200 4
E / V vs. Ag/AgCl/KCl (sat.)
a` 3
200 100
2
b 1
0
0

-100
-0.2 0.0 0.2 0.4 0.6
-200
-0.2 0.0 0.2 0.4 0.6
E / V vs. Ag/AgCl/KCl (sat.)
E / V vs. Ag/AgCl/KCl (sat.)
1200
B
Fig. 5. LSV responses obtained at (a) NiOx /GC, (b) MnOx /NiOx /GC, and (c) NiOx/MnOx/GC
1 min
NiOx /MnOx /GC electrodes in 0.5 M NaOH solutions containing 20 mM glucose at 1000 2 min
a scan rate 100 mV/s. Inset shows CV responses obtained at (a ) NiOx /GC, (b )
4 min
MnOx /NiOx /GC, and (c ) NiOx /MnOx /GC electrodes in glucose-free 0.5 M NaOH solu- 6 min
tion at a scan rate of 100 mV/s. 800 10 min
20 min
600
partial coverage of the previously deposited NiOx . It becomes clear I/ A 6
that the exposition of the two oxides is essential for the electrocat-
400 5
alytic oxidation of glucose. 4
3
200 2
3.3. Effect of the loading level of NiOx
1
0
The extent of NiOx loading level has been investigated at the
GC and MnOx /GC electrodes (MnOx loading is kept constant at 60
-200
cycles for all experiments), toward the electrocatalytic oxidation -0.2 0.0 0.2 0.4 0.6
of glucose. NiOx and MnOx were electrodeposited (as described in
E / V vs. Ag/AgCl/KCl (sat.)
Section 2.2). As mentioned above, NiOx is responsible for the elec-
trocatalytic oxidation of glucose due to presence of the Ni(II)/Ni(III) Fig. 6. LSV response obtained at (A) NiOx /GC, (B) NiOx /MnOx /GC with different load-
redox couple; so small loadings of the NiOx at the GCE results in a ing levels of NiOx in 0.5 M NaOH solutions containing 20 mM glucose at a scan rate
significant enhancement in the electrocatalytic activity of the GCE of 100 mV/s. In panel (B) the MnOx loading is fixed 60 cycles of MnOx deposition.
toward glucose oxidation. Fig. 6 compares linear scan vlotammo-
grams of NiOx /GC (A) and NiOx /MnOx /GC (B) electrodes, at different
characteristic feature of catalytic reactions [44]. It becomes clear
loading levels of NiOx deposition in 0.5 M NaOH solution con-
that the deposition of NiOx onto MnOx /GC modified electrode sig-
taining 20 mM glucose, At both electrodes, as the loading level
nificantly enhances the glucose electrooxidation via a dual role
of NiOx increases, the peak current of glucose oxidation increase
exerted by the mixed oxides; one (MnOx ) enhances the adsorption
and the onset potential shifts to higher positive values. This is con-
of glucose followed by the mediation by the second oxide (NiOx ) in
sistent with the voltammetric behavior shown in Fig. 4, in which
an EC mechanism as represented by Eqs. (4) and (5) and confirmed
also the highest loading, shows a significant positive potential
by the Ip /v1/2 –v relation.
shift.
In order to get further insight, Tafel plot of E vs. log I was
Fig. 7 shows the relations between Ip against QNi and Qpass for
plotted using the data of the arising part of the current–voltage
NiOx /GC and NiOx /MnOx /GC electrodes in 0.5 M NaOH containing
at scan rate 5 mV/s for a 0.5 M NaOH containing 20 mM glucose
20 mM glucose. For the NiOx /GC electrode (curves (A, B)), as the
(Fig. 8). Where Tafel slopes for MnOx /NiOx /GC (a), NiOx /GC (b)
amount (QNi ) of deposited nickel and (Qpass ) of the NiOx increase,
and NiOx /MnOx /GC (c) are 115.25, 108.44 and 113.54 mV decade−1 ,
the peak current of glucose oxidation increases until it approaches
respectively. The nominal similarity of the Tafel slopes (average
nearly constant values at higher loading levels. Similar behav-
value ca. 112 mV decade−1 ) indicates that, glucose oxidation pro-
ior is obtained at NiOx /MnOx /GC electrode (curves C and D) but
ceeds via a common rate-determining step in the all cases, which
with much higher current. At NiOx /MnOx /GC, at large loading level
is one-electron transfer step (Eq. (5)).
(20 min), a slight decrease in the peak current occurs. However, the
peak current is much larger than the relevant one at NiOx /GC elec-
trode of the same time of deposition. Thus the optimum loading 3.4. Long-term stability of the prepared electrocatalysts
level for NiOx /MnOx /GC under the present conditions is 60 poten-
tial cycles for the deposition of MnOx followed by 10 min deposition One of the main objectives of using binary oxide of NiOx and
of nickel. MnOx is to enhance the stability of the NiOx (the active oxide) mod-
The effect of scan rate on the electrooxidation of glucose at ified GCE. So, to investigate the stability of the proposed catalysts,
the optimum loading level was performed (data not shown), and current–time curves were recorded for glucose oxidation at the
it was found that, at scan rate larger than 100 mV/s, the Ip /v1/2 proposed electrodes at a constant potential of 0.5 V and 0.52 V for
functions does not change significantly with the scan rate, as a NiOx /GC and NiOx /MnOx /GC electrodes respectively and data are
 466 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467

1000 1000
A B
800 800

NiOx/GC NiOx/GC
600 600

Ip / A
Ip / A

400 400

200 200

0 0
0 20 40 60 80 100 0 200 400 600 800 1000

QNi (mQ) Qpass ( Q)

C
1000
1000
D
800
800

NiOx/MnOx/GC NiOx/MnOx/GC
Ip / A

600
Ip / A 600

400
400

200 200

0 0
0 20 40 60 80 100 120 0 200 400 600 800 1000 1200

QNi (mQ) Qpass ( Q)

Fig. 7. (A, C) Effect of QNi (charge consumed during Ni electrodeposition) on the peak current of glucose oxidation at NiOx /GC and NiOx /MnOx /GC, respectively, and (B, D)
effect of Qpass (charge consumed during Ni passivation) on the same peak current for NiOx /GC and NiOx /MnOx /GC, respectively, in 0.5 M NaOH containing 20 mM glucose.

0.46 350
NiOx/GC b a c
MnOx/NiOx/GC 300
0.44 NiOx/MnOx/GC
E / V vs. Ag/AgCl/KCl (sat.)

250
0.42
200
b
I/ A

0.40
150

0.38
100
a
0.36 50
NiOx/GC
NiOx/MnOx/GC
0
0.34
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8
0 50 100 150 200
-2
log(I/ ACm ) time (min)
Fig. 8. Tafel plots for (a) MnOx /NiOx /GC, (b) NiOx /GC and (c) NiOx /MnOx /GC elec- Fig. 9. Current–time relation obtained during glucose oxidation at (a) NiOx /GC,
trodes in 0.5 M NaOH solution containing 20 mM glucose at a scan rate 5 mV/s. (b) NiOx /MnOx /GC in 0.5 M NaOH containing 20 mM glucose at 0.5 V and 0.52 V,
respectively.

shown in Fig. 9. This figure depicts that, NiOx /MnOx /GC electrode 3.5. Conclusions
supports higher oxidation current than that obtained at NiOx /GC
electrode. This level of enhancement could still be observed after A novel binary catalyst of nickel and manganese oxide, with con-
3 h of continuous measurement. This indicates a better mechanical siderable stability, was electrochemically fabricated on the GCE in
stability and good adhesion of the coexisting oxides. a consecutive manner. It was found that electrochemical activity
 S.M. El-Refaei et al. / Electrochimica Acta 92 (2013) 460–467
toward glucose oxidation depends critically on the loading level
and order of electrodeposition of the two catalysts. Under the
present conditions, it has been found that, the optimum loading
level is 60 cycles of MnOx followed by 10 min of nickel deposition.
At this loading level, the relation between Ip /v1/2 function and scan
rate gives the characteristic feature of a catalytic process. The rate
determining step was found to be one electron transfer process,
which demonstrates the catalytic role of nickel hydroxide.
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