Journal of Electroanalytical Chemistry 735 (2014) 3642

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Electrochemical synthesis of mixed-valence manganese/copper hybrid

composite using graphene oxide and multi-walled carbon nanotubes for
nonenzymatic glucose sensor
Kuo-Chiang Lin, Lin-Hsiang Huang, Shen-Ming Chen
Electroanalysis and Bioelectrochemistry Lab, Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao
East Road, Taipei 106, Taiwan

a r t i c l e

i n f o

Article history:
Received 24 July 2014
Received in revised form 19 September 2014
Accepted 8 October 2014
Available online 20 October 2014
Keywords:
Glucose sensor
Graphene oxide
Carbon nanotubes
Manganese
Copper

a b s t r a c t
Electrochemical synthesis of mixed-valence manganese/copper hybrid composite has been successfully
performed using graphene oxide (GO) and multi-walled carbon nanotubes (MWCNT) as a conductive
and steric hybrid nanotemplate. The MnCu/MWCNT/GO hybrid composite shows compact and nanoporous structure due to high conductivity and high specic surface of the MWCNT/GO nanotemplate. XRD
result indicates a mixed-valence hybrid composite including copper manganese oxide (CuMn2O4), tenorite (CuO), and hausmannite (Mn3O4). It is electroactive, pH-dependent, and stable in the electrochemical
system. It shows eletrocatalytic activity to glucose oxidation with high current response and low overpotential by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and differential pulse voltammetry
(DPV). Particularly, DPV shows lower oxidation peak potential (Epa = 0.05 V) due to suitable control of
pulse parameters. CV, LSV, and DPV response of MnCu/MWCNT/GO shows linear correlation between
current response and glucose concentration estimated with sensitivity of 49.1, 58.6, and 59.3 lA mM1
cm2, respectively. It shows linear concentration range of 132 mM with a detection limit of
1  106 M (S/N = 3). Coimmobilization and activity of manganese/copper hybrid composite can be
effectively enhanced by MWCNT/GO. The MnCu/MWCNT/GO sensor shows high recovery and low
coefcient of variation in bovine serum albumin samples for nonenzymatic glucose sensor.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Regular measurements of blood glucose levels are required to
determine whether the treatments are working effectively for diabetic patients [1]. Enzyme-modied electrodes have some disadvantages, such as instability, the high cost of enzymes,
complicated immobilisation procedures, and critical operating
conditions. Therefore, considerable attention had been paid to
developing nonenzymatic electrodes to overcome these problems.
The direct electrocatalytic oxidation of glucose at a nonenzymatic
electrode would have advantages over enzymatic electrodes.
Recently, efforts to develop a practical nonenzymatic glucose sensor have been centred on achieving a breakthrough in electrocatalysis. In this context, different substrates, such as platinum [2], gold
[3], copper [4], alloys (containing Pt, Pb, Au, Pd, Ir, and Ru) [58],
and metal oxidates (IrO2, MnO2, and CuO) [911], have been
studied. The most important nding in this area to date is that

Corresponding author. Tel.: +886 2 27017147; fax: +886 2 27025238.

E-mail address: smchen78@ms15.hinet.net (S.-M. Chen).
http://dx.doi.org/10.1016/j.jelechem.2014.10.009
1572-6657/ 2014 Elsevier B.V. All rights reserved.

the highly active surface area of the electrode material plays a

key role in the electrooxidation of glucose.
During recent years, nanomaterials, such as carbon nanotubes
(CNTs) and transition metallic nanoparticles (NPs), have been
widely applied in sensors and biosensors. CNTs are an attractive
material for electroanalysis due to their high surface/volume ratio
and chemical stability [1215]. Transition metallic NPs, including
gold (Au), platinum (Pt), palladium (Pd), copper (Cu), nickel (Ni),
and silver (Ag), can be used to increase electrochemical activities.
Sensors and biosensors modied with metallic NPs have demonstrated good performances due to their increased surface area
and enhanced mass transport and catalysis as well as good biocompatibility, with control over the microenvironment, relative
to macroelectrodes [1517]. Therefore, their use has been an
important strategy in the construction of glucose nonenzymatic
sensors with nanomaterials, such as nanoporous Pt electrodes
[18,19] and electrodes modied with CNTs [20,21], Ni NPs [22],
Au NPs [23,24], Cu NPs [25,26], CNTs with Cu NPs [27,28], and
CNTs with Ni and Cu NPs [29].
Graphene oxide (GO) consists of a single atomic layer of
sp2-hybridized carbon atoms functionalized with mainly phenol,

K.-C. Lin et al. / Journal of Electroanalytical Chemistry 735 (2014) 3642

hydroxyl, and epoxide groups on the basal plane and ionizable carboxyl groups at the edges; it is obtained after treating graphite
with strong oxidizers. GO can form stable single-layer aqueous dispersions due to the charge repulsion of the ionized edge acid
groups. As a derivatized graphite nanomaterial, GO features a
highly hydrophobic surface with non-oxidized polyaromatic nanographene domains on the basal plane. The abundance of highly
conjugated structures on the surface of GO allows it to adhere
readily to conjugated materials through pp interactions, making
GO function as a unique tethered 2D surfactant sheet [3035].
Recently, many studies have conrmed that GO is a good candidate
for use as an advanced carbon material in electrochemical applications [3638]. Because CNTs and GO exhibit many similar properties, while being structurally dissimilar, then on covalent
preparation of rGO/CNT composites provides attractive building
blocks for the development of nanocarbon materials with potentially improved conductivity and catalytic ability for electrochemical research.
High sensitivity and fast amperometric detection of glucose had
been reported using the methods mentioned above due to an
increase in the electrocatalytic active area and the promotion of
electron transfer in glucose oxidation reactions. However, its complicated for a directly and wildly used screen printed carbon electrode in the practical applications due to the difculty of electrode
rotation in the pre-study by amperometry. In order to overcome
this issue, we present a study focused on the electrochemical synthesis of manganese/copper hybrid composite using CNTs and GO
by different electrochemical techniques, including cyclic voltammetry (CV), linear sweep voltammetry (LSV), and differential pulse
voltammetry (DPV), respectively.
In the present work, the facile electrocatalytic oxidation of glucose was demonstrated by the MnCu/MWCNT/GO hybrid nanocomposites. Manganese acetate and copper sulphate were used
to prepare manganese/copper hybrid composite on a MWCNT/
GO-modied electrode by electrochemical synthesis. The mixedvalence nanoporous composite was studied by XRD and SEM. The
electrocatalytic properties of MnCu/MWCNT/GO for glucose oxidation was investigated and compared with other modiers including GO, MnCu, and MnCu/GO. The composite modied screen
printed carbon electrode (SPCE) was also used to determine glucose in bovine serum albumin (BSA) samples.
2. Experimental
2.1. Reagents and materials
Glucose, manganese acetate, copper sulphate, and multi-walled
carbon nanotubes (MWCNT) were purchased from SigmaAldrich
(USA) and were used as-received. All other chemicals (Merck) used
were of analytical grade (99%). Double-distilled deionized water
(>18.1 MX cm1) was used to prepare all the solutions. All other
reagents were of analytical grade and used without further purication. A pH 5.5 acetic solution was prepared with 0.1 M sodium
acetate and adjusted to pH 5.5 by acetic acid.
2.2. Apparatus and measurements
The MnCu/MWCNT/GO hybrid composite was characterized by
cyclic voltammetry (CV), SEM, linear sweep voltammetry (LSV),
and differential pulse voltammetry (DPV). A glassy carbon electrode (GCE) purchased from Bioanalytical Systems (BAS) Inc.,
USA. A screen printed carbon electrode (SPCE) was purchased from
Zensor Inc., TW. All GCEs and SPCEs were used with diameter of
0.3 cm (exposed geometric surface area of A = 0.0707 cm2) for all
electrochemical techniques. Electrochemical experiments were

37

completed by a CHI 1205a electrochemical workstation (CH Instruments, USA) with a conventional three-electrode setup containing
a GCE or a SPCE (working electrode), an Ag/AgCl (3 M KCl) (reference electrode), and a platinum wire (counter electrode). The buffer solution was entirely deaerated using nitrogen gas atmosphere.
The morphological characterization of composite lms was examined by means of SEM (S-3000H, Hitachi). Indium tin oxide (ITO)
substrates were used in morphological and composite analysis
for convenience.
2.3. Preparation of manganese/copper hybrid composite using MWCNT
and graphene oxide
The electrodeposition of manganese/copper hybrid composite
was carried out in pH 5.5 acetic solution containing 0.2 M manganese acetate and 0.1 M copper sulphate by consecutive cyclic voltammetry. Potential cycling was controlled in the potential range
of 0.6 to +0.6 V with scan rate of 0.1 V s1 and 20 scan cycles.
Bare, GO, and MWCNT/GO modied electrodes were used to study
the electrodeposition of manganese/copper hybrid composite.
These modiers were noted as MnCu, MnCu/GO, and MnCu/
MWCNT/GO, respectively.
The MWCNT/GO modied electrode was prepared by two steps:
rstly, the electrochemical reduction of graphene oxide (GO), then,
the adsorption of MWCNT. The electrochemical reduction of graphene oxide was carried out in 0.5 M sulphuric acid containing
0.5 mg ml1 GO solution. It was achieved by employing consecutive cyclic voltammetry in the potential range of 0.5 to 1.2 V
(15 scan cycles, scan rate = 0.05 V s1). All MWCNT were carboxylic-functionalized and well-dispersed in double distillationdeionized water (1 mg ml1) with sonication for 10 min before
using [39]. By drop casting method, 10 ll of the MWCNT solution
was dropped on electrode surface and dried out in the oven at
40 C. After this procedure, it was mentioned as MWCNT/GO
modied electrode for convenience. It was used to have the electrodeposition of manganese/copper hybrid composite as aforementioned. After these procedures, the MnCu, MnCu/GO, and
MnCu/MWCNT/GO modied electrodes were prepared to study.
3. Results and discussion
3.1. Preparation and characterization of MnCu/MWCNT/GO hybrid
composite
The electrodeposition of manganese/copper hybrid composite
was studied with bare, GO, and MWCNT modied glassy carbon
electrode (GCE) by consecutive cyclic voltammetry. Generally,
electrodeposition of different metal ions (Mn and Cu ions) might
suffer the competition problem resulted in poor electrodeposition.
Fig. 1A shows the voltammogram of manganese/copper hybrid
composite electrodeposition using a bare GCE. In the rst scan segment (negative scan), it shows two signicant cathodic peaks
related to the electroreduction of Mn and Cu ions, respectively.
In the second scan segment (positive scan), it shows two anodic
peaks corresponded to the oxidation of manganese/copper hybrid
composite. However, both cathodic and anodic peak currents are
decreasing as increasing the scan cycles. By potential cycling, current decreases at redox peaks might indicate that the electrodeposition of manganese/copper hybrid composite is not perfect. In our
strategy, GO and MWCNT/GO were used as conductive nanotemplates to enhance the hybrid electrodeposition of different metal
ions (Mn and Cu ions). Inset of Fig. 1B shows the electroreduction
of graphene oxide. All modied electrodes prepared by this procedure were called GO-modied electrodes. Fig. 1B and C shows the
voltammograms of manganese/copper electrodeposition using a

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K.-C. Lin et al. / Journal of Electroanalytical Chemistry 735 (2014) 3642

Fig. 1. Consecutive cyclic voltammograms (A) bare GCE, (B) GO/GCE, and (C)
MWCNT/GO/GCE examined in pH 5.5 acetic solution containing 0.2 M manganese
acetate and 0.1 M copper sulphate. Scan rate = 0.1 V s1.

GO/GCE and MWCNT/GO/GCE, respectively. When using a GO/GCE

(Fig. 1B), it also exhibits poor current development of redox peaks
although it has higher current response compared to bare GCE
(Fig. 1A). When using a MWCNT/GO/GCE (Fig. 1C), the cyclic voltammogram depicts the well current development of redox peaks
indicating the manganese/copper hybrid composite electrodeposition at MWCNT/GO/GCE is better than that of bare GCE or GO/
GCE. It exhibits three redox peaks at Epc1 = 0.07 V, Epc2 = 0.15 V,
and Epa1 = +0.2 V, related to the manganese/copper redox processes. No symmetric redox processes of oxidation/reduction peaks
might be caused by the similar oxidation/reduction potential of
copper and manganese in the electrochemical system. Both anodic
and cathodic peak currents are increasing as the increase in the
scan cycles. Good current development indicates that MWCNT/
GO can effectively enhance the hybrid electrodeposition of different metal ions (Mn and Cu ions). This phenomenon proves that
the conductive and steric MWCNT/GO structure can provide more
active sites to immobilize different metal ions, avoiding the
problem of competitive deposition. One can conclude that the

hybrid formation of manganese/copper hybrid composite can be

improved by MWCNT/GO.
Surface morphology of these modied electrodes was studied
by SEM. Fig. 2 shows the SEM images for (A) MnCu, (B) GO, (C)
MnCu/GO, and (D) MnCu/MWCNT/GO, respectively. Fig. 2A exhibits the image of MnCu hybrid composite without using any templates (GO or MWCNT/GO). It exhibits stacked cluster structure
among these modiers. Fig. 2B presents the image of GO modied
electrode surface with unique structure consists of thin stacked
akes. Fig. 2C and D presents the specic images with snowake
clusters (MnCu/GO) and compact nanoporous structures (MnCu/
MWCNT/GO), respectively. By comparison, Fig. 2A shows large
clusters indicating the hybrid electrodeposition of manganese/copper hybrid composite is poor and not easy to generate nanocomposite without MWCNT/GO. Fig. 2D displays the nanoporous
image of the hybrid electrodeposition of manganese/copper hybrid
composite using MWCNT/GO. The smaller clusters of MnCu/
MWCNT/GO might also indicate that the formation of GO reduction, MWCNT adsorption, and manganese/copper electrodeposition is very successful and compact. This phenomenon can be
explained by that MWCNT/GO can provide more conductive and
steric space for the hybrid electrodeposition of manganese/copper
hybrid composite.
Fig. 3A shows the XRD spectrum of MnCu/MWCNT/GO hybrid
composites. It was checked with the standard XRD patterns related
to (B) ITO (In1.875Sn0.125O3), (C) copper manganese oxide (CuMn2O4),
(D) tenorite (CuO), and (E) hausmannite (Mn3O4), respectively. One
can know that the MnCu/MWCNT/GO is a mixed-valence hybrid
composite including copper manganese oxide (CuMn2O4), tenorite
(CuO), and hausmannite (Mn3O4). This result indicates that the
MWCNT/GO is an active and steric nanotemplate to immobilize
manganese/copper hybrid composite, and therefore the more compact nanoporous structure of MnCu/MWCNT/GO is observed as
shown in Fig. 2D. One can conclude that the nanocomposite
(MnCu/MWCNT/GO) can be easily prepared by that using a high
conductive and high specic area (MWCNT/GO) to enhance the
hybrid electrodeposition of different metal ions (Mn and Cu ions).
Fig. 4 shows the voltammograms of (a) GO, (b) MnCu, (c) MnCu/
GO, and (d) MnCu/MWCNT/GO modied electrodes. Inset of Fig. 4
presents the scale-up voltammograms of (a) GO and (b) MnCu. The
MnCu composite shows a redox couple with formal potential of
E00 = 0.16 V estimating from oxidation peak (Epa = 0.05 V) and
cathodic peak (Epc = 0.27 V). It means that the MnCu hybrid composite show only one redox couple in the alkaline solution. The GO
modied electrode exhibits no obvious redox couples although it
shows higher current signal in the voltammogram compared to
that of MnCu hybrid composite. It means that the GO modier
can only enhance the conductivity of electrode surface without
electrochemical process. Both MnCu/GO and MnCu/MWCNT/GO
show one obvious redox couple related to similar redox peaks
(E00
estimated from Epa = 0.05 V and Epc =
MnCu=GO 0:17 V
0.29 V; E00
MnCu=MWCNT=GO 0:13 V estimated from Epa = +0.02 V
and Epc = 0.28 V), indicating they have the same redox process.
Particularly, the MnCu/MWCNT/GO hybrid composite shows the
highest current response among these modiers. It means that
the MWCNT/GO can effectively enhance the electrodeposition of
manganese/copper hybrid composite resulted in one signicant
redox couple with high current response.
Fig. 5 shows the voltammograms of MnCu/MWCNT/GO examined in pH 13 alkaline solution with different scan rate of 10
500 mV s1. In the potential range of 0.65 to +0.1 V, one can see
that it shows two obvious redox couples related to Mn(II)/Mn(III)
and Mn(III)/Mn(IV) redox processes with small peak-to-peak
separation and higher current response. One obvious redox couple
represents that MnCu/MWCNT/GO can be well immobilized on
GCE and it shows stable current response in the scan rate of

K.-C. Lin et al. / Journal of Electroanalytical Chemistry 735 (2014) 3642

39

Fig. 2. SEM images of (A) MnCu, (B) GO, (C), MnCu/GO and (D) MnCu/MWCNT/GO coated ITO electrodes.

Fig. 4. Cyclic voltammograms of (a) GO, (b) MnCu, (c) MnCu/GO, and (d) MnCu/
MWCNT/GO modied glassy carbon electrodes examined in pH 13 alkaline solution.
Scan rate = 0.1 V s1. Inset: the scale-up voltammograms of (a) GO and (b) MnCu
modied electrodes.
Fig. 3. (A) XRD spectra of (A) MnCu/MWCNT/GO coated ITO electrode. Standard
XRD patterns of: (B) (In1.875Sn0.125)O3, (C) CuMn2O4, (D) CuO, and (E) Mn3O4.

10500 mV s1. MnCu/MWCNT/GO has small peak-to-peak separation indicating reversible and fast electron transfer processes.
Both anodic and cathodic peak currents are directly proportional
to scan rate (inset of Fig. 5), suggesting a surface controlled process
in the electrochemical system. The observation of well-dened
and persistent cyclic voltammetric peaks indicates that MnCu/
MWCNT/GO/GCE exhibits electrochemical response characteristics
of redox species conned on the electrode. The apparent surface
coverage (C) was estimated by following equation:

Ip n2 F 2 v AC=4RT

where Ip is the peak current of the MnCu/MWCNT/GO composite

electrode; n is the number of electron transfer; F is Faraday constant
(96,485 C mol1); v is the scan rate (mV s1); A is the area of the

electrode surface (0.07 cm2); R is gas constant (8.314 J mol1 K1);

and T is the room temperature (298.15 K). Assuming a oneelectron transfer, the C was calculated in 5.2  109 mol cm2
and 7.9  109 mol cm2 for Mn(II)/Mn(III) and Mn(III)/Mn(IV)
redox processes, respectively. High surface coverage indicates that
the hybrid composite might be compact with more electroactive
species on electrode surface. One can conclude that MWCNT/GO
provides more active sites to load more electroactive species.
To ascertain the effect of pH, MnCu/MWCNT/GO/GCE was
examined in different pH solutions (pH 113). Fig. 6 presents the
MnCu/MWCNT/GO redox peaks which are shifted to more negative
potential as increasing pH value of solution. It can be seen that only
one obvious redox couple below pH 11 (case (a) to (e) in Fig. 6)
especially for more strong acidic condition with more high current
response. The phenomenon means that the redox process of
manganese/copper hybrid composite might prefer acidic solution
so that higher current response in higher pH condition. Only one

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K.-C. Lin et al. / Journal of Electroanalytical Chemistry 735 (2014) 3642

Fig. 5. Cyclic voltammograms of MnCu/MWCNT/GO/GCE examined in pH 13

alkaline solutions with various scan rates of (a) 10 to (n) 500 mV s1, respectively.
Inset: the plot of peak current vs. scan rate.

Fig. 7. Voltammograms of MnCu/MWCNT/GO/GCE examined in pH 13 alkaline

solutions with glucose additions using (A) CV, (B) LSV, and (C) DPV techniques.
[Glucose] = 040 mM glucose. Scan arte = 0.1 V s1. Inset: the plot of peak current
vs. glucose concentration.

Fig. 6. Cyclic voltammograms of MnCu/MWCNT/GO modied glassy carbon

electrode examined with various pH conditions of (a) pH 1 to (g) pH 13,
respectively. Scan rate = 0.1 V s1.

redox couple in the condition of pH 19 (case (a) to (e) in Fig. 6)

indicate that the same potential of copper and manganese redox
processes. Particularly, it is found with two redox couples when
the pH condition above pH 9 (case (f) and (g) in Fig. 6). It implies
that the MnCu/MWCNT/GO hybrid composite exhibits two redox
processes involving Mn(II)/Mn(III) and Mn(III)/Mn(IV) redox processes in strong basic solutions. This result is the same even though
MnCu/MWCNT/GO is repeatedly examined and change testing
order of pH condition. It indicates that the manganese/copper
hybrid composite electrodeposition can be effectively immobilized
by MWCNT/GO and the MnCu/MWCNT/GO hybrid composite can
maintain the electrochemical properties of copper and manganese.
It can be concluded that the MnCu/MWCNT/GO hybrid composite
is active and stable in wide pH condition.

3.2. Electrocatalytic oxidation of glucose using MnCu/MWCNT/GO

electrode
The electrocatalytic activity of the MnCu/MWCNT/GO electrode
towards the oxidation of glucose in pH 13 alkaline was investigated by cyclic voltammetry (CV), linear sweep voltammetry
(LSV), and differential pulse voltammetry (DPV), respectively.
Fig. 7 displays the voltammograms of MnCu/MWCNT/GO/GCE in
pH 13 alkaline with addition of 040 mM glucose using (A) CV,
(B) LSV, and (C) DPV techniques. The MnCu/MWCNT/GO/GCE
shows one obvious oxidation peaks at about +0.05 V when using
CV and LSV techniques. It shows lower oxidation potential at
0.05 V with suitable control of pulse parameters when using
DPV technique. Insets of Fig. 7 present good correlation between
peak current and glucose concentration. As indicated in the literature, the oxidation of glucose to gluconolactone was catalyzed by
the Mn(III)/Mn(II), Mn(IV)/Mn(III), and Cu(III)/Cu(II) redox couples
according to the following reactions:

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K.-C. Lin et al. / Journal of Electroanalytical Chemistry 735 (2014) 3642

Table 1
Net current response of the relative modiers examined for 10 mM glucose (pH 13
alkaline solution).
Modiers

DIpaa (lA)

Current ratiob

GO
MnCu
MnCu/GO
MnCu/MWCNT/GO

0.82
6.36
54
217

1
7.8
65.9
264.6

a
DIpa: net current response which is estimated from the current in the absence/
presence of 10 mM glucose at the oxidation peak of 0.05 V.
b
Current ratio: the current ratio is obtained by the calculation based on the net
current response of GO modier.

For CuMn2O4 composite:

II
II


CuII MnIII
2 O4 2Glucose ! Cu Mn2 O4 2Gluconolactone 2H 2e

2
II
III


CuII MnIV
2 O4 2Glucose ! Cu Mn2 O4 2Gluconolactone 2H 2e

3
For Mn3O4 composite:
II
III


MnII MnIV
2 O4 2Glucose ! Mn Mn2 O4 2Gluconolactone 2H 2e

MnIV MnII2 O4 Glucose ! MnIII MnII2 O4 Gluconolactone H e

5
For CuO composite:

CuOOH Glucose ! CuOH2 Gluconolactone e

6
1

The sensitivity is estimated with 49.1 lA mM cm2,

58.6 lA mM1 cm2, and 59.3 lA mM1 cm2 for using CV, LSV,
and DPV techniques, respectively. It shows larger slope (high sensitivity value) to glucose oxidation using DPV technique, indicating
that DPV is the suitable technique applied to determine glucose
among these techniques. The characteristics of MnCu/MWCNT/
GO hybrid composite provide the possibility to simply determine
glucose using DPV technique without enzyme.
To explore the analytical applicability of the hybrid composites,
the electrocatalytic activity of the different composite modied
electrodes towards glucose oxidation was investigated by cyclic
voltammetry. All cyclic voltammograms were obtained for the
modied electrodes in deoxygenated NaOH solution. The net current
(DIpa) and current ratio were estimated for the electrocatalytic

activity towards glucose oxidation by different modiers. As

shown in Table 1, DIpa was estimated using the anodic peak current at Epa = 0.05 V in the absence/presence of 10 mM glucose.
The MnCu/MWCNT/GO shows the highest values of DIpa and about
4264 folds of the related modiers, suggesting this composite to
be an active electrocatalyst towards glucose oxidation. Compared
to the related modiers, the high net current response of the
MnCu/MWCNT/GO for glucose oxidation might be caused by the
enhancement of MWCNT/GO. As shown in Fig. 1C, the MnCu electrodeposition can be enhanced by MWCNT/GO. The MWCNT/GO
might provide high conductive and steric substrate to load more
MnCu hybrid composite result in high sensitivity. One can conclude that the MnCu/MWCNT/GO shows the higher sensitivity for
glucose oxidation among the related materials.
Various nonenzymatic glucose sensors are summarized in
Table 2. The MnCu/MWCNT/GO modied electrode shows competitive performance to other sensors even using DPV technique. It
shows the lowest overpotential for glucose oxidation in the literature due to the active hybrid nanocomposite. Compared with the
related modiers such as CuO and MWCNT, the MnCu/MWCNT/
GO shows competitive sensitivity. The sensitivity is not as high
as those using CuO/MWCNT, Cu/MWCNT, and SWCNT. According
to the correlation between current response and rotation speed
(KouteckyLevich equation), it provides higher current response
with rotation speed by amperometry. In this work, we try to
directly test glucose by voltammetry (not amperometry) for more
practical system. Moreover, it shows very low overpotential for
glucose oxidation. Although the sensitivity is not too much high,
it provides a practical linear concentration range of 132 mM. Particularly, the work is mainly focused on using a SPCE to test with
DPV electrochemical technique for a more simple and practical
condition. The use of MWCNT and GO can help the immobilization
of MnCu hybrid composite onto a SPCE. It is a novel subject to
directly immobilize metal oxidates (including MnO2, CuO), graphene oxide and CNTs onto a SPCE to be a DPV sensor instead of an
amperometric sensor for approaching a more convenient, simple
and practical condition. By the results, one can know that it promises the practical SPCE applications in the pre-study using DPV
electrochemical technique instead of amperometry.
3.3. Interference study of the MnCu/MWCNT/GO composite
The MnCu/MWCNT/GO modied electrode was studied with
the interference effect on voltammetric response for glucose. It
was examined in the presence of several interferants including

Table 2
Performance of the MnCu/MWCNT/GO electrode compared with other modiers for nonenzymatic glucose oxidation.
Modiers

Applied potential
(V vs. Ag/AgCl)

Sensitivity
(lA mM1 cm2)

Linear range (M)

Detection
limit (lM)

Reference

Porous Au (Amperometry)
MnO2/MWCNT (Amperometry)
CuO nanowires (Amperometry)
Mesoporous Pt (Amperometry)
MWCNT (Amperometry)
Cu nanoparticles (Amperometry)
Ni/Cu/MWCNT (Amperometry)

0.35
0.3
0.33
0.4
0.2
0.65
0.575
0.575
0.55
0.65
0.6
0.4
0.3

0.4
0.6
0.05

11.8
33.2 lA mM1
0.5
9.6
4.4

2633
2437
1043
251.4
248.6
0.1
17.8
160
2596
67.19
59.3

2  1031  102
1  1052.8  102
4  1072  103
01  102
2  1061.1  102
1  1065  103
2.5  1088  104
2  1038  103
5  1077  103
7  1043.5  103
1  1052.16  103
2  1031.4  102
Up to 1.1  102
5  1048  103
4  1071.2  103
3.2  1061.75  102
1  1033.2  102

0.049

1
0.5
0.025
0.025
0.1
0.21
10
1
1.8

0.2
0.89
1

[3]
[10]
[11]
[18]
[20]
[26]
[29]

Ni nanowires (Amperometry)
Cu/MWCNT (Amperometry)
Freestanding SWCNT lm (Amperometry)
Pt nanotubes (Amperometry)
PtPb/CNTs (Amperometry)
Au nanoparticles (Amperometry)
CuO/MWCNT (Amperometry)
NiMWCNT (Amperometry)
MnCu/MWCNT/GO (DPV)

[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
This work

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K.-C. Lin et al. / Journal of Electroanalytical Chemistry 735 (2014) 3642

Table 3
Recovery of glucose obtained in bovine serum albumin (BSA) using MnCu/MWCNT/
GO modied electrodes.

a
b
c

Sample no.

Added (A) (mM)

Found (B)a (mM)

Recoveryb (%)

CVc (%)

1
2
3
4
5

2
4
6
8
10

1.98 0.12
3.96 0.08
5.98 0.30
8.16 0.10
10.2 0.40

99
99
99.7
102
102

5.3
5.5
4.8
5.2
5.2

The detected amounts of glucose were obtained from n = 3 analyses.

Recovery (%) = (B/A)  100%.
CV: coefcient of variation.

ascorbic acid, dopamine, uric acid, fructose, lactose, and galactose.

Voltammetric response was observed at anodic peak of Eapp. =
0.05 V, it shows almost no current response of MnCu/MWCNT/
GO with various interferants. This information indicates that glucose can be determined by MnCu/MWCNT/GO modied electrode.
One can conclude that the active composite can be a good electrocatalyst to determine glucose avoiding of interference.
3.4. Bovine serum albumin samples measurement
In an attempt to assess the feasibility of using the MnCu/
MWCNT/GO coated SPCE for practical applications, the sensor
was applied to determine glucose in bovine serum albumin samples. The recovery of glucose was determined by the standard addition of pure glucose to the solutions containing the serum samples,
and the corresponding results were presented in Table 3. The
MnCu/MWCNT/GO sensor showed high recovery and low coefcient of variation. The results demonstrated herein support the
potential application of the MnCu/MWCNT/GO sensor for the
determination of glucose in biological uids.
4. Conclusions
Coimmobilization of manganese/copper hybrid composite can
be successfully prepared on electrode surface and further
enhanced by MWCNT/GO. MnCu/MWCNT/GO shows specic nanostructure indicating that manganese/copper hybrid composite can
be easily immobilized on MWCNT and GO due to high conductive
and high specic surface area. The modied electrode is electrochemically characterized and examined as a novel glucose sensor,
which presents attractive analytical features such as low overpotential, high linear concentration range, low detection limit, good
stability, and good reproducibility.
Conict of interest
In this work, we try to directly test glucose by voltammetry (not
amperometry) for more practical system. Particularly, the work is
mainly focused on using a SPCE to test with DPV electrochemical
technique for a more simple and practical condition.
Acknowledgement
We acknowledge National Science Council (Project No.
NSC1012113M027001MY3), Taiwan.

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