Electrochimica Acta 115 (2014) 126–130

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

Enzyme-free sensing of hydrogen peroxide and glucose at a CuS

nanoflowers modified glassy carbon electrode
Yu Jun Yang ∗ , Junfeng Zi, Weikun Li
School of Chemistry and Chemical Engineering, Xuchang University, Xuchang 461000, Henan, PR China

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

Article history: Flower-like CuS nanoparticles (NPs) were synthesized with a simple and mild hydrothermal method.
Received 14 June 2013 XRD analysis indicated that the product is pure hexagonal phase CuS. The morphology of the particles
Received in revised form 17 October 2013 was studied by TEM. The electrode modified with CuS nanoflowers showed excellent electrocatalytic
Accepted 21 October 2013
activities to the oxidation of glucose and reduction of hydrogen peroxide in pH 7.2 phosphate buffer. It
Available online 2 November 2013
is the first reported copper sulfide based sensor of both glucose and hydrogen peroxide. Electrochemical
analysis of the particulate CuS for detecting H2 O2 and glucose is described, showing remarkable sensitivity
Keywords:
in both cases. The estimated detection linear ranges and sensitivities for H2 O2 (1 × 10−6 –1 × 10−4 M,
Catalysis
Copper sulfide
3.64 × 104 ␮A M−1 ) and glucose (1 × 10−5 M–1 × 10−2 M, 5.86 × 103 ␮A M−1 ) suggest that the response
Hydrogen peroxide for H2 O2 detection is higher than that for glucose detection. The good analytical performance makes
Glucose CuS NPs/chitosan modified glassy carbon electrode (CuS/CS/GCE) a promising electrochemical sensor for
Enzyme-free sensor. glucose and hydrogen peroxide.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction expensive and easy to synthesize. Their size and morphologies

The electrocatalytic oxidation of glucose has been a focal subject
of many investigations, because of the great importance of glucose
sensing in human blood and their potential use for fuel cell applica-
tions [1–5]. Glucose oxidase as enzymatic catalyst has been widely
used for glucose biosensor fabrication [6–11]. Good selectivity and
high sensitivity have been achieved for glucose detection by enzy-
matic glucose sensors. However, owing to the nature of enzymes,
the most common and serious problem with enzymatic glucose
sensors lies in their lack of long-term stability [12–14]. Direct elec-
trocatalytic oxidation of glucose at an enzyme-free electrode would
exhibit conveniences and advantages to avoid the drawbacks of the
enzyme electrode. Early researches have been focused on the use of
noble metal-based [15–18] and alloy-based [19–25] electrodes for
developing enzyme-free sensors. Various attempts have been made
during recent years and electrodes modified with carbon nanotubes
[26], CuO nanowire [27], CuO nanospheres [28], metallophthalo-
cyanines [29–32] and MnO2 with various crystalline structures
[33,34] have been developed.
In recent years, copper sulfides have been investigated for their
potential sensing capabilities. Cu–Cu2 S nanocomposite [35], CuS
nanotubes [36,37] were used in the fabrication of nonenzymatic
glucose biosensors. Copper chalcogenide nanomaterials are not
∗ Corresponding author. Tel.: +86 371 63671510; fax: +86 371 63671510.
E-mail address: yangyujun@yahoo.com (Y.J. Yang).
can be tuned by simply varying the experimental parameters. The
glucose sensors based on CuS or CuO nanomaterials showed high
sensitivity, low detection limit and wide linear range in a neutral
solution [35–37].
Hydrogen peroxide is an intermediate or a product in biochem-
ical reactions catalyzed by oxidase. Thus, the monitoring of H2 O2
with a reliable, rapid and economic method is of great significance
[38]. Cu2 S nanoparticles were reported for the construction of a
sensor for hydrogen peroxide [39].
In this article, CuS nanoflowers modified GCE shows excellent
electrocatalytic activity toward the oxidation of glucose in pH 7.2
phosphate buffer solution. It is highly tolerant to chloride ions and
generates more stable, reproducible and larger current responses
compared with other enzyme-free electrodes. Further study shows
that the CuS/CS/GCE could also effectively catalyze the reduction
of hydrogen peroxide in pH 7.2 phosphate buffer solution. To our
knowledge, it is the first reported copper sulfide based nonenzy-
matic sensor of both glucose and hydrogen hydroxide.
2. Experimental
All chemical reagents were of analytical grade and used as
received. The CuS nanoparticles were prepared by a synthetic route
developed by Zhang et al. with small changes. The detailed pro-
cesses of synthesizing CuS nanoflowers were as follows: CuCl2
(3 mmol) and CTAB (0.5 mmol) were, respectively, dissolved in
50 mL mixed solvent of ethanol/H2 O (4:1 vol%) in a flask. After

0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.10.168
 Y.J. Yang et al. / Electrochimica Acta 115 (2014) 126–130 127

sonicating vibration for 10 min, 5 mL CS2 was added, and then con-

(110)
tinuously stirring for 10 min. Finally, the mixtures were added to a 1200
Teflon-lined autoclave of 100 mL capacity, which was heated and

(100, 101, 102)

1000
maintained at 80 ◦ C for 6 h, and then gradually cooled to room

(103, 006)
temperature. All of the black powders were carefully collected,

(203, 116)
800

Intensity/A.U.
washed with distilled water and ethanol for several times and
dried in vacuum at 40 ◦ C for 4 h. Disperse 0.0050 g produced CuS 600

(108)
nanoparticles in 2 mL 0.2% chitosan 1% acetic acid solution under
400
ultrasonic agitation. The CuS modified GCE was prepared by casting
4 ␮L CuS dispersion on the GCE surface and dried at room temper- 200
ature.
Cyclic voltammetric (CV) was performed on CHI 660B (Chen- 0
hua, Shanghai). A three-electrode system comprising of a platinum
-200
wire as the auxiliary, a saturated calomel electrode (SCE) as the
0 20 40 60 80 100
reference and the CuS nanoparticles-modified electrode as the
2θ/degree
working electrodes was used for all the electrochemical exper-
iments. The electrochemical experiments were carried out in a Fig. 1. XRD data of synthesized CuS nanoparticles.
cell containing 10 mL 0.1 M phosphate buffer solution (PBS, pH
7.2).
The morphology and the crystal structure of the produced 60
CuS NPs were observed with a transmission electron microscope
(TEM) and an X-ray diffractometer (XRD). The X-ray diffraction 40 b
(XRD) patterns are obtained by Shimadzu XRD-6000 diffractome-
ter with a Ni filter and Cu K␣ radiation ( = 1.54056 Å). TEM
20
experiments were carried out employing Jeol 100CX II transmis-

I/μA
sion electron microscope (TEM), using an accelerating voltage of
100 kV. The samples used for TEM were prepared by dispers- 0
a
ing some products in ethanol followed by ultrasonic vibration for
15 min. -20

3. Results and discussion -40

The X-ray diffraction pattern of the CuS nanoparticles is shown
in Fig. 1. The well-defined peaks are observed in the XRD pattern.
The films are polycrystalline. The diffraction peaks can be per-
fectly indexed to hexagonal CuS with lattice constants a = 3.796 Å
and c = 16.38 Å (JCPDS 78-0876). No other peaks arising from the
possible impurity phases were observed.
The size of particles can be determined from imaging by TEM.
Fig. 2a depicts the TEM micrographs of CuS NPs. Most of the CuS
NPs are flower-shaped. It can be distinctly seen that the flower-like
pattern have 6-fold symmetry and take progressively the different
large ferns issuing from a common center, which are subdivided in
branches at center and along 60◦ angle from the center. In order to
investigate the electrochemical behaviors of the CuS NPs, the GCE
was modified with thin film of CuS NPs. SEM study of the CuS mod-
ified GCE showed that the flower-shaped CuS NPs are uniformly
distributed on the GCE surface.
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8
E/V
Fig. 3. The cyclic voltagramm of CS/GCE (curve a) and CuS/CS/GCE (curve b) in 0.1 M
phosphate buffer (pH 7.2). Scan rate: 100 mV/s. Scan range: −0.3–−0.8 V.
Fig. 3 shows the CV curves at a chitosan modified GCE (CS/GCE)
and the as-prepared CuS NPs-modified GCE (CuS/CS/GCE) in pH 7.2
phosphate buffer solution. There are no redox peaks on the CS/GCE.
The cyclic voltammogram of the CuS/CS/GCE in 0.1 M phosphate
buffer (pH 7.2) displays a pair of well-defined redox peaks (curve
b) which are assigned to the CuS/Cu2 S couple [36,37,39].
The electrocatalytic performance of the bare GCE, CS/GCE and
CuS/CS/GCE toward the oxidation of glucose was investigated by
CV. Fig. 4 illustrates the CV behaviors of the bare GCE, CS/GCE

Fig. 2. (a) TEM images of the CuS NPs; (b) SEM of the CuS/CS/GCE.
128 Y.J. Yang et al. / Electrochimica Acta 115 (2014) 126–130
150
d 120
100
I/μA
50
c 40
0 a
b
-50
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8
E/V
Fig. 4. The cyclic voltagramm of bare GCE (curve a), CS/GCE (curve b) and
CuS/CS/GCE (curve d) in 0.1 M phosphate buffer (pH 7.2) containing 1 mM glucose.
Curve c is the cyclic voltagramm of CuS/CS/GCE in 0.1 M phosphate buffer (pH 7.2).
Scan rate: 100 mV/s. Scan range: −0.2–−0.8 V.
and CuS/CS/GCE in 0.10 M phosphate buffer (pH 7.2) solution
containing 1.0 mM glucose. No current response was observed at
the bare GCE (cure a) and CS/GCE (curve b). The cyclic voltagramms
of CuS/CS/GCE in 0.1 M phosphate buffer (pH 7.2) in the absence
(curve c) and in the presence (curve d) of 1 mM glucose are shown
in Fig. 4. In comparison with that of curve c, the anodic peak at
0.46 V increased significantly after the addition of 1 mM glucose.
It can be concluded that CuS/CS/GCE exhibited excellent catalytic
capability toward the electro-oxidation of glucose.
The CVs of the CuS/CS/GCE in different concentrations of glucose
were also measured. Fig. 5 shows the voltammetric response after
each standard addition of 100 ␮M glucose. These results clearly
indicated that, as the concentration of glucose increased, the peak
currents of the anodic peak at 0.46 V also increased. The variation of
the peak current at 0.46 V vs. glucose concentration was linear in the
glucose concentration range of 10 ␮M to 10 mM with a sensitivity
and correlation coefficient of 5.86 ␮A mM−1 and 0.9970, respec-
tively. This linear concentration range of 1 × 10−5 M–1 × 10−2 M
is of advantage as the likely glucose level in normal and diabetic
people usually varies from 0.2 to 20 mM [40]. The fabrication repro-
ducibility of eight biosensors, prepared under the same conditions,
showed an acceptable reproducibility with a R.S.D. of 2.7% for the
peak current obtained in the glucose concentration of 1.0 mM.
These results indicated that the CuS/CS/GCE has a good operational
stability. The activity of the electrode retained almost the same of
its initial current response after it was stored at room temperature
for 30 days, indicating the excellent stability of the sensor.
To evaluate the selectivity of the proposed biosensor, three pos-
sible interfering biomolecules, AA, DA, and UA, which normally
coexists with glucose in real samples (human blood) were exam-
ined [41]. Considering that the concentration of glucose in the
human blood is about 30 times of AA, DA or UA, the voltammetric
response of the CuS/CS/GCE toward the addition of 1 mM glucose
and 0.1 mM AA, DA, and UA was examined in 0.1 M phosphate
buffer solution and the Iglucose+interferent /iglucose is 109%, 90% and
103%, respectively (Fig. S1). To sum up, the selectivity was improved
so much on this enzyme-free biosensor that the three common
interfering biomolecules, AA, DA, and UA caused negligible inter-
ference to the response of glucose at the CuS/CS/GCE.
Electrodes based on metals [15,17] or alloys [18,24] toward the
oxidation of glucose usually lose their activity due to the poison-
ing of chloride ions [42]. In order to understand whether chloride
ions will poison the CuS/CS/GCE, the CV was measured in the solu-
tion with high concentration of chloride ions (i.e., replacing 0.10 M
phosphate buffer with 0.10 M KCl + 0.10 M phosphate buffer as the
160 a
80
I/μA
0
-40
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8
E/V
120
b
90
I/μA
60
30
0.0 0.5 1.0
Cglucose/mM
Fig. 5. (a) CVs of CuS/CS/GCE in 0.10 M phosphate buffer solution (pH 7.2) containing
0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 mM glucose at 100 mV s−1 ; (b) the
plot of the oxidation peak current with the concentration of glucose.
electrolyte). As shown in Fig. S2 (supporting information), the cur-
rent response of CuS/CS/GCE toward glucose oxidation remained
almost unchanged, implying that the CuS/CS/GCE was also highly
resistant to poisoning by chloride ions.
To evaluate the ability of the sensor for routine analysis, the
sensor was applied in the determination of glucose in blood
serum samples. Here, 200 ␮L of blood serum sample was added
to 10 mL PBS (pH 7.2) under stirring and the cyclic voltagramm
was recorded with CuS/CS/GCE as the working electrode. Accord-
ing to the calibration curve, the current response corresponded to
the glucose concentration around 7.1 (±0.2) mM. The hospital anal-
ysis, obtained by application of a routine enzymatic method (using
glucose oxidase), showed that the glucose level in the blood sample
was 6.9 mM. It showed that there is a very good agreement between
the results obtained by the proposed sensor.
Fig. 6 displays the amperometric current–time curve of the
CuS/CS/GCE under 0.46 V with successive additions of glucose. As
expected, the modified electrode showed good linear response to
the changes of glucose concentration. It took less than 3 s to achieve
the steady-state current, indicating the fast amperometric response
of the modified electrode. The calibration curve for the glucose
sensor was shown in the inset of Fig. 6. The modified electrode
gave a linear dependence in the glucose concentration range of
1 × 10−6 mol L−1 –1 × 10−3 mol L−1 with a correlation coefficient of
0.99805, a sensitivity of 2.519 ␮A ␮mol L−1 , and a detection limit of
3 × 10−7 mol L−1 . The above electrocatalytic studies of CuS/CS/GCE
modified electrode revealed the properties of high sensitivity, low
detection limit and fast response.
 Y.J. Yang et al. / Electrochimica Acta 115 (2014) 126–130 129

-6 a
0

-20 -9

I/μΑ
I/μA

-40
-12
-60

-15
-80
-500 0 500 1000 1500 2000 2500
0 1000 2000
t/s
t/s
Fig. 6. Amperometric responses of the CuS/CS/GCE toward the successive additions
of 10 ␮L 10 mM glucose into 10 mL 0.1 M phosphate buffer solution (pH 7.2) at
0.46 V. The inset summarizes the relation between response current and the glucose
14 b
concentration (R = 0.99805). 13
12
The electrocatalytic capability of CuS/CS/GCE toward the reduc-
tion of hydrogen peroxide was also examined. Before experiments 11
the phosphate buffer solution was degassed with high purity nitro- 10

gen gas for 20 min. As shown in Fig. 7, in the absence of hydrogen
peroxide, there is a pair of well-defined redox peaks which are
assigned to the CuS/Cu2 S redox couple. In the presence of H2 O2 ,
the CV displayed a broad cathodic peak at −0.1 V (curve b) while
the anodic peak current significantly increased with the addition
of H2 O2 . The cathodic peak at −0.1 V in the presence of H2 O2 was
due to the reduction of H2 O2 . The increase of the anodic peak cur-
rent upon the addition of H2 O2 was probably due to a parallel
catalytic reaction. As soon as Cu(II) is reduced to Cu(I) by H2 O2 ,
it is electro-oxidized back to Cu(II) at the electrode surface:
2Cu(II) + 2H2 O2 → 2Cu(I) + O2 + 2H2 O
Cu(I) → Cu(II) + e
Since the above two reactions are fast, the parallel current was
much higher than the oxidation current of Cu(I) on the electrode
surface without H2 O2 .
Amperometry was adopted to determine the concentration of
H2 O2 . The pH 7.2 phosphate buffer solution was degassed for
20 min before the amperometric experiments and kept under nitro-
gen atmosphere during the experiment. Effect of applied potential
on the amperometric response of 10 ␮M H2 O2 in phosphate buffer
solution was studied. Although at −0.2 V the signal was the high-
60
b from 1 × 10−6 to 1 × 10−4 M. The upper limit of linearity range
40
a
20
I/μA
I/μΑ
9
8
7
6
0 2 4 6 8 10 12 14 16 18 20 22
cH2O2/10μM
Fig. 8. Dynamic current responses of CuS/CS/GCE to successive addition of H2 O2
(1) at pH 7.2. Inject 20 ␮L 5 × 10−2 M H2 O2 solution into 10 mL phosphate buffer (pH
7.2) with a microsyringe. The concentration change of H2 O2 is 10 ␮M per addition.
(2) Applied potential: −0.1 V; (c) calibration curve of H2 O2 amperometric biosensor
based on CuS/CS/GCE in phosphate buffer buffer (pH 7.2). Applied potential: −0.1 V.
est, we chose −0.1 V as the operating potential because there is
increased noise above −0.1 V, which was a disadvantage for mea-
suring low H2 O2 concentrations. The relationship between the
reduction current and the concentration of H2 O2 was examined
in a phosphate buffer solution (pH 7.2). The solution was stirred to
ensure uniform distribution of H2 O2 in the cell. Fig. 8a displayed
the amperometric response for H2 O2 . When the same amount of
H2 O2 was injected into the cell, the concentration change of H2 O2
in the cell was 10 ␮M per addition and the current was recorded
instantly. Calibration curves for H2 O2 measurement were also pre-
sented in Fig. 8b. The current was linear for concentrations of H2 O2
(1 × 10−4 M) was attained by examining the relationship between
the oxidation current and the concentration of H2 O2 after injecting
same amount of H2 O2 (concentration change: 1 × 10−5 M/addition)
into the cell. The sensitivity of the sensor to H2 O2 was calculated

to be 3.64 × 104 ␮A M−1 . The detection limit was estimated to be

0 3 × 10−7 M (signal/noise = 3).

-20 4. Conclusion

-40 In summary, flower-like CuS nanoparticles were synthesized by

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 a simple chemical way. By coating CuS/Chitosan onto GCE surface,
enzyme-free sensors were constructed for detecting hydrogen per-
E/V
oxide and glucose. The modified electrodes showed fast response
Fig. 7. (a) CVs of H2 O2 on CuS/CS/GCE in 0.1 M phosphate buffer solution (pH = 7.2) and high sensitivity because of the increased electroactive sur-
in the absence (curve a) and presence of 0.5 mM H2 O2 (curve b). Scan rate: 100 mV/s. face area. The detection limits for H2 O2 and glucose are 3 × 10−7 M
130 Y.J. Yang et al. / Electrochimica Acta 115 (2014) 126–130
and 1 × 10−5 M, respectively. These properties are very helpful for
developing new biosensors and biodevices without enzyme.
Acknowledgment
The authors acknowledge financial support by the National
Nature Science Foundation of China (Nos. 21107090 and
21271152).
Appendix A. Supplementary data
Supplementary material related to this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.electacta.2013.10.168.
References
[1] J.L.C. Clark, C. Lyons, A.N.Y. Aead, Electrode systems for continuous monitoring
in cardiovascular surgery, Ann. NY Acad. Sci. 102 (1962) 29.
[2] G. Reach, G.S. Wilson, Can continuous glucose monitoring be used for the treat-
ment of diabetes, Anal. Chem. 64 (1992) 381A.
[3] A.P.F. Turner, B. Chen, A.P. Sergey, In vitro diagnostics in diabetes: meeting the
challenge, Clin. Chem. 45 (1999) 1596.
[4] E. Katz, I. Willner, A.B. Kotlyar, A non-compartmentalized glucose | O2 bio-
fuel cell by bioengineered electrode surfaces, J. Electroanal. Chem. 479 (1999)
64.
[5] N. Mano, F. Mao, A. Heller, Characteristics of a miniature compartment-less
glucose-O2 biofuel cell and its operation in a living plant, J. Am. Chem. Soc. 125
(2003) 6588.
[6] X.H. Kang, Z.B. Mai, X.Y. Zou, P.X. Cai, J.Y. Mo, A novel glucose biosensor based
on immobilization of glucose oxidase in chitosan on a glassy carbon electrode
modified with gold–platinum alloy nanoparticles/multiwall carbon nanotubes,
Anal. Biochem. 369 (2007) 71.
[7] S.G. Wang, Q. Zhang, R.L. Wang, S.F. Yoon, J. Ahn, D.J. Yang, J.Z. Tian, J.Q. Li,
Q. Zhou, Multi-walled carbon nanotubes for the immobilization of enzyme in
glucose biosensors, Electrochem. Commun. 5 (2003) 800.
[8] H. Tang, J.H. Chen, S.Z. Yao, L.H. Nie, G.H. Deng, Y.F. Kuang, Amperomet-
ric glucose biosensor based on adsorption of glucose oxidase at platinum
nanoparticle-modified carbon nanotube electrode, Anal. Biochem. 331 (2004)
89.
[9] X. Chu, D.X. Duan, G.L. Shen, R.Q. Yu, Amperometric glucose biosensor based
on electrodeposition of platinum nanoparticles onto covalently immobilized
carbon nanotube electrode, Talanta 71 (2007) 2040.
[10] Y.J. Zou, C.L. Xiang, L.X. Sun, F. Xu, Glucose biosensor based on electrode-
position of platinum nanoparticles onto carbon nanotubes and immobi-
lizing enzyme with chitosan-SiO2 sol–gel, Biosens. Bioelectron. 23 (2008)
1010.
[11] Y.C. Tsai, S.C. Li, J.M. Chen, Cast thin film biosensor design based on a Nafion
backbone, a multiwalled carbon nanotube conduit, and a glucose oxidase func-
tion, Langmuir 21 (2005) 3653.
[12] R. Wilson, A.P.F. Turner, Glucose oxidase: an ideal enzyme, Biosen. Bioelectron.
7 (1992) 165.
[13] F. Shoji, M.S. Freund, Potentiometric sensors based on the inductive effect on
the pKa of poly(aniline): a nonenzymatic glucose sensor, J. Am. Chem. Soc. 123
(2001) 3383.
[14] S.J. Park, H.K. Boo, T.D. Chung, Electrochemical non-enzymatic glucose sensors,
Anal. Chim. Acta 556 (2006) 46.
[15] B. Beden, F. Largeaud, K.B. Kokoh, C. Lamy, Fourier transform infrared
reflectance spectroscopic investigation of the electrocatalytic oxidation of
D-glucose: identification of reactive intermediates and reaction products, Elec-
trochim. Acta 41 (1996) 701.
[16] A.N. Gracea, K. Pandian, Synthesis of gold and platinum nanoparticles using
tetraaniline as reducing and phase transfer agent—a brief study and their role
in the electrocatalytic oxidation of glucose, J. Phys. Chem. Solids 68 (2007) 2278.
[17] X.H. Kang, Z.B. Mai, X.Y. Zou, P.X. Cai, J.Y. Mo, Glucose biosensors based on
platinum nanoparticles-deposited carbon nanotubes in sol–gel chitosan/silica
hybrid, Talanta 74 (2008) 879.
[18] M. Tominaga, T. Shimazoe, M. Nagashima, H. Kusuda, A. Kubo, Y. Kuwahara, I.
Taniguchi, Electrocatalytic oxidation of glucose at gold–silver alloy, silver and
gold nanoparticles in an alkaline solution, J. Electroanal. Chem. 590 (2006) 37.
[19] Y.P. Sun, H. Buck, T.E. Mallouk, Combinatorial discovery of alloy electrocatalysts
for amperometric glucose sensors, Anal. Chem. 73 (2001) 1599.
[20] R. Qiu, X.L. Zhang, R. Qiao, Y. Li, Y.I. Kim, Y.S. Kang, CuNi dendritic material: syn-
thesis, mechanism discussion, and application as glucose sensor, Chem. Mater.
19 (2007) 4174.
[21] S.B. Aoun, Z. Dursun, T. Koga, G.S. Bang, T. Sotomura, I. Taniguchi, Effect of metal
ad-layers on Au (1 1 1) electrodes on electrocatalytic oxidation of glucose in an
alkaline solution, J. Electroanal. Chem. 567 (2004) 175.
[22] H.F. Cui, J.S. Ye, X. Liu, W.D. Zhang, F.S. Sheu, Nanotech, Pt–Pb alloy nanopar-
ticle/carbon nanotube nanocomposite: a strong electrocatalyst for glucose
oxidation, Nanotechnology 17 (2006) 2334.
[23] C.C. Jin, Z.D. Chen, Electrocatalytic oxidation of glucose on gold–platinum
nanocomposite electrodes and platinum-modified gold electrodes, Synthetic
Met. 157 (2007) 592.
[24] J.P. Wang, D.F. Thomas, A.C. Chen, Nonenzymatic electrochemical glucose sen-
sor based on nanoporous PtPb networks, Anal. Chem. 80 (2008) 997.
[25] Y. Bai, Y.Y. Sun, C.Q. Sun, Pt–Pb nanowire array electrode for enzyme-free glu-
cose detection, Biosens. Bioelectron. 24 (2008) 579.
[26] J.S. Ye, Y. Wen, W.D. Zhang, L.M. Gan, G.Q. Xu, F.S. Sheu, Nonenzymatic glu-
cose detection using multi-walled carbon nanotube electrodes, Electrochem.
Commun. 6 (2004) 66.
[27] Z.J. Zhuang, X.D. Su, H.Y. Yuan, Q. Sun, D. Xiao, M.M.F. Choi, An improved sen-
sitivity non-enzymatic glucose sensor based on a CuO nanowire modified Cu
electrode, Analyst 133 (2008) 126.
[28] E. Reitz, W.Z. Jia, M. Gentile, Y. Wang, Y. Lei, CuO nanospheres based nonenzy-
matic glucose sensor, Electroanalysis 20 (2008) 2482.
[29] C. Barrera, I. Zhukov, E. Villagra, F. Bedioui, M.A. Paez, J. Costamagna, J.H. Zagal,
Trends in reactivity of unsubstituted and substituted cobalt-phthalocyanines
for the electrocatalysis of glucose oxidation, J. Electroanal. Chem. 589 (2006)
212.
[30] K.I. Ozoemena, T. Nyokong, Novel amperometric glucose biosensor based on
an ether-linked cobalt(II) phthalocyanine-cobalt(II) tetraphenylporphyrin pen-
tamer as a redox mediator, Electrochim. Acta 51 (2006) 5131.
[31] P.N. Mashazi, K.I. Ozoemena, T. Nyokong, Tetracarboxylic acid cobalt phthalo-
cyanine SAM on gold: potential applications as amperometric sensor for H2 O2
and fabrication of glucose biosensor, Electrochim. Acta 52 (2006) 177.
[32] L. Ozcan, Y. Sahin, H. Turk, Non-enzymatic glucose biosensor based on overoxi-
dized polypyrrole nanofiber electrode modified with cobalt(II) phthalocyanine
tetrasulfonate, Biosen. Bioelectron. 24 (2008) 512.
[33] D. Das, P.K. Sen, K. Das, Carbohydrate electro-oxidation on chemically prepared
MnO2 , J. Electroanal. Chem. 611 (2007) 19.
[34] J. Chen, W.D. Zhang, J.S. Ye, Nonenzymatic electrochemical glucose sensor
based on MnO2 /MWNTs nanocomposite, Electrochem. Commun. 10 (2008)
1268.
[35] X.J. Zhang, L.L. Wang, R. Ji, G.F. Wang, Nonenzymatic glucose sensor based on
Cu–Cu2 S nanocomposite electrode, Electrochem. Commun. 24 (2012) 53.
[36] J. Liu, D.F. Xue, Rapid and scalable route to CuS biosensors: a microwave-
assisted Cu-complex transformation into CuS nanotubes for ultrasensitive
nonenzymatic glucose sensor, J. Mater. Chem. 21 (2011) 223.
[37] X.J. Zhang, G.F. Wang, A.X. Gu, Y. Wei, B. Fang, CuS nanotubes for ultrasensitive
nonenzymatic glucose sensors, Chem. Commun. 45 (2008) 5945.
[38] K. Schachl, H. Alemu, K. Kalcher, J. Jezkova, I. Svancara, K. Vytras, Amperomet-
ric determination of hydrogen peroxide with a manganese dioxide-modified
carbon paste electrode using flow injection analysis, Analyst 122 (1997) 985.
[39] X. Bo, J. Bai, L. Wang, L. Guo, In situ growth of copper sulfide nanoparticles on
ordered mesoporous carbon and their application as nonenzymatic ampero-
metric sensor of hydrogen peroxide, Talanta 81 (2010) 339–345.
[40] B.R. Eggins, Chemical Sensors and Biosensors, John Wiley & Sons, UK, 2003.
[41] B.H. Liu, R.Q. Hu, J.Q. Deng, Characterization of immobilization of an enzyme
in a modified Y zeolite matrix and Its application to an amperometric glucose
biosensor, Anal. Chem. 69 (1997) 2343.
[42] Y.P. Sun, H. Buck, T.E. Mallouk, Combinatorial discovery of alloy electrocatalysts
for amperometric glucose sensors, Anal. Chem. 73 (2001) 1599.