Sensors and Actuators B 144 (2010) 220225

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Sensors and Actuators B: Chemical
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Synthesis of CuO nanostructures and their application for nonenzymatic
glucose sensing
Xue Wang
a
, Chenguo Hu
a,
, Hong Liu
b
, Guojun Du
b
, Xiaoshan He
a
, Yi Xi
a
a
Department of Applied Physics, Chongqing University, 174 Shapingba Street, Chongqing 400044, PR China
b
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
a r t i c l e i n f o
Article history:
Received 12 August 2009
Received in revised form
16 September 2009
Accepted 24 September 2009
Available online 30 October 2009
Keywords:
CuO nanostructures
Chemical synthesis
Glucose
Nonenzymatic sensor
a b s t r a c t
CuOowers andnanorods have beensynthesizedfor the rst time bythe composite-hydroxide-mediated
and the composite-molten-salt method, respectively, with advantages of one-step, ambient pressure,
low temperature, template-free and low cost. Both nanostructures have been applied to modify the
graphite substrates for nonenzymatic glucose detection. Compared with bare graphite electrode, the
newelectrodes exhibit excellent catalysis to direct glucose oxidation. Though the electrode based on the
CuO owers has higher sensitivity than that of the CuO nanorods modied electrode, the latter presents
a much better linear range of glucose concentration and a shorter response time. Both electrodes exhibit
the same detection limit of glucose as low as 4M. In addition, the detection of dopamine and ascorbic
acidhas also beencarriedout onthese CuOnanostructure modiedelectrodes, indicating goodselectivity
for glucose detection.
2009 Elsevier B.V. All rights reserved.
1. Introduction
As an important p-type semiconductor metal oxide with a
narrow band gap (1.2eV), copper oxide (CuO) has been exten-
sively studied because of its diverse applications as material for
heterogeneous catalysts, gas sensors, optical switch, magnetic stor-
age media, lithium-ion electrode materials, eld emission devices,
solar cells, etc. [18]. During the past few years, a variety of CuO
nanostructures have been prepared. However, most of the prepa-
rations are somewhat similar, which involve multiple steps, such
as the fabrication of Cu(OH)
2
previously as a sacricial precur-
sor/template followed by thermal decomposition [919].
Nanostructured CuOis promising in the development of nonen-
zymatic glucose sensor because of its highly specic surface area,
good electrochemical activity, and the possibility of promoting
electron transfer reactions at a lower overpotential [9,10,20]. Pre-
vious attempts are limited by complex fabrication processes and
the fabricated sensors exhibit a poor linear detection range. Prop-
erties of materials at nanoscale strongly depend on their shape and
dimensions. It would be interesting to seek simpler processes for
the synthesis of different CuO nanostructures with superior cat-
alytic properties for fast, sensitive, and stable detection of glucose.
We note that the synthesis of ower-shaped CuO nanos-
tructures have been reported previously by Hahns group and

Corresponding author. Tel.: +86 2365104741; fax: +86 2365111245.

E-mail address: hucg@cqu.edu.cn (C. Hu).
Zhangs group [8,1719]. However, their processes employ an
organic directing agent and complex synthesis steps. Herein,
we present two novel synthesis methods for the preparation of
CuO nanostructures, one is the composite-hydroxide-mediated
(CHM) method [21,22], another is the composite-molten-salt
(CMS) method. CuO ower- and rod-shaped nanostructures have
been synthesized by the CHM and CMS method, respectively.
Nonenzymatic glucose sensors based on these CuO nanostructures
have been fabricated to detect glucose through electrochemical
measurement. The electrochemical characteristics of the elec-
trodes modied by the two different CuO nanostructure have
been studied by electrochemical impedance spectrum (EIS), cyclic
voltammetry (CV) and amperometry, in comparison with that
of a pure graphite electrode. The high selectivity of the CuO
nanostructure modied electrodes has been proved by detect-
ing glucose in presence of dopamine (DA) and ascorbic acid
(AA).
2. Experimental
2.1. Chemicals
CuCl
2
2H
2
O, KOH, NaOH, KNO
3
, LiNO
3
, Na
2
S9H
2
O, Na
2
SO
4
, and
glucose were of analytical grade and purchased from Chongqing
Chemical Reagent Company. DA, AA and Naon were purchased
from SigmaAldrich while silver paste was bought from Struc-
ture Probe, Inc. All solutions were freshly prepared with deionized
water.
0925-4005/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2009.09.067
X. Wang et al. / Sensors and Actuators B 144 (2010) 220225 221
Fig. 1. (A) XRD pattern of CuO synthesized by the CMS method (a) and CHM method (b). EDS spectrum of CuO synthesized by the CMS method (B) and CHM method (C).
2.2. Synthesis of ower-shaped CuO nanostructures and CuO
nanorods
Flower-shaped CuO nanostructures were synthesized by the
CHM method. In a typical reaction: (1) an amount of 9g of mixed
hydroxides (NaOH/KOH=51.5:48.5) was placed in a 25mL Teon
vessel. (2) 2mmol CuCl
2
2H
2
O and 0.1g Na
2
S9H
2
O were added
into the vessel. (3) The vessel was sealed and put in a furnace pre-
heated to 200

C. (4) After reacting for 24h, the vessel was taken

out and let cool down to roomtemperature naturally. (5) The black
product was washed with deionized water and ethanol several
times.
CuO nanorods were synthesized by the CMS method in the
process much similar to the steps mentioned above, except that
the reaction mediate was replaced by 9g mixed KNO
3
and LiNO
3
(KNO
3
/LiNO
3
=58:42) in the rst step and the reactants were
changed into a mixture of 2mmol CuCl
2
2H
2
O and 4mmol KOH
in the second step.
2.3. Characterization
X-ray powder diffraction (XRD) was used to identify the crys-
talline phase of the as-prepared samples and energy dispersive
X-ray spectroscopy (EDS) was used to investigate the chemi-
cal composition. The surface morphology and the size of the
as-synthesized CuO nanostructures were observed using eld-
emission scanning electron microscopy (FE-SEM) and transmission
electron microscopy (TEM).
Fig. 2. (A) FE-SEM image and (B) TEM image of CuO synthesized by the CHM method, and its SAED pattern in the inset of (B). (C) FE-SEM image and (D) TEM image of CuO
synthesized by the CMS method.
222 X. Wang et al. / Sensors and Actuators B 144 (2010) 220225
Fig. 3. EIS of the three different modied electrodes in 0.1M Na
2
SO
4
at a bias
potential of 0.1V (vs. Ag/AgCl), and inset shows a magnied plot of high frequency
domain.
2.4. Electrode fabrication and electrochemical measurements
The CuO nanostructure modied electrodes were prepared as
follows: (1) a graphite substrate (810mm
2
) was carefully pol-
ished, rinsed with deionized water and ethanol, and then dried
at 60

C. (2) 10mg of the as-synthesized CuO nanomaterial was

dispersed in 5mL ethanol and then ultrasonicated for 5min to let
it disperse uniformly. (3) 0.5mL of the obtained suspension was
sprayed on the graphite substrate surface and then dried at 60

C.
(4) Ohmic contact for the planar lmwithcopper wire was made by
silver paste. To make the CuO nanostructure lmstable in aqueous
media, 0.1mL of Naon(0.5wt%) solutionwas cast onthe surface of
the electrode. (5) The edges and back of the electrode were covered
by epoxy leaving an open area of about 67mm
2
. For comparison,
a pure graphite electrode covered with 0.1mL of Naon (0.5wt%)
solutiononits surface was fabricated. The obtainedelectrodes were
referredas CuOowers/Gelectrode, CuOnanorods/Gelectrode and
G electrode, respectively.
Electrochemical experiments were performed using the elec-
trochemical analyzers (LK98 BII and CHI600C) with a conventional
three-electrode system. The auxiliary electrode was planar plat-
inum and the referential electrode was Ag/AgCl electrode. Before
each measurement, the background solution was deaerated with
nitrogengas for 15min. Amperometric measurements were carried
out under a magnetically stirred condition. All the measurements
were taken at room temperature.
3. Results and discussion
3.1. Characterization of the as-prepared CuO nanostructures
XRD patterns of the CuO nanostructures obtained by the CMS
and CHMmethod are shown in Fig. 1A. All the peaks can be indexed
to the monoclinic phase of CuO (JCPDS 89-2530), and no peaks of
impurities are detected, indicating that the CuOnanostructures are
pure and well crystallined. Fig. 1B and C showtypical EDS results of
the obtained CuO nanostructures, further revealing that the sam-
ples contain elements of copper and oxygen (the peaks of silicon
and carbon come from the substrate).
Fig. 2 shows typical FE-SEMand TEMimages of the as-prepared
samples. It is clearly seen fromFig. 2A that the sample synthesized
by the CHM method is of ower-shaped structure consisting of
dense CuO nanosheets with typical thickness around 2050nm,
and the size of a single ower is about 3.5m. The nanosheets
Fig. 4. CVs of the (A) G electrode, (B) CuO owers/G electrode and (C) CuO
nanorods/G electrode ran at 10mVs
1
in 0.1MNaOHwith absence and presence of
glucose.
are connected together on the bases, rooted in one centre and
assembled into the beautiful ower-like morphology. The size
and morphology of ower-like CuO nanostructures in TEM image
(Fig. 2B) are consistent with FE-SEMobservation. The selected-area
electron diffraction (SAED) pattern of the CuO nanopetal con-
rms its single crystalline nature. Fig. 2C and D show the typical
FE-SEM and TEM image of the sample synthesized via the CMS
method, respectively, which illustrate that the obtained product
is of tiny CuOnanorods with 60150nmin length and 2040nmin
diameter.
X. Wang et al. / Sensors and Actuators B 144 (2010) 220225 223
3.2. Electrochemical measurements
Tostudythe interface properties of surface-modiedelectrodes,
EIS was used to analyze the three different electrodes with a
frequency ranging from 1 to 100kHz at the electrode potential
0.1V (vs. Ag/AgCl) in 0.1M Na
2
SO
4
solution. The Nyquist com-
plex plane plots of these three electrodes are shown in Fig. 3.
The impedance spectrum exhibits a semicircle portion at high fre-
quencies corresponding to an electron transfer limited process
and a linear portion at low frequencies resulting from a diffusion
limited process. The semicircle diameter of EIS equals the elec-
tron transfer resistance, R
et
. This resistance reveals the electron
transfer resistance of the modied layer [11,23,24]. Only a part
of the semicircles can be seen at high frequency due to the lim-
itation of the electrochemical analyzer used here, as is shown in
the inset of Fig. 3. After being modied with the CuO nanoma-
terials on the graphite substrate, the semicircle diameter of EIS
increases, indicating the adsorption of the CuO nanomaterials on
the substrate surface [11,23,24]. It is also shown that R
et
of the
CuO owers/G electrode is larger than that of the CuO nanorods/G
electrode, indicating that the electron transfer speed of the CuO
nanorods/G electrode is faster than that of the CuO owers/G
electrode.
The cyclic voltammograms (CVs) of the three obtained elec-
trodes were conducted in 50mL NaOH (0.1M) solution in the
Fig. 5. Amperometric response to successive additions of 0.5mM glucose to 0.1M
NaOH at an applied potential of 0.6V (vs. Ag/AgCl) (A) and the corresponding
calibrate sensitivity plot (B) of the CuO nanorods/G electrode (a), CuO owers/G
electrode (b) and G electrode (c). Inset of (A) displays the response to 4M glucose
of the CuO nanorods/G electrode (a) and CuO owers/G electrode (b).
absence and presence of glucose, respectively. As is shown in
Fig. 4A, no redox peaks can be observed at the G electrode. How-
ever, a gradual increase in current can be observed at around 0.6V
(vs. Ag/AgCl) on the CuO owers/G electrode (Fig. 4B) and CuO
nanorods/Gelectrode (Fig. 4C) when the glucose was added in. This
indicates that CuO nanostructures have greatly improved the per-
formance of the electrode and increased the electrocatalytic ability
Fig. 6. Amperometric response to successive additions of 1mMglucose, 0.1mMAA
and DAto 0.1MNaOHat an applied potential of 0.6V(vs. Ag/AgCl) of the Gelectrode
(A), CuO owers/G electrode (B) and CuO nanorods/G electrode (C).
224 X. Wang et al. / Sensors and Actuators B 144 (2010) 220225
towards glucose oxidation, which may be attributed to their large
surface area, high surface energy, and enhanced electron transfer
ability [20,25].
Chronoamperometry was utilized to ascertain the detection of
glucose. A 50mL 0.1M NaOH was used as the supporting solution
with an injection of 0.5mM glucose every 30s. The potential was
set at 0.6V (vs. Ag/AgCl), and the results are shown in Fig. 5. As is
expected from the CVs data (Fig. 4), the G electrode exhibits low
response (9.2A/mMcm
2
, curve c in Fig. 5B) with the addition
of glucose, while the two CuO nanostructure modied electrodes
show highly enhanced response to changes of glucose concentra-
tion. We can see that the CuO nanorods/G electrode provides a
steady current increase of 371.43A/mMcm
2
within 10s (curve a
in Fig. 5A) with a detection limit of 4M(curve a in inset of Fig. 5A),
and it gives a linear amperometric response in the glucose concen-
trationfrom4Mto 8mM(curve a inFig. 5B), whichis muchwider
than that of those congeneric sensors reported before [2224]. In
contrast, though the CuO owers/G electrode produces a much
higher sensitivity (about 709.52A/mMcm
2
with the initial injec-
tion of 0.5mMglucose, curve b in Fig. 5B) than the CuOnanorods/G
electrode owing to its high surface structure, and the same detec-
tion limit of 4M (curve b in inset of Fig. 5A), it has a longer
response time (about 15s, as is shown in curve b in Fig. 5A) and
a poor linear range (curve b in Fig. 5B), indicating a slow electron
transfer speed and adsorption of the intermediate product pro-
ducedduring the glucose oxidationprocess onthe ower-structure
surfaces.
To evaluate the selectivity of the new sensors, two possible
interfering biomolecules, dopamine (DA), ascorbic acid (AA), which
normally coexist with glucose in real samples (e.g. human blood),
were examined. Considering that the concentration of glucose
in the human blood is about 30 times of AA or DA [26,27], the
amperometric responses toward the addition of 1mM glucose,
0.1mM AA and DA were examined in 50mL NaOH (0.1M) solu-
tion at a potential of 0.6V (vs. Ag/AgCl). The results are shown
in Fig. 6. It is worth noting that the G electrode (Fig. 6A) gives
muchlarger current response to 0.1mMAA(60A) andDA(75A)
than that to 1mM glucose (3.86A). However, the CuO nanos-
tructure modied electrodes can effectively inhibit the oxidation
of AA and DA. The interferences from 0.1mM AA and 0.1mM DA
are only 4.5% and 1.9% on the CuO owers/G electrode (Fig. 6B),
and 3.8% and 2.6% on the CuO nanorods/G electrode (Fig. 6C), in
comparison with the response to 1mM glucose, respectively. This
indicates good selectivity of the CuO nanostructure modied elec-
trodes.
4. Conclusions
Flower-shaped CuO nanostructures and CuO nanorods have
been synthesized via the CHMand CMS method, respectively. Both
methods are novel, one-step, template-free and cost-effective. The
as-synthesized samples have been used to construct nonenzy-
matic glucose sensors, and these sensors have exhibited highly
enhanced electrocatalysis towards glucose oxidation compared
with that of a bare graphite electrode. Though the CuO owers/G
electrode can produce a high sensitivity of 709.52A/mMcm
2
with the initial injection of 0.5mM glucose and a low detection
limit of 4M, it cannot provide a large linear range due to its
slow electron transfer and foulness of intermediate product. In
contrast, the CuO nanorods/G electrode shows a steady sensitiv-
ity of 371.43A/mMcm
2
within 10s with successive injections of
0.5mM glucose, and a detection limit of 4M to glucose, as well
as a wide linear response from 4M to 8mM. It has been demon-
strated that the CuO nanostructure modied electrodes have good
selectivity of glucose in the presence of dopamine and ascorbic
acid.
Acknowledgments
This work has been funded by the NSFC (60976055,
50872070, 20741006), Postgraduates Science and InnovationFund
(200904B1A0010309) and, Innovative Talent Training Project (S-
09109) of the 3rd-211 Project of Chongqing University.
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Biographies
Xue Wang received her MS degree from Chongqing University in 2009. At present
she is a PhD student under the supervision of Prof. Chenguo Hu of the Department
of Applied Physics at Chongqing University.
Chenguo Hu is a professor of Physics in Chongqing University. She received
her PhD in materials from Chongqing University in 2003. Her research interests
include methodology of synthesizing nanomaterials, investigation of morphology-
dependent properties of nanomaterials and gas- or bio-sensors.
Hong Liu is a professor of the State Key Laboratory of Crystal Materials in
Shandong University. He received his PhD from the State Key Laboratory of
Crystal Materials of Shandong University in 2001. His main elds of inter-
est are the synthesis of functional crystal, ceramic materials and its properties
investigation.
Guojun Du obtained his BSc in 2007 fromShandong University, China. Currently he
is pursuing his MSc degree under the supervision of Prof. Hong Liu in Shandong Uni-
versity, China. His research interest in the study is mainly focused on modication
and application of titania-based nanobelts.
Xiaoshan He received her BS degree from Chongqing University in 2006. Cur-
rently she is a PhD student of the Department of Applied Physics at Chongqing
University.
Yi Xi obtained her MS degree in 2007 from Chongqing University. Currently
she is a PhD student of the Department of Applied Physics at Chongqing
University.