J Mater Sci: Mater Electron (2014) 25:1485–1491
DOI 10.1007/s10854-014-1757-x
Copper vanadate nanoparticles: synthesis, characterization
and its electrochemical sensing property
V. Sivakumar • R. Suresh • K. Giribabu •
R. Manigandan • S. Munusamy • S. Praveen Kumar
S. Muthamizh • V. Narayanan
Received: 6 November 2013 / Accepted: 21 January 2014 / Published online: 1 February 2014
Ó Springer Science+Business Media New York 2014
Abstract Copper vanadate (Cu2V2O7) nanoparticles
were synthesized by a simple thermal decomposition
method. The synthesized copper vanadate nanorods were
characterized by X-ray diffraction analysis, and it is found
that the synthesized sample belongs to monoclinic
Cu2V2O7. Fourier transform infrared spectroscopy (FT-IR)
confirms the formation of Cu–O bond in the sample.
Ultraviolet–visible (DRS-UV–visible) spectroscopy and
photoluminescence spectroscopy reveals the optical prop-
erty of the Cu2V2O7 nanoparticles. The nanobar-like
morphology was confirmed by both scanning electron
microscopy and high resolution transmission electron
microscopy. Further, the electrochemical sensing behavior
of Cu2V2O7 nanoparticles was investigated by cyclic vol-
tammetry using lidocaine as an analyte. The electrochem-
ical sensing experiment suggests that the Cu2V2O7
nanoparticles will become a potential candidate in the field
of drug sensor.
1 Introduction
The nanoparticles have considerable interest because of
their wide range of applications in various fields like
V. Sivakumar  R. Suresh  K. Giribabu  R. Manigandan 
S. Munusamy  S. Praveen Kumar  S. Muthamizh 
V. Narayanan (&)
Department of Inorganic Chemistry, School of Chemical
Sciences, University of Madras, Guindy Maraimalai Campus,
Chennai 600 025, Tamil Nadu, India
e-mail: vnnara@yahoo.co.in
V. Sivakumar
Orchid Chemicals and Pharmaceuticals Limited, Research and
Development Centre, Chennai 600119, India
•
catalysis, sensor, batteries, photocatalysis and data storage
devices. The nanostructured transition metal vanadates are
important functional materials due to their fascinating
structures, electronic, optical, and magnetic properties [1].
Hence, they have been used in various areas such as
catalysis [2], cathode materials in batteries [3] and
implantable cardiac defibrillators (ICDs) [4]. For example,
MVO4 (M = Pr, Er, Gd, Dy and Nd) shows catalytic
performance in the oxidative dehydrogenation of propane
[5]. Because of good conductivity and high lithium inser-
tion capability, silver vanadium oxide (SVO) has been used
as a cathode material in a primary lithium anode cell [6].
Copper vanadate has also been widely used in lithium
batteries as the anode material, and even can be used for
rechargeable lithium batteries to yield specific capacity [7].
Among the various metal vanadates, the copper vanadate
nanoparticles, which possess high discharge capacity,
superior high-rate capability and safety, have been studied
intensively as a promising cathode material for lithium ion
batteries in recent years. Several methods have been
developed for the synthesis of copper vanadate nano-
structures, such as hydrothermal method, a template-free
solution method, and co-precipitation method [8–10].
Among these methods, the thermal decomposition method
has much attraction because of low cost, less time con-
sumption and good crystallized products with high homo-
geneity. It must be indicated that there are several reports
about the synthesis and electrochemical properties of
nanosized metal vanadates. However, to the best of our
knowledge, there is no report published so far regarding the
synthesis of copper vanadate nanoparticles and their stud-
ies for electrochemical sensing applications. Here, we have
selected a convenient thermal decomposition approach to
synthesis Cu2V2O7 nanoparticles, and the electrochemical
sensing property of the nanoparticles was investigated.
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In this paper, we report a facile approach to synthesize
the copper vanadate (Cu2V2O7) nanoparticles using a
thermal decomposition method. XRD, FT-IR, UV–visible,
PL, HR-SEM and HR-TEM have been used to characterize
the nanoparticles. The prepared nanoparticles have been
used to modify the glassy carbon electrode (GCE). The
modified GCE shows lower anodic peak potential with
larger current response for the electrochemical oxidation of
lidocaine (LD) when compared to the bare GCE.
2 Experimental section
2.1 Materials
Ammonium metavanadate (NH4VO3), cupric acetate
(Cu(CH3COO)2.H2O), and 1-dodecanol used in the
experimental work were of analytical grade, supplied by
Sigma-Aldrich and used as received (i.e., without any
further purification).
2.2 Experimental procedure
The Cu2V2O7 nanoparticles were synthesized by thermal
decomposition method. In a typical synthesis, ammonium
metavanadate (0.1 mmol), cupric acetate (0.1 mmol) and
1.0 mL of 1-dodecanol were mixed and then calcined at
450 °C for 5 h in a muffle furnace. The resulting Cu2V2O7
nanoparticles were collected and subjected to further
analysis.
2.3 Characterization techniques
The structure of the sample was analyzed by a Rich Siefert
3000 diffractometer with Cu-Ka1 radiation (k = 1.5406 Å).
The sample was studied by FT-IR spectroscopy using a
Schimadzu FT-IR 8300 series instrument. The UV–Vis
absorption spectrum was obtained on a CARY 5E UV–Vis–
NIR spectrophotometer. The fluorescence measurements
were carried out on a Cary Eclipse FL1201M002 fluores-
cence spectrophotometer. The morphology of the sample
was analyzed by HR-SEM using a HITACHI SU6600 field
emission-scanning electron microscopy. HR-TEM was
recorded using a FEI TECNAI G2 model T-30 at accelerating
voltage of 250 kV. Cyclic voltammetric (CV) properties of
the Cu2V2O7 were investigated with a three electrode cell
with a platinum counter electrode and a saturated calomel
electrode (SCE) as a reference electrode. The working
electrode, was the modified GCE (Cu2V2O7/GCE) in 0.1 M
PBS (pH = 7) as the electrolyte.
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J Mater Sci: Mater Electron (2014) 25:1485–1491
Fig. 1 XRD pattern of Cu2V2O7 nanoparticles
2.4 Preparation of the modified electrode [11]
Ultrasonic agitation for 30 min was used to disperse 1 mg
of Cu2V2O7 into 5 mL of ethanol to make a homogeneous
suspension. The polished GCE was coated with 5 lL of the
above suspension. The modified GCE was activated in
0.1 M PBS solution by successive cyclic scans between
-0.2 and ?0.8 V. Before and after each experiment, the
modified GCE was washed with distilled water and reac-
tivated by the method mentioned above.
3 Results and discussion
3.1 Structural characterization
Figure 1 shows the typical XRD pattern of the as-prepared
Cu2V2O7 nanoparticles. All the diffraction peaks can be
readily indexed to the b-Cu2V2O7 [12] with the monoclinic
structure (JCPDS No. 73-1032). The obtained diffraction
peaks 16.6°, 21.1°, 21.6°, 22.2°, 24.1°, 24.7°, 28.2°, 28.9°,
29.2°, 33.9°, 35.9°, 38.1°, 39.1°, 40.1°, 42.8°, 43.3°, 49.4°,
51.4°, 54.2°, 57.2°, 58.9°, 61.4°, and 65.1° corresponding

to (110), (111), (112), 
(020), (021), (200), (112), (113),
   
(022), (222), (131), (004), (310), (313), (132), (133), (042),

(225), 
(423), 
(424), 
(316), 
(335) and (243) planes respec-
tively. As synthesized Cu2V2O7 has the lattice parameter
value a = 7.687 Å, b = 8.00 Å, c = 10.09 Å. No peaks
from other phases have been detected, indicating that the
product is highly pure. It was observed that the diffraction
peaks are narrow. The average crystallite size of the
Cu2V2O7 nanoparticles were calculated as 59 nm using
Scherrer formula,
J Mater Sci: Mater Electron (2014) 25:1485–1491 1487

Fig. 3 DRS UV–visible absorption spectrum of Cu2V2O7

Fig. 2 FT-IR spectrum of Cu2V2O7 nanoparticles nanoparticles

D ¼ Kk=ðb cos hÞ
where, K is a shape factor, k is the wavelength, b is the full
width at the half-maximum of the line and h is the dif-
fraction angle.
The structural information of the Cu2V2O7 nanoparticles
was further identified by the FTIR spectrum as shown in
Fig. 2. The FTIR spectrum of the Cu2V2O7 nanoparticles
acquired in the range of 400–4,000 cm-1 is very similar to
that reported for Cu2V2O7 [13]. It shows the bands at
3,435, 1,634, 1,385, 1,119, 943, 828, 713 and 551 cm-1.
The band present at 3,435 and 1,634 cm-1 correspond to
the OH stretching vibration and bending vibration of water
molecules [14]. The band at 943 cm-1 is attributed to the
VO3 symmetric stretching vibrations and bands at 828, and
713 cm-1 are connected to the VO3 antisymmetric
stretching vibrations [15]. The band at 551 cm-1 is cor- Fig. 4 PL emission spectrum of Cu2V2O7 nanoparticles
responding to the symmetric stretching mode of V–O–V
units [16]. Furthermore, the band observed at 1,385 cm-1
is caused by overtone band. the absorption edge. Eg can be calculated by the following
equation as follows:
3.2 Optical property
ðahmÞn ¼ Bðhm  Eg Þ ð1Þ
The optical absorption spectrum of the as-synthesized where, hm is the photon energy, a is the absorption coef-
Cu2V2O7 nanoparticles is displayed in Fig. 3. The two ficient, B is a constant relative to the material and n is equal
broad peaks in the range of 300–320 nm and 420–500 nm to 2 and 1/2 for a direct transition and indirect transition
are due ligand to metal charge transfer band [17]. Essen- respectively. The estimated band gap of the synthesized
tially, the optical properties of nanoparticles are deter- Cu2V2O7 nanoparticles is about 2.8 eV. Note that very few
mined by their energy band. The optical bandgap (Eg) can literatures reported the UV–Vis absorption of copper van-
be usually estimated using the classical Tauc approach adate nanostructures. Meanwhile, the classic Tauc’s
[18], which presents the relationship between the incident approach shows the Cu2V2O7 phases with broad bandgap,
photon energy (hv) and the absorption coefficient (a) near which may have further applications in nanodevices.

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Fig. 5 FE-SEM images of Cu2V2O7 nanoparticles at a lower magnification, and b higher magnification, c EDS spectrum of Cu2V2O7
nanoparticles
The optical property of the Cu2V2O7 nanoparticles has
been further investigated using PL. The room temperature
PL spectrum of the Cu2V2O7 nanoparticles prepared at
450 °C for 5 h exhibits strong blue and green light emis-
sion centered at 484 and 528 nm, respectively (Fig. 4).
Similar results have been observed by Nakajima et al. [19]
for M2V2O7 (M = Ca, Sr and Ba). The origin of the blue
and green emission bands of Cu2V2O7 may be the charge
transfer transition from O 2p to V 3d orbitals in the VO4
tetrahedra.
3.3 Morphology
The morphology of the as-prepared Cu2V2O7 was charac-
terized by SEM and HR-TEM, which is shown in Figs. 5
and 6 respectively. The SEM image of Cu2V2O7 nano-
particles, prepared by calcination of the mixture of
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J Mater Sci: Mater Electron (2014) 25:1485–1491
NH3VO4 and Cu(CH3COO)2 at 450 °C for 5 h is shown in
Fig. 5a–c. It shows that the synthesized product is mostly
in sphere-like particles. The energy dispersive spectros-
copy (EDS) shows that they consist of Cu, V and O only
(Fig. 5d). Further quantitative analysis of EDS finds that
the atomic ratio of Cu:V:O is about 2:2:7, indicating that a
stoichiometric sample (Cu/V/O = 2:2:7) is obtained and is
consistent with stoichiometric Cu2V2O7, in agreement with
XRD results. From the TEM images (Fig. 6a, b), it can be
seen that there are pores on the surface of the particles
which mainly formed by the release of gaseous product
from the interior of the precursor particles.
3.4 Electrochemical sensing property
LD is one of the commonly used local anesthetics in sur-
gery, and dentistry [20]. In the case of excess intake, it
J Mater Sci: Mater Electron (2014) 25:1485–1491
Fig. 6 HR-TEM images of
Cu2V2O7 nanoparticles a lower
magnification , b higher
magnification and c SAED
pattern of Cu2V2O7
nanoparticles
may have some serious side effects on cardiovascular
systems. In adequate concentrations of LD produces a
sensory nerve blockade. Higher concentrations of LD may
be also neurotoxic. Hence, quantitative determination of
LD in blood and other biological materials is important
[21].
In this work, the synthesized Cu2V2O7 nanoparticles
were coated onto the GCE and it was used as electro-
chemical sensor for LD. The electrochemical redox
1489
behaviour of lidocaine LD at Cu2V2O7/GCE was studied
using CV. Figure 7 shows the CV of 1 9 10-4 M LD at
bare and Cu2V2O7/GCE. At bare GCE, no redox peaks
were observed for LD. However, the LD voltammogram
obtained for Cu2V2O7/GCE showed well defined redox
wave with anodic and cathodic peak potential of -0.01 and
-0.34 V respectively. The obtained redox peak may be
due to the N-oxidation of LD and the possible reaction is
given below.
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1490 J Mater Sci: Mater Electron (2014) 25:1485–1491

Fig. 7 Cyclic voltammograms of 1 9 10-4 M Lidocaine at a bare

GCE and b Cu2V2O7/GCE at the scan rate of 50 mVs-1 in PBS
(pH = 7.4) solution

N
N

O
O

NH
N - oxidation
NH

Lidocaine
It is clear that when compared with bare GCE, the
Cu2V2O7/GCE shows well defined redox peaks with
enhanced current response than the GCE. It indicates the
strong electrocatalytic ability of the Cu2V2O7/GCE. This
electrocatalytic effect was mainly attributed to the excess
available surface area of the modified electrode due to the
nanometer size of the sample [22–24].
Figure 8A shows the effect of scan rate on the electro-
chemical response of 1 9 10-4 M LD at the Cu2V2O7/GCE.
As seen in Fig. 8A, the anodic peak potential moved posi-
tively and the cathodic peak potential moved negatively, and
the value of DE was \ 200 mV. Figure 8B shows that the
reduction peak currents were linearly proportional to the
scan rate in the range from 150 to 425 mVs-1. It suggests
that the Cu2V2O7 layer has good electrochemical activity
and fast electron transfer at pH 7.4. It also suggests that the
electrode reaction corresponds to a diffusion-controlled
process [25]. The obtained linear regression equation was
I (Al) = -0.01 m (mVs-1)–3.318 (R2 = 0.9947).
Fig. 8 a Cyclic voltammetric responses of Cu2V2O7/GCE for
1 9 10-4 M Lidocaine at different scan rates: a 50, b 100, c 150,
d 175, e 200, f 225, g 250, h 275, i 300, j 325, k 350, l 375, m 400,
n 425, o 450 and p 500 mVs-1 in 0.1 M PBS (pH = 7.4) solution.
b Plot of scan rate versus cathodic peak current
The electrochemical results indicate that catalytic reac-
tion occurred between the Cu2V2O7/GCE with LD which
facilitates electron transfer between LD and the modified
electrode; as a result the electrochemical oxidation of LD
becomes easier. The reason is that the synthesized
Cu2V2O7 nanoparticles can act as a catalyst to increase the
rate of electron transfer, lower the overpotential of LD at
the bare GCE, and the anodic peak shifts to less positive
potential. Thus, it is clear that Cu2V2O7/GCE can be suc-
cessfully used for the electrochemical sensing of LD.
4 Conclusions
In summary, we demonstrated the synthesis and sensing
property of Cu2V2O7 nanoparticles prepared in high yields

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J Mater Sci: Mater Electron (2014) 25:1485–1491
through simple thermal decomposition method. The XRD
and FTIR spectroscopy confirms the formation of
Cu2V2O7. The optical absorption property was studied by
UV–visible and PL spectroscopy. The electrochemical
sensing of LD by Cu2V2O7 nanoparticles was examined by
CV. The results suggest that the Cu2V2O7 nanoparticles
have higher electrocatalytic activity for the detection of LD
and we hope that the Cu2V2O7 nanoparticles will have a
great potential for LD determination.
Acknowledgments The authors acknowledge the HR-TEM facility
provided by the National Centre for Nanoscience and Nanotechnol-
ogy, University of Madras.
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