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Nanoscience and Nanotechnology
All rights reserved Vol. 15, 4855–4862, 2015
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Cerium Oxide Nanoparticles Decorated Graphene

Nanosheets for Selective Detection of Dopamine
Pranati Nayak1
2 , P. N. Santhosh2 , and S. Ramaprabhu1
∗
1
Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC);
2
Low Temperature Physics Laboratory, Department of Physics, Indian Institute of Technology Madras, Chennai 600036, India

The fabrication of a novel amperometric biosensor based on selective determination of dopamine

(DA) using nafion coated cerium oxide nanoparticles (NPs) decorated graphene nanosheets (CeO2 -
HEG-nafion) as a transducer candidate is reported. Graphene was synthesized by hydrogen exfolia-
tion technique. Decoration of CeO2 NPs over graphene nanosheets was done by chemical reduction
method. The electrochemical impedance spectroscopy (EIS) study shows the enhanced electron
transfer kinetics of the composite compared to HEG modified and bare glassy carbon electrode
(GCE). The response of the composite towards dopamine displays a lower oxidation potential of
0.23 V and a high oxidation current. The sensor exhibits linearity from 10
M to 780
M with
a detection limit of 1
M. In the presence of nafion, it shows excellent selectivity for coexisting
interference species like Ascorbic acid (AA) and Uric acid (UA). The excellent performance of the
biosensor can be attributed to large active surface area, enhanced electron transfer kinetics and
Delivered by Publishing Technology to: University of Waterloo
high catalytic activity of the composite.
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Copyright:
Keywords: Amperometric American
Biosensor, Scientific
Graphene, Publishers Selectivity, Dopamine.
CeO2 , Nanoparticles,

1. INTRODUCTION over potential of DA at traditional electrode surface and

Dopamine, a monoamine neurotransmitter, plays a signifi-
cant role in physiological function of central nervous sys-
tem in mammals. Any abnormality in concentration of DA
leads to severe neurological diseases like Parkinson’s and
Schizophrenia.1 So it’s accurate selective detection is a
subject of intense importance. Over past few years, several
methods like high performance liquid chromatography,
capillary electrophoresis, fluorescence, and colorimetric
have been employed for quantification of DA.2–6 However,
many shortcomings like instrumental complicacy, expen-
sive, time consuming and requirement of experts for
instrument handling limits the commercialization of these
biosensors. On the other hand, being an electrochemi-
cally active species, the electrochemical detection has been
received more people interest due to its easy operation,
high sensitivity and low cost. In electrochemical sensing,
DA oxidizes on electrode surface giving a current propor-
tional to DA concentration.7 But monitoring low concen-
tration of DA electrochemically is practically challenging.
The drawbacks of this approach are the high oxidation
∗
Author to whom correspondence should be addressed.
the coexistence of many active interference species like
UA and AA in the biofluid.8 The redox potential of these
species is very similar to that of DA. For this reason, it is
difficult to separate the current produced due to DA electro
oxidation from the interference. The only strategy to this
problem is to establish a platform that will reduce the oxi-
dation over potential and be permeable to DA selectively.
In this regard various attempts have been done in fabri-
cating different surface modified electrodes using various
functional nanostructure materials such as carbon nano-
tubes, metal/metal oxide nanostructures, polymers and dif-
ferent surfactant modified nanostructures. Over coating
of the functional nanostructures by anionic species like
nafion, chitosan also makes the sensing matrix robust.
Firstly, the functionalized nanometerials reduce the over
potential and secondly the anionic membrane makes a per-
meable platform for positively charged DA simultaneously
blocking the negatively charged interfering species.9
10
Recently graphene, one atom thick architecture of hexag-
onal arranged carbon atoms, has been procured an impor-
tant place in material research due to its extraordinary
properties like high electrical and thermal conductivity,
huge specific surface area, mechanical strength and unique

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Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine Nayak et al.

electronic properties.11–13 Besides these, the superior elec-
trochemical activity of graphene has also attracted focused
attentions for different sensing and energy related applica-
tions. It has been reported as a potential transducer element is represented in the schematic. Briefly, GO was pre-
in electrochemical biosensing applications.14
15 In particu- pared by Hummer’s method using flake graphite as source
lar, many attempts have been done in fabricating biosen-
sors like glucose, cholesterol, organophosphorus, DNA and
immune sensors using graphene as well as graphene based
16–18
composites with different functional nanostructures.
These functional nanostructures decrease the oxidation
over potential as well as gives enhanced redox current due
to its ultra high surface chemistry.19
Being an excellently active rare-earth based metal oxide,
CeO2 has been attracted tremendous interest in recent
years. Different nanostructure CeO2 showed superior cat-
alytic performance in supercapacitors, fuel cells, lithium
ion battery, CO oxidation, hydrogen production and as
electrolyte in solid oxide fuel cell due to its excellent
electro catalytic activity.20–23 It is one of the most abun-
dant, cheap and biocompatible rare earth metal oxides.
Furthermore, in nano size CeO2 , Ce remains in a mixed
valence state (Ce3+ /Ce4+ ), which is related to the num-
ber of oxygen vacancies. This facilities the generation of
localized electrons in ceria surface thereby enhancing the
charge transfer mechanism and hence the catalytic activity
of CeO2 nanostructures.24
The present work explores the fabrication of a DA
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biosensor using nafion coated IP: cerium oxide decorated change
117.244.26.166 On: Wed, 14 Oct 2015 07:35:05 to dark black which is the confirmation
graphene nanosheets as a transducer candidate.
Copyright:The deco- Scientific
American
ration of ceria over graphene surface prevents the nanopar-
ticles from agglomeration and hence preserves its catalytic
activity. The electrochemistry of the composite towards
was investigated in detail. For DA electro oxidation,
it showed good electrochemical response which can be
attributed to the excellent catalytic activity of the CeO2
decorated graphene sheets. In the presence of nafion, it
showed excellent selectivity over coexisting interference
species like AA and UA. To the best of our knowledge
CeO2 -HEG-nafion modified electrodes have not yet been
employed for DA sensing.
2. EXPERIMENTAL DETAILS
2.1. Materials and Methods
Flake Graphite powder (99.99% SP-1, Bay carbon, aver-
age particle size 45 m), Concentrated Sulphuric acid
(H2 SO4 , 99%), Concentrated Nitric acid (HNO3 , 98%)
(from Rankem chemicals, India) were used as received.
Dopamine hydrochloride was purchased from Sigma
Aldrich. L-AA and UA were purchased from sd fine-
chem. Ltd., Mumbai, India and Sisco research laborato-
ries respectively. Sodium phosphate buffer solution (PBS,
pH 7.4) was prepared using sodium dihydrogen phosphate
(NaH2 PO4 , 99.5%) and Di sodium hydrogen phosphate
(Na2 HPO4 , 98%) using de-ionized water (DI water). All
the electrochemical studies were done using PBS.
Synthesis of CeO2 -HEG was done by chemical reduc-
tion technique using cerium nitrate hexahydrate as pre-
cursor and GO for HEG. The whole synthesis procedure
material and treating it with concentrated sulphuric acid
(H2 SO4 ), sodium nitrate (NaNO3 ) and potassium perman-
ganate (KMnO4 ).25 In this method 1 gram of flake graphite
was dispersed in 23 ml of concentrated H2 SO4 and con-
tinuously stirred in an ice bath. Then 500 mg of NaNO3
and 3 gm of KMnO4 were added to the suspension grad-
ually. After removing the suspension from ice bath, it was
allowed to cool to room temperature. Then about 46 ml of
water was added to it. After 15 minutes the diluted brown
suspension was again added by worm water and treated
with 3% H2 O2 till it turns bright yellow. The suspension
was filtered and residue was repeatedly washed with copi-
ous amount of worm water. The final brown filter cake of
GO was dried under vacuum at 50  C temperature.
To prepare graphene, hydrogen exfoliation technique
was followed.26 In short, GO was sprinkled in a quartz
boat and kept in the sealed furnace. Initially argon gas was
allowed to flow for 15 minutes in order to maintain inert
atmosphere and the temperature of the furnace was raised
up to 200  C. Then highly pure H2 gas was allowed at this
temperature. Within few minutes the exfoliation occurred
giving
to: aUniversity
noticeableofvolume expansion and visible colour
Waterloo
from brown
Publishers
of conversion of GO to graphene. In order to prepare CeO2
decorated graphene, 100 mg of HEG was dispersed in DI
water under ultrasonication for 1 hour. Further 60 mg of
Ce(NO3 )3 , 6H2 O was added to the above prepared suspen-
sion and ultrasonicated for another 30 minutes. Then 0.1 M
NaOH solution was added drop wise till the pH of the sus-
pension becomes 11. The prepared composite was washed
with DI water several times and dried at 60  C temperature.
2.2. Characterization Techniques
The above-synthesized material was characterized by High
resolution transmission electron microscopy (HRTEM, FEI
Technie), Field emission scanning electron microscopy
(FESEM, FEI QUANTA), and X-ray diffractometer (PAN-
alytica Cu-K as X-ray source). Raman spectra analysis
was done by Confocal Raman spectrometer (Witec Alpha
300) with Nd:YAG laser (532 nm) as excitation source.
X-ray photoelectron spectra were recorded with SPECS
X-ray Photoelectron Spectrometer (Germany) using Mg
K as X-ray source and PHOIBOS 100MCD energy anal-
yser. All the spectra were recorded at ultra high vacuum
(10−10 mbar range). The data were analysed using CASA
XPS software. The electrochemical studies were carried
out by CH Instrument, electrochemical work station with
a three electrode electrochemical cell comprising a glassy
carbon electrode GCE (3 mm dia.) as working electrode,
Ag/AgCl (1 M KCl solution) as reference electrode and Pt

4856 J. Nanosci. Nanotechnol. 15, 4855–4862, 2015

Nayak et al. Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine

wire counter electrode. Potassium phosphate buffer solu-
tion (PBS, pH 7.4) was used as supporting electrolyte for
all electrochemical studies at ambient temperature.
2.3. Working Electrode Fabrication
The GCE was polished mirror like in sequence by 1, 0.3
and 0.05 m alumina (Al2 O3 ) slurry followed by rins-
ing thoroughly by deionised water (DI water). 1 mg of
CeO2 -HEG was dispersed in 1 ml of nafion solution (0.5%
wt diluted with ethanol) by ultrasonication. About 20 l
of the prepared dispersion was drop casted on the sign-
ing surface of GCE and allowed to dry at room tempera-
ture. The modified surface of GCE was over coated with
5 l of nafion solution and can be named as CeO2 -HEG-
nafion@GCE for further studies. For comparative studies,
HEG-nafion@GCE was prepared following the same way.
3. RESULTS AND DISCUSSION
3.1. Characterization of Materials
Anchoring of CeO2 NPs on graphene surface was observed
by electron microscopy. The Figures 1(a) and (b) shows
the FESEM images of CeO2 -HEG at different resolu-
tions. As shown, here a uniform distribution of CeO2 NPs
over two dimensional graphene surfaces is seen. The tiny
CeO2 particles of average particle size 5–10 nm is clearly
revealed from HRTEM images shown in Figures 1(c) and
(d). Insets show the high magnification HRTEM image at
a resolution of 5 nm. A clear lattice spacing of 0.35 nm
interprets the good crystallinity of CeO2 nanostructures.
The crystallinity of the material was again studied by
powder X-ray diffraction technique. The 2 value ranges
from 5 to 90 with a step size of 0.016. Figure 2
shows the XRD pattern of (a) CeO2 -HEG, (b) HEG and
(c) GO. Compared to GO, the characteristic C(002) peak
for HEG shifts from 11 to 26 which is a confirmation
of complete conversion of GO to HEG. For CeO2 -HEG,
again additional peaks appear along with graphene C(002)
peak, which were indexed to highly crystalline CeO2 struc-
tures (JCPDS No-810792). The Ce(111) peak is partially
merged with C(002) peak in the XRD pattern. The XRD
pattern reveals the good crystallinity of the composite.
Figure 3 shows the Raman spectra of (a) CeO2 -HEG
compared to (b) HEG and (c) GO. The D-band and G-band
appears at 1355 cm−1 and 1594 cm−1 for GO. Basically
the G-band is sensitive to in planar vibration of SP2 carbon
atoms where as D-band is mainly dependent on defects.
Being incorporated with oxygen containing functional

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Figure 1. (a) and (b) Field emission scanning electron microscope (FESEM) and (c) and (d) high resolution transmission electron microscope
(HRTEM) images of CeO2 -HEG. Insets: High magnification HRTEM image of CeO2 NPs.

J. Nanosci. Nanotechnol. 15, 4855–4862, 2015 4857

Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine
Figure 2. X-ray diffraction pattern of of (a) CeO2 -HEG, (b) HEG and
(c) GO.
groups in the edges as well as in-plane sp2 domains, GO
exhibits a dominant D-band over G-band which is an evi-
dence of highly disordered morphology of GO. When con-
verts to HEG, the D-band intensity decreases significantly
which is a confirmation of conversion of GO to HEG
after hydrogen reduction. Along with this, a peak shift of
the D-band and G-band to 1365 cm−1 and 1589 cm−1
Delivered
was observed which is close to that by
of Publishing
pristine graphite.
IP: 117.244.26.166
Again for CeO2 -HEG nanocomposite, a prominent peak
Copyright:
464 cm−1 appears along with D-band and G-band in the
spectrum, assigned to F2g peak. This originates from the
symmetrical stretching vibration of oxygen atoms around
cerium ion (Ce-8O) in ceria lattice.27
28
The chemical states of CeO2 NPs on graphene surface
were investigated by X-ray photoelectron spectroscopy.
Figure 4(A) depicts the comparison of survey spectrum
(SS) of (a) CeO2 -HEG, (b) HEG and (c) GO. In com-
parison to GO, the peak intensity of O 1s decreases
significantly in HEG indicating the removal of oxygen
Figure 3. Raman spectra of (a) CeO2 -HEG, (b) HEG and (c) GO.
4858
Nayak et al.
containing functional groups in hydrogen reduction. After
decoration of CeO2 NPs over graphene again the O 1s peak
becomes prominent which could be due to the oxygen
present in ceria. Including this, the peak corresponding
to Ce 3d energy band appears in the range from 878 to
925 eV in the SS. Figure 4(B) shows the deconvoluted C
1s XPS spectra of (a) CeO2 -HEG, (b) HEG and (c) GO.
The GO basal plane as wel as edges contain a consider-
able amount of functional groups in the form of carboxyl
(C–COOH), hydroxyl (C–OH), epoxide (C O C) and
carbonyl (C O). As expected, in the deconvoluted C 1S
spectra of GO (Fig. 4B(c)), the major peaks appear at
286.2 eV, 287.6 eV and 289.9 eV corresponding to C O,
C O and C C O respectively. This depicts GO surface
rich in oxygen containing functional groups. When con-
verts to graphene by hydrogen reduction, these peak inten-
sities decreases considerably (Fig. 4B(b)) which shows
negligible amount of functional groups in HEG. Similar
feature was observed in C 1s after CeO2 decoration which
is shown in Figure 4(B)(a). Figure 4(C) shows the high res-
olution Ce 3d spectra. The peaks assigned as u and v cor-
responds to the Ce 3d3/2 and Ce 3d5/2 spin-orbit coupling
states of cerium cations. Deconvolution of these peaks
results 9 peaks labelled as u, u , u , u corresponding to
Ce 3d3/2 and v0 , v, v , v , v corresponding to Ce 3d5/2
respectively.29 The u /v doublet in the spectra results
Waterloofrom Ce cations and u/v,
4+
fromto:primary photoofemission
Technology
 
University
On: u /v doublets are the shakedown peaks which basically
at Wed, 14 Oct 2015 07:35:05
American Scientific
originatesPublishers
from the transfer of electron from filled O 2p
orbitals to empty Ce 4f orbitals.30 The u /v and v0 are the
characteristic peaks of Ce3+ state. The presence of both
Ce4+ and Ce3+ ions in XPS spectra indicates the mixed
valence state of Ce in nanostructured CeO2 . The concen-
tration of Ce3+ is a measure of oxygen vacancies in ceria
lattice which intern enhances the electrochemical catalytic
activity of CeO2 .31
3.2. Electrochemical Activity Study
3.2.1. EIS of the Biosensor
Electrochemical impedance spectroscopy (EIS) is an
important tool to study different aspects of interfa-
cial behaviour in surface modified electrodes. Figure 5
shows the EIS response for (a) CeO2 -HEG-nafion@GCE,
(b) HEG-nafion@GCE and (c) bare GCE in the fre-
quency range of 100 kHz to 1 mHz using 5 mM of
K4 [Fe(CN6 ]/K3 [Fe(CN6 ] redox couple as the electro-
chemical probe. The Nyquist plot of EIS spectra consists
of a semi-circular part at high frequency domain repre-
senting charge transfer limited region and a linear part
at low frequency domain representing diffusion controlled
region. At high frequency, the diameter of the semicircle
gives the electron transfer resistance (Rct ).32 The Rct value
for CeO2 -HEG-nafion was found to be less compared to
HEG-nafion and bare GCE. This reveals enhanced electron
transfer kinetics in comparison to bare and HEG-nafion
J. Nanosci. Nanotechnol. 15, 4855–4862, 2015
Nayak et al. Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine

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Copyright: American Scientific Publishers

Figure 4. (A) Comparison of X-ray photoelectron survey spectrum survey spectrum (SS) (a) CeO2 -HEG, (b) HEG and (c) GO. (B) Deconvoluted C
1s XPS spectra of (a) CeO2 -HEG, (b) HEG and (c) GO. (C) High resolution XPS spectra of Ce 3d region.

modified GCE. This suggests a very less resistance on the
conduction pathway of electron at the modified electrode
and solution electrolyte interface. Being rich in oxygen
vacancies, and hence ease of change of oxidation state of
Ce in CeO2 , it could result a better charge transfer mecha-
nism. This illustrates good electrochemical activity of the
material.
3.2.2. Catalytic Activity Towards Dopamine
Anchoring catalytic nanostructure materials over graphene
surface is of great importance as it preserves its catalytic
activity due to high surface area of graphene and also
it impacts on the electrochemical activity of graphene.
Figure 6 shows the electrochemical response for 0.5 mM
DA in PBS (pH 7) for (a) CeO2 -HEG-nafion@GCE,
(b) HEG-nafion@GCE and (c) bare GCE at a scan rate of
50 mV/sec. The electrochemical reaction of DA at elec-
trode surface involves release of two electrons and n-dopa
quinone as oxidation product. For bare GCE, an oxida-
tion potential at 0.3 V and reduction potential at 0.05 V
was observed for 0.5 mM DA. For same dopamine con-
centration, a well-defined redox peak appears for HEG-
nafion@GCE with an oxidation potential at 0.25 V and
reduction potential at 0.07 V. The cathodic and anodic
peak current observed was also 6 fold than that of bare
GCE. The shift of redox potential towords lower value and
enhanced redox current can be attributed to the high sur-
face area and excellent charge transfer kinetics of HEG
which agrees with the previous EIS studies of modified
electrodes. For CeO2 -HEG-nafion@GCE, the CV exhibits
oxidation peak at 0.23 V and reduction peak at 0.115 V
which is better in comparison to HEG-nafion@GCE and
bare GCE. Furthermore, the redox peak current was about
8 times more than that for bare GCE. This enhanced cur-
rent at low potential can be attributed to the presence of
CeO2 NPs on graphene surfaces which enhances the cat-
alytic activity of the composite and facilitates the charge
transfer mechanism at modified electrode interface. More-
over, the effect of redox peak current on scan rate was also
studied for 0.5 mM DA which is shown in Figure 7. Insets

J. Nanosci. Nanotechnol. 15, 4855–4862, 2015 4859

Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine Nayak et al.

Figure 7. Plot of cathodic peak current (Ipc ) and anodic peak current
(Ipa ) with square root of scan rate for 0.5 mM DA for CeO2 -HEG-
Figure 5. Nyquist plot for (a) CeO2 -HEG-nafion@GCE, (b) HEG-
nafion@GCE. Insets: Cyclic voltamogram at different scan rates from
nafion@GCE and (c) bare GCE in 5 mM of K4 [Fe(CN6 ]/K3 [Fe(CN6 ]
10 mV/sec to 100 mV/sec.
with 0.1 M KCl solution as supporting electrolyte.
shifts negatively to 0.06 V giving an enhanced current
show the CV for CeO2 -HEG-nafion@GCE at different for CeO2 -HEG@GCE. But for CeO2 -HEG-nafion@GCE,
scan rate values. The redox peak current increases with again the oxidation peak disappears revealing a non-
square root of scan rate which reveals a linear behaviour conductive pathway for AA in nafion modified composite
with correlation coefficient of R2 = 0996 (for Ipc ) and
R2 = 0986 (for Ipa ). This implies the charge transfer
through CeO2 -HEG-nafion to be diffusion controlled.33

3.2.3. Interference Study Delivered by Publishing Technology to: University of Waterloo

IP: 117.244.26.166 On: Wed, 14 Oct 2015 07:35:05
As we know, AA and UA are the Copyright:
two major American
interfer- Scientific Publishers
ing species, which coexist with DA in biological fluid.
The oxidation potential of AA and UA is close to that
of DA making its accurate quantification tedious. There-
fore, the sensing platform should be able to block the
oxidation of AA and UA but simultaneously allow DA.
Figure 8(A) shows the cyclic voltamograms for 2 mM
AA for different electrodes. It is seen that for bare elec-
trode the oxidation of AA occurs at 0.29 V, which again

Figure 6. Cyclic voltamogram for 0.5 mM DA at (a) CeO2 -HEG- Figure 8. Cyclic voltamogram for (A) 2 mM UA for (a) CeO2 -HEG-
nafion@GCE, (b) HEG-nafion@GCE and (c) bare GCE in 0.1 M PBS at nafion@GCE, (b) CeO2 -HEG@GCE and (a) bare GCE. (B) 2 mM AA for
50 mV/sec scan rate. (a) CeO2 -HEG-nafion@GCE, (b) CeO2 -HEG@GCE and (c) bare GCE.

4860 J. Nanosci. Nanotechnol. 15, 4855–4862, 2015

Nayak et al. Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine
Figure 9. Amperometric response at different concentration of DA
for CeO2 -HEG-nafion@GCE. Insets: Calibration curve for different DA
concentration.
electrode. This could be due to the negatively charged
sulfonated groups in nafion, which prevents the diffusion
of negatively charged AA to modified electrode interface.
Similarly for UA also the oxidation peak gets suppressed
in the presence of nafion, which are shown in Figure 8(B).
On the other hand it facilitates the diffusion of positively
charged DA by electrostatic force of attraction. This study
reveals good catalytic behaviour of the composite for UA
and AA redox reaction andDelivered
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selectivity Technology
of nafion
modified electrodes. IP: 117.244.26.166 On: Wed, 14 Oct 2015 07:35:05 the composite.
Copyright: American Scientific Publishers
3.2.4. Amperometric i–t Analysis
Based on the above voltametric performance, the amper-
ometric response of the biosensor was recorded for suc-
cessive addition of different concentration of DA. Figure 9
shows the amperometry i–t response curve for CeO2 -
HEG-nafion@GCE at a potential of 0.23 V in pH 7 PBS
(0.1 M). After each addition of DA the solution was stirred
for 10 seconds followed by stabilization for 10 seconds in
Figure 10. Amperometric response in presence of UA and AA.
J. Nanosci. Nanotechnol. 15, 4855–4862, 2015
Table I. Comparison of the performance of CeO2 -HEG-nafion based
biosensor with very similar systems for DA detection.
Sensing material Range of detection Detection limit References
Nafion coated 0.1 M–50 M – [34]
micro electrode
Graphene 4 M–100 M 2.64 M [35]
N doped graphene 0.5 M–170 M 0.25 M [36]
Cu2 O–Graphene 0.1 M–10 M 10 nM [37]
CeO2 -HEG-nafion 10 M–780 M 1 M Present work
order to make the total solution homogeneous. It is clear
that the response current increases linearly with different
DA concentration. The sensor showed a very fast and sta-
ble response towards DA which can be attributed to high
electrocatalytic activity as well as huge active surface area
of CeO2 -HEG-nafion@GCE. The insets show the corre-
sponding calibration curve. A linear increase of current
versus DA concentration from 10 M to 780 M was
observed with a detection limit of 1 M. Furthermore,
the amperometric response in the presence of interference
species was also studied which is shown in Figure 10. No
significant change in current was observed which implies
better selectivity of the biosensor. The present results are
compared with different simillar electrochemical sensors,
which are summarized in Table I.34–37 It can be seen that
the sensor shows a good linearity over a wide range com-
paredto:toUniversity
similar systems. This can be attributed to high
of Waterloo
electrochemical activity of
4. CONCLUSION
CeO2 NPs decorated graphene nanosheets have been pre-
pared by a simple and effective chemical reduction method
and a DA biosensor has been fabricated using CeO2 -HEG
as sensing matrix. Based on low DA oxidation poten-
tial and high oxidation current, the biosensor shows a
high electrochemical response in comparison to HEG-
nafion@GCE and bare GCE. In presence of nafion, the
biosensor exhibits excellent selectivity to words major
interference species like UA and AA. The observed linear-
ity for the biosensor covers a wide range from 10 M to
780 M DA with a detection limit of 1 M. The excel-
lent electro catalytic activity, enhanced electron transfer
kinetics, wide range linearity and good selectivity show
that CeO2 -HEG based matrix can be a good platform for
electrochemical sensing of dopamine.
Acknowledgment: The authors acknowledge Indian
Institute of Technology Madras (IITM), Chennai for the
financial supports.
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Delivered
M. Kalyva, K. Triantafyllidis, byN.Publishing
D. Niarchos, Technology
Boukos, G. Basina, to:Zhang,
37. F. University
Y. Li, Y. of
Gu,Waterloo
Z. Wang, and C. Wang, Microchim Acta 173,
IP: 117.244.26.166
and V. Tzitzios, J. Nanosci. Nanotechnol. 11, 8593 (2011). On: Wed, 14 103Oct 2015 07:35:05
(2011).
Copyright: American Scientific Publishers

Received: 7 August 2013. Accepted: 25 March 2014.

4862 J. Nanosci. Nanotechnol. 15, 4855–4862, 2015