Graphene/CeO2 hybrid materials for the simultaneous electrochemical detec-

tion of cadmium(II), lead(II), copper(II), and mercury(II)

Yu-Long Xie, Su-Qing Zhao, He-Lin Ye, Jing Yuan, Ping Song, Shu-
Qing Hu

PII: S1572-6657(15)30139-9
DOI: doi: 10.1016/j.jelechem.2015.09.043
Reference: JEAC 2306

To appear in: Journal of Electroanalytical Chemistry

Received date: 30 June 2015

Revised date: 28 September 2015
Accepted date: 30 September 2015

Please cite this article as: Yu-Long Xie, Su-Qing Zhao, He-Lin Ye, Jing Yuan, Ping Song,
Shu-Qing Hu, Graphene/CeO2 hybrid materials for the simultaneous electrochemical de-
tection of cadmium(II), lead(II), copper(II), and mercury(II), Journal of Electroanalytical
Chemistry (2015), doi: 10.1016/j.jelechem.2015.09.043

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Graphene/CeO2 hybrid materials for the simultaneous

electrochemical detection of cadmium(II), lead(II), copper(II),

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and mercury(II)

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Yu-Long Xiea,*, Su-Qing Zhaob, He-Lin Yec, Jing Yuanb, Ping Songa, Shu-Qing Hua

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a: College of Chemistry and Chemical Engineering, Qinghai University for
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Nationalities, Xining, Qinghai, 810007, China

b: College of Physics and Electronic Information Engineering, Qinghai University for

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Nationalities, Xining, Qinghai, 810007, China

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c: School of Chemistry and Environmental Science, Lanzhou City University,

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Lanzhou, Gansu , 730070, China

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Abstract
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The CeO2 nanoparticle-decorated graphene hybrid was prepared by hydro-thermal

method and their application in electrochemical detection of heavy metal ions was

investigated. It was characterized by X-ray diffraction (XRD), scanning electron

microscope (SEM), and transmission electron microscopy (TEM). The

electrochemical behavior of four heavy metal ions (cadmium(II), lead(II), copper(II),

and mercury(II)) on the graphene/CeO2 hybrid nanocomposite modified glassy carbon

electrode (GCE) was investigated in acetate buffer solution by differential pulse

anodic stripping voltammetric (DPASV). Compared with the bare GCE, the proposed

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electrode showed improved analytical performance characteristics in dectecting heavy

metal ions. By using DPASV method, it shows that the graphene/CeO2 hybrid

nanocomposite modified GCE could be used for tracing Cd2+, Pb2+, Cu2+, and Hg2+

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simultaneously and selectively. Under optimum conditions, we can detect Cd2+, Pb2+,

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Cu2+, and Hg2+ simultaneously with high sensitivity in low concentration in the

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experiments.

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Keywords: Graphene/CeO2 hybrid materials, Electrochemical detection, Cadmium(II),

Lead(II), Copper(II), Mercury(II)

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*Corresponding author. Tel.: +86 15897149181

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E-mail: yulongxie2012@126.com
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1. Introduction

Heavy metals constitute a serious environmental problem [1], because these

substances are not only biodegradable but also highly toxic to living organisms [2, 3].

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Toxic metals such as Cd2+, Pb2+, Cu2+, and Hg2+ have become ecotoxicological

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hazards of prime interest and increasing significance owing to their tendency of

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accumulating in the vital organs in living beings. Cadmium, lead, copper and mercury

are cumulative toxic metals, the presence of which in the environment has been

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increasingly concerned. The pollution of cadmium, lead, and mercury has been one of
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the most serious environmental problems because of their stability in contaminated

site and complexity of mechanism in biological toxicity. Once absorbed, these metals
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can be accumulated in the body and greatly threaten the health of human [4]. Copper
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is an essential element widely distributed and always present in various shellfish,

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some dry materials, food and animal livers, which are the major contributor to dietary
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exposure of copper. It is necessary for maintaining normal biological activities of

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tyrosinase enzymes and trace level of copper (i.e. catalytic action in heme synthesis)

[5], but the intake of large quantities can be toxic. Therefore, it is necessary to

develop simple, sensitive and inexpensive methods to detect and remove these

pollutants

. The surface modification of electrodes with nano-materials has led to some

latest developments of electrochemical sensors. Several nano-materials modified

electrodes were shown to be useful for the determination of toxic heavy metals, such

as: gold nanoparticles [6], SnO2/reduced grapheme [7], carbon nanotubes [8],

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mesoporous silica [9] and so on. Currently, many efficient adsorbents and sensitive

detection devices which are based on nanomaterials especially grapheme, have been

designed due to their unique chemical, thermal, electronic, and mechanical properties

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[10].

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Graphene, a two-dimensional, single-layer sheet of sp2 hybridized carbon atom, has

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been quickly becoming a highly promising material owing to its wide variety of

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properties, such as large surface area [11], excellent electrical conductivity [12],

extraordinary electrocatalytic activity [13], good mechanical flexibility [14] and low
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cost [15]. These outstanding properties make the graphene to be optimal candidates
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for the sensitive detection devices. However, aggregations of graphene decrease its
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available surface area and reduce its adsorption capacity. These disadvatages of

graphene can be changed by synthesizing Graphene-based metal oxide hybrid.

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Graphene-based metal oxide hybrid materials have received great attention

because of their excellent properties and potential applications in many technological

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fields [16-18]. In the hybrid materials, graphene is herein assigned as an important

intermedium for the electron transmission, and also plays an efficient and traditional

role in the loading of metal oxides. Meanwhile, the rigid structure of metal oxides,

which increases the stability of the grapheme, prevents the graphene from restacking.

So the hybrid materials show a synergistic effect to induce properties that are different

from those of each individual component, and further combined the advatanges of

both materials. CeO2 is one of the most important rare earth materials, which has been

extensively studied for many technological applications including catalytist, fuel cells,

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and oxygen sensors due to its chemical stability, high mechanical strength and unique

optical properties [15, 19-22]. Therefore, the unique properties of the combination of

graphene with nano-sized CeO2 hybrid materials make them extremely attractive for

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the fabrication of metal ion sensor.

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Due to the harmful effects of heavy metals, there is a pressing need to find

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efficient methods to detect this kind of pollutions. The simultaneous detection of

cadmium(II), lead(II), copper(II), and mercury(II) was investigated by using an

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electrode modified with graphene/CeO2 in this work. The graphene/CeO2 hybrid
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materials were prepared by a solvent-thermal method. The use of graphene/CeO2

hybrid materials in the preparation of modified glassy carbon electrodes is described.

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A differential pulse anodic stripping voltammetric (DPASV) procedure were used and
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the electrode was applied in the simultaneous determination of Cd2+, Pb2+, Cu2+, and
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Hg2+ in 0.1 M NaAc-HAc buffer solution. The graphene/CeO2 modified electrode

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offers great promise for wider application as a metal ion sensor.

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2. Experimental

2.1. Reagents and apparatus

All chemicals were of analytical reagent grade and used without further

purification. Acetate buffer solutions of 0.1 M for pH 5.0 were prepared by mixing

stock solutions of 0.1 M NaAc and HAc. Double-distilled deionized water was used

throughout the study. All reagents were commercially available from Sinopharm

Chemical Reagent Co., Ltd. (China) with analytical grade and were used without

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further purification.

All electrochemical experiments were performed on an IviumStat (Ivium

Technologies, Netherlands) electrochemical workstation. A standard three-electrode

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system was used with a saturated Hg/Hg2Cl2 electrode as the reference electrode, a

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platinum wire as the counter electrode and a bare or modified glassy carbon electrode

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(GCE) as the working electrode. The morphologies of the samples were characterized

by a (Hitachi S4800, Hitachi High-Technologies Corporation, Tokyo, Japan) scanning

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electron microscope (SEM) operating at 20 kV, and (JSM-6500, JEOL Ltd., Tokyo,
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Japan) transmission electron microscopy (TEM). The crystalline features of the

samples were characterized by a powder X-ray diffraction (XRD) on (Rigaku

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D/MAX-2500, Japan Rigaku Corporation，Japan) X-ray diffractometer with Cu Kα

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irradiation (λ=0.15406 nm).

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2.2. Synthesis of graphene/CeO2

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Graphene oxide (GO) was synthesized by the modified Hummers method [23].
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Graphene/CeO2 hybrid materials was prepared as follows with some improvements

according to the references [24, 25]. An amount of 50 mg of GO was dissolved in 100

mL of distilled water with ultrasonic treatment for 2 h, then a light yellow-brown

suspension formed. Subsequently, 20 mg of Ce(NO3)3·6H2O was added into the

suspension under magnetic stirring and 2 mL of NH3·H2O was dropwised into the

mixture. Then the mixture was transferred into a Teflon stainless steel autoclave and

reacted at 180 °C for 8 h. The resulting product was separated by centrifuging and

washed several times with distilled water and ethanol, respectively. Finally, the

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obtained hybrids were dried in a vacuum desiccators at room temperature.

2.3. Fabrication of the electrochemical sensor

Prior to modification, the bare GCE was carefully polished to a mirror-like

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surface with 0.3, 0.05 mm alumina slurry, respectively. After successive sonication in

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ethanol and double distilled water, the electrode was rinsed with double distilled

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water and then dried at room temperature. The graphene/CeO2 hybrid materials were

dispersed into 0.05% Nafion aqueous solution at a concentration of 3.0 mg·mL–1 with

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the aid of ultrasonication, resulting in a homogeneous black suspension. Afterward, 5
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μL of graphene/CeO2 hybrid materials solution was dropped on the pretreated GCE

and dried at the room temperature. For comparison, graphene/GCE and CeO2/GCE
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were also prepared using the same procedure respectively.

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2.4. Electrochemical measurements

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DPASV was used for the detection under optimized conditions. The scan rate of
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50 mV·s−1 was chosen because it presented higher anodic peak currents for Cd2+, Pb2+,
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Cu2+, and Hg2+. The peak current increased in higher pulse amplitude up to 50 mV. So,

the optimized parameters of DPASV for simultaneous determination of Cd2+, Pb2+,

Cu2+, and Hg2+ in the samples were potential interval −1.0 to +0.6 V (versus

Hg/Hg2Cl2); deposition potential, −1.0 V; deposition time, 120 s; pulse amplitude, 50

mV; pulse time, 10 ms; increment potential, 4 mV; scan rate, 0.05 V/s. Bare graphene,

CeO2 nanoparticle, and graphene/CeO2 modified GCE were measured with the cyclic

voltammograms in the solution of 5 mM Fe(CN)63−/4− containing 0.1 M KCl.

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3. Results and discussion

The morphology of GO and graphene/CeO2 hybrid materials was characterized

by SEM as shown in Fig. 1a and 1b. It can be observed that the GO sheets (Fig. 1a)

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were smooth with small wrinkles at the edges. Fig. 1b showed an image of

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graphene/CeO2 sheets, and the graphene/CeO2 sheets were much rougher compared

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with GO sheets. Fig. 1c showed the morphology of graphene/CeO2 was characterized

by TEM. It also demonstrated that a large number of CeO2 nanoparticles were

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homogeneously anchored onto the surface of graphene sheets. It was attributed to the
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oxygen-containing groups’ uniform distribution on GO sheets which supplied

chemical active centers for CeO2 deposition. Furthermore, owing to the large special
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surface areas of graphene sheets, the CeO2 nanoparticles could be deposited on both
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sides of these sheets [26]. The obtained graphene sheets played the role of a stabilizer
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for its surface anchored CeO2 nanoparticles. At the same time the well-dispersed
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CeO2 nanoparticles on the graphene sheet surface could also be served as spacers to
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prevent the graphene sheets from aggregating and restacking after removal of solvents,

which increased the stability of the graphene sheets [17]. So, well-dispersed CeO2 on

supports with larger surface areas had advantages in sensor sensitivity [15, 27]. The

sample compositions were studied by energy dispersive X-ray spectroscopy (EDS)

analysis (Fig. 1d). The Ce and O peaks were from the CeO2 and graphene nanosheet;

and the C peak, clearly visible in the EDS spectrum, was from the GS. Quantitative

analysis of the EDS spectrum (the inset of Fig. 1d) revealed that the atomic ratio of

Ce versus O was not 1, indicating that the extra O was likely from graphene

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nanosheet.

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Fig. 1. (a) FE-SEM images of GO. (b) graphene/CeO2 hybrid nanocomposite. (c)
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TEM image of graphene/CeO2. (d) EDS spectrum of the graphene/CeO2 hybrid

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nanocomposite.
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Fig. 2 showed the XRD patterns of GO and graphene/CeO2. The evident

diffraction peak was found at 2θ = 11.6° in the pattern of GO, corresponding to a

plane (002) and a d-spacing of 0.746 nm, which matched well with the values

reported in an earlier literature [28]. This d-spacing was significantly expanded

compared to that of 0.337 nm for pristine graphite (2θ = 26.3°) [29]. The increase in

interlayer spacing could be attributed to the destruction of the ordinal structures of

graphite and the insertion of oxygenic groups in the interspaces. However, as shown

in Fig. 2, after the reduction reactions, the diffraction peaks of GO disappeared at

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11.6°. This gave the direct proof that GO was further converted into the graphene in

the reduction process. The other (graphene/CeO2 sample) peaks at 28.2°, 32.5°, 47.4°,

56.2° and 76.3° in the graphene/CeO2 were corresponding to the diffraction peaks of

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CeO2 [30] (JCPDS card No. 43-1002). Furthermore, except the peaks assigned to

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CeO2, not any other diffraction peaks resulted from GO or graphene can be found,

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which suggested that GO was effectively reduced into graphene and the stacking of

graphenes in the graphene/CeO2 hybrid materials was disordered [31].

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Fig. 2. XRD patterns of GO and graphene/CeO2 hybrid nanocomposite.

The cyclic voltammetric response of bare, graphene, CeO2 nanoparticle, and

graphene/CeO2 hybrid nanocomposite modified GCE had been examined using the

Fe(CN)63−/4− redox couple in neutral solution of 5 mM Fe(CN)63−/4− containing 0.1 M

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KCl (Fig. 3). As compared with the bare GCE, graphene modified electrode gave the

well-defined peak and higher current, which was attributed to its large 2-D electrical

conductivity [32]. In the case of single CeO2 modified electrode, a similar current

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response was observed compare with the bare GCE, whereas the peak separations

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increased obviously. This result indicated that the rate of electron transfer at the

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electrode surface was hindered with the attachment of CeO2 to GCE surface. After

modifying the graphene/CeO2 hybrid nanocomposite, the electrode showed the

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highest current. This revealed that the combination of CeO2 and graphene may
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provide the necessary conduction pathways on the electrode surface and a better

electrochemical catalytic behavior, resulting in the promotion of electron transfer

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process at the modified electrode surface. The cyclic voltammograms of

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graphene/CeO2 electrode was also observed to have huge capacitive current compared
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with other electrodes. Moreover, the higher peak current clearly suggested that
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graphene/CeO2 showed much better electrocatalytic activity toward Fe(CN)63−/4−

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redox couple than CeO2 nanoparticles. The remarkably enhanced voltammetric

response of Fe(CN)63−/4− could be reasonably ascribed to the synergistic effect

between CeO2 nanoparticles and graphene. The loading of CeO2, lead to the

separation of neighboring graphene and, consequently, resulted in a rich porous

texture and an enhanced available surface area. The well-dispersed CeO2 on the

graphene surface consequently ensured more exposed surfaces for a better

electrochemical of the Fe(CN)63−/4−. In addition, due to the introduction of graphenes

as a support in the hybrid, the conductivity of the hybrid should be greatly increased,

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which resulted in a faster charge transfer during the reaction and thus an improved

catalytic efficiency [33].

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Fig. 3. Cyclic voltammograms measured with bare, CeO2, graphene, and

graphene/CeO2 hybrid nanocomposite modified GCE in the solution of 5 mM

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Fe(CN)63−/4− containing 0.1 M KCl, vs. SCE.

Fig. 4 presents the DPASV analytical characteristics of bare, graphene, CeO2

nanoparticle, and graphene/CeO2 modified GCE. When the DPASV process was

carried out in a solution containing 1.0 μM, each of Cd2+, Pb2+, Cu2+, and Hg2+ in 0.1

M acetate buffer (pH 5.0), there were weak responses at bare GCE, and also weak

peaks at CeO2 nanoparticle and graphene modified GCE were observed in the

potential range of −1.0 to +0.6 V (versus Hg/Hg2Cl2). Unlikely, the sharper and

higher peak current for the four target metal ions were obtained at the graphene/CeO2

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hybrid nanocomposite electrode.

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Fig. 4. DPASV for 1.0 μM each of Cd(II), Pb(II), Cu(II), and Hg(II) on bare, CeO2,

graphene, and graphene/CeO2 hybrid nanocomposite modified GCE in 0.1 M acetate

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buffer (pH 5.0), vs. SCE.

Under the optimal experimental conditions, Cd(II), Pb(II), Cu(II) and Hg(II)
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were determined individually and simultaneously at the graphene/CeO2 hybrid

nanocomposite electrode using DPASV. Figure 5a showed the DPASV responses

toward Cd(II) at different concentrations. Well-defined peaks, proportional to the

concentration of Cd(II), were observed in the range of 0.02 to 2.5 μM. The linear

equation was i/μA = 4.9525 + 5.5461C (μM), with the correlation coefficients of

0.9985 (inset of Fig. 5a). The limit of detection (LOD) was calculated to be 2.3441 ×

10–10 M (3σ method). The DPASV responses of the graphene/CeO2 hybrid

nanocomposite electrode toward Pb(II) over a concentration range of was from 0.01

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to 2.5 μM, which was shown in Figure 5b. The linear equation was i/μA = 8.0486 +

9.5301C (μM), with the correlation coefficient of 0.9935 (inset of Figure 5b) and with

the LOD of 1.046 × 10–10 M (3σ method). The DPASV responses of the

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graphene/CeO2 hybrid nanocomposite electrode toward Cu(II) over a concentration

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range from 0.04 to 1.0 μM was shown in Figure 5c. The linear equation was i/μA =

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9.0147 + 14.7197C (μM), with the correlation coefficient of 0.9882 (inset of Figure

5c) and with the LOD of 1.124 × 10–10 M (3σ method). The DPASV responses of the

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graphene/CeO2 hybrid nanocomposite electrode toward Hg(II) over a concentration
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range from 0.002 to 0.12 μM was shown in Figure 5d. The linear equation was i/μA =

4.1077 + 103.4819C (μM), with the correlation coefficient of 0.9974 (inset of Figure
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5d) and with the LOD of 2.187 × 10–11 M (3σ method). Therefore, the graphene/CeO2
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hybrid nanocomposite electrode could serve as a good platform for the determination
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of of heavy metal ions.

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Fig. 5. DPASV response of the graphene/CeO2 hybrid nanocomposite modified GCE

for the individual analysis of (a) Cd(II) over a concentration range of 0.02 to 2.5 μM,

(b) Pb(II) over a concentration range of 0.01 to 2.5 μM, (c) Cu(II) over a

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concentration range of 0.04 to 1.0 μM, and (d) Hg(II) over a concentration range of

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0.002 to 0.12 μM.

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The typical records of DPASV analysis for the simultaneous analysis of Cd(II),

Pb(II), Cu(II), and Hg(II) at increasing concentrations by graphene/CeO2 hybrid

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nanocomposite electrode under the optimal experimental conditions were displayed in
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Fig. 6. The proposed nanocomposite was successfully applied to the simultaneous

determination for the four target metal ions. It showed individual peaks in their
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coexistence at approximately −0.76, −0.54, −0.06, and 0.31 V versus Hg/Hg2Cl2 for
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Cd(II), Pb(II), Cu(II), and Hg(II), respectively. The separation between the
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voltammetric peaks is large enough, and hence the simultaneous and selective
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detection using the graphene/CeO2 hybrid nanocomposite electrode is feasible.

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However, the poor shape of the Hg(II) stripping peaks were also observed. This result

was probably due to the formation of Cu−Hg intermetallic compound [34, 35]. As

shown in Fig. 7a, the corresponding calibration curves for Cd(II) was built from 0.2

μM up to 2.5 μM. The linear equations were I (μA) = -0.0646 + 6.6886 C (μΜ), with

the corresponding correlation coefficient of 0.9981 (inset of Fig. 7a). The limit of

detection (LOD) was calculated to be 1.944 × 10−10 M (3σ method). As shown in Fig.

7b, the corresponding calibration curves for Pb(II) was built from 0.2 μM up to 2.5

μM. The linearization equations were I (μA) = -0.0039 + 9.4289 C (μΜ), with the

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corresponding correlation coefficient of 0.9911 (inset of Fig. 7b). LOD was calculated

to be 1.0572 × 10−10 M (3σ method). As shown in Fig. 7c, the corresponding

calibration curves for Cu(II) was built from 0.2 μM up to 2.5 μM. The linear equation

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were I (μA) = 1.033 + 10.1134 C (μΜ), with the corresponding correlation coefficient

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of 0.9978 (inset of Fig. 7c). LOD was calculated to be 1.636 × 10−10 M (3σ method).

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As shown in Fig. 7d, the corresponding calibration curves for Hg(II) was built from

0.2 μM up to 2.5 μM. The linear equation was I (μA) = 3.4025 + 8.1339 C (μΜ), with

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the corresponding correlation coefficient of 0.9751 (inset of Fig. 7d). LOD was
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calculated to be 2.771 × 10−10 M (3σ method). These obtained LOD were far more

below the guideline value given by the World Health Organization (WHO).
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Fig. 6. DPASV response of the graphene/CeO2 hybrid nanocomposite modified GCE

for the simultaneous analysis of Cd(II), Pb(II), Cu(II), and Hg(II) over a concentration

range of 0.2 to 2.5 μM for each metal ions, vs. SCE.

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Fig. 7. The respective calibration curves of Cd(II), Pb(II), Cu(II), and Hg(II)

corresponding to Fig. 6.
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Toward a better understanding of the enhancement in sensitivity, when Cu(II)

and Hg(II) were analyzed simultaneously, we further studied the effect of the
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concentrations of Cd(II) or Pb(II) on the anodic peak currents of Cu(II) and Hg(II).

Fig. 8a revealed the DPASV responses of the graphene/CeO2 hybrid nanocomposite

electrode at different concentrations of Cd(II) in the presence of 1.0 μM Cu(II) and

1.0 μM Hg(II), suggesting the interference of the concentrations of Cd(II) on the

anodic peak currents of Cu(II) and Hg(II). From Fig. 8b, it can be observed that with

the addition of Cd(II), the peak current of Cu(II) increased slightly while the peak

current of Hg(II) increased significantly. This result was probably due to the

formation of Cd film and followed by the formation of Cd−Hg [36] intermetallic

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compounds during the deposition step.

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Fig. 8. (a) DPASV response of the graphene/CeO2 hybrid nanocomposite modified

GCE at 0, 0.5, 1.2, and 2.4 μM Cd(II) in the presence of 1.0 μM Cu(II) and 1.0 μM

Hg(II) in 0.1 M NaAc-HAc (pH 5.0), showing the interference of the concentrations

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of Cd(II) on the anodic peak currents of 1.0 μM Cu(II) and 1.0 μM Hg(II). (b)

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Comparison of the voltammetric peak current of Cu(II) and Hg(II) at different

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concentrations of Cd(II) corresponding to panel a.

Similarly, the DPASV responses of the graphene/CeO2 hybrid nanocomposite

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electrode at different concentrations of Pb(II) in the presence of 1.0 μM Cu(II) and 1.0
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μM Hg(II) was studied (Fig. 9). It can be observed that with the addition of Pb(II), the

peak currents of Cu(II) and Hg(II) almost remained the same at first. However, when
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the concentration of Pb(II) reached a certain high value, the peak currents of Hg(II)
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significantly increased. In addition, a slight shift for the peak of Hg(II) was observed.
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As the same with prior situation, this result was likely due to the formation of Pb film
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and followed by the formation of Pb−Hg [36] intermetallic compounds during the
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deposition step. At low level concentration of Pb(II), there were not enough Pb(II)

ions to create the film. Hence, when the measurements were carried out at high level

concentration of Pb(II), the significant increase of analytical signals were observed.

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Fig. 9. (a) DPASV response of the graphene/CeO2 hybrid nanocomposite modified

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GCE at 0, 0.2, 0.6, and 1.2 μM Pb(II) in the presence of 1.0 μM Cu(II) and 1.0 μM

Hg(II) in 0.1 M NaAc-HAc (pH 5.0), showing the interference of the concentrations

of Pb(II) on the anodic peak currents of 1.0 μM Cu(II) and 1.0 μM Hg(II). (b)

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Comparison of the voltammetric peak current of Cu(II) and Hg(II) at different

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concentrations of Pb(II) corresponding to panel a.

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Additionally, the interferences from Na+ and Ca+ were tested (Fig. 10). In all

cases, the peaks height depend on concentration of the Na+ and Ca+ ions, where the

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effect were small. So there was no significant interference upon the detection of heavy
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metal ions at high concentration.
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Fig. 10. The interference of different species in the DPASV response for the

simultaneous analysis of Cd(II), Pb(II), Cu(II), and Hg(II) over a concentration of 2.0
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μM for each metal ions, vs. SCE. (a) in different concentration of NaCl, (b) in 10 μM

NaCl and different concentration of CaCl2.

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Table 1 Comparison of the response characteristics for the present work and

some recently reported.

Method LOD LOD LOD LOD Refs.

Cd2+ (nM) Pb2+(nM) Cu2+(nM) Hg2+(nM)
SASV 1 nM 0.05 nM – – [37]
DPASV 0.044 – – – [38]
DPASV – 40.0 200.0 400.0 [39]
DPASV – – – 0.2 [40]

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SWASV – – – 1.9 [41]

SWASV 0.1015 0.1839 0.2269 0.2789 [7]
DPASV 0.1944 0.1057 0.1636 0.2771 This work

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Although the sensing properties of LOD and linear concentration range at the

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graphene/CeO2 hybrid nanocomposite were not the best compared with some work

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reported previously (Table 1), the modified electrode described here can

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simultaneously provide analysis for four target heavy metal ions. By studying the

influence of test conditions to optimize the electrochemical detection, we can detect

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Cd2+, Pb2+, Cu2+, and Hg2+ simultaneously at a low concentration level in the

experiments. Moreover, the sensing performance is good enough for implication in

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practice.
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4. Conclusions
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A novel graphene/CeO2 hybrid nanocomposite has been successfully prepared.

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The graphene/CeO2 hybrid nanocomposite can be used in the development of

modified electrodes for the simultaneous determination of Cd(II), Pb(II), Cu(II), and

Hg(II). The obtained results suggest that graphene/CeO2 hybrid nanocomposite is a

promising material which possesses the advantages of both CeO2 and graphene in

electrochemically detecting heavy metal ions. The graphene/CeO2 hybrid

nanocomposite, has proved to be a sensitive electrode for Cd(II), Pb(II), Cu(II), and

Hg(II) analysis using DPASV with satisfactory results. The obtained LOD were far

more below the guideline value given by the World Health Organization (WHO). The

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graphene/CeO2 hybrid nanocomposite, has proved to be a sensitive and effective for

simultaneous determination of Cd(II), Pb(II), Cu(II), and Hg(II) in aqueous solutions

or waste water using DPASV with satisfactory results.

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Acknowledgements

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This work is supported financially by the Natural Science Foundation of Qinghai

province (No. 2013-Z-924Q, 2013-Z-901), and the Research Program of Application

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Foundation of Qinghai Province (No. 2015-ZJ-738).
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