Highly sensitive simultaneous determination of cadmium (II), lead (II), copper

(II), and mercury (II) ions on N-doped graphene modified electrode

Huakun Xing, Jingkun Xu, Xiaofei Zhu, Xuemin Duan, Limin Lu, Wenmin
Wang, Youshan Zhang, Taotao Yang

PII: S1572-6657(15)30221-6
DOI: doi: 10.1016/j.jelechem.2015.11.043
Reference: JEAC 2390

To appear in: Journal of Electroanalytical Chemistry

Received date: 25 August 2015

Revised date: 18 November 2015
Accepted date: 30 November 2015

Please cite this article as: Huakun Xing, Jingkun Xu, Xiaofei Zhu, Xuemin Duan,
Limin Lu, Wenmin Wang, Youshan Zhang, Taotao Yang, Highly sensitive simultane-
ous determination of cadmium (II), lead (II), copper (II), and mercury (II) ions on
N-doped graphene modified electrode, Journal of Electroanalytical Chemistry (2015), doi:
10.1016/j.jelechem.2015.11.043

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 ACCEPTED MANUSCRIPT

Highly sensitive simultaneous determination of cadmium (II),

lead (II), copper (II), and mercury (II) ions on N-doped
graphene modified electrode

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Huakun Xing , Jingkun Xu a, †, Xiaofei Zhu a, Xuemin Duan a,*, Limin Lu b,* ,
a,b†

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Wenmin Wang b, Youshan Zhang a, Taotao Yang a

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a
School of Pharmacy, Jiangxi Science and Technology Normal University, Nanchang

330013, PR China
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b
College of Science, Jiangxi Agricultural University, Nanchang 330045, PR China
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†
These authors contributed equally to this work and should be considered co-first
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authors.
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*To whom correspondence should be addressed.

E-mail: duanxuemin@126.com (X. Duan), lulimin816@hotmail.com (L. Lu).

Tel.: +86 791 83802632; Fax: +86 791 83805385.

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Abstract

Toxic heavy-metal ions are well known to be severely harmful to human health.

Therefore, the development of fast and sensitive methods for their detection has

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drawn a great attention in recent years. Herein, a sensitive electrochemical platform

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for the simultaneous determination of Cd2+, Pb2+, Cu2+, and Hg2+ has been constructed

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based on N-doped graphene (NG) modified electrode using differential pulse stripping

voltammetry (DPSV). NG was synthesized by a facile, efficient and green

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electrochemical method. The structure and composition of NG were studied by
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scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS),

X-ray photoelectron microscopy (XPS) techniques, chronocoulometry and N2

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adsorption-desorption measurements. The NG modified electrode showed excellent

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catalytic activity for selective detection of Cd2+, Pb2+, Cu2+, and Hg2+ due to its
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particular structure and unique electronic properties. Under optimal conditions, the
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limits of detection were estimated to be 0.05 μM for Cd2+ and Hg2+, 0.005 μM for
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Pb2+ and Cu2+, respectively. Finally, the method was applied to the simultaneous

detection of trace metal ions in the tap water samples.

Keywords: Nitrogen doped graphene; Simultaneous determination; Heavy metal ions;

Differential pulse stripping voltammetry; Sensor

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1. Introduction

The presence of heavy metals in the environment is a major concern because of

their toxicity and threat to human life and environment [1,2]. Therefore, developing

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rapid, sensitive and simple analytical methods for the detection and monitoring of

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these toxic metal ions is urgently needed. Until now, various techniques and methods

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have been employed for analysis of heavy metals, including atomic absorption

spectroscopy [3], UV-vis spectrometry [4], surface enhanced Raman spectrometry [5],

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inductively coupled plasma mass spectrometry [6] and electroanalytical techniques
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[7-10]. Among them, electrochemical method, such as differential pulse stripping

voltammetry (DPSV) is an efficient technique for detecting heavy metal ions owing to
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its low cost and high sensitivity. Moreover, stripping analysis using chemically
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modified electrode has been proved to show significant selectivity toward some metal
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ions.
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Graphene is an interesting two-dimensional carbon material that has received

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great attention in the field of electrochemical sensors due to its unique planar structure,

high chemical stability, high specific surface area, and unique electronic and

mechanical properties. Recently, many graphene-based electrochemical sensors have

been designed for detecting heavy metal ions. For example, Muralikrishna et al. [11]

reported simultaneous reduction and functionalization of GO with L-cysteine at the

edges and basal planes in a single step and the obtained composites have been used

for simultaneous electrochemical determination of four heavy metal ions. Zhao et al.

[12] presented an ultra-sensitive and selective electroanalytical method for the

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detection of lead at trace levels using a polypyrrole-reduced graphene oxide

nanocomposite modified electrode. Zhang et al. [13] used graphene modified carbon

nanosheet as an efficient electrochemical sensing material for sensitive detection of

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trace amounts of Pb(II) in an aqueous solution. Although all the above materials

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showed improved stripping signals, new materials are still needed to develop highly

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sensitive sensing platform.

In fact, chemical dopants in carbon materials with foreign atoms such as

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phosphorus [14], boron [15], and nitrogen [16,17], is an effective method to
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intrinsically modify the properties of host materials. Among them, nitrogen doping

plays a critical role in regulating the electronic properties and tuning the mechanical
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properties and enhancing the electrocatalytic activity of carbon materials [18,19]. For
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instance, recent studies have demonstrated NG exhibited higher catalytic activity

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toward the oxygen reduction reaction than traditional Pt/C [20,21]. It has also been
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reported that N doping enhanced the biocompatibility and sensitivity of graphene in

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biosensing applications [22]. However, to the best of our knowledge, electrochemical

determination of heavy metal ions using NG has not been reported.

Inspired by the advantages of NG, the NG material was synthesized through a

one-step electrochemical strategy at room temperature and firstly used as the active

material for simultaneously electrochemical detection of Hg2+, Cu2+, Cd2+ and Pb2+ in

this present work. The detection was performed by DPSV. The NG modified

electrode showed an excellent sensitivity selectivity and stability for the analysis of

Hg2+, Cu2+, Cd2+ and Pb2+ due to its particular structure and unique electronic

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properties. The developed sensor was also successfully applied for the detection of

trace Hg2+, Cu2+, Cd2+ and Pb2+ in tap water with satisfactory results.

2. Experimental

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2.1. Chemicals and reagents

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GO was purchased from Nanjing Xianfeng Nanomaterials Technology Co., Ltd.

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(Nanjing, China). HAc was obtained from Tianjin Institute of chemical reagents and

NaAc was got from chemical reagent factory in Tianjin (Tianjin, China). 0.1 mol/L

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acetate buffer solutions (different pH) were prepared by mixing a balanced amount of
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0.1 mol/L HAC and 0.1 mol/L NaAc. NH3•H2O and NH4Cl were obtained from

Qigang nanqiao town feng xian (Shanghai, China) and Hengxing Chemical Reagen
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Co., LTD, respectively. Hg2+, Cu2+, Cd2+ and Pb2+ stock solutions (10 mg·L-1) were
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prepared using mercury, copper, lead and cadmium hydrochloride salts, respectively.
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All reagents were of analytical grade, and doubly distilled water was used throughout
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the experiments.
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2.2. Apparatus

Scanning electron microscope (SEM) images and energy dispersive X-ray

spectroscopy (EDS) were performed by JEOL JSM-6700F microscope (Japan). X-ray

photoelectron spectra (XPS) were recorded by a K-Alpha spectrometer (Thermo

Fisher Scientific Inc., Switzerland) equipped with a monochromatic Al Kα source

operated at 150 W. The BET surface area was obtained by SSA4300 Specific surface

area and pore size analyzer. Electrochemical measurements were carried out on CHI

660D electrochemical workstation (Shanghai, China). The conventional

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three-electrode system involved modified electrodes as working electrode, a platinum

wire as auxiliary electrode and a saturated calomel as reference electrode (SCE).

Nitrogen gas porosimetry measurements were performed on a Quantachrome NOVA

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2000e surface area and porosity analyzer.

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2.3. Preparation of NG modified GCE

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Prior to modification, bare GCE was carefully polished with 0.05 mm alumina

slurry until a mirror shine surface was obtained, followed by successively sonicating

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in doubly deionized water and absolute ethanol and doubly deinozed water each for 5
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min, respectively.

GO was dissolved in aqueous solution containing 0.05 M NH4Cl/NH3·H2O (1:1,

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molar ratio) to form 0.25 mg mL-1 solution. To fabricate the NG modified electrode, a
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one-step electrochemical reduction was carried out according to the previous

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reference [16]: using the potentiostatic technique, NG was deposited on the bare GCE
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at a potential of -1.3 V (vs. SCE) in an GO suspension (0.25 mg mL-1) containing 0.05

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M NH4Cl/NH3 for 400 s. For comparison, the reduced graphene oxide (rGO) modified

GCE was also prepared by employing similar electrodeposition procedure in an

aqueous electrolyte of 0.25 mg mL-1 GO.

2.4. Anodic stripping voltammetric measurement of Hg2+, Cu2+, Cd2+ and Pb2+ at the

modified electrodes

The modified electrode was immersed in 0.1 M pH 4.5 acetate buffer solution

containing Hg2+, Cu2+, Cd2+ and Pb2+. The deposition potential of -1.1 V was applied

to the NG modified GCE for 300 s while the solution was stirred. Following the

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preconcentration step, the stirring was stopped and the responses were recorded by

applying a differential pulse voltammetric (DPV) scan with a scan rate of 50 mV s-1 in

the range from -0.9 to +0.5 V. Prior to the next determination, the modified electrode

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was activated for 120 s at 0.3 V in a pH 4.5 acetate buffer to remove the previous

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deposits completely.

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3. Results and Discussion

3.1. Characterization of modified electrodes

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The surface morphology of rGO and NG deposited on the indium-tin oxide (ITO)
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substrates were investigated by SEM. As shown in Fig. 1, their morphology and size

were obviously different. The rGO film obtained from the aqueous solution was rough
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and compact structure (Fig. 1A). Whereas the morphology of NG film exhibited a
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three-dimensional (3D) morphological structure which was composed of a great

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number of homogeneous and smooth nanospheres (Fig. 1B). The NG material with
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3D structure can provide a large surface area, which is beneficial to enhancing

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adsorption capacity and maintaining large electroactive area on the electrode surface.

The 3D structure may give a high sensitivity for the detection of analytes.

In addition, energy dispersive spectrum (EDS) analysis was performed to

confirm the components of the NG film (Fig. 1C). The presence of C, O, and N came

from the component elements of the NG composite. Other elements mainly originated

from electrolysis solution and ITO.

The elemental composition and nitrogen configurations of NG were analyzed by

X-ray photoelectron spectroscopy (XPS, Fig. 2). The XPS spectrum of GO dispalyed

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that GO contained only carbon and oxygen atoms (Fig. 2A). While, XPS spectra for

NG samples clearly revealed nitrogen atoms were incorporated into rGO sheets.

Moreover, from Fig. 2B, it can be seen that the total surface N content in NG was

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around 1.85% and the atomic content of O was reduced to 22.85%, which was lower

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than the O content in GO (33.45%). These results indicated the N doping process was

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accompanied by the electrochemical reduction of GO. In addition, high-resolution

C1s spectra of NG (Fig. 2C) showed three distinct peaks. A band at 284.5 eV

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corresponded to the sp2-hybridized C atoms, and the other one at 286.9 eV was
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attributed from C–O bonds and C–N bonds [23,24]. Similarly, the high-resolution N1s

spectra can generally be deconvoluted into three primary peaks (Fig. 2d), which
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corresponded to pyridine-like N (398.3 eV) and pyrrole-like N (399.5 eV),

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respectively [15,25]. Based on the information given above, the formation mechanism
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of NG at the cathodic potential is speculated that some carbon active sites appear
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temporarily during the removal of these oxygen containing species. The NH3 or other
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N containing species can thus react with these carbon active sites to form NG [16,26].

The electrochemically effective surface areas of bare GCE (Fig. 3a), rGO/GCE

(Fig. 3b) and NG/GCE (Fig. 3c) were determined by chronocoulometry using 1 mM

K3[Fe(CN)6] as model complex based on Anson equation [27]:

2nFAcD 1/ 2T 1/ 2
Q(t )   Qdl  Qads
 1/ 2

where c is the substrate concentration; n is the number of the electrons transferred

involved in the electrode reaction; F is the Faraday constant(96.485 C mol-1); D refers

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to the diffusion coefficient of K3[Fe(CN)6] in 0.1 M KCl (7.6 × 10-6 cm2 s-1) [27]; Qads

and Qdl are the surface charge and double-layer charge, respectively. Based on the

slopes of the curves of Q versus t1/2 (insert of Fig. 3), the effective surface areas of

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bare GCE, rGO/GCE and NG/GCE were estimated to be 0.084 ± 0.002 cm2, 0.266 ±

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0.04 cm2, and 0.421 ± 0.004 cm2, respectively. The effective working area of

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NG/GCE was almost 5 times larger than that of the bare GCE and 1.6 times larger

than rGO/GCE. The larger effective surface area of NG/GCE can effetely increase the

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electrochemical active site, enhance the electrochemical response and decrease the
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detection limit.

In addition, the surface area properties of rGO and NG were characterized by N2

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adsorption-desorption measurements. The Brunauer-Emmett-Teller (BET) surface

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areas of NG and rGO were 535.4 m2/g and 348.6 m2/g, respectively. The larger BET
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surface area of NG might be attributed to its 3D morphological structure.

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3.2. Voltammetric behavior of metal ions

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In order to show the outstanding advantages of the NG/GCE for the simultaneous

detection of heavy metal ions, the DPSV curves for bare GCE, rGO/GCE and

NG/GCE measured in the same solution containing 3 μM Cd2+, 6 μM Pb2+, 3 μM Cu2+

and 3 μM Hg2+ were shown in Fig. 4. As shown, four well defined stripping peaks can

be observed on three different modified electrodes. However, NG/GCE showed a

much higher peak current than those on bare GCE and rGO/GCE. The enhanced

performance was mainly attributed to nitrogen functional groups in NG. The 3D

morphological structures also contributed to the enhanced electrocatalytic activity of

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NG.

3.3. Optimization of experimental conditions

In order to develop a highly sensitive method for simultaneous determination of

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Cd2+, Pb2+, Cu2+ and Hg2+ by DPSV at NG/GCE, various experimental conditions

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were optimized.

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3.3.1. Optimization of pH value

The electrochemical responses of the mixed metal ions in 0.1 M acetate buffer

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with different pH values at NG/GCE were studied by DPSV and the results were
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shown in Fig. 5. As shown, all the stripping peak currents of the metal ions increased

with pH value ranging from 3.0 to 4.5. When pH value was above 4.5, the peak
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current of Cd2+, Cu2+ and Hg2+ decreased with increase of pH value. Whereas the peak
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currents of Pb2+ decreased only when pH value was above 5.0. Overall consideration
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of the sensitivity and stability of simultaneous determination of mixed ions, pH 4.5

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was selected in this work.

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3.3.2. Optimization of deposition potential

The investigation about the effect of deposition potential was performed by

varying the applied potential and a voltammogram was recorded. Fig. 6 showed a plot

of peak current versus deposition time in the work solution. As shown, the peak

currents of mixed ions increased remarkably as the deposition potential negatively

shifts from −0.8 to −1.1 V. When the deposition potential became more negative, the

peak currents of these ions decreased gradually. So, the deposition potential of −1.1 V

was chosen for the further work.

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3.3.3. Optimization of deposition time

Accumulation can improve the amount of metal ions absorbed on the electrode

surface, and then improve sensitivity determination. Fig. 7 showed a plot of peak

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current versus deposition time. The effect of deposition time (in the range 60–420 s)

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on the anodic peak current responses of Cd2+, Pb2+, Cu2+ and Hg2+ ions was studied.

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The peak currents of mixed ions increased with the deposition time changed from 60 s

to 300 s, which might be ascribed to the fact that the amount of metal ions at the

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modified electrode surface greatly increased with the longer preconcentration time.
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With further increase of deposition time, the peak currents of Pb2+, Cd2+ and Cu2+

decreased gradually, whereas the peak current of Hg2+ increased slightly, indicating
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that the amounts of metal ions accumulated at the surface of NG/GCE tend to limiting
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values because of competitive reaction between different ions at the modified

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electrode [28]. In consideration of the high sensitivity within relatively short analysis
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time, a deposition time of 300 s was used as the accumulation time.

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3.4. Simultaneous/individual determination of Cd2+, Pb2+, Cu2+ and Hg2+ using

NG/GCE

For the individual determination of Cd2+, Pb2+, Cu2+ and Hg2+ at NG/GCE,

DPSV was carried out in the potential range of -0.9 to 0.4 V under the optimized

experimental conditions. As shown in Fig. 8, the DPSV response of Cd2+, Pb2+, Cu2+

or Hg2+ increased linearly with the increase of the target ions concentration while the

other three ions were kept at the constant concentration of 5 µM. At NG/GCE, the

linear ranges for the determination of Cd2+, Pb2+, Cu2+ and Hg2+ were 0.05-9 µM,

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0.007-9 µM, 0.009-5 µM and 0.07-9 µM with limits of detection of 0.03 µM for

Cd2+, 0.002 µM for Pb2+, 0.001 µM for Cu2+ and 0.01 µM for Hg2+ (S/N = 3). The

sensitivities for detection of Cd2+, Pb2+ and Cu2+ Hg2+ were 2.842 µA/µM, 4.517

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µA/µM and 7.281 µA/µM, respectively. For Hg2+, the sensitivities were 15.734

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µA/µM and 4.241 µA/µM.

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Under the optimized conditions, the DPSV experiments for the simultaneous

determination of Cd2+, Pb2+, Cu2+ and Hg2+ were performed in 0.1 M acetate buffer by

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using NG/GCE. The peak currents response for different concentrations of four metal
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ions, together with the calibration plots were shown in Fig. 9. As can be seen, with the

increase of ions concentrations, the peak currents of four ions also increased (Fig. 9A).
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The resulting calibration plots (Fig. 9B) were observed to be linear over the range
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from 0.1 to 9 µM for Cd2+, 0.01 to 9 µM for Pb2+, 0.01 to 5 µM for Cu2+, together
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with 0.2 to 1 µM and 1 µM to 9 µM for Hg2+, respectively. The limit of detection for
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Cd2+, Pb2+, Cu2+, Hg2+ were determined to be 0.05 µM, 0.005 µM, 0.005 µM and 0.05
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µM, respectively. The comparison of NG/GCE with other modified electrodes for

these metal ions determination was listed in Table 1. It could be seen the proposed

sensor was comparable and even better to the previous reports. These results indicated

that NG/GCE is an appropriate platform for the determination of these metal ions.

3.5 Reproducibility, stability and interference study

The reproducibility was estimated with six different NG/GCE that were prepared

independently by the same procedure. The values of relative standard deviation (RSD)

were 0.89% for Cd2+, 1.1% for Pb2+, 0.56% for Cu2+ and 2.1% for Hg2+ in the

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presence of 5 µM metal ions, which demonstrated the reliability of the fabrication

procedure. Additionally, the stability of NG/GCE was investigated. The results

indicated that the current signal changes were less than 5% for four metal ions after 3

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weeks, indicating the modified electrode showed excellent long-term stability.

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Furthermore, the interference study was performed by adding some possible

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interfering metal cations including K+, Ca2+, Mg2+, Na+, Al3+, Ni2+, Zn2+, Mn2+, Co2+

and Li+ in 50 fold excess with analytes into a standard solution containing 5 µM Cd2+,

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5 µM Pb2+, 5 µM Cu2+ and 5 µM Hg2+ ions under the optimized working conditions.
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The current signal changes were shown in Table 2. It was found that the peak current

changes were within ±6% of DPSV signals for four metal ions. The results indicate
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that this method has acceptable selectivity.

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3.6 Determination in real samples

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In order to evaluate the applicability of the developed electrode, the analytical

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application in the simultaneous determination of four metal ions in tap water under the
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optimal DPSV conditions. The samples were acidied to pH 4.5 with HAc and NaAc

before determination. The recovery was performed with the standard addition method

to evaluate the accuracy of the method and the results are presented in Table 3. The

recoveries in the range from 98.0% to 102.4% were obtained, indicating that the

proposed electrode could be efficiently applied to mixed metal ions simultaneous

detection in real samples.

4. Conclusion

In summary, NG was prepared by electrochemical reduction of GO in ammonia

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containing aqueous solutions, and then was used as modified electrode for stripping

analysis of Cd2+, Pb2+, Cu2+, and Hg2+. Owing to nitrogen functional groups and the

specific properties of graphene, the NG modified electrode greatly enhanced the

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stripping peak currents of Cd2+, Pb2+, Cu2+, and Hg2+. In addition, the NG modified

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electrode was confirmed to have high selectivity and a long-term usage possibility as

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well as superior practical application ability for heavy metal ions detection. These

results demonstrate that NG is a promising candidate of advanced electrode material

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in electrochemical sensing and other electrocatalytic applications.
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Acknowledgements

We are grateful to the National Natural Science Foundation of China (51302117 and
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51272096), the Natural Science Foundation of Jiangxi Province (20122BAB216011

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and 20151BAB203018), Jiangxi Provincial Department of Education (GJJ13258), the

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Science and Technology Landing Plan of Universities in Jiangxi province

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(KJLD12081 and KJLD14069), Postdoctoral Science Foundation of China

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(2014M551857 and 2015T80688), Postdoctoral Science Foundation of Jiangxi

Province (2014KY14) and Jiangxi Provincial Innovation Fund of Postgraduates

(YC2015-S394) for their financial support of this work.

References

[1] I. Turyan, D. Mandler. Nature. 362 (1993) 703–704.

[2]X.B. Feng, P. Li, G. Qiu, S.F. Wang, G. H. Li, L.H. Shang, B. Meng, H.M. Jiang,

W.Y. Bai, Z.G. Li, X.W. Fu. Environ. Sci. Technol. 42 (2008) 326-332.

[3] H. Bagheri, A.Afkhami, M. Saber-Tehrani, H. Khoshsafar. Talanta. 97 (2012)

14
 ACCEPTED MANUSCRIPT

87-95.

[4] J.P. Cornard, A. Caudron, J.C. Merlin. Polyhedron. 25 (2006) 2215-2222.

[5] Y. Ma, H. Liu, K. Qian, L. Yang, J. Liu, J. Colloid Inter. Sci. 386 (2012) 451-455.

T
IP
[6] S. Arpadjan, G. Celix, S. Taskesen, S. Gucer, Arsenic. Food Chem. Toxicol. 46

R
(2008) 2871-2875.

SC
[7] G.S. Liu, J.P. Chen, X.D. Hou, W.S. Huang. Anal. Methods. 6 (2014) 5760-5765.

[8] J. Li, S.J. Guo, Y.M. Zhai, E.K. Wang. Anal Chim Acta. 649 (2009) 196-201.

NU
[9] K.B. Wu, S.S. Hu, J.J. Fei, W. Bai, Anal. Chim. Acta 489 (2003) 215-221.
MA
[10] Y.S. Gao, L.P. Wu, K.X. Zhang, J.K. Xu, L.M. Lu. Chinese Chem Lett. 26 (2015)

613-618.
D

[11] S. Muralikrishna, K. Sureshkumar, Thomas S. Varley, D.H. Nagaraju, T.

TE

Ramakrishnappa. Anal. Methods. 6 (2014) 8698-8705.

P

[12] Z.Q. Zhao, X. Chen, Q. Yang, J.H. Liu, X.J. Huang. Electrochem Commun. 23
CE

(2012) 21-24.
AC

[13] J.T. Zhang, Z.Y. Jin, W.C. Li, A.H. Lu. J. Mater. Chem. A. 1 (2003)

13139-13145.

[14] T. D. Tran, J. H. Feikert, X. Song, K. Kinoshita. J. Electrochem. Soc. 142 (1995)

3297-3302.

[15] S. Flandrois, O. Derre. J. Phys. Chem. Solids. 57 (1996) 741-744.

[16] F.X. Ma, J. Wang, F.B. Wang, X.H. Xia. Chem. Commun. 51 (2015) 1198-1201.

[17] A.L.M. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, P.M. Ajayan.

ACS Nano. 4 (2010) 6337-6342.

15
 ACCEPTED MANUSCRIPT

[18] Y.Y. Shao, J.H. Sui. G.P. Yin, Y.Z. Gao. Appl. Catal. B. 79 (2008) 89-99.

[19] B.G. Sumpter, V. Meunier, J.M. Romo-Herrera, E. Cruz-Silva, D.A. Cullen, H.

Terrones, D.J. Smith, M. Terrones. ACS Nano. 1 (2007) 369-375.

T
IP
[20] L.F. Lai, J.R. Potts, D. Zhan, L. Wang, C.K. Poh, C.H. Tang, H. Gong, Z.X. Shen,

R
J.Y. Lin, R.S. Ruoff. Energy Environ. Sci. 5 (2012) 7936-7942.

SC
[21] Y.Y. Shao, S. Zhang, M.H. Engelhard, G.S. Li, G.C. Shao, Y. Wang, J. Liu, I.A.

Aksay, Y.H. Lin. J. Mater. Chem. 20 (2010) 7491-7496.

NU
[22] Y. Wang, Y.Y. Shao, D.W. Matson, J.H. Li, Y.H. Lin. ACS Nano. 4（2010）
MA
1790-1798.

[23] Z.W. Xu, H.J. Li, B. Yin, Y. Shu, X.N. Zhao, D.S. Zhang, L.J. Zhang, K.Z. Li,
D

X.H. Hou, J.H. Lu. RSC Adv. 3 (2013) 9344-9351.

TE

[24] K.A. Worsley, P. Ramesh, S. K. Mandal, S. Niyogi, M.E. Itkis, R.C. Haddon,
P

Chem. Phys. Lett, Carbon. 45 (2007) 1558-1565.

CE

[25] X.J. Zhou, Z.Y. Bai, M.J. Wu, J.L. Qiao, Z.W. Chen. J. Mater. Chem. A. 3 (2015)
AC

3343-3350.

[26] C.Y. He, Z.S. Li, M.L Cai, M Cai, J.Q. Wang, Z.Q. Tian, X. Zhang. J. Mater.

Chem. A, 1 (2013) 1401-1406.

[27] F. Anson, Anal. Chem. 36 (1964) 932-934.

[28] R. Adams, Electrochemistry at Solid Electrodes, Marcel Dekker, New York,

1969.

[29] H. Lin, M.X. Li, D. Mihailovič, Electrochim. Acta.154 (2015) 184-189.

[30] I. Cesarino, G. Marino, J.R. Matos ,E.T.G. Cavalheiro, I. Cesarinoetal. Talanta. 75

16
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(2008) 15-21.

[31] H. Huang, T. Chen, X.Y. Liu, H.Y. Ma, Anal Chim Acta. 852 (2014) 45-54.

[32] J. Li, S.J. Guo, Y.M. Zhai, E.K. Wang. Anal Chim Acta. 649 (2009) 196-201.

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[33] A. Chira, B. Bucur, M.P. Bucur, G.L. Radu, New J. Chem. 38 (2014) 5641-5646.

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Figure Captions

Figure.1 SEM images of rGO (A) and NG (B). EDS image (C) of the NG. All the
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samples were deposited on indium tin oxide (ITO) substrates.

Figure.2 (A) XPS spectra of GO and NG. (B) Atomic percentage of N and O in GO

and NG. High-resolution C 1s (C) and N 1s (D) spectra of NG.

Figure.3 Plot of Q–t curves of bare GCE, rGO/GCE and NG/GCE in 1 mM

K3[Fe(CN)6] containing 0.1 M KCl. Insert: plots of Q–t1/2 curves on bare GCE,

rGO/GCE and NG/GCE.

Figure.4 DPSV curves at the bare GCE, rGO/GCE and NG/GCE in the presence of 3

μM Hg2+, 3 μM Cu2+, 3 μM Cd2+ and 6 μM Pb2+ together in 0.1 M acetate buffer (pH

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4.5). Deposition potential: -1.1 V, deposition time: 300 s, pulse amplitude: 50 mV,

pulse width: 50 ms.

Figure. 5 DPSV carried out on the NG/GCE in 0.1 M acetate buffer of different pH

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conditions (deposition time: 300 s, deposition potential: -1.1 V).

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Figure.6 DPSV carried out on the NG/GCE in 0.1 M acetate buffer (pH 4.5) with

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different deposition potential (deposition time: 300 s).

Figure.7 DPSV carried out on the NG/GCE in 0.1 M acetate buffer (pH 4.5) with

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different deposition time (deposition potential -1.1 V).
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Figure.8 DPSV for the each different increment of Cd2+, Pb2+, Cu2+ and Hg2+ at

NG/GCE in 0.1 M acetate buffer (pH 4.5). Inset: calibration plots of the oxidation
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peak currents as a function of Cd2+, Pb2+, Cu2+ and Hg2+ concentrations, respectively.
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Figure.9 (A) DPSV responses of the NG/GCE for the simultaneous detection of
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different concentrations of Hg2+, Cu2+, Pb2+, and Cd2+ mixed ions in 0.1 M acetate
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buffer (pH 4.5); (B) The corresponding linear calibration plots of stripping peak
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currents for Hg2+, Cu2+, Pb2+, and Cd2+.

Table 1 Comparison of the proposed sensor for determination of Hg2+, Cu2+, Pb2+, and

Cd2+ with others.

Table 2 Effect of interfering ions on the peak current change.

Table 3 Recovery measurements of the four metal ions in the tap water samples using

the modified electrode (n = 3).

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Figure 1
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Figure 3
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Figure 5
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Figure 6
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Figure 8
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Table 1

Comparison of the proposed sensor for determination of Hg2+, Cu2+, Pb2+, and Cd2+
with others.

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Determination
Electrodes Method Liner Ranges (μM) Reference
Limits (μM)

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Cd(II),0.004.5～1.3, 0.001
Mo6S9-xIxNWs/GCE DPASV [29]

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Pb(II),0.007～2.2 0.002
Cu(II),0.012～3.800 0.003

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Pb(II),0.3～7 0.04
BTPSBA/CPEa [30]
DPASV Cu(II),0.8～10 0.2

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Hg(II),2～10 0.4
Cd(II),0.005～0.28 0.001 [31]
(G)-MWCNTs/CPEb ASV
Pb(II),0.002～0.14 0.001
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Nafion-G/GCEc Cd(II),0.01～0.28 0.0002
ASV [32]
Pb(II),0.002～0.24 0.0001
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Cd(II),0.4～2 0.03
Pb(II),0.4～1.2 0.02
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L-cys-rGO/GCEd DPASV [11]

Cu(II),0.4～2 0.04
Hg(II),0.4～2 0.01
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Pb(II),0.02～0.1 0.01
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Ag-bipy-CP/PMB/GCE. DPV Cu(II),0.02～0.1 0.01

Hg(II),0.001～0.05 0.0005
Cd(II),0.05～1008 0.05
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Pb(II),0.01～9 0.005
NG/GCE DPSV This work
Cu(II),0.01～5 0.005
Hg(II),0.2～9 0.05
a: SBA-15nanostructured silica organofunction alised with 2-benzothiazolethiol
modified carbon paste electrode;

b: Graphene multi-walled carbon nanotubes;

c: Nafion-Graphene;

d: L-cysteine functionalized reduced graphene oxide.

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Table 2
Effect of interfering ions on the peak current change.
Concentration Current changes (%)
Ions
(μM) Hg2+ Cu2+ Pb2+ Cd2+
Ca2+ 50 3.85 4.82 3.59 5.34

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Mg 50 1.13 5.77 2.98 4.83
3+

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Al 50 1.22 3.10 4.02 2.99
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Na 50 0.05 1.09 2.11 0.76
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K 50 0.18 0.97 2.04 2.33
Ni2+ 50 1.55 0.57 2.84 0.74

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Zn 50 2.34 0.91 3.10 4.09
2+
Co 50 2.54 1.89 1.86 3.33
2+
Mn 50 2.43 1.36 3.90 2.79

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Table 3

Recovery measurements of the four metal ions in the tap water samples using the
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Added Found Recovery

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Analyte
(μM) (μM) (%)

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0 0 -

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0.4 0.387 96.75
Hg2+
0.8 0.803 100.38
4 4.216 105.40

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0 0 -
0.4 0.412 103.00
Cu2+
0.8 0.791 98.88
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4 4.083 102.08
0 0 -
0.4 0.413 103.25
Pb2+
0.8 0.785 98.13
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4 3.876 96.90
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0 0 -
0.4 0.391 97.75
Cd2+
0.8 0.779 97.38
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4 3.847 96.18
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Highlights

►The N-doped graphene was obtained by a one-step electrochemical strategy.

►The N-doped graphene can be used for the simultaneous detection of four metal ions.

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►Low detection limit with wide linear range could be obtained.

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►The method was successfully applied in real samples.

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