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In situ reduction and functionalization of graphene

oxide with L-cysteine for simultaneous
Cite this: DOI: 10.1039/c4ay01945h
electrochemical determination of cadmium(II),
lead(II), copper(II), and mercury(II) ions†
S. Muralikrishna,a K. Sureshkumar,a Thomas S. Varley,b D. H. Nagaraju*c
and T. Ramakrishnappa*a

Received 19th August 2014
Accepted 2nd September 2014
DOI: 10.1039/c4ay01945h
www.rsc.org/methods
One pot reduction and functionalization of graphene oxide (GO) with L-cysteine (L-cys-rGO) at the edges
and basal planes of the carbon layers are presented. The L-cys-rGO was characterized by X-ray diffraction
studies (XRD), X-ray photoelectron spectroscopy (XPS), attenuated infrared spectroscopy (ATIR), and Raman
spectroscopy. The surface morphology was studied by scanning electron microscopy (SEM) and
transmittance electron microscopy (TEM). The L-cys-rGO was further utilized for the simultaneous
electrochemical quantification of environmentally harmful metal ions such as, Cd2+, Pb2+, Cu2+ and
Hg2+. Detection limits obtained for these metal ions were 0.366, 0.416, 0.261 and 1.113 mg L
1
respectively. The linear range obtained for Cd2+, Cu2+ and Hg2+ was 0.4 to 2.0 mM and for Pb2+ was 0.4
to 1.2 mM. The detection limits were found to be less than the World Health Organization (WHO) limits.
The developed protocol was applied for the determination of the above metal ions in various
environmental samples and the results obtained were validated by atomic absorption spectroscopy (AAS).

with organic nucleophiles such as amines or hydroxyls through

Introduction
Graphene, a two dimensional (2D) layered material composed
of sp2 hybridized carbon atoms, has exceptional electronic,
thermal and mechanical properties.1 GO is the oxidized form of
graphene which possesses oxygen functional moieties such as
hydroxyl and epoxy groups on the basal planes and carboxylic
acid groups at the edges.2 The chemical reduction of GO to
graphene/reduced graphene oxide (rGO) was found to be
economically advantageous due to bulk production compared
to other established methods such as mechanical exfoliation,
chemical vapour deposition etc.3 However, the chemically
reduced GO undergoes agglomeration which may lead to the
restacking of some of the graphene layers. On the other hand,
chemical functionalization of graphene/rGO is the viable route
to prevent agglomeration and has been used for wide applica-
tions such as sensors, water purication, ‘paper-like’ materials,
energy-related materials, eld-effect transistors and biomedical
applications.4 In general, the covalent functionalization of GO
a
Centre for Nano and Material Sciences, Jain University, Jakkasandra, India. E-mail: t.
ramakrishnappa@jainuniversity.ac.in; dhnagu@gmail.com; Tel: +91-9035925504;
+91-80-27506270
b
Department of Chemistry, University College London, 20 Gordon St., London, WC1H
0AJ, UK
c
King Abdullah University of Science and Technology, Thuwal, Saudi Arabia
† Electronic supplementary information (ESI) available. See
10.1039/c4ay01945h
amides or esters was carried out by utilizing carboxylic groups
present at the edges of GO in the presence of coupling agents
such as N,N0 -dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-
dimethylaminopropyl)-carbodiimide (EDC), 2-(7-aza-1H-benzo-
triazole-1-yl)-1,1,3,3-tetramethyluronium hexauorophosphate
(HATU) or by converting carboxylic acid to acyl chloride using
thionyl chloride or in the presence of reducing agents. The
other way of covalent modication is by making the epoxy group
present on the basal plane of GO react with organic nucleophilic
amines in the basic medium.5 More recently, Lee et al. func-
tionalized ethylenediamine at both edges and basal planes of
GO in the presence of EDC as a coupling agent through epoxy
and carboxylic acid groups.6 Mo et al. have functionalized ionic
liquid by silane through the hydroxyl group on the surface of
GO.7 However, reduction and functionalization of GO at the
edges and basal planes of the GO layers in a single step remains
a challenge.
The presence of heavy metal ions in drinking water
exceeding WHO guideline values causes serious health issues to
both humans and aquatic life.8 It is necessary to monitor the
ux of heavy metals, which are present in micromolar levels in
drinking water aer pre-treatment before supplying to the
public. For this, electrochemical methods were found to be
advantageous because they offer excellent sensitivity, short
analysis time, portability, and lower cost than the reported
DOI: spectroscopic methods. Thus, some investigations have been

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reported by using graphene based organic and inorganic
composite electrodes for heavy metal ion detection.
The reported organic–graphene composites were restricted
to determination of one or two metal ions.9
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Here, we report simultaneous reduction and functionaliza-
tion of GO with L-cysteine at the edges and basal planes in a
single step which reduces the synthesis time and is also cost
effective over multistep reactions. The L-cys-rGO has been used
for simultaneous electrochemical determination of four heavy
metal ions such as Cd2+, Pb2+, Cu2+, and Hg2+ ions with low
detection limits 0.366, 0.416, 0.261 and 1.113 mg L
1 respec-
tively, the linear range obtained for Cd2+, Cu2+ and Hg2+ was 0.4
to 2.0 mM and for Pb2+ was 0.4 to 1.2 mM. To the best of our
knowledge it is the rst report of a graphene/rGO based organic
composite electrode used for the simultaneous detection of four
heavy metal ions in aqueous media.
Experimental
Instrumentation
All electrochemical measurements were performed using a
CHI660D potentiostat (CH instruments, Austin, USA) in a
standard three electrode system with a modied glassy carbon
as a working electrode, platinum wire as a counter electrode and
Ag/AgCl (1 M KCl) as a reference electrode. A Shimadzu Atomic
Absorption Spectrophotometer (ASS, model: AA-7000) was used
for validating the results obtained with the proposed method.
Powder X-ray diffraction data were recorded using a Philips
X'pert PRO PANalytical X-ray diffractometer with graphite
monochromatized Cu-Ka (1.5418 Å) radiation. Infrared
measurements were recorded using a ATIR Shimadzu Scanning
spectrometer (model 8400S). “X-ray photoelectron spectroscopy
(XPS) was carried out with a Thermo K alpha spectrometer using
Al K alpha X-rays (1486.6 eV) with a spot size of 400 microns and
a dual beam charge compensation system. The analyser was
operated at a pass energy of 200 eV for survey spectra (consisting
of 10 scans) and 50 eV for high resolution core line measure-
ments (consisting of 20 scans). XPS operation and spectrum
analysis was performed using Thermo Avantage soware
(version 5.41). SEM was carried out using FEI (Nova nano) and
Raman studies were carried out using Horiba Aramis using 473
nm laser. A JEOL3000F Transmission Electron Microscope (300
kV accelerating voltage) was used for generating images of GO,
rGO and L-cys-rGO.
Materials and reagents
All the chemical reagents were used without any further puri-
cation. Deionised water was used in all the experiments.
Graphite powder (<20 mm diameter) was purchased from
Aldrich. Potassium permanganate (99%) was purchased from
SD Fine chemicals. Sodium nitrate ($98%), hydrogen peroxide
($30%), sodium acetate anhydrous ($99%), acetic acid glacial
(99–100%), hydrochloric acid ($35%), ammonia solution
(>25%), cadmium(II) nitrate tetrahydrate puried ($99%), lea-
d(II) nitrate ($99%), copper(II) nitrate trihydrate ($99%),
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mercury(II) bromide and sulphuric acid (95–98%) were analyt-
ical grade reagents (AR) purchased from Merck.
Synthesis of graphene oxide
Graphite oxide was synthesized from oxidation of graphite
powder by using a modied Hummers and Offmann method.10
In a typical procedure, 3 g of graphite powder, 1.5 g of NaNO3
and 69 mL of conc. H2SO4 were mixed by constant stirring and
the mixture was cooled to below 5  C in an ice bath. Then, 9 g of
KMnO4 was added gradually under vigorous stirring and the
temperature was maintained below 10  C. The reaction mixture
was stirred for 30 min at room temperature followed by addition
of 138 mL of deionized water slowly with stirring. The temper-
ature of the mixture was increased to 98  C and maintained at
this temperature for 15 min. Finally, the reaction was termi-
nated by adding 3 mL of H2O2 followed by continuous stirring
for another 30 min at room temperature. The resultant precip-
itate was washed with 5% HCl to remove metal ions followed by
copious washing with distilled water until the supernatant of
the solution become neutral. The obtained graphite oxide was
sonicated in deionized water (0.1 mg mL
1) for 30 min to get
GO, then centrifuged and dried at room temperature.
Synthesis of L-cysteine functionalized reduced graphene oxide
The schematic representation of L-cysteine functionalised rGO
is shown in Scheme 1. Typically, 100 mg of graphene oxide (GO)
was dispersed in 20 mL of distilled water in a round-bottom
ask and 80 mg of DCC was added aer which the mixture was
stirred at room temperature for 30 min and then sonicated for
30 min. 80 mg of L-cysteine was added into 80 mL of distilled
water contained in a beaker and the pH of the solution was
adjusted to 10.4 by using ammonium hydroxide. The pH 10.4 L-
cysteine solution was added to the GO–DCC mixture and the
reaction mixture was reuxed (temperature ¼ 80  C) for 24 h.
The obtained product was ltered by washing with acetone,
ethanol and acetonitrile followed by water. Finally, the resulting
product was dried under an oven at 60  C for 12 h. Similarly,
rGO was synthesized in the presence of ammonium hydroxide
without adding DCC and L-cysteine.
Electrode modication
Prior to electrode modication, the glassy carbon (GC, 3 mm
diameter) electrode was polished with an alumina slurry of
different particle sizes (1, 0.3 and 0.05 microns) followed by
rinsing with a copious amount of distilled water. Then the
Scheme 1 Schematic representation for the synthesis of GO followed
by L-cys-rGO.
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Fig. 1 XRD patterns of (a) GO, (b) L-cys-rGO and (c) rGO.
Fig. 2 AT-IR spectra of (a) GO, (b) L-cys-rGO and (c) rGO.
electrodes were sonicated in the ethanol–water (1 : 1) mixture
for about 5 min. Finally, rinsed with distilled water and dried at
room temperature. 1 mg of L-cys-rGO was dissolved in 1 mL of
the water–ethanol mixture (0.7 : 0.3) and sonicated for 30 min.
10 mL of that solution was drop cast on the surface of the glassy
carbon electrode and dried under room temperature.
Results and discussion
Spectroscopic characterisation
XRD studies. The XRD patterns of synthesized GO, L-cys-rGO
and rGO are shown in Fig. 1. The interlayer basal spacing due to
the presence of oxygen functional groups of GO calculated from
the rst reection was found to be 7.72 Å. The basal spacing
increases from 7.72 Å to 8.78 Å for L-cys-rGO due to intercalation
of L-cysteine molecules in between the layers. However, the rGO
obtained using ammonium hydroxide show a decrease in the
Fig. 3 Raman spectra of (a) GO, (b) L-cys-rGO and (c) rGO.
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basal spacing from 7.72 Å to 3.52 Å. The decrease in the basal
spacing conrms that GO is converted to rGO, the observed
basal spacing matches with the previously synthesized gra-
phene from the solvothermal method.11
AT-IR studies. The AT-IR spectra of GO, L-cys-rGO and rGO
are shown in Fig. 2. GO shows the characteristic peaks at 1043,
1221, 1721 and around 3200–3400 cm
1 for alkoxy, epoxy
carboxyl and hydroxyl groups, respectively (Fig. 2a). These peak
intensities decrease in the case of L-cys-rGO and rGO and the
new peaks appear at 1566 and 1288 cm
1 in the case of L-cys-
rGO, 1476 and 1288 cm
1 for rGO due to the presence of strong
in-plane C–N scissoring absorptions and C–O stretching vibra-
tion. This conrms nucleophilic substitution of –NH2 to the
epoxide carbon and the b-carbon of –OH groups [Fig. 2b and
c].12
Raman spectroscopic studies. Raman spectra of GO, L-cys-
rGO and rGO are shown in Fig. 3. GO shows two prominent
peaks, one at 1350 cm
1, the defect (D) peak which appears due
to breathing mode of k-point phonons with A1g symmetry and
the other at 1594 cm
1, the graphitic lattice (G) peak which
arises due to the rst order scattering of the E2g phonon of the
sp2 carbon lattice. In the case of L-cys-rGO, the D-band shis
from 1351 cm
1 to 1348 cm
1 and G band shis from 1594
cm
1 to 1581 cm
1 respectively. The deviation of D and G bands
corresponds to the functionalization of organic molecules on
the surfaces of carbon layers.13 This conrms that L-cysteine
molecules are functionalized on the surface of the GO layer. The
intensities of the two bands are interchanged; this conrms
that GO is converted to functionalized rGO.
XPS studies of graphene oxide. The wide scan XPS spectrum
of GO is shown in Fig. 4. (a). The C1s core level high resolution
spectra show four components that correspond to carbon atoms
in different functional groups [Fig. 4b]. The non-oxygenated
ring C]C appears at 284.64 eV, the C in C–OH bonds at 285.34
eV, the carbonyl C (C]O) at 287.28 eV and the carboxylate
carbon (HO–C]O) at 289.07 eV. Similarly O1s core level high
resolution spectra consist of two O components, one at 532.19
eV (C–OH) and another at 533.15 eV (C–O–C) [Fig. 4c].
XPS studies of L-cysteine functionalized reduced graphene
oxide. The wide scan XPS spectrum of L-cys-rGO shows the S2p3/
2
peak at 164.02 eV, whereas this peak was not observed in the
case of GO as well as chemically reduced GO. This conrms that
the L-cysteine molecule is covalently functionalized with GO
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Fig. 4 (a) The wide scan XPS spectrum of graphene oxide, (b) core
level high resolution C1s spectra, and (c) core level high resolution O1s
spectra.
Fig. 5 (a) The wide scan spectrum of L-Cys-rGO, (b) core level C1s XPS
spectra, (c) core level N1s XPS spectra, (d) core level O1s XPS spectra,
and (e) core level S2p XPS spectra.
[Fig. 5a]. Then the core level high resolution C1s XPS spectra
also indicates a considerable degree of reduction in oxygen
functionalities. The deconvolution spectra show four
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components which corresponds to carbon atoms in different
functional groups. The non-oxygenated ring C]C appears at
284.65 eV, the C in C–OH bonds at 286 eV, the carbonyl C (C]O)
at 288.4 eV and the carboxylate carbon (HO–C]O) at 291.99 eV.
But there is drastic increase in C]C atomic % of L-cys-rGO as
compared to C]C atomic % of GO due to reduction of oxygen
functional moieties and there is decrease in atomic % of C–OH
and HO–C]O [Fig. 5b]. The further increase in nitrogen N1s
peak intensity in L-cys-rGO as compared to aminated rGO
indicates that L-cysteine was functionalized at edges and basal
planes through amide and the C–N bond [Fig. 5c] The decrease
in the peak intensity of O1s peaks [(531.09 eV (C–OH) and
532.43 eV (C–O–C))] in the L-cys-rGO as compared to GO,
suggests that GO was found to be converted into rGO along with
functionalization by L-cysteine [Fig. 5d].
XPS studies of reduced graphene oxide. The wide scan XPS
spectrum has been shown in Fig. 6a. The core level high reso-
lution C1s XPS spectrum of rGO show four components such as
C]C at 284.35 eV, C–OH at 286.06 eV, C]O at 288.34 eV, and
C]O (OH) at 290.88 eV, as shown in Fig. 6b. In comparison to
those of the pristine GO and L-cys-rGO, the XPS peak intensities
of oxygen-containing functional groups of aminated rGO are
relatively decreased, indicating that a considerable amount of
functional groups in GO have been reduced by ammonia.
Furthermore the N1s scan spectra of this GO has a new peak at
399.57 eV [Fig. 6c], attributable to the N1s species of C–N bonds,
which indicates that the amine group of ammonia is covalently
linked to the graphene oxide. The core level high resolution O1s
spectral peaks are considerably less intense compared to O1s
spectral peaks of GO as well as L-cys-rGO [Fig. 6d]. This conrms
that GO has been converted to rGO. (The atomic percentage
composition of GO, L-cys-rGO and rGO are given in Tables 1, 2
and 3 in ESI†.)
Fig. 6 (a) The wide scan XPS spectrum of rGO, (b) core level C1s XPS
spectra, (c) core level N1s XPS spectra, and (d) core level O1s XPS
spectra.
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Fig. 7 SEM images of i: (a) GO, (b) rGO and (c) L-cys-rGO. TEM images of ii: (a) GO, (b) rGO and (c) L-cys-rGO.
Fig. 8 DPASV carried out on the L-cys-rGO modified GC electrode in
0.1 M sodium acetate buffer of different pH conditions (deposition
time 300 s, deposition potential
1.2 vs. Ag/AgCl, [M2+] ¼ 3 mM).
Morphological studies
The surface morphology of GO, rGO and L-cys-rGO was studied
by SEM and TEM and are shown in Fig. 7. GO shows the pres-
ence of thin folded sheets and these sheets remain unaltered
even aer reducing GO to rGO and also in L-cys-rGO.
Fig. 9 DPASV carried out on the L-cys-rGO modified GC electrode
with different deposition potentials (pH 6 sodium acetate buffer,
deposition time 300 s, [M2+] ¼ 3 mM).
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Optimization studies for metal ions sensing
Effect of pH. The effect of pH on the current response of the
L-cys-rGO composite modied glassy carbon electrode in the pH
range 3.5–7 (sodium acetate–acetic acid solution) was investi-
gated by DPASV studies. From Fig. 8 it is clear that current
response increases with increase in pH and reaches maximum
at pH 6. This may be due to the increase in deprotonation of the
ligands like thiol and carboxylic groups present in the L-cysteine
molecule. But anodic peak current decreases with increase in
pH beyond 6, this is because of the formation of the corre-
sponding hydroxides of the metal ions. Therefore, further all
experiments were carried out with optimum pH 6.
Effect of deposition potential. The effect of deposition
potential on stripping peak current responses of Cd2+, Pb2+,
Cu2+, and Hg2+ ions were studied in the range
0.5 to
1.3 V vs.
Ag/AgCl as shown in Fig. 9. The investigation was performed by
varying the applied potential and a voltammogram was recor-
ded. The anodic peak current of the above said metal ions
increases with increase in the deposition potential. Finally, the
peak current gets saturated above
1.2 V vs. Ag/AgCl. Therefore,
Fig. 10 DPASV carried out on the L-cys-rGO modified GC electrode
with different deposition times (pH 6 sodium acetate buffer, deposi-
tion potential
1.2 V vs. Ag/AgCl, [M2+] ¼ 3 mM).
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Table 1 Detection limits obtained for Cd2+, Pb2+, Cu2+ and Hg2+ with the L-cys-rGO electrode and WHO8 threshold limits (LOD – limit Of
Detection, a – individual analysis, b – simultaneous analysis, and * for inorganic mercury)

Metal Sensitivity Sensitivity WHO guideline

LODa nM (mg L
1) (mA mM
1) LODb nM (mg L
1) (mA mM
1) values (mg L
1)
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ions R R

Cd2+ 0.138 (0.015) 2.744 0.989 3.252 (0.366) 2.226 0.991 0.003
Pb2+ 1.040 (0.215) 4.731 0.993 2.013 (0.416) 4.759 0.994 0.01
Cu2+ 4.743 (0.301) 4.000 0.995 4.104 (0.261) 2.356 0.995 2.0
Hg2+ 4.958 (0.995) 5.551 0.995 5.547 (1.113) 2.179 0.995 0.006*

Fig. 12 (a) DPASV plots obtained with the L-cys-rGO electrode in 0.1
M sodium acetate buffer of pH 6. The concentrations of metal ions
(Cd2+, Pb2+, Cu2+ and Hg2+) were from 0.4–2.0 mM (deposition
potential
1.2 V vs. Ag/AgCl, deposition time 450 s); (b) the plots of
current as a function of concentration of Cd(II), Pb(II), Cu(II), and Hg(II)
ions (n ¼ 3).

Fig. 11 DPASV of (a) Cd2+ (0–1.6 mM); (b) Pb2+ (0–1.2 mM); (c) Cu2+ (0–
1.0 mM) and (d) Hg2+ (0–1.6 mM) on the L-cys-rGO modified GC
electrode in 0.1 M sodium acetate buffer of pH 6 (deposition potential

1.2 V vs. Ag/AgCl, deposition time 450 s). (e) The linear plots of
current as a function of concentration of Cd(II), Pb(II), Cu(II), and Hg(II)
ions (n ¼ 3).
Fig. 13 DPASV carried out for Cd2+, Pb2+, Cu2+ and Hg2+ on bare, rGO
modified and L-cys-rGO modified GC electrodes (pH 6 sodium acetate
buffer, deposition time 450 s, deposition potential
1.2 V vs. Ag/AgCl,
the deposition potential of
1.2 V vs. Ag/AgCl was used as [M2+] ¼ 2 mM).
optimum deposition potential.
Effect of deposition time. The effect of deposition time (in
the range 60–450 s) on the anodic peak current responses of
Cd2+, Pb2+, Cu2+, and Hg2+ ions was studied. From Fig. 10, it is stripping voltammetry (DPASV) studies were carried out for the
evident that the anodic peak current increases with increasing electrochemical determination of heavy metal ions such as
deposition time up to 420 s, above which it remained almost Cd2+, Pb2+, Cu2+ and Hg2+ under optimized conditions. The
constant. Therefore, a deposition time of 450 s was selected for oxidation potentials obtained for individual Cd2+, Pb2+, Cu2+
all further studies. and Hg2+ ions are
0.77 V,
0.52 V,
0.053 V and 0.29 V vs. Ag/
Differential pulse anodic stripping voltammetry studies for AgCl respectively shown in Fig. 11a–d. The peak current
individual metal ions. The L-cys-rGO was drop cast on the increases with increasing the metal ion concentration and the
surface of the GC electrode. The differential pulse anodic corresponding plots of peak current vs. concentration of

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Table 2 Determination of Cd2+, Pb2+, Cu2+ and Hg2+ in environmental and industrial effluents (n ¼ 3)

Recovery %
AAS method Added AAS method
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Proposed method (mM) (mM) (mM) Proposed method (mM) (mM) Proposed method AAS method

a
Sample 1
Cd2+ ND ND — — — — —
Pb2+ 0.4903  0.0051 0.4913 — — — — —
Cu2+ ND ND — — — — —
Hg2+ ND ND — — — — —

b
Sample 2
Cd2+ ND ND 0.70 0.6826  0.0053 0.6824 97.51 97.485
Pb2+ ND ND 0.70 0.7137  0.0039 0.7135 101.95 101.928
Cu2+ ND ND 0.70 0.7272  0.0046 0.7164 103.88 102.34
Hg2+ ND ND 0.70 0.7153  0.0032 0.7102 102.18 101.45

c
Sample 3
Cd2+ ND ND — — — — —
Pb2+ ND ND — — — — —
Cu2+ 1.4903  0.0142 1.4923 — — — — —
Hg2+ ND ND — — — — —
a
Industrial effluent. b Pond water. c Lake water.

different metal ions have been shown in Fig. 11e. The limit of
detections (LODs) has been calculated using LOD ¼ 3S/b where
S is the standard deviation of the blank solution and b is the
slope of the calibration curve14 and given in Table 1. The
observed detection limit values are less than those of WHO
guidelines. The separation of oxidation peaks between the
metal ions is about 0.2–0.45 V vs. Ag/AgCl which is large enough
and feasible for selective determination of above said metal
ions. We further carried out simultaneous detection of the Cd2+,
Pb2+, Cu2+ and Hg2+ ions under the same optimized conditions.
Differential pulse anodic stripping voltammetry studies for
simultaneous metal ions. DPASV for simultaneous determina-
tion of Cd2+, Pb2+, Cu2+ and Hg2+ ions from the concentration
0.4–2.0 mM mL
1 in pH 6 sodium acetate buffer are shown in
Fig. 12a and the corresponding current vs. concentration plots
are shown in Fig. 12b. The oxidation peak potentials obtained
for simultaneous determination of Cd2+, Pb2+, Cu2+ and Hg2+
ions are
0.77 V,
0.53 V,
0.063 V and 0.28 V vs. Ag/AgCl
respectively which are almost the same as those obtained
during the individual metal ion determination (Fig. 11).
The peak current shows maximum response on the L-cys-rGO
modied GC electrode as compared to the rGO modied GC
electrode and the bare GC electrode as shown in Fig. 13. The
peak current increases linearly with increase in concentration of
metal ions (Fig. 12b). The calculated LODs for the simultaneous
analysis are almost equal to individual analysis and are listed in
Table 1. The LODs obtained in this method are higher than the
previous reports.8 We believe that our developed method is
suitable for simultaneous determination of four environmen-
tally harmful metal ions in the real samples.
Application study. The developed protocol was applied for
monitoring Cd2+, Pb2+, Cu2+ and Hg2+ ions in environmental
and industrial effluents. In the industrial effluent about 0.49 mM
of Pb2+ and in the lake water about 1.49 mM of Cu2+ were
detected. In the pond water we have not found stripping peaks
for Cd2+, Pb2+, Cu2+ and Hg2+ ions from the proposed method.
Then this sample was spiked with a known amount of above
said metal ions and analysed. The recoveries were found to be
more than 95%. The results obtained with the proposed method
were validated by the AAS method (Table 2).
Conclusion
In summary we report the simultaneous reduction and the
functionalization of GO with L-cysteine through amidation
(between COOH of GO and NH2 of L-cysteine) and nucleophilic
substitution (between epoxide of GO and NH2 of L-cysteine) in a
single step. The L-cys-rGO material was used as a cathode for
simultaneous determination of Cd2+, Pb2+, Cu2+ and Hg2+ ions
in aqueous medium. The LODs obtained are less than the WHO
guideline values and also provide a platform for simultaneous
determination of four target metal ions. Further, the L-cys-rGO
modied electrode was used for determination of Cd2+, Pb2+,
Cu2+ and Hg2+ ions in environmental samples and the results
obtained with the proposed method were validated by the AAS
method.
Acknowledgements
The authors would like to thank Jain University for the nancial
support. We also wish to extend our gratitude to Dr Rishi Par-
ajuli, Dr Narayanappa Sivasankar, Liquid Light Inc., Monmouth
Junction, New Jersey, USA 08852, for pre-review of the manu-
script and Rajesh Chalasani, Inorganic and Physical Chemistry
Department, IISc, Bangalore, India, for helping to draw sche-
matic diagrams.

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