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Electrochemistry Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e l e c o m
College of Materials Science and Engineering, Hunan University, Changsha 410082, PR China
State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082, PR China
a r t i c l e
i n f o
Article history:
Received 29 October 2010
Received in revised form 25 November 2010
Accepted 25 November 2010
Available online 3 December 2010
a b s t r a c t
Graphene nanosheets were directly deposited onto a glassy carbon electrode through cyclic voltammetric
reduction of a graphene oxide colloidal solution. The resulting electrodes were characterized by
electrochemical methods and scanning electron microscopy. The application of the graphene modied
electrodes in simultaneous determination of hydroquinone and catechol was investigated.
2010 Elsevier B.V. All rights reserved.
Keywords:
Electrodeposition
Graphene
Sensor
Hydroquinone
Catechol
1. Introduction
Direct simultaneous determination of isomers is a challenge because
of their similar structures and physicochemical properties. Hydroquinone (1,4-dihydroxybenzene, HQ), catechol (1,2-dihydroxybenzene,
CC), and resorcinol (1,3-dihydroxybenzene, RC) are three isomers of
phenolic compounds, and due to their high toxicity, their determination
is of interest in environmental analysis. At present, a number of methods
for dihydroxybenzene analysis have been proposed [15], among which
electrochemical technique has the advantages such as simplicity and
convenience. Unfortunately, however, due to the same electro-active
groups, the isomers, especially HQ and CC, usually present overlapped
redox peaks so that they can't be resolved at conventional electrodes
such as gold and glassy carbon electrode (GCE).
Graphene has recently attracted tremendous interest because of its
unique thermal, mechanical, and electrical properties [6]. One of the
promising applications of graphene is electrochemical sensing [7,8].
Since every atom in a graphene sheet is a surface atom, molecular
interaction and thus electron transport through graphene can be
highly sensitive to adsorbed molecules [9]. In this regard, it is believed
that graphene, when used for the modication of the conventional
electrodes, has the great potential for distinguishing a diverse range of
aromatic isomers. Here, we show that the graphene-based electrode
readily allows the simultaneous detection of HQ and CC.
134
and the Pt foil and saturated calomel electrode (SCE) acted as the
counter and reference electrodes, respectively.
The scanning electron microscopic (SEM) and transmission
electron microscopic (TEM) images were carried out on a JEOL
JSM-6700F eld emission scanning electron microscope and a JEOL
JEM-3010 high-resolution transmission electron microscope,
respectively.
Fig. 1. (A) TEM image of GO dispersed in 0.067 M, pH 9.18 PBS, (B) CVs depicting electrochemical reduction of 1.0 mg mL1 GO in PBS (0.067 M, pH 9.18) on a GCE at 10 mV s1,
(C) CV of an EG/GCE in PBS (0.067 M, pH 9.18) at 10 mV s1, and (D) SEM image of EG lm (10 electrodeposition cycles) modied GCE.
135
130
(A)
120
I / A
(B)
110
75
0
-75
GCE
GCE+EG (3 Cycles)
GCE+EG (9 Cycles)
GCE+EG (12 Cycles)
GCE+EG (18 Cycles)
-150
-0.2
0.0
0.2
0.4
P/ mV
150
100
90
80
70
60
0
0.6
12
15
18
electrodeposition cycle
E / V (vs. SCE)
30
30
(C)
(D)
HQ
20
CC
I / A
I / A
15
0
-15
0.1
0.2
0.3
GCE
EG/GCE
-20
-30
0.0
0
-10
GCE
EG/GCE
-0.1
10
0.4
0.0
0.1
30
(E)
HQ
0.2
0.3
0.4
0.5
E / V (vs. SCE)
E / V (vs. SCE)
50
CC
40
(F)
CC
HQ
I / A
I / A
15
0
-15
GCE
EG/GCE
20
10
GCE
EG/GCE
-30
-0.1
30
0.0
0.1
0.2
0.3
0.4
0
0.5
E / V (vs. SCE)
0.0
0.1
0.2
0.3
0.4
E / V (vs. SCE)
Fig. 2. (A) CVs of 5.0 mM K3Fe(CN)6 in 0.1 M KCl on bare GCE and EG/GCE with the EG lms prepared under various electrodeposition cycles, (B) dependence of Ep on
electrodeposition cycle, (C) and (D) CVs of HQ (0.2 mM) and CC (0.2 mM) in 0.2 M acetate buffer solution (ABS, pH 5.8) at bare GCE and EG/GCE at 50 mV s1, respectively, (E) CVs of
HQ (0.2 mM) + CC (0.2 mM) in 0.2 M, pH 5.8 ABS at bare GCE and EG/GCE at 50 mV s1, (F) Differential pulse voltammograms (DPVs) of HQ (0.2 mM) + CC (0.2 mM) in 0.2 M, pH
5.8 ABS at bare GCE and EG/GCE, the DPV parameters were at a scan rate of 4 mV s1, 50 mV pulse amplitude, and 20 ms pulse width.
136
(A)
HQ
30
200M
150
100
80
40
6
0 M
I / A
40
30
20
(A)
15
I / A
50
0
pH 2.6
pH 4.0
pH 4.6
pH 5.8
-15
10
-30
0
0.1
0.2
0.3
0.0
0.4
45
(B)
200M
150
100
80
40
10
6
1
0 M
CC
I / A
60
40
20
30
0.4
0.6
0.8
(B)
15
I / A
80
0.2
E / V (vs. SCE)
E / V (vs. SCE)
0
pH 2.6
pH 4.0
pH 4.6
pH 5.8
-15
-30
0
0.0
0.1
0.2
0.3
0.0
0.4
60
0.4
0.6
0.8
Fig. 4. CVs of (A) 0.2 mM HQ and (B) 0.2 mM CC in 0.2 M ABS with different pHs.
(C)
CC
I(A)=1.29+0.298C(M)
r=0.9977
I / A
40
0.2
E / V (vs. SCE)
E / V (vs. SCE)
HQ
OH
20
40
80
120
160
+ 2 H+ + 2e-
HQ:
I(A)=0.373+0.129C(M)
r=0.9996
200
OH
C / M
OH
O
OH
Fig. 3. DPVs showing the oxidation peak current of (A) HQ vs. HQ concentration in the
presence of 0.1 mM CC and (B) CC vs. CC concentration in the presence of 0.1 mM HQ.
(C) Calibration plots. The electrolyte: ABS (0.2 M, pH 5.8). The DPV parameters were at
a scan rate of 4 mV s1, 50 mV pulse amplitude, and 20 ms pulse width.
CC:
O
+ 2 H+ + 2e-
4. Conclusion
and 0.37%, respectively, suggesting a high reproducibility. The
stability of the electrode was checked by performing 30 consecutive
potential scans in 0.2 M, pH 5.8 ABS containing 0.1 mM HQ. On
comparison, the graphene electrode exhibited a 5.5% decrease in the
signal, whereas the bare GCE exhibited about a 24% change in the
signal.
3.4. Mechanism for reactions
Fig. 4A and B shows CVs of EG/GCE in 0.2 M ABS containing
0.2 mM HQ and 0.2 mM CC, respectively, with different pH values.
In both cases, negative shifts in anodic and cathodic peak
potentials as well as enhanced current responses are observed
with increasing pH values from 2.6 to 5.8, which suggest the
involvement of proton in the electrode reactions. The anodic peak
potential (Epa) has a linear relationship with pH from 2.6 to 5.8,
where the linear regression equations are Epa (V) = 0.495 0.055
pH (r = 0.982) and Epa (V) = 0.601 0.057 pH (r = 0.980) for HQ
and CC, respectively. The slopes of Epa vs. pH for both HQ and CC
are very close to the theoretical value of 59 mV/pH (25C) for a
reversible electrochemical process involved with equal number of
We have demonstrated a straightforward one-step electrodeposition method to prepare graphene lm for simultaneous determination
of HQ and CC. The graphene modied electrode showed enhanced
electron transfer properties and high resolution capacity to the HQ
and CC isomers. Wide linear concentration ranges, low detection
limits, and excellent reproducibility and stability were achieved on
the EG/GCE, indicating graphene a promising sensing platform for
isomers determination.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (50878079, 51078129, 21047004) and the
National Basic Research Program of China (2009CB421601).
References
[1] G.N. Chen, J.S. Liu, J.P. Duan, H.Q. Chen, Talanta 53 (2000) 651.
[2] P.J. Kerzic, W.S. Liu, M.T. Pan, H. Fu, Y. Zhou, A.R. Schnatter, R.D. Irons, Chem. Bio.
Interact. 184 (2010) 182.
[3] M.A. Ghanem, Electrochem. Commun. 9 (2007) 2501.
137
[13] M. Zhou, Y.L. Wang, Y.M. Zhai, J.F. Zhai, W. Ren, F. Wang, S.J. Dong, Chem. Eur. J. 15
(2009) 6116.
[14] S. William, J.R. Hummers, E.O. Richard, J. Am. Chem. Soc. 80 (1958) 1339.
[15] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S.
T. Nguyen, R.S. Ruoff, Carbon 45 (2007) 1558.
[16] M. Pumera, Chem. Soc. Rev. 39 (2010) 4146.
[17] M. Pumera, Chem. Rec. 9 (2009) 211.
[18] P.H. Chen, M.A. Fryling, R.L. McCreery, Anal. Chem. 67 (1995) 3115.
[19] D.K. Kampouris, C.E. Banks, Chem. Commun. 46 (2010) 8986.
[20] D.A.C. Brownson, C.E. Banks, Analyst 135 (2010) 2768.