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Anodic stripping voltammetric detection of mercury(II) using Au-PEDOT
modified carbon paste electrode
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S. Anandhakumar,* J. Mathiyarasu and K. L. N. Phani

Received 17th February 2012, Accepted 18th May 2012
DOI: 10.1039/c2ay25170a

Gold-poly(3,4-)ethylenedioxythiophene (Au-PEDOT) was synthesized using a novel interfacial

synthetic route. Using Au-PEDOT, carbon paste electrodes were fabricated and mercury detection was
attempted exploiting gold–mercury interaction chemistry. Anodic stripping voltammetric analysis
shows excellent sensitivity for micromolar level detection of mercury (LOD ¼ 5 mM). In the
amperometric detection of mercury, electrode fouling is a major problem since the memory effect
cannot easily be removed. Hence, colorimetric/fluorescence techniques mostly dominate the field, using
gold nanoparticle probes for the detection of mercury. Au-PEDOT carbon composite film electrodes
showed excellent repeatable measurements avoiding the memory effect while detecting the mercury
using anodic stripping voltammetry. As a preliminary investigation, the present carbon composite has
been successfully demonstrated for mercury detection in tap water.

Introduction electrochemical and mechanical pretreatments are required to

Mercury has many unique properties that make it useful in many
industrial applications.1 At the same time, mercury and its
compounds are highly toxic, even at trace levels, when they
accumulate in vital organs such as liver, heart muscle, brain, etc.,
and can cause kidney injury, central nervous system disorders
and even death.2 Thus, monitoring of mercury in the environ-
ment, foodstuffs and pharmaceutical products has been the focus
of numerous investigations.3 Several techniques, such as atomic
absorption/emission spectrometry, and inductively coupled
plasma mass spectrometry techniques have been employed for
the sensitive detection of mercury during the past decades.4,5
However, these methods are somewhat cumbersome, time
consuming and, especially, not suitable for on-site monitoring. In
contrast, electroanalytical techniques, in particular anodic
stripping voltammetry (ASV), for mercury detection have been
well acknowledged for decades since they are portable,
economic, easy to use and applicable for on-site monitoring of
environmental pollutants.6
In ASV, different types of electrode materials have been used,
such as gold,7 glassy carbon,8 carbon paste9 and modified elec-
trodes.10–12 Among these, gold was found to be the superior
choice of electrode material owing to its high affinity towards
mercury that enhances the sensitivity.13 However, the major
setback of gold electrodes is the structural changes on the elec-
trode surface caused by amalgam formation,14 and complex
Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical
Research Institute, Karaikudi-630006, India. E-mail: anandchemist@
yahoo.com; Fax: +91 04565-227779; Tel: +91 04565-241340
achieve reproducibility.15
Here, we have attempted to produce a novel gold composite
material for the determination of mercury without changing the
structural morphology of the electrode surface and mechanical
pretreatment to achieve reproducibility. The Au-PEDOT in the
form of a carbon paste electrode was used for the determination
of mercury using anodic stripping voltammetry. The present
electrode showed better sensitivity without changing the struc-
ture of the electrode surface and can be utilized for repeated
measurements.
Experimental
Reagents
All the chemicals used in this work were of analytical purity and
used as received. 0.1 M acetate buffer solution of pH 4.5 was
prepared using sodium acetate (Merck) and acetic acid (Merck).
Hg2+ solutions were prepared by diluting an appropriate amount
of stock solution (1000 mM). All aqueous solutions were
prepared using Milli-Q water of 18.2 MU resistivity (Millipore).
Apparatus and measurements
Square wave anodic stripping voltammetric (SWASV)
measurements were carried out using a PalmSens portable elec-
trochemical analyzer (PalmSens BV, Netherlands). A three-
electrode system was used, with Au-PEDOT modified carbon
paste electrode, Ag/AgCl (3 M NaCl), and platinum foil as
working, reference, and counter electrodes, respectively.
All measurements were performed at ambient temperature
(25  1  C).

2486 | Anal. Methods, 2012, 4, 2486–2489 This journal is ª The Royal Society of Chemistry 2012
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X-ray diffraction (XRD) patterns were recorded in a PAN-

alytical diffractometer Model PW3040/60 X’pert PRO operating
with Cu Ka radiation (K ¼ 0.15406 nm) generated at 40 kV and
20 mA. Scans were carried out at 3 min1 for 2q values between
20 and 90. Scanning electron microscopy (SEM) was done with a
Hitachi Model S-3000H with 10 kV (acceleration voltage).
Energy dispersive X-ray analysis (EDAX) was collected using an
instrument from Thermo Electron Corporation, USA at an
accelerating voltage of 20 kV. Transmission electron microscopy
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(TEM) images were collected from a Philips CM200 microscope.

Fig. 1 (A) X-ray diffraction pattern (B) energy dispersive X-ray anal-
Interfacial synthesis of Au-PEDOT ysis; of interfacial synthesis of Au-PEDOT powder.

The Au-PEDOT composite was synthesised through interfacial

polymerization at room temperature according to the procedure
reported elsewhere.16–18 Briefly, one pot biphasic reactions were
carried out in a 30 ml cylindrical glass container. About 0.01 M
of EDOT in 10 ml of toluene and an equal concentration
(0.01 M) of auric chloride were dissolved in 10 ml of water. In a
typical synthesis, the above solutions were carefully transferred
to the reaction vessel one by one and set aside for 24 hours. After
that, the interfacial product in the form of a powder was carefully
collected and washed several times with acetone.
Preparation of Au-PEDOT modified carbon paste electrode
The Au-PEDOT modified carbon paste electrodes were prepared
by mixing a known quantity of Vulcan carbon [Cabot corpo-
ration, USA], Au-PEDOT powder and paraffin oil [Uvasol,
Merck] and were packed in a cavity electrode [Bio Analytical
Inc., USA]. Typically, 8 mg of the Vulcan carbon and 2 mg of
Au-PEDOT powder was mixed with 20 ml of paraffin oil in a
glass plate by exhaustively hand mixing with a glass rod, and this
ratio was made uniform for the entire measurement. The
resulting Au-PEDOT modified carbon paste was packed into the
cavity (outer diameter 3 mm and inner diameter 1.6 mm) of the
electrode and a bronze rod was used for the purpose of electrical
contact. The electrode surface was made smooth and cleaned
carefully before performing the experiments.
at 2q values 38.4091, 44.6552, 64.7342, 77.7657 and 81.8878
corresponding to the Bragg reflections (111), (200), (220), (311)
and (222) of the face centred cubic (fcc) structure. EDAX anal-
ysis indicated the presence of Au, S, and O atoms in the powder
and shows 68.12 wt% of Au present in the composite.
The typical microscopic images of SEM, TEM and SAED
patterns of Au-PEDOT are shown in Fig. 2. The SEM image
(Fig. 2A) indicated that Au-PEDOT has a nanocrystalline form
and a uniform size of approx. 50 nm. TEM images showed that
the Au nanoparticles incorporated in the polymer matrix were of
around 1–2 nm in size and spherical in nature (Fig. 2B). Further
magnification (Fig. 2C) revealed that Au nanoparticles were
highly mono-dispersed and uniformly distributed within the
PEDOT matrix. A selected-area electron diffraction pattern
(SAED) (Fig. 2D), obtained by focusing an electron beam
(50 nm in diameter) onto an individual nanocrystal, confirmed
the polycrystalline features of the composite material.
Fig. 3 shows the cyclic voltammetric behaviour of the
Au-PEDOT modified carbon paste electrode in 0.5 M sulphuric
acid. The spectrum clearly reveals the ‘‘signature’’ of the vol-
tammetric Au stripping peak at 0.414 V, confirming the presence
of Au in the PEDOT matrix.

Analytical procedure
Voltammetric measurements were carried out in 0.1 M acetate
buffer solution (pH 4.5). Square wave anodic stripping voltam-
metry (SWASV) was used for the deposition and stripping steps
with the following parameters: initial potential, 0.1 V; final
potential, 0.7 V; pulse amplitude 50 mV, frequency 10 Hz and
deposition time 2 minutes. During the deposition period the
solution was stirred at approximately 1000 rpm and the potential
was held at 0.5 V. Stirring was required during the deposition
process only and it was stopped at the end of the deposition.

Results and discussion

Microscopic and electrochemical characterisation of interfacial
product

Fig. 1A and B show the XRD and EDAX analysis of the as-
synthesised Au-PEDOT powder. The X-ray diffraction analysis Fig. 2 Microscopic images of Au-PEDOT powder: (A) SEM; (B) TEM;
confirms the polycrystalline nature of Au with high intense peaks (C) higher magnification of TEM; and (D) SAED pattern.

This journal is ª The Royal Society of Chemistry 2012 Anal. Methods, 2012, 4, 2486–2489 | 2487

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Fig. 3 Cyclic voltammetric behavior of Au-PEDOT modified carbon
paste electrode in 0.5 M sulphuric acid at a scan rate of 50 mV s1.
Comparison of Au-PEDOT/unmodified carbon paste electrode
and optimization of parameters
Fig. 4A shows the comparison of mercury detection character-
istics of Au-PEDOT modified and pure carbon paste electrodes
using SWASV in 0.1 M acetate buffer solution (pH 4.5). The
unmodified carbon paste electrode resulted in a broad stripping
peak whereas the Au-PEDOT modified carbon paste electrode
showed a well-defined sharp stripping peak around 0.3 V vs.
Ag/AgCl reference electrode. The modifications led to a 3-fold
increase in the stripping current, and the resultant stripping
potential was shifted towards the cathodic region, asserting the
catalytic nature of the modifier compared to the previous
reports.10–12 The increased current signal could be rationalised as
the combined effect of the presence of catalytic Au nanoparticles
and anti-fouling characteristics of the polymer matrix.
Further optimization of experimental parameters, such as
deposition potential and time against peak current, were shown
in Fig. 4B and C. The deposition potential was varied from 0.1
to 1.0 V using the Au-PEDOT modified carbon paste electrode
with a deposition time of 2 minutes. The peak current increased
significantly with a deposition potential up to 0.5 V. Beyond
this potential, the current decreases which was attributed to the
strong interaction between Au and Hg, and the difficulty in
stripping away from the electrode surface. Hence, the deposition
potential of 0.5 V was declared optimal and was used for the
subsequent measurements. Similarly, the deposition time was
varied from 1 to 5 minutes and the peak current increases line-
arly. Considering the memory effect of mercury on the electrode
Fig. 4 (A) SWASV of 50 mM Hg2+ in 0.1 M acetate buffer (pH 4.5)
solution; background [a]; carbon paste electrode [b]; Au-PEDOT modi-
fied carbon paste electrode [c]; (B) effect of deposition potential, (C) effect
of deposition time.
2488 | Anal. Methods, 2012, 4, 2486–2489
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surface and the reproducibility, it was decided to use a short time
deposition period of 2 minutes for Hg2+ determination.
SWASV determination of Hg2+
Fig. 5A shows the SWASV of successive Hg2+ determination in
0.1 M acetate buffer solution (pH 4.5) using the Au-PEDOT
modified carbon paste electrode. The voltammogram showed a
distinct mercury stripping peak at around 0.3 V vs. Ag/AgCl. The
corresponding calibration plot (Fig. 5B) revealed that peak
current increases linearly with Hg2+ concentration between 10
and 70 mM of 10 mM additions. The correlation coefficient of
Hg2+ was found to 0.9973 and the calculated limit of detection
was observed as 5 mM. The present modification showed good
stability and reproducibility with the relative standard deviation
(RSD) of 1.3% calculated from 20 successive measurements of
50 mM Hg2+ in 0.1 M acetate buffer solution. The RSD for six
similar sensors prepared under same conditions in response to
50 mM Hg2+ in 0.1 M acetate buffer solution was 1.9%.
Analytical application
The utility of the Au-PEDOT modified carbon paste electrode
was assessed by determining the Hg2+ levels in spiked tap water
samples as shown in Fig. 5C. Prior to analysis, the tap water was
acidified by nitric acid to adjust the pH value to 4.5. The
successive standard additions of 10 mM of Hg2+ were added to
the tap water in the concentration range 10–50 mM. After the
deposition time of 2 min, SWV protocols were applied for the
stripping analysis. The standard addition plots were found to be
linear with a correlation coefficient of 0.9950 (Fig. 5D). The
Fig. 5 (A) SWASV of Hg2+ (10–70 mM) in 0.1 M acetate buffer (pH 4.5)
solution using Au-PEDOT modified carbon paste electrode, (B) corre-
sponding calibration plot; (C) SWASV of Hg2+ (10–50 mM) in tap
water using the Au-PEDOT modified carbon paste electrode and (D)
corresponding calibration plot.
This journal is ª The Royal Society of Chemistry 2012

present experiments demonstrated that it is possible to employ
the optimized anodic stripping protocols to determine Hg2+ in
environmental samples using the Au-PEDOT modified carbon
paste electrode without fouling of the electrode surface for
repeated measurements.
Conclusions
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In this work, a Au-PEDOT modified carbon paste electrode for
the determination of Hg2+ using ASV was demonstrated without
fouling the electrode surface. The Au-PEDOT powder was
synthesized using an interfacial polymerization method at room
temperature in the absence of a template, phase transfer catalyst
or surfactant. The synthesised interfacial product was charac-
terized using different techniques such as XRD, EDAX, SEM,
TEM and cyclic voltammetry. Electroanalysis of the Au-PEDOT
modified carbon paste electrode showed an interesting perfor-
mance, i.e. a 3-fold increase in stripping current signal and a
catalytic nature. The modified electrode was found to be highly
stable and reproducible without changing the structure of the
electrode surface while determining Hg2+ at micromolar levels.
As a preliminary investigation, the present Au-PEDOT modified
carbon paste electrode has been successfully demonstrated for
the detection of mercury in tap water samples.
Acknowledgements
The authors thank the Department of Biotechnology, New Delhi
for financial assistance [BT/PR- 10459/BCE/08/651/2008].
This journal is ª The Royal Society of Chemistry 2012
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Notes and references
1 M. Morita, J. Yoshinaga and J. Edmondst, Pure Appl. Chem., 1998,
70, 1585.
2 I. Bontidean, A. Mortari, S. Leth, N. L. Brown, U. Karlson,
M. M. Larsen, J. Vangronsveld and P. Corbisier, Environ. Pollut.,
2004, 131, 255.
3 M. Pesavento, G. Alberti and R. Biesuz, Anal. Chim. Acta, 2009, 631,
129.
4 T. C. Duan, X. J. Song, P. R. Guo, H. T. Chen and H. F. Li,
Spectrochim. Acta, Part B, 2006, 61, 1069.
5 P. Ugo, S. Zamperi, L. M. Moretto and D. Paolucci, Anal. Chim.
Acta, 2001, 434, 191.
6 P. Richter, M. I. Toral and B. Abbott, Electroanalysis, 2002, 14,
1288.
7 Y. Bonfil, M. Brand and E. Kirowa-Eisner, Anal. Chim. Acta, 2000,
424, 65.
8 M. Hatle, Talanta, 1987, 34, 1001.
9 I. Svancara, K. Vytras, K. Kalcher, A. Walcarius and J. Wang,
Electroanalysis, 2009, 21, 7.
10 J. Gong, T. Zhou, S. Dandan, Z. Lizhi and H. Xianluo, Anal. Chem.,
2010, 82, 567.
11 O. Abollino, A. Giacomino, M. Malandrino, G. Piscionieri and
E. Mentasti, Electroanalysis, 2008, 20, 75.
12 M. Giannetto, G. Mori, F. Terzi, C. Zanardi and R. Seeber,
Electroanalysis, 2011, 23, 456.
13 O. Ordeig, C. E. Banks, J. Del Campo, F. X. Munoz and
R. G. Compton, Electroanalysis, 2006, 18, 573.
14 C. Welch, O. Nekrassova, X. Dai, M. Hyde and R. G. Compton,
ChemPhysChem, 2004, 5, 1405.
15 K. Z. Brainnina, N. Y. Stozhko and J. Shalygina, J. Anal. Chem.,
2004, 59, 753.
16 J. Huang, S. Virji, B. H. Weiller and R. B. Kaner, J. Am. Chem. Soc.,
2003, 125, 314.
17 S. Harish, J. Mathiyarasu and K. L. N. Phani, Mater. Res. Bull., 2009,
44, 1828.
18 G. Lu, C. Li, J. Shen, Z. Chen and G. Shi, J. Phys. Chem. C, 2007,
111, 5926.
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