ISSN 10619348, Journal of Analytical Chemistry, 2015, Vol. 70, No. 1, pp. 60–66. © Pleiades Publishing, Ltd., 2015.

ARTICLES

Nitrate Detection Activity of Cu Particles Deposited on Pencil

Graphite by Fast Scan Cyclic Voltammetry1
M. M. Alama, M. A. Hasnata, *, M. A. Rasheda, S. M. Nizam Uddina, Mohammed M. Rahmanb,
S. Amertharajc, N. Ahmedd, and N. Mohamedc, **
aDepartment of Chemistry, Graduate School of Physical Sciences, Shahjalal University of Science and Technology,
Sylhet3114, Bangladesh
b
Centre of Excellence for Advanced Materials Research (CEAMR) & Chemistry department, Faculty of Science,
King Abdulaziz University Jeddah 21589, P.O. Box 80203, Saudi Arabia
cSchool of Chemical Sciences, Universiti Sains Malaysia Minden, Penang, 11800 Malaysia
d
Institute of Nuclear Science & Technology, Bangladesh Atomic Energy Commission Ganak Bari,
Savar GPO Box3787, Dhaka1000, Bangladesh
email: mahche@sust.edu*; mnorita@usm.my**
Received December 27, 2012; in final form, February 19, 2014

Abstract—Electrocatalytic nitrate reduction and sensing activities of Cu deposits from 0.01 M CuSO4 ⋅ 5H2O
solution by fast scan (1000 mV/s) cyclic voltammetry on pencil graphite (PG) was investigated. The content
of Cu particles on PG surface was controlled by fixing the deposition cycles between 0 and –300 mV. The per
formance of the different Cu/PG electrodes has been explained in terms of reduction current, kinetic order,
exchange current density, specific electrical capacitance and nitrate sensing abilities. All these activities were
modestly dependent on the content of Cu particles on the PG surface. The minimum catalytic sites on PG
surface were generated even by the single Cu deposition cycle. Depending on the Cu content, the electrodes
exhibited lowest nitrate detection limits in the range between 1.0 × 10–4 to 1.1 × 10–3 M. The nitrate detection
performance of the Cu/PG electrode was justified with the ion chromatographic method.

Keywords: nitrate, electrocatalysis, voltammetry, kinetics, sensitivity

DOI: 10.1134/S1061934815010037

1 –
Nitrate is one of the most commonly found con
taminants in surface and groundwater worldwide.
There are numerous potential sources of nitrate,
including animal wastes, septic tanks, municipal
wastewater treatment system and decaying plant
debris. But nitrogenenriched fertilizers for farming
accounts for the majority of nitrate entering into the
environment [1]. When present in surfeit in aquatic
systems, nitrate poses two important environmental
problems: eutrophication of surface waters and con
tamination of groundwater. High levels of nitrate have
been associated with serious health issues, including
methemoglobin (blue baby syndrome in babies), mis
carriages and nonHodgkin’s lymphoma. Because of
bacterial action, nitrate ions are converted into nitrite
ions, which may have damaging consequences via two
mechanisms. These ions may be combined with blood
pigments producing methahemoglobin in which oxy
gen is no longer available to the tissues. Also they may
create networks in the stomach with amines and
amides forming highly carcinogenic Nnitrosamine
compounds [2]. It has been reported that the permis
1 The article is published in the original.
sible levels of NO 3 in drinking water are as 50 mg/L
[3]. Therefore, nitrate reduction and determination is
essential for environment and for public health issues.
In the last couple of decades, this environmental
issue has been allured as an intense attention of
research. A number of spectroscopic techniques have
been reported to sense nitrate ions from water [4–13].
Even though spectroscopic techniques represent con
siderably high sensitivity, these methods require luxu
rious instrumentation and wide experimental proce
dures. Meanwhile, electrochemical methods are quite
selective, easy and quite cost effective in sensing
nitrate ions. Recently, several reports have been pub
lished describing the mechanistic ways of nitrate
reduction from water [14–19]. According to previous
reports, the straight forward reduction/determination
of nitrate is not normally possible at the most com
monly used electrodes, such as glassy carbon, plati
num, gold and mercury electrodes. However, several
electrochemical methods have been reported for the
reduction/determination of nitrate ions based on the
use of modified solid electrode materials that are capa
ble of catalyzing the reduction of nitrate. So far it is
known that numerous nitrate selective electrodes have

60
 NITRATE DETECTION ACTIVITY OF Cu PARTICLES 61

Table 1. Electrocatalytic activity of Cu particles as electrodes on PG surface

Limit of detection
Electrode N m (order) j0, µA/cm2 Cs, mF/cm2
c/104, M Ep, V
A 0 – – – – –
B 1 0.46 ± 0.01 4.39 0.15 10.0 –1.16
C 15 0.89 ± 0.02 11.28 0.24 6.5 –1.18
D 30 0.83 ± 0.01 15.60 0.25 5.0 –1.19
E 50 1.01 ± 0.01 22.18 0.28 2.1 –1.21
F 75 1.04 ± 0.02 29.19 0.32 1.1 –1.26
N—Cu deposition cycle number, scanned between 0 and –300 mV in 0.1 M CuSO4 ⋅ 5H2O solution at rate of 1000 mV/s; Cs—specific
electrical capacitance; jo—exchange current density; electrode area 0.67 cm2.

been reported that include Ag [20], boron doped dia
mond [21], cadmium [22, 23], copper [24–27] and
bimetallic electrodes [14–19].
Pencil graphite is a very cheap and available mate
rial in pure state. Copper is known to have great elec
trochemical properties in sensing nitrate ions [25–27].
However, dependence of electrocatalytic reducing
properties of nitrate ions as a function of variable Cu
particles as electrode materials on a support has never
been done. In this report, variable content of Cu par
ticles were deposited on the PG by controlling the
number potential scans to investigate the electrocata
lytic reduction and nitrate sensing activities in water.
PG was used as the support of Cu particles instead of
the more commonly used glassy carbon because it is
cheaper and readily available.
EXPERIMENTAL
Reagents and equipment. All the chemicals and
reagents used in this work were of the analytical grade
and used as received without further purification. The
chemicals used to conduct this research were CuSO4 ⋅
5H2O, KCl, KNO3, etc. supplied by Merck (Ger
many). PG was supplied by Unicorn, Malaysia. All the
solutions were prepared by using deionized water hav
ing resistivity not less than 18.2 MΩ. Voltammetric
measurements were carried out using an EDAQ model
potentiostat/Metrohm 797VA automatic electro
chemical polarization system. All measurements were
conducted under thermostatic (23°C) and N2 atmo
spheric conditions using a conventional threeelec
trode cell. The working electrode was PG upon which
Cu particles were deposited. The counter electrode
was a Pt wire and the reference electrode was Ag/AgCl
(std. KCl). The scanning electron microscope (SEM)
image of the surface was taken with a JEOL model
JSM6060LV instrument. The concentrations of
nitrate ions in waste water samples were verified using
an ion chromatograph (Metrohm 792 Basic IC).
Electrode modification. The Cu particles were
deposited on the PG surface by applying the elec
trodeposition method. In order to do this, 1 cm length
of PG having area of 0.67 cm2 was dipped in 20 mL
0.01 M solution of CuSO4 ⋅ 5H2O. Then the system
was cycled between 0 and –300 mV where the rest
potential was maintained at –50 mV for 3 s. A faster
scan rate (1000 mV/s) was chosen to deposit Cu parti
cles in order to avoid aggregation of deposited parti
cles. The variable amount of Cu deposition was main
tained by the cycle number (N, 0–75). Based on the
number of Cu deposition cycles, the electrodes have
been termed as 0 cycle (A), 1 cycle (B), 15 cycles (C),
30 cycles (D), 50 cycles (E) and 75 cycles (F), respec
tively, as listed in Table 1. After Cu deposition, the as
prepared working electrodes were washed with deion
ized water. Prior to use for nitrate reduction experi
ments, each electrode was cycled between 0 and –
1500 mV in 0.05 M KCl solution to confirm the reduc
tion of all Cu2+ adhered to the PG surface so that the
presence of this ion would not interfere with the nitrate
reduction current.
RESULTS AND DISCUSSION
Cyclic voltammetry. In order to examine the elec
trocatalytic performance of Cu particles on PG sur
faces, the cyclic voltammetric (CV) method was
employed. Figure 1 shows CV curves (forward)
obtained for 1.3 × 10–3 M KNO3 in 0.05 M KCl solu
tion in the range of –0.4 to –1.6 V (vs. Ag/AgCl refer
ence electrode) at a scan rate of 50 mV/s using differ
ent Cu particles modified PG electrodes prepared by
cycling 0–75 times in 0.1 M CuSO4 ⋅ 5H2O solution.
–
Many studies have shown that NO 3 is reduced elec
trocatalytically at the Cu electrode using a consecutive
mechanism [25–27]. In our experiments, it has been
observed that the PG electrode alone could not reduce
nitrate ions (curve A, Fig. 1). However, the reduction
wave was seen even at –1.27 V when the least amount
of Cu particles was deposited on PG by applying a sin
gle deposition cycle, as is seen by curve B in Fig. 1. The
reduction peak was shifted negatively as well as the
peak current was increased with the population of Cu

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70 No. 1 2015