Microchimica Acta (2019) 186: 440

https://doi.org/10.1007/s00604-019-3552-0

ORIGINAL PAPER

Voltammetric determination of cadmium(II), lead(II) and copper(II)

with a glassy carbon electrode modified with silver nanoparticles
deposited on poly(1,8-diaminonaphthalene)
Khalid M. Hassan 1 & Ghada M. Elhaddad 2 & Magdi AbdelAzzem 2

Received: 31 January 2019 / Accepted: 24 May 2019 / Published online: 13 June 2019
# Springer-Verlag GmbH Austria, part of Springer Nature 2019

Abstract
A glassy carbon (GC) electrode was modified with poly(1,8-diaminonaphthalene) (p-1,8-DAN) that was coated with silver
nanoparticles (Ag NPs) (size: 10.0–60.0 nm by TEM) by electrodeposition process using cyclic voltammetry (CV) technique.
The resulting nanocomposite was characterized by FE-SEM, AFM, EDX, XPS, TEM and XRD. The surface area and the
electrochemical characteristics of the electrode were investigated by CV and square wave voltammetry (SWV) techniques,
and the probe preparation conditions were optimized. The electrode was used for individual and simultaneous determination
of the heavy metal ions cadmium(II) (Cd2+), lead(II) (Pb2+) and copper(II) (Cu2+) in water samples by square wave anodic
stripping voltammetry (ASV) using scan rate 0.005 V. s−1. The probe showed well separated anodic stripping peaks for Cd2+,
Pb2+, and Cu2+. Attractive features of the method include (a) peak voltages of −1.02, −0.78 and − 0.32 V (vs. Ag/AgCl) for the
three ions, and (b) low limits of detection (19, 30 and 6 ng.L−1, respectively. The electrode can also detect zinc(II) (Zn2+) and
mercury(II) (Hg2+), typically at −1.36 V and + 0.9, respectively.

Keywords Nanoprobe . Electrodeposition . Individual and simultaneous determination . Stripping anodic voltammetry

Introduction ical techniques, specifically electrochemical stripping tech-

nique were extensively proved to be suitable for determina-
One of the major involvement of the environmental pollu- tion of heavy metals because of its good selectivity, cost
tion is heavy metals such as cadmium (Cd), lead (Pb) and effectiveness, compactness and the ability for accurate si-
Copper (Cu) owing to their contribution in different natural multaneous determination elements at trace levels [3].
and industrial activates, and playing a vital role in numerous Modified electrodes have noticeable advantages in the water
biological activities in organisms [1]. Different analytical heavy metals determinations. Introducing specific binding
techniques such as atomic absorption developed for determi- groups as thiol or cyano groups accelerate the rate of elec-
nation of metal traces [2]. On the other hand, electrochem- tron transfer rate at the surface of the electrode and increase
the efficiency of preconcentration [4].
Silver (Ag) is regarded as the most inexpensive element
Electronic supplementary material The online version of this article among noble metals. Its unique optoelectronic properties and
(https://doi.org/10.1007/s00604-019-3552-0) contains supplementary
material, which is available to authorized users. stability, make it has a versatile candidate to be utilized for the
fabrication of polymer nanocomposites [5]. Ag shows excel-
* Khalid M. Hassan lent characteristics for detection of Cd and Pb with high re-
drkhalidhassan73@gmail.com peatability and stability without any requirement for pretreat-
ment, in addition to lower limits of detection (LOD) [6].
1
Electrochemistry Research Laboratory, Physics and Mathematics
In this field of environmental monitoring, the application of
Engineering Department, Faculty of Electronic Engineering, nanoparticles (NPs) as a functional probe for analyzing inor-
Menoufia University, Menouf 23952, Egypt ganic and organic pollutants in water has been extensively
2
Electrochemistry Laboratory, Chemistry Department, Faculty of studied [7, 8]. NPs usually exhibit unique characteristics rath-
Science, Menoufia University, Shibin El-Kom 32511, Egypt er than bulk-sized materials, principally due to the electron
440 Page 2 of 10 Microchim Acta (2019) 186: 440

confinement of the NPs [9]. From a sensing standpoint, the CV-50w software. All obtained voltammograms were per-
smaller size of them results in large aspect ratio, surface-to- formed in a conventional three-electrode cell composed of
volume, which lead to quick responses with high sensitivity. 3.0 mm GC (working), a platinum wire (auxiliary) and Ag/
In addition, the optoelectronic and magnetic properties of NPs AgCl (reference) electrodes. Working electrode cleaning was
can be adjusted via manage its particle size, composition, accomplished by its polishing with diamond paste, rinsing in
morphology and the surface chemistry, to produce highly ethanol followed by used solvents.
functional molecular probes [10]. Morphology and composition of the modified electrode
Ag NP modified surfaces are substantial to improve optical surface were studied using field emission scanning electron
and electrochemical characteristics and applications of poten- microscopy (FE-SEM) and energy dispersive x-ray (EDX)
tial such as catalytic and electro catalytic materials [11]. techniques by a JEOL JSM-7001F operating at 120 kV. An
Therefore, the means of Ag NPs deposition have been widely Agilent 5420 atomic force microscope (AFM) was used to
investigated [12]. Besides the chemical methods, the electro- study the film hardness and its topography. The measure-
chemical double-pulse method has previously disclosed the ments of transmission electron microscopy (TEM) were
successful dispersion of Ag NPs on an ITO surface [13]. achieved via Joel JEM 1230 with CCD camera (USC1000,
Though, the particle size and the distributed density of Ag Gatan Inc.) operating at 100kv. X-ray diffraction (XRD)
NPs are highly reliant on the methods of preparations [14]. measurements were carried on a Bruker, D8 ADVANCE
In the present work, Ag NPs were successfully deposited X-ray powder diffractometer (range: 20–80°). X-ray photo-
onto poly1,8-diaminonaphthalene/glassy carbon (p-1,8-DAN/ electron spectroscopy (XPS) was performed by using model
GC) modified electrode by cyclic voltammetry (CV) tech- thermo ESCA Lab 250xi. For its calibration, the binding
nique. The modified silver nanoparticles/p-1,8-DAN/GC energy was calibrated to the C 1 s line at 284.6 eV as a
(AgNPs@p-1,8-DAN/GC) electrode was assessed towards in- reference.
dividual and simultaneous electrochemical determination of River samples were analyzed by inductively coupled plas-
heavy metal ions such as lead (II) (Pb2+), cadmium (II) ma optical emission spectrometry (ICP-OES).
(Cd2+), and copper (II) (Cu2+) in 0.1 M acetate buffer solution
(ABS) adjusted at pH value of 4.6 using anodic stripping Electrochemical preparation of the
voltammetry (ASV) technique. To the best of our knowledge, p-1,8-DAN-modified glassy carbon electrode
this is the first nanoprobe composed of an organic polymer
and Ag NPs as a new green electrode material. P-1,8-DAN/GC modified electrode was prepared by electro
polymerization of 1.0 mM 1,8-DAN in a mixed solvent of
4.5 M H2SO4 in ACN with a volume ratio of (1: 3) at GC
Experimental electrode, for which 2.50 mL of H2SO4 was added to 7.50 mL
of ACN to complete a total volume of 10.0 mL. This system
Materials was subjected to CV technique with potential range of +0.2 to
+1.2 V at scan rate of 0.1 V. s−1 for 20 cycles as described in
1,8-Diaminonaphthalene (1,8-DAN) (Aldrich, https://www. our previous work [15].
sigmaaldrich.com), sulphuric acid (H2SO4) (Merck, https://
www.merckmillipore.com) (98%), acetonitrile (CH3CN) Electrodeposition of Ag NPs onto p-1,8-DAN film
(ACN) (99.9%) HPLC (LAB-SCAN, http://www.
hurstscientific.com.au/chemicals/labscan.html), ethanol Different techniques for electrodeposition of Ag NPs onto
(CH 3 CH 2 OH) (ADWIC, https://www.nasrpharma.com/ p-1,8-DAN film was conducted such as pulse voltamme-
index.html) (96%) and diamond paste (Presi) were used as try (PV), double pulse voltammetry (DPV), in situ proce-
received. Sodium acetate (CH 3 COONa), acetic acid dure (Ag+ ions in situ), and CV protocol. Firstly, PV was
(CH3COOH), silver nitrate (AgNO3), potassium nitrate performed at p-1,8-DAN/GC modified electrode in
(KNO3), lead nitrate (Pb(NO3)2), cadmium chloride (CdCl2) 25.0 mL of aqueous solution of 0.01 M potassium nitrate
and copper chloride (CuCl2) were of analytical grade. (KNO3) containing 0.01 M AgNO3 for which a potential
0.1 M ABS (pH = 4.6) was performed by addition of 5.4 g of −0.8 was applied with accumulation time of 300 s for
CH3COONa to 2.4 mL glacial CH3COOH (0.1 M) and diluted Ag deposition. DPV technique was conducted in two
with distilled H2O until 100.0 mL. steps at p-1,8-DAN/GC modified electrode in the previ-
ously mentioned solution (in the last point). The first step
Instruments was nucleation pulse at an applied potential of +0.13 V
for 50 s, and the second step was growth pulse at an
A potentiostat voltammetric analyzer (BioAnalytical System applied potential of +0.24 V for 120 s. Secondly, Ag
(BAS)) was utilized for electrochemical measurements using NPs electrodeposition was achieved in situ (Ag+ ions in
Microchim Acta (2019) 186: 440 Page 3 of 10 440

situ) for which 0.01 M AgNO3 (0.0169 g) was added to -50 b

10.0 mL of the polymerization mixed solvent (4.5 M
H2SO4 in ACN) system during the electro polymerization -40

Current ( µA )
process of 1.0 mM 1,8-DAN monomer using CV tech- -30
nique with scan rate of 0.1 V. s−1 at potential range of
+0.2 to +1.2 V for 20 cycles. Final technique was per- -20
formed by CV protocol by cycling a freshly prepared p-
-10 Pot. Window
1,8-DAN/GC electrode in a solution of 0.01 M potassium
nitrate (KNO3) containing 0.01 M AgNO3 in a potential a
0
range from −0.9 to +0.6 V at a scan rate 0.05 V. s−1 for
2 cycles [16]. Based on anodic peaks currents of electro- -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
chemical responses (using CV technique at scan rate Potential ( V )
0.05 V. s−1) of different AgNPs@p-1,8-DAN/GC modi- Fig. 1 Square wave voltammograms of: (a) p-1,8-DAN/GC and (b)
fied electrodes prepared by different techniques in 0.1 M AgNPs@p-1,8-DAN/GC electrodes in ABS using scan rate of 0.005 V.
ABS, CV technique was chosen as it showed the highest s−1, time duration of 1 s and amplitude of 0.025 V in the potential range −
1.0 to +0.6 V (vs. Ag/AgCl)
and favorable current response (figure not shown).

potential space offers a pronounced improvement of the elec-

Results and discussion
trode applications for ASV of heavy metals.
Analytical parameters for Ag NP electrodeposition
Surface and bulk characterization
P-1,8-DAN film thickness was controlled using different of AgNPs@p-1,8-DAN-modified glassy
number of polymerization cycles from 5 to 25 cycles. Film carbon electrode
thickness performed using 20 cycles arises to give the favor-
able electrochemical response in ABS using CV technique at Characterization of AgNPs@p-1,8-DAN-modified elec-
scan rate 0.05 V. s−1 in the potential range − 0.9 to +0.6 V (vs. trode was carried out using different techniques like
Ag/AgCl) (Fig. S1 A). For studying the effect of Ag+ ions FE-SEM, EDX, XPS and AFM (for surface analysis),
concentration, p-1,8-DAN/GC electrode was immersed in dif- while XRD and TEM (for bulk analysis). FE-SEM is
ferent AgNO3 concentrations (0.1, 0.5, 1.0, 5.0, and 10.0 mM) employed to characterize the surface morphology of the
for which the corresponding current responses were mea- electrode. Figure 2a shows a rough grayish black surface
sured. Fig. S1 B indicated that the current response of indicative for the presence of p-1,8-DAN/GC electrode.
AgNPs@ p-1,8-DAN/GC increases gradually as Ag+ concen- SEM image (Fig. 2b) indicates a homogenous dispersion
tration raised from 0.1 to 10.0 mM. Number of cycles of Ag of Ag NPs at p-1,8-DAN/GC surface. Furthermore, EDX
electrodeposition was also studied by scanning p-1,8-DAN/ experiments confirm the Ag deposition giving signals
GC electrode in Ag+ solution using different cycles like 2, 3, corresponding to Ag metal with a percentage of 97.4%
5, 10, and 15 cycles giving the optimum results for 2 cycles (Fig. 2c).
(Fig. S1 C). Optimum conditions for Ag+ electrodeposition TEM image represents the morphology of Ag NPs al-
were detected by applying CV technique to p-1,8-DAN/GC most as a spherical in shape (Fig. 2 D) for which the par-
electrode (formed by 20 cycles) in a solution of 0.01 M KNO3 ticles size ranges from 10.0 nm to 60.0 nm with an average
containing 0.01 M AgNO3 in the potential range from −0.9 to size around 35.5 nm as shown in Fig. 2c inset (diameter
+0.6 V with scan rate of 0.05 V. s−1 for 2 cycles. (figure not distribution histogram).
shown) [16]. The crystallinity of Ag NPs was studied by XRD pattern
Figure 1 shows the electrochemical responses of p-1,8- for which diffractions peaks appeared at 38.3°, 44.25°, 64.72°,
DAN/GC and AgNPs@p-1,8-DAN/GC modified electrodes and 77.40° which are related to the (111), (200), (220), and
s in ABS using square wave voltammetry (SWV) technique in (311) planes of Ag face-centered cubic, respectively (Fig. 3a)
the potential range from - 0.9 V to +0.3 V. No electrochemical [17]. The strongest diffraction that arises from the (111) plane
response was detected at p-1,8-DAN/GC electrode (Fig. 1a). is a characteristic of such phase. The crystallite size was de-
The modified electrode has a well-defined anodic peak ap- termined from the full-width at half maximum (FWHM) of the
peared at +0.45 V for Ag+ ions stripping with an anodic peak highest reflection of the (111) peak at 2θ = 38.3°. Determined
current of 49.0 μA (Fig. 1b). This indicates that the working crystallite size came out to be 39 nm.
potential window from - 0.9 V to 0.0 V is suitable for the Surface elemental analysis via XPS enabled further in-
studied heavy metal ions determination. The wide-range sight into the composition of the AgNPs@p-1,8-DAN/GC
440 Page 4 of 10 Microchim Acta (2019) 186: 440

Fig. 2 a FE-SEM image of p-1,8-

DAN/GC electrode, b FE-SEM
image of AgNPs@p-1,8-DAN/
GC electrode, c EDX for the
surface of AgNPs@p-1,8-DAN/
GC electrode and d TEM image
of Ag NPs (inset: diameter
distribution histogram)

Fig. 3 a XRD pattern, b

Deconvoluted XPS for C1s, and c
a (111) * Holder peaks
15
Deconvoluted XPS for Ag3d of
AgNPs@p-1,8-DAN/GC
Intensity, A.U.

modified electrode
10
* (200)

5
*
* (220) (311)

0
20 30 40 50 60 70 80
θ
2-Theta, 2θ
30000
12000
b c Ag 3d5/2
C1s 25000
10000
Ag 3d3/2
20000
Counts, S

8000
Counts, S

6000 15000

4000 C1s A 10000

C1s B
2000 5000

292 290 288 286 284 282 378 376 374 372 370 368 366 364
Binding Energy, eV Binding Energy, eV
Microchim Acta (2019) 186: 440 Page 5 of 10 440

electrode surface. The modified electrode surface showed Electrochemical behavior and effective surface area
the presence of carbon, silver and nitrogen elements (not of AgNPs@p-1,8-DAN-modified glassy
shown). The presence of three components in C1s high carbon electrode
resolution region at 284.6, 285.8, and 288.2 eV (Fig. 3b)
are ascribed to C–C, C–N, and amide bonding in the p- The electrochemical behaviors of GC, p-1,8-DAN/GC and
1,8-DAN film, respectively. For determination of the AgNPs@p-1,8-DAN/GC electrodes were examined in
chemical environment and oxidation state of Ag NPs, 2.0 mM potassium ferrocyanide (K4[Fe (CN)6]) in 0.10 M
XPS measurements were carried out at the Ag 3d core KCl aqueous solution using CV technique as illustrated in
levels. Figure 3c displays the spectrum Ag 3d involves Fig. S2 (a, b and c). Peak-to-peak separation (ΔEp) values
two peaks at 374.15 and 368.15 eV, which are attributed were recorded at 0.93, 0.12 and 0.011 V for the three elec-
to binding energies for Ag 3d3/2 and Ag 3d5/2 of metallic trodes, respectively with increasing of peak current of
Ag, respectively. Results are in good approval with other AgNPs@p-1,8-DAN/GC electrode due to the presence of
results which obtained from XRD which implies the pres- Ag NPs. The low ΔE p for the previous electrode
ence of pure metallic Ag NPs. (nanoprobe) indicates a fast electron transfer higher than both
Electrodes surfaces were visualized using tapping GC and p-1,8-DAN/GC electrodes. This means that introduc-
mode AFM. The root-mean-square (rms) roughness ing Ag NPs at the surface of p-1,8-DAN/GC electrode de-
values were evaluated from 3D image topographies of p- velops its electrochemical performance.
1,8-DAN/GC and AgNPs@p-1,8-DAN/GC modified elec- The effective surface areas of p-1,8-DAN/GC and
trodes surfaces with 5.6 nm and 15.9 nm, respectively AgNPs@p-1,8-DAN/GC electrodes were calculated using
(Fig. 4a and b). Also, small protuberant peaks which were Randles-Sevcik equation for a reversible process in [Fe
detected in 2D and 3D AFM images of the nanoprobe (CN)6]3−/4− [18] as presented in Eq. 1:
electrode surface confirming the successful deposition of
I p ¼ 2:69  105 D =2 n =2 Aυ =2 C
1 3 1
Ag NPs on the electrode. ð1Þ

a b
Fig. 4 AFM images of 3D and 2D of (a) p-1,8-DAN/GC, and (b) AgNPs@p-1,8-DAN/GC modified electrodes
440 Page 6 of 10 Microchim Acta (2019) 186: 440

where A (effective surface area of electrode), D (diffusion a

-20 16
coefficient of [Fe (CN)6]3−/4− equal 7.6 × 10−5 cm2 s−1), C 14
-18 12
(bulk concentration of redox probe [1.0 mM [Fe (CN)6]3

Cureent ( µA )
10
-16
−/4−]), n (number of transferred electrons in [Fe (CN)6]3 8

Current ( µA )
−/4− -14 6
and equals equal one). The effective surface area of p- 4

1,8-DAN/GC electrode was found to be 0.1311 cm2. The -12 2

0

surface area increased by about 5 times when Ag NPs in- -10 -2

0 2 4 6 8 10

corporated into p-1,8-DAN film to reach 0.5536 cm2. -8 Conc. ( µM )

-6
-4
Electrochemical determination of individual Pb2+, -2
Cd2+ and Cu2+ heavy metal ions 0
-1.2 -1.1 -1.0 -0.9 -0.8 -0.7
The electrochemical determination of 10.0 μM Cd 2+ Potential ( V )
ions in ABS at both GC and p-1,8-DAN/GC electrodes b
using ASV technique with accumulation time 120 s and -30
10

scan rate of 0.005 V. s−1 were not detected (Fig. S3 A, 8

-25
a and b). At AgNPs@p-1,8-DAN/GC modified elec- 6

Current ( µA )
trode, an anodic peak appeared at −0.98 V with an

Current ( µA )
-20 4

anodic peak current of 4.31 μA (Fig. S3 A, c). The 2

electrochemical determination of 10.0 μM Pb2+ ions at -15 0

the three electrodes were examined (Fig. S3 B). No -2

-2 0 2 4 6 8 10 12 14 16 18
peaks were detected at GC electrode (Fig. S3 B, a). -10 Conc. (µM)

Two anodic peaks appeared at −0.77 V and - 0.82 V

-5
with anodic peak currents of 3.6 μA and 7.2 μA were
detected for both p-1,8-DAN/GC and AgNPs@P-1,8-
0
DA/GC electrodes, respectively with a favorable higher -1.00 -0.95 -0.90 -0.85 -0.80 -0.75 -0.70
value for the last electrode (Fig. S3 B, b and c). The Potential ( V )
anodic stripping voltammograms in Fig. S3 C illustrates
the ability of GC electrode and p-1,8-DAN/GC elec- c -10
trode to detect 25.0 μM of Cu2+ ions at −0.27 V and 8
-9
- 0.23 V with anodic peaks currents of 0.4 μA and 7
6
8.4 μA, respectively (Fig. S3 C a and b). AgNPs@p- -8
Current ( µA )
Current ( µA )

5
4
1,8-DAN/GC modified electrode showed more sensitiv- -7 3
ity as indicated by higher anodic peak current value to -6 2

reach 11.9 μA at −0.29 V (Fig. S3 C c).

1

-5 0

Previous results indicated that Pb2+ and Cu2+ ions -1

0 2 4 6 8 10
-4
can be detected individually at p-1,8-DAN/GC electrode Conc. ( µM )

while Cd2+ ions were not detected. This can be corre- -3

lated to the presence of amine/imine function groups -2
acting as chelating sites with for Pb2+ and Cu2+ ions -1
[19]. On the other hand, the three ions were detected -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0
at AgNPs@P-1,8-DAN nanoprobe with peak potentials Potential ( V )
−0.82 V, −0.29 V and − 0.98 V, respectively with a re- Fig. 5 Anodic stripping voltammograms of 1.5–9.0 μM for Cd2+, 2.00–
24.0 μM for Pb2+, and 2.00–9.0 μM for Cu2+ in ABS at AgNPs@p-1,8-
markable raise in their current. The synergistic contribu-
DAN/GC electrode with accumulation time 120 s, scan rate of 0.005 V.
tions from both P-1,8-DAN and Ag NPs improve the s−1 and amplitude of 0.025 V between −1.20 to 0.0 V (vs. Ag/AgCl).
accumulation efficiency and the rate of charge transfer Insets, relations between different ions concentrations and the
of the metal ions throughout ASV analysis. Additionally, corresponding anodic peaks currents
Ag creates fused alloys with several heavy metals mak-
ing it more readily to be reduced [19]. Such Ag alloys
facilitated the nucleation process during heavy metal
depositions in a similar manner to early described by Cd2+ ions were detected only at AgNPs@p-1,8-DAN/
Wang for Bi electrodes [3]. This can also explain why GC electrode.
Microchim Acta (2019) 186: 440 Page 7 of 10 440

Fig. 6 Anodic stripping 8 35 50

voltammograms of Cd2+ ions -60 7

6
30
40
concentrations (0.25–3.0 μM), 5
25
30

Current ( µA )

Current ( µA )

Current ( µA )
Pb2+ and Cu2+ ions 4
20

concentrations (1.0–12.0 μM) at -50 3

15
10
20

2 10
AgNPs@p-1,8-DAN/GC 5
1
electrode in ABS with 0
0

Current ( µA )
0
accumulation time 120 s, scan -40 -1 -5 -10
rate of 0.005 V. s−1 and amplitude 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 2 4 6 8 10 12 0 2 4 6 8 10 12
Conc. (µM) Conc. (µM
) Conc. (µM)
of 0.025 V between −1.20 to
0.0 V (vs. Ag/AgCl). Insets, -30
relations between different ions
concentrations and the
corresponding anodic peaks -20
currents

-10
2+
0 2+ Pb
2+ Cu
Cd
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential ( V )

Effect of individual heavy metal Pb2+, Cd2+ and Cu2+ currents. The anodic stripping peak currents were raised linearly
ions concentrations upon increasing the concentrations of the studied metal ions.
The calculated correlation coefficients (R2), LOD and limit of
Individual determination of low concentrations of different quantification (LOQ) are collected in Table S1 indicating the
heavy metal ions were studied between −1.20 to 0.0 V (vs. high sensitivity of the modified electrode towards the three
Ag/AgCl) at ranges like: 0.90 nM - 9.0 μM for Cd2+, 2.0 nM heavy metal ions individual determination.
- 24.0 μM for Pb2+, and 1.3 nM - 9.0 μM for Cu2+, while the
presented data are in the concentration windows of 1.5–9.0 μM Simultaneous electrochemical determination of Pb2+,
for Cd2+, 2.00–24.0 μM for Pb2+, and 2.00–9.0 μM for Cu2+. Cd2+, and Cu2+ heavy metal ions in a ternary mixture
Figure 5a, b and c represents the anodic stripping voltammo-
grams recorded at AgNPs@p-1,8-DAN/GC electrode with ac- The goal of this work is to detect Cd2+, Pb2+, and Cu2+ ions
cumulation time 120 s and scan rate of 0.005 V. s−1, while Fig. 5 simultaneously. Anodic stripping voltammograms of a mixture
insets, represent the relation between different ions concentra- of 0.5 μA Cd2+, 2.0 μA Pb2+ and 2.0 μA Cu2+ at p-1,8-DAN/
tions (in all ranges) and the corresponding anodic peaks GC and AgNPs@p-1,8-DAN/GC electrodes in ABS at a scan

Fig. 7 Anodic stripping

voltammograms of 0.5 μM Cd2+, 2+
-40 Cu
2.0 μM Pb2+, and 2.0 μM Cu2+
ions in presence of 2.0 μM Zn2+ -35
and 0.5 μM Hg2+ ions at 2+
Pb
AgNPs@p-1,8-DAN/GC -30
Current ( µA)

electrode in ABS with

-25
accumulation time 120 s, scan
rate of 0.005 V. s−1 and amplitude
2+
-20 Hg
of 0.025 V between −1.60 to
+0.2 V (vs. Ag/AgCl) -15
2+
-10 Cd
2+
Zn
-5
0
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4
Potential ( V )
440 Page 8 of 10 Microchim Acta (2019) 186: 440

rate of 0.005 V. s−1 with accumulation time 120 s were recorded Figure 6 insets, represent the relation between different
(Fig. S4 a and b). In Fig. S4 a, Cd2+, Pb2+ and Cu2+ ions were ions concentrations (in all ranges) and the corresponding an-
simultaneously detected at p-1,8-DAN/GC electrode at −1.06, odic peaks currents. Results reveal that the anodic stripping
−0,82 and 0.35 V with anodic stripping currents of 0.33 μA, peaks heights of all the studied heavy metal ions improved
1.52 μA and 3.54 μA, respectively. At AgNPs@p-1,8-DAN/ linearly with increasing their concentrations.
GC electrode (Fig. S4 b), peak potentials of Cd2+, Pb2+, and The resulting calibration plots exhibited an excellent line-
Cu2+ ions were detected at −1.02, −0.78 and − 0.32 V with arity of current dependence for their corresponding concentra-
anodic stripping currents of 1.22 μA, 5.43 μA and 9.76 μA, tions with R2 values of 0.9938 for Cd2+, 0.9946 for Pb2+, and
respectively. The remarkable differences in stripping peak po- 0.9934 for Cu2+. LOD values were estimated to be 0.17 nM,
tentials between Pb2+, Cd2+ and Cu2+ indicated the possibility 0.15 nM and 0.09 nM for Cd2+, Pb2+, and Cu2+ ions, respec-
of their simultaneous detection due to the strong activity of Ag tively as collected in Table S2. As represented, the nanoprobe
NPs decorated p-1,8-DAN film. Peak currents at AgNPs@p- is highly sensitive for simultaneous determination of Cd2+,
1,8-DAN/GC electrode compared with p-1,8-DAN/GC elec- Pb2+, and Cu2+ ions in ternary mixture with lower LOD and
trode demonstrates the role of Ag NPs towards the enhanced LOQ values.
responses of Pb2+, Cd2+, and Cu2+ ions.
Simultaneous determination of different concentrations of Repeatability
studied heavy metal ions were studied in the voltage range
from −1.20 to 0.0 V (vs. Ag/AgCl) at low concentrations Repeatability was evaluated by six times successive determi-
ranges like: 0.15 nM - 3.0 μM for Cd2+, 0.13 nM - 12.0 μM nation of 0.5 μM Cd2+, 2.0 μM Pb2+ and 2.0 μM Cu2+ ions at
for Pb2+, and 0.07 nM - 12.0 μM for Cu2+, while an ASVs of the same nanoprobe by recording their peak responses (Fig.
several Cd2+ ions concentrations (0.25–3.0 μM), Pb2+ and S5). The nanoprobe exhibited good repeatability and stability
Cu 2+ ions concentrations (1.0–12.0 μM) in ABS at due to the high adsorption between Ag NPs and Cd2+, Pb2+
AgNPs@p-1,8-DAN/GC are presented in Fig. 6. Stripping and Cu2+ ions [21].
peaks were appeared at −0.98, −0.74 and − 0.28 V for Cd2+,
Pb2+ and Cu2+, respectively. It is important to mention that at Interference studies
the higher concentration like1.0 μM, a second stripping peak
appeared for Pb2+ ions. As the concentration was increased Interferences of additional metal ions were examined for eval-
further, the magnitude of this second peak was also found to uating the ability of the nanoprobe for determination of Cd2+,
increase as presented in literature [20]. Pb2+, and Cu2+ ions in presence of zinc (II) (Zn2+) and

Table 1 Comparison of analytical performance of AgNPs@p-1,8-DAN/GC modified electrode with other similar systems

Electrode substrate Measurement technique Medium Limits of detection (μg. L−1) Ref.

Cd2+ Pb2+ Cu2+

MWCNT/P1,5-DAN ASV ABS pH 4.5 3.20 2.10 – [22]

RGO-CS/PLL/GCE DPASV ABS pH 4.5 0.01 0.02 0.02 [23]
Bi/CNT/GCE ASV ABS pH 4.5 0.70 1.30 – [24]
Bi/CNT/SPE ASV ABS pH 4.5 0.80 0.20 – [25]
Hg-Bi /SWNTs/GCE ASV KCl + ABS pH 6.0 0.076 0.18 – [26]
Bi/Graphene/MWCNT/GCE DPASV ABS pH 4.5 0.10 0.20 – [27]
Bi/Nafion/Graphene/GCE DPASV ABS pH 4.5 0.02 0.02 – [28]
Bi/EG/PG ASV ABS pH 4.6 0.10 0.13 – [29]
Pt/MWCNT/P1,5-DAN electrode ASV ABS pH 4.5 2.10 3.20 – [22]
GCE-MWCNT/poly (PCV)/Bi DPASV ABS pH 5.0 0.20 0.40 [30]
CB-18-crown-6-GEC DPASV ABS pH 4.5 2.40 1.50 1.50 [31]
RGO/Bi/CPE DPASV ABS pH 5.5 2.80 0.55 26.0 [32]
GC/CNT/nanoAu-SiO2 DPASV HCl – 0.47 0.34 [33]
Ag-bipy-CP/PMB/GCE DPV ABS pH 5.0 – 2.30 0.71 [34]
AgNPs/RGO ASV ABS pH 5.0 0.254 μM 0.141 μM 0.178 μM [35]
AgNPs@P-1,8-DAN/GC ASV ABS pH 4.6 0.019 0.031 0.005 This work
(0.17 nM) (0.15 nM) (0.09 nM)
Microchim Acta (2019) 186: 440 Page 9 of 10 440

mercury (II) (Hg2+) ions. Interference studies performed using electrodeposited onto p-1,8-DAN film by CV technique and
ASV technique with accumulation time 120 s and a scan rate characterized via different surface and bulk analytical tech-
of 0.005 V. s−1 by addition of 2.0 μM Zn2+ and 0.5 μM Hg2+ niques. The AgNPs@p-1,8-DAN/GC modified electrode
ions into the ABS containing 0.5 μM Cd2+, 2.0 μM Pb2+, and used for individual and simultaneous determination of Cd2+,
2.0 μM Cu2+ ions. Well-defined sharp peaks of Cd2+, Pb2+, Pb2+ and Cu2+ ions in ABS using ASV technique with high
and Cu2+ were observed as illustrated in Fig. 7. The presence sensitivity and low values of LOD and LOQ. Additionally, it
of both Zn2+ and Hg2+ ions did not affect peak responses for can detect other heavy metal ions like Zn2+ and Hg2+ in the
other ions with working voltages of −1.36 and + 0.9 V, respec- same system. The presented nanoprobe exhibited highly elec-
tively. The high surface area of Ag NPs supports high sensi- trocatalytic activity compared to the previous electrodes for
tivity for heavy metals ions detection and diminishes the in- electrochemical determination of these ions and the perfor-
terference for their simultaneously determination devoid of mance of the electrode shows high stability and sensitivity
losing response intensities. beside selectivity.

Real sample determination Acknowledgements The authors are appreciative to Alexander von
Humboldt Foundation for providing some electrodes and accessories.

The nanoprobe was tested in tap water collected and adjusted

with ABS for estimating its performance. Neither Cd2+, Pb2+
Compliance with ethical standards The author(s) declare that
they have no competing interests.
nor Cu2+ traces were found (Fig. S6 a). Then, typical addition
method had been used as an identified quantity were spiked
into the water sample (of the previous ions) and ASV re-
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