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Simultaneous Determination of Cd2+

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DOI: 10.5012/bkcs.2010.31.10.2949

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 2+ 2+ 2+ 2+
Simultaneous Determination of Cd , Pb , Cu and Hg Bull. Korean Chem. Soc. 2010, Vol. 31, No. 10 2949
DOI 10.5012/bkcs.2010.31.10.2949
2+ 2+ 2+ 2+
Simultaneous Determination of Cd , Pb , Cu and Hg at a Carbon Paste
Electrode Modified with Ionic Liquid-functionalized Ordered Mesoporous Silica
Penghui Zhang, Sheying Dong,* Guangzhe Gu, and Tinglin Huang†

College of Sciences, Xi′an University of Architecture and Technology, Xi′an 710055, P. R. China
*
E-mail: [email protected]
†
College of Environmental and Municipal Engineering, Xi′an University of Architecture and Technology,
Xi′an 71005, P. R. China
Received July 17, 2010, Accepted September 1, 2010

Ionic liquid-functionalized ordered mesoporous silica SBA-15 modified carbon paste electrode (CISPE) was fabricated
and its electrochemical performance was investigated by cyclic voltammetry, electrochemical impedance spectra.
The electrochemical behavior of Cd2+, Pb2+, Cu2+ and Hg2+ at CISPE was studied by differential pulse anodic stripping
voltammetry (DPASV). Compared with carbon paste electrode, the stripping peak currents had a significant increase
at CISPE. Under the optimized conditions, the detection limits were 8.0 × 10‒8 M (Cd2+), 4.0 × 10‒8 M (Pb2+), 6.0 ×
10‒8 M (Cu2+), 1.0 × 10‒8 M (Hg2+), respectively. Furthermore, the present method was applied to the determination
of Cd2+, Pb2+, Cu2+ and Hg2+ in water samples and people hair sample.

Key Words: Carbon paste electrode, Ionic liquid, SBA-15, Heavy metal ion

Introduction exhibited an excellent electrochemical behavior.

Mesoporous materials attracted much attention for their large
Heavy metal pollution, always caused by the waste streams surface area, fast adsorption kinetics, controllable pore size and
of many industries, such as metal plating facilities, mining pore arrangement. Due to the abundant silanol groups located
operations, and tanneries, has become a serious threat to human at the internal surfaces, the mesoporous materials could be func-
health, living resources, and ecological systems. They are not tionalized with alkoxy silanes containing different organic
20-22
biodegradable and tend to accumulate in living organisms, groups. These functionalized silica23,24 behaved as effective
causing various diseases and disorders to the nervous, immune, sorbents in the removal of heavy metals from contaminated
1
reproductive and gastrointestinal systems. Thus, different sen- water, while the functionalized silica modified CPE also ex-
sitive methods have been developed to the simultaneous deter- hibited high selectivity to the simultaneous determination of
mination of heavy metals. The typical methods for the simulta- heavy metal ions.25 However, the poor conductivity of silica
26
neous analysis include inductively coupled plasma-mass spectro- decreased the sensitivity of the determination. To improve
2 3
metry (ICP-MS), X-ray fluorescence spectrometry (XRF), and the conductivity of the silica, ionic liquid was immobilized on
4
atomic absorption spectrometry (AAS). However, time con- SBA-15, one of the mesoporous silica possessing large pores
suming process, high cost of maintenance, expensive and sophi- and thick pore walls that led to good thermal stability. This
sticated instruments severely restrict their practical applications. ionic liquid functionalized SBA-15 (ILs-SBA-15) not only had
Electrochemical method is one of the most favorable tech- the unique structure of SBA-15, but also exhibited high conduc-
niques for the determination of environmental pollutants because tivity and catalytic activity of ionic liquid. At the same time,
of its low cost, high sensitivity and easy operation. Among di- the use of ILs-SBA-15 in the fabrication of CPE could avoid
fferent electrochemical methods, anodic stripping voltammetry the high background current caused by the direct use of ionic
27
(ASV) has been proved to be a simple and effective method liquid as a binder.
for the determination of heavy metal ions. Traditional working In the present work, the first challenge was made to fabri-
electrodes for simultaneously voltammetric determination were cate a novel ILs-SBA-15 functionalized carbon paste electrode
5
generally based on a hanging drop mercury electrode (HDME) (CISPE). K3Fe(CN)6/K4Fe(CN)6 was selected as a probe to
6
or a mercury film electrode (MFE). However, the toxicity of evaluate CISPE by cyclic voltammetry, electrochemical im-
Hg and its precursors made these materials undesirable for dis- pedance spectra. Based on the good performance of CISPE, the
2+ 2+ 2+ 2+
posable in situ sensing applications. Therefore, various mercury- electrochemical behaviors of Cd , Pb , Cu and Hg at CISPE
7,8
free electrodes including bismuth film electrode, gold-coated were studied by differential pulse anodic stripping voltammetry
electrode, silver electrode, carbon paste electrode (CPE)11-13
9 10
(DPASV). In addition, a DPASV method for the simultaneous
14,15 2+ 2+ 2+ 2+
and glassy carbon electrode were applied for sensitive metal determination of Cd , Pb , Cu and Hg with sensitive, sim-
determinations. In the fabrication of these modified electrodes, ple and rapid characteristics was presented.
CPE was usually preferred for its low cost and simple prepara-
tion procedure. Moreover, through the replacement of paraffin Experimental
16
with different binders, the modification of the electrode sur-
face, or the addition of new materials,18,19 the modified CPE
17
Reagents and solutions. The chemicals used in this study
2950 Bull. Korean Chem. Soc. 2010, Vol. 31, No. 10 Penghui Zhang et al.

include tri-block copolymer poly(ethylene oxide)-poly(pro- conditioning step: potential 0.6 V for 60 s was applied before
pylene oxide)-poly(ethylene oxide) (P123, MW: 5800), 1-me- each measurement to ensure dissolution of the remaining de-
thylimidazole from Aldrich, tetraethyl orthosilicate (TEOS), posits; (b) the pre-concentration step proceeded at ‒1.2 V for
3-(chloropropyl)-trimethoxysilane (CPTE), high purity graphite 6 min while the mixture solution was stirred; (c) the stripping
powder, paraffin liquid, Cd(NO3)2, Pb(NO3)2, Cu(NO3)2 and voltammograms were recorded when swept from ‒1.0 V to
Hg(NO3)2 from China National Medicine Corporation, ethyl 0.6 V after a 20 s quiescence. All the experiments were con-
acetate, hydrochloric acid (36 - 38%), K3Fe(CN)6, K4Fe(CN)6, ducted by CHI660B electrochemical workstation at room tem-
KNO3 and KCl from Xi’an Chemical Reagent Factory. All the perature.
chemicals were of analytical reagent grade and used without
further purification. Results and Discussion
0.10 M PBS (NaH2PO4-Na2HPO4) was employed as support-
ing electrolyte and adjusting the pH with H3PO4 or NaOH. Characterization of different electrodes. K3Fe(CN)6/K4Fe
2+ 2+ 2+ 2+
Stock solutions (1.0 mM) of Cd , Pb , Cu and Hg were pre- (CN)6 was selected as a probe to evaluate the performance of
pared by dissolving their corresponding nitrate salts into water the prepared electrodes. Fig. 1 presented the electrochemical
and diluted to various concentrations. The hair sample was responses of CPE, CSPE, and CISPE in 5.0 mM K3Fe(CN)6/
prepared as follows: the hair was washed with detergent and K4Fe(CN)6 solution. It was observed that the peak current of
water to remove the external contamination or unnecessary dirt CISPE greatly increased together with an obvious decrease of
and grease from its surface. The washed hair was dried and ∆Ep, behaving as a quasi-reversible electron transfer process.
digested with HNO3-HClO4 (4/1) solution for 2 h at room tem- The inset of Fig. 1 showed the effect of CISPE compositions
perature. Then the digested solution was diluted to prepare on the CV responses. It was found that the redox peak currents
‒1
1.00 g mL hair sample. The tap water sample and river water significantly increased with the increase of ILs-SBA-15. But
sample were used without further treatment. All solutions were when the modified silica was more than 10% (w/w), the rever-
prepared with twice-distilled water. sibility of the electrode reaction and the stability of CISPE de-
Apparatus. All electrochemical measurement was carried creased obviously, which attributed to the water adsorption of
out with a CHI660B electrochemical workstation (Shanghai ILs-SBA-15. These results presented that the reversibility of the
Chenhua Co.) controlled by a microcomputer with CHI660 soft- electrode reaction and the conductivity of CISPE were greatly
ware. A three-electrode system was used, where a saturated improved.
calomel electrode (SCE) served as the reference electrode, a To further study the capability of the electron transfer on these
platinum wire electrode served as the auxiliary electrode and electrodes, EIS of CPE, CSPE and CISPE were determined in
a CPE, a SBA-15 modified carbon paste electrode (CSPE) or a 5.0 mM K3Fe(CN)6/K4Fe(CN)6 solution. As shown in Fig. 2(A),
CISPE served as the working electrode. All potentials reported the semicircular part at higher frequencies corresponded to the
were referred to the SCE. In the measurements of electrochemi- electron transfer-limited process and its diameter was equal to
cal impedance spectra (EIS), the applied perturbation amplitude the electron transfer resistance (Rct), which controlled the elec-
5 ‒2
was 0.005 V, the frequencies swept from 10 to 10 Hz, the tron transfer kinetics of the redox probe at the electrode inter-
number of points per frequency decade was 12 and initial po- face. Meanwhile, the linear part at lower frequencies fitted in
tential was 0.20 V. with the diffusion process. The equivalent circuit (Fig. 2(B))
Preparation of the modified carbon paste electrodes. The used to model the above behavior was a modification of the
ILs-SBA-15 based on imidazolium ionic liquid was prepared well-known Randles circuit,29 which approximated the behavior
28
following the similar procedures according to the literature.
The CISPE was prepared as follows: graphite powder was -6
mixed with ILs-SBA-15, then 0.80 g of the mixture was added
to 0.20 g of paraffin liquid and mixed for at least 20 min to -4

produce the final paste containing 5.0% ILs-SBA-15 (w/w).

-2
Then the prepared carbon paste was tightly packed into a PVC
tube (3 mm internal diameter) and a copper wire was introduced 0
i /µA

into the other end for electrical contact. The preparation of CSPE
was similar to that of CISPE but only SBA-15 was used for the 2
construction of CSPE, while CPE was prepared by mixing
graphite powder and paraffin liquid with a ratio of 80/20 (w/w). 4

A new surface was obtained by smoothing the electrode onto

6
a weighing paper.
Analytical procedure. A certain amount of standard or sample -0.2 0.0 0.2 0.4 0.6 0.8
solution was mixed with 0.10 M PBS into 20 mL volumetric E/V
flask. The prepared solution was transferred into electroche-
mical cell. The electrochemical behavior of CISPE was inve- Figure 1. CV curves of CPE, CSPE and CISPE in 5.0 mM K3Fe(CN)6/
K4Fe(CN)6 (1:1, pH = 6.9) solution containing 0.10 M KNO3, scan
stigated by cyclic voltammetry (CV) and EIS in K3Fe(CN)6/ rate 0.10 V s‒1. Inset shows CV curves (a-e) of CISPE with different
2+ 2+ 2+ 2+
K4Fe(CN)6 solution. The analysis of Cd , Pb , Cu and Hg compositions (containing ILs-SBA-15 (w/w) 0%, 2.5%, 5.0%, 7.5%
using DPASV was carried out in the following steps: (a) pre- and 10.0%, respectively).
 2+ 2+ 2+ 2+
Simultaneous Determination of Cd , Pb , Cu and Hg Bull. Korean Chem. Soc. 2010, Vol. 31, No. 10 2951

(A) 40
10
12 Pb
2+ Hg2+
-Z''/103 ohm

-Z''/103 ohm
10

-Z''/103 ohm
1200 30
6 8
20 6
4
4
10 2 2
Cu2+
-Z''/103 ohm

900 0 0 0
0 5 10 15 20 25 30 0 1 2 3 4 5 6 0 2 4 6 8 10
3
Z'/10 ohm Z'/103 ohm Z'/103 ohm

20 µA
600
2+
Cd
300

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6

0
0 300 600 900 1200 1500 E/V
3
Z'/10 ohm Figure 3. DPSAV curves of 1.0 × 10‒7 M Cd2+, Pb2+, Cu2+ and Hg2+ at
CPE, CSPE and CISPE in pH 3.0 PBS buffer solution. Accumula-
(B) R1 CPE1 tion potential: ‒1200 mV; accumulation time: 6 min; pulse amplitude:
‒1
60 mV; scan rate: 20 mV s ; pulse width: 60 ms.
R2 W1

Figure 2. (A) Electrochemical impedance spectroscopy of (a) CPE, 35

(b-e) CISPE (containing ILs-SBA-15 (w/w) 2.5%, 5.0%, 7.5%, 10.0%,
30
respectively), (f) CSPE (containing SBA-15 5.0%) in 5.0 mM K3Fe
(CN)6/K4Fe(CN)6 (1:1) solution containing 0.10 M KNO3. The appli-
25
ed perturbation amplitude was 0.005 V, the frequencies swept from
5
10 to 0.01 Hz and initial potential 0.20 V. (B) Equivalent circuit mo-
20
ip/µA

del of the electrochemical impedance behavior of the electrodes. Rsol:

the resistance of the solution; Rct: charge transfer resistance; CPE: con- 15
stant phase element, which is a complex of various elements; W: War-
burg resistance, which reflects diffuse barrier at low-frequency part. 10

5
of a solid electrode participating in single-electron faradaic
charge-transfer process. It was found that the fitted plots ob- 0
sol.1 sol.2 sol.3 sol.4 sol.5 sol.6 sol.7
tained were quite well in agreement with the measured plots.
The resistances of solution at different electrodes had slight Different buffer solutions
change, while Rct of CPE and CSPE were far higher than that
Figure 4. The effect of different electrolytes (sol. 1: 0.10 M HAc-NaAc,
of CISPE (CISPE<CSPE<CPE). 2: 0.10 M sodium citrate-HCl, 3: Mcllvaine buffer solution, 4: 0.20 M
The obtained results showed that with the addition of SBA-15, potassium biphthalate-NaOH, 5: 0.10 M PBS, 6: 0.10 M KCl, 7: 0.10 M
the electron transfer ability of the electrode was improved a ‒7 2+
KNO3) on the stripping peak currents of 1.0 × 10 M Cd , Pb , Cu
2+ 2+
2+
little because the uniform pore structure and high surface area and Hg at CISPE. Inset shows the stripping peak currents in 0.10 M
of the SBA-15 provided a microenvironment to accelerate the PBS with different pH (2.0 - 7.0). Other conditions are the same as in
electron transfer of the electrode reaction. However, the poor Fig. 3.
conductivity of silica led to the dissatisfactory performance.
The improved electron transfer kinetics at CISPE was likely for the increase of the background current. Therefore, a carbon
3‒ 4‒
associated with the interaction between Fe(CN)6 /Fe(CN)6 paste composition of 5.0% (w/w) ILs-SBA-15, 75.0% (w/w)
inner-sphere redox couple and imidazolium cation at the ILs- graphite and 20.0% (w/w) paraffin liquid was used for further
30
SBA-15. On the other hand, the large surface area of meso- experiments.
2+ 2+ 2+ 2+
porous material resulted in the high concentration of imida- The electrochemical responses of Cd , Pb , Cu and Hg
zolium cation on the surface of ILs-SBA-15. Thus, the unique at different electrodes. Fig. 3 showed differential pulse anodic
2+ 2+ 2+ 2+
structure and electrocatalytic effect of the ILs-SBA-15 contri- stripping voltammograms of Cd , Pb , Cu and Hg at CPE,
buted to the promotion of the electron transfer, improvement of CSPE and CISPE. The stripping peak potential separations of
2+ 2+ 2+ 2+
the reversibility and enhancement of the sensitivity at CISPE. Cd , Pb , Cu and Hg at the three electrodes were all su-
Effect of electrode composition. The effect of electrode com- fficient for simultaneous determination. It was obvious that the
position on the electrochemical behaviors of 1.0 × 10‒7 M Cd2+, stripping peak currents at CPE were low, while the perfor-
2+ 2+ 2+
Pb , Cu and Hg was investigated in pH 3.0 NaH2PO4-H3PO4 mance of CSPE had a little improvement. At CISPE, four well-
buffer solution. The stripping peak currents of the four metal defined stripping peaks were obtained and the striping currents
ions increased with the amount of ILs-SBA-15 in the paste up significantly increased. The reason might be that the nitrogen
to 5.0% (w/w). When the modified silica was more than 5.0%, atom of the imidazolium group at the surface of ILs-SBA-15
2+ 31
the determination sensitivity of Cd decreased dramatically was a very strong N-ligating donor for d-metal ions. The co-
2952 Bull. Korean Chem. Soc. 2010, Vol. 31, No. 10 Penghui Zhang et al.

ordination of the metal ions and imidazolium group led to an deposition potential, amplitude and scan rate were evaluated.
enhancing response. At the same time, ILs-SBA-15 could pro- As shown in Fig. 5(A), the stripping peak currents were
mote the electron transfer rate, so more metal ions were de- proportional to the accumulation time up to 6 min. For longer
posited on the electrode surface in a shorter time and the large preconcentration times, currents were found to level off and
13
stripping currents were obtained. In addition, the unique struc- reach to constant values after 10 min owing to the saturation
ture of ILs-SBA-15 might also accelerate the enrichment of loading of active sites at the electrode surface. Furthermore,
metal ions. the long accumulation time might lead to the separation of the
Effect of electrolyte and pH. The speciation of metal ions in stripping peak which attributed to the formation of intermetallic
an aqueous solution significantly affects their interaction with compounds. Thus, the accumulation time of 6 min was chosen
32 2+ 2+ 2+ 2+
a solid adsorbent. In a dilute solution, Pb , Cd , Cu and Hg in the following experiments.
are mainly present in the form of mononuclear hydrolysis Fig. 5(B) displayed the effect of the deposition potential from
products, but their species distributions are related to many ‒900 to ‒1300 mV on the stripping signals of the four metal
factors, such as pH, ionic strength, anions, and metal ion con- ions. The negative shifts of deposition potential could improve
centration. As shown in Fig. 4, the influence of different electro- the reduction of the metal ions on the surface of modified elect-
‒7 2+ 2+
lytes in the stripping peak currents of 1.0 × 10 M Pb , Cd , rode and increase the peak currents. However, when deposition
2+ 2+
Cu and Hg was investigated. The results showed when 0.10 M potentials were more negative than ‒1300 mV, the background
PBS was chosen as the electrolyte, the larger stripping peak currents increased and some interferent might be reduced at
currents, the lower background current and the better shape of these potentials, which depressed the sensitivity of the deter-
peaks were obtained. mination. So the deposition potential of ‒1200 mV was used in
The inset of Fig. 4 showed the effect of pH on the stripping the following experiments.
2+ 2+ 2+ 2+
peak currents in 0.10 M PBS in the range of 1.0 - 7.0. As pH < The stripping peak currents for Cd , Pb , Cu and Hg in
2.0, the current signals measured at CISPE were not steady and DPASV were evaluated as a function of pulse amplitude from
-1
the interferences were serious. With the increase of pH, the 10 to 120 mV and scan rate between 10 and 50 mV s in Fig.
currents of the four metal ions increased at first and then de- 5(C) and Fig. 5(D). It was observed that with the increase of
2+ 2+ 2+
creased. The reason might be that at pH < 5.0, Pb , Cd , Cu scan rate and amplitude, the stripping peak currents and back-
2+
and Hg species were totally present in ionic states. While ground currents both increased. To achieve higher sensitivity
‒1
increasing pH, these species started to hydrolyze and entirely and better response, 80 mV and 30 mV s were employed in
precipitate at high pH value. The largest stripping currents of the following experiments.
2+ 2+ 2+ 2+
Cd , Pb and Hg were obtained at pH 3.0, while the cu- Calibration graph. A series of standard solutions of Cd ,
2+ 2+ 2+ 2+
rrents of Cu had a slight change from 3.0 to 6.0. Thus, 0.10 M Pb , Cu and Hg were determined by DPASV under the opti-
pH 3.0 PBS was chosen as the electrolyte in the following mized working conditions described above. The results pre-
experiments. sented that the stripping peak currents of the four metal ions
Optimization of experimental parameters. In order to opti- had linear relationships with the concentrations in the range of
‒7 ‒5
mize the experimental parameters that might affect the deter- 6.0 × 10 to 3.0 × 10 M (i(µA) = ‒20.51c(µM) + 8.817, R =
2+ 2+ 2+ 2+ 2+ ‒7 ‒5
mination of Cd , Pb , Cu and Hg , the accumulation time, 0.9984) for Cd , 4.0 × 10 to 9.0 × 10 M (i(µA) = ‒37.35c
2+ ‒7 ‒4
(µM) + 9.958, R = 0.9986) for Pb , 3.0 × 10 to 1.0 × 10 M
2+
(i(µA) = ‒27.15c(µM) + 1.926, R = 0.9970) for Cu and 8.0 ×
: Cd : Pb : Cu : Hg 10‒8 to 5.0 × 10‒5 M (i(µA) = ‒75.29c(µM) ‒ 3.037, R = 0.9983)
2+
for Hg . When the signal noise ratio (SNR) was 3, the detec-
-40
-30
(A) (B) ‒8 2+ ‒8
tion limits were 8.0 × 10 M (Cd ), 4.0 × 10 M (Pb ), 6.0 ×
2+
‒8 2+ ‒8 2+
-30 10 M (Cu ), 1.0 × 10 M (Hg ), respectively. Compared with
-20 other modified electrodes at Table 1, CISPE had a better sen-
i /µA

-20
-10
sitivity and lager linear range, indicating its potential in simulta-
-10
neous determination of practical samples containing Cd2+, Pb2+,
2+ 2+
0
100 200 300 400 500 600
0
-1300 -1200 -1100 -1000 -900
Cu and Hg .
Stability of CISPE. The reproducibility of CISPE was inve-
t/s E/mV
stigated by repetitively determining the mixed solution contain-
‒7 2+ 2+ 2+ 2+
-30
(C) (D) ing 1.0 × 10 M Cd , Pb , Cu and Hg . It was found that
-30 the relative standard deviations (RSD) of peak currents for the
-20
four metal ions were 2.0% (Cd2+, n = 5), 1.1% (Pb2+, n = 5),
i /µA

-20
2+ 2+
-10
2.8% (Cu , n = 5) and 3.4% (Hg , n = 5), respectively. The
-10 response sensitivity retained more than 90% over two weeks
o
0 0 when the electrodes was kept at 4 C. In addition, RSD of peak
0 20 40 60 80 100 120 10 20 30 40 50
currents using CISPE prepared at the same time were 2.4%
‒1 2+ 2+ 2+
Amplitude/mV ν/(mV s ) (Cd , n = 5), 1.8% (Pb , n = 5), 2.8% (Cu , n = 5) and 3.2%
2+
Figure 5. Effects of (A) time, (B) accumulation potential, (C) amplitude
(Hg , n = 5). The high reproducibility and stability indicated
‒7
and (D) scan rate on the stripping peak currents of 1.0 × 10 M Cd ,
2+ that CISPE was suitable for analysis of practical samples.
2+ 2+ 2+
Pb , Cu and Hg at CISPE in 0.10 M PBS. Interferences. The possible mutual Interferences of the four
 2+ 2+ 2+ 2+
Simultaneous Determination of Cd , Pb , Cu and Hg Bull. Korean Chem. Soc. 2010, Vol. 31, No. 10 2953

Table 1. The detection ranges and detection limits of metal ions at Table 2. Interferences of some inorganic species on the stripping
different electrodes peak currents of 1.0 × 10‒6 M Cd2+, Pb2+, Cu2+ and Hg2+

Cd2+ Pb2+ Cu2+ Hg2+ Concentration Signal change (%)

Electrode Reference Interferent
(µM) (µM) (µM) (µM) (mM) 2+
Cd Pb2+ Cu2+ Hg2+
DR 0.6 - 30 0.4 - 90 0.3 - 100 0.08 - 50 2+
CISPE This work Ca 1.0 1.3 1.3 0.7 2.8
DL 0.08 0.04 0.06 0.01
Al3+ 0.5 4.4 4.4 3.6 4.0
DR 0.2 - 2 0.4 - 4 0.8 - 8 - Co2+ 1.0 3.2 1.9 2.7 0.1
GC [33]
DL 0.09 0.08 0.6 -
Cr3+ 1.0 3.5 1.9 1.8 4.7
BTPSBA- DR - 0.3 - 7 0.8 - 10 2 - 10 Mn2+ 1.0 0.5 0.8 0.1 0.4
[26]
MCPE DL - 0.04 0.2 0.4 Ni2+ 1.0 2.2 0.4 1.4 2.1
DR: detection range; DL: detection limit. GC: glass carbon electrode. Zn2+ 1.0 3.9 1.0 1.2 0.5
BTPSBA-MCPE: a carbon paste electrode modified with SBA-15 silica
Bi3+ 0.1 2.3 1.9 2.6 1.5
organofunctionalised with 2-benzothiazolethiol.
Sr2+ 1.0 2.3 2.1 2.5 4.7
Fe2+ 0.1 1.2 3.5 2.2 3.6
-600 Fe3+ 0.1 1.3 7.9 3.1 5.7
Ag+ 0.1 11.3 10.9 10.1
i /µA

-500
SO42‒ 1.0 1.5 0.9 1.8 2.1
-400 Cl‒ 1.0 0.2 0.1 0.3 0.2
i /µA

-300
Table 3. Recovery of Cd2+, Pb2+, Cu2+ and Hg2+ (n = 3)
-200
Added Expected Found RSD Recovery
Samples Ions
-100 (µM) (µM) (µM) (%) (%)
0 ND
0 Cd2+ 1.00 1.37 105.0
1.00 1.05
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
2+ 0 ND
Pb 1.00 1.62 102.0
E/V 1.00 1.02
1
2+ 0 0.71
Figure 6. DPSAV curves of different concentrations of Cd , Pb , Cu 2+ 2+ 2+ Cu 1.71 1.64 98.8
1.00 1.69
and Hg2+ (a-i, 0.6, 0.8, 1.0, 1.2, 1.4, 2.0, 4.0, 6.0, 8.0 µM) at CISPE in 2+ 0 ND
0.10 M pH 3.0 NaH2PO4-H3PO4 buffer solution. Accumulation poten- Hg
1.00 1.00 1.04 0.68 104.0
tial: ‒1200 mV; accumulation time: 6 min; pulse amplitude: 80 mV;
‒1
scan rate: 30 mV s ; pulse width: 80 ms. 2+ 0 ND
Cd 1.00 1.85 102.0
1.00 1.02
2+ 0 1.59
metal ions were evaluated by the single or simultaneous deter- Pb 2.59 1.35 99.2
1.00 2.57
‒6 2+ 2+ 2+ 2+ 2
mination of 1.0 × 10 M Cd , Pb , Cu and Hg . The results 2+ 0 11.65
Cu 12.65 0.98 104.3
showed that there was no obvious shift for the stripping peaks 1.00 13.02
2+ 0 0.14
obtained by simultaneous and single determination, while their Hg
1.14 2.04 104.4
1.00 1.19
stripping currents had a deviation below 5.0%. The possible
2+ 0 ND
interferences in the wastewater were also tested in Table 2. A Cd 1.00 2.35 104.0
2+ 2+ 3+ 2+ 2+ 2+ 1.00 1.04
great of species, including Ca , Co , Cr , Mn , Ni , Zn , 2+ 0 11.53
2+ 2‒ ‒ ‒3
Sr , SO4 and Cl (each of c = 1.0 × 10 M) had no signi- Pb 12.53 1.26 98.7
1.00 12.37
‒6 2+ 2+ 2+ 3
ficant influence on the signals of 1.0×10 M Cd , Pb , Cu Cu2+
0 69.85
2+ 1.00 70.85 71.20 1.19 100.5
and Hg with deviations below 5.0%. The concentrations of
3+ 3+ 2+ 3+
Al , Bi , Fe and Fe should be taken into account due to 0 1.07
Hg2+
+ 1.00 2.07 2.04 0.77 98.6
their interfere with the determination. Ag was a strong inter- a
2+ 2+ 2+ 2+
ferent to the determination of Cd , Pb , Cu and Hg , which ND: not detectable. bSample 1: tap water sample; 2: river water sample
c
(from Bahe river in Xi’an); 3: people hair sample. The working conditions
must be separated or masked before determination. are the same as in Figure 6.
Applications. To evaluate the proposed method, CISPE was
employed to determine Cd2+, Pb2+, Cu2+ and Hg2+ in tap water
samples, river water samples and people hair samples. As shown Conclusions
in Table 3, the recovery and RSD were acceptable. In addition,
to testify the accuracy of this method, the results obtained by In conclusion, CISPE modified with ILs-SBA-15 exhibited
CISPE were compared with that by atomic absorption spectro- excellent electrocatalytic activity, electron transfer ability and
metry. The satisfactory RSD indicated the proposed method stability owing to the advantages of both ionic liquids and hetero-
had great potential in the practical sample analysis. geneous supports. The unique structure and imidazolium cation
2954 Bull. Korean Chem. Soc. 2010, Vol. 31, No. 10 Penghui Zhang et al.

2+
of ILs-SBA-15 made the simultaneous determination of Cd , 12. Gabriela, R. M.; Ramírez-Silva, M. T.; González, R. L.; Galicia, L.;
2+ 2+ 2+
Pb , Cu and Hg at CISPE by DPASV present high sensi- Romero-Romo, M. Electroanalysis 2005, 17, 694.
tivity. The proposed DPASV method was applied to the deter- 13. Li, Y. H.; Liu, X. Y.; Zeng, X. D.; Liu, Y.; Liu, X. T.; Wei, W. Z.;
2+ 2+ 2+ 2+ Luo, S. L. Sens. Actuators, B 2009, 139, 604.
mination of Cd , Pb , Cu and Hg in practical samples and 14. Yuan, S.; Chen, W. H.; Hu, S. S. Talanta 2004, 64, 922.
satisfactory results were obtained. Thus, this study was expected 15. Zheng, H.; Yan, Z. N.; Dong, H. M.; Ye, B. X. Sens. Actuators, B
to provide important insight into the application of ILs-SBA-15 2007, 120, 603.
in electroanalysis. 16. Albertúsa, F.; Llerenaa, A.; Alpízara, J.; Cerdáb, V.; Luquec, M.;
Ríosc, A.; Valcárcel, M. Anal. Chim. Acta 1997, 355, 23.
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Acknowledgments. The authors appreciate the support from 18. Shahrokhian, S.; Fotouhi, L. Sens. Actuators, B 2007, 123, 942.
the National Natural Science Foundation of China (No. 5083 19. Mashhadizadeh, M. H.; Khani, H. Anal. Methods 2010, 2, 24.
0303), Program for Changjiang Scholars and Innovative Re- 20. Christabel, E. F.; Burkett, S. L.; Mann, S. Chem. Commun. 1997,
search Team in University (PCSIRT) (Grant No. IRT0853) and 18, 1769.
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