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A novel electrochemical cyanide sensor using gold nanoparticles decorated carbon ceramic electrode
Accepted Manuscript A novel electrochemical cyanide sensor using gold nanoparticles decorated carbon ceramic electrode
Mojtaba Shamsipur, Ziba Karimi, Mahmoud Amouzadeh Tabrizi PII: DOI: Reference:
S0026-265X(17)30351-X doi: 10.1016/j.microc.2017.04.017 MICROC 2794
To appear in:
Microchemical Journal
Received date: Revised date: Accepted date:
23 May 2016 15 February 2017 11 April 2017
Please cite this article as: Mojtaba Shamsipur, Ziba Karimi, Mahmoud Amouzadeh Tabrizi , A novel electrochemical cyanide sensor using gold nanoparticles decorated carbon ceramic electrode. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Microc(2017), doi: 10.1016/j.microc.2017.04.017
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ACCEPTED MANUSCRIPT
A novel electrochemical cyanide sensor using gold nanoparticles decorated carbon
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ceramic electrode
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Mojtaba Shamsipur*a, Ziba Karimi a,b and Mahmoud Amouzadeh Tabrizi c Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran.
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Department of Chemistry, Payame Noor University, 19395-3697 Tehran, I. R. Iran.
c
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a
Research Center for Science and Technology in Medicine, Tehran University of Medical Sciences,
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Tehran, Iran.
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*Corresponding authors: Mojtaba Shamsipur, Email: [email protected]
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ACCEPTED MANUSCRIPT Abstract The high toxicity of cyanide and its great variety of uses in industrial processes make it necessary to develop sensitive and selective sensors for its determination in natural and waste waters. In this work, using modified carbon ceramic electrode with gold nanoparticles (GNPs) was reported. The
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electrodeposition of GNPs on carbon ceramic electrode (CCE) was confirmed by scanning electron
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microscopy (SEM). The SEM image showed that the size of gold nanoparticles was examined around 75
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nm. The GNPs/CCE was used for the determination of cyanide (CN−) in solution (pH 12). The cyclic voltammetry (CV) and square wave voltammetry (SWV) mthodes were used for the determination of
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CN−. The linear dynamic range from 0.5 µM to 14.0 µM and a detection limit was found to be 0.09 µM
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(S/N = 3) by SWV method. Interference studies were performed with typical anions present in natural and waste waters. Based on obtained result, the proposed sensor suffer from the interefering of
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thiocyanide (SCN-) ion.
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Keywords: Electrocatalysis; Cyanide; Carbon Ceramic Electrode; Gold nanoparticles; Real samples
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1. Introduction Among inorganic anions, cyanide (CN− ) is one of the best known and most hazardous pollutants of the environment because of its toxic effect at very low levels [1]. It is produced by man-made as well
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as natural sources. It is used in industry in electroplating, refining precious metals (gold and silver) and
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for fumigation [2]. For this reason, considerable efforts have been put into the design some probes or
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sensors for the detection of chemically and biologically important ionic species [3]. With respect to the
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limits of CN− in drinking water and environmental, the U.S. EPA regulates cyanide content at very low levels of 0.2 ppm and 0.005 ppm for drinking water and environmental primary standards, respectively
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[4]. Therefore, several conventional methods such as titrimetry [5], quartz crystal microbalance [6], spectrofluorimetry [7], atomic absorption spectrometry [8], gas chromatography [9] and
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electrochemistry [10-18] methods were employed for CN− determination. Sol–gel technology has
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aroused great interest in designing and application of electrochemical sensors due to its simplicity,
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stability, physical rigidity, transparency, porosity, permeability, versatility and flexibility in the preparation procedure [19, 20]. Recently, the sol–gel process conducted in the presence of graphite
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powder was proposed for the fabrication of carbon ceramic electrode (CCE) as a new kind of chemically
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modified electrodes [21, 22]. Considering the stability, permeability, simplicity and especially low cost, easy production and porosity of carbon ceramic electrode [23-25], it is one of the best materials that can be used as an electrode. The porosity in CCE increases the effective surface of deposited gold and the use of CCE as supporting. Recent research focuses mainly on electrochemistry, without or with the use of enzymes [26-28]. In the past few decades, nanomaterials have attracted widespread attention in the field of electrochemical sensors because of their specific features that differ from bulk materials. It is well known that CN− is
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ACCEPTED MANUSCRIPT capable of complexion with metals such as gold (Au) and silver (Ag) with the formation of soluble metal CN− complexes [29, 30]. Au and Ag nanoparticles are widely used in material science, physics and chemistry fields because of its particular optical, magnetic, electronic and catalytic properties [31]. In this study, the gold nanoparticles modified CCE (GNPs/CCE) was used for determination of
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CN−. The GNPs/CCE was prepared to detect cyanide based on the specific reaction of CN− ions with
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gold ions by square wave voltammetry technique.
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The electrochemical system was applicable for analysis of CN− in water real samples. Significantly lower detection limit, greater analytical sensitivity and stability response of this modified
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electrode compare favorably to other modified electrodes employed as CN− sensors.
2. Experimental
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2.1. Reagents and solutions
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All chemicals were of analytical reagent grade and used without further purification. High purity
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graphite powder was obtained from Aldrich. Methyltrimethoxysilane (MTMOS) was purchased from Fluka and used without any further purification. All solutions were prepared with double distilled water
2.2. Apparatus
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and all other chemicals used were of analytical reagent grade.
All the electrochemical experiments were performed on a μ-AUTOLAB type Ш and FRA2 board computer controlled Potentiostat/Galvanostat (ECO-Chemie, The Switzerland). A three-electrode system was employed with an Ag/AgCl (saturated KCl) electrode as a reference electrode, a Pt wire as a counter electrode and the gold nanoparticles modified carbon ceramic electrode (GNPs/CCE) with a tip
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ACCEPTED MANUSCRIPT diameter of 3-mm as a working electrode. All of the used electrodes were from Metrohm. The electrochemical measurements were carried out at a thermostated temperature of 25.0+0.1oC. 2.3. Preparation of the bare CCE The blank CCE was prepared according to the procedure described by Lev and coworkers [32]
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by mixing 0.20 mL methyltrimethoxysilane (MTMOS), 0.30 mL methanol and 10.0 μL hydrochloric
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acid (11 M). This mixture was magnetically stirred for 2 min, after which 0.3 g graphite powder was
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added and the resultant mixture was shaken for additional 1 min. A 5-mm length of a 3-mm inner diameter Teflon tube was filled with the sol-gel carbon mixture and dried under ambient conditions (25
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°C) for 48 h.
2.4. Preparation of the GNPs/CCE
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The fabrication of the GNPs/CCE is described as follows. The electrodes were polished with
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polishing paper and subsequently rinsed with distilled water. For electrodepositing gold nanoparticles on the surface of CCE, After removal of oxygen the potential, CCE, was kept on −200 mV versus Ag/AgCl
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for 400 s in an aqueous solution containing 1 mM HAuCl4 and 0.5 M H2SO4.
3. Results and discussion
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3.1. Characterization of the GNPs/CCE The SEM images of CCE (A) and GNPs/CCE (B) are shown in Fig. 1. As shown in this Figure, the surface of CCE has a multi-pore and scale network. After the electro-deposition, the gold nanoparticles with an average size of 100 nm were deposited on the surface of CCE, homogeneously. Fig. 1.
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3.2. Electrochemical impedance spectroscopy Electrochemical impedance spectroscopy (EIS) is a powerful tool for studying the interface properties of
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the modified electrode and can provide information on the impedance changes of the interface of the
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electrode surface/ electrolyte solution [33]. Thus, Nyquist plots for different modified electrodes were
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obtained by using 5 mM [Fe(CN)6 ] 3−/4− redox couples, as the electrochemical probe, and the results are shown in Fig. 2. As shown, the semicircle diameter of the Nyquist diagram equals surface charge
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transfer resistance (Rct) of the electrode, the increase in diameter of the semicircle reflects an increase in
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the interfacial Rct (Fig. 2A). For the common species, the curve of the EIS includes a semicircular part and a linear part. As shown in Fig. 2, the diameter of the semicircular part for bare CCE (curve a) has
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nanoparticles greatly improve the conductivity.
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been found to be 1100 Ω that is higher than GNPs/CCE (400 Ω, curve b). This indicates the gold
The cyclic voltammetry of CCE (a) and (b) were performed in 5.0 mM Fe(CN)6 3−/4− + 0.1 M KNO3
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(Fig. 2B). As shown in this figure, the peak current on GNPs/CCE was higher than that observed on
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CCE. These results are in agreement with EIS data, indicating the GNPs/CCE provide a higher electron
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conduction pathways in compare with CCE.
Fig. 2.
3.3. Electrocatalytic behavior of GNPs/CCE Fig. 3 shows cyclic voltammogram of CCE and GNP/CCE in the absence (a,c ) and presence (b,d ) of CN− in pH=12 recorded at a potential sweep rate of 25 mV s−1. Fig. 6 shows cyclic voltammogram of
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ACCEPTED MANUSCRIPT CCE in the absence (a) and in 1 mM CN− (b). As Shown, in the absence and presence of CN−, no peak is observed on the voltammograms. Fig. 3 (c) presents cyclic voltammograms (CV) of a GNPs/CCE in 0.1 M KNO3 (pH=12) solution, which the cyclic voltammetry of GNP on CCE shows the formation of gold oxide (or ‘‘gold hydroxide’’, ‘‘AuOH’’) at 0.346 V and the reduction of the formed gold oxide at 0.027
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V.
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Au(OH) + e −→ Au + OH−
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After addition of CN−, GNPs on the surface of electrode react with CN−to form a gold- CN− complex. Previous studies showed that CN− forms very stable [Au(CN)2]− complex with Au(0) through strong
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covalent bondingace on the surface of electrode, which is described by the Elsner reaction [Eq. (1)] [34]. (1)
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4Au + 8CN− + 2H2O + O2 → 4 [4Au(CN)2 ]2−
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Fig. 3.
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The above experimental results confirmed this reaction: on the addition of CN−, the peak current of modified electrode reduced, since the more stable Au(CN)2− ions were formed [Eq. (1)] . Typical cyclic
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voltammograms and calibration graph are shown in Fig. 4. Under the optimized conditions, the
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decreasing of the Ipc was found to be proportional to CN− concentration over the range of 0 µM to 1.6 mM. The correlation coefficient (R2) and the equation for first calibration graph were 0.9919 and Ipc =
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38.443[CN−] −70.88, respectively.
Fig. 4. 3.4. Effect of scan rate Fig. 5 shows the typical CVs of GNPs/CCE in a KNO3 (0.1 M, pH=12.0) containing 0.5 mM CN at the different scan rate. The anodic and cathodic peak currents were linearly proportional to the square root of scan rate (ν½) in the range between 10 to 150 mV s−1 (Fig. 3, inset), corresponding to the 7
ACCEPTED MANUSCRIPT Auox/Aured system. The result indicates that the electrochemical kinetics is controlled by the diffusion of CN−. An electrochemical reaction on the surface of an electrode can occur by two limiting mechanisms: the reaction is controlled by kinetics and the reaction is controlled by the diffusion of the electroactive species. When the diffusion of the species is infinitely fast, the phenomenon is controlled by kinetics.
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When the kinetics are extremely fast, the phenomenon is controlled by the diffusion (mass transport) of
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the species that enters or leaves the electrode surface [35]. Therefore, with the increasing of scan rate
the surface of GNPs/CCE.
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Fig. 5.
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from 10 to 150 mV s−1, the electrochemical response of sensor depend on the rate of transport of CN− to
3.5. Optimization of CN−determination conditions
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The influence pH value on the response of CN− (1.5×10−5 M) has also been studied (Fig 6A). As
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can be seen, with increasing pH from 7.0 to 13.0 the response of CN− increased from pH 7.0 to 12.0 and reached the maximum at pH 12.0 and then decreased with higher pH value. Therefore, pH 12.0 has been
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chosen as the optimum condition for determination of CN− in throughout this work. The plot of Epc
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versus pH ranging also yielded a straight line with a slope equal to −70.0 mV pH−1 (Fig 6B), which was
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close to the theoretical value of −59.0 mV pH−1 for a 1e−/1H+ redox process. Fig. 6.
3.6. Calibration curve, linear range and detection limit of the method The SWV using the GNPs/CCE was used as a very sensitive method with a low detection limit for determination of CN−. The square wave voltammetry (SWV) was immediately performed from −0.2 to 0.4 V in 0.1 M KNO3 (pH 12) are shown in Fig. 7. It was found that the peak current is linearly
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ACCEPTED MANUSCRIPT increased with the increase of CN− concentration ranging from 5.0 to 20.0 µM (Figure 7, inset). The detection limit was 0.09 µM (S/N = 3). Fig. 7. A comparison of analytical performances of GNPs/CCE with other CN− sensors was shown in Table 1.
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It can be seen that the analytical performances of GNPs/CCE are comparable and even better than those
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obtained at several electrodes reported recently. Therefore, by a combination of the advantages of good
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analytical performances and simple preparation procedure, the GNPs/CCE can be used for the
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preparation of a good sensor for CN−.
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Table 1.
3.7. Interferences study
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The selectivity of the GNPs/CCE was verified in the presence of 100 μM different anions, such
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as F−, Cl−, Br−, I−, H2PO4−, HSO4−, SCN− and CH3COO−, that currently presented in waste waters for the determination of cyanide (5.0 µM) using the proposed method. As shown in table 1, proposed sensor
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was practically insensitive to almost all of the anions, except for SCN−. The higher concentration of
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SCN (4 times) had decreased 25% current of the cathodic peak. In all these Ip was retained without any change, while Icat suddenly changed upon addition of CN−. The results are summarized in Table 2.
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Almost all the ions examined did not interfere with CN− in electroplating wastewater samples and it was used as a criterion for the selectivity of the GNPs/CCE. Table 2.
3.8. Reproducibility, stability and recovery test of the modified electrode
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ACCEPTED MANUSCRIPT The relative standard deviation (RSD) for five repeated measurements of 2.2×10-5 M CN− was 3.2%, which illustrated that the response of proposed sensor was reproducible. The long time stability of the GNPs/CCE was studied. After 12 days, its voltammetric current decreased by approximately 7.8%.
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3.9. Application to industrial samples
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The GNPs/CCE was also used for the determination of CN− in local groundwater, tap water and
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boiled water. Briefly, 1.0 mL of real water added to 9.0 mL of 0.1 M KNO3 solution. Then, the solution was transferred into the voltammetric cell to be analyzed. After that, 100 µL of CN− 0.1 mM injected to
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this cell and SWV analysis has done by GNPs/CCE (Table 3). The considered the values were
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determined by the standard method.
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Table 3.
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4. Conclusion
In summary, electrochemical detections of CN− has been achieved by using GNPs/CCE. The proposed
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sensor exhibited a good linear range and low limit of detection. Moreover, the proposed sensor was
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ACCEPTED MANUSCRIPT Figure captions Fig. 1. The SEM images of (A) bare CCE and (B) GNPs/GCE. Fig. 2. (A) Nyquist plot for the Faradaic impedance (A) and cyclic voltammograms (B) of (a) bare CCE and (b) GNPs /CCE in the presence of 5 mM K3Fe(CN)6/ K4Fe(CN)6 (1:1 mixture) as a redox probe,
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containing 0.1 M KNO3.
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Fig. 3. Cyclic voltammograms of CCE and GNP/CCE in the absence (a,c) and presence (b,d) of 1 mM
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CN− at scan rate 25 mV s-1 of CN− solution, respectively.
Fig.4. (A) Cyclic voltammograms of the GNPs/ CCE in 0.1 M KNO3 (pH 12) containing 0.1 M KNO3
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of the cathodic peak current versus CN− concentrations.
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with different concentrations (from: 0, 0.4, 0.8, 1.2 and 2.5 mM) at the scan rate of 50 mV s-1. inset: Plot
Fig.5. (A) Cyclic voltammgrams of the GNPs/CCE 0.1 M KNO3 (pH 12) containing 1 mM CN− at
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various scan rates: (1-10): 10, 20, 30, 40, 50, 70, 80, 100, 125 and 150 mV s−1, inset: the variation of
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anodic and cathodic peak currents versus square root of scan rate. Fig.6. (A) Square wave voltammetry of GNPs/CCE in the absence and presence of 1 mM CN− for
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different pH values; (7-13). (B) Effect of solution pH on ΔIpc (where ΔIpc is the difference between Ipc
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in absence and presence of CN−). Supporting electrolyte: 0.1 M KNO3 (pH=12). Fig.7. Square wave voltammetry of GNPs/CCE in 0.1 M KNO3 ( pH 12) with various concentrations of
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CN− from outer to inner. Inset: Plot of the cathodic peak current vs. cyanide concentrations. Square wave voltammetric parameters were as follows: step potential, 20 mV; pulse amplitude, 50 mV; and frequency, 5 Hz.
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ACCEPTED MANUSCRIPT Table captions Table 1. Comparison the proposed method with other electroanalytical methods for CN− determination. Table 2. Analysis of sample from different industrial electroplating waste waters (average of five replicates).
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Table 3. The effects of various possible interference ions on the analysis of 1.5 ×10-5 M CN−.
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Fig. 1
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E/V
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Fig. 4.
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0.1
0.5
1
1.5
2
C/mM
0.3
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20 50
-10
y = 2.4012x - 2.2023 R² = 0.9955
25 0
-25
-20
y = -2.6445x + 6.721 R² = 0.9958
-50 2
10
14
ν1/2
0.25
0.45
0.65 E/V
0.85
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Fig. 5
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E/V -0.2
0
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-20
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in presence cyanide
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in absence cyanide
-80
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35 30 25 20 15 10
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I/µA
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7
9
pH
11
13
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-200
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I/μA
0.8
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B 0.5
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y = -0.0706x + 0.8948 R² = 0.9895
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Epc/V
0.35
0.05
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-0.1
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6
8
10 pH Fig. 6.
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-0.2
-0.1
E/V 0.1
0
0.2
0.3
0.4
0
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I/μA
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-20
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0 -10 -20 -30
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I/μA
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y = -2.4134x - 2.7897 R² = 0.9957
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3
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-60
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Fig. 7
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ACCEPTED MANUSCRIPT Table 1 Electrochemical method
Sample
Linear range (M)
Limit of
Ref.
detection (M) Amperometry
Up to 120 ×10−6
3.8 ×10−6
Blood plasma
2.3×10−6 to1.85 ×10−5
1.54 × 10−6
Industrial
5×10−8 to 8 ×10−7
Physiological
[36]
Adsorptive stripping
wastewater
Cyclic voltammetry
Industrial
1.5×10−6 to 2.1×10−4
5×10−7 to 14 ×10−6
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waste water
Added (mM)
Deionized water
0.1
Groundwater
0.1
Tap water
0.1
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Sample
0.1
1.4 × 10−7
[39]
9×10−8
This work
Found(mM)
Recovery (%)
RSD (% n=5)
0.102
102
3.3
0.095
95
3.7
0.104
104
4.3
0.103
103
2.6
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Table 2
[38]
M
Industrial
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waste water SWV
1 × 10−8
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voltammetry
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polarography (DPP)
Boiled water
[37]
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Differential pulse
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solutions
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Table 3
Tolerance
NO3−, SO42−, F−, CO32−,
100
Br−,Cl−,CrO42−, Cr2O72−, CH3COO−
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S2O42−, S2O82−, I−, S2−
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SCN−
4
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M
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Interference ion
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ACCEPTED MANUSCRIPT Highlights The GNPs/CCEs were used for the determination of cyanide in water. The catalatic performances of the sensor are characterized by CV and SWV.
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The proposed sensor was applied to the determination of cyanide in water samples.
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Mojtaba Shamsipur, Ziba Karimi, Mahmoud Amouzadeh Tabrizi PII: DOI: Reference:
S0026-265X(17)30351-X doi: 10.1016/j.microc.2017.04.017 MICROC 2794
To appear in:
Microchemical Journal
Received date: Revised date: Accepted date:
23 May 2016 15 February 2017 11 April 2017
Please cite this article as: Mojtaba Shamsipur, Ziba Karimi, Mahmoud Amouzadeh Tabrizi , A novel electrochemical cyanide sensor using gold nanoparticles decorated carbon ceramic electrode. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Microc(2017), doi: 10.1016/j.microc.2017.04.017
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ACCEPTED MANUSCRIPT
A novel electrochemical cyanide sensor using gold nanoparticles decorated carbon
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ceramic electrode
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Mojtaba Shamsipur*a, Ziba Karimi a,b and Mahmoud Amouzadeh Tabrizi c Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran.
b
Department of Chemistry, Payame Noor University, 19395-3697 Tehran, I. R. Iran.
c
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a
Research Center for Science and Technology in Medicine, Tehran University of Medical Sciences,
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Tehran, Iran.
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*Corresponding authors: Mojtaba Shamsipur, Email: [email protected]
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ACCEPTED MANUSCRIPT Abstract The high toxicity of cyanide and its great variety of uses in industrial processes make it necessary to develop sensitive and selective sensors for its determination in natural and waste waters. In this work, using modified carbon ceramic electrode with gold nanoparticles (GNPs) was reported. The
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electrodeposition of GNPs on carbon ceramic electrode (CCE) was confirmed by scanning electron
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microscopy (SEM). The SEM image showed that the size of gold nanoparticles was examined around 75
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nm. The GNPs/CCE was used for the determination of cyanide (CN−) in solution (pH 12). The cyclic voltammetry (CV) and square wave voltammetry (SWV) mthodes were used for the determination of
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CN−. The linear dynamic range from 0.5 µM to 14.0 µM and a detection limit was found to be 0.09 µM
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(S/N = 3) by SWV method. Interference studies were performed with typical anions present in natural and waste waters. Based on obtained result, the proposed sensor suffer from the interefering of
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thiocyanide (SCN-) ion.
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Keywords: Electrocatalysis; Cyanide; Carbon Ceramic Electrode; Gold nanoparticles; Real samples
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1. Introduction Among inorganic anions, cyanide (CN− ) is one of the best known and most hazardous pollutants of the environment because of its toxic effect at very low levels [1]. It is produced by man-made as well
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as natural sources. It is used in industry in electroplating, refining precious metals (gold and silver) and
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for fumigation [2]. For this reason, considerable efforts have been put into the design some probes or
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sensors for the detection of chemically and biologically important ionic species [3]. With respect to the
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limits of CN− in drinking water and environmental, the U.S. EPA regulates cyanide content at very low levels of 0.2 ppm and 0.005 ppm for drinking water and environmental primary standards, respectively
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[4]. Therefore, several conventional methods such as titrimetry [5], quartz crystal microbalance [6], spectrofluorimetry [7], atomic absorption spectrometry [8], gas chromatography [9] and
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electrochemistry [10-18] methods were employed for CN− determination. Sol–gel technology has
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aroused great interest in designing and application of electrochemical sensors due to its simplicity,
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stability, physical rigidity, transparency, porosity, permeability, versatility and flexibility in the preparation procedure [19, 20]. Recently, the sol–gel process conducted in the presence of graphite
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powder was proposed for the fabrication of carbon ceramic electrode (CCE) as a new kind of chemically
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modified electrodes [21, 22]. Considering the stability, permeability, simplicity and especially low cost, easy production and porosity of carbon ceramic electrode [23-25], it is one of the best materials that can be used as an electrode. The porosity in CCE increases the effective surface of deposited gold and the use of CCE as supporting. Recent research focuses mainly on electrochemistry, without or with the use of enzymes [26-28]. In the past few decades, nanomaterials have attracted widespread attention in the field of electrochemical sensors because of their specific features that differ from bulk materials. It is well known that CN− is
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ACCEPTED MANUSCRIPT capable of complexion with metals such as gold (Au) and silver (Ag) with the formation of soluble metal CN− complexes [29, 30]. Au and Ag nanoparticles are widely used in material science, physics and chemistry fields because of its particular optical, magnetic, electronic and catalytic properties [31]. In this study, the gold nanoparticles modified CCE (GNPs/CCE) was used for determination of
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CN−. The GNPs/CCE was prepared to detect cyanide based on the specific reaction of CN− ions with
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gold ions by square wave voltammetry technique.
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The electrochemical system was applicable for analysis of CN− in water real samples. Significantly lower detection limit, greater analytical sensitivity and stability response of this modified
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electrode compare favorably to other modified electrodes employed as CN− sensors.
2. Experimental
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2.1. Reagents and solutions
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All chemicals were of analytical reagent grade and used without further purification. High purity
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graphite powder was obtained from Aldrich. Methyltrimethoxysilane (MTMOS) was purchased from Fluka and used without any further purification. All solutions were prepared with double distilled water
2.2. Apparatus
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and all other chemicals used were of analytical reagent grade.
All the electrochemical experiments were performed on a μ-AUTOLAB type Ш and FRA2 board computer controlled Potentiostat/Galvanostat (ECO-Chemie, The Switzerland). A three-electrode system was employed with an Ag/AgCl (saturated KCl) electrode as a reference electrode, a Pt wire as a counter electrode and the gold nanoparticles modified carbon ceramic electrode (GNPs/CCE) with a tip
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ACCEPTED MANUSCRIPT diameter of 3-mm as a working electrode. All of the used electrodes were from Metrohm. The electrochemical measurements were carried out at a thermostated temperature of 25.0+0.1oC. 2.3. Preparation of the bare CCE The blank CCE was prepared according to the procedure described by Lev and coworkers [32]
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by mixing 0.20 mL methyltrimethoxysilane (MTMOS), 0.30 mL methanol and 10.0 μL hydrochloric
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acid (11 M). This mixture was magnetically stirred for 2 min, after which 0.3 g graphite powder was
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added and the resultant mixture was shaken for additional 1 min. A 5-mm length of a 3-mm inner diameter Teflon tube was filled with the sol-gel carbon mixture and dried under ambient conditions (25
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°C) for 48 h.
2.4. Preparation of the GNPs/CCE
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The fabrication of the GNPs/CCE is described as follows. The electrodes were polished with
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polishing paper and subsequently rinsed with distilled water. For electrodepositing gold nanoparticles on the surface of CCE, After removal of oxygen the potential, CCE, was kept on −200 mV versus Ag/AgCl
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for 400 s in an aqueous solution containing 1 mM HAuCl4 and 0.5 M H2SO4.
3. Results and discussion
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3.1. Characterization of the GNPs/CCE The SEM images of CCE (A) and GNPs/CCE (B) are shown in Fig. 1. As shown in this Figure, the surface of CCE has a multi-pore and scale network. After the electro-deposition, the gold nanoparticles with an average size of 100 nm were deposited on the surface of CCE, homogeneously. Fig. 1.
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3.2. Electrochemical impedance spectroscopy Electrochemical impedance spectroscopy (EIS) is a powerful tool for studying the interface properties of
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the modified electrode and can provide information on the impedance changes of the interface of the
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electrode surface/ electrolyte solution [33]. Thus, Nyquist plots for different modified electrodes were
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obtained by using 5 mM [Fe(CN)6 ] 3−/4− redox couples, as the electrochemical probe, and the results are shown in Fig. 2. As shown, the semicircle diameter of the Nyquist diagram equals surface charge
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transfer resistance (Rct) of the electrode, the increase in diameter of the semicircle reflects an increase in
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the interfacial Rct (Fig. 2A). For the common species, the curve of the EIS includes a semicircular part and a linear part. As shown in Fig. 2, the diameter of the semicircular part for bare CCE (curve a) has
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nanoparticles greatly improve the conductivity.
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been found to be 1100 Ω that is higher than GNPs/CCE (400 Ω, curve b). This indicates the gold
The cyclic voltammetry of CCE (a) and (b) were performed in 5.0 mM Fe(CN)6 3−/4− + 0.1 M KNO3
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(Fig. 2B). As shown in this figure, the peak current on GNPs/CCE was higher than that observed on
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CCE. These results are in agreement with EIS data, indicating the GNPs/CCE provide a higher electron
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conduction pathways in compare with CCE.
Fig. 2.
3.3. Electrocatalytic behavior of GNPs/CCE Fig. 3 shows cyclic voltammogram of CCE and GNP/CCE in the absence (a,c ) and presence (b,d ) of CN− in pH=12 recorded at a potential sweep rate of 25 mV s−1. Fig. 6 shows cyclic voltammogram of
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ACCEPTED MANUSCRIPT CCE in the absence (a) and in 1 mM CN− (b). As Shown, in the absence and presence of CN−, no peak is observed on the voltammograms. Fig. 3 (c) presents cyclic voltammograms (CV) of a GNPs/CCE in 0.1 M KNO3 (pH=12) solution, which the cyclic voltammetry of GNP on CCE shows the formation of gold oxide (or ‘‘gold hydroxide’’, ‘‘AuOH’’) at 0.346 V and the reduction of the formed gold oxide at 0.027
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V.
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Au(OH) + e −→ Au + OH−
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After addition of CN−, GNPs on the surface of electrode react with CN−to form a gold- CN− complex. Previous studies showed that CN− forms very stable [Au(CN)2]− complex with Au(0) through strong
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covalent bondingace on the surface of electrode, which is described by the Elsner reaction [Eq. (1)] [34]. (1)
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4Au + 8CN− + 2H2O + O2 → 4 [4Au(CN)2 ]2−
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Fig. 3.
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The above experimental results confirmed this reaction: on the addition of CN−, the peak current of modified electrode reduced, since the more stable Au(CN)2− ions were formed [Eq. (1)] . Typical cyclic
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voltammograms and calibration graph are shown in Fig. 4. Under the optimized conditions, the
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decreasing of the Ipc was found to be proportional to CN− concentration over the range of 0 µM to 1.6 mM. The correlation coefficient (R2) and the equation for first calibration graph were 0.9919 and Ipc =
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38.443[CN−] −70.88, respectively.
Fig. 4. 3.4. Effect of scan rate Fig. 5 shows the typical CVs of GNPs/CCE in a KNO3 (0.1 M, pH=12.0) containing 0.5 mM CN at the different scan rate. The anodic and cathodic peak currents were linearly proportional to the square root of scan rate (ν½) in the range between 10 to 150 mV s−1 (Fig. 3, inset), corresponding to the 7
ACCEPTED MANUSCRIPT Auox/Aured system. The result indicates that the electrochemical kinetics is controlled by the diffusion of CN−. An electrochemical reaction on the surface of an electrode can occur by two limiting mechanisms: the reaction is controlled by kinetics and the reaction is controlled by the diffusion of the electroactive species. When the diffusion of the species is infinitely fast, the phenomenon is controlled by kinetics.
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When the kinetics are extremely fast, the phenomenon is controlled by the diffusion (mass transport) of
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the species that enters or leaves the electrode surface [35]. Therefore, with the increasing of scan rate
the surface of GNPs/CCE.
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Fig. 5.
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from 10 to 150 mV s−1, the electrochemical response of sensor depend on the rate of transport of CN− to
3.5. Optimization of CN−determination conditions
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The influence pH value on the response of CN− (1.5×10−5 M) has also been studied (Fig 6A). As
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can be seen, with increasing pH from 7.0 to 13.0 the response of CN− increased from pH 7.0 to 12.0 and reached the maximum at pH 12.0 and then decreased with higher pH value. Therefore, pH 12.0 has been
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chosen as the optimum condition for determination of CN− in throughout this work. The plot of Epc
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versus pH ranging also yielded a straight line with a slope equal to −70.0 mV pH−1 (Fig 6B), which was
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close to the theoretical value of −59.0 mV pH−1 for a 1e−/1H+ redox process. Fig. 6.
3.6. Calibration curve, linear range and detection limit of the method The SWV using the GNPs/CCE was used as a very sensitive method with a low detection limit for determination of CN−. The square wave voltammetry (SWV) was immediately performed from −0.2 to 0.4 V in 0.1 M KNO3 (pH 12) are shown in Fig. 7. It was found that the peak current is linearly
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ACCEPTED MANUSCRIPT increased with the increase of CN− concentration ranging from 5.0 to 20.0 µM (Figure 7, inset). The detection limit was 0.09 µM (S/N = 3). Fig. 7. A comparison of analytical performances of GNPs/CCE with other CN− sensors was shown in Table 1.
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It can be seen that the analytical performances of GNPs/CCE are comparable and even better than those
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obtained at several electrodes reported recently. Therefore, by a combination of the advantages of good
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analytical performances and simple preparation procedure, the GNPs/CCE can be used for the
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preparation of a good sensor for CN−.
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Table 1.
3.7. Interferences study
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The selectivity of the GNPs/CCE was verified in the presence of 100 μM different anions, such
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as F−, Cl−, Br−, I−, H2PO4−, HSO4−, SCN− and CH3COO−, that currently presented in waste waters for the determination of cyanide (5.0 µM) using the proposed method. As shown in table 1, proposed sensor
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was practically insensitive to almost all of the anions, except for SCN−. The higher concentration of
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SCN (4 times) had decreased 25% current of the cathodic peak. In all these Ip was retained without any change, while Icat suddenly changed upon addition of CN−. The results are summarized in Table 2.
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Almost all the ions examined did not interfere with CN− in electroplating wastewater samples and it was used as a criterion for the selectivity of the GNPs/CCE. Table 2.
3.8. Reproducibility, stability and recovery test of the modified electrode
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ACCEPTED MANUSCRIPT The relative standard deviation (RSD) for five repeated measurements of 2.2×10-5 M CN− was 3.2%, which illustrated that the response of proposed sensor was reproducible. The long time stability of the GNPs/CCE was studied. After 12 days, its voltammetric current decreased by approximately 7.8%.
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3.9. Application to industrial samples
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The GNPs/CCE was also used for the determination of CN− in local groundwater, tap water and
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boiled water. Briefly, 1.0 mL of real water added to 9.0 mL of 0.1 M KNO3 solution. Then, the solution was transferred into the voltammetric cell to be analyzed. After that, 100 µL of CN− 0.1 mM injected to
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this cell and SWV analysis has done by GNPs/CCE (Table 3). The considered the values were
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determined by the standard method.
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Table 3.
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4. Conclusion
In summary, electrochemical detections of CN− has been achieved by using GNPs/CCE. The proposed
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sensor exhibited a good linear range and low limit of detection. Moreover, the proposed sensor was
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[36] A. Lindsay, D. O’Hare, The development of an electrochemical sensor for the determination of cyanide in physiological solutions, Analytica chimica acta, 558 (2006) 158-163. [37] D. Bohrer, P. Do Nascimento, S.G. Pomblum, E. Seibert, L.M. de Carvalho, Polarographic determination of cyanide as nickelcyano complex in blood plasma after selective extraction in a methylene blue impregnated polyethylene column, Fresenius' journal of analytical chemistry, 361 (1998) 780-783.
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ACCEPTED MANUSCRIPT [38] A. Safavi, N. Maleki, H. Shahbaazi, Indirect determination of cyanide ion and hydrogen cyanide by adsorptive stripping voltammetry at a mercury electrode, Analytica chimica acta, 503 (2004) 213-221. [39] A. Taheri, M. Noroozifar, M. Khorasani-Motlagh, Investigation of a new electrochemical cyanide sensor based on Ag nanoparticles embedded in a three-dimensional sol–gel, Journal of Electroanalytical
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Chemistry, 628 (2009) 48-54.
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ACCEPTED MANUSCRIPT Figure captions Fig. 1. The SEM images of (A) bare CCE and (B) GNPs/GCE. Fig. 2. (A) Nyquist plot for the Faradaic impedance (A) and cyclic voltammograms (B) of (a) bare CCE and (b) GNPs /CCE in the presence of 5 mM K3Fe(CN)6/ K4Fe(CN)6 (1:1 mixture) as a redox probe,
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containing 0.1 M KNO3.
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Fig. 3. Cyclic voltammograms of CCE and GNP/CCE in the absence (a,c) and presence (b,d) of 1 mM
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CN− at scan rate 25 mV s-1 of CN− solution, respectively.
Fig.4. (A) Cyclic voltammograms of the GNPs/ CCE in 0.1 M KNO3 (pH 12) containing 0.1 M KNO3
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of the cathodic peak current versus CN− concentrations.
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with different concentrations (from: 0, 0.4, 0.8, 1.2 and 2.5 mM) at the scan rate of 50 mV s-1. inset: Plot
Fig.5. (A) Cyclic voltammgrams of the GNPs/CCE 0.1 M KNO3 (pH 12) containing 1 mM CN− at
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various scan rates: (1-10): 10, 20, 30, 40, 50, 70, 80, 100, 125 and 150 mV s−1, inset: the variation of
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anodic and cathodic peak currents versus square root of scan rate. Fig.6. (A) Square wave voltammetry of GNPs/CCE in the absence and presence of 1 mM CN− for
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different pH values; (7-13). (B) Effect of solution pH on ΔIpc (where ΔIpc is the difference between Ipc
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in absence and presence of CN−). Supporting electrolyte: 0.1 M KNO3 (pH=12). Fig.7. Square wave voltammetry of GNPs/CCE in 0.1 M KNO3 ( pH 12) with various concentrations of
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CN− from outer to inner. Inset: Plot of the cathodic peak current vs. cyanide concentrations. Square wave voltammetric parameters were as follows: step potential, 20 mV; pulse amplitude, 50 mV; and frequency, 5 Hz.
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ACCEPTED MANUSCRIPT Table captions Table 1. Comparison the proposed method with other electroanalytical methods for CN− determination. Table 2. Analysis of sample from different industrial electroplating waste waters (average of five replicates).
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Table 3. The effects of various possible interference ions on the analysis of 1.5 ×10-5 M CN−.
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Fig. 1
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1.5
A
B
50
0.9
10
a
0.3
b
-10
2
-50
2.5
-0.4
-0.1
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1 1.5 Z'/kΩ
Fig. 2
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I/µA
1.2
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-Z''/kΩ
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120 a 80
b
10 0 -10 -20
I/µA
-40 b' -80
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c
d
-0.5 -0.2 0.1 0.4 0.7 E/V
a' -120
0.1
0.3 E/V
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-0.2
d
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I/μA
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-20
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a
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-20 -40
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I/µA
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y = 38.443x - 70.884 R² = 0.9919
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0.1
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1.5
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C/mM
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20 50
-10
y = 2.4012x - 2.2023 R² = 0.9955
25 0
-25
-20
y = -2.6445x + 6.721 R² = 0.9958
-50 2
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ν1/2
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0.45
0.65 E/V
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E/V -0.2
0
0.2
0.4
0.6
-20
1
in presence cyanide
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in absence cyanide
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7
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35 30 25 20 15 10
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I/µA
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7
9
pH
11
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I/μA
0.8
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B 0.5
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y = -0.0706x + 0.8948 R² = 0.9895
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Epc/V
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-0.2
-0.1
E/V 0.1
0
0.2
0.3
0.4
0
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I/μA
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-20
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0 -10 -20 -30
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I/μA
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y = -2.4134x - 2.7897 R² = 0.9957
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ACCEPTED MANUSCRIPT Table 1 Electrochemical method
Sample
Linear range (M)
Limit of
Ref.
detection (M) Amperometry
Up to 120 ×10−6
3.8 ×10−6
Blood plasma
2.3×10−6 to1.85 ×10−5
1.54 × 10−6
Industrial
5×10−8 to 8 ×10−7
Physiological
[36]
Adsorptive stripping
wastewater
Cyclic voltammetry
Industrial
1.5×10−6 to 2.1×10−4
5×10−7 to 14 ×10−6
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waste water
Added (mM)
Deionized water
0.1
Groundwater
0.1
Tap water
0.1
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Sample
0.1
1.4 × 10−7
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9×10−8
This work
Found(mM)
Recovery (%)
RSD (% n=5)
0.102
102
3.3
0.095
95
3.7
0.104
104
4.3
0.103
103
2.6
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Table 2
[38]
M
Industrial
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waste water SWV
1 × 10−8
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voltammetry
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polarography (DPP)
Boiled water
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solutions
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Table 3
Tolerance
NO3−, SO42−, F−, CO32−,
100
Br−,Cl−,CrO42−, Cr2O72−, CH3COO−
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S2O42−, S2O82−, I−, S2−
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SCN−
4
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Interference ion
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ACCEPTED MANUSCRIPT Highlights The GNPs/CCEs were used for the determination of cyanide in water. The catalatic performances of the sensor are characterized by CV and SWV.
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The proposed sensor was applied to the determination of cyanide in water samples.
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