Materials Science and Engineering C 32 (2012) 11791183

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Materials Science and Engineering C

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Potentiometric detection of silver (I) ion based on carbon paste electrode modied with diazo-thiophenol-functionalized nanoporous silica gel
Ting Zhang, Yaqin Chai , Ruo Yuan, Junxiang Guo
Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China

a r t i c l e

i n f o

a b s t r a c t
For the rst time, triazene compound functionalized silica gel was incorporated into carbon paste electrode for the potentiometric detection of silver (I) ion. A novel diazo-thiophenol-functionalized silica gel (DTPSG) was synthesized, and the presence of DTPSG acted as not only a paste binder, but also a reactive material. The electrode with optimum composition, exhibited an excellent Nernstian response to Ag+ ion ranging from 1.0 10 6 to 1.0 10 1 M with a detection limit of 9.5 10 7 M and a slope of 60.4 0.2 mV dec 1 over a wide pH range (4.09.0) with a fast response time (50 s) at 25 C. The electrode also showed a long-time stability, high selectivity and reproducibility. The response mechanism of the proposed electrode was investigated by using AC impedance. Moreover, the electrode was successfully applied for the determination of silver ions in radiology lms, and for potentiometric titration of the mixture solution of Cl and Br ions. 2012 Elsevier B.V. All rights reserved.

Article history: Received 23 April 2011 Received in revised form 14 January 2012 Accepted 7 March 2012 Available online 16 March 2012 Keywords: Carbon paste electrode Potentiometric Silver Nanoporous Silica gel

1. Introduction Nowadays silver appears in a wide range of products such as electronic products, alloys, jewelry and photographic material. On account of their antibacterial properties, silver and its compounds have been widely used today in the medical and health care elds. Consequently, large amounts of silver are released into the environment annually. It is reported that the concentration of silver in water higher than 1.6 nM is toxic to sh and microorganisms. It has also been found that silver is toxic to humans at a concentration as high as 0.9 M in drinking water [15]. With due attention to the above, determination of silver (I) in samples is necessary. In the past ve decades, a number of silver selective electrodes have been developed based on different ionophores including Schiff base [6], crown ethers [79] and benzothiazole calix[4]arene [10]. However, complicated and tedious synthesis of the above ionophores limits the analytical applications of the sensors. In addition, the plasticizer, carrier or ionic site leaching from the polymeric lm into solution results in the limited lifetime of the above PVC membrane electrodes. In principle, this shift reduces the selectivity and deteriorates the response of electrodes [11]. To date, the silica-based organicinorganic hybrids have become attractive electrode modiers. On the one hand, they are robust inorganic solids with the properties of a rigid three-dimensional structure. On the other hand, they possess the particular chemical reactivity of

Corresponding author. Tel.: + 86 23 68252277; fax: + 86 23 68253172. E-mail address: yqchai@swu.edu.cn (Y. Chai). 0928-4931/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.msec.2012.03.005

organic component. The electrode modier, able to preconcentrate metallic ions on the electrode surface either by complexation or electrostatic attraction, can lead to more sensitive electroanalytical procedures with lower detection limit values [1214]. Carbon paste electrode (CPE) is one of the convenient conductive matrixes to prepare the chemically modied electrodes (CMEs), because a selective agent is incorporated into the surface by simple mixing with graphite powder and parafn oil [15]. Thus, carbon paste electrode has aroused attention due to its advantages such as easy construction and regeneration, stable electrochemical response and lower ohmic resistance [16,17]. In recent years, carbon paste electrodes based on functionalized nanoporous silica gels have been used for detection of Ag [14,15], Cu [12,18], Hg [19,20] and Cd [21]. To the best of our knowledge, this work is the rst attempt to apply triazene compound functionalized silica gel for the determination of silver ion. Triazene compounds possessing a diazoamino group (\N_N\N\) have been studied for over 130 years due to their interesting structural, anticancer and reactivity properties. However, in spite of extensive reports on the synthesis, characterization and crystalline structure of the transition metal triazenide complexes, reports on analytical application of these ligands are quite spare [2224]. The functionalized nanoporous silica gels with diazo-thiophenol groups were covalently attached to the solid framework via N-(2-aminoethyl)3-aminopropyl chains. According to the hardsoft acid base (HSAB) concept [25], the presence of aminothiophenol molecules, carrying soft S-donor atoms as part of a macrocyclic ligand, has a marked inuence on the coordination of silver (I) as a soft Lewis acid. The diazothiophenol-functionalized silica gel (DTPSG), with group containing S,

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N and O atoms, is expected to provide a much-needed hydrophobic environment and high complex stability. Meanwhile, the possible cation- interactions could have a marked inuence on the coordination geometry at the metal center [10,12]. So, DTPSG is a very efcient material to improve the lifetime of the proposed modied carbon paste electrode. Finally the sensor properties were successfully evaluated by its application to the potentiometric titration of the mixture of chlorine, bromine ions and the determination of silver ions in radiology lms. 2. Experimental 2.1. Reagents and apparatus Silica gel 60 was purchased from Merch and activated by reuxing in hydrochloric acid (4 M) for 24 h before use. N-(2-aminoethyl)-3aminopropyl-trimethoxy silane and 2-aminothiophenol were purchased from J&K Chemical Ltd. Graphite powder was purchased from Sigma. Reagent grade parafn oil and the nitrate salts of the used cations were purchased from Chongqing Chemicals (Chongqing, China). All of the chemicals used were of analytical-regent grade. All aqueous solutions were prepared with deionized distilled water. Potentiometric measurements were performed with a MP230 pH meter (Mettler Toledo, Switzerland) and a pHS-3C digital ion analyzer (Dazhong Analytical Instruments, Shanghai, China). IR spectra were recorded with a Spectrum GX FTIR instrument (Mattson RK-6000, USA). The AC impedance was recorded with an impedance measurement unit (IM6e, ZAHNER elektrick Co., Germany) and the frequency range used was 10 2106 Hz (25 C). A Model TAS-986 atomic absorption spectrophotometer (AAS) (Purkinje, Beijing, China) was used for the analysis of real samples. 2.2. Synthesis of diazo-thiophenol-functionalized silica gel (DTPSG) A mixture of 10 g of activated silica gel with 30 mmol of N-(2aminoethyl)-3-aminopropyl-trimethoxy silane was reuxed in toluene under nitrogen atmosphere for 24 h [18,20]. The attained solid, grafted amino silica gel (GANSG), was washed with warm toluene several times. For the preparation of the surface bound DTPSG ligand (Fig. 1), 2-aminothiophenol (0.63 g) was dissolved in 0.6 mL 37% hydrochloric acid and the solution was then cooled to 05 C. Then, 2 mL of 20% NaNO2 was added to the above mentioned mixture and the resulting solution was stirred for 1 h to give a bright yellow solution [26]. GANSG (0.6 g) was dispersed in the solution of Na2CO3 (1.8 g Na2CO3 + 15 mL H2O). Then the solution of GANSG was added dropwise to the bright yellow solution. After stirring for 4 h, the reaction mixture was neutralized with HCl. The brown crude solid was ltered and then was washed with water three times. Last, the brown crude solid was recrystallized from ethanol to afford a pure product. IR characterization of DTPSG was measured by using KBr squash method. Solid DTPSG (2 mg) was used in 200 mg KBr to prepare KBr Tablet.

Then, IR spectra were recorded with a Spectrum GX FTIR instrument (Mattson RK-6000, USA). Infrared spectral data are as follows: (IR KBr): 3417 cm 1 (N\H), 3205 cm 1 (Ar\H), 2364 cm 1 (N\N_N), 1108 cm 1 (Si\O), and 784 cm 1 (Si\C). 2.3. Preparation of the chemically modied carbon paste electrodes The chemically modied carbon paste electrodes were prepared by thoroughly hand-mixing graphite powder, parafn oil and DTPSG. A disposable polyethylene syringe (3 mm i.d., 3 cm) was used as the electrode body. After the mixture homogenization, the paste was packed into the plastic tube tip to avoid possible air gaps, often enhancing the electrode resistance. A copper wire was inserted into the opposite end to establish electrical contact. The external electrode surface was polished on a soft paper. A new surface was produced by scraping out the old surface. 2.4. Electrode conditioning and EMF measurement The electrodes were conditioned for 24 h in pH 4.0 HNO3 solution. A digital ion analyzer Model pHS-3C was used for the potential measurements at ambient temperature. Saturated calomel electrode was used as the reference electrode. The electrochemical cell can be represented as follows:
HgHg2 Cl2 ; KC1satd:j 1:0 M KNO3 j test solution jj carbon paste electrode jj Cu:

Activities were calculated according to the DebyeHckel procedure [27]. 3. Results and discussion 3.1. Electrode composition and response characteristics of the CPEs In initial experiments, carbon paste electrodes containing diazo-thiophenol-functionalized silica gel (DTPSG) were used for the detection of different cations (Fig. 2). The electrode exhibited a good selectivity for Ag + in comparison with other cations. It is possible that the presence of S, N and O atoms in DTPSG may generate a great afnity between the ionophore and the Ag + ion. On the one hand, DTPSG containing soft S-donor atoms has a marked inuence on the coordination of silver (I) as a soft Lewis acid [25]. On the other hand, DTPSG contains strong covalent bonds (diazothiophenol groups covalently attached to the solid framework via N-(2-aminoethyl)-3-aminopropyl chains), which are likely to provide a much-needed hydrophobic environment to stabilize the complexes formed by ions and ionophore [28,29].

Fig. 1. Schematic representation of the synthetic procedure of DTPSG.

Fig. 2. Potential responses of carbon paste electrode based on DTPSG for various cations.

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It's well known that the potentiometric response characteristics of the electrode depend signicantly not only on the nature of neutral carrier but also on the membrane composition [30,31]. Thus, the effect of the DTPSG composition on the potentiometric response of the electrodes was investigated (Table 1). Seen from Table 1, the DTPSG modied electrode with graphite power/parafn oil/DTPSG percentage ratio of 63.5/30.5/6.0 exhibited higher sensitivity (slope: 60.4 mV decade 1) and wider linear range (1.0 10 6 to 1.0 10 1 M) than other electrodes. Therefore, the No.3 electrode was selected as the optimal electrode composition in the further experiments. The stability of DTPSG modied electrode was tested by putting the electrode into a nitrate solution (pH 4.0) containing 1.0 10 3 M Ag+ over a period of 12 h, and the standard deviation (SD) of the electrode potential readings was 1.07 mV (n = 50). The same electrode dipped alternatively into solutions of 1.0 10 3 and 1.0 10 2 M AgNO3 demonstrated a SD of 1.21 mV over 2 h (n = 12), which indicates the electrode has a good reproducibility. 3.2. Response time and lifetime Rapid response is an important factor for the silver selective electrodes. The response time was obtained by measuring a series of Ag + solutions from 1.0 10 6 to 1.0 10 1 M. Fig. 3 clearly indicates that the response time is about 50 s. We periodically recalibrated the potentiometric response to Ag + ion in standard silver nitrate solutions. The developed electrode could be used for at least three months without any measurable divergence. The electrode was kept in pH 4.0 nitrate solution to avoid drying, cracking and poisoning when it was not in use. 3.3. Optimization of pH The effect of pH of test solution on the responses of electrodes was respectively investigated over the range of 1.010.0 for 1.0 10 3 and 1.0 10 4 M AgNO3 solutions. The pH was adjusted with dilute nitric acid and sodium hydroxide solutions. It is clear from Fig. 4 that the potential remains constant in the range of 4.09.0. At pH lower than 4.0, the increased potential seemed ascribable to the competitive binding of protons (or hydrated protons) to the ligands on the electrode surface. The sharp change in potential at pH > 9.0 was due to the formation of the metal hydroxide. 3.4. Selectivity of the developed CPEs The potentiometric selectivity coefcient of an electrode is dened by its relative response for the primary ion over other ions present in the solution [11]. In this work, the selectivity coefcients of the sensors toward different cationic species were evaluated by using the
Table 1 The optimization of the carbon paste ingredients. Number Composition (%) DTPSG 1 2 3 4 5 6 7 5.2 6.0 6.7 7.5 8.3 9.8 Graphite powder 67.6 64.1 63.5 63.1 62.5 61.9 61.0 Parafn oil 32.4 30.7 30.5 30.2 30.0 29.8 29.2 Slope (mV dec 1) Linear rang (M) Detection Limit (M)

Fig. 3. Dynamic response time of the proposed electrode for the step changes in the different Ag+ ion concentrations.

separate solution method (SSM) [32]. Selectivity coefcients by this method were determined using the following equation: log K A;B
pot

E B E A Z A =Z B 1 log A : S

EA and EB mean the potentiometric response of the primary ion and interfering ion, respectively. S is the Nernstian slope. ZA and ZB are the charge of the primary ion and interfering ion, respectively. A is the primary ion activity. In this work, A (1.0 10 1 M Ag + ion) and interfering ions (1.0 10 1 M) were used to measure the selectivity coefcients. The resulting values of logarithm of selectivity coefcients for various interfering ions are listed in Table 2. As can be seen, the logarithm of selectivity coefcients is quite small, probably indicating that the disturbance produced by interfering ions in the functioning of the Ag + sensors is negligible. A comparative study of the response characteristics of the previously reported papers on silver ion selective electrodes is showed in Table 3. The comparison indicates that the proposed electrode is superior to these reported Ag + ion selective electrodes with regard to the linear range, pH range and selectivity over other cations. 3.5. Impedance characterization Electrochemical impedance spectroscopy (EIS) has been regarded as an effective method for providing information on the impedance changes of the electrode surface function with different concentrations of Ag + ion. The A.C. impedance spectra of the electrode membrane based on the DTPSG were investigated for 1.0 10 5 and 1.0 10 3 M AgNO3 at pH 4.0 nitrate solution. A perfect semicircle bulk impedance at the high frequency region and Warburg impedance at the low frequency are observed in Fig. 5. When the concentrations of the Ag + ion solutions are 1.0 10 5 and 1.0 10 3 M, the

56.5 60.4 60.1 54.5 61.6 61.1

7.0 10 6 1.0 10 1 1.0 10 6 1.0 10 1 6.5 10 6 1.0 10 1 3.9 10 6 1.0 10 1 7.3 10 6 1.0 10 1 3.9 10 5 1.0 10 1

5.1 10 6 9.5 10 7 4.1 10 6 2.2 10 6 5.4 10 6 9.1 10 6 Fig. 4. Effect of pH on potential at different concentrations of Ag+ ion solutions.

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Table 2 The selectivity coefcients of various interfering cations. Interfering ion Na+ K+ Li+ + NH4 Ba2 + Cd2 + Ca2 + Mg2 + Pb2 + Zn2 + log KAg+, B 5.55 5.66 5.12 5.48 4.88 4.75 4.90 4.78 4.83 4.91
pot

Interfering ion Co2 + Ni2 + Sr2 + Mn2 + Cu2 + Cr3 + Ce3 + Al3 + Nd3 + La3 +

log KAg+, B 5.36 4.98 4.80 4.67 3.11 3.10 4.33 2.26 3.47 4.35 Fig. 5. Impedance plots of membrane with DTPSG carriers.

pot

corresponding impedances of the membrane are 3.94 and 2.96 k, respectively. The bulk resistance decreases with the increasing of Ag+ ion concentration. The results show that the carrier DTPSG takes Ag + ions across membrane phase and the transfer process is controlled by diffusion [33]. The carbon paste electrode response is attributed to the electron-exchange mechanism at the membranecontact interface and the ion exchange at the membranesolution interface [34]. 4. Preliminary application 4.1. Titration of the mixture solution of Cl and Br ions The proposed electrode (number 3 in Table 1) was used as an indicator electrode for the titration of the mixture of chlorine and bromine ions with AgNO3 as the titrant. Ksp (solubility product) represents the product of the ion concentrations when the slightly soluble solid and the corresponding ions in solution reach equilibrium. Due to the large difference between the Ksp values of AgCl and AgBr, it is theoretically possible to potentiometrically titrate the mixture of chlorine and bromine ions in one experiment [35]. Titration curves of the 10 mL 1.0 10 3 M mixture of chlorine and bromine ions with 0.01 M AgNO3 are illustrated in Fig. 6. The endpoint of titration could be explicitly observed from the two sharp break points. 4.2. Determination of silver content in radiology lms To evaluate its practical applicability to real samples, the proposed sensor was applied in the direct determination of the concentration of Ag (I) ions in radiology lms. The sample was prepared as follows [36]: radiology lms (1.50 g) were dry ashed in a mufe furnace at 450 C for 90 min. The residue was dissolved in 50 mL 6 M nitric acid, boiled for 3 h and evaporated to dryness at low heating rate. The residue was dissolved in 80 mL of distilled water and ltered.

Fig. 6. Titration curves of 10 mL 1.0 10 3 M mixture of chloride and bromide ions with 0.01 M AgNO3.

The ltrate was adjusted to pH 4.0 using NaOH solution and quantitatively diluted to 100 mL with double distilled water. The concentrations of Ag+ in the samples were evaluated by the proposed CPE and AAS. The results are shown in Table 4.

5. Conclusion The results of this study show that DTPSG can be considered as a suitable carrier to construct a carbon paste electrode for silver (I) ion. The electrode is easy to prepare, selective to silver ion over other cations and presents a fast response time (50 s). Moreover, the electrode shows a high sensitivity, reproducibility, wide linear range, and low detection limit to Ag+ ion. Meanwhile, the proposed sensor can be successfully applied to the determination of silver ions in radiology lms and the potentiometric titration of the mixture solution of Cl and Br ions.

Table 3 Comparison of the response characteristics of different silver ion selective electrodes.
pot (log KAg + , B)

Ref. [6] SSM

Ref. [7] SSM 3.63 5.85 6.47 6.27 3.69.2 54.9 1.0 10 6 1.0 10 3

Ref. [9] FIM 1.80 1.28 1.28 1.24 55.4 5.0 10 5 1.0 10 1

Ref. [10] SSM 5.10 6.25 8.20 4.00 2.58.0 59.8 1.0 10 6 1.0 10 2

This work SSM 5.66 4.83 4.75 5.36 3.11 4.33 4.09.0 60.4 1.0 10 6 1.0 10 1

K+ Pb2 + Cd2 + Co2 + Cu2 + Ce3 + pH range Slope (mV dec 1) Linear range (M)

4.10 4.44 4.60 5.10 1.80 4.50 4.010.0 59.3 1.0 10 6 1.0 10 1

T. Zhang et al. / Materials Science and Engineering C 32 (2012) 11791183 Table 4 Determination of the concentration of silver (I) in radiology lms by use of the proposed electrodes and comparison with the atomic absorption spectrometry (AAS). Sample Ag (I) added Silver (I) ion concentrationa Found by AAS Radiology lms 0.0 0.25 mg.g 1 0.50 mg.g 1 1.50 0.12 mg.g 1.72 0.11 mg.g 1 1.98 0.10 mg.g 1
1

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Found by CPE 1.47 0.14 mg.g 1 1.70 0.15 mg.g 1 1.95 0.13 mg.g 1

The average of three measurements standard deviation (%).

Acknowledgments This work was supported by the 211 Project of Southwest University (the Third Term), the National Natural Science Foundation of China (21075100) and the National Natural Science Foundation of Chongqing city, China (CSTC2009BA1003). References
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