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A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes modied glassy carbon electrode
Qiaoli Zheng1 , Ping Yang1 , He Xu1, , Jianshe Liu1, , Litong Jin2
1. School of Environmental Science and Engineering, Donghua University, Shanghai 201620, China. E-mail: zhengqiaoli2005@163.com 2. Department of Chemistry, East China Normal University, Shanghai 200062, China Received 21 October 2011; revised 02 March 2012; accepted 27 March 2012
Abstract A simple and sensitive electroanalytical method was presented for the determination of 4-n-octylphenol (OP) based on multi-walled carbon nanotubes (MWCNTs) modied glassy carbon electrode (GCE). OP was directly oxidized on the MWCNTs/GCE, and the electrochemical oxidation mechanism was demonstrated by a one-electron and one-proton process in the reaction. The oxidation peak current of OP was signicantly enhanced by the use of MWCNTs/GCE compared with those of bare glassy carbon electrode, suggesting that the modied electrode can remarkably improve the performance for OP determination. Factors inuencing the detection processes were optimized. Under these optimal conditions, a linear relationship between concentration of OP and current response was obtained in the range of 5 108 to 1 105 mol/L with a detection limit of 1.5 108 mol/L and correlation coecient 0.9986. The modied electrode showed good selectivity, sensitivity, reproducibility and high stability. Key words: multi-walled carbon nanotubes; 4-n-octylphenol; electrochemical analysis; linear sweep voltammetry DOI: 10.1016/S1001-0742(11)60970-4
Introduction
Alkylphenols, especially nonylphenols (NP) and octylphenols (OP) are widely distributed in the environment, have estrogenic activity and can bio-accumulate in the lipids of organisms. In order to control the level of these compounds in environment, it is necessary to select appropriate analytical methods. The proposed methods including high performance liquid chromatography (HPLC), gas chromatographic-mass spectrometric analysis (GCMS) and solid phase extraction (SPE) (Gadzala-Kopciuch et al., 2008; Lopez-Espinosa et al., 2009; Cai et al., 2003) have high sensitivity and low detection limits, however, they have the disadvantages of being complex, timeconsuming and expensive. Compared to other options, electroanalysis has the advantages of quick response, simplicity, time-saving, high sensitivity and selectivity. It has been widely applied in various elds, in particular during the determination of chemical substances with electroactive groups, such as the hydroxide group in alkylphenols. Carbon nanotubes (CNTs) have raised interest in nanoscience and nanotechnology due to their large surface area, unique structure, and remarkable mechanical and electrical properties (Coleman et al., 2006; Valc arcel et al., 2008). Moreover, since the discovery of their electrocatalytic properties by Britto et al. (1996), CNTs have been
* Corresponding author. E-mail: hexu@dhu.edu.cn (He Xu); liujianshe@dhu.edu.cn (Jianshe Liu)
widely used in both electrochemistry and electroanalytical chemistry (Gooding et al., 2007; Tedim et al., 2008; Alexeyeva et al., 2006). Multi-walled carbon nanotubes (MWCNTs) modied glassy carbon electrodes have been reported for the electrochemical determination of various environmental pollutants. For example, Yi (2003) has reported the determination of trace levels of mercury based on a MWCNTs modied glassy carbon electrode. Wen et al. (2008) fabricated MWCNTs modied glassy carbon electrode for the electrochemical analysis of the endocrine-disrupting chemical triuralin. Luo et al. (2008) has reported the electrochemical reduction of nitrophenol isomers at the carbon nanotubes modied glassy carbon electrode. However, there are few reports about the determination of 4-n-octylphenol (OP) with MWCNTs modied glassy carbon electrode. In this work, MWCNTs modied glassy carbon electrode for the electrochemical determination of OP was employed. The MWCNTs modied electrode signicantly enhanced the electrochemical response toward OP oxidation, leading to better performance for OP detection. The electrochemical reaction mechanism of OP on the modied electrode was investigated. Factors inuencing the detection processes, such as pH, scan rate and accumulation time were optimized. The reproducibility and stability of the modied electrode were also tested.
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0.2 0.0 -0.2 E (V) Fig. 2 Cyclic voltammograms of GCE (curve a) and MWCNTs/GCE (curve b) in 5 mmol/L [Fe(CN)6 ]3/4 solution containing 0.2 mol/L KCl at a scan rate of 50 mV/sec.
-120
0.6
0.4
where, n is the number of electrons participating in the redox reaction, C (mol/L) is the concentration of the redox probe, D (cm2 /sec) is diusion coecient of the redox probe, and (V/sec) is the scan rate. The [Fe(CN)6 ]3/4 redox system used in this study exhibited a one-electron transfer, n is equal to 1, C is equal to 5 mmol/L and D is 6.7 106 cm2 /sec. Thus, A can be calculated to be 0.075 and 0.16 cm2 for GCE and MWCNTs/GCE, respectively, indicating that MWCNTs could obviously increase the active surface area of the electrode. 2.2 Cyclic voltammetric behavior of 4-n-octylphenol The cyclic voltammograms of the GCE and MWCNTs/GCE in BR buer solution (pH 5) in the presence of 5 106 mol/L OP were obtained. Voltammograms as shown in Fig. 3 (curves a and b) only have anodic peaks. The absence of cathode peaks suggests that the oxidation of OP at these electrodes is totally irreversible under studied experimental conditions. Moreover, the oxidation peak current of OP at the MWCNTs/GCE is much higher than at GCE (I pMWCNTs /I pGCE is about 12.2), indicating that MWCNTs could increase the active area and adsorption sites of the electrode and improve the electrochemical behavior of OP, leading to enhance current response for OP detection.
(1)
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A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes
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10 5 0 Current (A) -5 -10 -15 -20 -25 -30 0.4 0.2 0.0 E (V) Fig. 3 Cyclic voltammograms of GCE (curve a) and MWCNTs/GCE (curve b) in BR buer solution (pH 5) containing 5 106 mol/L OP at a scan rate of 50 mV/sec. Curve c: blank solution. 1.0 0.8 0.6 b c a
for the subsequent analytical experiments. The relationship between the oxidation peak potential (E p ) and pH is shown in Fig. 4b. A linear shift of E p towards the negative potential with increasing pH indicates that protons were directly involved in the oxidation of OP. It obeyed the following Eq. (2): Ep = 0.0618 pH + 0.9553 (R = 0.9976) (2)
The slope is close to the theoretical Nernstian value of 0.059 V, indicating that the number of protons and electrons involved during the oxidation reaction is the same (Luczak, 2008). 2.4 Eect of scan rate In order to investigate the eect of scan rate on the oxidation of OP at MWCNTs/GCE, cyclic volammograms of 5 106 mol/L OP at dierent scan rates of 20250 mV/sec were obtained (Fig. 5a). Figure 5b shows that the plot of the oxidation peak current (I p ) versus the square root of scan rate (1/2 ) is linear and can be expressed as Eq. (3): Ip = 6.19421/2 + 13.7030 (R = 0.9992) (3)
2.3 Eect of pH The eect of pH on the electrochemical oxidation of OP at the MWCNTs/GCE was investigated in dierent BR buer solutions (pH 310). As shown in Fig. 4a, the current response of OP increases gradually from pH 3 to 5 and then decreases at pH values higher than 5. It is likely that under high pH conditions, hydroxyl ions (OH ) in the solution increase and combine with the carboxyl group (COOH) of MWCNTs, which reduces the adsorption of OP on MWCNTs, leading to decrease the current response (Chen et al., 2000). Therefore, pH 5 was chosen as optimum pH
0 -10 -20 Current (A) -30 -40 -50 -60 -70 -80 -90 1.0 pH 3 a 0.8 0.6 pH 10
This result suggests that the oxidation of OP at MWCNTs/GCE is a typical diusion-controlled process. The oxidation peak potential (E p ) versus the natural logarithm of scan rate (ln) is linear as shown in Fig. 5c and the linear regression equation can be expressed as: Ep = 0.0512ln + 0.4177 (R = 0.9930)
0.8 0.7 Ep (V) 0.6 0.5 0.4 0.3 b
(4)
2 4 6 8 10 12 0.4 0.2 0.0 pH E (V) Fig. 4 (a) Linear sweep voltammograms (LSV) of MWCNTs/GCE in dierent BR buer solutions containing 5106 mol/L OP at a scan rate of 100 mV/sec (pH: 3, 4, 5, 7, 8, 9, 10); (b) eect of pH on the oxidation potential (Ep ). 20 0 -20 -40 -60 -80 -100 -120 a -10 -20 -30 -40 -50 -60 -70 -80 -90 4 6 8 b 0.72 0.70 0.68 0.66 0.64 0.62 0.60 0.58 c
Current (A)
Ip (A)
20 mV/sec
250 mV/sec
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 10 12 14 16 ln 1/2 (mV/sec)1/2 Fig. 5 (a) Cyclic voltammograms of 5 106 mol/L OP at MWVNTs/GCE with dierent scan rates (20, 40, 60, 80, 120, 160, 200 and 250 mV/sec); (b) the plot of the peak current (Ip ) versus the square root of scan rate ; (c) the relationship between E p and ln. 1.0 0.8 0.6 0.4 E (V) 0.2 0.0
Ep (V)
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For a totally irreversible electrode process, the relationship between the peak potential and scan rate can be expressed as follows (Laviron, 1974): RT RT k0 RT Ep = E + ln( )+ ln nF nF nF
0
80 70 60 Ip (A)
(5)
50 40 30 20
where, n is the number of electron transfer, is the electron transfer coecient which is assumed to be 0.5 during a totally irreversible electrode process, E 0 is formal potential, k0 is standard rate constant of the reaction, and R, T and F are gas-constant, temperature and Faraday constant, respectively. In the present case, the calculated value of n is 1.003, therefore the number of electron transfer during the electrochemical oxidation of OP is 1. It has been demonstrated that the number of electrons and protons involved in the anodic oxidation reaction of OP is the same (see Section 2.3), thus the electrochemical oxidation of OP at MWCNTs/GCE is a one-electron and one-proton process. The hydroxyl radicals might play an important role in the electrochemical oxidation of OP (Comninellis, 1994; Simod and Comninellis, 1997). It is generally considered that OP oxidation begins with an electron transfer that leads to phenoxy radicals. The radicals reactions result in the formation of quinone structures, which is believed to an important intermediate of OP oxidation. Therefore, the oxidation reaction is promoted and the oxidative current is obtained (Ngundi et al., 2003; Li et al., 2005). The proposed reaction mechanism for the electrochemical oxidation of OP is as the following.
OH -e-H+ C8H17 C8H17 O O O
10 12 14 16 18 20 22 Tim (min) Fig. 6 Eect of accumulation time on the oxidation current response of 5 106 mol/L OP.
2.6 Calibration curve The determination of OP at the MWCNTs/GCE was performed using linear sweep voltammetry (LSV) at a scan rate of 100 mV/sec. Figure 7 shows that the oxidation peak current (I p ) is proportional to OP concentration in the range of 5 108 to 1 105 mol/L (about 10 to 2060 g/L) with a detection limit of 1.5 108 mol/L (about 3 g/L), and the linear regression equation can be expressed as I p = 6.5406 OP concentration 4.204 (R = 0.9986). The result of the analytical determination of OP by this method shows a low detection limit, which is much better than some of the previous reports based on chromatography (Table 1), suggesting that this proposed method could potentially be used for monitoring of trace OPs in environment. 2.7 Reproducibility, stability and interference In the reproducibility tests, it was found that the relative standard deviations of linear sweep voltammetric responses of 5 106 mol/L OP obtained at the MWCNTs/GCE for 10 replicates was 2.4%, exhibiting an excellent reproducibility. The stability of the modied electrode was also investigated by measuring the current response of 5 106 mol/L OP every 10 days by LSV. Between measurements the electrode was stored at 4C in a refrigerator. The current response decreased to 98% after 10 days, while 90% of the initial response retained after 20 days. The response still retained 85% after over 30 days. In addition, the selectivity of MWCNTs/GCE for the detection of OP was tested in the presence of various interferents in BR buer solution containing 1 106 mol/L OP. The results suggested that phenol, hydroquinone, dichlorophenol and some ions such as Ca2+ , Mg2+ , Al3+ , Cu2+ , Cl and SO4 2 did not show interference to the determination of OP.
C8H17
C-C7H16
(6)
2.5 Eect of accumulation time The eect of accumulation time on the current response of 5 106 mol/L OP obtained at the MWCNTs/GCE was investigated. As shown in Fig. 6, the oxidation peak current increases gradually with accumulation time (1 to 15 min), other conditions remaining unchanged indicating that OP could be adsorbed on the electrode surface with extending accumulation time. The peak current reaches a maximum value with no indication of further increase with accumulation time. This phenomenon can be attributed to the saturated adsorption of OP at the electrode surface. Accordingly, the optimal accumulation time was chosen as 15 min in the further experiments.
Table 1 Comparison of the analytical parameters obtained using other methods for the determination of OP Method Gas chromatography mass spectrometry Micellar electrokinetic chromatography Liquid chromatography mass spectrometry Concentration range 0.021.00 mg/L 5200 mg/L 0.110 mg/kg Limit of detection 0.01 mg/L 5 mg/L 0.03 mg/kg Reference Tsuda et al., 1999 Cai et al., 2004 Andreu et al., 2007
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A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes
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0 -10 -20 Current (A) -30 -40 -50 -60 -70 -80
10 mol/L
0 2 4 6 8 10 0.6 0.4 0.2 0.0 OP concentration (mol/L) E (V) Fig. 7 (a) Linear sweep voltammograms of MWCNTs/GCE in BR buer solution (pH 5) containing dierent concentration of OPs (0, 0.05, 0.1, 0.2, 0.4, 0.8, 1.0, 2.0, 4.0, 6.0, 8.0, 10 mol/L); (b) calibration curve of the peak current against the concentration of OP. Accumulation time: 15 min, scan rate: 100 mV/sec, potential: 01.0 V. 1.0 0.8
3 Conclusions
In this work, a simple and sensitive electrochemical method was proposed for the determination of 4-noctylphenol based on MWCNTs/GCE. The oxidation peak current of OP was signicantly enhanced after electrode modication. The electrochemical oxidation mechanism of OP was demonstrated by a one-electron and one-proton process in the electrode reaction. The method exhibited some obvious advantages, such as simple preparation process, high sensitivity, low cost and good stability, suggesting that it has a potential application for trace OPs detection in environment. Acknowledgments This work was supported by the National Natural Science Foundation of China (No. 21005014, 41073060), the Fundamental Research Funds for the Central Universities (No. 2011D11307) and the Chen Guang project of Shanghai Municipal Education Commission and Shanghai Education Development Foundation (No. 11CG34).
References
Alexeyeva N, Laaksonen T, Kontturi K, Mirkhalaf F, Schirin D J, Tammeveski K, 2006. Oxygen reduction on gold nanoparticle/multi-walled carbon nanotubes modied glassy carbon electrodes in acid solution. Electrochemistry Communications, 8(9): 14751480. Andreu V, Ferrer E, Rubio J L, Font G, Pico Y, 2007. Quantitative determination of octylphenol, nonylphenol, alkylphenol ethoxylates and alcohol ethoxylates by pressurized liquid extraction and liquid chromatography-mass spectrometry in soils treated with sewage sludges. Science of the Total Environment, 378(1-2): 124129. Britto P J, Santhanam K S V, Ajayan P M, 1996. Carbon nanotube electrode for oxidation of dopamine. Bioelectrochemistry and Bioenergetics, 41(1): 121125. Cai Y Q, Jiang G B, Liu J F, Zhou Q X, 2003. Multiwalled carbon nanotubes as a solid-phase extraction adsorbent for the determination of Bisphenol A, 4-n-nonylphenol and 4-tert-octylphenol. Organic Analytical Chemistry, 75(10):
25172521. Cai Y Q, Jiang G B, Zhou Q X, 2004. Separation and determination of bisphenol A, 4-n-nonylphenol and 4-tertOctylphenol by micellar electrokinetic chromatogra phy. Chinese Journal of Analytical Chemistry, 32(9): 1179 1181. Chen W, Tomalia D, Thomas J, 2000. Unusual pH-dependent polarity changes in PAMAM dendrimers: Evidence for pH-responsive conformational changes. Macromolecules, 33(25): 91699172. Coleman J N, Khan U, Blau W J, Gunko Y K, 2006. A review of the mechanical properties of carbon nanotube-polymer composites. Carbon, 44(9): 16241652. Comninellis C, 1994. Electrocatalysis in the electrochemical conversion/combustion of organic pollutants for waste-water treatment. Electrochimica Acta, 39(11-12): 18571862. Gadzala-Kopciuch R, Filipiak A, Buszewski B, 2008. Isolation, purication and determination for 4-n-nonylphenol and 4-tert-octylphenol in aqueous and biological samples. Talanta, 74(4): 655660. Gooding J J, Chou A, Liu J Q, Losic D, Shapter J G, Hibbert D B, 2007. The eects of the lengths and orientations of single-walled carbon nanotubes on the electrochemistry of nanotube-modied electrodes. Electrochemistry Communications, 9(7): 16771683. Laviron E, 1974. Adsorption, autoinhibition and autocatalysis in polarography and in linear potential sweep voltammetry. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 52(3): 355393. Li X Y, Cui Y H, Feng Y J, Xie Z M, Gu J D, 2005. Reaction pathways and mechanisms of the electrochemical degradation of phenol on dierent electrodes. Water Research, 39(10): 19721981. Lopez-Espinosa M J, Freire C, Arrebola J P, Navea N, Taouki J, Fernandez M F et al., 2009. Nonylphenol and octylphenol in adipose tissue of women in southern Spain. Chemosphere, 76(6): 847852. Luczak T, 2008. Preparation and characterization of the dopamine lm electrochemically deposited on a gold template and its applications for dopamine sensing in aqueous solution. Electrochimica Acta, 53(19): 57255731. Luo L Q, Zou X L, Ding Y P, Wu Q S, 2008. Derivative voltammetric direct simultaneous determination of nitrophenol isomers at a carbon nanotube modied electrode. Sensors and Actuators B: Chemical, 135(1): 6165.
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Ngundi M M, Sadik O A, Yamaguchi T, Suye S, 2003. First comparative reaction mechanisms of -estradiol and selected environmental hormones in a redox environment. Electrochemistry Communications, 5(1): 6167. Simod O, Comninellis C, 1997. Anodic oxidation of organics on Ti/IrO2 anodes using Naon as electrolyte. Electrochimica Acta, 42(13-14): 20132018. Tedim J, Goncalves F, Pereira M F R, Figueiredo J L, Moura C, Freire C et al., 2008. Preparation and characterization of poly[Ni(salen)(crown receptor)]/multi-walled carbon nanotube composite lms. Electrochimica Acta, 53(23): 67226731. Tsuda T, Takino A, Kojima M, Harada H, Muraki K, 1999. Gas chromatographic-mass spectrometric determination of
4-nonylphenols and 4-tert-octylphenol in biological samples. Journal of Chromatography B, 723(1-2): 273279. Valc arcel M, C ardenas S, Simonet B M, Moliner-Martnez Y, Lucena R, 2008. Carbon nanostructures as sorbent materials in analytical processes. Trends in Analytical Chemistry, 27(1): 3443. Wen X Q, Fei J J, Chen X M, Yi L H, Ge F, Huang M H, 2008. Electrochemical analysis of triuralin using a nanostructuring electrode with multi-walled carbon nanotubes. Environmental Pollution, 156(3): 10151020. Yi H C, 2003. Anodic stripping voltammetric determination of mercury using multi-walled carbon nanotubes lm coated glassy carbon electrode. Analytical and Bioanalytical Chemistry, 377(4): 770774.