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Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate
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Research paper
Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate J. Pishahang a,b , H.Barzegar Amiri a,c , H. Heli d,∗ a
Central Laboratory of Jam Petrochemical Complex, South Pars Special Economy and Energy Zone, Assaluyeh, Iran Department of Chemistry, Lamerd Branch, Islamic Azad University, Lamerd, Iran Department of Chemistry, Faculty of Science, Payame Noor Univercity, Assaluyeh, Iran d Nanomedicine and Nanobiology Research Center, Shiraz University of Medical Sciences, Shiraz, Iran b c
a r t i c l e
i n f o
Article history: Received 15 June 2017 Received in revised form 26 September 2017 Accepted 4 October 2017 Available online xxx Keywords: Poly(ortho-aminophenol) Carbon dots Electrocatalysis Electroanalysis Composite
a b s t r a c t A nanocomposite was fabricated comprising nanoparticles of carbon and poly(ortho-aminophenol) by electropolymerization technique. The nanocomposite was characterized by field emission-scanning electron microscopy. The kinetics of charge transfer between the nanocomposite and the adjacent electrolyte was measured using cyclic voltammetry (CV). The kinetics of the electroreduction of iodate on the nanocomposite surface was then evaluated by CV and chronoamperometry. Iodate was electroreduced by low-valence redox species of poly(ortho-aminophenol) in an electrocatalytic manner. The nanocomposite was applied as an amperometric sensor for iodate, and an amperometry route was proposed for determination of iodate. Sensitivity and detection limit of the amperometry method were attained as 242.6 mA L mol−1 cm−2 and 0.01 mmol L−1 , respectively. © 2017 Elsevier B.V. All rights reserved.
1. Introduction Iodine has a high concern on health and environmental protection. It has important effects on the cell growth and brain function, and its deficiency can cause mental retardation, brain damage and endemic goiter [1]. Addition of iodine in the form of iodate to the table salt is one of the successful strategies used to prevent iodine deficiency disorders. However, excess iodate can produce goiter, hypothyroidism and hyperthyroidism. On the other side, iodate is the major oxidant toward many organic and inorganic compounds [2]. Potassium iodate is used as a reference material in voltammetric analyses for direct or indirect titrations [2]. Therefore, determination of iodate is important in human health and food industries [1,3,4]. There have been some methods for the determination of iodate, including amperometry [5], voltammetry [6], ion chromatography [7], photometry [8], fluorimetry [9], liquid-phase microextraction-gas chromatography-mass spectrometry [10] and resonance scattering spectral method [11]. Although there are advantages for these methods, some drawbacks such as timeconsuming, low sensitivity, susceptibility to interference and
∗ Corresponding author. E-mail addresses: [email protected], [email protected] (H. Heli).
difficulties of automation for some of these methods are still present. On the other hand, electrochemical methods have such advantages as simplicity, inexpensiveness, and sensitivity. Recent developments in nanotechnology and specific properties of nanostructured materials have provided usage of these materials in different branches of science and technology [12–22]. Nanostructured materials have been extensively employed to fabricate modified electrodes, and electrochemical sensors and biosensors [17–19,23]. Sensing tools and devices fabricated by these materials have enhanced conductivity, electron transfer rate, charge transport rate and catalytic activity, with alterations in absorption, adsorption, chemical reactivity and molecular interactions leading to enhanced sensitivity, selectivity and efficiency [17–19,23]. Up to now, different nanocomposites of carbonaceous materials/conducting polymers such as graphene-poly(orthoaminophenol) (POAP) [24,25], graphene-polyluminol graphene/poly(o-phenylenediamine) [27], carbon [26], fibers/polypyrrole [28] and polyaniline grafted on carbon nanotube-embedded carbon nanofibers [29] have been synthesized. Carbonaceous materials employed for synthesis of the nanocomposites have been carbon black, carbon fibers, carbon nanotubes, graphene, carbon nanocoil and carbon nanospheres [30–33]. These composites have been synthesized using techniques of electropolymerization [24–27,34] or chemical oxidation of a vapor [28] of a monomer on a pre-deposited carbon nanos-
https://doi.org/10.1016/j.snb.2017.10.030 0925-4005/© 2017 Elsevier B.V. All rights reserved.
Please cite this article in press as: J. Pishahang, et al., Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate, Sens. Actuators B: Chem. (2017), https://doi.org/10.1016/j.snb.2017.10.030
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Fig 1. FE-SEM (A-D) and TEM (E) images of the synthesized CNPs.
tructures surface, conducting polymer grafting by plasma [29], and chemical polymerization of a monomer on the carbon nanostructure surfaces [31,35,36]. Some of these nanocomposites
represented synergetic effects arising from differences in the structure and properties of conducting polymers arising from the carbon nanostructures [24–27,32,35]. The nanocomposites
Please cite this article in press as: J. Pishahang, et al., Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate, Sens. Actuators B: Chem. (2017), https://doi.org/10.1016/j.snb.2017.10.030
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Fig. 2. FE-SEM images of POAP.
have had applications in fabrication of sensors and biosensors, and anti-corrosion materials, supercapacitors, drug delivery, and catalysis [24–36]. In the present study, a nanocomposite of carbon nanoparticles (CNPs) with POAP was synthesized, characterized and then applied for the electroanalysis of iodate.
two min to complete the dehydration of glucose. The final color of the solution turned black, indicating the formation of carbon nanoparticles. After cooling the solution to room temperature, the mixture was added dropwise to 100 mL cold water with vigorous stirring. A black precipitate was obtained and separated by centrifugation. CNPs were washed several times with water and then dried at room temperature.
2. Experimental section 2.1. Materials All chemicals were of analytical grade from Merck or Scharlau and were used without further purification. All solutions were prepared with redistilled water. 2.2. Synthesis of CNPs CNPs was synthesized based on the method reported elsewhere [37]. Briefly, 500 mg of D-glucose was suspended in 20 mL concentrated sulfuric acid with constant stirring until the color of the solution turned faint yellow. The mixture was then digested for 30 min and after that, the solution was heated to 140–150 ◦ C for
2.3. Preparation of the nanocomposite The nanocomposite of CNPs-POAP was synthesized on the surface of a glassy carbon (GC) electrode (3 mm of diameter). Firstly, the GC electrode was polished with alumina powder on a polishing pad and rinsed thoroughly with redistilled water. It was then sonicated in a 1:1 water/acetone mixture for ∼5 min. This GC electrode was placed in the electrochemical cell and potential between −0.5 and +1.2 V in a regime of cyclic voltammetry (CV) for 10 cycles and a potential scan rate of 50 mV s−1 in 1.0 mol L−1 H2 SO4 was applied. 10 mg CNPs were dispersed in 1.0 mL water by sonication for 10 min. The GC electrode was coated by casting 10 L of the CNPs suspension and dried under an infrared lamp to form the CNPs adsorbed GC (GC/CNPs) electrode. The GC/CNPs electrode
Please cite this article in press as: J. Pishahang, et al., Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate, Sens. Actuators B: Chem. (2017), https://doi.org/10.1016/j.snb.2017.10.030
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Fig. 3. FE-SEM images of CNPs-POAP.
was transferred to a 0.1 mol L−1 ortho-aminophenol + 1.0 mol L−1 sulfuric acid solution and potential in a range of −0.1–1.0 V in a regime of CV for 100 cycles with a potential scan rate of 50 mV s−1 was applied to prepare the CNPs-POAP nanocomposite on the GC surface (GC/CNPs-POAP electrode). Following these procedures, ortho-aminophenol was electropolymerized and formed a nanocomposite with CNPs.
2.4. Apparatus Electrochemical measurements were performed in a threeelectrode cell powered by a -Autolab potentiostat/galvanostat, type III, FRA2 (The Netherlands). The system was run by a PC through GPES 4.9 software. A Pt wire and an Ag/AgCl, 3 mol L−1 KCl (from Metrohm) were used as the counter and reference electrodes, respectively. The supporting electrolyte was 1.0 mol L−1 H2 SO4 . Field emission-scanning electron microscopy (FE-SEM) was performed by a MIRA3 TESCAN-XMU (Czech Republic) microscope. Transmission electron microscopy (TEM) was done using a Zeiss-EM10C transmission electron microscope (Germany) with an operating voltage of 80 kV on a carbon formvar-coated copper grid.
3. Results and discussion In order to study the size and surface morphology, FE-SEM images from CNPs, POAP and CNPs-POAP at different magnifications, and a TEM image from CNPs were recorded and are displayed in Figs. 1–3. Microscopic images of CNPs (Fig. 1) show agglomerated particles with a mean diameter of 8.6 ± 1.7 nm. The size of CNPs is lower than those synthesized using ascorbic acid as a precursor [38], and can be considered as carbon quantum dots. Microscopic images of POAP deposited on the GC surface (Fig. 2) show a uniform layer with a vesicles-like morphology. FE-SEM images of CNPsPOAP (Fig. 3) represent a composite comprised CNPs covered by a POAP layer. There are changes in the morphology of POAP upon coating on CNPs surface where POAP do not have vesicles-like morphology. Apparently, CNPs caused to changes in the morphology of POAP due to changes in the electropolymerization mechanisms of ortho-aminophenol on the surface of CNPs, compared to the GC surface. A cyclic voltammogram of a 1.0 mol L−1 H2 SO4 solution recorded using GC/CNPs-POAP electrode is presented in Fig. 4A. One couple of peaks having a mid-peak potential equal to 121 mV is observed in the voltammogram with a quasi-reversible kinetics. The voltammogram pattern is similar to those reported elsewhere [24,25,39].
Please cite this article in press as: J. Pishahang, et al., Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate, Sens. Actuators B: Chem. (2017), https://doi.org/10.1016/j.snb.2017.10.030
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Fig. 4. A) CVs of GC/CNPs-POAP electrode recorded in a 1.0 mol L−1 H2 SO4 solution with a potential scan rate of 50 mV s−1 . B) CVs of GC/CNPs-POAP electrode recorded in a 1.0 mol L−1 H2 SO4 solution at different potential scan rates of 5, 7.5, 10, 15, 20, 25, 30, 40, 50, 60, 75, 100, 125, 150, 175, 200, 250, 275, 300, 350, 375, 400, 450, 500, 550, 600, 750, 1000, 1250, 1500, 1750 and 2000 mV s−1 . C) Dependency of the anodic and cathodic peak currents on the square root of the potential scan rate. D) Dependency of the anodic and cathodic peak potentials on the natural logarithm of the potential scan rate.
Cyclic voltammograms of a 1.0 mol L−1 H2 SO4 solution recorded using the GC/CNPs-POAP electrode at different values of potential scan rates of 5–2000 mV s−1 are presented in Fig. 4B. Well-defined peaks were appeared in the voltammograms with a peak potential separation of ∼103 mV at the potential scan rate of 5 mV s−1 . This peak separation is larger than the theoretical value of zero for the immobilized redox species and it increases upon potential scan rate increment. Therefore, there was a limitation in the kinetics of charge transfer process in the immobilized redox species. This can be related to interactions of redox species with electrolyte ions, interactions between redox sites, diffusion-migration coupling of ion insertion/deinsertion into the bulk of the nanocomposite, and
non-equivalency of redox sites. For the voltammogram recorded at 5 mV s−1 , the value of full width at half height of anodic peak is ∼98 mV. This is larger than that for non-interacting immobilized redox species with single electron exchange, equals to 90 mV [40]. Therefore, repulsive interactions were dominated between the immobilized redox species in the nanocomposite [41,42]. In the voltammograms shown in Fig. 4B, both the cathodic and anodic peak currents linearly change with the square root of the potential scan rate (Fig. 4C). The results imply that the diffusion of electrolyte ions into/from the nanocomposite was dominated for the redox reaction [43].
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Fig. 5. CVs recorded using GC, GC/CNPs, GC/POAP and GC/CNPs-POAP electrodes in the absence and presence (-Io) of 2.2 mmol L−1 iodate. The potential scan rate was 50 mV s−1 .
To measure the kinetic parameters for the redox reaction occurring in the nanocomposite, Laviron’s equations were employed [44] as follows: Ep,a = E0 + Gln[(1-␣s )/K]
(1)
Ep,c = E0 + Hln[␣s /K]
(2)
lnks = ␣s ln(1-␣s ) + (1-␣s )ln␣s −ln(RT/nF)−˛s (1-˛s )nFEp /RT (3) where G = RT/(1-˛s )nF
(4)
H = RT/˛s nF
(5)
K = (RT/F)(ks /n)
(6)
ical reduction of iodate by the low-valence sites of POAP occured (EC’ mechanism): Poly(ox) + ne → Poly(red) ←−
(7)
Poly(red) + IO3 − → Poly(ox) + I− ←−
(8)
To measure the kinetic parameters of the reduction reaction of iodate, CV and chronoamperometry were employed. Voltammograms of the GC/CNPs-POAP electrode measured without and with 2.0 mmol L−1 iodate at different potential scan rates are shown in Fig. 6A. The cathodic peak potential depend on the logarithm of the potential scan rate, as shown in Fig. 6B. Using this linear plot and the equation [45]: Ep,c,Io = (RT/2˛Io F)ln + constant
n is the number of electrons, Ep,c , Ep,a and E0 are cathodic and anodic peaks, and formal potentials, ␣s is the electron transfer coefficient, ks is the rate constant, is the potential scan rate and Ep is the peak potential separation. Changes in the cathodic and anodic peak potentials with potential scan rate are presented in Fig. 4D. For ≥750 mV s−1 , changes of the peak potential with the logarithm of the potential scan rate are linear and using these lines, the values of ␣s and ks are obtained as 0.55 and 7.29 s−1 , respectively. In Fig. 5, voltammograms measured using GC, GC/CNPs, GC/POAP and GC/CNPs-POAP electrodes without and with 2.2 mmol L−1 iodate are presented. Using GC and GC/CNPs electrodes, negligible anodic currents related to a slow-rate electroreduction of iodate are observed in the voltammograms, while, using GC/POAP and GC/CNPs-POAP electrodes, iodate was reduced wherein the cathodic currents increase and simultaneously the anodic currents decrease. Therefore, it can be inferred that iodate was electroreduced on these two electrode surfaces via a surfacemediated electron transfer process with a higher cathodic current passing through the GC/CNPs-POAP electrode, compared to the GC/POAP electrode. After the redox transition of POAP, the chem-
(9)
where Ep,c,Io and ␣Io are the cathodic peak potential and the electron transfer coefficient for the electroreduction of iodate, respectively, ␣Io is obtained as 0.51. The cathodic peak currents in Fig. 6A depend on the square root of the potential scan rate for > 200 mV s−1 , as shown in Fig. 6C. This linear dependency indicates that the electroreduction process of iodate was diffusion controlled in the bulk of the electrolyte. Also, using the equation [46]: Ip,c,Io = 2.99 × 105 ␣Io 1/2 n3/2 A CIo DIo 1/2 1/2
(10)
where A, Ip,c,Io , DIo , CIo are the electrode surface area, the cathodic peak current, the iodate diffusion coefficient and concentration, DIo is obtained as 4.09 × 10−6 cm2 s−1 . Chronoamperograms recorded using the GC/CNPs-POAP electrode without and with different concentrations of iodate are shown in Fig. 7A. The current depend on the square root of time in a Cottrellian manner and is shown in Fig. 7B. It further confirms that the iodate electroreduction process was controlled by diffusion. Using the Cottrell’s equation [46]: IIo = nFACIo DIo 1/2 /(t)1/2
(11)
where IIo is the transient current and t is time, the value of DIo is obtained as 4.03 × 10−6 cm2 s−1 . This value is in closed agreement
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Fig. 7. A) Chronoamperograms recorded using the GC/CNPs-POAP electrode in the absence (a) and presence of iodate of 0.38 (b), 0.76 (c), 1.15 (d), 1.52 (e), 2.28 (f), 3.03 (g), 3.8 (h), 4.5 (i), and 5.6 mmol L−1 (j). B) Dependency of the transient current on the square root of time for curve (j) in panel (A). C) Dependency of Icat /Id on t1/2 for curve (j) in panel (A).
Table 1 Analytical parameters for the amperometric determination of iodate using the nanocomposite. Fig. 6. A) CVs of the GC/CNPs-POAP electrode recorded in the presence of 2.0 mmol L−1 iodate at different potential scan rates of 5, 7.5, 10, 15, 20, 25, 30, 40, 50, 60, 75, 100, 125, 150, 175, 200, 250, 275, 300, 350, 375, 400, 450, 500, 550, 600, 750, 1000, 1250, 1500, 1750 and 2000 mV s−1 . B) Dependency of the cathodic peak potential on the natural logarithm of the potential scan rate. C) Dependency of the cathodic peak current in the voltammograms of panel (A) on the square root of the potential scan rate for > 200 mV s−1 .
with that found by CV. The catalytic rate constant of the iodate electroreduction is obtained using the equation [46]: Icat /Id = ␥1/2 [1/2 erf(␥1/2 ) + exp(-␥)/␥1/2 ]
(12)
where Id and Icat and are the currents in the absence and presence of iodate, respectively. In addition, ␥ = kcat CIo is the argument of the error function, and kcat is the catalytic rate constant. For ␥ > 1.5, erf (␥1/2 )∼ =1, and equation (12) becomes: Icat /Id = ␥1/2 1/2 = 1/2 (kcat CIo t)1/2
(13)
The dependency of Icat /Id on t1/2 is presented in Fig. 7C, and using the plot, kcat is obtained as 3.53 × 104 cm3 mol−1 s−1 . To propose a new method for determination of iodate, the nanocomposite was evaluated for amperometric determination. Typical amperometric signals recorded using the GC/CNPs-POAP electrode toward iodate concentration is shown in Fig. 8A. Based on the signals, a calibration curve was derived and is presented in
Linear range/mmol L−1 Sensitivity (Slope)/mA L mol−1 cm−2 Intercept/A cm−2 R2 Slope standard error (P = 0.005) Intercept standard error (P = 0.005) Detection limit/mmol L−1 Quantitation limit/mmol L−1 RSD%a Bias%a a
0.5–6.5 242.6 −62.6 0.9986 0.246 0.977 0.01 0.03 4.01 2.40
The value is for 2.5 mmol L−1 iodate.
Fig. 8B. The detection and quantitation limits were calculated using the formulas 3SD/b and 10SD/b, respectively. In these formulas, SD is the standard deviation of the signal without the analyte, and b is the slope of the calibration curve [47]. The determination parameters of iodate using the GC/CNPs-POAP electrode are reported in Table 1. A comparison between different methods of iodate analysis is also presented in Table 2. To explore the stability of the GC/CNPs-POAP electrode, consecutive CVs were measured. After 200 cycles, change in the cathodic peak currents was obtained to be <5%. To store the electrode, it was placed in water with keeping its electrochemical activity for at least 15 days.
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Fig. 8. A) Typical amperometric signals recorded using the GC/CNPs-POAP electrode toward the successive increments of iodate concentrations. B) A calibration plot based on the data in panel (A).
Table 2 A comparison between different methods for analysis of iodate. Method
Linear range
Flow injection analysis-spectrophotometry Flow injection analysis-spectrophotometry Amperometry Ion chromatography-UV detection Ionic chromatography-amperometric detection Ionic chromatography-conductivity detection Micro-flow-batch analysis-spectrophotometry HPLC-UV detection Capillary zone electrophoresis Raman spectroscopy Spectrophotometry Layered double hydroxide-modified electrode Catalase/carminic acid/multiwalled carbon nanotubes biosensor Flavin adenine dinucleotide-modified SiO2 /ZrO2 /C ceramic electrode Photometry Attapulgite/polyaniline/phosphomolybdic acid-modified electrode Silver nanoparticles-modified electrode Carbon nanoparticles-poly(ortho-aminophenol)-modified electrode
−1
0.57–171 mol L 0.57–17.1 mol L−1 5–500 mol L−1 0.57–57 mol L−1 114.3–228.6 mol L−1 5.7–571 mol L−1 0.06–57 mol L−1 0.029–28.6 mol L−1 – 0.004–0.74 mol L−1 – 1–2000 mol L−1 0.01–2.16 mmol L−1 0.05–2.42 mmol L−1 0.006–0.06 mol L−1 2.0–5200 mol L−1 0.1–0.8 mmol L−1 0.5–6.5 mmol L−1
Detection limit/mol L−1
Reference
0.11 0.1 1.4 0.26 – 0.08 0.02 0.06 0.03 0.01 0.17 0.25 – 1.46 0.001, 0.002 0.53 50 10
[48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58] [59] [60] [61] [62] [63] [64] This work
Table 3 Recovery results for iodate in a table salt using the GC/CNPs-POAP electrode. Sample NO 1 2 3 4
Iodate content −1
30.7 mg kg
Amount added/mg kg−1
Amount found/mg kg−1
Recovery%
Bias%
10.0 20.0 30.0 40.0
9.82 19.52 29.7 38.84
98.2 97.6 99.0 97.1
−1.8 −2.4 −1.0 −2.9
To inspect the GC/CNPs-POAP electrode selectivity during determination of iodate, voltammograms of different concentrations of ammonium ferrosulfate, potassium nitrate, zinc sulfate (reducible), aluminiom nitrate, calcium chloride (electroinactive), sodium iodide, sodium sulfite (oxidizable), and hydrogen peroxide (both reducible and oxidizable) were recorded. It aimed at investigating the interfering effects of both anions and cations. Based on the obtained results (Supplementary materials S1), no interfering effect was observed for all these species. Therefore, the GC/CNPs-
POAP electrode is able to determine iodate without interfering effects, and can be considered to be selective. In order to inspect the applicability of the GC/CNPs-POAP electrode for routine analysis, it was applied for iodate determination in a salt sample. 3.0 g of salt powder was dissolved in 30 mL water and the iodate content was found as 30.7 mg kg−1 . Then, recovery studies were performed on the sample by standard addition, and the results were presented in Table 3 confirming good agreement between the obtained values with the recommended contents.
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4. Conclusion A nanocomposite of carbon nanoparticles-poly(orthoaminophenol) was synthesized electrochemically and immobilized at the GC electrode surface with a high surface area and synergism properties. The synthesis route is extendable for the synthesis of carbonaceous materials/conducting polymers at surfaces. The nanocomposite showed an enhanced electrocatalytic property for electroreduction of iodate. Voltammetric and chronoamperometric measurements were successfully employed to obtain the kinetic parameters of iodate electroreduction through the low-valence of redox species of the polymer. The nanocomposite was employed as a nanosensor for iodate. Acknowledgments We would like to thank the Research Council of Shiraz University of Medical Sciences (12574) for supporting this research. We also thank the Iran National Science Foundation (Grant No. 96005985). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.snb.2017.10.030. References [1] Z. Xie, J. Zhao, Reverse flow injection spectrophotometric determination of iodate and iodide in table salt, Talanta 63 (2004) 339–343. [2] G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denney, Vogel’s Text Book for Quantitative Chemical Analysis, 5th ed., Longman Scientific & Technical Press, England, 1989. [3] Y. Li, Y. Zhou, H. Xian, L. Wang, J. Xuo, Electrochemical determination of nitrite and iodate based on Pt nanoparticles self-assembled on a chitosan modified glassy carbon electrode, Anal. Sci. 27 (2001) 1223–1228. [4] Y. Subhash, M.M. Godbole, Sushil Kumar Gupta, Manoj Jain, Uttam Singh, V. Pavithran Praveen, Raman Boddula, Anand Mishra, Ashutosh Shrivastava, Ashwani Tandon, Manish Ora, Amit Chowhan, Manoj Shukla, Narendra Yadav, Satish Babu, Manoj Dubey, P.K. Awasthi, Persistence of severe iodine deficiency disorders despite universal salt iodization in an iodine deficient area in northern India, Public Health Nutr. 13 (2010) 424. [5] M. Li, F. Ni, Y. Wang, S. Xu, D. Zhang, L. Wang, LDH modified electrode for sensitive and facile determination of iodate, Appl. Clay Sci. 46 (2009) 396–400. [6] L. Guadagnini, D. Tonelli, Carbon electrodes unmodified and decorated with silver nanoparticles for the determination of nitrite, nitrate and iodate, Sens. Actuators 188 B (2013) 806–814. [7] Z. Huang, Z. Zhu, Q. Subhani, W. Yan, W. Guo, Y. Zhu, Simultaneous determination of iodide and iodate in povidone iodine solution by ion chromatography with homemade and exchange capacity controllable columns and column-switching technique, J.Chromatogr 1251A (2012) 154–159. [8] M.B. Lima, I.S. Barreto, S.I.E. Andrade, L.F. Almeida, M.C.U. Araújo, A micro-flow-batch analyzer with solenoid micro-pumps for the photometric determination of iodate in table salt, Talanta 100 (2012) 308–312. [9] C.-R. Tang, Z.-H. Su, B.-G. Lin, H.-W. Huang, Y.-L. Zeng, S. Li, H. Huang, Y.-J. Wang, C.-X. Li, G.-L. Shen, R.-Q. Yu, A novel method for iodate determination using cadmium sulfide quantum dots as fluorescence probes, Anal. Chim. Acta 678 (2010) 203–207. [10] K. Reddy-Noone, A. Jain, K.K. Verma, Liquid-phase microextraction-gas chromatography-mass spectrometry for the determination of bromate, iodate, bromide and iodide in high-chloride matrix, J. Chromatogr. 1148A (2007) 145–151. [11] A.-H. Liang, Z.-L. Jiang, B.-M. Zhang, Q.-Y. Liu, J. Lan, X. Lu, A new resonance scattering spectral method for the determination of trace amounts of iodate with rhodamine 6G, Anal. Chim. Acta 530 (2005) 131–134. [12] H. Nalwa (Ed.), Encyclopedia of Nanoscience and Nanotechnology, American Scientific Publishers, USA, 2017 (25-Volume Set). [13] H. Heli, Electrochemical studies of vitamin k3 and its interaction with human serum albumin using a carbon nanoparticles-modified electrode, J. Nanomater. Mol. Nanotechnol. 2 (2013) 7. [14] M. Sedigh-Ardekani, M.A. Sahmeddini, N. Sattarahmady, H. Mirkhani, Lactic acidosis treatment by nanomole level of spermidine in an animal model, Regul. Toxicol. Pharmacol. 70 (2014) 514–518. [15] E. Sharifi, N. Sattarahmady, M. Habibi-Rezaei, M. Farhadi, N. Sheibani, F. Ahmad, A.A. Moosavi-Movahedi, Inhibitory effects beta-cyclodextrin and trehalose on nanofibril and age formation during glycation of human serum albumin, Protein Pept. Lett. 16 (2009) 653–659.
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Biographies J. Pishahang received his MSc degree in Analytical Chemistry from Islamic Azad University, Firouzabad, Iran, and is currently a PhD student. His research interest is focused on the design of novel electrochemical sensors. H. Barzegar Amiri his MSc degree in Analytical Chemistry from Ilam University, Ilam, Iran. His research interest is focused on the design of novel electrochemical sensors. H. Heli received his PhD in electrochemistry from K. N. Toosi University of Technology, Tehran, Iran. He currently is an assistant professor of chemistry at Shiraz University of Medical Sciences, Shiraz, Iran. His major interests are synthesis of new nanostructured and targeted materials and their applications in electrocatalysis, bioelectrocatalysis, and electrochemical and medical nano-devices.
Please cite this article in press as: J. Pishahang, et al., Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate, Sens. Actuators B: Chem. (2017), https://doi.org/10.1016/j.snb.2017.10.030
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Research paper
Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate J. Pishahang a,b , H.Barzegar Amiri a,c , H. Heli d,∗ a
Central Laboratory of Jam Petrochemical Complex, South Pars Special Economy and Energy Zone, Assaluyeh, Iran Department of Chemistry, Lamerd Branch, Islamic Azad University, Lamerd, Iran Department of Chemistry, Faculty of Science, Payame Noor Univercity, Assaluyeh, Iran d Nanomedicine and Nanobiology Research Center, Shiraz University of Medical Sciences, Shiraz, Iran b c
a r t i c l e
i n f o
Article history: Received 15 June 2017 Received in revised form 26 September 2017 Accepted 4 October 2017 Available online xxx Keywords: Poly(ortho-aminophenol) Carbon dots Electrocatalysis Electroanalysis Composite
a b s t r a c t A nanocomposite was fabricated comprising nanoparticles of carbon and poly(ortho-aminophenol) by electropolymerization technique. The nanocomposite was characterized by field emission-scanning electron microscopy. The kinetics of charge transfer between the nanocomposite and the adjacent electrolyte was measured using cyclic voltammetry (CV). The kinetics of the electroreduction of iodate on the nanocomposite surface was then evaluated by CV and chronoamperometry. Iodate was electroreduced by low-valence redox species of poly(ortho-aminophenol) in an electrocatalytic manner. The nanocomposite was applied as an amperometric sensor for iodate, and an amperometry route was proposed for determination of iodate. Sensitivity and detection limit of the amperometry method were attained as 242.6 mA L mol−1 cm−2 and 0.01 mmol L−1 , respectively. © 2017 Elsevier B.V. All rights reserved.
1. Introduction Iodine has a high concern on health and environmental protection. It has important effects on the cell growth and brain function, and its deficiency can cause mental retardation, brain damage and endemic goiter [1]. Addition of iodine in the form of iodate to the table salt is one of the successful strategies used to prevent iodine deficiency disorders. However, excess iodate can produce goiter, hypothyroidism and hyperthyroidism. On the other side, iodate is the major oxidant toward many organic and inorganic compounds [2]. Potassium iodate is used as a reference material in voltammetric analyses for direct or indirect titrations [2]. Therefore, determination of iodate is important in human health and food industries [1,3,4]. There have been some methods for the determination of iodate, including amperometry [5], voltammetry [6], ion chromatography [7], photometry [8], fluorimetry [9], liquid-phase microextraction-gas chromatography-mass spectrometry [10] and resonance scattering spectral method [11]. Although there are advantages for these methods, some drawbacks such as timeconsuming, low sensitivity, susceptibility to interference and
∗ Corresponding author. E-mail addresses: [email protected], [email protected] (H. Heli).
difficulties of automation for some of these methods are still present. On the other hand, electrochemical methods have such advantages as simplicity, inexpensiveness, and sensitivity. Recent developments in nanotechnology and specific properties of nanostructured materials have provided usage of these materials in different branches of science and technology [12–22]. Nanostructured materials have been extensively employed to fabricate modified electrodes, and electrochemical sensors and biosensors [17–19,23]. Sensing tools and devices fabricated by these materials have enhanced conductivity, electron transfer rate, charge transport rate and catalytic activity, with alterations in absorption, adsorption, chemical reactivity and molecular interactions leading to enhanced sensitivity, selectivity and efficiency [17–19,23]. Up to now, different nanocomposites of carbonaceous materials/conducting polymers such as graphene-poly(orthoaminophenol) (POAP) [24,25], graphene-polyluminol graphene/poly(o-phenylenediamine) [27], carbon [26], fibers/polypyrrole [28] and polyaniline grafted on carbon nanotube-embedded carbon nanofibers [29] have been synthesized. Carbonaceous materials employed for synthesis of the nanocomposites have been carbon black, carbon fibers, carbon nanotubes, graphene, carbon nanocoil and carbon nanospheres [30–33]. These composites have been synthesized using techniques of electropolymerization [24–27,34] or chemical oxidation of a vapor [28] of a monomer on a pre-deposited carbon nanos-
https://doi.org/10.1016/j.snb.2017.10.030 0925-4005/© 2017 Elsevier B.V. All rights reserved.
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Fig 1. FE-SEM (A-D) and TEM (E) images of the synthesized CNPs.
tructures surface, conducting polymer grafting by plasma [29], and chemical polymerization of a monomer on the carbon nanostructure surfaces [31,35,36]. Some of these nanocomposites
represented synergetic effects arising from differences in the structure and properties of conducting polymers arising from the carbon nanostructures [24–27,32,35]. The nanocomposites
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Fig. 2. FE-SEM images of POAP.
have had applications in fabrication of sensors and biosensors, and anti-corrosion materials, supercapacitors, drug delivery, and catalysis [24–36]. In the present study, a nanocomposite of carbon nanoparticles (CNPs) with POAP was synthesized, characterized and then applied for the electroanalysis of iodate.
two min to complete the dehydration of glucose. The final color of the solution turned black, indicating the formation of carbon nanoparticles. After cooling the solution to room temperature, the mixture was added dropwise to 100 mL cold water with vigorous stirring. A black precipitate was obtained and separated by centrifugation. CNPs were washed several times with water and then dried at room temperature.
2. Experimental section 2.1. Materials All chemicals were of analytical grade from Merck or Scharlau and were used without further purification. All solutions were prepared with redistilled water. 2.2. Synthesis of CNPs CNPs was synthesized based on the method reported elsewhere [37]. Briefly, 500 mg of D-glucose was suspended in 20 mL concentrated sulfuric acid with constant stirring until the color of the solution turned faint yellow. The mixture was then digested for 30 min and after that, the solution was heated to 140–150 ◦ C for
2.3. Preparation of the nanocomposite The nanocomposite of CNPs-POAP was synthesized on the surface of a glassy carbon (GC) electrode (3 mm of diameter). Firstly, the GC electrode was polished with alumina powder on a polishing pad and rinsed thoroughly with redistilled water. It was then sonicated in a 1:1 water/acetone mixture for ∼5 min. This GC electrode was placed in the electrochemical cell and potential between −0.5 and +1.2 V in a regime of cyclic voltammetry (CV) for 10 cycles and a potential scan rate of 50 mV s−1 in 1.0 mol L−1 H2 SO4 was applied. 10 mg CNPs were dispersed in 1.0 mL water by sonication for 10 min. The GC electrode was coated by casting 10 L of the CNPs suspension and dried under an infrared lamp to form the CNPs adsorbed GC (GC/CNPs) electrode. The GC/CNPs electrode
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Fig. 3. FE-SEM images of CNPs-POAP.
was transferred to a 0.1 mol L−1 ortho-aminophenol + 1.0 mol L−1 sulfuric acid solution and potential in a range of −0.1–1.0 V in a regime of CV for 100 cycles with a potential scan rate of 50 mV s−1 was applied to prepare the CNPs-POAP nanocomposite on the GC surface (GC/CNPs-POAP electrode). Following these procedures, ortho-aminophenol was electropolymerized and formed a nanocomposite with CNPs.
2.4. Apparatus Electrochemical measurements were performed in a threeelectrode cell powered by a -Autolab potentiostat/galvanostat, type III, FRA2 (The Netherlands). The system was run by a PC through GPES 4.9 software. A Pt wire and an Ag/AgCl, 3 mol L−1 KCl (from Metrohm) were used as the counter and reference electrodes, respectively. The supporting electrolyte was 1.0 mol L−1 H2 SO4 . Field emission-scanning electron microscopy (FE-SEM) was performed by a MIRA3 TESCAN-XMU (Czech Republic) microscope. Transmission electron microscopy (TEM) was done using a Zeiss-EM10C transmission electron microscope (Germany) with an operating voltage of 80 kV on a carbon formvar-coated copper grid.
3. Results and discussion In order to study the size and surface morphology, FE-SEM images from CNPs, POAP and CNPs-POAP at different magnifications, and a TEM image from CNPs were recorded and are displayed in Figs. 1–3. Microscopic images of CNPs (Fig. 1) show agglomerated particles with a mean diameter of 8.6 ± 1.7 nm. The size of CNPs is lower than those synthesized using ascorbic acid as a precursor [38], and can be considered as carbon quantum dots. Microscopic images of POAP deposited on the GC surface (Fig. 2) show a uniform layer with a vesicles-like morphology. FE-SEM images of CNPsPOAP (Fig. 3) represent a composite comprised CNPs covered by a POAP layer. There are changes in the morphology of POAP upon coating on CNPs surface where POAP do not have vesicles-like morphology. Apparently, CNPs caused to changes in the morphology of POAP due to changes in the electropolymerization mechanisms of ortho-aminophenol on the surface of CNPs, compared to the GC surface. A cyclic voltammogram of a 1.0 mol L−1 H2 SO4 solution recorded using GC/CNPs-POAP electrode is presented in Fig. 4A. One couple of peaks having a mid-peak potential equal to 121 mV is observed in the voltammogram with a quasi-reversible kinetics. The voltammogram pattern is similar to those reported elsewhere [24,25,39].
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Fig. 4. A) CVs of GC/CNPs-POAP electrode recorded in a 1.0 mol L−1 H2 SO4 solution with a potential scan rate of 50 mV s−1 . B) CVs of GC/CNPs-POAP electrode recorded in a 1.0 mol L−1 H2 SO4 solution at different potential scan rates of 5, 7.5, 10, 15, 20, 25, 30, 40, 50, 60, 75, 100, 125, 150, 175, 200, 250, 275, 300, 350, 375, 400, 450, 500, 550, 600, 750, 1000, 1250, 1500, 1750 and 2000 mV s−1 . C) Dependency of the anodic and cathodic peak currents on the square root of the potential scan rate. D) Dependency of the anodic and cathodic peak potentials on the natural logarithm of the potential scan rate.
Cyclic voltammograms of a 1.0 mol L−1 H2 SO4 solution recorded using the GC/CNPs-POAP electrode at different values of potential scan rates of 5–2000 mV s−1 are presented in Fig. 4B. Well-defined peaks were appeared in the voltammograms with a peak potential separation of ∼103 mV at the potential scan rate of 5 mV s−1 . This peak separation is larger than the theoretical value of zero for the immobilized redox species and it increases upon potential scan rate increment. Therefore, there was a limitation in the kinetics of charge transfer process in the immobilized redox species. This can be related to interactions of redox species with electrolyte ions, interactions between redox sites, diffusion-migration coupling of ion insertion/deinsertion into the bulk of the nanocomposite, and
non-equivalency of redox sites. For the voltammogram recorded at 5 mV s−1 , the value of full width at half height of anodic peak is ∼98 mV. This is larger than that for non-interacting immobilized redox species with single electron exchange, equals to 90 mV [40]. Therefore, repulsive interactions were dominated between the immobilized redox species in the nanocomposite [41,42]. In the voltammograms shown in Fig. 4B, both the cathodic and anodic peak currents linearly change with the square root of the potential scan rate (Fig. 4C). The results imply that the diffusion of electrolyte ions into/from the nanocomposite was dominated for the redox reaction [43].
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Fig. 5. CVs recorded using GC, GC/CNPs, GC/POAP and GC/CNPs-POAP electrodes in the absence and presence (-Io) of 2.2 mmol L−1 iodate. The potential scan rate was 50 mV s−1 .
To measure the kinetic parameters for the redox reaction occurring in the nanocomposite, Laviron’s equations were employed [44] as follows: Ep,a = E0 + Gln[(1-␣s )/K]
(1)
Ep,c = E0 + Hln[␣s /K]
(2)
lnks = ␣s ln(1-␣s ) + (1-␣s )ln␣s −ln(RT/nF)−˛s (1-˛s )nFEp /RT (3) where G = RT/(1-˛s )nF
(4)
H = RT/˛s nF
(5)
K = (RT/F)(ks /n)
(6)
ical reduction of iodate by the low-valence sites of POAP occured (EC’ mechanism): Poly(ox) + ne → Poly(red) ←−
(7)
Poly(red) + IO3 − → Poly(ox) + I− ←−
(8)
To measure the kinetic parameters of the reduction reaction of iodate, CV and chronoamperometry were employed. Voltammograms of the GC/CNPs-POAP electrode measured without and with 2.0 mmol L−1 iodate at different potential scan rates are shown in Fig. 6A. The cathodic peak potential depend on the logarithm of the potential scan rate, as shown in Fig. 6B. Using this linear plot and the equation [45]: Ep,c,Io = (RT/2˛Io F)ln + constant
n is the number of electrons, Ep,c , Ep,a and E0 are cathodic and anodic peaks, and formal potentials, ␣s is the electron transfer coefficient, ks is the rate constant, is the potential scan rate and Ep is the peak potential separation. Changes in the cathodic and anodic peak potentials with potential scan rate are presented in Fig. 4D. For ≥750 mV s−1 , changes of the peak potential with the logarithm of the potential scan rate are linear and using these lines, the values of ␣s and ks are obtained as 0.55 and 7.29 s−1 , respectively. In Fig. 5, voltammograms measured using GC, GC/CNPs, GC/POAP and GC/CNPs-POAP electrodes without and with 2.2 mmol L−1 iodate are presented. Using GC and GC/CNPs electrodes, negligible anodic currents related to a slow-rate electroreduction of iodate are observed in the voltammograms, while, using GC/POAP and GC/CNPs-POAP electrodes, iodate was reduced wherein the cathodic currents increase and simultaneously the anodic currents decrease. Therefore, it can be inferred that iodate was electroreduced on these two electrode surfaces via a surfacemediated electron transfer process with a higher cathodic current passing through the GC/CNPs-POAP electrode, compared to the GC/POAP electrode. After the redox transition of POAP, the chem-
(9)
where Ep,c,Io and ␣Io are the cathodic peak potential and the electron transfer coefficient for the electroreduction of iodate, respectively, ␣Io is obtained as 0.51. The cathodic peak currents in Fig. 6A depend on the square root of the potential scan rate for > 200 mV s−1 , as shown in Fig. 6C. This linear dependency indicates that the electroreduction process of iodate was diffusion controlled in the bulk of the electrolyte. Also, using the equation [46]: Ip,c,Io = 2.99 × 105 ␣Io 1/2 n3/2 A CIo DIo 1/2 1/2
(10)
where A, Ip,c,Io , DIo , CIo are the electrode surface area, the cathodic peak current, the iodate diffusion coefficient and concentration, DIo is obtained as 4.09 × 10−6 cm2 s−1 . Chronoamperograms recorded using the GC/CNPs-POAP electrode without and with different concentrations of iodate are shown in Fig. 7A. The current depend on the square root of time in a Cottrellian manner and is shown in Fig. 7B. It further confirms that the iodate electroreduction process was controlled by diffusion. Using the Cottrell’s equation [46]: IIo = nFACIo DIo 1/2 /(t)1/2
(11)
where IIo is the transient current and t is time, the value of DIo is obtained as 4.03 × 10−6 cm2 s−1 . This value is in closed agreement
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Fig. 7. A) Chronoamperograms recorded using the GC/CNPs-POAP electrode in the absence (a) and presence of iodate of 0.38 (b), 0.76 (c), 1.15 (d), 1.52 (e), 2.28 (f), 3.03 (g), 3.8 (h), 4.5 (i), and 5.6 mmol L−1 (j). B) Dependency of the transient current on the square root of time for curve (j) in panel (A). C) Dependency of Icat /Id on t1/2 for curve (j) in panel (A).
Table 1 Analytical parameters for the amperometric determination of iodate using the nanocomposite. Fig. 6. A) CVs of the GC/CNPs-POAP electrode recorded in the presence of 2.0 mmol L−1 iodate at different potential scan rates of 5, 7.5, 10, 15, 20, 25, 30, 40, 50, 60, 75, 100, 125, 150, 175, 200, 250, 275, 300, 350, 375, 400, 450, 500, 550, 600, 750, 1000, 1250, 1500, 1750 and 2000 mV s−1 . B) Dependency of the cathodic peak potential on the natural logarithm of the potential scan rate. C) Dependency of the cathodic peak current in the voltammograms of panel (A) on the square root of the potential scan rate for > 200 mV s−1 .
with that found by CV. The catalytic rate constant of the iodate electroreduction is obtained using the equation [46]: Icat /Id = ␥1/2 [1/2 erf(␥1/2 ) + exp(-␥)/␥1/2 ]
(12)
where Id and Icat and are the currents in the absence and presence of iodate, respectively. In addition, ␥ = kcat CIo is the argument of the error function, and kcat is the catalytic rate constant. For ␥ > 1.5, erf (␥1/2 )∼ =1, and equation (12) becomes: Icat /Id = ␥1/2 1/2 = 1/2 (kcat CIo t)1/2
(13)
The dependency of Icat /Id on t1/2 is presented in Fig. 7C, and using the plot, kcat is obtained as 3.53 × 104 cm3 mol−1 s−1 . To propose a new method for determination of iodate, the nanocomposite was evaluated for amperometric determination. Typical amperometric signals recorded using the GC/CNPs-POAP electrode toward iodate concentration is shown in Fig. 8A. Based on the signals, a calibration curve was derived and is presented in
Linear range/mmol L−1 Sensitivity (Slope)/mA L mol−1 cm−2 Intercept/A cm−2 R2 Slope standard error (P = 0.005) Intercept standard error (P = 0.005) Detection limit/mmol L−1 Quantitation limit/mmol L−1 RSD%a Bias%a a
0.5–6.5 242.6 −62.6 0.9986 0.246 0.977 0.01 0.03 4.01 2.40
The value is for 2.5 mmol L−1 iodate.
Fig. 8B. The detection and quantitation limits were calculated using the formulas 3SD/b and 10SD/b, respectively. In these formulas, SD is the standard deviation of the signal without the analyte, and b is the slope of the calibration curve [47]. The determination parameters of iodate using the GC/CNPs-POAP electrode are reported in Table 1. A comparison between different methods of iodate analysis is also presented in Table 2. To explore the stability of the GC/CNPs-POAP electrode, consecutive CVs were measured. After 200 cycles, change in the cathodic peak currents was obtained to be <5%. To store the electrode, it was placed in water with keeping its electrochemical activity for at least 15 days.
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Fig. 8. A) Typical amperometric signals recorded using the GC/CNPs-POAP electrode toward the successive increments of iodate concentrations. B) A calibration plot based on the data in panel (A).
Table 2 A comparison between different methods for analysis of iodate. Method
Linear range
Flow injection analysis-spectrophotometry Flow injection analysis-spectrophotometry Amperometry Ion chromatography-UV detection Ionic chromatography-amperometric detection Ionic chromatography-conductivity detection Micro-flow-batch analysis-spectrophotometry HPLC-UV detection Capillary zone electrophoresis Raman spectroscopy Spectrophotometry Layered double hydroxide-modified electrode Catalase/carminic acid/multiwalled carbon nanotubes biosensor Flavin adenine dinucleotide-modified SiO2 /ZrO2 /C ceramic electrode Photometry Attapulgite/polyaniline/phosphomolybdic acid-modified electrode Silver nanoparticles-modified electrode Carbon nanoparticles-poly(ortho-aminophenol)-modified electrode
−1
0.57–171 mol L 0.57–17.1 mol L−1 5–500 mol L−1 0.57–57 mol L−1 114.3–228.6 mol L−1 5.7–571 mol L−1 0.06–57 mol L−1 0.029–28.6 mol L−1 – 0.004–0.74 mol L−1 – 1–2000 mol L−1 0.01–2.16 mmol L−1 0.05–2.42 mmol L−1 0.006–0.06 mol L−1 2.0–5200 mol L−1 0.1–0.8 mmol L−1 0.5–6.5 mmol L−1
Detection limit/mol L−1
Reference
0.11 0.1 1.4 0.26 – 0.08 0.02 0.06 0.03 0.01 0.17 0.25 – 1.46 0.001, 0.002 0.53 50 10
[48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58] [59] [60] [61] [62] [63] [64] This work
Table 3 Recovery results for iodate in a table salt using the GC/CNPs-POAP electrode. Sample NO 1 2 3 4
Iodate content −1
30.7 mg kg
Amount added/mg kg−1
Amount found/mg kg−1
Recovery%
Bias%
10.0 20.0 30.0 40.0
9.82 19.52 29.7 38.84
98.2 97.6 99.0 97.1
−1.8 −2.4 −1.0 −2.9
To inspect the GC/CNPs-POAP electrode selectivity during determination of iodate, voltammograms of different concentrations of ammonium ferrosulfate, potassium nitrate, zinc sulfate (reducible), aluminiom nitrate, calcium chloride (electroinactive), sodium iodide, sodium sulfite (oxidizable), and hydrogen peroxide (both reducible and oxidizable) were recorded. It aimed at investigating the interfering effects of both anions and cations. Based on the obtained results (Supplementary materials S1), no interfering effect was observed for all these species. Therefore, the GC/CNPs-
POAP electrode is able to determine iodate without interfering effects, and can be considered to be selective. In order to inspect the applicability of the GC/CNPs-POAP electrode for routine analysis, it was applied for iodate determination in a salt sample. 3.0 g of salt powder was dissolved in 30 mL water and the iodate content was found as 30.7 mg kg−1 . Then, recovery studies were performed on the sample by standard addition, and the results were presented in Table 3 confirming good agreement between the obtained values with the recommended contents.
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4. Conclusion A nanocomposite of carbon nanoparticles-poly(orthoaminophenol) was synthesized electrochemically and immobilized at the GC electrode surface with a high surface area and synergism properties. The synthesis route is extendable for the synthesis of carbonaceous materials/conducting polymers at surfaces. The nanocomposite showed an enhanced electrocatalytic property for electroreduction of iodate. Voltammetric and chronoamperometric measurements were successfully employed to obtain the kinetic parameters of iodate electroreduction through the low-valence of redox species of the polymer. The nanocomposite was employed as a nanosensor for iodate. Acknowledgments We would like to thank the Research Council of Shiraz University of Medical Sciences (12574) for supporting this research. We also thank the Iran National Science Foundation (Grant No. 96005985). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.snb.2017.10.030. References [1] Z. Xie, J. Zhao, Reverse flow injection spectrophotometric determination of iodate and iodide in table salt, Talanta 63 (2004) 339–343. [2] G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denney, Vogel’s Text Book for Quantitative Chemical Analysis, 5th ed., Longman Scientific & Technical Press, England, 1989. [3] Y. Li, Y. Zhou, H. Xian, L. Wang, J. Xuo, Electrochemical determination of nitrite and iodate based on Pt nanoparticles self-assembled on a chitosan modified glassy carbon electrode, Anal. Sci. 27 (2001) 1223–1228. [4] Y. Subhash, M.M. Godbole, Sushil Kumar Gupta, Manoj Jain, Uttam Singh, V. Pavithran Praveen, Raman Boddula, Anand Mishra, Ashutosh Shrivastava, Ashwani Tandon, Manish Ora, Amit Chowhan, Manoj Shukla, Narendra Yadav, Satish Babu, Manoj Dubey, P.K. Awasthi, Persistence of severe iodine deficiency disorders despite universal salt iodization in an iodine deficient area in northern India, Public Health Nutr. 13 (2010) 424. [5] M. Li, F. Ni, Y. Wang, S. Xu, D. Zhang, L. Wang, LDH modified electrode for sensitive and facile determination of iodate, Appl. Clay Sci. 46 (2009) 396–400. [6] L. Guadagnini, D. Tonelli, Carbon electrodes unmodified and decorated with silver nanoparticles for the determination of nitrite, nitrate and iodate, Sens. Actuators 188 B (2013) 806–814. [7] Z. Huang, Z. Zhu, Q. Subhani, W. Yan, W. Guo, Y. Zhu, Simultaneous determination of iodide and iodate in povidone iodine solution by ion chromatography with homemade and exchange capacity controllable columns and column-switching technique, J.Chromatogr 1251A (2012) 154–159. [8] M.B. Lima, I.S. Barreto, S.I.E. Andrade, L.F. Almeida, M.C.U. Araújo, A micro-flow-batch analyzer with solenoid micro-pumps for the photometric determination of iodate in table salt, Talanta 100 (2012) 308–312. [9] C.-R. Tang, Z.-H. Su, B.-G. Lin, H.-W. Huang, Y.-L. Zeng, S. Li, H. Huang, Y.-J. Wang, C.-X. Li, G.-L. Shen, R.-Q. Yu, A novel method for iodate determination using cadmium sulfide quantum dots as fluorescence probes, Anal. Chim. Acta 678 (2010) 203–207. [10] K. Reddy-Noone, A. Jain, K.K. Verma, Liquid-phase microextraction-gas chromatography-mass spectrometry for the determination of bromate, iodate, bromide and iodide in high-chloride matrix, J. Chromatogr. 1148A (2007) 145–151. [11] A.-H. Liang, Z.-L. Jiang, B.-M. Zhang, Q.-Y. Liu, J. Lan, X. Lu, A new resonance scattering spectral method for the determination of trace amounts of iodate with rhodamine 6G, Anal. Chim. Acta 530 (2005) 131–134. [12] H. Nalwa (Ed.), Encyclopedia of Nanoscience and Nanotechnology, American Scientific Publishers, USA, 2017 (25-Volume Set). [13] H. Heli, Electrochemical studies of vitamin k3 and its interaction with human serum albumin using a carbon nanoparticles-modified electrode, J. Nanomater. Mol. Nanotechnol. 2 (2013) 7. [14] M. Sedigh-Ardekani, M.A. Sahmeddini, N. Sattarahmady, H. Mirkhani, Lactic acidosis treatment by nanomole level of spermidine in an animal model, Regul. Toxicol. Pharmacol. 70 (2014) 514–518. [15] E. Sharifi, N. Sattarahmady, M. Habibi-Rezaei, M. Farhadi, N. Sheibani, F. Ahmad, A.A. Moosavi-Movahedi, Inhibitory effects beta-cyclodextrin and trehalose on nanofibril and age formation during glycation of human serum albumin, Protein Pept. Lett. 16 (2009) 653–659.
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Biographies J. Pishahang received his MSc degree in Analytical Chemistry from Islamic Azad University, Firouzabad, Iran, and is currently a PhD student. His research interest is focused on the design of novel electrochemical sensors. H. Barzegar Amiri his MSc degree in Analytical Chemistry from Ilam University, Ilam, Iran. His research interest is focused on the design of novel electrochemical sensors. H. Heli received his PhD in electrochemistry from K. N. Toosi University of Technology, Tehran, Iran. He currently is an assistant professor of chemistry at Shiraz University of Medical Sciences, Shiraz, Iran. His major interests are synthesis of new nanostructured and targeted materials and their applications in electrocatalysis, bioelectrocatalysis, and electrochemical and medical nano-devices.
Please cite this article in press as: J. Pishahang, et al., Synthesis of carbon nanoparticles-poly(ortho-aminophenol) nanocomposite and its application for electroanalysis of iodate, Sens. Actuators B: Chem. (2017), https://doi.org/10.1016/j.snb.2017.10.030