全部 标题 作者
关键词 摘要


Cyclic Voltammetry and Impedance Spectroscopy Behavior Studies of Polyterthiophene Modified Electrode

DOI: 10.4061/2011/670513

Full-Text   Cite this paper   Add to My Lib

Abstract:

We present in this work a study of the electrochemical behaviour of terthiophene and its corresponding polymer, which is obtained electrochemically as a film by cyclic voltammetry (CV) on platinum electrode. The analysis focuses essentially on the effect of two solvents acetonitrile and dichloromethane on the electrochemical behaviour of the obtained polymer. The electrochemical behavior of this material was investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The voltammograms show that the film of polyterthiophene can oxide and reduce in two solutions; in acetonitrile, the oxidation current intensity is more important than in dichloromethane. The impedance plots show the semicircle which is characteristic of charge-transfer resistance at the electrode/polymer interface at high frequency and the diffusion process at low frequency. 1. Introduction As other conjugated conducting polymers, polythiophene and its oligomers can be polymerized from their monomers in solutions by electrochemical methods. The electrochemical synthesis is advantageous method: polymers are formed in the doped state; films generally possess interesting electrochemical and good semiconductor properties [1] and relatively good stability in air for both the neutral and oxidised states [2–7]. The mechanism of the electropolymerisation of conducting polymers and polyheterocycles occurred by the coupling via α-α bonding of monomer radical cation after its oxidation at the electrode, and the protons are removed from dihydrodication leading to neutral species [8–10]. As the dimer is more easily oxidized than the monomer, it is immediately oxidized. The chain elongation occurs by the addition of new monomer radical cation leading to polymerization and forms the insoluble polymeric species, which subsequently deposits onto the electrode [11]. Conducting polymer-modified electrodes have been widely investigated because of their potential application in areas such as electrocatalysis [12, 13], sensors [14, 15], corrosion [16–18], batteries [19, 20], electronic displays, and devices [21–24]. In our previous work [25], we have studied the role of P3T in corrosion of stainless steel; the results were important and show effectively that the film of P3T will decrease the corrosion rate. In this paper, we are interested in performing an electrochemical characterisation of P3T films electrochemically synthesized, in two organic solvents: acetonitrile (CH3CN) and dichloromethane (CH2Cl2), at platinum substrates. We want to show how the medium of the analysis is

References

[1]  M. Biserni, A. Marinangeli, and M. Mastragostino, “Doiped polydithienothiophene: a new cathode-active material,” Journal of the Electrochemical Society, vol. 132, no. 7, pp. 1597–1601, 1985.
[2]  G. Schopf and G. Kossmehl, Advances in Polymer Science, vol. 34, p. 1, 1997.
[3]  C. A. Cutler, A. K. Burrell, D. L. Officer, C. O. Too, and G. G. Wallace, “Effect of electron withdrawing or donating substituents on the photovoltaic performance of polythiophenes,” Synthetic Metals, vol. 128, no. 1, pp. 35–42, 2002.
[4]  T. A. Skotheim, R. L. Elsenbaumer, and J. R. Reynolds, Handbook of Conducting Polymers, Marcel Dekker, New York, NY, USA, 1997.
[5]  J. Roncali, “Conjugated poly(thiophenes): synthesis, functionalization, and applications,” Chemical Reviews, vol. 92, no. 4, pp. 711–738, 1992.
[6]  R. D. McCullough, “The chemistry of conducting polythiophenes,” Advanced Materials, vol. 10, no. 2, pp. 93–116, 1998.
[7]  L. B. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, and J. R. Reynolds, “Poly(3,4-ethylenedioxythiophene) and its derivatives: past, present, and future,” Advanced Materials, vol. 12, no. 7, pp. 481–494, 2000.
[8]  E. M. Genies, G. Bidan, and A. F. Diaz, “Spectroelectrochemical study of polypyrrole films,” Journal of Electroanalytical Chemistry, vol. 149, no. 1-2, pp. 101–113, 1983.
[9]  T. A. Skotheim, Handbook of Conducting Polymers, Marcel Dekker, New York, NY, USA, 1986.
[10]  Y. Wei, C.-C. Chan, J. Tian, G.-W. Jang, and K. F. Hsueh, “Electrochemical polymerization of thiophenes in the presence of bithiophene or terthiophene: kinetics and mechanism of the polymerization,” Chemistry of Materials, vol. 3, no. 5, pp. 888–897, 1991.
[11]  S. N. Hoier and S.-M. Park, “Electrochemistry of conductive polymers xiv. In suit spectroelectrochemical and kinetic studies on poly(3-methylthiophene) growth,” Journal of the Electrochemical Society, vol. 140, no. 9, pp. 2454–2463, 1993.
[12]  M. Trueba, S. P. Trasatti, and S. Trasatti, “Electrocatalytic activity for hydrogen evolution of polypyrrole films modified with noble metal particles,” Materials Chemistry and Physics, vol. 98, no. 1, pp. 165–171, 2006.
[13]  V. Selvaraj, M. Alagar, and I. Hamerton, “Nanocatalysts impregnated polythiophene electrodes for the electrooxidation of formic acid,” Applied Catalysis B, vol. 73, no. 1-2, pp. 172–179, 2007.
[14]  M. Boopathi, M.-S. Won, and Y.-B. Shim, “A sensor for acetaminophen in a blood medium using a Cu(II)-conducting polymer complex modified electrode,” Analytica Chimica Acta, vol. 512, no. 2, pp. 191–197, 2004.
[15]  K. B. Crawford, M. B. Goldfinger, and T. M. Swager, “Na+ specific emission changes in an ionophoric conjugated polymer,” Journal of the American Chemical Society, vol. 120, no. 21, pp. 5187–5192, 1998.
[16]  D. W. DeBerry, “Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive coating,” Journal of the Electrochemical Society, vol. 132, no. 5, pp. 1022–1026, 1985.
[17]  H. Hammache, L. Makhloufi, and B. Saidani, “Corrosion protection of iron by polypyrrole modified by copper using the cementation process,” Corrosion Science, vol. 45, no. 9, pp. 2031–2042, 2003.
[18]  R. Hasanov and S. Bilgi?, “Monolayer and bilayer conducting polymer coatings for corrosion protection of steel in 1 M H2SO4 solution,” Progress in Organic Coatings, vol. 64, no. 4, pp. 435–445, 2009.
[19]  C. Y. Wang, G. Tsekouras, P. Wagner et al., “Functionalised polyterthiophenes as anode materials in polymer/polymer batteries,” Synthetic Metals, vol. 160, no. 1-2, pp. 76–82, 2010.
[20]  P. Novák, K. Müller, K. S. V. Santhanam, and O. Haas, “Electrochemically active polymers for rechargeable batteries,” Chemical Reviews, vol. 97, no. 1, pp. 207–281, 1997.
[21]  B. Yin, C. Jiang, Y. Wang, M. La, P. Liu, and W. Deng, “Synthesis and electrochromic properties of oligothiophene derivatives,” Synthetic Metals, vol. 160, no. 5-6, pp. 432–435, 2010.
[22]  C. M. Casado, I. Cuadrado, M. Morán, B. Alonso, B. González, and J. Losada, “Redox-active ferrocenyl dendrimers and polymers in solution and immobilised on electrode surfaces,” Coordination Chemistry Reviews, vol. 185-186, pp. 53–79, 1999.
[23]  L. M. Goldenberg, M. R. Bryce, and M. C. Petty, “Chemosensor devices: voltammetric molecular recognition at solid interfaces,” Journal of Materials Chemistry, vol. 9, no. 9, pp. 1957–1974, 1999.
[24]  J. Chen, A. K. Burrell, G. E. Collis et al., “Preparation, characterisation and biosensor application of conducting polymers based on ferrocene substituted thiophene and terthiophene,” Electrochimica Acta, vol. 47, no. 17, pp. 2715–2724, 2002.
[25]  N. Maouche and B. Nessark, “Electrochemical behavior of polyterthiophene-coated types 304 and 316 stainless steels and its corrosion performance,” Corrosion, vol. 64, no. 4, pp. 315–324, 2008.
[26]  B. Sari, M. Talu, F. Yildirim, and E. K. Balci, “Synthesis and characterization of polyurethane/polythiophene conducting copolymer by electrochemical method,” Applied Surface Science, vol. 205, no. 1–4, pp. 27–38, 2002.
[27]  S. Asavapiriyanont, G. K. Chandler, G. A. Gunawardena, and D. Pletcher, “The electrodeposition of polypyrrole films from aqueous solutions,” Journal of Electroanalytical Chemistry, vol. 177, no. 1-2, pp. 229–244, 1984.
[28]  D. L. Wakeham, S. W. Donne, W. J. Belcher, and P. C. Dastoor, “Electrochemical and morphological characterization of electrodeposited poly(2,2':5',2“-terthiophene) for photovoltaic applications,” Synthetic Metals, vol. 158, no. 16, pp. 661–669, 2008.
[29]  G. Tourillon and F. Garnier, “Structural effect on the electrochemical properties of polythiophene and derivatives,” Journal of Electroanalytical Chemistry, vol. 161, no. 1, pp. 51–58, 1984.
[30]  M. A. Sato, S. Tanaka, and K. Kaeriyama, “Electrochemical preparation of conducting poly(3-methylthiophene): comparison with polythiophene and poly(3-ethylthiophene),” Synthetic Metals, vol. 14, no. 4, pp. 279–288, 1986.
[31]  G. Zotti, G. Schiavon, A. Berlin, and G. Pagani, “Thiophene oligomers as polythiophene models. 2. Electrochemistry and in situ ESR of end-capped oligothienyls in the solid state. Evidence for π-dimerization of hexameric polarons in polythiophene,” Chemistry of Materials, vol. 5, no. 5, pp. 620–624, 1993.
[32]  R. Berthelot, C. Rozé, M. M. Granger, and E. Raoult, “Anodic oxidation of various arylene-cyanovinylenes made of alternating fluorenyl, thienyl and/or phenyl units,” Journal of Electroanalytical Chemistry, vol. 466, no. 2, pp. 144–154, 1999.
[33]  T.-Y. Lee, Y.-B. Shim, and S. C. Shin, “Simple preparation of terthiophene-3'-carboxylic acid and characterization of its polymer,” Synthetic Metals, vol. 126, no. 1, pp. 105–110, 2002.
[34]  G. Schopf and G. Kossmehl, Advances in Polymer Science, vol. 34, p. 1, 1997.
[35]  W. C. Chen, T. C. Wen, and A. Gopalan, “Negative capacitance for polyaniline: an analysis via electrochemical impedance spectroscopy,” Synthetic Metals, vol. 128, no. 2, pp. 179–189, 2002.
[36]  C. C. Hu and C. H. Chu, “Electrochemical impedance characterization of polyaniline-coated graphite electrodes for electrochemical capacitors—effects of film coverage/thickness and anions,” Journal of Electroanalytical Chemistry, vol. 503, no. 1-2, pp. 105–116, 2001.
[37]  L. Niu, Q. Li, F. Wei, X. Chen, and H. Wang, “Electrochemical impedance and morphological characterization of platinum-modified polyaniline film electrodes and their electrocatalytic activity for methanol oxidation,” Journal of Electroanalytical Chemistry, vol. 544, pp. 121–128, 2003.
[38]  W. C. Chen, T. C. Wen, and A. Gopalan, “The inductive behavior derived from hydrolysis of polyaniline,” Electrochimica Acta, vol. 47, no. 26, pp. 4195–4206, 2002.

Full-Text

comments powered by Disqus