Skip to main content
Log in

Electrochemical synthesis and characterization of thiophene conducting polymer in aqueous micellar medium

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

In opposite with the usually applied synthesis in organic media, the polymerization of bithiophene in aqueous media has been studied. The use of a non-ionic surfactant (polyoxyethylene octyl phenyl ether (Triton X-100)) is useful not only to solubilize the hydrophobic monomer but it is also important to incorporate various—biologically and catalytically active—additives. In this paper, the optimization of the polymerization conditions as well as the characterization of the electrochemical, spectral and mass exchange behavior of these composite films is summarized. The layers have shown imperceptible electroactivity in monomer-free aqueous LiClO4 solutions, and electrochemical quartz crystal microbalance (EQCM) studies exhibited scarce ion movements, caused assumingly by the fact that the dopant species—moving together with their hydrate shell in the aqueous media—could not penetrate into the hydrophobic film. In contrast, nice reversible redox transformation could be obtained in organic medium such as acetonitrile, where—according to the EQCM results—the charge carrier formation/depletion is accompanied by the incorporation/removal of ClO4 anions. In this solution, the spectral changes have proved the transformation into the conducting state, connected to both mono- and di-cation forms. The incorporation of the surfactant has been demonstrated by the extraordinary surface morphology of the polybithiophene (pBT) films, characterized by scanning electron microscopy. The elementary composition of the curious shell-shaped objects, monitored by energy dispersive X-ray spectroscopy (EDX), evidenced the presence of Triton X-100 by the increased C/S ratio compared to neat polybithiophene, while the Cl/S data reflected the changes connected to the doping level as a consequence of ClO4 anion movements. Moreover, ex situ attenuated total reflectance (ATR) FT–IR measurements clearly showed the existence of C―O bonds, also proving the successful functionalization by the surfactant, built permanently into the redox active films.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Kim J, Kang DM, Shin SC, Choi MY, Kim J, Lee SS, Kim JS (2008) Functional polyterthiophene-appended uranyl–salophen complex: electropolymerization and ion-selective response for monohydrogen phosphate. Anal Chim Acta 614:85–92

    Article  CAS  Google Scholar 

  2. Han ZY, Zhang JC, Yang XY, Zhu H, Cao WL (2010) Synthesis and application in solar cell of poly(3-octylthiophene)/titania nanotubes composite. Org Electron 11:1449–1460

    Article  CAS  Google Scholar 

  3. de Freitas JN, Pivrikas A, Nowacki B, Akcelrud LC, Sariciftci NS, Nogueira AF (2010) Investigation of new PPV-type polymeric materials containing fluorene and thiophene units and their application in organic solar cells. Synth Met 160:1654–1661

    Article  Google Scholar 

  4. Cabaj J, Soloducho J, Chyla A, Jedrychowska A (2011) Hybrid phenol biosensor based on modified phenoloxidase electrode. Sens Actuators B 157:225–231

    Article  CAS  Google Scholar 

  5. Janaky C, Visy C (2008) Synthesis and characterization of poly(3-octylthiophene)/gamma-Fe2O3 nanocomposite—a promising combination of superparamagnetic-thermoelectric-conducting properties. Synth Met 158:1009–1014

    Article  CAS  Google Scholar 

  6. Janaky C, Bencsik G, Racz A, Visy C (2010) Electrochemical grafting of poly(3,4-ethylenedioxythiophene) into a titanium dioxide nanotube host network. Langmuir 26:13697–13702

    Article  CAS  Google Scholar 

  7. Yue RR, Chen S, Liu CC, Lu BY, Xu JK, Wang JM, Liu GD (2012) Synthesis, characterization, and thermoelectric properties of a conducting copolymer of 1,12-bis(carbazolyl)dodecane and thieno[3,2-b]thiophene. J Solid State Electrochem 16:117–126

    Article  CAS  Google Scholar 

  8. Jeong S, Woo SH, Lyu HK, Han YS (2011) Effects of a perfluorinated compound as an additive on the power conversion efficiencies of polymer solar cells. Sol Energy Mater Sol Cells 95:1908–1914

    Article  CAS  Google Scholar 

  9. Zhang ZG, Zhang S, Min J, Chui C, Zhang J, Zhang M, Li Y (2012) Conjugated side-chain isolated polythiophene: synthesis and photovoltaic application. Macromolecules 45:113–118

    Article  CAS  Google Scholar 

  10. McCullough RD, Lowe RD (1992) Enhanced electrical conductivity in regioselectively synthesized poly(3-alkylthiophenes). J Chem Soc Chem Commun 1:70–72

    Article  Google Scholar 

  11. Bayley PM, Winther-Jensen B, MacFarlane DR, Rocher NM, Forsyth M (2008) Enhanced properties in chemically polymerized poly(terthiophene) using vapour phase techniques. React Funct Polym 72:1119–1126

    Article  Google Scholar 

  12. Visy C, Krivan E, Peintler G (1999) MRA combined spectroelectrochemical studies on the redox stability of PPy/DS films. J Electroanal Chem 462:1–11

    Article  CAS  Google Scholar 

  13. Dobay R, Harsanyi G, Visy C (1999) Conducting polymer based electrochemical sensors on thick film substrate. Electroanalysis 11:804–808

    Article  CAS  Google Scholar 

  14. Bazzaoui EA, Aeiyach S, Lacaze PC (1996) Electropolymerization of bithiophene on Pt and Fe electrodes in an aqueous sodium dodecylsulfate (SDS) micellar medium. Synth Met 83:159–165

    Article  CAS  Google Scholar 

  15. Sakmeche N, Bazzaoui EA, Fall M, Aeiyach S, Jouini M, Lacroix JC, Aaron JJ, Lacaze PC (1997) Application of sodium dodecylsulfate (SDS) micellar solution as an organized medium for electropolymerization of thiophene derivatives in water. Synth Met 84:191–192

    Article  CAS  Google Scholar 

  16. Lagrost C, Jouini M, Tanguy J, Aeiyach S, Lacroix JC, Chane-Ching KI, Lacaze PC (2001) Bithiophene electropolymerization in aqueous media: a specific effect of SDS and β-cyclodextrin. Electrochim Acta 46:3985–3992

    Article  CAS  Google Scholar 

  17. Sonmez G, Schottland P, Reynolds JR (2005) PEDOT/PAMPS: an electrically conductive polymer composite with electrochromic and cation exchange properties. Synth Met 155:130–137

    Article  CAS  Google Scholar 

  18. Yoshioka Y, Jabbour GE (2007) Inkjet printing and patterning of PEDOT-PSS: application to optoelectronic devices. In: Skotheim TA, Reynolds JR (eds) Handbook of conducting polymers—processing and applications. New York, CRC, pp 3-1–3-21

    Google Scholar 

  19. Zhang S, Hou J, Zhang R, Xu J, Nie G, Pu S (2006) Electrochemical polymerization of 3,4-ethylenedioxythiophene in aqueous solution containing N-dodecyl-β-d-maltoside. Eur Polym J 42:149–160

    Article  CAS  Google Scholar 

  20. Winkels S, Tsakova V, Schultze JW (1999) Electrochemical formation of polyethylenedioxythiophene in aqueous micellar solution. Electrochem Soc Proc 98–26:97–104

    Google Scholar 

  21. Goral M, Jouini M, Perruchot C, Miecznikowski K, Rutkowska IA, Kulesza PJ (2011) Integration of vanadium-mixed addenda Dawson heteropolytungstate within poly(3,4-ethylenedioxythiophene) and poly(2,2′-bithiophene) films by electrodeposition from the nonionic micellar aqueous medium. Electrochim Acta 56:3605–3615

    Article  CAS  Google Scholar 

  22. Lavina S, Negro E, Gliubizzi R, Depaoli G, Pace G, Di Noto V (2007) New hybrid inorganic-organic complexes based on poly (3-butylthiophene) and titanium tetrachloride: synthesis, structure and conductivity. Electrochim Acta 52:5062–5070

    Article  CAS  Google Scholar 

  23. Xu MJ, Zhang J, Wang S, Guo X, Xia H, Wang Y, Zhang S, Huang W, Wu S (2010) Gas sensing properties of SnO2 hollow spheres/polythiophene inorganic–organic hybrids. Sens Actuators B 146:8–13

    Article  Google Scholar 

  24. Hornok V, Bujdoso T, Toldi J, Nagy K, Demeter I, Fazakas C, Krizbai I, Vecsei L, Dekany I (2012) Preparation and properties of nanoscale containers for biomedical application in drug delivery: preliminary studies with kynurenic acid. J Neural Transm 119:115–121

    Article  CAS  Google Scholar 

  25. Rojruthai P, Sakdapipanich JT, Takahashi S, Hyegin L, Noike M, Koyama T, Tanaka Y (2010) In vitro synthesis of high molecular weight rubber by Hevea small rubber particles. J Biosci Bioeng 109:107–114

    Article  CAS  Google Scholar 

  26. Geng Y, Liu MY, Li J, Shi MX, Kim JK (2008) Effects of surfactant treatment on mechanical and electrical properties of CNT/epoxy nanocomposites. Compos A 39:1876–1883

    Article  Google Scholar 

  27. Skompska M, Jackson A, Hillman AR (2000) Evolution from gravimetric to viscoelastic response of poly(3-methylthiophene)-loaded acoustic wave resonators. PCCP 2:4748–4757

    Article  CAS  Google Scholar 

  28. Janaky C, Cseh G, Toth PS, Visy C (2010) Application of classical and new, direct analytical methods for the elucidation of ion movements during the redox transformation of polypyrrole. J Solid State Electrochem 14:1967–1973

    Article  CAS  Google Scholar 

  29. Audebert P, Hapiot P (1995) Fast electrochemical studies of the polymerization mechanisms of pyrroles and thiophenes. Identification of the first steps. Existence of π-dimers in solution. Synth Met 75:95–102

    Article  CAS  Google Scholar 

  30. Heinze J, Bilger R (1993) Ion movements during redox switching of polypyrrole—experiment and simulation. PCCP 97:502–506

    CAS  Google Scholar 

  31. Vorotyntsev MA, Vieil E, Heinze J (1995) Ionic exchange of a conducting-polymer film with the solution during the cyclic-voltammetry process. Russ J Electrochem 31:1027–1035

    CAS  Google Scholar 

  32. Rapta P, Fáber R, Dunsch L, Neudeck A, Nuyken O (2000) In situ EPR and UV-vis spectroelectrochemistry of hole-transporting organic substrates. Spectrochim Acta Part A 56:357–362

    Article  Google Scholar 

  33. Byrne PD, Lee D, Müller P, Swager TM (2006) Polymerization of thiophene containing cyclobutadiene Co cyclopentadiene complexes. Synth Met 156:784–791

    Article  CAS  Google Scholar 

  34. Ding J, Price WE, Ralph SF, Wallace GG (2000) Synthesis and properties of a mechanically strong poly(bithiophene) composite polymer containing a polyelectrolyte dopant. Synth Met 110:123–132

    Article  CAS  Google Scholar 

  35. Bello A, Giannetto M, Mori G (2005) Electrochemically induced derivatization of poly(2,2-bithiophene) and characterization of functionalized polymers by FT-IR microscopy, SEM microanalysis and EQCM. J Electroanal Chem 575:257–266

    Article  CAS  Google Scholar 

  36. Socrates G (1980) Infrared characteristic group frequencies. Wiley, New York

    Google Scholar 

  37. Nakamoto K (1997) Infrared and Raman spectra of inorganic and coordination compounds. Wiley, New York

    Google Scholar 

Download references

Acknowledgment

This work was supported by TÉT/PHC–Balaton Hungarian/French bilateral programme no.:10-1-2011-0713.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Csaba Visy.

Additional information

Péter S Tóth, Christian Perruchot, Mohamed Jouini, and Csaba Visy are ISE members.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Tóth, P.S., Perruchot, C., Chams, A. et al. Electrochemical synthesis and characterization of thiophene conducting polymer in aqueous micellar medium. J Solid State Electrochem 17, 635–641 (2013). https://doi.org/10.1007/s10008-012-1899-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-012-1899-9

Keywords

Navigation