Skip to main content

Development of polymer–dopant interactions during electropolymerization, a key factor in determining the redox behaviour of conducting polymers

Abstract

Investigation of ionic motion in connection with the redox transformation of conjugated polymers (CP) has always been at the leading edge of research. Motivated by recent proofs for the chemical bond formation between chloride ion and α-positioned carbon in poly (3,4–ethylenedioxythiophene) (PEDOT), comprehensive studies have been extended to another strongly electronegative halide (F) and to another CP, polypyrrole (PPy). As the electrochemical quartz crystal nanobalance (EQCN) results proved, the movement of the bulky Bu4N+ cations has been exclusively experienced during the redox processes of both systems. Moreover, the decisive role of the anions being present in the polymerization solution in determining the redox capacity and, consequently, the maximum doping level of the films was evidenced. On the grounds of the systematic experiments, the strong and permanent chemical interaction of highly electronegative anions and the polymer has been demonstrated as a general phenomenon. Importantly, this observation requires the necessary reconsideration of specific polymer–dopant interactions and calls attention to the necessity of careful design of the polymerization procedure.

This is a preview of subscription content, access via your institution.

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

References

  1. Shirakawa H, Louis EJ, Macdiarmid AG, Chiang CK, Heeger AJ (1977) Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x. J Chem Soc Chem Commun 16:578–580

    Article  Google Scholar 

  2. Michalska A, Galuszkiewicz A, Ogonowska M, Ocypa M, Maksymiuk K (2004) PEDOT films: multifunctional membranes for electrochemical ion sensing. J Solid State Electrochem 8:381–389

    CAS  Article  Google Scholar 

  3. Bauermann LP, Bartlett PN (2005) EQCM measurements of the ion and solvent flux in thin poly(aniline)–poly(styrenesulfonate) films during redox switching. Electrochim Acta 50:1537–1546

    CAS  Article  Google Scholar 

  4. Inzelt G (2008) Conducting polymers. Springer, Berlin

    Google Scholar 

  5. Plieth W, Bund A, Rammelt U, Neudeck S, Duc LM (2006) The role of ion and solvent transport during the redox process of conducting polymers. Electrochim Acta 51:2366–2372

    CAS  Article  Google Scholar 

  6. Bund A, Neudeck S (2004) Effect of the solvent and the anion on the doping/dedoping behavior of poly(3,4-ethylenedioxythiophene) films studied with the electrochemical quartz microbalance. J Phys Chem B 108:17845–17850

    CAS  Article  Google Scholar 

  7. Marceline NA, Varga A, Latonen RM, Ralph SF, Bobacka J, Ivaska A (2011) Simultaneous monitoring of the transport of anions and cations across polypyrrole based composite membranes. Electrochim Acta 56:3507–3515

    Article  Google Scholar 

  8. Zhou M, Pagels M, Geschke B, Heinze J (2002) Electropolymerization of pyrrole and electrochemical study of polypyrrole. 5. Controlled electrochemical synthesis and solid-state transition of well-defined polypyrrole variants. J Phys Chem B 106:10065–10073

    CAS  Article  Google Scholar 

  9. 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

    CAS  Article  Google Scholar 

  10. Mangold KM, Weidlich C, Schuster J, Jüttner K (2005) Ion exchange properties and selectivity of PSS in an electrochemically switchable PPy matrix. J Appl Electrochem 35:1293–1301

    CAS  Article  Google Scholar 

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

    CAS  Google Scholar 

  12. 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 

  13. Efimov I, Winkels S, Schultze JW (2001) EQCM study of electropolymerization and redox cycling of 3,4-polyethylenedioxythiophene. J Electroanal Chem 499:169–175

    CAS  Article  Google Scholar 

  14. Can M, Sevin F, Yildiz A (2003) The effect of the proton on electropolymerization of the thiophene. Appl Surf Sci 210:338–345

    CAS  Article  Google Scholar 

  15. Chiu WW, Travas-Sejdic J, Cooney RP, Bowmaker GA (2006) Studies of dopant effects in poly(3,4-ethylenedioxythiophene) using raman spectroscopy. J Raman Spectrosc 37:1354–1361

    CAS  Article  Google Scholar 

  16. Tóth PS, Janáky C, Berkesi O, Tamm T, Visy C (2012) On the unexpected cation exchange behavior, caused by covalent bond formation between PEDOT and Cl ions: extending the conception for the polymer−dopant interactions. J Phys Chem B 116:5491–5500

    Article  Google Scholar 

  17. Niu L, Kvarnström C, Ivaska A (2004) Mixed ion transfer in redox processes of poly(3,4-ethylenedioxythiophene). J Electroanal Chem 569:151–160

    CAS  Article  Google Scholar 

  18. Janáky C, Cseh G, Tóth 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  Google Scholar 

  19. Krische B, Zagorska M (1989) Overoxidation in conducting polymers. Synth Met 28:257–262

    Article  Google Scholar 

  20. Refaey SAM, Schwitzgebel G, Schneider O (1999) Electrochemical impedance studies on oxidative degradation, overoxidative degradation, deactivation and reactivation of conducting polymers. Synth Met 98:183–192

    Article  Google Scholar 

  21. Otero TF, Márquez M, Suárez IJ (2004) Polypyrrole: diffusion coefficients and degradation by overoxidation. J Phys Chem B 108:15429–15433

    CAS  Article  Google Scholar 

  22. Visy C, Lukkari J, Pajunen T, Kankare J (1989) Effect of anions on the transient redox behavior of polypyrrole in anhydrous acetonitrile. Synth Met 33:289–299

    CAS  Article  Google Scholar 

  23. Visy C, Lukkari J, Kankare J (1997) Change from a bulk to a surface coupling mechanism in the electrochemical polymerization of thiophene. Synth Met 87:81–87

    CAS  Article  Google Scholar 

  24. Skompska M, Jackson A, Hillman AR (2000) Evolution from gravimetric to viscoelastic response of poly(3-methylthiophene)-loaded acoustic wave resonators. PCCP 20:4748–4757

    Article  Google Scholar 

  25. Hillman AR, Daisley SJ, Bruckenstein S (2007) Kinetics and mechanism of the electrochemical p-doping of PEDOT. Electrochem Commun 9:1316–1322

    CAS  Article  Google Scholar 

  26. Sakmeche N, Aeiyach S, Aaron JJ, Jouini M, Lacroix JC, Lacaze PC (1999) Improvement of the electrosynthesis and physicochemical properties of poly(3,4-ethylenedioxythiophene) using a sodium dodecyl sulfate micellar aqueous medium. Langmuir 15:2566–2574

    CAS  Article  Google Scholar 

Download references

Acknowledgments

This work has been sponsored by the National Development Agency (NFÜ) under contract no. TÁMOP-4.2.2.A-11/1/KONV-2012-0047.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Csaba Visy.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Tóth, P.S., Endrődi, B., Janáky, C. et al. Development of polymer–dopant interactions during electropolymerization, a key factor in determining the redox behaviour of conducting polymers. J Solid State Electrochem 19, 2891–2896 (2015). https://doi.org/10.1007/s10008-015-2791-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-015-2791-1

Keywords

  • PEDOT
  • Polypyrrole
  • EQCN
  • Electronegative anions
  • Polymer–dopant interactions