Electrochemical and Spectroscopic Dynamics of Nanostructured Polynuclear Sulphonic Acid-Doped Poly(2, 5-dimethoxyaniline)

Abstract:

Conducting and electroactive nanostructured poly(2, 5-dimethoxyaniline), PDMA, doped with anthracene sulphonic acid, ASA, and phenanthrene sulphonic acid, PSA, respectively, were prepared by oxidative polymerisation of 2, 5-dimethoxyaniline, DMA, with ammonium persulphate as oxidant. Scanning electron microscope, SEM, images of the polymers showed well defined nanotubes and fibrils with diameters of between 50 to 100 nm and 200 to 300 nm for PDMA-ASA and PDMA-PSA, respectively. Evidence of the incorporation of ASA and PSA into the PDMA backbone was provided by UV-Vis and FTIR analyses. Electrochemical interrogation of the sulphonic acid-doped polymers by cyclic voltammetry showed that both PDMA-ASA and PDMA-PSA exhibit quazi-reversible electrochemistry. The standard rate constant, ko, for the charge transfer reactions of PDMA-ASA and PDMA-PSA were 3.81 x 10-4 cm s-1 and 3.27 x 10-5 cm s-1, respectively. There was a relationship between the ko value and the formal potential, E0ʹ, of the polymeric nanomaterial. PDMA-ASA that had larger ko value gave an E0ʹ value of 134 mV which was lower than that of PDMA-PSA by 19 mV, indicating that PDMA-ASA has lower activation energy than PDMA-PSA for the electron transfer process Electrochemical impedance spectroscopy over a range of potentials showed that the polymeric nanotubues exhibited high conductivities, though the SA-doped polymer was more conducting.

• Periodical: Materials Science Forum (Volume 657)
• Pages: 231-248
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.657.231
• Online since: July 2010
• Authors: Michael Klink, Richard Akinyeye, Vernon Somerset, Mantoa Sekota, Priscilla Gloria Lorraine Baker, Emmanuel Iwuoha
• Keywords: Anthracene Sulphonic Acid, Phenanthrene Sulphonic Acid, Poly (2, 5-Dimethoxyaniline), Polyaniline Nanotubes, Spectroelectrochemistry

References

[1] C. Johans, J. Clohessy, S. Fantini, K. Kontturi and V.J. Cunnane: Electrochem. Commun. Vol. 4 (2002), p.227.

[2] A.R. Hopkins, R.A. Lipeles and W.H. Kao: Thin Solid Films, Vol. 474 (2004), p.447.

[3] P. Bernier, S. Lefrant and G. Bidan: Advances in Synthetic Metals - Twenty years of Progress in Science and Technology (Elsevier 1999).

[4] M.G. Han, S.K. Cho, S.G. Oh and S.S. Im: Synth. Met. Vol. 126 (2002), p.53.

[5] B. Schrader: Infrared and Raman Spectroscopy - Methods and Applications (VCH 1995).

[6] G. Zerby: Modern Polymer Spectroscopy (Wiley-VCH 1999).

[7] Z. Wei, Z. Zhang and M. Wan: Langmuir Vol. 18 (2000), p.917.

[8] S.J. Su and N. Kuramoto: Synth. Met. Vol. 108(2000), p.121.

[9] I. D. Norris, L.A.P. Kane-Maguire and G.G. Wallace: Macromolecules Vol. 33 (2000), p.3237.

[10] G. Appela, R. Mikaloa, K. Henkela, A. Opreaa, A. Yfantisa, I. Paloumpaa and D. Schmeiûera: Solid-State Electronics Viol. 44 (2000), p.855.

[11] A. Pud, N. Ogurtsov, A. Korzhenko and G. Shapoval: Prog. Polym. Sci. Vol. 28 (2003), p.1701.

[12] L. Zhang and M. Wan: Thin Solid Films Vol. 477 (2005), p.24.

[13] R.O. Akinyeye, M. Sekota, P. Baker and E. Iwuoha: Fullerenes, Nanotubes and Carbon Nanostructures Vol. 14 (2006), p.49.

DOI: 10.1080/15363830500540900

[14] R.O. Akinyeye, I. Michira, M. Sekota, A. Al-Ahmed P. Baker and E. Iwuoha: Electroanalysis Vol. 18(24) (2006), p.2441.

DOI: 10.1002/elan.200603699

[15] I.N. Michira, M. Klink, R.O. Akinyeye, V. Somerset, M. Sekota, A. Al-Ahmed, P.G.L. Baker and E.I. Iwuoha, in: Recent Advances in Analytical Electrochemistry edited by K. Ozoemena, Transworld Research Network, India (2007).

DOI: 10.1002/masy.200750905

[16] E.I. Iwuoha D.S. de Villaverde, N.P. Garcia, M.R. Smyth and J.M. Pingarron: Biosens. and Bioelectr. Vol. 12 (1997), p.749.

[17] J. McMurry: Organic Chemistry, 2nd Edition (Brooks/Cole publishing company, California, USA 1988).

[18] R.T. Morrison and R. N. Boyd: Organic Chemistry, 5th Edition (Allyn and Bacon Inc., USA 1987).

[19] T.N. Sorrell: Organic Chemistry (University Science Books, California, USA 1999).

[20] A.I. Vogel: Vogel's Text Book of Practical Organic Chemistry, 5th Edition (Wiley, New York 1989).

[21] Z. Zhang and M. Wan: Synth. Met. Vol. 128 (2002), p.83.

[22] Z. Zhang and M. Wan: Synth. Met. Vol. 132 (2003), p.205.

[23] K.R. Prasad and N. Munichandraiah: Synth. Met. Vol. 123 (2001), p.459.

[24] L. Huang, T. Wen and A. Gopalan: Synth. Met. Vol. 130 (2002), p.155.

[25] L. Huang, T. Wen and A. Gopalan: Mat. Chem. & Phys. Vol. 77 (2002), p.726.

[26] N.G.R. Mathebe, A. Morrin and E. I. Iwuoha: Talanta Vol. 64 (2004), p.115.

[27] F. Cataldo and P. Maltese: Euro. Polym. J. Vol. 28 (2002), p.1791.

[28] W.A. Gazotti and M. dePaoli: Synth. Met. Vol. 80 (1996), p.263.

[29] A.J. Bard, L.R. Faulkner: Electrochemical methods - Fundamentals and Applications, 2nd edition (John Wiley & Sons, Inc. USA 2001).

[30] A.P. Brown, F.C. Anson: Anal. Chem. Vol. 49 (1977), P. 1589.

[31] S. Brahim, A. N Wilson, D. Nariesingh and E. Iwuoha, A. Guiseppi-Elie : Michrochim. Acta Vol. 143 (2003), p.127.

[32] P. Zanello, Inorganic Electrochemistry (Theory, Practice and Applications), Royal Society of Chemistry, Cambridge, UK, 2003, 49.

[33] R.S. Nicholson: Anal. Chem. Vol. 37 (1965), p.1351.

[34] R.S. Nicholson and I. Shain: Anal. Chem. Vol. 36 (1964), p.706.

[35] P.M.S. Monk: Fundamentals of Electroanalytical Chemistry (John Willy and Sons Ltd, England 2005).