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Volume 67, Issue 8

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Polyaniline doped with poly(acrylamidomethylpropanesulphonic acid): electrochemical behaviour and conductive properties in neutral solutions

Vladimir Lyutov / Svetlozar Ivanov
  • Institute of Physical Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria
  • Department of Electrochemistry and Electroplating II, Technical University Ilmenau, 98693, Ilmenau, Germany
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/ Vladimir Mirsky / Vessela Tsakova
Published Online: 2013-05-03 | DOI: https://doi.org/10.2478/s11696-013-0341-9

Abstract

Poly(2-acrylamido-2-methyl-1-propanesulphonic acid) (PAMPSA)-doped polyaniline (PANI) layers are synthesised in the presence of sulphuric and perchloric acids. The effects of the inorganic acid as well as of the electrochemical synthetic procedure (potentiostatic and potentiodynamic deposition) and thickness of the polymer layers are studied. The focus is directed towards the pH dependence of the electrochemical redox activity and conductivity of the PAMPSA-doped PANI layers obtained under different conditions. Ascorbic acid oxidation is used as a test reaction to study the electrocatalytic behaviour of various PAMPSA-doped PANI layers in neutral solution. It is found that the type of inorganic component present in the polymerisation solution has a marked effect on the extent of doping in acidic solutions as well as on the redox electroactivity in neutral solutions. A comparison between potentiostatically and potentiodynamically synthesised layers at pH 7 shows a markedly lower conductance and lower extent of redox charge preservation in the case of potentiodynamic synthesis. The PANI electrocatalytic activity for ascorbic acid oxidation is also dependent on the polymer electrodeposition procedure, with potentiostatically synthesised layers exhibiting better electrocatalytic performance.

Keywords: polyaniline; polyacids; PAMPSA; conductance; electrochemical

  • [1] Bartlett, P. N., & Wallace, E. N. K. (2001). The oxidation of ascorbate at poly(aniline)-poly(vinylsulfonate) composite coated electrodes. Physical Chemistry Chemical Physics, 3, 1491–1496. DOI: 10.1039/b009377g. http://dx.doi.org/10.1039/b009377gCrossrefGoogle Scholar

  • [2] Bonastre, A. M., & Bartlett, P. N. (2010). Electrodepositionof PANI films on platinum needle type microelectrodes. Application to the oxidation of ascorbate in human plasma. Analytica Chimica Acta, 676, 1–8. DOI: 10.1016/j.aca.2010.07.003. http://dx.doi.org/10.1016/j.aca.2010.07.003CrossrefWeb of ScienceGoogle Scholar

  • [3] Casella, I. G., & Guascito, M. R. (1997). Electrocatalysis of ascorbic acid on the glassy carbon electrode chemically modified with polyaniline films. Electroanalysis, 9, 1381–1386. DOI: 10.1002/elan.1140091802. http://dx.doi.org/10.1002/elan.1140091802CrossrefGoogle Scholar

  • [4] Ding, H., & Park, S. M. (2003). Electrochemistry of conductive polymers. XXVII. Effects of polystyrene sulfonate on electrochemical behavior of polyaniline. Journal of Electrochemical Society, 150, E33–E38. DOI: 10.1149/1.1525271. http://dx.doi.org/10.1149/1.1525271CrossrefGoogle Scholar

  • [5] Eftekhari, A. (2010). Nanostructured conductive polymers. Chichester, UK: Wiley. http://dx.doi.org/10.1002/9780470661338Google Scholar

  • [6] Ge, C. H., Armstrong, N. R., & Saavedra, S. S. (2007). pH-sensing properties of poly(aniline) ultrathin films self-assembled on indium-tin oxide. Analytical Chemistry, 79, 1401–1410. DOI: 10.1021/ac061740e. http://dx.doi.org/10.1021/ac061740eCrossrefWeb of ScienceGoogle Scholar

  • [7] Gribkova, O. L., Nekrasov, A. A., Isakova, A. A., Ivanov, V. F., & Vannikov, A. V. (2006). Specific features characterizing electrochemical synthesis of polyaniline conducted in the presence of poly(2-acryalamido-2-methyl-1-propanesulfonic acid) and the spectroelectrochemical characteristics of the obtained films. Russian Journal of Electrochemistry, 42, 1085–1092. DOI: 10.1134/s1023193506100156. http://dx.doi.org/10.1134/S1023193506100156CrossrefGoogle Scholar

  • [8] Gribkova, O. L., Ivanov, V. F., Nekrasov, A. A., Vorob’ev, S. A., Omelchenko, O. D., & Vannikov, A. V. (2011). Dominating influence of rigid-backbone polyacid matrix during electropolymerization of aniline in the presence of mixtures of poly(sulfonic acids). Electrochimica Acta, 56, 3460–3467. DOI: 10.1016/j.electacta.2010.12.058. http://dx.doi.org/10.1016/j.electacta.2010.12.058CrossrefWeb of ScienceGoogle Scholar

  • [9] Hao, Q. L., Kulikov, V., & Mirsky, V. M. (2003). Investigation of contact and bulk resistance of conductive polymers by simultaneous two- and four-point technique. Sensors and Actuators B: Chemical, 94, 352–357. DOI: 10.1016/s0925-4005(03)00456-8. http://dx.doi.org/10.1016/S0925-4005(03)00456-8CrossrefGoogle Scholar

  • [10] Hyodo, K., & Nozaki, M. (1988). High ion selective electrochemical synthesis of polyaniline. Electrochimica Acta, 33, 165–166. DOI: 10.1016/0013-4686(88)80050-1. http://dx.doi.org/10.1016/0013-4686(88)80050-1CrossrefGoogle Scholar

  • [11] Hyodo, K., Omae, M., & Kagami, Y. (1991a). Effect of the polymer electrolyte on the electrochemical polymerization of aniline. Electrochimica Acta, 36, 87–91. DOI: 10.1016/0013-4686(91)85183-8. http://dx.doi.org/10.1016/0013-4686(91)85183-8CrossrefGoogle Scholar

  • [12] Hyodo, K., Omae, M., & Kagami, Y. (1991b). Effect of molecular weight on the ion selective electrochemical polymerization of aniline. Electrochimica Acta, 36, 357–360. DOI: 10.1016/0013-4686(91)85262-6. http://dx.doi.org/10.1016/0013-4686(91)85262-6CrossrefGoogle Scholar

  • [13] Inzelt, G. (2008). Conducting polymers: A new era in electrochemistry. Leipzig, Germany: Springer. Google Scholar

  • [14] Ivanov, S., Tsakova, V., & Mirsky, V. M. (2006). Conductometric transducing in electrocatalytical sensors: Detection of ascorbic acid. Electrochemistry Communications, 8, 643–646. DOI: 10.1016/j.elecom.2006.02.006. http://dx.doi.org/10.1016/j.elecom.2006.02.006CrossrefGoogle Scholar

  • [15] Ivanov, V. F., Gribkova, O. L., Omelchenko, O. D., Nekrasov, A. A., Tverskoy, V. A., & Vannikov, A. V. (2010). Effect of matrix domination in PANI interpolymer complexes with polyamidosulfonic acids. Journal of Solid State Electrochemistry, 14, 2011–2019. DOI: 10.1007/s10008-010-1049-1. http://dx.doi.org/10.1007/s10008-010-1049-1CrossrefWeb of ScienceGoogle Scholar

  • [16] Karyakin, A. A., Strakhova, A. K., & Yatsimirsky, A. K. (1994). Self-doped polyanilines electrochemically active in neutral and basic aqueous solutions: Electropolymerization of substituted anilines. Journal of Electroanalytical Chemistry, 371, 259–265. DOI: 10.1016/0022-0728(93)03244-j. http://dx.doi.org/10.1016/0022-0728(93)03244-JCrossrefGoogle Scholar

  • [17] Karyakin, A. A., Maltsev, I. A., & Lukachova, L. V. (1996). The influence of defects in polyaniline structure on its electroactivity: optimization of ’self-doped’ polyaniline synthesis. Journal of Electroanalytical Chemistry, 402, 217–219. DOI: 10.1016/0022-0728(95)04303-9. http://dx.doi.org/10.1016/0022-0728(95)04303-9CrossrefGoogle Scholar

  • [18] Kilmartin, P. A., Martinez, A., & Bartlett, P. N. (2008). Polyaniline-based microelectrodes for sensing ascorbic acid in beverages. Current Applied Physics, 8, 320–323. DOI: 10.1016/j.cap.2007.10.021. http://dx.doi.org/10.1016/j.cap.2007.10.021Web of ScienceCrossrefGoogle Scholar

  • [19] Komsiyska, L., & Tsakova, V. (2006). Ascorbic acid oxidation at nonmodified and copper-modified polyaniline and polyortho-methoxyaniline coated electrodes. Electroanalysis, 18, 807–813. DOI: 10.1002/elan.200503464. http://dx.doi.org/10.1002/elan.200503464CrossrefGoogle Scholar

  • [20] Kulikov, V, Mirsky, V. M., Delaney, T. L., Donoval, D., Koch, A. W., & Wolfbeis, O. S. (2005). High-throughput analysis of bulk and contact conductance of polymer layers on electrodes. Measuring Science and Technology, 16, 95–99. DOI: 10.1088/0957-0233/16/1/013. http://dx.doi.org/10.1088/0957-0233/16/1/013CrossrefGoogle Scholar

  • [21] Lange, U., & Mirsky, V. M. (2008). Separated analysis of bulk and contact resistance of conducting polymers: Comparison of simultaneous two- and four-point measurements with impedance measurements. Journal of Electroanalytical Chemistry, 622, 246–251. DOI: 10.1016/j.jelechem.2008.06.013. http://dx.doi.org/10.1016/j.jelechem.2008.06.013CrossrefWeb of ScienceGoogle Scholar

  • [22] Lange, U., & Mirsky, V. M. (2011). Chemiresistors based on conducting polymers: A review on measurement techniques. Analytica Chimica Acta, 687, 105–113. DOI: 10.1016/j.aca.2010.11.030. http://dx.doi.org/10.1016/j.aca.2010.11.030CrossrefWeb of ScienceGoogle Scholar

  • [23] Łapkowski, M. (1993). Electrochemical synthesis of polyaniline/poly(2-acryl-amido-2-methyl-1-propane-sulfonic acid) composite. Synthetic Metals, 55, 1558–1563. DOI: 10.1016/0379-6779(93)90284-4. http://dx.doi.org/10.1016/0379-6779(93)90284-4CrossrefGoogle Scholar

  • [24] Lyutov, V., & Tsakova, V. (2008). Effect of anions on the electrochemical synthesis, stability and surface morphology of polyaniline films. In D. Kashchiev, & M. Drinov (Eds.), Nanoscale phenomena and structures (pp. 293–296). Sofia, Bulgaria: Academic Publishing House. Google Scholar

  • [25] Lyutov, V., Georgiev, G., & Tsakova, V. (2009). Comparative study on the electrochemical synthesis of polyaniline in the presence of mono- and poly(2-acrylamido-2-methyl-1-propanesulfonic) acid. Thin Solid Films, 517, 6681–6688. DOI: 10.1016/j.tsf.2009.05.010. http://dx.doi.org/10.1016/j.tsf.2009.05.010Web of ScienceCrossrefGoogle Scholar

  • [26] Lyutov, V., & Tsakova, V. (2011a). Silver particles-modified polysulfonic acid-doped polyaniline layers: electroless deposition of silver in slightly acidic and neutral solutions. Journal of Solid State Electrochemistry, 15, 2553–2562. DOI: 10.1007/s10008-011-1451-3. http://dx.doi.org/10.1007/s10008-011-1451-3CrossrefWeb of ScienceGoogle Scholar

  • [27] Lyutov, V., & Tsakova, V. (2011b). Palladium-modified polysulfonic acid-doped polyaniline layers for hydrazine oxidation in neutral solutions. Journal of Electroanalytical Chemistry, 661, 186–191. DOI: 10.1016/j.jelechem.2011.07.043. http://dx.doi.org/10.1016/j.jelechem.2011.07.043CrossrefWeb of ScienceGoogle Scholar

  • [28] Lyutov, V., Tsakova, V., & Bund, A. (2011). Microgravimetric study on the formation and redox behavior of poly(2-acrylamido-2-methyl-1-propanesulfonate)-doped thin polyaniline layers. Electrochimica Acta, 56, 4803–4811. DOI: 10.1016/j.electacta.2011.03.079. http://dx.doi.org/10.1016/j.electacta.2011.03.079CrossrefWeb of ScienceGoogle Scholar

  • [29] Mello, R. M. Q., Torresi, R. M., Córdoba de Torresi, S. I., & Ticianelli, E. A. (2000). Ellipsometric, electrogravimetric, and spectroelectrochemical studies of the redox process of sulfonated polyaniline. Langmuir, 16, 7835–7841. DOI: 10.1021/la000391v. http://dx.doi.org/10.1021/la000391vCrossrefGoogle Scholar

  • [30] Nekrasov, A. A., Gribkova, O. L., Eremina, T. V., Isakova, A. A., Ivanov, V. F., Tverskoj, V. A., & Vannikov, A. V. (2008). Electrochemical synthesis of polyaniline in the presence of poly(amidosulfonic acid)s with different rigidity of polymer backbone and characterization of the films obtained. Electrochimica Acta, 53, 3789–3797. DOI: 10.1016/j.electacta.2007.08.060. http://dx.doi.org/10.1016/j.electacta.2007.08.060CrossrefGoogle Scholar

  • [31] Nekrasov, A. A., Gribkova, O. L., Ivanov, V. F., & Vannikov, A. V. (2010). Electroactive films of interpolymer complexes of polyaniline with polyamidosulfonic acids: advantageous features in some possible applications. Journal of Solid State Electrochemistry, 14, 1975–1984. DOI: 10.1007/s10008-010-1057-1. http://dx.doi.org/10.1007/s10008-010-1057-1CrossrefWeb of ScienceGoogle Scholar

  • [32] O’Connell, P. J., Gormally, C., Pravda, M., & Guilbault, G. G. (2001). Development of amperometric L-ascorbic acid (Vitamin C) sensor based on electropolymerised aniline for pharmaceutical and food analysis. Analytica Chimica Acta, 431, 239–247. DOI: 10.1016/s0003-2670(00)01330-1. http://dx.doi.org/10.1016/S0003-2670(00)01330-1CrossrefGoogle Scholar

  • [33] Sun, J. J., Zhou, D. M., Fang, H. Q., & Chen, H. Y. (1998). The electrochemical copolymerization of 3,4-dihydroxybenzoic acid and aniline at microdisk gold electrode and its amperometric determination for ascorbic acid. Talanta, 45, 851–856. DOI: 10.1016/s0039-9140(97)00183-5. http://dx.doi.org/10.1016/S0039-9140(97)00183-5CrossrefGoogle Scholar

  • [34] Tarver, J., Yoo, J. E., Dennes, T. J., Schwartz, J., & Loo, Y. L. (2009). Polymer acid doped polyaniline is electrochemically stable beyond pH 9. Chemistry of Materials, 21, 280–286. DOI: 10.1021/cm802314h. http://dx.doi.org/10.1021/cm802314hCrossrefGoogle Scholar

  • [35] Wei, X. L., Wang, Y. Z., Long, S. M., Bobeczko, C., & Epstein, A. J. (1996). Synthesis and physical properties of highly sulfonated polyaniline. Journal of the American Chemical Society, 118, 2545–2555. DOI: 10.1021/ja952277i. http://dx.doi.org/10.1021/ja952277iCrossrefGoogle Scholar

  • [36] Yue, J., & Epstein, A. J. (1990). Synthesis of self-doped conducting polyaniline. Journal of American Chemical Society, 112, 2800–2801. DOI: 10.1021/ja00163a051. http://dx.doi.org/10.1021/ja00163a051CrossrefGoogle Scholar

  • [37] Yue, J., Wang, Z. H., Cromack, K. R., Epstein, A. J., & MacDiarmid, A. G. (1991). Effect of sulfonic acid group on polyaniline backbone. Journal of the American Chemical Society, 113, 2665–2671. DOI: 10.1021/ja00007a046. http://dx.doi.org/10.1021/ja00007a046CrossrefGoogle Scholar

  • [38] Yue, J., & Epstein, A. J. (1992). Electronic control of pH at sulfonated polyaniline electrodes. Journal of the Chemical Society, Chemical Communications, 21, 1540–1542. DOI: 10.1039/c39920001540. http://dx.doi.org/10.1039/c39920001540CrossrefGoogle Scholar

  • [39] Zhou, D. M., Xu, J. J., Chen, H. Y., & Fang, H. Q. (1997). Ascorbate sensor based on “self-doped” polyaniline. Electroanalysis, 9, 1185–1188. DOI: 10.1002/elan.1140091512. http://dx.doi.org/10.1002/elan.1140091512CrossrefGoogle Scholar

About the article

Published Online: 2013-05-03

Published in Print: 2013-08-01


Citation Information: Chemical Papers, Volume 67, Issue 8, Pages 1002–1011, ISSN (Online) 1336-9075, DOI: https://doi.org/10.2478/s11696-013-0341-9.

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