Experimental and Computational Study of the Effect of Temperature on the Electro-Polymerization Process of Thiophene

Abstract

Temperature effect on the nucleation and growth mechanisms (NGM) of poly(thiophene) (PTh) was investigated through experimental and computational tools. The computational simulation method was based on a kinetic Monte Carlo algorithm. It reproduced key processes such as diffusion, oligomerization, and the precipitation of oligomers onto the electrode surface. Electrochemical synthesis conditions at temperatures between 263 and 303 K were optimized. The deconvolution of the i-t transients reflected two contributions: a progressive nucleation with three-dimensional growth controlled by diffusion and the other by charge transfer, PN3Ddif and PN3Dct, respectively. As temperature decreased, a diminution of the charge associated to each contribution was observed and the nucleation induction time increased. Experimental and computational evidence indicated that temperature does not change the nucleation and growth mechanism (NGM). This effect was ascribed to kinetic factors rather than to film conductivity. This work contrasts simulation and experimental evidence and demonstrates how computational simulations can help to understand the electrochemical process of conducting polymers formation.

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M. Camarada, M. Romero, M. Giménez, W. Schmickler and M. Valle, "Experimental and Computational Study of the Effect of Temperature on the Electro-Polymerization Process of Thiophene," Open Journal of Organic Polymer Materials, Vol. 3 No. 3, 2013, pp. 59-67. doi: 10.4236/ojopm.2013.33010.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] H. Chelawat, S. Vaddiraju and K. Gleason, “Conformal, Conducting Poly(3,4-ethylenedioxythiophene) Thin Films Deposited Using Bromine as the Oxidant in a Completely Dry Oxidative Chemical Vapor Deposition Process,” Chemistry of Materials, Vol. 22, No. 9, 2010, pp. 2864-2868. doi:10.1021/cm100092c
[2] M. A. del Valle, F. R. Díaz, M. E. Bodini, G. Alfonso, G. M. Soto and E. D. Borrego, “Electrosynthesis and Characterization of O-phenylenediamine Oligomers,” Polymer International, Vol. 54, No. 3, 2005, pp. 526-532. doi:10.1002/pi.1700
[3] M. Romero, M. A. del Valle, R. del Río, F. R. Díaz and F. Armijo, “Polymers Nucleation and Growth Mechanism: Solubility, a Determining Factor,” International Journal of Electrochemical Science, Vol. 7, No. 10, 2012, pp. 10132-10141.
[4] R. Schrebler, P. Grez, P. Cury, C. Veas, M. Merino, H. Gomez, R. Cordova and M. A. del Valle, “Nucleation and Growth Mechanisms of Poly(thiophene) Part 1. Effect of Electrolyte and Monomer Concentration in Dichloromethane,” Journal of Electroanalytical Chemistry, Vol. 430, No. 1, 2005, pp. 77-90.
[5] J. Mostany, B. Scharifker, K. Saavedra and C. Borrás, “Electrochemical Nucleation and the Classical Theory: Overpotential and Temperature Dependence of the Nucleation Rate,” Russian Journal of Electrochemistry, Vol. 44, No. 6, 2008, pp. 652-658. doi:10.1134/S1023193508060049
[6] M. B. Camarada, M. C. Giménez, W. Schmickler and M. A. del Valle, “A First Approximation to Simulate the Electro-Polymerization Process,” Journal of the Chilean Chemical Society, Vol. 57, No. 3, 2012, pp. 1267-1271. doi:10.4067/S0717-97072012000300015
[7] G. A. East and M. A. del Valle, “Easy-To-Make Ag/AgCl Reference Electrode,” Journal of Chemical Education, Vol. 77, No. 1, 2000, p. 97. doi:10.1021/ed077p97
[8] M. B. Camarada, P. Jaque, F. R. Díaz and M. A. del Valle, “Oxidation Potential of Thiophene Oligomers: Theoretical and Experimental Approach,” Journal of Polymer Science Part B: Polymer Physics, Vol. 49, No. 24, 2011, pp. 1723-1733. doi:10.1002/polb.22360
[9] A. Almenninger, O. Bastiansen and P. Svendas, “Electron Diffraction Studies of 2,2’-Dithienyl Vapour,” Acta Chemica Scandinavica, Vol. 12, 1958, pp. 1671-1674. doi:10.3891/acta.chem.scand.12-1671
[10] P. Lang, F. Chao, M. Costa and F. Garnier, “Electrochemical Grafting of Poly(methylthiophene) onto Platinum in Acetonitrile,” Polymer, Vol. 28, No. 4, 1987, pp. 668-674. doi:10.1016/0032-3861(87)90486-1
[11] W. Press, S. Teukolsky, W. Vetterling and B. Flannery, “Numerical Recipes in Fortran 77, The Art of Scientific Computing,” Vol. 1, Cambridge University Press, Cambridge, 1992.
[12] J. Heinze, B. A. Frontana-Uribe and S. Ludwigs, “Electrochemistry of Conducting Polymers Persistent Models and New Concepts,” Chemistry Reviews, Vol. 110, No. 8, 2010, pp. 4724-4771. doi:10.1021/cr900226k
[13] M. B. Camarada, J. A. Olmos-Asar, M. M. Mariscal and M. A. del Valle, “Calculation of the Diffusion Coefficient of Thiophene Oligomers Using Molecular Dynamics,” Molecular Simulation, Vol. 38, No. 11, 2012, pp. 882-885. doi:10.1080/08927022.2012.664772
[14] M. A. del Valle, P. Cury and R. Schrebler, “Solvent Effect on the Nucleation and Growth Mechanisms of Poly (thiophene),” Electrochimica Acta, Vol. 48, No. 4, 2002, pp. 397-405. doi:10.1016/S0013-4686(02)00685-0
[15] A. J. Bard and L. R. Faulkner, “Electrochemical Methods: Fundamentals and Applications,” 2nd Edition, John Wiley & Sons Inc., Hoboken, 2001.
[16] D. Spångberg, “ymol,” 1998.

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