Electroreductive deposition of polymeric coatings having Ru^II redox centers on Pt, Pd and sintered Fe–(5–10)%Ni electrodes

Abstract

Pt, Pd and sintered Fe–(5–10)%Ni electrodes were coated by reductive electrodeposition of electrochemically generatedtrans-[RuCl₂(vpy)₄ ]-based films (vpy=4-vinylpyridine). The complex trans-[RuCl₂(vpy)₄ ] was synthesized from a ruthenium blue solution and characterized by various techniques including electronic spectroscopy (446 nm), FTIR, ¹H and ¹³C NMR elemental analysis and cyclic voltammetry (E_1/2=–103.5 mV vs. Ag–Ag⁺). The results obtained confirmed the proposed structure of the monomer. Electrochemical studies carried out on films generated by either a potentiostatic or a galvanostatic approach revealed that the redox properties of poly-trans-[RuCl₂(vpy)₄ ] were similar to those of the monomer in solution. The morphology of the films was investigated by scanning electron microscopy (SEM). Microprobe X-ray dispersive energy analysis (EDS) was also performed on the polymer surface. The feasibility of film formation on Fe–5%Ni and Fe–10%Ni sintered electrodes has been demonstrated.

References

1. G. Troch-Nagels, R. Winand, A. Weymeersch and L. Renard, J. Appl. Electrochem., 1992, 22, 756.
2. F. Beck, Electrochim. Acta, 1988, 33, 839.
3. A. De Bruyne, J. L. DelPlancke and R. Winand, J. Appl. Electrochem., 1997, 27, 867.
4. David W. DeBerry, J. Electrochem. Soc., 1985, 132, 1022.
5. F. Beck, R. Michaelis, F. Schloten and B. Zinger, Electrochim. Acta, 1994, 39, 229.
6. F. Beck and R. Michaelis, J. Coat. Technol., 1992, 64, 59.
7. F. Beck and H. Guder, J. Electrochem. Soc., 1987, 134, 2416.
8. M. M. S. Paula and C. V. Franco, J. Coord. Chem., 1995, 36, 247.
9. M. M. S. Paula and C. V. Franco, J. Coord. Chem., 1996, 40, 71.
10. C. V. Franco, M. M. S. Paula, M. M. Meier and B. Szpoganicz, J. Coord. Chem., in press.
11. H. Nagao, H. Nishimura, Y. Kitanaka, F. S. Howel, M. Mukaida and H. Kakihana, Inorg. Chem., 1990, 29, 1693.
12. M. M. S. Paula and C. V. Franco, Quím. Nova, 1994, 17, 451.
13. C. V. Franco, M. M. S. Paula, P. Bodanese Prates and V. N. Moraes Jr., Synth. Met., 1997, 90, 81.
14. C. V. Franco, V. N. de Moraes Jr, F. Mocellin and M. M. S. Paula, unpublished work.
15. A. C. Boblitz Parente, A. V. C. Sobral, A. N. Klein, J. L. R. Muzart and C. V. Franco, Adv. Powder Metall. Particulate Mater., 1996, 13, 167.
16. J. D. Gilbert, D. Rose and G. Wilkinson, J. Chem. Soc. A, 1970, 2765.
17. C. J. Puchert, The Aldrich Library of Infrared Spectra, Aldrich Chemical, Milwaukee, 3rd edn., 1981.
18. R. M. Silverstein, G. C. Bassler and T. C. Morril, Identificação Espectrométrica de Compostos Orgânicos(Portuguese Edition), ed. Guanabara Dois S. A., Rio de Janeiro, Brazil, 3rd edn., 1979.
19. R. J. H. Clark and G. S. Williams, Inorg. Chem., 1965, 4, 350.
20. R. J. H. Clark and G. S. Williams, Chem. Ind., 1964, 3117.
21. D. W. Raichart and H. Taube, Inorg. Chem., 1972, 11, 999.
22. Model 271 COOL, Kinetic Analysis Software, User's Guide EG&G Instruments Corporation, 1992.
23. R. Kalir and A. Zilkha, Eur. Polym. J., 1978, 14, 557.
24. M. M. S. Paula and C. V. Franco, unpublished work.
25. T. F. Guarr and F. C. Anson, J. Phys. Chem., 1987, 91, 4037.
26. C. M. Elliott, C. J. Baldy, L. M. Nuwaysir and C. L. Wilkins, Inorg. Chem., 1990, 29, 389.
27. H. D. Abruña, P. Denisevich, M. Umaña, T. J. Meyer and R. W. Murray, J. Am. Chem. Soc., 1981, 103, 1.
28. P. Denisevich, H. D. Abruña, C. R. Leidner, T. J. Meyer and R. W. Murray, Inorg. Chem., 1982, 21, 2153.
29. P. G. Pickup, W. Kutner, C. R. Leidner and R. W. Murray, J. Am. Chem. Soc., 1984, 106, 1991.