View PDF Version
 
DOI: 10.1039/A608368D (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1997, 93, 1803-1812

Surface-enhanced resonance Raman spectroscopy of Ru and Os polyvinylpyridine adsorbed on silver electrodes

(Note: The full text of this document is currently only available in the PDF Version )

Andrew P. Taylor, Joe A. Crayston and Trevor J. Dines

Abstract

Surface-enhanced resonance Raman spectroscopy (SERRS) of [(PVP)xM(bpy)2Cl]Cl polymers (x=3, 10, 20, 100 with M=Ru; x=10 with M=Os) coated onto silver electrodes has been investigated and major bands in the spectra have been assigned. The SERR spectra of the adsorbed polymer layers are dominated by 2,2′-bipyridine assigned bands. Small changes in band positions owing to the oxidation of OsII to OsIII were observed at a gold electrode in the 1400–1700 cm-1 region. The Ru metallopolymers are used as model systems for the quantification of the SERRS signal in polymer-modified electrodes. Plots of intensity vs. surface coverage of metal centres were obtained as a function of loading (py:M ratio) at a constant deposition mass and as a function of deposition mass at a constant loading. At low surface coverages the variation of attenuation adjusted intensity with loading can be modelled as a Langmuir isotherm with I/Imax=kc/(1+kc) (c=the concentration, in mol dm-3, of Ru centres in the film; k=10.6). At higher coverages the increasing importance of bulk resonance Raman scattering led to substantial deviations from this equation. A model was proposed which shows similar but weaker dependence on loading. We propose that the discrepancy with observation may be explained by the actual samples having a longer path-length, and thus a greater attenuation, than predicted.

References

  1. M. A. T. Gilmartin and J. P. Hart, Analyst, 1995, 120, 1029 RSC.
  2. J. P. Collman, P. S. Wagenknecht and J. E. Hutchison, Angew. Chem., 1994, 33, 1537.
  3. R. W. Murray, in Electroanalytical Chemistry, ed. A. J. Bard, Marcel Dekker, New York, 1984, vol. 13, p. 191 Search PubMed; A. R. Hillman, in Electrochemical Science and Technology of Polymers, ed. R. G. Linford, Elsevier, London, 1987, vol. 1, p. 103 Search PubMed.
  4. T. Onikubo, R.-J. Lin and M. Kaneko, J. Electroanal. Chem., 1993, 361, 143 CrossRef CAS; L. A. Worl, G. F. Strouse, J. N. Younathan, S. M. Baxter and T. J. Meyer, J. Am. Chem. Soc., 1990, 112, 7571 CrossRef CAS; D. Wöhrle and D. Meissner, Adv. Mater., 1991, 3, 129 CrossRef CAS.
  5. C. M. Lindall, J. A. Crayston and D. J. Cole-Hamilton, J. Mater. Chem., 1995, 5, 955 RSC.
  6. C. M. Lindall, J. A. Crayston, D. J. Cole-Hamilton, A. Glidle and R. D. Peacock, J. Mater. Chem., 1996, 6, 1259 RSC.
  7. I. Rubinstein and A. J. Bard, J. Am. Chem. Soc., 1981, 103, 5007 CrossRef CAS.
  8. E. Csoregi, D. W. Schmidtke and A. Heller, Anal. Chem., 1995, 67, 1240 CrossRef CAS.
  9. A. P. Doherty, M. A. Stanley and J. G. Vos, Analyst, 1995, 120, 2371 RSC.
  10. A. P. Taylor, J. A. Crayston and T. J. Dines, in preparation.
  11. A. Otto, I. Mrozek, H. Grabhorn and W. Akemann, J. Phys.: Condens. Matter, 1992, 4, 1143 CrossRef CAS.
  12. R. K. Chang and T. E. Furtak, Surface Enhanced Scattering, Plenum Press, New York, 1982 Search PubMed.
  13. J. E. Pemberton, in Electrochemical Interfaces: Modern Techniques for in-situ Interface Characterization, ed. H. D. Abruna, VCH, New York, 1991, p. 193 Search PubMed.
  14. R. L. Birke, T. H. Lu and J. R. Lombardi, in Techniques for Characterization of Electrodes and Electrochemical Processes, ed. R. Varma and J. R. Selman, Wiley, New York, 1991, p. 211 Search PubMed.
  15. R. Aroca, in Vibrational Spectroscopy and Structure, ed. J. R. Durig, Elsevier, Amsterdam, 1991, vol. 19, p. 55 Search PubMed.
  16. P. Hildebrandt and M. Stockberger, J. Phys. Chem., 1984, 88, 5935 CrossRef CAS.
  17. T. J. Dines and R. D. Peacock, J. Chem. Soc., Faraday Trans. 1, 1988, 84, 3445 RSC.
  18. O. Siiman, A. Lepp and M. Kerker, J. Phys. Chem., 1983, 87, 5319 CrossRef CAS.
  19. D. A. Weitz, S. Garoff, J. L. Gersten and A. Nitzan, J. Chem. Phys., 1983, 78, 5324 CrossRef CAS.
  20. J. M. Clear, J. M. Kelly, C. M. O'Connell and J. G. Vos, J. Chem. Res. (M), 1981, 3039 Search PubMed.
  21. H. R. Virdee and R. E. Hester, J. Phys. Chem., 1984, 88, 451 CrossRef CAS.
  22. F. Vanhecke, K. Heremans, A. Kirsch-de Mesmaeker, L. Jacquet and A. Masschelein, J. Raman Spectrosc., 1989, 20, 617 CAS.
  23. Z. Y. Zhu, C. Mao, R. Y. Lang, L. X. Dai and C. S. Nie, J. Raman Spectrosc., 1993, 24, 221 CAS.
  24. A. M. Stacy and R. P. van Duyne, Chem. Phys. Lett., 1983, 102, 365 CrossRef CAS.
  25. M. J. Edmiston and R. D. Peacock, Spectrochim. Acta A, 1993, 49, 1481 CrossRef.
  26. P. G. Roth and F. J. Boerio, J. Polym. Sci. B, 1987, 25, 1923 CrossRef CAS.
  27. R. L. Garrell and K. D. Beer, Langmuir, 1989, 5, 452 CrossRef CAS.
  28. K. Tashiro, K. Matsushima and M. Kobayashi, J. Phys. Chem., 1990, 94, 3197 CrossRef CAS.
  29. J. A. Chambers and R. P. Buck, J. Electroanal. Chem., 1984, 163, 297 CrossRef CAS.
  30. J. A. Chambers and R. P. Buck, J. Electroanal. Chem., 1982, 140, 173 CrossRef CAS.
  31. J. A. Chambers and R. P. Buck, J. Raman Spectrosc., 1984, 15, 160 CAS.
  32. A. I. Vogel, Textbook of Practical Organic Chemistry, Longman, London, 1978 Search PubMed.
  33. G. Spritschnick, H. W. Spritschnick, P. P. Kirsch and D. G. Whitten, J. Am. Chem. Soc., 1977, 99, 4947 CrossRef CAS.
  34. D. A. Buckingham, F. P. Dwyer, H. A. Goodwin and A. M. Sargeson, Aust. J. Chem., 1964, 17, 325 CAS.
  35. R. J. Forster and J. G. Vos, Macromolecules, 1990, 23, 4372 CrossRef CAS.
  36. A. Katchalsky, K. Rosenheck and B. Altmann, J. Polym. Sci., 1957, 23, 795 Search PubMed.
  37. J. M. Calvert and T. J. Meyer, Inorg. Chem., 1981, 20, 27 CrossRef CAS.
  38. D. Ghesquiere, B. Ban and C. Chachaty, Macromolecules, 1979, 10, 743.
  39. D. Leech, R. J. Forster, M. R. Smyth and J. G. Vos, J. Mater. Chem., 1991, 1, 629 RSC.
  40. A. P. Taylor, J. A. Crayston, T. J. Dines, A. Glidle and R. D. Peacock, in preparation.
  41. B. Chase and B. Parkinson, J. Phys. Chem., 1991, 95, 7810 CrossRef CAS.
  42. O. Haas, M. Kriens and J. G. Vos, J. Am. Chem. Soc., 1981, 103, 1318 CrossRef CAS.
  43. A. P. Taylor, Ph. D. Thesis, University of St. Andrews, 1996.
  44. D. P. Strommen, P. K. Mallick, G. D. Danzer, R. S. Lumpkin and J. R. Kincaid, J. Phys. Chem., 1990, 94, 1357 CrossRef CAS.
  45. A. P. Clarke, J. G. Vos, A. Glidle and A. R. Hillman, J. Chem. Soc., Faraday Trans., 1993, 89, 1695 RSC.
  46. J. V. Caspar, T. D. Westmoreland, G. H. Allen, P. G. Bradley, T. J. Meyer and W. H. Woodruff, J. Am. Chem. Soc., 1984, 106, 3492 CrossRef CAS; J. G. Gaudiello, P. G. Bradley, K. A. Norton, W. H. Woodruff and A. J. Bard, Inorg. Chem., 1984, 23, 3 CrossRef CAS.
  47. J. S. Ard and H. Susi, Appl. Spectrosc., 1978, 32, 321 CAS.
  48. T. C. Strekas, D. H. Adams, A. Packer and T. G. Spiro, Appl. Spectrosc., 1978, 28, 32448.
  49. Q. Feng, W. Yue and T. M. Cotton, J. Phys. Chem., 1990, 94, 2082 CrossRef CAS and references therein.
  50. A. P. Taylor, J. A. Crayston and T. J. Dines, in preparation.
  51. J.-H. Kim, T. M. Cotton, R. A. Uphaus and D. Möbius, J. Phys. Chem., 1989, 93, 7313.
  52. E. J. Zeman, K. T. Carron, G. C. Schaltz and R. P. Van Duyne, J. Chem. Phys., 1987, 87, 4189 CrossRef CAS.
  53. R. Aroca and D. Battisti, Langmuir, 1990, 6, 250 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.