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Photostimulated formation of radicals on oxide surfaces

  • Part II: Structure And Reactivity Of Radicals On Surfaces
  • Published:
Molecular Engineering

Abstract

We present results ofin situ EPR investigations of the mechanism of photostimulated processes resulting in radical and ion-radical particle formation on the surfaces of oxide dielectrics (magnesium, calcium, aluminum oxides, zeolites). Three types of reactions are discussed:

  1. 1.

    Formation of oxygen anion-radicals on MgO and CaO surfaces.

  2. 2.

    Formation of benzene cation-radicals on ZSM-5 zeolites.

  3. 3.

    Formation of radical particles from aromatic nitrocompounds adsorbed on alumina.

On the basis of investigation of the spectral relationships and the properties of surface active centre, it is concluded that light is absorbed by coordinatively unsaturated surface sites in the first system, whereas in the other processes, electron donor-acceptor (EDA) complexes between adsorbed molecules and surface active sites are supposed to be key intermediates. These EDA complexes are shown to incorporate donor solvent molecules as well. In this case the energetic characteristics of the photoprocesses are substantially determined by the ionization potential of solvent molecules.

Mechanisms of photo- and thermostimulated processes are compared and possible similarities are discussed for all the reactions studied.

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References

  1. L. L. Basov, Yu. P. Solonitzin, and A. N. Terenin:Dokl. Akad. Nauk SSSR 164, 122 (1965).

    Google Scholar 

  2. A. A. Lisachenko and F. I. Vilesov:Uspekhi Fotoniki 4, 18 (1974).

    Google Scholar 

  3. L. L. Basov, G. N. Kuzmin, I. M. Prudnikov, and Yu. P. Solonitzin:Uspekhi Fotoniki 6, 82 (1977).

    Google Scholar 

  4. E. Garrone, A. Zecchina, and F. S. Stone:Phil. Mag. B 42, 683 (1980).

    Google Scholar 

  5. E. Garrone and F. S. Stone:J. Chem. Soc. Farad. Trans. I 83, 1237 (1987).

    Google Scholar 

  6. M. Che and A. J. Tench:Advances in Catal. 31, 77 (1982).

    Google Scholar 

  7. S. Coluccia, A. M. Deane, and A. J. Tench:J. Chem. Soc., Faraday Trans. I 74, 2913 (1978).

    Google Scholar 

  8. M. Anpo, Y. Yamada, Y. Kubokawa, S. Coluccia, A. Zecchina, and M. Che:J. Chem. Soc., Faraday Trans. I 84, 751 (1988).

    Google Scholar 

  9. V. N. Kuznetsov, A. O. Klimovsky, and A. A. Lisachenko:Kinetika i Kataliz 31, 659 (1990).

    Google Scholar 

  10. V. A. Shvets, A. V. Kuznetsov, V. A. Fenin, and V. B. Kazansky:J. Chem. Soc. Farad. Trans. I 81, 2913 (1985).

    Google Scholar 

  11. A. V. Kuznetsov and V. A. Shvets:Zhurn. Fiz. Khimii 64, 717 (1990).

    Google Scholar 

  12. A. M. Volodin:React. Kinet. Catal. Lett. 28, 189 (1985).

    Google Scholar 

  13. A. M. Volodin:Khimicheskaya Fizika 11, 1054 (1992).

    Google Scholar 

  14. A. M. Volodin:React. Kinet. Catal. Lett. 44, 171 (1991).

    Google Scholar 

  15. V. A. Bolshov and A. M. Volodin:React. Kinet. Catal. Lett. 46, 337 (1992).

    Google Scholar 

  16. T. A. Konovalova and A. M. Volodin:React. Kinet. Catal. Lett. 51, 227 (1993).

    Google Scholar 

  17. A. M. Volodin, A. E. Cherkashin, and V. S. Zakharenko:React. Kinet. Catal. Lett. 11, 103 (1979).

    Google Scholar 

  18. A. M. Volodin and A. E. Cherkashin:Kinetika i Kataliz 22, 598 (1981).

    Google Scholar 

  19. A. M. Volodin, V. S. Zakharenko, and A. E. Cherkashin:React. Kinet. Catal. Lett. 18, 321 (1981).

    Google Scholar 

  20. I. M. Prudnikov and Yu. P. Solonitzin:Kinetika i Kataliz 13, 426 (1972).

    Google Scholar 

  21. A. J. Tench and T. Lawson:Chem. Phys. Lett. 7, 459 (1970).

    Google Scholar 

  22. N.-B. Wong and J. H. Lunsford:J. Chem. Phys. 55, 3007 (1971).

    Google Scholar 

  23. A. J. Tench, T. Lawson, and J. F. Kibblewhite:J. Chem. Soc. Farad. Trans. I 68, 1169 (1972).

    Google Scholar 

  24. M. Ivamoto and J. H. Lunsford:Chem. Phys. Lett. 66, 48 (1979).

    Google Scholar 

  25. Yu. P. Solonitzin:Kinetika i Kataliz 7, 43 (1977).

    Google Scholar 

  26. M. Anpo and Y. Yamada: Material Chemistry and Physics18, 465 (1988).

    Google Scholar 

  27. A. M. Volodin, A. E. Cherkashin, and K. N. Prokopiev:React. Kinet. Catal. Lett. 46, 373 (1992).

    Google Scholar 

  28. A. M. Volodin, A. E. Cherkashin, and K. N. Prokopiev:Kinetika i Kataliz 33, 1190 (1992).

    Google Scholar 

  29. M. Che, S. Coluccia, and A. Zecchina:J. Chem. Soc. Farad. Trans. I 74, 1324 (1978).

    Google Scholar 

  30. D. Cordishi, V. Indovina, and M. Occhiuzzi:J. Chem. Soc. Farad. Trans. I 74, 883 (1978).

    Google Scholar 

  31. A. Terenin and A. Sidorova:Izv. Akad. Nauk. SSSR, Ser. Khim. 2, 152 (1950).

    Google Scholar 

  32. J. K. Fogo:J. Phys. Chem. 65, 1919 (1961).

    Google Scholar 

  33. J. J. Rooney and R. C. Pink:Trans. Faraday Soc. 58, 1632 (1962).

    Google Scholar 

  34. A. Terenin, V. Barachevsky, E. Kotov, and V. Kolmogorov:Spectrochim. Acta. 19, 1797 (1963).

    Google Scholar 

  35. D. N. Stamires and J. Turkevich:J. Am. Chem. Soc. 86, 749 (1964).

    Google Scholar 

  36. A. Terenin:J. Chim. Phys. 646 (1965).

  37. B. D. Flockhart, J. A. N. Scott, and R. C. Pink:Trans. Faraday Soc. 62, 730 (1966).

    Google Scholar 

  38. V. D. Pokhodenko, V. A. Khizhny, B. G. Koshetchko, and O. I. Shkreby:Dokl. Akad. Nauk SSSR 210, 640 (1973).

    Google Scholar 

  39. A. S. Morkovnik, N. M. Dobaeva, O. Yu. Okhlobystin, and V. V. Bessonov:Zhurn. Org. Khimii 17, 2618 (1981).

    Google Scholar 

  40. B. Reitstoen and V. D. Parker:J. Am. Chem. Soc. 113, 6954 (1991).

    Google Scholar 

  41. J. K. Kochi:Acta Chemica Scandinavica 44, 409 (1990).

    Google Scholar 

  42. A. J. Bard, A. Ledwith, and H. J. Shine:Adv. Phys. Org. Chem. 13, 155 (1976).

    Google Scholar 

  43. M. B. Loktev and A. A. Slinkin:Uspekhi Khimii 45, 1594 (1976).

    Google Scholar 

  44. Y. Kurita, T. Sonada, and M. Sato:J. Catal. 19, 82 (1970).

    Google Scholar 

  45. J. C. Vedrine, A. Auroux, V. Bolis, P. Dejaifve, C. Naccache, P. Wierzchowski, E. G. Derouane, J. B. Nagy, J.-P. Gilson, J. H. C. van Hooff, J. P. van den Berg, and J. Wolthuizen:J. Catal. 59, 248 (1979).

    Google Scholar 

  46. A. V. Kucherov, A. A. Slinkin, D. A. Kondratyev, T. N. Bondarenko, A. M. Rubinstein, and Kh. M. Minachev:J. Mol. Catal. 37, 107 (1986).

    Google Scholar 

  47. M. K. Carter and G. Vincow:J. Chem. Phys. 47, 292 (1967).

    Google Scholar 

  48. O. Edlung, P.-O. Kinel, A. Lund, and A. Shimizu:J. Chem. Phys. 46, 3679 (1967).

    Google Scholar 

  49. T. Tanei:Bull. Chem. Soc. Jap. 41, 833 (1968).

    Google Scholar 

  50. R. Foster:Organic Charge-Transfer Complexes, Academic Press, London (1969).

    Google Scholar 

  51. A. Ayame and T. Izumizava:J. Chem. Soc., Chem. Commun. 645 (1989).

  52. A. V. Zubkov, A. T. Koritsky, and Ya. S. Lebedev:Dokl. Akad. Nauk SSSR 180, 1150 (1968).

    Google Scholar 

  53. F. R. Chen and J. J. Fripiat:J. Phys. Chem. 96, 819 (1992).

    Google Scholar 

  54. V. A. Bolshov, A. M. Volodin, A. G. Maryasov, G. M. Zhidomirov, and V. F. Yudanov:Dokl. Akad. Nauk. SSSR 316, 141 (1991).

    Google Scholar 

  55. I. V. Yudanov, I. I. Zakharov, and G. M. Zhidomirov:React. Kinet. Catal. Lett. 48, 411 (1992).

    Google Scholar 

  56. B. D. Flockhart, I. R. Leith, and R. C. Pink:Trans. Faraday Soc. 66, 469 (1970).

    Google Scholar 

  57. B. D. Flockhart, M. C. Megarry, and C. Pink:Advances in Chem. 121, 509 (1973).

    Google Scholar 

  58. H. Kashiwagi:Bull. Chem. Soc. Jpn. 64, 423 (1991).

    Google Scholar 

  59. H. G. Aurich and W. Weiss:Topics in Current Chem. 59, 65 (1975).

    Google Scholar 

  60. J. A. Menapace and J. E. Marlin:J. Phys. Chem. 94, 1906 (1990).

    Google Scholar 

  61. A. L. Buchachenko and A. M. Vaserman:Stable Radicals, Khimiya, Moskva (1973).

    Google Scholar 

  62. D. H. Geske and A. H. Maki:J. Am. Chem. Soc. 82, 2671 (1960).

    Google Scholar 

  63. A. H. Maki and D. H. Geske:J. Chem. Phys. 33, 825 (1960).

    Google Scholar 

  64. R. L. Ward:J. Am. Chem. Soc. 83, 1296 (1961).

    Google Scholar 

  65. R. M. Morris and K. J. Klabunde:Inorg. Chem. 22, 682 (1983).

    Google Scholar 

  66. C. Lagercrantz and M. Yhland:Acta Chem. Scand. 16, 1043 (1962).

    Google Scholar 

  67. A. M. Volodin, T. A. Konovalova and A. F. Bedilo:XVIth International Conference on PhotochemistryICP’, August 1–6, 1993, Vancouver, Canada, p. 321 (1993).

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Volodin, A.M., Bolshov, V.A. & Konovalova, T.A. Photostimulated formation of radicals on oxide surfaces. Mol Eng 4, 201–226 (1994). https://doi.org/10.1007/BF01004055

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  • DOI: https://doi.org/10.1007/BF01004055

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