The role of mass transfer in solution photocatalysis at a supported titanium dioxide surface

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Samina Ahmed, Claire E. Jones, Terence J. Kemp and Patrick R. Unwin


Abstract

The kinetics of Cl- production from the UV-photocatalysed degradation of aqueous 4-chlorophenol (CP), by a thin TiO2 (Degussa P25) film, in both aerated and oxygenated solutions, have been determined by the channel flow method with electrochemical detection. The experimental approach allows surface kinetics and mass transport effects to be readily resolved. For typical irradiation intensities of (0.7–2.0)×1017 quanta cm-2 s-1, the results obtained with dilute CP solutions (⩽0.5 mM), in particular, clearly demonstrate that there is a range of practically important conditions where mass transport plays a role in controlling the kinetics of the process. When these effects are considered, the surface kinetics are consistent with the Langmuir–Hinshelwood model.


References

  1. See for example: (a) A. Mills and S. Le Hunte, J. Photochem. Photobiol. A: Chem., 1997, 108, 1 CrossRef CAS; (b) A. Mills, R. H. Davies and D. Worsley, Chem. Soc. Rev., 1993, 22, 417 RSC; (c) A. L. Linsebigler, G. Lu and J. T. Yates, Jr., Chem Rev., 1995, 95, 735 CrossRef CAS.
  2. (a) J. Cunningham and P. Sedlak, J. Photochem. Photobiol. A: Chem., 1994, 77, 255 CrossRef CAS; (b) M. Barbeni, E. Pramauro, E. Pelizzetti, E. Borgarello, M. Gratzel and N. Serpone, Nouv. J. Chim., 1984, 8, 547 Search PubMed; (c) J.-C. D'Oliveira, G. Al-Sayyed and P. Pichat, J. Environ. Sci. Technol., 1990, 24, 990 Search PubMed; (d) J.-C. D'Oliveira, C. Minero, E. Pelizzetti and P. Pichat, J. Photochem. Photobiol. A: Chem., 1993, 72, 261 CrossRef CAS; (e) R. W. Matthews, Water Res., 1986, 20, 569 CAS; (f) R. W. Matthews, Water Res., 1990, 24(5), 653 CrossRef CAS; (g) L. Rideh, A. Wahrer, D. Ronze and A. Zoulalian, Ind. Engg. Chem. Res., 1997, 36, 4712 Search PubMed.
  3. (a) M. Bideau, B. Claudel, C. Dubien, L. Faure and H. Kazouan, J. Photochem. Photobiol. A: Chem., 1995, 91, 137 CrossRef CAS; (b) K. Hofstadler, R. Bauer, S. Novalic and G. Heisler, J. Environ. Sci. Technol., 1994, 28, 670 Search PubMed; (c) H. Al-Ekabi and N. Serpone, J. Phys. Chem., 1988, 92, 5726 CrossRef CAS; (d) R. W. Matthews, J. Catal., 1988, 111, 264 CrossRef CAS; (e) R. W. Matthews, J. Phys. Chem., 1987, 91, 3328 CrossRef CAS; (f) K. Tennakone, C. T. K. Tilakaratne and I. R. M. Kottegoda, J. Photochem. Photobiol. A: Chem., 1995, 87, 177 CrossRef CAS; (g) R. W. Matthews and S. R. McEvoy, J. Photochem. Photobiol. A: Chem., 1992, 64, 231 CrossRef CAS; (h) A. Sclafani, A. Brucato and L. Rizzuti, Photocatalytic Treatment of Water and Air, ed. D. F. Ollis and H. Al-Ekabi, Elsevier, Amsterdam, 1993, 533 Search PubMed.
  4. C. S. Turchi and D. F. Ollis, J. Phys. Chem., 1988, 92, 6852 CrossRef CAS.
  5. A. Mills and J. Wang, J. Photochem, Photobiol. A: Chem., 1998, 118, 53 CrossRef CAS.
  6. E. L. Sjöberg and D. Rickard, Geochim. Cosmochim. Acta, 1983, 47, 2281 CrossRef.
  7. T. J. Kemp, P. R. Unwin and L. Vincze, J. Chem. Soc., Faraday Trans., 1995, 91(21), 3893 RSC.
  8. See for example: (a) P. R. Unwin, A. J. Barwise and R. G. Compton, J. Colloid Interface Sci., 1989, 128, 208 CAS; (b) R. G. Compton, K. L. Prichard and P. R. Unwin, Chem. Commun., 1989, 249 RSC; (c) R. G. Compton and P. R. Unwin, Philos. Trans. R. Soc. London, Ser. A, 1990, 330, 1 Search PubMed; (d) R. G. Compton and K. L. Prichard, Philos. Trans. R. Soc. London, Ser. A, London, 1990, 330, 47 Search PubMed; (e) C. A. Brown, R. G. Compton and C. A. Narramore, J. Colloid Interface Sci., 1993, 160, 1517 CrossRef CAS; (f) R. G. Compton and C. A. Brown, J. Colloid Interface Sci., 1994, 165, 445 CrossRef CAS.
  9. (a) P. R. Unwin and J. V. Macpherson, Chem. Soc. Rev., 1995, 24, 109 RSC; (b) J. V. Macpherson and P. R. Unwin, Prog. React. Kinet., 1995, 20, 185 Search PubMed; (c) P. R. Unwin, J. Chem. Soc., Faraday Trans., 1998, 94, 3183 RSC; (d) P. R. Unwin and R. G. Compton, Compr. Chem. Kinet., 1989, 29, 173 Search PubMed.
  10. For a review of photoelectrochemical applications of channel electrodes see: R. G. Compton and R. A. W. Dryfe, Prog. React. Kinet., 1995, 20, 245 Search PubMed.
  11. R. Orton and P. R. Unwin, J. Chem. Soc., Faraday Trans., 1993, 89, 3947 RSC.
  12. (a) C. G. Hatchard and C. A. Parker, Proc. R. Soc. London, Ser. A, 1956, 235, 518 Search PubMed; (b) L. Vincze, T. J. Kemp and P. R. Unwin, J. Photochem. Photobiol. A: Chem., 1999, 123, 7 CrossRef CAS.
  13. J. V. Macpherson and P. R. Unwin, J. Phys. Chem., 1995, 99, 14824 CrossRef CAS.
  14. A. Mills, D. Worsley and R. H. Davies, J. Chem. Soc., Chem. Commun., 1994, 2677 RSC.
  15. C. R. Wilke and P. Chang, AIChE J., 1955, 1(2), 264 CrossRef CAS.
  16. J. S. Newman, Electrochemical Systems, Prentice Hall, Englewood Cliffs, NJ, 1991 Search PubMed.
  17. A. Mills and S. Morris, J. Photochem. Photobiol. A: Chem., 1993, 70, 183 CrossRef CAS.
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