Abstract
The pulse radiolytic technique has been used to generate a variety of oxidising radicals in aqueous solution. The oxidants include halide radicals, bipy Ru 3+, porphyrin π-radical cations and oxidised prometh-azine. Most of the radicals are unstable with respect to dispropor- tionation, although the timescalė for this deactivation varies enormously. Addition of colloidal Ruo22H2o or Prussian Blue, both reasonable 02 — evolving catalysts, can enhance the rate of decay of the oxidising raaicals. With unstable radicals, the catalyst simply enhances disproportionation. Stable but weakly oxidising radicals can transfer charge to the catalyst until equilibrium is attained. This can involve storage of several hundred oxidising equivalents on each colloidal particle. With strong oxidising radicals that are also stable in water, the catalyst can cause water oxidation.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
A. Henglein, J. Phys. Chem., 1981, 85, 1627.
A. Henglein, J. Westerhausen and J. Lilie, Ber. Bunsenges Phys. Chem., 1981, 85, 182.
A. Henglein and J. Lilie, J. Am. Chem. Soc., 1981, 103, 1059
A. Henglein, B. Lindig and J. Westerhausen, J. Phys. Chem., 1981, 85, 1627.
A. Harriman, G. Porter and M.C. Richoux, J. Chem. Soc., Faraday Trane. 2, 1982, 78, 1985.
D. Meisel, W.A. Mulac and M.S. Matheson, J. Phys. Chem., 1981, 85, 179.
M. Venturi, Q.G. Mulazzani and M.Z. Hoffman, J. Phys. Chem., 1984, 88, 912
E. Pramauro and E. Pellizzetti, Abstracts 3rd. Int. Conf. Photo-chem. Conversion and Storage of Solar Energy, Colorado, U.S.A. August 1980.
E. Sutcliffe and M. Neuman-Spallart, Helv. Chim. Acta, 1981, 64, 2148.
M. Gratzel, in Energy Resources through Photochemistry and Catalysis, ed. M. Gratzel,(Academic Press, New York, 1983) Chap. 3.
K. Kalyanasundaram and M. Gratzel, in Photochemical, Photoelectro-chemical and Photobiological Processes, eds. D.O. Hall and W. Palz (D. Reidel, Dordrecht, 1981) Vol. 2, p. 129.
P.A. Christensen, A. Harriman, G. Porter and P. Neta, J. Chem.Soc. Faraday Trans. 2, 1984, 80, 1451.
A. Henglein, B. Lindig and J. Westerhausen, Radiat. Phys. Chem., 1984, 23, 199.
A. Harriman, G. Porter and D. Walters, J. Chem. Soc., Faraday Trans. 2, 1981, 77, 2373.
P.A. Christensen, A. Harriman and W. Erbs, J. Chem. Soc., Faraday Trans 2, 1985, 8l, 575.
A. Mills, A. Harriman and G. Porter, Anal Chem., 1981, 53, 1254.
J.F. Endicott, in Concepts in Inorganic Photochemistry, eds. A.W. Adamaon and P.D. Fleischauer (Wiley, New York, 1975), p. 8l.
P. Neta, J. Phys. Chem., 1981, 85, 3678.
P. Neta and A. Harriman, J. Chem. Soc., Faraday Trans. 2, 1985, 81, 123.
A. Harriman, P.A. Christensen, P. Neta and M.C. Richoux, Sci. Papers Inst. Phys. Chem. Res., 1984, 78, l43.
P.A. Christensen, A. Harriman, P. Neta and M.C. Richoux, J. Chem. Soc., Faraday Trans. 2, in press.
D.G. Davies, in The Porphyrins, ed. D. Dolphin (Academic Press, New York, 1979) Vol. 3, Chap 4
P. Neta, M.C. Richoux, A. Harriman and L.R. Milgrom, J. Chem. Soc., Faraday Trans. 2, in press.
P.A. Christensen and A. Harriman, unpublished results.
K. Itaya, N. Shaji and I. Uchida, J. Am. Chem. Soc., 1984, 106, 3423.
M.S. Matheson and L.M. Dorfman, in Pulse Radiolysis (M.I.T. Press, Cambridge, Mass.,1969) p. 51.
A. Harriman, P. Neta and M.C. Richoux, J. Chem. Soc., Faraday Trans. 2, in press.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1986 D. Reidel Publishing Company
About this chapter
Cite this chapter
Harriman, A., Neta, P., Richoux, M.C. (1986). Catalysed Decay of Oxidising Radicals in Water. In: Pelizzetti, E., Serpone, N. (eds) Homogeneous and Heterogeneous Photocatalysis. NATO ASI Series, vol 174. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4642-2_6
Download citation
DOI: https://doi.org/10.1007/978-94-009-4642-2_6
Publisher Name: Springer, Dordrecht
Print ISBN: 978-90-277-2221-8
Online ISBN: 978-94-009-4642-2
eBook Packages: Springer Book Archive