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Product studies and laser flash photolysis of direct and 2,4,6-triphenylpyrylium—zeolite Y photocatalyzed degradation of fenvalerate

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Abstract

Direct irradiation of fenvalerate (FV) in aqueous solution (4 × 10−3 M) gives rise to 2,3—diarylisohexanitrile through the homolytic CO—CH(i-Pr) bond cleavage, followed by a rapid decarboxylation of the primary carbonyloxy radical, and radical recombination. The unusual exclusive formation of the cross combination product suggests that the persistent free radical effect is operative in this system and controls product formation. Spectroscopic evidence of the intermediacy of benzylic radicals decaying in microsecond time scale has been obtained by laser flash photolysis. These studies also reveal a remarkable attenuation of radical reactivity toward oxygen resulting from cyano substitution at the radical center. TPY photocatalyzed degradation of FV also leads to decarboxylation products accompanied by oxidative mineralization (38%). The TPY-photocatalyzed degradation can occur through two operating mechanisms involving the generation of OH˙ radicals and/or FV˙+ radical cations. Evidence for the latter intermediate has been obtained by laser flash photolysis in acetonitrile solution (detection of TP˙ radical) and by the quenching by FV of the emission from the TPY solid.

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Authors and Affiliations

  1. Departamento de Química e Instituto de Tecnología Química, Universidad Politécnica de Valencia, Apartado 22012, 46071, Valencia, Spain

    Ana Sanjuán, Mercedes Alvaro & Hermenegildo García

  2. Gamaser S.L., Pedrapiquers 4-izqda, Vara de Quart, 46014, Valencia, Spain

    Guillermo Aguirre

  3. Center for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa, K1N 6NJ, Canada

    J. C. Scaiano, Michelle N. Chrétien & Kathy-Sarah Focsaneanu

Authors
  1. Ana Sanjuán
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  2. Guillermo Aguirre
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  3. Mercedes Alvaro
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  4. Hermenegildo García
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  5. J. C. Scaiano
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  6. Michelle N. Chrétien
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  7. Kathy-Sarah Focsaneanu
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Correspondence to Hermenegildo García or J. C. Scaiano.

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Sanjuán, A., Aguirre, G., Alvaro, M. et al. Product studies and laser flash photolysis of direct and 2,4,6-triphenylpyrylium—zeolite Y photocatalyzed degradation of fenvalerate. Photochem Photobiol Sci 1, 955–959 (2002). https://doi.org/10.1039/b205000e

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