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Photoreduction of Cr(vi) using hydroxoaluminiumtricarboxymonoamide phthalocyanine adsorbed on TiO2

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Abstract

Hydroxoaluminiumtricarboxymonoamide phthalocyanine (AlTCPc) adsorbed at different loadings on TiO2 Degussa P-25 was tested for Cr(vi) photocatalytic reduction under visible irradiation in the presence of 4-chlorophenol (4-CP) as sacrificial donor. A rapid reaction takes place in spite of the presumable aggregation of the dye on the TiO2 surface. The removal of Cr(vi) is fairly negligible under visible-light irradiation, either without photocatalyst or in the presence of bare TiO2. The fast capture of conduction band electrons by Cr(vi), which forms a surface complex with TiO2, inhibits the formation of reactive oxygen species in the reductive pathway. This fact and the easier oxidation of 4-CP as compared to AlTCPc hinder the photobleaching of the dye and make feasible Cr(vi) reduction under visible irradiation. The consumption of Cr(vi) follows a pseudo-first order kinetics; the decay constant depends, in the studied range, on the photocatalyst mass, but it is barely affected by dye loading. The presence of 4-CP is essential, but its concentration has no effect on the Cr(vi) decay rate. Oxidation products of 4-CP, such as hydroquinone, catechol or benzoquinone, are not observed. Direct evidence of the one-electron reduction of Cr(vi) to Cr(v) was obtained by EPR spectroscopy using citric acid as Cr(v) trapping agent. In this case, disappearance of Cr(v) also follows a first order decay, but conduction band electrons do not seem to be involved. The fact that oxidation products of 4-CP are not observed is consistent with the fast dark removal of reaction intermediates by Cr(v), proved by EPR.

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Authors and Affiliations

  1. Gerencia Química, Comisión Nacional de Energía Atómica, Av. Gral. Paz 1499, 1650, San Martín, Prov. de Buenos Aires, Argentina

    Jorge M. Meichtry, Verónica Rivera & Marta I. Litter

  2. Consejo Nacional de Investigaciones Científicas y Técnicas, Argentina

    Jorge M. Meichtry, Yesica Di Iorio, Hernán B. Rodríguez, Enrique San Román, María A. Grela & Marta I. Litter

  3. Departamento de Química, Universidad Nacional de Mar del Plata, Funes 3350, 7602, Mar del Plata, Argentina

    Yesica Di Iorio & María A. Grela

  4. INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, 1428, Ciudad de Buenos Aires, Argentina

    Hernán B. Rodríguez & Enrique San Román

  5. Instituto de Investigación e Ingeniería Ambiental, Universidad de Gral. San Martín, Peatonal Belgrano 3563, 1er piso, 1650, San Martín, Prov. de Buenos Aires, Argentina

    Marta I. Litter

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  1. Jorge M. Meichtry
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  2. Verónica Rivera
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Correspondence to Marta I. Litter.

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This paper was published as part of the themed issue of contributions from the 5th European Meeting on Solar Chemistry and Photocatalysis: Environmental Applications held in Palermo, Italy, October 2008.

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Meichtry, J.M., Rivera, V., Di Iorio, Y. et al. Photoreduction of Cr(vi) using hydroxoaluminiumtricarboxymonoamide phthalocyanine adsorbed on TiO2. Photochem Photobiol Sci 8, 604–612 (2009). https://doi.org/10.1039/b816441j

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