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Cobalt porphyrins immobilized on niobium(V) oxide grafted on a silica gel surface: study of the catalytic reduction of dissolved dioxygen

CHRISTIANA A. PESSÔA

Instituto de Química, Unicamp, CP 6154, 13083-970 Campinas, SP, Brazil

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and

YOSHITAKA GUSHIKEM

Instituto de Química, Unicamp, CP 6154, 13083-970 Campinas, SP, Brazil

Corresponding author, Instituto de Química, Unicamp, CP 6154, 13083-970 Campinas, SP, Brazil.

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https://doi.org/10.1002/jpp.360Cited by:26 (Source: Crossref)

Abstract

Hematoporphyrin IX, H₂HMP, 8,13-bis(1-hydroxyethyl)-3,7,12,17-tetramethyl-21H,23H-porphine-2,18-dipropionic acid and protoporphyrin IX, H₂PP, 8,13-divinyl-3,7,12,17-tetramethyl-21H,23H-porphine-2,18-dipropionic acid were efficiently immobilized on niobium oxide grafted on a silica gel surface, SiO₂/Nb₂O₅, by the -COO–Nb bond formed between the porphyrin carboxyl groups and the grafted Nb₂O₅. These immobilized porphyrins, SiO₂/Nb₂O₅/H₂HMP and SiO₂/Nb₂O₅/H₂PP, were further reacted with Co(II) in dimethylformamide, resulting in SiO₂/Nb₂O₅/CoHMP and SiO₂/Nb₂O₅/CoPP metallated complexes. The UV-vis spectra of the solid materials showed changes of the Q-bands (a_2u → e_g transition) upon metallation, indicating that by incorporation of Co(II) in the porphyrin ring the local symmetry changed from D_2h to D_4h. These materials, when incorporated in carbon paste electrodes, presented the property of electrocatalyzing O₂ reduction. Rotating disk experiments were performed in order to estimate the number of electrons involved in the process. It was observed that, for both modified electrodes, O₂ was reduced to water in a four-electron process. Amperometric studies showed the potentiality of both modified electrodes as sensors for the determination of dissolved dioxygen. The response time was less than 3 s. A linear response for both systems was obtained between 2 and 12 ppm.

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