Add time:08/22/2019         Source:sciencedirect.com

Composite films consisting of Co-porphyrin centres and a zeolitic ruthenium oxide/cyanoruthenate matrix were grown by oxidative electrodeposition, coupled with electrostatic attraction, from the colloidal suspension formed upon dispersion of a DMSO solution of Co(II) tetra(p-tolyl)porphyrin in an aqueous solution of RuCl3, K4Ru(CN)6 and KCl electrolyte at pH 2. Infrared spectroscopy showed the presence of a CN group, H2O and characteristic metalloporphyrin peaks in the deposit, but it also suggested that the system was not a simple mixture of the components. Further information about the chemical composition was obtained from the absorption spectra of the coatings prepared at SnO2-covered glass slide electrodes. Cyclic voltammetric studies of the composite film on glassy carbon are consistent with the observation that the formation of Ru(IV)-oxo species in the system induces oxidation of the co-existing Co-porphyrin species. The Co-porphyrin cation radicals seem to be both stabilized and activated by the ruthenium oxide/cyanoruthenate portions of the film. The composite system exhibits a notable electrocatalytic oxidation of otherwise highly electrochemically irreversible/inert propionaldehyde. The catalytic effect is related to the primary action of the Co-porphyrin radical, leading to H-abstraction from the aldehyde group, and the secondary action of Ru-oxo species, providing O-transfer pathways. Some analogies to the action of the high-valent iron porphyrin portions in cytochrome P450 are proposed here. The composite system also exhibited some reactivity towards the electro-oxidations of glucose and chloride.

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