Unveiling the structure of polytetraruthenated nickel porphyrin by raman spectroelectrochemistry
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2015-03-26
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The structure of polytetraruthenated nickel porphyrin was unveiled for the first time by electrochemistry, Raman spectroelectrochemistry, and a hydroxyl radical trapping assay. The electrocatalytic active material, precipitated on the electrode surface after successive cycling of [NiTPyP{Ru(bipy)2Cl}4]4+ species in strong aqueous alkaline solution (pH 13), was found to be a peroxo-bridged coordination polymer. The electropolymerization process involves hydroxyl radicals (as confirmed by the characteristic set of DMPO/•OH adduct EPR peaks) as reaction intermediates, electrocatalytically generated in the 0.80–1.10 V range, that induce the formation of Ni–O–O–Ni coordination polymers, as evidenced by Raman spectroelectrochemistry and molecular modeling studies. The film growth is halted above 1.10 V due to the formation of oxygen gas bubbles.
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FERREIRA, Luís M. C. et al. Unveiling the structure of polytetraruthenated nickel porphyrin by raman spectroelectrochemistry. Langmuir, Washington, v. 31, n. 14, p. 4351-4360, 2015. DOI: 10.1021/acs.langmuir.5b00250. Disponível em: https://pubs.acs.org/doi/10.1021/acs.langmuir.5b00250. Acesso em: 5 jul. 2024.