Unveiling the Structure of Polytetraruthenated Nickel Porphyrin by Raman Spectroelectrochemistry

Autor(es)

Ferreira, Luis M. C. ^[1] ; Grasseschi, Daniel ^[1] ; Santos, Mauro S. F. ^[1] ; Martins, Paulo R. ^[2] ; Gutz, Ivano G. R. ^[1] ; Ferreira, Ana Maria C. ^[1] ; Araki, Koiti ^[1] ; Toma, Henrique E. ^[1] ; Angnes, Lucio ^[1]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Inst Quim, BR-05508000 Sao Paulo, SP - Brazil

^[2] Univ Fed Goias, Inst Quim, BR-74001970 Goiania, Go - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Langmuir; v. 31, n. 14, p. 4351-4360, APR 14 2015.
• Citações Web of Science: 10

Resumo

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)(2)Cl](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 NiO-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. (AU)

• Processo FAPESP: 11/00037-6 - Estudo e aplicação das propriedades físicas e químicas de nanopartículas plasmônicas em dispositivos inteligentes
• Beneficiário: Daniel Grasseschi
• Modalidade de apoio: Bolsas no Brasil - Doutorado Direto