A New Supramolecular Tetraruthenated Cobalt (II) Porphyrazine Displaying Outstanding Electrocatalytical Performance in Oxygen Evolution Reaction |
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| Authors: | Hiago N. Silva,Sé rgio Hiroshi Toma,Artur Luí s Hennemann,Josué M. Gonç alves,Marcelo Nakamura,Koiti Araki,Marcos Makoto Toyama,Henrique Eisi Toma |
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| Affiliation: | 1.Department of Chemistry, Institute of Chemistry, University of Sao Paulo, Av. Lineu Prestes 748, Butanta, São Paulo 05508-000, SP, Brazil; (H.N.S.); (S.H.T.); (A.L.H.); (J.M.G.); (M.N.); (K.A.);2.Maua Institute of Technology, Praça Mauá, 1-Mauá, São Caetano do Sul 09580-900, SP, Brazil |
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| Abstract: | ![]()
A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)2Cl]+ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O2 evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system. |
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| Keywords: | porphyrazine supramolecular ruthenium bipyridine cobalt phthalocyanine water-splitting oxygen evolution reaction electrocatalysis |
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