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Volcano correlations for the reactivity of surface-confined cobalt N4-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate

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Abstract

We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B12, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin < Co–tetrasulfonatotetraphenylporphyrin < Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B12 exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N4-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site.

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Acknowledgment

This work was funded by Fondecyt Project 1060030. Financial support from ECOS-Sud (France)/Conicyt (Chile) program C03E02 and Conicyt/CNRS 2007/2006 for travel expenses is acknowledged.

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Author notes

  1. Miguel Gulppi

    Present address: Biosigma, Casilla 100, Correo El Cortijo, Santiago, Chile

Authors and Affiliations

  1. Facultad de Química y Biología, Departamento de Química de los Materiales, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago, Chile

    Gonzalo Ochoa, Maritza Páez, Juan Costamagna, Miguel Gulppi & José H. Zagal

  2. Department of Chemistry, Rhodes University, Grahamstown, 6140, South Africa

    Tebello Nyokong

  3. INSERM, U 640, CNRS, UMR 8151, École Nationale Supérieure de Chimie de Paris, René Descartes Paris 5, Chemical and Genetic Pharmacology Laboratory, Paris, France

    Fethi Bedioui

  4. Institut für Physikalische und Theoretische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 8, 72076, Tübingen, Germany

    Jan A. Claußen

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  1. Jan A. Claußen
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Correspondence to José H. Zagal.

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Dedicated to Prof. Dr. Teresa Iwasita on the occasion of her 65th birthday in recognition of her numerous contributions to interfacial electrochemistry.

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Claußen, J.A., Ochoa, G., Páez, M. et al. Volcano correlations for the reactivity of surface-confined cobalt N4-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate. J Solid State Electrochem 12, 473–481 (2008). https://doi.org/10.1007/s10008-007-0336-y

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