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Inverted Linear Correlation Between the Catalytic Activity of Iron Phthalocyanines and the Formal Potential of the Catalyst in the Electrooxidation of l-Cysteine

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Abstract

The formal potential of macrocyclic complexes is a reactivity index that can serve to predict their electrocatalytic activity. We have investigated the effect of the Fe(II)/(I) formal potential E°′ of several iron phthalocyanines preadsorbed on graphite electrodes on their catalytic activity for the electrooxidation of l-cysteine. A linear and inverted correlation is observed between the catalytic activity (as log I at constant E) versus the Fe(II)/(I) formal potential of the catalyst, i.e., the activity decreases as the driving force of the catalyst increases. The slope of the correlation is close to −2RT/F and seems to be the falling region of an incomplete volcano plot so the decrease of the activity with increasing E°′ can be attributed to a gradual increase in the coverage of l-cysteine molecules adsorbed on the Fe sites with a subsequent decrease in free Fe(II) active sites.

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Acknowledgments

This work has been supported by Fondecyt Project 1100773 CNRS-CONICYT (PICS France/Chile no. 5738 (2011–2013) and Núcleo Milenio Project P07-006-F, Iniciativa Científica Milenio del Ministerio de Economía, Fomento y Turismo. JFS acknowledges support from a Fondecyt-postdoctoral fellowship and to a Bicentenario grant PDA-23. CG thanks Conicyt for a Doctoral Scholarship AT-24110138.

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Authors and Affiliations

  1. Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago, 9170022, Chile

    Cristian Gutierrez, J. Francisco Silva, Jorge Pavez & José H. Zagal

  2. Chimie ParisTech, CNRS 8151, Paris, France

    Fethi Bedioui

  3. INSERM 1022, Université Paris Descartes, Paris, France

    Fethi Bedioui

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  1. Cristian Gutierrez
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  2. J. Francisco Silva
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  3. Jorge Pavez
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  4. Fethi Bedioui
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  5. José H. Zagal
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Correspondence to José H. Zagal.

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Gutierrez, C., Silva, J.F., Pavez, J. et al. Inverted Linear Correlation Between the Catalytic Activity of Iron Phthalocyanines and the Formal Potential of the Catalyst in the Electrooxidation of l-Cysteine. Electrocatalysis 3, 153–159 (2012). https://doi.org/10.1007/s12678-012-0097-y

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  • DOI: https://doi.org/10.1007/s12678-012-0097-y

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