Probing the Activity of Iron Peroxo Porphyrin Intermediates in the Reaction Layer during the Electrochemical Reductive Activation of O2

Jean-Marc Noel; Nikolaos Kostopoulos; Célia Achaibou; Claire Fave; Elodie Anxolabéhère-Mallart; Frédéric Kanoufi

doi:10.1002/anie.202004977

Probing the Activity of Iron Peroxo Porphyrin Intermediates in the Reaction Layer during the Electrochemical Reductive Activation of O₂

Angew Chem Int Ed Engl. 2020 Sep 14;59(38):16376-16380. doi: 10.1002/anie.202004977. Epub 2020 Jul 16.

Authors

Jean-Marc Noel¹, Nikolaos Kostopoulos², Célia Achaibou², Claire Fave², Elodie Anxolabéhère-Mallart², Frédéric Kanoufi¹

Affiliations

¹ Université de Paris, ITODYS, CNRS, 75006, Paris, France.
² Université de Paris, Laboratoire d'Electrochimie Moléculaire, CNRS, 75006, Paris, France.

PMID: 32543058
DOI: 10.1002/anie.202004977

Abstract

Herein we report the first example of using scanning electrochemical microscopy (SECM) to quantitatively analyze O₂ reductive activation in organic media catalyzed by three different Fe porphyrins. For each porphyrin, SECM can provide in one single experiment the redox potential of various intermediates, the association constant of Fe^II with O₂ , and the pK_a of the Fe^III (OOH^- )/ Fe^III (OO^2- ) couple. The results obtained can contribute to a further understanding of the parameters controlling the catalytic efficiency of the Fe porphyrin towards O₂ activation and reduction.

Keywords: O−O activation; electrocatalysis; iron porphyrins; molecular electrochemistry; scanning electrochemical microscopy.

Publication types

Research Support, Non-U.S. Gov't