title: Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion.
abstract: A very efficient electrogenerated Fe(0) porphyrin catalyst was obtained by substituting in tetraphenylporphyrin two of the opposite phenyl rings by ortho-, ortho'-phenol groups while the other two are perfluorinated. It proves to be an excellent catalyst of the CO2-to-CO conversion as to selectivity (the CO faradaic yield is nearly quantitative), overpotential, and turnover frequency. Benchmarking with other catalysts, through catalytic Tafel plots, shows that it is the most efficient, to the best of our knowledge, homogeneous molecular catalyst of the CO2-to-CO conversion at present. Comparison with another Fe(0) tetraphenylporphyrin bearing eight ortho-, ortho'-phenol functionalities launches a general strategy where changes in substituents will be designed so as to optimize the operational combination of all catalyst elements of merit.
authors.affiliation: Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université-Centre National de la Recherche Scientifique, 75205 Paris Cedex 13, France saveant@univ-paris-diderot.fr cyrille.costentin@univ-paris-diderot.fr robert@univ-paris-diderot.fr.
authors.forename: Cyrille
authors.initials: C
authors.lastname: Costentin
authors.affiliation: Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université-Centre National de la Recherche Scientifique, 75205 Paris Cedex 13, France.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Passard
authors.affiliation: Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université-Centre National de la Recherche Scientifique, 75205 Paris Cedex 13, France saveant@univ-paris-diderot.fr cyrille.costentin@univ-paris-diderot.fr robert@univ-paris-diderot.fr.
authors.forename: Marc
authors.initials: M
authors.lastname: Robert
authors.affiliation: Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université-Centre National de la Recherche Scientifique, 75205 Paris Cedex 13, France saveant@univ-paris-diderot.fr cyrille.costentin@univ-paris-diderot.fr robert@univ-paris-diderot.fr.
authors.forename: Jean-Michel
authors.initials: JM
authors.lastname: Savéant
keywords: CO2 reduction; catalysis; contemporary energy challenges; electrochemistry; solar fuels