Operando Spectroelectrochemistry Unravels the Mechanism of CO 2 Electrocatalytic Reduction by an Fe Porphyrin.

Autor: Salamé A; Laboratoire d'Electrochimie Moléculaire (LEM), Université Paris Cité, FF-75013, Paris, France., Hon Cheah M; Molecular Biomimetics, Department of Chemistry-Ångström, Uppsala University, 751 20, Uppsala, Sweden., Bonin J; Laboratoire d'Electrochimie Moléculaire (LEM), Université Paris Cité, FF-75013, Paris, France., Robert M; Laboratoire d'Electrochimie Moléculaire (LEM), Université Paris Cité, FF-75013, Paris, France.; Institut Universitaire de France (IUF), F-75005, Paris, France., Anxolabéhère-Mallart E; Laboratoire d'Electrochimie Moléculaire (LEM), Université Paris Cité, FF-75013, Paris, France.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Aug 19, pp. e202412417. Date of Electronic Publication: 2024 Aug 19.
DOI: 10.1002/anie.202412417
Abstrakt: Iron porphyrins are molecular catalysts recognized for their ability to electrochemically and photochemically reduce carbon dioxide (CO 2 ). The main reduction product is carbon monoxide (CO). CO holds significant industrial importance as it serves as a precursor for various valuable chemical products containing either a single carbon atom (C1), like methanol or methane, or multiple carbon atoms (Cn), such as ethanol or ethylene. Despite the long-established efficiency of these catalysts, optimizing their catalytic activity and stability and comprehending the intricate reaction mechanisms remain a significant challenge. This article presents a comprehensive investigation of the mechanistic aspects of the selective electroreduction of CO 2 to CO using an iron porphyrin substituted with four trimethylammonium groups in the para position [(pTMA)Fe III -Cl] 4+ . By employing infrared and UV/Visible spectroelectrochemistry, changes in the electronic structure and coordination environment of the iron center can be observed in real-time as the electrochemical potential is adjusted, offering new insights into the reaction mechanisms. Catalytic species were identified, and evidence of a secondary reaction pathway was uncovered, potentially prompting a re-evaluation of the nature of the catalytically active species.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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