Cobalt Tetracationic 3,4-Pyridinoporphyrazine for Direct CO 2 to Methanol Conversion Escaping the CO Intermediate Pathway.

Autor: Zhang C; Université Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91405, Orsay, France.; Current address: Electrochemical Excellent Center, Flemish Institute for Technological Research (VITO), Boeretang 200, 2400, Mol, Belgium., Follana-Berná J; Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Avda. de la Universidad s/n, 03203, Elche, Spain., Dragoe D; Université Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91405, Orsay, France., Halime Z; Université Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91405, Orsay, France., Gotico P; Institute for Integrative Biology of the Cell, CEA, CNRS, Université Paris-Saclay, 91191, Gif-sur-Yvette, France., Sastre-Santos Á; Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Avda. de la Universidad s/n, 03203, Elche, Spain., Aukauloo A; Université Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91405, Orsay, France.; Institute for Integrative Biology of the Cell, CEA, CNRS, Université Paris-Saclay, 91191, Gif-sur-Yvette, France.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 09; Vol. 63 (50), pp. e202411967. Date of Electronic Publication: 2024 Oct 16.
DOI: 10.1002/anie.202411967
Abstrakt: Molecular catalysts offer a unique opportunity to implement different chemical functionalities to steer the efficiency and selectivity for the CO 2 reduction for instance. Metalloporphyrins and metallophthalocyanines are under high scrutiny since their most classic derivatives the tetraphenylporphyrin (TPP) and parent phthalocyanine (Pc), have been used as the molecular platform to install, hydrogen bonds donors, proton relays, cationic fragments, incorporation in MOFs and COFs, to enhance the catalytic power of these catalysts. Herein, we examine the electrocatalytic properties of the tetramethyl cobalt (II) tetrapyridinoporphyrazine (CoTmTPyPz) for the reduction of CO 2 in heterogeneous medium when adsorbed on carbon nanotubes (CNT) at a carbon paper (CP) electrode. Unlike reported electrocatalysis with cobalt based phthalocyanine where CO was advocated as the two electron and two protons reduced intermediate on the way to the formation of methanol, we found here that CoTmTPyPz does not reduce CO to methanol. Henceforth, ruling out a mechanistic pathway where CO is a reaction intermediate.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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