Electrochemical Reduction of 4-Nitrobenzyl Phenyl Thioether for Activation and Capture of CO2
Mena Fernández, Silvia (Universitat Autònoma de Barcelona. Departament de Química)
Louault, Cyril (Universitat Autònoma de Barcelona. Departament de Química)
Mesa, Verónica (Universitat Autònoma de Barcelona. Departament de Química)
Gallardo, Iluminada (Universitat Autònoma de Barcelona. Departament de Química)
Guirado López, Gonzalo (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2021
Abstract:	In this work, a new simple molecule, 4-nitrobenzyl phenyl thioether (1), is prepared and used for controlling and tuning CO reactivity in function of the electrode potential. The first part of the study is devoted to determining the electrochemical reduction mechanism of 1 in N,N-dimethylformamide under nitrogen. The compound shows a first reversible one-electron transfer process, whereas the reaction cleavage of the C-S bond takes place after a second electron transfer process through a stepwise mechanism (thermodynamic and kinetic parameters are conveniently determined). In the second part of the study, the inert atmosphere was replaced by a CO atmosphere. At low potential values, compound 1 acts as a redox mediator that allows the reduction of CO at ca. -1. 2 V vs. SCE. The electrochemical generation of 1 at more negative potential values leads to a C-S bond cleavage reaction that yields the corresponding nitrobenzyl and thiosulfate anions, which react with CO. The nitro aromatic anion derivative makes it possible to obtain electrocarboxylated derivatives, whereas the thiophenolate anion captures CO reversibly. Hence, this research opens a new way of tuning and controlling the reaction processes associated with CO from homogenous catalysis at low negative potentials, to electrocarboxylation processes passing to CO reversible electrochemically triggered adsorption processes.
Grants:	Ministerio de Ciencia e Innovación CTQ-2015-65439-R Ministerio de Ciencia e Innovación PID2019-106171RB-I00
Note:	Altres ajuts: acords transformatius de la UAB
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Subject:	Carbon-sulfur cleavage ; Electrochemistry ; Carbon dioxide ; Electrocarboxylation ; Homogeneous catalysis ; CO2 capture
Published in:	ChemElectroChem, Vol. 8, Issue 14 (July 2021) , p. 2649-2661, ISSN 2196-0216

DOI: 10.1002/celc.202100329
DOI: 10.1002/celc.202100730

13 p, 5.1 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Group in Electrochemistry, Photochemistry and Organic Reactivity (GEFRO)
Articles > Research articles
Articles > Published articles