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Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials

[Image: see text] In this work, we report a fundamental mechanistic study of the electrochemical oxidative carbonylation of methanol with CO for the synthesis of dimethyl carbonate on metallic electrodes at low overpotentials. For the first time, the reaction was shown to take place on the metallic...

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Autores principales: Figueiredo, Marta C., Trieu, Vinh, Eiden, Stefanie, Koper, Marc T. M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5677764/
https://www.ncbi.nlm.nih.gov/pubmed/28929754
http://dx.doi.org/10.1021/jacs.7b08208
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author Figueiredo, Marta C.
Trieu, Vinh
Eiden, Stefanie
Koper, Marc T. M.
author_facet Figueiredo, Marta C.
Trieu, Vinh
Eiden, Stefanie
Koper, Marc T. M.
author_sort Figueiredo, Marta C.
collection PubMed
description [Image: see text] In this work, we report a fundamental mechanistic study of the electrochemical oxidative carbonylation of methanol with CO for the synthesis of dimethyl carbonate on metallic electrodes at low overpotentials. For the first time, the reaction was shown to take place on the metallic catalysts without need of oxidized metals or additives. Moreover, in-situ spectroelectrochemical techniques were applied to this electrosynthesis reaction in order to reveal the reaction intermediates and to shed light into the reaction mechanism. Fourier transformed infrared spectroscopy was used with different electrode materials (Au, Pd, Pt, and Ag) to assess the effect of the electrode material on the reaction and the dependence of products and intermediates on the applied potentials. It was observed that the dimethyl carbonate is only formed when the electrode is able to decompose/oxidize MeOH to form (adsorbed) methoxy groups that can further react with CO to dimethyl carbonate. Furthermore, the electrode needs to adsorb CO not too strongly; otherwise, further reaction will be inhibited because of surface poisoning by CO.
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spelling pubmed-56777642017-11-13 Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials Figueiredo, Marta C. Trieu, Vinh Eiden, Stefanie Koper, Marc T. M. J Am Chem Soc [Image: see text] In this work, we report a fundamental mechanistic study of the electrochemical oxidative carbonylation of methanol with CO for the synthesis of dimethyl carbonate on metallic electrodes at low overpotentials. For the first time, the reaction was shown to take place on the metallic catalysts without need of oxidized metals or additives. Moreover, in-situ spectroelectrochemical techniques were applied to this electrosynthesis reaction in order to reveal the reaction intermediates and to shed light into the reaction mechanism. Fourier transformed infrared spectroscopy was used with different electrode materials (Au, Pd, Pt, and Ag) to assess the effect of the electrode material on the reaction and the dependence of products and intermediates on the applied potentials. It was observed that the dimethyl carbonate is only formed when the electrode is able to decompose/oxidize MeOH to form (adsorbed) methoxy groups that can further react with CO to dimethyl carbonate. Furthermore, the electrode needs to adsorb CO not too strongly; otherwise, further reaction will be inhibited because of surface poisoning by CO. American Chemical Society 2017-09-20 2017-10-18 /pmc/articles/PMC5677764/ /pubmed/28929754 http://dx.doi.org/10.1021/jacs.7b08208 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Figueiredo, Marta C.
Trieu, Vinh
Eiden, Stefanie
Koper, Marc T. M.
Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials
title Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials
title_full Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials
title_fullStr Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials
title_full_unstemmed Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials
title_short Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials
title_sort spectro-electrochemical examination of the formation of dimethyl carbonate from co and methanol at different electrode materials
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5677764/
https://www.ncbi.nlm.nih.gov/pubmed/28929754
http://dx.doi.org/10.1021/jacs.7b08208
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