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Solubilities and Transport Properties of CO(2), Oxalic Acid, and Formic Acid in Mixed Solvents Composed of Deep Eutectic Solvents, Methanol, and Propylene Carbonate
[Image: see text] Recently, deep eutectic solvents (DES) have been considered as possible electrolytes for the electrochemical reduction of CO(2) to value-added products such as formic and oxalic acids. The applicability of pure DES as electrolytes is hindered by high viscosities. Mixtures of DES wi...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9125562/ https://www.ncbi.nlm.nih.gov/pubmed/35507866 http://dx.doi.org/10.1021/acs.jpcb.2c01425 |
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author | Dawass, Noura Langeveld, Jilles Ramdin, Mahinder Pérez-Gallent, Elena Villanueva, Angel A. Giling, Erwin J. M. Langerak, Jort van den Broeke, Leo J. P. Vlugt, Thijs J. H. Moultos, Othonas A. |
author_facet | Dawass, Noura Langeveld, Jilles Ramdin, Mahinder Pérez-Gallent, Elena Villanueva, Angel A. Giling, Erwin J. M. Langerak, Jort van den Broeke, Leo J. P. Vlugt, Thijs J. H. Moultos, Othonas A. |
author_sort | Dawass, Noura |
collection | PubMed |
description | [Image: see text] Recently, deep eutectic solvents (DES) have been considered as possible electrolytes for the electrochemical reduction of CO(2) to value-added products such as formic and oxalic acids. The applicability of pure DES as electrolytes is hindered by high viscosities. Mixtures of DES with organic solvents can be a promising way of designing superior electrolytes by exploiting the advantages of each solvent type. In this study, densities, viscosities, diffusivities, and ionic conductivities of mixed solvents comprising DES (i.e., reline and ethaline), methanol, and propylene carbonate were computed using molecular simulations. To provide a quantitative assessment of the affinity and mass transport of CO(2) and oxalic and formic acids in the mixed solvents, the solubilities and self-diffusivities of these solutes were also computed. Our results show that the addition of DES to the organic solvents enhances the solubilities of oxalic and formic acids, while the solubility of CO(2) in the ethaline-containing mixtures are in the same order of magnitude with the respective pure organic components. A monotonic increase in the densities and viscosities of the mixed solvents is observed as the mole fraction of DES in the mixture increases, with the exception of the density of ethaline-propylene carbonate which shows the opposite behavior due to the high viscosity of the pure organic component. The self-diffusivities of all species in the mixtures significantly decrease as the mole fraction of DES approaches unity. Similarly, the self-diffusivities of the dissolved CO(2) and the oxalic and formic acids also decrease by at least 1 order of magnitude as the composition of the mixture shifts from the pure organic component to pure DES. The computed ionic conductivities of all mixed solvents show a maximum value for mole fractions of DES in the range from 0.2 to 0.6 and decrease as more DES is added to the mixtures. Since for most mixtures studied here no prior experimental measurements exist, our findings can serve as a first data set based on which further investigation of DES-containing electrolyte solutions can be performed for the electrochemical reduction of CO(2) to useful chemicals. |
format | Online Article Text |
id | pubmed-9125562 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-91255622022-05-24 Solubilities and Transport Properties of CO(2), Oxalic Acid, and Formic Acid in Mixed Solvents Composed of Deep Eutectic Solvents, Methanol, and Propylene Carbonate Dawass, Noura Langeveld, Jilles Ramdin, Mahinder Pérez-Gallent, Elena Villanueva, Angel A. Giling, Erwin J. M. Langerak, Jort van den Broeke, Leo J. P. Vlugt, Thijs J. H. Moultos, Othonas A. J Phys Chem B [Image: see text] Recently, deep eutectic solvents (DES) have been considered as possible electrolytes for the electrochemical reduction of CO(2) to value-added products such as formic and oxalic acids. The applicability of pure DES as electrolytes is hindered by high viscosities. Mixtures of DES with organic solvents can be a promising way of designing superior electrolytes by exploiting the advantages of each solvent type. In this study, densities, viscosities, diffusivities, and ionic conductivities of mixed solvents comprising DES (i.e., reline and ethaline), methanol, and propylene carbonate were computed using molecular simulations. To provide a quantitative assessment of the affinity and mass transport of CO(2) and oxalic and formic acids in the mixed solvents, the solubilities and self-diffusivities of these solutes were also computed. Our results show that the addition of DES to the organic solvents enhances the solubilities of oxalic and formic acids, while the solubility of CO(2) in the ethaline-containing mixtures are in the same order of magnitude with the respective pure organic components. A monotonic increase in the densities and viscosities of the mixed solvents is observed as the mole fraction of DES in the mixture increases, with the exception of the density of ethaline-propylene carbonate which shows the opposite behavior due to the high viscosity of the pure organic component. The self-diffusivities of all species in the mixtures significantly decrease as the mole fraction of DES approaches unity. Similarly, the self-diffusivities of the dissolved CO(2) and the oxalic and formic acids also decrease by at least 1 order of magnitude as the composition of the mixture shifts from the pure organic component to pure DES. The computed ionic conductivities of all mixed solvents show a maximum value for mole fractions of DES in the range from 0.2 to 0.6 and decrease as more DES is added to the mixtures. Since for most mixtures studied here no prior experimental measurements exist, our findings can serve as a first data set based on which further investigation of DES-containing electrolyte solutions can be performed for the electrochemical reduction of CO(2) to useful chemicals. American Chemical Society 2022-05-04 2022-05-19 /pmc/articles/PMC9125562/ /pubmed/35507866 http://dx.doi.org/10.1021/acs.jpcb.2c01425 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Dawass, Noura Langeveld, Jilles Ramdin, Mahinder Pérez-Gallent, Elena Villanueva, Angel A. Giling, Erwin J. M. Langerak, Jort van den Broeke, Leo J. P. Vlugt, Thijs J. H. Moultos, Othonas A. Solubilities and Transport Properties of CO(2), Oxalic Acid, and Formic Acid in Mixed Solvents Composed of Deep Eutectic Solvents, Methanol, and Propylene Carbonate |
title | Solubilities and Transport Properties of CO(2), Oxalic Acid,
and Formic Acid in Mixed Solvents Composed of Deep
Eutectic Solvents, Methanol, and Propylene Carbonate |
title_full | Solubilities and Transport Properties of CO(2), Oxalic Acid,
and Formic Acid in Mixed Solvents Composed of Deep
Eutectic Solvents, Methanol, and Propylene Carbonate |
title_fullStr | Solubilities and Transport Properties of CO(2), Oxalic Acid,
and Formic Acid in Mixed Solvents Composed of Deep
Eutectic Solvents, Methanol, and Propylene Carbonate |
title_full_unstemmed | Solubilities and Transport Properties of CO(2), Oxalic Acid,
and Formic Acid in Mixed Solvents Composed of Deep
Eutectic Solvents, Methanol, and Propylene Carbonate |
title_short | Solubilities and Transport Properties of CO(2), Oxalic Acid,
and Formic Acid in Mixed Solvents Composed of Deep
Eutectic Solvents, Methanol, and Propylene Carbonate |
title_sort | solubilities and transport properties of co(2), oxalic acid,
and formic acid in mixed solvents composed of deep
eutectic solvents, methanol, and propylene carbonate |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9125562/ https://www.ncbi.nlm.nih.gov/pubmed/35507866 http://dx.doi.org/10.1021/acs.jpcb.2c01425 |
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