Abstract
We report a combined computational and experimental work aimed at estimating
the equilibrium potential for the electroreduction of CO2 to CO2-(widely accepted to be the first and overpotential-determining step) and at throwing new light on the reason behind the lower overpotentials for CO2 reduction in imidazolium-based ionic liquid/water mixtures. First, we obtained an eighty-picosecond ab-initio molecular dynamics trajectory of the CO2 solvation
structures in an 18% EMIM-BF4/water mixture, which delivered no evidence of interaction between EMIM+ and CO2. . Second, using the Fc+/Fc couple as the non-aqueous reference, we calculated the equilibrium potential of the CO2/CO2
-couple in the mixture and aligned it with the aqueous SHE scale, proving that the equilibrium potential of CO2/CO2-in the mixture is about 0.3 V less negative than in the aqueous medium. We then looked for the origin of this catalytic effect, by comparing the computed vibrational spectra with experimental FTIR spectra. This revealed the presence of two water populations in the mixture, namely, bulk-like water and water in the vicinity of EMIM-BF4. Finally, we compared the hydrogen bonding interactions between the CO2
-radical and H2O molecules in water and in the mixture, which showed that stabilization of CO2- by water molecules in the EMIM-BF4/water mixture is stronger than in the aqueous medium. This suggests that water in EMIM-BF4/water mixtures could be responsible for the low overpotentials reported in this kind of electrolytes.
the equilibrium potential for the electroreduction of CO2 to CO2-(widely accepted to be the first and overpotential-determining step) and at throwing new light on the reason behind the lower overpotentials for CO2 reduction in imidazolium-based ionic liquid/water mixtures. First, we obtained an eighty-picosecond ab-initio molecular dynamics trajectory of the CO2 solvation
structures in an 18% EMIM-BF4/water mixture, which delivered no evidence of interaction between EMIM+ and CO2. . Second, using the Fc+/Fc couple as the non-aqueous reference, we calculated the equilibrium potential of the CO2/CO2
-couple in the mixture and aligned it with the aqueous SHE scale, proving that the equilibrium potential of CO2/CO2-in the mixture is about 0.3 V less negative than in the aqueous medium. We then looked for the origin of this catalytic effect, by comparing the computed vibrational spectra with experimental FTIR spectra. This revealed the presence of two water populations in the mixture, namely, bulk-like water and water in the vicinity of EMIM-BF4. Finally, we compared the hydrogen bonding interactions between the CO2
-radical and H2O molecules in water and in the mixture, which showed that stabilization of CO2- by water molecules in the EMIM-BF4/water mixture is stronger than in the aqueous medium. This suggests that water in EMIM-BF4/water mixtures could be responsible for the low overpotentials reported in this kind of electrolytes.
| Original language | English |
|---|---|
| Pages (from-to) | 6770–6780 |
| Number of pages | 11 |
| Journal | ACS Catalysis |
| Volume | 12 |
| Issue number | 11 |
| Early online date | 24 May 2022 |
| DOIs | |
| Publication status | Published - 3 Jun 2022 |
Bibliographical note
ACKNOWLEDGMENTWe are grateful for funding support from the National Natural Science Foundation of China (Grants Nos 21861132015, 21991151, 21991150, 22021001, 91745103, 92161113, 91945301 and 3502Z20203027). The support of the Leverhulme Trust (RPG-2015-0400) is gratefully acknowledged. We are also very grateful to the reviewers for their helpful suggestions to improve readability.
Data Availability Statement
Supporting InformationThe Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.2c00395
Keywords
- electrochemical reduction of CO2
- room temperature ionic liquid
- ab initio molecular dynamics
- absorption infrared spectra
- hydrogen bond networks