The energetics of electron and proton transfer to CO<sub>2</sub> in aqueous solution

Yang, Xiaohui; Cuesta, Ángel; Cheng, Jun

doi:10.1039/d1cp02824c

Cited by 4 publications

(5 citation statements)

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“…Another advantage of computational methods is that the reaction environment can be fully controlled and quantifying the contribution of each component becomes feasible. 36 However, calculations of equilibrium potentials of redox couples (such as CO 2 /CO 2 − ) in non-aqueous solutions are difficult, even more so in mixtures like EMIM−BF 4 /H 2 O solutions. Conventional implicit solvation models 37−43 face challenges in describing the charged solute (e.g., the CO 2 − radical) in non-aqueous mixtures because of strong electrostatic interactions at the boundary between the solute and the implicit solvent.…”

Section: Introductionmentioning

confidence: 99%

“…Computational methods allow us to study reactions involving unstable radicals ,− like CO 2 – without having to design sophisticated experiments. Another advantage of computational methods is that the reaction environment can be fully controlled and quantifying the contribution of each component becomes feasible . However, calculations of equilibrium potentials of redox couples (such as CO 2 /CO 2 – ) in non-aqueous solutions are difficult, even more so in mixtures like EMIM–BF 4 /H 2 O solutions.…”

Section: Introductionmentioning

confidence: 99%

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Water-In-Salt Environment Reduces the Overpotential for Reduction of CO₂ to CO₂^– in Ionic Liquid/Water Mixtures

et al. 2022

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We report a combined computational and experimental work aimed at estimating the equilibrium potential for the electroreduction of CO 2 to CO 2 − (widely accepted to be a crucial and overpotential-determining step) and at providing an alternative view on the reason behind the lower overpotential for CO 2 reduction in imidazolium-based ionic liquid/water mixtures. To begin with, we obtained an 80 ps ab-initio molecular dynamics trajectory of the CO 2 − solvation structures in an 18% EMIM−BF 4 / water mixture, which delivered no evidence of interaction between EMIM + and CO 2 − . Next, using the Fc + /Fc couple as the nonaqueous reference, we calculated the equilibrium potential of the CO 2 /CO 2 − couple in the mixture and aligned it with the aqueous SHE scale, proving that the equilibrium potential of CO 2 /CO 2 − 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 Fourier transform infrared spectra. This revealed the presence of two water populations in the mixture, namely, bulk-like water and water in the vicinity of EMIM−BF 4 . Finally, we compared the hydrogen bonding interactions between the CO 2 − radical and H 2 O molecules in water and in the mixture, which showed that stabilization of CO 2 − by water molecules in the EMIM−BF 4 /water mixture is stronger than in the aqueous medium. This suggests that water in EMIM−BF 4 /water mixtures could be responsible for the low overpotential reported in these kinds of electrolytes.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO₂ to CO₂^– in Ionic Liquid/Water Mixtures

et al. 2022

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“…If the intermediate interacts weakly with the surface, an electrophilic attack from water followed by a second electron transfer forms formiate. Recent DFT-MD calculations 25 support that this is the preferred pathway in the solution. On the other hand, the formation of CO requires a strong interaction between the carbon of the anion radical and the surface.…”

Section: Discussionmentioning

confidence: 97%

CO2 reduction on adatom decorated platinum stepped surfaces

Kherbach,

Climent,

Feliu

2023

The Journal of Chemical Physics

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The rate of CO formation from CO2 reduction on Pt(111) vicinal surfaces containing (100) steps, Pt(S)[n(111) × (100)], has been investigated using cyclic voltammetry. To obtain further information about the different roles of terrace and step atoms in this reaction, selective modification of step sites with either bismuth or copper has been performed. In this way, two different mechanistic regimes have been differentiated, depending on the potential range. In the high potential region, between 0.2 and 0.4 V RHE, CO2 is activated on steps and proceeds to the formation of adsorbed CO even when there is no hydrogen adsorbed on the terrace. We suggest that protonation of the activated CO2 uses protons from the solution. In this potential range, the activity decreases after the selective blockage of step sites with bismuth, while the deposition of copper on steps increases the activity. Contrarily, in the low potential region, below 0.2 V RHE, the presence of copper on the steps does not increase the amount of CO formed from CO2 reduction. In fact, the amount of CO formed attains the same saturation value with or without copper. In addition, the CO formed in this potential region remains adsorbed near step sites as shown in the voltammetric profile. We rationalize these observations considering that, in this potential region, activated CO2 reacts with adsorbed hydrogen and the reactions stop when hydrogen near the steps is depleted.

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“…Photoelectrocatalytic CO 2 RR, which stores solar energy in a convenient form of chemical bonds in value-added products, offers a promising approach to producing clean energy and reducing CO 2 emissions. − Efficient conversion of CO 2 into liquid fuels offers a solution to mitigate climate challenges. The early studies of CO 2 RR focused on CO 2 hydrogenation at high temperatures, − though the usage of H 2 is associated with cost and safety concerns.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Pyridine as a Cocatalyst for the CO₂ Reduction Reaction on the Cu₂O Cathode Surface

Xu,

2024

ACS Catal.

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The energetics of electron and proton transfer to CO₂ in aqueous solution

Abstract: The electrocatalytic reduction of CO2 is considered an effective method to reduce CO2 emissions and achieve electrical/chemical energy conversion. It is crucial to determine the reaction mechanism so that the...

Cited by 4 publications

References 51 publications

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO₂ to CO₂^– in Ionic Liquid/Water Mixtures

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO₂ to CO₂^– in Ionic Liquid/Water Mixtures

CO2 reduction on adatom decorated platinum stepped surfaces

Investigation of Pyridine as a Cocatalyst for the CO₂ Reduction Reaction on the Cu₂O Cathode Surface

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The energetics of electron and proton transfer to CO2 in aqueous solution

Abstract: The electrocatalytic reduction of CO2 is considered an effective method to reduce CO2 emissions and achieve electrical/chemical energy conversion. It is crucial to determine the reaction mechanism so that the...

Cited by 4 publications

References 51 publications

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO2 to CO2– in Ionic Liquid/Water Mixtures

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO2 to CO2– in Ionic Liquid/Water Mixtures

CO2 reduction on adatom decorated platinum stepped surfaces

Investigation of Pyridine as a Cocatalyst for the CO2 Reduction Reaction on the Cu2O Cathode Surface

Contact Info

Product

Resources

About

The energetics of electron and proton transfer to CO₂ in aqueous solution

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO₂ to CO₂^– in Ionic Liquid/Water Mixtures

Water-In-Salt Environment Reduces the Overpotential for Reduction of CO₂ to CO₂^– in Ionic Liquid/Water Mixtures

Investigation of Pyridine as a Cocatalyst for the CO₂ Reduction Reaction on the Cu₂O Cathode Surface