Solubility of Carbon Dioxide in Ethane-1,2-diol–Water Mixtures

Serpa, Fabiane Santos; Vidal, Reginaldo Scariot; Filho, João Henrique Bernardo Amaral; Nascimento, Jaílton Ferreira do; Ciambelli, João R. P.; Figueiredo, C.; Salazar‐Banda, Giancarlo R.; Santos, Alexandre F.; Fortuny, Montserrat; Franceschi, Elton; Dariva, Cláudio

doi:10.1021/je400736w

Cited by 18 publications

(27 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…This results in spurious ∆G values for bimolecular reactions. Thus, we used reported experimental entropies in aqueous solution to compute the thermal corrections of these molecules (∆S sol− →gas = 126.0 and 118.9 J/mol•K for CO 2 and H 2 O, respectively [43][44][45]).…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Garza

Pakhira

Bell

et al. 2018

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The tetraaza [CoIIN4H]2+ complex (1) is remarkable for its ability to selectively reduce CO2 to CO with 45% Faradaic efficiency and a CO to H2 ratio of 3 : 2. We employ density functional theory (DFT) to determine the reasons behind the unusual catalytic properties of 1 and the most likely mechanism for CO2 reduction. The selectivity for CO2 over proton reduction is explained by analyzing the catalyst's affinity for the possible ligands present under typical reaction conditions: acetonitrile, water, CO2, and bicarbonate. After reduction of the catalyst by two electrons, formation of [CoIN4H]+-CO2- is strongly favored. Based on thermodynamic and kinetic data, we establish that the only likely route for producing CO from here consists of a protonation step to yield [CoIN4H]+-CO2H, followed by reaction with CO2 to form [CoIIN4H]2+-CO and bicarbonate. This conclusion corroborates the idea of a direct role of CO2 as a Lewis acid to assist in C-O bond dissociation, a conjecture put forward by other authors to explain recent experimental observations. The pathway to formic acid is predicted to be forbidden by high activation barriers, in accordance with the products that are known to be generated by 1. Calculated physical observables such as standard reduction potentials and the turnover frequency for our proposed catalytic cycle are in agreement with available experimental data reported in the literature. The mechanism also makes a prediction that may be experimentally verified: that the rate of CO formation should increase linearly with the partial pressure of CO2.

show abstract

Section: Theory and Computational Detailsmentioning

confidence: 99%

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Garza

Pakhira

Bell

et al. 2018

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…However, it is known that rigid rotor and harmonic oscillator formulas overestimate the entropy of molecules in solution because the translational and rotational motions of the solute are reduced by the surrounding solvent molecules 23,34. From Henry's law data, the entropy of CO 2(g) is 126.0 J/mol⋅K larger than that of CO 2(aq) ,35,36 which corresponds to an increase of 0.39 eV in the −TΔS term of the free energy of…”

mentioning

confidence: 99%

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO₂ on Copper?

Garza

Bell

Head‐Gordon

2018

J. Phys. Chem. Lett.

134

126

View full text Add to dashboard Cite

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. The rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 s. Oxygen can survive longer in deeper layers, but it does not promote CO adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 10 s). Once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO adsorption on copper.

show abstract

“…In the Supporting Information (Figure S2), we compare our simulations and experimental results with other experimental data from the literature. 14 , 62 , 63 …”

Section: Resultsmentioning

confidence: 99%

Solubility of Carbon Dioxide, Hydrogen Sulfide, Methane, and Nitrogen in Monoethylene Glycol; Experiments and Molecular Simulation

et al. 2020

View full text Add to dashboard Cite

Knowledge on the solubility of gases, especially carbon dioxide (CO 2 ), in monoethylene glycol (MEG) is relevant for a number of industrial applications such as separation processes and gas hydrate prevention. In this study, the solubility of CO 2 in MEG was measured experimentally at temperatures of 333.15, 353.15, and 373.15 K. Experimental data were used to validate Monte Carlo (MC) simulations. Continuous fractional component MC simulations in the osmotic ensemble were performed to compute the solubility of CO 2 in MEG at the same temperatures and at pressures up to 10 bar. MC simulations were also used to study the solubility of methane (CH 4 ), hydrogen sulfide (H 2 S), and nitrogen (N 2 ) in MEG at 373.15 K. Solubilities from experiments and simulations are in good agreement at low pressures, but deviations were observed at high pressures. Henry coefficients were also computed using MC simulations and compared to experimental values. The order of solubilities of the gases in MEG at 373.15 K was computed as H 2 S > CO 2 > CH 4 > N 2 . Force field modifications may be required to improve the prediction of solubilities of gases in MEG at high pressures and low temperatures.

show abstract

Solubility of Carbon Dioxide in Ethane-1,2-diol–Water Mixtures

Cited by 18 publications

References 20 publications

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO₂ on Copper?

Solubility of Carbon Dioxide, Hydrogen Sulfide, Methane, and Nitrogen in Monoethylene Glycol; Experiments and Molecular Simulation

Contact Info

Product

Resources

About

Solubility of Carbon Dioxide in Ethane-1,2-diol–Water Mixtures

Cited by 18 publications

References 20 publications

Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons

Reaction mechanism of the selective reduction of CO2 to CO by a tetraaza [CoIIN4H]2+ complex in the presence of protons

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?

Solubility of Carbon Dioxide, Hydrogen Sulfide, Methane, and Nitrogen in Monoethylene Glycol; Experiments and Molecular Simulation

Contact Info

Product

Resources

About

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Reaction mechanism of the selective reduction of CO₂ to CO by a tetraaza [Co^IIN₄H]²⁺ complex in the presence of protons

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO₂ on Copper?