Electrochemical behavior of tetrafluoro-p-benzoquinone at the presence of carbon dioxide: Experimental and theoretical studies

Namazian, Mansoor; Zare, Hamid R.; Yousofian-Varzaneh, Hassan

doi:10.1016/j.electacta.2016.02.159

Cited by 22 publications

(27 citation statements)

References 27 publications

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“…The oxidation of the bis(carbonate) dianion quinone would also be possible, but for weakly complexing quinones the fraction of bis(carbonate) dianion in solution would be small and thus we anticipate that only oxidation of the mono(carbonate) would be observed. This mechanistic explanation is largely in line with past work, 18,21 but we acknowledge other mechanisms could explain the observed behaviors.…”

Section: Electrochemistry Of Weakly Complexing Quinones In the Presen...supporting

confidence: 91%

Electrochemical and Molecular Assessment of Quinones as CO₂-Binding Redox Molecules for Carbon Capture

et al. 2022

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The complexation and decomplexation of CO2 with a series of quinones of different basicity during electrochemical cycling in dimethylformamide solutions were studied systematically by cyclic voltammetry. In the absence of CO2, all quinones exhibited two well-separated reduction waves. For weakly complexing quinones, a positive shift in the second reduction wave was observed in the presence of CO2, corresponding to the dianion quinone-CO2 complex formation. The peak position and peak height of the first reduction wave was unchanged, indicating no formation of complexes between the semiquinones and CO2. The relative heights of both reduction waves remained constant. In the case of strongly complexing quinones, the second reduction wave disappeared while the peak height of the first reduction wave approximately doubled, indicating that the two electrons transferred simultaneously at this potential. The observed voltammograms were rationalized through several equilibrium arguments. Both weakly and strongly complexing quinones underwent either stepwise or concerted mechanisms of oxidation and CO2 dissociation depending on the sweep rate in the cyclic voltammetric experiments. Relative to stepwise oxidation, the concerted process requires a more positive electrode potential to remove the electron from the carbonate complexes to release CO2 and regenerate the quinone. For weakly complexing quinones, the stepwise process corresponds to oxidation of the uncomplexed dianion and accompanying equilibrium shift, while for strongly complexing quinones the stepwise process would correspond to the oxidation of mono(carbonate) dianion to the complexed semiquinone and accompanying equilibrium shift. This study provides a mechanistic interpretation of the interactions that lead to the formation of quinone-CO2 complexes required for the potential development of an energy efficient electrochemical separation process and discusses important considerations for practical implementation of CO2 capture in the presence of oxygen with lower vapor pressure solvents.

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Section: Electrochemistry Of Weakly Complexing Quinones In the Presen...supporting

confidence: 91%

Electrochemical and Molecular Assessment of Quinones as CO₂-Binding Redox Molecules for Carbon Capture

et al. 2022

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“…A study on the effects of hydrogen bonds in different Q/HQ systems in non-aqueous media showed that the presence of oxygenated functional groups on the surface of the electrode could affect the interaction between dissolved compounds and the surface, which had a significant impact on the electron transfer process [ 23 ]. The electrochemistry of quinones in the presence of added hydroquinone as a hydrogen bonding proton donor, the effective pH at the electrode surface [ 24 ] as well as the electrochemical effect of CO 2 in dimethylformamide solution, were all studied [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

“…The prediction of accurate redox potentials is a main issue in all areas where electron transfer reactions are important [ 34 ]. Computational chemistry is a powerful tool in electrochemistry since it can predict redox potentials prior to the synthesis of the compounds [ 25 , 35 , 36 , 37 ]. One of the most common approaches to calculate redox potentials is the use of a thermodynamic cycle that involves the gas phase energies and free energies of solvation [ 38 , 39 , 40 , 41 , 42 ].…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Reduction Potentials of Some Biologically Active ortho-Carbonyl para-Quinones

et al. 2017

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The rational design of quinones with specific redox properties is an issue of great interest because of their applications in pharmaceutical and material sciences. In this work, the electrochemical behavior of a series of four p-quinones was studied experimentally and theoretically. The first and second one-electron reduction potentials of the quinones were determined using cyclic voltammetry and correlated with those calculated by density functional theory (DFT) using three different functionals, BHandHLYP, M06-2x and PBE0. The differences among the experimental reduction potentials were explained in terms of structural effects on the stabilities of the formed species. DFT calculations accurately reproduced the first one-electron experimental reduction potentials with R2 higher than 0.94. The BHandHLYP functional presented the best fit to the experimental values (R2 = 0.957), followed by M06-2x (R2 = 0.947) and PBE0 (R2 = 0.942).

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“…Several classes of redox-active carriers have been investigated for eCCC applications including bipyridines, [7][8][9] thiols, 10 and quinones. [11][12][13][14][15][16][17][18] However, eCCC systems generally degrade from aerobic input streams because the reduced carriers react with oxygen (O2) resulting in unproductive carrier oxidation and the generation of superoxide, which can cause destructive radical reactions with the carrier, solvent, or electrolyte (red reaction in Scheme 1). 19,20 Since oxygen is present in flue gas and atmospheric CO2 sources, practical eCCC methods must overcome this limitation.…”

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confidence: 99%

Oxygen Stable Electrochemical CO2 Capture and Concentration through Alcohol Additives

Yang

Barlow

2021

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Current methods for CO2 capture and concentration (CCC) are energy intensive due to their reliance on thermal cycles, which are intrinsically Carnot limited in efficiency. In contrast, electrochemically driven CCC (eCCC) can operate at much higher theoretical efficiencies. However, most reported systems are sensitive to O2, precluding their practical use. In order to achieve O2 stable eCCC, we pursued the development of molecular redox carriers with reduction potentials positive of the O2/O2- redox couple. Prior efforts to chemically modify redox carriers to operate at milder potentials resulted in a loss in CO2 binding. To overcome these limitations, we used common alcohols additives to anodically shift the reduction potential of a quinone redox carrier, 2,3,5,6-tetrachloro-p-benzoquinone (TCQ), by up to 350 mV, conferring O2 stability. Intermolecular hydrogen-bonding interactions to the dianion and CO2-bound forms of TCQ were correlated to alcohol pKa to identify ethanol as the optimal additive, as it imparts beneficial changes to both the reduction potential and CO2 binding constant, the two key properties for eCCC redox carriers. We demonstrate a full cycle of eCCC in aerobic simulated flue gas using TCQ and ethanol, two commercially available compounds. Based on the system properties, an estimated minimum of 21 kJ/mol is required to concentrate CO2 from 10% to 100%, or twice as efficient as state-of-the-art thermal amine capture systems and other reported redox carrier-based systems. Furthermore, this approach of using hydrogen-bond donor additives is general and can be used to tailor the redox properties of other quinones/alcohol combinations for specific CO2 capture applications.

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Electrochemical behavior of tetrafluoro-p-benzoquinone at the presence of carbon dioxide: Experimental and theoretical studies

Cited by 22 publications

References 27 publications

Electrochemical and Molecular Assessment of Quinones as CO₂-Binding Redox Molecules for Carbon Capture

Electrochemical and Molecular Assessment of Quinones as CO₂-Binding Redox Molecules for Carbon Capture

Experimental and Theoretical Reduction Potentials of Some Biologically Active ortho-Carbonyl para-Quinones

Oxygen Stable Electrochemical CO2 Capture and Concentration through Alcohol Additives

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Electrochemical behavior of tetrafluoro-p-benzoquinone at the presence of carbon dioxide: Experimental and theoretical studies

Cited by 22 publications

References 27 publications

Electrochemical and Molecular Assessment of Quinones as CO2-Binding Redox Molecules for Carbon Capture

Electrochemical and Molecular Assessment of Quinones as CO2-Binding Redox Molecules for Carbon Capture

Experimental and Theoretical Reduction Potentials of Some Biologically Active ortho-Carbonyl para-Quinones

Oxygen Stable Electrochemical CO2 Capture and Concentration through Alcohol Additives

Contact Info

Product

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Electrochemical and Molecular Assessment of Quinones as CO₂-Binding Redox Molecules for Carbon Capture

Electrochemical and Molecular Assessment of Quinones as CO₂-Binding Redox Molecules for Carbon Capture