Solubility and electrochemical determination of CO2 in some dipolar aprotic solvents

Gennaro, Armando; Isse, Abdirisak Ahmed; Vianello, E.

doi:10.1016/0022-0728(90)87217-8

Cited by 182 publications

(144 citation statements)

References 36 publications

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“…The parent complex, 1, however, has a λ max at 384 nm (3;900 M −1 cm −1 ) (14). Solutions of the reduced complex were mixed in the stopped-flow apparatus with either CO 2 -saturated tetrahydrofuran (THF) (0.20 M) (15) or with 0.20 M solutions of…”

Section: Uv-vis Stopped-flow Spectroscopy: Probing the Selectivity Ofmentioning

confidence: 99%

Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

Smieja

Benson

Kumar

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

195

235

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The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-visible (UV-vis) spectroscopy, X-ray crystallographic, density functional theory (DFT), and electrochemical kinetic studies of the Reðbipy-tBuÞðCOÞ 3 ðLÞ catalyst for the reduction of CO 2 to CO. A remarkable selectivity for CO 2 over H þ was observed by stopped-flow UV-vis spectroscopy of ½Reðbipy-tBuÞðCOÞ 3 −1 . The reaction with CO 2 is about 25 times faster than the reaction with water or methanol at the same concentrations. X-ray crystallography and DFT studies of the doubly reduced anionic species suggest that the highest occupied molecular orbital (HOMO) has mixed metal-ligand character rather than being purely doubly occupied d z 2 , which is believed to determine selectivity by favoring CO 2 (σ þ π) over H þ (σ only) binding. Electrocatalytic studies performed with the addition of Brönsted acids reveal a primary H∕D kinetic isotope effect, indicating that transfer of protons to Re-CO 2 is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed current densities for catalysis more than threefold, indicating that the properties of the electrode surface need to be addressed when developing a homogeneous artificial photosynthetic system. carbon dioxide reduction | electrochemistry | kinetics | electrocatalyst T he development of artificial photosynthetic systems is of immediate concern in view of the world's dependence on fossil fuels and the increasing emissions of CO 2 . Rapid industrial growth in developing nations will significantly increase the global energy demand in coming years, and although known reserves of fuels such as natural gas and coal are sufficient for the near future, they are becoming increasingly costly to obtain. As the use of fossil fuels is fundamentally unsustainable and generates greenhouse gases and other pollutants, the development of environmentally benign energy sources is important. Solar energy is an abundant alternative but suffers from being a diffuse energy source, and its availability varies by location and time of day. If we can capture solar energy and use CO 2 as a C 1 feedstock for liquid fuels, we can envision converting our global energy economy into a nearly carbon-neutral system (1).Photosynthesis is one of the great triumphs of nature and is the cornerstone for advanced life on the planet. Mankind has yet to master nature's ability to store sunlight as chemical energy by splitting CO 2 and H 2 O to form C─C, C─H, and O─O bonds. The energy-dense liquid fuels formed by this process would have the advantage of conforming to the existing infrastructure. Photosynthesis can be divided into two parts: water splitting and reduction of carbon dioxide. Water oxidation has been reviewed extensively by others (2-4).Our laboratory is currently exploring the development of C...

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Section: Uv-vis Stopped-flow Spectroscopy: Probing the Selectivity Ofmentioning

confidence: 99%

Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

Smieja

Benson

Kumar

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

195

235

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“…By contrast, the reduction of [PhBP À1 for THF (for the solubility in THF and an estimate for the solubility in 2-MeTHF, and 2,5-diMeTHF). 27 b The ratio 2 : 3 was determined by 31 P NMR integration of resonances associated with 2 and 9 against an internal standard of t Bu 3 P (see Experimental section of ESI and text for details). Fig.…”

Section: Ch2cymentioning

confidence: 99%

“…27 If CO 2 solubility were dictating the reaction outcome for the reaction between 7 and CO 2 , then a distinct product prole would be observed in THF relative to that in benzene and MeCy. This is not the case, as the reaction in MeCy is distinct from that in benzene and also that in THF.…”

mentioning

confidence: 99%

CO2 reduction by Fe(i): solvent control of C–O cleavage versus C–C coupling

Saouma

Day

et al. 2013

Chem. Sci.

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This manuscript explores the product distribution of the reaction of carbon dioxide with reactive iron(I) complexes supported by tris(phosphino)borate ligands,Cy, Ph, i Pr, mter; mter ¼ 3,5-meta-terphenyl). Our studies reveal an interesting and unexpected role for the solvent medium with respect to the course of the CO 2 activation reaction. For instance, exposure of methylcyclohexane (MeCy) solutions of ½PhBP CH2Cy 3 FeðPR 0 3 Þ to CO 2 yields the partial decarbonylation product f½PhBP CH2Cy 3 Feg 2 ðm-OÞðm-COÞ. When the reaction is instead carried out in benzene or THF, reductive coupling of CO 2 occurs to give the bridging oxalate species f½PhBP CH2Cy 3 Feg 2 ðm-kOO 0 :kOO 0 -oxalatoÞ.Reaction studies aimed at understanding this solvent effect are presented, and suggest that the product profile is ultimately determined by the ability of the solvent to coordinate the iron center. When more sterically encumbering auxiliary ligands are employed to support the iron(I) center (i.e., [PhBP Ph 3 ] À and [PhBP iPr 3 ] À ), complete decarbonylation is observed to afford structurally unusual diiron(II) products of the type {[PhBP R 3 ]Fe} 2 (m-O). A mechanistic hypothesis that is consistent with the collection of results described is offered, and suggests that reductive coupling of CO 2 likely occurs from an electronically saturated "Fe II -CO 2 _ À " species. CH2Cy 3Feg 2 ðm-OÞðm-COÞ (2) as the major product of a partial decarbonylation reaction. A red and paramagnetic bridging

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“…T also influenced the electrolysis reaction and mainly affected the thermodynamics and kinetics of the electrocarboxylation reaction and the solubility of CO 2 in the solvent [51]. In general, a low T increases the solubility of CO 2 in DMF, and is conducive to the reaction.…”

Section: Electrocarboxylation Of Dichlorobenzenementioning

confidence: 99%

“…The gas chromatography-mass spectrometry (GC-MS) analysis also confirmed the synthesis of chlorobenzene through potentiostatic electrolysis at the first reduction peak in the presence of N2. When the voltammetric characteristic of 1a was recorded in DMF saturated with CO2 (0.2 M) [51], a different behavior was observed. As shown in curve d of Figure 1A, the first reduction peak current increased, with its potential appreciably shifting to a more positive place, indicating that a chemical reaction may have occurred between the electroreduced intermediate and CO2.…”

Section: Electroanalytical Measurement Of 14-dichlorobenzenementioning

confidence: 99%

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

et al. 2017

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Carbon dioxide (CO 2 ) is the largest contributor to the greenhouse effect, and fixing and using this greenhouse gas in a facile manner is crucial. This work investigates the electrocarboxylation of dichlorobenzenes with the atmospheric pressure of CO 2 in an undivided cell with an Ag cathode and an Mg sacrificial anode. The corresponding carboxylic acids and their derivatives, which are important industrial and fine chemicals, are obtained. To deeply understand this reaction, we investigate the influence of various reaction conditions, such as supporting electrolyte, current density, electric charge, and reaction temperature, on the electrocarboxylation yield by using 1,4-dichlorobenzene as the model compound. The electrochemical behavior of dichlorobenzenes is studied through cyclic voltammetry. The relation among the distinct electronic effects of dichlorobenzenes, the electrochemical characteristics of their reduction, and the distribution law of target products is also established.

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Solubility and electrochemical determination of CO2 in some dipolar aprotic solvents

Cited by 182 publications

References 36 publications

Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO

CO2 reduction by Fe(i): solvent control of C–O cleavage versus C–C coupling

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

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