Infrared spectroscopy of adsorbed CO and intermediate species in electrochemical reduction of CO2 to hydrocarbons on a Cu electrode

Hori, Yoshio; Katoh, Osamu; Yamazaki, Hiroki; Matsuo, T.

doi:10.1016/0013-4686(95)00239-b

Cited by 134 publications

(133 citation statements)

References 28 publications

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“…2 (third curve) confirms the results in the literature that reported that the reduction of CO 2 would effectively occur at a pH between 7 and 9 i.e. the domain of pH where HCO 3 -is the predominant species [48,50,51]. In order to identify the rate-determining step of CO 2 electro-reduction, CV experiments were performed at various potential sweep rates.…”

Section: Eelectrochemical Behavior Of Carbon Dioxidesupporting

confidence: 71%

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Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium

et al. 2008

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The electrochemical reduction of carbon dioxide on a lead electrode was studied in aqueous medium. Preliminary investigations carried out by cyclic voltammetry were used to determine the optimized conditions of electrolysis. They revealed that the CO 2 reduction process was enhanced at a pH value of 8.6 for the cathodic solution i.e. when the predominant form of CO 2 was hydrogenocarbonate ion. Long-term electrolysis was carried out using both potentiometry and amperometry methods in a filterpress cell in which the two compartments were separated by a cation-exchange membrane (Nafion Ò 423). Formate was detected and quantified by chromatography as the exclusive organic compound produced with a high Faradaic yield (from 65% to 90%). This study also revealed that the operating temperature played a key role in the hydrogenation reaction of carbon dioxide into formate in aqueous medium.

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Section: Eelectrochemical Behavior Of Carbon Dioxidesupporting

confidence: 71%

“…when the HCO 3 -ions become more and more predominant in solution. At pH = 8.5 the bubbling of CO 2 in the cell is stopped and the equilibrium states between CO 2aq , HCO 3 -and CO 3 2-can be given as follows [48][49][50]: on the dissolution of gaseous carbon dioxide in water, a rapid equilibrium occurs…”

Section: Eelectrochemical Behavior Of Carbon Dioxidementioning

confidence: 99%

Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium

et al. 2008

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“…The CO 2 radical has been experimentally observed on other metals, and it is inferred that it also forms on copper. (18,34,37,38) If we assume that the surface coverage of the CO 2 radical θ ≪ 1, consistent with the observation that copper surfaces are predominantly covered in CO under CO 2 reduction conditions, (39)(40)(41) as a methanation current, is (3) where n is the total number of electron transfers needed to convert CO 2 1 to methane 5 and k 2 is the rate constant for the conversion of 2 to 3. Combining eqs 2 and 3, we obtain (4) This rate law is consistent with the second-order dependence on CO 2 partial pressure that we experimentally observe.…”

Section: Continuum From Nanoparticle-like To Foil-like Behaviorsupporting

confidence: 67%

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst

2014

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Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO 2 . The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO 2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/ C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic conditions and the resulting Faradaic efficiency for methane. The improved activity and Faradaic efficiency for methanation involves a mechanism that is distinct from what is generally thought to occur on copper foils. Electrochemical data indicate that the early steps of methanation on n-Cu/C involve a pre-equilibrium one-electron transfer to CO 2 to form an adsorbed radical, followed by a rate-limiting nonelectrochemical step in which the adsorbed CO 2 radical reacts with a second CO 2 molecule from solution. These nanoscale copper electrocatalysts represent a first step toward the preparation of practical methanation catalysts that can be incorporated into membrane-electrode assemblies in electrolyzers.

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“…It has been reported that the main products on a Cu-based electrode are hydrocarbons such as methane and ethylene in aqueous electrolytes [10][11][12]. Hori et al [13][14][15][16], who pioneered a series of experimental investigations into the mechanism of CO 2 electrochemical reduction on a copper-based electrode, suggested that the electrochemical reduction of CO 2 proceeds through CO or COderived intermediates, with the main products being CH 4 , C 2 H 4 and alcohols. The product distribution depends strongly upon the electrolytes that are employed.…”

Section: Introductionmentioning

confidence: 98%

A DFT study of CO2 electrochemical reduction on Pb(211) and Sn(112)

et al. 2015

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Electrochemical reduction of CO 2 has the benefit of turning greenhouse gas emissions into useful resources. We performed a comparative study of the electrochemical reduction of CO 2 on stepped Pb(211) and Sn(112) surfaces based on the results of density functional theory slab calculations. We mapped out the potential energy profiles for electrochemical reduction of CO 2 to formate and other possible products on both surfaces. Our results show that the first step is the formation of the adsorbed formate (HCOO*) species through an Eley-Rideal mechanism. The formate species can be reduced to HCOO  through a oneelectron reduction in basic solution, which produces formic acid as the predominant product. The respective potentials of forming HCOO* are predicted to be 0.72 and 0.58 V on Pb and Sn. Higher overpotentials make other reaction pathways accessible, leading to different products. On Sn(112), CO and CH 4 can be generated at 0.65 V following formate formation. In contrast, the limiting potential to access alternative reaction channels on Pb(211) is 1.33 V, significantly higher than that of Sn. electrochemical reduction, reaction mechanism, carbon dioxide, formate, DFT

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Infrared spectroscopy of adsorbed CO and intermediate species in electrochemical reduction of CO2 to hydrocarbons on a Cu electrode

Cited by 134 publications

References 28 publications

Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium

Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst

A DFT study of CO2 electrochemical reduction on Pb(211) and Sn(112)

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