Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media

Hori, Yoshio; Wakebe, Hidetoshi; Tsukamoto, T.; Katoh, Osamu

doi:10.1016/0013-4686(94)85172-7

Cited by 1,824 publications

(1,888 citation statements)

References 30 publications

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“…(a) formaldehyde to probe the key intermediate CH 2 OH ad that selects methane production over methanol in C 1 pathways (b) ketene to probe the predicted intermediate HO(CH) CH 2,ad that leads exclusively to ethanol production once formed (c) acetylene for verifying the predicted mechanisms for selectivity of C 2 H 4 vs C 2 H 6 With formaldehyde, we expect to form a surface methoxy intermediate CH 3 O ad by the H ad mechanism, which leads to methanol production exclusively, as suggested previously. 14,15 In contrast, the target CH 2 OH ad pathways are not switched on until pH ≥ 10.1, due to the potential limiting step of dehydration to CH 2,ad , at which point the methane production has comparable kinetics (see Tables S1 and S3 in the Supporting Information).…”

Section: Journal Of the American Chemical Societymentioning

confidence: 94%

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

2016

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Practical environmental and energy applications of the electrochemical reduction of CO 2 to chemicals and fuels require far more efficient and selective electrocatalysts beyond the only working material Cu, but the wealth of experimental data on Cu can serve to validate any proposed mechanisms. To provide design guidelines, we use quantum mechanics to predict the detailed atomistic mechanisms responsible for C 1 and C 2 products on Cu. Thus, we report the pH dependent routes to the major products, methane and ethylene, and identify the key intermediates where branches to methanol, ketene, ethanol, acetylene, and ethane are kinetically blocked. We discovered that surface water on Cu plays a key role in the selectivity for hydrocarbon products over the oxygencontaining alcohol products by serving as a strong proton donor for electrochemical dehydration reductions. We suggest new experiments to validate our predicted mechanisms.

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Section: Journal Of the American Chemical Societymentioning

confidence: 94%

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

2016

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“…Despite extensive efforts aimed at identifying electrocatalysts that can produce these products, copper (Cu) remains the only material capable of doing so with significant yields. [3][4][5] Nevertheless, Cu requires a high overpotential (~−1 V versus RHE) and produces a broad spectrum of products. 6,7 Clearly, the discovery of novel means for reducing CO 2 to desirable products with higher efficiency and selectivity is needed.…”

Section: Introductionmentioning

confidence: 99%

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

et al. 2017

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The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2 . Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably for HCOO The observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.

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“…3) High temperature CO 2 electrolysis by SOEC at 800-900°C has been reported for CO 2 and H 2 mixture, 4) and pure CO 2 , 5) and tube-type cell 6) in previous studies. It was already shown that electrodes based on La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O 3 (LSCM) had high performance for CO 2 electrolysis in CO and CO 2 mixture, 7) a LaGaO 3 -based electrolyte was capable to reduce CO 2 into CO at lower temperature up to 700°C.…”

Section: Introductionmentioning

confidence: 84%

Possibility of Application of Solid Oxide Electrolysis Cell on a Smart Iron-making Process Based on an Active Carbon Recycling Energy System

et al. 2015

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Efficient carbon dioxide (CO2) reduction into carbon monoxide (CO) is required to establish a smart ironmaking process based on an active carbon recycling energy system (iACRES). A disk-type solid oxide electrolysis cell (SOEC) was prepared and examined experimentally for application to the CO2 reduction process in iACRES. A SOEC with a cathode|electrolyte|anode structure of Ni-YSZ|YSZ|La0.6Sr0.4Co0.2Fe0.8O3-δ was fabricated. The electrolysis of carbon dioxide was conducted at 800-900°C. A current density of 107.1 mA cm -2 was measured between the cathode and anode at 900°C and at 2.52 V. The production rates of CO and O2 were in agreement with the theoretical values determined using Faraday's law. Evaluation of iACRES using the experimental results indicated that an estimated 0.73 high-temperature gas cooled reactor units as the primary energy source for CO2 reduction and a SOEC surface area of 0.098 km 2 were required for the reduction of 30% CO2 in blast furnace gas emitted from a conventional blast furnace.

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Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media

Cited by 1,824 publications

References 30 publications

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

Possibility of Application of Solid Oxide Electrolysis Cell on a Smart Iron-making Process Based on an Active Carbon Recycling Energy System

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Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media

Cited by 1,824 publications

References 30 publications

Atomistic Mechanisms Underlying Selectivities in C1 and C2 Products from Electrochemical Reduction of CO on Cu(111)

Atomistic Mechanisms Underlying Selectivities in C1 and C2 Products from Electrochemical Reduction of CO on Cu(111)

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

Possibility of Application of Solid Oxide Electrolysis Cell on a Smart Iron-making Process Based on an Active Carbon Recycling Energy System

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Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)