Polarographic Reduction of Carbon Dioxide. II. Polymerization and Adsorption at the Dropping Mercury Cathode<sup>1</sup>

P, Van Rysselberghe

doi:10.1021/ja01214a052

Cited by 13 publications

(5 citation statements)

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“…A typical polarogram showing the phenomena described above is given in figure 1. In figure 2 the previously observed reduction of carbon dioxide (15,16,17) at a half-wave potential of 2.16 v. with respect to the saturated calomel electrode appears in addition to the new wave observed at low potentials.…”

Section: Air-saturated Solutions With Various Additions Of Carbon Dio...mentioning

confidence: 53%

“…Other percarbonic acids could also be expected, such as H2CO5 and H2C2O6. Our previous polarographic studies on carbon dioxide (15,16,17) have shown that, in the absence of oxygen or hydrogen peroxide, the new wave now being discussed is not observed. We are definitely dealing with the reduction of a compound formed by reaction of carbon dioxide with hydrogen peroxide.…”

Section: Solutions Of Hydrogen Peroxide With Various Additions Of Car...mentioning

confidence: 91%

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The Polarographic Observations on Percarbonic Acids and Percarbonates.

P¹,

Delahay²,

Ah³

et al. 1950

J. Phys. Chem.

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Section: Air-saturated Solutions With Various Additions Of Carbon Dio...mentioning

confidence: 53%

Section: Solutions Of Hydrogen Peroxide With Various Additions Of Car...mentioning

confidence: 91%

The Polarographic Observations on Percarbonic Acids and Percarbonates.

P¹,

Delahay²,

Ah³

et al. 1950

J. Phys. Chem.

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“…The energy efficiency, e, for the reduction of carbon dioxide to formic acid can be expressed in the following manner ~H X (percent faradaic efficiency) , = [7] nF{Erev…”

Section: Resultsmentioning

confidence: 99%

“…This result led some workers to believe that the bicarbonate and carbonate anions were electroactive species and that the reduction of carbon dioxide occurred on electrodes having high hydrogen overpotentials (2,3). Polarographic waves observed in solutions containing carbon dioxide were interpreted as being due to the reduction of carbon dioxide (7)(8)(9). Later studies (10,11) confirmed the above interpretation and showed that carbon dioxide, and not the bicarbonate or carbonate anion, is the electroactive species.…”

mentioning

confidence: 92%

“…From these experiments a dynamic response equation for the sensor is obtained. Based on experimental data, rate-limiting processes, as for instance solvation-desolvation (7), adsorption (8), and diffusion (9), were proposed. However, it should be pointed out that the mathematical form of the semiempirical response equation may lead to an erroneous interpretation of the rate-limiting process (I0).…”

Section: Introductionmentioning

confidence: 99%

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The Electrochemical Reduction of Carbon Dioxide, Formic Acid, and Formaldehyde

Russell

Kovac

Srinivasan

et al. 1977

J. Electrochem. Soc.

187

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The prospects for the electrochemical reduction of carbon dioxide to methanol were examined by investigating the intermediate reactions. The reduction of carbon dioxide was carried out in a neutral electrolyte at a mercury electrode. The high overvoltage observed for carbon dioxide reduction to the formate anion reflects a low value for the efficiency of electric energy utilization for this process. Formic acid can be reduced to methanol in a perchloric acid electrolyte (at a lead electrode) or in a buffered formic acid electrolyte (at a tin electrode). The faradaic efficiency for methanol formation is close to 100% at the tin electrode in a narrow potential region corresponding to a low current density. The potential dependence of formic acid reduction to methanol suggests that the adsorption of formic acid on the electrode, near the pzc, may be the rate‐controlling step in the over‐all reaction. The reduction of formaldehyde to methanol occurs with a faradaic efficiency exceeding 90% in a basic solution. The Tafel slope decreases when either the formaldehyde concentration is increased (at constant pH) or when thepH of the solution is increased (at constant concentration). The polyoxymethylene glycols present as impurities in formaldehyde solutions may influence the mechanism of the electrode process through interaction with formaldehyde molecules and/or other adsorbed species resulting in small changes of the Tafel slope.

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Zum Mechanismus der elektrochemischen Dimerisierung von CO₂ zu Oxalsäure

Kaiser

Heitz

1973

Ber Bunsenges Phys Chem

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Bei der elektrochemischen Reduktion von CO2 in wäßrigen Elektrolyten entsteht Ameisensäure, während Versuche, mehrgliedrige Carbonsäuren herzustellen, bisher mißlangen. In aprotischen Lösungsmitteln ist die Reduktion von CO2 zu Oxalsäure möglich, da die zur Bildung von Ameisensäure notwendigen Protonen fehlen. Zwei Reaktionen sind zu diskutieren: Die Art der Reduktion wird durch das Elektrodenmaterial und das Lösungsmittel beeinflußt. Elektrodenmaterialien, die CO2 stark chemisorbieren, begünstigen Reaktion (3). Schwach nukleophile aprotische Lösungsmittel (Propylencarbonat, Acetonitril) begünstigen (2). Bei teilaprotischen Bedingungen entstehen neben Ameisensäure und Oxalsäure die Reduktionsprodukte der Oxalsäure: Glykoll‐, Glyoxyl‐, Wein‐, Äpfel‐ und Bernsteinsäure.Die Versuche wurden in zwei‐ oder dreigeteilten Zellen durchgeführt. Als Trennwände dienten Anionen‐ und Kationenaustauschermembranen, um die Migration und Diffusion der an der Kathode gebildeten Carbonsäureanionen in den Anodenraum und umgekehrt von anodisch gebildeten Produkten in den Kathodenraum zu verhindern. Die Stromausbeute ist abhängig von den Reaktionsbedingungen; bisher wurden etwa 60% erreicht.Das erhaltene Carbonsäure‐Produktgemisch wurde mittels der Hochdruckflüssigkeitschromatographie analysiert.

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Polarographic Reduction of Carbon Dioxide. II. Polymerization and Adsorption at the Dropping Mercury Cathode¹

Cited by 13 publications

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The Polarographic Observations on Percarbonic Acids and Percarbonates.

The Polarographic Observations on Percarbonic Acids and Percarbonates.

The Electrochemical Reduction of Carbon Dioxide, Formic Acid, and Formaldehyde

Zum Mechanismus der elektrochemischen Dimerisierung von CO₂ zu Oxalsäure

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Polarographic Reduction of Carbon Dioxide. II. Polymerization and Adsorption at the Dropping Mercury Cathode1

Cited by 13 publications

References 0 publications

The Polarographic Observations on Percarbonic Acids and Percarbonates.

The Polarographic Observations on Percarbonic Acids and Percarbonates.

The Electrochemical Reduction of Carbon Dioxide, Formic Acid, and Formaldehyde

Zum Mechanismus der elektrochemischen Dimerisierung von CO2 zu Oxalsäure

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Product

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Polarographic Reduction of Carbon Dioxide. II. Polymerization and Adsorption at the Dropping Mercury Cathode¹

Zum Mechanismus der elektrochemischen Dimerisierung von CO₂ zu Oxalsäure