Elsevier

Electrochimica Acta

Volume 12, Issue 9, September 1967, Pages 1213-1218
Electrochimica Acta

On the nature of reduced carbon dioxide

https://doi.org/10.1016/0013-4686(67)80036-7Get rights and content

Abstract

Carbon dioxide was allowed to interact at room temperature with different amounts of hydrogen chemisorbed on platinized platinum in sulphuric acid solutions. The reaction product, (CO2)r, was oxidized at constant current and constant rate of helium stirring. Analysis of the gas mixture by gas chromatography demonstrated that two electrons are required for the production of one CO2 molecule on the average. Similar experiments were carried out with carbon monoxide. The charging curves of (CO2)r and COads practically coincide in the potential region of the arrest of the charging curves and above, when measured with the same charging rate. It is suggested that (CO2)r is identical with carbon monoxide chemisorbed in the first layer on platinum.

Résumé

Du CO2 a été mis à réagir à la température ambiante avec différentes quantités d'hydrogène chimisorbé sur platine platiné, dans des solutions d'acide sulfurique. Le produit de réaction (CO2)r, a été oxydé à courant constant et à vitesse d'agitation constante au moyen d'hélium. L'analyse du mélange gazeux, par chromatographie en phase gazeuse, démontre que 2 électrons sont en moyenne nécessaires pour la production d'une molécule de CO2. Des expériences similaires ont été effectuées avec CO. Les courbes de charge de (CO2)r et COads coïncindent pratiquement dans la région du potentiel de leur arrêt et même audessus si elles sont établies avec la même vitesse de charge. Il est suggéré que (CO2)r est identique an CO chimisorbé de la première couche sur platine.

Zusammenfassung

Man liess bei Raumtemperatur variierte Mengen von an einer Platinelektrode chemisorbiertem Wasserstoff in Schwefelsäurelösungen auf Kohlendioxyd einwirken. Das Reaktionsprodukt (CO2)r wurde bei konstanter Rührung mit Helium galvanostatisch oxydiert. Die Analyse des Gasgemisches mittels Gaschromatographie ergab, dass im Mittel 2 Elektronen zur Bildung eines CO2-Moleküls notwendig sind. Analoge Untersuchungen wurden auch mit Kohlenmonoxyd durchgeführt. Die Ladekurve von (CO2r und (COads fallen im Potentialbereich des Plateaus der Ladungskurven und darüber praktisch zusammen, wenn sie bei gleicher Ladegeschwindigkeit gemessen werden. Es wird angenommen, dass (CO2)r identisch ist mit Kohlenmonoxyd, welches auf dem Platin chemisorbiertist.

References (10)

  • J. Giner

    Electrochim. Acta

    (1963)
  • J. Giner

    Electrochim. Acta

    (1964)
  • A. Slygin et al.

    Acta Phys.-chim. URSS

    (1935)
  • S.B. Brummer

    J. electrochem. Soc.

    (1966)
  • W. Vielstich et al.

    Z. Elektrochem.

    (1964)
There are more references available in the full text version of this article.

Cited by (99)

  • 4.15 - Liquid Fueled Fuel Cells

    2022, Comprehensive Renewable Energy, Second Edition: Volume 1-9
  • Surface engineering of nano-ceria facet dependent coupling effect on Pt nanocrystals for electro-catalysis of methanol oxidation reaction

    2020, Chemical Engineering Journal
    Citation Excerpt :

    MOR is a complex multistep reaction that requires catalytic sites for alcohol adsorption and dehydrogenation [39,40]. The electrooxidation of methanol on Pt would follow a dual-path mechanism, direct and indirect pathway, and the formation of CO in the indirect pathway will seriously poison the catalyst activity [39,41,42]. A bi-functional mechanism is often invoked for understanding the catalytic promotion effect, and this definition means joint activities of both metals, Pt being the one adsorbing and dissociating methanol as real active sites and the other oxophilic component, the one oxidizing the adsorbed residues like CO at low potentials.

  • CO <inf>2</inf> electroreduction characteristics of Pt-Ru/C powder and Pt-Ru sputtered electrodes under acidic condition

    2018, Applied Surface Science
    Citation Excerpt :

    However, the CO2-reduced species are strongly adsorbed on the surface of the Pt electrode [15–17]. During the adsorption phenomenon, the CO2 reductant adsorbed on the Pt electrode surface is suggested to be CO based on IR analyses [15–23]. The differential electrochemical mass spectrometric result of the CO2 electrode reaction by stripping voltammetry, described in our previous report, also supports the adsorption of CO [24].

  • Study of CO<inf>2</inf> reduction at Pt-Ru electrocatalyst in polymer electrolyte cell by differential electrochemical mass spectrometry and liquid chromatography

    2018, Electrochimica Acta
    Citation Excerpt :

    To the best of our knowledge, the production process of not only formic acid and acetic acid, but also lactic acid during the CO2 electroreduction with the Pt-Ru catalyst at around its theoretical potential was found for the first time in the present study, although the major production process of the CO2 electroreduction at the Pt-Ru catalyst remains unclear at present. One possible major process is the CO adsorption [32–34] since the DEMS result of the CO2 electrode reaction by stripping voltammetry at the Pt-Ru/C electrocatalyst demonstrated the CO adsorption [20]. It could also be considered that other carboxylic acids having higher molecular weight than those detected in this study is generated since the intensity of m/z 45 significantly increases with the increase in the reduction current in Figs. 3a and 4.

  • Pt-Ru/C anode performance of polymer electrolyte fuel cell under carbon dioxide atmosphere

    2016, Electrochimica Acta
    Citation Excerpt :

    Although CO2 is reduced at −1.5 V vs. NHE at Cu and Hg electrodes in a CO2-saturated aqueous solution, this electrode potential has no influence on the electrode reaction of the PEFC [14–19]. In contrast, when using Pt, Ir, Pd, Ru, Rh, Au, and Ag electrodes, CO2 electroreduction occurs at around −0.10–0.30 V vs. RHE, the potential region of which contains the electrode potential of the H2 oxidation reaction [20–30]. Especially, the CO2 is reduced at the Pt electrode from 0.06–0.3 V vs. DHE, and its reductant strongly adsorbs on the electrode surface [28,29].

View all citing articles on Scopus

Manuscript received 12 December 1966.

View full text