An electroanalytical investigation on the nickel-promoted electrochemical conversion of CO2 to CO

https://doi.org/10.1016/0022-0728(87)85044-1Get rights and content

Abstract

The electrochemical reduction of carbon dioxide is strongly catalysed when it is carried out by cathodically generated and continuously recycling nickel(O) from the nickel(II)-bipyridyl precursor complex. In such a way, equimolar amounts of carbon monoxide and carbonate ions are obtained in a good yield referred to the charge transferred. However, by performing this process under controlled potential conditions, unsatisfactorily low turnover numbers are found because these reduction products are able to abstract progressively the nickel promoter from the electrocatalytic cycle. Carbonate ions in fact enter the coordination sphere of nickel(II), giving a mixed complex which can be reduced at potentials more negative than the precursor species, while carbon monoxide reacts with nickel(O) leading to the formation of a quite inert carbonyl-bipyridyl compound. The negative effect of these side reactions can be overcome by performing this electrocatalytic process at constant current in a cell without any diaphragm separating the two electrode compartments. A reaction pathway is proposed which is consistent with the data obtained.

References (32)

  • B.R. Eggins et al.

    J. Electroanal. Chem.

    (1983)
  • Y.B. Vassiliev et al.

    J. Electroanal. Chem.

    (1985)
  • Y.B. Vassiliev et al.

    J. Electroanal. Chem.

    (1985)
  • D.J. Pearce et al.

    J. Electroanal. Chem.

    (1986)
  • G. Bontempelli et al.

    J. Electroanal. Chem.

    (1984)
  • G. Bontempelli et al.

    Ann. Chim. (Rome)

    (1985)
  • B. Corain et al.

    Inorg. Chim. Acta

    (1978)
  • G. Bontempelli et al.

    J. Electroanal. Chem.

    (1979)
  • L.V. Haynes et al.

    Anal. Chem.

    (1967)
  • C. Amatore et al.

    J. Am. Chem. Soc.

    (1981)
  • M.G. Bradley et al.

    J. Chem. Soc.

    (1983)
  • M. Koudelka et al.

    J. Electrochem. Soc.

    (1984)
  • J. Hawecker et al.

    J. Chem. Soc.

    (1984)
  • B.P. Sullivan et al.

    J. Chem. Soc.

    (1985)
  • T.R. O'Toole et al.

    J. Chem. Soc.

    (1985)
  • Cited by (66)

    • Electrochemical preparation of standard solutions of Pb(II) ions in ionic liquid for analysis of hydrophobic samples: The olive oil case

      2017, Talanta
      Citation Excerpt :

      Some decades ago, the problem of preparing anhydrous standard ionic solutions in aprotic organic solvents such as acetonitrile, DMSO, DMF, propylencarbonate etc., was faced by developing relatively easy electrochemical preparation methods [29,30]. It was demonstrated that, by oxidizing a metal anode under controlled anhydrous conditions in the aprotic medium, it was possible to generate metal ion solutions whose concentration could be controlled coulometrically [29,30]. The method showed to be feasible also for preparing with accuracy solutions of anhydrous HClO4 obtained by the electrochemical oxidation of hydrogen gas in pre-dried aprotic solvents, which were successfully used as standards to define an absolute pH scale from proton basicity in aprotic solvents [31,32].

    • Electrochemical Reactions Catalyzed by Transition Metal Complexes

      2004, Comprehensive Coordination Chemistry II
    View all citing articles on Scopus
    View full text