Reversible electrochemical insertion of anions in poly-p-phenylene from aqueous electrolytes

https://doi.org/10.1016/0022-0728(84)80192-8Get rights and content

Abstract

Poly-p-phenylene with 7.5% carbon black has been used as a pellet electrode in aqueous electrolytes. Using slow cyclic voltammetry, we have investigated the reversible electrochemical insertion of anions in 8–25 M hydrofluoric acid (H2F2) and 0.5–8 M NaClO4.

With H2F2, 100% cyclic current efficiency is attained in 20–24 M solutions. The cycling ability is good. The insertion potential is similar to graphite values and decreases linearly with increasing molarity of H2F2. This has been explained in terms of co-insertion of H2F2 solvate molecules. The maximum degree of insertion is calculated to be [(C6H4) · 0.15 HF2 · 0.30 H2F2]. With NaClO4, normal Nernstian behaviour of the insertion potential is observed. Round-trip current efficiencies are relatively poor.

Our results demonstrate clearly the relatively high stability of the polymer radical cation in aqueous electrolytes. The close similarity to the results with corresponding graphite intercalation compounds indicates their structural and energetic relationship.

References (20)

  • P. Kovacič et al.

    J. Org. Chem.

    (1964)
    P. Kovacič et al.

    Macromol. Synth.

    (1966)
    M.B. Jones et al.

    J. Polym. Sci. Polym. Chem. Ed.

    (1981)
  • F. Beck et al.
    (1984)
  • N.R. Rao

    Indian J. Phys.

    (1940)
  • P. Kovacič et al.

    J. Am. Chem. Soc.

    (1963)
    P. Kovacič et al.

    Tetrahedron Lett.

    (1962)
  • D.M. Ivory et al.

    J. Chem. Phys.

    (1979)
  • L.W. Shacklette et al.

    J. Chem. Soc.

    (1982)
  • F. Beck

    Ber. Bunsenges. Phys. Chem.

    (1964)
  • H. Naarmann

    Ber. Bunsenges. Phys. Chem.

    (1979)
  • G. Wegner

    Angew. Chem.

    (1981)
  • L.W. Shacklette et al.L.W. Shacklette et al.L.W. Shacklette et al.
There are more references available in the full text version of this article.

Cited by (17)

  • Anodic overoxidation of poly-p-phenylene in aqueous electrolytes

    1987, Journal of Electroanalytical Chemistry
View all citing articles on Scopus
View full text