Journal of Solid State Electrochemistry

, Volume 14, Issue 11, pp 1997–2010

EXAFS structural studies of electrodeposited Co and Ni hexacyanoferrate films

  • A. Robert Hillman
  • Magdalena A. Skopek
  • Stephen J. Gurman
Original Paper

DOI: 10.1007/s10008-010-1033-9

Cite this article as:
Hillman, A.R., Skopek, M.A. & Gurman, S.J. J Solid State Electrochem (2010) 14: 1997. doi:10.1007/s10008-010-1033-9

Abstract

XAS (EXAFS and XANES), XPS and IR spectroscopies were used to extract redox compositional and structural information on films of electrodeposited Co and Ni hexacyanoferrates whose redox state was manipulated electrochemically. The X-ray methods provided direct information on the metal species and IR provided indirect information via the behaviour of the ligand vibration. XPS responses showed that the electrochemical response of Co hexacyanoferrate is attributable to Co (except for a small amount of FeII oxidation at very positive potentials), and of Ni hexacyanoferrate to Fe; XANES edge shifts confirm these deductions. Local structure around the metal atoms was extracted from EXAFS data in terms of M′–N, M′–C and M′–Fe (M′ = Co or Ni) distances and the associated Debye-Waller factors as functions of film charge state. For Co hexacyanoferrate, the redox variation of static disorder was consistent with a molecular model involving discrete CoII and CoIII sites, whose populations respond to potential, but not with a solid-state model.

Keywords

EXAFS, XPS Electroactive film Hexacyanoferrate Co Ni 

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • A. Robert Hillman
    • 1
  • Magdalena A. Skopek
    • 1
  • Stephen J. Gurman
    • 2
  1. 1.Department of ChemistryUniversity of LeicesterLeicesterUK
  2. 2.Department of Physics and AstronomyUniversity of LeicesterLeicesterUK

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