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EXAFS structural studies of electrodeposited Co and Ni hexacyanoferrate films

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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.

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Acknowledgements

We thank Daresbury Laboratory for synchrotron beam time and Mr. R. Bilsborrow and Dr. Stephen Fiddy for technical support. MAS thanks Daresbury Laboratory and the Engineering and Physical Science Research Council for financial support.

We thank the NCESS Facility at Daresbury Laboratory for provision of XPS instrument time and Dr. Graham Beamson for helpful discussions.

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Authors and Affiliations

  1. Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK

    A. Robert Hillman & Magdalena A. Skopek

  2. Department of Physics and Astronomy, University of Leicester, Leicester, LE1 7RH, UK

    Stephen J. Gurman

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  1. A. Robert Hillman
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  2. Magdalena A. Skopek
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  3. Stephen J. Gurman
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Correspondence to A. Robert Hillman.

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Hillman, A.R., Skopek, M.A. & Gurman, S.J. EXAFS structural studies of electrodeposited Co and Ni hexacyanoferrate films. J Solid State Electrochem 14, 1997–2010 (2010). https://doi.org/10.1007/s10008-010-1033-9

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  • DOI: https://doi.org/10.1007/s10008-010-1033-9

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