Oxidized and reduced cobalt(II) hexacyanoferrates were
fabricated and characterized in the presence of alkali
metal (Li+, Na+, K+,
Cs+) and Co2+ countercations. Formal
potentials of hexacyanoferrate(III,II) redox
reactions are sensitive to the choice of electrolyte cation, and they
correlate well with the sizes of hydrated
Li+, Na+, and K+.
Electrochemical quartz crystal microbalance measurements clearly
indicate that
countercations, presumably in partially dehydrated form, are
incorporated into reduced cobalt(II) hexacyanoferrate(II). The color of the system reflects primarily the
oxidation state of iron sites. But the color of
the reduced form is also affected by the nature of an intercalated
hydrated countercation. This observation
is correlated with the reversible continuous thermochromism of
K2CoII[FeII(CN)6]*nH2O
that shall be attributed
to the release of structural water molecules interacting with
CoII during heating in the temperature range
25−85 °C. It is apparent from X-ray absorption near-edge
structure (XANES) experiments that the chemical
environment of cobalt(II) sites is influenced by the presence of
hydrated alkali metal countercations. The
results are consistent with the accommodation of countercations in the
lattice cavities at interstitial positions.
The structural environment of iron ions was the same in all
systems studied except that a chemical shift was
observed due to change of the oxidation state of iron.