The solid-state electrochemistry of metal octacyanomolybdates, octacyanotungstates, and hexacyanoferrates explained on the basis of dissolution and reprecipitation reactions, lattice structures, and crystallinities.

The electrochemical behavior of solid microparticles of metal (Ag+, Cd2+, Co2+, Cr2+, Cu2+, Fe2+, Mn2+, Ni2+, Pb2+, and Zn2+) octacyanomolybdates, octacyanotungstates, and hexacyanoferrates has been studied by voltammetry, electrochemical quartz crystal microbalance, and microscopic diffuse reflectance spectroelectrochemical measurements. The solid microparticles have been immobilized on the surface of graphite electrodes prior to the electrochemical measurements. A comparative study of the cyclic oxidation and reduction of these compounds in the presence of potassium ions revealed that any interpretation of the electrochemistry requires the solubility equilibria of the reduced compounds to be taken into account, such as in the case of the silver salts [Ag3K[X]] and [Ag4[X]] (with X = FeII(CN)6(4-), MIV(CN)8(4-) (M = Mo, W)). Because [Ag4[X]] has a lower solubility than [Ag3K[X]], the electrochemistry is accompanied by a conversion of solid [Ag3K[X]] into solid [Ag4[X]]. Two distinct voltammetric signal systems are generated by these two compounds according to [Ag3K[X]] reversible [Ag3[X]] + K(+) + e- and [Ag4[X]] reversible [Ag3[X]] + Ag(+) + e-. When silver ions are present in the solution adjacent to the microparticles, the silver octacyanometalates and silver hexacyanoferrate show a chemically reversible and very stable voltammetric behavior. Despite the fact that the electrochemistry is based upon a single-electron/single-ion transfer reaction ([Ag4[X]] reversible [Ag3[X]] + Ag(+) + e-), more than one electrochemical signal is observed because of the simultaneous presence of amorphous and crystalline particles. This study shows that the interplay of solubility equilibria and electrochemical equilibria is generally observed for the other metal octacyanomolybdates, octacyanotungstates, and hexacyanoferrates as well.