Electrocatalysis Characteristics of a Polynuclear Cyanide Complex, Ruthenium Purple, for Dihydrogen Oxidation

An electrocatalytic dihydrogen oxidation was found to take place on an electrode coated with iron(III) ruthenocyanide (i.e., repeating unit cell structure: Fe^III ₄Ru^II(CN)₆]₃ or MFe^IIIRu^II(CN)₆] and M = alkali metal counter ion) called ruthenium purple (RP). It was shown by voltammetric study that an electrocatalytic dihydrogen oxidation is induced on oxidizing the Fe^II ion in the cyanometallate. When the electrocatalysis characteristics of RP were investigated by voltammetry, especially in terms of the kinds of electrolyte used (K⁺ or Na⁺), RP exhibited a more efficient electrocatalysis in the K⁺ than in the Na⁺ electrolyte system. While a one-electron electro-oxidation of Fe^II to Fe^III occurs, there is also a release of hydrated alkali metal cation(s) from the anionic RP (i.e., reduced RP) to compensate for charge. Moreover, cation transport through the cyanometallate network is more facile for the K⁺ electrolyte system (cf., size of hydrated cation: Na⁺ at 0.36 nm lattice channel of RP at 0.35 nm > K⁺ at 0.24 nm). Therefore, it was most probable that the present electrocatalysis is kinetically dominated by the electro-oxidation.