An Electronic Perspective On The Electrochemical Changeover In Prussian Blue-Like Materials

Derivative voltabsometric scans together with previous electrogravimetric results allow to distinguish between the different electrochemical processes due to Fe-sites located into the Prussian Blue crystalline framework and other located next to ferrocyanide vacancies. The potassium, proton and hydrated proton counterions involved in these reactions are correlated to changes in near-UV/VIS/near-IR spectra. Potassium counter-ions show two different sites for insertion: one located into the crystalline framework and the other into ferrocyanide vacancies. From the monitoring of electroactive Fe-sites, it is possible to assume that the reduction of all Fe-sites located next to ferrocyanide vacancies is responsible for the PB magnetic ordering observed at room temperature.