Structural Analysis of K4Fe(CN)6·3H2O, K3Fe(CN)6 and Prussian Blue

XRD and XAS were used to characterize the bulk structure, while XPS was used to characterize the surface structure, of commercially obtained nominally K4Fe(CN)6·3H2O, K3Fe(CN)6 and our synthesized Prussian Blue (PB) material. K4Fe(CN)6·3H2O was found to consist of a fully hydrated phase, which crystallizes in the monoclinic form and a less hydrated or anhydrous phase which crystallizes in the orthorhombic form. K3Fe(CN)6 was found to consist of the well-established orthorhombic form rather than the monoclinic form. The structure of our synthesized Prussian Blue (PB) was found to be consistent with that reported for (KOH)0.7Fe(III)1.33Fe(II)(CN)6·4.0H2O which crystallizes in the cubic form. XPS and XAS confirmed the presence of ferrous Fe(II) at the surface and bulk levels in K4Fe(CN)6·xH2O. However, XPS revealed the presence of Fe(II) (∼30%) and Fe(III) (∼70%) in the surface region of K3Fe(CN)6 while XAS confirmed the presence of mostly Fe(III) at the bulk level. Both XPS and XANES confirmed the presence of Fe(II) and Fe(III) in the surface and bulk regions of PB. This ex situ XAS study will be used to support the analysis of an in situ XAS data collected on a PB containing supercapacitor to understand the mechanistic origin of pseudocapacitance in these devices.