Spectroelectrochemistry of New Prussian Blue Films Prepared by a Cast Method

Abstract

New Prussian Blue (PB) films were prepared by being cast from colloidal PB dispersions in an organic solvent containing cationic surfactants. The electrochromic behaviors of the cast PB films are similar to those of electrodeposited PB films. However, the cyclic voltammetries of both the PB films were quite different from each other. To make the difference clear, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and X-ray photospectroscopy (XPS) were used in measurements of these films grown on Pt and indium tin oxide electrodes. The EDX results for fresh PB films indicated that cast films contain K+ ions, suggesting a soluble-form PB, KFe[Fe(CN)6], while electrodeposited films do not, suggesting an insoluble-form PB, Fe4[Fe(CN)6]3. The transient spectral observations indicated the participation of a unique electrochemically active iron(III) site in the reductive cycles of a cast film, although the participation of a plural electrochemically active iron(III) sites was proposed for an electrodeposited film. After a repeated cyclic scan a cast PB film maintained its unique active site, while an electrodeposited film had plural sites comprising both a soluble and an insoluble form of PB.

Surfactant Promoted Enhancement in Electrochemical and Electrochromic Properties of Films of Prussian Blue and Its Analogs

“…18 Not much is known on the role of surface active agents in the surface-modified films. 19 In the present work we have undertaken to investigate the effect of chosen surface active agents (nonionic, cationic, and anionic) on surface films of metal hexacyanoferrates of Fe, Ni, and Co. Enhancements in electrochemical and electrochromic responses of the above films in the presence of CH 3 (CH 2 ) 15 (CH 3 )иN ϩ Br Ϫ , cetyl trimethyl ammonium bromide (CTAB), noted by us for the first time, are reported and discussed in this communication.…”

In Situ FT-IR/ATR Spectroelectrochemistry of Prussian Blue in the Solid State

“…In the present work, we propose coupling solid-state voltammetry with Fourier transform infrared attenuated total reflection (FT-IR/ATR) spectroscopy. , The approach permits monitoring of interfacial (i.e., in the vicinity of electrode surface) changes in the infrared spectrum of the investigated material as a function of applied potential. Prussian Blue (PB), iron(III) hexacyanoferrate(II), a prototype of polynuclear mixed-valence metal cyanometallates, ,− was chosen as a model system due to its suitability for both solid-state electrochemical 23 and IR 15 measurements.…”

Preparation of electrochromic Prussian blue nanoparticles dispersible into various solvents for realisation of printed electronics

“…5,7 The surface-covered cis-C 18 -amines insulated each PB NP on the ITO electrodes against the electrochromic response. 48 The chemisorbed longchain alkylamines were hardly removed from the PB NP thin film by heating at 150 °C to generate the electrochromic response; this temperature is the limit to keep the PB structure stable. According to the TG profile of PB, PB gradually loses the crystal and coordination waters up to 50 °C, and the cyanobridging 3D structure is oxidatively decomposed via the exothermic reaction with air at 260 °C to transform into iron oxides.…”