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The long-established ferric ferrocyanide chromophore Prussian Blue (PB) has often been studied for electrochromic use. New observations and conclusions are now presented. Detailed analyses, chemical and by means of EDX, of films deposited on Pt in a variety of conditions and solution compositions, are presented, and a remarkably efficient uptake of Cs+ noted. In particular, the pH for stablest film from KCl- containing solution should be high, ca 4-5. Details of the electrodeposition on ITO glass were examined, where earlier suppositions regarding the nature of the foundation layers are confirmed by direct observation. Unexpectedly, this is substantially of ferric-ferricyanide composition. The spectroscopic shifts of the intervalence charge-transfer absorption on incorporation of different univalent cations into PB are reported and analysed. The preparative precautions needed for deposition on larger (10 x 10 cm2) ITO glass electrodes are thoroughly examined. The electrochromic response of a dual-PB electrode setup in which one electrode can be switched to clear Prussian White and the other to the deep yellow of Prussian Yellow, presents an unlikely prospect for windows or other intensity-attenuation applications, but may serve e.g. in displays. In an alternative dual-PB array a metallic silver electrode is peripherally interposed, to act as a silver/silver- chloride counter electrode. The response time in the 10 x 10 cm2 system is approximately 90 s and is accompanied by a pronounced iris (racoon) effect. The assembly provides an interesting example of two-electrode operation of a larger (cf lab-scale) device. Two-electrode operation is discussed and clarified.
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