Electrochromism Prussian Blue

Metal Oxide Electrochromism Viologen Electrochromism Prussian Blue Electrochromism Conducting Polymer Electrochromism... 

Mortimer, R.J. and J.R. Reynolds. 2005. In situ colorimetric and composite coloration efficiency measurements for electrochromic Prussian blue. / Mater Chem 15 2226-2233. 

Polynuclear transition metal cyanides such as the well-known Prussian blue and its analogues with osmium and ruthenium have been intensely studied Prussian blue films on electrodes are formed as microcrystalline materials by the electrochemical reduction of FeFe(CN)g in aqueous solutionThey show two reversible redox reactions, and due to the intense color of the single oxidation states, they appear to be candidates for electrochromic displays Ion exchange properties in the reduced state are limited to certain ions having similar ionic radii. Thus, the reversible... 

Other Inorganic Compounds Prussian Blue represents another type of inorganic mixed valence electrochromic materials. This material is known in three states ... 

D. Ellis, M. Eckhoff, and V.D. Neff, Electrochromism in the mixed-valence hexacyanides. 1. Voltammetric and spectral studies of the oxidation and reduction of thin films of Prussian Blue. J. Phys. Chem. 85, 1225-1231 (1981). 

Figure 8.1 Beer s law-type plot of change in optical absorbance against charge density q for the cell WO3 polymer electrolyte Prussian Blue. Reprinted from Inaba, H Iwaka, M., Nakase, K., Yasukawa, H., Seo, I. and Oyama, N., Electrochromic display device of tungsten trioxide and Prussian Blue films using polymer gel electrolyte of methacrylate , Electrochim. Acta, 40, 227-232 (1995), Copyright 1995, with permission from Elsevier Science.

PB and its derivatives are of interest for a variety of reasons, the most important of which is its electrochromism [93]. In addition, it is an electrocatalyst for several different types of substrates, notably hydrogen peroxide, as will be seen below. Synthesis of nanopartides of Prussian Blue is relatively straightforward. It relies on many of the prindples of colloid chemistry, and produces ionically stabilized colloidal solutions (Figure 4.7). As a consequence, the electrochemical behavior of PB N Ps has been examined by several groups. In this section, we discuss the behavior of P B N Ps immobilized at electrodes. 

All inorganic electrochromes exist in the solid state in both the colourless and coloured states, e.g. Prussian Blue and tungsten trioxide. Conducting polymers such as polyanilines, polypyrroles and polythiophenes also fall into this class of electrochromes (see 1.5.3.5). 

One of the big drawbacks associated with the use of many conducting polymers as electrochromic materials is their low cycle life stability. To overcome this, and other electrochromic properties, many composite materials have been studied. These composites include mixtures with other optically complementary, conducting polymers and inorganic electrochromes, such as tungsten trioxide and Prussian Blue, and colour enhancing agents or redox indicators, exemplified by the inherently electrochromic indigo carmine (1.96). °... 

The preparation of film electrodes Prussian blue films are usually prepared by cycling an electrode in a freshly prepared solution containing iron(III) and hexacyanoferrate(III) ions [70-72]. As substrate, mostly platinum is used, sometimes glassy carbon [73] is used, and very frequently ITO electrodes [74] are used because the latter are very useful for electrochromism studies. Similar procedures using solutions containing metal ions and hexacyanoferrate(III) have been used to deposit cobalt hexacyanoferrate [75] and chromium hexacyanoferrate [76, 77]. Crumbliss et al. reported a plasma deposition of iron species from a plasma containing iron pentacarbonyl and ethane, followed by electrochemical derivatization of the deposited iron sites with the help of hexacyanoferrate solutions [78]. 

Not surprisingly, the very interesting and practically useful properties of Prussian blue have resulted in several studies of similar hexacyano derivatives [114] but only a few of them (e.g., ruthenium- and osmium-based systems) have found use in electrochromic devices. More systematic studies should, indeed, be called for in order to harvest the full potential of this group of compounds. 

A general schematic for a smart window is shown in Figure 13.10. This device is, quite literally, two chemically modified electrodes sandwiched together. In this case, the films coating the electrode surfaces are electrochromic materials. A polymer electrolyte, analogous to that used in the fuel cell discussed earlier, is sandwiched between these two electrochromic material-coated electrodes. In a recent example of this concept by Habib and Maheswari of General Motors Research Laboratories [94], the cathodic electrochromic material was a tungsten oxide and the cathodic electrochromic material was the material Prussian blue, discussed in Section II of this chapter. It seems likely that electrochromic cells will soon find their way into the commercial marketplace. 

Electrochromic materials are of three basic types [i]. In a given -> electrolyte solution, type I materials are soluble in both the reduced and oxidized (redox) states, an example being l,l -di-methyl-4,4 -bipyridylium ( methyl viologen ), which, on reduction, switches from the colorless di-cation to the blue radical cation. Type II materials are soluble in one redox state, but form a solid film on the surface of an electrode following electron transfer. An example here is l,l -di-heptyl-4,4 -bipyridylium ( heptyl viologen ). In type III materials, such as -> tungsten oxide, - Prussian blue, and electroactive conjugated polymers, both... 

The redox chemistry of the Prussian blue family (Table 7) has attracted considerable attention. The generation of thin films of Prussian blue has led to studies of its mediation in electron transfer reactions and of the electrochemical processes involved in its deposition and redox reactions. This work has been spurred by its electrochromic properties which have been used in prototype electronic display devices based, for example, on Prussian blue modified Sn02 electrodes. A recent review deals with the electrochemistry of electrodes modified by depositing thin films of PB and related compounds on them. Interestingly, true Prussian blue is somewhat difficult to process and modern iron blue pigments such as Milori blue are derived from the oxidation of rlin white Fe(NH4)2[Fe(CN)e] to give iron(III) ammonium ferrocyanides. 

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