Structure and electrochromic properties of ferric aquapentacyanoferrate—a new analogue of Prussian blue

Nechitayilo, V.B.; Styopkin, V. I.; Tkachenko, Z. A.; Gol’tsov, Yu. G.; Sherstyuk, V. P.; Zhilinskaya, V. V.

doi:10.1016/0013-4686(95)91226-x

Cited by 9 publications

(5 citation statements)

References 9 publications

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“…CT shift in Modified PB. The λ max of a kind of Prussian Blue containing the pentacyano-aquoiron(II) anion is reported 23 as being shifted 100 nm to longer wavelengths (cf that of PB). The weaker average ligand field at the Fe II arising from substitution of an H 2 O for a CNin part accounts for the lower-energy transition, and furthermore, the 3-anionic charge of the pentacyano-iron(II) ion diminishes the lattice energy cf Fe II (CN) 6 4-, which would also increase λ max .…”

Section: Resultsmentioning

confidence: 99%

Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies

et al. 2003

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The maximum of the color-conferring charge-transfer (CT) band in Prussian Blue (PB) varies with the electrochemically introduced cation M(z+) incorporated (as "supernumerary") for charge neutrality, and the dependence on particular properties of the M(z+) has been sought. With alkali-metal ions, the CT-maximum shifts are in the same sequence as the PB mass changes on M+ insertion; the effect on the CT ground state of the intra-lattice interaction of an M+ with the ferrocyanide CN- moiety (competing with cation hydration), is then implicated in shifts of the maxima, as the ferrocyanide is the donor center in the optical CT. More definitely, for M2+ and Ag+, solubility-products of the insoluble M(z+) ferrocyanides (that provide direct indicators of the intra-lattice M(z+)-[Fe(II)(CN)(6)](4- interactions) show a strong correlation with the spectral shifts. The determining interaction of M(z+) with ferrocyanide within PB is enhanced in some cases by the accessibility of M(z+) oxidation states +/- 1 different from the common values. PB lattice energies and the ground states of the optical CTs thus appear closely interlinked. The electrochemical uptake of appreciable amounts of the M(z+) within the lattices was confirmed by XPS.

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Section: Resultsmentioning

confidence: 99%

Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies

et al. 2003

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“…34 In support, the max of a PB, but containing the pentacyanoa-quoiron͑III͒ anion, is shifted 100 nm to longer wavelengths of PB. 35 The weaker average ligand field of the pentacyano ligands, from substituting an H 2 O for CN Ϫ , in part accounts for the lower-energy transition. Furthermore, the 3Ϫ anionic charge of the pentacyano-iron͑II͒ ion cf.…”

Section: Resultsmentioning

confidence: 99%

EDX, Spectroscopy, and Composition Studies of Electrochromic Iron(III) Hexacyanoferrate(II) Deposition

Rosseinsky

Glidle

2003

J. Electrochem. Soc.

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Persistent questions regarding the electrochromic ferric-ferrocyanide chromophore, Prussian blue (PB), are addressed and definitively resolved by detailed chemical and energy-dispersive X-ray analyses and spectroscopy: (i) What is the nature of the initially deposited film? (ii) Restructuring of freshly deposited PB that occurs in the first voltammetric cycle in KCl(aq): why is only one-third of the maximum possible K+ taken up? (iii) Is the presence of KCl in the electrodeposition solution beneficial or destructive? and (iv) What underlies the appreciable spectroscopic shifts of the charge-transfer peak at ∼700 nm, that depend on which alkali-metal ion M+ is incorporated in PB? The KCl-cycled PB after electrodeposition is shown to be K0.33+Fe0.332+Fe3+false[normalFefalse(CN)64−false] in a mechanism explaining the limited (0.33) uptake of K+. Similar compositions are found with other M+ except Cs+, which interacts exceptionally. © 2003 The Electrochemical Society. All rights reserved.

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“…Raman spectroscopy can be a useful tool to individuate different spectral signatures in different form of Prussian blue. PBS and PBI can show Raman spectra with some differences, indicator of possible alterations in the charge transfer mechanism due, for example, to the amount of vacancies inside the structure, the presence of cations, or coordinated water within vacancies . As shown in Figure , spectra collected inside the safe zone (0.0121 mW) on these two types of PB present some differences not only in the shape of the C ≡ N related peak but also at the level of the shoulder, present only in PBS, correspondent to CN − stretching.…”

Section: Discussionmentioning

confidence: 97%

Raman spectroscopy of the photosensitive pigment Prussian blue

Moretti

Gervais

2018

J Raman Spectroscopy

140

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Prussian blue is a pigment highly sensitive to electromagnetic radiation, visible light included. This photosensitivity, associated with a complex redox behavior, causes a vulnerability even to Raman lasers, with the possibility of sample alteration or irreversible damage. In this study, we systematically explored the influence of the laser wavelength and laser power on different types of Prussian blue pigments, soluble and insoluble. The use of different laser wavelengths does not influence the position of the characteristic peak, though it affects the signal‐to‐noise ratio. The latter can be improved by increasing the number of accumulations and/or the acquisition time. Furthermore, we evaluated a safe level of Raman laser excitation or “safe zone” with laser power between 0.005 and 0.06 mW, where Raman analysis can be performed without laser‐induced artifacts or damage for the sample. These artifacts may affect the characteristic spectral signature of the two different Prussian blue, leading to a wrong identification of the pigments. Moreover, artifacts can also hide features arisen from fading in objects presenting non‐visible alterations of Prussian blue.

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Structure and electrochromic properties of ferric aquapentacyanoferrate—a new analogue of Prussian blue

Cited by 9 publications

References 9 publications

Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies

Optical Charge-Transfer in Iron(III)hexacyanoferrate(II): Electro-intercalated Cations Induce Lattice-Energy-Dependent Ground-State Energies

EDX, Spectroscopy, and Composition Studies of Electrochromic Iron(III) Hexacyanoferrate(II) Deposition

Raman spectroscopy of the photosensitive pigment Prussian blue

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