A numerical approach to the voltammograms of the reduction of Prussian Blue films on ITO electrodes

Garcı́a-Jareño, J.J.; Navarro-Laboulais, J.; Vicente, F.

doi:10.1016/s0013-4686(96)00302-7

Cited by 44 publications

(63 citation statements)

References 27 publications

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“…Several approaches in the literature propose the existence of different redox processes in PB electrochemical systems. 22,23,47 However, our approach provides an immediate explanation of the different ionic exchanges and clearly identifies all of them thanks to simultaneous current and mass changes with respect to the potential. Furthermore, this paper proposes, probably for the first time, the participation in an electrochemical process of a crystalline structure constituted by water molecules embedded in a rigid skeleton.…”

Section: Discussionmentioning

confidence: 99%

Mechanism for Interplay between Electron and Ionic Fluxes in K_hFe_k[Fe(CN)₆]_l·mH₂O Compounds

et al. 2006

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This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula K(h)[Fe(2+) (CN)(6)](l).mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H(3)O(+) (hydrated protons) through the channels of the K(h)[Fe(2+) (CN)(6)](l).mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K(+) or H(+) (proton) exchange through the water crystalline structure existing in the channels of the K(h)[Fe(2+)(CN)(6)](l).mH(2)O structure.

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Section: Discussionmentioning

confidence: 99%

Mechanism for Interplay between Electron and Ionic Fluxes in K_hFe_k[Fe(CN)₆]_l·mH₂O Compounds

et al. 2006

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“…However, this electrode presents an intrinsic electrical resistance that causes unsymmetrical broadening of the voltammetric peaks [38]. This undesirable effect may be partially corrected if ohmic drop compensation is activated on the potentiostat control software [39,40].…”

Section: Fementioning

confidence: 99%

Identification of electroactive sites in Prussian Yellow films

Agrisuelas

Garcı́a-Jareño

Moreno-Guerrero

et al. 2013

Electrochimica Acta

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Abstract.Prussian Blue films were electrogenerated on the surface of the transparent ITO electrodes. The electrochemical oxidation to the Prussian Yellow form was investigated by means of in situ voltammetry and Vis-NIR spectroscopic techniques. Changes of the whole spectra between 400 and 950 nm were analyzed and three characteristic wavelengths were selected to in situ follow the electrochemical changes of the films.Voltammetric peaks and absorbance derivative curves at these three wavelengths were deconvoluted and were interpreted such as the overlapping of different electrochemical processes. The correlation between these overlapped processes has allowed proposing three different electrochemical processes for the interpretation of the whole electrochemical response. One of these processes corresponds to the oxidation of

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“…PB films were deposited on an ITO ͑indium tin oxide͒ electrode with a covering surface of 1 cm 2 ͑the ohmic drop of ITO electrodes causes the separation and widening of voltammetric peaks͒. 43,44 A platinum plate was used as the counter electrode and an Ag͉AgCl͉KCl sat electrode was used as the reference electrode. A PalmSens potentiostat ͑Palm Instrument BV͒ controlled the electrochemical measurements realized at steady-state conditions.…”

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Electronic Perspective on the Electrochemistry of Prussian Blue Films

Agrisuelas

Bueno

Ferreira

et al. 2009

J. Electrochem. Soc.

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The derivative of the voltabsommetric scans, together with previous nano-electrogravimetric and X-ray diffraction results, allow different electrochemical processes to be distinguished during the Prussian blue ͑PB͒ voltammetric scan. Potassium, proton, and hydrated proton counterions involved in PB electrochemistry are related here to the electrochemical reactions of specific Fe sites. Potassium counterions show two different sites for their insertion: one located in the crystalline framework and another in ferrocyanide vacancies. From the monitoring of electroactive Fe sites, the covalent-exchange model is suggested as one of the first approaches to explain the origin of the PB magnetic ordering observed at room temperature during voltammetric scanning. Systems that undergo reversible and controlled changes of their properties offer appealing perspectives for the fabrication of electronic switch devices. Thus, Prussian blue ͑PB͒-like materials have raised intense interest because of their electrochromic, ionexchange, ion-sensing, electrocatalytic, or photomagnetic properties, 1-5 because the PB Everitt's salt ͑ES͒ voltammetric scan is accompanied by reversible changes in these physicochemical properties.6-10 Likewise, they also display a wide range of important magnetic ͑e.g., room temperature magnetic ordering͒ and magnetooptical ͑e.g., ferromagnetism, photoinduced ͑de͒-magnetization͒ properties. [11][12][13][14] In particular, the PB electromagnetic properties can also be tailored by external conditions, such as the magnetic field, 15-17 light, 15,18,19 and by electrochemical methods. 18,[20][21][22][23][24] X-ray studies showed that the PB three-dimensional ͑3D͒ structure is face-centered cubic 25 with a general formula equal to Fe 4 ͓Fe͑CN͒ 6 ͔ 3 ·mH 2 O. Trivalent and divalent iron ions are in highand low-spin sites, Fe͑III͒ high-spin and Fe͑II͒ low-spin , respectively. 26Enclosed in this structure, high-and low-spin sites are both octahedral and surrounded by -NC and -CN units, respectively. Thus, the PB lattice is composed of repetitive units of Fe low-spin -CN-Fe high-spin in the three spatial directions. Nonetheless, 1 4 of low-spin Fe͑II͒ sites are missing and occupied by water molecules coordinated to Fe͑III͒ high-spin ions. The PB structure is completed with water molecules occupying interstitial positions. 27-29The above crystalline structure corresponds to the freshly deposited PB film following the electrochemical methodology described by Itaya et al. 22 and it is known as insoluble. The insoluble PB is electrochemically converted into the soluble PB by means of successive voltammetric cycles between the PB and ES forms 30,31 until a stable electrochemical response is achieved. 32 The soluble PB has been described as similar to the insoluble PB 3D structure. 33,34 Repetitive structural units of Fe low-spin -CN-Fe high-spin also compose its rigid framework, where 1 4 of the low-spin sites are missing. The position of the trivalent iron ions can be drawn as Fe͑II͒ low-spin -CN-Fe͑III͒ high-spin a...

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A numerical approach to the voltammograms of the reduction of Prussian Blue films on ITO electrodes

Cited by 44 publications

References 27 publications

Mechanism for Interplay between Electron and Ionic Fluxes in K_hFe_k[Fe(CN)₆]_l·mH₂O Compounds

Mechanism for Interplay between Electron and Ionic Fluxes in K_hFe_k[Fe(CN)₆]_l·mH₂O Compounds

Identification of electroactive sites in Prussian Yellow films

Electronic Perspective on the Electrochemistry of Prussian Blue Films

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A numerical approach to the voltammograms of the reduction of Prussian Blue films on ITO electrodes

Cited by 44 publications

References 27 publications

Mechanism for Interplay between Electron and Ionic Fluxes in KhFek[Fe(CN)6]l·mH2O Compounds

Mechanism for Interplay between Electron and Ionic Fluxes in KhFek[Fe(CN)6]l·mH2O Compounds

Identification of electroactive sites in Prussian Yellow films

Electronic Perspective on the Electrochemistry of Prussian Blue Films

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Mechanism for Interplay between Electron and Ionic Fluxes in K_hFe_k[Fe(CN)₆]_l·mH₂O Compounds

Mechanism for Interplay between Electron and Ionic Fluxes in K_hFe_k[Fe(CN)₆]_l·mH₂O Compounds