Temperature dependence of impedance spectra of Prussian Blue films deposited on ITO electrodes

Garcı́a-Jareño, J.J.; Sanmatı́as, A.; Navarro-Laboulais, J.; Benito, D.; Vicente, F.

doi:10.1016/s0013-4686(97)00089-3

Cited by 50 publications

(91 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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.…”

Section: Methodsmentioning

confidence: 99%

“…60 Furthermore, both arrangements imply a high electrical resistivity, in agreement with the resistivity observed in PB films. 40,50,61 An important increase in the exchange integral between iron ions located in high-and low-spin sites has recently been detected during the PB ES scan when the system reaches a ␣ Х 0.30, implying the optimization of double-exchange efficiency at this fractional content. 50 As a result, the Fe͑III͒/͓Fe͑II͒ + Fe͑III͔͒ ratio around 0.30 leads to the easier electronic exchange between neighboring iron ions.…”

Section: ͓2͔mentioning

confidence: 98%

“…Thus, this is in concordance with the fact that the electrochemical reaction of Fe͑II͒ low-spin -CNFe͑III͒ high-spin sites that is monitored at 686 nm involve the potassium counterion for reaching the film electroneutrality, because the electrochemical reaction that involves the exchange of potassium cations is the main reaction at these potentials. 21,29 An extra current density can be defined as the difference between the experimental and simulated currents, j extra Figure 4 shows the shape of this extra current. This shape does not correspond to only one process; it seems to be due to the overlapping of at least three different processes.…”

Section: ͓2͔mentioning

confidence: 99%

“…The PB structure is completed with water molecules occupying interstitial positions. [27][28][29] The 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.…”

mentioning

confidence: 99%

“…8 The main goal of this work is to distinguish the electrochemical reactions of the different electroactive Fe sites that compose the PB structure during the PB ES voltammetric scan. This study is based directly on new spectroscopic measurements and data processing associated with previous electrochemical 20,29,41 and electrogravimetric measurements 7,8,21,23,24,39,40 that allowed the counterions exchanged during this scan to be distinguished according to the applied potential. Previous structural results 33,34 allowed the electroactive Fe sites to be specified.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Electronic Perspective on the Electrochemistry of Prussian Blue Films

Agrisuelas

Bueno

Ferreira

et al. 2009

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

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...

show abstract

Section: Methodsmentioning

confidence: 99%

Section: ͓2͔mentioning

confidence: 98%

Section: ͓2͔mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Electronic Perspective on the Electrochemistry of Prussian Blue Films

Agrisuelas

Bueno

Ferreira

et al. 2009

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

show abstract

Analytical Applications of Silica-Modified Electrodes -A Comprehensive Review

Walcarius

1999

Electroanalysis

150

View full text Add to dashboard Cite

This article aims to review the electroanalytical applications of chemically modified electrodes involving silica and silica-containing matrices. After a brief introduction to silica chemistry, the implication of pure and grafted silicas in electrochemistry, as well as that of the silica-based materials originating from the sol-gel technology, will be discussed. The interest of silica-modified electrodes (SiO 2 -MEs) with respect to electroanalysis will be pointed out by means of several examples. In the last five years, successful applications of SiO 2 -MEs have been achieved. Among them, silica grafted with inorganic films or organic moieties was successfully applied to the selective preconcentration or the electrocatalytic detection of various analytes. Also, the ability of the sol-gel chemistry to encapsulate enzymes within a silica matrix without preventing its activity was exploited in the development of new amperometric biosensors. These promising fields are thought to lead to significant advances in the near future, because of the explosive growth in both the synthesis of novel mesoporous organically-modified silica-based materials and the huge development of sol-gel chemistry in tailoring and construction of new modified electrodes.

show abstract

Digital video electrochemistry (DVEC) applied to the study of Prussian Blue films

et al. 2022

View full text Add to dashboard Cite

Prussian Blue films were electrogenerated on a Pt disc electrode and color changes were studied by digital video electrochemistry together with cyclic voltammetry. Three systems of peaks were detected. Peaks corresponding to the reduction to the Everitt's Salt form and to the oxidation to Prussian Yellow are well related to color changes expressed as color intensities derivatives. Color changes showed that these peaks involved complexes mechanisms and intermediate species were detected. These also showed the existence of different sites of iron atoms in the crystal structure with different reactivity. A non-zero baseline and a third electrochemical process at the more negative potentials proved not related to color changes.

show abstract

Temperature dependence of impedance spectra of Prussian Blue films deposited on ITO electrodes

Cited by 50 publications

References 26 publications

Electronic Perspective on the Electrochemistry of Prussian Blue Films

Electronic Perspective on the Electrochemistry of Prussian Blue Films

Analytical Applications of Silica-Modified Electrodes -A Comprehensive Review

Digital video electrochemistry (DVEC) applied to the study of Prussian Blue films

Contact Info

Product

Resources

About