Metal Hexacyanoferrates:  Electrosynthesis, in Situ Characterization, and Applications

Tacconi, Norma R. de; Rajeshwar, Krishnan; Lezna, Reynaldo O.

doi:10.1021/cm0341540

Cited by 422 publications

(279 citation statements)

References 186 publications

(344 reference statements)

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“…Prussian blue analogues are the most intensively explored model systems, which can reversibly insert univalent ions, such as Li + , Na + , K + , Rb + and Cs + . 7,8 z E-mail: nikitina@elch.chem.msu.ru…”

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confidence: 99%

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Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

Nikitina

Fedotov

Vassiliev

et al. 2017

J. Electrochem. Soc.

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The effect of the cation nature is explored for the reaction of alkali metal ions intercalation into the AVPO 4 F material. Application of electrochemical methods allowed determining the key diffusional and kinetic parameters for Li + , Na + and K + intercalation reactions. The obtained formal redox potential values, apparent diffusion coefficients and charge transfer resistance values are contrasted, providing the possibility to assess the variation in the reaction energetics for metal ion insertion/extraction. The observed differences in reaction rates are rationalized in terms of different contributions of ion desolvation and transition through adsorbate layer/electrode interface for various ions. The mechanism of ion intercalation reactions is still poorly understood in spite of the obvious importance of intercalating systems in metal-ion batteries development for applications in energy conversion and storage. The research in the field of establishing ion intercalation kinetic patterns is mainly focused on evaluating charge transfer resistance parameters and diffusion coefficients for materials with presumably higher energy density and rate capability, while the fundamental aspects of the reaction mechanisms are typically overlooked. However, the research aimed at finding the limiting step of intercalation reaction might provide additional non-empirical approaches to control the rate of the intercalation reaction. In this regard, fundamental studies exploring the effects of solvent and cation nature on the overall reaction rate are of primary importance.In a series of recent publications, the intercalation reaction rate was shown to be highly dependent on the solvent nature, providing an implication to consider ion transfer rather than electron transfer or ion insertion into the host matrix step to be rate limiting. [1][2][3][4] It was also shown that intercalation of solvated cations is kinetically more facile as compared to the reaction of ions without the solvation shell. 5,6 These findings imply that the contribution of ion desolvation to the reaction activation barrier could be dominant. On the other hand, the reaction rate was shown to be dependent on the structure of electrode/electrolyte interface (EEI) especially in cases when adsorbate layers are formed at high potentials at the electrode surface (solid electrolyte interface, SEI, on anode, or cathode/electrolyte interface, CEI).2 All these results point to the complex interplay between the energetics of ion desolvation and the transition of the ion through the EEI. Variation of the solvent nature cannot be applied to distinguish between these two contributions, as changing the solvent results in simultaneous changes in the EEI structure, desolvation energy and the preexponential factor, which is determined by the solvent effective frequency. Variation of the intercalating ion provides another possibility to assess the mechanism of the intercalation reaction. The desolvation energy contributions should be very different for ions of different charge...

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confidence: 99%

“…8 However, no systematic studies on the variation of ion transfer kinetic parameters were performed for these systems to our knowledge.…”

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confidence: 99%

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

Nikitina

Fedotov

Vassiliev

et al. 2017

J. Electrochem. Soc.

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“…638 been demonstrated regarding oxidative processes. [7][8][9][10][11][12] A main drawback found when PB modified electrodes are applied for electroanalytical purposes is the poor stability of the film at potentials where Prussian White is cathodically generated. 13 Such negative potentials are required for selective monitoring of hydrogen peroxide in samples containing reducing species.…”

Section: Introductionmentioning

confidence: 99%

“…[3][4][5][6] The use of hexacyanometallates containing transition metals has also been investigated to modify electrode surfaces and the electrocatalytic properties of these interfaces have also been demonstrated regarding oxidative processes. [7][8][9][10][11][12] A main drawback found when PB modified electrodes are applied for electroanalytical purposes is the poor stability of the film at potentials where Prussian White is cathodically generated. 13 Such negative potentials are required for selective monitoring of hydrogen peroxide in samples containing reducing species.…”

Section: Introductionmentioning

confidence: 99%

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

Lowinsohn

Bertotti

2008

J. Braz. Chem. Soc.

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No presente trabalho são apresentados resultados referentes à fabricação de um biossensor para análise de lactato. O dispositivo foi preparado imobilizando-se a enzima lactato oxidase em filme de Azul da Prússia (PB, sigla em inglês) depositado na superfície de eletrodo de carbono vítreo em soluções de CTAB. Nestas condições experimentais observou-se melhoria na sensibilidade e seletividade das determinações de lactato, as quais foram conduzidas em sistema FIA com detecção amperométrica. Nas condições otimizadas (pH = 6,9 e E = −0,1 V), obteve-se curva analítica com limite superior igual a 0,28 mmol L -1 e um limite de detecção de 0,84 µmol L -1 . A repetibilidade do método foi avaliada por meio de injeções consecutivas de amostras de lactato 0,28 mmol L -1 , obtendo-se desvio padrão de 2,2 % (n = 18). O método foi aplicado em amostras de cerveja e houve boa concordância entre os resultados obtidos e aqueles oriundos do uso de procedimento espectrofotométrico de referência.An amperometric lactate biosensor with lactate oxidase immobilized into a Prussian Blue (PB) modified electrode was fabricated. The advantage of using cetyltrimethylammonium bromide (CTAB) in the electrodeposition step of PB films onto glassy carbon surfaces was confirmed taking into account both the stability and sensitivity of the measurements. The biosensor was used in the development of a FIA amperometric method for the determination of lactate. Under optimal operating conditions (pH = 6.9, E = −0.1 V), the linear response of the method was extended up to 0.28 mmol L -1 lactate with a limit of detection of 0.84 µmol L -1 . The repeatability of the method for injections of a 0.28 mmol L -1 lactate solution was 2.2 % (n = 18). The usefulness of the method was demonstrated by determining lactate in beer samples and the results were in good agreement with those obtained by using a reference spectrophotometric enzyme method.Keywords: lactate, biosensor, prussian blue modified electrodes, CTAB, FIA amperometric detection, beer IntroductionThe relevance of metal hexacyanoferrates for electroanalytical chemistry was firstly demonstrated in the pioneering studies of Itaya et al. 1,2 involving the electrocatalysis of oxygen and hydrogen peroxide reduction at surfaces covered by Prussian Blue (PB, iron(III) hexacyanoferrate(II)) films. The transfer of electrons and the movement of small hydrated counter-cations through the channels and holes of the solid for charge compensation is a typical feature of this kind of compound. Owing to the zeolite nature of metal hexacyanoferrates, their ability as effective three-dimensional electrocatalysts has been extensively recognized.Once sufficient negative potentials are applied to PB modified electrodes, electrons are injected into the film and the so-called Prussian-White film is generated which arises from the reduction of a high-spin Fe 3+ . The reduced form (Fe 2+ ) is catalytically active towards the electron-transfer step involving hydrogen peroxide, water being formed as a final product. At positive pot...

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“…1 These metal hexacyanoferrate compounds are usually prepared by chemical and electrochemical methods. To support films of these materials on solid surfaces, when necessary, inert substrates such as glassy carbon, graphite, platinum or gold have been used.…”

Section: Introductionmentioning

confidence: 99%

Thin film of copper hexacyanoferrate dispersed on the surface of a conducting carbon ceramic material, SiO2/ZrO2/C-graphite: characteristics and electrochemical studies

Marafon

Lucho

Francisco

et al. 2006

J. Braz. Chem. Soc.

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O material SiO 2 /ZrO 2 /C-graphite (SZC) foi preparado pelo método sol-gel apresentando duas composições, designadas por: (a) SZC30 (SiO 2 = 50%, ZrO 2 = 20%, C= 30%) e (b) SZC20 (SiO 2 =60%, ZrO 2 = 20%, C= 20%) em % m. A estrutura do material foi investigada por difração de raios X (XRD), microscopia eletrônica de transmissão de alta resolução (HR-TEM) e espectroscopia de fotoelétrons excitados por raios X (XPS). A condutividade elétrica dos discos prensados destes materiais foi 4 e 18 S cm -1 para SZC20 e SZC30, e a área superficial específica (determinado pelo método BET) dos compósitos carbono cerâmico foi 45 e 12 m 2 g -1 , respectivamente. Um filme fino de hexacianoferrato(II) de cobre foi formado in situ na superfície do material contendo 30 % (em massa) de grafite (SZC30). A espessura do filme foi estimada como sendo 110 nm. O potencial médio para o processo redox foi dependente da concentração de eletrólito suporte na faixa de 0,1 a 1,0 mol L -1 de KCl e a resistência de transferência de carga, determinada por espectroscopia de impedância eletroquímica (EIS), foi de 23,8 ohm cm 2 .SiO 2 /ZrO 2 /C-graphite materials (SZC) were prepared by the sol-gel method presenting two compositions and designated as: (a) SZC30 (SiO 2 = 50%, ZrO 2 = 20%, C= 30%) and (b) SZC20 (SiO 2 =60%, ZrO 2 = 20%, C= 20%) in wt.%. The material structure was investigated by X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The electrical conductivities obtained for the pressed disks of these materials were 4 and 18 S cm -1 for SZC20 and SZC30, and the specific surface areas (determined by the BET method) of the carbon ceramic composites were 45 and 12 m 2 g -1 , respectively. A copper hexacyanoferrate thin film was grown in situ on the material surface containing 30 wt.% C (SZC30). The thickness of the film was estimated as 110 nm. The midpoint potential for the redox process was dependent on the KCl supporting electrolyte concentrations in the range between 0.1 and 1.0 mol L -1 and the charge transfer resistance determined by electrochemical impedance spectroscopy experiment was 23.8 ohm cm 2 .Keywords: silica-zirconia-graphite, carbon ceramic material, conducting ceramic material, copper hexacyanoferrate film IntroductionTransition metal hexacyanoferrates have been the subject of widespread interest because of their electrocatalytic, electrochromic, ion exchange, ion sensing and photomagnetic properties, as recently pointed out in a review where electrosynthesis, in situ characterization and technological applications of Prussian Blue analogues are emphasized. 1 These metal hexacyanoferrate compounds are usually prepared by chemical and electrochemical methods. To support films of these materials on solid surfaces, when necessary, inert substrates such as glassy carbon, graphite, platinum or gold have been used. [2][3][4][5][6][7] Porous substrates such as SiO 2 coated with thin films of SnO 2 , TiO 2 and ZrO 2 have also been used as substrates to adher...

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Metal Hexacyanoferrates: Electrosynthesis, in Situ Characterization, and Applications

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 422 publications

References 186 publications

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

Thin film of copper hexacyanoferrate dispersed on the surface of a conducting carbon ceramic material, SiO2/ZrO2/C-graphite: characteristics and electrochemical studies

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Metal Hexacyanoferrates: Electrosynthesis, in Situ Characterization, and Applications

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 422 publications

References 186 publications

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO4F Framework

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO4F Framework

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

Thin film of copper hexacyanoferrate dispersed on the surface of a conducting carbon ceramic material, SiO2/ZrO2/C-graphite: characteristics and electrochemical studies

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Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework