Diffuse reflectance spectroelectrochemistry as a probe of the chemically derivatized electrode interface. Time-dependent diffussion

Humphrey, Brian D.; Sinha, Sujit; Bocarsly, Andrew Bruce

doi:10.1021/j150648a024

Cited by 52 publications

(29 citation statements)

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“…The cation dependence of the cyclic voltammetry, which has been seen before (Bocarsly and Sinha 1982b;Humphrey et al 1984), suggests that ion diffusion through the film is the rate limiting process, consistent with the known high affinity of metal hexacyanoferrates for cesium. This high affinity forms the basis for the use of these materials as ion exchangers for the removal of cesium from nuclear waste (Barton et al 1958;Harjula et al 1994;Loewenschuss 1982;Loos-Neskovic and Fedoroff 1989b;Tusa et al 1994).…”

Section: Cesium Uptake/elutionsupporting

confidence: 79%

“…In particular, the preparation and characteristics of ferrocyanide films have been reported by several groups (Bacskai et al 1995;Sinha 1982a, 1982b;Humphrey et al 1984Humphrey et al , 1987Itaya et al 1986; Lasky and Buttry 1988;Schneemeyer et al 1985;Sinha et al 1984). Nickel ferrocyanide films, M,NiFe(CN), (M = Na, K), have been prepared by dipping a nickel electrode into a Fe(CN)g3 solution, which oxidizes the metal electrode to precipitate the electroactive film, or more commonly by electrochemically oxidizing the nickel electrode in a Fe(CN)g3 solution (Bacskai et al 1995;Sinha et al 1984).…”

mentioning

confidence: 99%

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Electrically switched cesium ion exchange. FY 1997 annual report

Lilga¹,

Orth²,

Sukamto³

1997

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An electrochemical method for metal ion separations, called Electrically Switched Ion Exchange (ESIX), is described in this report. In this method, direct oxidation and reduction of an electroactive film attached to an electrode surface is used to load and unload the film with alkali metal cations. The electroactive films under investigation are nickel hexacyanoferrates, which are deposited on the surface by applying an anodic potential to a nickel electrode in a solution containing the ferricyanide anion. Reported film preparation procedures have been modified to produce films with improved capacity and stability. Electrochemical behavior of the derivatized electrodes has been investigated with use of cyclic voltammetry and chronocoulometry. The films show selectivity for cesium in concentrated sodium solutions. Raman spectroscopy has been used to directly monitor changes in oxidation state of the film and imaging experiments have demonstrated that the redox reactions are spatially homogeneous across the film. Requirements

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Section: Cesium Uptake/elutionsupporting

confidence: 79%

mentioning

confidence: 99%

Electrically switched cesium ion exchange. FY 1997 annual report

Lilga¹,

Orth²,

Sukamto³

1997

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“…In this work, mixed-metal HCFs were fabricated, where M was Ni, NiCo, or NiCu in various concentrations. In contrast to the nanoparticles that have been the focus of much of the PBA literature, the Ni-HCF electroformation method described by Borcarsly and coworkers [19][20][21][22][23][24] NiCu-HCF were produced in an all electrochemical process through potential cycling in the presence of K 3 [Fe(CN) 6 ]. The reactions leading to HCF formation can be written as Fe III (CN) 6 3− (aq) + M(s) + A + (aq) → Fe III (CN) 6 3− (aq) + M 2+ (aq) + A + (aq) + 2e − → AM II Fe III (CN) 6 (s) + 2e − , (2) where in this work, M = Ni, Co, Cu, or a mixture of metals.…”

Section: Introductionmentioning

confidence: 99%

Comparison of Charge Storage Properties of Prussian Blue Analogues Containing Cobalt and Copper

Rensmo

Hampton

2019

Metals

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Prussian blue analogues are of great interest as alternative battery materials because of their long life cycle and potential use of earth-abundant elements. In this work, thin film mixed-metal hexacyanoferrates (HCFs) based on NiCo and NiCu alloys were fabricated in an all electrochemical process. The structure and composition of the samples were characterized, along with the charge storage capacity and kinetics of the charge transfer reaction. For both NiCo-HCF and NiCu-HCF samples, the total charge capacity increased with the substitution of Ni with more Co or Cu, and the increase was larger for Cu samples than for Co samples. On the other hand, the charge storage kinetics had only a modest change with substituted metal, and these effects were independent of the amount of that substitution. Thus, the mixed-metal HCFs have promise for increasing overall storage capacity without negatively influencing the rate capability when used in battery applications.

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“…There are some applications of these complexes to such fields. However, there have been few investigations of the macromolecule metal complexes having mixed-valence or heterometal ions [11][12][13]. We have attempted to study the preparation and chemical functions of these polymer complexes.…”

Section: Introductionmentioning

confidence: 99%

Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

Koyama

Hayashi

Yamane

et al. 1987

Colloid & Polymer Sci

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Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm 9 HC1) containing FeII or FdII and M 2 § (M = Fe, Co, Cu) in a 1 : I molar ratio were obtained by the reaction of [Fe(CN)6 ] n-(n = 3, 4) with M 2+ ion-PVAm. HCI mixture in aqueous solution. Under a limited polymer concentration (Tv~/TFe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm. HC1 was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (FeII-, Fe m, CO I1 ~ Fe uI, Fe II ~ Cu lI) band for MFe(CN)6 ] (n-2)-bound to PVAm. HC1 (M = Fe, Co, Cu) were found to be 10,100-9601. mo1-1, cm -1 at 25 ~ The formation constants were found to be in the range ofl07 to 10 l~ M -1. The changes of enthalpy (A H) and entropy (A S) were found to be in the range of-10.4 to -22.5 kJ-mol -l and 5.7 to 52.9 J. K -1 mol -I respectively, at 25 ~

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Diffuse reflectance spectroelectrochemistry as a probe of the chemically derivatized electrode interface. Time-dependent diffussion

Cited by 52 publications

References 0 publications

Electrically switched cesium ion exchange. FY 1997 annual report

Electrically switched cesium ion exchange. FY 1997 annual report

Comparison of Charge Storage Properties of Prussian Blue Analogues Containing Cobalt and Copper

Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

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