Solid-State Voltammetry — Analytical Prospects

Kulesza, Paweł J.; Cox, James A.

doi:10.1002/(sici)1521-4109(199802)10:2<73::aid-elan73>3.0.co;2-k

Cited by 74 publications

(96 citation statements)

References 92 publications

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“…To determine the concentration of redox sites and the diffusion coefficient (C o and D app ) from voltammetric data, we used a previously described method [17,23,24,58]. On the basis of two appropriately different scan rates of 50 Vs −1 and 4 mVs −1 (short-time and long-time regimes), a system of two equations with two variables (the concentration of redox sites and the transport coefficient) were obtained for the results shown in Fig.…”

Section: Determination Of Transport Coefficientsmentioning

confidence: 99%

“…Moreover, the linearity of the plot could indicate a small or Fig. 4 absent ohmic drop, migration, or slow interfacial electron transfer during the measurement [17,58] 12 by applying a DPSC [46,47]. This method gives a unique opportunity to estimate the diffusion coefficient of the electrode reaction product generated in the first chronoamperometric step.…”

Section: Determination Of Transport Coefficientsmentioning

confidence: 99%

“…Among the important requirements for a material to reveal electroactivity in solid, rigid, or semirigid state, in the absence of external liquid electrolyte, essential is the existence of mixed-valence redox centers and mobile charge-compensating ions [16][17][18][19][20]. Moreover, to minimize such parameters as ohmic resistance and migration effect, the concentration of charged species, like mobile ions and electrons, should be fairly large in the system.…”

Section: Introductionmentioning

confidence: 99%

“…POMs have been studied as monolayers or organic-inorganic hybrids in contact with different supporting electrolytes [34,35], and as single crystals in the absence of external liquid phase [21][22][23][24][25][26]. The electrochemical analysis of the most popular Keggin-type POMs (phosphotungstate and tungstosilicate) in the presence of acidic solution revealed three reversible reduction peaks originating from two one-electron processes followed by one two-electron process [17,21,22,36]. Similar electrochemical behavior was described when these compounds were introduced into organic polymers or a silica matrix [6,23,24,[37][38][39][40][41].…”

Section: Introductionmentioning

confidence: 99%

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Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Adamczyk

Miecznikowski

2013

J Solid State Electrochem

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We demonstrate the electrochemical characteristics of the, poorly described in the literature, mixed-valence proton conducting solid borotungstic acid single crystal, H 5 BW 12 O 40 xH 2 O, in the absence of liquid electrolyte phase. We performed electrochemical measurements in an all-solid cell with a gold fiber ultramicrodisk (diameter 10, 25, and 40 μm) working electrode, a silver semi-reference disk electrode, and a glassy carbon ring counter electrode. Diagnostic experiments at different scan rates aimed at probing the model of mass transport and potential kinetic limitations. Such bulk parameters as the effective diffusion coefficient of charge propagation and the concentration of mixed-valence redox centers were determined by two methods. The first method is based on the analysis of both Cottrellian and steady-state currents (the mixed-regimes method), and the second method provides the true diffusion coefficient (transport coefficient free of the migration influence) for both the substrate and the product of the electrode reaction. Together, these methods constitute a double potential step chronoamperometry experiment. The data obtained with these electrochemical experiments (effective diffusion coefficients, concentration of mixed-valence redox centers, etc.) can support the results obtained with other techniques (XRD, FTIR, and TGA).

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Section: Determination Of Transport Coefficientsmentioning

confidence: 99%

Section: Determination Of Transport Coefficientsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Adamczyk

Miecznikowski

2013

J Solid State Electrochem

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“…Only when used in the solid-state as gas sensors, diffusion was facile enough and allowed reasonable responses [36]. During recent years a new approach aimed to combine sol-gel process and molecular imprinting as a means of designing chemically modified electrodes for organic substrates has been developed primarily by Collinson and her co-workers [37].…”

Section: Introductionmentioning

confidence: 99%

Application of Sol‐Gel Technology for Electroanalytical Sensing

et al. 2003

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The applicability of thin sol-gel films as selective interfaces in electrochemical sensors has been examined. This requires not only to create a selective interface but also to enable facile diffusion of the analytes across the films. Creation of selectivity has been aimed by molecularly imprinting an electroactive species in the course of sol-gel formation. We have focused primarily on imprinting an iron(II) complex, i.e., tris(2,2'-bipyridine)iron(II) (Fe(bpy) 2 3 , as a means of selectively determining iron(II) in aqueous solution. Hence, the effect of different parameters, such as the composition of the sol-gel film and the hydrolysis and drying time, on the diffusion of Fe(bpy) 2 3 , has been studied. We find that diffusion can be remarkably enhanced upon adding polyethylene glycol or a surfactant, such as decanoic acid. Nevertheless, so far we have not been able to develop thin films, which exhibit selectivity towards this inorganic species. The difficulties in designing such selective interfaces for heavy metals as opposed to organic species is demonstrated by successfully applying the same approach for designing a selective interface for diethyl-p-nitrophenyl phosphate (paraoxon).

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Analytical Applications of Silica-Modified Electrodes -A Comprehensive Review

Walcarius

1999

Electroanalysis

150

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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.

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Solid-State Voltammetry — Analytical Prospects

Cited by 74 publications

References 92 publications

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Solid-state electrochemical behavior of Keggin-type borotungstic acid single crystal

Application of Sol‐Gel Technology for Electroanalytical Sensing

Analytical Applications of Silica-Modified Electrodes -A Comprehensive Review

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