Electron-self-exchange reactions in solid-state voltammetry: the radical anion of 7,7,8,8-tetracyanoquinodimethane in polymer electrolytes. 1

Watanabe, Mikio; Wooster, T. T.; Murray, Royce W.

doi:10.1021/j100164a071

Cited by 49 publications

(17 citation statements)

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“…It has also been employed for studying the electron transfer mechanism of the redox moieties involved in supramolecular systems [10][11][12][13] relevant to biological electron transport as well as electric and photoelectric functional devices [14]. The electron propagation by redox species in a polymer film has been studied extensively in recent years, and many papers have been published on its kinetics [15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Electron transfer in the redox reaction of cobalt tetraphenylporphyrin incorporated in a Nafion film

Zhao

Zhang

Kaneko

2000

J. Porphyrins Phthalocyanines

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Potential step chronoamperospectrometry (PSCAS) was carried out to analyze electron transfer in the redox reaction processes of 5,10,15,20-tetraphenylporphyrinatocobalt(II) ( Co II TPP (-2)) incorporated in a Nafion film. The reactions of Co II TPP (-2) to [ Co III TPP (-2)]+ and of [ Co III TPP (-2)]+ to Co II TPP (-2) took place through a diffusion mechanism, as confirmed by the first-order initial reaction rate with respect to the complex concentration in the matrix. However, the reaction of [ Co III TPP (-2)]+ to [ Co III TPP (-1)]2+ occurred by an electron-hopping mechanism, as confirmed by the second-order initial reaction rate with respect to the complex concentration. The fraction of electroactive complex (Rct) increased with the sample time after the potential step until it reached saturation. In the reactions of Co II TPP (-2) to [ Co III TPP (-2)]+ and of [ Co III TPP (-2)]+ to Co II TPP (-2), Rct approached 1.0, while in the reaction of [ Co III TPP (-2)]+ to [ Co III TPP (-1)]2+, only about 0.3 was reached. The apparent diffusion coefficient (Dapp) decreased in the order of [ Co III TPP (-2)]+ to Co II TPP (-2) > Co II TPP (-2) to [ Co III TPP (-2)]+>[ Co III TPP (-2)]+ to [ Co III TPP (-1)]2+. The different behavior of these redox reactions was ascribed to the microenvironment of the redox species in the matrix, interaction of the redox centers, especially the product with the framework, and counter ion migration.

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Section: Introductionmentioning

confidence: 99%

Electron transfer in the redox reaction of cobalt tetraphenylporphyrin incorporated in a Nafion film

Zhao

Zhang

Kaneko

2000

J. Porphyrins Phthalocyanines

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“…Meanwhile, ionic conductive polymers or polymer electrolytes, such as poly(ethylene oxide) (PEO) with alkali metal salts (LiClO 4 or LiCF 3 SO 3 , etc.) that allows fast and selective transport of ions in the solid state, can readily incorporate many electroactive molecules to build up electrochemical active polymer system 1–9…”

Section: Introductionmentioning

confidence: 99%

“…There are two different ways to obtain electrochemical active polymers: blending electroactive small molecules with polymers,1–5 and chemically fixing redox species to the side or end of polymer chain 6–9. The second approach may circumvent problems related to dispersion stability or insufficient solubility of many interesting redox species in solid polymer matrices.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and electrochemical properties of redox active polyurethanes with ferrocene units in polyether soft segments

Shen

et al. 1999

J. Appl. Polym. Sci.

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Electrochemical active segmented polyurethane with ferrocene units in polyether soft segments (PU-S-Fc) has been originally synthesized and identified by 1 H-NMR spectra. Electrochemical behaviors of PU-S-Fc blending with lithium perchlorates were investigated by cyclic voltammetry. In N,NЈ-dimethyl formide solution, PU-S-Fc exhibited normal cathodic and anodic peaks of the ferrocene/ferricinium (Fc/ Fc ϩ ) couple. Compared with that of ferrocene molecules blended in ordinary polyurethane (PU-B-Fc), redox peaks of ferrocene units in PU-S-Fc were found to be broader, which may be ascribed to the weak adsorption of the polyurethane on the electrode surface. The influence of lithium perchlorate concentration on peak potentials indicated that supporting electrolytes played an important role in electrochemical redox of PU-S-Fc. In the solid state, PU-S-Fc/Li ϩ showed discernible redox peaks at temperatures higher than 60°C, and an exponential increase curve of electrochemical response with an increase of temperature was found. Temperature variations of the solid-state ionic conductivity for PU-S-Fc/Li ϩ can be interpreted by the Arrhenius equation. The similarity between the temperature dependence of ionic conductivity and electrochemical response revealed that transport mechanism of ionic and redox species in the polyurethane matrix was controlled by the mobility of polyether chains.

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“…We developed electrochemical measurement methods using microelectrodes and polymer electrolytes as solvents, so-called solid-state voltammetry. [11][12][13] We accumulated fundamental knowledge on the diffusion dynamics of redox solutes as well as their homogeneous and heterogeneous electron transfer dynamics in polymeric phases. [11][12][13] After returning to Japan and having been stimulated by a discussion with J. Kawamura at Tohoku University, I conceived the idea of using ionic liquids (roomtemperature molten salts; the term "ionic liquid " was not used at that time) as doping salts for polymer electrolytes.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13] We accumulated fundamental knowledge on the diffusion dynamics of redox solutes as well as their homogeneous and heterogeneous electron transfer dynamics in polymeric phases. [11][12][13] After returning to Japan and having been stimulated by a discussion with J. Kawamura at Tohoku University, I conceived the idea of using ionic liquids (roomtemperature molten salts; the term "ionic liquid " was not used at that time) as doping salts for polymer electrolytes. In conventional polymer electrolytes, typically consisting of a polyether solvent and a lithium salt, increases in the number of carrier ions and their mobility (diffusivity) are incompatible due to slowed polymer dynamics with salt doping and coupling transport of ions with the polymer dynamics, which limits their conductivity and utility at ambient temperatures.…”

Section: Introductionmentioning

confidence: 99%

Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Watanabe

2016

Electrochemistry

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Ionic liquids (ILs) are defined as salts that have melting points lower than 100°C. Most are organic salts, and these may be designed and tailored to have suitable properties. ILs are recognized as a third group of solvents (and electrolytes), after water and organic solvents. They are characterized by their unique properties such as nonvolatilities, high thermal stabilities, and high ionic conductivities. In this article, our work on the design and preparation of ILs is briefly reviewed. The concept of ionicity is proposed as a metric to characterize the basic nature (dissociativity) of ILs, which is affected by the Lewis acidity/basicity of cations/anions (i.e., coulombic interactions), the directionality of interactions between cations and anions, and van der Waals interactions between ions. The ionicity of ILs is dominated by a subtle balance between coulombic and van der Waals interactions, which clearly discriminates ILs from conventional high-temperature inorganic molten salts. Here, the design of protic ILs for fuel cell electrolytes, electron-transporting ILs for dye-sensitized solar cell electrolytes, and Li + -conducting solvate ILs for lithium battery electrolytes are discussed based on an understanding of the fundamental properties of ILs. Furthermore, the combination of ILs with polymers and colloidal particles affords intriguing quasi-solid materials (ion gels), and the ion transport in these gels is decoupled from the mechanical relaxation time of these materials, yielding new solid electrolytes. The possibility of temperature and photo-sensitive solubility dependence of polymers in ILs allows the creation of stimuli-responsive materials. Finally, protic ILs/protic salts are demonstrated to be good precursors for N-doped carbon materials.

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Electron-self-exchange reactions in solid-state voltammetry: the radical anion of 7,7,8,8-tetracyanoquinodimethane in polymer electrolytes. 1

Cited by 49 publications

References 0 publications

Electron transfer in the redox reaction of cobalt tetraphenylporphyrin incorporated in a Nafion film

Electron transfer in the redox reaction of cobalt tetraphenylporphyrin incorporated in a Nafion film

Synthesis and electrochemical properties of redox active polyurethanes with ferrocene units in polyether soft segments

Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

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