Examination of the cleavage and formation of the disulfide bond in poly[dithio-2,5-(1,3,4-thiadiazole)] by redox reaction

Shouji, Eiichi; Oyama, Noboru

doi:10.1016/0022-0728(96)04555-x

Cited by 24 publications

(35 citation statements)

References 18 publications

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“…TJV/vis: max329 nm (17,000 reference electrode (55CR), and a glassy carbon disk working electrode (BAS, MF-1012, 3.0 mm diam). We have continued with the previous strategy'3'9'2' of using synthetically isolated derivatives to illustrate how protonation state affects the redox activity of these compounds.…”

Section: Introductionmentioning

confidence: 99%

Organosulfur/Conducting Polymer Composite Cathodes: I. Voltammetric Study of the Polymerization and Depolymerization of 2,5‐Dimercapto‐1,3,4‐thiadiazole in Acetonitrile

Pope

Oyama

1998

J. Electrochem. Soc.

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This paper describes general trends in the redox potential and solubility of a dimercaptan, 2,5,-dimercapto-1,3,4thiadiazole (DMcT), and its various derivatives in acetonitrile, and illustrates how these trends manifest in the cyclic voltammetry observed at glassy carbon electrodes. Attention is focused on the polymerization/depolymerization processes which are the origins of the excellent charge-storage capabilities of electrodes based on the DMcT family of compounds. The extent of oligomerization/polymerization of DMcT at glassy carbon is shown to increase with increasing overpotential and/or oxidation time, as judged from its subsequently observed quasi-stable depolymerization wave. Oxidation of dimer DMcT results in extensive precipitation onto the electrode, relative to that observed for oxidation of monomer DMcT, as expected in light of solubilities observed for those compounds in acetonitrile. The protonation state of the compounds is shown to have a considerable effect on both their solubility and, as reported previously in part, redox potential. Similarly, chemical coupling of the redox processes of these compounds to their protonation state and, for DMcT, to a disproportionation reaction known to occur for its oxidation product(s) complicates analysis of the system as a whole. However, from consideration of all of the observed trends, a general picture emerges illustrating the redox character of DMcT during polymerization and depolymerization. Most importantly, it is shown that the electrochemical irreversibility typical of those processes can be avoided by careful control of the protonation state and solubility of the electroactive species, allowing the measurement of quasi-reversible redox couples. That and other results are discussed in the context of the use of DMcT in secondary battery electrodes.

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Section: Introductionmentioning

confidence: 99%

Organosulfur/Conducting Polymer Composite Cathodes: I. Voltammetric Study of the Polymerization and Depolymerization of 2,5‐Dimercapto‐1,3,4‐thiadiazole in Acetonitrile

Pope

Oyama

1998

J. Electrochem. Soc.

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“…[9][10][11] Electrochemical properties of DMcT and poly-DMcT have been previously well documented. [12][13][14] In our present work, the copper ions containing metallopolymers were prepared by controlled addition of 0.1 M CuSO 4 to 20 ml of 0.2 M 2,5dimercapto-1,3,4-Thiadiazole dipotassium salt solution (K 2 DMcT) under continuous stirring for 10 minutes. K 2 DMcT exhibits more aqueous solubility compared to DMcT, which favors the ease coordination polymerization in aqueous solution and in electropolymerization.…”

Section: Visible-light-active Mixed-valent Copper-ion-coordinated 25mentioning

confidence: 99%

Visible‐Light‐Active Mixed‐Valent Copper‐Ion‐Coordinated 2,5‐Dimercapto‐1,3,4‐thiadiazole‐Based p‐Type Metallopolymer

et al. 2018

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Visible‐light‐active coordination metallopolymer and metal‐organic frameworks have gained substantial attention in recent years, owing to their tunable electronic properties. Herein, we present a novel copper‐ion‐containing metallopolymer, which exhibits visible‐light absorption and p‐type photoelectrochemical behavior. The functional thiadiazole‐based metallopolymer thin films were prepared by using both chemical and electrochemical methods on fluorine‐doped tin oxide substrates. XPS, Raman, and FTIR spectral investigations evidence the presence of Cu(II), Cu(I), Cu−S, and disulfide (S−S)2− linkages in the polymeric network. The swift photoresponses, repeatable photovoltage of approximately 55 mV with zero applied current, and high photocurrent values at different bias potentials (ca. 24 μA cm−2 @ −0.6 V vs. Ag/AgCl in 0.1 KCl) in acidic electrolytes (0.5 M H2SO4) suggest that this metallopolymer as an acid‐stable p‐type photocathode material. In contrast, the electropolymerized non‐metallated polymers exhibit n‐type photoactivity. Photoelectrochemical sensing studies reveal the analyte‐induced reduction in photoactivity.

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“…Devido ao crescente interesse em compostos contendo DMcT, vários estudos fundamentais vêm sendo desenvolvidos no intuito de investigar os detalhes da interação entre o DMcT e a cadeia polimérica [152][153][154][155][156][157] .…”

Section: Figura 4 A) Perfis De Corrente (---) E Variação De Massa (-unclassified

Materiais para cátodos de baterias secundárias de lítio

Varela¹,

Huguenin²,

Malta³

et al. 2002

Quím. Nova

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Recebido em 21/12/00; aceito em 4/7/01 MATERIALS FOR CATHODES OF SECONDARY LITHIUM BATTERIES. In this work, cathodes employed in secondary lithium batteries are reviewed. These cathodes have great technologic and scientific importance, specifically, materials for cathodes as electronic conductor polymers (ECP), transition metal oxides (TMO) and nanocomposites of ECP/TMO. The use of a specific cathodic material is based in some intrinsic characteristics that improve the performance of the battery. Thus, some vantages and disvantages of these insertion compounds are discussed, as lithium insertion capacity, energy density, and the ciclability of these materials.Keywords: secondary lithium batteries; cathodic materials; transition metal oxides; electronic conducting polymers; nanocomposites. INTRODUÇÃOUma fonte eletroquímica de potência ou bateria pode ser definida como um dispositivo capaz de converter diretamente a energia liberada numa reação química em energia elétrica. As baterias apresentam basicamente duas funções principais, a primeira é agir como fontes portáteis de potência elétrica. A segunda, que tem crescido em importância nos últimos trinta anos, está baseada na habilidade de certos sistemas eletroquímicos de armazenar a energia suprida por uma fonte externa. Tais baterias são utilizadas, em veículos elé-tricos, fontes de emergência, como parte de um sistema de fornecimento de curta duração para demandas em pico e em conjunção com fontes renováveis de energia, como solar ou eólica, por exemplo.A primeira descrição de uma bateria eletroquímica foi feita pelo italiano Alessandro Volta em 1800. Tal "descoberta" representa o marco na história da eletroquímica e, particularmente, na história dos dispositivos denominados genericamente baterias. Desde então, um notável progresso tem sido feito na área de armazenamento eletroquímico de energia. Hoje, pode-se enumerar uma grande variedade de dispositivos englobados na categoria de baterias: células metal-ar, metal-hidreto metálico (Ni-HM), níquel-cádmio (Ni-Cd), células térmicas, íons-Lítio, entre outras.O mercado para dispositivos primários consiste basicamente na produção de baterias para aparelhos portáteis. As baterias secundá-rias ou recarregáveis representam maior interesse devido à grande demanda atual de aparelhos celulares e microcomputadores portá-teis. Em 1997, por exemplo, dos 34 bilhões de dólares movimentados com baterias, 24 foram destinados às baterias secundárias 1 .Graças à simplicidade e reversibilidade das reações eletroquímicas de inserção ou intercalação, a grande maioria dos dispositivos secundários que operam à temperatura ambiente é baseada nos chamados eletrodos de inserção. Como exemplos, têm-se os dispositivos secundários aquosos, como hidreto metálico/NiOOH ou Zn/MnO 2 , que envolvem a inserção de H + no hidreto metálico 2,3 ou MnO 2 4,5. Até mesmo o mecanismo de redução do eletrodo positivo das baterias de chumbo ácido, PbO 2 6,7 pode ser atribuído ao processo de inserção de H + 8 .Considerando-se a utilização de cátions metálicos...

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Examination of the cleavage and formation of the disulfide bond in poly[dithio-2,5-(1,3,4-thiadiazole)] by redox reaction

Cited by 24 publications

References 18 publications

Organosulfur/Conducting Polymer Composite Cathodes: I. Voltammetric Study of the Polymerization and Depolymerization of 2,5‐Dimercapto‐1,3,4‐thiadiazole in Acetonitrile

Organosulfur/Conducting Polymer Composite Cathodes: I. Voltammetric Study of the Polymerization and Depolymerization of 2,5‐Dimercapto‐1,3,4‐thiadiazole in Acetonitrile

Visible‐Light‐Active Mixed‐Valent Copper‐Ion‐Coordinated 2,5‐Dimercapto‐1,3,4‐thiadiazole‐Based p‐Type Metallopolymer

Materiais para cátodos de baterias secundárias de lítio

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