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Results of voltammetric and electroreflectance measurements were used to describe the mechanism of the two-step transition processes. When [Br-] \u003e 180 mM, the transition step at less negative potential was ascribed to a phase transition between a gas-like adsorption layer of dBV dication (dBV2+) and a mesophase of dBV radical cation (dBV+). Most likely, the mesophase is a two-dimensional (2D) ordered phase composed of co-adsorbed dBV+ and Br- where both are in direct contact with the HOPG surface. The transition step at more negative potential was ascribed to a phase transition between the dBV+ Br- mesophase and a 2D condensed phase of dBV+. In the condensed phase being denser than the mesophase, dBV+ molecules are π-stacked due to face-to-face interaction between bipyridinium radical cations. This transition step involves also a reduction process of dBV2+ to dBV+ followed by its incorporation into the condensed phase. 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Remarkable effect of bromide ion upon two-dimensional faradaic phase transition of dibenzyl viologen on an HOPG electrode surface: Emergence of two-step transition
http://hdl.handle.net/10069/34030
http://hdl.handle.net/10069/34030c36ab0b7-8ca8-450c-aa04-199e8e14be16
名前 / ファイル | ライセンス | アクション |
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Supple.pdf (524.0 kB)
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EleAct114_105.pdf (5.8 MB)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2013-12-20 | |||||
タイトル | ||||||
タイトル | Remarkable effect of bromide ion upon two-dimensional faradaic phase transition of dibenzyl viologen on an HOPG electrode surface: Emergence of two-step transition | |||||
言語 | ||||||
言語 | eng | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | Anion effect | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | Electroreflectance | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | HOPG | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | Phase transition | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | Viologen | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | journal article | |||||
著者 |
Higashi, Tomohiro
× Higashi, Tomohiro× Sagara, Takamasa |
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抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | We found that dibenzyl viologen (dBV) on an HOPG electrode undergoes a two-step first order faradaic phase transition at high concentrations of bromide ion (Br-). Results of voltammetric and electroreflectance measurements were used to describe the mechanism of the two-step transition processes. When [Br-] > 180 mM, the transition step at less negative potential was ascribed to a phase transition between a gas-like adsorption layer of dBV dication (dBV2+) and a mesophase of dBV radical cation (dBV+). Most likely, the mesophase is a two-dimensional (2D) ordered phase composed of co-adsorbed dBV+ and Br- where both are in direct contact with the HOPG surface. The transition step at more negative potential was ascribed to a phase transition between the dBV+ Br- mesophase and a 2D condensed phase of dBV+. In the condensed phase being denser than the mesophase, dBV+ molecules are π-stacked due to face-to-face interaction between bipyridinium radical cations. This transition step involves also a reduction process of dBV2+ to dBV+ followed by its incorporation into the condensed phase. The two-step transition was not observed in KCl solution of any concentration, either in KBr solution of [Br -] < 75 mM. Other viologens examined, including benzyl-heptyl viologen, did not exhibit such a two-step transition but single-step one. The nature of the transition, especially in the [Br-] range from 75 to 180 mM, was closely analyzed. | |||||
書誌情報 |
Electrochimica Acta 巻 114, p. 105-115, 発行日 2013-12-30 |
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出版者 | ||||||
出版者 | Elsevier Limited | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 00134686 | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | 10.1016/j.electacta.2013.09.168 | |||||
権利 | ||||||
権利情報 | © 2013 Elsevier Ltd. All rights reserved. | |||||
権利 | ||||||
権利情報 | NOTICE: this is the author’s version of a work that was accepted for publication in Electrochimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Electrochimica Acta, 114 (2013) | |||||
著者版フラグ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
引用 | ||||||
内容記述タイプ | Other | |||||
内容記述 | Electrochimica Acta, 114, pp.105-115; 2013 |