Does an electron transfer really occur at the oil/water interface?

电子转移真的发生在油/水界面吗？

• 批准号: 14540557
• 负责人: OSAKAI Toshiyuki
• 金额: $ 2.56万
• 依托单位: Kobe University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540557/
• 关键词: oil; water interface; electron transfer; reaction mechanism; diffusion-controlled rate constant; cyclic voltammetry; ECSOW system; 光誘起電子移動; ポルフィリン金属錯体; アスコルビン酸; グルコースオキシダーゼ; 速度定数; フェロセン; ルテチウムビフタロシアニン錯体; 金属微粒子; グルコースオキダーゼ

The previous study showed that the electron transfer (ET) between ferrocene in nitrobenzene and ferricyanide in water occurred not heterogeneously at the oil/water interface, but homogeneously in the water phase. This reaction mechanism is called "ion-transfer (IT) mechanism", as the current flowing through the interface is due to an IT of the product ion. The objective of this study is to know whether an ET really occurs at the oil/water interface.Because an ET at the oil/water interface is a bimolecular reaction, there should be an upper limit for the rate constant. In this study the diffusion-controlled rate constant for the interfacial ET has been theoretically obtained by an extension of the Smoluchowski-Debye theory for a bimolecular reaction in solutions.Experimental approaches have been carried out using several electrochemical techniques including digital simulation of cyclic voltammograms, ac impedance measurement, microflow electrolysis, electron-conductor separating oil-water (ECSOW) system, etc. The ET reactions in cloranil-ascorbate and dimethylferrocene-ferricyanide systems have been elucidated in terms of the IT mechanism. The reaction mechanism of a newly-found, glucoseoxydase-catalyzed ET between dimethylferrocene and glucose has been found to be an analogous IT mechanism.However, it has been clarified that when an extremely hydrophobic redox compound such as lutetium biphtharocyanine complex is employed as the redox species in the oil phase, a "trLte" (i.e.,heterogeneous) ET should occur at the oil/water interface. There have been reported only a few examples for such heterogeneous ET, and accordingly we have searched for new "true" ET systems. By making good use of the ECSOW system, we have found a new ET system in which tetraphenylporphyrin (TPP) Cd complex is employed for the redox species in the oil phase. Furthermore, a new photoinduced ET reaction between Zn-TPP complex in 1,2-dichloroethane and proton in water has been discovered.

先前的研究表明，硝基苯和水中铁烯化的二循环之间的电子转移（ET）在油/水界面上并非异质发生，而是在水相中均质。该反应机制称为“离子转移（IT）机理”，因为流过界面的电流是由于产物离子的IT引起的。这项研究的目的是知道一个ET是否真正发生在油/水接口处。因为在油/水界面处的ET是双分子反应，因此速率常数应该具有上限。在这项研究中，理论上通过smoluchowski-debye理论扩展了溶液中的双分子反应，从理论上获得了互化ET的扩散控制速率常数。已使用多种电化学技术进行了多种电化学技术，包括循环型型号的数字模拟型号的电压型，c impoftofs，microf，Microf，Microf，Microf，Microf，Microf，Microf，Microf，Microf，Microf，Microflow，Microflof，Microfforclof，Microfforclof，Microffiment comportional。油水（ECSOW）系统等。Cloranil-Ascorbate和Dimethylferrocene-Fricyanide系统的ET反应已根据IT机制阐明。已经发现，新发现的葡萄糖氧合酶在二甲基二世和葡萄糖之间进行的ET的反应机制已被发现是一种类似的IT机制。但是，已经澄清的是，当极疏水的氧化还原化合物（如富特弱）（如双脑苯胺复合物）等极疏水性氧化还原时，应采用I. Trepere here here herter in the trepere here herte here here here here n tene;发生在油/水界面。仅报道了这种异质ET的几个示例，因此我们搜索了新的“ True” ET系统。通过充分利用Ecsow系统，我们发现了一个新的ET系统，在该系统中，在油相中，在氧化还原物种中使用了四苯基卟啉（TPP）CD复合物。此外，已经发现了1,2-二氯乙烷中的Zn-TPP复合物与水中质子的Zn-TPP复合物之间的一种新的光诱导的ET反应。

项目成果

H.Hotta, S.Ichikawa, T.Sugihara, T.Osakai: "Clarification of the Mechanism of the Interfacial Electron-Transfer Reaction between Ferrocene and Hexacyanoferrate(III) by Digital Simulation of Cyclic Voltammograms"J.Phys.Chem.B. 107(36). 9717-9725 (2003)

H.Hotta、S.Ichikawa、T.Sugihara、T.Osakai：“通过循环伏安图的数字模拟阐明二茂铁和六氰铁酸盐（III）之间的界面电子转移反应的机理”J.Phys.Chem.B。

堀田弘樹: "油水界面電子移動の反応機構に関する研究"Rev.Polarogr.(Kyoto). 70巻・5号. 15-20 (2003)

Hiroki Hotta：“油水界面电子转移反应机理的研究”Rev. Polarogr. (京都)，第 70 卷，第 5. 15-20 期 (2003)。

A.G.Volkov: "Interfacial Catalysis"Marcel Dekker, Inc.. 680 (2002)

A.G.Volkov：“界面催化”Marcel Dekker, Inc.. 680 (2002)

T.Osakai: "Temperature Effect on the Selective Hydration of Sodium Ion in Nitrobenzene"Anal.Sci.. 19巻・10号. 1375-1380 (2003)

T.Osakai：“温度对硝基苯中钠离子选择性水合的影响”Anal.Sci..第 19 卷，第 10 期。1375-1380 (2003)

H.Hotta, N.Akagi, T.Sugihara, S.Ichikawa, T.Osakai: "Electron-Conductor Separating Oil-Water (ECSOW) System : a New Strategy for Characterizing Electron-Transfer Processes at the Oil/Water Interface"Electrochem.Commun.. 4(5). 472-477 (2002)

H.Hotta、N.Akagi、T.Sugihara、S.Ichikawa、T.Osakai：“电子导体分离油水（ECSOW）系统：表征油/水界面电子转移过程的新策略”Electrochem