【作者】 顾超越； 张欣； 邵元华；

【Author】 Chaoyue Gu;Xin Zhang;Yuanhua Shao;College of Chemistry and Molecular Engineering, Peking University;

【机构】 北京大学化学与分子工程学院；

【摘要】 液/液界面的电子转移-离子转移耦合反应对模拟生物膜、理解相转移催化机理、研究质子耦合的电子转移反应具有重要意义,近年来受到广泛关注。对于水相中Fe（CN）₆³与油相中二茂铁（Fc）的界面耦合反应体系,Fc⁺会与油相中的支持电解质发生反应^[1],但目前没有关于不同支持电解质对Fc⁺还原能力的比较研究。本文采用石英双（θ）管制备的微、纳米杂化电极作为工作电极,其一侧为碳电极,另一侧为液/液界面电极。通过在碳电极端施加正电位使有机相中的Fc氧化产生Fc⁺,同时在液/液界面收集Fc⁺,并根据收集效率对不同支持电解质的还原性进行比较。本文主要研究了TBATPB、TBATPBCl、TBATPBF₅三种支持电解质对Fc⁺的还原作用,结果表明三种支持电解质的还原能力依次减弱。这与具有拉电子效应的氯、氟原子分别取代支持电解质中苯环上的氢原子,使其还原性降低是相关的。该杂化电极具有可以产生Fc⁺并对其进行原位收集的优势,有望在研究液/液界面复杂机理上得到更广泛的应用。更多还原

【Abstract】 The electron transfer（ET） and ion transfer（IT） coupling process at a liquid/liquid（L/L） interface has attracted much attention in the past few decades since it is significant related to mimicking the function of biological membranes, understanding the mechanism of phase-transfer catalysis and studying proton-coupled electron transfer（PCET） reactions.In the system between Fe（CN）₆^3-in the aqueous phase（W） and ferrocene（Fc） in 1,2-dichloroethane（DCE）, the competing reaction that ferricenium（Fc⁺） with the organic supporting electrolyte should be taken into attention.However, there has not been thoroughly studied of this matter.Here, we utilize the micro and nano hybrid electrodes made by the quartz theta barrel as the working electrode.One of the barrels is carbon electrode, and another is a liquid/liquid interface electrode.Fc⁺is produced during the oxidation of the Fc by the carbon electrode, which is then collected by the liquid/liquid interface.The reducing capacity of the organic supporting electrolyte is defined by the collection efficiency.In this work, TBATPB、TBATPBCl、TBATPBF₅ are discussed and the phenomenon indicates that the reducing capacity of these organic supporting electrolytes weaken successively, the reason of which is that the chlorine atom and fluorine atom with the electron-withdrawing inductive effects replace the hydrogen of benzene.The hybrid electrodes would open a broad application in the complicated mechanism research.更多还原