项目名称: 协同异相质子耦合电子转移机理的电化学研究
项目编号: No.21303158
项目类型: 青年科学基金项目
立项/批准年度: 2014
项目学科: 数理科学和化学
项目作者: 张文彬
作者单位: 宜春学院
项目金额: 25万元
中文摘要: 基于前期通过电化学方法对异相质子耦合电子转移反应分步机理进行的研究,本项目将研究另外一个异相质子耦合电子转移机理:协同机理。首先,本项目选择2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)作为目标分子,将其修饰在金电极上以建立研究协同机理的体系。然后通过循环伏安法和计时电量法等电化学手段来测量体系转移过程热力学及动力学数据,体系调控参数包括电解液种类及pH值、外加电势、TEMPO修饰金电极内部微结构等。最后,经我们前期工作改进后的动力学同位素效应将首次应用作为协同机理存在的判据。本项目的目标是在对此TEMPO修饰金电极体系电化学分析的基础上,能够更深入地理解协同机理的控制因素。可预料的是,该项目将为人们理解重要的生物过程如光合作用及设计新型的能源转换过程提供有益的参考。
中文关键词: 电化学;质子耦合电子转移;机理;电催化;碱效应
英文摘要: Based on previous studies of stepwise mechanism of hetergeneous proton coupled electron transfer by electrochemical technqiues, this project will investigate another mechanism of heterogeneous proton coupled electron transfer:concerted mechanism. First of all, in order to build a model system for studies of concerted mechanism, 2,2,6,6-Tetramethyl-1-piperidinyloxy(TEMPO) will be chosen as a PCET reagent and it will be chemically modified onto a gold electrode. after that, electrochemical technqiues like cyclic voltammetry and chronocoulomletry will be used to obtain the thermodynamic and kientic information related to the transfer process of this system with adjustable parameters like electrolyte composition and pH, external potential,inert structure of TEMPO modified gold electrode and so on.Finally, kinetic isotope effect including our previous modification will be firstly used as the criterion of the concerted mechanism. The objective of this project is to understand the controlling parameters of concerted mechanism based on the electrochemical analysis of this TEMPO modified gold electrode system. It can be expected that this project will be very helpful in the understanding of important biologly processes like photosynthesis and designing of new energy conversion processes.
英文关键词: electrochemistry;proton coupled electron transfer;mechanism;electrocatalytic;base effect