Dynamics of Mediated Electrochemical Synthesis in Microemulsions

James Rusling摘要 该项目的目标是了解从微乳液吸附在电极上的表面活性剂微观结构的动力学及其对介导反应速率的影响。 电化学动力学研究用于将表面活性剂和反应物在电极上的吸附-脱附动力学与化学反应速率相关联。 表面动力学测量时间分辨流动伏安法和简化的电化学显微镜。 得到了介体在电极上的吸附动力学和反应活性。 使用搅拌，批处理，电化学反应器，介导的合成率，通过伏安法测量，并在微乳液和各向同性的解决方案中的本体电解进行比较，并寻求与吸附动力学的相关性。 选择用于研究的反应包括碳-碳键形成、官能团脱保护和烯烃的产生。 介体包括过渡金属咕啉和酞菁及其衍生物。 介导的电化学反应（涉及将电子（或空穴）从电极携带到感兴趣的基底的中间体或催化剂的反应）通过吸附在电极上的表面活性剂来增强。 微乳液提供了一种有吸引力的方式来引入和控制这些过程。 这种方法可以为生产高附加值的化学产品，如药物和染料提供清洁，高效，具有成本效益的工艺。

James Rusling Abstract The goal of this project is an understanding of the dynamics of surfactant microstructures adsorbed on electrodes from microemulsions and their influence on rates of mediated reactions. Electrochemical kinetic studies are used to relate surfactant and reactant adsorption-desorption dynamics on electrodes to chemical reaction rates. Surface dynamics are measured by time-resolved flow voltammetry and by simplified electrochemical microscopy. the adsorption dymanics and reactivity of mediators on electrodes are also obtained. Using a stirred, batch, electrochemical reactor, the rates of mediated syntheses, measured by voltammetry, and of bulk electrolysis in microemulsions and in isotropic solutions are compared and correlations with adsorption dynamics are sought. Reactions selected for study include carbon-carbon bond formation, functional group deprotection, and production of olefins. Mediators include transition-metal corrins and phthalocyanine an their derivatives. Mediated electrochemical reactions (reactions involving an intermediate or catalyst that carries the electron (or hole) from the electrode to the substrate of interest) are enhanced by surfactants adsorbed on electrodes. Microemulsions offer an attractive way to introduce and control these processes. This approach can provide clean, efficient, cost-effective processes for producing high-value-added chemical products such as drugs and dyes.