Dynamics of Mediated Electrochemical Synthesis in Microemulsions

这个项目的目标是了解微乳液吸附在电极上的表面活性剂微结构的动力学及其对中介反应速率的影响。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联系起来。用时间分辨流动伏安法和简化的电化学显微镜测量了表面动力学。还得到了介体在电极上的吸附动力学和反应活性。采用间歇搅拌电化学反应器，比较了在微乳液和各向同性溶液中用伏安法测量的介体合成速度和整体电解速度，并寻找了与吸附动力学的关联。选择研究的反应包括碳-碳键的形成、官能团的脱保护和烯烃的生产。介体包括过渡金属科林素和酞菁及其衍生物。介导性电化学反应(涉及将电子(或空穴)从电极输送到目标衬底的中间体或催化剂的反应)被吸附在电极上的表面活性剂强化。微乳液提供了一种引入和控制这些过程的有吸引力的方法。这种方法可以为生产药物和染料等高附加值化学产品提供清洁、高效、成本效益高的工艺。

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.