Dynamics of Mediated Electrochemical Synthesis in Microemulsions

微乳液介导电化学合成动力学

• 批准号: 9306961
• 负责人: James Rusling
• 金额: $ 31.1万
• 依托单位: University of Connecticut
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-09-01 至 1997-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9306961&HistoricalAwards=false
• 关键词: Dynamics; Mediated; Electrochemical; Synthesis; Microemulsions

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.

James Rusling 摘要 该项目的目标是了解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电极上的表面活性剂和反应物吸附-解吸动力学与化学反应速率联系起来。 表面动力学通过时间分辨流动伏安法和简化的电化学显微镜进行测量。 还获得了介体在电极上的吸附动力学和反应性。 使用搅拌的间歇式电化学反应器，比较了通过伏安法测量的介导合成速率以及微乳液和各向同性溶液中的本体电解速率，并寻求与吸附动力学的相关性。 选择研究的反应包括碳-碳键形成、官能团脱保护和烯烃生产。 介体包括过渡金属咕啉和酞菁及其衍生物。 吸附在电极上的表面活性剂可以增强介导的电化学反应（涉及将电子（或空穴）从电极携带到目标基材的中间体或催化剂的反应）。 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药物和染料等高附加值化学产品提供清洁、高效、具有成本效益的工艺。