Electron Transfer Mechanisms in Concentrated Organic Redox Solutions

有机化合物的电子转移反应 研究了浓缩的（1-10 M）氧化还原溶液。 广泛使用微电极技术来获得 溶液中的定量传输和动力学数据 含有摩尔浓度的电活性 物种 最初的研究集中在最近发现的几个 质量传输现象，包括加速传输 由均相电子转移反应产生的速率。 除了微电极技术，相位测量 干涉显微镜和石英晶体微量天平 方法被用来测量的物理参数的 电化学耗尽层 其他重点包括 详细描述了 非均相电子转移速率常数 浓度和调查的依赖性， 耦合化学反应（包括催化反应） 局部电场;酮的电化学还原;电化学反应 详细研究，以确定高电 反应选择性的领域。 商业电合成工艺通常在 高浓度的溶液，因为它们提供更好的能量 效率和更高的吞吐量比稀释溶液，但 几乎所有的实验室电化学都是在稀 变量更容易隔离的解决方案， 翻译。 通过创建一个基本框架， 性质的浓缩溶液，这项工作将使 一个合理的规模扩大的电化学范式可行 流程. 这是电化学联合倡议下的一个奖项， 由美国国家科学基金会和 电力科学研究院。

Electron-transfer reactions of organic compounds in highly concentrated (1-10 M) redox solutions are investigated. Extensive use is made of microelectrode techniques to obtain quantitative transport and kinetics data in solutions containing molar-level concentrations of electroactive species. Initial studies focus on several recently identified mass-transport phenomena, including accelerated transport rates resulting from homogeneous electron-transfer reactions. In addition to microelectrode techniques, phase-measurement interference microscopy and quartz-crystal microbalance methods are used to measure physical parameters of the electrochemical depletion layer. Other emphases include developing a detailed description of the dependence of heterogeneous electron-transfer rate constants on concentration and the investigation of the dependence of coupled chemical reactions (including catalytic reactions) on local electric fields; electrochemical reduction of ketones is studied in detail to determine the effects of high electric fields on reaction selectivity. Commercial electrosynthetic processes are usually run in highly concentrated solutions since these give a better energy efficiency and higher throughput than do dilute solutions, but almost all laboratory electrochemistry is done in dilute solutions where variables are more easily isolated and interpreted. By creating a fundamental framework for the properties of concentrated solutions, this work will make feasible a rational scale-up paradigm for electrochemical processes. This is an award under the joint Initiative on Electrochemical Synthesis sponsored by the National Science Foundation and the Electric Power Research Institute.