Electrons and Their Multiple Kinetic Fates in an Ionic Liquid

作者：Hung H. Nguyen, Katie Huber, Dhanjit Das, Bichitra Borah, Matthew S. Emerson, Meghan Knudtzon, James F. Wishart, David A. Blank, Claudio J. Margulis · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c07005 · 被引用次数：3 · 研究领域：Electrochemical Analysis and Applications、Ionic liquids properties and applications、Electrochemical sensors and biosensors

High Resolution Image Download MS PowerPoint Slide Ionic liquids (ILs) for electrochemical, nuclear, and solar energy applications operate under harsh conditions, where electrons and transient radical species can form. This communication discusses why anions such as bis(trifluoromethylsulfonyl)imide (Tf 2 N – ) are reduced at the electron-rich electrode whereas in laser photoionization or pulse radiolysis studies, where electrons are ejected from species in the bulk, we often detect long-lived electrons in cavities that interact with IL cations instead. This work argues that bulk excess electrons generated photolytically or radiolytically follow kinetically favored pathways. As such, cavity electrons may not be the most energetically favorable states, but when they form, and they do form, they are kinetically stable. Reduction reactions of anions or electron localization in cavities and subsequent reactions are all expected outcomes. Here we focus on a pyrrolidinium-based IL of the dicyanamide (N(CN) 2 – ) anion because of its large electrochemical window and very low viscosity, which are ideal for energy applications.