Journal article
Electrons and Their Multiple Kinetic Fates in an Ionic Liquid
Journal of the American Chemical Society, Vol.147(27), pp.23395-23398
06/27/2025
DOI: 10.1021/jacs.5c07005
PMCID: PMC12257543
PMID: 40576638
Appears in UI Libraries Support Open Access
Abstract
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 (Tf2N–) 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.
Details
- Title: Subtitle
- Electrons and Their Multiple Kinetic Fates in an Ionic Liquid
- Creators
- Hung H Nguyen - University of IowaKatie Huber - University of MinnesotaDishan Das - University of IowaBichitra Borah - University of IowaMatthew S Emerson - Brookhaven National LaboratoryMeghan Knudtzon - University of Minnesota SystemJames F Wishart - Brookhaven National LaboratoryDavid A Blank - University of Minnesota SystemClaudio J Margulis - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.147(27), pp.23395-23398
- DOI
- 10.1021/jacs.5c07005
- PMID
- 40576638
- PMCID
- PMC12257543
- NLM abbreviation
- J Am Chem Soc
- ISSN
- 1520-5126
- eISSN
- 1520-5126
- Publisher
- American Chemical Society
- Grant note
- Basic Energy Sciences: DE-SC0024181 U.S. Department of Energy, Office of Basic Energy Sciences, Condensed Phase and Interfacial Molecular Science (CPIMS) programUniversity of Minnesota: DE-SC0012704 U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
This research at Minnesota was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Condensed Phase and Interfacial Molecular Science (CPIMS) program under DE-SC0024181. The work at Iowa was supported via subcontract from the University of Minnesota under the same support. The work at BNL and the use of the Laser Electron Accelerator Facility of the BNL Accelerator Center for Energy Research were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under Contract DE-SC0012704. The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. The authors also acknowledge usage of the University of Iowa Argon cluster.
- Language
- English
- Date published
- 06/27/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984833489002771
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