Your browser doesn't support javascript.
loading
Redox-Responsive Halogen Bonding as a Highly Selective Interaction for Electrochemical Separations.
Kim, Nayeong; Jeyaraj, Vijaya S; Elbert, Johannes; Seo, Sung Jin; Mironenko, Alexander V; Su, Xiao.
Afiliación
  • Kim N; Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S Mathews Ave., Urbana, Illinois 61801, United States.
  • Jeyaraj VS; Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S Mathews Ave., Urbana, Illinois 61801, United States.
  • Elbert J; Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S Mathews Ave., Urbana, Illinois 61801, United States.
  • Seo SJ; Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S Mathews Ave., Urbana, Illinois 61801, United States.
  • Mironenko AV; Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S Mathews Ave., Urbana, Illinois 61801, United States.
  • Su X; Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S Mathews Ave., Urbana, Illinois 61801, United States.
JACS Au ; 4(7): 2523-2538, 2024 Jul 22.
Article en En | MEDLINE | ID: mdl-39055153
ABSTRACT
Leveraging specific noncovalent interactions can broaden the mechanims for selective electrochemical separations beyond solely electrostatic interactions. Here, we explore redox-responsive halogen bonding (XB) for selective electrosorption in nonaqueous media, by taking advantage of directional interactions of XB alongisde a cooperative and synergistic ferrocene redox-center. We designed and evaluated a new redox-active XB donor polymer, poly(5-iodo-4-ferrocenyl-1-(4-vinylbenzyl)-1H-1,2,3-triazole) (P(FcTS-I)), for the electrochemically switchable binding and release of target organic and inorganic ions at a heterogeneous interface. Under applied potential, the oxidized ferrocene amplifies the halogen binding site, leading to significantly enhanced uptake and selectivity towards key inorganic and organic species, including chloride, bisulfate, and benzenesulfonate, compared to the open-circuit potential or the hydrogen bonding donor analog. Density functional theory calculations, as well as spectroscopic analysis, offer mechanistic insight into the degree of amplification of σ-holes at a molecular level, with selectivity modulated by charge transfer and dispersion interactions. Our work highlights the potential of XB in selective electrosorption by uniquely leveraging noncovalent interactions for redox-mediated electrochemical separations.
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: JACS Au Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: JACS Au Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos