Ion correlations drive charge overscreening and heterogeneous nucleation at solid-aqueous electrolyte interfaces.
EDL
X-ray reflectivity
adsorption
molecular dynamics
salinity
Journal
Proceedings of the National Academy of Sciences of the United States of America
ISSN: 1091-6490
Titre abrégé: Proc Natl Acad Sci U S A
Pays: United States
ID NLM: 7505876
Informations de publication
Date de publication:
10 08 2021
10 08 2021
Historique:
entrez:
6
8
2021
pubmed:
7
8
2021
medline:
7
8
2021
Statut:
ppublish
Résumé
Classical electrical double layer (EDL) models are foundational to the representation of atomistic structure and reactivity at charged interfaces. An important limitation to these models is their dependence on a mean-field approximation that is strictly valid for dilute aqueous solutions. Theoretical efforts to overcome this limitation are severely impeded by the lack of visualization of the structure over a wide range of ion concentration. Here, we report the salinity-dependent evolution of EDL structure at negatively charged mica-water interfaces, revealing transition from the Langmuir-type charge compensation in dilute salt solutions to nonclassical charge overscreening in highly concentrated solutions. The EDL structure in this overcharging regime is characterized by the development of both lateral positional correlation between adsorbed ions and vertical layering of alternating cations and anions reminiscent of the structures of strongly correlated ionic liquids. These EDL ions can spontaneously grow into nanocrystalline nuclei of ionic compounds at threshold ion concentrations that are significantly lower than the bulk solubility limit. These results shed light on the impact of ion cooperativity that drives heterogeneous nonclassical behaviors of the EDL in high-salinity conditions.
Identifiants
pubmed: 34353907
pii: 2105154118
doi: 10.1073/pnas.2105154118
pmc: PMC8364158
pii:
doi:
Types de publication
Journal Article
Research Support, U.S. Gov't, Non-P.H.S.
Langues
eng
Sous-ensembles de citation
IM
Informations de copyright
Copyright © 2021 the Author(s). Published by PNAS.
Déclaration de conflit d'intérêts
The authors declare no competing interest.
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