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Updated: Jun 13, 2025

Characterization of Nanocrystal Size Distribution using Raman Spectroscopy with a Multi-particle Phonon Confinement Model
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Anion Size Controls Cation Wigner Crystal-Like Structures at Silica Interfaces.

Ho Hong Chau1, Hua Li1,2, Rob Atkin1

  • 1School of Molecular Sciences, The University of Western Australia, Perth, Western Australia 6009, Australia.

The Journal of Physical Chemistry Letters
|June 2, 2025
PubMed
Summary
This summary is machine-generated.

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Anion size dictates cation Wigner crystal-like structures at silica interfaces. Larger anions like bromide and iodide lead to hydrated calcium structures, while chloride allows direct contact, revealing insights into electrical double layer organization.

Area of Science:

  • Surface Science
  • Electrochemistry
  • Materials Science

Background:

  • The electrical double layer (EDL) governs interfacial phenomena.
  • Understanding ion organization in the Stern layer is crucial for controlling interfacial properties.
  • Previous studies have explored ion adsorption but lacked high-resolution structural details.

Purpose of the Study:

  • To investigate the influence of anion size on cation Wigner crystal-like structure (WCLS) formation at the silica-electrolyte interface.
  • To elucidate the role of ionic charge density and hydration in dictating ion arrangement.
  • To provide atomic-level insights into the structure of the Stern layer.

Main Methods:

  • High-resolution atomic force microscopy (AFM) imaging.
  • Systematic variation of calcium halide electrolytes (CaCl2, CaBr2, CaI2) at a controlled pH (10.5).

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  • Analysis of cation WCLS dimensions and inter-ionic spacings.

    • Main Results:

    • Anion size systematically controlled Ca2+ WCLS dimensions.
    • CaCl2 formed Ca2+ structures with spacing matching Cl- diameter (3.6-3.8 Å), indicating direct contact.
    • CaBr2 and CaI2 showed Ca2+ structures with spacings larger than the respective anion diameters (4.8 Å for Br-, 5.0-5.1 Å for I-), suggesting partial hydration.
    • Observed spacing differences correlate with anion charge density and hydration energy.

    Conclusions:

    • Anion size and hydration are key factors controlling cation organization in the Stern layer.
    • High charge density anions (Cl-) can displace hydration water, enabling direct cation-anion contact.
    • Lower charge density anions (Br-, I-) retain partial hydration shells, influencing cation spacing.
    • Findings advance the understanding of EDL structure and ion-adsorption mechanisms at charged interfaces.