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Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length

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journal contribution
posted on 09.04.2019, 00:00 by Vladislav Kamysbayev, Vishwas Srivastava, Nicholas B. Ludwig, Olaf J. Borkiewicz, Hao Zhang, Jan Ilavsky, Byeongdu Lee, Karena W. Chapman, Suriyanarayanan Vaikuntanathan, Dmitri V. Talapin
The nature of the interface between the solute and the solvent in a colloidal solution has attracted attention for a long time. For example, the surface of colloidal nanocrystals (NCs) is specially designed to impart colloidal stability in a variety of polar and nonpolar solvents. This work focuses on a special type of colloids where the solvent is a molten inorganic salt or organic ionic liquid. The stability of such colloids is hard to rationalize because solvents with high density of mobile charges efficiently screen the electrostatic double-layer repulsion, and purely ionic molten salts represent an extreme case where the Debye length is only ∼1 Å. We present a detailed investigation of NC dispersions in molten salts and ionic liquids using small-angle X-ray scattering (SAXS), atomic pair distribution function (PDF) analysis and molecular dynamics (MD) simulations. Our SAXS analysis confirms that a wide variety of NCs (Pt, CdSe/CdS, InP, InAs, ZrO2) can be uniformly dispersed in molten salts like AlCl3/NaCl/KCl (AlCl3/AlCl4) and NaSCN/KSCN and in ionic liquids like 1-butyl-3-methylimidazolium halides (BMIM+X, where X = Cl, Br, I). By using a combination of PDF analysis and molecular modeling, we demonstrate that the NC surface induces a solvent restructuring with electrostatic correlations extending an order of magnitude beyond the Debye screening length. These strong oscillatory ion–ion correlations, which are not accounted by the traditional mechanisms of steric and electrostatic stabilization of colloids, offer additional insight into solvent–solute interactions and enable apparently “impossible” colloidal stabilization in highly ionized media.