Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

While the traditional consensus dictates that high ion concentrations lead to negligible long-range electrostatic interactions, we demonstrate that electrostatic correlations prevail in deep eutectic solvents where intrinsic ion concentrations often surpass 2.5 M. Here we present an investigation of intermicellar interactions in 1:2 choline chloride:glycerol and 1:2 choline bromide:glycerol using small-angle neutron scattering. Our results show that long-range electrostatic repulsions between charged colloidal particles occur in these solvents. Interestingly, micelle morphology and electrostatic interactions are modulated by specific counterion condensation at the micelle interface despite the exceedingly high concentration of the native halide from the solvent. This modulation follows the trends described by the Hofmeister series for specific ion effects. The results are rationalized in terms of predominant ion-ion correlations, which explain the reduction in the effective ionic strength of the continuum and the observed specific ion effects.

Automated summary

This study demonstrates that in deep eutectic solvents, electrostatic correlations can prevail over long-range electrostatic interactions, and specific counterion condensation can modulate micelle morphology and electrostatic interactions. These findings are rationalized in terms of predominant ion-ion correlations and specific ion effects described by the Hofmeister series.