Ion specific tuning of nanoparticle dispersion in an ionic liquid: a structural, thermoelectric and thermo-diffusive investigation

Dispersions of charged maghemite nanoparticles (NPs) in EAN (ethylammonium nitrate) a reference Ionic Liquid (IL) are studied here using a number of static and dynamical experimental techniques; small angle scattering (SAS) of X-rays and of neutrons, dynamical light scattering and forced Rayleigh scattering. Particular insight is provided regarding the importance of tuning the ionic species present at the NP/IL interface. In this work we compare the effect of Li+, Na+ or Rb+ ions. Here, the nature of these species has a clear influence on the short-range spatial organisation of the ions at the interface and thus on the colloidal stability of the dispersions, governing both the NP/NP and NP/IL interactions, which are both evaluated here. The overall NP/NP interaction is either attractive or repulsive. It is characterised by determining, thanks to the SAS techniques, the second virial coefficient A2, which is found to be independent of temperature. The NP/IL interaction is featured by the dynamical effective charge xi eff0 of the NPs and by their entropy of transfer ?NP (or equivalently their heat of transport ) determined here thanks to thermoelectric and thermodiffusive measurements. For repulsive systems, an activated process rules the temperature dependence of these two latter quantities. Alkaline counterions at the nanoparticle/ethylammonium nitrate ionic liquid interface impact the macroscopic dispersion's properties, by tuning interparticle and particle/solvent interactions.