NMR studies on the influence of silica confinements on local and diffusive dynamics in LiCl aqueous solutions approaching their glass transitions.

Abstract

We use 1H, 2H, and 7Li NMR to investigate the molecular dynamics of glass-forming LiCl-7H2O and LiCl-7D2O solutions confined to MCM-41 or SBA-15 silica pores with diameters in the range of d = 2.8 nm-5.4 nm. Specifically, it is exploited that NMR experiments in homogeneous and gradient magnetic fields provide access to local and diffusive motions, respectively, and that the isotope selectivity of the method allows us to characterize the dynamics of the water molecules and the lithium ions separately. We find that the silica confinements cause a slowdown of the dynamics on all length scales, which is stronger at lower temperatures and in narrower pores and is more prominent for the lithium ions than the water molecules. However, we do not observe a temperature-dependent decoupling of short-range and long-range dynamics inside the pores. 7Li NMR correlation functions show bimodal decays when the pores are sufficiently wide (d > 3 nm) so that bulk-like ion dynamics in the pore centers can be distinguished from significantly retarded ion dynamics at the pore walls, possibly in a Stern layer. However, we do not find evidence for truly immobile fractions of water molecules or lithium ions and, hence, for the existence of a static Stern layer in any of the studied silica pores.