Deep Eutectic Solvents (DESs) are a novel class of solvents with potential industrial applications in separation processes, chemical reactions, metal recovery and metal finishing processes such as electrodeposition and electropolishing. Macroscopic physical properties such as viscosity, conductivity, eutectic composition and surface tension are already available for several DESs, but the microscopic transport properties for this class of compounds are not well understood and the literature lacks experimental data that could give a better insight into the understanding of such properties. This paper presents the first pulsed field gradient nuclear magnetic resonance (PFG-NMR) study of DESs. Several choline chloride based DESs were chosen as experimental samples, each of them with a different associated hydrogen bond donor. The molecular equilibrium self-diffusion coefficient of both the choline cation and hydrogen bond donor was probed using a standard stimulated echo PFG-NMR pulse sequence. It is shown that the increasing temperature leads to a weaker interaction between the choline cation and the correspondent hydrogen bond donor. The self-diffusion coefficients of the samples obey an Arrhenius law temperature-dependence, with values of self-diffusivity in the range of [10⁻¹⁰–10⁻¹³ m² s⁻¹]. In addition, the results also highlight that the molecular structure of the hydrogen bond donor can greatly affect the mobility of the whole system. While for ethaline, glyceline and reline the choline cation diffuses slower than the associated hydrogen bond donor, reflecting the trend of molecular size and molecular weight, the opposite behaviour is observed for maline, in which the hydrogen bond donor, i.e. malonic acid, diffuses slower than the choline cation, with self-diffusion coefficients values of the order of 10⁻¹³ m² s⁻¹ at room temperature, which are remarkably low values for a liquid. This is believed to be due to the formation of extensive dimer chains between malonic acid molecules, which restricts the mobility of the whole system at low temperature (<30 °C), with malonic acid and choline chloride having almost identical diffusivity values. Diffusion and viscosity data were combined together to gain insights into the diffusion mechanism, which was found to be the same as for ionic liquids with discrete anions.

Nuclear magnetic resonance (NMR) relaxation times are shown to provide a unique probe of adsorbate–adsorbent interactions in liquid‐saturated porous materials. A short theoretical analysis is presented, which shows that the ratio of the longitudinal to transverse relaxation times (T₁/T₂) is related to an adsorbate–adsorbent interaction energy, and we introduce a quantitative metric e_surf (based on the relaxation time ratio) characterising the strength of this surface interaction. We then consider the interaction of water with a range of oxide surfaces (TiO₂ anatase, TiO₂ rutile, γ‐Al₂O₃, SiO₂, θ‐Al₂O₃ and ZrO₂) and show that e_surf correlates with the strongest adsorption sites present, as determined by temperature programmed desorption (TPD). Thus we demonstrate that NMR relaxation measurements have a direct physical interpretation in terms of the characterisation of activation energy of desorption from the surface. Further, for a series of chemically similar solid materials, in this case a range of oxide materials, for which at least two calibration values are obtainable by TPD, the e_surf parameter yields a direct estimate of the maximum activation energy of desorption from the surface. The results suggest that T₁/T₂ measurements may become a useful addition to the methods available to characterise liquid‐phase adsorption in porous materials. The particular motivation for this work is to characterise adsorbate–surface interactions in liquid‐phase catalysis.