Possible Proton Conduction Mechanism in Pseudo-Protic Ionic Liquids: A Concept of Specific Proton Conduction

摘要

In a previous work, we have found that the pseudo-protic ionic liquid N-methylimidazolium acetate, [C(1)HIm] [OAc] or [Hmim] [OAc], mainly consists of the electrically neutral molecular species N-methylimidazole, C(1)Im, and acetic acid, AcOH, even though the mixture has significant ionic conductivity. This system was revisited by employing isotopic substitution Raman spectroscopy (ISRS) and pulsed field gradient (PFG) NMR self-diffusion measurements. The ISRS and PFG-NMR results obtained fully confirm our earlier findings. In particular, the self-diffusion coefficient of the hydroxyl hydrogen atom in AcOH is identical to that of the methyl hydrogen atoms within the experimental uncertainty, consistent with very little ionization. Therefore, a proton conduction mechanism similar to the Grotthuss mechanism for aqueous acid solutions is postulated to be responsible for the observed electrical conductivity. Laity resistance coefficients (r(ij)) are calculated from the transport properties, and the negative values obtained for the like-ion interactions are consistent with the pseudo-ionic liquid description, that is, the mixture is indeed a very weak electrolyte. The structure and rotational dynamics of the mixture were also investigated using high-energy X-ray total scattering experiments, molecular dynamics simulations, and dielectric relaxation spectroscopy. Based on a comparison of activation energies and the well-known linear free energy relationship between the kinetics and thermodynamics of autoprotolysis, we propose for [C(1)HIm] [OAc] a Grotthus-type proton conduction mechanism involving fast AcOH/AcO- rotation as a decisive step.