Relationship between Structure and Properties of Nonstoichiometric Protic Ionic Liquids: n-Butylammonium Butyrate...

Nonstoichiometric protic ionic liquids have drawn much attention in applications, including fuel cells, batteries, and reaction media. An understanding of the relationship between their structure and properties is instructive for further applications. However, there are only a few studies on nonstoichiometric protic ionic liquids. Herein, the density, viscosity, and conductivity of nonstoichiometric n-butylammonium butyrate protic ionic liquids were measured, and we used small/wide-angle scattering (S/WAXS), electron paramagnetic resonance (EPR), and molecular dynamics (MD) simulation to explore the effect of mesostructure on their properties. It is found that the hydrogen bonds drive excess N-butyric acid (PrCOOH) molecules to wrap around ion clusters, resulting in the higher density and viscosity of PrCOOH-rich PILs. The microenvironments around various radicals differ significantly in BuNH₂-rich and PrCOOH-rich PILs because of the distinct molecular arrangements. This research provided a link between the physicochemical properties and structures of nonstoichiometric PILs, which is essential for their applications in electrolytes and organic reactions.