Spectroscopic investigation of the structure of a pyrrolidinium-based ionic liquid at electrified interfaces

Abstract

The molecular structure of electric double layers (EDLs) at electrode–electrolyte interfaces is crucial for all types of electrochemical processes. Here, we probe the EDL structure of an ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPy-TFSI), using electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy. We extract the position and intensity of individual peaks corresponding to either intra- or inter-molecular vibrational modes and examine their dependence on the electrode potential. The observed trends suggest that the molecular reconfiguration mechanism is distinct between cations and anions. BMPy+ is found to always adsorb on the Au electrode surface via the pyrrolidinium ring while the alkyl chains strongly change their orientation at different potentials. In contrast, TFSI− is observed to have pronounced position shifts but negligible orientation changes as we sweep the electrode potential. Despite their distinct reconfiguration mechanisms, BMPy+ and TFSI− in the EDL are likely paired together through strong intermolecular interaction.