Ion and solvent transfer of polyaniline films electrodeposited from deep eutectic solvents via EQCM

We report herein the electrochemical polymerisation of aniline from a choline chloride (ChCl)-based deep eutectic solvent (DES) at room temperature in both the presence and absence of deionised water in the solvent. The current study used Propeline as the DES electrolyte, which we found to be rich in protons (i.e. similar to protic ionic liquids) and which allowed the polymerisation of aniline in this system. The morphology of films was characterised by scanning electron microscopy (SEM) and atomic force microscopy (AFM), which showed the polymer film to have a compact structure and rough surface. The electrochemical quartz crystal microbalance (EQCM) was used for the first time to investigate the mass changes that occur during the electrochemical deposition of polyaniline (PANI) in situ, and was used to monitor cation, anion, and solvent transport when PANI films were immersed in pure Propeline and 0.5 M H2SO4 solution (monomer free) at 25 degrees C and 50 degrees C. In the case of the PANI exposed to pure Propeline at room temperature, the mass change increased continuously in both oxidation and reduction switching due to anion transfer dominating the mass change, while the PANI exposed to pure Propeline at 50 degrees C was found to form due to a two-step combined mechanism, showing excellent redox switching stability with changing mass. These variations in mass tend to be dominated by cation expulsion in the first oxidative process (the later reductive process being cation insertion) and by anion insertion in the second oxidative stage (the early reductive process being anion expulsion). In aqueous systems, the mechanism of mass change was dominated by anion movement associated with solvent transfer. The movement of neutral species in Propeline and water is in the reverse direction to those of cation or anion transfer.