Abstract
The differential capacitance as a function of potential and composition for choline chloride (ChCl) and ethylene glycol (EG) at 1:2, 1:4, 1:6, and 1:20 molar ratios were studied using electrochemical impedance spectroscopy (EIS) on glassy carbon. In addition, ChCl:EG at the known ethaline DES composition (1:2) and 1:20 molar ratio were studied on Au and Pt electrodes, and compared to glyceline (ChCl:glycerol, 1:2). The capacitance-potential curves on glassy carbon were best interpreted by the modified Gouy-Chapman model. A dampened U-shape was observed similar to dilute electrolytes, however, the non-negligible ionic and H-bonding interactions in these electrolytes resulted in ambiguity about the point of zero charge where capacitance was weakly dependent on potential. Additionally, the differential capacitance was independent of composition on glassy carbon due to limited availability of mobile free ions and constraints by solvated ion sizes within the interface. Increases in capacitance are observed with Au as a result of desolvation and specific adsorption of Cl, and with Pt upon decreased Cl concentrations. These results indicate DESs and H-bonded electrolytes with high salt concentrations are distinct from ionic liquids and present no pronounced overscreening or crowding with applied potential.
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