Functionalization of Electrodes with Tunable [EMIM](x)[Cl](x+1)(-) Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (ILs), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. Herein, we report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM](x)[Cl](x+1)(-) ( x = 1-10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative-ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insights into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM](1)[Cl](2)(-), [EMIM](3)[Cl](4)(-), and [EMIM](5)[Cl](6)(-) clusters. Kelvin probe microscopy provides insights into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal the irreversible adsorption of Fe(CN)(6)(4-/3-) anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN)(6)(4-/3-). Overall, our findings demonstrate that IL clusters with different sizes and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.