Do solvation layers of ionic liquids influence electrochemical reactions?

In this discussion paper we discuss our recent results on the electrodeposition of materials and in situ STM/AFM measurements which demonstrate that ionic liquids should not be regarded as neutral solvents which all have similar properties. In particular, we focus on differences in interfacial structure (solvation layers) on metal electrodes as a function of ionic liquid species. Recent theoretical and experimental results show that conventional double layers do not form on metal electrodes in ionic liquid systems. Rather, a multilayer architecture is present, with the number of layers determined by the ionic liquid species and the properties of the surface; up to seven discrete interfacial solvent layers are present on electrode surfaces, consequently there is no simple electrochemical double layer. Both the electrodeposition of aluminium and of tantalum are strongly influenced by ionic liquids: in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py 1,4 ]TFSA, aluminium is obtained as a nanomaterial, whereas in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]TFSA, a microcrystalline material is made. Tantalum can be deposited from [Py 1,4 ]TFSA, whereas from [EMIm]TFSA only non-stoichiometric tantalum fluorides TaF x are obtained. It is likely that solvation layers influence these reactions. We discuss whether the solvation layers of ionic liquids on the Au(111) surface influence electrochemical reactions.