On the electrodeposition of titanium in ionic liquids.

The ability to electrodeposit titanium at low temperatures would be an important breakthrough for making corrosion resistant layers on a variety of technically important materials. Ionic liquids have often been considered as suitable solvents for the electrodeposition of titanium. In the present paper we have extensively investigated whether titanium can be electrodeposited from its halides (TiCl(4), TiF(4), TiI(4)) in different ionic liquids, namely1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm]Tf(2)N), 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)amide ([BMP]Tf(2)N), and trihexyltetradecyl-phosphonium bis(trifluoromethylsulfonyl)amide ([P(14,6,6,6)]Tf(2)N). Cyclic voltammetry and EQCM measurements show that, instead of elemental Ti, only non-stoichiometric halides are formed, for example with average stoichiometries of TiCl(0.2), TiCl(0.5) and TiCl(1.1). In situ STM measurements show that-in the best case-an ultrathin layer of Ti or TiCl(x) with thickness below 1 nm can be obtained. In addition, results from both electrochemical and chemical reduction experiments of TiCl(4) in a number of these ionic liquids support the formation of insoluble titanium cation-chloride complex species often involving the solvent. Solubility studies suggest that TiCl(3) and, particularly, TiCl(2) have very limited solubility in these Tf(2)N based ionic liquids. Therefore it does not appear possible to reduce Ti(4+) completely to the metal in the presence of chloride. Successful deposition processing for titanium in ionic liquids will require different maybe tailor-made titanium precursors that avoid these problems.

An EQCM study of the electropolymerization of benzene in an ionic liquid and ion exchange characteristics of the resulting polymer film.

The direct electropolymerization of benzene dissolved in the ionic liquid 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate was studied at room temperature applying the electrochemical quartz-crystal microbalance technique. Analysis of the damping changes showed that the Sauerbrey equation could be applied for data evaluation. In the polymer, every third to fourth benzene ring carried a positive charge in the oxidized state. During electropolymerization, some ionic liquid was absorbed in the growing polymer. The redox behavior was characterized by wide peaks typical for conducting polymers. Charge neutrality of the polymer during redox cycling was maintained by anion and cation exchange with the ionic liquid. With increasing scan rate, cation exchange became more and more important.