Electrochemistry of Titanium Tetrachloride in 1-Butyl-2,3-dimethyl Imidazolium Tetrafluoroborate

Abstract

The electrochemistry of titanium tetrachloride has been examined in trialkyl-substituted imidazolium tetrafluoroborate at 65 °C. Ti(IV) reduction was studied with chronopotentiometry and cyclic voltammetry in melts with different concentrations of TiCl4. The diffusion coefficient of Ti(IV) ranged between 1.1·10−7 and 7·10−8 cm2 s−1. The electroreduction of Ti(IV) was found to proceed via the sequence of one-electron steps, the relative stability of the low valence intermediates being dependent on the concentration of TiCl4 in the electrolyte. The kinetics of an overlapping disproportionation reaction of Ti(II) was examined and its rate constant at low concentration (0.025 mol/l) of TiCl- was found to be k = 2 · 106 cm3 mol−1 s−1, Ti(0) being the final product of the stepwise reduction process at higher concentrations (0.03 - 0.14 mol/l).

Electrochemical Studies of Titanium Chlorides in Ionic Liquids

“…The voltammetric behavior of TiCl 4 in BMPY T f O is characterized by splitting of the Ti(IV) to Ti(III) reduction process, behavior not observed in EMI BF 4 or other ionic liquids (3)(4)(5)(6)(7)(8). Attempted electrodeposition of titanium from TiCl 4 in BMPY T f O did not give an adherent deposit at copper electrodes.…”

“…Work in CaCl 2 has resulted in reduction of TiO 2 to titanium metal (2); however, production conditions at ambient temperature would be preferable. Recent work has involved the voltammetric study of TiCl 4 in various ionic liquids (3)(4)(5)(6)(7)(8), with only limited success in producing metallic titanium. In the present work, we are extending our previous work on TiCl 4 in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 ) to the 1-butyl-1methylpyrrolidinium triflate (BMPY T f O) system.…”

Ionometallurgy: an academic exercise or promising approach?

“…For example, the bulk electrodeposition of titanium from various ILs remains a challenge, as titanium forms stable intermediates, such as subhalides, precipitating from the IL. 88–93…”

“…For example, the bulk electrodeposition of titanium from various ILs remains a challenge, as titanium forms stable intermediates, such as subhalides, precipitating from the IL. [88][89][90][91][92][93] Since the rst report about electrodeposition of aluminum from acidic [BPy]Cl/AlCl 3 , 84,[94][95][96] the procedure attracted considerable interest due to the industrial relevance of aluminum coatings. Chloridoaluminate ILs appear to be especially well-suited for this purpose because of their high aluminum concentrations and good conductivities.…”

On the Electrodeposition of Titanium from TiCl4in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide: In Situ AFM and Spectroscopic Investigations

“…5,6 Owing to the properties such as wide electrochemical windows and thermal stabilities, Ionic Liquids (ILs) have been discussed as alternative media for the deposition of refractory metals such as tantalum and niobium and other elements such as lithium and silicon. [7][8][9][10][11][12][13][14][15] Quite a few liquids, with tetrafluoroborate or azide anions and alkylimidazolium cations have been employed for the electrodeposition of titanium, 16,17 wherein TiCl 4 was used a precursor. There were some claims that Ti has maybe been obtained from TiCl 4 in ILs.…”