Facile Synthesis of Anhydrous Rare‐Earth Trichlorides from their Oxides in Chloridoaluminate Ionic Liquids

Abstract

Wide applications of anhydrous rare‐earth (RE) trichlorides RECl3 in organometallic chemistry, for the synthesis of optical and magnetic materials, and as catalysts require a facile approach for their synthesis. The known methods use or produce toxic substances, are complicated and have limited reliability and upscaling. It has been shown that task‐specific ionic liquids (ILs) can dissolve many metal oxides without special reaction conditions at moderate temperature, making the metals accessible to downstream chemistry. Using imidazolium chloridoaluminate ILs, pure crystalline anhydrous RECl3 (RE=La−Nd, Sm−Dy) can be synthesized in one step from RE oxides in high yield. The Lewis acidic IL acts as solvent and reaction partner. The by‐product [Al4O2Cl10]2−, which was detected spectroscopically, remains in solution. The reacted IL can be removed quantitatively by washing. ILs with various imidazolium cations and AlCl3 content and the effect of temperature and reaction time were tested.

A Study on the Production of Anhydrous Neodymium Chloride through the Chlorination Reaction of Neodymium Oxide and Ammonium Chloride

“…However, the generation of CO/CO 2 gas due to the use of graphite anodes and the formation of harmful gases such as CF 4 and C 2 F 6 generated from the electrolyte during operation require improvement in terms of its environmental impact [4,5]. A method used for the chlorination of rare earth oxides using imidazolium chloridoaluminate ILs, such as [BMIm]Cl•nAlCl 3 , has been reported [6]. This method has the advantage of being able to prepare anhydrous RECl 3 (rare earth chloride) at a relatively low temperature of 175 • C using less toxic materials.…”

“…Based on Ref [10],. the thermodynamic reaction for the chlorination of Nd2O3 can be expressed as Nd2O3(s) + 2NH4Cl(s) → 2NdOCl(s) + 2NH3(g) + H2O(g), T < 306.47 °C(6) Nd2O3(s) + 2NH4Cl(s) → 2NdOCl(s) + 2NH3(g) + H2O(g) NdOCl(s) + 2NH4Cl(s) → NdCl3(s) + 2NH3(g) + H2O(g), T = 306.47 °C(7)Nd2O3(s) + 9.4NH4Cl(s) → 2NdCl3(s) + 9.4NH3(g) + 3H2O(g) + 3.4HCl(g), T = 400 °C, ∆G o 673.15K = −233.97 kJ(8)…”