Verma Parveen K, Mahanty Bholanath, Ali Sk Musharaf, Mohapatra Prasanta K
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India.
Chemical Engineering Division, Bhabha Atomic Research Centre, Mumbai 400085, India.
Inorg Chem. 2021 Jul 19;60(14):10147-10157. doi: 10.1021/acs.inorgchem.1c00202. Epub 2021 Jul 2.
Dissolution of uranium oxide was carried out using a solution of HD2EHP in Cmim·NTf, which was apparently facilitated by the generation of water during the complex formation reaction. The dissolved complex in the ionic liquid phase led to splitting of the latter into a light phase and a heavy phase where the former contained predominantly the UO(HL) complex (HL = HD2EHP), while the latter contained the ionic liquid as supported by FTIR and UV-Visible spectral analyses. The complexation of the uranyl ion was suggested to take place in the equatorial plane where two dimeric units of the H-bonded HD2EHP molecules took part in complexation. An increase in temperature facilitated the dissolution rate with an activation energy of 31.0 ± 2.8 kJ/mol. The cyclic voltammetry studies indicated potential chances of recovery of the dissolved uranium by electrodeposition at the cathode. The proposed dimeric structure of HD2EHP in the complexation with U(VI) was supported by DFT studies also.
使用HD2EHP在Cmim·NTf中的溶液进行氧化铀的溶解，在络合物形成反应过程中生成水显然促进了这一过程。离子液相中溶解的络合物导致后者分裂成轻相和重相，通过傅里叶变换红外光谱（FTIR）和紫外可见光谱分析表明，前者主要含有UO(HL)络合物（HL = HD2EHP），而后者含有离子液体。据推测，铀酰离子的络合发生在赤道平面，其中两个氢键连接的HD2EHP分子的二聚体单元参与络合。温度升高促进了溶解速率，活化能为31.0 ± 2.8 kJ/mol。循环伏安法研究表明，有可能通过在阴极进行电沉积来回收溶解的铀。密度泛函理论（DFT）研究也支持了所提出的HD2EHP与U(VI)络合时的二聚体结构。
