Material Research and Innovation Laboratory, Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996, USA.
Phys Chem Chem Phys. 2010 Dec 21;12(47):15406-9. doi: 10.1039/c0cp00953a. Epub 2010 Oct 21.
Liquid-liquid extraction of uranyl is studied by conducting atomistic molecular dynamics simulation using quantum chemistry calibrated force fields via restrained electrostatic potential fitting of atomic forces. The simulations depict the migration of uranyl nitrate complexes from the aqueous-organic interface into the tri-n-butyl phosphate (TBP)/dodecane organic phase, in the form of UO(2)(NO(3))(2)·H(2)O·2TBP and UO(2)(NO(3))(2)·3TBP. The migration process is characterized by the gradual breaking of all the hydrogen bonds between the complex and the water molecules at the interface. Moreover, our simulation results suggest that the experimentally observed complex UO(2)(NO(3))(2)·2TBP is formed after the migration of the aforementioned complexes into the organic phase by means of a reorganization of the nitrate binding mode from mono to bidentate which removes the excess oxygen atoms bound to uranyl.
通过使用量子化学校准力场进行原子分子动力学模拟，并通过原子力的受限静电势拟合，研究了铀酰的液-液萃取。模拟描绘了铀酰硝酸盐配合物从水-有机界面迁移到三丁基磷酸酯（TBP）/十二烷有机相中的过程，形式为 UO(2)(NO(3))(2)·H(2)O·2TBP 和 UO(2)(NO(3))(2)·3TBP。迁移过程的特征是逐渐破坏界面处配合物与水分子之间的所有氢键。此外，我们的模拟结果表明，实验观察到的配合物 UO(2)(NO(3))(2)·2TBP 是通过上述配合物迁移到有机相后，通过硝酸根结合模式从单齿到双齿的重排形成的，这种重排去除了与铀酰结合的多余氧原子。
