Development of Heavy Element Chemistry at Interfaces: Observing Actinide Complexes at the Oil/Water Interface in Solvent Extraction by Nonlinear Vibrational Spectroscopy.

Understanding the chemistry of elements at the bottom of the periodic table is a challenging goal in chemistry. Observing actinide species at interfaces by using interface-selective second-order nonlinear optical spectroscopy, such as vibrational sum frequency generation (VSFG) spectroscopy, is a promising route for developing heavy element chemistry; however, such attempts are scarce. Here, we investigated the phase transfer mechanism of uranyl ions (UO) in solvent extraction using the di(2-ethylhexyl)phosphoric acid (HDEHP) extractant dissolved in the dodecane organic phase by probing the oil/water liquid-liquid interface using VSFG spectroscopy. The POO symmetric stretch vibrational signals of the HDEHP ligands clearly demonstrated that uranyl ions form interfacial complexes with HDEHP at the oil/water interface. The interfacial uranyl-HDEHP complexes were formed with uranyl ions coming from both the aqueous and oil phases, strongly suggesting that the interfacial complex is an intermediate to cross the oil/water interface. Density functional theory calculations proposed the molecular structure of the interfacial uranyl-HDEHP complex.