Mechanism of liquid-liquid solvent extraction of uranyl by tributyl phosphate; A Study using vibrational sum frequency generation spectroscopy

Kusaka, Ryoji  ; Watanabe, Masayuki   

Liquid-liquid solvent extraction of uranyl using tributyl phosphate (TBP) is a significantly important technique in treatments of spent nuclear fuels. In the solvent extraction, TBP comes to an organic/aqueous interface and forms an organic/TBP monolayer/aqueous interface because of the surface activity of TBP. At the interface, it is believed that the complex formation between uranyl and TBP takes place, and subsequently the uranyl-TBP complex transfers to an organic phase. However, the structure of the uranyl-TBP complex formed at the interface is controversial. This is partly because of no experimental studies on molecular-level structure at interfaces pertaining to the solvent extraction of uranyl. Recently, we proposed that an extractant/aqueous interface, formed on the surface of an aqueous solution, is a good model of an organic/extractant/aqueous interface, to investigate the structure of interfacial metal complexes using vibrational sum frequency generation (VSFG) spectroscopy. In the present study, we investigated the structure of theuranyl-TBP complex at the TBP/uranyl aqueous solution interface by VSFG spectroscopy. Surprisingly, interface-selective vibrational spectra obtained by VSFG suggests that uranyl does not form a complex with TBP at the TBP/uranyl aqueous solution interface. This result proposes that we should reconsider the mechanism of the solvent extraction of uranyl by TBP.