Development of heavy element chemistry at interfaces; Observing actinide complexes at the oil/water interface in solvent extraction by nonlinear vibrational spectroscopy

日下 良二; 渡邉 雅之

Journal of Physical Chemistry Letters (Internet), 13(30), p.7065 - 7071, 2022/08

https://doi.org/10.1021/acs.jpclett.2c01550

Understanding the chemistry of elements at the bottom of the periodic table is a challenging goal in chemistry. Observing actinide species at interfaces 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 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 (DFT) calculations proposed the molecular structure of the interfacial uranyl-HDEHP complex.

液/液界面電気化学

北辻 章浩

ぶんせき, 2015(6), p.239 - 244, 2015/06

AA2014-0843.pdf:3.48MB

https://cir.nii.ac.jp/crid/1050564287525685120

混じり合わない二つの液相界面におけるイオンの移動反応あるいは電荷移動反応を、電気化学的手法を用いて調べた研究について、2012年から2014年までの文献を調査した。用いられた測定法ごとに分類して、その特長と発展、適用例などをまとめた。酸化還元非活性イオンの分析への適用や、界面吸着反応を利用した高感度分析の報告が多く、界面反応を利用する新規機能性材料開発などの応用研究が盛んになされている。