Fluorous and organic extraction systems; A Comparison from the perspectives of coordination structures, interfaces, and bulk extraction phases

Ueda, Yuki; Micheau, C.; Akutsu, Kazuhiro*; Tokunaga, Kohei; Yamada, Masako*; Yamada, Norifumi*; Bourgeois, D.*; Motokawa, Ryuhei

Langmuir, 40(46), p.24257 - 24271, 2024/11

https://doi.org/10.1021/acs.langmuir.4c02268

Microscopic structures in liquid-liquid extraction, such as structuration between extractants or extracted complexes in bulk organic phases and at interfaces, can influence macroscopic phenomena, such as the distribution behavior of solutes, including extraction efficiency, selectivity, and phase separation of the organic phase. In this study, we correlated the macroscopic behavior of the extraction of Zr(IV) ions from nitric acid solutions with microscopic structural information in order to understand at the molecular level the key factors contributing to the higher metal ion extraction performance in the fluorous extraction system comprising fluorous phosphate (TFP) in perfluorohexane as compared to the analogous organic extraction system comprising organic phosphate (THP) in n-hexane. Extended X-ray absorption fine structure, neutron reflectometry, and small-angle neutron scattering revealed the local coordination structure around the Zr(IV) ion, the accumulation of extractant molecules at the interface, and the structuration of extractant molecules in the bulk extraction phase, respectively. In the fluorous extraction system, extractant aggregates with were formed after contact with nitric acid. In contrast, in the organic extraction system, only extractant dimers were formed. We speculate that differences in the local coordination structure around the Zr(IV) ion and the structuration of the extractant molecules in the bulk extraction phase contribute to the high Zr(IV) extraction performance in the fluorous extraction system. In particular, the size of the aggregates hardly changed with increasing Zr(IV) concentration in the fluorous phase, which may be closely related to the absence of phase splitting in the fluorous extraction system.

Singular continuous and nonreciprocal phonons in quasicrystal AlPdMn

Matsuura, Masato*; Zhang, J.*; Kamimura, Yasushi*; Kofu, Maiko; Edagawa, Keiichi*

Physical Review Letters, 133(13), p.136101_1 - 136101_5, 2024/09

https://doi.org/10.1103/PhysRevLett.133.136101

Development of an Fe complex exhibiting intermolecular proton shifting coupled spin transition

Ji, T.*; Su, S.*; Wu, S.*; Hori, Yuta*; Shigeta, Yasuteru*; Huang, Y.*; Zheng, W.*; Xu, W.*; Zhang, X.*; Kiyanagi, Ryoji; et al.

Angewandte Chemie; International Edition, 63(25), p.e202404843_1 - e202404843_6, 2024/04

https://doi.org/10.1002/anie.202404843

Tuning of spin-orbit coupling in chiral molecule-incorporated two-dimensional organic-inorganic hybrid perovskite copper halides with ferromagnetic exchange interactions

Taniguchi, Koji*; Huang, P.-J.*; Sagayama, Hajime*; Kiyanagi, Ryoji; Oishi, Kazuki*; Kito, Shunsuke*; Nakamura, Yuiga*; Miyasaka, Hitoshi*

Physical Review Materials (Internet), 8(2), p.024409_1 - 024409_10, 2024/02

https://doi.org/10.1103/PhysRevMaterials.8.024409

Magnetic boson peak in classical spin glasses

Kofu, Maiko; Kawamura, Seiko; Murai, Naoki; Ishii, Rieko*; Hirai, Daigoro*; Arima, Hiroshi*; Funakoshi, Kenichi*

Physical Review Research (Internet), 6(1), p.013006_1 - 013006_9, 2024/01

https://doi.org/10.1103/PhysRevResearch.6.013006

In situ neutron imaging of lithium-ion batteries during heating to thermal runaway

Nozaki, Hiroshi*; Kondo, Hiroki*; Shinohara, Takenao; Setoyama, Daigo*; Matsumoto, Yoshihiro*; Sasaki, Tsuyoshi*; Isegawa, Kazuhisa*; Hayashida, Hirotoshi*

Scientific Reports (Internet), 13, p.22082_1 - 22082_8, 2023/12

https://doi.org/10.1038/s41598-023-49399-1

Development of an iron(II) complex exhibiting thermal- and photoinduced double proton-transfer-coupled spin transition in a short hydrogen bond

Nakanishi, Takumi*; Hori, Yuta*; Shigeta, Yasuteru*; Sato, Hiroyasu*; Kiyanagi, Ryoji; Munakata, Koji*; Ohara, Takashi; Okazawa, Atsushi*; Shimada, Rintaro*; Sakamoto, Akira*; et al.

Journal of the American Chemical Society, 145(35), p.19177 - 19181, 2023/08

https://doi.org/10.1021/jacs.3c06323

Magnetic ordering and structural phase transitions of NdSn ( = Rh and Ir)

Shimoda, Ami*; Iwasa, Kazuaki*; Kuwahara, Keitaro*; Sagayama, Hajime*; Nakao, Hironori*; Ishikado, Motoyuki*; Ohara, Takashi; Nakao, Akiko*; Hoshikawa, Akinori*; Ishigaki, Toru*

JPS Conference Proceedings (Internet), 38, p.011091_1 - 011091_6, 2023/05

https://doi.org/10.7566/JPSCP.38.011091

Analysis of the electric double layer structure formed in an ionic liquid using neutron reflectivity

Tamura, Kazuhisa; Akutsu-Suyama, Kazuhiro*; Cagnes, M.*; Darwish, T. A.*

ECS Advances (Internet), 1(2), p.020503_1 - 020503_5, 2022/06

AA2021-0622.pdf:1.08MB

https://doi.org/10.1149/2754-2734/ac6963

The ionic liquid/Si electrode interface was investigated using neutron reflectivity. We precisely elucidated the structure of the electrical double layer formed at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([BMIM]TFSA)/Si(100) electrode interface with the orientation of the [BMIM]TFSA molecule using a partially deuterated [BMIM]TFSA. The results revealed that [BMIM]TFSA molecules form a layered structure. Cation and anion molecules are alternatingly stacked and molecules in the first three layers are horizontally oriented to the electrode surface at E = -1.2 V, i.e., on the negatively charged electrode surface. It was also revealed that the imidazole ring in [BMIM] cation is parallel to the electrode surface.

Experimental analysis on dynamics of liquid molecules adjacent to particles in nanofluids

Hashimoto, Shunsuke*; Nakajima, Kenji; Kikuchi, Tatsuya*; Kamazawa, Kazuya*; Shibata, Kaoru; Yamada, Takeshi*

Journal of Molecular Liquids, 342, p.117580_1 - 117580_8, 2021/11

https://doi.org/10.1016/j.molliq.2021.117580

Quasi-elastic neutron scattering (QENS) and pulsed-field-gradient nuclear magnetic resonance (PFGNMR) analyses of a nanofluid composed of silicon dioxide (SiO) nanoparticles and a base fluid of ethylene glycol aqueous solution were performed. The aim was to elucidate the mechanism increase in the thermal conductivity of the nanofluid above its theoretical value. The obtained experimental results indicate that SiO particles may decrease the self-diffusion coefficient of the liquid molecules in the ethylene glycol aqueous solution because of their highly restricted motion around these nanoparticles. At a constant temperature, the thermal conductivity increases as the self-diffusion coefficient of the liquid molecules decreases in the SiO nanofluids.