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.

Mn L-edge EXAFS and magnetic EXAFS studies on the halfmetallic ferromagnet CoMnSi

Kogo, Junya*; Fujiwara, Hidenori*; Sekiyama, Akira*; Saito, Yuji; Umetsu, Rie*; Niki, Kaori*

Journal of the Physical Society of Japan, 91(3), p.034702_1 - 034702_12, 2022/03

https://doi.org/10.7566/JPSJ.91.034702

Speciation of cesium in tree tissues and its implication for uptake and translocation of radiocesium in tree bodies

Tanaka, Kazuya; Kanasashi, Tsutomu*; Takenaka, Chisato*; Takahashi, Yoshio*

Science of the Total Environment, 755(Part 2), p.142598_1 - 142598_8, 2021/02

https://doi.org/10.1016/j.scitotenv.2020.142598

In this study, we investigated coordination structures of Cs in Cs-doped bark, sapwood, heartwood, needle, and branch samples of trees collected in Fukushima by extended X-ray absorption fine structure (EXAFS) spectroscopy. We examined four representative tree species in Fukushima, , , , and . EXAFS spectra suggested that Cs was adsorbed as an outer-sphere complex on all parts of the four species, with electrostatic binding to negatively charged functional groups in components of tree tissues. These results were supported by extraction experiments where most of the sorbed Cs was desorbed from all parts of each tree species using 1 M CHCOONH.

Structural characterization of Eu-HONTA complexes by IBIL and EXAFS analyses

Watanabe, So; Sano, Yuichi; Okada, Makoto*; Matsuura, Haruaki*; Hagura, Naoto*; Kada, Wataru*

Nuclear Instruments and Methods in Physics Research B, 477, p.60 - 65, 2020/08

https://doi.org/10.1016/j.nimb.2019.10.004

IBIL and EXAFS analyses were applied on strucutral analysis of Eu complex formed in adsorbent developed for extraction chromatography. Those analyses revealed slight structural difference between adsorbent and solvent systems.

Local structure study of the iron-based systems of BaFeAs and LiFeAs by X-ray PDF and XAFS analyses

Li, S.*; Toyoda, Masayuki*; Kobayashi, Yoshiaki*; Ito, Masayuki*; Ikeuchi, Kazuhiko*; Yoneda, Yasuhiro; Otani, Akira*; Matsumura, Daiju; Asano, Shun*; Mizuki, Junichiro*; et al.

Physica C, 555, p.45 - 53, 2018/12

https://doi.org/10.1016/j.physc.2018.10.003

-dependence of local distortions in BaFeAs and LiFeAs by X-ray PDF and XAFS methods. Although PDF data exhibit anomaly at the structure transition temperature, EXAFS data exhibit no anomaly. Data supporting the local orthorhombicity at 300 K in the tetragonal phase for BaFeAs. Arguments on the origins of the 4-fold symmetry breaking in the ground average structure of the tetragonal phase.

Photo-oxidative doping in -conjugated zig-zag chain of carbon atoms with sulfur-functional group

Ikeura, Hiromi*; Sekiguchi, Tetsuhiro

Applied Physics Letters, 111(23), p.231605_1 - 231605_4, 2017/12

https://doi.org/10.1063/1.4990570

Photo-oxidative doping processes were studied for the trans-polyacetylene (PA) backbone with the -SCH side group as a chemically representative of the S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH with atmospheric O forms selectively oxidized products such as -S(O)CH and -SO bound to the (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CHS -PA has been estimated. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

Microscopic analyses of complexes formed in adsorbent for Mo and Zr separation chromatography

Abe, Ryoji*; Nagoshi, Kohei*; Arai, Tsuyoshi*; Watanabe, So; Sano, Yuichi; Matsuura, Haruaki*; Takagi, Hideaki*; Shimizu, Nobutaka*; Koka, Masashi*; Sato, Takahiro*

Nuclear Instruments and Methods in Physics Research B, 404, p.173 - 178, 2017/08

https://doi.org/10.1016/j.nimb.2017.02.082

Micro-orientation control of silicon polymer thin films on graphite surfaces modified by heteroatom doping

Shimoyama, Iwao; Baba, Yuji; Hirao, Norie*

Applied Surface Science, 405, p.255 - 266, 2017/05

https://doi.org/10.1016/j.apsusc.2017.01.297

NEXAFS spectroscopy is applied to study orientation structures of polydimethylsilane (PDMS) films deposited on heteroatom-doped graphite substrates prepared by ion beam doping. The Si -edge NEXAFS spectra of PDMS show opposite trends of polarization dependence for non irradiated and N-irradiated substrates, and show no polarization dependence for an Ar-irradiated substrate. Based on a theoretical interpretation of the NEXAFS spectra via first-principles calculations, we clarify that PDMS films have lying, standing, and random orientations on the non irradiated, N-irradiated, and Ar-irradiated substrates, respectively. Furthermore, photoemission electron microscopy indicates that the orientation of a PDMS film can be controlled with microstructures on the order of m by separating irradiated and non irradiated areas on the graphite surface. These results suggest that surface modification of graphite using ion beam doping is useful for micro-orientation control of organic thin films.

Radiation enhanced precipitation of solute atoms in AlCu binary alloys; Energetic ion irradiation experiment and computer simulation

Mayumi, Ren*; Semboshi, Satoshi*; Okamoto, Yoshihiro; Saito, Yuichi*; Yoshiie, Toshimasa*; Iwase, Akihiro*

Transactions of the Materials Research Society of Japan, 42(1), p.9 - 14, 2017/02

https://doi.org/10.14723/tmrsj.42.9

AlCu binary alloys were irradiated with 16 MeV Au, 4.5 MeV Ni or 4.5 MeV Al ions at room temperature. Changes in surface hardness and the local atomic structure around Cu atoms were examined by using the Vickers hardness measurement and the EXAFS measurements, respectively. Some specimens were aged at 453 K and Vickers hardness was measured. The computer simulation was also performed by using the rate equation method. The hardness of irradiated specimens increased much faster than that of the aged specimens and it became larger than the maximum value of the hardness for the aged specimens. The comparison of the experimental EXAFS result with that of FEFF simulation suggests that the ion irradiation produced small Cu precipitates in the specimens. The computer simulation visualized the growth process of Cu precipitates during the irradiation, and the result qualitatively corresponds to the experimental result.

Electronic structures at phosphorus sites doped in graphite; Spectral analysis of P K-edge NEXAFS with DVX calculations

Shimoyama, Iwao; Baba, Yuji

DV-X Kenkyu Kyokai Kaiho, 28(1&2), p.62 - 69, 2016/03

We studied electronic structures at phosphorus sites doped in graphite to clarify the dopant effect on catalytic activity of P-doped graphite using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. A sample prepared by high-temperature doping at 700 C showed graphite-like clear polarization dependence of P K-edge NEXAFS spectra indicating planar structure at phosphorus sites. We calculated electronic structures at phosphorus sites in carbon model clusters using the DV-X method and compare them with NEXAFS. The electronic structure at planar phosphorus site with three carbon coordination reproduced the NEXAFS spectra. On the other hand, samples prepared by room-temperature doping and post annealing at 800 C showed deterioration of polarization dependence of NEXAFS. We clarified that an electronic structure of a curved carbon model cluster with a pentagon reproduced change of polarization dependence and spectral shape of NEXAFS. This means local structures at phosphorus sites can be controlled by substrate temperatures during ion dopings.