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Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Suzuki, Hideya*
Journal of Nuclear Science and Technology, 61(7), p.883 - 893, 2024/07
Times Cited Count:0 Percentile:0.01(Nuclear Science & Technology)The mutual separation of Am and Cm is conducted using an alkyl-diamide amine (ADAAM) extractant. ADAAM exhibits extremely high separation factor with respect to Am and Cm separation (5.9) in a nitric acid--dodecane system. The batch-wise multistage extractions are performed using a system containing 0.2 M ADAAM and 1.5 M nitric acid. In this multistage extraction, an organic solvent give 96.5% and 1.06% yields of Am and Cm. After the mutual separation of Am and Cm, an additional extraction step is included to reduce the volumes of these aqueous and organic phases. Taking these steps, Am and Cm can be recovered in just two or three stages in the aqueous phases.
Matsumura, Takeshi*; Tabata, Chihiro; Kaneko, Koji; Nakao, Hironori*; Kakihana, Masashi*; Hedo, Masato*; Nakama, Takao*; Onuki, Yoshichika*
Physical Review B, 109(17), p.174437_1 - 174437_8, 2024/05
Kinoshita, Ryoma; Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*
Hydrometallurgy, 222, p.106159_1 - 106159_12, 2023/10
Solvent extraction is conducted using a total of 20 metals revealing high stability constants with Cl and hexahexyl-nitrilotriacetamide (NTAamide(C6)) extractant. The metals used here may behave as anions at high Cl concentrations, and NTAamide(C6), which contains a tertiary N atom, is protonated under acidic conditions. Most of the metal ions in this study display higher distribution ratios (D(M)) from HCl than those from HNO, and exhibit 1:1 stoichiometries with NTAamide. Following the experimental results, the association constants and distribution coefficients of the group 12 elements are calculated via ion-pair extraction modeling using density functional theory calculations, and the simulations of D yield calculated values with the same trend as that of the measured values.
Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Kinoshita, Ryoma; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*
Analytical Sciences, 39(9), p.1575 - 1583, 2023/09
Times Cited Count:0 Percentile:0.00(Chemistry, Analytical)Extraction of Rh from HCl can be performed by NTAamide(C6) (hexahexyl-nitrilotriacetamide) and other related compounds into n-dodecane. We use ion-pair extraction of anionic species of Rh-chloride and protonated extractant. Rh behave as anion in hydrochloric acid and the tertiary nitrogen atom in extractant may be protonated to produce the quaternary amine in acidic condition. From the present work, the maximum distribution ratio of Rh(III) is 16. The D(Rh) values are changeable during preparation of the aqueous solutions because different Rh-Cl-HO complexes are formed in HCl media and show the slow exchange rate between Cl and HO. Using the UV spectrum, Rh-chloride solution having the peak of spectrum at 504 nm can be extracted effectively, where RhCl(HO) and RhCl(HO) exist mainly from DFT calculation. Stoichiometry of one-one complex of Rh and NTAamide is obtained from slope analysis, and 85 mM of concentrated Rh ion can be extracted.
Kido, Kentaro; Kaneko, Masashi
Journal of Computational Chemistry, 44(4), p.546 - 558, 2023/02
Times Cited Count:1 Percentile:12.61(Chemistry, Multidisciplinary)Sasaki, Yuji; Nakase, Masahiko*; Kaneko, Masashi; Kobayashi, Toru; Takeshita, Kenji*; Matsumiya, Masahiko*
Analytical Sciences, 5 Pages, 2023/00
Times Cited Count:0 Percentile:0.00(Chemistry, Analytical)We conducted three field researches on Ru-extraction, XANES, and DFT-calculation. The order of the distribution ratio, D(Ru), from acid, HCl HSO HNO HClO, by MIDOA is studied by XANES spectra, which indicates the valency change of Ru in HCl media and supports the ion pairing extraction of anionic Ru ion and cationic MIDOA. The same extractant trend, NTAamide MIDOA IDOA, due to D values as the energy gap of HOMO and LUMO could be found by DFT calculation, which suggests that the reaction heat has a positive correlation with extractability for extractant.
Matsumura, Takeshi*; Tsukakoshi, Mitsuru*; Ueda, Yoshihisa*; Higa, Nonoka*; Nakao, Akiko*; Kaneko, Koji; Kakihana, Masashi*; Hedo, Masato*; Nakama, Takao*; Onuki, Yoshichika*
Journal of the Physical Society of Japan, 91(7), p.073703_1 - 073703_5, 2022/07
Times Cited Count:6 Percentile:74.91(Physics, Multidisciplinary)Mizumachi, Takumi*; Sato, Minami*; Kaneko, Masashi; Takeyama, Tomoyuki*; Tsushima, Satoru*; Takao, Koichiro*
Inorganic Chemistry, 61(16), p.6175 - 6181, 2022/04
Times Cited Count:4 Percentile:58.46(Chemistry, Inorganic & Nuclear)Based on unique 5-fold equatorial coordination of UO, water-compatible pentadentate planar ligands, Hsaldian and its derivatives, were designed as strong and selective capture of UO in seawater. In the simulated seawater condition (0.5 M NaCl + 2.3 mM HCO/CO, pH 8), saldian shows the strongest complexation with UO to form UO(saldian) (log = 28.05 0.07), which is more than 10 order of magnitude greater than amidoxime-based or -inspired ligand systems most commonly employed for U capture from seawater. Good selectivity for UO from other metal ions coexisting in seawater was also demonstrated.
Nomizu, Daiki; Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Katsuta, Shoichi*
Journal of Radioanalytical and Nuclear Chemistry, 331(3), p.1483 - 1493, 2022/03
Times Cited Count:4 Percentile:74.52(Chemistry, Analytical)We studied the successive formation of water soluble DGA (diglycolamide) and DOODA (dioxaoctanediamide) for the mutual separation of Ln in this extraction system. TODGA (tetraoctyl-diglycolamide) and DOODA(C8) (tetraoctyl-dioxaoctanediamide) have the opposite trend to extract light and heavy Ln through Ln-patterns. Metal-complexes of two folding Ln ions with water-soluble DOODA and three folding with DGA are found and their observed formation constants are calculated. The suitable separation condition (aqueous phase: 30 mM DOODA(C2) in 1 M nitric acid, organic phase: 0.1 M TODGA in n-dodecane) of multi-stage extraction (10 10) is conducted. From the present work, it is clear that La, Pr and Nd are mainly present in aqueous phase, instead Sm-Dy exist in the organic phase.
Kaneko, Masashi
Nihon Genshiryoku Gakkai-Shi ATOMO, 64(1), p.30 - 34, 2022/01
Partitioning of minor actinides from rare earths is one of the most important techniques to develop group separation of high-level radioactive liquid waste. In this issue, the results of prediction of separation performance between minor actinides and rare earths observed in solvent extraction and the separation mechanism by means of using density functional theory are explained.
Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Matsumiya, Masahiko*; Nakase, Masahiko*; Takeshita, Kenji*
Separation Science and Technology, 57(16), p.2543 - 2553, 2022/00
Times Cited Count:3 Percentile:38.23(Chemistry, Multidisciplinary)The mutual separation of actinides (An) from lanthanides (Ln) using the masking agent of DTPA (diethylenetriamine-pentaacetic acid) or DTBA (diethylenetriamine-triacetic acid-bis(diethylacetamide)) in the aqueous phase through DGA extraction, referring TALSPEAK method, is focused. We investigate to obtain the same separation performance using commercially available DTPA on that using DTBA. In this work, we select lactic acid (LA) of pH buffer from 10 organic acids and ethylenediamine (ED) for the pH adjustment. Almost the same D and SF values are obtained among the conditions: TODGA-DTPA-LA-NaOH, TODGA-DTPA-LA-ED, and TODGA-DTBA-LA. The experimental results using batchwise multi-stage extractions show the average yields of Ln (La to Gd) and Am to be 3.73 and 98.1% in the aqueous phase using DGA-DTPA-LA-ED, to be 3.1 and 97.0% using DGA-DTPA-LA-NaOH, and to be 1.61 and 98.7% using DGA-DTBA-LA.
Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Nakase, Masahiko*; Takeshita, Kenji*
Solvent Extraction and Ion Exchange, 40(6), p.620 - 640, 2022/00
Times Cited Count:1 Percentile:12.61(Chemistry, Multidisciplinary)Owing to the chemical behavior of trivalent lanthanide and actinide ions with similar ionic radii, realizing this separation is still challenging. All lanthanides, Am, and Cm can be extracted using diglycolamide (DGA), and relatively high An/Ln separation efficiencies have been obtained using diethylenetriamine-triacetic-bisamide (DTBA). To improve the previous results as well as the separation conditions, we used organic acids for pH adjustment. The advantages of this modification included low HNO, DTBA concentrations and pH stability owing to the addition of lactic acid. Under these modified conditions, the recovery rates observed were as follows: 97.1% for Nd with the co-existence of 1.59% Am in organic phase, and 98.4% for Am with the co-existence of 2.95% Nd in aqueous phase.
Kaneko, Masashi; Sasaki, Yuji; Wada, Eriko*; Nakase, Masahiko*; Takeshita, Kenji*
Chemistry Letters, 50(10), p.1765 - 1769, 2021/10
Times Cited Count:0 Percentile:0.00(Chemistry, Multidisciplinary)Density functional theory calculation is applied to predict the stability constants for Eu and Am complexes in aqueous solution for molecular modelling of novel separation agents for minor actinides over lanthanides. Logarithm of experimental stability constants correlates with calculated complex formation enthalpies with high reproducibility (R 0.98). Prediction of stability constants of novel chelates is demonstrated and indicates a potential availability of the derivatives of diethylenetriaminepentaacetic acid type chelate in acidic condition and enhancement of Am selectivity over Eu.
Kaneko, Masashi; Nakashima, Satoru*
Inorganic Chemistry, 60(17), p.12740 - 12752, 2021/09
Times Cited Count:3 Percentile:30.69(Chemistry, Inorganic & Nuclear)In the present study, density functional theory (DFT) calculation was applied to Vaska's complexes of formula -[IrCl(CO)(PPh)], and their oxidative adducts with small molecules (YZ) including H, i.e., -[IrCl(YZ)(CO))(PPh)], to successfully correlate the electronic states of the complexes with the corresponding Ir Mssbauer spectroscopic parameters. After confirming the reproducibility of the DFT methods for elucidating the equilibrium structures and Ir Mssbauer isomer shifts of the octahedral Ir complexes, the isomer shifts and quadrupole splitting values of Vaska's complexes and their oxidative adducts were calculated. A bond critical point analysis revealed that the tendency in the isomer shifts was correlated with the strength of the covalent interaction in the coordination bonds. In an electric field gradient (EFG) analysis of the oxidative adducts, the sign of the principal axis was found to be positive for the complex with YZ = Cl and negative for the complex with YZ = H. This reversal of the sign of the EFG principal axis was caused by the difference in the electron density distribution for the coordination bonds between Ir and YZ, according to a density of states analysis.
Fukasawa, Yuto*; Kaneko, Masashi; Nakashima, Satoru*
Journal of Radioanalytical and Nuclear Chemistry, 329(1), p.77 - 84, 2021/07
Times Cited Count:1 Percentile:15.09(Chemistry, Analytical)Density functional theory calculations were applied to understand the selectivity between Am and Eu ions with the crown ethers type ligands. 18C6 is predicted to form the most stable complex with Eu and show the higher stability for Am over Eu, being consistent with previously reported Am/Eu selectivity. We modeled N- and S-donor complexes by using framework of 18C6 complex and analyzed the complexation Gibbs energies, indicating that 18C6 with N-donor atoms is suitable for both complexation and higher Am stability over Eu due to the stronger covalent interaction.
Kaneko, Masashi; Sasaki, Yuji; Matsumiya, Masahiko*; Nakase, Masahiko*; Takeshita, Kenji*
Journal of Nuclear Science and Technology, 58(5), p.515 - 526, 2021/05
Times Cited Count:3 Percentile:34.17(Nuclear Science & Technology)Density-functional theory calculations were applied to molecular structure and complex formation reaction modelings of metal ion complexes with diethylenetriaminepentaacetic acid (DTPA) and its bisamide (DTPABA) chelates to understand the metal ions selectivity between Am and Eu. The calculated complexes with DTPA and DTPABA chelates reproduced the coordination geometries of experimental crystal structures. Calculated Gibbs free energies of the complex formation reactions indicated that Am ion forms higher stable complexes with both chelates than Eu ion, being consistent with the experimental results. The higher Am selectivity over Eu was suggested to originate in the larger bond overlap between Am 5f-orbital and N 2s, 2p-orbital. This mean that the covalent contribution between metal ion and donor atoms differentiates the complex formation stabilities, leading to the Am/Eu selectivity. We expect that this study contributes to systematize the origin of metal ions selectivity and to accelerate novel ligands exploration.
Schnaars, K.; Kaneko, Masashi; Fujisawa, Kiyoshi*
Inorganic Chemistry, 60(4), p.2477 - 2491, 2021/02
Times Cited Count:6 Percentile:56.62(Chemistry, Inorganic & Nuclear)To reduce high-level radiotoxic waste generated by nuclear power plants, highly selective separation agents for minor actinides are mandatory. The mixed N,O-donor ligand -tetrakis[(6-carboxypyridin-2-yl)methyl]ethylenediamine (HTPAEN) has shown good performance as a masking agent in Am/Eu separation studies. In this work, we examine whether a decrease in O-donor basicity can promote the M-N interactions. Therefore, we replace the deprotonated "charged" carboxylic acid groups of TPAEN by neutral amide groups and introduce -tetrakis[(6--diethylcarbamoylpyridin-2-yl)methyl]ethylenediamine (TPAMEN) as a new ligand. TPAMEN was crystallized with Eu(OTf) and Eu(NO) 6HO to form positively charged 1:1 [Eu(TPAMEN)] complexes in the solid state. Alterations in the M-O/N bond distances are compared to [Eu(TPAEN)] and investigated by DFT calculations to expose the differences in charge/energy density distributions at europium(III) and the donor functionalities of the TPAEN and TPAMEN. On the basis of estimations of the bond orders, atomic charges spin populations, and density of states in the Eu and potential Am and Cm complexes, the specific contributions of the donor-metal interaction are analyzed. The prediction of complex formation energy differences for the [M(TPAEN)] and [M(TPAMEN)] (M = Eu, Am) complexes provide an outlook on the potential performance of TPAMEN in Am/Eu separation.
Kaneko, Koji; Kakihana, Masashi*; Hedo, Masato*; Nakama, Takao*; Onuki, Yoshichika*
Hamon, 30(3), p.160 - 165, 2020/08
no abstracts in English
Kato, Akane*; Kaneko, Masashi; Nakashima, Satoru*
RSC Advances (Internet), 10(41), p.24434 - 24443, 2020/06
Times Cited Count:6 Percentile:30.44(Chemistry, Multidisciplinary)Complexation reactions of ruthenium-nitrosyl complexes in HNO solution were investigated by density functional theory (DFT) calculations in order to predict the stability of Ru species in high-level radioactive liquid waste (HLLW) solution. Equilibrium structure of [Ru(NO)(NO)(HO)] obtained by DFT calculations reproduced the experimental Ru-ligands bond lengths and IR frequencies reported previously. Comparison of the Gibbs energies among the geometrical isomers revealed that the complexation reactions of the ruthenium-nitrosyl complexes with NO proceed via the NO coordination to the equatorial plane toward the Ru-NO axis. We also estimated Gibbs energy differences on the stepwise complexation reactions to succeed in reproducing the fraction of Ru-NO species in 6 M HNO solution, such as in HLLW, by considering the association energy between the Ru-NO species and the substituting ligands. Electron density analyses of the complexes indicated that the strength of the Ru-ligands coordination bonds depends on the stability of the Ru species and the Ru complex without NO at the axial position is more stable than that wit NO, which might attribute to the difference in the trans influence between HO and NO. Finally, we demonstrated the complexation kinetics in the reactions . The present study is expected to enable us to model the precise complexation reactions of platinum-group metals in HNO solution.
Kaneko, Koji; Kakihana, Masashi*; Hedo, Masato*; Nakama, Takao*; Onuki, Yoshichika*
Kotai Butsuri, 54(12), p.757 - 766, 2019/12
no abstracts in English