Organization of malonamides from the interface to the organic bulk phase

Micheau, C.; Ueda, Yuki; Motokawa, Ryuhei; Akutsu, Kazuhiro*; Yamada, Norifumi*; Yamada, Masako*; Moussaoui, S. A.*; Makombe, E.*; Meyer, D.*; Berthon, L.*; et al.

Journal of Molecular Liquids, 401, p.124372_1 - 124372_12, 2024/05

https://doi.org/10.1016/j.molliq.2024.124372

Supramolecular organization of extractant molecules impacts metal ions separation behavior. Probing bulk and interfacial structures of the relevant systems is expected to provide key insights into the metal ion selectivity and kinetic aspects. The supramolecular features of two solvent extraction systems based on malonamide extractants THMA in toluene and DBMA in n-heptane were studied using small-angle X-ray scattering for the organic bulk phases, as well as interfacial tension and neutron reflectivity measurements for the interfaces. In the bulk solution, THMA forms dimeric/trimeric associates but no aggregates in toluene, while DBMA forms large aggregates in n-heptane. On the other hand, THMA accumulates in a diffuse layer at the interface at high THMA concentration, whereas DBMA forms a compact but thinner layer. After Pd(II) extraction, the thickness of interfacial layers decreases in the case of THMA, and totally vanishes in the case of DBMA. Based on these new structural information, two mechanisms are proposed for Pd(II) and Nd(III) extraction with malonamides. In toluene, THMA associates slightly accumulate in the vicinity of the interface, then coordinate Pd(II) and diffuse into the organic bulk phase. In n-heptane, DBMA aggregates adsorb at the interface then pick up Nd(III) cations in their polar cores and finally diffuse into the bulk.

Development of genetic and electrochemical diagnosis and inhibition technologies for invisible corrosion caused by microorganisms (Contract research); FY2022 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; National Institute for Materials Science*

JAEA-Review 2023-031, 101 Pages, 2024/01

JAEA-Review-2023-031.pdf:24.47MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2022. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station (1F), Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2020, this report summarizes the research results of the "Development of genetic and electrochemical diagnosis and inhibition technologies for invisible corrosion caused by microorganisms" conducted from FY2020 to FY2022. The present study aims to develop innovative diagnostic techniques such as accelerated test specimens and on-site genetic testing for microbially induced and accelerated corrosion of metallic materials (microbially influenced corrosion, MIC), and to identify the conditions that promote MIC at 1F for proposing methods to prevent MIC through water quality and environmental control.

Extraction of Rh(III) from hydrochloric acid by protonated NTAamide(C6) and analogous compounds and understanding of extraction equilibria by using UV spectroscopy and DFT calculations

Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Kinoshita, Ryoma; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*

Analytical Sciences, 39(9), p.1575 - 1583, 2023/09

https://doi.org/10.1007/s44211-023-00376-8

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.

Extraction of Se(iv) and Se(vi) from aqueous HCl solution by using a diamide-containing tertiary amine

Narita, Hirokazu*; Maeda, Motoki*; Tokoro, Chiharu*; Suzuki, Tomoya*; Tanaka, Mikiya*; Shiwaku, Hideaki; Yaita, Tsuyoshi

RSC Advances (Internet), 13(25), p.17001 - 17007, 2023/06

https://doi.org/10.1039/D3RA01341C

no abstracts in English

Development of genetic and electrochemical diagnosis and inhibition technologies for invisible corrosion caused by microorganisms (Contract Research); FY2021 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; National Institute for Materials Science*

JAEA-Review 2022-045, 82 Pages, 2023/01

JAEA-Review-2022-045.pdf:4.6MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2021. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station (1F), Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2020, this report summarizes the research results of the "Development of genetic and electrochemical diagnosis and inhibition technologies for invisible corrosion caused by microorganisms" conducted in FY2021. The present study aims to develop innovative diagnostic techniques such as accelerated test specimens and on-site genetic testing for microbially induced and accelerated corrosion of metallic materials (microbially influenced corrosion, MIC), and to identify the conditions that promote MIC at 1F for proposing methods to prevent MIC through water quality and environmental control. We also aim to develop a research base based on materials, microorganisms, and electrochemistry, to develop technologies that can be used by engineers in the field, …

Acid dissociation constant of bis(2-ethylhexyl) hydrogen phosphate impregnated in a polymer layer coated on silica microparticles

Miyagawa, Akihisa*; Takeuchi, Masayuki; Arai, Tsuyoshi*; Watanabe, So; Sano, Yuichi; Nakatani, Kiyoharu*

Bulletin of the Chemical Society of Japan, 95(4), p.566 - 568, 2022/04

https://doi.org/10.1246/bcsj.20220011

We demonstrate that pKa of extractant impregnated in a polymer phase varies with the cross-linking degree and the coexistence of other extractants, which induces a change in the hydrophobicity of the polymer phase. The results presented herein will be beneficial for the development of novel solid-extraction adsorbents.

Development of genetic and electrochemical diagnosis and inhibition technologies for invisible corrosion caused by microorganisms (Contract research); FY2020 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; National Institute for Materials Science*

JAEA-Review 2021-059, 71 Pages, 2022/02

JAEA-Review-2021-059.pdf:4.25MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2020. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station (1F), Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2020, this report summarizes the research results of the "Development of genetic and electrochemical diagnosis and inhibition technologies for invisible corrosion caused by microorganisms" conducted in FY2020. The present study aims to develop innovative diagnostic techniques such as accelerated test specimens and on-site genetic testing for microbially induced and accelerated corrosion of metallic materials (microbially influenced corrosion, MIC), and to identify the conditions that promote MIC at 1F for proposing methods to prevent MIC through water quality and environmental control.

Additive-free hydrothermal leaching method with low environmental burden for screening of strontium in soil

Kato, Takuma*; Nagaoka, Mika; Guo, H.*; Fujita, Hiroki; Aida, Taku*; Smith, R. L. Jr.*

Environmental Science and Pollution Research, 28(39), p.55725 - 55735, 2021/10

https://doi.org/10.1007/s11356-021-14916-0

In this work, hydrothermal leaching was applied to simulated soils (clay minerals vermiculite, montmorillonite, kaolinite) and actual soils (Terunuma, Japan) to generate organic acids with the objective to develop an additive-free screening method for determination of Sr in soil. Stable strontium (SrCl) was adsorbed onto soils for study and ten organic acids were evaluated for leaching Sr from simulated soils under hydrothermal conditions (120 to 200C) at concentrations up to 0.3 M. For strontium-adsorbed vermiculite (Sr-V), 0.1 M citric acid was found to be effective for leaching Sr at 150C and 1 h treatment time. Based on these results, the formation of organic acids from organic matter in Terunuma soil was studied. Hydrothermal treatment of Terunuma soil produced a maximum amount of organic acids at 200C and 0.5 h reaction time. To confirm the possibility for leaching of Sr from Terunuma soil, strontium-adsorbed Terunuma soil (Sr-S) was studied. For Sr-S, hydrothermal treatment at 200C for 0.5 h reaction time allowed 40% of the Sr to be leached at room temperature, thus demonstrating an additive-free method for screening of Sr in soil. The additive-free hydrothermal leaching method avoids calcination of solids in the first step of chemical analysis and has application to both routine monitoring of metals in soils and to emergency situations.

Fundamental study on multistage extraction using TDdDGA for separation of lanthanides present in Nd magnets

Sasaki, Yuji; Morita, Keisuke; Matsumiya, Masahiko*; Ono, Ryoma*; Shiroishi, Hidenobu*

JOM, 73(4), p.1037 - 1043, 2021/04

https://doi.org/10.1007/s11837-021-04586-1

The separation of Dy from Nd is studied from the viewpoint of recycling Dy from Nd magnets. Both metals are lanthanide elements, which means their mutual separation is difficult because of their similar chemical behaviors. All lanthanide elements can be extracted easily by using tetradodecyl-diglycolamide (TDdDGA) extractants, and it has a relatively high separation factor (SF) between Dy and Nd (SF over 10). In the present study, by performing eight extraction steps with the organic phase (0.1M TDdDGA in dodecane), ten steps with an aqueous phase (0.7 M HNO with metals), and six steps with another aqueous phase (0.7 M HNO without metals), approximately 99% Dy was recovered into the organic phase with 1% co-extraction of Nd.

Solvent extraction of cesium using DtBuDB18C6 into various organic solvents

Sasaki, Yuji; Morita, Keisuke; Kitatsuji, Yoshihiro; Ito, Keisuke*; Yoshizuka, Kazuharu*

Solvent Extraction Research and Development, Japan, 28(2), p.121 - 131, 2021/00

https://doi.org/10.15261/serdj.28.121

High concentration of Cs is present in high-level radioactive waste. It is well-known that Cs is an alkali element and difficult to extract completely into an organic phase. Crown ether compounds are widely available for Cs extractants; DtBuDB18C6 (di--butyl-dibenzo-18crown6), was used in this study. Organic solvents used for the industrial applications, such as -dodecane and 1-octanol, have low solubility concerning the compound; other solvents were employed and tested. In this study, ketone-, ether-, and ester-type solvents showed high solubility for DtBuDB18C6 and DtBuDB18C6, when dissolved in ketones and alcohols, exhibited relatively high Cs distribution ratios ((Cs)), closely to 10.