Selective adsorption of Pd(II) over Ag(I) in nitric acid solutions using nitrogen-donor-type adsorbents

Suzuki, Tomoya*; Otsubo, Ukyo*; Ogata, Takeshi*; Shiwaku, Hideaki; Kobayashi, Toru; Yaita, Tsuyoshi; Matsuoka, Mitsuaki*; Murayama, Norihiro*; Narita, Hirokazu*

Separation and Purification Technology, 308, p.122943_1 - 122943_7, 2023/03

https://doi.org/10.1016/j.seppur.2022.122943

HNO leaching is used in recycling Pd metal from spent products that primarily contain Ag, and most Pd residues are separated from solutions containing Ag(I). However, a small amount of Pd(II) often remains in these Ag(I) solutions. Therefore, the separation of Pd(II) and Ag(I) in HNO solutions is essential to promote efficient Pd recycling. In this study, the separation of Pd(II) and Ag(I) in HNO solutions was investigated using four N-donor-type adsorbents functionalized with amine (R-Amine), iminodiacetic acid (R-IDA), pyridine (R-Py), or bis-picolylamine (R-BPA). R-Amine, R-IDA, and R-Py selectively adsorbed Pd(II) over Ag(I), Cu(II), Ni(II), and Fe(III) from HNO solutions (0.3-7 M), but R-Amine exhibited a lower Pd adsorption efficiency. In contrast, 90% of Pd(II), Ag(I), and Cu(II) were adsorbed by R-BPA over the entire range of HNO concentrations. Structural analyses of the adsorbed metal ions using Fourier transform infrared spectroscopy and extended X-ray absorption fine structure spectroscopy revealed the separation mechanisms of the N-donor-type adsorbents. Pd(II) adsorption on R-IDA, R-Py, and R-BPA occurred via Pd(II) coordination of the functional groups (iminodiacetic acid, pyridine, and bis-picolylamine, respectively), whereas that on R-Amine occurred via anion exchange of NO with [Pd(NO)]. The coordinative adsorption mechanisms resulted in the higher Pd(II) adsorption behaviors of R-IDA, R-Py, and R-BPA. HCl (5.0 M) and thiourea (0.1 M) eluents desorbed 83% of Pd(II) from R-IDA and 95% from R-Py, respectively. R-Py was the most effective Pd(II) adsorbent based on adsorption selectivity and desorption efficiency.

Hydrogen absorption and diffusion behaviors in cube-shaped palladium nanoparticles revealed by ambient-pressure X-ray photoelectron spectroscopy

Tang, J.*; Seo, O.*; Rivera Rocabado, D. S.*; Koitaya, Takanori*; Yamamoto, Susumu*; Namba, Yusuke*; Song, C.*; Kim, J.*; Yoshigoe, Akitaka; Koyama, Michihisa*; et al.

Applied Surface Science, 587, p.152797_1 - 152797_8, 2022/06

https://doi.org/10.1016/j.apsusc.2022.152797

The hydrogen absorption and diffusion mechanisms on cube-shaped Pd nanoparticles (NPs) which are important hydrogen-storage materials were studied using X-ray photoelectron spectroscopy and DFT calculations. In the surface region, hydrogen absorption showed almost similar behavior regardless of the NPs size. It was found that the octahedral sites are more favorable than the tetrahedral sites for hydrogen occupation. We also clarified that the hydrogen atoms absorbing on the smaller-sized Pd NPs diffuse to the subsurface more actively because of the weakened Pd-H bond by the surface disordering, which plays an important role in hydrogen adsorption at a low H pressure.

Optimizing TiO through water-soluble Ti complexes as raw material for controlling particle size and distribution of synthesized BaTiO nanocubes

Nakashima, Koichi*; Hironaka, Kota*; Ouchi, Kazuma*; Ajioka, Mao*; Kobayashi, Yoshio*; Yoneda, Yasuhiro; Yin, S.*; Kakihana, Masato*; Sekino, Toru*

ACS Omega (Internet), 6(48), p.32517 - 32527, 2021/12

https://doi.org/10.1021/acsomega.1c04013

The BaTiO nanoparticles synthesized by the hydrothermal method is examined by synchrotron X-ray and TEM observation. It was found that the particle size of synthesized BaTiO depends on the particle size of the raw material of TiO. Succeeded in synthesizing 100 nm size BaTiO nanocrystals showing uniform particle size distribution using TiO nanoparticles with optimized particle size. The obtained BaTiO nanocrystal is a tetragonal system of ferroelectric phase. A three-dimensional structure of BaTiO nanoparticles could be obtained by the electron beam tomography.

Study on the radioactivity evaluation method of biological shielding concrete of JPDR for near surface disposal

Kochiyama, Mami; Okada, Shota; Sakai, Akihiro

JAEA-Technology 2021-010, 61 Pages, 2021/07

JAEA-Technology-2021-010.pdf:3.56MB
JAEA-Technology-2021-010(errata).pdf:0.75MB

It is necessary to evaluate the radioactivity inventory in wastes in order to dispose of radioactive wastes generated from dismantling nuclear reactor in the shallow ground. In this report, we examined radioactivity evaluation method for near surface disposal about biological shield concrete near the core generated from the dismantling of JPDR. We calculated radioactive concentration of the target biological concrete using the DORT code and the ORIGEN-S code, and we estimated radioactivity concentration Di (Bq/t). For DORT calculation, the cross-section library created from the MATXSLIB-J40 file from JENDL-4.0 was used, and for ORIGEN-S, the attached library of SCALE6.0 was used. As a result of comparing the calculation results of the radioactivity concentration with the past measured values in the radial direction and the vertical direction, we found that the trends were generally the same. We calculated radioactive concentration of the target biological concrete Di (Bq/t), and we compared with the estimated Ci (Bq/t) equivalent to the dose criteria of trench disposal calculated for 140 nuclides. As a result we inferred that the except for about 2% of target waste could be disposed of in the trench disposal facility. We also preselected important nuclides for trench disposal based on the ratios (Di/Ci) for each nuclide, H-3, C-14, Cl-36, Ca-41, Co-60, Sr-90, Eu-152 and Cs-137 were selected as important nuclides.

JAEA-TDB-RN in 2020; Update of JAEA's thermodynamic database for solubility and speciation of radionuclides for performance assessment of geological disposal of high-level and TRU wastes

Kitamura, Akira

JAEA-Data/Code 2020-020, 164 Pages, 2021/03

JAEA-Data-Code-2020-020.pdf:3.11MB
JAEA-Data-Code-2020-020-appendix(DVD-ROM).zip:0.56MB

Part of JAEA's Thermodynamic Database (JAEA-TDB) for solubility and speciation of radionuclides (JAEA-TDB-RN) for performance assessment of geological disposal of high-level radioactive and TRU wastes has been updated with subsuming the database for geochemical calculations (JAEA-TDB-GC). This report has focused to update JAEA-TDB-RN after selecting change in standard Gibbs free energy of formation (), change in standard enthalpy change of formation (), standard molar entropy () and, heat capacity (), change in standard Gibbs free energy of reaction (), change in standard enthalpy change of reaction () and standard entropy change of reaction () as well as logarithm of equilibrium constant (log) at standard state. The extent of selection of these thermodynamic data enables to evaluate solubility and speciation of radionuclides at temperatures other than 298.15 K. Furthermore, the latest thermodynamic data for iron which have been critically reviewed, selected and compiled by the Nuclear Energy Agency within Organisation for Economic Co-operation and Development (OECD/NEA) have been accepted. Most of previously selected log have been refined to confirm internal consistency with JAEA-TDB-GC. Text files of the updated JAEA-TDB have been provided for geochemical calculation programs of PHREEQC and Geochemist's Workbench.

Determination of atomistic deformation of tricalcium silicate paste with high-volume fly ash

Jee, H.*; Im, S.*; Kanematsu, Manabu*; Suzuki, Hiroshi; Morooka, Satoshi; Koyama, Taku*; Machida, Akihiko*; Bae, S.*

Journal of the American Ceramic Society, 103(12), p.7188 - 7201, 2020/12

https://doi.org/10.1111/jace.17404

-electron states of NpPdAl and the isostructural family; Heavy fermion superconductivity accompanied by valence crossover

Metoki, Naoto

Kotai Butsuri, 55(7), p.285 - 296, 2020/07

Electron states are the main theme of "solid-state physics", which is essential for microscopic understanding of multipoles and superconductivity, etc. Rare earths (4) and actinides (5) provide variety of interesting states realized with competing interactions between the increasing number of electrons. Since crystal field splitting of many-body electron system is smaller than the bandwidth, (1) high resolution experiments are needed, (2) essentially no clear spectrum with well defined peaks is expected in itinerant Ce and U compounds, and (3) Np and Pu is strictly regulated. Therefore, systematic research on magnetic excitations by neutron scattering experiments of localized compounds and rare earth iso-structural reference is useful. We describe the electron states of heavy electron compounds NpPdAl and actinide and rare earth based iso-structural family.

Analysis of atomistic structural deformation characteristics of calcium silicate hydrate in 53-year-old tricalcium silicate paste using atomic pair distribution function

Bae, S.*; Jee, H.*; Suh, H.*; Kanematsu, Manabu*; Shiro, Ayumi*; Machida, Akihiko*; Watanuki, Tetsu*; Shobu, Takahisa; Morooka, Satoshi; Geng, G.*; et al.

Construction and Building Materials, 237, p.117714_1 - 117714_10, 2020/03

https://doi.org/10.1016/j.conbuildmat.2019.117714

Pseudo-triplet 5 electron state in the heavy fermion superconductor NpPdAl

Metoki, Naoto; Aoki, Dai*; Griveau, J.-C.*; Otsuki, Junya*

Journal of the Physical Society of Japan, 89(2), p.024707_1 - 024707_6, 2020/02

https://doi.org/10.7566/JPSJ.89.024707

The pseudo triplet ground state in the heavy-fermion superconductor NpPdAl was concluded. The magnetic susceptibility can be reproduced by the singlet ground state with the main component of and the first excited doublet dominated by at ,K. The magnetization curve can be explained from the effective local hamiltonian for pseudo spin =1 with () equivalent to the quadrupole operator . The specific heat can be described with the Kondo model normalized to give the entropy R, corresponding to the pseudo triplet state. The derived Kondo temperature ,K comparable to the level splitting ,K indicates the contribution of the excited doublet to the possible multi-channel Kondo effect.

The Regional-scale 3D geological model in the Horonobe Underground Research Laboratory Project

Sakai, Toshihiro; Matsuoka, Toshiyuki

JAEA-Data/Code 2019-007, 29 Pages, 2019/09

JAEA-Data-Code-2019-007.pdf:53.07MB
JAEA-Data-Code-2019-007-appendix(CD-ROM).zip:340.04MB

Japan Atomic Energy Agency is performing the Horonobe Underground Research Laboratory Project, which includes a scientific study of the deep geological environment as a basis of research and development for the geological disposal of high level radioactive wastes, in order to establish comprehensive techniques for the investigation, analysis and assessment of the deep geological environment in the sedimentary rock. This report summarize numerical data of 3D geological model in regional-scale constructed by Maptek Vulcan.