Ga K-edge XANES study of Ga-exchanged zeolites at high temperatures under different atmospheres including vacuum, CO, and pressurized H

Huang, M.*; 金城 哲弥*; 安村 駿作*; 鳥屋尾 隆*; 松村 大樹; 齋藤 寛之*; 清水 研一*; 並木 則和*; 前野 禅*

Catalysis Science & Technology, 13(23), p.6832 - 6838, 2023/12

https://doi.org/10.1039/D3CY01250F

Ga-exchanged zeolites are promising catalysts for dehydrogenative alkane transformations. Reduced Ga species, such as Ga hydrides and Ga cations, are possible active sites for alkane dehydrogenation based on in situ spectroscopic studies. However, most of the reported studies were conducted at lower temperatures compared with those encountered in actual operating conditions. In this study, the in situ Ga K-edge XANES analysis of Ga-exchanged MFI zeolite was performed under actual operating temperatures and different atmospheres (H, He, CO, vacuum, and CH). The absorption edge appeared at similarly lower energy values than that of GaO in all atmospheres, whereas the main absorption peak intensity differed depending on the presence or absence of a hydride source in the gas phase. Higher intensities were observed under H and CH atmospheres than under CO and vacuum atmospheres.

Intruder configurations in Ne at the transition into the island of inversion; Detailed structure study of Ne

Wang, H.*; 安田 昌弘*; 近藤 洋介*; 中村 隆司*; Tostevin, J. A.*; 緒方 一介*; 大塚 孝治*; Poves, A.*; 清水 則孝*; 吉田 数貴; et al.

Physics Letters B, 843, p.138038_1 - 138038_9, 2023/08

https://doi.org/10.1016/j.physletb.2023.138038

Neからの1中性子除去反応を用いて、Neの詳細な線分光を行った。平行運動量分布の解析に基づき、Neの準位構造とスピンパリティを決定し、初めて負のパリティ状態を同定した。測定された断面積と運動量分布から、N=20とN=28のシェルギャップの消失の証拠となる有意なintruder p-wave強度が明らかになった。束縛状態については、弱いf-waveの可能性のある強度が観測された。いくつかの有効相互作用を用いた大規模殻模型計算では、実験的に観測された大きなp-wave強度と小さなf-wave強度は再現されず、Ne同位体に沿った反転の島への遷移の完全な理論的記述への挑戦が続いていることを示している。

Lanthanide and actinide ion complexes containing organic ligands investigated by surface-enhanced infrared absorption spectroscopy

平田 早紀子*; 日下 良二; 明地 省吾*; 為国 誠太*; 奥寺 洸介*; 浜田 昇賢*; 坂本 知優*; 本田 匠*; 松下 高輔*; 村松 悟*; et al.

Inorganic Chemistry, 62(1), p.474 - 486, 2023/01

https://doi.org/10.1021/acs.inorgchem.2c03618

A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of diglycolamide (DGA), Cyanex-272, and -tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands. Aqueous solutions of Ln (Eu, Gd, Tb) and An (Am) ions were loaded onto the gold surface to form ion complexes. The IR spectra of the ion complexes were obtained using FT-IR spectroscopy in the attenuated total reflection mode. In this study, we developed a new sample preparation method for SEIRA spectroscopy that enabled us to obtain the IR spectra of the complexes with a small amount of ion solution (5 L). This is a significant advantage for the IR measurement of radiotoxic Am complexes. In the IR spectra of DGA, the band attributed to C=O stretching vibrations at 1630 cm shifted to a lower wavenumber by 20 cm upon complexation with Ln and An ions. Moreover, the amount of the red-shift was inversely proportional to the extraction equilibrium constant reported in previous studies on solvent extraction. The coordination ability of DGA toward Ln and An ions could be assessed using the band position of the C=O band. The Cyanex-272- and TPEN-like ligands synthesized in this report also showed noticeable SEIRA signals for Ln and An complexes. This study indicates that SEIRA spectroscopy can be used for the structural investigation of ion complexes and provides a microscopic understanding of selective extraction of Ln and An.

Measurements of pressure drop and void fraction of air-water two-phase flow in a sphere-packed bed

山本 誠士郎*; 大平 直也*; 伊藤 大介*; 伊藤 啓*; 齊藤 泰司*; 今泉 悠也; 松場 賢一; 神山 健司

Proceedings of 12th Japan-Korea Symposium on Nuclear Thermal Hydraulics and Safety (NTHAS12) (Internet), 4 Pages, 2022/10

To develop a microscopic pressure drop prediction model based on detailed measurement data of gas liquid two-phase flow, the pressure drop was measured in the vertical upward gas-liquid two-phase flow formed in quasi-2D test section. The measurement results showed that the pressure drop in the quasi-2D test section was much smaller than that in the ordinal packed bed system, which suggests that the pressure drop mechanism in the quasi-2D test section could be different from that in the ordinal packed bed system due to differences in two-phase flow characteristics in the two systems. The void fraction distribution was also measured in the quasi-2D test section by the X-ray imaging technique, which revealed that there was a local distribution of the void fraction in the channel unit structure of the closest packed bed.

Chemical-pressure-induced point defects enable low thermal conductivity for MgSn and MgSi single crystals

齋藤 亘*; 林 慶*; Huang, Z.*; 杉本 和哉*; 大山 研司*; 八方 直久*; 原田 正英; 及川 健一; 稲村 泰弘; 林 好一*; et al.

ACS Applied Energy Materials (Internet), 4(5), p.5123 - 5131, 2021/05

https://doi.org/10.1021/acsaem.1c00670

The development of thermoelectric (TE) materials, which can directly convert waste heat into electricity, is vital to reduce the use of fossil fuels. MgSn and MgSi are promising TE materials because of their superior TE performance. In this study, for future improvement of the TE performance, point defect engineering was applied to the MgSn and MgSi single crystals (SCs) via boron (B) doping. Their crystal structures were analyzed via white neutron holography and SC X-ray diffraction. Moreover, nanostructures and TE properties of the B-doped MgSn and MgSi SCs were investigated. The B-doping increased the chemical pressure on the MgSn and MgSi SCs, leading to induce vacancy defects as a point defect. No apparent change was observed in electronic transport, but thermal transport was significantly prevented. This study demonstrates that the vacancy defects can be controlled by the chemical pressure, and can aid in achieving a high TE performance for the MgSn and MgSi SCs.

Remote handling technology for lead-bismuth spallation target system

大林 寛生; 吉元 秀光*; 北 智士*; 八巻 賢一*; Wan, T.*; 斎藤 滋; 佐々 敏信

JPS Conference Proceedings (Internet), 33, p.011048_1 - 011048_6, 2021/03

https://doi.org/10.7566/JPSCP.33.011048

J-PARC is performing R&Ds aimed at realizing an experimental facility applying a spallation target system in order to contribute to development of a lead-bismuth eutectic (LBE) cooled accelerator-driven system. The target system utilizes LBE as a spallation target material and as a primary coolant. The main purpose of the facility is to understand the compatibility of candidate structural materials under flowing high temperature LBE with proton / neutron irradiation, and reflect it in ADS design. 400 MeV - 250 kW pulsed proton beam strikes a target vessel containing irradiation samples during operation. Among the components installed to the target system, in particular the target vessel is exposed not only the corrosive LBE flow, but also highly irradiation by the target operation. It is essential to establish remote exchanging technology of the target vessel that can avoid exposing workers to high radiation environment. This paper describes recent status of a planning remote exchanging procedure of the target vessel and presents the result of a demonstrative experiment. The series of remote operation procedure was successfully demonstrated by experiments using a mock-up apparatus and developed remote jigs. As further issues, we planning several minor modification capable shortening of operation time.

Quasifree neutron knockout reaction reveals a small -Orbital component in the Borromean nucleus B

Yang, Z. H.*; 久保田 悠樹*; Corsi, A.*; 吉田 数貴; Sun, X.-X.*; Li, J. G.*; 木村 真明*; Michel, N.*; 緒方 一介*; Yuan, C. X.*; et al.

Physical Review Letters, 126(8), p.082501_1 - 082501_8, 2021/02

AA2020-0819.pdf:1.29MB

https://doi.org/10.1103/PhysRevLett.126.082501

ボロミアン核であり中性子ハロー構造が期待されるBに対する(,)反応実験を行った。断面積の運動量分布を分析することで、と軌道の分光学的因子を決定した。驚くべきことに、の分光学的因子は9(2)%と小さいことが明らかになった。この結果は、連続状態を含むdeformed relativistic Hartree-Bogoliubov理論によってよく説明された。本研究の結果によると、現在知られているハロー構造を持つとされる原子核の中でBはおよび軌道の成分が最も小さく、または軌道成分が支配的であることが必ずしもハロー構造の前提条件ではない可能性を示唆している。

Neutron diffraction study of hydrogen site occupancy in FeSi at 14.7 GPa and 800 K

森 悠一郎*; 鍵 裕之*; 柿澤 翔*; 小松 一生*; 市東 力*; 飯塚 理子*; 青木 勝敏*; 服部 高典; 佐野 亜沙美; 舟越 賢一*; et al.

Journal of Mineralogical and Petrological Sciences, 116(6), p.309 - 313, 2021/00

https://doi.org/10.2465/jmps.210825

地球のコアは、対応する圧力温度条件下で純鉄よりも密度が10%低いため、いくつかの軽元素を含んでいると考えられている。水素はその有力候補であるため、これまで主にFe-H系の相平衡関係や物性が調べられてきた。この研究では、14.7GPaおよび800Kでのhcp-FeSi水素化物の重水素のサイト占有率を調べるために、その場中性子回折実験によりFe-Si-Hシステムを具体的に調べた。リートベルト解析の結果、hcp-FeSi水素化物はhcp格子の格子間八面体サイトにのみ重水素(D)が0.24(2)占有することが判明した。Feに2.6wt%Siを添加する(つまりFeSi)ことによるDのサイト占有率への影響は、Fe-D系の先行研究で得られた結果と比較して無視できる程度であった(Machida et al., 2019)。

Neutron diffraction study on the deuterium composition of nickel deuteride at high temperatures and high pressures

齋藤 寛之*; 町田 晃彦*; 服部 高典; 佐野 亜沙美; 舟越 賢一*; 佐藤 豊人*; 折茂 慎一*; 青木 勝敏*

Physica B; Condensed Matter, 587, p.412153_1 - 412153_6, 2020/06

https://doi.org/10.1016/j.physb.2020.412153

重水素を含んだfcc Niを、3.36GPaで1073Kから300Kへ冷却した際の、構造中の重水素(D)の席占有率を中性子その場観察により調べた。多くの重水素はfccの金属格子の八面体サイトを占め、またわずかながら四面体サイトへの占有も見られた。八面体サイトの占有率は、1073Kから300Kへの冷却で0.4から0.85へ増大した。一方、四面体サイトの占有率は約0.02のままであった。この温度に依存しない四面体サイトの占有率は普通でなく、その理由はよくわからない。水素による膨張の体積と水素組成の直線関係から、重水素の侵入による体積膨張は、2.09(13) 原子と求められた。この値は、過去NiやNi Fe合金で報告されている2.14-2.2 原子とよく一致している。

Preparation, thermoelectric properties, and crystal structure of boron-doped MgSi single crystals

林 慶*; 齋藤 亘*; 杉本 和哉*; 大山 研司*; 林 好一*; 八方 直久*; 原田 正英; 及川 健一; 稲村 泰弘; 宮崎 譲*

AIP Advances (Internet), 10(3), p.035115_1 - 035115_7, 2020/03

https://doi.org/10.1063/1.5143839

MgSi is a potential thermoelectric (TE) material that can directly convert waste energy into electricity. In expectation of improving its TE performance by increasing electron carrier concentration, the element boron (B) is doped in MgSi single crystals (SCs). Their detailed crystal structures are definitely determined by using white neutron holography and single-crystal X-ray diffraction (SC-XRD) measurements. The white neutron holography measurement proves that the doped B atom successfully substitutes for the Mg site. The SC-XRD measurement confirms the B-doping site and also reveals the presence of the defect of Si vacancy (VSi) in the B-doped MgSi SCs. Regarding TE properties, the electrical conductivity, , and the Seebeck coefficient, S, decreases and increases, respectively, due to the decrease in the electron carrier concentration, contrary to the expectation. The power factor of the B-doped MgSi SCs evaluated from and S does not increase but rather decreases by the B-doping.