Electrochemical adsorption on Pt nanoparticles in alkaline solution observed using in situ high energy resolution X-ray absorption spectroscopy

草野 翔吾*; 松村 大樹; 石井 賢司*; 田中 裕久*; 水木 純一郎*

Nanomaterials (Internet), 9(4), p.642_1 - 642_14, 2019/04

https://doi.org/10.3390/nano9040642

The oxygen reduction reaction (ORR) on Pt/C in alkaline solution was studied by in situ high energy resolution X-ray absorption spectroscopy. To discuss the X-ray absorption near-edge structure (XANES), this paper introduced the rate of change of the (RCD), which is an analysis method that is sensitive to surface adsorption. The surface adsorptions as hydrogen (below 0.34 V), superoxide anion (from 0.34 V to 0.74 V), hydroxyl species (from 0.44 V to 0.74 V), atomic oxygen (above 0.74 V), and -PtO (above 0.94 V) were distinguished. It is clarified that the catalytic activity in an alkaline solution is enhanced by the stability of atomic oxygen and the low stability of superoxide anion/peroxide adsorption on the platinum surface.

原子力施設等の緊急時における被ばく評価事例集

川崎 将亜; 中嶌 純也; 吉田 圭佑; 加藤 小織; 西野 翔; 野崎 天生; 中川 雅博; 角田 潤一; 菅谷 雄基; 長谷川 里絵; et al.

JAEA-Data/Code 2017-004, 57 Pages, 2017/03

JAEA-Data-Code-2017-004.pdf:2.34MB

原子力施設の事故発生時においては、事故による影響及びその範囲を迅速に把握するために、放出された放射性物質による一般公衆への影響や事故による作業者の個人被ばく線量を早期に評価し報告することが求められる。そのため、原子力科学研究所放射線管理部においては、事故発生時の迅速な対応に資するために、一般公衆及び作業者の被ばく線量評価について、評価方法及び必要となる各種パラメータ等を想定される事故事例ごとにまとめ、事例集を整備した。本事例集では、原子力科学研究所で想定される各種事故に加え、過去の原子力事故で放出された放射性物質による被ばく評価について扱っており、これらは緊急時における被ばく評価についての知見・技術の継承にも用いることができる。

Large trigonal-field effect on spin-orbit coupled states in a pyrochlore iridate

植松 大介*; 佐賀山 基*; 有馬 孝尚*; 石川 洵*; 中辻 知*; 高木 英典*; 吉田 雅洋*; 水木 純一郎; 石井 賢司

Physical Review B, 92(9), p.094405_1 - 094405_6, 2015/09

https://doi.org/10.1103/PhysRevB.92.094405

The half-filled topmost valence band of Ir in several iridates such as SrIrO, IrO, and CaIrO has been proposed to originate mainly from the spin-orbit coupled states. In pyrochlore iridates IrO (: rare earth), some exotic electronic states are theoretically proposed by assuming states. However, the octahedral coordination around Ir is trigonally distorted, which may affect the energy level scheme of Ir states. Here, we report spectra of resonant elastic and inelastic X-ray scattering in EuIrO at the Ir edges. A large suppression of the magnetic scattering signal at the Ir edge supports the picture rather than the one. The inelastic scattering spectrum indicates that the magnitude of the trigonal field on the Ir states is evaluated to be comparable to the spin-orbit interaction. The energy diagram of the state is proposed based on the simple cluster model.

Towards optimizing the performance of self-regenerating Pt-based perovskite catalysts

Jarrige, I.*; 石井 賢司; 松村 大樹; 西畑 保雄; 吉田 雅洋*; 岸 浩史*; 谷口 昌司*; 上西 真里*; 田中 裕久*; 笠井 秀明*; et al.

ACS Catalysis, 5(2), p.1112 - 1118, 2015/02

https://doi.org/10.1021/cs501608k

Self-regenerating automotive catalysts owe their remarkable performance to the repeated motion of the precious metal atoms in and out of the perovskite lattice under fluctuating oxidizing and reducing conditions, preventing coalescence of the metal nanoparticles. Here we use resonant inelastic X-ray scattering to characterize the occupied and unoccupied Pt 5d states in two self-regenerating Pt-perovskite catalysts, CaTiPtO and CaZrPtO. Upon reduction, the element and symmetry-specific charge excitation spectra reveal a sizeable hybridization between the Pt 5d and the Ti 3d or Zr 4d states at the interface between the nanoparticles and the perovskite, which involves the occupied states and is thus invisible in X-ray absorption spectra. A correlation is found between the strength of this d-band hybridization and the proportion of Pt nanoparticles that remain buried below the surface during reduction, indicating that the motion of the Pt atoms towards the surface is hindered by this hybridization specifically, rather than by the Pt-O bonding. These results provide direct evidence that the strength of the metal-metal d-band hybridization plays a pivotal role in determining the efficiency of self-regeneration in perovskite catalysts.

Spin-orbit coupling induced semi-metallic state in the 1/3 hole-doped hyper-kagome NaIrO

高山 知弘*; Yaresko, A.*; 松本 章代*; Nuss, J.*; 石井 賢司; 吉田 雅洋*; 水木 純一郎; 高木 英典*

Scientific Reports (Internet), 4, p.6818_1 - 6818_6, 2014/10

https://doi.org/10.1038/srep06818

The complex iridium oxide NaIrO with a B-site ordered spinel structure was synthesized in single crystalline form, where the chiral hyper-kagome lattice of Irions, as observed in the spin-liquid candidate NaIrO, was identified. The average valence of Ir is 4.33+ and, therefore, NaIrO can be viewed as a doped analogue of the hyper-kagome spin liquid with Ir. The transport measurements, combined with the electronic structure calculations, indicate that the ground state of NaIrO is a low carrier density semi-metal. We argue that the semi-metallic state is produced by a competition of the molecular orbital splitting of orbitals on Ir triangles with strong spin-orbit coupling inherent to heavy Ir ions.

High-energy spin and charge excitations in electron-doped copper oxide superconductors

石井 賢司; 藤田 全基*; 佐々木 隆了*; Minola, M.*; Dellea, G.*; Mazzoli, C.*; Kummer, K.*; Ghiringhelli, G.*; Braicovich, L.*; 遠山 貴己*; et al.

Nature Communications (Internet), 5, p.3714_1 - 3714_8, 2014/04

https://doi.org/10.1038/ncomms4714

We combine X-ray and neutron inelastic scattering measurements to track the doping dependence of both spin and charge excitations in electron-doped materials. Copper resonant inelastic X-ray scattering spectra show that magnetic excitations shift to higher energy upon doping. Their dispersion becomes steeper near the magnetic zone center and they deeply mix with charge excitations, indicating that electrons acquire a highly itinerant character in the doped metallic state. Moreover, above the magnetic excitations, an additional dispersing feature is observed near the -point, and we ascribe it to particle-hole charge excitations. These properties are in stark contrast with the more localized spin-excitations (paramagnons) recently observed in hole-doped compounds even at high doping-levels.

Momentum-resolved resonant inelastic X-ray scattering on a single crystal under high pressure

吉田 雅洋*; 石井 賢司; Jarrige, I.*; 綿貫 徹; 工藤 一貴*; 小池 洋二*; 熊谷 健一*; 平岡 望*; 石井 啓文*; Tsuei, K.-D.*; et al.

Journal of Synchrotron Radiation, 21(1), p.131 - 135, 2014/01

https://doi.org/10.1107/S1600577513028944

A single-crystal momentum-resolved resonant inelastic X-ray scattering (RIXS) experiment under high pressure using an originally designed diamond anvil cell (DAC) is reported. The diamond-in/diamond-out geometry was adopted with both the incident and scattered beams passing through a 1 mm-thick diamond. This enabled us to cover wide momentum space keeping the scattering angle condition near 90. Elastic and inelastic scattering from the diamond was drastically reduced using a pinhole placed after the DAC. Measurement of the momentum-resolved RIXS spectra of SrCaCuO at the Cu -edge was thus successful. Though the inelastic intensity becomes weaker by two orders than the ambient pressure, RIXS spectra both at the center and the edge of the Brillouin zone were obtained at 3 GPa and low-energy electronic excitations of the cuprate were found to change with pressure.

Resonant inelastic X-ray scattering study of intraband charge excitations in hole-doped high- cuprates

脇本 秀一; 石井 賢司; 木村 宏之*; 池内 和彦*; 吉田 雅洋*; 足立 匡*; Casa, D.*; 藤田 全基*; 福永 靖*; Gog, T.*; et al.

Physical Review B, 87(10), p.104511_1 - 104511_7, 2013/03

https://doi.org/10.1103/PhysRevB.87.104511

We have performed resonant inelastic X-ray scattering (RIXS) near the Cu- edge on various cuprate superconductors, covering underdoped to heavily overdoped regimes and focusing on charge excitations inside the charge-transfer gap. RIXS measurements with = 9.003 keV on metallic LaSrCuO and BiPbSrCuO exhibit a dispersive intraband excitation below 4 eV, similar to that observed in the electron-doped NdCeCuO. This is the first observation of a dispersive intraband excitation in a hole-doped system, evidencing that both electron- and hole-doped systems have a similar dynamical charge correlation function.

Inelastic X-ray scattering studies of electronic excitations

石井 賢司; 遠山 貴己*; 水木 純一郎

Journal of the Physical Society of Japan, 82(2), p.021015_1 - 021015_24, 2013/02

https://doi.org/10.7566/JPSJ.82.021015

Inelastic X-ray Scattering (IXS) has developed as one of the most powerful momentum-resolved spectroscopies. Especially in the last decade, it achieved significant progress by utilizing brilliant X-rays from third generation synchrotron radiation facilities. Simultaneously, theoretical efforts have been made to predict or interpret the experimental spectra. One of the scientific fields studied intensively by means of IXS is strongly correlated electron systems, where the interplay of charge, spin, and orbital degrees of freedom determines their physical properties. IXS can provide a new insight into electron dynamics of the systems through the observation of charge, spin, and orbital excitations. Focusing on the momentum-resolved electronic excitations in strongly correlated electron systems, we review IXS studies and present capabilities of IXS for the study of dynamics of materials.

概要調査段階における設計・性能評価手法の高度化; NUMO-JAEA共同研究報告書(2011年度)(共同研究)

柴田 雅博; 澤田 淳; 舘 幸男; 牧野 仁史; 早野 明; 三ツ井 誠一郎; 谷口 直樹; 小田 治恵; 北村 暁; 大澤 英昭; et al.

JAEA-Research 2012-032, 298 Pages, 2012/09

JAEA-Research-2012-032.pdf:33.68MB

原子力機構(JAEA)と原子力発電環境整備機構(NUMO)は、概要調査段階における処分場の設計・性能評価に関連する主要な技術テーマについて、原子力機構が蓄積してきた技術やノウハウを、NUMOが今後の処分事業に適用できるよう、実施主体の視点に沿って実用化を図っていくための具体的な考え方と進め方を策定するとともに、必要な開発課題と今後の計画を明らかにすることを目的として、2011年度に共同研究を実施した。実施テーマと概要は以下の通り。(1)対象母岩の選定に関する検討:母岩特性のうち水理に着目し、母岩特性を評価するための項目、及び地下水移行時間の評価手法について、地質環境の調査・評価と関連付けたうえで整理した。(2)シナリオの構築に関する検討:シナリオ構築手順を具体化するとともに、ガラス固化体の溶解と核種の浸出、オーバーパックの腐食、緩衝材の長期変遷について、現象理解に関する最新の知見を構造的に整理した。(3)核種移行パラメータの設定に関する検討:緩衝材の分配係数と拡散係数、母岩の分配係数を対象として、パラメータ設定の方法論を検討し、その方法論に従った試行を行った。(4)知識情報の品質確保に関する検討:知識情報の品質を確保するための考え方や手法を、(2)シナリオの構築で検討した状態設定に対する論拠に関する情報を例として検討した。