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大内 和希; 松村 大樹; 辻 卓也; 小林 徹; 音部 治幹; 北辻 章浩
RSC Advances (Internet), 13(24), p.16321 - 16326, 2023/05
被引用回数:0 パーセンタイル:0(Chemistry, Multidisciplinary)電気化学水晶振動子マイクロバランス、インピーダンススペクトル及びX線吸収微細構造測定の結果から、ウラニルイオン(UO
)の還元に伴う析出物の化学状態変化を明らかにした。U
O
の還元に伴い、(1)U
の不均化によりU
が生成する。(2)U
はU
水酸化物として析出物を形成し、(3)最終的に水酸化物より大きな電気抵抗を持つU
酸化物に変化する析出機構が提案される。
池田 侑典*; 松村 大樹; 辻 卓也; 生井 飛鳥*; 井元 健太*; 所 裕子*; 中林 耕二*; 大越 慎一*
Inorganica Chimica Acta, 550, p.121434_1 - 121434_8, 2023/03
被引用回数:0 パーセンタイル:0.02(Chemistry, Inorganic & Nuclear)A film of a cyanido-bridged Cu-Mo assembly Cu[Mo(CN)
]
8H
O (CuMo-film) was electrochemically synthesized. Unlike analogs with a formula of M
[Mo(CN)
]
zH
O (M = Mn, Fe, Co), which show tetragonal crystal structures, the CuMo-film shows a monoclinic structure in the C2/m space group with cell parameters of a = 17.2461
= 125.1089
, and V = 1774.44
. Extended X-ray absorption fine structure analysis traced the bond distances around the Cu site as 1.93-2.30
for Cu-N and 2.01-2.40
for Cu-O. CuMo-film exhibits photo-switchable magnetization with T
= 18 K and dielectric relaxation related to the hydrogen bond network. The change of activation energy (E
) of the dielectric relaxation around 157 K (from E
= 49.9 kJ mol
to E
= 27.3 kJ mol
on cooling) suggests that the development of the hydrogen bond network occurs below 157 K.
山本 直生*; 松村 大樹; 萩原 悠人*; 田中 啓偉*; 長谷川 優太*; 石井 賢司*; 田中 裕久*
Journal of Power Sources, 557, p.232508_1 - 232508_10, 2023/02
被引用回数:0 パーセンタイル:0.01(Chemistry, Physical)Oxygen Reduction Reaction (ORR) is one of the key electrochemical reactions, especially in Polymer Electrolyte Fuel Cells (PEFCs). In this work, the reaction pathway and intermediate species such as molecular-type oxygen during ORR were discussed. High energy resolution X-ray absorption fine structure spectra at the Pt L-edge were obtained to observe the electronic structure of Pt catalyst. Carbon-supported Pt nanoparticles as powder catalysts were used for measurement as more realistic conditions, and the species adsorbed on the Pt nanoparticles were analyzed while controlling under the potentials in acidic electrolyte solution with N
or O
gas bubbling. Molecular-type oxygen adsorption species is observed only in the O
-bubbled electrolyte solution. This intermediate adsorption species is assigned to a hydrogen superoxide.
辻 卓也; 松村 大樹; 小林 徹; 矢板 毅
SPring-8/SACLA利用研究成果集(インターネット), 11(1), p.15 - 18, 2023/02
風化黒雲母の様な層状粘土鉱物では様々な収着サイトが存在すると考えられており、その中でもCsイオンは層間に取り込まれると考えられている。一方でカオリナイトのような粘土鉱物においては、層間に陽イオンを持たないことから、表面・端面サイトにのみ収着すると考えられている。本研究では福島第一原子力発電所事故後に放射性Csにより汚染された実土壌に近い濃度のCs収着粘土鉱物試料を調製しCs K吸収端におけるX-ray Absorption Fine Structure (XAFS)測定を行い、風化黒雲母とカオリナイトにおけるCs周りの局所構造の違いを観測した。結果、層間サイトに収着していると思われる風化黒雲母と表面・端面サイトに収着していると思われるカオリナイトとでは、特に低濃度領域においてCs周りの局所構造が大きく異なることが判明し、Cs収着様式によってCsイオンの収着安定性が大きく異なることが示唆された。
若松 勝洋*; 関原 輝昇*; 山口 慶彦*; 松島 諒*; 松村 大樹; Kuila, T.*; 吉川 浩史*
Batteries & Supercaps (Internet), 6(1), p.e202200385_1 - e202200385_8, 2023/01
被引用回数:1 パーセンタイル:0.01(Electrochemistry)Nanohybrid materials comprising polyoxometalates (POMs) and nanocarbons have attracted considerable attention as electrode-active materials for rechargeable lithium-ion batteries (LIBs). These materials exhibit multi-electron redox reactions, resulting in an improved battery capacity. This study focuses on carbon nanohorns (CNHs) as a nanocarbon material and evaluates the battery performance using POM/CNH hybrids as cathode-active materials. X-ray absorption fine structural analysis was performed to investigate the reaction mechanism of these hybrids. POM/oxidized CNH (CNHox) hybrid materials maintain high capacities at high current densities as the high surface area availability of CNHox leads to high electrical double-layer capacitances. These findings show an improved performance of the as-developed material when compared with those reported in previous papers and can contribute toward an improved design of cathode-active materials for high-performance supercapacitors.
Zheng, X.*; 加藤 優*; 上村 洋平*; 松村 大樹; 八木 一三*; 高橋 仁徳*; 野呂 真一郎*; 中村 貴義*
Inorganic Chemistry, 62(3), p.1257 - 1263, 2023/01
被引用回数:0 パーセンタイル:0.02(Chemistry, Inorganic & Nuclear)A glass-crystal composite (g-NCP/PCP), comprising a glassy nonporous coordination polymer (g-NCP) and a crystalline porous coordination polymer (PCP)/metal-organic framework, was synthesized by using a melt-quenched method. Compared to that of the PCP itself, g-NCP/PCP has an enhanced gas adsorption selectivity. The results should stimulate further studies of the chemistry of g-NCP/PCP glass-crystal composites.
富田 夏奈*; 岸 哲生*; 松村 大樹; 矢野 哲司*
Journal of Non-Crystalline Solids, 597, p.121891_1 - 121891_10, 2022/12
被引用回数:1 パーセンタイル:0.01(Materials Science, Ceramics)NaO-B
O
-SiO
glass plate phase separated in spinodal was partially remelted and homogenized by laser heating. As heat generation source, 0.8 mol% NiO was added to absorb continuous-wave laser with
=1064 nm. After acid leaching, borate phase with NiO was remaining partially in laser irradiated area. X-ray Absorption Fine Structure (XAFS) spectra revealed that Ni
in laser irradiated area showed coordination change from 6 coordinated octahedral to 5 coordinated in square pyramid along with apparent color change from green to brown. Similar change was observed in water-quenched specimen from 1000
C. Ni
transition gave additional structural information in phase separate / homogeneous glass, which was difficult to be distinguished by spectroscopy which focuses on covalent bonding of glass network.
Liu, B.*; Feng, R.*; Busch, M.*; Wang, S.*; Wu, H.*; Liu, P.*; Gu, J.*; Bahadoran, A.*; 松村 大樹; 辻 卓也; et al.
ACS Nano, 16(9), p.14121 - 14133, 2022/09
被引用回数:23 パーセンタイル:97.78(Chemistry, Multidisciplinary)Pt single-atom materials possess an ideal atom economy but suffer from limited intrinsic activity and side reaction of producing HO
in catalyzing the oxygen reduction reaction (ORR). Here, we demonstrate that anchoring platinum alloys on single-atom Pt-decorated carbon (Pt- SAC) surmounts their inherent deficiencies, thereby enabling a complete four-electron ORR pathway catalysis with high efficiency and durability. Pt
Co@Pt-SAC demonstrates an exceptional mass and specific activities 1 order of magnitude higher than those of commercial Pt/C. They are durable throughout 50000 cycles, showing only a 10 mV decay in halfwave potential. The superior durability is attributed to the shielding effect of the Pt-SAC coating, which significantly mitigates the dissolution of Pt
Co cores.
榊 浩司*; Kim, H.*; Majzoub, E. H.*; 町田 晃彦*; 綿貫 徹*; 池田 一貴*; 大友 季哉*; 水野 正隆*; 松村 大樹; 中村 優美子*
Acta Materialia, 234, p.118055_1 - 118055_10, 2022/08
被引用回数:6 パーセンタイル:77.31(Materials Science, Multidisciplinary)Local structure in the di-hydride phases of V-Ti-Cr solid solution alloys were investigated using synchrotron X-ray and neutron total scattering experiments. Both Rietveld refinement and pair distribution function (PDF) refinement of the X-ray scattering data indicated that the crystal structure of the metal lattice was a face centered cubic (FCC) structure and no difference between their local structure and average structure was observed. However, the CaF structure model did not reproduce the first peak corresponding to the metal-hydrogen correlation in neutron PDF patterns. When special quasi-random structure (SQS) models are applied for the refinements, the whole neutron PDF patterns were reproduced. Distribution of interatomic distances between hydrogen and metal atoms in the relaxed SQS models showed that interatomic distance of hydrogen with Cr was shorter than that with V and that with Ti was longer than that with V, independently of the chemical compositions.
伊藤 仁彦*; 松村 大樹; Song, C.*; 久保 佳美*
ACS Energy Letters (Internet), 7(6), p.2024 - 2028, 2022/06
被引用回数:1 パーセンタイル:29.58(Chemistry, Physical)The behavior of Br/Br
redox mediator (RM), which has been shown to suppress charging overpotential in lithium-air batteries, has been detected for the first time using operando Br K-edge dispersive X-ray absorption fine structure. Br
ions in the electrolyte increase monotonically after
30% charging, which indicates that a part of Br
formed via the oxidation of Br
during charging does not oxidize Li
O
as RM but gets accumulated in the cell. Consistent with this result, the O
evolution efficiency gradually decreases from the initial 100% as the charging progresses, and CO
is emitted at the end of the charging. All these results clearly show that the Br
/Br
RM functions effectively at the beginning of charging but gradually loses its function as charging proceeds.
上原 章寛*; 松村 大樹; 辻 卓也; 薬丸 晴子*; 田中 泉*; 城 鮎美*; 齋藤 寛之*; 石原 弘*; 武田(本間) 志乃*
Analytical Methods, 14(24), p.2439 - 2445, 2022/06
被引用回数:2 パーセンタイル:67.88(Chemistry, Analytical)Internal exposure to actinides such as uranium and plutonium has been reduced using chelating agents for decorporation because of their potential to induce both radiological and chemical toxicities. This study measures uranium chemical forms in serum in the presence and absence of chelating agents based on X-ray absorption spectroscopy (XAS). The chelating agents used were 1-hydroxyethane 1,1-bisphosphonate (EHBP), inositol hexaphosphate (IP6), deferoxamine B (DFO), and diethylenetriaminepentaacetate (DTPA). The main ligands forming complexes with uranium in the serum were estimated as follows: IP6 EHBP
bioligands
DFO
DTPA when the concentration ratio of the chelating agent to uranium was 10. Measurements of uranium chemical forms and their concentrations in the serum would be useful for the appropriate treatment using chelating agents for the decorporation of uranium.
八木 祐太朗*; 脇田 雄大*; 籠宮 功*; 松江 郁弥*; 柿本 健一*; 松村 大樹; 米田 安宏
ChemistrySelect (Internet), 7(21), p.e202104575_1 - e202104575_7, 2022/06
被引用回数:0 パーセンタイル:0(Chemistry, Multidisciplinary)The layered perovskite LaSrFe
O
(LSF) easily hydrates under ambient air. The hydrated LSF transports hydroxides in the middle-temperature range of 100
C - 250
C. This study used X-ray absorption fine structure analysis on normal and hydrated LSF from room temperature to 350
C to evaluate the relationship between local structures and ion transport characteristics. The H
O molecules are mainly intercalated into rock-salt interlayers, which are close to the La1 and O3 sites. The generated OH
ions are found at O3 sites, which are closer to Sr ions than La ions. The intercalated H
O molecules and formed OH
ions expand the spaces of the rock-salt interlayers. The temperature dependence of the local crystal structure was also studied in this study. According to the findings, the presence of OH
ions on the O3 sites, which are closer to Sr ions, plays a significant role in OH
transport in the medium temperature range.
小松 遊矢*; 清水 亮太*; 佐藤 龍平*; Wilde, M.*; 西尾 和記*; 片瀬 貴義*; 松村 大樹; 齋藤 寛之*; 宮内 雅浩*; Adelman, J. R.*; et al.
Chemistry of Materials, 34(8), p.3616 - 3623, 2022/04
被引用回数:6 パーセンタイル:83.58(Chemistry, Physical)Here, we demonstrate such a highly repeatable photoinduced insulator-to-metal transition in yttrium oxyhydride (YOH
) epitaxial thin films. The temperature (
) dependence of the electrical resistivity (
) of the films transforms from insulating to metallic (
) under ultraviolet laser illumination. The sample is heated (125
C) under an Ar atmosphere to recover its original insulating state. The films recover their original metallic conductivity when subsequently subjected to ultraviolet laser illumination, showing repeatable photoinduced insulator-to-metal transition. First principles calculations show that the itinerant carriers originate from the variations in the charge states of the hydrogen atoms that occupy octahedral interstitial sites. This study indicates that tuning the site occupancy (octahedral/tetrahedral) of the hydrogen atoms exerts a significant effect on the photoresponse of metal hydrides.
Francisco, P. C. M.; 松村 大樹; 菊池 亮佑*; 石寺 孝充; 舘 幸男
Environmental Science & Technology, 56(5), p.3011 - 3020, 2022/03
被引用回数:2 パーセンタイル:51.09(Engineering, Environmental)The radionuclide selenium-79 (Se-79) is predicted to be a key contributor to the long-term radiologic hazards associated with geological high-level waste (HLW) repositories, hence its release is of pertinent concern in the safety assessment of repositories. In this study, we examined the immobilization mechanisms of Se(-II)-prevalent under anoxic and reducing repository conditions-during interaction with aqueous Fe(II) and freshly precipitated Fe(OH) at circumneutral and alkaline conditions, respectively, its response to changes in pH, and its behavior during aging at 90
C. Using microscopic and spectroscopic techniques, we observed that Se(-II) was readily immobilized via iron selenide precipitation regardless of whether Se(-II) reacts with aqueous species or solid phases and that modifying the pH following initial immobilization did not immediately remobilize Se(-II). These observations indicate that Se(-II) migration beyond the overpack can be effectively and rapidly retarded via interaction with Fe(II) species arising from overpack corrosion. Thermodynamic calculations, however, showed that at alkaline conditions, iron selenides immediately became metastable and will likely dissolve in the long term. Aging experiments at 90
C showed that Se(-II) can be completely retained via the crystallization of ferroselite at circumneutral conditions, while it will be largely remobilized at alkaline conditions. Our results show that Se(-II) mobility can be significantly influenced by its interactions with the corrosion products of the steel overpack and that these behaviors will have to be considered in repository safety assessments.
佐伯 盛久*; 松村 大樹; 中西 隆造*; 蓬田 匠; 辻 卓也; 齋藤 寛之*; 大場 弘則*
Journal of Physical Chemistry C, 126(12), p.5607 - 5616, 2022/03
被引用回数:1 パーセンタイル:29.58(Chemistry, Physical)パルス紫外線レーザー照射によって引き起こされるRhイオン錯体のRh
種への直接光還元反応機構を、分散型X線吸収微細構造(DXAFS)分光法によって調べた。時間分解X線吸収端近傍構造(XANES)には等吸収点がなく、Rh
の直接光還元に2種類以上のRh
が寄与することを示した。時間分解XANESデータの特異値解析から、直接光還元には3つのRh
種が関与することが示唆された。時間分解XANESデータを、交互最小二乗法による多変量解析(MCR-ALS)により解析したところ、3つのRh
種の純粋なスペクトルと濃度プロファイルが得られた。Rh
種は、3つのXANESスペクトルの特徴から、Rh
, Rh
, Rh
種に分類できた。得られた濃度プロファイルから、Rhの直接光還元はRh
Rh
Rh
の順で進行することが示唆され、Rh
とRh
の光還元、Rh
とRh
の光による自己触媒的還元、Rh
の光酸化による反応機構により、3種のRh
の濃度プロファイルがよく再現できることが示された。
村瀬 知志*; 吉川 裕未*; 藤原 孝将*; 深田 幸正*; 寺西 貴志*; 狩野 旬*; 藤井 達生*; 稲田 康宏*; 片山 真祥*; 吉井 賢資; et al.
Journal of Physics and Chemistry of Solids, 162, p.110468_1 - 110468_6, 2022/03
被引用回数:0 パーセンタイル:0(Chemistry, Multidisciplinary)混合原子価系YbFeO
における原子価制御の可能性を検討するため、電荷化学的手法によりLi
イオンの挿入を試みた。対象物質をLiイオンバッテリー類似のセル状にして実験を行い、Li
の挿入による格子定数および原子間距離の系統的変化を観測した。イオンの挿入は、電荷量に換算し300mAh/g以上であった。放射光吸収分光による局所構造観測を行ったところ、Li
はYb層とFe層の間に挿入されることが分かった。本測定からは、金属鉄の微粒子が析出することも示唆された。このため、Li
の挿入による鉄イオンの原子価の系統的な変化は明瞭に観測されなかった。メスバウア分光法などからは、Li
は空間的に不均一に挿入されることが示唆されたものの、本研究の結果は、YbFe
O
の原子価や物性が電気化学的手法によって制御できる可能性を示すものである。
木全 哲也*; 垣谷 健太*; 山本 春也*; 下山 巖; 松村 大樹; 岩瀬 彰宏*; Mao, W.*; 小林 知洋*; 八巻 徹也*; 寺井 隆幸*
Physical Review Materials (Internet), 6(3), p.035801_1 - 035801_7, 2022/03
被引用回数:4 パーセンタイル:63.89(Materials Science, Multidisciplinary)High activity is one of the primary requirements for the catalysts in proton exchange membrane fuel cell applications. Previous computational studies suggested that the catalytic activity of Pt nanoparticles could be enhanced by a Pt-carbon (C) support interaction. We have recently found that an enhanced electronic interaction occurs at the interface between an argon-ion (Ar)-irradiated glassy carbon (GC) surface and Pt nanoparticles. Here, we report a more than two-fold increase in specific activity (SA) for the Pt nanoparticles on the Ar
-irradiated GC substrate compared to that on the non-irradiated GC substrate. The mechanism of this activity enhancement was investigated by local structure analysis of the interface. Ar
irradiation of the carbon support led to the formation of the Pt-C bonding, thus protecting the deposited Pt nanoparticles from oxidation.
田中 裕久*; 正木 清香*; 青谷 拓朗*; 稲川 康平*; 岩田 宗悟*; 相田 樹哉*; 山本 忠亮*; 喜多 知輝*; 大野 瞳*; 竹中 啓恭*; et al.
SAE Technical Paper 2022-01-0534 (Internet), 10 Pages, 2022/03
The catalyst called a Passive Autocatalytic Recombiner (PAR) is required to have robustness that can maintain its activity for more than 30 years in an environment where temperature, humidity, gas concentration, etc. cannot be controlled. Here, it is expected that "An Intelligent Catalyst" for automotive emissions control exhibits excellent performance even in such a harsh environment. The intelligent catalyst is the nanostructure designed perovskite catalyst that has the rejuvenating function instead of preventing aging. The authors emphasize that the technology developed as a catalyst for automobiles is expected to be useful not only in other industries but also as a relief technology from the national crisis.
上原 章寛*; Shuhui, X.*; 佐藤 遼太朗*; 松村 大樹; 辻 卓也; 薬丸 晴子*; 城 鮎美*; 齋藤 寛之*; 田中 泉*; 石原 弘*; et al.
X線分析の進歩,53, p.223 - 229, 2022/03
体内にアクチニドなどの放射性物質が取り込まれると、生体内配位子がアクチニドと化合物を生成し、体内滞留の原因となりうる。本研究では、アクチニドを体外に排出させるためのキレート剤の結合性評価を行うため、キレート剤と結合した元素の局所構造をX線吸収分光法によって解析し結合力を評価した。プルトニウム模擬元素としてジルコニウム(Zr),キレート剤として、EHBP(1-hydroxyethylidene-1,1-diphosphonate)およびDTPA (diethylenetriaminepentaacetate)を用いた。ZrはEHBPと八面体構造の錯体を形成するとともに、Zr-EHBP錯体はZr-DTPA錯体より強い結合を有することが分かった。これらの知見は、放射性元素による内部被ばく線量評価や、放射性元素を体外に取り除くための適切な除染方法の提案につながる。
熊添 博之*; 五十嵐 康彦*; Iesari, F.*; 清水 亮太*; 小松 遊矢*; 一杉 太郎*; 松村 大樹; 齋藤 寛之*; 岩満 一功*; 岡島 敏浩*; et al.
AIP Advances (Internet), 11(12), p.125013_1 - 125013_5, 2021/12
被引用回数:1 パーセンタイル:11.39(Nanoscience & Nanotechnology)This letter presents a Bayesian sparse modeling method to analyze extended X-ray absorption fine structure (EXAFS) data with basis functions built on two-body signals. This method allows us to evaluate regression coefficients proportional to the radial distribution functions of the respective elements and their errors and is very effective for analysis of EXAFS with weak absorption intensity and severe signal-to-noise ratio. As an application example, we used it to analyze EXAFS of an yttrium oxyhydride (YOH
) epitaxial thin film. This EXAFS data shows weak absorption intensity due to the small amount of X-ray absorption in the thin film sample. However, this approach revealed that the radial distance ratio of the second neighbor yttrium to the first neighbor oxygen coincides with that of a tetrahedral configuration. This result demonstrates that the interstitial oxygen position is tetrahedral in the YO
H
thin film.