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佐伯 盛久*; 蓬田 匠; 松村 大樹; 斉藤 拓巳*; 中西 隆造*; 辻 卓也; 大場 弘則*
Analytical Sciences, 36(11), p.1371 - 1378, 2020/11
モリブデンイオンMoO水溶液に酸を加えると、複数のモリブデン原子が酸素を介して結合したポリモリブデン酸が形成され、さらに酸濃度に応じてポリモリブデン酸の化学形態は大きく変化する。我々は、これまで研究例の少なかった高酸性水溶液中(0.15-4.0M)でのポリモリブデン酸の化学形態を、ラマン分光法およびX線吸収微細構造(XAFS)分光法により調べ、測定したスペクトルを多変量スペクトル分解法(MCR-ALS)により解析した。MCR-ALS解析では実験データ解析により得られるスペクトルの任意性が問題になり、XAFSデータのみの解析ではこれが顕著になるが、XAFSデータとラマンデータを同時にMCR-ALS解析することで、信頼性の高い3成分のXAFSスペクトルを得ることに成功した。構造解析の結果から、硝酸濃度が高くなるにつれポリモリブデン酸の化学種が[Mo
O
(H
O)
]
[Mo
O
(H
O)
]
[HMoO
(H
O)
]
へと変化する様子を明らかにした。
杉浦 佑樹; 戸村 努*; 石寺 孝充; 土井 玲祐; Francisco, P. C. M.; 塩飽 秀啓; 小林 徹; 松村 大樹; 高橋 嘉夫*; 舘 幸男
Journal of Radioanalytical and Nuclear Chemistry, 324(2), p.615 - 622, 2020/05
被引用回数:0 パーセンタイル:100(Chemistry, Analytical)Batch sorption experiments were performed to investigate the sorption mechanism of Se on montmorillonite under reducing conditions in deep geological environments. Based on Eh-pH diagrams and ultraviolet-visible spectra, Se was dissolved as selenide (Se(-II)) anions under the experimental conditions. The distribution coefficients (; m
kg
) of Se(-II) indicated ionic strength independence and slight pH dependence. The
values of Se(-II) were higher than those of Se(IV), which also exists as an anionic species. X-ray absorption near edge spectroscopy showed that the oxidation state of Se-sorbed on montmorillonite was zero even though selenide remained in the solution. These results suggest that Se(-II) was oxidized and precipitated on the montmorillonite surface. Therefore, it is implied that a redox reaction on the montmorillonite surface contributed to high
values for Se(-II).
Zhang, Z,*; Wang, H.*; 吉川 浩史*; 松村 大樹; 畑尾 秀哉*; 石川 理史*; 上田 渉*
ACS Applied Materials & Interfaces, 12(5), p.6056 - 6063, 2020/02
被引用回数:0 パーセンタイル:100(Nanoscience & Nanotechnology)Developing new cathode-active materials for rechargeable batteries is important to fulfill the growing demands of energy transformation, storage, and utilization. Zeolitic transition-metal oxides based on vanadomolybdate, constructed by pentagon metal-oxygen clusters as building blocks and metal ions as linkers in a trigonal symmetry, are good candidates for cathodes of Na rechargeable batteries. The material is activated via amorphization of the crystal structure in the ab plane during discharging process, keeping the molecular structure of the building blocks stable, which causes high specific capacity and good cycle performance.
米田 安宏; 吉越 章隆; 竹田 幸治; 塩飽 秀啓; 松村 大樹; 菖蒲 敬久; 田村 和久
まてりあ, 58(12), p.763 - 769, 2019/12
文部科学省ナノプラットフォーム委託事業において、微細構造解析プラットフォームに属する各実施機関の提供している装置紹介である。
松村 大樹; 辻 卓也; 吉井 賢資
Materials Chemistry and Physics, 238, p.121885_1 - 121885_5, 2019/12
被引用回数:0 パーセンタイル:100(Materials Science, Multidisciplinary)ペロブスカイトPrSr
CoO
(0
0.5)についてX線吸収分光測定を行うとともに、x=0.5で観測される110Kの磁気異常の起源を探るため磁気熱量効果測定を行った。Co
吸収端のX線吸収測定からは、xが増えるとともにCoの原子価が増加し、Co-O結合距離が縮まることが分かった。また、CoO
多面体の歪みも増大することが分かった。Co-O結合距離の縮み方は、xが大きいほど大きいことも分かった。測定温度範囲である17-300Kでは、Co
吸収端の吸収スペクトルには異常は見られなかった。磁気熱量効果の結果と合わせ、110Kの異常は磁気構造の変化であることが分かった。
小林 大志*; 中嶋 翔梧*; 元川 竜平; 松村 大樹; 斉藤 拓巳*; 佐々木 隆之*
Langmuir, 35(24), p.7995 - 8006, 2019/06
被引用回数:1 パーセンタイル:78.85(Chemistry, Multidisciplinary)We report the hierarchical structure of zirconium hydroxide after aging at different temperatures to elucidate the factors governing zirconium solubility in aqueous solutions. Zirconium hydroxide solid phases after aging at 25, 40, 60, and 90C under acidic to alkaline conditions were investigated using extended X-ray absorption fine structure (EXAFS) and wide- and small-angle X-ray scattering (WAXS and SAXS) techniques to reveal the bulk and surface structures of the solid phases from the nanoscale to submicroscale. After aging at 25
C, the fundamental building unit of the solid phase was a zirconium hydroxide tetramer. The tetramers formed primary particles approximately 3 nm in size, which in turn formed aggregates hundreds of nanometers in size. This hierarchical structure was found to be stable up to 60
C under acidic and neutral conditions and up to 40
C under alkaline conditions. After aging at 90
C under acidic conditions and at 60 and 90
C under alkaline conditions, the WAXS and EXAFS measurements suggested the crystallization of the solid phase. The transformation of the solid-phase structure by temperature was discussed in relation to the solubility product to understand the solubility-limiting solid phase. The solubility of zirconium hydroxide after aging at different temperatures was governed not only by the size of the primary particles, but also by their surface configuration.
大野 瞳*; 竹中 啓恭*; 喜多 知輝*; 谷口 昌司*; 松村 大樹; 西畑 保雄; 日野 竜太郎; Reinecke, E.-A.*; 高瀬 和之*; 田中 裕久*
E-Journal of Advanced Maintenance (Internet), 11(1), p.40 - 45, 2019/05
Safety management technology of hydrogen gas is extremely important not only for nuclear power generation but also for future society. A brand-new passive autocatalytic recombiner (PAR) system utilizing the monolithic "intelligent catalyst" has been studied for the long-term storage of high-concentration radioactive materials related to the decommissioning of nuclear reactors. The monolith-type automotive catalyst showed high hydrogen conversion activity from a room temperature in a large scale reactor of REKO-4. It became clear that natural convection by reaction is greatly improved by roughening the cell density of the monolith catalyst especially under static environmental conditions such as in a storage container. Taking advantage of this superior catalytic property, we aim to complete the safety technology for storage containers at an early stage and advance the development of highly active catalyst from further low temperature.
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
被引用回数:1 パーセンタイル:100(Nanoscience & Nanotechnology)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.
佐伯 盛久*; 松村 大樹; 蓬田 匠; 田口 富嗣*; 辻 卓也; 齋藤 寛之*; 大場 弘則*
Journal of Physical Chemistry C, 123(1), p.817 - 824, 2019/01
被引用回数:1 パーセンタイル:79.12(Chemistry, Physical)PdCl水溶液にパルスレーザーを照射した際の、パラジウム(Pd)微粒子の形成反応メカニズムを透過型電子顕微鏡(TEM)、およびエネルギー分散型X線吸収分光法(DXAFS)を用いて調べた。266 nmの波長のナノ秒レーザー照射により形成されたPd微粒子をTEMにより観測した結果、微粒子径が照射レーザーのフルエンスに依存し、高フルエンスのレーザー照射が微粒子形成を促進することを明らかにした。DXAFSの結果よりPd
の濃度を算出し、Finke-Watzkyの二段階反応に基づいた解析を行った。その結果、照射するレーザーのフォトンは、1光子過程のPdCl
の還元と、多光子過程のPd微粒子の自己触媒的な成長に寄与することを見出した。
岸 浩史*; 坂本 友和*; 朝澤 浩一郎*; 山口 進*; 加藤 豪士*; Zulevi, B.*; Serov, A.*; Artyushkova, K.*; Atanassov, P.*; 松村 大樹; et al.
Nanomaterials (Internet), 8(12), p.965_1 - 965_13, 2018/12
被引用回数:4 パーセンタイル:62.48(Nanoscience & Nanotechnology)Platinum group metal-free catalysts based on transition metal-nitrogen-carbon nanomaterials have been studied by a combination of in situ X-ray spectroscopy techniques, high-resolution transmission electron microscope, Mssbauer spectroscopy, electrochemical methods and density functional theory. Fe-N-C oxygen reduction reaction electrocatalysts were synthesized by varying several synthetic parameters to obtain nanomaterials with different composition and morphology. Associated with Fe-N
motive and the presence of Fe metallic particles in the electrocatalysts showed the clear differences in the variation of composition; processing and treatment conditions of sacrificial support method. From the results of material characterization; catalytic activity and theoretical studies; Fe metallic particles (coated with carbon) are main contributors into the HO
generation.
Li, S.*; 豊田 真幸*; 小林 義明*; 伊藤 正行*; 池内 和彦*; 米田 安宏; 大谷 彬*; 松村 大樹; 浅野 駿*; 水木 純一郎*; et al.
Physica C, 555, p.45 - 53, 2018/12
被引用回数:0 パーセンタイル:100(Physics, Applied)鉄系超伝導体のBaFeAs
とLiFeAsの局所構造解析をX線PDF解析とXAFSを利用して行った。BaFe
As
の構造相転移温度ではPDFで得られた局所構造には変化が見られたが、EXAFSで得られた局所構造には変化を見出すことができなかった。これらのデータは室温の平均構造が正方晶相において、局所的な斜方歪みを考慮する必要があることを示唆している。
垣谷 健太*; 木全 哲也*; 八巻 徹也*; 山本 春也*; 松村 大樹; 田口 富嗣*; 寺井 隆幸*
Radiation Physics and Chemistry, 153, p.152 - 155, 2018/12
被引用回数:1 パーセンタイル:75.54(Chemistry, Physical)The chemical state and local structure of 2.6-nm-sized platinum (Pt) nanoparticles on an ion-irradiated glassy carbon (GC) substrate were investigated by X-ray absorption fine structure measurements. The partial oxidation of the Pt nanoparticles was confirmed by the peak intensity in the near-edge region of the absorption spectrum. The analysis of the extended region revealed a higher coordination number and shorter bond length of Pt-Pt compared to those of the Pt nanoparticles on the non-ion-irradiated GC. Thus, Pt nanoparticles on the ionirradiated GC substrate were found to hold a rigid metallic coordination during the oxidation.
平賀 晴弘*; 大山 研司*; 小坂 昌史*; 松村 大樹
AIP Advances (Internet), 8(10), p.101424_1 - 101424_5, 2018/10
被引用回数:0 パーセンタイル:100(Nanoscience & Nanotechnology)The specific heat of MnFe
Si was measured over a wide temperature range. Aside from the lattice and electronic specific heat components, another component had a significant contribution to the specific heat at low temperatures in the case of
= 0.2; however, its contribution decreased when
= 1.0. It is observed that the net component was retained at temperatures significantly higher than
for both
. The XAFS spectra of the Mn
-edge for
= 0 not only indicated a smooth structure near the edge, but also an unusually small amplitude in the extended high energy region; however, these features disappeared with Fe doping. The specific heat and XAFS data were discussed interms of the charge degree of freedom or electronic inhomogeneity.
浅野 駿*; 石井 賢司*; 松村 大樹; 辻 卓也; 伊奈 稔哲*; 鈴木 謙介*; 藤田 全基*
Journal of the Physical Society of Japan, 87(9), p.094710_1 - 094710_5, 2018/09
被引用回数:4 パーセンタイル:42.19(Physics, Multidisciplinary)We investigated the Ce substitution and reduction annealing effects on the electronic states at copper sites by Cu -edge X-ray absorption near-edge structure measurements in Pr
Ce
CuO
(PCCO) with varying
and
(amount of oxygen loss during annealing). Absorption near-edge spectra were modified by Ce substitution and reduction annealing similarly with increasing
and
. Considering electron doping by Ce substitution, this similarity indicates an increase in electron number at the copper sites due to annealing (
). Furthermore, quantitative analyses of the spectra clarified that the number of Cu
sites, corresponding to the induced electron number by Ce substitution increases linearly with
in the as-sintered PCCO, whereas
is not exactly equal to 2
. For each
-fixed sample,
tends to exceed 2
with increasing
, suggesting the emergence of two types of carrier due to annealing.
Cui, Y.-T.*; 原田 慈久*; 丹羽 秀治*; 尾嶋 正治*; 畑中 達也*; 中村 直樹*; 安藤 雅樹*; 吉田 利彦*; 石井 賢司*; 松村 大樹
NanotechJapan Bulletin (インターネット), 11(4), 6 Pages, 2018/08
固体高分子形燃料電池の正極には白金ナノ粒子触媒が使用されているが、加湿によって活性化過電圧が発生して性能が低下することが知られている。この原因を解明し、低減する技術を確立することが、燃料電池の性能向上とコスト低減に向けた喫緊の課題となっている。しかしながら、従来の方法で測定した白金ナノ粒子触媒のX線吸収スペクトルでは、白金の内殻正孔の寿命によるスペクトル幅の広がりで微細な構造がぼやけてしまい、吸着に起因する電子状態の変化を捉えることが困難であった。そこで本研究では、非弾性X線散乱装置を利用した高分解能型の蛍光X線吸収分光法による測定を行った。結果、酸素が水と共存することにより、白金の酸化を促進することが明瞭に検出でき、実験的に初めて明らかにすることができた。本来、触媒である白金は反応前後で不変であるべきものであるが、この反応では、白金上で酸素が水と共吸着することにより安定化して反応の進行を遅らせた結果、過電圧がより大きく生じていると解釈できる。また、白金コバルト合金ナノ粒子についても調べたところ、酸素と水の共吸着による酸化促進効果がほとんど起こらないことを見出した。
Wang, H.*; 磯部 仁*; 松村 大樹; 吉川 浩史*
Journal of Solid State Electrochemistry, 22(7), p.2067 - 2071, 2018/07
被引用回数:11 パーセンタイル:40.38(Electrochemistry)Amorphous and crystalline MetfV10 electrodes for lithium ion batteries were prepared by mixing MetfV10 with different binders: polyvinylidenefluoride (PVDF) or polytetrafluoroethylene (PTFE). The reaction mechanism was studied using in situ X-ray absorption fine structure (XAFS) and impedance measurements. The X-ray absorption near-edge structure (XANES) results exhibited a 10-electron reduction per the formula of MetfV10 during discharge, resulting in a large capacity. Extended X-ray absorption fine structure (EXAFS) analyses suggested a slight expansion in the molecular size of MetfV10. The impedance measurements reveal that an increase of discharge capacities for the amorphous cathode is due to lower resistance than in the crystalline cathode. This study presents a rational selection of amorphous or crystalline cathode materials for high power and high energy density lithium batteries.
加藤 優*; 武藤 毬佳*; 松原 直啓*; 上村 洋平*; 脇坂 祐輝*; 米内 翼*; 松村 大樹; 石原 知子*; 徳島 高*; 野呂 真一郎*; et al.
ACS Applied Energy Materials (Internet), 1(5), p.2358 - 2364, 2018/05
被引用回数:2 パーセンタイル:80.16(Chemistry, Physical)Multinuclear metal active sites are widely used as catalytic reaction centers in metalloenzymes and generally show high catalytic activity. The oxygen reduction reaction (ORR) is an important reaction not only in oxygenic respiration but also in future energy generation devices such as polymer electrolyte fuel cells and metal-air batteries. Incorporation of multinuclear metal active sites in conductive materials such as carbon will allow us to develop highly active electrocatalysts like metalloenzymes. Herein, we report a copper-based ORR electrocatalyst with multinuclear copper active sites in nitrogen-doped graphene. Electrochemical measurements revealed that the obtained electrocatalyst showed the highest electrocatalytic activity for the ORR in the Cu-based electrocatalysts in neutral aqueous solution. In situ X-ray absorption spectroscopy revealed the incorporation of multinuclear copper sites.
清水 剛志*; Wang, H.*; 谷藤 尚貴*; 松村 大樹; 吉村 真史*; 中西 康次*; 太田 俊明*; 吉川 浩史*
Chemistry Letters, 47(5), p.678 - 681, 2018/05
被引用回数:3 パーセンタイル:70.3(Chemistry, Multidisciplinary)Disulfide, which is a sub-group of organosulfides, has been studied as a promising cathode active material. Herein, to improve battery performance, we inserted disulfide into Cu-based metal organic framework (MOF) as a ligand. As a result, the disulfide inserted MOF exhibited a high capacity based on dual redox reactions of Cu ions and disulfide ligands, and a stable cycle performance. The S -edge X-ray absorption fine structure analyses revealed a reversible cleavage and formation of S-S bond in the MOF during discharge and charge process.
浅野 駿*; 鈴木 謙介*; 松村 大樹; 石井 賢司*; 伊奈 稔哲*; 藤田 全基*
Journal of Physics; Conference Series, 969, p.012051_1 - 012051_5, 2018/04
被引用回数:2 パーセンタイル:9.99Reduction and oxidation annealing effects on the electronic states around the copper sites for PrCe
CuO
and Nd
Ce
CuO
with
= 0 and
= 0.15 were investigated by Cu
-edge X-ray absorption measurements. Cu
near-edge spectra were changed by the reduction annealing in a manner similar to the case of Ce substitution for both
= 0 and
= 0.15. This means an increase of electron density at the copper sites, indicating the aspect of electron doping in the reduction annealing. This reduction annealing effect on the near-edge spectra are reverted by the additional oxidation annealing. The amount of electron density around the copper sites is varied by the reduction and oxidation annealing, reversibly, corresponding to the reversible variation of the physical property from insulating to superconductivity.
本倉 健*; 福田 拓磨*; 上村 洋平*; 松村 大樹; 池田 まりか*; 南保 雅之*; Chun, W.-J.*
Catalysts, 8(3), p.106_1 - 106_8, 2018/03
被引用回数:1 パーセンタイル:94.58(Chemistry, Physical)In this study, mesoporous and nonporous silica-supported Pd complexes were synthesized and characterized. Variable-temperature XAFS measurements and a curve-fitting analysis showed a slightly larger contribution of when the Pd complexes were on a nonporous support in comparison to a mesoporous support. In contrast, the catalytic performance of the attached Pd complex in the Suzuki-Miyaura cross-coupling reaction was not affected by such small differences in the static disorder of the Pd complex.