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MnCoNiCu)VO
山本 孟*; 辻 卓也; 松村 大樹; 他16名*
Inorganic Chemistry, 64(34), p.17496 - 17502, 2025/08
V-V dimerization in ilmenite-type vanadium oxides is an intriguing phenomenon that induces structural and metal-to-insulator transitions. Herein, we report the high-pressure synthesis, crystal structure, and electronic states of high-entropy ilmenite-type (MgMnCoNiCu)VO. Although all the parent ilmenite-type compounds exhibit triclinic (
) symmetry, this compound crystallizes in a rhombohedral (
) structure, indicating the absence of V-V dimer ordering. The temperature dependence of the resistivity below room temperature follows a variable-range hopping conduction mechanism, suggesting the presence of short-range V-V dimer ordering. Magnetic susceptibility and heat capacity measurements revealed multi-step spin-glass transitions. This study demonstrates that a high-entropy composition hinders electronic and magnetic long-range ordering due to severe lattice distortions and competition between magnetic exchange interactions.
O
and/or SiO for methanol synthesis; Deciphering the additive-induced boost in catalytic performance by XAFSIwasaki, Kosei*; Ashida, Yuya*; 松村 大樹; Kawakami, Kotaro*; Shibuya, Kana*; Tazawa, Masaru*; 辻 卓也; Shimizu, Hajime*
Journal of CO Utilization, 97, p.103111_1 - 103111_9, 2025/07
The development of active, long-lived methanol synthesis catalysts can be expedited by thoroughly understanding the operating mechanisms of promoter additives. SiO serves as an effective support and promoter for Cu/ZnO-type methanol synthesis catalysts; however, it has not been studied as extensively as the industrially predominant AlO, despite being similarly potent. Therefore, we conducted X-ray absorption fine structure predominant AlO, despite being similarly potent. Therefore, we conducted X-ray absorption fine structure studies to probe the effects of incorporating AlO and SiO additives into Cu/ZnO-based heterogeneous catalysts. The results revealed that the additive elements primarily affected the ability of the Zn species to generate oxygen vacancies by distorting the local structure around element-doped ZnO and that the number of oxygen vacancies correlated to the catalytic activity. Additionally, the oxygen vacancies in ZnO in the Al/Si-incorporated catalysts diminished under catalytic reaction conditions, thereby providing information on the deactivation of catalytic reactions. Our findings can facilitate the development of highly active industrial-grade methanol synthesis catalysts.
田中 裕久*; 松村 大樹; 他10名*
International Journal of Hydrogen Energy, 141, p.1088 - 1097, 2025/06
Global efforts are being made to decarbonize the energy sector. Liquefied (cryogenic) hydrogen is suitable for large-scale storage and transportation due to its high storage density, so it is likely to play a fundamental role in the future hydrogen economy. The STACY project, "Towards the Safe Storage and Transport of Cryogenic Hydrogen", is investigating safety aspects of liquid hydrogen in order to overcome potential safety risks. Research is being conducted into passive autocatalytic recombiners using cutting-edge catalyst technology to enable them to be used in conditions where liquid hydrogen escapes, evaporates and forms a cold (
50
C) explosive gas mixture with the ambient air. To this end, the crystal structure of the catalyst was designed at the atomic level, an actual catalyst was prototyped, and repeated tests were carried out on a laboratory scale and in a large reaction vessel. Progress has been made in developing catalysts that can oxidize hydrogen even at very low temperatures, high expansion, and low-oxygen environments, are resistant to catalyst poisons, and can prevent spontaneous unintended ignition. The tested catalyst technologies use different carrier materials (alumina and ceria) to control the surface state of precious metals and suppress hydrogen ignition through a multilevel configuration.
田中 裕久*; 松村 大樹; 他8名*
International Journal of Hydrogen Energy, 141, p.1317 - 1327, 2025/06
The safe removal, transportation, and long-term storage of fuel debris in the decommissioning of Fukushima Daiichi is the biggest challenge facing Japan. In the nuclear power field, passive autocatalytic recombiners (PARs) have become established as a technology to prevent hydrogen explosions inside the containment vessel. To utilize PAR as a measure to reduce the concentration of hydrogen generated in the fuel debris storage canister, which is currently an issue, it is required to perform in a sealed environment with high doses of radiation, low temperature, and high humidity, and there are many challenges different from conventional PAR. A honeycomb-shaped catalyst based on automotive catalyst technology has been newly designed as a PAR, and research has been conducted to solve unique problems such as high dose radiation, low temperature, high humidity, coexistence of hydrogen and low oxygen, and catalyst poisons. This paper summarizes the challenges of hydrogen generation in a sealed container, the results of research, and a guide to how to use the PAR for fuel debris storage canisters.
by solvent extraction as a potential method to determine Fe in glass containing Sn菅野 直樹*; 中瀬 正彦*; 西條 佳孝*; 松村 大樹; 辻 卓也; 竹下 健二*; 塚原 剛彦*
Progress in Nuclear Science and Technology (Internet), 7, p.154 - 160, 2025/03
The amounts of Fe and Fe
present in glass are important indicators of its optical properties because even small amounts have significant effects. However, it is challenging to use wet chemical analysis to determine the concentration and the ratio of Fe and Fe in glass when it contains Sn because of the redox reaction between Sn and Fe in the glass decomposition solution. A two-step approach was tested to determine the concentrations of Fe and Fe in a glass decomposition solution in the presence of Sn. In the first step, the redox reaction between Sn and Fe was suppressed by increased pH. In the second step, Sn was removed from the glass decomposition solution by solvent extraction. To understand the kinetics of the redox reaction between Sn and Fe, time-resolved dispersive X-ray absorption fine structure and ultraviolet-visible absorption spectroscopy (UV-vis) were used with standard chloride solutions of Sn and Fe in respective valences. We found that lowering the acid concentration suppressed redox reactions. The partitioning behaviors of Sn, Sn
, Fe, and Fe by bis(2-ethylhexyl) hydrogen phosphate (D2EHPA) as an extractant in 
-dodecane were investigated to see the removal ability of Sn from the glass decomposition solution. As a result, D2EHPA in -dodecane could extract Sn, Sn, and Fe into the organic phase, and Fe remained in the aqueous phase. The simultaneous removal of Sn and Sn and the separation of Fe and Fe became possible. This method can potentially apply to the rapid analysis of the concentration of Fe and Fe in a glass containing tin oxide.
-orbital transition metal multielemental alloy nanoparticles by atomically dispersed 4-orbital Pd for a 100-fold extended lifetimeZhu, B.*; Huang, S.*; Seo, O.*; Cao, M.*; 松村 大樹; Gu, H.*; Wu, D.*
Journal of the American Chemical Society, 147(13), p.11250 - 11256, 2025/02
Earth-abundant 3-orbital late transition metals are the most used and highly desired catalysts for the oxygen evolution reaction (OER) but are prone to quick oxidative dissolution, leading to poor durability. We first report that FeCoNiCu multielemental alloy nanoparticles (MEANPs) can be stabilized with only 0.3 at.%Pd, a 4-orbital element. Although pure Pd is known for extremely poor OER activity and durability, Pd-FeCoNiCu sustains 1000 h at 10 mA cm
. In an accelerating durability test (ADT) at 100 mA cm, it exhibits a mere 8.9 mV increase over 25 h with a degradation rate of 0.356 mVh
, which is 1/350th that of FeCoNiCu (125 mVh) and among the most stable OER catalysts reported so far. Aberration-corrected HAADF-STEM and X-ray absorption fine structure (XAFS) reveal that atomically dispersed Pd atoms, surrounded by Fe, Co, Ni, and Cu atoms, contributed to a more delocalized electronic structure and stronger bonding via strong -/
hybridization and the vibronic coupling induced by atomic displacement. The altered local density of states (LDOS) of Fe, Co, Ni, and Cu mitigates the oxidation of FeCoNiCu in OER by over 50%, quantified by hard X-ray photoelectron spectroscopy (HAXPES), making the combination of these five dissoluble elements a durable catalyst.
小林 大志*; 佐藤 祐太郎*; 頓名 龍太郎*; 松村 大樹; 佐々木 隆之*; 池田 篤史
Dalton Transactions (Internet), 53(46), p.18616 - 18628, 2024/10
被引用回数：0 パーセンタイル：22.23(Chemistry, Inorganic & Nuclear)This study investigates the dissolution behaviour of zirconium-cerium oxide solid solution ((Zr,Ce)O/(Ce,Zr)O), which contains a redox-active metal of Ce (Ce(III/IV)) and is of particular importance in nuclear industry. The solid phases of the solid-solution were comprehensively characterised by powder X-ray diffraction (PXRD) with the Rietveld analysis and X-ray absorption spectroscopy (XAS) with factor analysis, indicating that the solid-solution is primarily composed of tetragonal-(Zr,Ce)O and cubic-(Ce,Zr)O. Water immersion of the solid-solution leads to the dissolution of the solid phase at the solid-liquid interface. The addition of a reductant to the system reduces Ce(IV) in the solid-solution to -(III) at the surface, promoting the dissolution of Ce from the solid-solution phase. The release of Ce from the solid-solution also enriches the Zr content in the remaining solid-solution phase at the surface to be more insoluble.
辻 卓也; 松村 大樹; 小林 徹
SPring-8/SACLA利用研究成果集(インターネット), 12(5), p.259 - 262, 2024/10
2:1型層状粘土鉱物には層を構成する陽イオンが同形置換することで層電荷を持ち、層間に陽イオンを取り込むことで電荷を補償する。また、層電荷の大小により異なる膨潤性を示す。風化黒雲母は比較的大きい層電荷をもつため膨潤性が低く、モンモリロナイトは層電荷が小さいため膨潤性が高い。アルミノケイ酸塩であるゼオライトは様々な細孔を持ち、その内部に水分子を持つ。これらの粘土鉱物中では、降雨等の環境の変化により異なるセシウム収着構造をとることが考えられるため、本研究では湿潤・乾燥・再湿潤状態の粘土鉱物試料に対し、Cs K吸収端X線吸収分光(X-ray Absorption Fine Structure, XAFS)測定によりセシウム近傍の局所構造解析を行った。その結果、湿潤・乾燥試料においては水分子の存在により、一部の収着サイトではセシウムを収着しにくくなり、乾燥・再湿潤試料においては収着構造に差はなく、不可逆的にセシウムが収着していることが示唆された。
Krajewska, A.*; 辻 卓也; 松村 大樹; 他15名*
Science Advances (Internet), 10(41), p.eadn3880_1 - eadn3880_10, 2024/10
被引用回数：4 パーセンタイル：70.50(Multidisciplinary Sciences)The interplay of spin-orbit coupling with other relevant parameters gives rise to the rich phase competition in complex ruthenates featuring octahedrally coordinated Ru. While locally, spin-orbit coupling stabilizes a non-magnetic 
= 0 state, intersite interactions resolve one of two distinct phases at low temperatures: an excitonicmagnet stabilized by the magnetic exchange of upper-lying = 1 states or Ru molecular orbital dimers driven by direct orbital overlap. Pyrochlore ruthenates ARuO
(A = rare earth, Y) are candidate excitonic magnets with geometrical frustration. We synthesized InRuO with covalent In-O bonds. This pyrochlore ruthenate hosts alocal = 0 state at high temperatures; however, at low temperatures, it forms a unique nonmagnetic ground state with nearly linear Ru-O-Ru molecules, in stark contrast to other ARuO compounds. The disproportionation of covalent In-O bonds drives RuO molecule formation, quenching not only the local spin-orbit singlet but also geometrical frustration.
, AgNbO, and KNbO米田 安宏; 小林 徹; 辻 卓也; 松村 大樹; 斎藤 祐児; 野口 祐二*
Japanese Journal of Applied Physics, 63(9), p.09SP12_1 - 09SP12_10, 2024/09
被引用回数：2 パーセンタイル：52.00(Physics, Applied)NaNbO、AgNbO、KNbOのABO型ペロブスカイト系は良好な強誘電特性を持つことが知られている。我々は局所構造解析により各原子のラットリング空間を直接決定した。この解析により、大きな揺らぎを持つ結合サイトがイオンサイズの変化によって変化することを明らかにした。軟X線吸収分光法を含む実験から、Aサイトイオンは酸素と混成していることがわかった。
山本 孟*; 池田 理*; 本田 孝志*; 木村 健太*; 青山 拓也*; 大串 研也*; 鈴木 昭夫*; 石井 賢司*; 松村 大樹; 辻 卓也; et al.
Physical Review Materials (Internet), 8(9), p.094402_1 - 094402_6, 2024/09
被引用回数：3 パーセンタイル：43.86(Materials Science, Multidisciplinary)We investigate the crystal and electronic structures as well as magnetic properties of ilmenite-type NiVO, which has attracted research interest as an 
= 1 honeycomb lattice magnet. Ilmenite-type NiVO samples were synthesized under high-pressure and high-temperature conditions. Synchrotron X-ray diffraction and Rietveld refinement results demonstrated that NiVO underwent a continuous structural phase transition from the triclinic (
) phase to the rhombohedral (
) phase at 450 K. This transition is concomitant with the decomposition of the V-V dimers formed by the tetravalent V ions. X-ray absorption spectroscopy measurements confirmed that the Ni and V ions were divalent and tetravalent, respectively. Magnetic and specific heat measurements revealed that NiVO underwent an antiferromagnetic transition at 140 K, and a zigzag-type magnetic order with magnetic propagation vector 
=(0,1/2,0) was observed by neutron diffraction measurements.
O-BO-SiO glass and melt through high-temperature Ni K-edge XAFS and time-resolved SAXS measurements富田 夏奈*; 岸 哲生*; 大坂 恵一*; 松村 大樹; 矢野 哲司*
Journal of Non-Crystalline Solids, 634, p.122975_1 - 122975_19, 2024/06
被引用回数：0 パーセンタイル：0.00(Materials Science, Ceramics)High-temperature in-situ Ni-K edge XAFS and SAXS measurements were conducted on borosilicate glasses with low alkali content with/without phase separation tendency, which have been investigated to understand immiscibility into silica-rich phase and borate-rich one on the samples heat-treated at certain temperature followed by fast quenching. In this work, using in-situ analyzing techniques, in-situ time-domain evolution of phases along temperature and time was obtained to understand high-temperature behavior. Ni ion probes phase separation behavior using its high selectivity favoring borate-rich phase and sensitivity to electron donating ability of surrounding oxygens. Taking advantage of these characters, local compositional change was tracked during phase separation under heat treatment. Time-resolved SAXS profiles revealed the speed of phase transformation in addition to changes of morphology at respective temperature. The phase-separation transformation mechanism via different phase separation scheme (homogeneous 
spinodal binodal homogeneous) was clearly described, revealing effect of NiO clustering at higher temperature.
Jung, H.*; 松村 大樹; 他12名*
ACS Energy Letters (Internet), 9(5), p.2162 - 2172, 2024/04
被引用回数：13 パーセンタイル：89.85(Chemistry, Physical)A strategic approach has been proposed for designing robust, high-performing oxygen evolution reaction (OER) catalysts tailored for saline water splitting. By employing a density functional theory (DFT)-based computational screening process, a set of promising dopants were identified from a range of 26 3d to 5d transition metals, with the aim of enhancing the activity and saline water resilience of the catalysts. The screening methodology was 3-fold, encompassing evaluations of OER energetics, chlorine evolution reaction (ClER) energetics, and chloride-corrosion energetics. The screening led to the selection of Sc as a promising dopant, which substantially elevated the performance of the NiFeOOH catalysts. This improvement was validated by an 87 mV decrease in OER overpotential at 100 mA/cm
and a 100 h stability test under 1 M KOH + 0.5 M NaCl conditions. This study contributes to the understanding of the alkaline ClER and chloride-corrosion mechanisms, providing insights into catalyst behavior under saline conditions.
Lei, Y.-J.*; 松村 大樹; 他15名*
Nature Communications (Internet), 15, p.3325_1 - 3325_12, 2024/04
被引用回数：53 パーセンタイル：99.03(Multidisciplinary Sciences)The effective flow of electrons through bulk electrodes is crucial for achieving high-performance batteries, although the poor conductivity of homocyclic sulfur molecules results in high barriers against the passage of electrons through electrode structures. This phenomenon causes incomplete reactions and the formation of metastable products. To enhance the performance of the electrode, it is important to place substitutable electrification units to accelerate the cleavage of sulfur molecules and increase the selectivity of stable products during charging and discharging. Herein, we develop a single-atom-charging strategy to address the electron transport issues in bulk sulfur electrodes. The establishment of the synergistic interaction between the adsorption model and electronic transfer helps us achieve a high level of selectivity towards the desirable short-chain sodium polysulfides during the practical battery test. These finding indicates that the atomic manganese sites have an enhanced ability to capture and donate electrons. Additionally, the charge transfer process facilitates the rearrangement of sodium ions, thereby accelerating the kinetics of the sodium ions through the electrostatic force. These combined effects improve pathway selectivity and conversion to stable products during the redox process, leading to superior electrochemical performance for room temperature sodium-sulfur batteries.
南川 卓也; 関根 由莉奈; 松村 大樹; 廣井 孝介; 高田 慎一; 神谷 嘉美*; 本多 貴之*
Langmuir, 40(11), p.5725 - 5730, 2024/03
被引用回数：0 パーセンタイル：16.77(Chemistry, Multidisciplinary)鉄と漆の化学反応を利用して、古くから黒漆が作られている。しかし、鉄と漆の反応については、ほとんど知られていない。本研究では、黒漆中のFeイオンの化学状態を、XANES, EXAFS、SAXS, SANSおよびFT-IRを使用して調査した。Fe(II)またはFe(III)を生漆に添加し、空気乾燥,加熱、またはUV照射により黒漆フィルムを作成した。これらのサンプルのXANESスペクトルの測定結果から、最初に添加したFeの酸化状態に関係なく、サンプル内のFeイオンが3価の状態で存在していることが明らかとなった。また、すべてのフィルムサンプルのEXAFSスペクトルは同様の形状であったが、ピーク強度は、空気乾燥
UV照射加熱の順に減少した。この結果は、加熱やUV照射により黒漆中のFeの配位構造が不均一になり、加熱が最も不均一になったことを示している。サンプルのFT-IRスペクトルの変化は、ウルシオールの重合挙動が空気乾燥,加熱、およびUV照射下でも異なり、漆中での反応により、Feの配位構造が不均一になることが明らかとなった。このような結果から、XANESやEXAFSスペクトルは、黒漆の情報を簡易に得る手法として有用であり、貴重な文化財の黒漆の非破壊分析に特に有効である。
池田 一貴*; 佐次田 頌*; 大友 季哉*; 大下 英敏*; 本田 孝志*; 羽合 孝文*; 齋藤 開*; 伊藤 晋一*; 横尾 哲也*; 榊 浩司*; et al.
International Journal of Hydrogen Energy, 51(Part A), p.79 - 87, 2024/01
被引用回数：6 パーセンタイル：37.32(Chemistry, Physical)Low-vanadium-concentration alloys have low durability, and their hydrogen absorption and desorption amounts decrease by 20% after 100 cycles. In this study, we conducted reverse Monte Carlo modeling on X-ray diffraction patterns and neutron pair distribution functions of the hydrogen-absorbed and desorbed samples of a V
Ti
Cr
alloy to analyze the variations in the local structure. The local structure surrounding the hydrogen atom in the hydrogen-absorbed phase exhibited minimal changes. In contrast, hydrogen occupied both tetrahedral and octahedral sites of the hydrogen-desorbed phase almost equally during the early cycles; however, the amount of hydrogen occupying the tetrahedral sites increased with the number of cycles.
Ga K-edge XANES study of Ga-exchanged zeolites at high temperatures under different atmospheres including vacuum, CO, and pressurized HHuang, 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
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)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.
岡崎 宏之*; 出崎 亮*; 越川 博*; 松村 大樹; 池田 隆司*; 山本 春也*; 八巻 徹也*
Journal of Physical Chemistry C, 127(49), p.23628 - 23633, 2023/12
被引用回数：2 パーセンタイル：15.01(Chemistry, Physical)The change in the oxygen adsorption states of Pt nanoparticles by ion irradiation of the carbon support is studied by in situ X-ray absorption spectroscopy measurements. The difference spectra around a Pt L edge due to oxygen adsorption are recorded, and a lowering in the Pt-O antibonding level by the ion irradiation is observed, thus resulting in a weakening of the Pt-O bond. This indicates that the introduction of vacancies in the carbon support would result in weak Pt-O bonds assumable through the stronger Pt-C interaction, which is considered to enhance the oxygen reduction reaction activity of the deposited Pt nanoparticles. Theoretical studies have demonstrated that the vacancies affect Pt through the Pt-C interaction and then result in the weakening of the Pt-O bond.
NaTiO
BaTiO solid solutions米田 安宏; 小林 徹; 辻 卓也; 松村 大樹; 斎藤 祐児; 野口 祐二*
Japanese Journal of Applied Physics, 62(SM), p.SM1006_1 - SM1006_8, 2023/11
被引用回数：5 パーセンタイル：47.28(Physics, Applied)BiNaTiOBaTiO (BNT
BT)固溶体は良い圧電特性を示すため多くの研究が行われてきた。また、BT組成に応じてバラエティーに富んだ相が観測される。BNTBT固溶体の軟X線吸収分光実験と高エネルギーX線回折実験を放射光を利用して行った。得られたBNTBT固溶体の電子構造と局所構造から、BTの置換効果は主にBaの置換サイトであるAサイトで起こっていることがわかった。BT組成の変化に対してTiO
八面体の菱面体晶ひずみは変化しておらず、O-K吸収端で生じた電子構造の変化は混成状態の変化であると考えられる。
松村 大樹; 木村 優作*; 辻 卓也; 水木 純一郎*
SPring-8/SACLA利用研究成果集(インターネット), 11(5), p.296 - 299, 2023/11
自発振動現象を起こすRh金属微粒子触媒上のCO酸化反応について、分散型光学系による時間分解X線吸収分光法を用いた研究を実施した。定常ガスを一定温度で導入して、触媒反応の振動現象が起こっている最中のRh金属微粒子の構造変化について、1Hz程度のフレームレートで詳細観測した。触媒反応生成物であるCO濃度の時間変化とX線吸収分光法によるRh金属微粒子構造の時間変化とを比べると、両者は強く相関していることが見て取れた。振動構造の様式には、Rhの平均価数変化は階段状のものである一方COの生成量はパルス状の変化であるという違いがあり、これは金属Rh表面で短時間のみ吸着COが無い状態が実現されるという考えで解釈できた。
