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論文

Dissolution of zirconium-cerium oxide solid solution in an aqueous system

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

https://doi.org/10.1039/D4DT02272F
 被引用回数：0 パーセンタイル：0.00(Chemistry, Inorganic & Nuclear)

This study investigates the dissolution behaviour of zirconium-cerium oxide solid solution ((Zr,Ce)O$$_{2}$$/(Ce,Zr)O$$_{2}$$), 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$$_{2}$$ and cubic-(Ce,Zr)O$$_{2}$$. 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.

論文

乾燥-湿潤過程における粘土鉱物のCs収着構造の解明

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

https://doi.org/10.18957/rr.12.5.259

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。

論文

Nearly linear orbital molecules on a pyrochlore lattice

Krajewska, A.*; 辻 卓也; 松村 大樹; 他15名*

Science Advances (Internet), 10(41), p.eadn3880_1 - eadn3880_10, 2024/10

https://doi.org/10.1126/sciadv.adn3880
 被引用回数：3 パーセンタイル：43.84(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$$^{4+}$$. While locally, spin-orbit coupling stabilizes a non-magnetic $$J_{rm eff}$$ = 0 state, intersite interactions resolve one of two distinct phases at low temperatures: an excitonicmagnet stabilized by the magnetic exchange of upper-lying $$J_{rm eff}$$ = 1 states or Ru$$_{2}$$ molecular orbital dimers driven by direct orbital overlap. Pyrochlore ruthenates A$$_{2}$$Ru$$_{2}$$O$$_{7}$$ (A = rare earth, Y) are candidate excitonic magnets with geometrical frustration. We synthesized In$$_{2}$$Ru$$_{2}$$O$$_{7}$$ with covalent In-O bonds. This pyrochlore ruthenate hosts alocal $$J_{rm eff}$$ = 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 A$$_{2}$$Ru$$_{2}$$O$$_{7}$$ compounds. The disproportionation of covalent In-O bonds drives Ru$$_{2}$$O molecule formation, quenching not only the local spin-orbit singlet but also geometrical frustration.

論文

Local and electronic structures of NaNbO$$_3$$, AgNbO$$_3$$, and KNbO$$_3$$

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

https://doi.org/10.35848/1347-4065/ad72fc
 被引用回数：1 パーセンタイル：35.22(Physics, Applied)

NaNbO$$_3$$、AgNbO$$_3$$、KNbO$$_3$$のABO$$_3$$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。

論文

Continuous structural phase transition and antiferromagnetic order in ilmenite-type NiVO$$_{3}$$

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

https://doi.org/10.1103/PhysRevMaterials.8.094402
 被引用回数：2 パーセンタイル：51.02(Materials Science, Multidisciplinary)

We investigate the crystal and electronic structures as well as magnetic properties of ilmenite-type NiVO$$_{3}$$, which has attracted research interest as an ${it S}$ = 1 honeycomb lattice magnet. Ilmenite-type NiVO$$_{3}$$ samples were synthesized under high-pressure and high-temperature conditions. Synchrotron X-ray diffraction and Rietveld refinement results demonstrated that NiVO$$_{3}$$ underwent a continuous structural phase transition from the triclinic (${it P$bar{1}$}$) phase to the rhombohedral (${it R$bar{3}$}$) 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$$_{3}$$ underwent an antiferromagnetic transition at 140 K, and a zigzag-type magnetic order with magnetic propagation vector ${it k}$=(0,1/2,0) was observed by neutron diffraction measurements.

論文

Computational discovery of optimal dopants for nickel iron oxyhydroxide to enhance OER activity and saline water compatibility

Jung, H.*; 松村 大樹; 他12名*

ACS Energy Letters (Internet), 9(5), p.2162 - 2172, 2024/04

https://doi.org/10.1021/acsenergylett.4c00442
 被引用回数：11 パーセンタイル：92.35(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$$^{2}$$ 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.

論文

Understanding the charge transfer effects of single atoms for boosting the performance of Na-S batteries

Lei, Y.-J.*; 松村 大樹; 他15名*

Nature Communications (Internet), 15, p.3325_1 - 3325_12, 2024/04

https://doi.org/10.1038/s41467-024-47628-3
 被引用回数：38 パーセンタイル：98.58(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.

論文

Effects of Fe ions, ultraviolet irradiation, and heating on microscopic structures of black lacquer films

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

https://doi.org/10.1021/acs.langmuir.3c03412
 被引用回数：0 パーセンタイル：0.00(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。

論文

Local structural changes in V-Ti-Cr alloy hydrides with hydrogen absorption/desorption cycling

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

https://doi.org/10.1016/j.ijhydene.2023.10.318
 被引用回数：6 パーセンタイル：46.16(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$$_{0.10}$$Ti$$_{0.36}$$Cr$$_{0.54}$$ 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.

論文

${it In situ}$ Ga K-edge XANES study of Ga-exchanged zeolites at high temperatures under different atmospheres including vacuum, CO, and pressurized H$$_{2}$$

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
 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$$_{2}$$, He, CO, vacuum, and C$$_{2}$$H$$_{6}$$). The absorption edge appeared at similarly lower energy values than that of Ga$$_{2}$$O$$_{3}$$ 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$$_{2}$$ and C$$_{2}$$H$$_{6}$$ atmospheres than under CO and vacuum atmospheres.

論文

Weakened oxygen adsorbing the Pt-O bond of the Pt catalyst induced by vacancy introduction into carbon support

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

https://doi.org/10.1021/acs.jpcc.3c04117
 被引用回数：1 パーセンタイル：9.61(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$$_{3}$$ 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.

論文

Local structure analysis of Bi$$_{0.5}$$Na$$_{0.5}$$TiO$$_3-$$BaTiO$$_3$$ 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

https://doi.org/10.35848/1347-4065/ace3cd
 被引用回数：5 パーセンタイル：47.87(Physics, Applied)

Bi$$_{0.5}$$Na$$_{0.5}$$TiO$$_3-$$BaTiO$$_3$$ (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。BNT$$-$$BT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BNT$$-$$BT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$$_6$$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。

論文

分散型光学系を用いた時間分解X線吸収分光法によるRh金属微粒子触媒のCO酸化反応における自発振動現象の詳細観測

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

https://doi.org/10.18957/rr.11.5.296

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$$_{2}$$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$$_{2}$$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。

論文

Local atomic displacements and sign of the structural transformation in medium-entropy alloys observed in extended X-ray absorption fine structure spectra

池田 陽一*; 梅本 好日古*; 松村 大樹; 辻 卓也; 橋本 勇輝*; 北澤 崇文*; 藤田 全基*

Materials Transactions, 64(9), p.2254 - 2260, 2023/09

https://doi.org/10.2320/matertrans.MT-M2023043
 被引用回数：4 パーセンタイル：44.33(Materials Science, Multidisciplinary)

Extended X-ray absorption fine structure (EXAFS) and neutron diffraction experiments were carried out to clarify the typical features of the local structure of a family of medium-entropy alloys (CrCoNi, MnCoNi, and FeCoNi). A simple random cluster model was constructed for analyzing EXAFS spectra, and static and dynamic components of the mean-square relative displacement (MSRD) were separately extracted. In our analysis, the static MSRD of the MnCoNi sample was slightly larger than those of the CrCoNi and FeCoNi samples, whereas the dynamic MSRDs of these samples were almost identical. Based on the complementary neutron diffraction data, we argued that the origin of the large static displacement in the MnCoNi alloy can be associated with a short-range structural transformation through long-term structural relaxation.

論文

Local structure analysis of DyN-ZrN solid solutions

米田 安宏; 辻 卓也; 松村 大樹; 岡本 芳浩; 高木 聖也; 高野 公秀

Physica B; Condensed Matter, 663, p.414960_1 - 414960_9, 2023/08

https://doi.org/10.1016/j.physb.2023.414960
 被引用回数：0 パーセンタイル：0.00(Physics, Condensed Matter)

DyN-ZrN固溶体の局所構造と平均構造を抽出するために、放射光X線を用いた種々の測定を行った。X線吸収微細構造(XAFS)と高エネルギーX線回折を組み合わせてナノスケールの構造解析を行い、DyN-ZrN固溶体の構造不安定性を議論した。DyN-ZrN固溶体は岩塩型立方晶の結晶構造を持ち、金属サイトの化学秩序や窒素サイトの結合長分布などの不安定性があり、相分離や構造不連続の原因となっていることがわかった。

論文

Cs ${it L$_{1}$}$吸収端XAFS測定による各種粘土鉱物中におけるセシウムの収着構造

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), 11(4), p.214 - 217, 2023/08

https://doi.org/10.18957/rr.11.4.214

天然に存在する粘土鉱物は様々な層構造をもち、セシウムイオン等の陽イオン収着サイトは複数存在すると考えられており、層間サイト、表面サイトや端面サイト等が存在すると考えられている。福島第一原子力発電所事故後に放射性セシウムにより汚染された土壌中での詳細な収着構造解明のため、本研究ではセシウムを飽和収着させた粘土鉱物試料に対しCs ${it L$_{1}$}$吸収端X線吸収分光(X-ray absorption fine structure, XAFS)測定を行い、セシウム収着様式の比較を行った。その結果、各種粘土鉱物においてスペクトルの詳細構造に差がみられ、四面体シートや八面体シートへの収着等、収着構造の違いに起因するセシウム収着様式の違いが明らかになった。

論文

Development of hydrogen oxidation reaction catalysts to overcome CO poisoning and elucidation of reaction mechanism

稲川 康平*; 松村 大樹; 谷口 昌司*; 上垣 伸弥*; 中山 智仁*; 浦野 純乃介*; 青谷 拓朗*; 田中 裕久*

Journal of Physical Chemistry C, 127(24), p.11542 - 11549, 2023/06

https://doi.org/10.1021/acs.jpcc.3c02237
 被引用回数：3 パーセンタイル：20.33(Chemistry, Physical)

Passive autocatalytic recombiner (PAR) represents a potential technology for ensuring process safety in the hydrogen society. PARs function through the catalytic oxidation of generated or leaked hydrogen, facilitating its conversion into water and effectively mitigating the risk of hydrogen explosions. CO is recognized as a catalyst poison that hampers surface catalytic reactions. To investigate the negative effects of CO on the local structure of platinum metal nanoparticle catalysts during water formation, in situ and time-resolved X-ray absorption spectroscopy analyses were conducted. The results revealed that the Pt-Fe/CZY catalyst exhibited notable hydrogen oxidation activity even in the presence of CO. The enhanced performance can be attributed to the combined effects of Pt-Fe alloy composition and CZY support materials.

論文

Cu $$K$$-edge X-ray absorption fine structure study of $$T'$$-type $$RE$$$$_{2}$$CuO$$_{4+alpha-delta}$$ ($$RE$$ = Rare Earth); Toward unified understanding of electronic state of $$T'$$-type cuprate

Chen, Y.*; 浅野 駿*; Wang, T.*; Xie, P.*; 北山 慎之介*; 石井 賢司*; 松村 大樹; 辻 卓也; 谷口 貴紀*; 藤田 全基*

JPS Conference Proceedings (Internet), 38, p.011050_1 - 011050_6, 2023/05

https://doi.org/10.7566/JPSCP.38.011050

To investigate the variation of the electronic state of $$T'$$-type cuprate due to annealing, we performed Cu $$K$$-edge X-ray absorption fine structure measurements on Pr$$_{2}$$CuO$$_{4+alpha-delta}$$ (PCO) and Pr$$_{1.3}$$La$$_{0.7}$$CuO$$_{4+alpha-delta}$$ (PLCO). The induced electrons due to annealing ($$n_{AN}$$) in PCO and PLCO were approximately 2$$delta$$, consistent with a model of electron doping to Mott insulator. Here, $$alpha$$ and $$delta$$ represent the amount of excess oxygen from the stoichiometric composition in the as-sintered compound and that of oxygen loss due to annealing, respectively. Furthermore, the energy of the Einstein oscillator ($$hbaromega_{E}$$) for the Cu-O$$_{p}$$ bond was evaluated by extended X-ray absorption fine structure analysis. (O$$_{p}$$ denotes the in-plane oxygen.) We found a small annealing effect on $$hbaromega_{E}$$ for both PCO and PLCO.

論文

Uranium hydroxide/oxide deposits on uranyl reduction

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

https://doi.org/10.1039/D3RA02899B
 被引用回数：1 パーセンタイル：10.11(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(U$$^{rm VI}$$O$$_{2}$$$$^{2+}$$)の還元に伴う析出物の化学状態変化を明らかにした。U$$^{rm VI}$$O$$_{2}$$$$^{2+}$$の還元に伴い、(1)U$$^{rm V}$$の不均化によりU$$^{rm IV}$$が生成する。(2)U$$^{rm IV}$$はU$$^{rm IV}$$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$$^{rm IV}$$酸化物に変化する析出機構が提案される。

論文

Crystal structure, photomagnetic and dielectric properties of a cyanido-bridged Cu-Mo assembly film

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

https://doi.org/10.1016/j.ica.2023.121434
 被引用回数：0 パーセンタイル：0.00(Chemistry, Inorganic & Nuclear)

A film of a cyanido-bridged Cu-Mo assembly Cu$$_{2}$$[Mo(CN)$$_{8}$$]$$cdot$$8H$$_{2}$$O (CuMo-film) was electrochemically synthesized. Unlike analogs with a formula of M$$_{2}$$[Mo(CN)$$_{8}$$]$$cdot$$zH$$_{2}$$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 $AA, b = 11.1681 AA, c = 11.2618 AA, $beta$$ = 125.1089$$^{circ}$$, and V = 1774.44 $AA$^{3}$$. Extended X-ray absorption fine structure analysis traced the bond distances around the Cu site as 1.93-2.30 $r{A}$ for Cu-N and 2.01-2.40 $r{A}$ for Cu-O. CuMo-film exhibits photo-switchable magnetization with T$$_{C}$$ = 18 K and dielectric relaxation related to the hydrogen bond network. The change of activation energy (E$$_{a}$$) of the dielectric relaxation around 157 K (from E$$_{a}$$ = 49.9 kJ mol$$^{-1}$$ to E$$_{a}$$ = 27.3 kJ mol$$^{-1}$$ on cooling) suggests that the development of the hydrogen bond network occurs below 157 K.

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