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論文

Spontaneous formations of nanoconfined water in ionic liquids by small-angle neutron scattering

阿部 洋*; 根本 文也*; 廣井 孝介; 大石 一城*; 高田 慎一

Journal of Molecular Liquids, 346, p.117035_1 - 117035_6, 2022/01

 被引用回数:4 パーセンタイル:61.27(Chemistry, Physical)

In this study, monodispersive nanoconfined water ("water pocket") is organized spontaneously in hydrophilic ionic liquid (IL). The IL is 1-alkyl-3-methylimidazolium nitrate ([C$$_{n}$$mim][NO$$_{3}$$] $$n$$ = 2, 6, and 8). By small-angle neutron scattering (SANS), D$$_{2}$$O aggregations in the IL are detected. There are no SANS peaks for [C$$_{2}$$mim][NO$$_{3}$$]-D$$_{2}$$O, but, in [C$$_{6}$$mim][NO$$_{3}$$]-$$x$$ mol% D$$_{2}$$O, a SANS peak can be observed at $$70 < x < 90$$ mol%. The peak intensity, position, and profile change according to water concentration and temperature. Pure [C$$_{8}$$mim][NO$$_{3}$$] has a distinct SANS peak, reflecting on the nanodomains at room temperature. Above 70 mol%, the SANS peak of [C$$_{8}$$mim][NO$$_{3}$$]-D$$_{2}$$O sharply increases and shifts to the low-Q position. The water pocket develops proportionate to water concentration, and its morphologies are visualized using an ${it ab initio}$ bead model. The alkyl chain length dependence of the water pocket is clarified by a three-dimensional reconstruction method.

論文

Neutron scattering studies on short- and long-range layer structures and related dynamics in imidazolium-based ionic liquids

根本 文也*; 古府 麻衣子; 長尾 道弘*; 大石 一城*; 高田 慎一; 鈴木 淳市*; 山田 武*; 柴田 薫; 上木 岳士*; 北沢 侑造*; et al.

Journal of Chemical Physics, 149(5), p.054502_1 - 054502_11, 2018/08

 被引用回数:19 パーセンタイル:70.02(Chemistry, Physical)

Alkyl-methyl-imidazolium ionic liquids C$$n$$mimX ($$n$$: alkyl-carbon number, X: anion) have short-range layer structures consisting of ionic and neutral (alkylchain) domains. To investigate the temperature dependences of the interlayer, interionic group, and inter-alkylchain correlations, we have measured the neutron diffraction (ND) of C$$n$$mimPF$$_6$$ ($$n$$ = 16, 9.5, 8). The quasielastic neutron scattering (QENS) of C16mimPF$$_6$$ was also measured to study the dynamics of each correlation. C16mimPF$$_6$$ shows a first-order transition between the liquid (L) and liquid crystalline (LC) phases at $$T_{rm c}$$ = 394 K. C8mimPF$$_6$$ exhibits a glass transition at $$T_{rm g}$$ = 200 K. C9.5mimPF$$_6$$ has both transitions at $$T_{rm c}$$ = 225 K and $$T_{rm g}$$ = 203 K. In the ND experiments, all samples exhibit three peaks corresponding to the correlations mentioned above. The widths of the interlayer peak at ca. 0.2 $AA$^{-1}$$ changed drastically at the L-LC transitions, while the interionic peaks at ca. 1 $AA$^{-1}$$ exhibited a small jump at $$T_{rm c}$$. The peak position and area of the three peaks did not change much at the transition. The structural changes were minimal at $$T_{rm g}$$. The QENS experiments demonstrated that the relaxation time of the interlayer motion increased tenfold at $$T_{rm c}$$, while those of other motions were monotonous in the whole temperature region. The structural and dynamical changes are characteristic of the L-LC transition in imidazolium-based ionic liquids.

論文

Preferred site occupation of 3$$d$$ atoms in Ni$$_{x}$$Fe$$_{4-x}$$N (${it x}$ = 1 and 3) films revealed by X-ray absorption spectroscopy and magnetic circular dichroism

高田 郁弥*; 伊藤 啓太*; 竹田 幸治; 斎藤 祐児; 高梨 弘毅*; 木村 昭夫*; 末益 崇*

Physical Review Materials (Internet), 2(2), p.024407_1 - 024407_5, 2018/02

 被引用回数:14 パーセンタイル:48.52(Materials Science, Multidisciplinary)

X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism measurements were performed at the Ni and Fe $$L_{2,3}$$ absorption edges for Ni$$_{x}$$Fe$$_{4-x}$$N (${it x}$ = 1 and 3) epitaxial films. Shoulders at approximately 2 eV above the Ni $$L_{2,3}$$ main peaks in the XAS spectrum of Ni$$_{3}$$FeN were interpreted to originate from hybridization of orbitals between Ni 3$$d$$ at face-centered (II) sites and N 2$$p$$ at body-centered sites, while such features were missing in NiFe$$_{3}$$N film. Similar shoulders were observed at Fe $$L_{2,3}$$ edges in both films. Hence, Ni atoms preferentially occupied corner (I) sites, where the hybridization was weak because of the relatively long distance between Ni at I sites and N atoms. The relatively large magnetic moment deduced from sum-rule analysis of NiFe$$_{3}$$N also showed a good agreement with the presence of Ni atoms at I sites.

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