研究者詳細 - 中戸　晃之

論文 - 中戸　晃之

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Real-Time Monitoring of Adsorption-Induced Scrolling of Colloidal Inorganic Nanosheets 査読有り国際誌

Harada T., Suzuki Y., Nakato T., Breu J., Kawamata J.

Langmuir 2024年01月

記述言語：英語掲載種別：研究論文（学術雑誌）

Inorganic nanotubes have attracted much attention due to their unique physicochemical properties. Nanotubes can be prepared by scrolling exfoliated nanosheets under ambient conditions. However, how the nanosheet scrolled in its colloidal state has not been experimentally visualized. In this paper, we directly observed the scrolling process of nanosheets upon adsorption of organic cations. Exfoliated flat nanosheets of niobate and clay in aqueous colloids were found to scroll by adding organic cations, such as exfoliation reagents, to the colloids. Employment of cationic stilbazolium dye enabled in situ observation of the dye adsorption and scrolling by optical microscopy based on changes in color and morphology of the nanosheets. The scrolling was promoted for nanosheets adsorbed with a stilbazolium dye with a longer alkyl chain, suggesting that the interaction between the hydrophobic parts of the dye cations is the driving force of the scrolling. This finding should encourage research on the formation of nanotubes from nanosheets and also provides important guidelines for the selection of appropriate exfoliation reagents when exfoliating nanosheets from layered crystals.

DOI： 10.1021/acs.langmuir.4c00560

Kyutacar

Scopus

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Swelling and delamination of inorganic homoionic montmorillonite clay in water-polar organic mixed solvents 査読有り国際誌

Nakato T., Kubota M., Otsuka Y., Yane Y., Orio K., Mouri E., Yamauchi Y., Miyata H.

Dalton Transactions 53 ( 17 ) 7571 - 7579 2024年01月

担当区分：筆頭著者,　最終著者記述言語：英語掲載種別：研究論文（学術雑誌）

The smectite group of clay minerals (smectites) consists of negatively charged clay layers and interlayer exchangeable cations. They are spontaneously delaminated in water to form single clay layers when the interlayer cations are small alkaline cations such as Na+ or Li+. This phenomenon known as osmotic swelling has fundamental importance in constructing novel clay-based nanomaterials. However, osmotic swelling of smectites has not been systematically investigated in organic solvents although this phenomenon should be useful for developing novel clay-organic nanocomposites. We report herein that montmorillonite, a typical smectite, with monovalent and divalent inorganic interlayer cations shows osmotic swelling accompanied by delamination of clay layers in water-acetonitrile and water-2-propanol mixed solvents, although inorganic interlayer cations have been believed to be inappropriate for delamination of smectites in organic solvents. The delamination is confirmed by a combination of macroscopic sample appearances, XRD patterns, and SEM images. Montmorillonite with interlayer Na+ or Li+ ions shows osmotic swelling in pure water and the mixed solvents but not in pure organic solvents. Montmorillonite with alkaline earth dications in the interlayer spaces is swollen in water-organic mixed solvents but not in either pure water or organic solvents alone. Partial delamination in several systems can be clarified from SEM images even though the sample appearances and XRD patterns do not give firm evidence. Such non-uniform swelling behavior of montmorillonite is related to the disordered stacking of the aluminosilicate layers with different morphologies in the clay powders as observed by SEM.

DOI： 10.1039/d4dt00192c

Kyutacar

Scopus

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Negatively Charged Clay Particles Influence Spectroscopic Properties of Anionic Organic Dyes in Aqueous Colloids 査読有り国際誌

T. Nakato, Y. Kawanami, K. Taninaka, E. Mouri

Bull. Chem. Soc. Jpn. 95 1486 - 1490 2022年10月

Formation of a Giant Anisotropically Ordered Assembled Structure of Inorganic Nanosheets through an Optically Induced Stream 査読有り国際誌

Suzuki Y., Nagashita T., Ikeda A., Ishii K., Iwai T., Nakato T., Kawamata J.

Langmuir 38 ( 21 ) 6647 - 6652 2022年05月

記述言語：英語掲載種別：研究論文（学術雑誌）

Formation of a desirable submillimeter-scaled assembled structure of particles in the colloid is a difficult subject in colloidal chemistry. Herein, a submillimeter-scaled ordered assembled structure consisting of highly anisotropic two-dimensional plate-like particles, niobate nanosheets, was obtained through an optical manipulation technique that was assisted by a scattering-force-induced stream. A 532 nm continuous wave laser beam with a power of 400 mW was used to illuminate a liquid crystalline niobate nanosheet colloid from the bottom side of a sample cell, inducing the stream of oriented nanosheets toward the upper side of the sample cell. As a result, a 200 μm ordered assembled structure consisting of oriented nanosheets was formed. The assembled structure was also characterized by two-dimensional anisotropy, reflecting that the highly anisotropic morphologies of each nanosheet and the shape of that structure were dependent on the polarization of incident illumination. This study has revealed a new noncontact and on-demand way to obtain submillimeter-scaled ordered anisotropic colloidal assembled structures of nanosized particles such as nanosheets, contributing to fundamental materials science and expanding the utilities of nanosheets.

DOI： 10.1021/acs.langmuir.2c00528

Kyutacar

Scopus

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Impacts of negatively charged colloidal clay particles on photoisomerization of both anionic and cationic azobenzene molecules 査読有り国際誌

Mouri E., Kajiwara K., Kawasaki S., Shimizu Y., Bando H., Sakai H., Nakato T.

RSC Advances 12 ( 17 ) 10855 - 10861 2022年04月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Although smectite-type clays are used as heterogeneous media for photofunctional guest molecules, the guest species are limited to cationic or polar molecules because of the intrinsic negative electric charges of clay particles. Nevertheless, in this study, aqueous clay colloids are reported to affect the photoisomerization kinetics of anionic and cationic azobenzene molecules dissolved in the colloids. Under UV-light irradiation, the clay colloids decelerate trans-to-cis isomerization, while under visible-light irradiation, the clay colloids accelerate cis-to-trans isomerization. In addition, the sol-gel transition of clay colloids affects the kinetics. The results considerably expand the applicability of clay colloids as matrixes for functional organic species.

DOI： 10.1039/d2ra01020h

Kyutacar

Scopus

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Electrically Induced Alignment of Semiconductor Nanosheets in Niobate-Clay Binary Nanosheet Colloids toward Significantly Enhanced Photocatalysis 査読有り

Nakato T., Ishitobi W., Yabuuchi M., Miyagawa M., Mouri E., Yamauchi Y.

Langmuir 2021年01月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Aqueous binary colloids of niobate and clay nanosheets, prepared by the exfoliation of their mother layered crystals, are unique colloidal systems characterized by the separation of niobate and clay nanosheet phases, where niobate nanosheets form liquid crystalline domains with the size of several tens of micrometers among isotropically dispersed clay nanosheets. The binary colloids show unusual photocatalytic reactions because of the spatial separation of photocatalytically active niobate and photochemically inert clay nanosheets. The present study shows structural conversion of the binary colloids with an external electric field, resulting in the onsite alignment of colloidal nanosheets to improve the photocatalytic performance of the system. The colloidal structure is reshaped by the growth of liquid crystalline domains of photocatalytic niobate nanosheets and by their electric alignment. Niobate nanosheets are assembled by the domain growth process and then aligned by AC voltage, although clay nanosheets do not respond to the electric field. Photocatalytic decomposition of the cationic rhodamine 6G dye, which is selectively adsorbed on clay nanosheets, is examined for the niobate-clay binary nanosheet colloids with or without domain growth and electric field. The fastest decomposition is observed for the electrically aligned colloid without the domain growth, whereas the sample with the domain growth and without the electric alignment shows the slowest decomposition. The results demonstrate the improvement of the photocatalytic performance by changing the colloidal structure, even though the sample composition is the same.

DOI： 10.1021/acs.langmuir.1c01051

Scopus

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Cooperative Electric Alignment of Colloidal Graphene Oxide Particles with Liquid Crystalline Niobate Nanosheets 査読有り国際誌

Nakato T., Sirinakorn T., Ishitobi W., Mouri E., Ogawa M.

Bulletin of the Chemical Society of Japan ( 公益社団法人日本化学会 ) 94 ( 12 ) 2871 - 2879 2021年01月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Binary colloids of two morphologically different particle species cause phase separation containing liquid crystalline phases. Although electric alignment of colloidal nanosheets has been investigated for colloidal systems consisting of single nanosheet species, that of binary nanosheet colloids has scarcely been examined. We report herein the electric alignment of aqueous binary colloids composed of niobate (NB) nanosheets from K4Nb6O17 and commercially available graphene oxide (GO) platelets. The NBGO binary colloids show multiphase coexistence involving liquid crystalline phases induced by the NB nanosheets, whereas the employed GO particles do not contribute to the liquid crystallinity. The NB nanosheets in the binary colloids are electrically aligned in parallel to an AC voltage (1 kV cm11 peak to peak, 50 kHz) applied to the sample. When the concentration of GO in the binary colloids is low enough, the GO particles are also electrically aligned although they hardly respond to electric field in the absence of NB nanosheets. Combined optical microscopy of bright-field, polarized, and fluorescence observations demonstrates that isolated GO particles are dragged by the aligning motion of the NB nanosheets forming liquid crystalline domains. The results indicate that collective motions of colloidal nanosheets can induce participation of isolated particles.

DOI： 10.1246/bcsj.20210314

Scopus

CiNii Article

CiNii Research

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Universal Access to Two-Dimensional Mesoporous Heterostructures by Micelle-Directed Interfacial Assembly 査読有り国際誌

Wang J., Chang Z., Ding B., Li T., Yang G., Pang Z., Nakato T., Eguchi M., Kang Y.M., Na J., Guan B.Y., Yamauchi Y.

Angewandte Chemie - International Edition 59 ( 44 ) 19570 - 19575 2020年10月

記述言語：英語掲載種別：研究論文（学術雑誌）

© 2020 Wiley-VCH GmbH Two-dimensional (2D) mesoporous heterostructures combining ultrathin nanosheet morphology, periodic porous surface structures, and diverse hybrid compositions have become increasingly important for renewable energy storage and electronics. However, it remains a great challenge to develop a universal method to prepare 2D mesoporous heterostructures. Herein, we report a composite-micelle-directed interfacial assembly method to synthesize heterostructures of an ultrathin 2D material covered with mesoporous monolayers assembled on both sides. To demonstrate the concept, we first fabricated a new sandwichlike carbon@MXene@carbon mesoporous heterostructure through the self-assembly of exfoliated MXene nanosheets and block copolymer F127/melamine-formaldehyde resin composite micelles and subsequent thermal treatment. Finally, we demonstrate that the carbon@MXene@carbon mesoporous heterostructured nanosheets manifest remarkably enhanced electrochemical performance as a cathode material for lithium–sulfur batteries.

DOI： 10.1002/anie.202007063

Scopus

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Mesoscopic Architectures Made of Electrically Charged Binary Colloidal Nanosheets in Aqueous System 査読有り国際誌

Nakato T., Takahashi A., Terada S., Yamaguchi S., Mouri E., Shintate M., Yamamoto S., Yamauchi Y., Miyamoto N.

Langmuir 35 ( 45 ) 14543 - 14552 2019年11月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Copyright © 2019 American Chemical Society. Inorganic layered materials can be converted to colloidal liquid crystals through exfoliation into inorganic nanosheets, and binary nanosheet colloids exhibit rich phase behavior characterized by multiphase coexistence. In particular, niobate-clay binary nanosheet colloids are characterized by phase separation at a mesoscopic (aseveral tens of micrometers) scale whereas they are apparently homogeneous at a macroscopic scale. Although the mesoscopic structure of the niobate-clay binary colloid is advantageous to realize unusual photochemical functions, the structure itself has not been clearly demonstrated in real space. The present study investigated the structure of niobate-clay binary nanosheet colloids in detail. Four clay nanosheets (hectorite, saponite, fluorohectorite, and tetrasilisic mica) with different lateral sizes were compared. Small-angle X-ray scattering (SAXS) indicated lamellar ordering of niobate nanosheets in the binary colloid. The basal spacing of the lamellar phase was reduced by increasing the concentration of clay nanosheets, indicating the compression of the liquid crystalline niobate phase by the isotropic clay phase. Scattering and fluorescence microscope observations using confocal laser scanning microscopy (CLSM) demonstrated the phase separation of niobate and clay nanosheets in real space. Niobate nanosheets assembled into domains of several tens of micrometers whereas clay nanosheets were located in voids between the niobate domains. The results clearly confirmed the spatial separation of two nanosheets and the phase separation at a mesoscopic scale. Distribution of clay nanosheets is dependent on the employed clay nanosheets; the nanosheets with large lateral length are more localized or assembled. This is in harmony with larger basal spacings of niobate lamellar phase for large clay particles. Although three-dimensional compression of the niobate phase by the coexisting clay phase was observed at low clay concentrations, the basal spacing of niobate phase was almost constant irrespective of niobate concentrations at high clay concentrations, which was ascribed to competition of compression by clay phase and restoring of the niobate phase.

DOI： 10.1021/acs.langmuir.9b02474

Kyutacar

Scopus

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Microscope Observation of Morphology of Colloidally Dispersed Niobate Nanosheets Combined with Optical Trapping 査読有り国際誌

Nakato T., Higashi Y., Ishitobi W., Nagashita T., Tominaga M., Suzuki Y., Iwai T., Kawamata J.

Langmuir 35 ( 16 ) 5568 - 5573 2019年04月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

© 2019 American Chemical Society. Although inorganic nanosheets prepared by exfoliation (delamination) of layered crystals have attracted great attention as 2D nanoparticles, in situ real space observations of exfoliated nanosheets in the colloidally dispersed state have not been conducted. In the present study, colloidally dispersed inorganic nanosheets prepared by exfoliation of layered niobate are directly observed with bright-field optical microscopy, which detects large nanosheets with lateral length larger than several micrometers. The observed nanosheets are not strictly flat but rounded, undulated, or folded in many cases. Optical trapping of nanosheets by laser radiation pressure has clarified their uneven cross-sectional shapes. Their morphology is retained under the relation between Brownian motion and optical trapping.

DOI： 10.1021/acs.langmuir.9b00356

Kyutacar

Scopus

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Photoinduced electron transfer in semiconductor–clay binary nanosheet colloids controlled by clay particles as a turnout switch 査読有り

T. Nakato, S. Terada, T. Ishiku, S. Abe, S. Kamimura, E. Mouri, T. Ohno

Applied Catalysis B: Environmental 241 499 - 505 2019年01月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Although semiconductor photocatalysis has been investigated actively for a long time, control of dark processes successive to electron transfer from photocatalysts is almost unexplored compared with designing photocatalysts themselves. The present study proposes employment of clay particles as for controlling the dark processes independently of semiconductor photocatalyst particles. We employed niobate–clay binary nanosheet colloids, where colloidal niobate and clay nanosheets are spatially separated at a micrometer level. Niobate nanosheets worked as the semiconductor photocatalyst that released electrons upon UV excitation, and clay nanosheets worked as the turnout switch of the released electrons to determine their destination. When methylviologen (MV2+) molecules that accept the electrons released from niobate were adsorbed on clay nanosheets, reduction of MV2+ predominantly occurred, and hydrogen was little evolved from the colloid. When Pt nanoparticles were deposited on clay nanosheets, photocatalytic hydrogen evolution occurred because Pt loaded on the clay nanoparticles played a role of cocatalyst. When MV2+ and Pt were co-loaded on clay nanosheets, both of MV2+ reduction and hydrogen evolution occurred competitively. The photocatalytic hydrogen evolution carried out by stirring the colloid sample was worse than that conducted without stirring, which indicated positive contribution of the spatial separation of photocatalytic niobate and cocatalytic clay nanosheets.

DOI： 10.1016/j.apcatb.2018.09.047

Kyutacar

Scopus

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Electric-Alignment Immobilization of Liquid Crystalline Colloidal Nanosheets with the Aid of a Natural Organic Polymer 査読有り国際誌

Mouri E., Irie A., Nakato T.

Langmuir 35 ( 21 ) 7003 - 7008 2019年01月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

© 2019 American Chemical Society. Inorganic nanosheets obtained by exfoliation of a layered crystal in water form colloidal liquid crystals, and their alignment can be controlled by an electric field. In order to realize the immobilization of the electrically aligned niobate nanosheets without external forces, an aqueous gelator, agar, is introduced to the niobate nanosheet system to utilize the thermosensitive sol-gel transition property of agar. Alignment of nanosheets in a niobate-agar system is performed by applying an electric field above the sol-gel transition temperature, and then, the sample is cooled down, followed by cooling below the transition temperature with the electric field turned off. The aligned structure is kept for more than 24 h after the removal of the electric field. The concentration of agar is a key parameter for both the orientation of nanosheets and the retention of the orientation.

DOI： 10.1021/acs.langmuir.9b00651

Kyutacar

Scopus

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Radiation Pressure Induced Hierarchical Structure of Liquid Crystalline Inorganic Nanosheets 査読有り国際誌

Tominaga M., Nagashita T., Kumamoto T., Higashi Y., Iwai T., Nakato T., Suzuki Y., Kawamata J.

ACS Photonics 5 ( 4 ) 1288 - 1293 2018年04月

記述言語：英語掲載種別：研究論文（学術雑誌）

© 2018 American Chemical Society. Although hierarchical assemblies of colloidal particles add novel structure-based functions to systems, few local and on-demand colloidal structures have been developed. We have combined the colloidal liquid crystallinity of two-dimensional inorganic particles and laser radiation pressure to obtain a large hierarchical and local structure in a colloidal system. The scattering force of the laser beam converted the parallel nanosheet alignment to the direction of the incident laser beam. At the focal point, the nanosheet orientation depends on the electric field of the polarized laser beam. In contrast, a giant tree-ring-like nanosheet texture of more than 100 μm, and which is independent of the polarization direction, was organized at the periphery of the focal point. This organization resulted from a cooperative effect between the liquid-crystalline nanosheets, which indicates an effectiveness of optical manipulation to construct hierarchical colloidal structures with the aid of interparticle interactions.

DOI： 10.1021/acsphotonics.7b01230

Kyutacar

Scopus

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Time evolution of the inner structure of antimony phosphate nanosheet suspension developing structural colouration 査読有り国際誌

Mouri E., Fukumoto T., Kato R., Miyamoto N., Nakato T.

Soft Matter 2024年01月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Structural colouration observed in antimony phosphate nanosheet suspensions has been known for two decades, but the stability of their inner structures has not been a topic in colloidal nanosheet systems. In this study, we investigate the time evolution of structures in suspension using UV-visible spectrometry and small-angle X-ray scattering. Here, we report that antimony phosphate nanosheet systems re-organise their inner structures, especially at lower concentrations (isotropic or biphasic region), and that the basal spacing decreases with time after sample preparation, although the evolution speed depends on the sample concentration. The stability of the inner structure of the suspension is essential for their application as structural colour materials in sensors and colourants.

DOI： 10.1039/d4sm00647j

Scopus

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無機層状結晶を用いる吸着剤の開発 — 歴史ある分野のアップデート招待有り

中戸晃之

化学 ( 化学同人 ) 78 ( 12 ) 64 - 65 2023年12月

A new method of reinforcing graphene nanoplatelets in glass/epoxy composites: Eine neue Methode zur Verstärkung von Glas-/Epoxid-Verbundwerkstoffen mit Graphen-Nanoplättchen 査読有り国際誌

Malik K., Ahmad F., Yunus N.A., Nakato T., Mouri E., Dawood S., Memon I.R.

Materialwissenschaft und Werkstofftechnik 54 ( 9 ) 1157 - 1166 2023年09月

記述言語：英語掲載種別：研究論文（学術雑誌）

This research aims to develop a method for the amalgamation of graphene nanoplatelets in glass/epoxy composites. The poor interface bonding between the fiber and matrix is critical and hinders the full performance of the composites. Glass fabric and epoxy were used as reinforcement and matrix in the composite, respectively. Graphene nanoplatelets were utilized as an additional nano-materials filler for the composites. Glass/graphene/epoxy and glass/epoxy composites were fabricated via vacuum infusion molding. The new method of applying graphene nanoplatelets as secondary reinforcement in the composite was developed based on proper functionalization in the sonication process. The physical, tensile, flexural, and short beam interlaminar properties of fabricated composites were examined to analyze the method's effectiveness. The results showed that density decreased by around 5 %; however, thickness increased by around 34 % after introducing graphene nanoplatelets into the composites. The tensile strength and modulus of the composites declined by approximately 19 %, on the other hand, flexural strength and modulus increased by around 63.3 % and 8.3 %, respectively, after the addition of graphene nanoplatelets into the composites. Moreover, interlaminar shear strength of the composite was enhanced by approximately 50 %.

DOI： 10.1002/mawe.202100374

Scopus

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２成分系無機ナノシート液晶の構造と機能招待有り査読有り

中戸晃之

セラミックス 2023年07月

無機粒子の自己組織化招待有り査読有り

中戸晃之，毛利恵美子

液晶 27 118 - 124 2023年04月

ELECTRIC ALIGNMENT OF LIQUID CRYSTALLINE BINARY COLLOIDS OF MICROMETER-SIZED NIOBATE AND CLAY NANOSHEETS 査読有り国際誌

Nakato Teruyuki, Ishitobi Wataru, Mouri Emiko

Ｃｌａｙ　Ｓｃｉｅｎｃｅ ( 一般社団法人日本粘土学会 ) 26 ( 1-2 ) 17 - 24 2022年06月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Among colloidal systems of inorganic nanosheets prepared by exfoliation of inorganic layered crystals, binary colloids of two different nanosheet species are important for their multicomponent and multiphase coexistence, which is applicable to new materials. Nevertheless, electric response of binary nanosheet colloids has scarcely been paid attention although that of single-component nanosheet colloids has recently been investigated. We report herein the electric alignment of aqueous binary nanosheet colloids of niobate K4Nb6O17 and synthetic fluorohectorite, both of which have large lateral sizes of a few micrometers. In the binary colloids, the niobate nanosheets respond to an applied AC electric voltage to be aligned in parallel to the electric field. Although the clay nanosheets also respond to an AC electric field in their single-component colloids, their alignment is basically suppressed in the binary colloids. However, combined optical microscope observations of bright-field, polarized, and fluorescence detections indicate that large clay platelets are partly involved in the aligning motion of the niobate nanosheets. As a result, some of the clay platelets are aligned in parallel to the electric field. Colloidal liquid crystallinity of the niobate nanosheets contribute to the alignment of the clay particles by incorporating the latter particles to the liquid crystalline domains of the former ones.

DOI： 10.11362/jcssjclayscience.ms-21-13

CiNii Research

その他リンク： http://id.ndl.go.jp/bib/032224817

酸化物半導体のコロイド科学が切りひらく光・電子デバイス招待有り

横野照尚，中戸晃之，村上直也

クリーンテクノロジー 32 ( 6 ) 59 - 64 2022年06月

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