超臨界法によるナノ粒子ポリマー創成

2015 Fiscal Year Annual Research Report

• Project/Area Number: 25249108
• Research Institution: Tohoku University
• Principal Investigator: 阿尻 雅文 東北大学, 原子分子材料科学高等研究機構, 教授 (60182995)
• Co-Investigator(Kenkyū-buntansha): 中山 忠親 長岡技術科学大学, 工学(系)研究科(研究院), 准教授 (10324849) ; 山口 雅彦 東北大学, 薬学研究科(研究院), 教授 (30158117) ; 高見 誠一 東北大学, 多元物質科学研究所, 准教授 (40311550) ; 青木 画奈 神戸大学, 自然科学系先端融合研究環重点研究部, 助教 (90332254)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Keywords: 超臨界 / ナノ結晶 / 有機無機ナノハイブリッド / 酸化セリウム / 水熱合成

Outline of Annual Research Achievements

本年度は、ナノ粒子ポリマーを作成するために必要な表面修飾ナノ粒子の合成を行った。流通式反応装置を用い、高圧ポンプにより蒸留水、硝酸セリウム水溶液と表面修飾剤を送液した。表面修飾剤として両端にアミノ基とカルボキシル基を有する直鎖のアミノ酸を用いた。蒸留水は混合後の温度が反応温度である300 ℃となるように予熱し、Ｔ字部分で原料溶液と混合し、所定の長さの均熱帯を通過後、冷却して回収した。系内の圧力は背圧弁により25 MPaに保った。また、未修飾で合成する場合も同様の操作を行った。回収液は蒸留水で洗浄・遠心分離を行った後、凍結乾燥し固体試料を得た。得られた試料はX線回折、透過型電子顕微鏡、赤外分光法により解析を行った。生成物のXRDパターン測定した結果、全ての条件で酸化セリウムと一致するピークが見られ、表面修飾剤の存在下でも酸化セリウムナノ結晶が合成することを確認した。透過型電子顕微鏡像を測定した結果、未修飾条件で合成した粒子は100 nm程度の粒径で粒子形態が八面体構造であった。一方、表面修飾剤存在下で合成した粒子は、粒径が10 nm程度で球状粒子であることを確認した。これは有機修飾基により粒子の成長表面がキャッピングされ、粒子成長が抑制されたためであると考える。赤外分光法により表面修飾の有無を確認した結果、表面修飾剤存在下で合成した試料は2900～2850 cm-1付近に炭化水素鎖に由来するピークを示したことから、各修飾剤が酸化セリウム粒子に結合していることを確認した。このことから、表面修飾剤のカルボキシ基が酸化セリウム酸化セリウムナノ粒子の表面と結合し、アミノ基を表面に表出することで、ナノ粒子ポリマーの合成を実現する粒子が生成したと結論づける。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Kinetics study to identify reaction-controlled conditions for supercritical hydrothermal nanoparticle synthesis with flow-type reactors (2016)
  • Author(s): N. Aoki, A. Sato, H. Sasaki, AA. Litwinowicz, G. Seong, T. Aida, Hojo, S. Takami, T. Adschiri
  • Journal Title: JOURNAL OF SUPERCRITICAL FLUIDS Volume: 110 Pages: 161-166
  • DOI: 10.1016/j.supflu.2015.11.015
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Relationship between size distribution of synthesized nanoparticles and flow and thermal fields in a flow-type reactor for supercritical hydrothermal synthesis (2016)
  • Author(s): K. Sugioka, K. Ozawa, M. Kubo, T. Tsukada, S. Takami, T. Adschiri, K. Sugimoto, N. Takenaka, Y. Saito
  • Journal Title: JOURNAL OF SUPERCRITICAL FLUIDS Volume: 109 Pages: 43-50
  • DOI: 10.1016/j.supflu.2015.11.008
  • Peer Reviewed / Open Access
• [Journal Article] Tuning surface grafting density of CeO2 nanocrystals with near- and supercritical solvent characteristics (2016)
  • Author(s): B .Giroire, C. Slostowski, S. Marre, C. Aymonier, T. Aida, D. Hojo, N .Aoki, S. Takami, T. Adschiri
  • Journal Title: PHYSICAL CHEMISTRY CHEMICAL PHYSICS Volume: 18 Pages: 1727-1734
  • DOI: 10.1039/c5cp07034a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Magneto-optical Kerr effect characterization of a uniform nanocrystalline Fe3O4 monolayer fabricated on a silicon substrate functionalized with catechol groups (2016)
  • Author(s): D. Hojo, KZ. Suzuki, S. Mizukami, T. Adschiri
  • Journal Title: JOURNAL OF MATERIALS CHEMISTRY C Volume: 4 Pages: 1263-1270
  • DOI: 10.1039/c5tc04310g
  • Peer Reviewed
• [Journal Article] Polymer nanocomposite films with thicknesses (≤ 30 μm) corresponding to the lateral dimension of graphite nanosheets as straigh (2016)
  • Author(s): Cho, H.-B., Huynh, D.P., Nakayama, T., Shin, J.H., Suematsu, H., Niihara, K., Sung, K., Lee, Y., Kim, S., Song, Y., Choa, Y.-H
  • Journal Title: Composites Science and Technology Volume: 127 Pages: 106-112
  • DOI: 10.1016/j.compscitech.2016.03.002
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Fabrication of stacked-cup carbon nanotube/polymer nanocomposite films with linear controlled percolation routes (2016)
  • Author(s): Huynh, M.T.T., Nakayama, T., Kawamoto, A., Nguyen, S.T., Suzuki, T., Suematsu, H., Niihara, K., Cho, H.-B., Choa, Y.-H.
  • Journal Title: Materials Chemistry and Physics Volume: 171 Pages: 39-44
  • DOI: 10.1016/j.matchemphys.2016.01.027
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Texture-controlled hybrid materials fabricated using nanosecond technology (2016)
  • Author(s): Cho, H.-B., Nakayama, T., Huynh, M.T.T., Nguyen, S.T., Jiang, W., Suzuki, T., Suematsu, H., Niihara, K., Shin, J.H., Choa, Y.-H.
  • Journal Title: Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi/Journal of the Ceramic Society of Japan Volume: 124 Pages: 197-202
  • DOI: 10.2109/jcersj2.15215
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Green solvent for green materials: a supercritical hydrothermal method and shape-controlled synthesis of Cr-doped CeO2 nanoparticles (2015)
  • Author(s): YZ. Zhu, S. Takami, GY. Seong, M. Dejhosseini, MZ .Hossain, T .Noguchi, D. Hojo, N. Aoki, T. Aida, T. Adschiri
  • Journal Title: PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES Volume: 373 Pages: 20150012
  • DOI: 10.1098/rsta.2015.0012
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Beneficial use of CeO2 nanocatalyst for black liquor conversion under sub and supercritical conditions (2015)
  • Author(s): H. Boucard, M. Watanabe, S. Takami, E. Weiss-Hortala, R. Barna, T. Adschiri
  • Journal Title: JOURNAL OF SUPERCRITICAL FLUIDS Volume: 105 Pages: 66-76
  • DOI: 10.1016/j.supflu.2015.02.008
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Helicene-grafted Silica Nanoparticles Capture Hetero-double-helix Intermediates During Self-assembly Gel Formation (2015)
  • Author(s): M. Miyagawa, and M. Yamaguchi
  • Journal Title: Chem. Eur. J Volume: 21 Pages: 8408-8415
  • DOI: 10.1002/chem.201406482
  • Peer Reviewed
• [Journal Article] Materials Clocking by Silica Nanoparticles Precipitation in Solution Phase that is Tunable by Organic Molecules (2015)
  • Author(s): M. Miyagawa and M. Yamaguchi
  • Journal Title: ChemPlusChem Volume: 80 Pages: 1502-1507
  • DOI: 10.1002/cplu.201500300
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 3Equilibrium Shift Induced by Chiral nanoparticle Precipitation in Rhodium-catalyzed Disulfide Exchange Reaction (2015)
  • Author(s): Masamichi Miyagawa, Mieko Arisawa, Masahiko Yamaguchi
  • Journal Title: Tetrahedron Volume: 71 Pages: 4920-4926
  • DOI: 10.1016/j.tet.2015.05.106
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nanotwin hardening in a cubic chromium oxide thin film (2015)
  • Author(s): Suzuki, K., Suzuki, T., Nakajima, Y., Matsui, Y., Suematsu, H., Nakayama, T., Niihara, K.
  • Journal Title: APL Materials Volume: 3 Pages: 96105
  • DOI: 10.1063/1.4931749
  • Peer Reviewed / Open Access
• [Journal Article] Graphene oxide as a template for a complex functional oxide (2015)
  • Author(s): Boston, R., Bell, A., Ting, V.P., Rhead, A.T., Nakayama, T., Faul, C.F.J., Hall, S.R.
  • Journal Title: CrystEngComm Volume: 17 Pages: 6094\t- 6097
  • DOI: 10.1039/c5ce00922g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Preparation of palladium nanoparticles and a grain-size determining equation of pulsed wire discharge in N2, Ar, and He ambient gasses (2015)
  • Author(s): Sato, Y., Suematsu, H., Sarathi, R., Kikuchi, T., Sasaki, T., Tokoi, Y., Suzuki, T., Nakayama, T., Niihara, K.
  • Journal Title: Japanese Journal of Applied Physics Volume: 54 Pages: 45002
  • DOI: 10.7567/JJAP.54.045002
  • Peer Reviewed
• [Journal Article] Synthesis of molten-metal corrosion resistant yttria-based refractory by hot-pressing and densification (2015)
  • Author(s): Nguyen, S.T., Nakayama, T., Suematsu, H., Suzuki, T., Nanko, M., Cho, H.-B., Huynh, M.T.T., Jiang, W., Niihara, K.
  • Journal Title: Journal of the European Ceramic Society Volume: 35 Pages: 2651-2662
  • DOI: 10.1016/j.jeurceramsoc.2015.02.023
  • Peer Reviewed
• [Journal Article] Epitaxial growth of chromium nitride thin films with addition of silicon (2015)
  • Author(s): Suzuki, K., Suzuki, T., Endo, T., Nakayama, T., Suematsu, H., Niihara, K.
  • Journal Title: Physica Status Solidi (C) Current Topics in Solid State Physics Volume: 12 Pages: 545-548
  • DOI: 10.1002/pssc.201400281
  • Peer Reviewed
• [Journal Article] Novel Electrothermodynamic Power Generation (2015)
  • Author(s): Kim, Y., Kim, J., Yamanaka, S., Nakajima, A., Ogawa, T., Serizawa, T., Tanaka, H., Baba, M., Fukuda, T., Yoshii, K., Takeda, M., Yamada, N., Nakayama, T., Niihara, K.
  • Journal Title: Advanced Energy Materials Volume: 5 Pages: 1401942
  • DOI: 10.1002/aenm.201401942
  • Peer Reviewed
• [Presentation] Development of Synthetic Reactions Based on Novel Molecular Activation Methods and Studies on Dynamic Functions of Synthetic Helical Molecules and Molecular System (2016)
  • Author(s): M. Yamaguchi
  • Organizer: 日本化学会 化学会賞受賞講演
  • Place of Presentation: 同志社大学 （京都府・京都市）
  • Year and Date: 2016-03-24 – 2016-03-27
  • Invited
• [Presentation] 帯電ナノ微粒子の自発的配列を用いた表面プラズモン共鳴構造色 (2016)
  • Author(s): 米山貴之、青木画奈、藤井稔
  • Organizer: 第63回応用物理学会春季学術講演会
  • Place of Presentation: 東京工業大学大岡山 (東京都・大田区)
  • Year and Date: 2016-03-19 – 2016-03-22
• [Presentation] Continuous production of nanoparticles by supercritical hydrothermal synthesis (2016)
  • Author(s): Tadafumi Adschiri
  • Organizer: 3th International Workshop on WATER DYNAMICS Fluids in Solid Earth・Deep Carbon Cycle・-Deeper, Hotter and Frontier World-
  • Place of Presentation: 青葉記念会館（宮城県・仙台市）
  • Year and Date: 2016-03-17 – 2016-03-17
  • Int'l Joint Research / Invited
• [Presentation] Supercritical Route for Functional Nano Particles (2015)
  • Author(s): Tadafumi Adschiri
  • Organizer: The World Engineering Conference and Convention
  • Place of Presentation: 国立京都国際会館 (京都府・京都市)
  • Year and Date: 2015-11-29 – 2015-12-02
  • Int'l Joint Research / Invited
• [Presentation] M. Yamaguchi, Molecular Switching Involving Metastable State Using Synthetic Chiral Helicene Oligomers (2015)
  • Author(s): M. Yamaguchi
  • Organizer: The 10th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-10)
  • Place of Presentation: KaoHsiung(Taiwan)
  • Year and Date: 2015-11-02 – 2015-11-05
  • Int'l Joint Research / Invited
• [Presentation] Magnetic assembly of microspheres into ordered two-dimensional arrays (2015)
  • Author(s): Kanna Aoki and Minoru Fujii
  • Organizer: 41st. Micro and Nano Engineering
  • Place of Presentation: Hague（Netherlands）
  • Year and Date: 2015-09-21 – 2015-09-24
  • Int'l Joint Research
• [Presentation] Supercritical Route as Process Intensification and Sustainability (2015)
  • Author(s): Tadafumi Adschiri
  • Organizer: 2nd Asia-Pacific Symposium on Process Intensification and Sustainability
  • Place of Presentation: Sydney(Australia)
  • Year and Date: 2015-09-20 – 2015-09-22
  • Int'l Joint Research / Invited
• [Presentation] 超濃厚Nano Fluids とその応用展開 ―超高濃度ナノフルイド、プリンテドエレクトロニクス３Dプリンティング― (2015)
  • Author(s): 阿尻 雅文
  • Organizer: 化学工学会第47回秋季大会 特別シンポジウム
  • Place of Presentation: 北海道大学（北海道・札幌市）
  • Year and Date: 2015-09-09 – 2015-09-11
  • Invited
• [Presentation] Synthesis of surface-modified metal oxide nanocrystals and their application (2015)
  • Author(s): S. Takami
  • Organizer: nd Japan-France Symposium on Green-Materials and Advanced Characterization (GMAC2015)
  • Place of Presentation: 筑波大学（茨城県・つくば市）
  • Year and Date: 2015-08-30 – 2015-08-31
  • Int'l Joint Research / Invited
• [Presentation] 帯電ナノ微粒子の自己組織的配列構造を鋳型としたプラズモニックカラーフィルタ形成 (2015)
  • Author(s): 青木画奈、米山貴之、藤井稔
  • Organizer: 電気学会 マイクロマシン・センサシステム研究会
  • Place of Presentation: 九州大学医学部百年講堂(福岡県・福岡市）)
  • Year and Date: 2015-07-02 – 2015-07-03
• [Presentation] Supercritical Route for Functional Nano Particles (2015)
  • Author(s): Tadafumi Adschiri
  • Organizer: 8th International Conference on Materials for Advanced Technologies ICMAT2015
  • Place of Presentation: Singapore (Singapore)
  • Year and Date: 2015-06-28 – 2015-07-03
  • Int'l Joint Research / Invited