Formation of ultralong ordered hydration structure of molecularly thin oxide layers and its application

• Project/Area Number: 16K13631
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Nanomaterials chemistry
• Research Institution: National Institute for Materials Science
• Principal Investigator: Sasaki Takayoshi 国立研究開発法人物質・材料研究機構, 国際ナノアーキテクトニクス研究拠点, 拠点長 (70354404)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2018: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2017: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: 遷移金属層状酸化物 / 酸化物ナノシート / 巨大水和膨潤 / 長周期配列 / 構造色 / ２次元ナノシート / ナノシート / 長周期構造

Outline of Final Research Achievements

We showed that platelet crystals of layered metal oxides undergo accordion-like massibve swelling in aqueous solutions of amines and organoammonium ions. The interlayer separation expanded to several nm to over 100 nm, depending on their concentration. These swollen crystals could be disintegrated into molecularly thin 2D oxide layers by applying some external force. The resulting oxide nanosheets formed a unique lamellar structure with a huge intersheet separation, which reached several hundreds nm after removing the electrolyte used for exfoliation.

Academic Significance and Societal Importance of the Research Achievements

無機層状結晶が大きな水和膨潤現象を示すことは、一部の粘土鉱物を除いて知られていなかった。今回、層状遷移金属酸化物が水溶液中でその層間隔が100nmを超える極めて大きな膨潤反応を示すことを明らかにしたことは、現象そのものの特異性に加え、剥離ナノシート化していく過程を理解する上で学術的に大きな意義がある。さらに得られた酸化物ナノシートが可視光を干渉できるレベルの超長周期構造を形成することも基礎科学的に大変興味深い現象であるとともに、得られる構造色を活用した応用展開も期待される。

Research Products

• [Journal Article] Massive hydration-driven swelling of layered perovskite niobate crystals in aqueous solutions of organo-ammonium bases (2018)
  • Author(s): Y. Song, N. Iyi, T. Hoshide, T. C. Ozawa, Y. Ebina, R. Ma, S. Yamamoto, N. Miyamoto, T. Sasaki
  • Journal Title: Dalton Trans. Volume: 47 Issue: 9 Pages: 3022-3028
  • DOI: 10.1039/c7dt03413j
  • Peer Reviewed
• [Journal Article] Extra-Large Mechanical Anisotropy of a Hydrogel with Maximized Electrostatic Repulsion between Cofacially Aligned 2D Electrolytes (2018)
  • Author(s): K. Sano, Y. Onuma-Arazoe, Y. Ishida, Y. Ebina, M. Osada, T. Sasaki, T. Hikima, T. Aida
  • Journal Title: Angew. Chem. Int. Ed. Volume: 57 Issue: 38 Pages: 12508-12513
  • DOI: 10.1002/anie.201807240
  • Peer Reviewed
• [Journal Article] An Anisotropic Hydrogel Actuator Enabling Earthworm-Like Directed Peristaltic Crawling (2018)
  • Author(s): Zhifang Sun, Yoshihiro Yamauchi, Fumito Araoka, Youn Soo Kim, Julian Bergueiro, Yasuhiro Ishida, Yasuo Ebina, Takayoshi Sasaki, Takaaki Hikima, Takuzo Aida
  • Journal Title: Angewandte Chemie Volume: 130 Issue: 48 Pages: 15998-16002
  • DOI: 10.1002/ange.201810052
  • Peer Reviewed
• [Journal Article] Reversible Switching of the Magnetic Orientation of Titanate Nanosheets by Photochemical Reduction and Autoxidation (2018)
  • Author(s): X. Wang, X. Li, S. Aya, F. Araoka, Y. Ishida, A. Kikkawa, M. Kriener, Y. Taguchi, Y. Ebina, T. Sasaki, S. Koshiya, K. Kimoto, and T. Aida
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 48 Pages: 16396-16401
  • DOI: 10.1021/jacs.8b09625
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photonic water dynamically responsive to external stimuli (2016)
  • Author(s): Koki Sano, Youn Soo Kim, Yasuhiro Ishida, Yasuo Ebina, Takayoshi Sasaki, Takaaki Hikima and Takuzo Aida
  • Journal Title: Nature Communications Volume: 7 Issue: 1 Pages: 12559-12559
  • DOI: 10.1038/ncomms12559
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Presentation] Swelling and delamination behaviors of layered perovskite niobate crystals with a series of quaternary ammonium ions (2019)
  • Author(s): ソン イェジ, 井伊 伸夫, 海老名 保男, 馬 仁志, 佐々木 高義
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] Swelling and Delamination Behaviors of Layered Transition Metal Oxide with a Series of Quaternary Ammonium Ions (2019)
  • Author(s): ソン イェジ, 井伊 伸夫, 海老名 保男, 馬 仁志, 佐々木 高義
  • Organizer: The 2nd International Symposium on Chemistry of Nanomaterials
  • Int'l Joint Research
• [Presentation] Swelling to Delamination of Layered Metal Oxides into 2D Nanosheets and Their Layer-by-Layer Reassembly into Functional Systems (2018)
  • Author(s): 佐々木高義
  • Organizer: 7th International Workshop on Layered Materials
  • Int'l Joint Research / Invited
• [Presentation] 無機ナノシート間の静電反発力制御によるヒドロゲルの構造転移：構成要素間の引力および反発力が支配する2種類のゲル化機構 (2018)
  • Author(s): 五十嵐尚紀、佐野航季、海老名保男、佐々木高義、石田康博、相田卓三
  • Organizer: 日本化学会 第98春季年会
• [Presentation] Hydration-driven swelling and exfoliation behaviors of a layered perovskite niobate in four tetraalkylammonium hydroxide solutions (2017)
  • Author(s): SONG Yeji、井伊伸夫、海老名保男、馬仁志、佐々木高義
  • Organizer: Tsukuba Global Science Week 2017
  • Int'l Joint Research
• [Presentation] 2D Oxide Nanosheets: Synthesis, Assembly and Applications (2017)
  • Author(s): 佐々木高義
  • Organizer: Workshop on the Chemistry of 2D Materials
  • Int'l Joint Research / Invited
• [Presentation] 無機ナノシート間の静電反発力制御による可逆な 反発ゲル－引力ゲル相転移挙動 (2017)
  • Author(s): 五十嵐尚紀、佐野航季、海老名保男、佐々木高義、石田康博、相田卓三
  • Organizer: 日本化学会秋季事業 第7回CSJ化学フェスタ2017
• [Presentation] 無機ナノシートの超巨大周期構造とその時空間パターン形成 (2017)
  • Author(s): 佐野航季、海老名保男、佐々木高義、石田康博、相田卓三
  • Organizer: 第66回高分子討論会
• [Presentation] 無機ナノシートからなる動的フォトニック構造体とその時空間パターン形成 (2017)
  • Author(s): 佐野航季、海老名保男、佐々木高義、石田康博、相田卓三
  • Organizer: 第68回コロイドおよび界面化学討論会
• [Presentation] 静電反発力を利用した超巨大周期構造からなる動的フォトニック構造体 (2017)
  • Author(s): 佐野航季、海老名保男、佐々木高義、石田康博、相田卓三
  • Organizer: 2017年日本液晶学会討論会
• [Presentation] アミノ酸の包接による層状ペロブスカイト酸化物結晶の巨大水和膨潤 (2016)
  • Author(s): 井上和樹,井伊伸夫,SONGYeji,藤本憲次郎,佐々木高義
  • Organizer: 第67回コロイドおよび界面化学討論会
  • Place of Presentation: 北海道教育大学旭川校（北海道、旭川市）
  • Year and Date: 2016-09-22
• [Presentation] Massive hydration-driven swelling of a layered perovskite niobate in aqueous solutions containing (2016)
  • Author(s): SONGYeji,井伊伸夫,海老名保男,馬仁志
  • Organizer: Tsukuba Global Science Week
  • Place of Presentation: つくば国際会議場（茨城県、つくば市）
  • Year and Date: 2016-09-17
• [Presentation] Light-Powered Hydrogel Actuators Embedded with Anisotropic Electrostatics and Photothermal-Conversion Mechanisms (2016)
  • Author(s): Zhifang SUN,Yoshihiro YAMAUCHI,Youn Soo KIM,佐々木高義,Yasuhiro ISHIDA,Takuzo AIDA
  • Organizer: 第65回高分子討論会
  • Place of Presentation: 神奈川大学 横浜キャンパス（神奈川県、横浜市）
  • Year and Date: 2016-09-14
• [Presentation] Massive hydration-driven swelling and exfoliation of a layered perovskite niobate in aqueous solutions containing quaternary ammonium hydroxides (2016)
  • Author(s): SONGYeji,井伊伸夫,海老名保男,馬仁志,宮元展義,佐々木高義
  • Organizer: RIKEN CEMS Topical Meeting 2016
  • Place of Presentation: 理化学研究所 和光地区（埼玉県、和光市）
  • Year and Date: 2016-09-07
• [Presentation] ”Artificial Layered Systems” Reconstructed with 2D Nanosheets and Function Design (2016)
  • Author(s): 佐々木高義
  • Organizer: VI. INTERNATIONAL WORKSHOP ON LAYERED MATERIALS
  • Place of Presentation: Kutna Hora,チェコ
  • Year and Date: 2016-09-05
  • Int'l Joint Research / Invited
• [Patent(Industrial Property Rights)] ナノシートを含むNMR測定用配向剤 (2017)
  • Inventor(s): 佐々木高義、内田紀之の他７名
  • Industrial Property Rights Holder: 物質・材料研究機構、理化学研究所
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2017-105022
  • Filing Date: 2017
  • Acquisition Date: 2017