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無機ナノ結晶によるアシンメトリー化学の展開

Planned

Project AreaCoordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
Project/Area Number 16H06520
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyoto University

Principal Investigator

寺西 利治  京都大学, 化学研究所, 教授 (50262598)

Project Period (FY) 2016-06-30 – 2021-03-31
Project Status Granted (Fiscal Year 2020)
Budget Amount *help
¥115,570,000 (Direct Cost: ¥88,900,000、Indirect Cost: ¥26,670,000)
Fiscal Year 2020: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000)
Fiscal Year 2019: ¥21,190,000 (Direct Cost: ¥16,300,000、Indirect Cost: ¥4,890,000)
Fiscal Year 2018: ¥20,280,000 (Direct Cost: ¥15,600,000、Indirect Cost: ¥4,680,000)
Fiscal Year 2017: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000)
Fiscal Year 2016: ¥35,100,000 (Direct Cost: ¥27,000,000、Indirect Cost: ¥8,100,000)
Keywordsナノ材料 / アシンメトリー / イオン結晶 / キラル物性 / 不斉反応
Outline of Annual Research Achievements

ポルフィリン誘導体が平面配位した無機ナノ結晶は、表面積対体積比が大きいために有機配位子によって量子化された電子構造が摂動を受けやすく、その触媒活性や光学特性が大きく影響を受ける可能性がある。そこで平成31年度は、Auナノ粒子表面に対するポルフィリン平面の傾きが、電子構造へ及ぼす影響について、実験・理論両面から検討した。その結果、Auナノ粒子のサイズ(1.1~3 nm)やポルフィリン環-Auナノ粒子表面距離(0.24~0.5 nm)等に関係なく、ポルフィリンの吸収スペクトルがシフトすることが明らかとなり、分子-金属界面を利用するデバイス作製への指針を与えることができた。
次に、空間電荷分離の高効率化による可視光誘起水素発生効率向上を目的に、可視領域に局在表面プラズモン共鳴(LSPR)吸収のあるAgナノ粒子Ag2S相およびCdS相が非対称に接合したAg-Ag2S-CdSヘテロ構造ナノ結晶を合成した。CdSが光活性層として働き、AgとCdSの間に挟まれたAg2S相はCdSからAgへの電子移動を妨げ、ホールのみを受け取るキャリア選択的なブロッキング層として働く。Ag-Ag2S-CdSナノ粒子は、Ag-CdSナノ粒子と比べて13倍高い光触媒HER活性を示した。さらに、Ag-Ag2S-CdSナノ粒子は、ホールによる自己溶解が抑制され、CdSナノ粒子に比べて光安定性が大きく向上することが分かった。さらに、タイプI構造をもつCdS@メソポーラスZnSコアシェル構造ナノ粒子において、ZnS相の欠陥準位を利用することにより、タイプI構造をタイプII構造に扱えることを明らかにし、効果的な可視光長誘起水素発生触媒となることが分かった。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

○ 大環状π共役分子が配位した無機ナノ結晶の合成と触媒能評価
昨年度に引き続き、1~2 nmの金属および半導体ナノ結晶から集積非対称ナノ結晶を構築するために、ナノ結晶への配位能とMOF形成能を有する非対称金属ポルフィリン誘導体分子が2分子、4分子、6分子が配位した金属・半導体ナノ結晶を合成する。次に、ポルフィリンーナノ結晶間相互作用を利用した触媒能評価を行う。また、キラル磁性や不斉触媒能発現に向けた、Auナノ粒子表面への異種金属原子非対称配列を検討する。
○ アシンメトリー無機ナノ結晶構造体の構築
上記金属ポルフィリン誘導体が配位した金属および半導体ナノ結晶間の配位結合やナノ結晶表面のエピタキシャル成長・イオン交換を利用し、光エネルギーあるいはキャリアがナノ結晶間をなめらかに移動できるポテンシャル階段をもつ集積非対称ナノ結晶を構築する。本年度は昨年度に引き続き、CdE(E = S, Se, Te)ナノ結晶と他の無機ナノ結晶との非対称集積体を創製し、高効率エネルギー・キャリア移動系の構築を図るとともに、高効率近赤外光エネルギー変換システムを構築する。

Strategy for Future Research Activity

○ 大環状π共役分子が配位した無機ナノ結晶の合成と触媒能評価
昨年度に引き続き、1~2 nmの金属および半導体ナノ結晶から集積非対称ナノ結晶を構築するために、ナノ結晶への配位能とMOF形成能を有する非対称金属ポルフィリン誘導体分子が2分子、4分子、6分子が配位した金属・半導体ナノ結晶を合成する。次に、ポルフィリンーナノ結晶間相互作用を利用した触媒能評価を行う。また、キラル磁性や不斉触媒能発現に向けた、Auナノ粒子表面への異種金属原子非対称配列を検討する。
○ アシンメトリー無機ナノ結晶構造体の構築
上記金属ポルフィリン誘導体が配位した金属および半導体ナノ結晶間の配位結合やナノ結晶表面のエピタキシャル成長・イオン交換を利用し、光エネルギーあるいはキャリアがナノ結晶間をなめらかに移動できるポテンシャル階段をもつ集積非対称ナノ結晶を構築する。本年度は昨年度に引き続き、CdE(E = S, Se, Te)ナノ結晶と他の無機ナノ結晶との非対称集積体を創製し、高効率エネルギー・キャリア移動系の構築を図るとともに、高効率近赤外光エネルギー変換システムを構築する。

Report

(4 results)
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • 2016 Annual Research Report

Research Products

(47 results)

All 2020 2019 2018 2017 2016 Other

All Int'l Joint Research (2 results) Journal Article (15 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 15 results,  Open Access: 6 results,  Acknowledgement Compliant: 2 results) Presentation (23 results) (of which Int'l Joint Research: 13 results,  Invited: 23 results) Book (1 results) Remarks (5 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] RMIT University(オーストラリア)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] University of Castilla-La Mancha(スペイン)

    • Related Report
      2019 Annual Research Report
  • [Journal Article] Phase Segregated Cu2-xS-Ni3Se4 Bimetallic Selenide Nanocrystals Formed through Cation Exchange Reaction for Active Water Oxidation Precatalyst2020

    • Author(s)
      1.S. Kim, H. Mizuno, M. Saruyama, M. Sakamoto, M. Haruta, H. Kurata, T. Yamada, K. Domen, and T. Teranishi
    • Journal Title

      Chem. Sci.,

      Volume: 11 Pages: 1523-1530

    • DOI

      10.1039/c9sc04371c

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Carrier-Selective Blocking Layer Synergistically Improves the Plasmonic Enhancement Effect2019

    • Author(s)
      Kawawaki Tokuhisa、Nakagawa Tatsuo、Sakamoto Masanori、Teranishi Toshiharu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 印刷中 Pages: 8402-8406

    • DOI

      10.1021/jacs.9b01419

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Anomalous Photoinduced Hole Transport in Type I Core/Mesoporous-Shell Nanocrystals for Efficient Photocatalytic H2 Evolution2019

    • Author(s)
      Lian Zichao、Sakamoto Masanori、Kobayashi Yoichi、Tamai Naoto、Ma Jun、Sakurai Tsuneaki、Seki Shu、Nakagawa Tatsuo、Lai Ming-Wei、Haruta Mitsutaka、Kurata Hiroki、Teranishi Toshiharu
    • Journal Title

      ACS Nano

      Volume: 13 Pages: 8356-8363

    • DOI

      10.1021/acsnano.9b03826

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Impact of Orbital Hybridization at Molecule?Metal Interface on Carrier Dynamics2019

    • Author(s)
      Sakamoto Masanori、Hyeon-Deuk Kim、Eguchi Daichi、Chang I.-Y.、Tanaka Daisuke、Tahara Hirokazu、Furube Akihiro、Minagawa Yoshihiro、Majima Yutaka、Kanemitsu Yoshihiko、Teranishi Toshiharu
    • Journal Title

      J. Phys. Chem. C

      Volume: 123 Pages: 25877-25882

    • DOI

      10.1021/acs.jpcc.9b04231

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Clear and transparent nanocrystals for infrared-responsive carrier transfer2019

    • Author(s)
      Sakamoto Masanori、Kawawaki Tokuhisa、Kimura Masato、Vequizo Junie Jhon M.、Matsunaga Hironori、Ranasinghe Chandana Sampath Kumara、Yamakata Akira、Matsuzaki Hiroyuki、Furube Akihiro、Teranishi Toshiharu
    • Journal Title

      Nature Communnications

      Volume: 10 Pages: 406-406

    • DOI

      10.1038/s41467-018-08226-2

    • NAID

      120006554836

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Plasmonic p-n Junction for Infrared Light to Chemical Energy Conversion2019

    • Author(s)
      Lian Zichao, Sakamoto Masanori, Vequizo Junie J. M., Ranasinghe C. S. Kumara, Yamakata Akira, Nagai Takuro, Kimoto Koji, Kobayashi Yoichi, Tamai Naoto, Teranishi Toshiharu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Pages: 2446-2450

    • DOI

      10.1021/jacs.8b11544

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Durian-Shaped CdS@ZnSe Core@Mesoporous-Shell Nanoparticles for Enhanced and Sustainable Photocatalytic Hydrogen Evolution2018

    • Author(s)
      Lian Zichao、Sakamoto Masanori、Kobayashi Yoichi、Tamai Naoto、Ma Jun、Sakurai Tsuneaki、Seki Shu、Nakagawa Tatsuo、Lai Mingwei、Haruta Mitsutaka、Kurata Hiroki、Teranishi Toshiharu
    • Journal Title

      J. Phys. Chem. Lett.

      Volume: 9 Pages: 2212-2217

    • DOI

      10.1021/acs.jpclett.8b00789

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Near Infrared Light Induced Plasmonic Hot Hole Transfer at a Nano-Heterointerface2018

    • Author(s)
      Z. Lian M. Sakamoto H. Matsunaga J. J. M. Vequizo A. Yamakata M. Haruta H. Kurata W. Ota T. Sato T. Teranishi
    • Journal Title

      Nature Communications

      Volume: 9 Pages: 2314-2314

    • DOI

      10.1038/s41467-018-04630-w

    • NAID

      120006488580

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Phase-segregated NiPx@FePyOz core@shell nanoparticles: ready-to-use nanocatalysts for electro- and photo-catalytic water oxidation through in situ activation by structural transformation and spontaneous ligand removal2018

    • Author(s)
      Saruyama Masaki、Kim Sunwon、Nishino Toshio、Sakamoto Masanori、Haruta Mitsutaka、Kurata Hiroki、Akiyama Seiji、Yamada Taro、Domen Kazunari、Teranishi Toshiharu
    • Journal Title

      Chemical Science

      Volume: 印刷中 Pages: 4830-4836

    • DOI

      10.1039/c8sc00420j

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ligand Effect on the Catalytic Activity of Gold Clusters in the Electrochemical Hydrogen Evolution Reaction2018

    • Author(s)
      D. Eguchi, M. Sakamoto, and T. Teranishi
    • Journal Title

      Chem. Sci.

      Volume: 9 Pages: 261-265

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Boosting photocatalytic overall water splitting by Co doping into Mn3O4 nanoparticles as oxygen evolution cocatalysts2018

    • Author(s)
      Yoshinaga Taizo、Saruyama Masaki、Xiong Anke、Ham Yeilin、Kuang Yongbo、Niishiro Ryo、Akiyama Seiji、Sakamoto Masanori、Hisatomi Takashi、Domen Kazunari、Teranishi Toshiharu
    • Journal Title

      Nanoscale

      Volume: 印刷中 Pages: 10420-10427

    • DOI

      10.1039/c8nr00377g

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Molecular floating-gate single-electron transistor2017

    • Author(s)
      Yamamoto Makoto、Azuma Yasuo、Sakamoto Masanori、Teranishi Toshiharu、Ishii Hisao、Majima Yutaka、Noguchi Yutaka
    • Journal Title

      Sci. Rep.

      Volume: 7 Pages: 1589-1589

    • DOI

      10.1038/s41598-017-01578-7

    • NAID

      120006366775

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Formation of Layer-by-Layer Assembled Cocatalyst Films of S2?-Stabilized Ni3S4 Nanoparticles for Hydrogen Evolution Reaction2017

    • Author(s)
      Kim Sungwon、Nishino Toshio、Saruyama Masaki、Sakamoto Masanori、Kobayashi Hiroyuki、Akiyama Seiji、Yamada Taro、Domen Kazunari、Teranishi Toshiharu
    • Journal Title

      ChemNanoMat

      Volume: 3 Pages: 764-771

    • DOI

      10.1002/cnma.201700220

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Porphyrin Derivative-Protected Gold Cluster with a Pseudotetrahedral Shape2017

    • Author(s)
      Daichi Eguchi, Masanori Sakamoto, Daisuke Tanaka, Yasuo Okamoto, Toshiharu Teranishi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 印刷中 Pages: 10760-10766

    • DOI

      10.1021/acs.jpcc.6b10972

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Memory Operations in Au Nanoparticle Single-electron Transistors with Floating Gate Electrodes2016

    • Author(s)
      Yasuo Azuma, Masanori Sakamoto, Toshiharu Teranishi, Yutaka Majima
    • Journal Title

      Appl. Phys. Lett.

      Volume: 109

    • DOI

      10.1063/1.4971190

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Novel Plasmonic Nanomaterials for Near Infrared Light Energy Conversion2020

    • Author(s)
      T. Teranishi
    • Organizer
      8th International Conference on Nanoscience and Nanotechnology (ICONN 2020)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Novel Plasmonic Nanomaterials for Near Infrared Light Energy Conversion2019

    • Author(s)
      T. Teranishi
    • Organizer
      235rd ECS Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Novel Plasmonic Nanoparticles for Near Infrared Light Energy Conversion2019

    • Author(s)
      T. Teranishi
    • Organizer
      10th International Conference on Materials for Advanced Technologies (ICMAT 2019)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Novel Plasmonic Nanomaterials for Near Infrared Light Energy Conversion2019

    • Author(s)
      T. Teranishi
    • Organizer
      ChinaNano
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Plasmon-induced Hot Carrier Chemistry2019

    • Author(s)
      T. Teranishi
    • Organizer
      ASNANO-2 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 新しい可視・近赤外プラズモン合金ナノ粒子2019

    • Author(s)
      寺西利治
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Plasmon-induced Hot Carrier Chemistry2019

    • Author(s)
      T. Teranishi
    • Organizer
      KU-UNIST Joint Symposium
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Plasmon-induced Hot Carrier Chemistry in Inorganic Nanoparticles2019

    • Author(s)
      T. Teranishi
    • Organizer
      12th China‐Japan Joint Symposium on Metal Cluster Compounds
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Novel Plasmonic Nanomaterials for Near Infrared Light Energy Conversion2019

    • Author(s)
      T. Teranishi
    • Organizer
      Okinawa Colloids 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ヘテロ構造ナノ粒子の近赤外プラズモン励起キャリアダイナミクス計測2019

    • Author(s)
      寺西利治
    • Organizer
      2019 OCUシンポジウム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Near Infrared Plasmon-Induced Charge Separation in Heterostructured Nanoparticles2018

    • Author(s)
      T. Teranishi
    • Organizer
      233rd ECS Meeting
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ナノプラズモニクスの新展開2018

    • Author(s)
      寺西利治
    • Organizer
      第3回固体化学フォーラム研究会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Pseudomorphic Transformation of Nanocrystals by Element Replacement2018

    • Author(s)
      T. Teranishi
    • Organizer
      ISMANAM2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] New Plasmonic Chemistry of Nanocrystals toward Photoenergy Conversion2018

    • Author(s)
      T. Teranishi
    • Organizer
      北京大学セミナー
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] ナノ仮晶化学:元素置換による新しいナノ粒子の創り方 -プラズモニクスにおける錬金術-2018

    • Author(s)
      寺西利治
    • Organizer
      日本セラミックス協会第31回秋季シンポジウム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Novel Plasmonic Alloy Nanocrystals formed by Pseudomorphic Reaction2018

    • Author(s)
      T. Teranishi
    • Organizer
      KJF International Conference on Organic Materials for Electronics and Photonics
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ナノ仮晶化学の開拓と近赤外プラズモニクスへの展開2018

    • Author(s)
      寺西利治
    • Organizer
      錯体化学若手の会夏の学校
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] ナノ仮晶化学:元素置換による新しいナノ粒子の創り方 -プラズモニクスにおける錬金術-2018

    • Author(s)
      寺西利治
    • Organizer
      第3回精密無機有機合成化学研究会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] ナノ結晶の特異構造がもたらす高効率光エネルギー変換特性2018

    • Author(s)
      寺西利治
    • Organizer
      第22回名古屋大学VBLシンポジウム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Anisotropic Assembly of Nanoparticles for Photoenergy Conversion2017

    • Author(s)
      T. Teranishi
    • Organizer
      The 2nd Japan-US Bilateral Meeting on Coordination Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 原子を集めて入れ替える ~新しいナノ粒子の創り方と使い方~2017

    • Author(s)
      寺西利治
    • Organizer
      第7回CSJフェスタ
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Efficient Charge Separation in Heterostructured Nanoparticles2017

    • Author(s)
      T. Teranishi
    • Organizer
      5th CMS International Symposium on Photofunctional Chemistry and Molecular Systems
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 無機ナノ粒子:設計の重要性と偶発の面白さ2016

    • Author(s)
      寺西利治
    • Organizer
      日本セラミックス協会資源・環境関連材料部会講演会
    • Place of Presentation
      東京都立産業技術センター(東京)
    • Year and Date
      2016-10-21
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Book] CSJ Current Review 32 プラズモンと光圧が導く物質科学2019

    • Author(s)
      寺西利治 他
    • Total Pages
      196
    • Publisher
      化学同人
    • ISBN
      9784759813920
    • Related Report
      2018 Annual Research Report
  • [Remarks] 寺西研

    • URL

      https://www.scl.kyoto-u.ac.jp/~teranisi/

    • Related Report
      2019 Annual Research Report
  • [Remarks] 新学術領域webページ

    • URL

      http://www.asymmetallic.jp

    • Related Report
      2017 Annual Research Report
  • [Remarks] 研究室webページ

    • URL

      http://www.scl.kyoto-u.ac.jp/~teranisi/

    • Related Report
      2017 Annual Research Report
  • [Remarks] 新学術領域「配位アシンメトリー」

    • URL

      http://www.asymmetallic.jp

    • Related Report
      2016 Annual Research Report
  • [Remarks] Teranishi Laboratory

    • URL

      http://www.scl.kyoto-u.ac.jp/~teranisi/

    • Related Report
      2016 Annual Research Report
  • [Patent(Industrial Property Rights)] テトラフェニルポルフィリン誘導体2017

    • Inventor(s)
      坂本雅典、寺西利治、川脇徳久
    • Industrial Property Rights Holder
      坂本雅典、寺西利治、川脇徳久
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2017-101193
    • Filing Date
      2017
    • Related Report
      2017 Annual Research Report

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Published: 2016-07-04   Modified: 2021-01-27  

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