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Functional Nanomaterials based on Porous Ionic Crystals and Metal Nanoparticles/Nanoclusters

Research Project

Project/Area Number 21K14639
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionThe University of Tokyo

Principal Investigator

Ogiwara Naoki  東京大学, 大学院総合文化研究科, 助教 (70848267)

Project Period (FY) 2021-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2022: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2021: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywordsポリオキソメタレート / 金属錯体 / ナノ金属 / 触媒 / 金属ナノ粒子 / 多孔性イオン結晶
Outline of Research at the Start

無機金属酸化物クラスターであるポリオキソメタレートを構成要素とするレドックス活性な多孔性イオン結晶 (Porous Ionic Crystals, PICs)を利用して、ナノ金属の電子状態、特にフェルミ準位の状態密度 (DOS)の制御を目指す。具体的には、
(1)水素吸蔵や触媒機能に適したナノ金属に着目し、レドックス活性なPICsで被覆させたPICs/ナノ金属複合物質をボトムアップ合成する。
(2)得られたナノ複合物質に対して表面分析を行うことで、PICsとナノ金属との間での電子授受-ナノ金属の電子状態の相関を明確化する。
(3)複合物質の電子状態制御により、新しい物性化学・触媒科学への展開を図る。

Outline of Final Research Achievements

Porous ionic crystals (PICs) are crystalline porous materials composed of polyoxometalates (POMs), which are anionic metal-oxo clusters comprising early transition metals, and macro cations (cationic multinuclear metal complexes, cationic metal-oxo clusters, etc). In this study, we applied the PIC itself and composite nanomaterials composed of PICs and metal nanoparticles/nanoclusters as functional materials. In particular, PICs effectively catalyzed a wide range of reactions including acid-catalyzed pinacol rearrangements, base-catalyzed Knoevenagel condensation, and electrochemical oxygen evolution reaction. The composite nanomaterials offered controllable photoluminescence properties.

Academic Significance and Societal Importance of the Research Achievements

PICは高い設計性を有する物質群であり、機能性材料として有望であるが、その機能発現はガス・イオン吸着やイオン伝導等の一部の機能に制限されていた。そのなかで、本研究ではPICおよびPICを基盤としたナノ複合物質が触媒機能や発光特性を有することを見出すことができた点で学術的意義を有すると考えられる。PICは組成-構造-機能を明確化するのに適した物質系であり、本課題で獲得した高機能化のための組成・構造の設計指針は高機能材料を構築する上で重要な知見を与えると思われる。今後、PICを用いたナノ物質における組成・構造をさらに洗練することにより、革新的な機能性材料の創出に繋がると期待される。

Report

(3 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • Research Products

    (33 results)

All 2023 2022 2021

All Journal Article (12 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 12 results,  Open Access: 2 results) Presentation (21 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Size-Controlled Synthesis of Luminescent Few-Atom Silver Clusters via Electron Transfer in Isostructural Redox-Active Porous Ionic Crystals2023

    • Author(s)
      N. Haraguchi, N. Ogiwara, Y. Kumabe, S. Kikkawa, S. Yamazoe, T. Tachikawa*, S. Uchida*
    • Journal Title

      Small

      Volume: - Issue: 23 Pages: 2300743-2300743

    • DOI

      10.1002/smll.202300743

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Metalーoxo-cluster-based crystals as solid catalysts2023

    • Author(s)
      Ogiwara Naoki、Uchida Sayaka
    • Journal Title

      Chem Catalysis

      Volume: 3 Issue: 7 Pages: 100607-100607

    • DOI

      10.1016/j.checat.2023.100607

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Basicity of isostructural porous ionic crystals composed of Nb/Ta-substituted Keggin-type polyoxotungstates2022

    • Author(s)
      Weng Zhewei、Ogiwara Naoki、Yokogawa Daisuke、Kitao Takashi、Kikukawa Yuji、Uchida Sayaka
    • Journal Title

      Dalton Transactions

      Volume: 51 Issue: 21 Pages: 8186-8191

    • DOI

      10.1039/d2dt00478j

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Vanadium-Substituted Polycationic Al-Oxo Cluster in a Porous Ionic Crystal Exhibiting Lewis Acidity2022

    • Author(s)
      W. Zhou, N. Ogiwara*, Z. Weng, C. Zhao, L. Yan, Y. Kikukawa, S. Uchida*
    • Journal Title

      Chem. Commun.

      Volume: 58 Issue: 90 Pages: 12548-12548

    • DOI

      10.1039/d2cc03545f

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Oxygen Evolution Reaction Driven by Charge Transfer from a Cr Complex to Co-Containing Polyoxometalate in a Porous Ionic Crystal2022

    • Author(s)
      Shimoyama Yuto、Ogiwara Naoki、Weng Zhewei、Uchida Sayaka
    • Journal Title

      Journal of the American Chemical Society

      Volume: 144 Issue: 7 Pages: 2980-2986

    • DOI

      10.1021/jacs.1c10471

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Proton conduction in ionic crystals based on polyoxometalates2022

    • Author(s)
      Ogiwara Naoki、Iwano Tsukasa、Ito Takeru、Uchida Sayaka
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 462 Pages: 214524-214524

    • DOI

      10.1016/j.ccr.2022.214524

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Syntheses, Polymorphic Transformations, and Functions of Ionic Crystals Based on Mononuclear Bismuth(III) Complexes and Polyoxometalates2022

    • Author(s)
      T. Iwano, D. Akutsu, Z. Weng, N. Ogiwara, S. Uchid
    • Journal Title

      ChemNanoMat

      Volume: 8 Issue: 5 Pages: 2980-2986

    • DOI

      10.1002/cnma.202100479

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Isomeric effects on the acidity of Al13 Keggin clusters in porous ionic crystals2021

    • Author(s)
      W. Zhou, N. Ogiwara, Z. Weng, N. Tamai, C. Zhao, L. Yan, S. Uchid
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 71 Pages: 8893-8896

    • DOI

      10.1039/d1cc03600a

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Recording the Pt-beyond hydrogen production electrocatalysis by dirhodium phosphide with an overpotential of only 4.3?mV in alkaline electrolyte2021

    • Author(s)
      Xin Hongqiang、Dai Zhengfei、Zhao Yiwei、Guo Shengwu、Sun Jun、Luo Qiaomei、Zhang Pengfei、Sun Lan、Ogiwara Naoki、Kitagawa Hiroshi、Huang Bo、Ma Fei
    • Journal Title

      Applied Catalysis B: Environmental

      Volume: 297 Pages: 120457-120457

    • DOI

      10.1016/j.apcatb.2021.120457

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Fabrication of Integrated Copper‐Based Nanoparticles/Amorphous Metal-Organic Framework by a Facile Spray‐Drying Method: Highly Enhanced CO <sub>2</sub> Hydrogenation Activity for Methanol Synthesis2021

    • Author(s)
      Mitsuka Yuko、Ogiwara Naoki、Mukoyoshi Megumi、Kitagawa Hiroshi、Yamamoto Tomokazu、Toriyama Takaaki、Matsumura Syo、Haneda Masaaki、Kawaguchi Shogo、Kubota Yoshiki、Kobayashi Hirokazu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 41 Pages: 22283-22288

    • DOI

      10.1002/anie.202110585

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Incorporating highly-basic polyoxometalate anions comprising Nb or Ta into nanoscale reaction fields of porous ionic crystals2021

    • Author(s)
      Z. Weng, N. Ogiwara, T. Kitao, Y. Kikukawa, Y. Gao, L. Yan, S. Uchid
    • Journal Title

      Nanoscale

      Volume: 13 Issue: 44 Pages: 18451-18457

    • DOI

      10.1039/d1nr04762k

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Phase Control of Solid-Solution Nanoparticles beyond the Phase Diagram for Enhanced Catalytic Properties2021

    • Author(s)
      Wu Dongshuang、Kusada Kohei、Aspera Susan Me?ez、Nakanishi Hiroshi、Chen Yanna、Seo Okkyun、Song Chulho、Kim Jaemyung、Hiroi Satoshi、Sakata Osami、Yamamoto Tomokazu、Matsumura Syo、Nanba Yusuke、Koyama Michihisa、Ogiwara Naoki、Kawaguchi Shogo、Kubota Yoshiki、Kitagawa Hiroshi
    • Journal Title

      ACS Materials Au

      Volume: 2 Issue: 2 Pages: 110-116

    • DOI

      10.1021/acsmaterialsau.1c00048

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Vanadium-substituted polycationic Al13 dimer in a porous ionic crystal exhibiting Lewis acidity2023

    • Author(s)
      Wei ZHOU, Naoki OGIWARA, Sayaka UCHIDA
    • Organizer
      錯体化学会 第72回討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Basicity of Isostructural Porous Ionic Crystals Composed of Nb/Ta-Substituted Keggin-Type Polyoxotungstates2023

    • Author(s)
      Zhewei Weng, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      錯体化学会 第72回討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 等構造な多孔性イオン結晶を用いた小核銀クラスターの合成2023

    • Author(s)
      黒﨑 大誠, 荻原 直希, 内田 さやか
    • Organizer
      錯体化学会 第72回討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Reduction-induced cesium ion capture with polyoxometalate encapsulated metalーorganic frameworks2023

    • Author(s)
      Cocoro A. Nagasaka, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      錯体化学会 第72回討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Tris修飾Anderson型ポリオキソメタレートを用いた多孔性イオン結晶の創製2023

    • Author(s)
      望月 舜介、翁 哲偉、荻原 直希、内田 さやか
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 等構造な多孔性イオン結晶を鋳型とした小核銀クラスターの合成2023

    • Author(s)
      黒﨑 大誠、荻原 直希、内田 さやか
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] POMを構成要素とする多孔性イオン結晶とPdナノ粒子からなる複合体合成2023

    • Author(s)
      岩田 友樹、荻原 直希、内田 さやか
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 多孔性金属錯体に内包されたポリオキソ酸の還元を利用したCs+イオン吸着2023

    • Author(s)
      荻原 直希、永坂 心、内田 さやか
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 多孔性イオン結晶を鋳型としたサイズ制御された小核銀クラスターの合成2023

    • Author(s)
      原口 直哉、荻原 直希、内田 さやか
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Co含有ポリ酸を基盤とする多孔性イオン結晶の酸素生成触媒能:結晶内電荷移動を駆動力とする相乗的触媒活性2022

    • Author(s)
      下山 雄人, 翁 哲偉, 荻原 直希, 内田 さやか
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] Dawson型POMとポリエチレングリコール誘導体を基盤とした中温領域作動のプロトン伝導体2022

    • Author(s)
      荻原 直希, 友田 雅大, 宮崎 翔太郎, 翁 哲偉, 内田 さやか
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] ポリ酸とビスマス単核錯体を基盤としたイオン結晶の合成と結晶多形の観測2022

    • Author(s)
      岩野 司, 阿久津 大貴, 翁 哲偉, 荻原 直希, 内田 さやか
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] The Formation of Al28V4 Polycation in Porous Ionic Crystal for Acetalization Reaction2022

    • Author(s)
      Wei Zhou, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] 多孔性イオン結晶の内部空間を利用した小核銀クラスターの合成2022

    • Author(s)
      原口 直哉, 荻原 直希, 内田 さやか
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] 等構造な多孔性イオン結晶を用いた小核銀クラスターの合成2022

    • Author(s)
      黒﨑 大誠, 荻原 直希, 内田 さやか
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] Reduction-induced alkali ion capture with polyoxometalate encapsulated metal-organic frameworks2022

    • Author(s)
      Cocoro Andrew Nagasaka, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] Enhancing the basicity of polyoxometalates-based porous ionic crystals by substitution of Nb/Ta2022

    • Author(s)
      Zhewei Weng, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] Isomeric Effect on the Acidity of Porous Ionic Crystals Based on Oppositely-Charged Keggin-type Polyoxometalates2021

    • Author(s)
      Wei Zhou, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      錯体化学会第71回討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] コバルト含有ポリ酸を基盤とする多孔性イオン結晶の合成と相乗的な酸素生成触媒活性の解析2021

    • Author(s)
      下山雄人, 荻原直希, 内田 さやか
    • Organizer
      錯体化学会第71回討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] Incorporating Higly-Basic Polyoxometalate Anions Comprising Nb or Ta into Nanoscale Reaction Fields of Porous Ionic Crystals2021

    • Author(s)
      Zhewei Weng, Naoki Ogiwara, Sayaka Uchida
    • Organizer
      錯体化学会第71回討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] The Effect of Amorphization on the Molecular Motion of the 2-Methylimidazolate Linkers in ZIF-82021

    • Author(s)
      Naoki Ogiwara, Daniil I. Kolokolov, Masaki Donoshita, Hirokazu Kobayashi, Satoshi Horike, Hiroshi Kitagawa
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research

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Published: 2021-04-28   Modified: 2024-01-30  

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