• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

On the Reactivity of Ammonia in Metal-Organic Frameworks

Research Project

Project/Area Number 19K23648
Research Category

Grant-in-Aid for Research Activity Start-up

Allocation TypeMulti-year Fund
Review Section 0502:Inorganic/coordination chemistry, analytical chemistry, inorganic materials chemistry, energy-related chemistry, and related fields
Research InstitutionThe University of Tokyo (2020)
Tokyo Institute of Technology (2019)

Principal Investigator

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

Project Period (FY) 2019-08-30 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords多孔性金属錯体 / ナノ結晶 / 触媒 / ポリオキソメタレート / イオン伝導 / 金属ナノ粒子 / アンモニア
Outline of Research at the Start

本研究では多孔性金属錯体(MOF)に吸着されたアンモニア分子が、バルク状態とは異なる化学状態を有することに着目し、その特異なアンモニア分子の化学反応性を理解することを目指す。そのために、高い触媒反応性を有する金属ナノ粒子に着目し、金属ナノ粒子とMOFを複合化させた研究対象となる新たな物質系を開拓する。
さらに、MOFの高い設計性を活かし、その細孔サイズや細孔環境を適切に設計することにより、MOF細孔中に束縛されたアンモニアの化学状態の制御、さらにはアンモニアの反応活性の制御を試みる。

Outline of Final Research Achievements

The reactivity of H2O vapor in metal-organic frameworks (MOFs) was first studied with Pt nanocrystals (NCs) through the water-gas shift (WGS) reaction. A water-stable MOF, UiO-66, serves as a highly effective support material for the WGS reaction compared with ZrO2. The origin of the high catalytic performance was investigated using in situ IR spectroscopy. Besides, the ligand functionalization of UiO-66 significantly affected the catalytic performance of the WGS reaction. The introduction of a -Br group lowered the reactivity of Pt@UiO-66 by nearly half, whereas the substitution of -Br with a -Me2 group triply enhanced the activity. The origin of the enhanced catalytic activity was found to be the change in H2O activity in the UiO-66 pores by the ligand functionalization, which was investigated using H2O sorption, solid-state NMR, X-ray photoelectron spectroscopy, and in situ IR measurements. This work opens a new prospect to develop MOFs as a platform to activate H2O.

Academic Significance and Societal Importance of the Research Achievements

本成果はこれまで未開拓であったMOFに吸着された水の反応性についての知見を与えるものであり、水を活性化する場としてのMOFの有用性を世界に先駆けて見出した点で学術的意義を有すると考えられる。本課題で解明された水の吸着状態と反応性との相関は、水をはじめとする種々の分子の反応場を構築する上で重要な指針を与えると思われる。今後、水だけでなくアンモニアや有機分子等の分子変換に、得られた知見を適用すれば革新的触媒の創出に繋がると期待される。このように本成果は小分子活性という基礎学問の発展に寄与するだけでなく、既存の触媒を凌駕する高活性触媒の開発にも貢献するため、応用面でも波及効果をもたらすと考えられる。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (14 results)

All 2021 2020 2019

All Journal Article (9 results) (of which Int'l Joint Research: 6 results,  Peer Reviewed: 9 results,  Open Access: 2 results) Presentation (5 results)

  • [Journal Article] Formation of Mixed‐Valence Luminescent Silver Clusters via Cation‐Coupled Electron‐Transfer in a Redox‐Active Ionic Crystal Based on a Dawson‐type Polyoxometalate with Closed Pores2021

    • Author(s)
      Haraguchi Naoya、Okunaga Tomoki、Shimoyama Yuto、Ogiwara Naoki、Kikkawa Soichi、Yamazoe Seiji、Inada Miki、Tachikawa Takashi、Uchida Sayaka
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2021 Issue: 16 Pages: 1531-1535

    • DOI

      10.1002/ejic.202100101

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Integrating molecular design and crystal engineering approaches in non-humidified intermediate-temperature proton conductors based on a Dawson-type polyoxometalate and poly(ethylene glycol) derivatives2021

    • Author(s)
      Ogiwara Naoki、Tomoda Masahiro、Miyazaki Shotaro、Weng Zhewei、Takatsu Hiroshi、Kageyama Hiroshi、Misawa Toshiyuki、Ito Takeru、Uchida Sayaka
    • Journal Title

      Nanoscale

      Volume: 印刷中 Issue: 17 Pages: 8049-8057

    • DOI

      10.1039/d1nr01220g

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ultrahigh Proton Conduction via Extended Hydrogen-Bonding Network in a Preyssler-Type Polyoxometalate-Based Framework Functionalized with Lanthanide Ion2021

    • Author(s)
      T. Iwano, K. Shitamatsu, N. Ogiwara, M. Okuno, Y. Kikukawa, S. Ikemoto, S. Shirai, S. Muratsugu, P. Waddell, R. J. Errington, M. Sadakane, S. Uchida
    • Journal Title

      ACS Appl. Mater. Interfaces

      Volume: 13 Issue: 16 Pages: 19138-19147

    • DOI

      10.1021/acsami.1c01752

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Probing dynamics of carbon dioxide in a metal-organic framework under high pressure by high-resolution solid-state NMR2020

    • Author(s)
      Munehiro Inukai, Takuya Kurihara, Yasuto Noda, Weiming Jiang, Kiyonori Takegoshi, Naoki Ogiwara, Hiroshi Kitagawa and Koichi Nakamura
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: - Issue: 26 Pages: 14465-14470

    • DOI

      10.1039/d0cp01216e

    • NAID

      120007027673

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Isostructural Mesoporous Ionic Crystals as a Tunable Platform for Acid Catalysis2020

    • Author(s)
      Y. Shimoyama, Z. Weng, N. Ogiwara, T. Kitao, Y. Kikukawa, S. Uchida
    • Journal Title

      Dalton Trans

      Volume: 49 Issue: 30 Pages: 10328-10333

    • DOI

      10.1039/d0dt01202e

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Crystalline to amorphous transformation in solid-solution alloy nanoparticles induced by boron doping2020

    • Author(s)
      Kobayashi Keigo、Kusada Kohei、Wu Dongshuang、Ogiwara Naoki、Kobayashi Hirokazu、Haruta Mitsutaka、Kurata Hiroki、Hiroi Satoshi、Seo Okkyun、Song Chulho、Chen Yanna、Kim Jaemyung、Tayal Akhil、Sakata Osami、Ohara Koji、Honma Tetsuo、Kitagawa Hiroshi
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 85 Pages: 12941-12944

    • DOI

      10.1039/d0cc05418f

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ligand-Functionalization-Controlled Activity of Metal-Organic Framework-Encapsulated Pt Nanocatalyst toward Activation of Water2020

    • Author(s)
      Ogiwara Naoki、Kobayashi Hirokazu、Inukai Munehiro、Nishiyama Yusuke、Concepcion Patricia、Rey Fernando、Kitagawa Hiroshi
    • Journal Title

      Nano Letters

      Volume: 20 Issue: 1 Pages: 426-432

    • DOI

      10.1021/acs.nanolett.9b04124

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] The First Study on the Reactivity of Water Vapor in Metal-Organic Frameworks with Platinum Nanocrystals2019

    • Author(s)
      Ogiwara Naoki、Kobayashi Hirokazu、Concepcion Patricia、Rey Fernando、Kitagawa Hiroshi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 34 Pages: 11731-11736

    • DOI

      10.1002/anie.201905667

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Missing-linker metal-organic frameworks for oxygen evolution reaction2019

    • Author(s)
      Xue Ziqian、Liu Kang、Liu Qinglin、Li Yinle、Li Manrong、Su Cheng-Yong、Ogiwara Naoki、Kobayashi Hirokazu、Kitagawa Hiroshi、Liu Min、Li Guangqin
    • Journal Title

      Nature Communications

      Volume: 10 Issue: 1 Pages: 5048-5048

    • DOI

      10.1038/s41467-019-13051-2

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] ホウ素を含む3元系合金ナノ粒子PdーTMーBの合成と構造変化の観測2021

    • Author(s)
      小林 佳吾、草田 康平、Dongshuang Wu、荻原 直希、小林 浩和、治田 充貴、倉田 博基、山本 知一、鳥山 誉亮、松村 晶、廣井 慧、Okkyun Seo、Chulho Song、Yanna Chen、Jaemyung Kim、Akhil Tayal、坂田 修身、尾原 幸治、本間 徹生、北川 宏
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and structure of porous ionic crystals based on delta-Keggin-type aluminum polyoxocation2021

    • Author(s)
      Wei Zhou、Sayaka Uchida、 Naoki Ogiwara、Zhewei Weng
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Dawson型ポリ酸とポリマーを基盤とした中温領域作動のプロトン伝導体の設計2020

    • Author(s)
      荻原 直希、 友田 雅大、 宮崎 翔太郎、 内田 さやか
    • Organizer
      第14 回 物性科学領域横断研究会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Dawson型ポリ酸とポリマーを基盤としたプロトン伝導物質2020

    • Author(s)
      宮崎 翔太郎、友田 雅大、荻原 直希、内田 さやか
    • Organizer
      第10回CSJ化学フェスタ
    • Related Report
      2020 Annual Research Report
  • [Presentation] Systematic control of isomerization of glucose to fructose by tailoring acid sites in metal-organic frameworks2020

    • Author(s)
      Liu Yimin、Ogiwara Naoki、Hattori Masashi、Hara Michikazu
    • Organizer
      第125回触媒討論会
    • Related Report
      2019 Research-status Report

URL: 

Published: 2019-09-03   Modified: 2022-01-27  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi