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前期遷移金属ヒドリド化合物触媒の開拓と機構解明

Research Project

Project/Area Number 21J15834
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Review Section Basic Section 36010:Inorganic compounds and inorganic materials chemistry-related
Research InstitutionKyoto University

Principal Investigator

Cao Yu  京都大学, 工学研究科, 特別研究員(DC2)

Project Period (FY) 2021-04-28 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2022: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2021: ¥800,000 (Direct Cost: ¥800,000)
Keywordsammonia synthesis / hydride
Outline of Research at the Start

1. Catalyst synthesis: 1) early transition metal-based nitride-hydrides 2) intermetallic hydrides
2. Catalyst Characterization: 1) structure 2) composition 3) surface
3. Ammonia synthesis: 1) catalytic activity 2) stability
4. Kinetic studies and isotopic experiments

Outline of Annual Research Achievements

Early 3d transition metals, such as Ti, V, Nb or Cr are known to be inactive for the Haber-Bosch process, due to their strong M-N bonds. I expanded the study to hydrides of other early transition metals, i.e., V and Nb. These metals benefit from body-centered cubic (bcc) related structures which enhance hydride diffusion, in addition to having relatively lower M-N bond strengths. The activity of vanadium hydride, most likely with an active composition of VH0.44N0.16, is superior to the previously reported TiH2 and BaTiO2.5H0.5, and comparable to Cs-Ru/MgO. These results show that there is more potential for developing new single-phase hydride catalysts of previously overlooked elements without sacrificing activity.
Topochemical reactions have led to great progress in the discovery of new metastable compounds with novel chemical and physical properties, making it an effective method of synthesizing new hydride materials. I reported a topochemical synthesis of a new hexagonal nitride hydride, h-Ca3CrN3H, by heating an orthorhombic nitride, o-Ca3CrN3, under hydrogen at 673 K, accompanied by a rotational structural transformation. The hydrogen intercalation modifies the Ca-N rock-salt-like atomic packing in o-Ca3CrN3 to a face-sharing octahedral chain in h-Ca3CrN3H. Impressively, the h-Ca3CrN3H exhibited stable ammonia synthesis activity when used as a catalyst, even though the early transition metal Cr is not an active element for ammonia synthesis. DFT calculations reveal that nitrogen reduction could be effectively achieved through an associative mechanism.

Research Progress Status

令和4年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和4年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (4 results)

All 2023 2022 2021

All Journal Article (3 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 1 results) Presentation (1 results)

  • [Journal Article] Ammonia Synthesis via an Associative Mechanism on Alkali Earth Metal Sites of Ca3CrN3H2023

    • Author(s)
      Cao Yu、Toshcheva Ekaterina、Almaksoud Walid、Ahmad Rafia、Tsumori Tatsuya、Rai Rohit、Tang Ya、Cavallo Luigi、Kageyama Hiroshi、Kobayashi Yoji
    • Journal Title

      ChemSusChem

      Volume: 1 Issue: 22

    • DOI

      10.1002/cssc.202300234

    • Related Report
      2022 Annual Research Report
  • [Journal Article] Topochemical Synthesis of Ca3CrN3H Involving a Rotational Structural Transformation for Catalytic Ammonia Synthesis2022

    • Author(s)
      Cao Yu、Kirsanova Maria A.、Ochi Masayuki、Al Maksoud Walid、Zhu Tong、Rai Rohit、Gao Shenghan、Tsumori Tatsuya、Kobayashi Shintaro、Kawaguchi Shogo、Abou‐Hamad Edy、Kuroki Kazuhiko、Tassel Cedric、Abakumov Artem M.、Kobayashi Yoji、Kageyama Hiroshi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 39

    • DOI

      10.1002/anie.202209187

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Vanadium Hydride as an Ammonia Synthesis Catalyst2021

    • Author(s)
      Cao Yu、Saito Ayaka、Kobayashi Yoji、Ubukata Hiroki、Tang Ya、Kageyama Hiroshi
    • Journal Title

      ChemCatChem

      Volume: 13 Issue: 1 Pages: 191-195

    • DOI

      10.1002/cctc.202001084

    • Related Report
      2021 Annual Research Report
  • [Presentation] Topochemical Synthesis of Ca3CrN3H Involving a Rotational Structural Transformation for Catalytic Ammonia Synthesis2022

    • Author(s)
      Yu Cao
    • Organizer
      CSJ Annual meeting 2023
    • Related Report
      2022 Annual Research Report

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Published: 2021-05-27   Modified: 2024-03-26  

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