Research on creation of high-entropy alloy nanoparticles and their new catalytic function development

• Project/Area Number: 19K22082
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 27:Chemical engineering and related fields
• Research Institution: Osaka University
• Principal Investigator: Mori Kohsuke 大阪大学, 工学研究科, 准教授 (90423087)
• Project Period (FY): 2019-06-28 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000); Fiscal Year 2021: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: ハイエントロピー合金 / ナノ粒子 / 触媒 / ハイエントロピー合金ナノ粒子 / スピルオーバー / 金属触媒 / 触媒材料 / 水素スピルオーバー / ハイエントロピー合金ナノ粒子触媒

Outline of Research at the Start

『ハイエントロピー合金』は、1) 構成元素が5成分以上の多成分系、2) 等原子組成比、3) 単相固溶体を形成する、などの特徴から従来の合金とは異なる高い比強度、破壊靭性、高延性、高温強度、耐食性を示す、次世代金属材料である。しかしながら、触媒材料として利用例はもちろんのこと、ハイエントロピー合金のナノ粒子化成功例に関する報告は皆無である。本課題では、触媒材料とし未開拓なハイエントロピー合金に着目し、触媒機能発現を目指したナノ粒子化法を確立する。さらに創製した合金ナノ粒子の触媒的性能を選択的水素化反応にて評価し、その利用可能性探索を世界に先駆け行う。

Outline of Final Research Achievements

The facile fabrication of high-entropy alloy (HEA) nanoparticles (NPs) over conventional catalyst supports remains challenging. We demonstrate that titanium dioxide (TiO2) is a promising platform for the low-temperature synthesis of supported CoNiCuRuPd HEA NPs at 400 °C. This process is driven by the hydrogen spillover effect on TiO2. The CoNiCuRuPd HEA NPs on TiO2 produced were found to be both active and extremely durable during the CO2 hydrogenation reaction. Characterization by means of various in situ techniques and theoretical calculations elucidated that cocktail effect and sluggish diffusion originating from the synergistic effect obtained by this combination of elements.

Academic Significance and Societal Importance of the Research Achievements

本研究で開発した担持合金ナノ粒子は、調製が極めて簡便である、過酷な環境下においても安定性が高く分離・回収の容易な粉末状であるなど、実用化触媒に不可欠な基盤要素を兼ね備えている。また、CO2資源化反応において、単一金属から成る既存の触媒より数倍優れた性能を示した。さらに本研究では、カクテル効果、遅い拡散効果が、触媒活性やナノ粒子の構造安定性に起因していることを、理論計算を用いて証明しており学術的な意義も極めて高い。

Research Products

• [Int'l Joint Research] Sorbonne Universités(フランス)
• [Journal Article] Crystal Facet Engineering and Hydrogen Spillover-Assisted Synthesis of Defective Pt/TiO2-x Nanorods with Enhanced Visible Light-Driven Photocatalytic Activity (2022)
  • Author(s): Y. Yamazaki, T. Toyonagak, N. Doshita, K. Mori, Y. Kuwahara, S. Yamazaki, H. Yamashita
  • Journal Title: ACS Applied Materials & Interfaces Volume: 14 Issue: 1 Pages: 2291-2300
  • DOI: 10.1021/acsami.1c20148
  • Peer Reviewed / Open Access
• [Journal Article] 水素スピルオーバーを利用した五元系ハイエントロピー合金ナノ粒子の調製と触媒機能 (2022)
  • Author(s): 森浩亮、橋本直樹、山下弘巳
  • Journal Title: 触媒 Volume: 64 Pages: 79-85
• [Journal Article] Hydrogen spillover-driven synthesis of high-entropy alloy nanoparticles as a robust catalyst for CO2 hydrogenation (2021)
  • Author(s): K. Mori, N. Hashimoto, N. Kamiuchi, H. Yoshida, H. Kobayashi, H. Yamashita
  • Journal Title: Nature Communications Volume: 12 Issue: 1 Pages: 3884-3893
  • DOI: 10.1038/s41467-021-24228-z
  • Peer Reviewed / Open Access
• [Journal Article] The Promotional Effects of Heteroatom Doping and Alloy Nanoparticle Confinement (2021)
  • Author(s): K. Mori, J. Matsuo, Y. Kondo, H. Hata, H. Yamashita
  • Journal Title: ACS Applied Energy Materials Volume: 4 Issue: 10 Pages: 11634-11642
  • DOI: 10.1021/acsaem.1c02369
  • Peer Reviewed
• [Journal Article] Defect Engineering of Pt/TiO2-x Photocatalysts via Reduction Treatment Assisted by Hydrogen Spillover (2021)
  • Author(s): Y. Yamazaki, K. Mori, Y. Kuwahara, H. Kobayashi, H. Yamashita
  • Journal Title: ACS Applied Materials & Interfaces Volume: 13 Issue: 41 Pages: 48669-48678
  • DOI: 10.1021/acsami.1c13756
  • Peer Reviewed / Open Access
• [Journal Article] PdAg Nanoparticles Supported on an Amine-functionalized MOF as a Photo-switchable Catalyst for Hydrogen Storage/Delivery Mediated by CO2/Formic Acid (2021)
  • Author(s): Mori Kohsuke、Matsuo Jumpei、Yamashita Hiromi
  • Journal Title: Chemistry Letters Volume: 50 Issue: 4 Pages: 607-610
  • DOI: 10.1246/cl.200905
  • NAID: 130008025833
  • Peer Reviewed / Open Access
• [Journal Article] Additive-Free Aqueous Phase Synthesis of Formic Acid by Direct CO2 Hydrogenation over a PdAg Catalyst on a Hydrophilic N-Doped Polymer Silica Composite Support with High CO2 Affinity (2020)
  • Author(s): Masuda Shinya、Mori Kohsuke、Kuwahara Yasutaka、Louis Catherine、Yamashita Hiromi
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 6 Pages: 5847-5855
  • DOI: 10.1021/acsaem.0c00771
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Interconversion of Formate/Bicarbonate for Hydrogen Storage/Release: Improved Activity Following Sacrificial Surface Modification of a Ag@Pd/TiO2 Catalyst with a TiOx Shell (2020)
  • Author(s): Masuda Shinya、Shimoji Yuki、Mori Kohsuke、Kuwahara Yasutaka、Yamashita Hiromi
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 6 Pages: 5819-5829
  • DOI: 10.1021/acsaem.0c00744
  • Peer Reviewed / Open Access
• [Journal Article] Interfacial Engineering of PdAg/TiO2 with a Metal Organic Framework to Promote the Hydrogenation of CO2 to Formic Acid (2020)
  • Author(s): Mori Kohsuke、Konishi Atsushi、Yamashita Hiromi
  • Journal Title: The Journal of Physical Chemistry C Volume: 124 Issue: 21 Pages: 11499-11505
  • DOI: 10.1021/acs.jpcc.0c02457
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of a binary alloy nanoparticle catalyst with an immiscible combination of Rh and Cu assisted by hydrogen spillover on a TiO2 support (2020)
  • Author(s): Masuda Shinya、Shun Kazuki、Mori Kohsuke、Kuwahara Yasutaka、Yamashita Hiromi
  • Journal Title: Chemical Science Volume: 11 Issue: 16 Pages: 4194-4203
  • DOI: 10.1039/c9sc05612b
  • Peer Reviewed / Open Access
• [Journal Article] Controlled Release of Hydrogen Isotope Compounds and Tunneling Effect in the Heterogeneously-Catalyzed Formic Acid Dehydrogenation (2019)
  • Author(s): Kohsuke Mori, Yuya Futamura, Shinya Masuda, Hisayoshi Kobayashi, Hiromi Yamashita
  • Journal Title: Nature Communications Volume: 10 Issue: 7 Pages: 4094-4104
  • DOI: 10.1002/tcr.201900085
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Encapsulation of PdAg Nanoparticles within Zeolitic Imidazolate Framework with Core-Shell Structure: A Bifunctional Catalyst for Formic Acid-based Hydrogen Storage/Delivery (2019)
  • Author(s): Meicheng Wen, Kohsuke Mori, Yasutaka Kuwahara, Mirim Navlani-Garacia, Taicheng An, and Hiromi Yamashita
  • Journal Title: Scientific Report Volume: 9 Issue: 1 Pages: 15675-15685
  • DOI: 10.1038/s41598-019-52133-5
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] PdAg Nanoparticles Supported on Resorcinol-Formaldehyde Polymers Containing Amine Groups: The Promotional Effect of Phenylamine Moieties on CO2 Transformation to Formic Acid (2019)
  • Author(s): Shinya Masuda, Kohsuke Mori, Yasutaka Kuwahara, and Hiromi Yamashita
  • Journal Title: Journal of Materials Chemistry A Volume: 7 Issue: 47 Pages: 16356-16363
  • DOI: 10.1039/c9cc02380a
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Nanocatalyst Engineering for CO2 Hydrogenation to Formic Acid as a Promising Hydrogen Carrier (2021)
  • Author(s): Kohsuke Mori
  • Organizer: 18th International Conference on Carbon Dioxide Utilization (ICCDU2021)
  • Int'l Joint Research / Invited
• [Presentation] Nanocatalyst Engineering for Formic acid/CO2-mediated Chemical Hydrogen Delivery/Storage (2021)
  • Author(s): Kohsuke Mori
  • Organizer: 1st Japan-China Symposium on Catalysis (1stJCSC)
  • Int'l Joint Research / Invited
• [Presentation] Nanocatalyst Engineering for CO2 Hydrogenation to Formic Acid as a Promising Hydrogen Storage Material (2021)
  • Author(s): Kohsuke Mori
  • Organizer: 17th Japan-Taiwan Joint Symposium on Catalysis
  • Int'l Joint Research / Invited
• [Presentation] ギ酸/CO2相互変換を指向した金属触媒ナノエンジニアリング (2021)
  • Author(s): 森浩亮
  • Organizer: 日本化学会第101春季年会イノベーション共創プログラム（CIP）グリーン水素製造・貯蔵・利用技術の最前線
  • Invited
• [Presentation] Nanocatalyst Engineering for Hydrogen Storage and Release Based on Formic Acid (2021)
  • Author(s): Kohsuke Mori
  • Organizer: Osaka-Shanghai Joint Workshop for Energy/Environmental Materials and Applications (JWEEMA2021)
  • Int'l Joint Research / Invited
• [Presentation] Nano-catalyst Engineering for Storage and Release of Hydrogen Energy using Formic Acid as a Promising Liquid Carrier (2020)
  • Author(s): Kohsuke Mori
  • Organizer: 第50回石油・石油化学討論会
  • Int'l Joint Research / Invited
• [Presentation] 水素エネルギーキャリアを合成・分解するための金属触媒ナノエンジニアリング (2020)
  • Author(s): 森浩亮
  • Organizer: 第126回触媒討論会
  • Invited
• [Presentation] 水素エネルギー分野への応用を指向した金属触媒ナノエンジニアリング (2020)
  • Author(s): 森浩亮
  • Organizer: 大阪大学ナノテクノロジー設備供用拠点 微細構造解析プラットフォーム, 2020年度 第1回地域セミナー
  • Invited
• [Presentation] Nano-catalyst Engineering for Hydrogen Storage and Delivery Utilizing Formic Acid as a Carrier (2020)
  • Author(s): Kohsuke Mori
  • Organizer: International Chemical Engineering Symposia 2020
  • Int'l Joint Research / Invited
• [Presentation] ギ酸/CO2相互変換のための金属触媒ナノエンジニアリング (2020)
  • Author(s): 森浩亮
  • Organizer: 日本化学会第100春季年会ATP化学が導く未来のエネルギー
  • Invited
• [Presentation] ハイエントロピー合金ナノ粒子担持触媒の開発とCO2水素化活性 (2019)
  • Author(s): 橋本 直樹、森 浩亮、山下 弘巳
  • Organizer: 日本金属学会2020年春期講演大会
• [Presentation] ギ酸/CO2相互変換のための金属触媒ナノエンジニアリング (2019)
  • Author(s): 森浩亮
  • Organizer: 界面分子変換研究会ワークショップ－表面界面での新規分子変換に向けた取り組み
  • Invited
• [Presentation] 水素エネルギーの貯蔵・供給のための金属触媒ナノエンジニアリング (2019)
  • Author(s): 森浩亮
  • Organizer: 触媒材料の金属学研究会 第４回ミニシンポジウム
  • Invited
• [Presentation] Nanocatalyst Engineering for Hydrogen Storage and Delivery Based on Formic Acid (2019)
  • Author(s): Kohsuke Mori
  • Organizer: Osaka-Shanghai Joint Workshop for Energy/Environmental Materials and Applications (JWEEMA2019)
  • Int'l Joint Research / Invited
• [Remarks]
  • URL: https://researchmap.jp/7000018582
• [Remarks] 研究者総覧
  • URL: http://www.mat.eng.osaka-u.ac.jp/msp1/MSP1-HomeJ.htm