Design and creation of catalytic reaction fields using operando ME spectroscopy

• Project/Area Number: 20KK0111
• Research Category: Fund for the Promotion of Joint International Research (Fostering Joint International Research (B))
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 27:Chemical engineering and related fields
• Research Institution: Hokkaido University
• Principal Investigator: Toyao Takashi 北海道大学, 触媒科学研究所, 准教授 (80775388)
• Co-Investigator(Kenkyū-buntansha): 前野 禅 工学院大学, 先進工学部, 准教授 (30721154)
• Project Period (FY): 2020-10-27 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2023: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2022: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2021: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2020: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
• Keywords: 固体触媒 / Modulation Excitation / 触媒反応場 / オペランド分光 / 不均一系触媒 / in situ/operando分光 / Operando分光 / 計算科学 / 放射光 / X線吸収分光

Outline of Research at the Start

Modulation Excitation (ME)法は分光法におけるシグナル/ノイズ(S/N)比を劇的に向上させ、物理・化学現象の動的過程に関与する種を選択的に解析することのできる強力な手法である。本研究では、このME分光と、触媒動作条件下で触媒の分光学的評価と触媒活性・選択性の測定を同時に行う手法と定義されているOperando観測とを組み合わせることで触媒反応機構研究を行い、触媒反応場の設計指針を確立する。触媒反応としては主に二酸化炭素の水素化反応を扱う。得られる触媒設計指針に基づいて実触媒を開発するとともに、当該分野の学術基盤を確立する。

Outline of Final Research Achievements

Modulation Excitation (ME) is a powerful method that can dramatically improve the signal/noise (S/N) ratio in spectroscopy and selectively analyze species involved in the dynamic processes of physical and chemical phenomena. It is. The purpose of this study was to design an effective catalytic reaction site for CO2 hydrogenation reactions through studies using Operando ME spectroscopy. More specifically, we applied Operando ME spectroscopy to methanol synthesis from CO2/H2 at a low temperature of about 150 ℃ with the aim of elucidating the reaction mechanism and establishing guidelines for designing a catalytic reaction field.

Academic Significance and Societal Importance of the Research Achievements

Operando ME分光を用いた検討により、CO2水素化反応、特に、CO2/H2からの低温メタノール合成反応に有効な触媒設計を行うにあたって重要な知見が得られた。得られた結果および触媒設計指針を基に、更なる触媒性能の向上と実用化に向けた研究開発を進めることを計画している。また本研究では、反応場での触媒の活性化というより一般性の高いユニークな現象も発見した。CO2水素化反応のみならず、他の触媒反応や、物質のダイナミクスが関わる幅広い科学分野において本研究成果が活用されると期待できる。

Research Products

• [Int'l Joint Research] デルフト工科大学(オランダ)
• [Int'l Joint Research] デルフト工科大学(オランダ)
• [Int'l Joint Research] デルフト工科大学(オランダ)
• [Int'l Joint Research] Paul Scherrer Institute(スイス)
• [Journal Article] Enhanced N2O decomposition on Rh/ZrO2 catalysts through the promotional effect of palladium (2024)
  • Author(s): Zhang Ningqiang、He Chenxi、Jing Yuan、Qian Yucheng、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: Surfaces and Interfaces Volume: 46 Pages: 104120-104120
  • DOI: 10.1016/j.surfin.2024.104120
  • Peer Reviewed
• [Journal Article] Mechanism of NH3-SCR over P/CeO2 Catalysts Investigated by Operando Spectroscopies (2023)
  • Author(s): Zhang Ningqiang、Tong Jiahuan、Miyazaki Shinta、Zhao Shirun、Kubota Hiroe、Jing Yuan、Mine Shinya、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: Environmental Science & Technology Volume: 57 Issue: 43 Pages: 16289-16295
  • DOI: 10.1021/acs.est.3c05787
  • Peer Reviewed
• [Journal Article] Continuous Unsteady-State De-NOx System via Tandem Water Gas Shift, NH3 Synthesis, and NH3-SCR under Periodic Lean/Rich Conditions (2023)
  • Author(s): Zhang Ningqiang、Qian Yucheng、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: Environmental Science & Technology Volume: 57 Issue: 48 Pages: 19584-19593
  • DOI: 10.1021/acs.est.3c06390
  • Peer Reviewed
• [Journal Article] Promotional Effect of Ag on the Catalytic Decomposition of N2O in the Presence of O2 over the Al2O3-Supported Rh Catalyst (2023)
  • Author(s): Jing Yuan、He Chenxi、Zhang Ningqiang、Murano Yu、Toyoshima Ryo、Kondoh Hiroshi、Kageyama Yuuta、Inomata Hironori、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: ACS Catalysis Volume: 13 Issue: 19 Pages: 12983-12993
  • DOI: 10.1021/acscatal.3c02446
  • Peer Reviewed
• [Journal Article] Operando Spectroscopic Study of Reduction and Oxidation Half-Cycles in NH3-SCR over CeO2-Supported WO3 (2023)
  • Author(s): Kubota Hiroe、Jing Yuan、Wan Li、Tong Jiahuan、Zhang Ningqiang、Mine Shinya、Toyao Takashi、Toyoshima Ryo、Kondoh Hiroshi、Ferri Davide、Shimizu Ken-ichi
  • Journal Title: ACS Catalysis Volume: 13 Issue: 13 Pages: 9274-9288
  • DOI: 10.1021/acscatal.3c01665
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Bifunctionality of Re Supported on TiO2 in Driving Methanol Formation in Low-Temperature CO2 Hydrogenation (2023)
  • Author(s): Phongprueksathat Nat、Ting Kah Wei、Mine Shinya、Jing Yuan、Toyoshima Ryo、Kondoh Hiroshi、Shimizu Ken-ichi、Toyao Takashi、Urakawa Atsushi
  • Journal Title: ACS Catalysis Volume: 13 Issue: 16 Pages: 10734-10750
  • DOI: 10.1021/acscatal.3c01599
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] The reducibility and oxidation states of oxide-supported rhenium: experimental and theoretical investigations (2022)
  • Author(s): Ting Kah Wei、Mine Shinya、Ait El Fakir Abdellah、Du Pengfei、Li Lingcong、Siddiki S. M. A. Hakim、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: Physical Chemistry Chemical Physics Volume: 24 Issue: 46 Pages: 28621-28631
  • DOI: 10.1039/d2cp04784e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Promoting effect of basic metal additives on DeNOx reactions over Pt-based three-way catalysts (2022)
  • Author(s): Jing Yuan、Wang Gang、Mine Shinya、Kawai Jumpei、Toyoshima Ryo、Kondoh Hiroshi、Zhang Xiaorui、Nagaoka Shuhei、Shimizu Ken-ichi、Toyao Takashi
  • Journal Title: Journal of Catalysis Volume: 416 Pages: 209-221
  • DOI: 10.1016/j.jcat.2022.10.018
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Mechanism of NH3-Selective Catalytic Reduction (SCR) of NO/NO2 (Fast SCR) over Cu-CHA Zeolites Studied by In Situ/Operando Infrared Spectroscopy and Density Functional Theory (2021)
  • Author(s): Liu Chong、Malta Grazia、Kubota Hiroe、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: The Journal of Physical Chemistry C Volume: 125 Issue: 40 Pages: 21975-21987
  • DOI: 10.1021/acs.jpcc.1c06651
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Analogous Mechanistic Features of NH3-SCR over Vanadium Oxide and Copper Zeolite Catalysts (2021)
  • Author(s): Kubota Hiroe、Toyao Takashi、Maeno Zen、Inomata Yusuke、Murayama Toru、Nakazawa Naoto、Inagaki Satoshi、Kubota Yoshihiro、Shimizu Ken-ichi
  • Journal Title: ACS Catalysis Volume: 11 Issue: 17 Pages: 11180-11192
  • DOI: 10.1021/acscatal.1c02860
  • Peer Reviewed
• [Journal Article] Roles of the basic metals La, Ba, and Sr as additives in Al2O3-supported Pd-based three-way catalysts (2021)
  • Author(s): Jing Yuan、Wang Gang、Ting Kah Wei、Maeno Zen、Oshima Kazumasa、Satokawa Shigeo、Nagaoka Shuhei、Shimizu Ken-ichi、Toyao Takashi
  • Journal Title: Journal of Catalysis Volume: 400 Pages: 387-396
  • DOI: 10.1016/j.jcat.2021.06.016
  • Peer Reviewed
• [Journal Article] Reverse water-gas shift reaction over Pt/MoOx/TiO2: reverse Mars-van Krevelen mechanism via redox of supported MoOx (2021)
  • Author(s): Mine Shinya、Yamaguchi Taichi、Ting Kah Wei、Maeno Zen、Siddiki S. M. A. Hakim、Oshima Kazumasa、Satokawa Shigeo、Shimizu Ken-ichi、Toyao Takashi
  • Journal Title: Catalysis Science & Technology Volume: 11 Issue: 12 Pages: 4172-4180
  • DOI: 10.1039/d1cy00289a
  • Peer Reviewed
• [Presentation] Machine-learning-assisted discovery of multi-elemental RWGS catalyst and its mechanistic study using in situ/operando spectroscopies (2023)
  • Author(s): Takashi Toyao
  • Organizer: Operando VII - the 7th International Congress on Operando Spectroscopy
  • Int'l Joint Research / Invited
• [Presentation] データ駆動型固体触媒開発と放射光を用いた触媒作用機構研究 (2023)
  • Author(s): 鳥屋尾隆
  • Organizer: 第1回 先端放射光活用研究会「放射光を用いた触媒キャラクタリゼーションの現在と未来」
  • Int'l Joint Research / Invited
• [Presentation] 固体触媒を用いた二酸化炭素水素化による低温メタノール合成 (2022)
  • Author(s): 鳥屋尾隆
  • Organizer: 2022 年度触媒学会「水素の製造と利用に関するシンポジウム」
  • Invited
• [Presentation] 機械学習を用いたCO2水素化触媒の開発とin situ/operando実験による作用機構調査 (2022)
  • Author(s): 鳥屋尾隆
  • Organizer: NanospecFY2022mini
  • Invited
• [Presentation] In situ/operando分光を用いた固体触媒研究 (2021)
  • Author(s): 鳥屋尾隆
  • Organizer: 「低次元系光機能材料研究会」第10回サマーセミナー2021
  • Invited
• [Presentation] Roles of Ba on Al2O3-Supported Pd-based Catalyst under Practical Three-Way Catalysis Condition (2021)
  • Author(s): Yuan Jing・Gang Wang・Shinya Mine・Takashi Toyao・Zen Maeno・Shuhei Nagaoka・Ken-ichi Shimizu
  • Organizer: 第128回 触媒討論会