Development of non-noble metal-hydride catalysts for alkane dehydrogenations

• Project/Area Number: 20H02518
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 27030:Catalyst and resource chemical process-related
• Research Institution: Kogakuin University (2022); Hokkaido University (2020-2021)
• Principal Investigator: Maeno Zen 工学院大学, 先進工学部, 准教授 (30721154)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥17,680,000 (Direct Cost: ¥13,600,000、Indirect Cost: ¥4,080,000); Fiscal Year 2022: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2021: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2020: ¥10,400,000 (Direct Cost: ¥8,000,000、Indirect Cost: ¥2,400,000)
• Keywords: 金属水素化物 / 表面ヒドリド / 水素欠陥 / 低級アルカン / 非酸化的脱水素 / 表面金属ヒドリド / 卑金属元素 / 典型金属元素 / 脱水素反応 / ゼオライト / 水素化物 / 金属ヒドリド

Outline of Research at the Start

本研究では、(i)卑金属元素の水素化物の脱水素能の発現因子と反応メカニズム、(ii)脱水素反応に有効な卑金属元素の表面ヒドリドの創成、(iii) 高効率アルカン脱水素反応を促進する革新的触媒の開発、の計画で研究に取り組む。典型元素やユビキタス元素を用いた触媒材料・機能開発を行うことで、貴金属触媒が研究対象の中心である脱水素反応に新たな設計指針を提示できる可能性を有し、新しい触媒科学の開拓と日本の化学産業界に大きく貢献できる研究である。

Outline of Final Research Achievements

We developed zeolite-encapsulated 13 group metal hydride catalysts for selective ethane dehydrogenation. Their local structures and relationship with selectivity/durability, and the effect of different zeolite framework were elucidated. We also studied the propane dehydrogenation catalysis of group 3 and 4 metal hydrides. Hydrogen vacancies were involved in the propane dehydrogenation using bulk metal hydrides.

Academic Significance and Societal Importance of the Research Achievements

貴金属ナノ粒子触媒による高効率水素化・脱水素反応において、CaH2などの水素化物が触媒担体として有効である例がいくつか報告されてた。しかしながら、金属水素化物自体の脱水素能を網羅的に検討した研究は例がなく、機能発現因子・メカニズムの解明や触媒設計指針の提案まで行った例はなかった。本研究の達成により、触媒合成を含めた資源有効利用を実現する革新的脱水素プロセスの開発につながるだけではなく、表面金属ヒドリドや水素化物を基盤とする触媒科学の学理の構築に貢献しうる。

Research Products

• [Journal Article] Ga speciation and ethane dehydrogenation catalysis of Ga-CHA and MOR: Comparative investigation with Ga-MFI (2023)
  • Author(s): Huang Mengwen、Maeno Zen、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: Catalysis Today Volume: 411-412 Pages: 113824-113824
  • DOI: 10.1016/j.cattod.2022.06.039
  • Peer Reviewed
• [Journal Article] In- and Ga-oxo clusters/hydrides in zeolites: speciation and catalysis for light-alkane activations/transformations (2023)
  • Author(s): Mengwen Huang、Yasumura Shinsaku、Toyao Takashi、Shimizu Ken-ichi、Maeno Zen
  • Journal Title: Physical Chemistry Chemical Physics Volume: 25 Issue: 15 Pages: 10211-10230
  • DOI: 10.1039/d3cp00478c
  • Peer Reviewed
• [Journal Article] Dynamic Structural Evolution of [Rh(NO)2]+ Complex/Rh Metal Cluster in Zeolite during de-NOx via in situ Formed NH3 under Lean/Rich Periodic Conditions (2022)
  • Author(s): Yasumura Shunsaku、Kato Taisetsu、Qian Yucheng、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: The Journal of Physical Chemistry C Volume: 126 Issue: 45 Pages: 19147-19158
  • DOI: 10.1021/acs.jpcc.2c05705
  • Peer Reviewed
• [Journal Article] In Situ/Operando Spectroscopic Studies on the NH3SCR Mechanism over Fe-Zeolites (2022)
  • Author(s): Yasumura Shunsaku、Qian Yucheng、Kato Taisetsu、Mine Shinya、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: ACS Catalysis Volume: 12 Issue: 16 Pages: 9983-9993
  • DOI: 10.1021/acscatal.2c02904
  • Peer Reviewed
• [Journal Article] Experimental and Theoretical Investigation of Metal-Support Interactions in Metal-Oxide-Supported Rhenium Materials (2022)
  • Author(s): Mine Shinya、Ting Kah Wei、Li Lingcong、Hinuma Yoyo、Maeno Zen、Siddiki S. M. A. Hakim、Toyao Takashi、Shimizu Ken-ichi
  • Journal Title: The Journal of Physical Chemistry C Volume: 126 Issue: 9 Pages: 4472-4482
  • DOI: 10.1021/acs.jpcc.2c00955
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Continuous CO2 Capture and Selective Hydrogenation to CO over Na-Promoted Pt Nanoparticles on Al2O3 (2022)
  • Author(s): Li Lingcong、Miyazaki Shinta、Yasumura Shunsaku、Ting Kah Wei、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: ACS Catalysis Volume: 12 Issue: 4 Pages: 2639-2650
  • DOI: 10.1021/acscatal.1c05339
  • Peer Reviewed
• [Journal Article] Machine Learning Analysis of Literature Data on the Water Gas Shift Reaction Toward Extrapolative Prediction of Novel Catalysts (2022)
  • Author(s): Mine Shinya、Jing Yuan、Mukaiyama Takumi、Takao Motoshi、Maeno Zen、Shimizu Ken-ichi、Takigawa Ichigaku、Toyao Takashi
  • Journal Title: Chemistry Letters Volume: 51 Issue: 3 Pages: 269-273
  • DOI: 10.1246/cl.210645
  • Peer Reviewed
• [Journal Article] Catalytic Methylation of Benzene over Pt/MoOx/TiO2 and Zeolite Catalyst Using CO2 and H2 (2022)
  • Author(s): Ting Kah Wei、Imbe Takuto、Kamakura Haruka、Maeno Zen、Siddiki S. M. A. Hakim、Matsushita Koichi、Shimizu Ken-ichi、Toyao Takashi
  • Journal Title: Chemistry Letters Volume: 51 Issue: 2 Pages: 149-152
  • DOI: 10.1246/cl.210664
  • NAID: 130008161574
  • Peer Reviewed
• [Journal Article] High-loading Ga-exchanged MFI zeolites as selective and coke-resistant catalysts for nonoxidative ethane dehydrogenation (2022)
  • Author(s): Huang Mengwen、Yasumura Shunsaku、Li Lingcong、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: Catalysis Science & Technology Volume: 12 Issue: 3 Pages: 986-995
  • DOI: 10.1039/d1cy01799c
  • Peer Reviewed
• [Journal Article] Propane Dehydrogenation Catalysis of Titanium Hydrides: Positive Effect of Hydrogen Co-feeding (2022)
  • Author(s): Yasumura Shunsaku、Wen Yuxiang、Toyao Takashi、Kanda Yasuharu、Shimizu Ken-ichi、Maeno Zen
  • Journal Title: Chemistry Letters Volume: 51 Issue: 1 Pages: 88-90
  • DOI: 10.1246/cl.210577
  • NAID: 130008137496
  • Peer Reviewed
• [Journal Article] Redox-Driven Reversible Structural Evolution of Isolated Silver Atoms Anchored to Specific Sites on γ-Al2O3 (2022)
  • Author(s): H. Kubota, S. Mine, T. Toyao, Z. Maeno, K. Shimizu
  • Journal Title: ACS Catalysis Volume: 12 Issue: 1 Pages: 544-559
  • DOI: 10.1021/acscatal.1c04924
  • Peer Reviewed
• [Journal Article] Lean NOx Reduction by In-Situ-Formed NH3 under Periodic Lean/Rich Conditions over Rhodium-Loaded Al-Rich Beta Zeolites (2021)
  • Author(s): , Shunsaku Yasumura, Takashi Toyao, Zen Maeno, and Ken-ichi Shimizu
  • Journal Title: ACS Catalysis Volume: 11 Issue: 19 Pages: 12293-12300
  • DOI: 10.1021/acscatal.1c03396
  • Peer Reviewed
• [Journal Article] Local structure and NO adsorption/desorption property of Pd2+ cations at different paired Al sites in CHA zeolite (2021)
  • Author(s): Yasumura Shunsaku、Ueda Taihei、Ide Hajime、Otsubo Katsumasa、Liu Chong、Tsunoji Nao、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: Physical Chemistry Chemical Physics Volume: 23 Issue: 39 Pages: 22273-22282
  • DOI: 10.1039/d1cp02668b
  • Peer Reviewed
• [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] Surface activation by electron scavenger metal nanorod adsorption on TiH2, TiC, TiN, and Ti2O3 (2021)
  • Author(s): Hinuma Yoyo、Mine Shinya、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: Physical Chemistry Chemical Physics Volume: 23 Issue: 31 Pages: 16577-16593
  • DOI: 10.1039/d1cp02068d
  • 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
• [Journal Article] Reverse Water-Gas Shift Reaction via Redox of Re Nanoclusters Supported on TiO2 (2021)
  • Author(s): Kah Wei Ting, Zen Maeno, S. M. A. Hakim Siddiki, Ken-ichi Shimizu, Takashi Toyao
  • Journal Title: Chemistry Letters Volume: 50 Issue: 1 Pages: 158-161
  • DOI: 10.1246/cl.200692
  • NAID: 130007965965
  • Peer Reviewed / Open Access
• [Journal Article] Hydrolysis of amides to carboxylic acids catalyzed by Nb2O5 (2021)
  • Author(s): Siddiki S. M. A. Hakim、Rashed Md. Nurnobi、Touchy Abeda Sultana、Jamil Md. A. R.、Jing Yuan、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: Catalysis Science & Technology Volume: 11 Issue: 5 Pages: 1949-1960
  • DOI: 10.1039/d0cy02230f
  • Peer Reviewed
• [Journal Article] Transformation of Bulk Pd to Pd Cations in Small-Pore CHA Zeolites Facilitated by NO (2021)
  • Author(s): Yasumura Shunsaku、Ide Hajime、Ueda Taihei、Jing Yuan、Liu Chong、Kon Kenichi、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: JACS Au Volume: 1 Issue: 2 Pages: 201-211
  • DOI: 10.1021/jacsau.0c00112
  • NAID: 120007026914
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Lean NOx Capture and Reduction by NH3 via NO+ Intermediates over H-CHA at Room Temperature (2021)
  • Author(s): Yasumura Shunsaku、Liu Chong、Toyao Takashi、Maeno Zen、Shimizu Ken-ichi
  • Journal Title: The Journal of Physical Chemistry C Volume: 125 Issue: 3 Pages: 1913-1922
  • DOI: 10.1021/acs.jpcc.0c10913
  • NAID: 120007187741
  • Peer Reviewed
• [Journal Article] In-Exchanged CHA Zeolites for Selective Dehydrogenation of Ethane: Characterization and Effect of Zeolite Framework Type (2020)
  • Author(s): Maeno Zen、Wu Xiaopeng、Yasumura Shunsaku、Toyao Takashi、Kanda Yasuharu、Shimizu Ken-ichi
  • Journal Title: Catalysts Volume: 10 Issue: 7 Pages: 807-807
  • DOI: 10.3390/catal10070807
  • Peer Reviewed / Open Access
• [Journal Article] In situ/operando spectroscopic studies on NH3-SCR reactions catalyzed by a phosphorus-modified Cu-CHA zeolite (2020)
  • Author(s): Kubota Hiroe、Liu Chong、Amada Takehiro、Kon Kenichi、Toyao Takashi、Maeno Zen、Ueda Kakuya、Satsuma Atsushi、Tsunoji Nao、Sano Tsuneji、Shimizu Kenichi
  • Journal Title: Catalysis Today Volume: - Pages: 73-80
  • DOI: 10.1016/j.cattod.2020.07.084
  • Peer Reviewed
• [Presentation] 高担持量Ga導入MFIゼオライト触媒を用いたエタン脱水素反応 (2022)
  • Author(s): 前野禅、Huang Mengwen、鳥屋尾隆、清水研一
  • Organizer: 石油学会第64回年会/第70回研究発表会
• [Presentation] ゼオライト細孔内に生成した InおよびPd活性種の機能開拓 (2022)
  • Author(s): 前野禅
  • Organizer: 第130回触媒討論会
  • Invited
• [Presentation] ゼオライト細孔内での表面ヒドリド種の精密制御による白金族フリー脱水素触媒の開発 (2022)
  • Author(s): 前野禅
  • Organizer: ハイドロジェノミクス第９回若手育成スクール
  • Invited
• [Presentation] 固相イオン交換によりゼオライト内に生成する金属錯体種のin situ分光測定と触媒機能 (2022)
  • Author(s): 前野禅
  • Organizer: 第 11 回 SPring-8 グリーンサスティナブルケミストリー研究会
  • Invited
• [Presentation] 金属水素化物による低級アルカン変換反応 (2022)
  • Author(s): 前野禅、安村駿作、胡笑鳴、鳥屋尾隆、清水研一
  • Organizer: 石油学会長野大会(第52回石油・石油化学討論会)
• [Presentation] バルク金属・酸化物の分散化現象を利用した 固相イオン交換反応による 金属導入ゼオライト触媒の開発 (2022)
  • Author(s): 前野禅
  • Organizer: 2022 年度触媒学会・触媒工業協会交流サロン
  • Invited
• [Presentation] 高担持Pd導入CHAゼオライトの固相合成とNO吸着脱離特性 (2022)
  • Author(s): 安村駿作, 鳥屋尾隆 ,前野 禅 ,清水 研一
  • Organizer: 第129回 触媒討論会
• [Presentation] ゼオライト内にin situ生成する新規金属錯体種の局所構造解析と触媒機能開拓 (2022)
  • Author(s): 前野禅
  • Organizer: 日本化学会第102春季年会
  • Invited
• [Presentation] 規則性ナノ空間に着目した触媒研究 (2021)
  • Author(s): 前野禅
  • Organizer: 触媒学会若手会「第 32 回フレッシュマンゼミナール」
  • Invited
• [Presentation] 連続的CO2吸蔵・還元的有効利用に向けた二元機能触媒の開発 (2021)
  • Author(s): 宮﨑眞太・呉子陽・鳥屋尾 隆・前野 禅・清水 研一
  • Organizer: 第10回 JACI/GSCシンポジウム
• [Presentation] CO2吸蔵・水素化による選択的CO生成反応に有効な固定化Pt触媒の開発 (2021)
  • Author(s): 宮﨑眞太・鳥屋尾 隆・前野 禅・清水 研一
  • Organizer: 第128回 触媒討論会
• [Presentation] インジウム交換ゼオライト触媒による選択的エタン脱水素反応 (2021)
  • Author(s): 前野禅・安村駿作・鳥屋尾隆・清水研一
  • Organizer: 第128回 触媒討論会
• [Presentation] In situ分光・電子顕微鏡を用いた銀アルミナ触媒上のアンカーサイトの研究 (2021)
  • Author(s): 窪田博愛・峯真也・鳥屋尾隆・前野禅・清水 研一
  • Organizer: 第128回 触媒討論会
• [Presentation] Effect of Oxygen Storage Materials on the Performance of Pt-based Three-Way Catalysts (2021)
  • Author(s): Gang Wang・Yuan Jing・Takashi Toyao・Zen Maeno・Xiaorui Zhang・Shuhei Nagaoka・Ken-ichi Shimizu
  • Organizer: 第128回 触媒討論会
• [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
• [Presentation] Isolated [GaH2]+ in MFI zeolites as selective and coke-resistant active sites for ethane dehydrogenation (2021)
  • Author(s): Mengwen Huang・Lingcong Li・Takashi Toyao・Zen Maeno・Ken-ichi Shimizu
  • Organizer: 第128回 触媒討論会
• [Presentation] ZrO2担持Rh触媒を用いたO2共存下での触媒的N2O分解 (2021)
  • Author(s): 竹歳昂一郎・鳥屋尾隆・前野禅・大堀鉄平・石川直也・清水 研一
  • Organizer: 第129回 触媒討論会
• [Presentation] 外挿的探索を可能にする機械学習モデルを用いた新規触媒探索 (2021)
  • Author(s): 向山拓実 ・ 峯真也 ・ 鳥屋尾隆 ・ 前野禅 ・ 高草木達 ・ 瀧川一学 ・ 清水研一
  • Organizer: 第128回 触媒討論会
• [Presentation] Local structure of In-hydride species in zeolite and its reactivity for C2H6 dehydrogenation (2021)
  • Author(s): S. Yasumura,T. Toyao, Z. Maeno,K. Shimizu
  • Organizer: 第51回石油・石油化学討論会
• [Presentation] 選択的エタン脱水素反応に有効なインジウム導入ゼオライト触媒の開発 (2021)
  • Author(s): 前野禅・鳥屋尾隆・清水研一
  • Organizer: 第51回石油・石油化学討論会
• [Presentation] ゼオライト内13族金属ヒドリド種を基盤とする高機能エタン脱水素触媒の開発 (2021)
  • Author(s): 前野禅
  • Organizer: 2021年度JPIJS講演会
  • Invited
• [Presentation] Preparation of high-loading Pd-CHA via atomic dispersion of bulk Pd and their NO adsorption/desorption property (2021)
  • Author(s): Shunsaku Yasumura, Taihei Ueda, Hajime Ide, Takashi Toyao, Zen Maeno, Ken-ichi Shimizu
  • Organizer: 18th Japan-Korea Symposium on Catalysis (18JKSC)
  • Int'l Joint Research
• [Presentation] Isolated [GaH2]+ in MFI zeolites as coke-resistant active sites for selective ethane dehydrogenation (2021)
  • Author(s): Mengwen Huang, Zen Maeno, Takashi Toyao, Ken-ichi Shimizu
  • Organizer: 18th Japan-Korea Symposium on Catalysis (18JKSC)
  • Int'l Joint Research
• [Presentation] ゼオライト内でin situ生成する金属錯体種の触媒機能開拓 (2021)
  • Author(s): 前野禅
  • Organizer: フロンティア材料研究所学術講演会
  • Invited
• [Presentation] Experimental and Theoretical Studies on Isolated Indium Hydrides in CHA Zeolites and Their Catalysis for Ethane Dehydrogenation (2021)
  • Author(s): Zen Maeno, Shunsaku Yasumura, Xiaopeng Wu, Mengwsen Huang, Takashi Toyao, Ken-ichi Shimizu
  • Organizer: Pacifichem 2021
  • Int'l Joint Research / Invited
• [Presentation] ゼオライト内Gaヒドリドの構造制御による選択的エタン脱水素触媒の開発 (2021)
  • Author(s): 前野禅・Huang Mengwen・安村駿作・鳥屋尾隆・清水研一
  • Organizer: 第127回触媒討論会
• [Presentation] CHAゼオライト内Inヒドリドを触媒活性点とする選択的エタン脱水素反応 (2020)
  • Author(s): 安村駿作・Wu Xiaopeng・Chong Liu1・鳥屋尾隆・前野禅・清水研一
  • Organizer: 第126回触媒討論会
• [Presentation] 固相イオン交換反応によるPd導入CHAゼオライトの調製とNO吸着特性 (2020)
  • Author(s): 前野禅・安村駿作・井出 創・植田泰平・ 鳥屋尾隆・清水 研一
  • Organizer: 第126回触媒討論会
• [Remarks] 本課題の研究成果を含む総説がPCCP誌のHOT Articleに選定
  • URL: https://pubs.rsc.org/en/content/articlelanding/2023/cp/d3cp00478c
• [Remarks] 2021年度触媒学会奨励賞
  • URL: https://catsj.jp/news/11608
• [Remarks] 日本化学会第102春季年会「若い世代の特別講演」
  • URL: https://confit.atlas.jp/guide/event/csj102nd/sessions/classlist/APSL01
• [Remarks] 指導学生(安村駿作)が第126回触媒討論会で学生口頭発表賞を受賞
  • URL: https://catsj.jp/news/8138