Development of highly efficient plasma-catalyzed reaction for ammonia synthesis at atmospheric pressure

• Project/Area Number: 17H03460
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Catalyst/Resource chemical process
• Research Institution: Waseda University
• Principal Investigator: Iwamoto Masakazu 早稲田大学, 理工学術院, その他(招聘研究員) (10108342)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000); Fiscal Year 2019: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2018: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2017: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
• Keywords: アンモニア / プラズマ法 / 固体触媒反応 / 電極 / プラズマ / 生成可能エネルギー / 再生可能エネルギー / アンモニア合成 / 金属細線 / 触媒 / 気相流通系 / 触媒・化学プロセス

Outline of Final Research Achievements

The activation of nitrogen molecules in atmospheric-pressure non-thermal plasma and conversion of them to ammonia under unheated conditions has widely reported. The present study revealed that high catalytic activity could be achieved when a fine metal wire was used as the internal electrode. The instability of nitrogen atoms adsorbed on the metal surface well agreed with the order of catalytic activity. It was also clarified that the catalytic activity is further improved by filling the plasma space generated by using the rod-shaped electrode with Ni-supported Al2O3. The NH3 yield reached 6% or more with one pass at normal temperature and pressure.

Academic Significance and Societal Importance of the Research Achievements

アンモニアNH3は水素社会のエネルギーキャリヤーとして注目されている。現行法であるハーバー・ボッシュHB法は多くのエネルギーを消費しており（CO2を排出しており）、改良／代替法の登場が待たれている。このため固体触媒、錯体触媒、電気化学、プラズマの分野でより効率的な合成法の開発が競争的に展開されている。我々はプラズマ法を研究した。これまでのプラズマ法ではHB法に活性な触媒成分がそのまま採用されることが多かったが、我々は研究の途上で内部金属電極が良い触媒となることを見いだした。次いで、Ni担持アルミナ等がこの反応の良い触媒となることを究明した。本研究の収率6%はこれまでの最高の成績である。

Research Products

• [Journal Article] Higher Activity of Ni/Al2O3 over Fe/Al2O3 and Ru/Al2O3 for Catalytic Ammonia Synthesis in Nonthermal Atmospheric‐Pressure Plasma of N2 and H2 (2020)
  • Author(s): M. Iwamoto,* M. Horikoshi, R. Hashimoto, K. Shimano, T. Sawaguchi, H. Teduka, M. Matsukata
  • Journal Title: Catalysts Volume: 10 Issue: 5 Pages: 590-590
  • DOI: 10.3390/catal10050590
  • Peer Reviewed / Open Access
• [Journal Article] 次世代アンモニア合成法の開発競争 (2019)
  • Author(s): 岩本正和
  • Journal Title: ファインケミカル Volume: 48 Pages: 5-5
• [Journal Article] 内部電極金属を触媒とする大気圧プラズマ法アンモニア合成 (2019)
  • Author(s): 岩本正和、松方雅彦
  • Journal Title: ファインケミカル Volume: 48 Pages: 46-52
• [Journal Article] バイオエタノールを原料とする新しいプロピレン接触合成法の開発 (2019)
  • Author(s): 岩本正和，松方正彦
  • Journal Title: ファインケミカル Volume: 6
• [Journal Article] Conversion of plasma-generated N2* to ammonia on metal catalysts (2019)
  • Author(s): M. Iwamoto, M. Matsukata
  • Journal Title: Sustainable Ammonia Production Volume: 6
  • Peer Reviewed
• [Journal Article] Ammonia decomposition to clean hydrogen using non-thermal atmospheric-pressure plasma (2018)
  • Author(s): M. Akiyama, K. Aihara, T. Sawaguchi, M. Matsukata, M. Iwamoto
  • Journal Title: International Journal of Hydrogen Energy Volume: 43 Issue: 31 Pages: 14493-14497
  • DOI: 10.1016/j.ijhydene.2018.06.022
  • Peer Reviewed
• [Journal Article] Enhancement of catalytic activity of Pd-PVP colloid for direct H2O2 synthesis from H2 and O2 in water with addition of 0.5 atom% Pt or Ir (2018)
  • Author(s): T. Deguchi, H. Yamano, S. Takenouchi, M. Iwamoto
  • Journal Title: Catalysis Science & Technology Volume: 8 Issue: 4 Pages: 1002-1015
  • DOI: 10.1039/c7cy01890h
  • Peer Reviewed
• [Journal Article] Depolymerization of cellulose with superheated steam: remarkable obstruction effects of sodium and high reactivity of crystalline cellulose (2018)
  • Author(s): M. Iwamoto, A. Shimatai, M. Honda, M., Matsukata
  • Journal Title: ACS Sustainable Chem. Eng. Volume: 印刷中 Issue: 5 Pages: 6570-6576
  • DOI: 10.1021/acssuschemeng.8b00375
  • Peer Reviewed
• [Journal Article] Ammonia Decomposition to Clean Hydrogen using Non-Thermal Atmospheric-Pressure Plasma (2018)
  • Author(s): M. Akiyama, K. Aihara, T. S., M. Matsukata, M. Iwamoto
  • Journal Title: Inter. J. Hydrogen Energy Volume: 修正論文査読中
  • Peer Reviewed
• [Journal Article] Higher activity of Ni/Al2O3 over Fe/ or Ru/Al2O3 for catalytic ammonia synthesis in non-thermal atmospheric-pressure plasma of N2 and H2 (2018)
  • Author(s): M. Iwamoto, K. Aihara, R. Hashimoto, M. Horikoshi, T. Sawaguchi, M. Matsukata
  • Journal Title: Catal. Sci. Technol. Volume: 投稿中
  • Peer Reviewed
• [Journal Article] mmonia Synthesis on Wool-Like Au, Pt, Pd, Ag, or Cu Electrode Catalysts in Nonthermal Atmospheric-Pressure Plasma of N2 and H2 (2017)
  • Author(s): M. Iwamoto, M. Akiyama, K. Aihara, T. Deguchi
  • Journal Title: ACS Catal. Volume: 7 Issue: 10 Pages: 6924-6929
  • DOI: 10.1021/acscatal.7b01624
  • Peer Reviewed
• [Presentation] ハーバーボッシュ法の革新を目指して－新しいアンモニア合成法実現へ向けての私たちの試行錯誤 (2019)
  • Author(s): 岩本正和
  • Organizer: 物理化学トークシャワー in 愛媛
• [Presentation] Higher activity of Ni/Al2O3 over Fe/ and Ru/Al2O3 for catalytic NH3 synthesis in non-thermal atmospheric-pressure plasma of N2 and H2 (2019)
  • Author(s): M. Iwamoto, K. Aihara, R. Hashimoto, M. Horikoshi, T. Sawaguchi, M. Matsukata
  • Organizer: EuropaCat 2019
  • Int'l Joint Research
• [Presentation] Wool-like Au, Pt, Pd, Ag, or Cu electrodes as active catalysts for ammonia synthesis in nonthermal atmospheric-pressure plasma of N2 and H2 (2018)
  • Author(s): M. Iwamoto, M. Akiyama, K. Aihara, T. Deguchi
  • Organizer: TOCAT 8
  • Int'l Joint Research / Invited
• [Presentation] プラズマ法アンモニア合成におけるNi/Al2O3の高い触媒活性 (2018)
  • Author(s): 相原敬吾、堀越正孝、澤口登美子、松方正彦、岩本正和
  • Organizer: 第122回触媒討論会
• [Presentation] Wool-like Au, Pt, Pd, Ag, or Cu electrodes as active catalysts for ammonia synthesis in nonthermal atmospheric-pressure plasma of N2 and H2 (2018)
  • Author(s): M. Iwamoto, M. Akiyama, K. Aihara, T. Deguchi
  • Organizer: Tocat8
  • Int'l Joint Research / Invited
• [Presentation] Catalytic activity of metal electrodes for ammonia synthesis from N2 and H2 in atmospheric-pressure non-thermal plasma (2017)
  • Author(s): M. Akiyama, K. Aihara, M. Tanaka, T. Deguchi, M. Iwamoto
  • Organizer: 6th Korea-Japan Symposium on Catalysis
  • Int'l Joint Research
• [Presentation] Catalytic ammonia synthesis from N2 and H2 on metal electrodes in atmospheric-pressure non-thermal plasma (2017)
  • Author(s): M. Akiyama, K. Aihara, T. Deguchi, M. Tanaka, M. Iwamoto
  • Organizer: Europacat 2017
  • Int'l Joint Research
• [Presentation] 外部アンモニアの供給を必要としないアンモニア選択還元法の開拓 (2017)
  • Author(s): 岩本正和
  • Organizer: 化学工学会第49秋季大会
  • Invited
• [Presentation] アンモニアフリー脱硝はどこまできたか (2017)
  • Author(s): 岩本正和
  • Organizer: 文部科学省元素戦略プロジェクト研究拠点形成型 第11回公開シンポジウム
  • Invited
• [Book] 有機ハイドライド・アンモニアの合成と利用プロセス有機ハイドライド・アンモニアの合成と利用プロセス (2021)
  • Author(s): 岩本正和
  • Total Pages: 344
  • Publisher: シーエムシー
  • ISBN: 9784781316000