イオン支援パルスプラズマ活用単層カーボンナノチューブの完全カイラリティ制御合成

• Project/Area Number: 15J01481
• Research Category: Grant-in-Aid for JSPS Fellows
• Allocation Type: Single-year Grants
• Section: 国内
• Research Field: Plasma science
• Research Institution: Tohoku University
• Principal Investigator: 許 斌 東北大学, 工学研究科, 特別研究員(DC1)
• Project Period (FY): 2015-04-24 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥3,400,000 (Direct Cost: ¥3,400,000); Fiscal Year 2017: ¥1,100,000 (Direct Cost: ¥1,100,000); Fiscal Year 2016: ¥1,100,000 (Direct Cost: ¥1,100,000); Fiscal Year 2015: ¥1,200,000 (Direct Cost: ¥1,200,000)
• Keywords: 単層カーボンナノチューブ / 触媒前処理 / カイラリティ制御 / メカニズム解明 / 第一原理計算 / パルスプラズマ

Outline of Annual Research Achievements

三年計画の最終年度における今年度は，カイラリティ制御単層カーボンナノチューブ(SWNTs)合成実現に向け，系統的実験と理論解析を合わせて，触媒前処理によるSWNTsのカイラリティ選択機構の解明に関する研究を行った．
１．触媒前処理による成長活性化エネルギー変化．前年度までの研究では，微量ガス添加触媒前処理方法により触媒表面酸化度合を変化させることで，(6,4)SWNTsと(6,5)SWNTsの存在比制御を実現した．今年度はさらなる詳細な機構を解明するために研究を行った．触媒の表面状態変化に伴い，SWNTsの成長活性化エネルギーEaの変化を実験的に測定したところ，前処理により，SWNTsのEaが大幅に増加し，(6,4)SWNTsと(6,5)SWNTsの活性化エネルギーの差ΔEaも前処理により増加することが判明した．この結果より，カイラリティ選択性の変化はSWNTsの活性化エネルギー制御によるものであることが明らかとなった．
２．理論的計算によるカイラリティ選択機構解明．活性化エネルギーの変化がカイラリティ選択性に与える効果の詳細を明らかにするために，第一原理計算によって検討した．キャップ形成段階において，前処理により，キャップ形成に必要なリフトオフエネルギーEBC-M が増加し，特に，キャップ中に炭素数の多い(6,5)SWNTsのEBC-Mがより大きく増大することが判明した．この計算結果より， (6,5)SWNTsが(6,4)SWNTsに比べより大きくキャップ形成確率が低下することが説明できる．次に，キャップ形成後SWNTsが軸方向に成長する段階において，最も高い合成効率を示すSWNTsのカイラル角xが高角度側へシフトする理論計算結果が得られた．この結果より，大きいカイラル角ｘをもつ (6,4)SWNTsの優先的合成が説明できることが明らかとなった．

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Preferential synthesis of (6,4) single-walled carbon nanotubes by controlling oxidation degree of Co catalyst (2017)
  • Author(s): B. Xu, T. Kaneko, Y. Shibuta, and T. Kato
  • Journal Title: Scientific Reports Volume: 7 Issue: 1
  • DOI: 10.1038/s41598-017-11712-0
  • Peer Reviewed / Open Access
• [Journal Article] How the alignment of adsorbed ortho H pairs determines the onset of selective carbon nanotube etching (2017)
  • Author(s): U. Khalilov, A. Bogaerts, B. Xu, T. Kato, T. Kaneko, and E. C. Neyts
  • Journal Title: Nanoscale Volume: 9 Issue: 4 Pages: 1653-1661
  • DOI: 10.1039/c6nr08005g
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Mass production of narrow chirality distributed single-walled carbon nanotubes by pulse plasma CVD (2016)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Journal Title: Proceedings of IEEE Nano Volume: 1 Pages: 620-621
  • DOI: 10.1109/nano.2016.7751458
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Individualized p-Doped Carbon Nanohorns (2016)
  • Author(s): A. Stergiou, Z. Liu, B. Xu, T. Kaneko, C. P. Ewels, K. Suenaga, M. F. Zhang, M. Yudasaka, and N. Tagmatarchis
  • Journal Title: Angewandte Chemie-International Edition Volume: 55 Issue: 35 Pages: 10468-10472
  • DOI: 10.1002/anie.201605644
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Effects of Time Parameter in Pulse Plasma CVD on Narrow-Chirality Distributed growth of Single-Walled Carbon Nanotubes (2015)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Journal Title: Proceedings of 9th International Conference on Reactive Plasmas Volume: QR2
  • Peer Reviewed
• [Presentation] Mechanism of preferential synthesis of (6,4) single-walled carbon nanotube (2018)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: The 54th Fullerenes-Nanotubes-Graphene General Symposium
• [Presentation] Catalyst structure control towards chirality controlled synthesis of single-walled carbon nanotube with plasma CVD (2017)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: iPlasmaNano 2017
  • Int'l Joint Research
• [Presentation] Elucidation of Direct Correlation between Catalyst Surface State and Chirality Species of Single-Walled Carbon Nanotube Grown by Diffusion Plasma CVD (2017)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: 5th International Conference on Advanced Materials
  • Int'l Joint Research
• [Presentation] High Purity Synthesis of (6,4) Single-Walled Carbon Nanotube by Surface State Control of Co Catalyst (2017)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: 第78回応用物理学会 秋季学術講演会
• [Presentation] Chirality control of single-walled carbon nanotubes with precise catalyst surface tuning using plasma CVD (2017)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: The 53th Fullerenes-Nanotubes-Graphene General Symposium
• [Presentation] High Purity Synthesis of (6,4) Single-Walled Carbon Nanotubes with Plasma CVD (2017)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: The 2017 International Conference on Functional Carbons
  • Int'l Joint Research
• [Presentation] 表面機能化触媒を用いたプラズマCVDによる単層カーボンナノチューブのカイラリティ制御合成 (2016)
  • Author(s): 許 斌, 金子 俊郎，加藤俊顕
  • Organizer: 第33回プラズマ・核融合学会年会
  • Place of Presentation: 東北大学（宮城県）
  • Year and Date: 2016-11-29
• [Presentation] Control of catalyst surface states towards synthesis of single chirality single-walled carbon nanotubes using plasma CVD (2016)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: The 51th Fullerenes-Nanotubes-Graphene General Symposium
  • Place of Presentation: 札幌市民活動サポートセンター（北海道）
  • Year and Date: 2016-09-07
• [Presentation] Mass production of narrow chirality distributed single-walled carbon nanotubes by pulse plasma CVD (2016)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Organizer: 16th International Conference on Nanotechnology（国際学会）
  • Place of Presentation: 仙台国際センター（宮城県）
  • Year and Date: 2016-08-22
  • Int'l Joint Research
• [Presentation] Correlation of catalyst surface states and chirality distribution of single-walled carbon nanotubes during plasma CVD (2016)
  • Author(s): Bin Xu, Toshiro Kaneko, Toshiaki Kato
  • Organizer: The 17th International Conference on the Science and Application of Nanotubes
  • Place of Presentation: ウイン大学（オーストリア）
  • Year and Date: 2016-08-07
  • Int'l Joint Research
• [Presentation] Optical Properties of High Purity Nitrogen Atom Endohedral Fullerene Synthesized by Controlled Plasma Ion Irradiation (2015)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Organizer: The 9th Asia-Pacific Internal Symposium on the Basics and Applications of Plasma Technology and the 28th Symposium on Plasma Science for Materials
  • Place of Presentation: Nagasaki University (Nagasaki, Japan)
  • Year and Date: 2015-12-12
  • Int'l Joint Research
• [Presentation] Effects of Time Parameter in Pulse Plasma CVD on Narrow-Chirality Distributed growth of Single-Walled Carbon Nanotubes (2015)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Organizer: 9th International Conference on Reactive Plasmas / 68th Gaseous Electronics Conference / 68th Symposium on Plasma Processing
  • Place of Presentation: Hawaii Convention Center (Honolulu, Hawaii, USA)
  • Year and Date: 2015-10-12
  • Int'l Joint Research
• [Presentation] Study of Narrow-Chirality Distributed Single-Walled Carbon Nanotubes Synthesis during Pulse Plasma CVD (2015)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Organizer: The 49th Fullerenes-Nanotubes-Graphene General Symposium
  • Place of Presentation: 北九州会議場（福岡県，北九州市）
  • Year and Date: 2015-09-07
• [Presentation] High purity synthesis of narrow-chirality distributed single-walled carbon nanotube and its growth mechanism by pulse plasma CVD (2015)
  • Author(s): Bin Xu, Toshiaki Kato, Toshiro Kaneko
  • Organizer: The 16th International Conference on the Science and Application of Nanotubes
  • Place of Presentation: Nagoya University (Nagoya, Japan)
  • Year and Date: 2015-06-29
  • Int'l Joint Research