異種金属間相乗効果を機軸とする多孔質系機能触媒の開発

2011 Fiscal Year Annual Research Report

• Project Area: Nano Materials Science for Atomic Scale Modification
• Project/Area Number: 22015003
• Research Institution: Tohoku University
• Principal Investigator: 浅尾 直樹 東北大学, 原子分子材料科学高等研究機構, 教授 (60241519)
• Co-Investigator(Kenkyū-buntansha): 山本 嘉則 東北大学, 原子分子材料科学高等研究機構, 教授 (60029519)
• Keywords: ナノ多孔質金 / ナノ多孔質パラジウム / 不均一系触媒 / 鈴木カップリング / Heck反応 / 金属ガラス

Research Abstract

報告者は、前年度にナノ多孔質金やナノ多孔質パラジウムの作成法を検討し、それら金属材料が様々な分子変換反応において、優れた触媒として機能することを明らかにした。そこで今年度は、本特定領域研究の計測班との連携研究により、ナノポーラス金における触媒機能の発現メカニズムの解明を目的として、透過電子顕微鏡(TEM-EDS)を用いて触媒活性なナノ多孔質金の微細組織及び表面原子構造解析と元素分析を行った。さらには走査透過電子顕微鏡(STEM)を用いて原子構造計測(HAADF観察)を行った。EDS測定から微量の銀が含まれることを明らかにした。また、HAADF-STEMからナノ多孔質化による多数のステップ構造が存在することが観察された。本金属材料の多孔質化(スポンジ構造)は、金銀合金薄板を酸性条件下で処理して銀を選択的に溶出させることにより構築される。この脱合金化条件を調節するとスポンジ構造のリガメントやポアのサイズを制御することができ、それに伴い触媒活性が変化するが、本研究によりこの触媒活性の変化は、原子ステップ構造の変化による配位不飽和状態の金原子の増減に大きく起因することが明らかになった。また、残留する極微量の銀が触媒活性化に対して機能元素として働く可能性を示唆する結果も得られた。一方、ナノ多孔質パラジウムの触媒活性について検討を行い、この金属材料がHeck反応の優れた触媒として機能することを見出した。一般的な固体パラジウム触媒とその表面積あたりのリーチング量を調べたところ、ナノ多孔質パラジウムからの溶出が最も少ないことを明らかにした。この結果は、本触媒がリーチングの少ない耐久性の高い触媒であることを示している。

Research Products

• [Journal Article] Aerobic oxidation of alcohols in the liquid phase with nanoporous gold catalysts (2012)
  • Author(s): Asao, N.; Hatakeyama, N.; Menggenbateer, Minato, T.; Ito, E.; Hara, M.; Kim, Y.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Chem.Commun. Volume: 48 Pages: 4540-4542
  • DOI: 10.1039/c2cc17245c
  • Peer Reviewed
• [Journal Article] Donor-acceptor Dyes Incorporating Stable Dibenzosilole π-Conjugated Spacer for Dye-sensitized Solar Cells (2012)
  • Author(s): Akhtaruzzaman, Md.; Seya, Y.; Asao, N.; Islam, A.; Kwon, E.; El-Shafei, A.; Han, L.; Yamamoto, Y.
  • Journal Title: J.Mater.Chem. Volume: 22 Pages: 10771-10778
  • DOI: 10.1039/c2jm30978e
  • Peer Reviewed
• [Journal Article] Nanoporous Gold-Catalyzed [4+2] Benzannulation between ortho-Alkynylbenzaldehydes and Alkynes (2012)
  • Author(s): Asao, N.; Menggenbateer, Seya, Y.; Yamamoto, Y; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Synlett Volume: 23 Pages: 66-69
  • DOI: 10.1055/s-0031-1289527
  • Peer Reviewed
• [Journal Article] A novel metal-free panchromatic TiO_2 sensitizer based on a phenylen evinylene-conjugated unit and an indoline derivative for highly efficient dye-sensitized solar cells (2011)
  • Author(s): Akhtaruzzaman, Md.; Islam, A.; Yang, E; Asao, N.; Kwon, E.; Singh, S.P.; Han, L.; Yamamoto, Y.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 12400-12402
  • DOI: 10.1039/c1cc15580f
  • Peer Reviewed
• [Journal Article] Reusable and Sustainable Nanostructured Skeleton Catalyst : Heck Reaction with Nanoporous Metallic Pd (PdNPore) as a Support, Stabilizer and Ligand Free Catalyst (2011)
  • Author(s): Kaneko, T.; Tanaka, S.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Adv.Synth.Catal. Volume: 353 Pages: 2927-2932
  • DOI: 10.1002/adcs.201100358
  • Peer Reviewed
• [Journal Article] Formation and properties of Au-based nanograined metallic glasses (2011)
  • Author(s): Chen, N.; Frank, R.; Asao, N.; Louzguine-Luzgin, D.V.; Sharma, P.; Wang, J.Q.; Xie, G.Q.; Ishikawa, Y.; Hatakeyama, N.; Lin, Y.C.; Esashi, M.; Yamamoto, Y.; Inoue, A.
  • Journal Title: Acta Mater. Volume: 59 Pages: 6433-6440
  • DOI: 10.1016/j.actamat.2011.07.007
  • Peer Reviewed
• [Journal Article] Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters (2011)
  • Author(s): Aikawa, H.; Kaneko, T.: Asao, N.; Yamamoto, Y.
  • Journal Title: Beilstein J.Org.Chem. Volume: 7 Pages: 648-652
  • DOI: 10.3762/bjoc.7.76
  • Peer Reviewed
• [Journal Article] A nanostructured skeleton catalyst : Suzuki-coupling with a reusable and sustainable nanoporous metallic glass Pd-catalyst (2011)
  • Author(s): Tanaka, S.; Kaneko, T.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 5985-5987
  • DOI: 10.1039/c1cc10710k
  • Peer Reviewed
• [Presentation] Mechanism of organic chemical reactions on nano-porous gold (2012)
  • Author(s): Minato, T.; Ito, E.; Ishikawa, Y.; Hatakeyama, N.; Hara, M.; Kim, Y.; Asao, N.; Yamamoto, Y.
  • Organizer: Towards Reality in Nanoscale Materials V
  • Place of Presentation: Levi, Finland
  • Year and Date: 20120220-20120222
• [Presentation] Nanoporous materials as skeleton catalysts for molecular transformations (2012)
  • Author(s): Asao, N.
  • Organizer: UCSB ICMR/CNSI and Tohoku University Joint Workshop
  • Place of Presentation: Santa Barbara, USA(招待講演)
  • Year and Date: 20120110-20120112
• [Presentation] Atomic defect control on titanium dioxide surface by scanning tunneling microscopy (2011)
  • Author(s): Minato, T.; Pang, C.-L.; Kajita, S.; Asao, N.; Yamamoto, Y.; Nakayama, T.; Kawai, M.; Kim, Y.
  • Organizer: International Symposium on Surface Science (ISSS-6)
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 20111211-20111215
• [Presentation] Molecular transformation with nanoporous materials skeleton catalysts (2011)
  • Author(s): Asao, N.
  • Organizer: Frontier Materials and Processes (Frontier 2011)
  • Place of Presentation: Sendai, Japan(招待講演)
  • Year and Date: 20111204-20111207
• [Presentation] Nanoporous Metals as Effective Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: Tateshina Conference on Organic Chemistry 2011
  • Place of Presentation: Tateshina, Japan
  • Year and Date: 20111111-20111113
• [Presentation] Integrated Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): Asao, N.; Hatakeyama, N.; Yamamoto, Y.
  • Organizer: The Seventh International Symposium on Integrated Synthesis (ISIS-7)
  • Place of Presentation: Kobe, Japan
  • Year and Date: 20111009-20111010
• [Presentation] Nanoporous Metallic Materials as Effective Green Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: 14th Asian Chemical Congress 2011 (14 ACC)
  • Place of Presentation: Bangkok, Thailand(招待講演)
  • Year and Date: 20110905-20110908
• [Presentation] Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): Hatakeyama, N.; Menggenbateer; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-20110728
• [Presentation] Nanoporous gold as a catalyst for the oxidation of organosilanes (2011)
  • Author(s): Ishikawa, Y.; Hatakeyama, N.; Menggenbateer; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-20110728
• [Presentation] Nanostructured Skeleton Catalyst : Suzuki-coupling and Heck Reaction with Nanoporous Pd-catalyst as a Non-supported Catalyst (2011)
  • Author(s): Tanaka, S.; Kaneko, T.; Asao, N.: Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-20110728
• [Presentation] Nanoporous Gold Catalyzed Benzannulation Reaction (2011)
  • Author(s): Menggenbateer; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-20110728