異種金属上に形成した貴金属超薄層触媒の構築過程の追跡とその３Ｄ活性サイトの探索

• Project Area: 3D Active-Site Science
• Project/Area Number: 15H01045
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Ochanomizu University
• Principal Investigator: 近藤 敏啓 お茶の水女子大学, 基幹研究院, 教授 (70240629)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000); Fiscal Year 2016: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2015: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 単結晶電極 / 異種金属析出 / 表面X線散乱法 / 電極触媒 / ３Ｄ活性点 / 表面Ｘ線散乱法

Outline of Annual Research Achievements

Au(111)単結晶上に自己終端化析出法で形成させた白金超薄膜は、下地構造を反映したpseudomorphic構造をとっていることを明らかとした。
その他、今年度の成果として、1) カーボネート系溶媒中において、Si(111)上に形成させたLixSiy合金相は、三角錐状の形状をしたLi15Si4単結晶相、Li15Si4またはLi13Si4合金のアモルファス相、及びSi単結晶相とLi15/13Si4合金のアモルファス相との混合相から成る３層構造であったのに対し、Si(100)上に形成させたそれでは、四角錐状の形状をしたLi15Si4単結晶相、Li15Si4またはLi13Si4合金のアモルファス相、及びSi単結晶相中にLi金属が入り込んだ混合相から成る３層構造であることを証明、2) Si(111)単結晶上に構築したビオロゲン自己組織化単分子層に種々の貴金属イオンを吸着させて作成した貴金属触媒層の水素発生及び二酸化炭素還元能について、構造と触媒能との定量的関係を解明、3) Au(111)単結晶上に、金属イオンと有機配位子から成る３次元有機金属錯体の構造制御した状態で１層ずつ積層して行くことに成功、4) 卑金属で安価なニッケルをコアに、貴金属で触媒活性が高い白金をシェルにもつ、コアシェル型微粒子触媒を電気化学的に構築することに成功し、非常に高い酸素還元触媒活性を達成、があげられる。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Layer-by-Layer Construction of Three-dimensional MOF [Cu2(bdc)2dabco]n on Au Surface (2017)
  • Author(s): M. Hase, W.-J. Chun, and T. Kondo
  • Journal Title: ECS Transactions Volume: 75 Issue: 52 Pages: 49-53
  • DOI: 10.1149/07552.0049ecst
  • Peer Reviewed
• [Journal Article] Structural Study of Electrochemically Lithiated Si (2017)
  • Author(s): A. Omachi, N. Aoki, K. Uosaki, and T. Kondo
  • Journal Title: ECS Transactions Volume: 75 Issue: 52 Pages: 67-72
  • DOI: 10.1149/07552.0067ecst
  • Peer Reviewed
• [Journal Article] Electrocatalytic Activity for Oxygen Reduction Reaction of Electrochemically Prepared Ni Core - Pt Shell Nanoparticles (2017)
  • Author(s): M. Ueda and T. Kondo
  • Journal Title: ECS Transactions Volume: 75 Issue: 52 Pages: 43-47
  • DOI: 10.1149/07552.0043ecst
  • Peer Reviewed
• [Journal Article] 軟Ｘ線発光分光を用いたリチウム-シリコン合金の構造・組成分析 (2017)
  • Author(s): 青木菜々, 大間知麻未, 魚崎浩平, 近藤敏啓
  • Journal Title: ぶんせき Volume: 290 Pages: 30-33
  • Peer Reviewed
• [Journal Article] Structural Study of Electrochemically Lithiated Si(111) by Soft X-ray Emission Spectroscopy Combined with Scanning Electron Microscopy and through X-ray Diffraction (2016)
  • Author(s): N. Aoki, A. Omachi, K. Uosaki, and T. Kondo
  • Journal Title: ChemElectroChem Volume: 3 Issue: 6 Pages: 959-965
  • DOI: 10.1002/celc.201600030
  • Peer Reviewed / Open Access
• [Journal Article] Potential-Dependent Structures and Potential-Induced Structure Changes at Pt(111) Single-Crystal Electrode/Sulfuric and Perchloric Acid Interfaces in the Potential Region between Hydrogen Underpotential Deposition and Surface Oxide Formation by In Situ Surface X-ray Scattering (2016)
  • Author(s): T. Kondo, T. Masuda, N. Aoki, and K. Uosaki
  • Journal Title: J. Phys. Chem. C Volume: 120 Issue: 29 Pages: 16118-16131
  • DOI: 10.1021/acs.jpcc.5b12766
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Various Active Metal Species Incorporated within Molecular Layers on Si(111) Electrodes for Hydrogen Evolution and CO2 Reduction Reaction (2016)
  • Author(s): T. Masuda, Y. Sun, H. Fukumitsu, H. Uehara, S. Takakusagi, W.-J. Chun, T. Kondo, K. Asakura, and K. Uosaki
  • Journal Title: J. Phys. Chem. C Volume: 120 Issue: 29 Pages: 16200-16210
  • DOI: 10.1021/acs.jpcc.6b00895
  • Peer Reviewed / Open Access
• [Journal Article] Size Dependent Lattice Constant Change of Thiol Self-Assembled Monolayer Modified Au Nanoclusters Studied by Grazing Incidence X-ray Diffraction (2016)
  • Author(s): Toshihiro Kondo, Takuya Masuda, Motoko Harada, Osami Sakata, Yoshio Katsuya, Kohei Uosaki
  • Journal Title: Electrochemistry Communications Volume: 65 Pages: 35-38
  • DOI: 10.1016/j.elecom.2016.02.007
  • NAID: 120006415983
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] 放射光利用SXS法による電極触媒のその場構造追跡 -金単結晶電極／電解質溶液界面の電位依存性の動的追跡- (2016)
  • Author(s): 近藤敏啓, 魚崎浩平
  • Journal Title: 表面科学 Volume: 37 Pages: 72-77
  • NAID: 130005127228
  • Peer Reviewed
• [Journal Article] In situ real-time study on potential induced structure change at Au(111) and Au(100) single crystal electrode/sulfuric acid solution interfaces by surface x-ray scattering (2015)
  • Author(s): Toshihiro Kondo, Joerg Zegenhagen, Satoru Takakusagi, Kohei Uosaki
  • Journal Title: SURFACE SCIENCE Volume: 631 Pages: 95-104
  • DOI: 10.1016/j.susc.2014.06.013
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] ニッケルコア白金シェル微粒子の電気化学的作製とその酸素還元触媒能 (2016)
  • Author(s): 上田摩耶, 宇津木美咲, 吉岡里紗, 近藤敏啓
  • Organizer: 2016年電池討論会
  • Place of Presentation: 千葉
  • Year and Date: 2016-11-29
• [Presentation] ニッケルコア-白金シェル微粒子の構築とその酸素還元触媒活性 (2016)
  • Author(s): 近藤敏啓, 上田摩耶, 宇津木美咲, 吉岡里紗
  • Organizer: 第36回表面科学学術講演会
  • Place of Presentation: 名古屋
  • Year and Date: 2016-11-29
• [Presentation] Electrochemical Lithiation/Delithiation Process of Si (2016)
  • Author(s): T. Kondo, N. Aoki, A. Omachi, and K. Uosaki
  • Organizer: PRiME2016
  • Place of Presentation: Honolulu (USA)
  • Year and Date: 2016-10-02
  • Int'l Joint Research
• [Presentation] Electrocatalytic Activity for Oxygen Reduction Reaction of Electrochemically Prepared Ni Core - Pt Shell Nanoparticles (2016)
  • Author(s): M. Ueda and T. Kondo
  • Organizer: PRiME2016
  • Place of Presentation: Honolulu (USA)
  • Year and Date: 2016-10-02
  • Int'l Joint Research
• [Presentation] Layer-by-Layer Construction of Three-Dimensional MOF [Cu2(bdc)2dabco]n on Au Surface (2016)
  • Author(s): M. Hase, W.-J. Chun, and T. Kondo
  • Organizer: PRiE2016
  • Place of Presentation: Honolulu (USA)
  • Year and Date: 2016-10-02
  • Int'l Joint Research
• [Presentation] Structural Study of Electrochemically Lithiated Si (2016)
  • Author(s): A. Omachi, N. Aoki, K. Uosaki, and T. Kondo
  • Organizer: PRiME2016
  • Place of Presentation: Honolulu (USA)
  • Year and Date: 2016-10-02
  • Int'l Joint Research
• [Presentation] Photo-Electrochemical Characteristics of Two-Dimensional Porphyrin Molecular Layers on Semiconductor Surfaces (2016)
  • Author(s): Y. Kondo, A. Shokai, M. Hase, and T. Kondo
  • Organizer: PRiME2016
  • Place of Presentation: Honolulu (USA)
  • Year and Date: 2016-10-02
  • Int'l Joint Research
• [Presentation] 軟Ｘ線発光分光によるLiSi合金の構造評価 (2016)
  • Author(s): 近藤敏啓
  • Organizer: 日本顕微鏡学会第72回学術講演会,
  • Place of Presentation: 仙台
  • Year and Date: 2016-06-14
  • Invited
• [Presentation] Electrochemical Insertion Process of Li into n-Si(111) (2015)
  • Author(s): T. Kondo, N. Aoki, K. Uosaki
  • Organizer: 228th ECS Meeting
  • Place of Presentation: Phoenix
  • Year and Date: 2015-10-11
  • Int'l Joint Research
• [Presentation] ニッケルコア-白金シェル微粒子の電気化学的調製とその酸素還元触媒活性 (2015)
  • Author(s): 近藤敏啓, 上田摩耶, 弘田美紗子
  • Organizer: 2015年電気化学秋季大会
  • Place of Presentation: 深谷工大
  • Year and Date: 2015-09-11
• [Presentation] In situ Structural Studies on Pt(111) Single-Crystal Electrode/Electrolyte Interfaces (2015)
  • Author(s): T. Kondo, N. Aoki, T. Masuda, K. Uosaki
  • Organizer: NIMS Conference 2015
  • Place of Presentation: Tsukuba
  • Year and Date: 2015-07-14
  • Int'l Joint Research
• [Book] 金属界面の基礎と計測 (2016)
  • Author(s): 魚崎浩平, 近藤敏啓
  • Publisher: 共立出版
• [Book] X-ray and Neutron Techniques for Nanomaterials Characterization (2016)
  • Author(s): T. Kondo, T. Masuda, K. Uosaki
  • Publisher: Springer
• [Book] XAFS Techniques for Catalysts, Nanomaterials, and Surfaces (2016)
  • Author(s): T. Masuda, T. Kondo, K. Uosaki
  • Publisher: Springer