金属ポルフィリン自己組織化分子層の構造制御積層化による新規機能性界面構造の構築

• Project Area: Molecular Architectonics: Orchestration of Single Molecules for Novel Function
• Project/Area Number: 26110510
• 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): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2014: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 自己組織化 / 金属ポルフィリン / 表面・界面物性 / 構造・機能材料 / 光物性

Outline of Annual Research Achievements

今年度は前年度に構築条件を確立したAu(111)基板上の鉄およびコバルトポルフィリン（FeTPP、CoTPP）分子層の酸素還元触媒能を評価するとともに、新たに亜鉛ポルフィリン（ZnTPP）のSi(111)基板上への構築条件を確立し、その可視光誘起電子移動について評価した。
金属ポルフィリンとの結合性官能基としてのチオール基を有する、1,4-Benzene-dithiol（1,4-BDT）の自己組織化単分子層(SAM）をAu(111)単結晶基板上に構築し、そのSAM修飾Au(111)基板をFeTPPおよびCoTPP溶液に浸漬して、FeTPP分子層修飾Au(111)基板およびCoTPP分子層修飾Au(111)基板を作製した。両分子層修飾Au(111)電極の酸素飽和0.05 M硫酸電解質溶液中で測定したリニアスイープボルタモグラムにより、下地の1,4-BDT SAM修飾Au(111)電極ではほとんど観測されなかった酸素還元電流が、両修飾電極では大きく観測された。また、回転リングディスク電極を用いて、四電子還元はバルクと同様CoTPPの方がFeTPPより大きいことを明らかとした。
金属ポルフィリンとの結合性官能基としてのカルボキシ基を有するMethyl acrylate（MA）およびEthyl undecylenate（EU）のSAMをSi(111)単結晶基板上に構築し、そのSAM修飾Si(111)基板をZnTPP溶液に浸漬して、ZnTPP分子層修飾Si(111)基板を作製した。作製した修飾Si(111)電極の可視光誘起電子移動による光電流測定によって、その効率を評価するとともに、偏光変調反射赤外分光やＸ線光電子分光によって、高効率な修飾電極構築条件を確立した。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [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 / Open Access / Acknowledgement Compliant
• [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
• [Journal Article] Thin Film Structures of Metal-Organic Framework [Cu₃(BTC)₂(H₂O)₃]<i>_n</i> on TiO₂(110) (2014)
  • Author(s): Hashimoto, M.; Okajima, S.; Kondo, T.; Hara, K.; Chun, W.-J.
  • Journal Title: Electrochemistry Volume: 82 Issue: 5 Pages: 335-337
  • DOI: 10.5796/electrochemistry.82.335
  • NAID: 130004562463
  • ISSN: 1344-3542, 2186-2451
  • Peer Reviewed / Open Access
• [Journal Article] Step-by-step Investigation of Atomically Flattening Processes of Au(111) Single Crystal Surfaces (2014)
  • Author(s): N. Umezawa, S. Sano, N. Aoki, G. Friedbacher, and T. Kondo
  • Journal Title: Electrochemistry Volume: 82 Issue: 5 Pages: 346-350
  • DOI: 10.5796/electrochemistry.82.346
  • NAID: 130004562455
  • ISSN: 1344-3542, 2186-2451
  • Peer Reviewed / Open Access
• [Journal Article] Self-Assembly Process of Flatly Adsorbed Porphyrin Self-Assembled Monolayer on a Au(111) Surface Studied by ex situ Scanning Tunneling Microscopy and Electrochemical Reductive Desorption Measurements (2014)
  • Author(s): N. Aoki, K. Sato, K. Hasegawa, S. Sano, M. Kageyama, N. Umezawa, and T. Kondo
  • Journal Title: Electrochemistry Volume: 82 Issue: 5 Pages: 385-390
  • DOI: 10.5796/electrochemistry.82.385
  • NAID: 130004562452
  • ISSN: 1344-3542, 2186-2451
  • Peer Reviewed / Open Access
• [Journal Article] Electrochemical Construction of Ni and Co Core - Pt Shell Nanoparticles as Catalysts for Oxygen Reduction Reaction (2014)
  • Author(s): H. Nagai, H. Aso, M. Kawabuchi, and T. Kondo
  • Journal Title: ECS Transactions Volume: 58 Issue: 25 Pages: 27-31
  • DOI: 10.1149/05825.0027ecst
  • Open Access
• [Presentation] Photoelectrochemical Characteristics of Two-dimensional Porphyrin Molecular Layers on Si(111) (2016)
  • Author(s): A. Shokai, Y. Ishikawa, M. Hase, T. Kondo
  • Organizer: 第96日本化学会春季年会
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-24
• [Presentation] Structure Controlled Construction of Metal-Porphyrin Molecular Layers by Self-Assembly Technique (2015)
  • Author(s): Y. Ishikawa, A. Shokai, M. Hase, N. Aoki, T. Kondo
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [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: Phonix
  • 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] Construction of Binding Group Terminated Self-Assembled Monolayers (SAMs) for Multilayer Formation (2015)
  • Author(s): T. Kondo, Y. Ishikawa, A. Shokai, M. Hase, H. Terasaki
  • Organizer: International Workshop on Molecular Architectonics
  • Place of Presentation: Shiretoko
  • Year and Date: 2015-08-03
  • Int'l Joint Research
• [Presentation] 平面吸着型金属ポルフィリン分子層の構築とその機能性評価 (2014)
  • Author(s): 近藤敏啓, 有阪朋子, 石川友利香, 青木菜々
  • Organizer: 第５回分子アーキテクトニクス研究会
  • Place of Presentation: 大阪大学
  • Year and Date: 2014-11-25 – 2014-11-26
• [Presentation] Construction of Binding Group Terminated Self-Assembled Monolayers for Multilayer Formation (2014)
  • Author(s): T. Arisaka, Y. Ishikawa, N. Aoki, and T. Kondo
  • Organizer: 226th ECS Meeting
  • Place of Presentation: Cancun, Mexico
  • Year and Date: 2014-10-04 – 2014-10-09
• [Presentation] Layer-by-layer Construction of Flatly Adsorbed Porphyrin Monolayers on a Au(111) Surface (2014)
  • Author(s): N. Aoki, T. Arisaka, B. Zhang, and T. Kondo
  • Organizer: 248th ACS National Meeting
  • Place of Presentation: San Francisco, U.S.A.
  • Year and Date: 2014-08-10 – 2014-08-14
• [Presentation] Construction and Structural Analyses of Carboxylate Terminated Self-Assembled Monolayers on Si(111) (2014)
  • Author(s): Y. Ishikawa, T. Arisaka, N. Aoki, and T. Kondo
  • Organizer: 248th ACS National Meeting
  • Place of Presentation: San Francisco, U.S.A.
  • Year and Date: 2014-08-10 – 2014-08-14
• [Presentation] Structural Studies on First-Ordered Self-Assembly Process of Flatly Adsorbed Porphyrin Derivatives on Au(111) (2014)
  • Author(s): N. Aoki, K. Sato, K. Hasegawa, S. Sano, M. Kageyama, N. Umezawa, and T. Kondo
  • Organizer: 248th ACS National Meeting
  • Place of Presentation: San Francisco, U.S.A.
  • Year and Date: 2014-08-10 – 2014-08-14