電子移動反応場の設計と制御

1993 Fiscal Year Annual Research Report

• Project/Area Number: 05235103
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 野中 勉 東京工業大学, 大学院・総合理工学研究科, 教授 (00016528)
• Co-Investigator(Kenkyū-buntansha): 渡辺 正 東京大学, 生産技術研究所, 教授 (70092385) ; 茂木 巌 東北大学, 金属材料研究所, 助手 (50210084) ; 松岡 英明 東京農工大学, 工学部, 教授 (10143653) ; 藤嶋 昭 東京大学, 工学部, 教授 (30078307) ; 池田 篤治 京都大学, 農学部, 教授 (40026422)
• Keywords: 電子移動 / 電極界面 / 電極修飾 / 電極反応

Research Abstract

本研究課題である「電子移動反応場の設計と制御」は、電極表面のみならず、電極界面全体に及ぶ新しい電極修飾の概念、原理および手法の確立によって初めて達成されうるとの基本理念が、以下に述べる研究成果に基づいて検証された。すなわち、電極修飾の新しい概念は下記の4つに大別され、その各々が独立して、また相互に連携して、次世代の有機電気化学の展開を主導するものであり、その骨子とするところは有機電極反応の帰納的、能動的かつ合目的な超精密制御にあると結論された。以下の記述は計画班員による成果を中心にするが、公募班員による貢献も大きい。
(1)電極界面の物資修飾のよる反応場の設計と制御
レドックス対、分子識別物資、不斉誘導物資、親/疎水性物資、光感応物資、触媒、酵素、生体系物資などの広範な機能性物資で修飾した電極が設計・作製され、それらの高度な機能を活用した高効率あるいは新規な分子変換が実現された。
(2)電極界面の形態/状態修飾による反応場の設計と制御
電極表面の超高表面積化、巨視的不均一化、浸透性化など、並びに電解液界面の気相化、固相化、超流動化などによる新しいタイプの有機電気化学分子変換が創成され、従来の古典的な電解質溶液論や電気二重層概念を超越した理論の萌芽をみた。
(3)電解液界面のエネルギー照射修飾による反応場の設計と制御
電導体電極系の電解液界面にプラズマ、光、磁場、超音波などの物理的エネルギーを照射することにより、電気化学的エネルギーだけでは不可能な新しい有機電極反応が実現された。
(4)超微小電極界面反応場の設計と制御
公募研究のより着手され、炭素繊維電極について成果が出つつある。

Research Products

• [Publications] M.Umezawa: "Electroreductive Polymerization of Dichlorocarbosilanes" Electrochimica Acta. 38. 529-533 (1993)
• [Publications] Po-Chung Cheng: "Electroreduction of Methyl Cinnamate Using a Rotating Cylinder Electrode" Journal of Electrochemical Society of Japan. 61. 218-223 (1993)
• [Publications] Shu-Yong Guo: "Maximum in Oxidizing Power of Anodically-Generated Br-Cl Composite-Regagents" Journal of Electrochemical Society of Japan. 61. 245-246 (1993)
• [Publications] Po-Chang Chen: "Electron-Transfer Process in Emulsion Electrolysis" Journal of Electrochemical Society of Japan. 61. 886-887 (1993)
• [Publications] Yoshihito Kunugi: "Electroorganic Reactions on Organic Electrodes.Part 18" Journal of Electroanalytical Chemistry. 353. 209-215 (1993)
• [Publications] Yoshihito Kunugi: "Preparation of Hydrophobic Zinc and Lead Electrodes and Their Application to Electroreduction of Organic Compounds" Journal of Electroanalytical Chemistry. 356. 163-169 (1993)
• [Publications] Yoshihito Kunugi: "Electrolysis of Emulsions of Organic Compounds" Journal of Electrochemical Society. 140. 2833-2836 (1993)
• [Publications] 野中 勉: "電極電子化学" 電気学会誌. 113. 727-731 (1993)
• [Publications] 野中 勉: "有機電解用電極材料の新展開" 表面. 31. 737-745 (1993)
• [Publications] 野中 勉: "疎水性電極による有機電解" 化学工業. 45. 127-130 (1994)
• [Publications] Y.Iijima: "Influence of Magnetic Fields on Growth Pattern and Microstructure of Electrochemically Polymerized Thiophene(I)" Proc.of the Symp.on Electrochemically Deposited Thin Films. 93-26. 237-246 (1993)
• [Publications] S.Yamanaka: "Magnetic Field Effect on Electron Transfer Process in Electrochemical Reaction" Sci.Rep.RITU. 38. 399-405 (1993)
• [Publications] I.Mogi: "Effect of High Magnetic Fields on Morphology in Electroless Deposition of Silver" Proc.of the 2nd Int.Symp.on Electrochemical Processing of Tailored Materials. 93-12. 136-146 (1993)
• [Publications] S.Okubo: "A Morphological Study of Electroless Deposition in High Magnetic Fields" Sci.Rep.RITU. 38. 383-389 (1993)
• [Publications] I.Mogi: "Effect of High Magnetic Fields on Fractal Growth of Lead Metal-Leaves" J.Cryst.Growth. 128. 258-261 (1993)
• [Publications] Y.Sasaki: "Mixed Chromium (III)-Ruthenium (III) Trinuclear Complex,[CrRu_2(M_3-O)(M-CH_3COO)6(pyridine)_3]^+" Chemistry Letters. 69-72 (1993)
• [Publications] Mikako Saito: "Intracellular Potential Change of Tradescantia virginiana L.Leaf in Response to CO_2 Stress" Bioelectrochem.Bioenerg.32(2). 133-143 (1993)
• [Publications] Mikako Saito: "Estimation of Intracellular and Extracellular Concentrations of H^+,K^+,and Cl^- in a Leaf of Tradescantia virginiana L." Denki Kagaku. 61(7). 836-837 (1993)
• [Publications] Hideaki Matsuoka: "Effect of Flavor Compounds Emitted by White Birch on the Seed Germination of the Same Plant" J.Plant Nutrition. 16(3). 471-478 (1993)
• [Publications] 松岡英明: "植物センサー機能-新しい視点で植物の環境認識機能を探る" 日本の科学と技術. 34(268). 64-69 (1993)
• [Publications] 松岡英明: "植物で匂いを感じる" 数理化学. 31(3). 52-58 (1993)
• [Publications] 斉藤美佳子: "センサー材料としての生葉におけるシグナル伝達解析" 化学工業. 44(10). 822-826 (1993)
• [Publications] T.Tatsuma 他: "Polypyrrole Bienzyme Electrodes with Glucose Oxidase and Peroxidase" Sensors and Actuators. B13-14. 752-753 (1993)
• [Publications] T.Tatsuma 他: "Electrochemical Characterization of Polypyrrole Bienzyme Electrodes with Glucose Oxidase and Peroxidase" J.Electro anal.Chem.356. 245-253 (1993)
• [Publications] T.Tatsuma 他: "Theoretical Evaluation of Mediation Efficiency in Enzyme-Incorporated Electrodes" Anal.Chem.65. 3129-3133 (1993)
• [Publications] T.Tatsuma 他: "Substrate-Purging Enzyme Electrodes.Peroxidase/Catalase Electrodes for H_2O_2 with an Improved Upper Sensing Limit" Anal.Chem.66. 290-294 (1994)
• [Publications] 斉藤美佳子: "微小電極による細胞間情報伝達の解析" 化学工業. 44(12). 978-982 (1993)
• [Publications] Seiichi Miyazaki: "Intense Visible Luminescence from Thermally-Oxidized Porous Silicon" Materials Research Society Symposium Proceedings. 283. 269-274 (1993)
• [Publications] Seiichi Miyazaki: "Metastability of Luminescent Porous Silicon" Materials Research Society Symposium Proceedings. 283. 299-304 (1993)
• [Publications] Kazutoshi Shiba: "Luminescence from Thermally Oxidized Porous Silicon" Japanese Journal of Applied Physics. 32. 2722-2724 (1993)
• [Publications] T.Amemiya: "Faradic Charge Transfer with Double-Layer Charging and/or Adsorption-Related Charging at Polymer-Modified Electrodes As Observed by Colar Impedance Spectroscopy" J.Phys.Chem.97. 9736-9740 (1993)
• [Publications] K.Morigaki: "In-Site Electrochemical Actinometry Using an Monolayer Film" Ber.Bensengs.Phys.Chem.97. 860-864 (1993)
• [Publications] L.A.Nagahara: "Effects of HF Solution in the Electroless Deposition Process on Silicon Surfacs" J.Vac.Sci.Technol,A. 11. 763-767 (1993)
• [Publications] R.Baba: "Characterization of the Molecular Orientation in LB Films of Rhodamine B Derivatives by the Optical Second Harmonic Generation Coherent Interferometry" 電気化学. 61. 1030-1031 (1993)
• [Publications] L.A.Nagahara: "Scanning Probe and Transmission Electron Microscopy Observations of Cobalt Naphthalocyanine Molecules Deposited onto a NaCl Substrate" J.Vac.Sci.Technol.A. 11. 781-785 (1993)
• [Publications] K.Morigaki: "Electrochemical Counting of Photon Number Using the Assembled Monolayer Film of Azo Compound" Sensors and Actuators B. 13-14. 226-229 (1993)
• [Publications] O.Sato: "Self-Ordered Film of Hemicyanine Derivative Characterized by Phase-Sensitive Optical Second-Harmonic Generation" Jpn.J.Appl.Phys.32. 1201-1203 (1993)
• [Publications] K.Ohkawa: "Electrochemical Reduction of Carbon Dioxide on Hydrogen-Storing Materilas.Part II.Copper-Modified Palladium Electrode" J.Electroanal.Chem.348. 459-464 (1993)
• [Publications] T.Amemiya: "Dynamics of Faradic Procssed in Polypyrrole/Polystyrenesulfonate Composite Films in the Presence and Absence of Redox Species in Aqueou Solutions" J.Phys.Chem.97. 4192-4195 (1993)
• [Publications] Z.F.Liu: "Direct Observation of the Secondary Structure of Unfolded Pseudomonas-Cytochrome C_<551> by Scanning Tunneling Microscopy" Surface Sci.Lett.284. L411-L415 (1993)
• [Publications] T.Amemiya: "Frequency-Resolved Faradaic Processes in Polypyrrole Films Observed by Electromodulation Techniques:Electrochemical Impedance and Color Impedance Spectroscopies" J.Phys.Chem.97. 4187-4191 (1993)
• [Publications] K.Ohkawa: "Electrochemical Reduction of Carbon Dioxide on Hydrogen-Storing Materials Part I.The Effect of Hydrogen Absorption on the Electrochemical Behavior on Palladium Electrodes" J.Electroanal.Chem.345. 445-456 (1993)
• [Publications] T.Nonaka: "New Functionality Materials,Vol.C(ed by M.Doyama)" Elsevier Sci.Bub.B.V., 6 (1993)