電子構造制御表面における界面電子移動ダイナミクス

• Project/Area Number: 12042202
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas (A)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 魚崎 浩平 北海道大学, 大学院・理学研究科, 教授 (20133697)
• Co-Investigator(Kenkyū-buntansha): 近藤 敏啓 北海道大学, 大学院・理学研究科, 助手 (70240629) ; 八木 一三 北海道大学, 大学院・理学研究科, 講師 (40292776) ; 叶 深 北海道大学, 触媒化学研究センター, 助教授 (40250419)
• Project Period (FY): 2000 – 2001
• Project Status: Completed (Fiscal Year 2001)
• Budget Amount: ¥3,600,000 (Direct Cost: ¥3,600,000); Fiscal Year 2001: ¥1,700,000 (Direct Cost: ¥1,700,000); Fiscal Year 2000: ¥1,900,000 (Direct Cost: ¥1,900,000)
• Keywords: 電気化学 / 電析 / 走査プローブ顕微鏡 / 電極触媒 / 非線形分光法 / 二次高調波発生 / 表面X線散乱

Research Abstract

構造規制した異種金属原子層を表面に構築した電極表面における電極触媒活性を評価し、電子状態計算で得られる表面電子構造と反応特性の相関を明らかにした。
具体的には金単結晶を基板として、既に我々が確立した電気化学的エピタキシャル成長法により種々の被覆率の白金あるいはパラジウム原子層を構築した。この表面の構造を走査型トンネル顕微鏡(STM)、表面X線散乱(SXS)法などにより厳密に規定し、また表面電子構造を紫外線光電子分光(UPS)法や電気化学環境下での二次高調波発生(SHG)分光法により評価した。このようにして構造と電子状態を厳密に規制した表面における電極触媒活性を、主としてホルムアルデヒドの電解酸化反応により評価した。
特に、様々な被覆率のパラジウム原子層を金単結晶上に構築し、その構造をSTM、SXSで規定した後に、in situ SHG法などで評価し、異種原子の種類や表面濃度についての依存性を明らかにした。
本研究では単結晶Au(111)及びAu(100)電極表面上へのPd析出の測定を行った。
Au(111)電極表面上へのPd析出の場合では、多結晶Au電極表面で見られた同様のSHG信号応答が観測された。一方、Au(100)電極表面の場合では、Pd析出に伴うSHG信号の変化は殆ど無かった。この結果は、SHG信号の増強は面方位依存性を有していることを示しており、共鳴SHG信号は(111)面に局在していることが明確にわかった。また、Pd/Au(111)表面における波長依存性と表面方位角依存性についての測定および解析を実施した。

Research Products

• [Publications] Hideo Naohara et al.: "Thickness Dependent Electrochemical Reactivity of Epitaxially Electrodeposited Palladium Thin Layers on Au(111) and Au(100)"Journal of Electroanalytical Chemistry. 500・1-2. 435-445 (2001)
• [Publications] Shen Ye et al.: "Stability of the Si-H Bond on the Hydrogen Terminated Si(111) Surface Studied by Sum Frequency Generation"Surface Science. 476. (2001)
• [Publications] Shen Ye et al.: "Conformational Order of Octadecanethiol (ODT) Monolayer at Gold/Solution Interface : Internal Reflection Sum Frequency Generation (SFG) Study"Studies in Surf. Sci. and Catal.. 132. 705-710 (2001)
• [Publications] Shen Ye et al.: "Spectroscopic Studies on Electroless Deposition of Copper on a Hydrogen Terminated Si(111) Surface in Eluoride Solutions"Journal of Electrochemical Society. 148・6. C421-C426 (2001)
• [Publications] Ryo Yamada et al.: "Structural Investigation of the Self-Assembled Monolayer of Decanethiol on the Reconstructed-and (1x1)-Au(100) Surfaces by Scanning Tunneling Microscopy"Langmuir. 17・14. 4148-4150 (2001)
• [Publications] A.Sato et al.: "A Ligand Substitution Reaction of Oxo-centred Triruthenium Complexes Assembled as Monolayers on Gold Electrodes"Physical Chemistry Chemical Physics. 3. 3420-3426 (2001)
• [Publications] Shen Ye et al.: "Sum Frequency Generation (SFG) Study of the pH-dependent Water Structure on the Fused Quartz Surface Modified by Octadecyltrichlorosilane (OTS) Monolayer"Physical Chemistry Chemical Physics. 3. 3463-3469 (2001)
• [Publications] Satoshi Nihonyanagi et al.: "Sum Frequency Generation Study on the Molecular Structures at the Interfaces Between Quartz Modified with Amino-Terminated Self-Assembled Monolayer and Electrolyte, Solutions of Various pH and Ionic Strengths"Electrochimica Acta. 46・20-21. 3057-3061 (2001)
• [Publications] Toshihiro Kondo et al.: "Control of the Charge Transfer Rate at a Gold Electrode Modified with a Self-Assembled Monolayer Containing Ferrocene and Azobenzene by Electro-and Photochemical Structural Conversion of cis-and trans-forms of the Azobenzene Moiety"Langmuir. 17・20. 6317-6324 (2001)
• [Publications] Toshihiro Kondo et al.: "Formation an Electrochemical Characteristics of Multilayers of Au Nanoclusters Covered by Mixed Self-Assembled Monolayers of Three Kinds of Alkanethiols with Methyl, Ferrocene, or Carboxylate Terminal Group on Au(111) Surface"Chemistry Letters. 930-931 (2001)
• [Publications] H.Koshima et al.: "Synthesis, Structure and Second-harmonic Generation of Noncentrosymmetric Cocrystals of 2-amino-5-nitropyridine with Achiral Benzenesulfonic Acids"Crystal Growth & Design. 1・6. 467-471 (2001)
• [Publications] Jianwei Zhao et al.: "A Novel Nanolithography Technique for Self-Assembled Monolayer Using Current Sensing Atomic Force Microscope"Langmuir. 17・25. 7784-7788 (2001)
• [Publications] Toshihiro Kondo et al.: "Anion effect on the electrochemical characteristics of a gold electrode modified with a self-assembled monolayer of ferrocenylhexanethiol in aqueous and dichloromethane solutions"Journal of Organometallic Chemistry. 637-639・1. 841-844 (2001)
• [Publications] Hiromi Wano et al.: "In Situ, Real Time Monitoring of the Reductive Desorption Process of Self-Assembled Monolayer of Hexanethiol on Au (111) Surface in Acidic and Alkaline Aqueous Solutions by Scanning Tunneling Microscopy"Langmuir. 17・26. 8224-8228 (2001)
• [Publications] Ichizo Yagi et al.: "The Effects of Nitrogen and Plasma Power on Electrochemical Properties of Boron-doped Diamond Electrodes Grown by MPCVD"Journal of Electrochemical Society. 149・1. E1-E5 (2002)
• [Publications] H.Kawamura et al.: "Evidence for the Diffusion of Au Atoms into the Te UPD Layer Formed on a Au(111) Substrate"Journal of Electrochemical Society. 149・2. C83-C88 (2002)
• [Publications] T.Nakanishi et al.: "Enantioselective Adsorption of Phenylalanine onto Self-Assembled Monolayer of 1, 1'-Binaphthalene-2,2'-dithiol on Gold"Journal of American Chemical Society. 124・5. 740-741 (2002)
• [Publications] M.E.Quayam et al.: "Formation of Organic Monolayer on a Hydrogen Terminated Si(111) Surface via Silicon-Carbon Bond Monitored by ATR FT-IR and SFG Spectroscopy : Effect of Orientational Order on the Reaction Rate"Chemistry Letters. 2. 208-209 (2002)
• [Publications] Jianwei Zhao et al.: "Formation of Nano-patterns of a Self-Assembled Monolayer (SAM) within a SAM of Different Molecules Using a Current Sensing Atomic Force Microscope"Nano Letters. 2・2. 137-140 (2002)
• [Publications] M.E.Quayam et al.: "Mechanism for Nucleation and Growth of Electrochemical Palladium Deposition on an Au (111) Electrode"Journal of Electroanalytical Chemistry. (in press).
• [Publications] Tadashi Awatani et al.: "Second Harmonic Generation Study on Electrochemical Deposition of Palladium on a Polycrystalline Gold Electrode"Journal of Electroanalytical Chemistry. (in press).
• [Publications] Toshihiro Kondo et al.: "In situ Structural Study on Underpotential Deposition of Ag on Au(111) Electrode Using Surface X-ray Scattering Technique"Journal of Electroanalytical Chemistry. (in press).
• [Publications] M.Takahashi et al.: "Heteroepitaxial Growth of CdTe on p-Si(111) Substrate by Pulsed-light Assisted Electrodeposition"Applied Physics Letters. (in press).
• [Publications] Toshiya Saito et al.: "In situ Study of Ultra-thin Film Formation on Au(111) Surface in Propylene Carbonate by Scanning Tunneling Microscopy Under Potential Control"Journal of Electrochemical Society. (in press).
• [Publications] H.Naohara: "Electrocatalytic Reactivity for Oxygen Reduction at Epitaxially Grown Pd Thin Layers of Various Thickness on Au(111)andAu(100)"Electrochim.Acta. 45・20. 3305-3309 (2000)
• [Publications] M.Takahasi: "Pseudomorphic growth of Pd monolayer on Au(111)electrode surface"PCCP.. 3. 267-273 (2001)
• [Publications] H.Naohara: "Thickess Dependent Electrochemical Reactivity of Epitaxially Electrodeposited Palladium Thin Layers on Au(111)and Au(100)Surfaces"J.Electroanal.Chem.. 500・1-2. 435-445 (2001)