表面増強赤外吸収・ラマン散乱の比較による増強機構の検討

• Project Area: Strong Photons-Molecules Coupling Fields for Chemical Reactions
• Project/Area Number: 21020003
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 大澤 雅俊 北海道大学, 触媒化学研究センター, 教授 (00108466)
• Project Period (FY): 2009 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥3,800,000 (Direct Cost: ¥3,800,000); Fiscal Year 2010: ¥1,900,000 (Direct Cost: ¥1,900,000); Fiscal Year 2009: ¥1,900,000 (Direct Cost: ¥1,900,000)
• Keywords: 化学物理 / 表面・界面物性 / フォトニック結晶 / 触媒反応 / 表面増強赤外吸収 / 表面増強ラマン散乱 / 固液界面 / 表面振動分光 / 金属ナノ微粒子 / 電極触媒 / 機能表面

Research Abstract

表面増強赤外吸収(SEIRA)と表面増強ラマン散乱(SERS)の比較によりそれらの増強機構を考察するとともに、応用を検討した。
1.燃料電池触媒反応の解析:メタノールならびにギ酸は燃料電池の燃料と期待され、Pt表面におけるこれら化合物の酸化反応が古くから検討されてきた。しかし、その反応機構は現在でも解決されていない、SEIRA分光を用いて、われわれは、反応が起こっている電極触媒表面にギ酸イオンが吸着していることを初めて見出し、反応の中間体であることを示唆した。これに対して、ドイツのグループは、ギ酸イオンは単に吸着しているだけで反応を妨害していると主張した。そこで、時間分解SEIRA分光によるより詳細な解析を行い、我々が以前から主張しているように、吸着ギ酸イオンを経由して反応していることを証明した。
2.陽イオンの水和構造と荷電固体表面との相互作用解析:固液界面反応を理解するうえで分子ならびにイオンの水和構造と表面との相互作用を理解することが必須である。電極電位で表面の電荷量を制御することによりイオン濃度を増加させ、SEIRASを用いて界面を選択的に測定するという新しいアプローチを提案し、陽イオン(金属イオンならびにテトラアルキルアンモニウムイオン)の水和構造を明らかにした。また、強い界面電場中で水和イオンを電極表面に強く押し付けることにより、水和イオンと表面の相互作用を詳しく検討し、一定以上の力を加えると水和殻が崩壊すること、崩壊の程度が水和殻の構造に依存すること、疎水性水和殻と疎水表面の間に4kcal/mol程度のエネルギー障壁があることなどを初めて明らかにした。
3.半導体表面でのSERSとSEIRAの理論解析:SERSとSEIRAは、実験的には金属表面でのみ観測されているが、理論計算の結果、半導体表面でも起こり得ることを理論的に示した。

Research Products

• [Journal Article] A butadiyne-linked diruthenium molecular wire self-assembled on a gold electrode surface (2011)
  • Author(s): Li-Yi Zhang
  • Journal Title: Chemical Communications Volume: 47 Pages: 923-925
  • Peer Reviewed
• [Journal Article] The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum (2011)
  • Author(s): Masatoshi Osawa
  • Journal Title: Angewandte Chemie International Edition Volume: 50 Pages: 1159-1163
  • Peer Reviewed
• [Journal Article] 表面増強赤外分光でみた電極-電解液界面の水の構造と挙動 (2011)
  • Author(s): 大澤雅俊
  • Journal Title: 分析化学 Volume: 60 Pages: 1-9
  • Peer Reviewed
• [Journal Article] Anisotropic light absorption by localized surface plasmon resonance in a thin film of gold nanoparticles studied by visible multiple-angle incidence resolution spectrometry (2011)
  • Author(s): Akiyoshi Kasuya
  • Journal Title: Physical Chemistry Chemical Physics Volume: 13(印刷中)
  • Peer Reviewed
• [Journal Article] DME Dissociation Reaction on Platinum Electrode Surface : A Quantitative Kinetic Analysis by In Situ IR Spectroscopy (2010)
  • Author(s): Yi Zhang
  • Journal Title: Journal of Electrochemical Society Volume: 157
  • Peer Reviewed
• [Journal Article] Surface-Enhanced Infrared Absorption Spectroscopic Studies of Adsorbed Nitrate, Nitric Oxide, and Related Compounds.3.Formation and Reduction of Adsorbed Nitrite at a Platinum Electrode (2010)
  • Author(s): Farhana Rahman Rima
  • Journal Title: Journal of Physical Chemistry C Volume: 114 Pages: 6011-6018
  • Peer Reviewed
• [Journal Article] Mechanistic Studies by Sum-Frequency Generation Spectroscopy : Hydrolysis of a Supported Phospholipid Bilayer by Phospholipase A(2) (2010)
  • Author(s): Yujin Tong
  • Journal Title: Angewandte Chemie International Edition Volume: 49 Pages: 2319-2323
  • Peer Reviewed
• [Journal Article] Electrochemical behaviors of dimethyl ether on platinum single crystal electrodes.Part II : Pt(100) (2010)
  • Author(s): Leilei Lu
  • Journal Title: Journal of Electroanalytical Chemistry Volume: 642 Pages: 82-91
  • Peer Reviewed
• [Journal Article] Destruction of the Water Layer on a Hydrophobic Surface Induced by the Forced Approach of Hydrophilic and Hydrophobic Cations (2010)
  • Author(s): Akira Yamakata
  • Journal Title: Journal of Physical Chemistry Letter Volume: 1 Pages: 1487-1491
  • Peer Reviewed
• [Journal Article] Interference effects in the sum frequency generation spectra of thin organic films.I.Theoretical modeling and simulation (2010)
  • Author(s): Yujin Tong
  • Journal Title: Journal of Chemical Physics Volume: 133
  • Peer Reviewed
• [Journal Article] Interference effects in the sum frequency generation spectra of thin organic films.II : Applications to different thin-film systems (2010)
  • Author(s): Yujin Tong
  • Journal Title: Journal of Chemical Physics Volume: 133
  • Peer Reviewed
• [Journal Article] 赤外分光測定法-基礎と最新手法、第II部 各種分光法、第6回9B.表面増強赤外測定法 (2010)
  • Author(s): 大澤雅俊
  • Journal Title: 分光研究 Volume: 59 Pages: 305-312
  • Peer Reviewed
• [Journal Article] DME Dissociation Reaction on Platinum Electrode Surface : A Quantitative Kinetic Analysis by In Situ IR Spectroscopy (2010)
  • Author(s): Zhang, Y, Tong, Y.-J., Lu, L.-L., Osawa, M., Ye, S.
  • Journal Title: J.Electrochem.Soc. 157
  • Peer Reviewed
• [Journal Article] Mechanistic Studies by Sum-Frequency Generation Spectroscopy : Hydrolysis of a Supported Phospholipid Bilayer by Phospholipase A2 (2010)
  • Author(s): Tong, Y., Li, N., Liu, H., Ge, A., Osawa, M., Ye, S.
  • Journal Title: Angew.Chem.Int.Ed. 49 Pages: 2319-2323
  • Peer Reviewed
• [Journal Article] Surface-Enhanced Infrared Absorption Spectroscopic Studies of Adsorbed Nitrate, Nitric Oxide, and Related Compounds.3.Formation and Reduction of Adsorbed Nitrite at a Platinum Electrode (2010)
  • Author(s): Rima, F.R., Nakata, Ko, Shimazu, K., Osawa, M.
  • Journal Title: J.Phys.Chem.C 114 Pages: 6011-6018
  • Peer Reviewed
• [Journal Article] Dynamics of CO Oxidation on a Polycrystalline Platinum Electrode : A Time-Resolved Infrared Study (2009)
  • Author(s): Samjeske, G., Komatsu, K., Osawa, M.
  • Journal Title: J.Phys.Chem.C. 113 Pages: 10222-10228
  • Peer Reviewed
• [Journal Article] Molecular Structures on Solid Substrates Probed by Sum Frequency Generation(SFG)Vibration Spectroscopy (2009)
  • Author(s): Ye, S., Osawa, M.
  • Journal Title: Chem.Lett. 38 Pages: 386-391
  • Peer Reviewed
• [Journal Article] Destruction of the Hydration Shell around Tetraalkylammonium Ions at the Electrochemical Interface (2009)
  • Author(s): 山方啓、大澤雅俊
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 6892-6893
  • Peer Reviewed
• [Journal Article] ATR-SEIRAS Investigation of the Fermi Level of Pt Cocatalyst on a GaN Photocatalyst for Hydrogen Evolution under Irradiation (2009)
  • Author(s): Yoshida, M., Yamakata, A., Takanabe, K., Kubota, J., Osawa, M., Domen K.
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 13218-13219
  • Peer Reviewed
• [Journal Article] In Situ Scanning Tunneling Microscopy Observation of Metal-Cluster Redox Interconversion and CO Dissociation Reactions at a Solution/Au(111)Interface (2009)
  • Author(s): Noda, H., Uehara, H., Abe M., Michi, T., Osawa, M., Uosaki, K., Sasaki, Y.
  • Journal Title: Bull.Chem.Soc.Jpn. 82 Pages: 1227-1231
  • Peer Reviewed
• [Journal Article] Adsorption of Propylene Carbonate(PC)on the LiCoO_2 Surface Investigated by Nonlinear Vibrational Spectroscopy (2009)
  • Author(s): Liu, H.-J., Tong, Y.-J., Kuwata, N., Osawa, M., Kawamura, J., Ye, S.
  • Journal Title: J.Phys.Chem.C 113 Pages: 20531-20534
  • Peer Reviewed
• [Journal Article] 金属表面の光照射プロセス -固気界面から固液界面へ- (2009)
  • Author(s): 山方啓、大澤雅俊
  • Journal Title: 光化学 40 Pages: 78-84
• [Presentation] ロジウム電極上に吸着したNOの赤外分光法によるキャラクタリゼーション (2011)
  • Author(s): 中田耕
  • Organizer: 電気化学78大会
  • Place of Presentation: 横浜国立大学常盤台キャンパス(横浜市)
  • Year and Date: 2011-03-29
• [Presentation] 赤外分光法によるCu/Pd電極上の硝酸イオンおよび関連物質の吸着状態解析 (2011)
  • Author(s): 山木邦亮
  • Organizer: 電気化学78大会
  • Place of Presentation: 横浜国立大学常盤台キャンパス(横浜市)
  • Year and Date: 2011-03-29
• [Presentation] Structural studies of quaternary ammonium surfactant monolayers (2010)
  • Author(s): Shen Ye
  • Organizer: PacifiChem 2010
  • Place of Presentation: Sheraton Waikiki (Honolulu, USA)
  • Year and Date: 2010-12-18
• [Presentation] Destruction of water layers around ions and electrode surface by their forced approach (2010)
  • Author(s): Akira Yamakata
  • Organizer: PacifiChem 2010
  • Place of Presentation: Sheraton Waikiki (Honolulu, USA)
  • Year and Date: 2010-12-17
• [Presentation] Solvent adsorption on the LiCoO2 surface studied by SFG spectroscopy (2010)
  • Author(s): Shen Ye
  • Organizer: PacifiChem 2010
  • Place of Presentation: Sheraton Waikiki (Honolulu, USA)
  • Year and Date: 2010-12-17
• [Presentation] Role of bridge-bonded formate in the electrocatalytic oxidation of formicacid on platinum (2010)
  • Author(s): Masatoshi Osawa
  • Organizer: PacifiChem 2010
  • Place of Presentation: Sheraton Waikiki (Honolulu, USA)(招待講演)
  • Year and Date: 2010-12-16
• [Presentation] In situ AFM observation on the hydrolysis process of the supported lipid bilayer catalyzed by enzyme (2010)
  • Author(s): Henlian Wu
  • Organizer: PacifiChem 2010
  • Place of Presentation: Sheraton Waikiki (Honolulu, USA)
  • Year and Date: 2010-12-16
• [Presentation] Electrochemical oxidation of dimethyl ether (DME) on platinum electrodes (2010)
  • Author(s): Shen Ye
  • Organizer: PacifiChem 2010
  • Place of Presentation: Sheraton Waikiki (Honolulu, USA)
  • Year and Date: 2010-12-15
• [Presentation] Pt電極表面でのギ酸酸化反応機構:吸着フォルメートの役割 (2010)
  • Author(s): 大澤雅俊
  • Organizer: 表面科学学術講演会
  • Place of Presentation: 大阪大学(大阪市)(招待講演)
  • Year and Date: 2010-11-12
• [Presentation] Role of bridge-bonded formate in the electrocatalytic oxidation of formicacid on platinum (2010)
  • Author(s): Masatoshi Osawa
  • Organizer: The 61th Annual Meetingt of International Society of Electrochemistry
  • Place of Presentation: Convention Center (Nice, France)(招待講演)
  • Year and Date: 2010-10-28
• [Presentation] Kinetics of the destruction of hydration shells around tetraalkyl-ammonium ions at the electrochemical interface (2010)
  • Author(s): Akira Yamakata
  • Organizer: The 61th Annual Meeting of International Society of Electrochemistry
  • Place of Presentation: Convention Center (Nice, France)
  • Year and Date: 2010-10-27
• [Presentation] 硝酸イオンおよび関連物質の還元に対するスズの効果の赤外分光法による解明 (2010)
  • Author(s): Rima Farhana Rahman
  • Organizer: 2010年電気化学秋季大会
  • Place of Presentation: 神奈川工科大学(神奈川県厚木)
  • Year and Date: 2010-09-03
• [Presentation] 銀電極上の吸着チオ尿素が促進する水素発生反応 (2010)
  • Author(s): 内出太郎
  • Organizer: 2010年電気化学秋季大会
  • Place of Presentation: 神奈川工科大学(神奈川県厚木)
  • Year and Date: 2010-09-03
• [Presentation] Pt電極表面に吸着したCOの定電流酸化ダイナミクスの赤外分光解析 (2010)
  • Author(s): Gabor Samjeske
  • Organizer: 2010年電気化学秋季大会
  • Place of Presentation: 神奈川工科大学(神奈川県厚木)
  • Year and Date: 2010-09-03
• [Presentation] Role of bridge-bonded formate in formic acid electro-oxidation on Pt : Reactive intermediate or site-blocking spectator? (2010)
  • Author(s): Masatoshi Osawa
  • Organizer: 1st Ertl Symposium on Electrochemistry and Catalysis
  • Place of Presentation: Gwangjyu Institute of Technology (South Korea)(招待講演)
  • Year and Date: 2010-04-14
• [Presentation] Mechanism of hydrogen evolution reaction catalyzed by 4,4'-bipyridine a dsorbed metal electrodes : A combined electrochemical and infrared study (2010)
  • Author(s): Taro Uchida
  • Organizer: 1st Ertl Symposium on Electrochemistry and Catalysis
  • Place of Presentation: Gwangjyu Institute of Technology (South Korea)
  • Year and Date: 2010-04-11
• [Presentation] GaN光電極の光励起キャリアーダイナミクス (2010)
  • Author(s): 山方啓、吉田真明、久保田純、堂免一成、大澤雅俊
  • Organizer: 電気化学会第77回大会
  • Place of Presentation: 富山大学(富山県)
  • Year and Date: 2010-03-30
• [Presentation] 固液界面におけるイオンの水和殻崩壊の時間分解赤外分光観察 (2010)
  • Author(s): 山方啓、大澤雅俊
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪府)
  • Year and Date: 2010-03-28
• [Presentation] タングステン酸ビスマス粒子の光触媒活性と励起電子寿命の相関 (2010)
  • Author(s): 天野史章・山方啓・野上皓平・大澤雅俊・大谷文章
  • Organizer: 第105回触媒討論会
  • Place of Presentation: 京都テルサ(京都府)
  • Year and Date: 2010-03-24
• [Presentation] Electrooxidation of formic acid on Pt studied by surface-enhanced infrared absorption spectroscpoy(SEIRAS) : Is formate a reactive intermediate or site-blocking spectator? (2010)
  • Author(s): Samjeske, Gabor, 小松圭一, 大澤雅俊
  • Organizer: ACS 239th National Meeting
  • Place of Presentation: San Francisco, USA
  • Year and Date: 2010-03-22
• [Presentation] Theoretical study of surface-enhanced infrared absorption(SEIRA) (2009)
  • Author(s): 大澤雅俊
  • Organizer: FACSS 2009(The Federation of Analytical Chemistry and Spectroscopy Societies)
  • Place of Presentation: Louisville, USA
  • Year and Date: 2009-10-22
• [Presentation] Structure of water at the electrified platinum-water interface studied by infrared spectroscopy (2009)
  • Author(s): Osawa, M., Tsushima, M., Mogami, H., Samjeske, G., Yamakata, A.
  • Organizer: The 3rd Horiba International Symposium and The 11th ISSP International Symposium(ISSP-11)on Hydrogen and Water in Condensed Matter Physics
  • Place of Presentation: 生命の森リゾート(千葉県)
  • Year and Date: 2009-10-14
• [Presentation] Hydrogen evolution reaction catalyzed by the redox cycles of 4,4'-bipyridine adsorbed on silver electrodes (2009)
  • Author(s): 内田太郎、山方啓、佐々木陽一、大澤雅俊
  • Organizer: 216th Meeting of The Electrochemical Society
  • Place of Presentation: Vienna, Austria
  • Year and Date: 2009-10-07
• [Presentation] 表面増強赤外分光で観る電極触媒反応-Pt表面におけるC1化合物の酸化反応 (2009)
  • Author(s): 大澤雅俊
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学(宮崎県)
  • Year and Date: 2009-09-29
• [Presentation] ATR-SEIRAS法によるPt/GaN水分解光触媒のフェルミレベルの観測 (2009)
  • Author(s): 吉田真明、山方啓、久保田純、大澤雅俊、堂免一成
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学(宮崎県)
  • Year and Date: 2009-09-28
• [Presentation] 赤外分光法を用いた光電極の光励起ダイナミクス (2009)
  • Author(s): 山方啓、吉田真明、久保田純、堂免一成、大澤雅俊
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学(宮崎県)
  • Year and Date: 2009-09-27
• [Presentation] 電極界面とイオンの水和構造と構造破壊 (2009)
  • Author(s): 山方啓、大澤雅俊
  • Organizer: 第3回分子科学討論会2009
  • Place of Presentation: 名古屋大学(愛知県)
  • Year and Date: 2009-09-22
• [Presentation] Pt電極表面におけるC1化合物の酸化反応機構:現状と問題点 (2009)
  • Author(s): 大澤雅俊
  • Organizer: 2009年電気化学会秋季大会
  • Place of Presentation: 東京農工大学(東京都)
  • Year and Date: 2009-09-11
• [Presentation] イオンと電極界面の水和構造の変化 (2009)
  • Author(s): 山方啓、大澤雅俊
  • Organizer: 2009年電気化学会秋季大会
  • Place of Presentation: 東京農工大学(東京都)
  • Year and Date: 2009-09-11
• [Presentation] 電極表面に吸着した4,4'ビピリジンが触媒する水素発生促進反応機構 (2009)
  • Author(s): 内田太郎、山方啓、佐々木陽一、大澤雅俊
  • Organizer: 2009年電気化学会秋季大会
  • Place of Presentation: 東京農工大学(東京都)
  • Year and Date: 2009-09-11
• [Presentation] 電位による亜硝酸イオンの吸着状態の変化 (2009)
  • Author(s): Rima Falhana Rafman, 中田耕, 嶋津克明, 大澤雅俊
  • Organizer: 2009年電気化学会秋季大会
  • Place of Presentation: 東京農工大学(東京都)
  • Year and Date: 2009-09-11
• [Presentation] Pt電極表面におけるCO酸化反応ダイナミクス:時間分解赤外分光解析 (2009)
  • Author(s): Samjeske, Gabor, 小松圭一, 大澤雅俊
  • Organizer: 2009年電気化学会秋季大会
  • Place of Presentation: 東京農工大学(東京都)
  • Year and Date: 2009-09-11
• [Presentation] 表面増強赤外分光 (2009)
  • Author(s): 大澤雅俊
  • Organizer: 日本分光学会夏季セミナー
  • Place of Presentation: 幕張メッセ(千葉県)
  • Year and Date: 2009-09-01
• [Presentation] Infrared study of hydration shells around tetra-alkylammonium cations at the electrochemical interface (2009)
  • Author(s): 山方啓、大澤雅俊
  • Organizer: International Symposium on Nanoelectrochemistry and Spectroelectrochemistry
  • Place of Presentation: アモイ大学(アモイ、中国)
  • Year and Date: 2009-08-25
• [Presentation] Dynamics of CO electro-oxidation on a Pt electrode : A time-resolved infrared study (2009)
  • Author(s): Samjeske, Gabor, 小松圭一, 大澤雅俊
  • Organizer: 60th Annual Meeting of International Society of Electrochemistry
  • Place of Presentation: 北京大学(北京、中国)
  • Year and Date: 2009-08-18
• [Remarks]
  • URL: http://www.cat.hokudai.ac.jp/osawa/
• [Remarks]
  • URL: http://www.cat.hokudai.ac.jp/osawa/