固体表面における光反応と光触媒反応

1995 Fiscal Year Annual Research Report

• Project/Area Number: 06239110
• Research Institution: Osaka Prefecture University
• Principal Investigator: 安保 正一 大阪府立大学, 工学部, 教授 (70094498)
• Co-Investigator(Kenkyū-buntansha): 佐藤 真理 北海道大学, 触媒化学研究センター, 教授 (70001724) ; 堂免 一成 東京工業大学, 資源化学研究所, 助教授 (10155624) ; 橋本 和仁 東京大学, 工学部, 助教授 (00172859) ; 川崎 昌博 北海道大学, 電子科学研究所, 教授 (70110723)
• Keywords: 光化学 / 固体光触媒 / 反応ダイナミックス / 固体表面 / ミクロ空間 / ゼオライト / 光反応過程 / 光機能分子

Research Abstract

研究代表者・
安保正一: ゼオライト細孔内を反応場とするケトンの光化学反応とゼオライト細孔内にイオン交換法を駆使して構築した固定化銅や銀イオンを光触媒とするNOxの直接分解反応を取り上げ、ゼオライト細孔内の光化学過程と光触媒反応の特徴を明らかにした。これらの研究の実施とともに研究分担者の研究の実施状況を把握し密接な連携のもとで効率的に高度な成果が得られるように研究を掌握し成果の総括を行った。
研究分担者・
川崎昌博: GaAs表面でのHC1,C12の光ドライエッチング反応機構を角度分解型光電子分光法を用いて研究した。エキシマレーザー(193nm,248nm),YAGレーザー(355nm,532nm)で調べたところ,193nmの場合にのみ,エッチング生成物の脱離が促進されることを見い出した。
橋本和人: アセトアルデヒド分解について光触媒表面への入射フォトン数と拡散分子数との関係のモデル計算結果をもとに反応機構について考察した。光照射された酸化チタン薄膜の示す防汚効果と抗菌効果の光強度依存性を調べ,またそれに影響を及ぼす因子について考察した。
堂面一成: ピコ秒赤外パルスのポンプープローブ法により,ゼオライト表面水酸基の振動励起状態の寿命が水酸基に希ガスが吸着する事で著しく短くなることを見いだした。寿命の減少は,水酸基と下地のゼオライトのフォトンとのエネルギーの授受が容易になるためと結論した。
佐藤真理: 金(111)単結晶表面上のペンタ鉄カルボニルの光分解は,平均1個のカルボニルが脱離し,その量子収率は吸収端付近できわめて高い。また,吸収端付近の光分解は表面付近でのみ起こっているのに対し,これより短波長側では表面から離れる方が収率は高くなる。

Research Products

• [Publications] Masakazu Anpo: "Approach to Photocatalysis at the Molecular Level:Design of Photocatalysts,Detection of Intermediate species,and Reaction Mechanism." Solar Energ.Mater.Solar Cells.38. 221-238 (1995)
• [Publications] Masakazu Anpo: "ESR,XPS,UV-VIS and FT-IR Investigation on the Interaction of NO and O_2 with Dispersed C_<60> Supported on Silica,Titanium and Alkali Cation-exchanged Y-zeolites" Res.Chem.Intermedi.21. 631-639 (1995)
• [Publications] Masakazu Anpo: "The Photocatalytic Reduction of CO_2 with H_2O on Titanium Oxide Catalysts" Sekiyu Gakkaishi. 38. 300-310 (1995)
• [Publications] Masakazu Anpo: "Photocatalytic reduction CO_2 with H_2O on Various Titanium Oxide Catalysts" J.Electroanal.Chem.396. 21-26 (1995)
• [Publications] Hiromi Yamashita: "Photocatalytic Synthesis of CH_4 and CH_3OH From CO_2 and H_2O on Highly Dispersed Active Titanium Oxide Catalysts" Energy.Conv.Manag.36. 617-620 (1995)
• [Publications] Sang-Chul Moon: "The Photocatalytic Isomerization of 2-Butenes on ZrO_2 Catalyst with Low Coordinated Surface Sites" Chem.Lett.447-448 (1995)
• [Publications] Masaya Matsuoka: "The Photocatalytic Decomposition of Nitric Oxide on the Silver(I)Ion-exchanged ZSM-5 Catalyst" Chem.Lett.375-376 (1995)
• [Publications] Hiroyasu Nishiguchi: "Photophysical and Photochemical Processes in Zeolite Cavities:The effect of Ion-exchanged Alkali Metal Cations on the Excited States of Xanthone and the Photolysis of 2-Pentanone," Res.Chem.Intermedi.21. 885-898 (1995)
• [Publications] Hiroyasu Nishiguchi: "The effect of Ion-exchanged Alkali Metal Cations on the Excited States of Xanthone and the Photolysis of 2-Pentanone Included within the Zeolite Cavities" J.Photochem.Photobiol,A:Chem.92. 85-90 (1995)
• [Publications] M.C.Martinez: "Metal-Support Interaction in Pt/C Catalysts.Influence of the Support Surface Chemistry and the Metal Precursor" Carbon. 33. 3-15 (1995)
• [Publications] S.Tanaka: "CO_2 Gasification of Iron-Loaded Carbons:Activation of the Iron Catalyst with CO" Energy&Fuels. 9. 45-52 (1995)
• [Publications] 文相吉: "酸化ジルコニウム上での触触反応および光触媒反応における配位不飽和サイトの役割" 触媒. 37. 132-135 (1995)
• [Publications] Tsuneo Fujii: "Influence of Pore Size on the Intensity of the Monomer and Excimer-like Fluorescence of Pyrene Adsorbed onto Porous Glasses" J.Photochem.Photobiol,A:Chem.86. 219-225 (1995)
• [Publications] 山下弘巳: "超微粒子半導体の光触媒・光表面反応" 表面科学. 16. 194-200 (1995)
• [Publications] 松岡雅也: "ゼオライト細孔内での光触媒反応(I)金属イオンを光触媒とするNOx分解反応" 表面. 33. 773-781 (1995)
• [Publications] Tsuneo Fujii: "Characteristic Changes in the Fluorescence Spectra of 1-Naphthol at the Gelation Point of the Sol-Gel Xerogel Transitions" Res.Chem.Intermedi.21. 643-654 (1995)
• [Publications] Tsuneo Fujii: "Fluorescence Spectra of Methyl Salicylate During the Sol Gel Xerogel Transitions of Mixed Si-Al Alkoxides" J.Chem.Soc.,Faraday Trans.91. 4297-4285 (1995)
• [Publications] Hiromi Yamashita: "In Situ XAFS,Photoluminescence,and IR Investigtions of Copper Ions Included within Various Kinds of Zeolites" J.Phys.Chem.100. 397-402 (1996)
• [Publications] Hiromi Yamashita: "Photocatalytic Degradation of 1-Octanol on Anchored Titanium Oxide and on TiO_2 Powder Catalysts" J.Catal.158. 97-101 (1995)
• [Publications] Masaya Matsuoka: "The Photocatalytic Decomposition of Nitric Oxide on Ag^+/ZSM-5 Catalyst Prepared by Ion-Exchang" J.Mol.Catal.(in press).
• [Publications] Masakazu Anpo: "In Situ Investigations of the Photocatalytic Decomposition of NOx on Ion-exchanged Silver(I)ZSM-5 Catalysts21GC21:Catal.Today" (in press).
• [Publications] 大橋勝文: "表面吸着種の光化学" 表面技術協会誌. 46. 692-696 (1995)
• [Publications] K.Tohda: "Cation permselectivity at the phase boundary of ionophore-incorporated solvent polymeric membranes as studies by optical second harmonic generation" Anal.Chem. 67. 570-577 (1995)
• [Publications] Z.Song: "X-ray photoelectron spectroscopy and atomic force microscopy surface study of GaAs(100)cleanig procedures" J.Vac.Technol.B. 13. 77-82 (1995)
• [Publications] Y.Sato: "Ion imaging of the photodissociation of OCS near 217 and 230 nm" J.Phys.Chem.99. 16307-16314 (1995)
• [Publications] M.Kawasaki: "Ion imaging of the photodissociation of HNCO near 217 nm" Chem.Phys.Lett.(in press).
• [Publications] H.Sakai: "Separate Monitoring of Reaction Products Formed at Oxidation and Rduction Sites of TiO2 Photocatalysts Using a Microelectrode" J.Electroanal.Chem.379. 199-205 (1995)
• [Publications] H.Sakai: "Selective Killing of a Single Cancerous T24 Cell with TiO2 Semiconducting Microelectrode under Irradiation" Chem.Lett.185-186 (1995)
• [Publications] H.Yoshiki: "Reaction Mechanism of Electrodes Metal Deposition Using ZnO Thin Film (1):Process of Catalyst Formation" J.Electrochem.Soc.142. 428-432 (1995)
• [Publications] B.H.Loo: "A Raman Microprobe Study of theElectrochromic and Photochromic Thin Films of Molybdenum Trioxide and Tungsten Trioxide" Appl.Sur.Sci.81. 175-181 (1995)
• [Publications] K.Ajito: "Combained Raman and Photoelectrochemical Imaging System.Application to TiO2 Films Grown and Anodically on Ti-Ag Alloy" J.Electoroanal.Chem.386. 229-233 (1995)
• [Publications] H.Sakai: "Local Detection of Photoelectrochemically Produced H2O2 with a"Wired" Horseradish Peroxidase Microsensor" J.Phys.Chem. 99. 11896-11900 (1995)
• [Publications] H.Matsubara: "Photoactive TiO2 Containing Paper Preparation and its Photocatalytic Activity under weak UV Light Illumination" Chem.Lett.767-768 (1995)
• [Publications] N.Negishi: "Preparation of Transparent TiO2Thin Film Photocatalyst and its Photocatlytic Activity" Chem.Lett.841-842 (1995)
• [Publications] K.Ajito: "Strain Imaging Analysis of Si Using Raman Microscopy" J.Vac.Sci.Technol.A13. 1234-1238 (1995)
• [Publications] K.Ajito: "A Study of the Photochromic Properties of Amorphous MoO3 Films Using Raman Microscopy" J.Phys.Chem.99. 16383-16388 (1995)
• [Publications] F.Wakabayashi,: "Direct comparison of N2 and CO as IR-spectroscopic probes of acid sites in H-ZSM-5 zeolite" J.Phys.Chem. 99. 10573-10580 (1995)
• [Publications] S.S.Kano: "Vibrational relaxation of hydroxyl group in zeolite:the effect of adsorbed Xe" Surf.Sci.(in press).
• [Publications] T.Urisu,: "Molecular orientation and phtochemical reaction of arganoaluminum compounds investigated by buried metal layer infrared reflection absorption spectroscopy." Jpn.J.Appl.Phys.,. 33. 7123-7129 (1995)
• [Publications] S.Sato: "Thermal and photo-decomposition of iron pentacarbonyl adsorbed on silver surfaces." Trans.Mat.Res.Soc.Jpn,. 19A. 135-138 (1995)
• [Publications] Y.Imaizumi: "Infrared reflection absorption spectra of trimethylaluminum and dimethylaluminum hydride condenced layers on an SiO2 surface with a buried metal layer substrate." J.Molec.Struct.,. 352/353. 447-453 (1995)
• [Publications] S.Sato: "IRAS and TPD study on the photolytic decarbonylation of iron pentacarbonyl adsorbed on a SiO2 film with a buried metal layer." Appl.Surf.Sci,.90. 29-37 (1995)
• [Publications] K.Ikeda: "Microscopic obsevation of Photocatalytic Reaction Using Microelectrode Special Resolution for Reaction Products Distribution" Chem.Lett.979-980 (1995)
• [Publications] K.Hashimoto: "Structual Analysis of Diamond Film Grown on Photoelectrochemically Etched Silicon Substrate by Micro-Raman Spectroscopy" J.Electroanal.Chem.397. 339-341 (1995)
• [Publications] H.Yoshiki: "Pattern Formation of Cu Layer by Photocatalytic Reaction of ZnO Thin Film" J.Electrochem.Soc.142. 235-237 (1995)
• [Publications] I.Sopyan: "Efficient TiO2 Powder and Film Photocatalysts with Rutile Structure" Chem.Lett.69-70 (1995)
• [Publications] I.Sopyan: "An Efficient TiO2 Thin Film Photocatalyst:Photocatalytic Properties inGas-Phase Acetaldehyde Degradation" J.Photochem.Photobiol.(in press).
• [Publications] F.Wakabayashi: "FT-IR studies of interaction between zeolitic hydroxyl groups and small molecules.2.Adsorption of oxygen,hydrogen,and rare gases on H-mordenite at low temperatures" J.Phys.Chem.(in press).
• [Publications] T.Fujino: "The effect of adsorbed noble gas atoms on vibrational relaxation of hydroxylgroup in zeolite" J.Chem.phys.(in press).
• [Publications] F.Wakabayashi: "An attempt to semi-quantitative analysis of Lewis acid sites in H-ZSM-5 zeolite using water as an IR-spectroscopic titrant" Catal.Lett. (in press).
• [Publications] F.Wakabayashi: "FT-IR study of H218O adsorptionon H-ZSM-5:A direct evidence for the hydrogen-bonded adsorption of water" J.Phys.Chem.(in press).
• [Publications] T.Fujino: "FT-IR and quantum chemical studies of the interaction between dimethyl ether and H-ZSM-5 zeolite" J.Phys.Chem.(in press).
• [Publications] 横田敏也: "波長可変ピコ秒赤外パルス発生システム" 分光研究. 45. 28-29 (1995)
• [Publications] Hiromi Yamashita: "Science&Technology in Catalysis28HD01:1995" Kodansha, 467
• [Publications] Masakazu Anpo: "Surface Photochmistry" John Wiley&Sons Ltd, 174 (1995)