1996 Fiscal Year Annual Research Report

高次構造制御と機能複合化による特殊反応場の触媒設計

Research Project

Project/Area Number	07242107
Research Institution	Waseda University
Principal Investigator	菊地英一早稲田大学, 理工学部, 教授 (90063734)
Co-Investigator(Kenkyū-buntansha)	橋本和仁東京大学, 工学系研究科, 助教授 (00172859) 市川勝北海道大学, 触媒化学研究センター, 教授 (70176288) 大塚潔東京工業大学, 工学部, 助教授 (60016532) 堂免一成東京工業大学, 資源化学研究所, 教授 (10155624)
Keywords	NO選択還元反応 / intrapore catalysis / 光分解触媒 / 水の完全分解 / 触媒反応分離 / 錯体触媒 / メタンホモロゲーション / 光と熱のハイブリッド
Research Abstract	高次構造制御による二元機能触媒の設計メタン還元剤によるNO選択還元反応に対して,NO酸化活性点(Ir,Co)とNO_2+CH_4反応活性点(In,Pd)を組み合わせZSM-5ゼオライトに担持させるとNO転化率が向上した。Ir/In/H-ZSM-5上では高分散担持されたIr上でNOが酸化されゼオライトにイオン交換担持されたInO^+上にNO_2として吸着すること,NO_2吸着量が還元活性と相関があることを見いだした。本二元機能触媒反応を同一ゼオライト細孔内部で進行させる intrapore catalysis により,高活性高選択性を示す触媒の設計が可能となることがわかった。層状反応場の光触媒化学層状チタン酸塩A_<2-X>La_2Ti_<3-X>NbxO_<10>(A=K,Rb,Cs,X=0,0.5,1)は効率よく紫外光で水を完全分解できることを初めて見いだした。この光触媒は層構造,組成を容易に変えることができるため,可視光で触媒作用を発現できる可能性がある。また,層状金属酸化物光触媒K_4Nb_6O_<17>を機械的粉砕によって微粒子化し,水の完全分解効率を高めることに成功した。微粒子化による触媒活性の増加は単に表面積の増加に帰せないことが明らかになった。触媒反応分離による選択的合成 O_<2->H_2電池反応中にカソード上で発生した活性酸素によるメタン,エタン,プロパンの活性化と部分酸化反応を実施したところ,いずれの軽アルカンも室温で反応し,特にプロパンからはアセトンが選択的に生成した。ミクロ空間反応場を利用する複合金属触媒の分子設計と高機能化本年度には,[Pt_3(CO)_6]n^<2->/FSM-16(n=3-5)やRu/NaY上でメタンの直接ホモロゲーション反応に対して従来触媒に比べ格段に高い触媒活性を示すこと,またAu(I)NaY及びAu^0/NaY上でのNO分解・還元反応においてO_2及びH_2添加による顕著な促進効果が得られるなど高度な複合触媒性能の発現を見いだした。吸着剤と複合化した光触媒の設計と反応光触媒反応に何らかの暗反応を組み合わせ,フォトンが十分に供給される条件では光触媒反応が,足りないときには通常の暗反応(熱反応)が進行することにより,常にある程度の効果が期待できる系にしておくことが重要であることを見いだした。また,これまでに見い出されている暗反応とのハイブリッドした空気清浄,抗菌,防汚光触媒反応の作動機構を解明し,高機能触媒の設計が可能となることがわかった。

Research Products

(33 results)

All Other

All Publications (33 results)

[Publications] M.Ogura et al.: "Precious metal. loaded In/H-ZSM-5 for Reduction of Nitric Oxide with Methane in the Presence of Water Vapor" Stud.Surf.Sci.Cat.101. 671-680 (1996)
[Publications] E.Kikuchi et al.: "Selective Reduction of Nitric Oxide with Methane on Gallium and Indium Containing H-ZSM-5 Catalysts" J.Catal.161. 465-470 (1996)
[Publications] M.Ogura et al.: "Formation of Active Sites for Reduction of NO_2 with Methane by Solid State Exchange of In_2O_3 into H-ZSM-5" Stud.Surf.Sci.Cat.105. 1593-1600 (1996)
[Publications] M.Ogura et al.: "Reduction of Nitric Oxide with Methane on Pd/Co/H-ZSM-5 Catalysts : Cooperative Effects of Pd and Co" Catal.Lett.42. 185- (1996)
[Publications] M.Ogura et al.: "Intrapore Catalyst in NO Reduction with Methane on Ir/In/H-ZSM-5 Catalyst" Chem.Lett.1017-1018 (1996)
[Publications] E.Kikuchi et al.: "Selective Reduction of Nitric Oxide with Methane on In/H-ZSM-5 Based Catalysts" (印刷中).
[Publications] A.Tanaka et al.: "Photocatalytic Properties of Some Ion-Exchangeable Layered Oxides" Critical Rev.Surf Chem. (印刷中).
[Publications] S.Ikeda et al.: "Effect of the particle size for photocatalytic decomposition of water on Ni loaded K_4Nb_6O_<17>" Microporous Materials. (印刷中).
[Publications] T.Tanaka et al.: "Photocatalytic decomposition of water on spontaneously hydrated layered perovskites" Chemistry of Materials. (印刷中).
[Publications] K.Otsuka et al.: "A Hydrogen-Nitric Oxide Cell for the Synthesis of Hydroxylamine" J.Electrochem.Soc.143. 3491-3497 (1996)
[Publications] Q.Zhang et al.: "Partial Oxidation of Light Alkanes during O_<2->H_2Cell Reactions at Room Temperature" Chem.Lett.(印刷中).
[Publications] T.Yamamoto et al.: "Ship-in-Bottle Synthesis of [P_<+15>(CO)_<30>]^<2-> Encapsulated in Ordered Hexagonal Mesoporous Channels of FSM-16" J.Am.Chem.Soc.118. 5810-5811 (1996)
[Publications] M.Ichikawa et al.: "Surface-grafted Metal Oxide Clusters and Metal Carbonyl Clusters in Zeolite Micropores" J.Mol.Cat.A107. 23-38 (1996)
[Publications] M.Ichikawa et al.: "Ru,Pt and Co Clusters in Zeolite Micropores ; EXAFS/FTIR/TPI Characterization and Catalytic Behaviors for Methane Homologa" Stud.Surf.Sci.Cat.101. 1075-1084 (1996)
[Publications] T.M.Salama et al.: "EXAFS/XANES,XRD and UV-VIS Characterization of Intrazeolite Gold(I) Prepared by Monolayer Dispersion of AuCl_3" J.Phys.Chem.100. 3688-3694 (1996)
[Publications] T.M.Salama et al.: "Studies in Selective Reduction of Nitric Oxide by Carbon Monoxide in the Presence of Hydrogen over Au/NaY Catalysts" J.Chem.Soc.,Faraday Trans. 92. 301-306 (1996)
[Publications] Y.Imada et al.: "Structural Characterization of Photoreduced Complete and Incomplete Cubane Type Molybdenum Oxide Clusters" Catal.Lett.38. 101-108 (1996)
[Publications] T.M.Salama et al.: "Highly Selective Catalytic Reduction of NO by H_2 over Au^0 and Au(I) Impregnated in NaY Zeolite Catalysts" J.Catal. 162. 169-178 (1996)
[Publications] G.C.Shen et al.: "Synthesis and Reversible Decarbonylation of Zeolite-Entrappea Bimetallic Carbonyl Clusters [HCoRu_3(CO)_<13>]" J.Phys.Chem.100. 14265-14268 (1996)
[Publications] G.C.Shen et al.: "Cobalt Clusters in NaY Zeolite Cages : Synthesis and characterization" J.Phys.Chem.100. 16947-16956 (1996)
[Publications] M.Ichikawa et al.: "Ship-in-Bottle Synthesis of Pt and Ru Carbonyl Clusters in NaY Zeolite Micropore and Ordered Mesoporous Channels of FSM-16" Stud.Surf.Sci.Cat.105. 679-686 (1996)
[Publications] T.M.Salama et al.: "In situ FT-IR and Catalytic Studies of the Selective Reduction of Nitric Oxide by Carbon Monoxide over Au/NaY Catalysts" Stud.Surf.Sci.Cat.105. 1571-1578 (1996)
[Publications] F.-S.Xiao et al.: "Oxide-Supported Trirutenium Ketenylidene Clusters and their Catalytic Properties" J.Mol.Catal.A113. 427-444 (1996)
[Publications] I.Sopyan et al.: "Efficient TiO_2 Powder and Film Photocatalysts with Rutile Structure" Chem.Lett.69-70 (1996)
[Publications] I.Sopyan et al.: "An Efficient TiO_2 Thin Film Photocatalyst : Photocatalytic Properties in Gas-Phase Acetaldehyde Degradation" J.Photochem.Photobiol.98. 79-86 (1996)
[Publications] I.Sopyan et al.: "A Film-Type Photocatalyst Incorporating Highly Active TiO_2 Powder and Fluoresin Binder" J.Electroanal.415. 183-186 (1996)
[Publications] Y.Kikuchi et al.: "Photocatalytic Bactericidal Effect of TiO_2 Thin-Film : Dynamic View for the Active Oxygen Species Responsible" J.Photochem.Photobiol.(印刷中).
[Publications] K.Ikeda et al.: "Studies on Photocatalytic Reactions involving radical Chain Reaotions using Microelectrodes" J.Phys.Chem.(印刷中).
[Publications] 橋本和仁他: "光活性酸化チタンをコートしたセラミックス:抗菌、防汚機能の付与" ニューセラミックス. 48. 55-61 (1996)
[Publications] 藤嶋昭他: "光触媒が活躍開始:タイルの場合" 化学と工業. 49. 764-767 (1996)
[Publications] 池田勝佳他: "光触媒反応における酸素の関わり" 光化学. 22. 54-58 (1996)
[Publications] 橋本和仁他: "光が当たるときれいになる材料:酸化チタン光触媒の新しい応用" 現代化学. 305. 23-28 (1996)
[Publications] 橋本和仁他: "半導体光電極.光触媒反応" セラミックス. 31. 815-820 (1996)

1996 Fiscal Year Annual Research Report

高次構造制御と機能複合化による特殊反応場の触媒設計

Principal Investigator

菊地 英一 早稲田大学, 理工学部, 教授 (90063734)

Research Products

[Publications] M.Ogura et al.: "Precious metal. loaded In/H-ZSM-5 for Reduction of Nitric Oxide with Methane in the Presence of Water Vapor" Stud.Surf.Sci.Cat.101. 671-680 (1996)

[Publications] E.Kikuchi et al.: "Selective Reduction of Nitric Oxide with Methane on Gallium and Indium Containing H-ZSM-5 Catalysts" J.Catal.161. 465-470 (1996)

[Publications] M.Ogura et al.: "Formation of Active Sites for Reduction of NO_2 with Methane by Solid State Exchange of In_2O_3 into H-ZSM-5" Stud.Surf.Sci.Cat.105. 1593-1600 (1996)

[Publications] M.Ogura et al.: "Reduction of Nitric Oxide with Methane on Pd/Co/H-ZSM-5 Catalysts : Cooperative Effects of Pd and Co" Catal.Lett.42. 185- (1996)

[Publications] M.Ogura et al.: "Intrapore Catalyst in NO Reduction with Methane on Ir/In/H-ZSM-5 Catalyst" Chem.Lett.1017-1018 (1996)

[Publications] E.Kikuchi et al.: "Selective Reduction of Nitric Oxide with Methane on In/H-ZSM-5 Based Catalysts" (印刷中).

[Publications] A.Tanaka et al.: "Photocatalytic Properties of Some Ion-Exchangeable Layered Oxides" Critical Rev.Surf Chem. (印刷中).

[Publications] S.Ikeda et al.: "Effect of the particle size for photocatalytic decomposition of water on Ni loaded K_4Nb_6O_<17>" Microporous Materials. (印刷中).

[Publications] T.Tanaka et al.: "Photocatalytic decomposition of water on spontaneously hydrated layered perovskites" Chemistry of Materials. (印刷中).

[Publications] K.Otsuka et al.: "A Hydrogen-Nitric Oxide Cell for the Synthesis of Hydroxylamine" J.Electrochem.Soc.143. 3491-3497 (1996)

[Publications] Q.Zhang et al.: "Partial Oxidation of Light Alkanes during O_<2->H_2Cell Reactions at Room Temperature" Chem.Lett.(印刷中).

[Publications] T.Yamamoto et al.: "Ship-in-Bottle Synthesis of [P_<+15>(CO)_<30>]^<2-> Encapsulated in Ordered Hexagonal Mesoporous Channels of FSM-16" J.Am.Chem.Soc.118. 5810-5811 (1996)

[Publications] M.Ichikawa et al.: "Surface-grafted Metal Oxide Clusters and Metal Carbonyl Clusters in Zeolite Micropores" J.Mol.Cat.A107. 23-38 (1996)

[Publications] M.Ichikawa et al.: "Ru,Pt and Co Clusters in Zeolite Micropores ; EXAFS/FTIR/TPI Characterization and Catalytic Behaviors for Methane Homologa" Stud.Surf.Sci.Cat.101. 1075-1084 (1996)

[Publications] T.M.Salama et al.: "EXAFS/XANES,XRD and UV-VIS Characterization of Intrazeolite Gold(I) Prepared by Monolayer Dispersion of AuCl_3" J.Phys.Chem.100. 3688-3694 (1996)

[Publications] T.M.Salama et al.: "Studies in Selective Reduction of Nitric Oxide by Carbon Monoxide in the Presence of Hydrogen over Au/NaY Catalysts" J.Chem.Soc.,Faraday Trans. 92. 301-306 (1996)

[Publications] Y.Imada et al.: "Structural Characterization of Photoreduced Complete and Incomplete Cubane Type Molybdenum Oxide Clusters" Catal.Lett.38. 101-108 (1996)

[Publications] T.M.Salama et al.: "Highly Selective Catalytic Reduction of NO by H_2 over Au^0 and Au(I) Impregnated in NaY Zeolite Catalysts" J.Catal. 162. 169-178 (1996)

[Publications] G.C.Shen et al.: "Synthesis and Reversible Decarbonylation of Zeolite-Entrappea Bimetallic Carbonyl Clusters [HCoRu_3(CO)_<13>]" J.Phys.Chem.100. 14265-14268 (1996)

[Publications] G.C.Shen et al.: "Cobalt Clusters in NaY Zeolite Cages : Synthesis and characterization" J.Phys.Chem.100. 16947-16956 (1996)

[Publications] M.Ichikawa et al.: "Ship-in-Bottle Synthesis of Pt and Ru Carbonyl Clusters in NaY Zeolite Micropore and Ordered Mesoporous Channels of FSM-16" Stud.Surf.Sci.Cat.105. 679-686 (1996)

[Publications] T.M.Salama et al.: "In situ FT-IR and Catalytic Studies of the Selective Reduction of Nitric Oxide by Carbon Monoxide over Au/NaY Catalysts" Stud.Surf.Sci.Cat.105. 1571-1578 (1996)

[Publications] F.-S.Xiao et al.: "Oxide-Supported Trirutenium Ketenylidene Clusters and their Catalytic Properties" J.Mol.Catal.A113. 427-444 (1996)

[Publications] I.Sopyan et al.: "Efficient TiO_2 Powder and Film Photocatalysts with Rutile Structure" Chem.Lett.69-70 (1996)

[Publications] I.Sopyan et al.: "An Efficient TiO_2 Thin Film Photocatalyst : Photocatalytic Properties in Gas-Phase Acetaldehyde Degradation" J.Photochem.Photobiol.98. 79-86 (1996)

[Publications] I.Sopyan et al.: "A Film-Type Photocatalyst Incorporating Highly Active TiO_2 Powder and Fluoresin Binder" J.Electroanal.415. 183-186 (1996)

[Publications] Y.Kikuchi et al.: "Photocatalytic Bactericidal Effect of TiO_2 Thin-Film : Dynamic View for the Active Oxygen Species Responsible" J.Photochem.Photobiol.(印刷中).

[Publications] K.Ikeda et al.: "Studies on Photocatalytic Reactions involving radical Chain Reaotions using Microelectrodes" J.Phys.Chem.(印刷中).

[Publications] 橋本和仁他: "光活性酸化チタンをコートしたセラミックス:抗菌、防汚機能の付与" ニューセラミックス. 48. 55-61 (1996)

[Publications] 藤嶋昭他: "光触媒が活躍開始:タイルの場合" 化学と工業. 49. 764-767 (1996)

[Publications] 池田勝佳他: "光触媒反応における酸素の関わり" 光化学. 22. 54-58 (1996)

[Publications] 橋本和仁他: "光が当たるときれいになる材料:酸化チタン光触媒の新しい応用" 現代化学. 305. 23-28 (1996)

[Publications] 橋本和仁他: "半導体光電極.光触媒反応" セラミックス. 31. 815-820 (1996)

菊地英一早稲田大学, 理工学部, 教授 (90063734)