2003 Fiscal Year Annual Research Report

酸化チタン/ゼオライト光触媒系による二酸化炭素の水による還元固定化反応

Research Project

Project/Area Number	15033263
Research Institution	Osaka Prefecture University
Principal Investigator	安保正一大阪府立大学, 工学研究科, 教授 (70094498)
Co-Investigator(Kenkyū-buntansha)	ザンペイソフノルボシン大阪府立大学, 工学研究科, 助手 (10326275) 松岡雅也大阪府立大学, 工学研究科, 助手 (80305648) 山下弘巳大阪大学, 大学院・工学研究科, 教授 (40200688)
Keywords	光触媒 / 二酸化炭素還元固定化 / 可視光利用 / メソポーラスゼオライト / イオン注入 / メタノール生成 / 表面疎水化 / 高分散酸化チタン
Research Abstract	本研究では、メソ多孔体シリカ中にTiを含有した触媒(Ti-HMS)を合成し、それを光触媒として二酸化炭素の水による還元固定化反応について検討し、生成物選択性におよぼす触媒表面の疎水化処理の影響について検討した。各種分光測定によりTi-HMS中ではTi種は高分散かつ四配位構造の酸化物種として骨格内に構築されていることがわかった。また、Ti-MCM-41などの四配位構造の酸化チタン種を有する各種のTi含有メソ多孔体光触媒と比較するとTi-HMSではメタン選択性が高いことを見いだした。これはTi-HMS上では表面OH基が多いことに基づくものと考えられる。Ti-TMS光触媒のメタノール選択性の向上を図るためにNH_4F処理を行い、触媒表面の疎水化を検討した。NH_4F処理後の触媒では未処理の触媒と比較して表面OH基に基づくIRピークの強度が小さくなり、表面が疎水化することが確かめられた。この疎水化処理したTi-HMSを光触媒として二酸化炭素の水による還元固定化反応について検討した結果、NH_4F処理後では光触媒活性は低下するが、未処理のものと比較してメタノールの生成収量は増加し、約5倍以上の選択性でメタノールを生成できることを見いだした。さらに、イオン注入法を適用して、Ti-HMSの可視光化について検討した。Vイオンを注入するとTi-HMSのUV-Vis吸収スペクトルは長波長側にシフトし可視光を吸収することがわかった。また、Vイオン注入Ti-HMSのEXAFS測定により、Vイオンは孤立四配位状態で存在するとともに四配位構造のTi酸化物種に隣接しTi-O-V結合を形成し、このためTi酸化物種の電子状態に摂動が生じ可視光吸収が可能となることがわかった。この可視光応答型のVイオン注入Ti-HMSを光触媒として、390nmより長波長の光照射下で二酸化炭素の水による還元固定化反応が進行することを見いだした。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] Y.Hu, G.Martra, S.Higashimoto, JL.Zhang, M.Matsuoka, S.Coluccia, M.Anpo: "The Relationship between the Local Structures and Photocatalytic Reactivity of Ti-MCM-41 Catalysts"Stud.Surf.Sci.Catal.. 146. 593-596 (2003)
[Publications] Y.Shioya, K.Ikeue, M.Ogawa, M.Anpo: "Synthesis of Transparent Ti-containing Mesoporous Silica Thin Film Materials and Their Unique Photocatalytic Activity for the Reduction of CO_2 with H_2O"Appl.Catal.A : General. 254. 251-259 (2003)
[Publications] K.Iino, M.Anpo: "Atomic Level Characterization by Synchrotron Radiation for the Design of High Performance Catalysts"Res.Chem.Intermed.. 29. 773-782 (2003)
[Publications] M.Anpo, M.Takeuchi: "The Design and Development of Highly Reactive Titanium Oxide Photocatalysts Operating under Visible Light Irradiation"J.Catal.. 216. 505-516 (2003)
[Publications] M.Anpo, H.Yamashita, N.U.Zhanpeisov, M.Matsuoka, Y.Kanazawa, M.Okazaki: "Design and Development of Environmentally-Harmonious Ti/Zeolite Photocatalysts"Proc.4th Intern.Symp.on Eco-Mater.Process & Design. 63-66 (2003)
[Publications] M.Matsuoka, M.Anpo: "Local structures, Excited states, and Photocatalytic Reactivities of Highly Dispersed Catalysts Constructed within Zeolites"J.Photochem.Photobiol.C : Photochem.Rev.. 3. 225-252 (2003)
[Publications] S.Dohshi, M.Takeuchi, M.Anpo: "Effect of the Local Structure of Ti-oxide Species on the Photocatalytic Reactivity and Photoinduced Super-hydrophilic Properties of Ti/Si and Ti/B Binary Oxide Thin Films"Catal.Today. 85. 199-206 (2003)
[Publications] H.Yamashita, K.Maekawa, Y.Nakatani, J.-J.Park, M.Anpo: "Photocatalytic Degradation of 2-Propanol Diluted in Water with TiO_2 Photocatalyst Loaded on Si_3N_4"Chem.Lett.. 10. 930-931 (2003)
[Publications] J.Zhang, H.Xu, H.Chen, M.Anpo: "Study on the Formation of H_2O_2 on TiO_2 Photocatalysts and Their Activity for the Photocatalytic Degradation of X-GL dye"Res.Chem.Intermed.. 29. 839-848 (2003)
[Publications] M.Takeuchi, S.Dohshi, T.Eura, M.Anpo: "Preparation of Titanium-Silicon Binary Oxide Thin Film Photocatalysts by an Ionized Clust Beam Deposition Method. Their Photocatalytic Activity and Photoinduced Super-Hydrophilici"J.Phys.Chem.B. 107. 14278-14282 (2003)
[Publications] M.Takeuchi, K.Tsujimaru, K.Sakamoto, M.Matsuoka, H.Yamashita, M.Anpo: "Effect of Pt Loading on the Photocatalytic Reactivity of Titanium Oxide Thin Films Prepared by Ion Engineering Techniques"Res.Chem.Intermed. 29. 619-629 (2003)
[Publications] H.Yamashita, M.Harada, J.Misaka, H.Nakao, M.Takeuchi, M.Anpo: "Application of Ion Beams for Preparation of TiO_2 Thin Film Photocatalysts Operatable under Visible Light Irradiation : Ion-assisted Deposition and Metal Ion-implantation"Nuclear Instrument and Method in Physics Research B. 206. 889-892 (2003)
[Publications] H.Yamashita, H.Nakao, M.Okazaki, M.Anpo: "Preparation of Hydrophobic Ti-containing Mesoporous Silica by the F-modificatio and Their Photocatalytic Degradation of Organic Pollutant Diluted in Water"Stud.Surf.Sci.Catal.. 795-798 (2003)
[Publications] H.Yamashita, K.Kida, K.Ikeue, Y.Kanazawa, K.Yoshizawa, M.Anpo: "Photocatalytic Epoxidation of Propene with Molecular Oxygen under Visible Light Irradiation on V Ion-implanted Ti-HMS and Cr-HMS Mesoporous Molecular Sieve"Stud.Surf.Sci.Catal. 597-600 (2003)
[Publications] S.C.Moon, Y.Matsumura, M.Kitano, M.Matsuoka, M.Anpo: "Hydrogen production using semiconducting oxide photocatalysts"Res.Chem.Intermed. 29. 233-256 (2003)
[Publications] Y.Hu, S.Higashimoto, G.Martra, JL.Zhang, M.Matsuoka, S.Coluccia, M.Anpo: "Local Structures of Active Sites on Ti-MCM-41 and Their Photocatalytic Reactivity for the Decomposition of NO"Catal.Lett. 90. 161-163 (2003)
[Publications] H.Yamashita, M.Harada, J.Misaka, M.Takeuchi, B.Neppolian, M.Anpo: "Photocatalytic Degradation of Organic Compounds Diluted in Water using Visible Light-responsive Metal Ion-implanted TiO2 Catalysts : Fe Ion-implanted TiO2"Catal.Today. 84. 191-196 (2003)
[Publications] Y.Hu, JL.Zhang, M.Minagawa, T.Ayusawa, M.Matsuoka, H.Yamashita, M.Anpo: "The Origin of the Decline in the Photocatalytic Activity of TiO_2 in the Decomposition of NO : TPD Spectra of the Adsorbed NO Species"Res.Chem.Intermed. 29. 125-136 (2003)
[Publications] M.Anpo, M.Takeuchi, H.Yamashita, S.Kishiguchi, A.Davidson, M.Che: "Semiconductor Photochemistry and Photophysics "Design and Development of New Titanium Dioxide Semiconductor Photocatalysts"(Eds. by V.Ramamurthy and K.S.Schanze)"Marcel Dekker, New York. 283-299 (2003)
[Publications] 安保正一(分担執筆): "先端科学シリーズI"可視光応答型の高機能な酸化チタン光触媒の開発"(日本化学会編)"丸善. 170-179 (2003)
[Publications] 安保正一: "イオン工学ハンドブック"環境調和型触媒としての光触媒""イオン工学研究所. 955-964 (2003)

2003 Fiscal Year Annual Research Report

酸化チタン/ゼオライト光触媒系による二酸化炭素の水による還元固定化反応

Principal Investigator

安保 正一 大阪府立大学, 工学研究科, 教授 (70094498)

Research Products

[Publications] Y.Hu, G.Martra, S.Higashimoto, JL.Zhang, M.Matsuoka, S.Coluccia, M.Anpo: "The Relationship between the Local Structures and Photocatalytic Reactivity of Ti-MCM-41 Catalysts"Stud.Surf.Sci.Catal.. 146. 593-596 (2003)

[Publications] Y.Shioya, K.Ikeue, M.Ogawa, M.Anpo: "Synthesis of Transparent Ti-containing Mesoporous Silica Thin Film Materials and Their Unique Photocatalytic Activity for the Reduction of CO_2 with H_2O"Appl.Catal.A : General. 254. 251-259 (2003)

[Publications] K.Iino, M.Anpo: "Atomic Level Characterization by Synchrotron Radiation for the Design of High Performance Catalysts"Res.Chem.Intermed.. 29. 773-782 (2003)

[Publications] M.Anpo, M.Takeuchi: "The Design and Development of Highly Reactive Titanium Oxide Photocatalysts Operating under Visible Light Irradiation"J.Catal.. 216. 505-516 (2003)

[Publications] M.Anpo, H.Yamashita, N.U.Zhanpeisov, M.Matsuoka, Y.Kanazawa, M.Okazaki: "Design and Development of Environmentally-Harmonious Ti/Zeolite Photocatalysts"Proc.4th Intern.Symp.on Eco-Mater.Process & Design. 63-66 (2003)

[Publications] M.Matsuoka, M.Anpo: "Local structures, Excited states, and Photocatalytic Reactivities of Highly Dispersed Catalysts Constructed within Zeolites"J.Photochem.Photobiol.C : Photochem.Rev.. 3. 225-252 (2003)

[Publications] S.Dohshi, M.Takeuchi, M.Anpo: "Effect of the Local Structure of Ti-oxide Species on the Photocatalytic Reactivity and Photoinduced Super-hydrophilic Properties of Ti/Si and Ti/B Binary Oxide Thin Films"Catal.Today. 85. 199-206 (2003)

[Publications] H.Yamashita, K.Maekawa, Y.Nakatani, J.-J.Park, M.Anpo: "Photocatalytic Degradation of 2-Propanol Diluted in Water with TiO_2 Photocatalyst Loaded on Si_3N_4"Chem.Lett.. 10. 930-931 (2003)

[Publications] J.Zhang, H.Xu, H.Chen, M.Anpo: "Study on the Formation of H_2O_2 on TiO_2 Photocatalysts and Their Activity for the Photocatalytic Degradation of X-GL dye"Res.Chem.Intermed.. 29. 839-848 (2003)

[Publications] M.Takeuchi, S.Dohshi, T.Eura, M.Anpo: "Preparation of Titanium-Silicon Binary Oxide Thin Film Photocatalysts by an Ionized Clust Beam Deposition Method. Their Photocatalytic Activity and Photoinduced Super-Hydrophilici"J.Phys.Chem.B. 107. 14278-14282 (2003)

[Publications] M.Takeuchi, K.Tsujimaru, K.Sakamoto, M.Matsuoka, H.Yamashita, M.Anpo: "Effect of Pt Loading on the Photocatalytic Reactivity of Titanium Oxide Thin Films Prepared by Ion Engineering Techniques"Res.Chem.Intermed. 29. 619-629 (2003)

[Publications] H.Yamashita, H.Nakao, M.Okazaki, M.Anpo: "Preparation of Hydrophobic Ti-containing Mesoporous Silica by the F-modificatio and Their Photocatalytic Degradation of Organic Pollutant Diluted in Water"Stud.Surf.Sci.Catal.. 795-798 (2003)

[Publications] H.Yamashita, K.Kida, K.Ikeue, Y.Kanazawa, K.Yoshizawa, M.Anpo: "Photocatalytic Epoxidation of Propene with Molecular Oxygen under Visible Light Irradiation on V Ion-implanted Ti-HMS and Cr-HMS Mesoporous Molecular Sieve"Stud.Surf.Sci.Catal. 597-600 (2003)

[Publications] S.C.Moon, Y.Matsumura, M.Kitano, M.Matsuoka, M.Anpo: "Hydrogen production using semiconducting oxide photocatalysts"Res.Chem.Intermed. 29. 233-256 (2003)

[Publications] Y.Hu, S.Higashimoto, G.Martra, JL.Zhang, M.Matsuoka, S.Coluccia, M.Anpo: "Local Structures of Active Sites on Ti-MCM-41 and Their Photocatalytic Reactivity for the Decomposition of NO"Catal.Lett. 90. 161-163 (2003)

[Publications] H.Yamashita, M.Harada, J.Misaka, M.Takeuchi, B.Neppolian, M.Anpo: "Photocatalytic Degradation of Organic Compounds Diluted in Water using Visible Light-responsive Metal Ion-implanted TiO2 Catalysts : Fe Ion-implanted TiO2"Catal.Today. 84. 191-196 (2003)

[Publications] Y.Hu, JL.Zhang, M.Minagawa, T.Ayusawa, M.Matsuoka, H.Yamashita, M.Anpo: "The Origin of the Decline in the Photocatalytic Activity of TiO_2 in the Decomposition of NO : TPD Spectra of the Adsorbed NO Species"Res.Chem.Intermed. 29. 125-136 (2003)

[Publications] M.Anpo, M.Takeuchi, H.Yamashita, S.Kishiguchi, A.Davidson, M.Che: "Semiconductor Photochemistry and Photophysics "Design and Development of New Titanium Dioxide Semiconductor Photocatalysts"(Eds. by V.Ramamurthy and K.S.Schanze)"Marcel Dekker, New York. 283-299 (2003)

[Publications] 安保正一(分担執筆): "先端科学シリーズI"可視光応答型の高機能な酸化チタン光触媒の開発"(日本化学会編)"丸善. 170-179 (2003)

[Publications] 安保正一: "イオン工学ハンドブック"環境調和型触媒としての光触媒""イオン工学研究所. 955-964 (2003)

安保正一大阪府立大学, 工学研究科, 教授 (70094498)