2000 Fiscal Year Annual Research Report

ダイオキシンの低コスト無害化法の開発

Research Project

Project/Area Number	11555230
Research Institution	Osaka University
Principal Investigator	福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)
Co-Investigator(Kenkyū-buntansha)	伊東忍大阪市立大学, 大学院・理学研究科, 教授 (30184659) 末延知義大阪大学, 大学院・工学研究科, 助手 (90271030) 今堀博大阪大学, 大学院・工学研究科, 助教授 (90243261)
Keywords	ダイオキシン / 電子移動 / 触媒作用 / アクリジニウム / アルコール / ジヒドロアクリジン / 光触媒 / 反応機構
Research Abstract	人体に対する毒性が極めて強いダイオキシンが塩素系化合物を含むごみの燃焼により生成することから、大きな社会問題となっており、その対策は緊急の課題となっている。一方、アルコール工場の廃液は多量のエネルギーを消費して濃縮して焼却するか、あるいは廃液をタンカーに積んで外洋に廃棄しており、環境保全の点で問題である。本研究ではアルコール脱水素補酵素モデル化合物を光触媒として用い、アルコール工場廃液を還元剤として有効利用してダイオキシンのような有害塩素化物を太陽エネルギーにより光還元して無害化するプロセスを開発することを目的とした。この目的にかなう光触媒として電子供与性置換基を導入した各種ジヒドロアクリジン誘導体や各種合成し、その光物理,光化学,光触媒および酸化還元特性について検討することにより太陽光によるダイオキシン無害化処理のための光触媒を開発した。光触媒の構造解析および光化学特性についてはNMRおよび紫外可視分光光度計、蛍光分光光度計を用い、またその酸化還元特性についてはサイクリックボルタンメトリー装置を用いて検討した。さらにダイオキシンを濃縮して分解効率を高めるためにジヒドロアクリジン誘導体をアルミナなどの固体酸に担持した光触媒についても同様の検討を行なった。一方、光触媒としてアクリジニウム塩を用いることでパラキシレンの片側のメチル基だけを酸化して工業的に有用なパラトルアルデヒドを収率100%で得ることにも成功した。

Research Products
(32 results)

All Other

All Publications (32 results)

[Publications] Shunichi Fukuzumi et al.: "Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"J.Am.Chem.Soc.. 123・1. 100-110 (2001)
[Publications] Shunichi Fukuzumi et al.: "Photoactive Three-Dimensional Monolayers : Porphyrin-Alkanethiolate-Stabilizea Gold Clusters"J.Am.Chem.Soc.. 123・2. 335-336 (2001)
[Publications] Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on Physicochemical Properties and Redox Reactivity of Phenolates and Phenoxyl Radicals : Mechanistic Insight into Hydrogen Atom Abstraction by Phenoxyl Radical-Metal Complexes"J.Am.Chem.Soc.. 123・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Modulating Charge Separation and Charge Recombination Dynamics in Porphyrin-Fullerene Linked Dyads and Triads : Marcus-Normal versus Inverted Region,"J.Am.Chem.Soc.. 123・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on the Electronic, Redox, and Catalytic Properties of Cofactor TTQ of Quinoprotein Amine Dehydrogenases"J.Am.Chem.Soc.. 122・49. 12087-12097 (2000)
[Publications] Shunichi Fukuzumi et al.: "Photochemical Reactions of Coenzyme PQQ (Pyrroloquinolinequinone) and Analogues with Benzyl Alcohol Derivatives via Photoinduced Electron Transfer"J.Am.Chem.Soc.. 122・35. 8435-8443 (2000)
[Publications] Shunichi Fukuzumi et al.: "Hydride Transfer from 9-Substituted 10-Methyl-9, 10-dihydroacridines to Hydride Acceptors via Charge-Transfer Complexes and Sequential Electron-Proton-Electron Transfer.A Negative Temperature Dependence of the Rates"J.Am.Chem.Soc.. 122・18. 4286-4294 (2000)
[Publications] Shunichi Fukuzumi et al.: "Stepwise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122・10. 2236-2243 (2000)
[Publications] Shunichi Fukuzumi et al.: "Resonance Raman Spectroscopy as a Probe of the Bis (μ-oxo) dicopper Core"J.Am.Chem.Soc.. 122・5. 792-802 (2000)
[Publications] Shunichi Fukuzumi et al.: "Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu, Zn-SOD"J.Am.Chem.Soc.. 122・24. 5733-5741 (2000)
[Publications] Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J.Am.Chem.Soc.. 122・4. 563-570 (2000)
[Publications] Shunichi Fukuzumi et al.: "Photoinduced energy transfer in mixed self-assembled monolayers of pyrene and porphyrin"Chem.Commun.. ・8. 661-662 (2000)
[Publications] Shunichi Fukuzumi et al.: "Catalytic effect of monovalent cations on the amine oxidation by cofactor TTQ of quinoprotein amine dehydrogenases"Chem.Commun.. ・5. 329-330 (2000)
[Publications] Shunichi Fukuzumi et al.: "Regioreversed Thermal and Photochemical Reduction of 10-Methylacridinium and 1-Methylquinolinium Ions by Organosilanes and Oraganostannanes"J.Phys.Chem.A. 105・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・2. 325-332 (2001)
[Publications] Shunichi Fukuzumi et al.: "Effects of Lowering Symmetry on the ESR Spectra of Radical Anions of Fullerene Derivatives and the Reduction Potentials"J.Phys.Chem.A. 104・46. 10688-10694 (2000)
[Publications] Shunichi Fukuzumi et al.: "Effect of Addition Pattern on the Electrochemical and Spectroscopic Properties of Neutral and Reduced 1,2-and 1,4-(C_6H_5CH_2)_2C_<60> Isomers"J.Phys.Chem.A. 104・17. 3878-3883 (2000)
[Publications] Shunichi Fukuzumi et al.: "Splitting of Degenerate Orbitals of Dibenzyl and Tetrabenzyl Adducts of C_<60> : ESR of the Radical Anions and the Rotation Barriers of Benzyl Groups"J.Phys.Chem.A. 104・13. 2908-2913 (2000)
[Publications] Shunichi Fukuzumi et al.: "Electrogeneration and Characterization of (C_6H_5CH_2)_2C_<70>"J.Phys.Chem.A. 104・13. 2902-2907 (2000)
[Publications] Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2001)
[Publications] Shunichi Fukuzumi et al.: "Photochemical Generation of Cyclopentadienyliron Dicarbonyl Anion by a Nicotinamide Adenine Dinucleotide Dimer Analogue"Inorg.Chem.. 40・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Model Complexes for the Active Form of Galactose Oxidase. Physicochemical Properties of Cu(II)-and Zn(II)-Phenoxyl Radical Complexes"Inorg.Chem.. 39・16. 3708-3711 (2000)
[Publications] Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)
[Publications] Shunichi Fukuzumi et al.: "Aliphatic Hydroxylation by a Bis (μ-oxo) dicopper (III) Complex"Angew.Chem.Int.Ed.. 39・2. 398-400 (2000)
[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from the g Values of ESR Spectra of Superoxide : Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions"Chem.Eur.J. 6・24. 4532-4535 (2000)
[Publications] Shunichi Fukuzumi et al.: "The Essential Role of a Zn^<II> Ion in the Disproportionation of Semiquinone Radical Anion by an Imidazolate-Bridged Cu^<II>-Zn^<II> Model of Superoxide Dismutase"Angew.Chem.Int.Ed.. 39・24. 4537-4539 (2000)
[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu (II)-Zn (II) Heterodinuclear and Cu (II)-Cu (II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)
[Publications] Shunichi Fukuzumi et al.: "Remarkable enhancement of photocurrent generation by ITO electrodes modified with a self-assembled monolayer of porphyrin"Chem.Commun.. ・19. 1921-1922 (2000)
[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.2"Wiley-VCH (in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.4"Wiley-VCH (in press). (2001)

2000 Fiscal Year Annual Research Report

ダイオキシンの低コスト無害化法の開発

Principal Investigator

福住 俊一 大阪大学, 大学院・工学研究科, 教授 (40144430)

Research Products

[Publications] Shunichi Fukuzumi et al.: "Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"J.Am.Chem.Soc.. 123・1. 100-110 (2001)

[Publications] Shunichi Fukuzumi et al.: "Photoactive Three-Dimensional Monolayers : Porphyrin-Alkanethiolate-Stabilizea Gold Clusters"J.Am.Chem.Soc.. 123・2. 335-336 (2001)

[Publications] Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on Physicochemical Properties and Redox Reactivity of Phenolates and Phenoxyl Radicals : Mechanistic Insight into Hydrogen Atom Abstraction by Phenoxyl Radical-Metal Complexes"J.Am.Chem.Soc.. 123・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Modulating Charge Separation and Charge Recombination Dynamics in Porphyrin-Fullerene Linked Dyads and Triads : Marcus-Normal versus Inverted Region,"J.Am.Chem.Soc.. 123・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on the Electronic, Redox, and Catalytic Properties of Cofactor TTQ of Quinoprotein Amine Dehydrogenases"J.Am.Chem.Soc.. 122・49. 12087-12097 (2000)

[Publications] Shunichi Fukuzumi et al.: "Photochemical Reactions of Coenzyme PQQ (Pyrroloquinolinequinone) and Analogues with Benzyl Alcohol Derivatives via Photoinduced Electron Transfer"J.Am.Chem.Soc.. 122・35. 8435-8443 (2000)

[Publications] Shunichi Fukuzumi et al.: "Stepwise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122・10. 2236-2243 (2000)

[Publications] Shunichi Fukuzumi et al.: "Resonance Raman Spectroscopy as a Probe of the Bis (μ-oxo) dicopper Core"J.Am.Chem.Soc.. 122・5. 792-802 (2000)

[Publications] Shunichi Fukuzumi et al.: "Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu, Zn-SOD"J.Am.Chem.Soc.. 122・24. 5733-5741 (2000)

[Publications] Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J.Am.Chem.Soc.. 122・4. 563-570 (2000)

[Publications] Shunichi Fukuzumi et al.: "Photoinduced energy transfer in mixed self-assembled monolayers of pyrene and porphyrin"Chem.Commun.. ・8. 661-662 (2000)

[Publications] Shunichi Fukuzumi et al.: "Catalytic effect of monovalent cations on the amine oxidation by cofactor TTQ of quinoprotein amine dehydrogenases"Chem.Commun.. ・5. 329-330 (2000)

[Publications] Shunichi Fukuzumi et al.: "Regioreversed Thermal and Photochemical Reduction of 10-Methylacridinium and 1-Methylquinolinium Ions by Organosilanes and Oraganostannanes"J.Phys.Chem.A. 105・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・2. 325-332 (2001)

[Publications] Shunichi Fukuzumi et al.: "Effects of Lowering Symmetry on the ESR Spectra of Radical Anions of Fullerene Derivatives and the Reduction Potentials"J.Phys.Chem.A. 104・46. 10688-10694 (2000)

[Publications] Shunichi Fukuzumi et al.: "Effect of Addition Pattern on the Electrochemical and Spectroscopic Properties of Neutral and Reduced 1,2-and 1,4-(C_6H_5CH_2)_2C_<60> Isomers"J.Phys.Chem.A. 104・17. 3878-3883 (2000)

[Publications] Shunichi Fukuzumi et al.: "Splitting of Degenerate Orbitals of Dibenzyl and Tetrabenzyl Adducts of C_<60> : ESR of the Radical Anions and the Rotation Barriers of Benzyl Groups"J.Phys.Chem.A. 104・13. 2908-2913 (2000)

[Publications] Shunichi Fukuzumi et al.: "Electrogeneration and Characterization of (C_6H_5CH_2)_2C_<70>"J.Phys.Chem.A. 104・13. 2902-2907 (2000)

[Publications] Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2001)

[Publications] Shunichi Fukuzumi et al.: "Photochemical Generation of Cyclopentadienyliron Dicarbonyl Anion by a Nicotinamide Adenine Dinucleotide Dimer Analogue"Inorg.Chem.. 40・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Model Complexes for the Active Form of Galactose Oxidase. Physicochemical Properties of Cu(II)-and Zn(II)-Phenoxyl Radical Complexes"Inorg.Chem.. 39・16. 3708-3711 (2000)

[Publications] Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)

[Publications] Shunichi Fukuzumi et al.: "Aliphatic Hydroxylation by a Bis (μ-oxo) dicopper (III) Complex"Angew.Chem.Int.Ed.. 39・2. 398-400 (2000)

[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from the g Values of ESR Spectra of Superoxide : Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions"Chem.Eur.J. 6・24. 4532-4535 (2000)

[Publications] Shunichi Fukuzumi et al.: "The Essential Role of a Zn^<II> Ion in the Disproportionation of Semiquinone Radical Anion by an Imidazolate-Bridged Cu^<II>-Zn^<II> Model of Superoxide Dismutase"Angew.Chem.Int.Ed.. 39・24. 4537-4539 (2000)

[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu (II)-Zn (II) Heterodinuclear and Cu (II)-Cu (II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)

[Publications] Shunichi Fukuzumi et al.: "Remarkable enhancement of photocurrent generation by ITO electrodes modified with a self-assembled monolayer of porphyrin"Chem.Commun.. ・19. 1921-1922 (2000)

[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.2"Wiley-VCH (in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry,Vol.4"Wiley-VCH (in press). (2001)

福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)