2000 Fiscal Year Annual Research Report

半導体薄膜電極法による有機汚染物質の光分解に関する研究

Research Project

Project/Area Number	10640569
Research Institution	Meisei University
Principal Investigator	日高久夫明星大学, 理工学部, 教授 (70062312)
Keywords	光分解 / 光酸化 / 二酸化チタン / 半導体電極 / 光エネルギー変換 / 環境汚染物質分解 / ITO / TCO
Research Abstract	水質汚染有機化合物の代表的な物質の界面活性剤を光分解して、光電流のエネルギーに変換する方法を開発した。基礎的な原理は水溶性有機化合物を導電性ガラスに二酸化チタンを固定した電極の触媒の働きにより有機化合物を酸化する。CO_2ガスに無機化前に、ギ酸や酢酸のカルボン酸に分解できるが、電荷分離および分解に伴う電子発生(電流二倍効果)により光電流を取得した。最適なナノサイズTiO_2薄膜電極を作ることが最大のポイントである。NaCl電解質中での有機化合物の分解速度およびCO_2発生量に対する光電流値を求めた。外部電圧を加えることにより、光電流が増加した。特にTiO_2薄膜特性について(1)ゾルゲル法、(2)ペースト法とゾルゲル法を組み合わせたハイブリッド法、(3)パルスレーザー法による薄膜の作成について検討した。パルスCO_2レーザー法によるTiO_2/TCOガラス電極薄膜では、真空中の光反応容器中にTCO基板と四塩化チタン(TiCl_4)や水素(H_2)、酸素(O_2)をガス状態で導入し、レーザーの誘電破壊によりTCO基板上にTiO_2薄膜を生成した。この方法では高純度な均一薄膜で表面が平坦な基板が作成できた。H_2分圧とO_2の分圧の割合により高純度のアナターゼ型基板が作成できた。パルスレーザー法でTiCl_4:H_2:O_2が10:50:50torrの条件下では、98%アナターゼ結晶で高触媒活性の格子欠陥の少ない薄膜(膜厚0.4μm、典型的なモアレパターンの結晶格子)が得られた。光分解過程中で生じた最大光電流値は3mA/cm^2で、SEM観察によると4層分の厚さの二酸化チタン薄膜であつた。界面活性剤以外に、いろいろな色素、高分子、グルコースの糖類誘導体などについても、化学構造に対する光分解の関係を明らかにした。太陽光照射でも環境汚染化合物の分解が進行した。光酸化過程で生じる光電流を取得できる一種の"ソーラーセル"のシステムを考案した。

Research Products

(35 results)

All Other

All Publications (35 results)

[Publications] H.Hidaka,K.Ajisaka,S.Horikoshi,T.Oyama,: "Comparative assessment of the efficiency of TiO_2/OTE thin film electrodes fabrieated by three deposition methods. Photoelectrochemical degradation of two anione surfactants"J.Photochem.Photobiol.A : Chem.,. (in press). (2000)
[Publications] H.Hidaka,K.Ajisaka,: "Photodecomposition of amino acids and photocurrent generation on TiO_2/H_2O electrodes prepared by pulse laser deposition"Catal.Lett.. 60,. 95-98 (1999)
[Publications] 日高久夫,堀越智,趙進才: "二酸化チタン分散系における界面活性剤の光分解,"オレオサイエンス,(総説). 1,. 55-73 (2001)
[Publications] G.Liu,X.Li.,J.Zhao,H.Hidaka N.Serpone,: "Photoxidation pathway of sulforhodamine-B. Dependence on the adsorption mode on TiO_2 exposed to visible light radiation"Environ.Sci.Technol.,. 34. 3982-3990 (2000)
[Publications] N.Serpone,I.Texier,A.V.Emeline,P.Pichat,H.Hidaka and J.Zhao: "Post-irradiation effect and reductive dechlorination of chlorophenols at oxygen-free TiO_2/water inferfaces in the presence of prominent hole scavengers"J.Photochem.Photobiol.A : Chem.,. 136,. 145-155 (2000)
[Publications] S.Higashimoto,M.Matsuoka,H.Yamashita,M.Anpo,O.Kitao,H.Hidaka,: "Effect of the Si/Al ratio on the local structure of V-oxide/ZSM-5 catalysts prepared by the solid-state reaction of HZSM-5 with decomposition of NO in the abseuce and presence of propene"J.Phys.Chem.,. 104,. 10288-10292 (2000)
[Publications] G.Liu,J.Zhao and H.Hidaka: "ESR spin-trapping detection of radical intermediates in the TiO_2-assisted photooxidation of sulforhodamine B under visible irradiation"J.Photochem.Photobiol.A : Chem.,. 133,. 83-88 (2000)
[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Mechanistic study of the TiO_2-assisted photodegradation of squarylium cyanide dye in methanolic suspensions exposed to visible light"New J.Chem.,. 24,. 93-98 (2000)
[Publications] H.Horikoshi,N.Watanabe and H.Hidaka: "Photocatalyltic wastewater treatment for 4-nonylphenol of an endocrine disruptor and 4-nonyophenol polyethoxylate surfactant at the titania/water interface"J.Jpn.Oil Chem.Soc.,. 49,. 631-639 (2000)
[Publications] G.Liu,X.Li,J.Zhao,S.Horikoshi and H.Hidaka: "Photooxidation mechanism of dye alizarin red in TiO_2 dispersions under visible illumination : an experimental and theoretical examination"J.Mol.Catal.A : Chem.,. 153,. 221-229 (2000)
[Publications] K.Waki,J.Zhao,S.Horikoshi,K.Arai,N.Watanabe H.Hidaka,: "Photooxidation mechanism of nitrogen-containing compounds at TiO_2/H_2O interfaces : an experimental and theoretical examination of hydrazine derivatives"Chemoshere,. 41,. 337-343 (2000)
[Publications] G.Liu,T.Wu,J.Zhao,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants VIII : Irreversible degradation of Alizarin Red under visible light irradiation in air-equilibrated aqueous TiO_2 dispersion "Environ.Sci.Technol.,. 33,. 2081-2087 (1999)
[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Evidence for H_2O_2 generation during the TiO_2 assisted photodegradation of dyes in aqueous dispersions under visible light illumination"J.Phys.Chem.,. 103,. 4862-4867 (1999)
[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "TiO_2-assisted photodegradation of dyes IX : Photooxidation of squaryliu cyanine dye in aqueous dispersions under visible light irradiation"Environ.Sci.Technol.,. 33,. 1379-1387 (1999)
[Publications] K.Wu,Y.Xie,J.Zhao and H.Hidaka,: "Photo-Fenton degradation of a dye under visible light irradiation"J.Mol.Catal.A : Chem.,. 142,. 49-57 (1999)
[Publications] S.Horikoshi,J.Zhao and H.Hikaka,: "Photodegradation of surfactants. XIX : Photooxidation mechanism for nonionic dodecanoyl amide surfactants at TiO_2/H_2O interfaces"J.Jpn.Oil Chem.Soc.,. 48,. 767-774 (1999)
[Publications] S.Horikoshi,N.Serpone,S.Yoshizawa.J.Knowland and H.Hidaka,: "Photocatalyzed degradation of polymers in aqueous semiconductor suspensions. IV. Theoretical and experimental examination of the photooxidative mineralization of constituent bases in nucleic acids"J.Photochem.Photobiol.A : Chem.,. 120,. 63-74 (1999)
[Publications] A.Salinaro,A.Emeline,J.Zhao,H.Hidaka,V.Ryabchuck and N.Serpone,: "Terminology, relative photonic efficiency, and quantum yields in hetero-generous (solid/liquid) photocatalysis. Part II ; Experimental determination of quantum yields"Pure & Appl.Chem.,. 71,. 321-335 (1999)
[Publications] J.He,F.Chen,J.Zhao and H.Hidaka: "Adsorption mode of ethyl ester of fluorescein on colloidal TiO_2 and the mechanism of the interfacial electron transfer"Colloids & Surfaces,. 142,. 49-57 (1998)
[Publications] P.Qu,J.Zhao,L.Zang,T.Shen and H.Hidaka,: "Enhancement of the photoinduced electron transfer from cationic dyes to colloidal TiO_2 particles by addition of an anionic surfactant in acidic media"Colloids & Surfaces,. 138,. 39-50 (1998)
[Publications] J.He,J.Zhao,H.Hidaka and N.Serpone,: "EPR characteristics of a dye-colloidal TiO_2 system under visible light irradation"J.Chem.Soc.Faraday Trans.2.,. 94,. 2375-2378 (1998)
[Publications] S.Horikashi,N.Serpone,J.Zhao and H.Hidaka,: "Towards a better understanding of the initial steps in the photocatalyzed mineralization of amino acids at the titania/water interface.-An experimental and theoretical examination of L-alanine, L-serine and L-phenylalanine"J.Photochem.Photobiol.A : Chem.,. 118,. 123-129 (1998)
[Publications] 堀越智,日高久夫: "半導体触媒TiO_2を用いた高分子の光分解"色材,. 71,. 176-185 (1998)
[Publications] N.Serpone,A.Salinaro,H.Hidaka,S.Horikoshi,J.Knowland Dunford,: "Beneficial and deleterious effects of solar radiation"Solar Engineering 1998.J.M.Morehouse & R.E.Hogan, Eds.,ASME, New York,. 287-298 (1998)
[Publications] S.Horikoshi,H.Hidaka,Y.Hisamatsu and N.Serpone,: "Photocatalyzed degradation of polymers in aqueous semiconductor suspensions III. An optimum photooxidation for solid polymers of TiO_2-blended polyvinylchloride film"Environ.Sci.Technol.,. 32,. 4010-4016 (1998)
[Publications] J.Zhao,K.Wu,T.Wu,H.Hidaka and N.Serpone.: "Photodegradation of dyes with poor solubility in an aqueous solubility in an aqueous surfactat/TiO_2 dispersion under visible light irradiation"J.Chem.Soc.Faraday Trans.,. 94,. 673-676 (1998)
[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants. V. Self-photooxidative transformation of PhB under visible light irradiation in aqueous TiO_2 dispersions"J.Phys.Chem.,B,. 102,. 5848-5851 (1998)
[Publications] J.Zhao,T.Wu,K.Wu,K.Oikawa,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants.III. Evidence for the need of substrate adsorption on TiO_2 particles"Environ.Sci.Technol.,. 32,. 2394-2400 (1998)
[Publications] F.Zhang,J.Zhao,T.Shen,H.Hidaka,E.Pelizzeetti and N.Serpone,: "What becomes of nitrogen in the photoelectrochemical and photocatalyzed mineralization of N-containing substances at titania/water interfaces?"Appl.Catal.B.; Environ.,. 15,. 147-156 (1998)
[Publications] N.Serpone,P.Calze,A Slinaro,L.Cai,A.Emiline,H.Hidaka and E.Pelizzetti,: "Photoassisted degradation of dye pollutants II. Adsorption and degradation kietics of eosin in TiO_2 dispersions under visible light irradiation"Proc.of Conf.of Electrochem.Soc.,August 1997,Paris,. 97-20,. 301-320 (1998)
[Publications] K.Wu,T.Zhang,J.Zhao and H.Hidaka,: "Photodegradation of malachite green in the presence of Fe^<3+>/H_2O_2 under visible light"Chem.Lett.,. 857-858 (1998)
[Publications] Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants V : Self-photosensitized oxidative transformation of Rhodamine B under visible light irradiation in aqueous TiO_2 dispersions"J.Phys.Chem.,. 102,. 5845-5851 (1998)
[Publications] P.Qu,J.Zhao,T.Shen and H.Hidaka,: "TiO_2-assisted photodegradation of dyes : A study of two competitive primary processes in the degradation of RB in an aqueous TiO_2 colloidal solution"J.Mol.Catal.,. 129,. 257-268 (1998)
[Publications] H.Hidaka,: "Photodegradation of surfactants with TiO_2 semiconductor for the environmental wastewater treatment,"Proc.Indian Acad.Sci.(Chem.Sci.),. 110,. 215-228 (1998)
[Publications] J.Zhao,K.Wu,T.Wu,H.Hidaka and N.Serpone,: "Photodegradation of dyes with poor solubility in an aqueous srufactant/TiO_2 dispersion under visible light irradiation,"J.Chem.Soc.Faraday Trans.,. 94,. 673-676 (1998)

2000 Fiscal Year Annual Research Report

半導体薄膜電極法による有機汚染物質の光分解に関する研究

Principal Investigator

日高 久夫 明星大学, 理工学部, 教授 (70062312)

Research Products

[Publications] H.Hidaka,K.Ajisaka,S.Horikoshi,T.Oyama,: "Comparative assessment of the efficiency of TiO_2/OTE thin film electrodes fabrieated by three deposition methods. Photoelectrochemical degradation of two anione surfactants"J.Photochem.Photobiol.A : Chem.,. (in press). (2000)

[Publications] H.Hidaka,K.Ajisaka,: "Photodecomposition of amino acids and photocurrent generation on TiO_2/H_2O electrodes prepared by pulse laser deposition"Catal.Lett.. 60,. 95-98 (1999)

[Publications] 日高久夫,堀越智,趙進才: "二酸化チタン分散系における界面活性剤の光分解,"オレオサイエンス,(総説). 1,. 55-73 (2001)

[Publications] G.Liu,X.Li.,J.Zhao,H.Hidaka N.Serpone,: "Photoxidation pathway of sulforhodamine-B. Dependence on the adsorption mode on TiO_2 exposed to visible light radiation"Environ.Sci.Technol.,. 34. 3982-3990 (2000)

[Publications] N.Serpone,I.Texier,A.V.Emeline,P.Pichat,H.Hidaka and J.Zhao: "Post-irradiation effect and reductive dechlorination of chlorophenols at oxygen-free TiO_2/water inferfaces in the presence of prominent hole scavengers"J.Photochem.Photobiol.A : Chem.,. 136,. 145-155 (2000)

[Publications] G.Liu,J.Zhao and H.Hidaka: "ESR spin-trapping detection of radical intermediates in the TiO_2-assisted photooxidation of sulforhodamine B under visible irradiation"J.Photochem.Photobiol.A : Chem.,. 133,. 83-88 (2000)

[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Mechanistic study of the TiO_2-assisted photodegradation of squarylium cyanide dye in methanolic suspensions exposed to visible light"New J.Chem.,. 24,. 93-98 (2000)

[Publications] H.Horikoshi,N.Watanabe and H.Hidaka: "Photocatalyltic wastewater treatment for 4-nonylphenol of an endocrine disruptor and 4-nonyophenol polyethoxylate surfactant at the titania/water interface"J.Jpn.Oil Chem.Soc.,. 49,. 631-639 (2000)

[Publications] G.Liu,X.Li,J.Zhao,S.Horikoshi and H.Hidaka: "Photooxidation mechanism of dye alizarin red in TiO_2 dispersions under visible illumination : an experimental and theoretical examination"J.Mol.Catal.A : Chem.,. 153,. 221-229 (2000)

[Publications] K.Waki,J.Zhao,S.Horikoshi,K.Arai,N.Watanabe H.Hidaka,: "Photooxidation mechanism of nitrogen-containing compounds at TiO_2/H_2O interfaces : an experimental and theoretical examination of hydrazine derivatives"Chemoshere,. 41,. 337-343 (2000)

[Publications] G.Liu,T.Wu,J.Zhao,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants VIII : Irreversible degradation of Alizarin Red under visible light irradiation in air-equilibrated aqueous TiO_2 dispersion "Environ.Sci.Technol.,. 33,. 2081-2087 (1999)

[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Evidence for H_2O_2 generation during the TiO_2 assisted photodegradation of dyes in aqueous dispersions under visible light illumination"J.Phys.Chem.,. 103,. 4862-4867 (1999)

[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "TiO_2-assisted photodegradation of dyes IX : Photooxidation of squaryliu cyanine dye in aqueous dispersions under visible light irradiation"Environ.Sci.Technol.,. 33,. 1379-1387 (1999)

[Publications] K.Wu,Y.Xie,J.Zhao and H.Hidaka,: "Photo-Fenton degradation of a dye under visible light irradiation"J.Mol.Catal.A : Chem.,. 142,. 49-57 (1999)

[Publications] S.Horikoshi,J.Zhao and H.Hikaka,: "Photodegradation of surfactants. XIX : Photooxidation mechanism for nonionic dodecanoyl amide surfactants at TiO_2/H_2O interfaces"J.Jpn.Oil Chem.Soc.,. 48,. 767-774 (1999)

[Publications] A.Salinaro,A.Emeline,J.Zhao,H.Hidaka,V.Ryabchuck and N.Serpone,: "Terminology, relative photonic efficiency, and quantum yields in hetero-generous (solid/liquid) photocatalysis. Part II ; Experimental determination of quantum yields"Pure & Appl.Chem.,. 71,. 321-335 (1999)

[Publications] J.He,F.Chen,J.Zhao and H.Hidaka: "Adsorption mode of ethyl ester of fluorescein on colloidal TiO_2 and the mechanism of the interfacial electron transfer"Colloids & Surfaces,. 142,. 49-57 (1998)

[Publications] P.Qu,J.Zhao,L.Zang,T.Shen and H.Hidaka,: "Enhancement of the photoinduced electron transfer from cationic dyes to colloidal TiO_2 particles by addition of an anionic surfactant in acidic media"Colloids & Surfaces,. 138,. 39-50 (1998)

[Publications] J.He,J.Zhao,H.Hidaka and N.Serpone,: "EPR characteristics of a dye-colloidal TiO_2 system under visible light irradation"J.Chem.Soc.Faraday Trans.2.,. 94,. 2375-2378 (1998)

[Publications] 堀越智,日高久夫: "半導体触媒TiO_2を用いた高分子の光分解"色材,. 71,. 176-185 (1998)

[Publications] N.Serpone,A.Salinaro,H.Hidaka,S.Horikoshi,J.Knowland Dunford,: "Beneficial and deleterious effects of solar radiation"Solar Engineering 1998.J.M.Morehouse & R.E.Hogan, Eds.,ASME, New York,. 287-298 (1998)

[Publications] S.Horikoshi,H.Hidaka,Y.Hisamatsu and N.Serpone,: "Photocatalyzed degradation of polymers in aqueous semiconductor suspensions III. An optimum photooxidation for solid polymers of TiO_2-blended polyvinylchloride film"Environ.Sci.Technol.,. 32,. 4010-4016 (1998)

[Publications] J.Zhao,K.Wu,T.Wu,H.Hidaka and N.Serpone.: "Photodegradation of dyes with poor solubility in an aqueous solubility in an aqueous surfactat/TiO_2 dispersion under visible light irradiation"J.Chem.Soc.Faraday Trans.,. 94,. 673-676 (1998)

[Publications] T.Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants. V. Self-photooxidative transformation of PhB under visible light irradiation in aqueous TiO_2 dispersions"J.Phys.Chem.,B,. 102,. 5848-5851 (1998)

[Publications] J.Zhao,T.Wu,K.Wu,K.Oikawa,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants.III. Evidence for the need of substrate adsorption on TiO_2 particles"Environ.Sci.Technol.,. 32,. 2394-2400 (1998)

[Publications] F.Zhang,J.Zhao,T.Shen,H.Hidaka,E.Pelizzeetti and N.Serpone,: "What becomes of nitrogen in the photoelectrochemical and photocatalyzed mineralization of N-containing substances at titania/water interfaces?"Appl.Catal.B.; Environ.,. 15,. 147-156 (1998)

[Publications] K.Wu,T.Zhang,J.Zhao and H.Hidaka,: "Photodegradation of malachite green in the presence of Fe^<3+>/H_2O_2 under visible light"Chem.Lett.,. 857-858 (1998)

[Publications] Wu,G.Liu,J.Zhao,H.Hidaka and N.Serpone,: "Photoassisted degradation of dye pollutants V : Self-photosensitized oxidative transformation of Rhodamine B under visible light irradiation in aqueous TiO_2 dispersions"J.Phys.Chem.,. 102,. 5845-5851 (1998)

[Publications] P.Qu,J.Zhao,T.Shen and H.Hidaka,: "TiO_2-assisted photodegradation of dyes : A study of two competitive primary processes in the degradation of RB in an aqueous TiO_2 colloidal solution"J.Mol.Catal.,. 129,. 257-268 (1998)

[Publications] H.Hidaka,: "Photodegradation of surfactants with TiO_2 semiconductor for the environmental wastewater treatment,"Proc.Indian Acad.Sci.(Chem.Sci.),. 110,. 215-228 (1998)

[Publications] J.Zhao,K.Wu,T.Wu,H.Hidaka and N.Serpone,: "Photodegradation of dyes with poor solubility in an aqueous srufactant/TiO_2 dispersion under visible light irradiation,"J.Chem.Soc.Faraday Trans.,. 94,. 673-676 (1998)

日高久夫明星大学, 理工学部, 教授 (70062312)