TiO_2-ZnTiO_3纳米复合薄膜的制备及光催化性能
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摘要
将ZnO粉末加入TiO2溶胶中制备出TiO2/ZnTiO3复合薄膜。利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱、紫外-可见吸收光谱对其形貌、晶体结构、化学组成和光谱响应特征进行了表征。以亚甲基蓝(MB)溶液的脱色降解为模型反应,考察了不同ZnO掺入比例对复合薄膜光催化性能的影响。结果表明,所得材料的光催化性能与复合结构中TiO2的结晶结构有关。Ti/Zn=6∶1时,所得复合薄膜由锐钛矿相TiO2与钙钛矿相ZnTiO3构成,薄膜中晶粒尺寸较小(约为30nm)、结晶度较高、催化性能最好。在紫外光下5h可使亚甲基蓝(MB)溶液脱色降解率达到94%,明显高于纯TiO2薄膜(87%)。
TiO2/ZnTiO3 composite thin films were prepared by adding ZnO powder into TiO2 sol. The morphology,crystal structure,chemical composition and spectral response characteristics were studied by X-ray diffraction( XRD),scanning electron microscopy( SEM),X-ray photoelectron spectroscope( XPS)and UV-Visible spectroscopy. The photocatalytic activity of the samples with different properties of ZnO was evaluated by the photocatalytic degradation of methyl blue( MB) aqueous solution under ultraviolet light irradiation. The results indicate that the crystal structure of TiO2 in the composite film has a great impact on photocatalytic properties. When Ti / Zn = 6 ∶ 1,the phase structure is a compound phase of anatase TiO2 and perovskite ZnTiO3. The Ti / Zn = 6∶ 1 samples show smaller grain size,better dispersion performance,higher degree of crystallinity and the highest catalytic performance compared with other samples. The photocatalytic efficiency of methyl blue( MB) aqueous solution is approximate 94% in 5 h under ultraviolet light irradiation,significantly higher than the pure TiO2 films( 87%) under the same experimental conditions.
TiO2/ZnTiO3 composite thin films were prepared by adding ZnO powder into TiO2 sol. The morphology,crystal structure,chemical composition and spectral response characteristics were studied by X-ray diffraction( XRD),scanning electron microscopy( SEM),X-ray photoelectron spectroscope( XPS)and UV-Visible spectroscopy. The photocatalytic activity of the samples with different properties of ZnO was evaluated by the photocatalytic degradation of methyl blue( MB) aqueous solution under ultraviolet light irradiation. The results indicate that the crystal structure of TiO2 in the composite film has a great impact on photocatalytic properties. When Ti / Zn = 6 ∶ 1,the phase structure is a compound phase of anatase TiO2 and perovskite ZnTiO3. The Ti / Zn = 6∶ 1 samples show smaller grain size,better dispersion performance,higher degree of crystallinity and the highest catalytic performance compared with other samples. The photocatalytic efficiency of methyl blue( MB) aqueous solution is approximate 94% in 5 h under ultraviolet light irradiation,significantly higher than the pure TiO2 films( 87%) under the same experimental conditions.
引文
[1]Fujishuma A,Honda K.Electrochemical Photolysis of Water at a Semiconductor Electrode[J].Nature,1972,238(5358):37-38.
[2]宋兵,郑水林,李慧,等.Cu离子掺杂Ti O2光催化材料的研究进展[J].硅酸盐通报,2013,32(11):2669-2673.
[3]崔玉民.过渡金属离子修饰Ti O2光催化活性研究进展[J].材料科学与工程学报,2007,25:802-804.Cui Y M.Development of Ti O2photocatalytic Activity of Transition Metal Ions Modified[J].Journal of Materials Science and Engineering,2007,25:802-804(in Chinese).
[4]Robel I,Sabramanian V,Kuno M,et al.Harvesting Light Energy with Cd Se Nanocrystals Molecularly Linked to Mesoscopic Ti O2Films[J].J.Am.Chem.Soc.,2006,128:2385-2393.
[5]Ku Y,Huang Y H,Chou Y C.Preparation and Characterization of Zn O/Ti O2for the Photocatalytic Reduction of Cr(VI)in Aqueous[J].J.Mol.Catal.A-Chem.,2011,342:18-22.
[6]Miki Y M,Collins M V,Amezaga M P,et al.Thin Flms of Photocatalytic Ti O2and Zn O Deposited Inside a Tubing by Spray Pyrolysis[J].Thin Solid Films,2002,419:60-64.
[7]Kim K E,Jang,S R,Park J,et al.Enhancement in the Performance of Dye-sensitized Solar Cells Containing Zn O-covered Ti O2Electrodes Prepared by Thermalchemical Vapor Deposition[J].Sol.Energ.Mater.Sol.C,2007,91:366-370.
[8]Chung J L,Chen J C,Tseng C J.Electrical and Opticalproperties of Ti O2-doped Zn O Films Prepared by Radio-frequency Magnetron Sputtering[J].J.Phys.Chem.Solids,2008,69:535-539.
[9]Shahram M,Parviz A A,Sanaz R F,et al.The Effect of Different Molar Ratios of Zn O on Characterization and Photocatalytic Activity of Ti O2/Zn O Nanocomposite[J].Saudi Chemical Society,2012.
[10]陈丽娟,田进涛,李超,等.Ti O2/Zn O纳米复合薄膜溶胶-凝胶法制备与表征[J].功能材料,2008,12:1992-1996.Chen L J,Tian J T,Li C,et al.Preparation and Characterization of Nanocomposite Films Prepared by Sol-gel Method[J].Journal of Functional Materials,2008,12:1992-1996(in Chinese).
[11]Yin S,Aita Y,Komatsu M,et al.Visible-light-induced Photocatalytic Activity of Ti O2-xNyPrepared by Solvothermal Process in Urea-alcohol System[J].J.Eur.Ceram.Soc.,2006,26:2735-2742.
[12]Yang E L,Shi J J,Liang H C,et al.WO3/Ti O2Nanotubes/nanorods with High Visible Light Activity for the Photodegradation of 2,3-Dichlorophenol[J].Chem.Eng.J.,2011,174:539-545.
[13]Zhang Z,Yuan Y,Fang Y J,et al.Preparation of Photocatalytic Nano-Zn O/Ti O2Film and Application for Determination of Chemical Oxygen Demand[J].Talanta,2007,73:523-528.
[14]Mane R S,Lee W J,Pathan H M,et al.Nanocrystalline Ti O2/Zn O Thin Films:Fabrication and Application to Dy-sensitized Solar Cells[J].Phys.Chem.B.,2005,109:24254-9.
[15]Liu Z,Zhou D,Gong S,et al.Studies on a Basic Question of Zinc Titanates[J].J.Alloys.Compd.,2008,475:840-845.
[16]Kim H K,Byun J D,Kim Y,et al.Phase Structure and Dielectric Property of the Zn Nb2O6-(Mg0.3Zn0.7)Ti O3Multiphase Ceramics[J].Mater.Res.Bull.,1998,33:975-986.
[17]Chen Z X,Derking A,Koot W,et al.Coprecipitation Synthesis and Optical Absorption Property of Zn2TixSn1-xO4(0≤x≤1)Solid Solutions[J].Catal.,1996,161:730-741.
[18]Lin Y H,Zhang Z T,Huang S L,et al.Preparation of Nanometer Rutile Powder and Its Characterization[J].J.Inorg.Mater.,1999,14(6):853-860.
[19]Islam M N,Ghosh T B,Chopra K L,et al.XPS and X-ray Diffraction Studies of Aluminum-Doped Zinc Oxide Transparent Conducting Films[J].Thin Solid Films,1996,280:20-25.
[20]Chang Y S,Chang Y H,Chen I G,et al.Synthesis and Characterization of Zinc Titanate Nano-crystal Powders by Sol-gel Technique[J].J.Cryst.Growth,2002,243:319-326.
[21]García-Ramírez E,Mondragón-Chaparro M,Zelaya-Angel O.Band Gap Coupling in Photocatalytic Activity in Zn O-Ti O2Thin Films[J].Appl.Phys.A.,2012,108:291-297.
[2]宋兵,郑水林,李慧,等.Cu离子掺杂Ti O2光催化材料的研究进展[J].硅酸盐通报,2013,32(11):2669-2673.
[3]崔玉民.过渡金属离子修饰Ti O2光催化活性研究进展[J].材料科学与工程学报,2007,25:802-804.Cui Y M.Development of Ti O2photocatalytic Activity of Transition Metal Ions Modified[J].Journal of Materials Science and Engineering,2007,25:802-804(in Chinese).
[4]Robel I,Sabramanian V,Kuno M,et al.Harvesting Light Energy with Cd Se Nanocrystals Molecularly Linked to Mesoscopic Ti O2Films[J].J.Am.Chem.Soc.,2006,128:2385-2393.
[5]Ku Y,Huang Y H,Chou Y C.Preparation and Characterization of Zn O/Ti O2for the Photocatalytic Reduction of Cr(VI)in Aqueous[J].J.Mol.Catal.A-Chem.,2011,342:18-22.
[6]Miki Y M,Collins M V,Amezaga M P,et al.Thin Flms of Photocatalytic Ti O2and Zn O Deposited Inside a Tubing by Spray Pyrolysis[J].Thin Solid Films,2002,419:60-64.
[7]Kim K E,Jang,S R,Park J,et al.Enhancement in the Performance of Dye-sensitized Solar Cells Containing Zn O-covered Ti O2Electrodes Prepared by Thermalchemical Vapor Deposition[J].Sol.Energ.Mater.Sol.C,2007,91:366-370.
[8]Chung J L,Chen J C,Tseng C J.Electrical and Opticalproperties of Ti O2-doped Zn O Films Prepared by Radio-frequency Magnetron Sputtering[J].J.Phys.Chem.Solids,2008,69:535-539.
[9]Shahram M,Parviz A A,Sanaz R F,et al.The Effect of Different Molar Ratios of Zn O on Characterization and Photocatalytic Activity of Ti O2/Zn O Nanocomposite[J].Saudi Chemical Society,2012.
[10]陈丽娟,田进涛,李超,等.Ti O2/Zn O纳米复合薄膜溶胶-凝胶法制备与表征[J].功能材料,2008,12:1992-1996.Chen L J,Tian J T,Li C,et al.Preparation and Characterization of Nanocomposite Films Prepared by Sol-gel Method[J].Journal of Functional Materials,2008,12:1992-1996(in Chinese).
[11]Yin S,Aita Y,Komatsu M,et al.Visible-light-induced Photocatalytic Activity of Ti O2-xNyPrepared by Solvothermal Process in Urea-alcohol System[J].J.Eur.Ceram.Soc.,2006,26:2735-2742.
[12]Yang E L,Shi J J,Liang H C,et al.WO3/Ti O2Nanotubes/nanorods with High Visible Light Activity for the Photodegradation of 2,3-Dichlorophenol[J].Chem.Eng.J.,2011,174:539-545.
[13]Zhang Z,Yuan Y,Fang Y J,et al.Preparation of Photocatalytic Nano-Zn O/Ti O2Film and Application for Determination of Chemical Oxygen Demand[J].Talanta,2007,73:523-528.
[14]Mane R S,Lee W J,Pathan H M,et al.Nanocrystalline Ti O2/Zn O Thin Films:Fabrication and Application to Dy-sensitized Solar Cells[J].Phys.Chem.B.,2005,109:24254-9.
[15]Liu Z,Zhou D,Gong S,et al.Studies on a Basic Question of Zinc Titanates[J].J.Alloys.Compd.,2008,475:840-845.
[16]Kim H K,Byun J D,Kim Y,et al.Phase Structure and Dielectric Property of the Zn Nb2O6-(Mg0.3Zn0.7)Ti O3Multiphase Ceramics[J].Mater.Res.Bull.,1998,33:975-986.
[17]Chen Z X,Derking A,Koot W,et al.Coprecipitation Synthesis and Optical Absorption Property of Zn2TixSn1-xO4(0≤x≤1)Solid Solutions[J].Catal.,1996,161:730-741.
[18]Lin Y H,Zhang Z T,Huang S L,et al.Preparation of Nanometer Rutile Powder and Its Characterization[J].J.Inorg.Mater.,1999,14(6):853-860.
[19]Islam M N,Ghosh T B,Chopra K L,et al.XPS and X-ray Diffraction Studies of Aluminum-Doped Zinc Oxide Transparent Conducting Films[J].Thin Solid Films,1996,280:20-25.
[20]Chang Y S,Chang Y H,Chen I G,et al.Synthesis and Characterization of Zinc Titanate Nano-crystal Powders by Sol-gel Technique[J].J.Cryst.Growth,2002,243:319-326.
[21]García-Ramírez E,Mondragón-Chaparro M,Zelaya-Angel O.Band Gap Coupling in Photocatalytic Activity in Zn O-Ti O2Thin Films[J].Appl.Phys.A.,2012,108:291-297.