酞箐铜敏化二氧化钛光催化降解糠醛水溶液的研究
摘要
本文选取酞箐铜作为光敏剂敏化二氧化钛制得了复合催化剂,该催化剂在可见光的照射下表现出了较高的活性。使用糠醛水溶液作为目标污染物,利用该催化剂在氙灯的照射下降解糠醛水溶液。在负载酞箐铜以后,复合催化剂在降解实验中其光催化活性比纯二氧化钛提高了30%,该催化剂的最佳制备条件为:酞箐铜的负载量为1.5% ,乙酰丙酮的浓度为0.3%,搅拌时间为10h。
本文使用固体紫外漫反射光谱,X-射线衍射仪,以及比表面积测定仪来表征制得复合催化剂,表征复合催化剂的性质,验证光催化效果增强的原因。此外,还研究光强,阳离子,催化剂浓度,温度和反应液初始浓度对于光催化降解反应的影响。结果表明,在光强越大,温度越高的时候,越有利于光催化反应地进行,无机阳离子中,铁离子促进了光催化反应的进行,催化剂的最佳投放量为0.5mg/L。在进行降解过程的热力学和动力学的研究中,采用零级反应动力学方程和阿伦尼乌斯公式进行拟和,研究结果表明,反应符合零级动力学方程,光催化反应符合阿伦尼乌斯公式,此反应为基元反应。
Furfural waste water is identified as a serious environmentalproblem. Owing to its special property: low pH value (2-3), hightemperature (70 0C) and high COD concentration, it is generallyaccepted that the traditional biochemical method is unsuccessful todispose furfural waste water. Consequently, new technologies have tobe developed for the degradation of furfural waste water.
Advanced oxidation techniques have been extensively studied toeliminate the organic pollutants in water. TiO2 as an importantphotocatalyst which produces the reactive oxygen species is widelyused to degrade the organic pollutants, However, the light absorptionregion of anatase-typed TiO2 particles (λ≤385 nm) does not fit withthe solar spectrum, for the reason that the solar energy above 3.0 eV(λ≤ 410 nm) only makes up less than 5% of the whole sunlight. Sohow to effectively utilize the solar energy as most as we can degradethe pollutants comes to be a great challenge for researchers.
As an outstanding photo catalyst, TiO2 is applied extensively inthe environmental treatment technique. But it is hard for TiO2 todecompose the pollutant under the visible light. MPc is arepresentative photosensitizer, which can collect up to 50% of theenergy available in the solar spectrum. So the MPc is selected to
synthesize the composite catalyst. Using MPc to degradation of theliquid organic pollutants and the solid organic pollutants, the researchis widely studied. The MPc is inserted into the interlamellar space ofthe catalyst to synthesize the composite catalyst among most of theexperiments, the composite catalyst gets remarkable effects throughthe photo-oxidation reaction. And the synthesizing condition is easy tocontrol, the synthesizing process is very inconvenient. So Copperphthalocyanine is selected as the photosensitizer to sentitize TiO2 inour experiment. The composite catalysts obtained after the process ofsensitization show great activity under the visible light. Taking thefurfural as the target pollutant, we test the photo-oxidation activity ofthe composite catalysts under the visible light irradiation. After loadingdifferent CuPc, TiO2 shows higher photo-oxidation activity than thepure TiO2. Among the different percent of composition, the 1.5%TiO2/CuPc and the 0.3% acetylacetone are the optimal samplethroughout the synthesized process.Using Visible Reflectance Spectra, XRD and BET, the propertiesof different loading of CuPc composite catalyst are examined. Afterloading CuPc on the TiO2, the composite catalyst remains the samecrystal structure as the pure TiO2. The composite catalyst showsobvious adsorption peak in 600-700 nm and smaller surface area thanthat of the pure TiO2. To identify the adsorption activity and thestability of catalyst, the adsorption experiment and the repeatedexperiment are carried out. In the adsorption experiment, 2.5%TiO2/CuPc exhibiting good performance, however, it can not be
selected as the catalyst for the repeated experiment for its poorperformance in the photo-oxidation reaction. By reason of showing thehigher photo-oxidation activity, 1.5% TiO2/CuPc is selected as thecatalyst in the repeated experiment. After six times of the repeatedexperiment, the activity of the reclaimed catalys becomes weak.Furthermore, we obtain the composite catalyst which can becharacterized by XRD and the visible reflectance spectra. Moreover,we discuss the effects of intensity of light, metalions, the concentrationof catalysts, temperature and the initial concentration of the furfuralsolution on the photo-oxidation reaction. We find that the compositecatalyst shows great activity under the visible light, and exhibits abroader absorption range for the solar spectrum. The optimal catalystis the one which loaded with 1.5% CuPc. We can make the conversionrate of furfural increase 30% higher than using pure TiO2. So we getthe purpose that using visible light effectively.
本文使用固体紫外漫反射光谱,X-射线衍射仪,以及比表面积测定仪来表征制得复合催化剂,表征复合催化剂的性质,验证光催化效果增强的原因。此外,还研究光强,阳离子,催化剂浓度,温度和反应液初始浓度对于光催化降解反应的影响。结果表明,在光强越大,温度越高的时候,越有利于光催化反应地进行,无机阳离子中,铁离子促进了光催化反应的进行,催化剂的最佳投放量为0.5mg/L。在进行降解过程的热力学和动力学的研究中,采用零级反应动力学方程和阿伦尼乌斯公式进行拟和,研究结果表明,反应符合零级动力学方程,光催化反应符合阿伦尼乌斯公式,此反应为基元反应。
Furfural waste water is identified as a serious environmentalproblem. Owing to its special property: low pH value (2-3), hightemperature (70 0C) and high COD concentration, it is generallyaccepted that the traditional biochemical method is unsuccessful todispose furfural waste water. Consequently, new technologies have tobe developed for the degradation of furfural waste water.
Advanced oxidation techniques have been extensively studied toeliminate the organic pollutants in water. TiO2 as an importantphotocatalyst which produces the reactive oxygen species is widelyused to degrade the organic pollutants, However, the light absorptionregion of anatase-typed TiO2 particles (λ≤385 nm) does not fit withthe solar spectrum, for the reason that the solar energy above 3.0 eV(λ≤ 410 nm) only makes up less than 5% of the whole sunlight. Sohow to effectively utilize the solar energy as most as we can degradethe pollutants comes to be a great challenge for researchers.
As an outstanding photo catalyst, TiO2 is applied extensively inthe environmental treatment technique. But it is hard for TiO2 todecompose the pollutant under the visible light. MPc is arepresentative photosensitizer, which can collect up to 50% of theenergy available in the solar spectrum. So the MPc is selected to
synthesize the composite catalyst. Using MPc to degradation of theliquid organic pollutants and the solid organic pollutants, the researchis widely studied. The MPc is inserted into the interlamellar space ofthe catalyst to synthesize the composite catalyst among most of theexperiments, the composite catalyst gets remarkable effects throughthe photo-oxidation reaction. And the synthesizing condition is easy tocontrol, the synthesizing process is very inconvenient. So Copperphthalocyanine is selected as the photosensitizer to sentitize TiO2 inour experiment. The composite catalysts obtained after the process ofsensitization show great activity under the visible light. Taking thefurfural as the target pollutant, we test the photo-oxidation activity ofthe composite catalysts under the visible light irradiation. After loadingdifferent CuPc, TiO2 shows higher photo-oxidation activity than thepure TiO2. Among the different percent of composition, the 1.5%TiO2/CuPc and the 0.3% acetylacetone are the optimal samplethroughout the synthesized process.Using Visible Reflectance Spectra, XRD and BET, the propertiesof different loading of CuPc composite catalyst are examined. Afterloading CuPc on the TiO2, the composite catalyst remains the samecrystal structure as the pure TiO2. The composite catalyst showsobvious adsorption peak in 600-700 nm and smaller surface area thanthat of the pure TiO2. To identify the adsorption activity and thestability of catalyst, the adsorption experiment and the repeatedexperiment are carried out. In the adsorption experiment, 2.5%TiO2/CuPc exhibiting good performance, however, it can not be
selected as the catalyst for the repeated experiment for its poorperformance in the photo-oxidation reaction. By reason of showing thehigher photo-oxidation activity, 1.5% TiO2/CuPc is selected as thecatalyst in the repeated experiment. After six times of the repeatedexperiment, the activity of the reclaimed catalys becomes weak.Furthermore, we obtain the composite catalyst which can becharacterized by XRD and the visible reflectance spectra. Moreover,we discuss the effects of intensity of light, metalions, the concentrationof catalysts, temperature and the initial concentration of the furfuralsolution on the photo-oxidation reaction. We find that the compositecatalyst shows great activity under the visible light, and exhibits abroader absorption range for the solar spectrum. The optimal catalystis the one which loaded with 1.5% CuPc. We can make the conversionrate of furfural increase 30% higher than using pure TiO2. So we getthe purpose that using visible light effectively.
引文
1 李寻安,张占雪. 新型太阳能电池的问世. 中国科学报 .1998,4,22
2 LiQ S. Influence of Pt Nanocrystallinity on Electrochromism of TiO2 . Chem.Lett. 1983,135: 321-324
3 Frank S, N Bard A J. Synthesis of Single-Crystalline TiO2 Nanotubes. J. Phys.Chem.1977,81: 1484-1486
4 M L Trudeau, J Y Ying. Photocatalytic Transformation of 2,4,5-Trichlorophenol on TiO2 under Sub-Band-Gap Illumination. Nanostructured Mater.1996,7,245
5 M Anpo N, Aikawa, S Kosama. Gas Phase Tetrachloroethylene (PCE) Oxidation and Byproduct Formation Using TiO2 and Silica Photocatalysts. J. Phys.Chem,1984,88,2569
6 M Walden, X Lai ,D W Goodman. Rating performance of TiO2 pigments in coated paper applications . Science,1998,281,1647
7 Serpone N. Solar Energy Materials and Solar Cells.1995,38: 369-373
8 祖庸,雷闫盈,李筱娥. 现代化工,1999,19:46-48
9 Herrmann J M, Guillard C. Influence of modification of counter electrode on photoelectric properties of dye-sensitized TiO2 solar cells. Catalysis Today.1993,17: 7-20
10 李小平,徐宝琨,刘国范等. 功能材料。1999,30:242-245
11 Khalil L, B Mourad W E, Rophael M W. Modifying bandgap of tio2-based nanoparticles by cation doping. Appl.Catal.B: Environ.1998,17: 267-273
12 Yamashita H, Jchihashi Y. Bactericidal effect of an energy storage TiO2-WO3 photocatalyst in dark. J.Phys.Chem.1996,100: 16041-16044
13 Yamashita H, Jchihashi Y, Harada M. Dual cure photocatalyst systemset . Al. J.Catal.1996,158,97
14 Choi W, Termin A , Hoffmann M R .The role of mental dopants in quantum-sized TiO2;correlation between photoreactivity and change carrier recombination dynamics. J.PHYS.CHEM,1994,98: 13669-13679.
15 赵德明, 汪大翠, 使惠祥. 掺杂过渡金属离子的纳米二氧化钛光催化对氯苯酚的研究. 化工环保,2003,23(2):75-78。
16 沈伟韧, 赵文宽, 贺飞等 二氧化钛光催化反应及其在废水处理中的应用. 化学进展,1998,10(4):349-361。
17 李春雷, 麦碧闲,潘海洋等. 二氧化钛投加量及其表面在印对光催化降解的影响。环境科学,2002,23(2):120-122
18 Byung-Yong Lee ,Sang-Hyuk Park ,Sung-Chul Lee. preparation of Al/TiO2 nanometer photo-catalyst film and the effect of H2O addition on photo-catalytic performance for benzene removal. Applied Catalysis A General 253(2003) 371-380
19 李芳柏, 古国邦, 李新军. 纳米复合 Sb2O3/ TiO2 的光催化性能研究 无机化学学报 2001(1)Vol 17 No 1
20 王心晨, 刘平, 王旭旭 TiO2-ZrO2 复合催化剂上乙烯的光催化降解 福州大学学报 2001 29(5)
21 高永建, 张志军, 党鸿新 TiO2/聚丙烯酸丁酯纳米复合膜的 制备与摩擦性能 应用化学 2002 19(9)
22 张庆庆, 汤斌, 王进等 光催化过程中氧及过氧化氢对氧化钛的效应。安徽机电学院学报 2001 16 (4)。
23 K.NagaveinI ,G. SivaLlingam ,M.S. HEGDE. Photocatalytic Degradation of organic compounds over combusion-synthesized nano-TiO2. Environ .Sci. Techol 2004.38.1600-1604.
24 Sivalingam, G. nagaveni K, Development of photocatalyst materials for water splitting . Appl. Catal .2003.45. 23-28
25 Mattews R, W J . Influence of photocatalyst film forming conditions on CO2 reforming. Catal. 1988,111.,264-272
26 Hengrong Large oriented arrays and continuous films of TiO2-based nanotubes . JACS, 2003, 1, 27
27 Hang chengyu ,shang huamei , tao ying. properties and morphology of CdS compounded TiO2. visible-light photocatalytic nanofilms coated on glass surface and purification technology JACS 2003, 2 , 237
28 Kang YongSong , MyunKyuPark. Preparation of Transparent Particulate MoO3/ TiO2., and WO3/ TiO2 Films and Their Photocatalytic Properties. Chem. .Mater. 2001 13 .2349-2355
29 Song Zhu Chu , Atoru Iinoue High Porous (TiO2.-SiO2-TeO2)/Al2O3/ TiO2 Composite Nanostrures on Glass with Enhanced Photocatalysis Fabricated by Anodization and Sol –Gel Process. J. Phys. Chem.. B 2003, 107, 6586-6589
30 Zuko Yamazaki, Toshifumi Tanimura . Reaction Mechanism of Photocatalytic Degradation of Chlorinated Ethylenes on Porous TiO2 Pellets. J .Phys. Chem..A 2004,108.5183-5188
31 于向阳,程继健. 铁、铬离子掺杂对 TiO2 薄膜光催化活性的影响 无机材料学报 2001(16) 4
32 Donia Beydoun a, Helen Tse a, Rose Amala. Effect of Copper(II) on the Photocatalytic Degradation of Sucrose Journal of Molecular Catalysis A: Chemical 177 ,(2002) ,265–272
33 S.Nakade ,Y Saito, W. Kubo. Influence of TiO2. Nanoparticle Size on Electron Diffusion and Recombination in Dye-sensitized TiO2.VSolar Cells. J. Phys. Chem..B 2003,107,8607-8611
34 Huxin Tan , Jin zhai, bofei Xue . Property Influence of Polyanilines on Photovoltaic Behaviors of Dye –Sensitized Solar Cells. Langmuir 2004, 20. 2934-2937.
35 Unyong Bea , Wonyong Choi. Highly Enhanced Photoreductive Degradation of Perchlorinated Compounds On Dye-Sensitized Metal / TiO2 underVisible light Environ . Sci. Techol. 2003 37, 147-152
36 Kim.S: Choi.W. Environ .Sci. Techol. 2002 36. 2019
37 J Shang, Ming.Chai. Photocatalytic Degradation of Polystyrene Plastic under Fuorescent light. Environ .Sci. Techol 2003 ,37 4494-4499
38 Mei yang , David W Thompson . Dual Pathways for TiO2 Sensitization by Na2[Fe(bby) (CN)4].Inorg.Chem.. 2000,39,3738-3739
39 EVER, A . B. P. Destruction of organic compounds in water using fixed-bed photocatalysts Inorg. Chem.1990,29,1271
40 Gabor Benko, Pasi Myllyperkio. Photoinduced Electron Injection from Ru(dcbpy)2(NCS)2 to SnO2 and TiO2 Nanocrystalline Films JACS ,2003 .125. 1118-1119
41 Georg M Hasselmann, Gerald J Meyer. Molecular Rectification by Abimetallic RU-O Compound nchored to Nanocrystalline TiO2. Inorg .Chem..2000,39,1342-1343
42 Eizhao, wanhong , ma. efficient degradation of toxic organic pollutants with Ni2O3/TiO2-XBX under visible irradiation JACS 2004 3 26
43 Chung, Hak Lee,Teagh Wan Hyeon Visible Light-Induced Degradation of Carbon Tetrachloride on Dye-Sensitized TiO2 Environ .Sci. Techol 2001 .35, 966-970
44 Kimura m, yamamoto. Research advances in the second generation of visible-light photocatalysts of nonmetal-doped TiO2inorg.chim .acta 1986. 117.169
45 T.Yamase, Ntakabayashi, M.Kaji. Apatite-coated titanium dioxide photocatalyst J. Chem. Soc.Dalton Trans. 1984 793
46 C Hill, D A Bouchard. Preparation of TiO2 thin film photocatalysts by dip coating using a highly viscous solvent J. Am. Chem.'s. 1985,107,5148
47 E Papaconstantinou. Preparation and characterization of visible-light-active nitrogen-doped TiO2 photocatalyst. Chem. Soc.Rev.1989,18,1
48 J Mesilvstro, M Gratzel, L Kaven Porous TiO2 photocatalyst films prepared from peroxo titanic acid solution dispersing nano-sized silicate layer J.Am. Chem. Soc,1985,107,2988
49 X Tao, W Ma, T Zhang. Visible light active platinum-ion-doped TiO2 photocatalystAngrew. Chem.. Int. ED. 2001,40,16
50 Kuzenetsova L , I Chernyshova Y V, Maksimouskaya R I. Micro-patterning of functional thin films using photomask with photocatalystInorg Chim Acta.1990.167: 223
51 T Wu, G Liu, J Zhao. Decomposition of benzene by using a discharge plasma-photocatalyst hybrid system J. Phys. Chem.. 1999 103, 4862.
52 D A Friesen, J V headley, C H Langford. Synthesis and characterization of silica-capped titania nanorods: An enhanced photocatalyst Environ .Sci. Techol.1999, 33, 3193
53 Md k , Nazeeruddin, P Pechy . Solar radiation-induced polymerization of methyl methacrylate in the presence of semiconductor-based photocatalystChem.. Commun, 1997,1705
54 Md k, Nazeeruddin, Baker M Gratzel .Preparation of a transparent thin-film photocatalyst for elimination of VOC .Chem.. Commun, 1998,719
55 郭伊荇 东北师范大学博士学位论文 2001
56 孟祥举 吉林大学博士学位论文 2003
57 X Tao, W Ma ,T. Zhang. Development of photocatalyst materials for water splitting with the aim at photon energy conversion Angew. Chem.Int.Ed, 2001,40,16
58 T Wu, G. Liu , J.Zhao. NOx removal process in pulsed corona discharge combined with TiO2 photocatalyst J.Phys. Chem. 1999,103,4862
59 S Zheng, L Gao, J Guo Effect of formate and methanol on photoreduction/removal of toxic cadmium ions using TiO2 semiconductor as photocatalyst J.Mater. Chem. 2000,10,723
60 S Zheng, L Gao, J.Guo. Influence of mineralization products on the coagulation of TiO2 photocatalyst J.Mater. Chem ,2001,11,578
61 Ozoemena,Kenneth,Kuznetsova. Photosensitized transformation of 4-chlorophenol in the presence of aggregated and non-aggregated metallophthalocyanines J. Photo photobiol 2001 ,139(16), 217-224
62 王竹庭,鲁开娟 酞箐高分子及用途。高分子通报,1992(4):237-244
63 孙强,邓桂盛,姚小华 化学试剂。1996,18(3):138-140
64 孙强,邓桂盛,姚小华 有机化学,1996,16(1):83-87
65 Manassen J. Performance in a fluidized bed reactor of photocatalysts immobilized onto inert supports. Cat .Rev-Sci Eng,1974,9(2): 233-243
66 Masri Y, Hronec M , Stud Surf. Titanium dioxide/adsorbent hybrid photocatalysts for photodestruction of organic substances of dilute concentrations. Sci Catal,1991,66
67 Z G Xiong ,Y M Xu. Preparation and characterization of noble metal loaded/unloaded fullerenes (photocatalyst) for the visible light induced hydrogen production Environ. Sci. Technol.2005, 39,651-657
68 K Ozoemena, N Kuznetsova, T Nyokong. Preparation and characterization of noble metal loaded/unloaded fullerenes (photocatalyst) for the visible light induced hydrogen production . Mol. Catal., A 2001, 176, 29-40.
69 Meiqin Hu, Yiming Xu, Jincai Zhao. Photosensitezed Oxidation of substituted phenols on Aluminum phthalocyanine Intercalated
organoclay. Langmuir 2004, 20, 6302-6307
70 V Iliev, V Alexiev, L Bilyarska. J. Kinetics of the rapid dark reaction between methanol and oxygen in the presence of "photocatalyst"Mol. Catal. A: Chem. 2000,151(15) 161-169.
71 Meiqin Hu, Yiming Xu and Jincai Zhao. Photosensitezed Oxidation of substituted phenols on Aluminum phthalocyanine Intercalated organoclay. Langmuir 2004, 20, 6302-6307
72 Christophe J Barbe, Francine Arendse, Passcal Comte J. Am. Ceram. Electron-and hole-capture reactions on Pt/TiO2 photocatalyst exposed to methanol vapor studied with time-resolved infrared absorption spectroscopy Soc.1997,80(12) : 3157-3171
73 程沧沧,胡德文 TiO2—Fe3+体系降解耐酸大红染料的研究. 环境污染与防治,1998.20(4):17～19.
74 Teruhisa Ohono, Dsisuke Haga, Kan Fujihara. Effects of Iron (Ⅲ) Ions on Photocatalytic and Photoelectro-chemical Properties of Titanium Dioxide . J. Phys.Chem.B, 1997,101, 6415-6419.
2 LiQ S. Influence of Pt Nanocrystallinity on Electrochromism of TiO2 . Chem.Lett. 1983,135: 321-324
3 Frank S, N Bard A J. Synthesis of Single-Crystalline TiO2 Nanotubes. J. Phys.Chem.1977,81: 1484-1486
4 M L Trudeau, J Y Ying. Photocatalytic Transformation of 2,4,5-Trichlorophenol on TiO2 under Sub-Band-Gap Illumination. Nanostructured Mater.1996,7,245
5 M Anpo N, Aikawa, S Kosama. Gas Phase Tetrachloroethylene (PCE) Oxidation and Byproduct Formation Using TiO2 and Silica Photocatalysts. J. Phys.Chem,1984,88,2569
6 M Walden, X Lai ,D W Goodman. Rating performance of TiO2 pigments in coated paper applications . Science,1998,281,1647
7 Serpone N. Solar Energy Materials and Solar Cells.1995,38: 369-373
8 祖庸,雷闫盈,李筱娥. 现代化工,1999,19:46-48
9 Herrmann J M, Guillard C. Influence of modification of counter electrode on photoelectric properties of dye-sensitized TiO2 solar cells. Catalysis Today.1993,17: 7-20
10 李小平,徐宝琨,刘国范等. 功能材料。1999,30:242-245
11 Khalil L, B Mourad W E, Rophael M W. Modifying bandgap of tio2-based nanoparticles by cation doping. Appl.Catal.B: Environ.1998,17: 267-273
12 Yamashita H, Jchihashi Y. Bactericidal effect of an energy storage TiO2-WO3 photocatalyst in dark. J.Phys.Chem.1996,100: 16041-16044
13 Yamashita H, Jchihashi Y, Harada M. Dual cure photocatalyst systemset . Al. J.Catal.1996,158,97
14 Choi W, Termin A , Hoffmann M R .The role of mental dopants in quantum-sized TiO2;correlation between photoreactivity and change carrier recombination dynamics. J.PHYS.CHEM,1994,98: 13669-13679.
15 赵德明, 汪大翠, 使惠祥. 掺杂过渡金属离子的纳米二氧化钛光催化对氯苯酚的研究. 化工环保,2003,23(2):75-78。
16 沈伟韧, 赵文宽, 贺飞等 二氧化钛光催化反应及其在废水处理中的应用. 化学进展,1998,10(4):349-361。
17 李春雷, 麦碧闲,潘海洋等. 二氧化钛投加量及其表面在印对光催化降解的影响。环境科学,2002,23(2):120-122
18 Byung-Yong Lee ,Sang-Hyuk Park ,Sung-Chul Lee. preparation of Al/TiO2 nanometer photo-catalyst film and the effect of H2O addition on photo-catalytic performance for benzene removal. Applied Catalysis A General 253(2003) 371-380
19 李芳柏, 古国邦, 李新军. 纳米复合 Sb2O3/ TiO2 的光催化性能研究 无机化学学报 2001(1)Vol 17 No 1
20 王心晨, 刘平, 王旭旭 TiO2-ZrO2 复合催化剂上乙烯的光催化降解 福州大学学报 2001 29(5)
21 高永建, 张志军, 党鸿新 TiO2/聚丙烯酸丁酯纳米复合膜的 制备与摩擦性能 应用化学 2002 19(9)
22 张庆庆, 汤斌, 王进等 光催化过程中氧及过氧化氢对氧化钛的效应。安徽机电学院学报 2001 16 (4)。
23 K.NagaveinI ,G. SivaLlingam ,M.S. HEGDE. Photocatalytic Degradation of organic compounds over combusion-synthesized nano-TiO2. Environ .Sci. Techol 2004.38.1600-1604.
24 Sivalingam, G. nagaveni K, Development of photocatalyst materials for water splitting . Appl. Catal .2003.45. 23-28
25 Mattews R, W J . Influence of photocatalyst film forming conditions on CO2 reforming. Catal. 1988,111.,264-272
26 Hengrong Large oriented arrays and continuous films of TiO2-based nanotubes . JACS, 2003, 1, 27
27 Hang chengyu ,shang huamei , tao ying. properties and morphology of CdS compounded TiO2. visible-light photocatalytic nanofilms coated on glass surface and purification technology JACS 2003, 2 , 237
28 Kang YongSong , MyunKyuPark. Preparation of Transparent Particulate MoO3/ TiO2., and WO3/ TiO2 Films and Their Photocatalytic Properties. Chem. .Mater. 2001 13 .2349-2355
29 Song Zhu Chu , Atoru Iinoue High Porous (TiO2.-SiO2-TeO2)/Al2O3/ TiO2 Composite Nanostrures on Glass with Enhanced Photocatalysis Fabricated by Anodization and Sol –Gel Process. J. Phys. Chem.. B 2003, 107, 6586-6589
30 Zuko Yamazaki, Toshifumi Tanimura . Reaction Mechanism of Photocatalytic Degradation of Chlorinated Ethylenes on Porous TiO2 Pellets. J .Phys. Chem..A 2004,108.5183-5188
31 于向阳,程继健. 铁、铬离子掺杂对 TiO2 薄膜光催化活性的影响 无机材料学报 2001(16) 4
32 Donia Beydoun a, Helen Tse a, Rose Amala. Effect of Copper(II) on the Photocatalytic Degradation of Sucrose Journal of Molecular Catalysis A: Chemical 177 ,(2002) ,265–272
33 S.Nakade ,Y Saito, W. Kubo. Influence of TiO2. Nanoparticle Size on Electron Diffusion and Recombination in Dye-sensitized TiO2.VSolar Cells. J. Phys. Chem..B 2003,107,8607-8611
34 Huxin Tan , Jin zhai, bofei Xue . Property Influence of Polyanilines on Photovoltaic Behaviors of Dye –Sensitized Solar Cells. Langmuir 2004, 20. 2934-2937.
35 Unyong Bea , Wonyong Choi. Highly Enhanced Photoreductive Degradation of Perchlorinated Compounds On Dye-Sensitized Metal / TiO2 underVisible light Environ . Sci. Techol. 2003 37, 147-152
36 Kim.S: Choi.W. Environ .Sci. Techol. 2002 36. 2019
37 J Shang, Ming.Chai. Photocatalytic Degradation of Polystyrene Plastic under Fuorescent light. Environ .Sci. Techol 2003 ,37 4494-4499
38 Mei yang , David W Thompson . Dual Pathways for TiO2 Sensitization by Na2[Fe(bby) (CN)4].Inorg.Chem.. 2000,39,3738-3739
39 EVER, A . B. P. Destruction of organic compounds in water using fixed-bed photocatalysts Inorg. Chem.1990,29,1271
40 Gabor Benko, Pasi Myllyperkio. Photoinduced Electron Injection from Ru(dcbpy)2(NCS)2 to SnO2 and TiO2 Nanocrystalline Films JACS ,2003 .125. 1118-1119
41 Georg M Hasselmann, Gerald J Meyer. Molecular Rectification by Abimetallic RU-O Compound nchored to Nanocrystalline TiO2. Inorg .Chem..2000,39,1342-1343
42 Eizhao, wanhong , ma. efficient degradation of toxic organic pollutants with Ni2O3/TiO2-XBX under visible irradiation JACS 2004 3 26
43 Chung, Hak Lee,Teagh Wan Hyeon Visible Light-Induced Degradation of Carbon Tetrachloride on Dye-Sensitized TiO2 Environ .Sci. Techol 2001 .35, 966-970
44 Kimura m, yamamoto. Research advances in the second generation of visible-light photocatalysts of nonmetal-doped TiO2inorg.chim .acta 1986. 117.169
45 T.Yamase, Ntakabayashi, M.Kaji. Apatite-coated titanium dioxide photocatalyst J. Chem. Soc.Dalton Trans. 1984 793
46 C Hill, D A Bouchard. Preparation of TiO2 thin film photocatalysts by dip coating using a highly viscous solvent J. Am. Chem.'s. 1985,107,5148
47 E Papaconstantinou. Preparation and characterization of visible-light-active nitrogen-doped TiO2 photocatalyst. Chem. Soc.Rev.1989,18,1
48 J Mesilvstro, M Gratzel, L Kaven Porous TiO2 photocatalyst films prepared from peroxo titanic acid solution dispersing nano-sized silicate layer J.Am. Chem. Soc,1985,107,2988
49 X Tao, W Ma, T Zhang. Visible light active platinum-ion-doped TiO2 photocatalystAngrew. Chem.. Int. ED. 2001,40,16
50 Kuzenetsova L , I Chernyshova Y V, Maksimouskaya R I. Micro-patterning of functional thin films using photomask with photocatalystInorg Chim Acta.1990.167: 223
51 T Wu, G Liu, J Zhao. Decomposition of benzene by using a discharge plasma-photocatalyst hybrid system J. Phys. Chem.. 1999 103, 4862.
52 D A Friesen, J V headley, C H Langford. Synthesis and characterization of silica-capped titania nanorods: An enhanced photocatalyst Environ .Sci. Techol.1999, 33, 3193
53 Md k , Nazeeruddin, P Pechy . Solar radiation-induced polymerization of methyl methacrylate in the presence of semiconductor-based photocatalystChem.. Commun, 1997,1705
54 Md k, Nazeeruddin, Baker M Gratzel .Preparation of a transparent thin-film photocatalyst for elimination of VOC .Chem.. Commun, 1998,719
55 郭伊荇 东北师范大学博士学位论文 2001
56 孟祥举 吉林大学博士学位论文 2003
57 X Tao, W Ma ,T. Zhang. Development of photocatalyst materials for water splitting with the aim at photon energy conversion Angew. Chem.Int.Ed, 2001,40,16
58 T Wu, G. Liu , J.Zhao. NOx removal process in pulsed corona discharge combined with TiO2 photocatalyst J.Phys. Chem. 1999,103,4862
59 S Zheng, L Gao, J Guo Effect of formate and methanol on photoreduction/removal of toxic cadmium ions using TiO2 semiconductor as photocatalyst J.Mater. Chem. 2000,10,723
60 S Zheng, L Gao, J.Guo. Influence of mineralization products on the coagulation of TiO2 photocatalyst J.Mater. Chem ,2001,11,578
61 Ozoemena,Kenneth,Kuznetsova. Photosensitized transformation of 4-chlorophenol in the presence of aggregated and non-aggregated metallophthalocyanines J. Photo photobiol 2001 ,139(16), 217-224
62 王竹庭,鲁开娟 酞箐高分子及用途。高分子通报,1992(4):237-244
63 孙强,邓桂盛,姚小华 化学试剂。1996,18(3):138-140
64 孙强,邓桂盛,姚小华 有机化学,1996,16(1):83-87
65 Manassen J. Performance in a fluidized bed reactor of photocatalysts immobilized onto inert supports. Cat .Rev-Sci Eng,1974,9(2): 233-243
66 Masri Y, Hronec M , Stud Surf. Titanium dioxide/adsorbent hybrid photocatalysts for photodestruction of organic substances of dilute concentrations. Sci Catal,1991,66
67 Z G Xiong ,Y M Xu. Preparation and characterization of noble metal loaded/unloaded fullerenes (photocatalyst) for the visible light induced hydrogen production Environ. Sci. Technol.2005, 39,651-657
68 K Ozoemena, N Kuznetsova, T Nyokong. Preparation and characterization of noble metal loaded/unloaded fullerenes (photocatalyst) for the visible light induced hydrogen production . Mol. Catal., A 2001, 176, 29-40.
69 Meiqin Hu, Yiming Xu, Jincai Zhao. Photosensitezed Oxidation of substituted phenols on Aluminum phthalocyanine Intercalated
organoclay. Langmuir 2004, 20, 6302-6307
70 V Iliev, V Alexiev, L Bilyarska. J. Kinetics of the rapid dark reaction between methanol and oxygen in the presence of "photocatalyst"Mol. Catal. A: Chem. 2000,151(15) 161-169.
71 Meiqin Hu, Yiming Xu and Jincai Zhao. Photosensitezed Oxidation of substituted phenols on Aluminum phthalocyanine Intercalated organoclay. Langmuir 2004, 20, 6302-6307
72 Christophe J Barbe, Francine Arendse, Passcal Comte J. Am. Ceram. Electron-and hole-capture reactions on Pt/TiO2 photocatalyst exposed to methanol vapor studied with time-resolved infrared absorption spectroscopy Soc.1997,80(12) : 3157-3171
73 程沧沧,胡德文 TiO2—Fe3+体系降解耐酸大红染料的研究. 环境污染与防治,1998.20(4):17～19.
74 Teruhisa Ohono, Dsisuke Haga, Kan Fujihara. Effects of Iron (Ⅲ) Ions on Photocatalytic and Photoelectro-chemical Properties of Titanium Dioxide . J. Phys.Chem.B, 1997,101, 6415-6419.