掺铁二氧化钛光催化剂制备及其光催化性质的研究
摘要
在诸多半导体光催化材料中,由于TiO2具有化学稳定性好、光催化效率高,成本低、无毒等优点。已成为国内外环境科学工作者的研究热点。由于普通粉末状TiO2在使用过程中存在光活性不高、分离与回收困难以及易产生二次污染等问题,因此TiO_2改性、薄膜固载化逐渐成为新的研究热点。
本文对玻璃负载改性TiO_2膜的制备方法进行了研究。以钛酸四丁酯为前躯物,采用溶胶-凝胶法制备纳米TiO_2光催化材料。对含偶氮染料工业废水进行光催化降解,寻求光催化降解偶氮染料的工艺及条件。研究利用分光光度计、XRD、Raman、TG-DSC及HRTEM等测试手段对实验结果进行表征分析。
实验结果表明:Fe-TiO_2光催化材料的最优制备条件为驱体配比(摩尔比)为n=Ti(OC4H9)4:C2H5OH:HNO3:H2O=0.05:15:0.35:2;掺铁量W (Fe~(3+)/ TiO_2)=2.5%;煅烧温度为400℃;煅烧时间为2h;溶胶反应温度为40℃。
在此基础上,选择273nm波长的紫外灯和模拟阳光为光源对偶氮染料催化进行催化降解实验,实验结果表明:
紫外光下,TiO_2复合光催化剂对偶氮染料催化降解,偶氮废水初始吸光度A=0.104,废水初始pH值为4,最佳条件下Fe-TiO_2处理偶氮废水的脱色率达到94.7%,COD去除率达到85.2%。
自然光下,TiO_2光催化材料在酸性条件下对偶氮染料也有较理想的降解脱色效果,降解2h脱色率达53%。
研究表明,通过掺杂铁离子对二氧化钛进行的改性使反应的响应光谱向可见光拓展,并有效抑制电子—空穴对的复合,很大程度提高了光催化反应效率。
本文还研究了TiO_2光催化材料的重复利用。研究表明:该催化材料可重复使用,重复使用5次后脱色率仍达66.9%。
Photocatalytic materials in recent years,titanium dioxide has been widely used because of many advantages,such as better chemical stability,higher photocatalytic efficiency,cheapness and intoxicity. However powdered TiO_2 has some shortages such as low catalytic activity, difficulty in separation and recovery. Key problem in this research is modification of TiO_2 and immobilization technology.
In this paper,the methods of preparing Fe-TiO_2 thin film coated on glass-slide were investigated. It is suggested that sol-gel method using Ti(OC4H9)4 is the best method for preparation of TiO_2. Wastewater of azo dye was photodegraded by the photocatalyst TiO_2 and the optimal technique condition was obtained. Experimental results were characterized and analyzed by some modern measurements,such as UV-Vis,XRD,Raman,TG-DSC,HRTEM et al.
The optimal reaction condition was gotten after experiments and analysis: n=Ti(OC4H9)4:C2H5OH:HNO3:H2O=0.05:15:0.35:2 (mol ratio),hydrolysis at 40℃, W (Fe3+/ TiO_2)=2.5%(mol ratio) ,calcinations at 400℃for 2 hours.
On this basis,using ultraviolet germicidal lamp with wavelength of 273nm or vis-light as light-source,the contaminants removal effect in azo-dye wastewater.
Under UV irradiation, photocatalytic results of azo dye by TiO_2 compound photocatalyst showed that when initial concentration of azo-dye was A=0.104,solution pH was 4, decolorization rate after 2h could get to 94.7%. COD removal rate Could get to 85.2%.
Nevertheless,under solar irradiation,removal rate of azo-dye by TiO_2 compound photocatalyst could get to 53%.
The experiment results showed that photocatalytic activity was improved by sol-gel method by doping of Fe3+ and the photocatalytic efficiency were also raised obviously in sunlight. The addition of appropriate amount of Fe3+ is effective for improving the photo-catalytic activities of TiO_2 by inhibiting the formation of recombination centers of photo-generated electron-hole pairs on the surface of TiO_2 particles.
The reuse of photocatalytic material was also researched in this thesis. The experiment results showed that the material can be reused many times. The photocatalyst could be recycled several times and removal rate could get to 66.9% after reused 5 times.
本文对玻璃负载改性TiO_2膜的制备方法进行了研究。以钛酸四丁酯为前躯物,采用溶胶-凝胶法制备纳米TiO_2光催化材料。对含偶氮染料工业废水进行光催化降解,寻求光催化降解偶氮染料的工艺及条件。研究利用分光光度计、XRD、Raman、TG-DSC及HRTEM等测试手段对实验结果进行表征分析。
实验结果表明:Fe-TiO_2光催化材料的最优制备条件为驱体配比(摩尔比)为n=Ti(OC4H9)4:C2H5OH:HNO3:H2O=0.05:15:0.35:2;掺铁量W (Fe~(3+)/ TiO_2)=2.5%;煅烧温度为400℃;煅烧时间为2h;溶胶反应温度为40℃。
在此基础上,选择273nm波长的紫外灯和模拟阳光为光源对偶氮染料催化进行催化降解实验,实验结果表明:
紫外光下,TiO_2复合光催化剂对偶氮染料催化降解,偶氮废水初始吸光度A=0.104,废水初始pH值为4,最佳条件下Fe-TiO_2处理偶氮废水的脱色率达到94.7%,COD去除率达到85.2%。
自然光下,TiO_2光催化材料在酸性条件下对偶氮染料也有较理想的降解脱色效果,降解2h脱色率达53%。
研究表明,通过掺杂铁离子对二氧化钛进行的改性使反应的响应光谱向可见光拓展,并有效抑制电子—空穴对的复合,很大程度提高了光催化反应效率。
本文还研究了TiO_2光催化材料的重复利用。研究表明:该催化材料可重复使用,重复使用5次后脱色率仍达66.9%。
Photocatalytic materials in recent years,titanium dioxide has been widely used because of many advantages,such as better chemical stability,higher photocatalytic efficiency,cheapness and intoxicity. However powdered TiO_2 has some shortages such as low catalytic activity, difficulty in separation and recovery. Key problem in this research is modification of TiO_2 and immobilization technology.
In this paper,the methods of preparing Fe-TiO_2 thin film coated on glass-slide were investigated. It is suggested that sol-gel method using Ti(OC4H9)4 is the best method for preparation of TiO_2. Wastewater of azo dye was photodegraded by the photocatalyst TiO_2 and the optimal technique condition was obtained. Experimental results were characterized and analyzed by some modern measurements,such as UV-Vis,XRD,Raman,TG-DSC,HRTEM et al.
The optimal reaction condition was gotten after experiments and analysis: n=Ti(OC4H9)4:C2H5OH:HNO3:H2O=0.05:15:0.35:2 (mol ratio),hydrolysis at 40℃, W (Fe3+/ TiO_2)=2.5%(mol ratio) ,calcinations at 400℃for 2 hours.
On this basis,using ultraviolet germicidal lamp with wavelength of 273nm or vis-light as light-source,the contaminants removal effect in azo-dye wastewater.
Under UV irradiation, photocatalytic results of azo dye by TiO_2 compound photocatalyst showed that when initial concentration of azo-dye was A=0.104,solution pH was 4, decolorization rate after 2h could get to 94.7%. COD removal rate Could get to 85.2%.
Nevertheless,under solar irradiation,removal rate of azo-dye by TiO_2 compound photocatalyst could get to 53%.
The experiment results showed that photocatalytic activity was improved by sol-gel method by doping of Fe3+ and the photocatalytic efficiency were also raised obviously in sunlight. The addition of appropriate amount of Fe3+ is effective for improving the photo-catalytic activities of TiO_2 by inhibiting the formation of recombination centers of photo-generated electron-hole pairs on the surface of TiO_2 particles.
The reuse of photocatalytic material was also researched in this thesis. The experiment results showed that the material can be reused many times. The photocatalyst could be recycled several times and removal rate could get to 66.9% after reused 5 times.
引文
[1] A.Fujishima, K.Honda. Electrochemical photolysis of water at a semi conductor electrode,Nature,1972,37:238
[2] 邓南圣,吴峰.环境光化学[M].化学工业出版社.2005,18(10):308-316
[3] 井立强,袁福龙,侯海鸽,辛柏福.ZnO 纳米粒子的表面氧空位与其光致发光和光催化性能的关系.中国科学:B 辑.2004,34(4):310-314
[4] 吴玉琪,吕功煊,李树本.纳米 WO3 粉体的制备与光催化活性研究.化学学报.2004,62 (12):1134-1138,MJ03
[5] 冯新星,陈建勇,张建春.用丝素膜制备的纳米 CdS 及其光催化活性研究.功能高分子学报.2003,16 (4) :513-516
[6] 梁宇宁,黄智,覃思晗.Cu2O 光催化降解水中对硝基苯酚的研究.环境污染治理技术与设备.2003,4(10):36-39
[7] Reeves P,etal . Solar Energy,1992,48(6):413-420;(5)215-225
[8] 陈梅兰.二氧化钛光催化降解次甲基蓝的研究简报.浙江化工,2000(02):31-33
[9] 李芳柏,古国榜.亚甲基蓝溶液的光催化脱色及降解.环境污染与防治,1999 (06):1-4
[10] 张汝冰.均匀沉淀法制备纳米 TiO_2 及其在环保领域的应用.环境化学,1999,18(6):579-583
[11] 崔鹏,范益群. TiO_2 负载膜的制备、表征及光催化性能.催化学报,2000,21(5):494-496
[12] 马颖,管自生. TiO_2 薄膜的吸附能力对罗丹明 B 光降解过程的影响.催化学报,1999,20 (3):350-352
[13] 张坚亦,肖忠海.不锈钢负载半导体薄膜光催化降解有机污染物的研究.湖北化工2000,17 (04) :20-21
[14] 施利毅,古宏晨.SnO2-TiO_2 复合光催化剂的制备和性能.催化学报,1999,3(3):338-342
[15] 施利毅,李春忠.气相合成二氧化钦超细粒子光催化活性艳红 X-3B 脱色的研究.太阳能学报,2000 (1) :100-105
[16] 崔斌,杨亚婷. TiO_2 薄膜光催化降解 4- (2-吡啶偶氮)间苯二酚的研究[J],化学研究与应用,2000 (04) :394-397
[17] Dana Dvoranova,Vlasta Brezova,Milan Mazur,etal. Investigations of metal- doped titanium dioxide photocatalysts,Applied Catalysis B:Environmental,2002(37):91-105
[18] Yu-Hong Zhang,Armin Reller. Nanocrystalline iron-doped mesoporoustitania and its phase transition,J. Mater. Chem. 2001,11:2537-2541
[19] 张立,罗薇,王欣.Sn 掺杂的纳米 TiO_2 的拉曼散射.光散射学报 2000,11(4):365-367
[20] F B Li. Photocatalytic properties of gold/gold ion-modified titanium dioxide for wastewater treatment,Applied Catalysis A:Genera1,2002(228):15-17
[21] 张立德,牟季美.纳米材料和纳米结构.北京:科学出版社,2001,310
[22] Yongfa Zhu,Li Zhang,Wenqing Yao,et al. The chemical states andproperties of doped TiO_2 film photocatalyst prepared using the Sol-Gel methodwith TiCl4 as a precursor[J],Applied Surface Science,2000,158:32-37
[23] Heller A,Nair M,Davidson L,etal. Photocatalytic Purification andTreatment of Water and. Air[D] In:Ollis D、F,Al-Ekabi H. Elsevier.Amsterdam: 1993.139-150
[24] Rosenberg I,Brock J R,Heller A.-Collection Optics of TiO_2 Photocatalyst on Hollow Glass Microbeads Floating on OilSlicks,J.Phys.Chem.,1992,96:3423-3428
[25] 赵文宽,覃榆森.水面石油污染物的光催化降解,催化学报.1999,(03):369-372
[26] 陈士夫,程雪丽.空心玻璃微球附载 TiO_2 清除水面漂浮的油层.中国环境科学,1999,(01):47-50
[27] 方佑龄,赵文宽,尹少华,等.纳米 TiO_2 在空心陶瓷微球上的固定化及光催化分解辛烷.应用化学,1997,14 (2) :8183
[28] 方佑龄,赵文宽,张国华,等.用浸涂法制备漂浮负载型 TiO_2 薄膜光催化降解辛烷.环境化学,1997,16 (5): 413-417
[29] Harada K,Hisanaga T,Tanaka K. Photocatalytic degradation oforgano- phosphorous insecticides in aqueous semiconductor suspensions Wat.Res,1990,24(11):1415-1417.
[30] 陈梅兰. TiO_2 光催化降解低浓度溴氰菊酯.环境污染与防治,2000(1):13-14
[31] 霍爱群,谭欣.纳米 TiO_2 膜光催化降解废水中的阿特拉津的研究.工业水处理,1998,18 (3): 25-29
[32] 颜秀茹. TiO_2/SiO2 的制备及其光催化降解敌敌畏.应用化学,1999,16 (4):94-96
[33] 张新荣.负载型复合光催化剂 TiO_2.Al2O3/beads 降解有机磷农药.环境科学研究,2001,14 (2): 36-40
[34] 余家国,赵修建.太阳光 TiO_2 多孔膜光催化降解有机磷农药的研究.太阳能学报,2000,21(2):165-169
[35] Chen S F,Zhao M Y Photocatalytic degradation of organophosphorous pesticides using TiO_2 supported on fiber glass,Microchem.,1996,54(2):54-58
[36] Wen-Chen Wu. Adsorption and photo-oxidation of formamide on powdered TiO_2,Journal of Catalysis,2000 (195):416-419
[37] Lixin Cao,Zi Gao,Steven L,et al. Photocatalytic oxidation of tolueneon nanoscale TiO_2 catalysts: Studies of deactivation and regeneration,Journal of Catalysis 2000(196):253-261
[38] 孙福侠,吴鸣.纳米 TiO_2 光催化降解苯酚的动力学研究.催化学报,1999,20 (3):301-304
[39] 武正簧,田芳,赵君芙.利用 TiO_2 薄膜光催化降解苯酚.天然气化学杂志,2000 (04):164-174
[40] 吴合进,吴鸣.增强型电场协助光催化降解有机污染物.催化学报,2000(5):241-242
[41] Michael A,Gonzalez,Garry Howell. Photocatalytic selective oxidatioin of hydrocarbons in the aqueous phase,Joumal of Catalysis,1999,183:159-162
[42] Selli E. Role of Humic Acids in the TiO_2-photocatalyzed Degradation of Tetrachloroethene in Water,Wat. Res. 1999,33(8):1827-1836
[43] Chen D. Photodegradation Kinetics of 4-nitrophenolin TiO_2 Suspension, Wat.Res.,1998,32(11):3223-3234
[44] John C,Crittendden,Junbiao Liu,et al. Photocatalytic oxidation of chlorinated hydrocarbons in water,Wat.Res. 1997,31(3):429-438
[45] 武正簧. TiO_2 薄膜在光催化下处理含铬废水.太原理工大学学报,1999 (03):289-290
[46] 金华峰,李文戈.Fe/Ti/Si 复合纳米微粒光催化降解 NO2-.化学研究与应用,2001,13 (2):153-156
[47] 高远,徐安武.掺铁 TiO_2 用于 NO2-光催化降解研究.中山大学学报,2000,39(5):44-48
[48] A J Maira,K L Yeung,C Y Lee,et al.Size effects in gas-phasephoto-oxidatin oftrichloroethylene using nanometer sized TiO_2 catalysts,Journal of Catalysis 2000,192:185-196
[49] 陶跃武,赵梦月.空气中有害物质的光催化去除.催化学报,1999,18(4):345-347
[50] E Obuchi. Photocatalytic decomposition ofacetal-dehyde over TiO_2/ SiO2 catalyst,Chemical Engineering Science,1999(54):1525-1530
[51] 李功虎,马胡兰.纳米二氧化钦气相光催化降解三氯乙烯.催化学报,2000,21 (4): 350-354
[52] J S Kim,H K Joo,T K Lee,et al. Photocatalytic activity of TiO_2filmspreserved under different conditions: The gas-phase photocatalytic degradation reaction of trichloroethylene,Journal of Catalysis,2000(194):484-486
[53] 张峰,李庆霖. TiO_2 光催化剂的可见光敏化研究.催化学报,1999,3[J]:329-332
[54] 邱星林,徐安武.纳米级 TiO_2 光催化净化大气环保涂料的研制.中国涂料,2000(4):30-32
[55] 肖汉宁,李玉平.纳米二氧化钛的光催化特性及其应用.陶瓷学报,2001,22(3):191-195
[56] Aoyanna Yoshio,Nakanisi Ritsuko,Murai Keiko. Kenkyu Hokokusho-Toyo Shokuhin KogyoTanki Daigaku,Toyo Shokuhin Kenkyu Sho,2000,23:101-108
[57] Huang H, Wikes G L, etal .Structure-Property behavior of hybrid materials incorporating tetraethoxysilane with multifunctional poly (tetramethyene oxede)[J].Polymer,1989,30-37
[58] 武志刚,赵永祥,许临萍.气凝胶制备进展及其在催化方面的应用.化学研究与应用.2003,15(l):17-20
[59] 罗菊仙,赵中一. 半导体多相光催化氧化技术在环境保护中的应用研究进展.中国地质大学学报,2000,25(5):536-541
[60] Uinch Gesenhues. Calcination of metatitanic acid to titanium dioxide white pigments [J].Chem. Eng. Technol. 2001,24(7):685
[61] M. Koelsch,S. Cassaignon,J.F. Guillemoles,etal. Comparison of optical and lectro-chemical properties of anatase and brookite TiO_2 synthesized by the sol-gel method. Thin Solid Films,2002(403-404):312-319
[62] 张立德,牟季美.纳米材料和纳米结构[M].北京:科技出版社,2001,88-93
[63] Maira A J,Yeunf K L,Sorea J,et al. Gas-phase photo-oxidation of toluene using nanometer-size TiO_2catalysis [J].Applied Catalysis B. Environ. 2001, 29(4):327-336
[64] Kang M,Lee S Y,Chung C H,et al. Characterization of a TiO_2 photocatalyst synthesized by the solvothermal method and its catalytic performance for CHCl3 decomposition[J].J Photochem&Photobio A:Chem,2001,144 (2-3):185-191
[65] 张 梅,杨绪杰,陆路德等.提高二氧化钛光催化活性的研究进展.化工新型材料[J],2000,28(4):11-13
[66] Saquib M. Titanium Dioxide Mediated Photocatalytic Degradation of a Textile Dye Derivative,Acid Orange 8,in AqueousSuspensions[J].Desalination, 2003,155:255-263
[67] Saquib M,Muneer M. TiO_2-mediated Photocatalytic Degradation of a Triphenylethane Dye(gentian violet)in Aqueous Suspension[J].Dyes and Pigments,2003,56:37-49
[68] 王怡中.纳米二氧化钛的应用研究进展.催化学报[J],2000,21(4):327-331
[69] Goswami DY,Jof Solar Energy Engineering[J],1997,119:101-107
[70] 谷学谦,董秀芹.光催化氧化降解有机废物研究进展.化学工业与工程,2004,21(2)142-145
[71] 魏子栋,谭君,WalterZTang 等.第十届全国电化学会议论文集,G012,杭州,1999年 10 月
[72] ChenJ,DavidF,Ollisetal.Wat.Res.1999,33(3):661-668
[73] 王幼平,余家国,赵修建等. 掺铅 TiO_2 薄膜的制备及其光催化性能的研究.中国环境科学,1998,18(3):244-247
[74] 荆晶,王连军.过渡金属离子掺杂改性 TiO_2 的光催化性能研究进展.污染防治技术,1999,12(2):114-117
[75] 吴海宝,董晓. 过渡金属离子对阳离子蓝 X-GRRL 染料污水脱色率的影响.中国环境科学,1997,17(1):93-96
[76] KumarS,AllenP.WaterEnviorn.Res.1997,69:1238-1245.
[77] Wohrle D,Schneider G . Phortooxidation of 2-mercaptoethanol in the presence of water soluble phthalocyanine and perylene-3,4,9,10-tetracarboxylic acid derivatives [J].J. Mol.Catal.1992,75(2):L39-L44
[78] 于向阳,程继健,杨阳,等.稀土元素掺杂对光催化性能的影响[J].华东理工大学学报,2000,26(3):287-289
[79] 朱永法,张利,姚文清,等.溶胶凝胶法制备薄膜型 TiO_2 光催化剂[J].催化学报,1999,20(3):362-365
[80] 水淼,岳林海,徐铸德.稀土元素掺杂 TiO_2 的光催化特性[J].物理化学学报,2000,16(5):459-463
[81] 王承遇,钟萍,姜妍彦.掺杂铈对玻璃表明 TiO_2 薄膜上油酸的光催化降解的影响[J].催化学报,2000,21(50):443-446
[82] Dong Hyun Kim, MarcA Anderson. Environ Sci Technol.,1994,28:479-483
[83] Kvinodgopal,Ulick Stafford,Kimberly A Grayetal.J.Phys.Chem. 1994,98:6797-6803.
[84] 余锡宾,王桂华,罗衍庆,等.二氧化钛纳米微粒的制备与光催化活性.化学研究与应用,2000,12(1): 14-19
[85] Xie Y, Yuan C. Photocatalysis of neodymium mion modified TiO_2 sol under visible light irradiation[J].Applied Surface Science,2004,221(1-4):17-24
[86] AUGUGLIAROV. Azo-dyesphotocatalytic degradation in aqueous suspension of TiO_2 under solar irradiation [J]. Chemosphere,2002,49(10):1223-1230
[87] 於煌.可见光响应 TiO_2 光催化剂的研究进展.重庆共商大学学报,2006,23(2):21-26
[88] Zhu J.Fe3+-TiO_2 photocatalysts prepared by combining sol-gel method with hydrothermal treatment and their characterization[J].Journal of Photo chemistry and Photo biology A:Chemistry,2005,175(3):270-279
[89] Kosowskab,Mozias,Morawskiaw,et al.The preparation of TiO_2-nitrogen doped by calcinations of TiO_2 middle dotxH2O under ammonia at mosphere for visible light photocatalysis [J].Solar Energy Materials and SolarCells,2005,88(3):269-280
[90] Igor N,Martyanov and Kenneth J. Klabunde.Comparative study of TiO_2 particles in powder form and as a thin nanostructured film on quartz. Journal of Catalysis, 2004, 225:408-416
[91] Min Choa,Hyenmi Chungb,Wonyong Choic. Linear correlation between inactivation of E. coli and OH radical concentration in TiO_2 photocatalytic disinfection. Water Research, 2004 ,38: 1069-1077
[92] 鞠剑峰等.多孔纳米 Fe3+/ TiO_2 的制备及其光催化性能.精细化工,2006,5:45-49
[93] 余火根,余家国,程 蓓,赵修建.后处理对纳米 TiO_2 薄膜的表面结构和光催化活性的影响.无机化学学报,2003,19(8):873-878
[94] Parkhs,Kimdh,Kimsj,et al.The photocatalytic activity of 2.5wt% Cu-doped TiO_2 nano powders synthesized by mechanical alloying[J].Journal of Alloy sand Compounds,2005,400(12):100-105
[95] Wu Zhenghuang. Photocatalytic degradation of methylene blue over TiO_2 thin film. Journal of natural gas chemistry,2001,10(4):331-337
[96] 吴溪军.纳米材料的研究综述.黑龙江大学学报,2001,56(8):333-335
[97] 李慧蓉.黄孢原毛平革菌对两种双偶氮染料的脱色降解.染料工业,1999,36(2):42-47
[98] 陈荣圻.德国环保新法规对国产染料应用的影响(一) .印染,1995,21(1):5-10
[99] A. Stolz. Basic and applied aspects in the microbial degradation of azo dyes. Appl. Microbiol Biotechnol 2001(56):69–80
[100] Chantal Guillard,Hinda Lachheb,Ammar Houas,et al. Influence of chemical structure of dyes,of pH and of inorganic salts on their photocatalytic degradation by TiO_2 comparison of the efficiency of powder and supported TiO_2. Journal of Photochemistry and Photobiology A: Chemistry,2003,158(1):27-36
[101] Hinda Lachheb,Eric Puzenat,Ammar Houas. Photocatalytic degradation of various types of dyes(Alizarin S, Crocein Orange G,Methyl Red,Congo Red, Methylene Blue)in water by UV-irradiated titania Applied Catalysis B: Environmental. 2002,39(1):75-90
[102] N. Daneshvar,D. Salari,and A. R. Khataee. Photocatalytic degradation of azo dye acid red 14 in water: investigation of the effect of operational parameters. Journal of Photochemistry and Photobiology A: Chemistry,2003,157(1):111-116
[103] 王怡中,符雁,汤鸿霄.二氧化钛悬浆体系太阳光催化降解甲基橙研究.环境科学学报,1999,19(1):63-67
[104] Vincenzo Augugliaro,Claudio Baiocchi,Alessandra Bianco Prevot,etal. Azo-dyes photocatalytic degradation in aqueous suspension of TiO_2 under solar irradiation. Chemosphere,2002,49(10):1223-1230
[105] 李耀中,孔欣,周岳溪.流化床光催化反应器处理偶氮染料 4BS 废水中试研究.环境工程,2003,21(4):7-10
[106] N. Daneshvar,M. Rabbani,N. Modirshahla,etal. Kinetic modeling of photocatalytic degradation of Acid Red 27 in UV/TiO_2 process. Journal of Photochemistry and Photobiology A: Chemistry,2004,168(1-2):39-45
[2] 邓南圣,吴峰.环境光化学[M].化学工业出版社.2005,18(10):308-316
[3] 井立强,袁福龙,侯海鸽,辛柏福.ZnO 纳米粒子的表面氧空位与其光致发光和光催化性能的关系.中国科学:B 辑.2004,34(4):310-314
[4] 吴玉琪,吕功煊,李树本.纳米 WO3 粉体的制备与光催化活性研究.化学学报.2004,62 (12):1134-1138,MJ03
[5] 冯新星,陈建勇,张建春.用丝素膜制备的纳米 CdS 及其光催化活性研究.功能高分子学报.2003,16 (4) :513-516
[6] 梁宇宁,黄智,覃思晗.Cu2O 光催化降解水中对硝基苯酚的研究.环境污染治理技术与设备.2003,4(10):36-39
[7] Reeves P,etal . Solar Energy,1992,48(6):413-420;(5)215-225
[8] 陈梅兰.二氧化钛光催化降解次甲基蓝的研究简报.浙江化工,2000(02):31-33
[9] 李芳柏,古国榜.亚甲基蓝溶液的光催化脱色及降解.环境污染与防治,1999 (06):1-4
[10] 张汝冰.均匀沉淀法制备纳米 TiO_2 及其在环保领域的应用.环境化学,1999,18(6):579-583
[11] 崔鹏,范益群. TiO_2 负载膜的制备、表征及光催化性能.催化学报,2000,21(5):494-496
[12] 马颖,管自生. TiO_2 薄膜的吸附能力对罗丹明 B 光降解过程的影响.催化学报,1999,20 (3):350-352
[13] 张坚亦,肖忠海.不锈钢负载半导体薄膜光催化降解有机污染物的研究.湖北化工2000,17 (04) :20-21
[14] 施利毅,古宏晨.SnO2-TiO_2 复合光催化剂的制备和性能.催化学报,1999,3(3):338-342
[15] 施利毅,李春忠.气相合成二氧化钦超细粒子光催化活性艳红 X-3B 脱色的研究.太阳能学报,2000 (1) :100-105
[16] 崔斌,杨亚婷. TiO_2 薄膜光催化降解 4- (2-吡啶偶氮)间苯二酚的研究[J],化学研究与应用,2000 (04) :394-397
[17] Dana Dvoranova,Vlasta Brezova,Milan Mazur,etal. Investigations of metal- doped titanium dioxide photocatalysts,Applied Catalysis B:Environmental,2002(37):91-105
[18] Yu-Hong Zhang,Armin Reller. Nanocrystalline iron-doped mesoporoustitania and its phase transition,J. Mater. Chem. 2001,11:2537-2541
[19] 张立,罗薇,王欣.Sn 掺杂的纳米 TiO_2 的拉曼散射.光散射学报 2000,11(4):365-367
[20] F B Li. Photocatalytic properties of gold/gold ion-modified titanium dioxide for wastewater treatment,Applied Catalysis A:Genera1,2002(228):15-17
[21] 张立德,牟季美.纳米材料和纳米结构.北京:科学出版社,2001,310
[22] Yongfa Zhu,Li Zhang,Wenqing Yao,et al. The chemical states andproperties of doped TiO_2 film photocatalyst prepared using the Sol-Gel methodwith TiCl4 as a precursor[J],Applied Surface Science,2000,158:32-37
[23] Heller A,Nair M,Davidson L,etal. Photocatalytic Purification andTreatment of Water and. Air[D] In:Ollis D、F,Al-Ekabi H. Elsevier.Amsterdam: 1993.139-150
[24] Rosenberg I,Brock J R,Heller A.-Collection Optics of TiO_2 Photocatalyst on Hollow Glass Microbeads Floating on OilSlicks,J.Phys.Chem.,1992,96:3423-3428
[25] 赵文宽,覃榆森.水面石油污染物的光催化降解,催化学报.1999,(03):369-372
[26] 陈士夫,程雪丽.空心玻璃微球附载 TiO_2 清除水面漂浮的油层.中国环境科学,1999,(01):47-50
[27] 方佑龄,赵文宽,尹少华,等.纳米 TiO_2 在空心陶瓷微球上的固定化及光催化分解辛烷.应用化学,1997,14 (2) :8183
[28] 方佑龄,赵文宽,张国华,等.用浸涂法制备漂浮负载型 TiO_2 薄膜光催化降解辛烷.环境化学,1997,16 (5): 413-417
[29] Harada K,Hisanaga T,Tanaka K. Photocatalytic degradation oforgano- phosphorous insecticides in aqueous semiconductor suspensions Wat.Res,1990,24(11):1415-1417.
[30] 陈梅兰. TiO_2 光催化降解低浓度溴氰菊酯.环境污染与防治,2000(1):13-14
[31] 霍爱群,谭欣.纳米 TiO_2 膜光催化降解废水中的阿特拉津的研究.工业水处理,1998,18 (3): 25-29
[32] 颜秀茹. TiO_2/SiO2 的制备及其光催化降解敌敌畏.应用化学,1999,16 (4):94-96
[33] 张新荣.负载型复合光催化剂 TiO_2.Al2O3/beads 降解有机磷农药.环境科学研究,2001,14 (2): 36-40
[34] 余家国,赵修建.太阳光 TiO_2 多孔膜光催化降解有机磷农药的研究.太阳能学报,2000,21(2):165-169
[35] Chen S F,Zhao M Y Photocatalytic degradation of organophosphorous pesticides using TiO_2 supported on fiber glass,Microchem.,1996,54(2):54-58
[36] Wen-Chen Wu. Adsorption and photo-oxidation of formamide on powdered TiO_2,Journal of Catalysis,2000 (195):416-419
[37] Lixin Cao,Zi Gao,Steven L,et al. Photocatalytic oxidation of tolueneon nanoscale TiO_2 catalysts: Studies of deactivation and regeneration,Journal of Catalysis 2000(196):253-261
[38] 孙福侠,吴鸣.纳米 TiO_2 光催化降解苯酚的动力学研究.催化学报,1999,20 (3):301-304
[39] 武正簧,田芳,赵君芙.利用 TiO_2 薄膜光催化降解苯酚.天然气化学杂志,2000 (04):164-174
[40] 吴合进,吴鸣.增强型电场协助光催化降解有机污染物.催化学报,2000(5):241-242
[41] Michael A,Gonzalez,Garry Howell. Photocatalytic selective oxidatioin of hydrocarbons in the aqueous phase,Joumal of Catalysis,1999,183:159-162
[42] Selli E. Role of Humic Acids in the TiO_2-photocatalyzed Degradation of Tetrachloroethene in Water,Wat. Res. 1999,33(8):1827-1836
[43] Chen D. Photodegradation Kinetics of 4-nitrophenolin TiO_2 Suspension, Wat.Res.,1998,32(11):3223-3234
[44] John C,Crittendden,Junbiao Liu,et al. Photocatalytic oxidation of chlorinated hydrocarbons in water,Wat.Res. 1997,31(3):429-438
[45] 武正簧. TiO_2 薄膜在光催化下处理含铬废水.太原理工大学学报,1999 (03):289-290
[46] 金华峰,李文戈.Fe/Ti/Si 复合纳米微粒光催化降解 NO2-.化学研究与应用,2001,13 (2):153-156
[47] 高远,徐安武.掺铁 TiO_2 用于 NO2-光催化降解研究.中山大学学报,2000,39(5):44-48
[48] A J Maira,K L Yeung,C Y Lee,et al.Size effects in gas-phasephoto-oxidatin oftrichloroethylene using nanometer sized TiO_2 catalysts,Journal of Catalysis 2000,192:185-196
[49] 陶跃武,赵梦月.空气中有害物质的光催化去除.催化学报,1999,18(4):345-347
[50] E Obuchi. Photocatalytic decomposition ofacetal-dehyde over TiO_2/ SiO2 catalyst,Chemical Engineering Science,1999(54):1525-1530
[51] 李功虎,马胡兰.纳米二氧化钦气相光催化降解三氯乙烯.催化学报,2000,21 (4): 350-354
[52] J S Kim,H K Joo,T K Lee,et al. Photocatalytic activity of TiO_2filmspreserved under different conditions: The gas-phase photocatalytic degradation reaction of trichloroethylene,Journal of Catalysis,2000(194):484-486
[53] 张峰,李庆霖. TiO_2 光催化剂的可见光敏化研究.催化学报,1999,3[J]:329-332
[54] 邱星林,徐安武.纳米级 TiO_2 光催化净化大气环保涂料的研制.中国涂料,2000(4):30-32
[55] 肖汉宁,李玉平.纳米二氧化钛的光催化特性及其应用.陶瓷学报,2001,22(3):191-195
[56] Aoyanna Yoshio,Nakanisi Ritsuko,Murai Keiko. Kenkyu Hokokusho-Toyo Shokuhin KogyoTanki Daigaku,Toyo Shokuhin Kenkyu Sho,2000,23:101-108
[57] Huang H, Wikes G L, etal .Structure-Property behavior of hybrid materials incorporating tetraethoxysilane with multifunctional poly (tetramethyene oxede)[J].Polymer,1989,30-37
[58] 武志刚,赵永祥,许临萍.气凝胶制备进展及其在催化方面的应用.化学研究与应用.2003,15(l):17-20
[59] 罗菊仙,赵中一. 半导体多相光催化氧化技术在环境保护中的应用研究进展.中国地质大学学报,2000,25(5):536-541
[60] Uinch Gesenhues. Calcination of metatitanic acid to titanium dioxide white pigments [J].Chem. Eng. Technol. 2001,24(7):685
[61] M. Koelsch,S. Cassaignon,J.F. Guillemoles,etal. Comparison of optical and lectro-chemical properties of anatase and brookite TiO_2 synthesized by the sol-gel method. Thin Solid Films,2002(403-404):312-319
[62] 张立德,牟季美.纳米材料和纳米结构[M].北京:科技出版社,2001,88-93
[63] Maira A J,Yeunf K L,Sorea J,et al. Gas-phase photo-oxidation of toluene using nanometer-size TiO_2catalysis [J].Applied Catalysis B. Environ. 2001, 29(4):327-336
[64] Kang M,Lee S Y,Chung C H,et al. Characterization of a TiO_2 photocatalyst synthesized by the solvothermal method and its catalytic performance for CHCl3 decomposition[J].J Photochem&Photobio A:Chem,2001,144 (2-3):185-191
[65] 张 梅,杨绪杰,陆路德等.提高二氧化钛光催化活性的研究进展.化工新型材料[J],2000,28(4):11-13
[66] Saquib M. Titanium Dioxide Mediated Photocatalytic Degradation of a Textile Dye Derivative,Acid Orange 8,in AqueousSuspensions[J].Desalination, 2003,155:255-263
[67] Saquib M,Muneer M. TiO_2-mediated Photocatalytic Degradation of a Triphenylethane Dye(gentian violet)in Aqueous Suspension[J].Dyes and Pigments,2003,56:37-49
[68] 王怡中.纳米二氧化钛的应用研究进展.催化学报[J],2000,21(4):327-331
[69] Goswami DY,Jof Solar Energy Engineering[J],1997,119:101-107
[70] 谷学谦,董秀芹.光催化氧化降解有机废物研究进展.化学工业与工程,2004,21(2)142-145
[71] 魏子栋,谭君,WalterZTang 等.第十届全国电化学会议论文集,G012,杭州,1999年 10 月
[72] ChenJ,DavidF,Ollisetal.Wat.Res.1999,33(3):661-668
[73] 王幼平,余家国,赵修建等. 掺铅 TiO_2 薄膜的制备及其光催化性能的研究.中国环境科学,1998,18(3):244-247
[74] 荆晶,王连军.过渡金属离子掺杂改性 TiO_2 的光催化性能研究进展.污染防治技术,1999,12(2):114-117
[75] 吴海宝,董晓. 过渡金属离子对阳离子蓝 X-GRRL 染料污水脱色率的影响.中国环境科学,1997,17(1):93-96
[76] KumarS,AllenP.WaterEnviorn.Res.1997,69:1238-1245.
[77] Wohrle D,Schneider G . Phortooxidation of 2-mercaptoethanol in the presence of water soluble phthalocyanine and perylene-3,4,9,10-tetracarboxylic acid derivatives [J].J. Mol.Catal.1992,75(2):L39-L44
[78] 于向阳,程继健,杨阳,等.稀土元素掺杂对光催化性能的影响[J].华东理工大学学报,2000,26(3):287-289
[79] 朱永法,张利,姚文清,等.溶胶凝胶法制备薄膜型 TiO_2 光催化剂[J].催化学报,1999,20(3):362-365
[80] 水淼,岳林海,徐铸德.稀土元素掺杂 TiO_2 的光催化特性[J].物理化学学报,2000,16(5):459-463
[81] 王承遇,钟萍,姜妍彦.掺杂铈对玻璃表明 TiO_2 薄膜上油酸的光催化降解的影响[J].催化学报,2000,21(50):443-446
[82] Dong Hyun Kim, MarcA Anderson. Environ Sci Technol.,1994,28:479-483
[83] Kvinodgopal,Ulick Stafford,Kimberly A Grayetal.J.Phys.Chem. 1994,98:6797-6803.
[84] 余锡宾,王桂华,罗衍庆,等.二氧化钛纳米微粒的制备与光催化活性.化学研究与应用,2000,12(1): 14-19
[85] Xie Y, Yuan C. Photocatalysis of neodymium mion modified TiO_2 sol under visible light irradiation[J].Applied Surface Science,2004,221(1-4):17-24
[86] AUGUGLIAROV. Azo-dyesphotocatalytic degradation in aqueous suspension of TiO_2 under solar irradiation [J]. Chemosphere,2002,49(10):1223-1230
[87] 於煌.可见光响应 TiO_2 光催化剂的研究进展.重庆共商大学学报,2006,23(2):21-26
[88] Zhu J.Fe3+-TiO_2 photocatalysts prepared by combining sol-gel method with hydrothermal treatment and their characterization[J].Journal of Photo chemistry and Photo biology A:Chemistry,2005,175(3):270-279
[89] Kosowskab,Mozias,Morawskiaw,et al.The preparation of TiO_2-nitrogen doped by calcinations of TiO_2 middle dotxH2O under ammonia at mosphere for visible light photocatalysis [J].Solar Energy Materials and SolarCells,2005,88(3):269-280
[90] Igor N,Martyanov and Kenneth J. Klabunde.Comparative study of TiO_2 particles in powder form and as a thin nanostructured film on quartz. Journal of Catalysis, 2004, 225:408-416
[91] Min Choa,Hyenmi Chungb,Wonyong Choic. Linear correlation between inactivation of E. coli and OH radical concentration in TiO_2 photocatalytic disinfection. Water Research, 2004 ,38: 1069-1077
[92] 鞠剑峰等.多孔纳米 Fe3+/ TiO_2 的制备及其光催化性能.精细化工,2006,5:45-49
[93] 余火根,余家国,程 蓓,赵修建.后处理对纳米 TiO_2 薄膜的表面结构和光催化活性的影响.无机化学学报,2003,19(8):873-878
[94] Parkhs,Kimdh,Kimsj,et al.The photocatalytic activity of 2.5wt% Cu-doped TiO_2 nano powders synthesized by mechanical alloying[J].Journal of Alloy sand Compounds,2005,400(12):100-105
[95] Wu Zhenghuang. Photocatalytic degradation of methylene blue over TiO_2 thin film. Journal of natural gas chemistry,2001,10(4):331-337
[96] 吴溪军.纳米材料的研究综述.黑龙江大学学报,2001,56(8):333-335
[97] 李慧蓉.黄孢原毛平革菌对两种双偶氮染料的脱色降解.染料工业,1999,36(2):42-47
[98] 陈荣圻.德国环保新法规对国产染料应用的影响(一) .印染,1995,21(1):5-10
[99] A. Stolz. Basic and applied aspects in the microbial degradation of azo dyes. Appl. Microbiol Biotechnol 2001(56):69–80
[100] Chantal Guillard,Hinda Lachheb,Ammar Houas,et al. Influence of chemical structure of dyes,of pH and of inorganic salts on their photocatalytic degradation by TiO_2 comparison of the efficiency of powder and supported TiO_2. Journal of Photochemistry and Photobiology A: Chemistry,2003,158(1):27-36
[101] Hinda Lachheb,Eric Puzenat,Ammar Houas. Photocatalytic degradation of various types of dyes(Alizarin S, Crocein Orange G,Methyl Red,Congo Red, Methylene Blue)in water by UV-irradiated titania Applied Catalysis B: Environmental. 2002,39(1):75-90
[102] N. Daneshvar,D. Salari,and A. R. Khataee. Photocatalytic degradation of azo dye acid red 14 in water: investigation of the effect of operational parameters. Journal of Photochemistry and Photobiology A: Chemistry,2003,157(1):111-116
[103] 王怡中,符雁,汤鸿霄.二氧化钛悬浆体系太阳光催化降解甲基橙研究.环境科学学报,1999,19(1):63-67
[104] Vincenzo Augugliaro,Claudio Baiocchi,Alessandra Bianco Prevot,etal. Azo-dyes photocatalytic degradation in aqueous suspension of TiO_2 under solar irradiation. Chemosphere,2002,49(10):1223-1230
[105] 李耀中,孔欣,周岳溪.流化床光催化反应器处理偶氮染料 4BS 废水中试研究.环境工程,2003,21(4):7-10
[106] N. Daneshvar,M. Rabbani,N. Modirshahla,etal. Kinetic modeling of photocatalytic degradation of Acid Red 27 in UV/TiO_2 process. Journal of Photochemistry and Photobiology A: Chemistry,2004,168(1-2):39-45
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |