负载NiO的KA_2Nb_3O_（10）（A=Ca，Sr）制备及其光催化降解酸性红3B的研究
|
摘要
有机废水的处理是一个具有重大实用价值的研究课题。本文在综述光催化氧化技术和有机废水国内外处理技术的基础上，较为系统地研究了采用光催化氧化这种新技术来处理有机废水。研究表明，采用光催化氧化法处理有机废水，具有处理效率高、工艺简单、操作条件易控制、非选择性地降解有机污染物、无二次污染等突出优点，为有机废水的工业化处理提供了新思路和新途径，在有机废水治理方面有着广泛的应用前景。实验的主要内容包括：
1)暗反应和空白试验说明，单纯的光催化剂或单纯的光照都不能进行光催化氧化反应。光催化氧化反应必须在光催化剂存在下进行光照才能发生。
2)在光催化剂的筛选实验中，以酸性红3B为目标有机污染物，分别分析考察了钽酸盐、铌酸盐和一系列类钙钛矿型光催化剂的光催化活性，通过对酸性红3B光催化降解效果的比较，筛选得出负载NiO的铌酸钾钙和铌酸钾锶光催化性能较好。
3)以铌酸钾钙作为光催化剂，试验选择有代表性的有机污染物酸性红3B模拟有机废水为处理对象，分析考察了催化剂的投加量、负载量、光照时间、废水的初始浓度、pH值等因素对光催化氧化反应的影响规律，同时研究还从煅烧温度和时间、柱撑TiO_2等方面探讨了提高催化剂铌酸钾钙光催化反应活性的途径。
4)以铌酸钾锶作为光催化剂，再试验选择有代表性的有机污染物酸性红3B模拟有机废水为处理对象，分析考察了上述因素对光催化处理效果的影响。并在单因素试验的基础上着重考察了光催化剂的影响，即从煅烧温度、溶液的初始浓度、负载NiO等方面探讨了铌酸钾钙和铌酸钾锶两者之间光催化性能的差异。实验表明，无论它们负载NiO与否，铌酸钾锶的光催化性能总体来说比铌酸钾钙要好些，并用X射线衍射(XRD)和扫描电镜(SEM)对制备的催化剂进行了表征分析它们之间的区别。
5)较为详细地叙述了光催化氧化技术降解有机污染物的作用机理，并试着探讨了酸性红3B的降解机理。
Treatment of organic wastewater is an important task with practical value. On the basis of surveying photocatalytic oxidation technology and organic wastewater controlling approaches inside and outside country, organic wastewater treated by photocatalytic oxidation technology was in possession of the prominent virtues, such as high treatment efficiency, simple processing equipment, operation conditions controlled easily, organic pollutants degraded non-selectively, no secondary pollution, etc. So it can provide new thoughts and pathways for industrialization treatment of organic wastewater and will be endowed with extensive application prospect in the organic wastewater treatment. The main contents of experiment were as follows:
Dark reaction and blank experiment made out, simple photocatalyst or simple illumination can neither proceed photocatalytic oxidation reaction. Photocatalytic oxidation reaction can occur in the existence both of photocatalyst and of UV irradiation.
Using acid red 3B as objective pollutant in screening photocatalyst test, photocatalytic activity of tantalate, niobate and a series of perovskite-like catalyst was analyzed and reviewed respectively. The results indicated that the photocatalytic
activity of KCa2Nb3010 and KSr2Nb3010 loaded with NiO was good comparatively, when compared to their photodegradation effect for
acid red 3B.
Acid red 3B was selected as representative organic pollutant to simulate organic wastewater, which was treated by photocatalytic oxidation using KCa2Nb3010 as photocatalyst. Factors affecting photocatalytic oxidation reation were studied in details, such as catalyst amount, loaded content, time of UV irradiation, initial
concentration of wastewater, pH value, etc. the approaches to improve photocatalyst activity of KCa2Nb3010 were also investigated from the temperature and time of calcining, pillaring of TiO2 and other aspects.
Acid red 3B was again selected as representative organic pollutant to simulate organic wastewater which was treated by photocatalytic oxidation using KSr2Nb3O10 as photocatslyst, the influence of the above-described factors affecting photodegradation effect were further studied. On the basis of mono-factor test, effects of photocatalysts were reviewed stressly. Namely, the difference of photocatalytic performances of KCa2Nb3O10 and KSr2Nb3O10 was discussed from the temperature of calcining, initial concentration of solution, loading of NiO and so on. Experiment indicated, whether they were loaded with NiO or not, the photocatalytic performances of KSr2Nb3O10 were better than KCa2Nb3O10 generally. And catalysts prepared were characterized to analyze their difference by X-ray diffraction (XRD) and scanning electric microscope (SEM).
In addition, the mechanism of photocatalytic oxidation technology degrading organic pollutants was comparatively discussed in details, and the degrading mechanism of acid red 3B was tried to probe into.
1)暗反应和空白试验说明，单纯的光催化剂或单纯的光照都不能进行光催化氧化反应。光催化氧化反应必须在光催化剂存在下进行光照才能发生。
2)在光催化剂的筛选实验中，以酸性红3B为目标有机污染物，分别分析考察了钽酸盐、铌酸盐和一系列类钙钛矿型光催化剂的光催化活性，通过对酸性红3B光催化降解效果的比较，筛选得出负载NiO的铌酸钾钙和铌酸钾锶光催化性能较好。
3)以铌酸钾钙作为光催化剂，试验选择有代表性的有机污染物酸性红3B模拟有机废水为处理对象，分析考察了催化剂的投加量、负载量、光照时间、废水的初始浓度、pH值等因素对光催化氧化反应的影响规律，同时研究还从煅烧温度和时间、柱撑TiO_2等方面探讨了提高催化剂铌酸钾钙光催化反应活性的途径。
4)以铌酸钾锶作为光催化剂，再试验选择有代表性的有机污染物酸性红3B模拟有机废水为处理对象，分析考察了上述因素对光催化处理效果的影响。并在单因素试验的基础上着重考察了光催化剂的影响，即从煅烧温度、溶液的初始浓度、负载NiO等方面探讨了铌酸钾钙和铌酸钾锶两者之间光催化性能的差异。实验表明，无论它们负载NiO与否，铌酸钾锶的光催化性能总体来说比铌酸钾钙要好些，并用X射线衍射(XRD)和扫描电镜(SEM)对制备的催化剂进行了表征分析它们之间的区别。
5)较为详细地叙述了光催化氧化技术降解有机污染物的作用机理，并试着探讨了酸性红3B的降解机理。
Treatment of organic wastewater is an important task with practical value. On the basis of surveying photocatalytic oxidation technology and organic wastewater controlling approaches inside and outside country, organic wastewater treated by photocatalytic oxidation technology was in possession of the prominent virtues, such as high treatment efficiency, simple processing equipment, operation conditions controlled easily, organic pollutants degraded non-selectively, no secondary pollution, etc. So it can provide new thoughts and pathways for industrialization treatment of organic wastewater and will be endowed with extensive application prospect in the organic wastewater treatment. The main contents of experiment were as follows:
Dark reaction and blank experiment made out, simple photocatalyst or simple illumination can neither proceed photocatalytic oxidation reaction. Photocatalytic oxidation reaction can occur in the existence both of photocatalyst and of UV irradiation.
Using acid red 3B as objective pollutant in screening photocatalyst test, photocatalytic activity of tantalate, niobate and a series of perovskite-like catalyst was analyzed and reviewed respectively. The results indicated that the photocatalytic
activity of KCa2Nb3010 and KSr2Nb3010 loaded with NiO was good comparatively, when compared to their photodegradation effect for
acid red 3B.
Acid red 3B was selected as representative organic pollutant to simulate organic wastewater, which was treated by photocatalytic oxidation using KCa2Nb3010 as photocatalyst. Factors affecting photocatalytic oxidation reation were studied in details, such as catalyst amount, loaded content, time of UV irradiation, initial
concentration of wastewater, pH value, etc. the approaches to improve photocatalyst activity of KCa2Nb3010 were also investigated from the temperature and time of calcining, pillaring of TiO2 and other aspects.
Acid red 3B was again selected as representative organic pollutant to simulate organic wastewater which was treated by photocatalytic oxidation using KSr2Nb3O10 as photocatslyst, the influence of the above-described factors affecting photodegradation effect were further studied. On the basis of mono-factor test, effects of photocatalysts were reviewed stressly. Namely, the difference of photocatalytic performances of KCa2Nb3O10 and KSr2Nb3O10 was discussed from the temperature of calcining, initial concentration of solution, loading of NiO and so on. Experiment indicated, whether they were loaded with NiO or not, the photocatalytic performances of KSr2Nb3O10 were better than KCa2Nb3O10 generally. And catalysts prepared were characterized to analyze their difference by X-ray diffraction (XRD) and scanning electric microscope (SEM).
In addition, the mechanism of photocatalytic oxidation technology degrading organic pollutants was comparatively discussed in details, and the degrading mechanism of acid red 3B was tried to probe into.
引文
[1] 常振勇，崔连起．钙钛矿金属氧化物催化剂的研究与应用综述．精细石油化工，2002，3：49-53
[2] 张新荣，杨平，赵梦月．TiO_2／SiO_2／beads降解有机磷农药的研究[J]．工业水处理，2001，21(3)：13-15．
[3] Hindaka H, Asai Y, Zhao J et al. Photoelectrochemical Decomposition of Surfactants on a TiO_2/TCO Particulate Film. J. PHys. Chem, 1995, 99(20): 8244-8248
[4] Teichner S. J. Formenti M. Heterogenerous Photocatalysis. Photoelectrochemistry. Photocatalysis and Photoreactors, 1985: 457-489
[5] Hashimato K, Kawai T, Sakata T. Photocatalytic Reactions of Hydrocarbons and Fossil Fuels with Water Hydrogen Production and Oxidation. J. PHys. Chem, 1984, 88: 4083-4088
[6] Chiang K, Amal R, Tran T. Photocatalytic Oxidation of Cyanide: Kinetic and Mechanistic Studies. J Mol Catal A-Chem, 2003,193(1/2): 285-297
[7] Hoffmann M R, Martin S T, Choi Wonyong, et al. Environmental Applications of Semiconductor Photocatalysis [J]. Chem Rev, 1995, 95: 69-96
[8] Murabayashi M, Itoh E, Togashi K. Photocatalytic Degradation of Trichloroethylene in Liquid Phase and in Gas Phase by Using Titanium Dioxide with Platinum Position[J]. Denki Kagaku, 1998, 66(6): 671-672.
[9] 韦朝海，陈传好，王刚等．Fenton试剂催化氧化降解含硝基苯废水的特性[Z]．中国化学会第五届水处理化学学术研讨会会议论文集，2000年11月，北京：172-179．
[10] 程沧沧，胡德文．利用太阳光与固定床型反应器处理有机废水的研究[J]．环境科学与技术，1998，(2)：11-13．
[11] 李太友，刘琼玉．日光／H_2O_2／草酸铁络合物光解水溶液中的直接耐酸大红[J]．化工环保，2001，21(2)：84．
[12] 江立文，周岳溪，李耀中等．偶氮染料4BS光催化降解的特性研究[J]．环境工程，2001，19(1)：59-61
[13] 罗建中，齐水冰，操洲杏等．光催化氧化法处理垃圾填埋场渗滤液的研究[J]．环境污染与防治，2001，23(2)：63-65．
[14] Hidaka K, Nakamura T. J. Photochem. Photobiol. A: Chem. 1992, 66: 367-374
[15] Tanaka K, Harada K, Murata S. Photocatalytic Deposition of Metal Ions onto TiO_2 Powder. Solar Energy, 1986, 36: 159-161
[16] 戴遐明．半导体氧化物超细粉未对Cr(Ⅵ)的光催化还原作用研究．环境科学．1996，17(6)：34-36
[17] Serpone N, Borgarello E. Photochemical Reduction of Gold(Ⅲ) on Semicondutor Dispersion of TiO_2 in the Presence of CN Ions: Disposal of CN by Treatment with Hydrogen Peroxide. J. Photochem, 1987, 36: 273-288
[18] Laudise R.A. In: Dryburgh P M. et al. Advanced Crystal Growth. New York, London, Sydney, Tokyo: Prentice Hall, 1987, 267.
[19] 符小荣，张校刚，宋世庚，等．TiO_2 Pt-glass钠米薄膜的制备及对可溶性染料的光电催化降解[J]．应用化学，1997，14(4)：77-79．
[20] Dagan G, Tomkiewiez M. TiO_2 Aerogels for Photocatalytic Decomtamination of Aquatic Evironments[J]. J Phys Chem, 1993, 97(49): 12651-12655
[21] 傅希贤，桑丽霞，王俊珍，等．钙钛矿型(ABO_3)化合物的光催化活性极其影响因素[J]．天津大学学报，2001，34(2)：299-231．
[22] 谢有畅，杨乃芳，刘英骏，等．某些催化剂活性组分在载体表面分散的自发倾向[J]．中国科学(B辑)，1982(8)：673-682
[23] 张光旭，马沛生，吴元欣，等．非均相催化一步合成碳酸二苯酯的研究Ⅵ．活性组分及其负载方法对催化剂性能的影响．催化学报，2002，23(5)：413-416
[24] 张密林，周铭，景晓燕，等．柠檬酸法合成高性能BaFe_(12)O_(19)超微粉．硅酸盐通报，1996，4：22-25
[25] 杨海堃．气相氢氧焰水解法生产超微细二氧化钛[J]．中国粉体技术，2000，(2)：22-26．[J]．现代化工，1999，19(8)：46-48．
[26] 赵文宽．用高温热水解法制备高活性纳米TiO_2微晶光催化剂[J]．物理化学学报，1998，14(5)：424-428．
[27] 张立德．超微粉体制备与应用技术[M]．北京，中国石化出版社，2001：103-108．
[28] 林明，范以宁，刘浏，等．高能机械球磨法制备V_2O_5-TiO_2超细微粒催化剂[J]．催化学报，2001，22(6)：585-588．
[29] 赵文宽，方佑龄．光催化活性TiO_2薄膜的低温制备[J]．物理化学学报，2002，18(4)：368-371．
[30] 全燮，杨凤林，李和平．几种偶氮染料生物降解性研究[J]．环境科学，1991，12(3)：27
[31] 王文保，丁亚军，李学德等．碱性染料的半导体光催化降解研究[J]．农业环境保护，1997，16(4)：162
[32] 谭湘萍，蒋伟川，徐红等．载银半导体催化剂对印染废水的光解研究[J]．环境污染与防治，1994，15(5)：5
[33] Legrini O, Oliveros E and Braun A M. Photochemical Processes for Water Treatment[J]. Chem Rev, 1993, 93: 671～698
[34] Fox M. A and Dulay M. T. Heterogeneous Photocatalysis[J]. Chem Rev, 1993,93: 341～357
[35] Hoffmann M R, Martin S T, Choi W, et al. Environmental Applications of Semiconductor Photocatalysis[J]. Chem Rev, 1995, 95: 69～96
[36] Satoshi H, Nick S, Yoshiharu H, et al. Photocatalyzed Degradation of Polymers in Aqueous Semiconduetor Suspensions. 3. Photoxidation of a Solid Polymer: TiO_2-blended Poly(vinylchloride) Film[J]. Environ Sci Technol, 1998, 32: 4010～4016
[37] 岳林海，樊邦棠．半导体复合体系光催降解PVA研究[J]．环境污染与防治，1992，14(3)：5～8
[38] A. Wachtel, J. Electrochem. Soc, 1964, 111: 534
[39] G. Blasse, J. Solid State. Chem, 1988, 72: 72
[40] G. Blasse, L. H. Brixner, Mater. Res. Bull, 1989, 24: 363
[41] G. Blasse, G. J. Dirksen, P. Zhiwu, G. Wehrum, R. noppe, Chem. Phys. Lett,1993, 215: 363
[42] M. Wiegel, M. H. J. Emond, W. R. Stobbe, G. Blasse, J. Phys. Chem. Solids, 1994, 55: 773
[43] M. Wiegel, W. Middel, G. Blasse, J. Mater. Chem, 1995, 5: 981
[44] A.M. Srivastava, J. F. Ackerman, W. W. Beers, J. Solid State Chem, 1997, 134:
187
[45] H. Kato, A. Kudo. Photocatalytic Water Splitting into H_2 and O_2 over Various Tantalate Photocatalysts. Catalysis Today, 2003, 78: 561-569
[46] E.A. Zhurova, V.E. Zavodnik, V. G. Trirel' son, Kristakkografiya. 1995, 40: 816
[47] Hoffman, A. J, et al. J Phys Chem[J],1992,96: 5545
[48] 章杰，张皆怡．我国染料工业的现状和发展[J]．现代化工，2000，20(1)：2～5．
[49] 冀滨弘，章非娟．难降解有机污染物的处理技术[J]．污染与防治技术，1998，11(4)：250～253．
[50] Dion. M, Ganne. M, Tournoux. M. Mater. Res. Bull. 1981, 16
[51] 刘英骏，付立郡，唐有祺．NiO在TiO_2载体表面的分散状态．分子催化，1989，3(3)：173-180
[52] Lars Baetz Reutergardh, Mallika Langhasuk. Photocatalytic decoloouration of reactive azo dye: a comparison between TiO_2 and Cds photocatalysis[J]. Chemosphere, 1997, 35(3): 585-596
[53] Airoldi C, Nunes L M, Farias R F. The Intercalation of n-alkyldiamines into Crystalline Layered Titanate[J].Mater Res Bull, 2000, 35: 2081-2090
[54] Ogawa M, Takizawa Y. Intercalation of Alkylammonium Cations into a Layered Titanate in the Presence of Macrocyclic Compounds[J]. Chem Mater, 2000, 12(11): 3253-3255
[55] 张彭义，余刚，将展鹏．半导体光催化剂及其改性技术进展[J]．环境科学进展，1997，5(3)：1-10
[56] Hoffman M R, Martin S T. Environmental Applications of Semiconductor Photocatalysis. Chem. Rev, 1995, 95(1): 69-96
[57] 方亮，张辉，吴伯麟，等．层状类钙钛矿结构新铌酸盐KSr_2Nb_3O_(10)[J]．无机化学学报，1999，15(4)：504-506
[58] B. Krarutler and A.J. Bard, J. Am. Chem. Soc, 1978, 100: 5985
[59] M. Dion, M. Ganne and M. Tournoux, Mat, Res. Bull, 1981, 16: 1429
[60] M. Dion, M. Ganne and M. Tournoux, Rev, Chim. Miner, 1984, 21: 92
[61] A. J. Jacobson, J. W. Johnson and J. T. Lewandowski, Inorg, Chem, 1985, 24: 3729.
[62] M. Dion, M. Ganne and M. Tournoux, Rev. Chim. Miner, 1986, 23: 61
[63] J. Gopalakrishnan and V. Bhat, Mat. Res. Bull, 1987, 22: 413
[64] 朱毅青，林西平，马延风等．镍含量对超细粒子负载型催化剂性能的影响．分子催化，1998，12(6)：417-423
[65] Christophe B, Patriee J, Andre K.J Photochem Photobiol A: Chem. 2001,140: 87
[66] 黄志勇，杨惠芳，刘双江．沼泽红假单胞菌H3对酸性红B_(2GL)染料的厌氧脱色和降解作用．环境科学学报，1999，19(3)：307-312
[2] 张新荣，杨平，赵梦月．TiO_2／SiO_2／beads降解有机磷农药的研究[J]．工业水处理，2001，21(3)：13-15．
[3] Hindaka H, Asai Y, Zhao J et al. Photoelectrochemical Decomposition of Surfactants on a TiO_2/TCO Particulate Film. J. PHys. Chem, 1995, 99(20): 8244-8248
[4] Teichner S. J. Formenti M. Heterogenerous Photocatalysis. Photoelectrochemistry. Photocatalysis and Photoreactors, 1985: 457-489
[5] Hashimato K, Kawai T, Sakata T. Photocatalytic Reactions of Hydrocarbons and Fossil Fuels with Water Hydrogen Production and Oxidation. J. PHys. Chem, 1984, 88: 4083-4088
[6] Chiang K, Amal R, Tran T. Photocatalytic Oxidation of Cyanide: Kinetic and Mechanistic Studies. J Mol Catal A-Chem, 2003,193(1/2): 285-297
[7] Hoffmann M R, Martin S T, Choi Wonyong, et al. Environmental Applications of Semiconductor Photocatalysis [J]. Chem Rev, 1995, 95: 69-96
[8] Murabayashi M, Itoh E, Togashi K. Photocatalytic Degradation of Trichloroethylene in Liquid Phase and in Gas Phase by Using Titanium Dioxide with Platinum Position[J]. Denki Kagaku, 1998, 66(6): 671-672.
[9] 韦朝海，陈传好，王刚等．Fenton试剂催化氧化降解含硝基苯废水的特性[Z]．中国化学会第五届水处理化学学术研讨会会议论文集，2000年11月，北京：172-179．
[10] 程沧沧，胡德文．利用太阳光与固定床型反应器处理有机废水的研究[J]．环境科学与技术，1998，(2)：11-13．
[11] 李太友，刘琼玉．日光／H_2O_2／草酸铁络合物光解水溶液中的直接耐酸大红[J]．化工环保，2001，21(2)：84．
[12] 江立文，周岳溪，李耀中等．偶氮染料4BS光催化降解的特性研究[J]．环境工程，2001，19(1)：59-61
[13] 罗建中，齐水冰，操洲杏等．光催化氧化法处理垃圾填埋场渗滤液的研究[J]．环境污染与防治，2001，23(2)：63-65．
[14] Hidaka K, Nakamura T. J. Photochem. Photobiol. A: Chem. 1992, 66: 367-374
[15] Tanaka K, Harada K, Murata S. Photocatalytic Deposition of Metal Ions onto TiO_2 Powder. Solar Energy, 1986, 36: 159-161
[16] 戴遐明．半导体氧化物超细粉未对Cr(Ⅵ)的光催化还原作用研究．环境科学．1996，17(6)：34-36
[17] Serpone N, Borgarello E. Photochemical Reduction of Gold(Ⅲ) on Semicondutor Dispersion of TiO_2 in the Presence of CN Ions: Disposal of CN by Treatment with Hydrogen Peroxide. J. Photochem, 1987, 36: 273-288
[18] Laudise R.A. In: Dryburgh P M. et al. Advanced Crystal Growth. New York, London, Sydney, Tokyo: Prentice Hall, 1987, 267.
[19] 符小荣，张校刚，宋世庚，等．TiO_2 Pt-glass钠米薄膜的制备及对可溶性染料的光电催化降解[J]．应用化学，1997，14(4)：77-79．
[20] Dagan G, Tomkiewiez M. TiO_2 Aerogels for Photocatalytic Decomtamination of Aquatic Evironments[J]. J Phys Chem, 1993, 97(49): 12651-12655
[21] 傅希贤，桑丽霞，王俊珍，等．钙钛矿型(ABO_3)化合物的光催化活性极其影响因素[J]．天津大学学报，2001，34(2)：299-231．
[22] 谢有畅，杨乃芳，刘英骏，等．某些催化剂活性组分在载体表面分散的自发倾向[J]．中国科学(B辑)，1982(8)：673-682
[23] 张光旭，马沛生，吴元欣，等．非均相催化一步合成碳酸二苯酯的研究Ⅵ．活性组分及其负载方法对催化剂性能的影响．催化学报，2002，23(5)：413-416
[24] 张密林，周铭，景晓燕，等．柠檬酸法合成高性能BaFe_(12)O_(19)超微粉．硅酸盐通报，1996，4：22-25
[25] 杨海堃．气相氢氧焰水解法生产超微细二氧化钛[J]．中国粉体技术，2000，(2)：22-26．[J]．现代化工，1999，19(8)：46-48．
[26] 赵文宽．用高温热水解法制备高活性纳米TiO_2微晶光催化剂[J]．物理化学学报，1998，14(5)：424-428．
[27] 张立德．超微粉体制备与应用技术[M]．北京，中国石化出版社，2001：103-108．
[28] 林明，范以宁，刘浏，等．高能机械球磨法制备V_2O_5-TiO_2超细微粒催化剂[J]．催化学报，2001，22(6)：585-588．
[29] 赵文宽，方佑龄．光催化活性TiO_2薄膜的低温制备[J]．物理化学学报，2002，18(4)：368-371．
[30] 全燮，杨凤林，李和平．几种偶氮染料生物降解性研究[J]．环境科学，1991，12(3)：27
[31] 王文保，丁亚军，李学德等．碱性染料的半导体光催化降解研究[J]．农业环境保护，1997，16(4)：162
[32] 谭湘萍，蒋伟川，徐红等．载银半导体催化剂对印染废水的光解研究[J]．环境污染与防治，1994，15(5)：5
[33] Legrini O, Oliveros E and Braun A M. Photochemical Processes for Water Treatment[J]. Chem Rev, 1993, 93: 671～698
[34] Fox M. A and Dulay M. T. Heterogeneous Photocatalysis[J]. Chem Rev, 1993,93: 341～357
[35] Hoffmann M R, Martin S T, Choi W, et al. Environmental Applications of Semiconductor Photocatalysis[J]. Chem Rev, 1995, 95: 69～96
[36] Satoshi H, Nick S, Yoshiharu H, et al. Photocatalyzed Degradation of Polymers in Aqueous Semiconduetor Suspensions. 3. Photoxidation of a Solid Polymer: TiO_2-blended Poly(vinylchloride) Film[J]. Environ Sci Technol, 1998, 32: 4010～4016
[37] 岳林海，樊邦棠．半导体复合体系光催降解PVA研究[J]．环境污染与防治，1992，14(3)：5～8
[38] A. Wachtel, J. Electrochem. Soc, 1964, 111: 534
[39] G. Blasse, J. Solid State. Chem, 1988, 72: 72
[40] G. Blasse, L. H. Brixner, Mater. Res. Bull, 1989, 24: 363
[41] G. Blasse, G. J. Dirksen, P. Zhiwu, G. Wehrum, R. noppe, Chem. Phys. Lett,1993, 215: 363
[42] M. Wiegel, M. H. J. Emond, W. R. Stobbe, G. Blasse, J. Phys. Chem. Solids, 1994, 55: 773
[43] M. Wiegel, W. Middel, G. Blasse, J. Mater. Chem, 1995, 5: 981
[44] A.M. Srivastava, J. F. Ackerman, W. W. Beers, J. Solid State Chem, 1997, 134:
187
[45] H. Kato, A. Kudo. Photocatalytic Water Splitting into H_2 and O_2 over Various Tantalate Photocatalysts. Catalysis Today, 2003, 78: 561-569
[46] E.A. Zhurova, V.E. Zavodnik, V. G. Trirel' son, Kristakkografiya. 1995, 40: 816
[47] Hoffman, A. J, et al. J Phys Chem[J],1992,96: 5545
[48] 章杰，张皆怡．我国染料工业的现状和发展[J]．现代化工，2000，20(1)：2～5．
[49] 冀滨弘，章非娟．难降解有机污染物的处理技术[J]．污染与防治技术，1998，11(4)：250～253．
[50] Dion. M, Ganne. M, Tournoux. M. Mater. Res. Bull. 1981, 16
[51] 刘英骏，付立郡，唐有祺．NiO在TiO_2载体表面的分散状态．分子催化，1989，3(3)：173-180
[52] Lars Baetz Reutergardh, Mallika Langhasuk. Photocatalytic decoloouration of reactive azo dye: a comparison between TiO_2 and Cds photocatalysis[J]. Chemosphere, 1997, 35(3): 585-596
[53] Airoldi C, Nunes L M, Farias R F. The Intercalation of n-alkyldiamines into Crystalline Layered Titanate[J].Mater Res Bull, 2000, 35: 2081-2090
[54] Ogawa M, Takizawa Y. Intercalation of Alkylammonium Cations into a Layered Titanate in the Presence of Macrocyclic Compounds[J]. Chem Mater, 2000, 12(11): 3253-3255
[55] 张彭义，余刚，将展鹏．半导体光催化剂及其改性技术进展[J]．环境科学进展，1997，5(3)：1-10
[56] Hoffman M R, Martin S T. Environmental Applications of Semiconductor Photocatalysis. Chem. Rev, 1995, 95(1): 69-96
[57] 方亮，张辉，吴伯麟，等．层状类钙钛矿结构新铌酸盐KSr_2Nb_3O_(10)[J]．无机化学学报，1999，15(4)：504-506
[58] B. Krarutler and A.J. Bard, J. Am. Chem. Soc, 1978, 100: 5985
[59] M. Dion, M. Ganne and M. Tournoux, Mat, Res. Bull, 1981, 16: 1429
[60] M. Dion, M. Ganne and M. Tournoux, Rev, Chim. Miner, 1984, 21: 92
[61] A. J. Jacobson, J. W. Johnson and J. T. Lewandowski, Inorg, Chem, 1985, 24: 3729.
[62] M. Dion, M. Ganne and M. Tournoux, Rev. Chim. Miner, 1986, 23: 61
[63] J. Gopalakrishnan and V. Bhat, Mat. Res. Bull, 1987, 22: 413
[64] 朱毅青，林西平，马延风等．镍含量对超细粒子负载型催化剂性能的影响．分子催化，1998，12(6)：417-423
[65] Christophe B, Patriee J, Andre K.J Photochem Photobiol A: Chem. 2001,140: 87
[66] 黄志勇，杨惠芳，刘双江．沼泽红假单胞菌H3对酸性红B_(2GL)染料的厌氧脱色和降解作用．环境科学学报，1999，19(3)：307-312