TiO_2-γAl_2O_3球形颗粒光催化降解2，4-二氯酚
|
摘要
二氧化钛因其价廉、对人体无毒性及其具有的光催化性能,今天越来越多的研究者开始深入对其的研究和探索,其应用也越来越广泛。但目前的Ti02的应用还有它的局限性,主要原因在于其形态的不足,目前研究制备的Ti02纳米级光催化剂主要有粉体和溶胶两种形态,这两种形态在应用上都不利于回收,本实验采用溶胶-凝胶法制备出颗粒的粒径在1-2mm的TiO2-γAl2O3微球并用其进行光催化反应降解废水中的2,4-二氯酚有机物,发现制备的该微球具有很高的光催化性能。
在实验过程中,分别进行对比实验来研究pH、超声波时间、干燥蒸发水份的多少以及煅烧时的煅烧方法等各因素对制备出的微球的成球率的影响后确定最佳的一组制备工艺。
试验中还设计了在不同的铝钛摩尔比、制备微球的煅烧温度和煅烧时间等条件因素下制备TiO2-γAl2O3微球光催化剂,并对2,4-二氯酚进行光催化降解反应,通过采用XRD对制备的微球进行表征,以及用高效液相色谱法对光催化降解后的2,4-二氯酚溶液进行浓度的测定,通过两种结果的对比后确定出一组最佳的制备TiO2-γAl2O3微球的最佳铝钛摩尔比、煅烧温度和煅烧时间等因素。
本论文实验还采用均匀设计法来设计实验考虑光催化反应中的反应液中的C1-浓度、pH值、微球的浓度和2,4-二氯酚的浓度对TiO2-γAl2O3微球光催化降解氯酚的反应速率的影响,通过高效液相测定后用回归分析法分析数据后确定最佳的反应条件,综合上述的所有条件在最佳工艺条件下制备和进行光催化降解反应进行微球的重复使用实验,看TiO2-γAl2O3微球的重复使用率,并液质联用仪对光催化液进行测定分析其中间产物和降解机理。
TiO2 is being increasingly researched and explored by researchers and implemented more widely, for its inexpensive, non-toxic to humans and photochemical catalysis. However, there are also some limitations of its implementation for its shape shortages. There are two shapes of TiO2 nanometer photocatalyst, powder and sol, are being researched and prepared nowadays, both of which are not conducive to recovery in implementation. The TiO2-γAl2O3 micro-balloons were prepared in this paper with the sol-gel method, whose grain diameter is between 1-2 mm. In a photocatalytic reactions degradation 2,4-DCP, we found it has high photocatalytic performance.
During the experiment process, comparative experiments were carried out respectively to research the influences of such elements as pH, ultrasonic time, amount of water being dried and evaporated and calcinations methods, in granulation rate of micro-balloons being prepared. An optimum preparation technology was settled at last.
The TiO2-γAl2O3 micro-balloon photochemical catalysis was prepared in this experiment with the different conditional factors such as Al-Ti molar ratio, calcination temperature of micro-balloon preparation and calcination time. And the photocatalytic degradation of 2,4-DCP was carried out. The solution concentration of 2,4-DCP had been photocatalytic degraded was measured by High Performance Liquid Chromatography, through representation of micro-balloon being prepared by XRD. By comparing the results, a set of factors including the best Al-Ti molar ratio of TiO2-γAl2O3 micro-balloon, calcination temperature and calcination time was defined.
Uniform design method was also adopted in this paper to design experiments, considering the influence of Cl" concentration, pH, concentration of micro-balloon and 2,4-DCP concentration in the reaction solution of photocatalytic reaction on photocatalytic degradation rate of TiO2-γAl2O3 micro-balloon chlorophenol photocatalytic. The best reaction condition was confirmed by regression analysis method after determined by high performance liquid. All of the conditions above were synthesized in the best preparation technology process and reuse of micro-balloon in photocatalytic degradation, to watch the reuse rate of TiO2-γAl2O3 micro-balloon. Also the intermediate product and degradation mechanism of photochemical catalysis solution were measured and analyzed byHPLC-MS.
在实验过程中,分别进行对比实验来研究pH、超声波时间、干燥蒸发水份的多少以及煅烧时的煅烧方法等各因素对制备出的微球的成球率的影响后确定最佳的一组制备工艺。
试验中还设计了在不同的铝钛摩尔比、制备微球的煅烧温度和煅烧时间等条件因素下制备TiO2-γAl2O3微球光催化剂,并对2,4-二氯酚进行光催化降解反应,通过采用XRD对制备的微球进行表征,以及用高效液相色谱法对光催化降解后的2,4-二氯酚溶液进行浓度的测定,通过两种结果的对比后确定出一组最佳的制备TiO2-γAl2O3微球的最佳铝钛摩尔比、煅烧温度和煅烧时间等因素。
本论文实验还采用均匀设计法来设计实验考虑光催化反应中的反应液中的C1-浓度、pH值、微球的浓度和2,4-二氯酚的浓度对TiO2-γAl2O3微球光催化降解氯酚的反应速率的影响,通过高效液相测定后用回归分析法分析数据后确定最佳的反应条件,综合上述的所有条件在最佳工艺条件下制备和进行光催化降解反应进行微球的重复使用实验,看TiO2-γAl2O3微球的重复使用率,并液质联用仪对光催化液进行测定分析其中间产物和降解机理。
TiO2 is being increasingly researched and explored by researchers and implemented more widely, for its inexpensive, non-toxic to humans and photochemical catalysis. However, there are also some limitations of its implementation for its shape shortages. There are two shapes of TiO2 nanometer photocatalyst, powder and sol, are being researched and prepared nowadays, both of which are not conducive to recovery in implementation. The TiO2-γAl2O3 micro-balloons were prepared in this paper with the sol-gel method, whose grain diameter is between 1-2 mm. In a photocatalytic reactions degradation 2,4-DCP, we found it has high photocatalytic performance.
During the experiment process, comparative experiments were carried out respectively to research the influences of such elements as pH, ultrasonic time, amount of water being dried and evaporated and calcinations methods, in granulation rate of micro-balloons being prepared. An optimum preparation technology was settled at last.
The TiO2-γAl2O3 micro-balloon photochemical catalysis was prepared in this experiment with the different conditional factors such as Al-Ti molar ratio, calcination temperature of micro-balloon preparation and calcination time. And the photocatalytic degradation of 2,4-DCP was carried out. The solution concentration of 2,4-DCP had been photocatalytic degraded was measured by High Performance Liquid Chromatography, through representation of micro-balloon being prepared by XRD. By comparing the results, a set of factors including the best Al-Ti molar ratio of TiO2-γAl2O3 micro-balloon, calcination temperature and calcination time was defined.
Uniform design method was also adopted in this paper to design experiments, considering the influence of Cl" concentration, pH, concentration of micro-balloon and 2,4-DCP concentration in the reaction solution of photocatalytic reaction on photocatalytic degradation rate of TiO2-γAl2O3 micro-balloon chlorophenol photocatalytic. The best reaction condition was confirmed by regression analysis method after determined by high performance liquid. All of the conditions above were synthesized in the best preparation technology process and reuse of micro-balloon in photocatalytic degradation, to watch the reuse rate of TiO2-γAl2O3 micro-balloon. Also the intermediate product and degradation mechanism of photochemical catalysis solution were measured and analyzed byHPLC-MS.
引文
[1]Fujishima Ahonda K. Electrochemical photocatalysis of water at a semiconductor electrode[J].Nature,1972,37 (1):238-245.
[2]Garey J H, Awrence J, Tosine HM. Photodechloriation of PCB's in the presence of titanium dioxide in aqueous suspensions[J].Bull.Environ.Contam.Toxicol,1976,16:697-701.
[3]张乐观,朱新锋.微球负载TiO2催化剂的制备与降解苯酚性能[J].化工进展,2008,27(4)：577-580.
[4]黄冬根,涂志斌等.光催化/生物三相流化床工艺处理4一氯酚废水[J].中国给水排水,2009,25(19)：74-76.
[5]范少华.含铜酸性废水与醋化废水综合治理试验[J].河南科技大学学报：自然科学版,2004,25(1)：103-107.
[6]崔玉民,范少华.复合纳米微粒Rh3+/TiO2/SnO2的合成、表征及光催化降解4-(2-吡啶偶氮)间苯二酚研究[J].感光科学与光化学,2003,21(3)：161-167.
[7]Dhanajeyan M R, Kandavelu V, Renganthan R.A Study on Photocatalytic Reaction of TiO2 with Certain Pyrimidine Bases:Effects of Dopants(Fe3+) and Calcinnation[J].J Molec Catal A,2000,151 (3):217-222.
[8]崔玉民.采用TiO2光催化剂对河水中污染物进行光催化降解[J].河南科技大学学报：自然科学版,2003,24(1)：94-97.
[9]张文彬,谢利群,白元峰.纳米Ti02光催化机理及改性研究进展[J].化工科技,2005,13(6)：52-57.
[10]孙晓君,蔡伟民,井立强等.二氧化钛半导体光催化技术进展[J].哈尔滨工业大学学报,2001,33(4)：534-541.
[11]黄艳娥,刘冬莲,纳米TiO2在水处理中的应用[J].河北化工,2000,(2):8-11.
[12]张立德,牟季美.纳米材料学[M].沈阳：辽宁科学出版社,1994.
[13]陈晓波.二氧化钛纳米材料及其能源应用[J].催化学报,2009,30(8)：839-851.
[14]符小荣,张校刚,宋世庚等TiO2/Pt/glass纳米薄膜的制备及对可溶性燃料的光催化降解[J].应用化学,1997,14(4)：77-79.
[15]席北斗,孔欣,刘纯新等.加铂修饰型催化剂光催化氧化五氛酚[J].环境化学,2001,20：27-31.
[16]Choi W K, Termin A, Hoffmann M R.The Role of Metal Ion Dopants in Quantum-size TiO2: Correlation Between Photoreactivity Charge Carrier Recombination Dynamics [J]. J Phys Chem,1994,98:13669-13672.
[17]Gratzel M, Howe R F.Electron Paramagnetic Resonance Studies of Doped TiO2 Colloids[J].J Phys Chem,1990,94:2566-2569.
[18]Deng H H, Lu Z H, Chen Y C.H2O2Enhanced Photocatalytic Oxidation of Microcystin-LR Using TiO2[J].J Chem Phys,1998,231:95-99.
[19]徐建华,戴维林,李静霞等.银修饰的二氧化钛多孔微管的制备、表征及光催化活性[J].化学学报,2007,65(12)：1172-1176.
[20]李海龙,罗武林,陈涛等.载Ag二氧化钛纳米管的制备及其光催化性能[J].物理化学学报,2008,24(8)：1383-1386.
[21]李芳柏,李湘中,李薪军等WO3/TiO2纳米材料的制备及光催化性能[J].化学学报,2001,59(7)：1072-1075.
[22]水淼,岳林海,徐铸德.稀土镧掺杂二氧化钛的光催化特性[J].物理化学学报,2000,16(5)：459-463.
[23]景文珩,王韦岗,邢卫红.大孔-介孔氮掺杂二氧化钛的制备及其光催化性能测试[J].催化学报,2009,30(5):426-432.
[24]Huang Dong gen, Liu Ai ming, Tu Zhi bin, Quan Shui-qing, Liu Lei. The preparation of a crystal nano N-F-Sm-TiO2 Sol and its photocatalytic degradation for 4-chlorophenol[J]. Journal of Nanchang University (Engineering & Technology),2009,31(3):286-292.
[25]张青红,高镰,郑珊.金红石相二氧化钛纳米晶的光催化活性[J]化学学报,2001,59(11):1909-1911.
[26]史载锋,范益群,徐南平等.不同光源对光催化降解亚甲基蓝的影响[J].南京化工大学学报,2000,22(1)：59-63.
[27]王怡中,符雁等.甲基橙溶液多相光催化降解的研究[J].环境科学,1998,19(1):1-4.
[28]赵梦月,罗菊芬.有机磷农药光催化分解的可行性研究[J].化工环保,1993,13(2):74-79.
[29]Mohammed A, Low G K, Matthews R W, Effects of common inorganic anions on rates of photocatalytic oxidation of organic carbon over illuminated titanium dioxide[J].J Phys Chem,1990,94 (17):6820-6825.
[30]Kormann C, Bahnemann D W, Hoffmann M R.Photolysis of.chloroform and other organic molecules in aqueous TiO2 suspensions[J].Environ Sic Technol,1991,25 (3):494-500.
[31]花日茂,岳永德,李学德.几种偶氮染料的光催化降解研究[J].安徽农业大学学报,2000,27(2)： 141-145.
[32]Bahneman D W, et al.Mechanistic studies of water detoxification in huminated TiO2 suspensions[J].Solar Energy Materials,1999,24:564-583.
[33]Claudis K, Bahnemann D W, Hoffmann M R, Photocatalytic production of H2O2 and organic peroxides in aqueous TiO2、ZnO and desert sand[J].Environ Sci Technol,1988,22 (7): 798-806.
[34]Hoffman A J, Carraway E R., Hoffmann M R.Photocatalytic production of H2O2 and organic peroxides on quantumsized semiconductor colloids[J].Environ Sci Technol,1994,28 (5): 776-785.
[35]Carraway E R, Hoffman A J, Hoffmann M R. Photocatalytic oxidation of organic acids on quantunsized semiconductor colloids[J].Environ Sci Tecnol,1994,28 (5):786-793.
[36]Fernando J B, Jose M E, Juan F G.Industrial wastewater advanced oxidation. Ozone combined with hydrogenperoxide or UV radiation[J].Wat Res,1997,31 (10):2415-2428.
[37]孟季如,赵磊,梁国正等.无机非金属纳米微粒的制备方法[J].化工新型材料,2000,28(4): 23-27.
[38]王世敏,许祖勋,傅晶.纳米材料制备技术[M].北京：化学工业出版社,2004.
[39]赵小远.纳米氧化钛的制备及应用[J].稀有金属与硬质合金,2003,31(1):26-27.
[40]解宪英.纳米级二氧化钛的制备及其应用进展(上)[J].上海化工,2001,26(3):37-38,54.
[41]陈晓波.二氧化钛纳米材料及其能源应用[J].催化学报,2009,30(8)：839-851.
[42]吴迪,王鼎聪,赵德智.纳米二氧化钛制备工艺研究进展[J].钛工业进展,2005(5):32-35.
[43]刘威,陈爱平,林嘉平等.均相水解法制备金红石含量可控的纳米TiO2[J].化学学报,2004,62(12)：1148-1152.
[44]张青红,高濂,郭景坤.四氯化钛水解法制备纳米氧化钛超细粉体[J].无机材料学报,2000(1)：21-23.
[45]李海龙,朱地,刘冉冉.Ti(S04)2水解一水热法制备锐钛型纳米Ti02及其光催化性能[J].光谱学与光谱分析学,2010,30(3)：767-769.
[46]祖庸,雷闫盈,樊安.纳米Ti02在化妆品中的应用[J].钛工业进展,1998(1):28-30.
[47]孙家跃,肖昂,杜海燕.均相沉淀-发泡法制备纳米氧化钛的应用[J].国外建材科技,2004(4)：57-59.
[48]王金敏,杜芳林,崔作林等.纳米氧化钛的沉淀法制备及表征[J].青岛化工学院学报,2001(2)：122-123.
[49]胡安正,唐超群.Sol-Gel法制备纳米氧化钛的原料配比和胶凝过程机理研究[J].功能材料,2002(4)：394-396.
[50]李海龙,朱地,刘冉冉.Ti(S04)2水解一水热法制备锐钛型纳米Ti02及其光催化性能[J].光谱学与光谱分析,2010,30(3)：767-769.
[51]Zhang Baolong, Chen Baishun, Shi Keyu, et al. Preparation and characterization of nanocrystal grain TiO2 porous microsphere[J].App lied Catalysis B:Enviromental, 2003(40):253-258.
[52]秦好丽,古国榜,柳松等.溶胶凝胶法制备氮掺杂二氧化钛及其可见光活性的研究[J].太阳能学报,2007,28(4)：363-367.
[53]李小兵,刘竞超.纳米粒子与纳米材料[J].塑料,1999,28(1)：19-22.
[54]周建斌,邓丛静,傅金和等.竹炭负载纳米Ti02吸附与降解甲苯的研究[J].新型炭材料,2009,24(2)：131-135.
[55]韦以,刘新香A12O3-TiO2复合载体的制备与表征[J].石油化工,2006,35(2)：173-177.
[56]Choi J, Ban J Y, Choung S. J. Kim Jinsoo, Haznan Abimanyu, Kye Sang Yoo, Sol-gel synthesis, characterization and photocatalytic activity of mesoporous TiO2/γ-Al2O3 granules[J]. Sol-Gel Sci. Techno.,2007,44(1):21-28.
[57]Choi J., Kim Jinsoo, Kye Sang Yoo, Tai Gyu Lee. Synthesis of mesoporous TiO2/γ-Al2O3 composite granules with different sol composition and calcination temperature[J]. Powder Technology,2008,181,83-88.
[58]陈士夫,梁新,赵梦月.不同制备条件对TiO2/beads光催化活性的影呼[J].感光科学与光化学,1999,(2)：25-31.
[59]方开泰.均匀设计及应用[J].数理统计与管理,1994,13(1)：57-63、56.
[60]王元,方开泰.关于均匀分布与试验设计(数论方法)[J].科学通报,1981,(26):65-70.
[61]高毅,高尚.均匀设计优化方法[J].科学技术与工程,2011,11(2):371-373.
[62]崔冬华,乔素琴.均匀设计在软件测试数据生成中的应用[J].软件时空.2009,3(3):181-183.
[63]黄俊强,陈仕周,慕海瑞,谢洪斌.均匀设计、回归分析在排水性混合料配比设计中的应用研究[J].中外公路,2009,10(5):239-242.
[64]靳志强,李平兰.拟水平均匀设计在乳酸菌冻干保护剂研究中的应用[J].食品工业科技,2007(10)：80-82.
[65]黄俊强,陈仕周,慕海瑞等.均匀设计、回归分析在排水性混合料配比设计中的应用研究[J].中外公路,2009,10(5):239-242.
[66]Haigler, R.E.et aL.Biodegradation of mixtures of substituted benzenes by pseudomonas sp.strainJS150[J].Appl Environ.Microbiol,1992,68(7):2237-2244.
[67]Maule, A.et al.Dehalogenation of organochlorine insectieides by mixed anaerobic mierobial populations[J].Pestic.Biochem.Physiol,1987,27(-):229-236.
[68]Armenante, P.M.et al.Integrated anaerobic—aerobic process for the biodegradation of chlorinated aromatic compounds[J].Environ.Prog.1992,11(2):113-22.
[69]Kramer, C.M.et al.Bacteria that degrade P—chlorophenol isolated from a continuous culture system[J].Can.J.Microbiol,1992,38(1):34-37.
[70]金相灿等,《有机化合物污染化学—有毒有机物污染化学》[M],北京：清华大学出版社,1990：250-255.
[71]胡望钧主编,《常见有毒化学品环境事故应急处理技术与监测方法》[M],1993,北京：中国环境科学出版社.
[72]Kennedy K J, Ning Z, Fernandes L. Modeling simultaneous removal of p rimary substrates and chlorinated phenols in upflow anaerobic sludge blanket reactors [J].Can J Civil Eng, 2001,28(6):910-921.
[73]Sponza D T, Ulukoy A E. Treatment of 2,4-dichlorophenol(DCP) in a sequential anaerobic (upflow anaerobic sludge blanket) aerobic (completely stirred tank) reactor system[J].Process Biochem,2005,40(11):3419-3428.
[74]Ning Z, Kennedy K J, Fernandes L.Anaerobic degradation kinetics of 2,4-dichlorophenol (2,4-DCP) with linear sorp tion[J].Water Sci Technol,1997,35(2-3):67-75.
[75]Collins G, Foy C, McHugh S, et al.Anaerobic treatment of 2,4,6-trichlorophenol in an expanded granular sludge bed-anaerobic filter (EGSB-AF) bioreactor at 15℃[J].FEMS Microbiol Ecol,2005,53(1):167-178.
[76]Alexievaa Z, Gerginova M, Zlateva P, et al. Comparison of growth kinetics and phenol metabolizing enzymes of Trichosporon cutaneum R57 and mutants with modified degradation abilities[J].Enzyme Microb Technol,2004,34(3-4):242-247.
[77]Fialova'A, Boschke E, Bley T. Rapid monitoring of the biodegradation of phenol-like compounds by the yeast Candida maltosa using BOD measurements[J]. Int Biodeterior Biodegrad,2004,54(1):69-76.
[78]Jiang Y, Wen J P, Lan L, et al. Biodegradation of phenol and 4-chlorophenol by the yeast Candida tropicalis[J].Biodegrad,2007,18(6):719-729.
[79]Tarek Mohamed Salama a, Ibraheem Othman Ali a, Mohamed Mokhtar Mohamed. Synthesis and characterization of mordenites encapsulated titania nanoparticles:Photocatalytic degradation of meta-chlorophenol[J]. Chemical 2007,198-210.
[80]刘香玲,潘家荣,李瑞萍等.紫外光照射下纳米Ti02降解水中有机氯酚类化合物[J].三峡大学学报,2006,28(2)：177-180.
[2]Garey J H, Awrence J, Tosine HM. Photodechloriation of PCB's in the presence of titanium dioxide in aqueous suspensions[J].Bull.Environ.Contam.Toxicol,1976,16:697-701.
[3]张乐观,朱新锋.微球负载TiO2催化剂的制备与降解苯酚性能[J].化工进展,2008,27(4)：577-580.
[4]黄冬根,涂志斌等.光催化/生物三相流化床工艺处理4一氯酚废水[J].中国给水排水,2009,25(19)：74-76.
[5]范少华.含铜酸性废水与醋化废水综合治理试验[J].河南科技大学学报：自然科学版,2004,25(1)：103-107.
[6]崔玉民,范少华.复合纳米微粒Rh3+/TiO2/SnO2的合成、表征及光催化降解4-(2-吡啶偶氮)间苯二酚研究[J].感光科学与光化学,2003,21(3)：161-167.
[7]Dhanajeyan M R, Kandavelu V, Renganthan R.A Study on Photocatalytic Reaction of TiO2 with Certain Pyrimidine Bases:Effects of Dopants(Fe3+) and Calcinnation[J].J Molec Catal A,2000,151 (3):217-222.
[8]崔玉民.采用TiO2光催化剂对河水中污染物进行光催化降解[J].河南科技大学学报：自然科学版,2003,24(1)：94-97.
[9]张文彬,谢利群,白元峰.纳米Ti02光催化机理及改性研究进展[J].化工科技,2005,13(6)：52-57.
[10]孙晓君,蔡伟民,井立强等.二氧化钛半导体光催化技术进展[J].哈尔滨工业大学学报,2001,33(4)：534-541.
[11]黄艳娥,刘冬莲,纳米TiO2在水处理中的应用[J].河北化工,2000,(2):8-11.
[12]张立德,牟季美.纳米材料学[M].沈阳：辽宁科学出版社,1994.
[13]陈晓波.二氧化钛纳米材料及其能源应用[J].催化学报,2009,30(8)：839-851.
[14]符小荣,张校刚,宋世庚等TiO2/Pt/glass纳米薄膜的制备及对可溶性燃料的光催化降解[J].应用化学,1997,14(4)：77-79.
[15]席北斗,孔欣,刘纯新等.加铂修饰型催化剂光催化氧化五氛酚[J].环境化学,2001,20：27-31.
[16]Choi W K, Termin A, Hoffmann M R.The Role of Metal Ion Dopants in Quantum-size TiO2: Correlation Between Photoreactivity Charge Carrier Recombination Dynamics [J]. J Phys Chem,1994,98:13669-13672.
[17]Gratzel M, Howe R F.Electron Paramagnetic Resonance Studies of Doped TiO2 Colloids[J].J Phys Chem,1990,94:2566-2569.
[18]Deng H H, Lu Z H, Chen Y C.H2O2Enhanced Photocatalytic Oxidation of Microcystin-LR Using TiO2[J].J Chem Phys,1998,231:95-99.
[19]徐建华,戴维林,李静霞等.银修饰的二氧化钛多孔微管的制备、表征及光催化活性[J].化学学报,2007,65(12)：1172-1176.
[20]李海龙,罗武林,陈涛等.载Ag二氧化钛纳米管的制备及其光催化性能[J].物理化学学报,2008,24(8)：1383-1386.
[21]李芳柏,李湘中,李薪军等WO3/TiO2纳米材料的制备及光催化性能[J].化学学报,2001,59(7)：1072-1075.
[22]水淼,岳林海,徐铸德.稀土镧掺杂二氧化钛的光催化特性[J].物理化学学报,2000,16(5)：459-463.
[23]景文珩,王韦岗,邢卫红.大孔-介孔氮掺杂二氧化钛的制备及其光催化性能测试[J].催化学报,2009,30(5):426-432.
[24]Huang Dong gen, Liu Ai ming, Tu Zhi bin, Quan Shui-qing, Liu Lei. The preparation of a crystal nano N-F-Sm-TiO2 Sol and its photocatalytic degradation for 4-chlorophenol[J]. Journal of Nanchang University (Engineering & Technology),2009,31(3):286-292.
[25]张青红,高镰,郑珊.金红石相二氧化钛纳米晶的光催化活性[J]化学学报,2001,59(11):1909-1911.
[26]史载锋,范益群,徐南平等.不同光源对光催化降解亚甲基蓝的影响[J].南京化工大学学报,2000,22(1)：59-63.
[27]王怡中,符雁等.甲基橙溶液多相光催化降解的研究[J].环境科学,1998,19(1):1-4.
[28]赵梦月,罗菊芬.有机磷农药光催化分解的可行性研究[J].化工环保,1993,13(2):74-79.
[29]Mohammed A, Low G K, Matthews R W, Effects of common inorganic anions on rates of photocatalytic oxidation of organic carbon over illuminated titanium dioxide[J].J Phys Chem,1990,94 (17):6820-6825.
[30]Kormann C, Bahnemann D W, Hoffmann M R.Photolysis of.chloroform and other organic molecules in aqueous TiO2 suspensions[J].Environ Sic Technol,1991,25 (3):494-500.
[31]花日茂,岳永德,李学德.几种偶氮染料的光催化降解研究[J].安徽农业大学学报,2000,27(2)： 141-145.
[32]Bahneman D W, et al.Mechanistic studies of water detoxification in huminated TiO2 suspensions[J].Solar Energy Materials,1999,24:564-583.
[33]Claudis K, Bahnemann D W, Hoffmann M R, Photocatalytic production of H2O2 and organic peroxides in aqueous TiO2、ZnO and desert sand[J].Environ Sci Technol,1988,22 (7): 798-806.
[34]Hoffman A J, Carraway E R., Hoffmann M R.Photocatalytic production of H2O2 and organic peroxides on quantumsized semiconductor colloids[J].Environ Sci Technol,1994,28 (5): 776-785.
[35]Carraway E R, Hoffman A J, Hoffmann M R. Photocatalytic oxidation of organic acids on quantunsized semiconductor colloids[J].Environ Sci Tecnol,1994,28 (5):786-793.
[36]Fernando J B, Jose M E, Juan F G.Industrial wastewater advanced oxidation. Ozone combined with hydrogenperoxide or UV radiation[J].Wat Res,1997,31 (10):2415-2428.
[37]孟季如,赵磊,梁国正等.无机非金属纳米微粒的制备方法[J].化工新型材料,2000,28(4): 23-27.
[38]王世敏,许祖勋,傅晶.纳米材料制备技术[M].北京：化学工业出版社,2004.
[39]赵小远.纳米氧化钛的制备及应用[J].稀有金属与硬质合金,2003,31(1):26-27.
[40]解宪英.纳米级二氧化钛的制备及其应用进展(上)[J].上海化工,2001,26(3):37-38,54.
[41]陈晓波.二氧化钛纳米材料及其能源应用[J].催化学报,2009,30(8)：839-851.
[42]吴迪,王鼎聪,赵德智.纳米二氧化钛制备工艺研究进展[J].钛工业进展,2005(5):32-35.
[43]刘威,陈爱平,林嘉平等.均相水解法制备金红石含量可控的纳米TiO2[J].化学学报,2004,62(12)：1148-1152.
[44]张青红,高濂,郭景坤.四氯化钛水解法制备纳米氧化钛超细粉体[J].无机材料学报,2000(1)：21-23.
[45]李海龙,朱地,刘冉冉.Ti(S04)2水解一水热法制备锐钛型纳米Ti02及其光催化性能[J].光谱学与光谱分析学,2010,30(3)：767-769.
[46]祖庸,雷闫盈,樊安.纳米Ti02在化妆品中的应用[J].钛工业进展,1998(1):28-30.
[47]孙家跃,肖昂,杜海燕.均相沉淀-发泡法制备纳米氧化钛的应用[J].国外建材科技,2004(4)：57-59.
[48]王金敏,杜芳林,崔作林等.纳米氧化钛的沉淀法制备及表征[J].青岛化工学院学报,2001(2)：122-123.
[49]胡安正,唐超群.Sol-Gel法制备纳米氧化钛的原料配比和胶凝过程机理研究[J].功能材料,2002(4)：394-396.
[50]李海龙,朱地,刘冉冉.Ti(S04)2水解一水热法制备锐钛型纳米Ti02及其光催化性能[J].光谱学与光谱分析,2010,30(3)：767-769.
[51]Zhang Baolong, Chen Baishun, Shi Keyu, et al. Preparation and characterization of nanocrystal grain TiO2 porous microsphere[J].App lied Catalysis B:Enviromental, 2003(40):253-258.
[52]秦好丽,古国榜,柳松等.溶胶凝胶法制备氮掺杂二氧化钛及其可见光活性的研究[J].太阳能学报,2007,28(4)：363-367.
[53]李小兵,刘竞超.纳米粒子与纳米材料[J].塑料,1999,28(1)：19-22.
[54]周建斌,邓丛静,傅金和等.竹炭负载纳米Ti02吸附与降解甲苯的研究[J].新型炭材料,2009,24(2)：131-135.
[55]韦以,刘新香A12O3-TiO2复合载体的制备与表征[J].石油化工,2006,35(2)：173-177.
[56]Choi J, Ban J Y, Choung S. J. Kim Jinsoo, Haznan Abimanyu, Kye Sang Yoo, Sol-gel synthesis, characterization and photocatalytic activity of mesoporous TiO2/γ-Al2O3 granules[J]. Sol-Gel Sci. Techno.,2007,44(1):21-28.
[57]Choi J., Kim Jinsoo, Kye Sang Yoo, Tai Gyu Lee. Synthesis of mesoporous TiO2/γ-Al2O3 composite granules with different sol composition and calcination temperature[J]. Powder Technology,2008,181,83-88.
[58]陈士夫,梁新,赵梦月.不同制备条件对TiO2/beads光催化活性的影呼[J].感光科学与光化学,1999,(2)：25-31.
[59]方开泰.均匀设计及应用[J].数理统计与管理,1994,13(1)：57-63、56.
[60]王元,方开泰.关于均匀分布与试验设计(数论方法)[J].科学通报,1981,(26):65-70.
[61]高毅,高尚.均匀设计优化方法[J].科学技术与工程,2011,11(2):371-373.
[62]崔冬华,乔素琴.均匀设计在软件测试数据生成中的应用[J].软件时空.2009,3(3):181-183.
[63]黄俊强,陈仕周,慕海瑞,谢洪斌.均匀设计、回归分析在排水性混合料配比设计中的应用研究[J].中外公路,2009,10(5):239-242.
[64]靳志强,李平兰.拟水平均匀设计在乳酸菌冻干保护剂研究中的应用[J].食品工业科技,2007(10)：80-82.
[65]黄俊强,陈仕周,慕海瑞等.均匀设计、回归分析在排水性混合料配比设计中的应用研究[J].中外公路,2009,10(5):239-242.
[66]Haigler, R.E.et aL.Biodegradation of mixtures of substituted benzenes by pseudomonas sp.strainJS150[J].Appl Environ.Microbiol,1992,68(7):2237-2244.
[67]Maule, A.et al.Dehalogenation of organochlorine insectieides by mixed anaerobic mierobial populations[J].Pestic.Biochem.Physiol,1987,27(-):229-236.
[68]Armenante, P.M.et al.Integrated anaerobic—aerobic process for the biodegradation of chlorinated aromatic compounds[J].Environ.Prog.1992,11(2):113-22.
[69]Kramer, C.M.et al.Bacteria that degrade P—chlorophenol isolated from a continuous culture system[J].Can.J.Microbiol,1992,38(1):34-37.
[70]金相灿等,《有机化合物污染化学—有毒有机物污染化学》[M],北京：清华大学出版社,1990：250-255.
[71]胡望钧主编,《常见有毒化学品环境事故应急处理技术与监测方法》[M],1993,北京：中国环境科学出版社.
[72]Kennedy K J, Ning Z, Fernandes L. Modeling simultaneous removal of p rimary substrates and chlorinated phenols in upflow anaerobic sludge blanket reactors [J].Can J Civil Eng, 2001,28(6):910-921.
[73]Sponza D T, Ulukoy A E. Treatment of 2,4-dichlorophenol(DCP) in a sequential anaerobic (upflow anaerobic sludge blanket) aerobic (completely stirred tank) reactor system[J].Process Biochem,2005,40(11):3419-3428.
[74]Ning Z, Kennedy K J, Fernandes L.Anaerobic degradation kinetics of 2,4-dichlorophenol (2,4-DCP) with linear sorp tion[J].Water Sci Technol,1997,35(2-3):67-75.
[75]Collins G, Foy C, McHugh S, et al.Anaerobic treatment of 2,4,6-trichlorophenol in an expanded granular sludge bed-anaerobic filter (EGSB-AF) bioreactor at 15℃[J].FEMS Microbiol Ecol,2005,53(1):167-178.
[76]Alexievaa Z, Gerginova M, Zlateva P, et al. Comparison of growth kinetics and phenol metabolizing enzymes of Trichosporon cutaneum R57 and mutants with modified degradation abilities[J].Enzyme Microb Technol,2004,34(3-4):242-247.
[77]Fialova'A, Boschke E, Bley T. Rapid monitoring of the biodegradation of phenol-like compounds by the yeast Candida maltosa using BOD measurements[J]. Int Biodeterior Biodegrad,2004,54(1):69-76.
[78]Jiang Y, Wen J P, Lan L, et al. Biodegradation of phenol and 4-chlorophenol by the yeast Candida tropicalis[J].Biodegrad,2007,18(6):719-729.
[79]Tarek Mohamed Salama a, Ibraheem Othman Ali a, Mohamed Mokhtar Mohamed. Synthesis and characterization of mordenites encapsulated titania nanoparticles:Photocatalytic degradation of meta-chlorophenol[J]. Chemical 2007,198-210.
[80]刘香玲,潘家荣,李瑞萍等.紫外光照射下纳米Ti02降解水中有机氯酚类化合物[J].三峡大学学报,2006,28(2)：177-180.