改性纳米TiO_2薄膜的制备及其光催化处理焦化废水
|
摘要
随着资源的过度利用和大自然的严重污染,生态环境遭受了严重的破坏。人们迫切需要开发能够经济有效地利用能源并具有不污染环境的功能意识材料。纳米TiO_2正是这种具有净化环境功能的绿色材料,它可完成环境净化、能源再生、能源贮备、不污染环境等多项功效。纳米TiO_2可通过多种技术制备,且日臻成熟,但仍普遍存在设备复杂、条件难控、产业化困难等问题。纳米TiO_2具有无毒、催化效率高、性能稳定、价廉等突出特点,以及在光催化氧化处理废水及净化空气中的应用,使它已成为目前光催化研究领域中最活跃的方向之一。
焦化废水是冶金工业废水中的一类,其危害大、处理困难,已成为我国目前重点控制的废水之一。光催化氧化技术是近年来发展起来的一种新型水处理技术,因高效、无二次污染,且具有可直接利用太阳能的潜力,而受到各国学者的关注。纳米TiO_2具有优异的光催化活性,它能将环境中存在的微量有机物降解为无污染的无机物,还能杀死细菌病毒,因此具有广泛的应用前景。但是,纳米TiO_2光催化剂须依赖于紫外光,对太阳光的利用率低,因而限制了它的应用。为了提高纳米TiO_2在可见光区的光催化活性,充分利用太阳光,必须对其进行改性。
以硫脲为掺杂剂制备了均匀分散的硫掺杂纳米TiO_2光催化剂,探讨了硫掺杂对纳米TiO_2的晶相结构、原子价态及催化剂表面状态的影响,并对其掺杂机理进行了研究。结果认为在高温热处理过程中,由于微量的硫以S~(4+)进入TiO_2的晶格中取代了部分Ti~(4+)而导致局部变形,导致TiO_2的价带和导带之间的带隙变窄,从而提高了TiO_2的可见光的光谱响应。本文用硫掺杂纳米TiO_2作为光催化剂催化降解焦化废水,实验结果表明经450℃热处理的硫掺杂纳米TiO_2薄膜能很好地降解焦化废水中的有机物,处理后水中的COD与NH_3-N等指标均达到排放要求。
With the excessive exploitation of natural resources and grave Pollution of environment,the deterioration of ecological environment becomes more and more serious.It is urgent to develop eco-materials,which use economically energy and have no harm to environment.With its renewal ability and storability of energy and friendliness of environment,nano-semieonductor TiO_2 is the very novel green purificant, Now its relevant study becomes the focus of the field of photocatalysis,especially in wastewater treatment.Although nano-TiO_2 Powders can be obtained by many methods such as Sol-Gel Process,chemical deposition,these methods are complex in equipments,strict in conditions of preparation..As a result,it is difficult to realize its commercialization.The pertinent research work has been carried out follows.
In environment protection field,it is one of key controlling objects to decontaminate wastewater coking,which poses great harm to environment and become a serious problem in metallurgy industry.Photocatalytic oxidation of water contaminants is a new method for wastewater treatment.It is widely and deeply studied by researchers for its high degradation efficiency,none secondary pollution caused and the potential of utilization of solar energy.Nano-titanium dioxide,used as a photocatalyst can degrade the trace organic compounds to non-toxic substances and can kill bacteria and virus,therefore,it is of great value in the practical applications. However,it suffered from the disadvantages that the nano-titanium dioxide cannot show the excellent photocatalytic activity until irradiated with UV light and the utilization of the solar rays is too limited and ineffective,which hinders its widespread applications to a great extent.In order to improve the photocatalytic activity and make full use of the solar rays,the nano-titanium dioxide must be modified.
S-doped uniform TiO_2 photocatalysts were prepared using thiourea as the doping agent for the first time in China.The influence of sulfur doping on the crystal structure of nano-TiO_2,the energy level state and the surface state were investigated.The doping mechanism was also discussed.The results of photocatalytic degradation coking-plant wasterwater demonstrated that the S-doped uniform TiO_2 exhibited the highest photocatalytic activity when calcined at 450℃for 4 hours.The COD and NH_3-N are accord to water's quality.
焦化废水是冶金工业废水中的一类,其危害大、处理困难,已成为我国目前重点控制的废水之一。光催化氧化技术是近年来发展起来的一种新型水处理技术,因高效、无二次污染,且具有可直接利用太阳能的潜力,而受到各国学者的关注。纳米TiO_2具有优异的光催化活性,它能将环境中存在的微量有机物降解为无污染的无机物,还能杀死细菌病毒,因此具有广泛的应用前景。但是,纳米TiO_2光催化剂须依赖于紫外光,对太阳光的利用率低,因而限制了它的应用。为了提高纳米TiO_2在可见光区的光催化活性,充分利用太阳光,必须对其进行改性。
以硫脲为掺杂剂制备了均匀分散的硫掺杂纳米TiO_2光催化剂,探讨了硫掺杂对纳米TiO_2的晶相结构、原子价态及催化剂表面状态的影响,并对其掺杂机理进行了研究。结果认为在高温热处理过程中,由于微量的硫以S~(4+)进入TiO_2的晶格中取代了部分Ti~(4+)而导致局部变形,导致TiO_2的价带和导带之间的带隙变窄,从而提高了TiO_2的可见光的光谱响应。本文用硫掺杂纳米TiO_2作为光催化剂催化降解焦化废水,实验结果表明经450℃热处理的硫掺杂纳米TiO_2薄膜能很好地降解焦化废水中的有机物,处理后水中的COD与NH_3-N等指标均达到排放要求。
With the excessive exploitation of natural resources and grave Pollution of environment,the deterioration of ecological environment becomes more and more serious.It is urgent to develop eco-materials,which use economically energy and have no harm to environment.With its renewal ability and storability of energy and friendliness of environment,nano-semieonductor TiO_2 is the very novel green purificant, Now its relevant study becomes the focus of the field of photocatalysis,especially in wastewater treatment.Although nano-TiO_2 Powders can be obtained by many methods such as Sol-Gel Process,chemical deposition,these methods are complex in equipments,strict in conditions of preparation..As a result,it is difficult to realize its commercialization.The pertinent research work has been carried out follows.
In environment protection field,it is one of key controlling objects to decontaminate wastewater coking,which poses great harm to environment and become a serious problem in metallurgy industry.Photocatalytic oxidation of water contaminants is a new method for wastewater treatment.It is widely and deeply studied by researchers for its high degradation efficiency,none secondary pollution caused and the potential of utilization of solar energy.Nano-titanium dioxide,used as a photocatalyst can degrade the trace organic compounds to non-toxic substances and can kill bacteria and virus,therefore,it is of great value in the practical applications. However,it suffered from the disadvantages that the nano-titanium dioxide cannot show the excellent photocatalytic activity until irradiated with UV light and the utilization of the solar rays is too limited and ineffective,which hinders its widespread applications to a great extent.In order to improve the photocatalytic activity and make full use of the solar rays,the nano-titanium dioxide must be modified.
S-doped uniform TiO_2 photocatalysts were prepared using thiourea as the doping agent for the first time in China.The influence of sulfur doping on the crystal structure of nano-TiO_2,the energy level state and the surface state were investigated.The doping mechanism was also discussed.The results of photocatalytic degradation coking-plant wasterwater demonstrated that the S-doped uniform TiO_2 exhibited the highest photocatalytic activity when calcined at 450℃for 4 hours.The COD and NH_3-N are accord to water's quality.
引文
[1]Fujishima A,Honda A.Electrochemical photolysis of water at a semiconductor electrode.Nature,1972,238:372-375
[2]J.H.Cary,J.Lawrence,H.M.Tosine.Photodechlorination of PCB's in the presence of titanium dioxide in aqueous suspension[J].Bull of Environ.Contam.Toxicol,1976,16:697-701
[3]Barnemann D W,Hlgendoreff M.Charge carrier dynamics at TiO2 particles:reactivity of free and trappedholes.J.Phys.Chem.B:1997,101:4265-4275
[4]黄艳娥,琚行松.纳米TiO2光催化降解水中有机污染物的研究进展.化工环保,2002,22(1):23-26
[5]Try D A,Fujishima A,Honda K.Recent topics in photoelectrochemistry:achievements and future prospects.Electrochimica Acta,2000,45:2363-2376
[6]范崇政,肖建平,丁延伟.纳米TiO2的制备与光催化反应进展.科学通报2001,46(4):265-273
[7]付贤智,李旦振.提高多相光催化氧化过程效率的新途径.福州大学学报(自科),2000,29(6):104-115
[8]Okte A N,Resat M S.Quantum yields and relative photonic efficiencies of substituted1,3-dihydroxybenzenes.J.Photochem.Photobiol.A:chemistry,2000,134:59-70
[9]Hsian V H,Chang C F,Chen Y H.Appl.Catal.,B:Environ,2001,31:241.
[10]Dijkstra M FJ,Michorius A,Buwalda H,Panneman H J,et al.Comparsion of the effency of immoblized and suspended systems in photocatalytic degradation.
[11]石建敏,李巧玲,周仁贤等 二氧化钛光催化降解水溶性分散染料的研究 水处理技术,2002,28(4):105-107
[12]Tanaka K,Padermpele K.Hisanaga T.Photocatalytic degradation of commercial ago dyes[J].Water Res,2000,34(1):327-333.
[13]彭贤玉,董君英.多相光催化氧化法处理焦化废水的研究[J].南华大学学报,2005,19(1):64-68.
[14]Shehukin D,Poznyak S,Kulak A,et al.TiO2-In203 photoeatalysts:preparation,characterizations and activity for 2-chlorophenol degradation in water[J]J.Photoch.Photobiolo,A,2004,162(2-3):423-430.
[15]Mansila n D,Yeber M C,Freer J,et al.Homogeneous and heterogeneous advanced oxidation of a bleaching efluent from the pulp and paper industry[J].Water Science and Technology,1997,35(4):273-278.
[16]Bocters T.Chovelon J M,Herrmann J M,et al.Syntheses of TiO2 photocatalysts by the molten salts method application to the photocatalytic degradation of Prosulfuron[J].Appl.Catal.B,2004,50(4);423-430
[17]岳林海.稀土元素掺杂二氧化钛催化剂光降解久效磷的研究[J]上海环境科学 1998,17(9):17-19
[18]张昌鸣,李爱英等.粉煤灰处理焦化废水的研究[J].燃料与化工.1998.(
[19]Li X Z,Li F B.Study of Au/Au3+-TiO2 photocatalysts toward visible photooxidation for water and wastewater treatment.Environ.Sci.Technol.,2001,35(11):2381-2387
[20]Paola A D,Marei G,Palmisano L,et al.Preparation of polycrystalline TiO2photocatalysts impregnated with various transition metal ions:characterization and photocatalytic activity for the degradation of 4-nitrophenol.J.Phys.Chem.B,2002,106(3):637-645
[21]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides.Science,2001,293:269-271
[22]Umebayashi T,Yamaki T,Tamaka S,et al.Visible light-induced degradation of methylene blue on s-doped TiO2.Chem.Lett.,2003,32(4):330-331
[23]Yu J G,Yu J C,Cheng B,et al.Effects of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders.J.Solid State Chem.,2003,174:372-380
[24]Soria J,Conesa J C,Augugliaro V,et al.Dinitrogen photoreduction to ammonia over titanium dioxide powders doped with ferric ions.J.Phys.Chem.,1991,95(1):274-282
[25]方世杰,徐明霞.纳米TiO2光催化剂的制备方法.硅酸盐通报,2002,(2):38-42.
[26]方晓明,陈焕钦等.液相合成纳米TiO2的进展.硅酸盐通报,2001,(6):30-33
[27]陶国忠,古宏晨.Sol-Gel法制备TiO2粉末的光催化性能研究.华东理工大学学报,2000,26(1):62-65
[28]吴风清,阮圣平,李晓平等.纳米TiO2的制备表征及光催化性能的研究.功能材料,2001,32(1):69-71
[29]张青红,高廉,郭景坤.四氯化钛水解法制备TiO2纳米晶的影响因素.无机材料学报,2000,15(6):992-998
[30]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.无机材料学报2000,15(1):21-24
[31]赵文宽方佑龄张开诚等.高热稳定性锐钛矿型TiO2纳米粉体的制备.无机材料学报,1998,13(4):608-612
[32]Maira A J,Yeung K L,Lee C Y,etc.Size effects in gas phase photo-oxidation of trichloroethylene using nanometer-sized TiO2 catalysts.J Catal,2000,192(1):185-196
[33]Sabate J,Anderson M A,Kikkawa H,etc.Nature and properties of pure and Nb-doped TiO2 ceramic menbranes affecting the photocatalytic degration of 3-chlorosalcylic acid as a model of halogenated organic compounds.J Catal,1992,134(1):36-46
[34]Yu J C,Tang H Y,Yu J G,etc.Bactericidal and photocatalytic activities of TiO2 thin films prepared by sol-gel and reverse micelle methods.J of Photochem and Photobiol A:Chem,2002,153:211-219
[35]高濂,郑珊,张青虹。纳米氧化钛光催化材料及应用[M]。化学工业出版社,2002
[36]Femandz A,Lassaletta G,Jimenez V M et al.Preparation and Characterization of Photocatalysts Supported on Various Rigid Supports(glass,quartz and stainless steel).Comparative studies of photocatalytic activity in water purification.Appl.Catal.B:Environ,1995,7:49-63
[37]刘凡新,崔作林,张志琨。纳米二氧化钛复合膜光催化降解甲基橙的研究。[J]感光科学与光化学。2003.2[2]:120
[38]廖东亮等。溶胶-凝胶法制备纳米二氧化钛的工艺研究。2003,10:257-258
[39]白春礼。扫描隧道显微技术及其应用。上海:上海科学技术出版社,1992
[40]Chenchi W,Zhibo Z H,Ying J Y.Photocatalytic Decomposition of Halogenated oranics over Nanocrystalline Titania.Nanostructured Materials,1997,9:583-586
[41]廖东亮等。溶胶-凝胶法制备纳米二氧化钛的工艺研究[J]。2003,10:257-259。240。
[42]赵青南,余家国,赵修建。玻璃表面TiO2涂层的溶胶-凝胶法制备及其光催化性能[J]。武汉工业大学材料研究与测试中心,武汉市 43007。
[43]周荣灿,梁勇,陈志远,等。纳米分体的分散性进展及激光法硅基纳米粉的分散性能的研究[C]。全国第二届纳米材料研讨会论文集(上册),2000,C32。
[44]孙静,高濂,王浚。聚丙烯酸在纳米氧化锆粉体中的分散作用[C]。全国第二届纳米材料研讨会论文集(上册),2000,C66。
[45]Masahiko Nakamura,Katsuhito Jyohzaki,Takatoshi Kimura.Ceramic dental modls for the precision casting of titanium and titanium alloys:1,relationship between particle-size distribution of aggregates and mold expansion [J].J.Am.Ceram.Soc.,1990,73(1):35.
[46]Tan T T Y,Yip C K,Beydoun D,etc.Effects of nano-Ag particles loading on TiO2photocatalytic reduction of selenate ions.Chem Engin J,2003,95:179-186
[47]于向阳程继建.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):742-746
[48]Dvoranova D,Brezova V,Mazura M,et al.Investigations of metal-doped titanium dioxide photocatalysts.Applied Catalysis B:Environmental,2002,37:91-105
[49]Herrmann J M,Tahiti H,Guillard C,etc.Photocatalytic degradation of aqueous hydroxy-butandioic acid(malicacid) in contact with powder ed and supported titania in water.Catalysis Today,1999,54:131-141
[50]Wilke K,Breuer H D.The influence of transition metal doping on the physical and photocatalytic properties of titania.J Photochem Photobiol A:Chem,1999,121(1):49-53
[51]Li X Z,Li F B,Yang C L,etc.Photocatalytic activity of WOx-TiO2 under visible light irradiation.Journal of Photochemistry and Photobiology A:Chemistry,2001,141:209-217
[52]Rampaul A,Parkin I P,Shane A.Titania and tungsten doped titania thin films on glass;active photocatalysts.Polyhedron,2003,22:35-44
[53]Dobosz A,Sobczynski A.The infuence of silver additives on titania photoactivity in the photooxidation of phenol.Water Research,2003,37:1489-1496
[54]Chao H E,Yun Y U,Xingfang H U,etc.Effect of silver doping on the phase transformation and grain growth of sol-gel titania powder.J of Europ Ceram,2003,23:1457-1464
[55]郭泉辉,杨建军,毛立群等.镧掺杂二氧化钛光催化性能的研究.化学研究,2002,13(4):22-27
[56]营盘铭夏亚穆,李德宏等.掺杂TiO2纳米粉的合成表征及催化性能研究.催化学报,2001,22(2):161-164
[57]孙晓君,蔡伟民,井立强.二氧化钛半导体光催化技术研究进展.哈尔滨工业大学学报,2001,23(4):534-541
[58]沈伟韧,赵文宽,贺飞等.TiO2光催化反应及其在废水处理中的应用.化学进展,1998,10(4):49 361
[59]Sclapant A.Influence of sliver deposits on the photocatalytic activity of titania.J of Catalyst,1997,168:117-120
[60]程沧沧,李太友.载银TiO2光催化降解2,4-二氯苯酚水溶液的研究.环境科学研究,1998,11(6):27-29
[61]Linsebigler A,Rusuc C.Absence of platinum enhancement of a photoreation on TiO2-CO photooxidation on Pt/TiO2(110).J Am Chem Soc,1996,118:5284-5289
[62]Sanches E,Lopex T.Synthesis and characterization of sol-gel Pt/TiO2 catalyst.J of Solid State Chem,1996,122:309-314
[63]姚晓斌.Ag和Pd及其离子对TiO2光催化分解CH3CHO的影响.感光科学与光化学,1999,17(1):12-15
[64]Choi W.The role of metal ion dopants in quantum-size TiO2:correlation between photoreactivity and charge carrier recombinnation dynamics.J Phys Chem,1994,98(5):13669-13679
[65]Vogel R.Quantum-sized PdS,CdS,Ag2S,Sb2S3 and Bi2S3 particles as sensitizers for various nanoporous wide-bandgap semiconductors.J Phys Chem,1994,98:3183-3191
[66]Patrick B,Kamat P V.Photosensitization of large-band gap semiconductors charge injection from triplet excited thiamine into ZnO colloids.J Phys Chem,1992,96:1423-1428
[67]袁锋,黎甜楷.荧光素衍生物LB膜对TiO2电极的光敏化作用.物理化学学报,1995,11(6):526-531
[68]Masakazu A,Masato T.The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation.J of Catalysis,2003,216:505-516
[69]LarrubialM A,Busca G.An ultraviolet-visible-near infrared study of the electronic structure of oxide-supported vanadia-tungsta and vanadia-molybdena.Materials Chemistry and Physics,2001,72:337-346
[70]Ye F X,Ohmori A.The photocatalytic activity and photo-absorption of plasma sprayed TiO2-Fe304 binary oxide coatings.Surf and Coat Technol,2002,160:62-67
[71]Myung S J,Tai K L,Dong H K,Hyunku J,etc.The enhancement of redox reactions with mixed oxide catalysts by the sol-gel process.Solar Energy Materials and Solar Cells,1999,57:217-227
[72]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides.Science,2001,293:269-271
[73]Umebayashi T,Yamaki T,Tamaka S,et al.Visible light-induced degradation of methylene blue on s-doped TiO2.Chem.Lett.,2003,32(4):330-331
[74]Umebayashi T,Yamaki T,Itoh H.Band gap narrowing of titanium dioxide by sulfur doping,Appl.Phy.Lett.,2002,81(3):454-546
[75]周武艺,唐绍裘,等.制备不同掺杂稀土纳米TiO2光催化剂及其光催化活性比较研究.硅酸盐学报2004,32(10):1203-1208.(EI)
[76]李景印,郭玉凤,张亚通.纳米TiO2光催化剂在环保方面的应用研究.河北科技大学学报,2001,22(2):25-31
[77]Willie J P,Matin S T.Development of a structure-reactivity relationship for the photohydrolysis of substituted aromatic halides.Enviroron Sci Technol,1992,26(11):2116-2121
[78]Prudent A L.Degradation of Chloroform by photoassisted heterogeneous catalysis in dilute queous suspensions of TiO2.Enviroron Sci Technol,1983,17(3):628-631
[79]瞿萍,张丰雷,吴凯群等.纳米材料光催化剂在合成染料废水处理中的应用.中国材料研究学会编.中国材料研讨会论文集生物及环境材料.北京:化学工业出版社,1997:600-602
[80]张汝冰,刘宏英,李风生等.均匀沉淀法制备纳米TiO2及其在环保方面的应用.环境化学,1999,18(6):579-583
[81]郑魏,刘维屏,宣日成等.附载TiO2光催化降解咪呀胺农药.环境科学,1999,20(1):73-76
[82]陈士夫,赵梦月,梁新等.玻璃纤维附载TiO2光催化降解处理有机磷农药.环境科学,1996,17(4):33-36
[83]Sherrard K B,Marriott P J.Electrospray mass spectrometric analysis and photocatalytic degradation of polyethoxylate surfactants used in wool scouring.Anal Chem,1994,44(20):3394-3399
[84]Oliveira J C,Jayalilaka W.Photodegradation of 2-and3-Chlorophenol in TiO2aqueous suepesions.Environ Sci Technol,1990,24(7):990-996
[85]王晓平,于云,高濂.TiO2薄膜的液相沉积法制备及其性能表征.无机材料学报,2000,15(3):573-577
[86]申绊文.无机化学.北京:化学工业出版社,2001,1:338-355
[87]姚秉华,杨莉,张键等.离子浸渍复合TiO2光催化剂的研究.西安理工大学学报,2002,18(4):327-331
[2]J.H.Cary,J.Lawrence,H.M.Tosine.Photodechlorination of PCB's in the presence of titanium dioxide in aqueous suspension[J].Bull of Environ.Contam.Toxicol,1976,16:697-701
[3]Barnemann D W,Hlgendoreff M.Charge carrier dynamics at TiO2 particles:reactivity of free and trappedholes.J.Phys.Chem.B:1997,101:4265-4275
[4]黄艳娥,琚行松.纳米TiO2光催化降解水中有机污染物的研究进展.化工环保,2002,22(1):23-26
[5]Try D A,Fujishima A,Honda K.Recent topics in photoelectrochemistry:achievements and future prospects.Electrochimica Acta,2000,45:2363-2376
[6]范崇政,肖建平,丁延伟.纳米TiO2的制备与光催化反应进展.科学通报2001,46(4):265-273
[7]付贤智,李旦振.提高多相光催化氧化过程效率的新途径.福州大学学报(自科),2000,29(6):104-115
[8]Okte A N,Resat M S.Quantum yields and relative photonic efficiencies of substituted1,3-dihydroxybenzenes.J.Photochem.Photobiol.A:chemistry,2000,134:59-70
[9]Hsian V H,Chang C F,Chen Y H.Appl.Catal.,B:Environ,2001,31:241.
[10]Dijkstra M FJ,Michorius A,Buwalda H,Panneman H J,et al.Comparsion of the effency of immoblized and suspended systems in photocatalytic degradation.
[11]石建敏,李巧玲,周仁贤等 二氧化钛光催化降解水溶性分散染料的研究 水处理技术,2002,28(4):105-107
[12]Tanaka K,Padermpele K.Hisanaga T.Photocatalytic degradation of commercial ago dyes[J].Water Res,2000,34(1):327-333.
[13]彭贤玉,董君英.多相光催化氧化法处理焦化废水的研究[J].南华大学学报,2005,19(1):64-68.
[14]Shehukin D,Poznyak S,Kulak A,et al.TiO2-In203 photoeatalysts:preparation,characterizations and activity for 2-chlorophenol degradation in water[J]J.Photoch.Photobiolo,A,2004,162(2-3):423-430.
[15]Mansila n D,Yeber M C,Freer J,et al.Homogeneous and heterogeneous advanced oxidation of a bleaching efluent from the pulp and paper industry[J].Water Science and Technology,1997,35(4):273-278.
[16]Bocters T.Chovelon J M,Herrmann J M,et al.Syntheses of TiO2 photocatalysts by the molten salts method application to the photocatalytic degradation of Prosulfuron[J].Appl.Catal.B,2004,50(4);423-430
[17]岳林海.稀土元素掺杂二氧化钛催化剂光降解久效磷的研究[J]上海环境科学 1998,17(9):17-19
[18]张昌鸣,李爱英等.粉煤灰处理焦化废水的研究[J].燃料与化工.1998.(
[19]Li X Z,Li F B.Study of Au/Au3+-TiO2 photocatalysts toward visible photooxidation for water and wastewater treatment.Environ.Sci.Technol.,2001,35(11):2381-2387
[20]Paola A D,Marei G,Palmisano L,et al.Preparation of polycrystalline TiO2photocatalysts impregnated with various transition metal ions:characterization and photocatalytic activity for the degradation of 4-nitrophenol.J.Phys.Chem.B,2002,106(3):637-645
[21]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides.Science,2001,293:269-271
[22]Umebayashi T,Yamaki T,Tamaka S,et al.Visible light-induced degradation of methylene blue on s-doped TiO2.Chem.Lett.,2003,32(4):330-331
[23]Yu J G,Yu J C,Cheng B,et al.Effects of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders.J.Solid State Chem.,2003,174:372-380
[24]Soria J,Conesa J C,Augugliaro V,et al.Dinitrogen photoreduction to ammonia over titanium dioxide powders doped with ferric ions.J.Phys.Chem.,1991,95(1):274-282
[25]方世杰,徐明霞.纳米TiO2光催化剂的制备方法.硅酸盐通报,2002,(2):38-42.
[26]方晓明,陈焕钦等.液相合成纳米TiO2的进展.硅酸盐通报,2001,(6):30-33
[27]陶国忠,古宏晨.Sol-Gel法制备TiO2粉末的光催化性能研究.华东理工大学学报,2000,26(1):62-65
[28]吴风清,阮圣平,李晓平等.纳米TiO2的制备表征及光催化性能的研究.功能材料,2001,32(1):69-71
[29]张青红,高廉,郭景坤.四氯化钛水解法制备TiO2纳米晶的影响因素.无机材料学报,2000,15(6):992-998
[30]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.无机材料学报2000,15(1):21-24
[31]赵文宽方佑龄张开诚等.高热稳定性锐钛矿型TiO2纳米粉体的制备.无机材料学报,1998,13(4):608-612
[32]Maira A J,Yeung K L,Lee C Y,etc.Size effects in gas phase photo-oxidation of trichloroethylene using nanometer-sized TiO2 catalysts.J Catal,2000,192(1):185-196
[33]Sabate J,Anderson M A,Kikkawa H,etc.Nature and properties of pure and Nb-doped TiO2 ceramic menbranes affecting the photocatalytic degration of 3-chlorosalcylic acid as a model of halogenated organic compounds.J Catal,1992,134(1):36-46
[34]Yu J C,Tang H Y,Yu J G,etc.Bactericidal and photocatalytic activities of TiO2 thin films prepared by sol-gel and reverse micelle methods.J of Photochem and Photobiol A:Chem,2002,153:211-219
[35]高濂,郑珊,张青虹。纳米氧化钛光催化材料及应用[M]。化学工业出版社,2002
[36]Femandz A,Lassaletta G,Jimenez V M et al.Preparation and Characterization of Photocatalysts Supported on Various Rigid Supports(glass,quartz and stainless steel).Comparative studies of photocatalytic activity in water purification.Appl.Catal.B:Environ,1995,7:49-63
[37]刘凡新,崔作林,张志琨。纳米二氧化钛复合膜光催化降解甲基橙的研究。[J]感光科学与光化学。2003.2[2]:120
[38]廖东亮等。溶胶-凝胶法制备纳米二氧化钛的工艺研究。2003,10:257-258
[39]白春礼。扫描隧道显微技术及其应用。上海:上海科学技术出版社,1992
[40]Chenchi W,Zhibo Z H,Ying J Y.Photocatalytic Decomposition of Halogenated oranics over Nanocrystalline Titania.Nanostructured Materials,1997,9:583-586
[41]廖东亮等。溶胶-凝胶法制备纳米二氧化钛的工艺研究[J]。2003,10:257-259。240。
[42]赵青南,余家国,赵修建。玻璃表面TiO2涂层的溶胶-凝胶法制备及其光催化性能[J]。武汉工业大学材料研究与测试中心,武汉市 43007。
[43]周荣灿,梁勇,陈志远,等。纳米分体的分散性进展及激光法硅基纳米粉的分散性能的研究[C]。全国第二届纳米材料研讨会论文集(上册),2000,C32。
[44]孙静,高濂,王浚。聚丙烯酸在纳米氧化锆粉体中的分散作用[C]。全国第二届纳米材料研讨会论文集(上册),2000,C66。
[45]Masahiko Nakamura,Katsuhito Jyohzaki,Takatoshi Kimura.Ceramic dental modls for the precision casting of titanium and titanium alloys:1,relationship between particle-size distribution of aggregates and mold expansion [J].J.Am.Ceram.Soc.,1990,73(1):35.
[46]Tan T T Y,Yip C K,Beydoun D,etc.Effects of nano-Ag particles loading on TiO2photocatalytic reduction of selenate ions.Chem Engin J,2003,95:179-186
[47]于向阳程继建.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):742-746
[48]Dvoranova D,Brezova V,Mazura M,et al.Investigations of metal-doped titanium dioxide photocatalysts.Applied Catalysis B:Environmental,2002,37:91-105
[49]Herrmann J M,Tahiti H,Guillard C,etc.Photocatalytic degradation of aqueous hydroxy-butandioic acid(malicacid) in contact with powder ed and supported titania in water.Catalysis Today,1999,54:131-141
[50]Wilke K,Breuer H D.The influence of transition metal doping on the physical and photocatalytic properties of titania.J Photochem Photobiol A:Chem,1999,121(1):49-53
[51]Li X Z,Li F B,Yang C L,etc.Photocatalytic activity of WOx-TiO2 under visible light irradiation.Journal of Photochemistry and Photobiology A:Chemistry,2001,141:209-217
[52]Rampaul A,Parkin I P,Shane A.Titania and tungsten doped titania thin films on glass;active photocatalysts.Polyhedron,2003,22:35-44
[53]Dobosz A,Sobczynski A.The infuence of silver additives on titania photoactivity in the photooxidation of phenol.Water Research,2003,37:1489-1496
[54]Chao H E,Yun Y U,Xingfang H U,etc.Effect of silver doping on the phase transformation and grain growth of sol-gel titania powder.J of Europ Ceram,2003,23:1457-1464
[55]郭泉辉,杨建军,毛立群等.镧掺杂二氧化钛光催化性能的研究.化学研究,2002,13(4):22-27
[56]营盘铭夏亚穆,李德宏等.掺杂TiO2纳米粉的合成表征及催化性能研究.催化学报,2001,22(2):161-164
[57]孙晓君,蔡伟民,井立强.二氧化钛半导体光催化技术研究进展.哈尔滨工业大学学报,2001,23(4):534-541
[58]沈伟韧,赵文宽,贺飞等.TiO2光催化反应及其在废水处理中的应用.化学进展,1998,10(4):49 361
[59]Sclapant A.Influence of sliver deposits on the photocatalytic activity of titania.J of Catalyst,1997,168:117-120
[60]程沧沧,李太友.载银TiO2光催化降解2,4-二氯苯酚水溶液的研究.环境科学研究,1998,11(6):27-29
[61]Linsebigler A,Rusuc C.Absence of platinum enhancement of a photoreation on TiO2-CO photooxidation on Pt/TiO2(110).J Am Chem Soc,1996,118:5284-5289
[62]Sanches E,Lopex T.Synthesis and characterization of sol-gel Pt/TiO2 catalyst.J of Solid State Chem,1996,122:309-314
[63]姚晓斌.Ag和Pd及其离子对TiO2光催化分解CH3CHO的影响.感光科学与光化学,1999,17(1):12-15
[64]Choi W.The role of metal ion dopants in quantum-size TiO2:correlation between photoreactivity and charge carrier recombinnation dynamics.J Phys Chem,1994,98(5):13669-13679
[65]Vogel R.Quantum-sized PdS,CdS,Ag2S,Sb2S3 and Bi2S3 particles as sensitizers for various nanoporous wide-bandgap semiconductors.J Phys Chem,1994,98:3183-3191
[66]Patrick B,Kamat P V.Photosensitization of large-band gap semiconductors charge injection from triplet excited thiamine into ZnO colloids.J Phys Chem,1992,96:1423-1428
[67]袁锋,黎甜楷.荧光素衍生物LB膜对TiO2电极的光敏化作用.物理化学学报,1995,11(6):526-531
[68]Masakazu A,Masato T.The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation.J of Catalysis,2003,216:505-516
[69]LarrubialM A,Busca G.An ultraviolet-visible-near infrared study of the electronic structure of oxide-supported vanadia-tungsta and vanadia-molybdena.Materials Chemistry and Physics,2001,72:337-346
[70]Ye F X,Ohmori A.The photocatalytic activity and photo-absorption of plasma sprayed TiO2-Fe304 binary oxide coatings.Surf and Coat Technol,2002,160:62-67
[71]Myung S J,Tai K L,Dong H K,Hyunku J,etc.The enhancement of redox reactions with mixed oxide catalysts by the sol-gel process.Solar Energy Materials and Solar Cells,1999,57:217-227
[72]Asahi R,Morikawa T,Ohwaki T,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides.Science,2001,293:269-271
[73]Umebayashi T,Yamaki T,Tamaka S,et al.Visible light-induced degradation of methylene blue on s-doped TiO2.Chem.Lett.,2003,32(4):330-331
[74]Umebayashi T,Yamaki T,Itoh H.Band gap narrowing of titanium dioxide by sulfur doping,Appl.Phy.Lett.,2002,81(3):454-546
[75]周武艺,唐绍裘,等.制备不同掺杂稀土纳米TiO2光催化剂及其光催化活性比较研究.硅酸盐学报2004,32(10):1203-1208.(EI)
[76]李景印,郭玉凤,张亚通.纳米TiO2光催化剂在环保方面的应用研究.河北科技大学学报,2001,22(2):25-31
[77]Willie J P,Matin S T.Development of a structure-reactivity relationship for the photohydrolysis of substituted aromatic halides.Enviroron Sci Technol,1992,26(11):2116-2121
[78]Prudent A L.Degradation of Chloroform by photoassisted heterogeneous catalysis in dilute queous suspensions of TiO2.Enviroron Sci Technol,1983,17(3):628-631
[79]瞿萍,张丰雷,吴凯群等.纳米材料光催化剂在合成染料废水处理中的应用.中国材料研究学会编.中国材料研讨会论文集生物及环境材料.北京:化学工业出版社,1997:600-602
[80]张汝冰,刘宏英,李风生等.均匀沉淀法制备纳米TiO2及其在环保方面的应用.环境化学,1999,18(6):579-583
[81]郑魏,刘维屏,宣日成等.附载TiO2光催化降解咪呀胺农药.环境科学,1999,20(1):73-76
[82]陈士夫,赵梦月,梁新等.玻璃纤维附载TiO2光催化降解处理有机磷农药.环境科学,1996,17(4):33-36
[83]Sherrard K B,Marriott P J.Electrospray mass spectrometric analysis and photocatalytic degradation of polyethoxylate surfactants used in wool scouring.Anal Chem,1994,44(20):3394-3399
[84]Oliveira J C,Jayalilaka W.Photodegradation of 2-and3-Chlorophenol in TiO2aqueous suepesions.Environ Sci Technol,1990,24(7):990-996
[85]王晓平,于云,高濂.TiO2薄膜的液相沉积法制备及其性能表征.无机材料学报,2000,15(3):573-577
[86]申绊文.无机化学.北京:化学工业出版社,2001,1:338-355
[87]姚秉华,杨莉,张键等.离子浸渍复合TiO2光催化剂的研究.西安理工大学学报,2002,18(4):327-331