TiO_2和钛酸盐的制备及光催化性能的研究
|
摘要
二氧化钛(TiO_2)以其价格低廉、无毒、化学性质稳定和催化效率高等优点,在光电转化和光催化领域倍受关注。由于TiO_2的禁带宽度较大,只能被紫外光激发,且光生电子和空穴易复合,因此限制了其在光催化领域的广泛应用。因此,通过多种手段对TiO_2催化剂进行改性,提高TiO_2的光催化效率是将这一技术推向实际应用的重要环节。二氧化钛的改性已被证明是提高光催化活性的简单有效的途径。
本文使用不同的方法对TiO_2光催化剂进行改性,采用溶胶-凝胶法合成了TiO_2,通过高温锻烧处理的合成路线,找到形成TiO_2锐钛矿相和金红石相混晶的最佳的温度;采用球磨法,以六次甲基四胺(HMT)为氮源掺杂TiO_2;采用光催化还原法制备Ag掺杂TiO_2。本文还选择了不同掺杂金属制成具有钙钛矿结构(ABO_3)的钛酸盐;再通过掺杂其他金属离子,改变其A位和B位离子,并寻找最佳的掺杂量。详细研究了反应条件对产物的晶相,晶化程度,光催化活性等的影响。使用XRD、TG、SEM等手段对催化剂结构和性能进行了表征,并研究了它们对亚甲基兰的光催化降解性能。
(1)用溶胶-凝胶法合成TiO_2煅烧温度有一个最佳值550℃,可形成锐钛矿和金红石两种晶相的混晶,煅烧温度过低或过高催化剂的活性都有所下降,不利于光催化反应。
(2)在日光和紫外光下,球磨法制备的N掺杂TiO_2光催化剂较未掺杂TiO_2混晶的光催化效率有很大增强,10%的N掺杂量为最佳。
(3)在日光下,光催化还原法制备的Ag掺杂TiO_2光催化剂较未掺杂TiO_2混晶的光催化效率提高不大,但在紫外光下,却有很大的提高。
(4)用溶胶-凝胶法合成的SrTiO_3、NiTiO_3、Ce_2TiO_5、La_2TiO_5、CoTiO_3、ZnTiO_3六类钙钛矿结构光催化剂,除了CoTiO_3以外都有比较好的光催化性能,尤其以SrTiO_3最佳。
(5)用溶胶-凝胶法合成的Zr:SrTiO_3与Ba:SrTiO_3光催化剂中,Zr~(4+)与Ba~(2+)的掺杂可以有效提高催化剂的光催化效率。但它有一个最佳掺杂量,高于或低于这个最佳掺杂量,催化剂的催化性能有所降低。在本实验中,8%Zr:SrTiO_3与6%Ba:SrTiO_3最佳。
Titanium dioxide,a photocatalyst,has received a great deal of attention owing to its advantages such as high chemical stability,non-toxicity and low cost etc.But only under UV, TiO_2 can be excited because of its wide band gap.And the electrons from the valence band to the conduction band and the holes in the valence band are easy to recombine,which restricts the application of TiO_2.Thus Photocatalyst with higher activity and efficiency is an essential for its application in large scale.Doped TiO_2 has been proved to be a simple and efficient technic to improve the photoactivity.
In this paper,there are different methods to improve the photocatalyst of TiO_2,including high-temperature calcinations based on the sol-gel,and search proper temperature of the formation for TiO_2 mixed crystal.And then,choose HMT to synthesize N:TiO_2 using ball-milling.By the way,the photocatalyst of Ag/TiO_2 is prepared by a simple chemical reduction method.At the same time,synthesize the Titanate by doped various metals.After that modify A-ion and B-ion with other metals,and discover the best amount of dopant.The impact of reaction condition on crystal phase,crystallization degree,and photocatalytic activities of methylene blue degradation are particularly investigated.Finally,the samples were characterized by Differential Thermal Analysis and Thermal Gravimetric analysis(DTA-TG)、X-ray diffraction(XRD) and Scanning Electron Microscopy(SEM).The conclusions of the paper show:
a.550℃is the best calcination temperature of TiO_2 in sol-gel,the mixed crystal of TiO_2 is formed.The experiment also shows that too high or low temperature of the calcinations is harmful to the photocatalytic activity.
b.Both in sunlight and UV-light,the photocatalysis of N:TiO_2 using bail-milling method is much better than the mixed crystal of TiO_2 and the best amount of dopant in N: TiO_2 is 10%.
c.In UVlight,the photocatalysis of Ag/TiO_2 prepared by a simple chemical reduction method is much better than the mixed crystal of TiO_2,but not good in the sunlight.The best amount of dopant in Ag/TiO_2 is 1%.
d.SrTiO_3、NiTiO_3、Ce_2TiO_5、La_2TiO_5、CoTiO_3 and ZnTiO_3 are synthesized by sol-gel under 550℃.Among these catalysts,the photoeatalytic activity of CoTiO_3 is worse than others,and SrTiO_3 is the best.
e.Doping Zr~(4+) and Ba~(2+) for SrTiO_3 by sol-gel can greatly improve efficiency of photocatalysis.But there is a best amount of dopant.The research indicates that with more dopant,the photoeatalysis is worse.The best amount of dopant in Zr:SrTiO_3 and Ba.SrTiO_3 are 8%and 6%.
本文使用不同的方法对TiO_2光催化剂进行改性,采用溶胶-凝胶法合成了TiO_2,通过高温锻烧处理的合成路线,找到形成TiO_2锐钛矿相和金红石相混晶的最佳的温度;采用球磨法,以六次甲基四胺(HMT)为氮源掺杂TiO_2;采用光催化还原法制备Ag掺杂TiO_2。本文还选择了不同掺杂金属制成具有钙钛矿结构(ABO_3)的钛酸盐;再通过掺杂其他金属离子,改变其A位和B位离子,并寻找最佳的掺杂量。详细研究了反应条件对产物的晶相,晶化程度,光催化活性等的影响。使用XRD、TG、SEM等手段对催化剂结构和性能进行了表征,并研究了它们对亚甲基兰的光催化降解性能。
(1)用溶胶-凝胶法合成TiO_2煅烧温度有一个最佳值550℃,可形成锐钛矿和金红石两种晶相的混晶,煅烧温度过低或过高催化剂的活性都有所下降,不利于光催化反应。
(2)在日光和紫外光下,球磨法制备的N掺杂TiO_2光催化剂较未掺杂TiO_2混晶的光催化效率有很大增强,10%的N掺杂量为最佳。
(3)在日光下,光催化还原法制备的Ag掺杂TiO_2光催化剂较未掺杂TiO_2混晶的光催化效率提高不大,但在紫外光下,却有很大的提高。
(4)用溶胶-凝胶法合成的SrTiO_3、NiTiO_3、Ce_2TiO_5、La_2TiO_5、CoTiO_3、ZnTiO_3六类钙钛矿结构光催化剂,除了CoTiO_3以外都有比较好的光催化性能,尤其以SrTiO_3最佳。
(5)用溶胶-凝胶法合成的Zr:SrTiO_3与Ba:SrTiO_3光催化剂中,Zr~(4+)与Ba~(2+)的掺杂可以有效提高催化剂的光催化效率。但它有一个最佳掺杂量,高于或低于这个最佳掺杂量,催化剂的催化性能有所降低。在本实验中,8%Zr:SrTiO_3与6%Ba:SrTiO_3最佳。
Titanium dioxide,a photocatalyst,has received a great deal of attention owing to its advantages such as high chemical stability,non-toxicity and low cost etc.But only under UV, TiO_2 can be excited because of its wide band gap.And the electrons from the valence band to the conduction band and the holes in the valence band are easy to recombine,which restricts the application of TiO_2.Thus Photocatalyst with higher activity and efficiency is an essential for its application in large scale.Doped TiO_2 has been proved to be a simple and efficient technic to improve the photoactivity.
In this paper,there are different methods to improve the photocatalyst of TiO_2,including high-temperature calcinations based on the sol-gel,and search proper temperature of the formation for TiO_2 mixed crystal.And then,choose HMT to synthesize N:TiO_2 using ball-milling.By the way,the photocatalyst of Ag/TiO_2 is prepared by a simple chemical reduction method.At the same time,synthesize the Titanate by doped various metals.After that modify A-ion and B-ion with other metals,and discover the best amount of dopant.The impact of reaction condition on crystal phase,crystallization degree,and photocatalytic activities of methylene blue degradation are particularly investigated.Finally,the samples were characterized by Differential Thermal Analysis and Thermal Gravimetric analysis(DTA-TG)、X-ray diffraction(XRD) and Scanning Electron Microscopy(SEM).The conclusions of the paper show:
a.550℃is the best calcination temperature of TiO_2 in sol-gel,the mixed crystal of TiO_2 is formed.The experiment also shows that too high or low temperature of the calcinations is harmful to the photocatalytic activity.
b.Both in sunlight and UV-light,the photocatalysis of N:TiO_2 using bail-milling method is much better than the mixed crystal of TiO_2 and the best amount of dopant in N: TiO_2 is 10%.
c.In UVlight,the photocatalysis of Ag/TiO_2 prepared by a simple chemical reduction method is much better than the mixed crystal of TiO_2,but not good in the sunlight.The best amount of dopant in Ag/TiO_2 is 1%.
d.SrTiO_3、NiTiO_3、Ce_2TiO_5、La_2TiO_5、CoTiO_3 and ZnTiO_3 are synthesized by sol-gel under 550℃.Among these catalysts,the photoeatalytic activity of CoTiO_3 is worse than others,and SrTiO_3 is the best.
e.Doping Zr~(4+) and Ba~(2+) for SrTiO_3 by sol-gel can greatly improve efficiency of photocatalysis.But there is a best amount of dopant.The research indicates that with more dopant,the photoeatalysis is worse.The best amount of dopant in Zr:SrTiO_3 and Ba.SrTiO_3 are 8%and 6%.
引文
[1]Fujishima A,Honda K.Electrochemical Proteolysis of Water at a Semiconductor Electrode.Nature,1972,238:37-39.
[2]Frank S N,Bard A J.Photooxidation of organic impurities in water using thin films of titanium dioxide.J.Phys.Chem.1987,91:5076-5083.
[3]Linsebigler Amy L,Lu G,Yates J T.Photocatalysis on TiO_2 surfaces:principles,Mechanisms,and selected results.Chem Rve,1995,95:735-758.
[4]黄艳娥,琚行松.纳米二氧化钛光催化降解水中有机污染物的研究.现代化工,2001,21(4):45-48.
[5]王红娟,李忠.半导体多相光催化氧化技术.现代化工,2002,22(2):56-60.
[6]Picht P,Guillard C,Amalric L,et al.Assessment of the importance of the role of H_2O_2and O_2~(。-) in the photocatalytic degradation of 1,2-dimethoxybenzene.Solar Energy Mater Solar Cells,1995,38(1-4):391-399
[7]冯良荣,谢卫国,吕绍洁等.纳米TiO_2催化剂微晶结构对光催化反应的影响.中国科学编辑),2001,31(6):536-542.
[8]胡军文,多相二氧化钛的低温制备及其高催化活性研究:(硕士学位论文).暨南大学,2006.
[9]赵晓红,纳米金红石相TiO_2的低温制备及其光催化性能研究:(硕士学位论文).暨南大学,2006.
[10]米杰,镧离子掺杂二氧化钛的水热制备及其光催化性能的研究:(硕士学位论文).暨南大学,2006.
[11]张昭,罗妮,沈俊等.二氧化钛光催化材料及其制备方法.中国,CN 1850333A,200610020859.4,2006.
[12]尹京花,赵莲花,武伦鹏,张海明.掺铁TiO2纳米微粒的制备及光催化活性.分子催化,2006,20(6):569-573.
[13]黄国军,黄新友.钛酸锶钡粉体制备方法研究进展.兵器材料科学与工程,2005,29(6):69-72.
[14]张晓丽,王花丽.钛酸钡粉体的制备及研究进展.湿法冶金,2005,26(1):17-21.
[15]杨秋萍,纳米二氧化钛光催化性能优化研究:(硕士学位论文).北京:中国地质大学,2006.
[16]桑丽霞,傅希贤,白树林等.ABO_3钙钛矿型复合氧化物光催化活性与B离子d电子结构的关.感光科学与光化学,2001,19(2):109-115.
[17]Tejuca L G,Fierro J L G,Tascon J M D.Structure andreactivity of perovskite-type oxides[J].Adv Catal,1989,36(2):237-328.
[18]白树林,傅希贤,桑丽霞等.钙钛矿(ABO_3)型复合氧化物的光催化活性变化趋势与分析.高等学校化学学报,2001,22(4):663-665.
[19]傅希贤,杨秋华,王俊珍等.钙钛矿型复合氧化物LaFeO_3和LaCoO_3的光催化活性[J].催化学报,1999,20(5):521-524.
[20]桑丽霞,傅希贤,杨秋华等.LaFeO_3和SrFeO_3对水溶性染料的光催化降解.环境科学与技术,2002,25(2):4-6.
[21]傅希贤,杨秋华,桑丽霞.钙钛矿型LaFe_(1-x)Cu_xO_3的光催化活性研究.高等学校化学学报,2002,23(2):283-286.
[22]古凤才,王金明,刘荫藩等.钛酸钙与钛酸铅及其掺杂物的光催化性能.催化学报,1997,18(3):247-249.
[23]徐惠,王毅,苟国俊等.纳米TiO2的制备表征及光催化性能研究.兰州理工大学学报,2005,31(4):68-71.
[24]冶银平,周惠娣,陈建敏.纳米TiO2的制备及其表征.纳米技术与精密工程,2005,3(1):19-21.
[25]夏金德.水热法制备二氧化钛纳米材料.安徽工业大学学报,2007,24(2):140-142.
[26]Wei F Yao,Wang Hong,Xu Xiao H,et al.Synthesis and photocatalytic property of bismuth titanate Bi_4Ti_3O_(12).materials letters,2003,57(13-14):1899-1902.
[27]Wei F Yao,Wang Hong,Xu Xiao H,et al.Photocatalytic property of bismuth titanate Bi_2Ti_2O_7.Applied Catalysis A:General,2004,259(1):29-33.
[28]Nitin K L,Watanabe A,Mitsuhashi T.New improved syntheses of LaRuO_3 perovskites and their applications in environmental catalysis.Applied Catalysis B:Environmental,2003,40(1):21-30.
[29]康振晋.共沉淀法制备La_(1-x)Pb_xMnO_3及其光催化活性研究.延边大学学报(自然科学版),2005,31(1):35-38.
[30]Bickley I B,Gonzalez-Carreno T,Lees J S,et al.A struetural investigation of titanium dioxide photocatalysts.J.Solid State Chem.,1991,92(1):178-190
[31]Hurum D C,GrayKA.Explaining of the enhanced photocatalytic activity of Degussa P25mixed-Phase TiO_2 using EPR.J.Phys.Chem.B.,2003,107(19):4545-4549
[32]Ohtani B,Ogawa Y,Nishimoto S.Photoeatalytic activity of amorphous-anatase Mixture of titianium oxide Partieles suspended in aqueous solutions.J.Phys.Chem.B.,1997,101(19):3746-3752
[33]樊彩梅,孙秀平.纳米TiO_2对水中腐殖酸的吸附及光催化降解.应用化学,2001,18(11):912-914.
[34]刘鸿,成少安,张鉴清等.泡沫镍载TiO_2光催化降解磺基水杨酸.中国环境科学,1998,18(6):548-551.
[35]胡德文,程沧沧.利用日能和斜板式光反应器降解耐晒翠监染料的研究.环境科学与技术,1999,3:28-30.
[36]Wang K H,Hsieh Y H,Chou M Y et al.Photocatalytic degradation of 2-chloro and 2-nitrophenol by titanium dioxide suspensions in aqueous solution,Appl.Catal.B,1999,21(1):128-131.
[37]曹亚安,陈咏梅,管自生等.TiO_2纳米粒子膜的表面态性质及其光催化活性的研究.感光材料与光化学,1999,17(2):100-103.
[38]Okamoto K,Yamamoto Y,Tanaka H et al.Heterogeneous photocatalytic decomposition of phenol over powder.Bull.Chem.Soc.Jpn.1985,58:2023-2027.
[39]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,1999,19(1):47-50.
[40]崔斌,韩欢牛,李淑妮等.Fe_2O_3掺杂TiO_2薄膜对甲基紫溶液光催化降解.应用化学,2001,18(12):958-961.
[41]黄玉明,李天安,章娴君等.TiO_2光催化降解印染废水的研究.西南师范大学学报(自然科学版),1999,24(4):443-446.
[42]Ara la J,Genz(?)lez O D,Miranda M S et al.Photocatalytic degradation of formic acid using Fe~(3+)/Fe~(2+) ions in thedegradation mechanism.Appl.catal.B,2001,32(1/2):49-61.
[43]Scnchez L,Poral J,Domnech X.Aniline degradation bycombined photocatalysis and ozonation.Appl.Catal.B,1998,19(1):59-65.
[44]Bahanemann D,Bockelmann D,Goslich R.Mechanism studies of water detoxification in illuminated TiO_2 suspensions.Solar Ener.Mater,1991,24:564-583
[45]胡将军,周荣迁,刘慧龙等.光催化氧化处理有机废水.环境污染与防治,2000,22(1):31-32.
[46]王琪全,蒋伟川.TiO_2光催化降解次甲基蓝的研究.环境科学与技术,1994,3:1-4.
[47]潘海祥,傅家漠,盛图英.在TiO_2催化剂上菲的光催化氧化反应研究.环境科学研究,2000,13(6):37-39.
[48]Anpo M.Utilization of TiO_2 photocatalysts in green chemistry.Pure APPl.Chem.,2000,72(7):1265-1270
[49]Asahi R,Mori kawa T,Ohwaki T et al.Visible-light photocatalysis in nitrogen—doped titanium oxides.Seience,2001,293(5528):269-271
[50]高远,徐安武,祝静艳,刘汉钦.RE/TiO_2用于NO_2光催化氧化的研究.催化学报,2001,22(1):53-56
[51]Choi W,Termin A,Honhlamm M R.The Role of Metal Ion Dopants Quantumsizeed TiO_2 Correlation Between Photoreactivity and Charge Carrier Reeombination Dynamies[J].J.Phys.Chem.1994(98):1369-1379
[52]Hemnann,et al.Photoeatalytie Degradation of Photocatalytic Degradation of Pestieide PirimiPhos-Mehyl,Determination of the Reaetion Pathway and Ideniification of Intermediates products by、Various Analytic Methods.Catalysis Today,1999,54(3):353-367
[53]Takeuchi,et al.Preparation of Visible-Light-Responsive Titanium Oxide photoeatalysts by plasma Treatment.Chem Lett,2000,12:1354-1366
[54]Thtstima,et al.Remote Bleaching of Methlene Blue by UV-lrradlated TiO_2 in the Gas Phase [J].PhysChem:B,1999,103(38):8033-8035
[55]Asahi R.,Morikawa T.,Ohwaki T.,et al.Visible-light Photoeatalysis in nitrogen-doped titanium oxides.Science.2001,293(5528):269-271
[56]Luo H.,Takata T.,Lee Y.,et al.Photocatalytic enhancing for titanium dioxide by Eo-doping with bromine and chlorine.Chemistry of Materials.2004,16(5):846-849
[57]Yu J.C.,Yu J·,Ho W.,et al.Effects of F-doping on the Photoeatalytic activity and mierostructures of nanocrystalline TiO_2 powders.Chemistry of Materials.2002,14(9) 3808-3816
[58]KhanS.U.M.,Ai-Shahry M.,lngler Jr W.B.Effieient photochemical water splitting by a chemically modified n-TiO_2.Science.2002,297(5590):2243-2245
[59]Lettmann C.,Hildenbrand K.,Kiseh H.,et al.Visible light Photodegradation of 4-chlorophenol with a coke-containing titanium photoeatalyst.Catalysis B,2001,32(4):215-227
[60]籍宏伟,马万红,赵进才等.可见光诱导TiO_2光催化的研究进展.科学通报,2003,48(21):2199-2204
[61]蒋伟川,谭湘萍等.载银TiO_2半导体光催化降解染料水溶液的研究.环境科学,1998,16(2):17-20
[62]张彭义,余刚,蒋展鹏。半导体光催化剂及其改性技术进展。环境科学进展,1997,5(3):7-10
[2]Frank S N,Bard A J.Photooxidation of organic impurities in water using thin films of titanium dioxide.J.Phys.Chem.1987,91:5076-5083.
[3]Linsebigler Amy L,Lu G,Yates J T.Photocatalysis on TiO_2 surfaces:principles,Mechanisms,and selected results.Chem Rve,1995,95:735-758.
[4]黄艳娥,琚行松.纳米二氧化钛光催化降解水中有机污染物的研究.现代化工,2001,21(4):45-48.
[5]王红娟,李忠.半导体多相光催化氧化技术.现代化工,2002,22(2):56-60.
[6]Picht P,Guillard C,Amalric L,et al.Assessment of the importance of the role of H_2O_2and O_2~(。-) in the photocatalytic degradation of 1,2-dimethoxybenzene.Solar Energy Mater Solar Cells,1995,38(1-4):391-399
[7]冯良荣,谢卫国,吕绍洁等.纳米TiO_2催化剂微晶结构对光催化反应的影响.中国科学编辑),2001,31(6):536-542.
[8]胡军文,多相二氧化钛的低温制备及其高催化活性研究:(硕士学位论文).暨南大学,2006.
[9]赵晓红,纳米金红石相TiO_2的低温制备及其光催化性能研究:(硕士学位论文).暨南大学,2006.
[10]米杰,镧离子掺杂二氧化钛的水热制备及其光催化性能的研究:(硕士学位论文).暨南大学,2006.
[11]张昭,罗妮,沈俊等.二氧化钛光催化材料及其制备方法.中国,CN 1850333A,200610020859.4,2006.
[12]尹京花,赵莲花,武伦鹏,张海明.掺铁TiO2纳米微粒的制备及光催化活性.分子催化,2006,20(6):569-573.
[13]黄国军,黄新友.钛酸锶钡粉体制备方法研究进展.兵器材料科学与工程,2005,29(6):69-72.
[14]张晓丽,王花丽.钛酸钡粉体的制备及研究进展.湿法冶金,2005,26(1):17-21.
[15]杨秋萍,纳米二氧化钛光催化性能优化研究:(硕士学位论文).北京:中国地质大学,2006.
[16]桑丽霞,傅希贤,白树林等.ABO_3钙钛矿型复合氧化物光催化活性与B离子d电子结构的关.感光科学与光化学,2001,19(2):109-115.
[17]Tejuca L G,Fierro J L G,Tascon J M D.Structure andreactivity of perovskite-type oxides[J].Adv Catal,1989,36(2):237-328.
[18]白树林,傅希贤,桑丽霞等.钙钛矿(ABO_3)型复合氧化物的光催化活性变化趋势与分析.高等学校化学学报,2001,22(4):663-665.
[19]傅希贤,杨秋华,王俊珍等.钙钛矿型复合氧化物LaFeO_3和LaCoO_3的光催化活性[J].催化学报,1999,20(5):521-524.
[20]桑丽霞,傅希贤,杨秋华等.LaFeO_3和SrFeO_3对水溶性染料的光催化降解.环境科学与技术,2002,25(2):4-6.
[21]傅希贤,杨秋华,桑丽霞.钙钛矿型LaFe_(1-x)Cu_xO_3的光催化活性研究.高等学校化学学报,2002,23(2):283-286.
[22]古凤才,王金明,刘荫藩等.钛酸钙与钛酸铅及其掺杂物的光催化性能.催化学报,1997,18(3):247-249.
[23]徐惠,王毅,苟国俊等.纳米TiO2的制备表征及光催化性能研究.兰州理工大学学报,2005,31(4):68-71.
[24]冶银平,周惠娣,陈建敏.纳米TiO2的制备及其表征.纳米技术与精密工程,2005,3(1):19-21.
[25]夏金德.水热法制备二氧化钛纳米材料.安徽工业大学学报,2007,24(2):140-142.
[26]Wei F Yao,Wang Hong,Xu Xiao H,et al.Synthesis and photocatalytic property of bismuth titanate Bi_4Ti_3O_(12).materials letters,2003,57(13-14):1899-1902.
[27]Wei F Yao,Wang Hong,Xu Xiao H,et al.Photocatalytic property of bismuth titanate Bi_2Ti_2O_7.Applied Catalysis A:General,2004,259(1):29-33.
[28]Nitin K L,Watanabe A,Mitsuhashi T.New improved syntheses of LaRuO_3 perovskites and their applications in environmental catalysis.Applied Catalysis B:Environmental,2003,40(1):21-30.
[29]康振晋.共沉淀法制备La_(1-x)Pb_xMnO_3及其光催化活性研究.延边大学学报(自然科学版),2005,31(1):35-38.
[30]Bickley I B,Gonzalez-Carreno T,Lees J S,et al.A struetural investigation of titanium dioxide photocatalysts.J.Solid State Chem.,1991,92(1):178-190
[31]Hurum D C,GrayKA.Explaining of the enhanced photocatalytic activity of Degussa P25mixed-Phase TiO_2 using EPR.J.Phys.Chem.B.,2003,107(19):4545-4549
[32]Ohtani B,Ogawa Y,Nishimoto S.Photoeatalytic activity of amorphous-anatase Mixture of titianium oxide Partieles suspended in aqueous solutions.J.Phys.Chem.B.,1997,101(19):3746-3752
[33]樊彩梅,孙秀平.纳米TiO_2对水中腐殖酸的吸附及光催化降解.应用化学,2001,18(11):912-914.
[34]刘鸿,成少安,张鉴清等.泡沫镍载TiO_2光催化降解磺基水杨酸.中国环境科学,1998,18(6):548-551.
[35]胡德文,程沧沧.利用日能和斜板式光反应器降解耐晒翠监染料的研究.环境科学与技术,1999,3:28-30.
[36]Wang K H,Hsieh Y H,Chou M Y et al.Photocatalytic degradation of 2-chloro and 2-nitrophenol by titanium dioxide suspensions in aqueous solution,Appl.Catal.B,1999,21(1):128-131.
[37]曹亚安,陈咏梅,管自生等.TiO_2纳米粒子膜的表面态性质及其光催化活性的研究.感光材料与光化学,1999,17(2):100-103.
[38]Okamoto K,Yamamoto Y,Tanaka H et al.Heterogeneous photocatalytic decomposition of phenol over powder.Bull.Chem.Soc.Jpn.1985,58:2023-2027.
[39]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,1999,19(1):47-50.
[40]崔斌,韩欢牛,李淑妮等.Fe_2O_3掺杂TiO_2薄膜对甲基紫溶液光催化降解.应用化学,2001,18(12):958-961.
[41]黄玉明,李天安,章娴君等.TiO_2光催化降解印染废水的研究.西南师范大学学报(自然科学版),1999,24(4):443-446.
[42]Ara la J,Genz(?)lez O D,Miranda M S et al.Photocatalytic degradation of formic acid using Fe~(3+)/Fe~(2+) ions in thedegradation mechanism.Appl.catal.B,2001,32(1/2):49-61.
[43]Scnchez L,Poral J,Domnech X.Aniline degradation bycombined photocatalysis and ozonation.Appl.Catal.B,1998,19(1):59-65.
[44]Bahanemann D,Bockelmann D,Goslich R.Mechanism studies of water detoxification in illuminated TiO_2 suspensions.Solar Ener.Mater,1991,24:564-583
[45]胡将军,周荣迁,刘慧龙等.光催化氧化处理有机废水.环境污染与防治,2000,22(1):31-32.
[46]王琪全,蒋伟川.TiO_2光催化降解次甲基蓝的研究.环境科学与技术,1994,3:1-4.
[47]潘海祥,傅家漠,盛图英.在TiO_2催化剂上菲的光催化氧化反应研究.环境科学研究,2000,13(6):37-39.
[48]Anpo M.Utilization of TiO_2 photocatalysts in green chemistry.Pure APPl.Chem.,2000,72(7):1265-1270
[49]Asahi R,Mori kawa T,Ohwaki T et al.Visible-light photocatalysis in nitrogen—doped titanium oxides.Seience,2001,293(5528):269-271
[50]高远,徐安武,祝静艳,刘汉钦.RE/TiO_2用于NO_2光催化氧化的研究.催化学报,2001,22(1):53-56
[51]Choi W,Termin A,Honhlamm M R.The Role of Metal Ion Dopants Quantumsizeed TiO_2 Correlation Between Photoreactivity and Charge Carrier Reeombination Dynamies[J].J.Phys.Chem.1994(98):1369-1379
[52]Hemnann,et al.Photoeatalytie Degradation of Photocatalytic Degradation of Pestieide PirimiPhos-Mehyl,Determination of the Reaetion Pathway and Ideniification of Intermediates products by、Various Analytic Methods.Catalysis Today,1999,54(3):353-367
[53]Takeuchi,et al.Preparation of Visible-Light-Responsive Titanium Oxide photoeatalysts by plasma Treatment.Chem Lett,2000,12:1354-1366
[54]Thtstima,et al.Remote Bleaching of Methlene Blue by UV-lrradlated TiO_2 in the Gas Phase [J].PhysChem:B,1999,103(38):8033-8035
[55]Asahi R.,Morikawa T.,Ohwaki T.,et al.Visible-light Photoeatalysis in nitrogen-doped titanium oxides.Science.2001,293(5528):269-271
[56]Luo H.,Takata T.,Lee Y.,et al.Photocatalytic enhancing for titanium dioxide by Eo-doping with bromine and chlorine.Chemistry of Materials.2004,16(5):846-849
[57]Yu J.C.,Yu J·,Ho W.,et al.Effects of F-doping on the Photoeatalytic activity and mierostructures of nanocrystalline TiO_2 powders.Chemistry of Materials.2002,14(9) 3808-3816
[58]KhanS.U.M.,Ai-Shahry M.,lngler Jr W.B.Effieient photochemical water splitting by a chemically modified n-TiO_2.Science.2002,297(5590):2243-2245
[59]Lettmann C.,Hildenbrand K.,Kiseh H.,et al.Visible light Photodegradation of 4-chlorophenol with a coke-containing titanium photoeatalyst.Catalysis B,2001,32(4):215-227
[60]籍宏伟,马万红,赵进才等.可见光诱导TiO_2光催化的研究进展.科学通报,2003,48(21):2199-2204
[61]蒋伟川,谭湘萍等.载银TiO_2半导体光催化降解染料水溶液的研究.环境科学,1998,16(2):17-20
[62]张彭义,余刚,蒋展鹏。半导体光催化剂及其改性技术进展。环境科学进展,1997,5(3):7-10