摘要
本文采用水热法制备了金属与非金属共掺杂、非金属共掺杂的纳米TiO_2和金属掺杂的TiO_2微球,并分别采用XRD、Uv-vis、XPS、FTIR和光催化降解甲基橙对其物相和光催化性能进行了研究。
以TiCl_4和FeCl_3为原料、在表面活性剂Span—80存在时,180℃下水热反应48h可成功制得直径为3—10μm的金红石、锐钛矿和板钛矿混合相的微球TiO_2-Fe-Span。XPS表明掺杂的铁以Fe~(3+)形式存在;Uv-vis结果表明,微球具有较高的可见光吸收性能,且吸收带边发生明显的红移。该微球在紫外光照射3h和太阳光照射6h时对甲基橙的降解率分别达100%和91%。特别地,光催化反应后微球可采用自然沉降的方法进行分离,这一特点为TiO_2光催化技术的实际应用提供了很好的基础。
用TiCl_4、FeCl_3和硫脲为原料,制得了硫和铁共掺杂的金红石和锐钛矿混合相的纳米二氧化钛(TiO_2-S-Fe)。160℃下制得的TiO_2-Fe-S样品催化活性最优,紫外光照射60min和太阳光照射50min时对甲基橙的降解率分别达97%和99%。UV-vis表明该催化剂对可见光吸收增强,吸收带边明显红移。XPS表明,掺杂的硫取代TiO_2中的晶格氧形成Ti-S键,使得TiO_2的带隙能窄化引起对可见光的响应;同时部分掺杂的硫以S~(6+)形式存在,从而增强了TiO_2-S-Fe的表面酸强度,提高了对氧和有机物的吸附;铁掺杂降低了电子和空穴的复合几率。阴阳离子的协同作用使得TiO_2-S-Fe具有很高的紫外和可见光催化活性。
以Ti(SO_4)_4、硼酸和硫酸为原料,制得了B、S共掺杂的锐钛矿型纳米二氧化钛(TiO_2-B-S)。UV-vis表明该催化剂对可见光吸收增强,吸收带边明显红移。XPS显示B、S共掺杂改性使得TiO_2-B-S表面羟基氧含量提高,这对提高光活性是有益的。240℃下制得的TiO_2-B-S具有较高的催化活性,紫外光照射50min后对甲基橙几乎全部降解,太阳光照射230min后的降解率达92%。硼硫共掺杂TiO_2具有较高的紫外光和可见光活性的原因可能是掺杂的硼以B~(3+)进入晶格中,导致TiO_2晶格畸变、带隙变窄,S掺杂提高了TiO_2的表面酸度;B、S共掺杂对提高TiO_2的光催化剂活性具有协同效应。
以Ti(SO_4)_4为钛源、硫脲为掺杂剂时,得到了N、S共掺的锐钛矿型纳米二氧化钛(TiO_2-N-S)。UV-vis表明该催化剂对可见光吸收增强,吸收带边红移;EA和XPS分析表明催化剂表面的N含量高于体相的;光催化实验表明TiO_2-N-S催化活性高于纯TiO_2和单掺硫TiO_2,在紫外光照射90min和太阳光照射120min下对甲基橙的降解率分别达88.2%、41.4%。TiO_2-N-S光催化活性的提高与UV-vis光区的强吸收、吸收带边的红移、氧缺的产生以及表面酸度的提高等因素引起的协同效应有关。
S-Fe,B-S,N-S-codoped TiO_2 nanoparticle and Fe doped microspheres had been prepared by hydrothermal method.Their characteristics were investigated by XRD,UV-vis,XPS,FTIR and photocatalytic degradation for methyl orange(MO).
Fe doped titania microspheres with a diameter of about 5-7μm have been synthesized using TiCl_4 and FeCl_3 as the precursor in the presence of Span-80 at 180℃for 48h.XRD indicated that the microspheres were a mixture of rutile,brookite and anatase.XPS showed that the oxidation state of iron in the lattices was probably Fe_2O_3.The UV-Vis DRS revealed that the absorption edge of microspheres had a remarkable shift to the visible light region,its absorption in the visible region was increased.The photocatalytic experiments revealed that the microspheres exhibited high photocatalytic activities under UV-light and solar irradiation.The degradation rate of MO were 100%under UV light irradiation for 3h and 91%under solar irradiation for 6h.In particular, the microspheres could be readily separated by sedimentation after the photocatalytic reaction.It is expected that the TiO_2 microspheres could be one of the ideal photocatalysts for the water purification.
S and Fe co-doped TiO_2 nanoparticles(TiO_2-S-Fe) were prepared by in situ hydrothermal method using TiCl_4,FeCl_3 and thiurea as the precursor.The results of photocatalytic degradation MO demonstrated that the TiO_2-S-Fe catalyst obtained at 160℃for 2 h exhibited the highest photocatalytic activity,the degradation ratio of MO were 99%and 97%under sunlight irradiation for 50 min and UV light irradiation for 60 min,respectively.XRD indicated that the TiO_2-S-Fe is in conformity with anatase and rutile mixed phase TiO_2 form.UV-vis DRS showed that its absorption in the visible light district was strengthened and the band edge moved to longer wave obviously.XPS indicated that the partial S atoms occupied O-atom sites in the TiO_2 to form Ti-S bond,lowered the band gap and caused the absorption edge of TiO_2 to be shifted into the lower-energy region.The partial sulfur atoms existed in a six-oxidation state(S~(6+)) and then enhanced the surface acidity that favored to the adsorption of both oxygen and organic molecules. Doping of Fe~(3+) reduced the recombination of electrons and holes.Both of the above doped effects are beneficial for improving the photocatalysis of TiO_2-S-Fe under UV-light and sun-light irradiation.
B-S-codoped anatase TiO_2 nanoparticles(TiO_2-B-S) was prepared using Ti(SO_4)_2,H_2SO_4 and H_3BO_3 as starting materials.UV-vis DRS showed that its absorption in the visible light district was strengthened and the band edge moved to longer wave obviously.XPS showed that the content of hydroxyl group on its surface increased,compared with that of B or S-doped TiO_2, which favored its photocatalysis.The photocatalytic experimental results indicated that TiO_2-B-S prepared at 240℃for 12 hours exhibited the highest photocatalytic activity,the degradation ratio prepared at 240℃for 12 hours exhibited the highest photocatalytic activity,the degradation ratio of methyl orange were 99.8%and 92.0%under UV light irradiation for 50 min and sunlight irradiation for 230 min,respectively.The higher visible light photocatalytic activity of B-S co-doped TiO_2 was attributed to the doped boron that lowered the band gap,resulted in the localized crystal deformation and the doped sulfur which enhanced the surface acidity of TiO_2. Doping of B and S possessed the synergistic effects on enhancement of TiO_2 photocatalytic activity.
N-S-codoped anatase TiO_2 nanoparticles(TiO_2-N-S) was prepared using Ti(SO_4)_2 with thiourea as N,S sources.A red shift of the absorption edge was brought out owing to N and S codoping, and the extension for photoabsorption range of it occurred.XPS and EA studies showed that N concentration decreased from the surface to the center.Especially,the photocatalytic tests indicated that it demonstrated a high photocatalytic activity for decomposition of methyl orange, comparing to S doped TiO_2 and undoped TiO_2.The degradation ratio of methyl orange were 88.2 %and 41.4%under UV light irradiation 90 min and sunlight irradiation for 120 min,respectively. The high activity of it can be related to the results of the synergetic effects of strong absorption in the UV-vis light region,red shift in adsorption edge,oxygen vacancies and the enhancement of surface acidity induced by N and S codoping.
引文
[1]Fujishima A,Honda A.Electrochemical photolysis of water at a semiconductor electrode[J].Nature,1972,238:37-38.
[2]李晓平,徐宝混,刘国范,吴风清.纳米TiO_2光催化降解水中有机污染物的研究与发展[J].功能材料,1999,30(3):242-248.
[3]Hoffmann M.R.,Martin S.T.,Choi W,et al.Environment alapplication of semiconductor photocatalysis[J].Chem.Rev.,1995,95(3):69-95.
[4]Linsebigler A.L.,Lu G.Q.,Yates J.T..Photocatalysis on TiO_2 surface:principles,mechanisms and selected results[J].Chem.Rev.,1995,95(3):735-758.
[5]Diebold U.,The surface science of titanium dioxide[J].Surface Sci.Reports,2003,48:53-229
[6]唐玉朝,胡春,王怡中.TiO_2光催化反应机理及动力学研究进展.化学进展,2002,14(3):192-199
[7]王光辉.纳米TiO_2光催化技术及其在环境污染治理中的应用[J].环境科学与技术,2001.11(6):42-46.
[8]Fujishima A.,Hashimoto K.Watanabe T.TiO_2 photocatalysis fundamentals and applications[M].BKC Inc,1999
[9]张志馄,宋志慧,张青山.纳米二氧化钛光催化作用及其在环境领的应用[J].青岛化工学院学报(自然科学版),2002,23(4):12-15.
[10]Taoda H.Development of TiO_2 photocatalysts suitable for practical use and their applications in environmental cleanup[J].Research on Chemical Intermediates,2008,34(4):417-426
[11]郝晓刚,李一兵,樊彩梅等.TiO_2光电催化水处理技术研究进展[J].化学通报,2003,5:306-311
[12]李晓平,徐宝混,刘国范等.纳米TiO_2光催化降解水中有机污染物的研究与发展[J].功能材料,1999,30(3):242-248.
[13]李耀中,孔欣,周岳溪等.光催化降解三类难降解有机工业废水[J].中国给水排水,2003,19:58.
[14]席北斗,孔欣,刘纯新等.加铂修饰型催化剂光催化氧化五氯酚[J].环境化学,2001,20(1):27-30.
[15]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.
[16]Shehukin D.,Poznyak S.,Kulak A.,et al.TiO_2-In_2O_3 photoeatalysts:preparation,characterizations and activity for 2-chlorophenol degradation in water[J].J.Photochem.Photobiol.A,2004,162(223):423-430.
[17]Mansila H,D.,Yeber M.C.,Freer J.,et al.Homogeneous and heterogeneous advanced oxidation of a bleaching effluent from the pulp and paper indust ry[J].Water Sci.Tech..,1997,35(4):273-278.
[18]Docters T.,Chovelon J.M.,Herrmann J.M.,et al.Syntheses of TiO_2 photocatalyst s by the molten salts method application to the photocatalytic degradation of Prosulfuron[J].Appl.Catal.B,2004,50(4):423-430.
[19]Zhang J.L.,Terukazu A.,Madoka M.,et al.Investigations of TiO_2 photocatalysts for the decomposition of NO in the flow system:The role of pretreatment and reaction conditions in the photocatalytic efficiency[J].Journal of catalysts,2001,198(1):1-8.
[20]Gao X.,Li J.,Gao W.T.Study on preparation of nano-TiO_2 by W/O microemulsion reactor and its photocatalytic degradation of air pollution[J].Colloid J.,2008,70(3):392-395
[21]Walid A.D.,John H.X.,Zhang Y.H.Surface functionalization of cellulose fibers with titanium dioxide nanoparticles and their combined bactericidal activities[J].Surface Sci.,2005,599:69-75
[22]Wong M.S.,Chu W.C.,Sun D.S.,et al.Visible- light- induced bactericidal activity of a nitrogen -doped titanium photocatalyst against human pathogens[J].Applied and Environ.Microbiology,2006,72(9):6111-6116
[23]Sun S.Q.,Sun B.,Zhang W.O.et al.Preparation and antibacterial activity of Ag-TiO_2 composite film by liquid phase deposition(LPD) method,Bulletin of Mater.Sci.,2008,31(1):61-66
[24]林少华,李田.太阳能固定膜光催化灭菌的特性[J].环境科学学报,2008,28(3):484-489
[25]Evans P.,Sheel D.W.Photoactive and antibacterial TiO_2 thin films on stainless steel[J].Surface Coatings Tech.,2007,201:22-23
[26]Yu J.,Zhao X.Effect of surface treatment on the photocatalytic activity and hydrophilic property of the sol-gel derived TiO_2 thin films[J].Mater.Res.Bull,2001,36:97-107.
[27]于书平,李新军,钟石等.玻璃表面光催化剂薄膜的制备及防雾性能.华南理工大学学报,2001,29(8):10-12
[28]Peruchon L., Puzenat E., Girard-Egrot A., et al. Characterization of self-cleaning glasses using Langmuir-Blodgett technique to control thickness of stearic acid multilayers Importance of spectral emission to define standard test [J]. J. Photochem. Photobiol. A: Chem., 2008, 197(2-3): 170-176
[1]Pozzo R.L.,Baltanas M.,Cassano A.Supported titanium oxide as photocatalyst in water decontamination:state of the art[J].Catal.Today,1997,39:219-231
[2]宋秀芹,杨晓辉,陈汝芬等.纳米结构TiO_2/PG及TiO_2空心球的自组装与表征[J].化学学报,2006,64(3):198-202
[3]王文宝,陆诚,杨平.TiO_2中孔分子筛的合成与X射线衍射分析[J].分析测试学报,2002,21(6):78-80
[4]Kawahashi N.,ShihoH S.Copper and Copper compounds as coatings on polystyrene particles and as hollowspheres[J].Mater Chem,2000,10(10):2294-2298.
[5]Giersig M,,Marzan L,,Mulvaney P.Direct observation of chemical reactions in Silica- coated Gold and Silver nanoparticles[J].Adv Mater,1997,9:570-572.
[6]Bamnolker H.,Nitzan B.,Gura S,et al.New solid and hollow,magnetic and non-magnetic,organic- inorganic monodisper- sed hybrid microspheres:synthesis and characterization[J].Mater Sci Lett,1997,16:1412-1416.
[7]彭祺,汪玉庭,张伟安等.纳米TiO_2-CS微球光催化降解亚甲基兰的研究[J1].环境科学与技术,2006,29(1):23-25
[8]Kim T.H.,Lee K.H.,Kwon Y.K.Monodisperse hollow titania nanospheres prepared using a cationic colloidal template[J].J Colloid and Interface Sci.,2006,304:370-377
[9]Kim Il-D.,Rothschild A.,D.J.Yang,et al.Macroporous TiO_2 thin film gas sensors obtained using colloidal templates[J].Sensors and Actuators B,2008,130:9-13
[10]麻明友.胶体模板法制备有序大孔TiO_2材料[J].化学学报,2006,64(13):1389-1392
[11]徐志兵,郭畅,隆兴兴等.三维大孔TiO_2光催化剂的制备及其催化性能[J].催化学报,2006,27(8):732-736
[12]徐志兵,魏先文.TiO_2空心微球的制备及其表征[J].电子显微学报,2006,25(3):226-230
[13]沈勇.邬泉周,李玉光等.溶胶凝胶法制备三维规则排列大孔TiO_2材料[J].中山大学学报,2002,41(3):45-47;
[14]郭红霞,赵晓鹏.Fe_3O_4/PSt/TiO_2多层包覆电磁响应微球的制备[J].功能材料,2003,34(1):34-36
[15]Yang F.Y.,Chu Y.,Huo L.,et al.Preparation of uniform rhodamine B-doped SiO_2/TiO_2 composite microspheres[J].Journal of Solid State Chemistry,2006,179:457-463
[16]刘国奇,靳正国,方宏等.硅球多层模板溶胶浸渍法制备有序多孔TiO_2薄膜[J].无机化学学报,2007,23(9):1528-1530
[17]Liu L.,Zhao Y.P.,Liu H.J.,et al.Directed growth of TiO_2 nanorods into microspheres[J].Nanotechnology,2006,17:5046-5050
[18]Ren T.Z.,Yuan Z.Y.,Su B.L.Surfactant-assisted preparation of hollow micro- spheres of mesoporous TiO_2[J].Chemical Physics Letters,2003,374:170-175
[19]Zhou Y.,Markus A.Synthesis of very small TiO_2 nanocrystals in a room-temperature ionic liquid and their self-assembly toward mesoporous spherical aggregates[J].J.Am.Chem.Soc.2003,125(49):14960-14961
[20]沈毅,张智丹,沈上越等.二氧化钛微米球形颗粒的制备与研究[J].硅酸盐通报,2005,3:96-101
[21]国伟林,王西奎.二氧化钛/微球光催化剂的溶胶-凝胶法制备与性能研究[J].化学推进剂与高分子材料,2004,2(2):32-34
[22]石可瑜,陈百顺,杨克莲等.纳米晶粒TiO_2多孔微球的合成与表征[J].催化学报,2002,23(4):301-403
[23]杨克莲,叶征琦,杜宗杰等.TiO_2多孔纳米微粒的制备及具物性表征[J].城市环境与城市生态,2002,15(1):22-24
[24]Wang Y.D.,Zhou A.N.,Z.Y.Yang.Preparation of hollow TiO_2 microspheres by the reverse microemulsions[J].Materials Letters,2008,62:1930-1932
[25]Han Y.,Li G.C.,Zhang Z.K.Synthesis and optical properties of rutile TiO_2 microspheres composed of radially aligned nanorods[J].Journal of Crystal Growth,2006,295:50-53
[26]Sheng Y.,Zhou B.,Liu Y.H.,et al.Close-packed nano-TiO_2 anatase microspheres synthesis and their luminescent properties[J].Materials Letters,2006,60:1327-1330
[27]Yang H.G.,Zeng H.C.Preparation of hollow anatase TiO_2 nanospheres via Ostwald ripening [J].J.Phys.Chem.B 2004,108:3492-3495
[28]Guo C.W.,Cao Y.,Xie S.H,et al.Fabrication of mesoporous core-shell structured titania microspheres with hollow interiors[J].Chem.Commun.,2003:700-701.
[29]Xu J.H.,Dai W.L.,Li J.X.,et al.Novel core-shell structured mesoporous titania microspheres Preparation,characterization and excellent photocatalytic activity in phenol abatement[J].J.Photochem.Photobiol.A:Chem.,2008,195:284-294
[30]Feng X.J.,Zhai J.,and Jiang L..The Fabrication and switchable superhydro- phobicity of TiO_2nanorod films[J].Angew.Chem.Int.Ed.2005,44,5115-5118
[31]张一兵,封心建,江雷.水热法合成由纳米棒自组装而成的TiO_2微米球[J].中国科学B辑:化学,2007,37(2):124-126
[32]Song B.,Liu S.W.,Jian J.K.,et al.Electrochemical properties of TiO_2 hollow microspheres from a template-free and green wet-chemical route[J].J.Power Sources.2008,180:869-874
[33]Yu J.G.,Wang G.H.Hydrothermal synthesis and photocatalytic activity of mesoporous titania hollow microspheres[J].J.Phy.Chem.Solids.2008,69:1147-1151
[34]Dong R.Y.,Chang S.M.,Hung Y.C.,et al.Preparation of highly ordered titanium dioxide porous films:Characterization and photocatalytic activity[J].Sep.Purification Tech,2007,58:192-199
[35]杨克莲,叶征琦,杜宗接等,纳米TiO_2微粒阳光催化降解活性艳蓝染料[J].城市环境与城市生态,2003,16(1):13-15
[36]黄浪欢,陈彩选,刘应亮.氮掺杂TiO_2/SiO_2核壳型复合微球的制备及其可见光催化性能[J].催化学报,2006,27(12):1101-1106
[37].Song X.F.,Gao L.Synthesis,characterization,and optical properties of well-defined N-doped,hollow Silica/Titania hybrid microspheres[J].Langmuir,2007,23:11850-11856
[38]Chi B.,Zhao L.,Jin T..One-Step Template-Free Route for synthesis of mesoporous N-doped Titania spheres[J].J.Phys.Chem.C,2007,111:6189-6193
[39]Zhou J.K.,L.Lv,Yu J.Q.,et al.Synthesis of self-organized polycrystalline F-doped TiO_2hollow microspheres and their photocatalytic Activity under Visible Light[J].J.Plays.Chem.C,2008,112:5316-5321
[40]Ren L.,Huang X.T.,Sun F.L.,et al.Preparation and characterization of doped TiO2nanodandelion[J].Materials Letters 2007,61:427-431
[41]Ikari H.,Okanishi K.,Tomita M.,et al.Fluorescence MDR features of Eu~(3-) doped sol-gel TiO2hydrate microspheres[J].Optical Materials,2008,30:1323-1326
[42]吕幼军,石可瑜,郭先芝等.含Sr纳米晶粒二氧化钛多孔微球的制备与表征[J].高等学校化学学报,2006,27(2):346-348
[43]Lv Y.J.,Shi K.Y.,Zhang Y.Y,et al.The characterization of Sr-doped nanocrystal grain microspheres and photodegradation of KN-R dye[J].Catal.Communications,2008,9:557-562
[44]Tong T.Z.,Zhang J.L.,Tian B.Z.,et al.Preparation and characterization of anatase TiO_2microspheres with porous frameworks via controlled hydrolysis of titanium alkoxide followed by hydrothermal treatment[J].Materials.Lett.,2008,62:2970-2972
[45]Tong T.Z.,Zhang J.L.,Tian B.Z.,et al.Preparation of Fe~(3+)-doped TiO_2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation[J].J.Hazardous Materials,2008,155:572-579
[46]Chang C.C.,Lin C.K.,Chan C.C.,et al.Photocatalytic properties of nanocrystalline TiO_2 thin film with Ag additions[J].Thin Solid Films,2006,494:274-278
[47]王昌运,俞建长.水热法合成单分散ZnS微球[J].化学学报,2006,64(22):2287-2290
[48]Zhu J.F.,Chen N.F.,Zhang J.L.,et al.Fe~(3+)-TiO_2 photocatalysts prepared by combining sol-gel method with hydrothermal treatment and their characterization[J].J.Photochem.Photobiol.A:Chem,2006,180:196-204
[49]Nahar M.S.,Hasegawa K.,Kagaya S.,et al.Comparative assessment of the efficiency of Fe-doped TiO_2 prepared by two doping methods and photocatalytic degradation of phenol in domestic water suspensions[J].Sci.Technol.Adv.Mater,2007,8:286-291.
[50]Zhu J.F.,Zheng W.,Bin B.,et al.Characterization of Fe-TiO_2 photocatalysts synthesized by hydrothermal method and their photocatalytic reactivity tbr photodegradation of XRG dye diluted in water[J].J.Mol.Catal.A:Chem.,2004,216:35-43.
[51]Lettmann C.,Hildenbrand K.,Kisch H.,et al.Visible light photodegradation of 4-chlorophenol with a coke-containing titanium dioxide photocatalyst[J],Appl.Catal.B:Environ.2001,32:215-227.
[52]Hurum D.C.,Agrios A.G.,Gray K.A.,Explaining the enhanced photoatalytic activity of Degussa P25 mixed-phase TiO2 using EPR[J].J.Phys.Chem.B:2003,107:4545-4549.
[53]Ohno T.,Miyamoto Z.,Nishijima K.,et al.Sensitization of photocatalytic activity of S- or N-doped TiO_2 particles by adsorbing Fe~(3+) cations[J].Appl.Catal.A:Gen.2006,302:62-68
[1]He C.,Xiong Y.,Shu D.,et al.Preparation and photoelectrocatalytic activity of Pt(TiO_2)-TiO_2hybrid films[J].Thin Solid Films,2006,503(1):1-7.
[2]Yu J.G.,Xiong J.F.,Cheng B.,et al.Fabrication and characterization of Ag-TiO_2 multiphase nanocomposite thin films with enhanced photocatalytic activity[J].Applied Catalysis B,2005,60(3):211-221.
[3]Sonawane R.S.,Dongare M.K.Sol-gel synthesis of Au/TiO_2 thin films for photocatalytic degradation of phenol in sunlight[J].Journal of Molecular Catalysis A,2006,243(1):68-76.
[4]Xie B.P.,Xiong Y.,Chen R.M.,et al.Catalytic activities of Pd-TiO_2 film towards the oxidation of formic acid[J].Catalysis Coroanunication,2005,6(11):699-704.
[5]Zuo P.,Li C.,Wu Y.S.,et al.Mechanism of squarylium cyanine and Ru(dcbpy)_2(NCS)_2co-sensitization of colloidal TiO_2[J].Journal of Photochemistry and Photobiology A,2006,183(1):138-145.
[6]Marcl G.,Augugliaro V.,Lopoz-munoz M.J.,et al.Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO_2 systems.surface,bulk characterization and 4-nitrophenol photodcgradation in liquid-solidregime[J].J.Phys.Chem.B,2001,105(5):1033-1040.
[7]Ismall A.A.Synthesis and characterization of Y_2O_3/Fe_2O_3/TiO_2 nanoparticles by sol-gel method [J].Appl.Catal.B..Environ.,2005,58(1):115-121.
[8]Liu H.Y.,Gao L.Synthesis and properties of CdSe-sensitized mile TiO_2 nanocrystals as a visible light-responsive photocatalyst[J].Journal of the American Ceramic Society,2005,88(4):1020-1022.
[9]Stylidi M.,Kondarides D.I.,Verykios X.E.Visible light-induced photocatalytie degradation of acid Orange 7 in aqueous TiO_2 suspensions[J].Applied Catalysis B:Environmental,2004,47(3):189-201.
[10]卢冠中,江娴.SO_4~(2-)/Ti-Al-0固体超强酸的酸强度及催化性能[J].催化学报,1995,16(1):21-25.
[11]Xie C.,Xu Z.,Yang Q.J.,et al.Comparative studies of heterogeneous photocatalytic oxidation of heptane and toluene on pure titania,titania-silica mixed oxides and sulfated titania[J].Journal of Molecular Catalysis A,2004,217(1):193-201.
[12]Colon G.,Hidalgo M.C.,Navio J.A.Photocatalytic behaviour of sulphated TiO_2 for phenol degradation[J].Applied Catalysis B:Environ.2003,45(1):39-50.
[13]付贤智,丁正新,苏文悦等.二氧化钛基固体超强酸的结构及其光催化氧化性能[J].催化 学报,1999,20(3):321-324.
[14]Choi W.,Terrain A.,Hofmann M.R.The role of metal ion dopants in quantum sized TiO_2:correlation between photoreactivity and charge carrier recombination dynamics[J].J.Phys.Chem.,1994,98(51):13669-13679.
[15]Wu X.A.,Gao Y.,Liu H.Q.The preparation,characterization,and their photocatalytic activities of rare-earthdoped TiO_2 nanoparticles[J].J Catal,2002,207(2):151-157.
[16]蔡邦宏.铁掺杂对二氧化钛结构和光催化性能的影响[J].云南大学学报(自然科学版),2005,27(3A):274-280
[17]Zhou M.H.,Yu J.G.,Cheng B.,et al.Preparation and photocatalytic activity of Fe-doped mesoporous titanium dioxide nanocrystalline photocatalysts[J].Materials Chemistry and Physics,2005,93(1):159-163.
[18]Zhu J.F.,Chen F.,Zhang J.L.,et al.Fe~(3+)-TiO_2 photocatalysts prepared by combining sol-gel method with hydrothermal treatment and their characterization[J].J Photochem Photobiol A:Chem,2006,180:196-204
[19]Asahi R.,Morikawa T.,Ohwaki T,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides[J].Sci.,2001,293(13):269-271.
[20]Ihara T.,Miyoshi M.,Iriyama,Y.,et al.Visible-light-active titanium oxide photocatalyst realized by an oxygen-deficient structure and by nitrogen doping,Appl.Catal.B,2003,42(4):403-409.
[21]Wang Z.P.,Cai W.M.,Hong X.T.,et al.Photocatalytic degradation of phenol in aqueous nitrogen-doped TiO_2 suspensions with various light sources[J].Appl.Catal.B:Environ,2005,57(3):223-231.
[22]Yu J.C.,Yu J.G.,Ho W.K.,et al.Effects of F-doping on the photocatalytis activity and microstructures of nanocrystaline TiO_2 powders[J].Chem Mater,2002,14(9):3808-3816.
[23]Khan S.U.M.,Al-Shahry M,Ingler W.B.Jr.Efficient photochemical water splitting by a chemically modified n-TiO_2[J].Sci.,2002,297(27):2243-2245.
[24]Ohno T.,Akiyoshi M.,Umebayashi T.,et al.Preparation of S-doped TiO_2 photocatalysts and their photocatalytic activities under visible light[J].Applied Catalysis A:General,2004,265:115-121
[25]Ho W.K.,Jimmy C.,Yu,et al.Low-temperature hydrothermal synthesis of S-doped TiO_2 with visible light photocatalytic activity[J].J.Solid State Chem.,2006,179(4):1171-1176.
[26]Umebayashi T.,Yamaki T.,Itoh H.,et al.Band gap narrowing of titanium dioxide by sulfur doping[J].Applied Physics Letters,2002,81(3):454-456.
[27]Ohno T.,Mitsui T.,Matsumura M.Photocatalytic activity of S-doped TiO_2 photocatalyst under visible light[J].Catal.lett.,2000,67(2):135-137.
[28]刘红艳,高濂.湿化学法原位合成硫掺杂的纳米金红石TiO_2可见光催化剂[J].无机材料学报,2005,20(2):470-474
[29]Zhao W.,Ma W.H.,Chen C.C.,et al.Eficiency degradation of toxic organic pollutants with Ni_2O_3/TiO_(2-x)B_x under visible irradiation[J].J.Am.Chem.Soc.,2004,126(15):4782-4783.
[30]Wei H.Y.,Wu Y.S.,Lun N.,et al.Influence of low temperature nitridization on the microstructure,morphology and optical properties of tin oxide nanocrystallines[J].Mater.Sci.and Eng.B,2004,110(1):1-5.
[31]Sakatsni Y,Nunoshige J.,Ando H.Photocatalytic decomposition of acetaldehyde under visible light irradiation over La~(3+) and N co-doped TiO_2[J].Chem Lett,2003,32(12):1156-1157
[32]Sakatani Y.,Ando H.,Okusako K.,et al.Metal ion and N co-doped TiO_2 as a visible-light photocatalyst.J Materials Research 2004,19(7):2100-2108
[33]Liu H.Y.,Gao L.Codoped rutile TiO_2 as a new photocatalyst for visible light irradiation[J].Chem Lett,2004,33(6):730-731
[34]Ohno T.,Miyamoto Zo,Nishijima K.,et al.Sensitization of photocatalytic activity of S- or N-doped TiO_2 particles by adsorbing Fe~(3+) cations.Applied Catalysis A:General,2006,302:62-68
[35]尹霞,向建南,翦立新等.Fe~(3+)—H掺杂TiO_2光催化剂的制备、表征与催化性能[J].应用化学,2005,22(6):634-637.
[36]翦立新,殷小秋,向建南等.Fe~(3+)-N改性二氧化钛光催化剂的研制[J].湖南大学学报(自然科学版),2006,33(1):79-82
[37]黄东升,陈朝凤,李玉花等.铁、氮共掺杂二氧化钛粉末的制备及光催化活性[J],无机化学学报,2007,23(4):738-742
[38]李立清,刘宗耀,唐新村.B/Fe_2O_3共掺杂纳米TiO_2可见光下的催化性能[J].中国有色金属学报,2006,16(12):2098-2103
[39]孙红旗,程友萍,金万勤等.镧、碳共掺杂TiO_2的制备及其可见光催化性能[J].化工学报,2006,57(7):1570-1574
[40]Liao Sh.J.,Huang D.G.,Yu D.H.,et al.Preparation and characterization of ZnO/TiO_2,SO_4~(2-)/ZnO/TiO_2 photocatalyst and their photocatalysis[J].J.Photochem.Photobiol.A:Chem.,2004,168:7-13.
[41]华南平,吴遵义,杜玉扣等.Pt、N共掺杂TiO_2在可见光下对三氯乙酸的催化降解作用[J].物理化学学报,2005,21(10):1081-1085.
[42]苗鸿雁,李永强,罗宏杰.掺铁二氧化钛纳米粉体的水热法制备与表征[J],中国工业,2003,10(5):1-5
[43]Ohtani B.,Ogawa Y.,Nishimoto S.Photocatalytic activity of amorphous-anatase mixture of titianium oxide particles suspended in aqueous solutions[J].J Phys.Chem.B,1997,101: 3746-3752.
[44]Hurum D.C.,Agrios A.G.,Gray K.A.,et al.Explaining of the enhanced photocatalytic activity of Degussa P25 mixed-phase TiO_2 using EPR[J].J Phys Chem B,2003,107:4545-4549.
[45]赵德明,金宁人.过渡金属Fe~(3+)离子掺杂改性TiO_2的光催化性能研究进展[J],浙江工业大学学报,2005,33(2):165-169
[46]余锡宾,王桂华,罗衍庆.Fe/Ti/Si复合微粒的表面结构与催化活性[J].化学学报,2000,58(6):548-553.
[47]Henrik J.,Alexei S.,Zheshen L.,et al.XPS and FTIR investigation of the surface properties of different prepared titania nano-powders[J].Appl Surf.Sci.,2005,246(1-3):239-249.
[48]Hebenstreit E.L.D,Hebenstreit W,Diebold U.Structures of sulfur on TiO_2(110) determined by scanning tunneling microscopy,X-ray photoelectron spectroscopy and low-energy electron diffraction[J].Surf.Sci.2001,470(3):347-360.
[49]Wang X.C.,Yu J.C.,Liu P.,et al.Probing of photocatalytic surface sites on SO_4~(2-)/TiO_2 solid acids by in situ FT-IR spectroscopy and pyridine adsorption[J].J Photochem Photobiol A:Chem,2006,179:339-347
[50]周林,郭秀生,掺杂铁纳米TiO_2的制备及其光催化性能研究[J].工业催化,2004,12(4):38-41
[51]王艳芹,张莉,程虎民等.掺杂过渡金属离子的TiO_2复合纳米粒子光催化剂-罗丹明B的光催化降解[J].高等学校化学学报,2000,21(60):958-960
[1]籍宏伟,马万红,黄应平等.可见光诱导TiO_2光催化的研究进展[J].科学通报,2003,48(21):2199
[2]赵秀峰,张志红,孟宪峰等.B掺杂TiO_2/AC光催化剂的制备及活性[J],分子催化,2003,17(4):292-296
[3]Chen D.M.,Yang D.,Wang Q.,et al.Effects of Boron Doping on Photocatalytic Activity and Microstructure of Titanium Dioxide Nanoparticles[J].Ind.Eng.Chem.Res.2006,45(12):4110-4116.
[4]Geng H.,Yin S.W.,Yang X.,et al.Geometric and electronic structures of the boron-doped photocatalyst TiO_2[J].J.Phys.:Condens.Matter,2006,18:87-96
[5]Zhao W.,Ma W.H.,Chen C.C.,et al.Efficient degradation of toxic organic pollutants with Ni_2O_3/TiO_(2-x)B_x under visible irradiation[J].J Am Chem Soc,2004,126(15):4782-4783
[6]汤心虎,韦朝海,梁洁荣等.硼掺杂CeO_2/TiO_2光催化剂的制备及其活性研究[J].环境科学,2006,27(7):1329-1333
[7]Jung K.Y.,Park S.B.,Ihm S.K.Local structure and photocatalytic activity of B_2O_3-SiO_2/TiO_2ternary mixed oxides prepared by sol-gel method[J].Appl.Catal.B:Environ.,2004,51:239-245
[8]Li D.,Ohashi N.,Hishita S.,et al.Origin of visible-light-driven photocatalysis:A comparative study on N/F-doped and N-F-codoped TiO_2 powders by means of experimental characterizations and theoretical calculations[J].J solid state chem.2005,178(11):3293-3302
[9]Li D.,Haneda H.,Hishita S.,et al.Visible-light-driven nitrogendoped TiO_2 photocatalysts:effect of nitrogen precursors on their photocatalysis for decomposition of gas-phase organic pollutants [J].Mater.Sci.Eng.B.,2005,17:2596-2602.
[10]Ohno T.,Tsubota T.,Nakamura Y.,et al.Preparation of S,C cation-codoped SrTiO_3 and its photocatalytic activity under visible light[J].Applied Catalysis A:General,2005,288(1-2):74-79
[11]沈少华,延卫,郭烈锦.碳氮共掺杂二氧化钛的合成与制氢性能研究[C].兰州:全国太阳能光化学与光催化学术会议论文集,2004,157-158.
[12]Yin S.,Ihara K.,Aita Y.,et al.Visible-light induced photocatalytic activity of TiO_(2-x)A_y(A=N,S)prepared by precipitation route[J].J Photochem.Photobiol.A:Chem.,2006,179(1-2):105-114.
[13]Yu J.G.,Zhou M.H.,Cheng B.,et al.Preparation,characterization and photocatalytic activity of in situ N,S-codoped TiO_2 powders.Journal of Molecular Catalysis A:Chemical 2006,246:176-184
[14]Liu H.Y.,Gao L.(Sulfur,nitrogen)-codoped rutile-titanium dioxide as a visible-light-activated photocatalyst[J],J.Am.Ceram.Soc.,2004,87:1582-1584
[15]钱逸泰.结晶化学导论(第3版)[M].中国科学技术大学出版社,合肥,2005:218
[16]Lettmann C.,Hildenbrand K.,Kisch H.,et al.Visible light photodegradation of 4-chlorophenol with a coke-containing titanium dioxide photocatalyst[J].Applied Catalysis B:Environment,2001,32(4):215-227.
[17]Wang X.C.,Yu J.C.,Liu P.,et al.Probing of photocatalytic surface sites on SO_4~(2-)/Ti_2 solid acids by in situ FT-IR spectroscopy and pyridine adsorption[J].J Photochem.Photobiol.A,2006,179:339-347
[18]Liao S.J.,Dong G.H.,Yu D.H.,et al.Preparation and characterization of ZnO/TiO_2,SO_4~(2-)/ZnO/TiO_2 photocatalyst and their photocatalysis[J].J.Photochem.Photobiol.A:Chem.,2004,168:7-13.
[19]Maldotti A.,Molinari A.,Amadelli R.Photocatalysis with organized systems for the oxofunctionalization of hydrocarbons by O_2[J].Chem Rev,2002,102(10):3811-3836.
[20]Ohno T,Akiyoshi M,Umebayashi T,et al.Preparation of S-doped TiO_2 photocatalysts and their photocatalytic activities under visible light[J],Applied Catalysis A:General,2004t,265:115-121
[21]李立清,刘宗耀,唐新村等.B/Fe_2O_3共掺杂纳米TiO_2可见光下的催化性能[J].中国有色金属学报,2006,16(12):2098-2103
[22]Umebayashi T.,Yamaki T.,Itoh H.,et al.Band gap narrowing of titanium dioxide by sulfur doping[J],Appl.Phys.Lett.,2002,81:454-456.
[23]Bacsa R.,Kiwi J.,Ohno T.,et al.Preparation,testing and characterization of doped TiO_2 active in the peroxidation of biomolecules under visible light[J].J.Phys.Chem.B,2005,109:5994-6003.
[24]Asahi R.,Morikawa T.,Ohwaki T.,et al.Visible-light photocatalysis in nitrogen-doped titanium oxides[J],Sci.2001,293:269-271.
[25]Miyauchi M.,Ikezawa A.,Tobimatsu H.,et al.Zeta potential and photocatalytic activity of nitrogen doped TiO_2 thin films[J],Phys.Chem.Chem.Phys.2004,6:865-870.
[26]Irie H.,Watanabe Y.,Hashimoto K.Nitrogen-concentration dependence on photocatalytic activity of TiO_(2-x)N_x powders[J],J.Plays.Chem.B,2003,107:5483-5486.
[27]Yang M.C.,Yang T.S.,Wong M.S.Nitrogen-doped titanium oxide films as visible light photocatalyst by vapor deposition[J],Thin Solid Films,2004,162:469-470.
[28]Suda Y.,Kawasaki H.,Ueda T.,et al,Preparation of high quality nitrogen doped TiO_2 thin film as a photocatalyst using a pulsed laser deposition method[J],Thin Solid Films,2004,162:453-454.
[29]Hong Y.C.,Bang C.U.,Shin D.H.,et al,Band gap narrowing of TiO_2 by nitrogen doping in atmospheric microwave plasma[J],Chem.Phys.Lett.2005,413:454-457.
[30]Ren L.,Huang X.T.,Sun F.L.,et al,Preparation and characterization of doped TiO_2nanodandelion[J],Mater.Lett.2007,61:427-431
[31]Umebayashi T.,Yamaki T.,Tanala S.,et al,Visible light-induced degradation of Methylene blue on S-doped TiO_2[J],Chem.Lett.,2003,32:330-331.
[32]Ihara T.,Miyoshi M.,Iriyama Y.,et al,Visbele- light-active titanium oxide photocatalyst realized by an oxygen-deficient structure and by nitrogen doping[J],Appl.Catah B:Environ.2003,42:403-409.