摘要
本文选择具有高稳定性和高催化活性的酞菁(直接耐晒翠兰GL)作为敏化剂,把酞菁在可见光区的强吸收性及催化特性与TiO2光催化特性集为一体,采用溶胶.凝胶法在Al2O3基底上制备出高催化活性和宽响应范围的酞菁/TiO2复合催化薄膜。以苯酚为模拟污染物,研究了复合催化薄膜的制备条件,光催化活性和光电催化活性,对其影响因素进行了讨论。并对光催化与光电催化过程作了动力学研究。利用X射线粉末衍射(XRD)、紫外可见近红外光谱法、红外光谱法(IR)和交流阻抗测试(EIS)等测试手段对复合膜的微观结构和性能进行了研究。结果表明,复合催化薄膜的催化活性及光响应范围明显高于TiO2,且在电化学辅助条件下催化活性更高。光电催化反应的活化能(11.15kJ/mol)小于光催化反应的活化能(14.81 kJ/mol),光电催化反应更容易进行。
The phthalocyanine (direct fast turquoise blue GL) was chosed as the sensitizied material, which has high stability and catalytic activity. Combining the advantages of the excellent properties of both phthalocyanine and TiO2, a composite catalyst with high photo-quantum yield and responsibility at widened spectrum range was prepared by sol-gel method on Al2O3 support in this paper. Using phenol degradation as the model reaction, the preparation conditions of the composite catalyst and its photocatalytic activity, photoelectrocatalytic activity were researched. As well as factors were discussed. The kinetics of photocatalysis and photoelectrocatalysis process were also studied. Its microstructure and properties were analyzed by XRD, IR spectrum, UV-Vis-NIR absorption spectrum, and impedance spectroscopy, et al. The results showed that its catalytic activity and absorbing spectrum range were apparently higher than those of TiO2, and much higer at electrochemical-assisted conditions. The activation energy of photoelectrocatalysis process(11.15kJ/mol) is smaller than that of photocatalysis process(14.81 kJ/mol). And the photoelectrocatalysis process happened easier.
引文
[1]A. Fujishim, K. Honda. Electrochemical photocatalysis of water at a semiconductor electrode[J]. Nature.1972,238.37-38
[2]S. N. Frank, A. J. Bard. Heterogeneous photocatalytic oxidation of cyanide ion in aqueous solution at powder[J]. J. Am. Chem. Soc.1977,99.303-304
[3]Jae-Seoun Hur, Youngjin Koh. Bactericidal activity and water purification of immobilized TiO2 photocatalyst in bean sprout cultivation[J]. Biotechnology Letters. 2002,24.23-25
[4]Yongjun Chen, Dionysios D. Dionysiou. Sol-gel synthesis of nanostructured TiO2 films for water purification [J]. Titania Films for Water Purification.2008,67-75
[5]Kerstin Hund-Rinke, Maphnids. Ecotoxic effect of photocatalytic active nanoparticls (TiO2) on algae and daphnids[J]. Photocatalytic Active Nanoparticles.2006,1-8
[6]王彦,苏会东,胥学鹏.活性炭负载TiO2光催化杀菌研究[J].环境保护科学.2007,8,33(4).40-45
[7]Hyeok Choi, Elias Stathatos, Dionysios D.Dionysiou. Photocatalytic TiO2 films and membranes for the development of efficient wastewater treatment and reuse systems[J]. Desalination.2007,202.199-206
[8]沈伟韧,赵文宽,贺飞.TiO2光催化反应及其在废水处理中的应用[J].化学进展.1998,12,10(4).349-361
[9]Peter K. J. Robertson, Detlef W. Bahnemann, Jeanette M. C. Robertson, et al. Photocatalytic detoxification of water and air [J]. Hdb Env Chem.2005,367-423
[10]王秀芹,李政一.TiO2对有机磷农药乐果光催化降解的影响[J].安全与环境学报.2008,6,8(3).82-84
[11]赵玲,尹平河,欧云付.十二烷基苯磺酸钠的光催化氧化[J].城市环境与城市生态.2004,6,17(3).27-29
[12]王海棠,朱银华,杨祝红等.新型Ni/TiO2催化剂用于对硝基苯酚催化加氢[J].催化学报.2009,3,30(53).414-420
[13]Xinle Zhu, Xiaogang Feng, Chunwei Yuan, et al. Photocatalytic degradation of pesticide pyridaben in suspension of TiO2:identification of intermediates and degradation pathways [J]. Journal of Molecular CatalysisA:Chemical.2004,214. 293-300
[14]Sheng Wen, Jincai Zhao, Guoying Sheng, et al. Photocatalytic reactions of phenanthrene at TiO2/water interfaces[J]. Chemosphere.2002,46.871-877
[15]吴娟,马东,包南等.高活性TiO2光催化剂降解酸性红B的研究[J].工业用水与废水.2008,6,39(3).33-36
[16]罗菊仙,赵中一.半导体多相光催化氧化技术在环境保护中的应用研究进展[J].地球科学.2000,9,25(5).537-543
[17]王红娟，奚红霞,夏启斌等.含酚废水处理技术的现状与开发前景[J].工业水处理.2002,6,22(6).6-9
[18]Ralph W. Matthews. Photooxidation of organic impurities in water using thin films of titanium dioxide[J]. J. Phys. Chem.1987,91.3328-3333
[19]武正簧.用TiO2薄膜作催化剂降解苯酚的研究[J].化学工业与工程.1999,4,16(2).102-104
[20]Chul Han Kwon, Hyunmin Shin, Je Hun Kim, et al. Degradation of methylene blue via photocatalysis of titanium dioxide [J]. Materials Chemistry and Physics.2004,86. 78-82
[21]刘守新,陈曦.TiO2/活性炭负载型光催化剂的溶胶-凝胶法合成及表征[J].催化学报.2008,1,29(1).19-24
[22]徐明霞,徐廷献,刘宁.由TiOSO4水解-沉淀制备TiO2薄膜[J].地球科学.1997,4,25(2).209-213
[23]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[J].无机材料学报.1998,8,13(4).608-611
[24]胡德文,程沧沧.日光下黄砂负载TiO2降解邻氯苯酚水溶液[J].环境污染与防治.1999,6,21(3).4-6
[25]Xingwang Zhang, Minghua Zhou, Lecheng Lei. TiO2 photocatalyst deposition by MOCVD on activated carbon[J]. Carbon.1994,98(51).13669-13679
[26]Lei Zhao, Mandi Han, Jianshe Lian. Photocatalytic activity of TiO2 films with mixed anatase and rutile structures prepared by pulsed laser deposition[J]. Thin Solid Films.2008,516.3394-3398
[27]董昊,张永熙,杨锡良等.直流反应磁控溅射制备二氧化钛薄膜的光催化性能研究[J].真空科学与技术.2000,7,20(4).252-255
[28]沈嘉年,宋江江,马寒冰等.钛上阳极氧化生成TiO2光催化薄膜的结构与性能[J].稀有金属材料与工程.2004,10,33(10).1076-1079
[29]张颖,姚明明,卢萍等.电泳法制备纳米TiO2薄膜光催化性能的研究[J].中国粉体技术.2006,(5).19-22
[30]Wonyong Choi, Andreas Termin, Michael R.Hoffmann. The role of metal ion dopants in quantum-sized TiO2:correlation between photoreactivity and charge carrier recombination dynamics [J]. The Journal of Physical Chemistry.1994,98(51). 13669-13679
[31]周艺,李志伟,徐协文.Pr3+,Ho3+掺杂TiO2纳米粒子的光催化性能[J].湖南师范大学自然科学学报.2003,6,26(2).16-17
[32]陈俊涛,李新军,杨莹等.稀土元素掺杂对TiO2薄膜光催化性能的影响[J].中国稀土学报.2003,12,21.67-71
[33]彭人勇,吕新莲.制备条件对纳米TiO2溶胶结构和性能的影响[J].工业用水与废水.2004,4,37(2).65-69
[34]N. Sobana, M. Muruganadham, M. Swaminathan. Nano-Ag particles doped TiO2 for efficient photodegradation of Direct azo dyes [J]. Journal of Molecular Catalysis A: Chemical.2006,258.124-132
[35]Galina N. Kryukova, Galina A. Zenkovets, Alexei A. Shutilov. Structural peculiarities of TiO2 and Pt/TiO2 catalysts for the photocatalytic oxidation of aqueous solution of Acid Orange 7 Dye upon ultraviolet light [J]. Applied Catalysis B: Environmental.2006,71.169-176
[36]Lei Ge, Mingxia Xu, Haibo Fang. Synthesis and characterization of the Pd/InVO4-TiO2 co-doped thin films with visible light photocatalytic activities[J]. Applied Surface Science.2006,253.2257-2263
[37]孙剑飞,翟玉春,石照信.TiO2光催化材料掺杂改性的研究进展[J].应用化工.2006,12,35(12).966-972
[38]Asahi.R, Ohwaki T, Aoki K, et al. Visible-light photocatalysis in nitrogen-doped titanium oxides [J]. Science.2001,293.269-271
[39]李红,赵高凌,刘琴华等.硅掺杂和硅钒共掺杂对TiO2光催化性能的影响[J].硅酸盐学报.2005,6,33(6).785-788
[40]Man Gu Kang, Hyea-Eun Han, Kang-Jin Kim. Enhanced photodecomposition of 4-chlorophenol in aqueous solution by deposition of CdS on TiO2 [J]. Journal of Photochemistry and Photobiology A:Chemistry.1999,125.119-125
[41]Wang Chengyu, Shang Huamei, Tao Ying, et al. Properties and morphology of CdS compounded TiO2 visible-light photocatalytic nanofilms coated on glass surface[J]. Separation and Purification Technology.2003,32.357-362
[42]Won-Wook So, Kwang-Je Kim, Sang-Jin Moon. Photo-production of hydrogen over the CdS-TiO2 nano-composite particulate films treated with TiCl4[J]. International Journal of Hydrogen Energy.2004,29.229-234
[43]宁青菊,肖昊江,武利娜.TiO2/Fe2O3异质结薄膜的制备及其光催化性能[J].硅酸盐通报.2007,10,26(5).914-917
[44]Sashikala Somasundaram, C. R. Chenthamarakshan, Norma R. de Tacconi, et al. Composite WO3-TiO2 films:Pulsed electrodeposition from a mixed bath versus sequential deposition from twin baths[J]. Electrochemistry Communications.2006,8. 539-543
[45]Betina Jorgensen, Steffen Buus Kristensen, Andreas Jonas Kunov-Kruse, et al. Gas-phase oxidation of aqueous ethanol by nanoparticle vanadia/anatase catalysts[J]. Top Catal.2009,52.253-257
[46]K. Vinodgopal, Prashant V. Kamat. Enhanced rates of photocatalytic degradation of an azo dye using SnO2/TiO2 coupled semiconductor thin films[J]. Environ. Sci. Technol.1995,29(3).841-845
[47]周秀文,朱祖良,赵君科等.TiO2/CdS复合半导体光催化剂降解甲基橙的实验研究[J].环境污染治理技术与设备.2006,1,7(1).701-901
[48]苏文悦,陈亦琳,付贤智等.SO42-/TiO2-SiO2固体超强酸的结构及其光催化性能[J].高等学校化学学报.2002,7,23(7).1398-1400
[49]毛海舫,田宏健,周庆复等.共吸附对卟啉、酞菁/二氧化钛复合电极光电特性的影响[J].高等学校化学学报.1997,2,18(2).268-272
[50]Brian O'Regan, Michael Gratzel. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films[J]. Nature,1991,353.737-740
[51]沈永嘉.酞菁的合成与应用.北京：化学工业出版社,2000.4
[52]赵志换,范济民,刘少华等.改进溶胶.凝胶法制备CoPc/TiO2及其光催化还原CO2反应的研究[J].现代化工.2007,6,27(1).238-241
[53]Xu Zhao, Zongwei Li, Yi Chen, et al. Enhancement of photocatalytic degradation of polyethylene plastic with CuPc modified TiO2 photocatalyst under solar light irradiation[J]. Applied Surface Science.2008,254.1825-1829
[54]Chao Pan, Cheng Sun, Hong-Mei Wei. Bio-inspired titanium dioxide film with extremely stable super-amphilicity [J]. Materials Research Bulletin.2006,1-7
[55]张含平,林原,周晓文等.CdSe敏化TiO2纳米晶多孔膜电极的制备及其光电性能研究[J].现代化工.2006,11,26(11).39-41
[56]Marian Nanu, Liesbeth Reijnen, Ben Meester, et al. CuInS2-TiO2 heterojunctions solar cells obtained by atomic layer deposition[J]. Thin Solid Films.2003,492-496
[57]T. Bak, J. Nowotny, M. Rekas, et al. Photo-electrochemical hydrogen generation from water using solar energy[J]. International Journal of Hydrogen Energy.2003,27. 991-1022
[58]柳闽生,詹寿发.光电化学的研究与进展[J].九江师专学报(自然科学版).1997,11,15(6).83-88
[59]黄翠英,由万胜,党利琴等.钕掺杂对纳米TiO2光催化分解水制氢活性的影响[J].催化学报.2006,3,27(3).203-209
[60]谭卫红.环保型锻铝化学抛光工艺[J].涂装与电镀.2007,12.41-43
[61]刘恺,沈淑引,许慧君.酞菁与TiO2超微粒间的光诱导电子转移相互作用[J].物理化学学报.2000,12,6(12).1103-1109
[62]沈淑引,刘恺,张先付等.烷氧基取代金属酞菁的合成和在有机溶液中聚集性质的研究[J].感光科学与光化学.1993,11,11(4).366-370
[63]王怡中,胡春,汤鸿霄.在催化剂上苯酚光催化氧化反应研究[J].环境科学学报.1995,10,15(4).472-478
[64]V. Iliev, V. Alexiev, L. Bilyarska. Effect of metal phthalocyanine complex aggregation on the catalytic and photocatalytic oxidation of sulfur containing compounds[J]. Journal of Molecular Catalysis A:Chemical.1999,137.15-22
[65]梁镇海,孙彦平.Ti/SnO2+Sb2O3+MnO2/PbO2阳极的性能研究[J].无机材料学报.2001,1,16(1).183-187
[66]梁镇海,王森,孙彦平等.Ti/SnO2+Sb2O3/PbO2阳极的性能研究[J].电化学.1995,11,1(4).456-460
[67]王峰,裴燕,俞斌.一种新型二氧化铅电极的研制[J].无机盐工业.2002,3,34(2).8-10