从工业TiOSO_4液合成介孔二氧化钛分子筛的工艺及机理研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
相对硅基、铝基骨架介孔材料，介孔二氧化钛合成中存在的困难较多，主要有合成用的起始钛源(钛醇盐、钛酸酯或试剂级无机钛等)成本高、模板剂脱除不理想并易引起孔结构破坏坍塌、介孔二氧化钛骨架晶型差等问题。本文的目的在于探索以价廉的粗原料合成高性能介孔二氧化钛的可能性，合成介孔二氧化钛前驱体的各影响因素，特别是超声波、微波等外场作用对介孔结构的影响、有效的脱模方式、介孔结构的形成和稳定机理等对介孔结构的影响，建立制备介孔二氧化钛的新工艺。
     本论文以钛铁矿酸解得到的工业硫酸氧钛溶液作为起始钛源，在复合表面活性剂自组装的超分子结构模板诱导作用下进行水解，使水解产物的结构受到控制，形成具有介孔结构的二氧化钛前驱体，之后采用氧化、萃取和焙烧相结合的方式脱除前驱体中的表面活性剂模板，制备出比表面积大、结构稳定的锐钛矿型介孔二氧化钛。通过实验研究和XRD、HRTEM、TEM、SEM、FT—IR、XPS、AFM、低温氮吸附脱附等分析测试表征，考察了介孔TiO_2合成的工艺条件和影响因素，特别是外场作用和模板剂脱除方法对其结构的影响，并选取光催化降解亚甲基蓝和酸催化体系评价其催化性能。基于实验和分析测试结果，对强酸性水介质中介孔TiO_2前驱体的形成过程及合成机理作了分析探讨，用Rietveld方法对XRD测试数据进行结构精修，说明前躯体脱模过程对晶体结构产生的影响。实验研究和分析结果可归纳如下：
     1．以工业硫酸氧钛液为原料，通过模板剂形成的超分子结构诱导钛水解合成介孔TiO_2前驱体的工艺条件对介孔结构的形成及晶型至关重要。(1)表面活性剂十二胺、十六烷基三甲基溴化铵(CTAB)、三嵌段共聚物P123等作模板剂有良好的结构导向作用，由CTAB／P123形成的复合模板剂更优；(2)采用工业钛液向表面活性剂溶液中滴加的方式，选择适当的模板剂用量及钛液浓度，并保持反应体系的pH值在1.5左右，可以很好地控制钛离子的水解缩聚速率及与模板剂之间的界面组装速率，可获得结构良好的介孔TiO_2前驱体，同时可避免杂质铁等的析出；(3)提高合成温度(75℃以上)和延长合成时间，利于孔壁的晶化和孔道有序性的提高；(4)提高陈化温度和进行水热后处理(120℃)利于前驱体孔壁晶化，提高孔道有序性和结构稳定性。在此基础上，采用复合模板(CTAB／P123)为结构导向剂，由工业硫酸氧钛液水解合成介孔前驱体，多步焙烧脱除模板，得到孔径分布窄、结构稳定的锐钛型介孔TiO_2分子筛，平均孔径为3.0nm，BET比表面积为132.6m~2／g。
     2．在介孔TiO_2前驱体合成中引入外场作用能促进产物的晶体结构完善和孔结构形成，所得产物的比表面积和稳定性均显著提高。超声辐照和微波辐照利于提高介孔结构的有序度；微波辐照所得产物的比表面积达146.6 m~2／g；水热合成强化了无机物种与表面活性剂的相互作用，同时使孔壁缩聚晶化，提高了介孔结构的稳定性。
     3．适宜的脱模方法对稳定介孔TiO_2结构有重要作用。采用臭氧氧化、多次萃取、多步焙烧的综合脱模路线脱除有机复合模板剂CTAB／P123较完全，得到比表面积高(S_(BET)=133m~2／g)，平均孔径大(D_(BJH)=4.65nm)的锐钛矿型介孔TiO_2。前驱体经臭氧氧化后，模板剂被氧化成短链、小分子有机物，可减小后续脱模过程的阻力；盐酸／无水乙醇的萃取体系使孔道中模板剂的表面活性降低，与骨架结构的作用减弱，通过多次萃取后，模板剂脱除率达53％以上，有效降低了后期热处理强度；采用125℃焙烧1h，300℃焙烧1h，450℃焙烧2h的多步焙烧方式，可减小因长时间高温焙烧容易造成的无机骨架网络收缩、骨架结构损坏、骨架电荷平衡破坏所致的分子筛孔结构破坏坍塌的负效应，使模板剂脱除干净，获得结构稳定的锐钛矿型介孔TiO_2。
     4．介孔TiO_2的结构及表面特性对其催化性能影响较大。由工业硫酸氧钛溶液合成的介孔TiO_2前驱体经脱模处理后呈锐钛矿晶型，有较大的比表面积和小的颗粒尺寸，表面吸附和键合的少量SO_4~(2-)使其表面具有催化活性的酸中心。介孔TiO_2在光氧化分解亚甲基蓝和乙酸乙醇酯化反应中有较高的催化活性，降解率和酯化率分别达98.4％和91％；介孔YiO_2对催化高酸值麻疯油与甲醇酯化反应也表现出一定催化活性。
     5．研究了在强酸性水体系中通过CTAB／P123复合模板的超分子诱导自组装合成路线，由工业硫酸氧钛溶液制备介孔TiO_2的形成过程，所得产物为具有二维六方孔道、比表面积大(S_(BET)=205.7 m~2／g)、孔径分布窄的锐钛型介孔TiO_2。介孔TiO_2前驱体的形成过程属协同作用机理，其特征归纳为如下几点：(1)反应体系pH值对钛水解初级粒子与模板剂协同作用影响较大，二者通过静电作用(S~+I~-)和氢键作用(N~0I~0)两种方式在界面协同作用：(2)调控pH值不仅使钛离子水解缩聚的速率与表面活性剂自组装速率相匹配，且能控制杂质的析出；(3)适当提高合成温度有利于大孔径介孔材料的形成；(4)增长复合表面活性剂疏水链有助于大孔径介孔材料的合成；(5)无机强电解质阴、阳离子的加入有一定扩孔作用；(6)介孔二氧化钛前驱体合成体系中钛水比和酸钛比对无机钛离子水解速率(H)或抑制速率(p)影响较大，硫酸氧钛液合成体系大的H／p比值导致钛离子水解加速，胶束尺寸变小，使介孔材料孔径缩小。
     6．介孔TiO_2脱模过程中，界面作用的变化对晶体结构和微观应变造成一定影响，同时产生原子缺位。萃取脱模对晶体结构影响远弱于焙烧处理，增大萃取脱模量可有效降低焙烧强度，提高介孔TiO_2的稳定性。
The study in this thesis was focused on the synthesis of mesoporous titania in view of the current problems and difficulties comparing with mesoporous silica and aluminate, such as high cost of titanium source (titanium alkoxide, titanyl ester or purified inorganic titanium salt, etc.), poor effect of simplex template removal method such as extraction or calcinations, which often resulted in destroying the pore structure, poor crystalline of mesoporous titania, and so on. Herein, it is very important and meaningful to explore the possibility of synthesizing high performance mesoporous titania from cheap titanium source, study on the synthesis influence factors for the precursor, probe into ultrasonic and microwave irradiation acting on the precursor structure, make a search for effective template removal method, establish a new process to prepare mesoporous titania, seek after mesostructure formation and stabilization mechanism, and so forth.
     The hydrolysis of industrial titanyl sulfate (TiOSO_4), obtained from sulfate process of ilmenite, was induced by a supermolecule template resulted from surfactants self-assembly, which oriented the precursor structure of mesoporous TiO_2. Then template in the precursor was removed by the combination of oxidation, extraction and calcinations, and anatase-phase mesoporous titania with high specific surface area and steady structure was obtained.
     The as-prepared mesoporous titania and precursors were studied through systematic experiments and characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared test (FT-IR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), nitrogen adsorption-desorption isothermos and so on. The technical conditions and influence factors for synthesis of mesopoorus titania were investigated, especially the outfield effects and template removal methods on the meso-structure. And its catalytic activities were evaluated by photo-catalytic decomposition of Methylene Blue and acid catalytic synthesis of ethyl acetate and Mafeng oil. Based on these results, formation procedure and synthesis mechanism of mesoporous titania precursor prepared under high acidic aqueous solution were analyzed and discussed. And the effects of template removal on the crystal structure were elementarily explored by using Rietveld profile refinement method. Experimental studies and analyzing results can be concluded as follows.
     1. The synthesis conditions have very important effect on formation of mesostructure and crystal phase for mesoporous titania precursors when industrial TiOSO_4 solution hydrolyzing is induced by self-assembly supermolecular template which orients the mesostructure. (1) Surfactants such as N-Dodecyl amine, Cetyltrimethyl Ammonium Bromide (CTAB) and triblock copolymer P123 have better structural directing ability than others, especially composite template (CTAB/P123). (2) By adding industrial TiOSO_4 solution to surfactant solution, selecting proper template dosage and titanium concentration and keeping the reaction system pH value at about 1.5, it is convenient for controlling hydrolysis and condensation rate of titanium ion and its interface assemble with template, which results in better structural mesoporous precursor and avoiding impurities such as iron separating out. (3) Elevating synthesis temperature (above 75℃) and prolonging synthesis time are beneficial to crystallizing pore wall and enhancing pore order degree. (4) Increasing aging temperature and adopting post hydrothermal treatment are favourable for pore wall crystallization and structural stability. On the basis of these factors, the mesoporous precursor, which structure is directed by composite template (CTAB/P123), is prepared via hydrolysis route from industrial TiOSO_4 solution. Then anatase mesoporous titania is obtained after template removal by step-by-step calcination. It is with narrow pore size distribution, stable mesostructure, average pore size of 3.0 nm and specific surface area of 132.6 m~2/g.
     2. Introducing outfield effect into the synthesis of mesoporous precursor can promote the crystal structure and the pore formation. The products are obviously with higher specific surface area and stability. Ultrasonic and microwave irradiations are helpful to form higher pore order, and the product under microwave irradiation is with the highest specific surface area, 146.6 m~2/g. While hydrothermal synthesis strengthens the interaction between the inorganic source and surfactants, condenses and crystallizes the pore wall, resulting in improving the mesoporous stability.
     3. Proper template removal method is also important for stabilizing mesoporous titania structure. Composite template (CTAB/ P-123) is entirely removed by compositive template removal route, i.e. ozone oxidizing first, then multistage extracting, and step-by-step calcining at last. After these treatments, mesoporous titania with anatase phase is prepared, with high specific area (SBET=133m~2/g), larger average pore size (D_(BJH)=4.65nm). Template is oxidized to short-chain and small molecular organic matter after ozone oxidation, which decreases the following resistance of removing template. The extraction system of non-aqueous ethanol/hydrochloride acid reduces the surface activity of surfactants in the pore, weakenes the action with the framework, and the ratio of template removal is larger than 53% after multistage extraction, effectively reducing intensity of the following heat-treatment. Adopting step-by-step calcinations (125℃for 1h, 300℃for 1h and 450℃for 2h ) thoroughly remove the template and anatase stable mesoporous TiO_2 is obtained, minishing the side effects of inorganic network shrinkage, the framework and pore structure destroying and collapse due to breakage of electric charge equilibrium, which is induced by long time and high temperature calcinations.
     4. The catalytic activities of mesoporous TiO_2 are primarily influenced by its structure and surface properties. Mesoporous TiO_2, obtained from hydrolysis of industrial TiOSO_4 solution and after template removal, is with anatase phase, high specific surface area and small particle size, still with a little SO_4~(2-) adsorpted or bonded on the surface, forming acidic center of the catalyst. Mesoporous TiO_2 has higher performance in the photocatalytic oxidation of Methylene Blue (MB) and esterification reaction of acetic acid and ethanol, with degradation of MB at 98.4% and yield of ester at 91%. It also shows some catalytic performance for the esterification of Jatropha curcas L. seed oil in high acid value with methanol as precursors to manufacture biodiesel.
     5. The formation procedure of mesoporous titania is studied via hydrolysis induced by supermolecule template under high acidic aqueous solution, using industrial TiOSO_4 as titanium source and composite surfactants (CTAB/P123) as template. The product is with narrow distribution of planar hexagonal pore and high specific surface area (205.7 m~2/g). The synthesis mechanism of the precursor belongs to cooperative formation mechanism, which could be summarized as follows: (1) The pH value greatly effects on cooperative action via static action( S~+I~-) and hydrogen bond action (N~0I~0) on the interface. (2) Controlling pH not only makes titanium ion hydrolysis and condensation rate and surfactants self-assembling rate matching, but also avoids impurities separating out. (3) Raising synthesis temperature properly is liable to form larger pore size mesoporous material. (4) Increasing hydrophobic chain length of surfactant is helpful for synthesizing large pore size mesoporous material. (5) Adding inorganic cationic and anionic strong electrolytes to the synthesis system could enlarge the pore size. (6) The mol ratio of Ti/H_2O and H~+/Ti has great effect on the hydrolysis rate (H) and restraining rate (p) of inorganic titanium ion, lager ratio of H/p led increasing hydrolysis rate, diminishing micelle size, resulting in smaller mesopore size.
     6. In the template removal procedure, the changes of interface action had some effect on the crystal structure and lattice strain, simultaneously produce atomic occupancy lacking. Template removal by extraction has weaker effect on crystal structure than calcination, and increasing template removal by extraction could effectively reduce calcinations intensity, improve the stability of mesoporous titania.
引文
[1] IUPAC. Manual of symbols and terminology [J]. Pure Appl Chem, 1978, 31:578
    [2] Barter R M. [M]. Hydrothermal Chemistry of Zeolites, Academic Press, 1982
    [3] 徐如人，庞文琴，于吉红，霍启升，陈接胜．[M]．分子筛与多孔材料化学，北京：科学出版社，2004
    [4] Chiola V, Ritsko J E, Vanderpool CD. Low bulk density silica [P]. US 3556725, 1971-01-19
    [5] DiRenzo F, Cambon H, Dutartre R. A 28-year-old synthesis of micelle-templated mesoporous silica [J]. Microporous Mater, 1997, 10(4-6):283～286
    [6] Ciesla Ulrike, Sehueth Ferdi. Ordered mesoporous materials [J]. Microporous and Mesoporous Materials, 1999,27(2-3): 131～149
    [7] Kresge C T, Leonowiez M E, Roth W J, et al. Ordered mesoporous molecular sieves synthesized by liquid-crystal template mechanism [J]. Nature, 1992, 359(6397):710～712
    [8] Beck J S, et al. Anew family of mesoporous molecular sieves prepared with liquid crystal templates [J]. J Am Chem Soc, 1992,114:10834～10843
    [9] Tanev P T, Pirmavaia T J. A neutral templating route to mesoporous molecular sieves [J]. Science, 1995,267 (10): 865～867
    [10] Bagshaw S A, Prouzet E, Pirmavaia T J. Templating of mesoporous molecular sieves by nonionic polyethylene oxide surfactants [J].Science, 1995,269 (1): 1242～1244
    [11] Zhao D Y, Feng J L, Huo Q S, Melosh N, Fredrickson G H, Chmelka B F, Stucky G D. Triblock copolymer synthesis of mesoporous silica with periodic 50 to 300 angstrom pores [J]. Science, 1998, 279:548-552
    [12] Zhao D Y, Huo Q S, Feng J L, Chmelka B F, Stucky G D. Nonionic triblock and star diblock copolymer and oligomeric surfactant synthesis of highly ordered, hydrothermally stable mesoporous silica structures [J]. J Am Chem Soc, 1998,120:6024～6036
    [13] Ryoo R, Kim J M, Shin C H. Disordered molecular sieves with branched mesoporous channel network. [J].J Phys Chem B, 1996,100 (45): 17718-17721
    [14] Blin J L, Leonard A, Su B L. Well-ordered spherical mesoporous materials CMI-1 synthesized via an assembly of decaoxyethylene cetyl ether and TMOS [J].Chem Mater, 2001,13(10): 3542-3553
    [15] Blin J L, Leonard A, Su B L. Synthesis of large pore disordered MSU-type mesoporous silicas through the assembly of C_(16)(EO)_(10) surfactant and TMOS silica source: Effect of the hydrothermal treatment and thermal stability of materials [J]. J Phys Chem B, 2001, 105(26): 6070-6079
    [16] Antonelli D M, Ying J Y. Mesoporous materials [J]. Current Opinion in Colloid & Interface Science,1996, 1(4):523～529; Corma A. From microporous to mesoporous molecular sieve materials and their use in catalysis [J]. Chem Rev, 1997,97(6): 2373-2419
    [17] Attard G S, Coleman N R B, Elliott J M. The preparation of mesoporous metals from preformed surfactant assemblies [J].Studies in Surface Science and Catalysis, 1998, 117: 89-94
    [18] Ryoo R, Joo S H, Jun S. Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation [J]. J Phys Chem B, 1999,103(37): 7743-746
    [19] Lee J, Yoon S, Hyeon T, et al. Synthesis of a new mesoporous carbon and its application to electrochemical double-layer capacitors [J]. Chem Commun, 1999, (21): 2177-2178
    [20] Lee J, Yoon S, Oh S M, et al. Development of a new mesoporous carbon using an HMS aluminosilicate template [J]. Adv Mater, 2000,12(5):359
    [21] Romero A A, Alba M D, Klinowski J. Aluminosilicate mesoporous molecular sieve MCM-48 [J]. Phys Chem, 1998,102:123-128
    [22] Eswara moorthy M N, Rao C N R. High catalytic efficiency of transition metal complexes encapsulated in a cubic mesoporous phase [J]. Chem Soc Chem Commun, 1998,615-616
    [23] Corma A, Nanarro M T, Pariente J P. Synthesis of an ultralarge pore titanium silicate isomorphous to MCM-41 and its application as a catalyst for selective oxidation of hydrocarbons [J]. Chem Soc Chem Commun, 1994,147-148
    [24] Tanev P T, Chibwe M & Pinnavaia T J. Titanium-containig mesoporous molecular sieves for catalytic oxidation of aromatic compounds [J]. Nature, 1994,368(24): 321-323
    [25] Zhaohua Luan, Estelle M Maes, Paul A W van der Heride, Dongyuan Zhao, Roman S Czemuszewicz, Larry Kevan. Incorporation of titanium into mesoporous silica molecular sieve SBA-15 [J]. Chem Mater, 1999,11(12): 3680-3686
    [26] Zhao D, Luan Z, Kevan L. Synthesis of thermally stable mesoporous hexagonal aluminophosphates molecular sieves [J]. Chem Soc Chem Commun, 1997,1009-1010
    
    [27] Chakraborty B, Pulikottil A C, Das S, et al. Synthesis and characterization of mesoporous SAPO [J]. Chem Soc Chem Commun, 1997, 911-912
    [28] Yang P, Zhao D, Margolese D I, et al. Eneralized synthesis of large-pore mesoporous metal oxides with semicrystalline frameworks [J]. Nature, 1998,396:152-155
    [29] Tolbert H, Sieger P, Stucky G D, et al. Control of inorganic layer thickness in self-assembled iron oxide/surfactant composites [J]. J Am Chem Soc, 1997,119 (37):8652～8661
    [30] Shen Y F, Zerger R P, De Guzman R N, et al. Manganese oxide octahedral molecular sieves preparation, characterization and applications [J]. Science, 1993,260:511-515
    [31] Attard G S, Bartlett P N, Coleman N R B, et al. Mesoporous platinum films from lyotropic liquid crystalline phase [J]. Science, 1997,278:838-840
    [32] Braun P V, Osenar P, Stupp S I. Semiconducting superlattices templated by molecular assemble [J]. Nature, 1996,380:325-328
    [33] Froba M, Osenar N. First synthesis of mesostructured thiogermanated [J]. Chem Soc Chem Commun, 1997,1729-1730
    [34] Xia Y N, Gates B, Yin Y D, et al. Monodispersed colloidal spheric old materials with new applications [J]. Adv Mater, 2000,12:693-713
    [35] Mercier L, Pinnavaia T J. Access in mesoporous materials:advantages of a uniform pore structure in the design of a heavy metal ion adsorbent for environmental remediation [J]. Adv Mater, 1997,9:500
    
    [36] Huo Q S, Leon R, Petroff P M et al. Mesostructure Design with Genini Surfactants-Supercage Formation in a 3-Dimensional Hexagonal Array [J]. Science, 1995,268:1324～1327
    [37] Antonelli D M,Ying J Y. Synthesis and characterization of hexagonally packed mesoporous tantalum oxide molecular sieves [J]. Chem Mater, 1996, 8:874～881
    [38] Yang P D, Deng T, Zhao D Y, et al. Hierarchically Ordered oxides [J]. Science, 1998, 282: 2244～2246
    [39] Yang P D,Zhao D Y, Margolese D I, et al. Generalized synthesis of large-pore mesoporous metal oxides with semicrystalline frameworks [J]. Nature, 1998,396:152～155
    [40] 戴劲草，萧子敬，叶玲等．粘土的层间交连和多孔材料的形成条件[J]．无机材料学报，1999，14(1)：89～93
    [41] 何宏平，谢先德，郭九皋．离子交换蒙脱石的热稳定性研究[J]．矿物岩石，2000，20(1)：1～3
    [42] 吴平宵，张慧芬，郭九皋等．柱撑蒙脱石的微结构变化研究[J]．无机材料学报，1999，14(1)：95～100
    [43] Huo O S, Leon R, Petroff P M, Stuky G D. Mesostructure design with Gemini surfactants: supercage formation in a three-dimensional hexagonal array [J]. Science,1995,268: 1324～1327
    [44] Kim S S, Zhang W Z, Pinnavaia T J. Ultrastable mesostruetured silica vesicles [J]. Science, 1998,282:1302～1305
    [45] Huo O S, Margolese D I, Ciesla U, et al. Generalized synthesis of periodic surfaetant / inorganic composite materials [J]. Nature, 1994, 368:318
    [46] 陈逢喜，黄茜丹，李全芝．分子筛研究进展[J]．科学通报，1999，44(18)：1905～1920
    [47] Soler-Illia Galo J DE A.A, Sanchez C, Lebeau B, et al. Chemical strategies to design textured materials: From microporous and mesoporous oxides to nanonetworks and hierarchical structures [J]. Chem Rev, 2002,102(11): 4093～4138.
    [48] Wei Y, Jin D L, Ding T Z, et al. A non-surfaetant templating route to mesoporous silica materials [J]. Adv Mater, 1998,10(4):313～316
    [49] 逢杰斌，丘坤元．中孔材料的研究进展Ⅰ：合成[J]．无机材料学报，2002，17(3)： 407～414
    [50] Pang J B, Qiu K Y, Wei Y, et al. A facile preparation of transparent and monolithic mesoporous silica materials [J]. Chem Commun, 2000:477～478
    [51] Lukens W W, Jr, Yang P D, Stuky G D. Synthesis of mesocellular silica foams with tunable windou and cell dimensions [J]. Chem Mater, 2001,13:28～34
    [52] Yam V W W, Li B, Zhu N Y. Synthesis of mesoporous silicates with controllable pore size using surfactant ruthenium(Ⅱ) complexes as templates [J]. Adv Mater, 2002.14(10): 719
    [53] Yang H, Coombs N, Ozin G A. Morphogenesis of shapes and surface patterns in mesoporous silica [J]. Nature, 1997, 386(6626): 692～695
    [54] 李军，龙英才．一种气相合成Silicalite-1沸石膜的新方法[J]．高等学校化学学报，2000，(2)：179～181
    [55] 张雄福，王金渠，殷德宏等．多孔陶瓷基膜上合成ZSM-5沸石膜新方法[J]．大连理工大学学报，2000，6(40)：672～675
    [56] 周群．导向剂法合成β沸石的晶化机制研究[J]．高等学校化学学报，2000，21(1)：1～4
    [57] Brinker C J, Lu Y F, Sellinger A, et al. Evaporation-induced self-assembly: nanostructures made easy [J]. Adv Mater, 1999,11:579
    [58] Melosh N A, Davidson P, Chmelka B F. Monolithic mesophase silica with large ordering domains. [J]. J Am Chem Soc, 2000,122:823～829
    [59] Yang P D,Zhao D Y, Margolese D I et al. Block copolymer templating syntheses of mesoporous metal oxides with large ordering lengths and semicrystalline frame work [J].Chem Mater, 1999,11: 2813～2826
    [60] Grosso D, Illia G. Crepaldi E L, et al. Nanocrystalline transition-metal oxide spheres with controlled multiscale porosity [J]. Adv Mater, 2003,13:37～42
    [61] Mormier A, Schuth F, Huo Q,et al.Cooperative formation of inorganic-organic interface in the synthesis of silicate mesostructures [J]. Science, 1993, 261:1299～1303
    [62] Chen C Y, Li H X, Davis ME. Studies on mesoporous materials. I. Synthesis and characterization ofMCM-41 [J]. Microporous Mater, 1993, 2:17～26
    [63] Chen C Y, Burkette S L, Li H X et al. Studies on mesoporous materials. Ⅱ. Synthesis mechanism of MCM-41 [J]. Microporous Mater, 1993, 2:27～34
    [64] Huo Q S, Margolese D I, Ciesla U et al. Organization of organic-molecules with inorganic molecular-species into nanocomposite biphase arrays [J]. Chem Mater, 1994, 6:1176～1191
    [65] Stucky G D, Huo Q S, Firouzi A, et al. Directed synthesis of organic/inorganic composite structures [J]. Studies in Surface Science and Catalysis, 1997,105(1): 3～28
    [66] 沈绍典．多头季铵盐表面活性剂导向下新结构介孔分子筛的合成与表征．[D]中国上 海：复旦大学，2003
    [67] Huo Q S, Margolese D I, Ciesla U, et al. Generalized synthesis of periodic surfactant/inorganic composite materials [J]. Nature, 1994,368 (6469): 317～321
    [68] Ying J Y, Mehnert C P, Wong M S. Synthesis and applications of supermolecular-templated mesoporous materials [J]. Angew Chem Int Ed Engl,1999,38:56～77
    [69] Regev O. Nucleation events during the synthesis of mesoporous materials using liquid crystalline templating [J]. LANGMUIR, 1996, 12(20): 4940～4944
    [70] Steel A, Cart S W, Anderson M W. ~(14)N NMR study of surfactant mesophases in the synthesis of mesoporous silicates [J]. J Chem Soc, Chem Commun, 1994:1571 ～ 1572
    [71] Yanagisawa T, Shimozu T, Kuroda K, et al. The preparation of alkyltrim ethylammonium-kanemite complexes and their conversion to microporous materials [J]. Bull Chem Soc[Jpn], 1990,63:988～992
    [72] Zana R, Frasch J, Soulard M, et al. Fluorescence probing investigations of the mechanism of formation of organized mesoporous silica [J]. LANGMUIR, 1999, 15(8): 2603～2606
    [73] Frasch J, Lebeau B, Soulard M, et al. In situ investigations on cetyltrimethyl ammonium surfactant/silicate systems, precursors of organized mesoporous MCM-41-type siliceous materials [J]. LANGMUIR, 2000, 16(23): 9049～9057
    [74] Cheng C F, Klinowski J. Synthesis and characterization of the mesoporous galloaluminosilicate molecular sieve MCM-41 [J]. J Chem Soc o Faraday Trans, 1996,92(2): 289～292
    [75] Tian B Z, Liu X Y, Zhao D Y, et al. Self-adjusted synthesis of ordered stable mesoporous minerals by acid-base pairs [J]. Nature Mater,2003, 2(3): 159～163
    [76] Firouzi A, Kumar D, Bull L M et al. Coorperative organization of inorganic-surfactant and biomimetic assemblies [J]. Science, 1995, 267:1138～1143
    [77] Lin H P, Mou C Y. 'Tubules-within-a-tubule' hierarchical order of mesoporous molecular sieves in MCM-41 [J].Science, 1996,273:765
    [78] Huo Q S, Margolese D I, Stucky G D. Surfactant Control of Phases in the Synthesis of Mesoporous Silica-Based Materials [J]. Chem Mater, 1996,8(5): 1147
    [79] Stein A, Melde B J, Schroden R C. Hybid inorganic-organic mesoporous silicates-Nanoscopic reactors coming of age [J]. Adv Mater, 2000,12:1403～1419
    [80] Chu C T, Husain A, Huss J A, Kresge C T, Roth W J. Isoparaffin-olefm alkylation process with zeolite MCM-36. [P]. US 5258569, 1993-11-02
    [81] 袁志庆，慎炼，刘华彦等．中孔硅基分子筛的催化应用研究进展[J]．化工生产与技术，2001，34：35～38
    [82] Sun Y Y, Zhu L, Lu H et al. Sulfated zirconia supported in meSoporous materials [J]. Appl Catal A: General, 2002, 237:21～31
    [83] Raimondo M, Perez G; Silibaldi Net al. Mesoporous M41S materials in capillary gas chromatography [J]. Chem Commun, 1997:1343～1344
    [84] Wu C G, Bein T. Conducting polyaniline filaments in mesoporous channel host [J]. Science, 1994, 264:1757～1759
    [85] Xu X H, Song C S, Andresen J Met al. Preparation and characterization of novel CO_2 "molecular basket" adsorbents based on polymer-modified mesoporous molecular sieve MCM-41 [J]. Microporous Mesoporous Mater, 2003, 62:29～45
    [86] Zhang L X, Zhang W H, Shi J L et al. A new thioether functionalized organic-inorganic mesoporous compositeas a highly selective and capacious Hg~(2+) adsorbent [J]. Chem Commun, 2003: 210～211
    [87] 谭欣，王榕树，霍爱群．载银介孔分子筛HMS(Ag)对大肠杆菌灭菌作用初探[J]．化学通报，1999：99030
    [88] Brieler F J, Grundmann P, Froba Met al. Size Dependence of the Magnetic and Optical Properties of Cdl-xMnxS Nanostructures Confined in Mesoporous Silica [J]. Chem Mater, 2005, 17(4): 795～803
    [89] Scott B J, Wirnsberge G, Stucky G D. Mesopoorus and mesostuctured materials for optical applications [J]. Chem Mater, 2001, 13:3140～3150
    [90] Karen L F, Bartl M H, Popitsch A, et al. Sensitized luminescence of trivalent europium by three-dimensionally arranged anatase nanocrystals in mesostructured titania thin films [J]. Angew Chem Int Ed, 2002, 41(6): 959～962
    [91] Wang Y Q, Chen S G, Tang X H et al. Mesoporous titanium dioxide: sonochemical synthesis and application in dye-sensitized solar cells [J]. J Mater Chem, 2001, 11:521～526
    [92] He X, Trudeau M, Antonelli D. Electronic Properties of Novel Mixed Oxidation-State Bis-Arene Chromium Nanowires Supported by a Mesoporous Niobium Oxide Host [J]. Adv Mater, 2000, 12:1036～1040
    [93] He X, .Trudeau M, Antonelli D. Bis(cyclopentadienyl) chromium and Bis- (cyclopentadienylvanadium) Composites of Mesoporous Niobium Oxide with Pseudo-One-Dimensional Organometallic Wires in the Pores [J].Chem Mater, 2001,13:4808～4816
    [94] 李晓芬，何静，马润宇等．青霉素酰化酶在介孔分子筛MCM-41上的固定化研究[J]．化学学报，2000，58：167～171
    [95] 高波，朱广山，傅学奇等．介孔分子筛SBA-15中α-胰凝乳蛋白酶组装及催化活性研究[J]．高等学校化学学报，2003，24：1100～1102
    [96] 高峰，赵建伟，张松等．中孔分子筛SBA-15作为液相色谱固定相以及在巯基化合物分离中的应用[J]．高等学校化学学报，2002，23：1494～1497
    [97] Scott B J, Wimsberger G, McGehee M D et al. Dye-doped mesostructured silica as a distributed feedback laser fabricated by soft lithography [J]. Adv Mater, 2001, 13(16):1231～1234
    [98] 唐振宁．[M]．钛白粉的生产与环境治理，北京：化学工业出版社，2000
    [99] Accelrys Corporation. Materials studio modeling [CP]. American
    [100] Antoneli D M, Ying J Y. Synthesis of hexagonally packed mesoporous TiO_2 by a modified Sol-Gel method [J]. Angew.Chem.Int.Ed.Engl. 1995,34 (18):2014～2017
    [101] Saul C, Jarnal E H. Generalised syntheses of ordered mesoporous oxides: the atrane route [J]. Solid State Sciences, 2000,2:405～420
    [102] Jimmy C Y, Lizhi Z, Jiaguo Y. Rapid synthesis of mesoporous TiO_2 with high photocatalytie activity by ultrasound-induced agglomeration [J]. New J Chem, 2002, 26(4): 416～420
    [103] 戴清，沈迅伟，何农跃，王兴利，袁春伟．纯二氧化钛介孔分子筛的合成与表征[J]．化学学报，1998，14(4)：460～466
    [104] Trong D. A simple route for the synthesis of mesostructured lamellar and hexagonal phosohorus-free titania (TiO_2)[J]. LANGMUIR, 1999, 15:8561～8564
    [105] Yusuf M M, Imai H, Hirashima H. Preparation of mesoporous TiO_2 thin films by surfaetant templating [J].J Non-Cryst Solids, 2001,285: 90～95
    [106] Miyake Y, Kondo T. Mesoporous titania prepared in the presence of alkylamine [J]. J Chem Eng Jpn, 2001,34(3):319～325
    [107] 赵文宽，孙育斌，马庆华，方佑龄．中孔二氧化钛的合成和表征[J]．催化学报，1999，20(3)：375～377
    [108] YUE Ying-Hong, MA Zhen, HUA Wei-Ming, GAO Zi. Synthesis and characterization of mesoporous titanium dioxide [J].Chem Commun, 2000, 58(7): 777～780
    [109] Kluson P, Kacer P. Prepparation of titania mesoporous materials using a surfactant-mediated sol-gel method [J]. J Mater Chem, 2001,11: 644～651
    [110] Stathatos E, Lianos P. Formation of TiO_2 nanoparticles in reverse micelles and their deposition as thin films on glass substrates [J]. LANGMUIR, 1997,13(16): 4295～4300
    [111] Yinghong Y, Zi Gao. Synthesis of mesoporous TiO2 with a crystalline framework [J]. Chem Commun, 2000,18: 1755～1756
    [112] David G, Galo J A A. Highly organized mesoporous titania thin films showing mono-oriented 2D hexagonal channels [J]. Adv Mater, 2001, 13(14): 1085～1090
    [113] 乐英红，马臻，华伟明，等．二氧化钛介孔分子筛的合成和表征[J]．化学学报，2000，58(7)：777
    [114] Yi-Yeol Lyu, Seung Hwan Yi, Jeong Kuk Shon et al. Highly Stable Mesoporous Metal Oxides Using Nano-Propping Hybrid Gemini surfactants [J]. J Am Chem Soc, 2004,126: 2310～2311
    [115] Wei Y, Jin D, Ding T, et al. Non-surfactant templating route to mesoporous silica materials [J]. Adv Mater, 1998,3(4): 313～316
    [116] 郑金玉，丘坤元，危岩．有机小分子模板法合成二氧化钛中孔材料[J]．高等学校化学学报，2000，21(4)：647～649
    [117] Jinyu Z, Jiebin P. Synthesis of mesoporous titanium dioxide materials by using a mixture of organic compounds as a non-surfactant template [J]. J Mater Chem, 2001,11: 3367～3372
    [118] Firouzi A, Kumar D, Bull L M et al. Cooperative organization of inorganic surfactant assemblies [J]. Science, 1995, 267(5201): 1138～1143
    [119] Yah H, Park S H, Finkelstein G et al. DNA-templated self-assembly of protein arrays and highly conductive nanowires [J]. Science, 2003, 301(5641): 1882～1884
    [120] He G, Dahl T, Veis A, George A. Nucleation of apatite crystals in nitro by self-assembled dentin matrix protein 1 [J]. Nature Materials, 2003, 2:552～558
    [121] Zhang W, Liao S S, Cui F Z. Hierarchical self-assembly of nano-fibrils in mineralized collagen [J]. Chem Mater, 2003, 15(16): 3221～3226
    [122] Davis S A, Burkett S L, Mendelson N H, Mann S. Bacterial templating of ordered macrostructures in silica and silica-surfactant mesophases [J]. Nature, 1997, 385(6615): 420～423
    [123] Hall S R, Bolger H, Mann S. Morphosynthesis of complex inorganic forms using pollen grain templates [J]. Chem Comm, 2003, (22):2784～2785
    [124] Lee J, Han S, Hyeon T. Synthesis of mesoporous carbon materials using nanostructured silica materials as templates [J]. J Mater Chem,2004, 14(4):478～486
    [125] Soler-Illia G J, Louis A, Sanchez C. Synthesis and characterization of mesostructured titania-based materials through evaporation-induced self-assembly [J]. Chem Mater, 2002,14(2): 750～759
    [126] Lianzhou W, Shinji T. Synthesis of mesoporous TiO_2 spheres under static condition [J]. Chem Lett, 2000,12:1414～1415
    [127] Ren T Z, Yuan Z Y, Su B L. A novel macroporous structure of mesoporous titanias: synthesis and characterization [J]. Colloids and Surfaces A: Physicochem. Eng. Aspects 2004,241: 67～73
    [128] Yoshitake H, Sugihara T, Tatsumi T. Preparation wormhole-like mesoporous TiO_2 with an extremely large surface area stabilization of its surface by chemical vapor deposition [J]. Chem Mater, 2002,14(3): 1023～1029
    [129] Victor F, Stone J, Davis R J. Synthesis, characterization and photocatalytic activity of titania and niobia mesoporous molecular sieves [J]. Chem Mater, 1998,10:1468
    [130] Jimmy C Y,Jiaguo Y,Jincai Z. Enhanced photocatalytic activity of mesoporous and ordinary TiO_2 thin films by sulfuric acid treatment [J].Appl Catal B: Environ, 2002,36(1):31～37
    [131] Elias S, Tatyana P, Panagiotis L. Study of the efficiency of visible-light photocatalytic degradation of basic blue adsorbed on pure and doped mesoporous titania films [J].LANGMUIR, 2001,17(16): 5025～5036
    [132] 王维波，李学萍，肖绪瑞．TiO_2多孔薄膜电极的制备、微结构及光电化学性能研究[J]．感光科学与光化学，1997，15(2)：161～164
    [133] MichaelG. Molecular photovoltaics that mimic photosynthesis [J].Pure Appl Chem, 2001,73(3): 459～467
    [134] 沈迅伟，袁春伟．基于二氧化钛多相光催化的环境净化技术研究及进展[J]．东南大学学报(自然科学版)，2004，34(6)：872～878
    [1] Antonelli D M, Ying J Y. Synthesis of hexagonally packed mesoporous TiO_2 by modified sol-gel method [J]. Angew Chem Int Ed Engl, 1995, 34(18): 2 014
    [2] Cabrera S, El Haskouri J, Beltran-Porter A et al. Enhanced surface area in thermally stable pure mesoporous TiO_2 [J]. Solid State Sci, 2000, 2(5): 513
    [3] Hui-suk Yun, Miyazawa Kuni'chi, Honma Itaru et al. Synthesis of semicrystallized mesoporous TiO_2 thin films using triblock copolymer templates [J]. Mater Sci Eng C, 2003, 23(4): 487
    [4] Cassiers Cristof, Linssen Thierry, Mathieu Mariska et al. Surfactant-directed synthesis of mesoporous tinaia with nanocrystalline anatase walls and remarkable thermal stability [J]. J Phys Chem B, 2004, 108(12): 3 713
    [5] Dai Q, Shi L Y, Luo Y G et al. Effects of templates on the structure, stability and photocatalytic activity of mesostructured TiO_2 [J]. Journal of Photochemistry and Photobiology A: Chemistry 2002, 148:295～301
    [6] Florence Bose, Andr Ayral, Pierre-Antoine Albouy et al. Mesostructure of anatase thin films prepared by mesophase templating [J].Chem. Mater., 2004,16:2208～2214
    [7] Hui-suk Yun, Kuni'chi Miyazawa, Itaru Honma et al. Synthesis of semicrystallized mesoporous TiO_2 thin films using triblock copolymer templates [J]. Materials Science and Engineering C, 2003,23 : 487～494
    [8] Kristof Cassiers, Thierry Linssen, Mariska Mathieu et al. Surfactant-directed synthesis of mesoporous titania with nanocrystalline anatase walls and remarkable thermal stability [J].J Phys Chem B, 2004,108:3713～3721
    [9] Yoon-Hee Cho, Gyoujin Cho, Jae-Suk Lee. Two-dimensional, open-Pored, mesoscopic titania layers using polymeric nanoparticle monolayers as a Template [J].Advanced Materials,2004,16(20): 1814～1817
    [10] Kartini I, Meredith P, Diniz Da Costa J C, et al. A novel route to the synthesis of mesoporous titania with full anatase nanocrystalline domains [J].Journal of Sol-Gel Science and Technology, 2004,31:185～189
    [11] Ren T Z, Yuan Z Y, Su B L. A novel macroporous structure of mesoporous titanias: synthesis and characterization [J].Colloids and Surfaces A: Physicochem. Eng. Aspects, 2004,241: 67～73
    [12] 刘月明，吴海虹，吴鹏，赵东元，何鸣元．具有锐钛矿骨架结构TiO_2介孔分子筛的合成[J]．化学学报，2005，63(24)：2241～2244
    [13] Chia-wen Wu, Tetsu Ohsuna, Makoto Kuwabara, Kazuyuki Kuroda. Formation of highly ordered mesoporous titania films consisting of crystalline nanopillars with inverse mesospace by structural transformation [J]. J Am Chem Soe, 2006,128(14):4544～4545
    [14] Jin Song Yin and Zhong L. Wang. Template-assisted self-assembly and cobalt doping of ordered mesoporous titania nanostructures [J].Advanced Materials, 1999,11 (6):469～472
    [15] 王金忠，赵岩，张彩碚．复合模板剂下有序介孔Ti02的制备研究[J]．物理化学学报，2003，19(3)：251～255
    [16] 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
    [17] 赵文宽，孙育斌，马庆华等．二氧化钛的合成和表征[J]．催化学报，1999，20(3)：375～377
    [18] Miah Muhammed Yusuf, Hiroaki Imai, Hiroshi Hirashima. Preparation of mesoporous titania by templating with polymer and surfaetant and its characterization [J]. Journal of Sol-Gel Science and Technology, 2003,28:97～104
    [19] Shuai Yuan, Qiaorong Sheng, Jinlong Zhang et al. The roles of acid in the synthesis of mesoporous titania with bicrystalline structure [J]. Materials Letters, 2004, 58:2757～2760
    [20] Chao Wang, Qin Li, Ruo-Ding Wang. Synthesis and characterization of mesoporous TiO_2 with anatase wall [J]. Materials Letters, 2004, 58:1424～1426
    [21] Wang Yu-de, Ma Chun-lai, Sun Xiao-dan, Li Heng-de. Synthesis and characterization of mesoporous TiO_2 with wormhole-like fi:amework structure [J]. Applied Catalysis A: General, 2003, 246:161～170
    [22] Jia X T, He W, Luo S Q et al. Mesoporous anatase with multi-morphologies synthesized by sol-gel method [J].Materials Letters, 2006, 60:1839～1842
    [23] Choi SY, Mamak M, Speakman S, et al. Evolution of Nanoerystallinity in Periodic Mesoporous Anatase Thin Films [J]. Small 2005, 1(2): 226～232
    [24] 郑金玉，丘坤元，危岩．有机小分子模板法合成二氧化钛中孔材料[J]．高等学校化学学报，2000，21(4)：647～649
    [25] Zheng J Y, Qiu K Y, W Y. Effects of templates contents on the physicochemical sorption properties of Zr-incorporated mesoporous titania [J]. Chinese journal of Chemistry, 2002,20: 951～957
    [26] 张雪红，罗来涛．室温水解法制备介孔二氧化钛的表征及应用[J]．感光科学与光化学，2005，23(1)：14～20
    [27] Choi S Y, Mamak M, Coombs N et al. Hexagonal mesoporous nanocrystalline anatase, meso-nc-TiO_2: bulk and crock-free thin film morphologies[J].Adv Funct Mater,14(4): 335～344
    [28] Yasuhiro Shimizu, Chunying Yu, Takeo Hyodo, Makoto Egashira. Development of a new preparation method of thermally stable mesoporous titania and its application to gas sensors. The 12~(th) international Conference on solid state sensors. Actuators and Microsystems, Boston, June 6-12,2003:536～539
    [29] David Grosso, Galo J. de A. A. Soler-Illia, Florence Babonneau et al. Highly organized mesoporous titania thin films showing mono-oriented 2D hexagonal channels [J]. Adv Mater, 2001, 13(14): 1085～1090
    [30] 于宏燕，杨儒，李敏等．锐钛相虫蛀状介孔二氧化钛的表征[J]．无机化学学报，2003，19(9)：963～966
    [31] Bokhimi X, Morales A, ORT'IZ E et al. Sulfate ions in titania polymorphs [J]. Journal of Sol-Gel Science and Technology,2004 29:31～40
    [32] Yang R, Yu H Y, Li M. Mesoporous properties of nanosized anatase titania powders prepared by urea hydrolysis with PEG dispersant [J]. J Mater Sci Let, 2003, 22:1131～1135
    [33] Chen H, Dai K, Peng T Yet al. Synthesis of thermally stable mesoporous titania nanoparticles via amine surfactant-mediated templating method [J]. Materials Chemistry and Physics, 2006, 96:176～181
    [34] Tan R Q, He Y, Zhu Y F, et al. Hydrothermal preparation of mesoporous TiO_2 powder from Ti(SO_4)_2 with poly(ethylene glycol) as template[J].J Mater Sci, 2003,38(19): 3973
    [35] Tengl V S, Bakardjieva S, Ubrt J S, Szatmary L. Titania aerogel prepared by low temperature supercritical drying [J].Microporous and Mesoporous Materials, 2006, 91: 1～6
    [36] Jiangrong Xiao, Tianyou Peng, Ran Lia et al. Preparation, phase transformation and photocatalytic activities of cerium-doped mesoporous titania nanoparticles [J].Journal of Solid State Chemistry,2006, 179:1161～1170
    [37] Saila Karvinen, Ralf-Johan Lamminmaki. Preparation and characterization of mesoporous visible-light-active anatase [J]. Solid State Sciences, 2003, 5:1159～1166
    [38] G. Sarala Devi, Takeo Hyodo, Yasuhiro Shimizu, Makoto Egashira. Synthesis of mesoporous TiO_2-based powders and their gas-sensing properties [J]. Sensors and Actuators B,2002, 87:122～129
    [39] 戴亚堂，陶宁，童云，涂铭旌．锐钛型介孔纳米二氧化钛粉体的制备和表征[J]．四川大学学报(工程科学版)，2006，38(2)：84～89
    [40] 唐振宁．[M]．钛白粉的生产与环境治理，北京：化学工业出版社，2000
    [41] 李志宏．SAXS方法及其在胶体和介孔材料研究中的应用[D]．中国科学院山西煤炭化学研究所，2002．6
    [42] 赵国玺，朱(王步)瑶著．[M]．表面活性剂作用原理，北京：中国轻工业出版社，2003．1
    [43] K·霍姆博格，B·琼森，B·科隆博格，B·林德曼著，韩丙勇，张学军译．[M]．水溶液中的表面活性剂和聚合物(第二版)，北京：化学工业出版社，2005．2
    [44] 张昭，彭少方，刘栋昌．[M]．无机精细化工工艺学，北京：化学工业出版社，2002：168
    [45] Yun Hui-Suk, Miyazawa Kuni'chi, Zhou Haoshen et al. Synthesis ofmesoporous thin TiO_2 films with hexagonal pore structures using triblock copolymer templates [J].Advanced Materials, 2001,13(18): 1377～1380
    [46] Bosc Florence, Ayral Andre, Albouy Pierre-Antoine, Guizard Christian. A Simple Route for Low-Temperature Synthesis of Mesoporous and Nanocrystalline Anatase Thin Films [J].Chemistry of Materials, 2003, 15(12): 2463～2468
    [47] Yu Jiaguo, Su Yaorong, Cheng Bei, Zhou Minghua. Effects of pH on the microstructures and photocatalytic activity of mesoporous nanocrystalline titania powders prepared via hydrothermal method [J].Journal of Molecular Catalysis A: Chemical, 2006,258(1-2): 104～112
    [1] Mark E Davis. Ordered porous materials for emerging applications [J]. Nature, 2002,417(6891): 813
    [2] 赵丽，余家国，赵修建等．介孔纳米结构材料的研究与发展[J]．稀有金属材料与工程，2004，33(1)：5～10
    [3] 徐如人，庞文琴，于吉红，霍启升，陈接胜．[M]．分子筛与多孔材料化学，2004，北京：科学出版社
    [4] 罗勇，卢冠忠，黄家桢等．用无机钛源合成Ti-MCM-41的研究[J]．化学学报，2001，59：1401～1405
    [5] Nicola H, Beatrice L, Dhaval D et al. Mesostructured Silica-Titania Mixed Oxide Thin Films [J].Chemistry of Materials, 2002,14(6):2429～2432
    [6] Toba M, Niwa S, Kijima Net al. Control of pore structures of titanias and titania/aluminas using complexing agents.[J].Studies in Surface Science and Catalysis, 2002,143(Scientific Bases for the Preparation of Heterogeneous Catalysts):723～729
    [7] Lee Dong-Wook, Ihm Son-Ki, Lee Kew-Ho. Mesostructure Control Using a Titania-Coated Silica Nanosphere Framework with Extremely High Thermal Stability [J].Chemistry of Materials, 2005,17(17):4461～4467
    [8] Aguado-Serrano J, Rojas-Cervantes M L. Titania aerogels influence of synthesis parameters on textural, crystalline, and surface acid properties [J]. Microporous and Mesoporous Materials, 2006:88(1-3):205～213
    [9] Linssen T, Cassiers K, Cool P et al. Mesoporous templated silicates: an overview of their synthesis, catalytic activation and evaluation of the stability [J]. Adv Colloid Interface Sci, 2003,103:121～147
    [10] Van Der Voort P, Morey M, Stucky G D et al. Creation of VO_x surface species on pure silica MCM-48 using gas-phase modification with VO(acac)_2 [J]. J Phys Chem B, 1998,102: 585～590
    [11] Huo Q S, Margolese D I, Stucky G D. Surfactant control of phases in the synthesis of mesoporous silica-based materials [J]. Chem Mater, 1996,8:1147～1160
    [12] 张震东，严晓霞，田博之等．非水溶剂快速挥发法合成大孔径高有序度介孔有机氧化硅材料[J]．高等学校化学学报，2005，26(4)：603～606
    [13] 吕彤，杜开峰．在非水体系中介孔磷酸铝分子筛的合成与表征[J]．精细石油化工，2005，1：1～4
    [14] 胡立，俞秋，邓斌等．非水体系合成蜂窝状金属氧化物介孔材料[J]．中山大学学报：自然科学版，2004，43(6)：128～130
    [15] Tiemann M, Schulz M, Jaeger C, et al. Mesoporous Aluminophosphate Molecular Sieves Synthesized under Nonaqueous Conditions [J]. Chemistry of Materials, 2001, 13(9): 2885～2891
    [16] Tian Bozhi, Liu Xiaoying, Zhang Zhendong, et al. Syntheses of High-Quality Mesoporous Materials Directed by Blends of Nonionic Amphiphiles under Nonaqueous Conditions [J]. Journal of Solid State Chemistry, 2002, 167(2):324～329
    [17] Wang L, Tian B, Fan J, et al. One-step synthesis of large pore mesoporous metallo-aluminophosphate under nonaqueous media [J]. Studies in Surface Science and Catalysis,2004,154A(Recent Advances in the Science and Technology of Zeolites and Related Materials): 1111～1117
    [18] Liu Lei, Zhang Gao Yong, Dong Jin Xiang. Synthesis of high-quality mesoporous MCM-41 templated CTAB in nonaqueous system [J]. Tenside, Surfactants, Detergents, 2004, 41(1):7～9
    [19] Yu C Z, Tian B Z, Fan B, et al. Salt effect in the synthesis of mesoporous silica templated by non-ionic block eopolymers [J]. Chem Commun, 2002, (24): 2726～2727
    [20] 叶红齐，王晓霞，林京福．晶化过程中无机盐及pH值调节对介孔分子筛水热稳定性的影响[J]．安徽化工，2004，30(3)：30～32
    [21] Meng Xiangju, Fan Weibin, Kubota Yoshihiro, Tatsumi Takashi. Improvement in thermal stability and catalytic activity of titanium species in mesoporous titanosilicates by addition of ammonium salts [J]. Journal of Catalysis, 2006, 244(2): 192～198
    [22] Chen Weifan, Li Fengsheng, Yu Jiyi, et al. Rapid synthesis of mesoporous ceria-zireonia solid solutions via a novel salt-assisted combustion process [J]. Materials Research Bulletin, 2006, 41(12): 2318～2324
    [23] Lin H P, Mou C Y. Structural and morphological control of cationic surfactant-templated mesoporous silica [J]. Accounts of Chemical Research, 2002, 35(11): 927～935
    [24] Lin H P, Kao C P, Mou C Y. Counterion and alcohol effect in the formation of mesoporous silica [J]. Microporous and mesoporous materials, 2001, 48:135～141
    [25] Lin H P, Mou C Y. Salt effect in post-synthesis hydrothermal treatment of MCM-41 [J]. Microporous and mesoporous materials, 2002, 49:69～80
    [26] Epameinondas Leontidis. Hofmeister self-assembly and the formation of mesoporous solids [J]. Current Opinion in Colloid & Interface Science, 2002, 7:81～91
    [27] 庞雪蕾，唐芳琼．不同酸对介孔二氧化硅球表面形貌和介相结构的影响[J]．无机化学学报，2004，20(8)：895～900
    [28] Boissiere C, Larbot A, van der Lee A, et al. A new synthesis of mesoporous MSU-X silica controlled by a two-step pathway [J]. Chem Mater, 2000,12 (10): 2902～2913
    [29] 赵春霞，陈文，刘琦，田高．HCI对有序介孔氧化硅结构与形貌的影响[J]．物理化学学报，2006，22(10)：1201～1205
    [30] 雷家珩，刘为，郭丽萍等．介孔氧化硅薄膜合成及酸根离子对介观相影响[J]．武汉理工大学学报，2006，28(11)：29～31
    [31] 张青红，高濂，郭景坤．四氯化钛水解法制备二氧化钛纳米晶的影响因素[J]．无机材料学报，2000，15(6)：992～998
    [32] 赵春霞，陈文，刘琦，田高．HCI对有序介孔氧化硅结构与形貌的影响[J]．物理化学学报，2006，22(10)：1201～1205
    [33] Chen Shih-Yuan, Jang Ling-Yun, Cheng Soofin. Synthesis of thermally stable zirconia-based mesoporous materials via a facile post-treatment [J]. The journal of physical chemistry, B, 2006, 110(24):11761～1171
    [34] Huang L M, Li Q Z. Improvement on thermal stability and acidity of mesoporous materials with post-treatment of phosphoric acid [J]. Studies in Surface Science and Catalysis ,2000,129:93～98
    [35] Liang Jinsheng, Feng Yanwen, Liang Guangchuan, et al. Effects of post-treatment on the photocatalytic activity of mesoporous TiO_2 thin films [J]. Journal of Materials Science Letters, 2003, 22(21): 1503～1506
    [36] Yuan Z Y, Su B L. Characterization of pore systems of mesoporous silicas templated by cetylpyridinium under mild-alkaline condition: the effect of low-temperature ammonia post-treatment [J]. Colloids and Surfaces, A: Physicochemical and Engineering Aspects, 2004, 241(1-3):95～102
    [37] Ruiqin Tan, Yu He, Yongfa Zhu, Boqing Xu, Lili Cao.Hydrothermal preparation of mesoporous TiO_2 powder from Ti(SO_4)_2 with poly(ethyleneglycol) as template. Journal of materials.science[J]. 2003,38:3973-3978
    [38] 赵文宽，孙育斌，马庆华，方佑龄．中孔二氧化钛的合成和表征[J]．催化学报，1999，20(3)：375～377
    [39] 张雪红，罗来淘．室温水解法制备介孔二氧化钛的表征及应用[J]．感光科学与光化学，2005，23(1)：14～20
    [40] Yun Hui-Suk, Miyazawa Kuni'chi, Zhou Haoshen et al.Synthesis of mesoporous thin TiO_2 films with hexagonal pore structures using tfiblock copolymer templates [J].Advanced Materials, 2001,13 (18): 1377～1380
    [41] G. Sarala Devi, Takeo Hyodo, Yasuhiro Shimizu, Makoto Egashira. Synthesis of mcsoporous TiO_2-based powders and their gas-sensing properties [J]. Sensors and Actuators B,2002, 87:122～129
    [42] 黄惠忠等．[M]．纳米材料分析，北京：化学工业出版社，2003：254～257
    [43] Jimmy C Yu, Xinehen Wang, Xianzhi Fu. Pore-wall chemistry and photocatalytic activity of mesoporous titania molecular sieve films [J]. Chem. Mater., 2004,16:1523～1530
    [1] Antoneli D M, Ying J Y. Synthesis of hexagonally packed mesoporous TiO_2 by a modified Sol-Gel method [J]. Angew.Chem.Int.Ed.Engl, 1995,34 (18):2014～2017
    [2] Hirobumi S, Taku O, Tatsuya M, et al. Direct synthesis of mesoporous titania particles having a crystalline wall [J]. J Am Chem Soc, 2005, 127(47): 16396～16397
    [3] 冯若，李化茂．[M]．声化学及其应用，合肥：安徽科学技术出版，1992
    [4] Huang W L, Liang K M, Cui S H et al. Influence of ultrasonic vibration on the mesoporosity and surface fractal dimensions of resultant silica xerogels [J]. Materials Research Bulletin,2001,36(3-4): 461～470
    [5] Run Mingtao, Wu Sizhu, Wu Gang. Ultrasonic synthesis of mesoporous molecular sieve [J]. Mieroporous and Mesoporous Materials,2004,74(1-3): 37～47
    [6] Perkas Nina, Wang Yanqin, Koltypin Yuri et al. Mesoporous iron-titania catalyst for eyelohexane oxidation [J]. Chemical Communications (Cambridge, United Kingdom), 2001, 11:988～989
    [7] Yu Jimmy C, Zhang Lizhi, Yu Jiaguo. Rapid synthesis of mesoporous TiO_2 with high photoeatalytie activity by ultrasound-induced agglomeration [J]. New Journal of Chemistry 2002,26(4): 416～420
    [8] Yu Jimmy C, Zhang Lizhi, Yu Jiaguo. Direct Sonochemical Preparation and Characterization of Highly Active Mesoporous TiO_2 with a Bicrystalline Framework [J]. Chemistry of Materials, 2002, 14(11): 4647～4653
    [9] Yu Jiaguo, Yu Jimmy C, Leung Mitch K P et al. Effects of acidic and basic hydrolysis catalysts on the photocatalytic activity and microstructures of bimodal mesoporous titania [J]. Journal of Catalysis, 2003,217(1): 69～78
    [10] Yu Jiaguo, Yu Jimmy C, Ho Wingkei et al. Effects of alcohol content and calcination temperature on the textural properties of bimodally mesoporous titania [J].Applied Catalysis, A: General, 2003,255(2): 309～320
    [11] Yu Ying, Yu Jimmy C, Yu Jia-Guo et al. Enhancement of photocatalytic activity of mesoporous TiO_2 by using carbon nanotubes [J]. Applied Catalysis, A: General ,2005,289(2): 186～196
    [12] Zhou Minghua, Yu Jiaguo, Cheng Bei. Effects of Fe-doping on the photocatalytic activity of mesoporous TiO_2 powders prepared by an ultrasonic method.[J].Journal of Hazardous Materials,2006, 137(3): 1838～1847
    [13] 张昭，沈俊，张明俊等．介孔二氧化钛及其SO_4~(2-)／TiO_2固体超强酸制备方法及SO_4~(2-)／TiO_2固体超强酸[P]．CN 1807259，2006-07-26
    [14] 金钦汉主编[M]．微波化学，北京：科学出版社，1999
    [15] Rao K J, Vaidhyanathan B, Ganguli Met al. Synthesis of inorganic solids using microwaves [J]. Chem Mater, 1999, 11:882
    [16] Liang J, Deng Z, Jiang X et al. Photoluminescence of tetragonal ZrO_2 nanoparticles synthesized by microwave irradiation [J]. Inorgehem, 2002, 41:3602
    [17] Boxall D L, Lukehart C M. Rapid synthesisof Pt or Pd / Carbon nanocomposites using microwave irradiation [J]. Chem Mater 2001, 13: 806
    [18] Han Yu, Ma Hao, Qiu Shilin et al. Preparation of zeolite A membranes by microwave heating [J]. Microporous andMesoporous Materials, 1999, 30:321
    [19] Kodaira Tetsuya, Miyazawa Kohji, Ikeda Takuji et al. Synthesis of AlPO_4-5 powder by microwave heating: Influence of starting gel pH and reaction time [J]. Microporous and Mesoporous Materials, 1999, 29:329
    [20] Tu W, Liu H. Continuous synthesis of colloidal metal nanoclusters by microwave irradiation [J]. Chem Mater, 2000, 12:564
    [21] Wu C G, Bein T. Microwave synthesis of molecular sieve MCM-41 [J]. Chem Commun, 1996:925
    [22] Park S E, Kim D S, Chang J S. Synthesis of MCM-41 using microwave heating with ethylene glycol [J]. Catalysis Today, 1998, 44:301
    [23] 张青山，张辉淼，郭炳南．以双子表面活性剂为模板全微波辐射合成介孔分子筛MCM-48[J]．北京理工大学学报，2003，23(3)：394
    [24] Newalkar B L, Komarneni Sridhar et al. Rapid synthesis of mesoporous SBA-15 molecular sieve by a mierowave-hydrothermal process [J]. Chem Comm, 2000, 23:2389
    [25] He Jing, Yang Xingbin, Evans D G et al. New methods to remove organic templates from porous materials [J]. Mater Chem Phys, 2002, 77:270
    [26] Tian Bozhi, Liu Xiaoying, Zhao Dongyuan et al. Microwave assisted template removal of siliceous porous materials [J]. Chem Comm, 2002, 11 : 1186
    [27] Fujii Yusuke, Kitamura Takayuki, Wada Yuji et al. Microwave-assisted pulverization of perylene pigment and fabrication of pigment-sensitized mesoporous TiO_2 solar cells [J]. Electrochemistry (Tokyo, Japan), 2004, 72(7): 490～494
    [28] Karthikeyan C S, Thelakkat M, Willert-Porada M. Dye senzitised solar cells: a comparative study using different nanoerystalline-titania [J]. Ceramic Transactions,2006, 172 (Ceramic Nanomaterials and Nanotechnologies Ⅳ): 115～128
    [29] Karthikeyan C S, Thelakkat M, Willert-Porada M. Different mesoporous titania films for solid-state dye sensitised solar cells [J]. Thin Solid Films,2006, 511-512:187～194
    [30] Zhang Guangyu, Jiang Xin, Wang Enge. Tubular graphite Cones [J]. Science,2003,300:47
    [31] 徐如人，庞文琴等著．[M]．分子筛与多孔材料化学，北京：科学出版社，2004
    [32] 徐如人，庞文琴主编．[M]．无机合成与制备化学，北京：高等教育出版社，2001．6
    [33] Liu Gang, Chen Zhigang, Dong Chunlei et al. Visible light photocatalyst: iodine-doped mesoporous titania with a bicrystalline framework [J]. The Journal of Physical Chemistry. B, Condensed matter, materials, surfaces, interfaces & biophysical,2006,110(42): 20823～20828
    [34] Shin Y S, Burleigh M C, Dai Sheng. Investigation of uranyl adsorption on mesoporous titanium-based sorbents [J]. Radiochimica Aeta,1999,84(1): 37～42
    [35] Hayashi Hiromichi, Iwasaki Takashi, Onodera Yoshio. Mesoporous titanium oxide porous articles and manufacture of same [P]. JP 3076844, 2000-08-14
    [36] Yue Y H, Gao Z. Synthesis of mesoporous TiO_2 with a crystalline framework [J].Chemical Communications (Cambridge),2000,18:1755～1756
    [37] Qi Limin, Wang Yimin, Ma Jiming. Synthesis of mesoporous TiO_2 (anatase) in the absence of templates [J]. Journal of Materials Science Letters, 2002,21 (16): 1301-1303
    [38] 杨儒，李敏等．锐钛矿型纳米TiO_2介孔粉体表面织构的研究[J]．高等学校化学学报，2003，24(1)：146～150
    [39] Tan Ruiqin, He Yu, Zhu Yongfa et al. Hydrothermal preparation of mesoporous TiO_2 powder from Ti(SO_4)_2 with poly (ethylene glycol) as template [J]. Journal of Materials Science [J]. 2003,38(19):3973～3978
    [40] Wang Chao, Li Qin, Wang Ruo-Ding. Synthesis and characterization of mesoporous TiO_2 with anatase wall [J]. Materials Letters, 2004,58(9): 1424～1426
    [41] Kolen'ko Yury V, Maximov Victor D, Garshev Alexei V et al. Hydrothermal synthesis of nanocrystalline and mesoporous titania from aqueous complex titanyl oxalate acid solutions [J]. Chemical Physics Letters,2004,388(4-6): 411～415
    [42] Liu Gang, Chen Zhigang, Dong Chunlei et al. Visible Light Photocatalyst: Iodine-Doped Mesoporous Titania with a Bicrystalline Framework [J].Journal of Physical Chemistry B, 2006,110(42): 20823～20828
    [43] Bavykin Dmitry V, Parrnon Valentin N, Lapkin Alexei A et al. The effect of hydrothermal conditions on the mesoporous structure of TiO_2 nanotubes [J].Journal of Materials Chemistry, 2004,14(22): 3370～3377
    [44] Gregg S J, Sing K S W. [M]. Adsorption, surface area and porosity, Academic, London, 1982
    [45] 李斌．[M]．聚氯乙烯(PVC)的抑烟与阻燃，黑龙江：东北林业大学出版社，2000：206
    [1] Chemin N, Klotz M, Rouessac V, Ayral A, Barthel E. Mechanical properties of mesoporous silica thin fills: Effect of the surfactant removal processes [J]. Thin Solid Films, 2006, 495: 210～213
    [2] He J, Yang X B, Evans D G, Duan Xue. New methods to remove organic templates from porous materials [J]. Materials Chemistry and Physics, 2002, 77:270～275
    [3] Corma A, Fomes V, Navarro M T, Perez-Pariente J. Acidity and stability of MCM-41 crystalline aluminosilicates [J]. Journal of Catalysis, 1994,148(2): 569～574
    [4] Pachtova' O, Kocirik M, Zikanova' A, et al. A comparative study of template removal from silicalite-1 crystals in pyrolytic and oxidizing regimes [J]. Microporous Meosporous Mater, 2002, 55:285～296
    [5] Xingtao Gao, Chuen Y Yeh, Philip Angevine. Mechanistic study of organic template removal from ZSM-5 precursors [J]. Microporous Meosporous Mater, 2004, 70:27～35.
    [6] Chia-Min Yang, Bodo Zibrowius, Wolfgang Schmidt, Ferdi Schüth. Stepwise removal of the copolymer templates from mesopores and micropores in SBA-15 [J]. Chemistry of Materials,2004, 16(15):2918～2925
    [7] Kruk M, Jaroniec M, Ko C H, Ryoo R. Characterization of the porous structure of SBA-15 [J]. Chem Mater, 2000, 12(7): 1961～1968
    [8] Kieitz F, Schmidt W, Schüth F. Calcination behavior of different surfactant-templated mesostmctured silica materials [J]. Microporous meosporous mater, 2003, 65(1): 1～29
    [9] Tian B Z, Liu X Y, Yu C Z, et al. Microwave assisted template removal of siliceous porous materials [J]. Chem Commun, 2002, (11): 1186～1187
    [10] Van Grieken R, Calleja G, Stucky G D, et al. Supereritical fluid extraction of a nonionic surfactant template from SBA-15 materials and consequences on the porous structure [J]. Langmuir, 2003, 19(9): 3966～3973
    [11] Yang C M, Zibrowius B, Schmidt W, et al. Consecutive generation of mesopores and mieropores in SBA-15 [J]. Chem Mater, 2003,15(20):3739～3741
    [12] Yang C M, Zibrowius B, Schuth F. A novel synthetic route for negatively charged ordered mesoporous silica SBA-15 [J]. Chem Mater, 2003(14): 1772～1773
    [13] Yang C M, Wang Y Q, Zibrowius B, Schüth F. Formation of cyanide-functionalized SBA-15 and its transformation to carboxylate-functionalized SBA-15 [J]. Phys Chem Chem Phys. 2004,6(9):2461～2467
    [14] 肖天存，安立敦，王弘立。SAPO-5，-11和-34分子筛模板剂的脱除及其结构的热致变化[J]．分子催化，1994，8(6)：429～436
    [15] 高雄厚，王智峰，张勇明，毛学文，唐荣荣．MCM-41分子筛的模板剂脱除方式对其结构和酸性的影响[J]．石油炼制与化工．1997，28(11)：37～40
    [16] Tian B Z, Liu X Y, Yu C Z et al. microwave assisted template removal of siliceous porous materials [J]. Chem Commun. 2002:1186～1187
    [17] He J, Yang X B, Evans D G et al. New methods to remove organic templates from porous materials [J]. Mater Chem Phys. 203,77:270～275
    [18] Kundu D, Zhou H S, Honma I. Thermally induced structural changes of lamellar and one-dimensional hexagonal mesoporous silica thin films [J]. J Mater Sci Lett, 1998,17(24): 2089～2092
    [19] Hozumi A, Yokogawa Y, Kameyama T et al. Photocalcination of mesoporous silica films using vacuum ultraviolet light [J]. Adv Mater. 2000,12(13): 985
    [20] Whitehurst D Duayne. Recovery of organic templates in the synthesis of molecular sieves [P]. US 5143879, 1992-09-01
    [21] Jones C W, Tsuji K, Davis M E. Organie-functionalized molecular sieves as shape-selective catalysts [J]. Nature, 1998, 393(6680):52～54
    [22] Jones C W, Tsuji K, Davis M E et al. Tailoring molecular sieve properties during SDA removal via solvent extraction [J]. Microporous meosporous mater, 2001,48:57～64
    [23] Hua Z L, Shi J L, Wang L, Zhang W H. Preparation of mesoporous silica films on a glass slide_ surfactant template removal by solvent extraction [J]. Journal of non-crystalline solids, 2001,292:177～183
    [24] Zhao L L, Yu Y, Song L X et al. Preparation of mesoporous titania film using nonionic triblock copolymer as surfactant template [J]. Appl Catal A Gen, 2004,263 (2): 171～177
    [25] Huang L, Poh C, Ng S C, Hidajat K, Kawi S. Preparation of supported mesoporous thin films concerning template removal by supercritical fluid extraction [J]. langmuir, 2005,21 (4): 1171～1174
    [26] Kawi S, Lai W W. Supercritical extraction of surfactant template from MCM-41 [J].Chem Commun,1998:1407～1408
    [27] Keene, Matthew T J, Denoyel R et al. Ozon Treatment for The Removal of Surfacant to from MCM-41 Type Materials [J].Chem Commun, 1998, 2203～2204
    [28] Meretei E, Mehn D, Halasz J, Kiricsi Ⅰ. Novel method for soft template removal in the synthesis of MCM-41 mesoporous materials [J]. Diffus Def Data Pt B, 2003,90-91:79～84
    [29] Meretei E, Halász, Méhn D et al. Structural consequences of mild oxidative template removal in the synthesis of modified MCM-41 silicates [J]. Journal of Molecular Structure, 2003, 651-653:323～330
    [30] Heng S, Lau P P S, Yeung K L et al. Low-temperature ozone treatment for organic template removal from zeolite membrane [J]. Journal of Membrane Science, 2004, 243:69～78
    [31] Kresnawahjuesa O, Olson D H, Gorte R J et al. Removal of tetramethylammonium cations from zeolites [J]. Microporous meosporous mater, 2002,51:175～188
    [32] Stone V F Jr, Davis R J. Synthesis, Characterization, and Photocatalytie Activity of Titania and Niobia Mesoporous Molecular Sieves [J]. Chemistry of Materials, 1998, 10(5):1468～1474
    [33] Khushalani D, Ozin G A, Kuperman A. Glycometallate surfactants Part 2: non-aqueous synthesis of mesoporous titanium, zirconium and niobium oxides [J]. Journal of Materials Chemistry, 1999, 9(7): 1491～1500
    [34] Yun, Hui-Suk; Miyazawa, Kuni'chi; Zhou, Haoshen; Houma, Itam; Kuwabara, Makoto.Synthesis of mesoporous thin TiO_2 films with hexagonal pore structures using triblock copolymer templates [J]. Advanced Materials, 2001,13 (18 ): 1377～1380
    [35] Kondo, Junko N.; Yamashita, Tomohiro; Nakajirna, Kiyotaka; Lu, Daling; Hara, Michikazu; Domen, Kazunari. Preparation and crystallization characteristics of mesoporous TiO_2 and mixed oxides. [J]. Journal of Materials Chemistry, 2005, 15(20):2035～2040
    [36] 彭天右，戴珂．一种锐钛矿相介孔纳米二氧化钛粉体的制备方法．[P]．CN 1752017， 2006-03-29
    [37] Zheng Jin-Yu, Pang Jie-Bin, Qiu Kun-Yuan, Wei Yen. Synthesis and characterization of mesoporons titania and silica-titania materials by urea templated sol-gel reactions [J]. Microporous and Mesoporous Materials, 2001, 49(1-3):189～195
    [38] Leroux, Fabrice; Dewar, Patricia J.; Intissar, Mourad; Ouvrard, Guy; Nazar, Linda F. Study of the formation of mesoporous titania via a template approach and of subsequent Li insertion [J]. Journal of Materials Chemistry, 2002, 12(11):3245～3253
    [39] Zheng Jin-Yu, Qiu Kun-Yuan, Wei Yen. Investigation of Zr-incorporated mesoporous titania materials via nonsurfactant templated sol-gel mute: Synthesis, characterization and stability [J]. Journal of Materials Science, 2003,38(3):437～444
    [40] 戴清，沈迅伟，何农跃，王兴利，袁春伟．纯二氧化钛介孔分子筛的合成与表征[J]．无机化学学报，1998，14(4)：460～466
    [41] Dai Qing, He Nong Yue, Wang Xing Li, Shen Xun Wei, Guo Yan, Yuan Chun Wei. Effect of templates on the structure and stability of Ti-TMS [J]. Chinese Chemical Letters, 1999, 10(3):267～268
    [42] Dai Qing, Zhang Zhenglin, He Nongyue, Li Ping, Yuan Chunwei. Preparation and characterization of mesostructured titanium dioxide and its application as a photocatalyst for the wastewater treatment [J]. Materials Science & Engineering, C: Biomimetic and Supramolecular Systems, 1999,C8-C9:417～423
    [43] Dai Q, Shi L Y, Luo Y G, et al. Effects of templates on the structure, stability and photocatalytic activity of mesostrutured TiO_2 [J]. Journal of Photochemistry and Photobiology, A: Chemistry, 2002, 148(1-3): 295～301
    [44] Wang Yu-de, Ma Chun-lai, Sun Xiao-dan, Li Heng-de. Synthesis and characterization of amorphous TiO_2 with wormhole-like framework mesostructure. [J]. Journal of Non-Crystalline Solids, 2003,319:109～116
    [45] Yanqin Wang, Xianghai Tang, Lunxiang Yin, et al. Sonochemical synthesis of mesoporous titanium oxide with wormhole-like framework structures [J]. Adv Mater, 2000, 12(16): 1183～1186
    [1] Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode [J]. Nature, 1972,238(5358): 37～38
    [2] Ollis D F, Al-Ekabi H, Eds. [M]. Photocatalystic purification and treatment of water and air, Elseevier, Amsterdam,1993
    [3] Fox M A, Dulay M T. Heterogeneous photocatalysis [J]. Chem Rev, 1993,93:341～357
    [4] Carey J H, Lawrence J, Tosine H M. Photodeclalorination of PCB's in the presence of titanium dioxide in aqueous suspensions [J]. Bull environ contam toxicol, 1976,16(6): 697～701
    [5] Pruden Ann Lorette, Ollis David F. Photoassisted heterogeneous catalysis: the degradation of trichloroethylene in water [J]. Journal of Catalysis, 1983, 82(2):404～417
    [6] Hsiao Chen Yung, Lee Chung Li, Ollis David F. Heterogeneous photocatalysis: degradation of dilute solutions of dichloromethane (CH_2Cl_2), chloroform (CHCl_3), and carbon tetrachloride (CCl_4) with illuminated titania photocatalyst [J]. Journal of Catalysis,1983, 82(2): 418～423
    [7] Ollis D F, Serpon N, Pelizzetti E, Serpon N. Photocatalyzed destruction of water contaminants [J]. Environmental Science and Technology, 1991, 25(9): 1522～1529
    [8] Kamat P V. Photochemistry on nonreactive and reactive (semiconductor) surfaces [J]. Chem rev, 1993, 93(1):267
    [9] Fox M A, Dulay M T. Acceleration of secondary dark reactions of intermediates derived from adsorbed dyes on irradiated TiO_2 powders [J]. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1996, 98(1-2): 91～101
    [10] Linsebigler A L, Lu G, Yates J T. Photoeatalysis on TiO_2 surfaces. Principles, mechanisms, and selected results [J]. Chem rev. 1995.95(3): 735
    [11] 沈伟韧，赵文宽，贺飞，方佑龄．TiO_2光催化反应及其在废水处理中的应用[J]．化学进展，1998，10(4)：349
    [12] Ohno T, Satio S, Fujihara K, et al. Photocatalyzed Production of Hydrogen and Iodine from Aqueous Solutions of Iodide Using Platinum-Loaded TiO_2 Powder [J].Bull Chem Soc Jpn, 1996,69(11): 3059～3064
    [13] Wong J C S, Linsebigler A, Lu G, et al. Photooxidation of CH_3Cl on TiO_2 (110) single crystal and powdered TiO_2 surfaces [J]. J Phys Chem, 1995, 99(1): 335～344
    [14] Frank S N, Bard A J. Semiconductor electrodes. Ⅱ. Electrochemistry at n-type titanium dioxide electrodes in acetonitrile solutions [J].J Am Chem Soc, 1975, 97(26):7427～7433
    [15] 崔玉民，单德杰，朱亦仁．TiO_2薄膜光催化氧化I~-的研究[J]．无机化学学报，2001，17(3)：401～406
    [16] Mills A, Hunte S L. An overview of semiconductor photocatalysis [J]. J Photochem. Photobiol. :A: Chem., 1997, 108(1):1
    [17] Sunada K, Kikuchi Y, Hashimoto K, et al. Bactericidal and detoxification effects of TiO_2 thin film photocatalysts [J].Enviro. Sci. Tech., 1998, 32(5):726～728
    [18] Shchukin Dmitry G, Sviridov Dmitry V. Photocatalytic processes in spatially confined micro- and nanoreactors [J]. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2006, 7(1): 23～39
    [19] Baesa R R, Kiwi J. Effect of rutile phase on the photocatalytic properties of nanocrystalline titania during the degradation of p-coumaric acid [J]. Applied Catalysis B: Environmental, 1998, 16(1): 19～29
    [20] Besson Michele, Gallezot Pierre, Pigamo Anne, et al. Development of an improved continuous hydrogenation process for the production of 1,3-propanediol using titania supported ruthenium catalysts [J]. Applied Catalysis A: General, 2003, 250 ( 1 ) : 117～124
    [21] Yuan Zhong-Yong, Ren Tie-Zhen, Su B L. Hierarchically mesostmctured titania materials with an unusual interior macroporous structure[J]. Advanced Materials, 2003, 15(17): 1462～1465
    [22] Stathatos Elias, Lianos Panagiotis, Falaras Polykarpos, Siokou A. Photocatalytieally deposited silver nanoparticles on mesoporous TiO_2 films [J]. Langrnuir, 2000, 16(5): 2398～2400
    [23] Wang Chao, Li Qing, Wang Ruoding. Synthesis and characterization of mesoporous iron-doped TiO_2 [J]. Journal of Materials Science, 2004, 39(5): 1899～1901
    [24] Wang Yan, Jiang Zhao-Hua, Yang Feng-Jie. Preparation and photocatalytic activity of mesoporous TiO_2 derived from hydrolysis condensation with TX-100 as template [J]. Materials Science & Engineering B (Solid-State Materials for Advanced Technology), 2006, 128(1-3): 229～233
    [25] Yoshikawa S, Sakulkhaemaruethai S, Pavasupree S, et al. Photocatalytic activity of titania nanocrystals prepared by surfactant-assisted templating method-Effect of calcination conditions [J]. Materials Letters, 2005, 59(23): 2965～2968
    [26] Sak-ulkhaemaruethai S, Suzuki Y, Yoshikaa S. Surfactant-assisted preparation and characterization of mesoporous titania nanocrystals - effect of various processing conditions[J]. Journal of the Ceramic Society of Japan, 2004, 112(10): 547～52
    [27] Andersson M, Birkedal H, Franklin N R, et al. Ag/AgCl-loaded ordered mesoporous anatase for photocatalysis [J]. Chemistry of Materials, 2005,17(6): 1409～1415
    [28] Li Yuanzhi, Lee Nam-Hee, Lee Eun Gu, et al. The characterization and photocatalytic properties of mesoporous rutile TiO_2 powder synthesized through self-assembly of nano crystals [J]. Chemical Physics Letters, 2004, 389(1-3): 124～128
    [29] Pizzio L R. Mesoporous titania: effect of thermal treatment on the texture and acidic properties [J]. Materials Letters, 2005, 59(8-9): 994～997
    [30] Yao Wenhua, Fang Hua, Ou Encai, et al. Highly efficient catalytic oxidation of cyclohexane over cobalt-doped mesoporous titania with anatase crystalline structure [J]. Catalysis Communications, 2006, 7(6): 387～390
    [31] Peng Tianyou, Xiao Jiangrong, Li Ran, et al. Preparation, phase transformation and photocatalytic activities of cerium-doped mesoporous titania nanoparticles[J]. Journal of Solid State Chemistry, 2006, 179(4): 1161～1170
    [32] Soria J, Conesa J C, Augugliaro V, et al. Dinitrogen photoreduction to ammonia over titanium dioxide powders doped with ferric ions [J].J Phys Chem, 1991,95(1):274
    [33] Brillas E, Mur E, Sauleda R. Aniline mineralization by AOP's: Anodic oxidation, photocatalysis, electro-Fenton and photoelectro-Fenton processes [J].Appl Catal,B: Environ,1998,16(1):31～42
    [34] 高濂，郑珊，张青红著[M]．纳米氧化钛光催化材料及其应用，北京：化学工业出版社，2002．12
    [35] 刘守新，刘鸿．[M]．光催化及光电催化基础与应用，北京：化学工业出版社，2006：64～74
    [36] 杨富兴．纳米固体超强酸SO_4~(2-)／TiO_2和SO_4~(2-)／TiO_2-SiO_2制备、表征及催化性能研究[D]．河北师范大学，2004
    [37] Arata K, Hino M, Yamagata N. Acidity and Catalytic Activity of Zirconinm and Tianium Sulfates Heat-treated at High Temperature.Solid Superacid Catalysts [J]. Bull Chem Soc Jpn, 1990, 63:244～266
    [38] 王维平，杨锦宗．复合固体超强酸SO_42~(2-)／ZrO_2-TiO_2催化合成马来酸双酯[J]．石油化工，1990，19(5)：315～319
    [39] 高根之，于世涛，杨锦宗．SO_4~(2-)／TiO_2-Al_2O_3-SnO_2催化剂的研制及其催化合成己二酸二辛酯[J]．催化学报，1996，17(1)：83～86
    [40] 于世涛，高根之，杨锦宗．SO_4~(2-)／TiO_2-SnO_2-Al_2O_3固体超强酸催化合成DOP[J]．精细石油化工，1997，3：29～32
    [41] 张明俊，沈俊，田从学，张昭．介孔SO_4~(2-)／TiO_2固体超强酸的制备与表征[J]．功能材料，2006，37(12)：1955～1958
    [42] 宋波，杨巍，邓启伟，崔宝军，郭祥峰．不同原料制备的SO_4~(2-)／TiO_2对酯化反应的催化性能[J]．齐齐哈尔大学学报，1999，15(1)：84～86
    [43] 张术华，毛友安．SO_4~(2-)M_xO_y型固体超强酸及其催化酯化[J]．化学研究与应用，1997，9(4)：327～331
    [44] Yamaguchi T, Jin T, Ishida T, et al. Structural identification of acid sites of sulfur-promoted solid super acid and construction of its strucrure on silica support [J]. Materials Chemistry and Physics, 1987, 17(1-2):3～19
    [45] 梁斌．生物柴油的生产技术[J]．化工进展，2005，24(6)：577～585
    [46] 梁斌，闵恩泽．利用西部可再生资源发展生物柴油产业[J]．四川大学学报：工程科学版，2006，38(5)：33～37
    [47] 任立国，高文艺．煤炭实验方法汇编[M]．SO_4~(2-)／TiO_2固体超强酸催化剂的表面化学研究[J]．抚顺石油学院学报，2003，2(23)：31～35
    [1] Kresge C T, Leonowiez M E, Roth W J, et al. Ordered mesoporous molecular sieves synthesized by liquid-crystal template mechanism[J]. Nature. 1992,359(6397):710～712
    [2] Beck J S, et al. Anew family of mesoporous molecular sieves prepared with liquid crystal templates [J]. J Am Chem Soc, 1992,114:10834～10843
    [3] 刘克松，张密林，王江，付宏刚．非硅基介孔材料和介孔复合体的合成与特性[J]应用化学，2006，23(1)：1～6
    [4] Antoneli D M, Ying J Y. Synthesis of hexagonally packed mesoporous TiO_2 by a modified Sol-Gel method [J]. Angew Chem Int Ed Engl, 1995,34 (18):2014～2017
    [5] Kolen'ko Y V, Maximov V D, Garshev A V, et al. Hydrothermal synthesis of nanocrystalline and mesoporous titania from aqueous complex titanyl oxalate acid solutions [J]. Chemical Physics Letters,2004,388(4-6): 411～15
    [6] Ren T Z, Yuan Z Y, Su B L. A novel macroporous structure of mesoporous titanias: synthesis and characterisation[J].Colloids and Surfaces A (Physicochemical and Engineering Aspects), 2004, 241 (1-3): 67～73
    [7] Hintz W, Nikolov T, Yordanova V, et al. Generation of titania nanopowder via sol-gel synthesis [C]. CHISA 2004 - 16th International Congress of Chemical and Process Engineering, 2004:3245～3257
    [8] Li Y Z, Lee N H, Lee E G, et al. The characterization and photocatalytic properties of mesoporous rutile TiO_2 powder synthesized through self-assembly of nano crystals [J]. Chemical Physics Letters, 2004, 389(1-3): 124～128
    [9] Yang P, Zhao D, Margolese D I, et al. Eneralized synthesis of large-pore mesoporous metal oxides with semicrystalline frameworks [J].Nature, 1998,396:152～155
    [10] Yang P D, Zhao D Y, Margolese D I et al. Block copolymer templating syntheses of mesoporous metal oxides with large ordering lengths and semicrystalline frame work [J].Chem Mater, 1999,11:2813～2826
    [11] Luca Vittorio, Watson Jonathan N, Ruschena Martin, et al. Anionic surfactant templated titanium oxide mesophase: Synthesis, characterization, and mechanism of formation [J]. Chemistry of Materials, 2006, 18(5): 1156～1168
    [12] Ren Nan, Wang Bo, Yang You-Hao, et al. General method for the fabrication of hollow microcapsules with adjustable shell compositions [J]. Chem Mater, 2005, 17(10): 2582-2587
    [13] 戴亚堂，潘宝风，涂铭旌等．锐钛型介孔纳米TiO_2粉体的制备与机理研究[J]．武汉理工大学学报，2006，28(4)：1～4
    [14] 王保国，张妍，李(韦华)等．模板剂在介孔分子筛合成中的作用机理[J]．化学工业与工程，2005，22(2)：115～119
    [15] Davis M E. Ordered porous materials for emerging applications [J]. Nature, 2002, 417 (6891): 813～821.
    [16] Devi G S, Hyodo T, Shimizu Y, et al. Synthesis of mesoporous TiO_2-based powders and their gas-sensing properties [J].Sensors and Actuators B- Chemical ,2002, 87(1): 122～129
    [17] 张立德．[M]．纳米材料，北京：化学工业出版社，2000．
    [18] Pedersen J S, Gerstenberg M C. The structure of P85 Pluronic block copolymer micelles determined by small-angle neutron scattering [J]. Colloids Surf A, 2003,213 (2~3): 175～187
    [19] Zhang K W, Khan A. Phase-behavior of Poly (Ethylene Oxide)- Poly (Propylene Oxide) -Poly (Ethylene Oxide) triblock copolymers in water [J].Macromolecules, 1995, 28(11):3807～3812
    [20] Yun H S, Miyazawa K, Zhou H S, et al. Synthesis of mesoporous thin TiO_2 films with hexagonal pore structures using triblock copolymer templates [J]. Adv Mater, 2001, 13(18):1377～1380
    [21] 黄惠忠等．[M]．纳米材料分析，北京：化学工业出版社，2003：254～257
    [22] 唐振宁．[M]．钛自粉的生产与环境治理，北京：化学工业出版社，2000：108～115
    [23] 酒井登，吉川克尔，铃木森林夫，小桥进吉．硫酸钛溶液的水解[M]．二氧化钛译文集：硫酸法，1965：11～29
    [24] 杜巧云，葛虹．[M]．表面活性剂基础及应用，北京：中国石化出版社，1996：181～183
    [25] Soler-Illia G J A A, Scolan E, Louis A, et al. Design ofmeso-structured titanium oxo based hybrid organic-inorganic networks [J].New J Chem, 2001,25:156～165
    [26] Soler-Illia G J D, Sanchez C, Lebeau B, Patarin J. Chemical strategies to design textured materials: From microporous and mesoporous oxides to nanonetworks and hierarchical structures [J]. Chem Rev, 2002, 102(11): 4093～4138
    [27] 刘克松．有序介观结构TiO_2及复合体的控制合成与性能研究[D]．哈尔滨工程大学，2006．5
    [28] 赵国玺，朱黟瑶著．[M]．表面活性剂作用原理，北京：中国轻工业出版社，2003．1
    [29] K·霍姆博格，B·琼森，B·科隆博格，B·林德曼著，韩丙勇，张学军译．[M]．水溶液中的表面活性剂和聚合物(第二版)，北京：化学工业出版社，2005．2
    [30] Israelachivili J N. [M]. Intermolecular and surface forces, London: Academic Press, 1991:271
    [31] Tanford C. [M]. The hydrophobic effect, New York: Wiley-Intersciece, 1973:52
    [32] Kim J M, Sakamoto Y, Hwang Y K, et al. Stmctml design of mesoporous silica by micelle-packing control using blends of amphiphilic block copolymers [J]. J Phys Chem B, 2002, 106:2552～2558
    [33] Rubingh D N, Holland, P M. [M]. Cationic surfactant: physical chemistry; surfactant science series 37, Marcel Dekker: New York, 1991
    [34] Shuji Saito. Solubilization properties of polymer-surfactant complexes [J]. Journal of Colloid and Interface Science, 1967, 24:227
    [35] Blanchard J, Barboux-Doeuef S, Maquet J, Sanchez C. Investigation on hydrolysis-condensation reactions of titanium(Ⅳ) butoxide [J]. New Journal of Chemistry, 1995, 19(8-9): 929～941
    [36] Addamo M, Augugliaro V, Di Paola A, et al. Preparation, characterization and photoaetivity of polycrystalline nanostructured TiO_2 catalysts [J]. J Phys Chem B, 2004, 108(10):3303～3310
    [37] Spuee R A, Myers H. Quantitative analysis of anatase-mtile mixtures with X-ray diffractometer [J]. Anal Chem, 1957, 29:760～762
    [38] Wu Y, Yu J C, Yu J G, et al. Enhancement of photocatalytic activity of mesoporous TiO_2 by using carbon nanotubes [J]. Appl Catal A: Gen, 2005, 289(2): 186～196
    [39] 许顺生．[M]．金属X射线学，上海：上海科学技术出版社，1962：357～359，417～420
    [40] 马札敦．[M]．近代X射线多晶衍射——实验技术与数据分析，北京：化学工业出版社，2004：399～441
    [41] 王乐飞．水合二氧化钛的超声洗涤研究[D]．四川大学，2005．5

© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号

地址：北京市海淀区学院路29号 邮编：100083

电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700