模板法制备介孔材料及其表征
|
摘要
有序介孔材料(如命名为MCM-41的介孔材料)因其较大且连续可调的孔径、大的比表面积和孔体积而在大分子的吸附、催化和分离，纳米组装技术以及光、电、磁等领域具有广泛的潜在应用价值而受到人们的关注，正成为众多领域的研究热点之一。本文主要做了以下几个方面的工作：
1．利用一种阳离子模板剂—十八烷基三甲基溴化铵(STAB)为模板在强酸性条件下合成出了具有MCM-41结构的介孔氧化硅材料，并分别利用煅烧和热乙醇萃取的方法除去模板剂。采用FT-IR、SAXRD、HRTEM和N_2的吸附—脱附等温线对介孔材料进行了表征。结果表明萃取的样品具有比煅烧样品更大的比表面积和更有序的介孔结构，在煅烧升温过程中适当提高升温速率可以使介孔孔壁有序化。SAXRD和HRTEM的结果进一步表明制备的介孔材料具有六方有序的结构，孔径大小在2-3nm且分布很窄，材料的N_2的吸附—脱附等温线呈现第Ⅳ型吸附曲线类型，表明合成的材料确为介孔结构，比表面积和孔体积分别高达1400 m~2／g和1.04cm~3／g。
2．尝试利用STAB作为模板剂来合成介孔氧化钛材料，并且利用FT-IR，SAXRD，HRTEM和N_2的吸附—脱附等温线对样品进行了表征。结果表明合成的介孔结构为短程有序的蠕虫状孔，孔径达8nm。N_2的吸附—脱附等温线呈现第Ⅳ型吸附曲线的特征，说明材料确为介孔结构，但比表面积和孔体积均只有86 m~2／g和0.23cm~3／g。
3．在常温常压下利用聚苯乙烯微乳液为模板制备出了有序介孔氧化硅，并分别利用热乙醇萃取和煅烧的方法除去模板剂。利用FT-IR，SAXRD，HRTEM和N_2的吸附—脱附等温线对介孔材料进行了表征。FT-IR的结果表明经过二次萃取可以有效的除去模板剂。SAXRD和HRTEM的结果则显示样品为具有六方有序结构的MCM-41氧化硅材料，孔径大小为4-5nm且分布较窄，材料的N_2吸附—脱附等温线的分析表明了样品确为呈现第Ⅳ型吸附曲线的介孔材料，而进一步的表征则表明样品的比表面积和孔体积高达1300 m~2／g和1.27cm~3／g。
Up to now, mesoporous materials with ordered pore structures, large and regulablepore diameter, BET surface area and pore volume were rapidly developed because oftheir potential applications in many fields such as adsorption, catalysis, separation ofmacromolecules, optics, nano-assembly technologies, electronics, magnetisms andchemical sensors.
1. In this thesis, the MCM-41 mesoporous silica was synthesized by using cationicsurfactant stearictrimethyl ammonium bromide (STAB) as template under strong acidconditions, and STAB was removed by calcination and hot ethanol-extraction. Thethree-dimension MCM-41 mesopores was characterized by FT-IR, SAXRD, nitrogenadsorption-desorption isotherm and HRTEM. The results showed that samples byextraction had bigger BET surface area and more ordered pore structure than those bycalcination, but pore structure could be more ordered under more rapid calefactiverate when calcining. SAXRD and TEM results indicated that all samples had ahexagon pore structures with narrow pore diameter distribution(2-3nm) and allnitrogen adsorption-desorption isotherm exhibited a LangmuirⅣcategory which isrelated to mesoporous materials with large BET surface area (more than 1400m~2/g)and pore volume (1.04cm~3/g).
2. In this part, a mesoporous titania materials was synthesized by using STAB astemplate, and FT-IR, SAXRD, HRTEM and nitrogen adsorption-desorption was takento the sample. The results showed that a worm-like pore structure with larger porediameter (8nm) was synthesized. Nitrogen adsorption-desorption isotherm showed aLangmuirⅣcategory which is related to mesoporous materials, and the BET surfacearea and pore volume was 86m~2/g and 0.23cm~3/g respective.
3. On the base of chapter 1 and 2, we synthesized ordered mesoporous silica bypolystyrene microemulsion as template under normal temperature and pressure, andtemplate was removed by calcination and hot ethanol-extraction, respectively.Similarly, the three-dimension MCM-41 mesopores was characterized by FT-IR, SAXRD, nitrogen adsorption-desorption isotherm and HRTEM. FT-IR results showedthat template could be thoroughly removed by two-time extraction. SAXRD andHRTEM results showed that the synthesized mesoporous materials had a hexagonpore structure same to MCM-41 with a pore diameter at 4-5nm. It was also analyzedthat all nitrogen adsorption-desorption isotherm exhibited a LangmuirⅣcategorywhich is related to mesoporous materials. And the samples had a uniform porediameter distribution, high surface area and pore volume (more than 1300m~2/g and1.27cm~3/g).
1．利用一种阳离子模板剂—十八烷基三甲基溴化铵(STAB)为模板在强酸性条件下合成出了具有MCM-41结构的介孔氧化硅材料，并分别利用煅烧和热乙醇萃取的方法除去模板剂。采用FT-IR、SAXRD、HRTEM和N_2的吸附—脱附等温线对介孔材料进行了表征。结果表明萃取的样品具有比煅烧样品更大的比表面积和更有序的介孔结构，在煅烧升温过程中适当提高升温速率可以使介孔孔壁有序化。SAXRD和HRTEM的结果进一步表明制备的介孔材料具有六方有序的结构，孔径大小在2-3nm且分布很窄，材料的N_2的吸附—脱附等温线呈现第Ⅳ型吸附曲线类型，表明合成的材料确为介孔结构，比表面积和孔体积分别高达1400 m~2／g和1.04cm~3／g。
2．尝试利用STAB作为模板剂来合成介孔氧化钛材料，并且利用FT-IR，SAXRD，HRTEM和N_2的吸附—脱附等温线对样品进行了表征。结果表明合成的介孔结构为短程有序的蠕虫状孔，孔径达8nm。N_2的吸附—脱附等温线呈现第Ⅳ型吸附曲线的特征，说明材料确为介孔结构，但比表面积和孔体积均只有86 m~2／g和0.23cm~3／g。
3．在常温常压下利用聚苯乙烯微乳液为模板制备出了有序介孔氧化硅，并分别利用热乙醇萃取和煅烧的方法除去模板剂。利用FT-IR，SAXRD，HRTEM和N_2的吸附—脱附等温线对介孔材料进行了表征。FT-IR的结果表明经过二次萃取可以有效的除去模板剂。SAXRD和HRTEM的结果则显示样品为具有六方有序结构的MCM-41氧化硅材料，孔径大小为4-5nm且分布较窄，材料的N_2吸附—脱附等温线的分析表明了样品确为呈现第Ⅳ型吸附曲线的介孔材料，而进一步的表征则表明样品的比表面积和孔体积高达1300 m~2／g和1.27cm~3／g。
Up to now, mesoporous materials with ordered pore structures, large and regulablepore diameter, BET surface area and pore volume were rapidly developed because oftheir potential applications in many fields such as adsorption, catalysis, separation ofmacromolecules, optics, nano-assembly technologies, electronics, magnetisms andchemical sensors.
1. In this thesis, the MCM-41 mesoporous silica was synthesized by using cationicsurfactant stearictrimethyl ammonium bromide (STAB) as template under strong acidconditions, and STAB was removed by calcination and hot ethanol-extraction. Thethree-dimension MCM-41 mesopores was characterized by FT-IR, SAXRD, nitrogenadsorption-desorption isotherm and HRTEM. The results showed that samples byextraction had bigger BET surface area and more ordered pore structure than those bycalcination, but pore structure could be more ordered under more rapid calefactiverate when calcining. SAXRD and TEM results indicated that all samples had ahexagon pore structures with narrow pore diameter distribution(2-3nm) and allnitrogen adsorption-desorption isotherm exhibited a LangmuirⅣcategory which isrelated to mesoporous materials with large BET surface area (more than 1400m~2/g)and pore volume (1.04cm~3/g).
2. In this part, a mesoporous titania materials was synthesized by using STAB astemplate, and FT-IR, SAXRD, HRTEM and nitrogen adsorption-desorption was takento the sample. The results showed that a worm-like pore structure with larger porediameter (8nm) was synthesized. Nitrogen adsorption-desorption isotherm showed aLangmuirⅣcategory which is related to mesoporous materials, and the BET surfacearea and pore volume was 86m~2/g and 0.23cm~3/g respective.
3. On the base of chapter 1 and 2, we synthesized ordered mesoporous silica bypolystyrene microemulsion as template under normal temperature and pressure, andtemplate was removed by calcination and hot ethanol-extraction, respectively.Similarly, the three-dimension MCM-41 mesopores was characterized by FT-IR, SAXRD, nitrogen adsorption-desorption isotherm and HRTEM. FT-IR results showedthat template could be thoroughly removed by two-time extraction. SAXRD andHRTEM results showed that the synthesized mesoporous materials had a hexagonpore structure same to MCM-41 with a pore diameter at 4-5nm. It was also analyzedthat all nitrogen adsorption-desorption isotherm exhibited a LangmuirⅣcategorywhich is related to mesoporous materials. And the samples had a uniform porediameter distribution, high surface area and pore volume (more than 1300m~2/g and1.27cm~3/g).
引文
[1] IUPAC manual of symbols and termeinology [J], Pure Appl. Chem., 1972, 31:578～680.
[2] 张立德，纳米材料[M]，北京：化学工业出版社，2000．95-96．
[3] Schmidt-Winkel P, W W Lukens. Jr, Zhao D Y, et al., Mesocellular siliceous foams with uniformly sized cells and windows [J]. J. Am. Chem. Soc. 1999, 121:254-255.
[4] Kresge C T, Leonowicz M E, Roth W J, et al., Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature, 1992, 359:710-712.
[5] Beck J S, Vartuli J C, Roth W J, et al., A new family of mesoporous molecular sieves prepared with liquid crystal templates [J]. J. Am. Chem. Soc., 1992, 114:10834-10843.
[6] 齐凯，牛忠伟，容建华等，有序孔材料的发展现状[J]．材料导报，2001，15(6)：47-51．
[7] 谢永贤，陈文，徐庆，有序介孔材料的合成及机理[J]．材料导报，2002，16(1)：51-53．
[8] Chuah G. K, Hu X, Zhan P, et al., Catalysts from MCM-41: Framework modification, pore size engineering, and organic-inorganic hybrid materials [J]. J. Mol. Catal. A: Chem. 2002, 181: 25-31.
[9] Sage V, Clark J H, Macquarrie D J, et al., Cationic polymerization of styrene using mesoporous silica supported aluminum chloride [J]. J. Mol. Catal. A. Chem. 2003, 198:349-358.
[10] Alain Moissette, Isabelle Gener, Claude Bremard, Probing the spontaneous ionization of aromatic amines by adsorption in activated acidic zeolite HZSM-5 [J]. J. Raman Spectrosc. 2002, 33(5):381-389.
[11] Ganschow M, Wark M, Wohrle D, et al,Anchoring of functional dye molecules in MCM-41 by microwave-assisted hydrothermal cocondensation [J]. Angew. Chem. Int. Ed. 2000, 39(1):161-163.
[12] 姚连增，叶长辉，牟季美等．纳米PbS／SiO_2气凝胶介孔组装体的制备及发光特性[J]．无机材料学报 2001，16(1)：93-97．
[13] Pan A L, Zheng H G., Yang Z P, et al., Gamma-irradiation-induced Ag/SiO_2 composite films and their optical absorption properties [J]. Mater. Res. Bull. 2003, 38: 789-796.
[14] Kalogeras M, Vassilikou-Dova A, Neagu E R, Dielectric characterization of poly(methyl methacrylate) geometrically confined into mesoporous SiO_2 glasses[J]. Mat. Res. Innovat. 2001, 4:322-333.
[15] Thibaud Coradin, Joulia Larionova, Andrew A.Smith, et al., Magnetic nanocomposites built by controlled incorporation of magnetic clusters into mesoporous silicates [J]. Adv. Mater. 2002, 14 (12): 896-898
[16] Napolsky K S, Eliseev A A, Knotko A V, et al., Preparation of ordered magnetic iron nanowires in mesoporous silica matrix [J]. Mater. Sci. Eng. C. 2003, 23:151-154.
[17] 陈航榕，施剑林，禹剑等，非硅组成有序介孔材料合成及应用[J]．硅酸盐学报，2000，28(3)：259-263．
[18] Monnier A, Schuth F, Huo Q et al, Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures [J].Science, 1993, 261: 1299-1303
[19] Huo Q S, Margoless D I, Ciesla U et al, Generalized synthesis of periodic surfactant inorganic composite-materials [J].Nature, 1994, 368:317-321
[20] Huo Q S, Margoless D I, Ciesla U et al, Organization of organic-molecules with inorganic molecule-species into nanocomposite biphase arrays [J]. Chemistry of Materials, 1994(6): 1176-1191.
[21] Attard G S, Glyde J C, Goltner C G, Liquid-crystalline phases as templates for the synthesis of mesoporous silica [J].Nature, 1995, 378:366-368
[22] Goltner C G, Antonietti M, Mesoporous materials by templating of liquid crystalline phases[J].Adv. Mater., 1997, 9:431
[23] Chen C Y, Burkett S L, Li H X, Studies on mesoporous materials Ⅱ. synthesis mechanism of MCM-41 [J]. Micropor. Mater., 1993, 2:27—34
[24] Stucky G D, Huo Q S, Firouzi A, et al., Directed synthesis of organic/inorganic composite structures [J]. Stud. Sur. Sci. Catal., 1997, 105:3-28.
[25] Firouzi A, Kumar D, Bull L M, et al., Cooperative organization of Inorganic-surfactant and biomimetic assembles [J]. Science, 1995(267):1138-1143.
[26] Behrens P. Voids in variable chemical surroundings-mesoporous metal oxides, [J]. Angew. Chem. Int. Ed. Engl. 1996, 35: 515-518.
[27] Ying J Y, Mehnert C P, Wong M S, Synthesis and application of supramolecular-templated mesoporous materials [J]. Angina: Chem. Int. Ed. Engl. 1999, 38: 56-77.
[28] Corma A, From microporous to mesoporous molecular sieve materials and their use in catalysis [J]. Chem. Rev., 1997(97):2373-2419.
[29] Yuan Z Y, Six Boulanger M F, Su B L, Do mesostructured materials have an unusual macrolamellar structure? [J]. Angew. Chem. Int. Ed., 2003, 42:1572-1573
[30] Ciesla U & Schuth F, Ordered mesoporous materials [J]. Microporous and Mesoporous Materials., 1999, 27:131-149.
[31] Zhao D Y, Feng J L, Huo Q S et al, Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores [J]. Science, 1998, 279:548-552.
[32] Kitazawa N, Namba H, Aono M et al, Sol-gel derived mesoporous silica films using amphiphilic triblock copolymers [J]. Journal of Non-Crystalline Solids, 2003, 332:199-206.
[33] Pei L H, Kurumada K I, Tanigaki M et al, Effect of drying on the mesoporous structure of sol-gel derived silica with PPO-PEO-PPO template block copolymer [J]. Journal of Colloid and Interface Science, 2005, 284:222-227.
[34] Christine G S, Non-ionic templating of silica: formation mechanism and structure [J]. Current Opinion in Colloid & Interface Science, 2002, 7:173-178.
[35] YAMADA T, ZHOU H S, ASAI K et al, Pore size controlled mesoporous Silicate powder prepared by triblock copolymer templates [J]. Materials Letters, 2002, 56:93-96.
[36] Sato Y, Nakanishi K, Hirao K et al, Formation of ordered macropores and templated nanopores in silica sol-gel system incorporated with EO-PO-EO triblock copolymer [J].Colloids and Surfaces,A: Physicochemical and Engineering Aspects,2001,187-188:117-122.
[37] Zayim E O, Liu P, Lee, S H et al, Mesoporous sol-gel WO_3 thin films viapoly(styrene-co-allyl-alcohol) copolymer templates [J]. Solid State Ionics, 2003, 165:65-72.
[38] Sepulveda -Guzman S, Perez -Camacho O, Rodriguez -Fernandez O et al, In situ preparation of magnetic nanocomposites of goethite in a styrene-maleimide copolymer template [J]. Journal of Magnetism and Magnetic Materials 2005, 294:c47-c50.
[39] Huang Z, Luan D Y, Shen S C et al, Supercritical fluid extraction of the organic template from synthesized porous materials: effect of pore size [J]. Journal of Supercritical Fluids', 2005, 35:40-48.
[40] Yang L M, Wang Y J, Luo G S et al, Simultaneous removal of copolymer template from SBA-15 in the crystallization process [J]. Microporous and Mesoporous Materials, 2005, 81: 107-114.
[41] Gomez-Vega J M, Teshima K, Hozumi A et al, Mesoporous silica thin films produced by calcination in oxygen plasma [J]. Surface and Coatings Technology, 2003, 169-170:504-507.
[42] Couttnho D, Yang Z W, Ferraris J P et al, Proton conducting polyaniline molecular sieve composites [J].Microporous and Mesoporous Materials, 2005,81:321-332.
[43] Zhou L, Liu X W, Li J W et al, Synthesis of ordered mesoporous carbon molecular sieve and its adsorption capacity for H_2, N_2, O_2, CH_4 and CO_2 [J]. Chemical Physics Letters, 2005, 413:6-9.
[44] Pitchumani R, Li W J, Coppens M O, Tuning of nanostructured SBA-15 silica using phosphoric acid[J]. Catalysis Today, 2005, 105:618-622.
[45] Fantini M C A, Matos J R, Cides Da Silva L C et al, Ordered mesoporous silica: microwave synthesis [J].Materials Science and Engineering B,2004,112:106-110.
[46] Zhao L L, Yu Y, Song L X et al, Preparation of mesoporous titania film using nonionic, triblock copolymer as surfactant template [J]. Applied Catalysis A. General, 2004, 263:171-177.
[47] Schacht S, Huo Q, Voigt-Martin I G et al,. Oil-Water Interface of Mesoporous Macroscale Structures [J]. Science, 1996, 273:768.
[48] Sen T, Tiddy G J T, Casci J Let al, Meso-cellular silica foams, macro-cellular silica foams and mesoporous solids: a study of emulsion-mediated synthesis [J]. Microporous and Mesoporous Materials, 2005, 78:255-263.
[49] Zhang X, Zhang F, Chan K Y, The synthesis of large mesopores alumina by microemulsion templating,their characterization and properties as catalyst support [J]. Materials Letters, 2004, 58:2872-2877
[50] Zhang X, Zhang F, Chan K Y, Synthesis and characterization of amino-functionalized mesostructured cellular foams with large mesopores using microemulsion templating [J]. Scripta Materialia, 2004, 51:343-347.
[51] Gugliotti L A, Feldheim D L, Eaton B E et al, RNA-Mediated Metal-Metal Bond Formation in the Synthesis of Hexagonal Palladium Nanoparticles [J]. Science,2004,304 (5672) :850-852,
[52] Cha J N, Stucky G D, Morse D E et al, Biomimetic synthesis of ordered silica structures mediated by block copolypeptides [J]. Nature,2000,403 (6767) :289-292.
[53]. Pedroni V, Schulz P C, Gscchaider De Ferreira M E et al, A chitosan-templated monolithic siliceous mesoporous-macroporous material [J]. Colloid Polymer Science,,2000,278: 964-971.
[54] Faiardo H V, Martins A O, De Almeid R M et al, Synthesis of mesoporous Al_2O_3 macrospheres using the biopolymer chitosan as a template: A novel active catalyst system for CO_2 reforming of methane [J]. Materials Letters, 2005, 59:3963-3967.
[55] Yang P D, Zhao D Y, Margolese D 1 et al. Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks [J]. Nature 1998, 396:152-155.
[1] Zhang L, Zhu Y, He Y et al, Preparation and performances of mesoporous TiO_2 film photocatalyst supported on stainless steel [J]. Applied Catalysis B: Environmental 2003, 40:287-292
[2] 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,2002, B, 87:122-129
[3] Yun H, Miyazawa K, Honma I et al, Synthesis of semicrystallized mesoporous TiO_2 thin films using triblock copolymer templates [J]. Materials Science and Engineering, 2003, C 23:487-494
[4] Wang Z, Jiang T, Du Y et al, Synthesis of mesoporous titania and the photocatalytic activity for decomposition of methyl orange [J]. Materials Letters, 2006, 60:2493-2496
[5] Xiao J, Peng T, Li R et al, Preparation, phase transformation and photocatalytic activities of cerium-doped mesoporous titania nanoparticles[J]. Journal of Solid State Chemistry, 2006, 179:1161-1170
[6] Mahurin S, Bao L,Yan W et al, Atomic layer deposition of TiO_2 on mesoporous silica[J]. Journal of Non-Crystalline Solids, 2006, 352:3280-3284
[7] 李春燕，李樊强，TiO_2的溶胶—凝胶过程研究[J]．硅酸盐学报，1996，24(3)： 338-341
[8] 王琳，吴忆宁，汪炎，溶胶—凝胶法制备纳米二氧化钛及其性能研究[J]．哈尔滨商业大学学报(自然科学版)，2006，22(3)：76-79
[9] 董素芳，制备纳米二氧化钛凝胶过程中若干因素对凝胶时间的影响[J]．山东理工大学学报(自然科学版)，2005，19(5)：94-97
[1] Imhof A, Pine D J, Ordered macroporous materials by emulsion templating [J].Nature, 1997, 389:948-951
[2] 齐凯，杨振忠，刘正平等，聚苯乙烯模板制备SiO_2三维有序孔材料[J]．科学通报，2000，45：992-994
[3] Fan H, Van Swol F, Lu Y et al, Multiphased assembly of nanoporous silica particles[J]. Journal of Non-Crystalline Solids, 2001, 285: 71-78
[4] Shane Carr C. Shantz D F, Non-ionic-microemulsion mediated growth of zeolite A[J]. Microporous and Mesoporous Materials 2005, 85: 284-292
[5] Axnanda S, Shantz D F, Cationic microemulsion-mediated synthesis of silicalite-1 [J]. Microporous and Mesoporous Materials, 2005, 84: 236-246
[6] Aikawa K, Kanoko K, Tamura T et al, Formation of fractal porous silica by hydrolysis of TEOS in a bicontinuous microemulsion [J]. Colloids and Surface A: Physicochemical and Engineering Aspects, 1999, 150: 95-104
[7] Moriguchi I, Hidaka R. Yamada H et al, Li-intercalation property of mesoporous anatase-TiO_2 synthesized by bicontinuous microemulsion-aided process [J]. Solid State Ionics, 2005, 176: 2361-2366
[8] Antonietti M, Bremser W, Muschenborn D et al, Synthesis and size control of polystyrene latices via polymerization in microemulsion [J]. Macromolecules. 1991, 24: 6636-6643
[9] Wu C, A simple model for the structure of spherical microemulsions [J]. Macromolecules, 1994, 27: 298-299
[10] Maria D A, Luan Z H, Klinowski J, Titanosilicate mesoporous molecular sieves MCM-41: synthesis and characterization [J]. Phys. Chem., 1996, 100: 2178-2182
[11] Jain S, Bates F S. On the origins of morphological complexity in block copolymer surfactants [J]. Science, 2003, 300: 460-464
[2] 张立德，纳米材料[M]，北京：化学工业出版社，2000．95-96．
[3] Schmidt-Winkel P, W W Lukens. Jr, Zhao D Y, et al., Mesocellular siliceous foams with uniformly sized cells and windows [J]. J. Am. Chem. Soc. 1999, 121:254-255.
[4] Kresge C T, Leonowicz M E, Roth W J, et al., Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature, 1992, 359:710-712.
[5] Beck J S, Vartuli J C, Roth W J, et al., A new family of mesoporous molecular sieves prepared with liquid crystal templates [J]. J. Am. Chem. Soc., 1992, 114:10834-10843.
[6] 齐凯，牛忠伟，容建华等，有序孔材料的发展现状[J]．材料导报，2001，15(6)：47-51．
[7] 谢永贤，陈文，徐庆，有序介孔材料的合成及机理[J]．材料导报，2002，16(1)：51-53．
[8] Chuah G. K, Hu X, Zhan P, et al., Catalysts from MCM-41: Framework modification, pore size engineering, and organic-inorganic hybrid materials [J]. J. Mol. Catal. A: Chem. 2002, 181: 25-31.
[9] Sage V, Clark J H, Macquarrie D J, et al., Cationic polymerization of styrene using mesoporous silica supported aluminum chloride [J]. J. Mol. Catal. A. Chem. 2003, 198:349-358.
[10] Alain Moissette, Isabelle Gener, Claude Bremard, Probing the spontaneous ionization of aromatic amines by adsorption in activated acidic zeolite HZSM-5 [J]. J. Raman Spectrosc. 2002, 33(5):381-389.
[11] Ganschow M, Wark M, Wohrle D, et al,Anchoring of functional dye molecules in MCM-41 by microwave-assisted hydrothermal cocondensation [J]. Angew. Chem. Int. Ed. 2000, 39(1):161-163.
[12] 姚连增，叶长辉，牟季美等．纳米PbS／SiO_2气凝胶介孔组装体的制备及发光特性[J]．无机材料学报 2001，16(1)：93-97．
[13] Pan A L, Zheng H G., Yang Z P, et al., Gamma-irradiation-induced Ag/SiO_2 composite films and their optical absorption properties [J]. Mater. Res. Bull. 2003, 38: 789-796.
[14] Kalogeras M, Vassilikou-Dova A, Neagu E R, Dielectric characterization of poly(methyl methacrylate) geometrically confined into mesoporous SiO_2 glasses[J]. Mat. Res. Innovat. 2001, 4:322-333.
[15] Thibaud Coradin, Joulia Larionova, Andrew A.Smith, et al., Magnetic nanocomposites built by controlled incorporation of magnetic clusters into mesoporous silicates [J]. Adv. Mater. 2002, 14 (12): 896-898
[16] Napolsky K S, Eliseev A A, Knotko A V, et al., Preparation of ordered magnetic iron nanowires in mesoporous silica matrix [J]. Mater. Sci. Eng. C. 2003, 23:151-154.
[17] 陈航榕，施剑林，禹剑等，非硅组成有序介孔材料合成及应用[J]．硅酸盐学报，2000，28(3)：259-263．
[18] Monnier A, Schuth F, Huo Q et al, Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures [J].Science, 1993, 261: 1299-1303
[19] Huo Q S, Margoless D I, Ciesla U et al, Generalized synthesis of periodic surfactant inorganic composite-materials [J].Nature, 1994, 368:317-321
[20] Huo Q S, Margoless D I, Ciesla U et al, Organization of organic-molecules with inorganic molecule-species into nanocomposite biphase arrays [J]. Chemistry of Materials, 1994(6): 1176-1191.
[21] Attard G S, Glyde J C, Goltner C G, Liquid-crystalline phases as templates for the synthesis of mesoporous silica [J].Nature, 1995, 378:366-368
[22] Goltner C G, Antonietti M, Mesoporous materials by templating of liquid crystalline phases[J].Adv. Mater., 1997, 9:431
[23] Chen C Y, Burkett S L, Li H X, Studies on mesoporous materials Ⅱ. synthesis mechanism of MCM-41 [J]. Micropor. Mater., 1993, 2:27—34
[24] Stucky G D, Huo Q S, Firouzi A, et al., Directed synthesis of organic/inorganic composite structures [J]. Stud. Sur. Sci. Catal., 1997, 105:3-28.
[25] Firouzi A, Kumar D, Bull L M, et al., Cooperative organization of Inorganic-surfactant and biomimetic assembles [J]. Science, 1995(267):1138-1143.
[26] Behrens P. Voids in variable chemical surroundings-mesoporous metal oxides, [J]. Angew. Chem. Int. Ed. Engl. 1996, 35: 515-518.
[27] Ying J Y, Mehnert C P, Wong M S, Synthesis and application of supramolecular-templated mesoporous materials [J]. Angina: Chem. Int. Ed. Engl. 1999, 38: 56-77.
[28] Corma A, From microporous to mesoporous molecular sieve materials and their use in catalysis [J]. Chem. Rev., 1997(97):2373-2419.
[29] Yuan Z Y, Six Boulanger M F, Su B L, Do mesostructured materials have an unusual macrolamellar structure? [J]. Angew. Chem. Int. Ed., 2003, 42:1572-1573
[30] Ciesla U & Schuth F, Ordered mesoporous materials [J]. Microporous and Mesoporous Materials., 1999, 27:131-149.
[31] Zhao D Y, Feng J L, Huo Q S et al, Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores [J]. Science, 1998, 279:548-552.
[32] Kitazawa N, Namba H, Aono M et al, Sol-gel derived mesoporous silica films using amphiphilic triblock copolymers [J]. Journal of Non-Crystalline Solids, 2003, 332:199-206.
[33] Pei L H, Kurumada K I, Tanigaki M et al, Effect of drying on the mesoporous structure of sol-gel derived silica with PPO-PEO-PPO template block copolymer [J]. Journal of Colloid and Interface Science, 2005, 284:222-227.
[34] Christine G S, Non-ionic templating of silica: formation mechanism and structure [J]. Current Opinion in Colloid & Interface Science, 2002, 7:173-178.
[35] YAMADA T, ZHOU H S, ASAI K et al, Pore size controlled mesoporous Silicate powder prepared by triblock copolymer templates [J]. Materials Letters, 2002, 56:93-96.
[36] Sato Y, Nakanishi K, Hirao K et al, Formation of ordered macropores and templated nanopores in silica sol-gel system incorporated with EO-PO-EO triblock copolymer [J].Colloids and Surfaces,A: Physicochemical and Engineering Aspects,2001,187-188:117-122.
[37] Zayim E O, Liu P, Lee, S H et al, Mesoporous sol-gel WO_3 thin films viapoly(styrene-co-allyl-alcohol) copolymer templates [J]. Solid State Ionics, 2003, 165:65-72.
[38] Sepulveda -Guzman S, Perez -Camacho O, Rodriguez -Fernandez O et al, In situ preparation of magnetic nanocomposites of goethite in a styrene-maleimide copolymer template [J]. Journal of Magnetism and Magnetic Materials 2005, 294:c47-c50.
[39] Huang Z, Luan D Y, Shen S C et al, Supercritical fluid extraction of the organic template from synthesized porous materials: effect of pore size [J]. Journal of Supercritical Fluids', 2005, 35:40-48.
[40] Yang L M, Wang Y J, Luo G S et al, Simultaneous removal of copolymer template from SBA-15 in the crystallization process [J]. Microporous and Mesoporous Materials, 2005, 81: 107-114.
[41] Gomez-Vega J M, Teshima K, Hozumi A et al, Mesoporous silica thin films produced by calcination in oxygen plasma [J]. Surface and Coatings Technology, 2003, 169-170:504-507.
[42] Couttnho D, Yang Z W, Ferraris J P et al, Proton conducting polyaniline molecular sieve composites [J].Microporous and Mesoporous Materials, 2005,81:321-332.
[43] Zhou L, Liu X W, Li J W et al, Synthesis of ordered mesoporous carbon molecular sieve and its adsorption capacity for H_2, N_2, O_2, CH_4 and CO_2 [J]. Chemical Physics Letters, 2005, 413:6-9.
[44] Pitchumani R, Li W J, Coppens M O, Tuning of nanostructured SBA-15 silica using phosphoric acid[J]. Catalysis Today, 2005, 105:618-622.
[45] Fantini M C A, Matos J R, Cides Da Silva L C et al, Ordered mesoporous silica: microwave synthesis [J].Materials Science and Engineering B,2004,112:106-110.
[46] Zhao L L, Yu Y, Song L X et al, Preparation of mesoporous titania film using nonionic, triblock copolymer as surfactant template [J]. Applied Catalysis A. General, 2004, 263:171-177.
[47] Schacht S, Huo Q, Voigt-Martin I G et al,. Oil-Water Interface of Mesoporous Macroscale Structures [J]. Science, 1996, 273:768.
[48] Sen T, Tiddy G J T, Casci J Let al, Meso-cellular silica foams, macro-cellular silica foams and mesoporous solids: a study of emulsion-mediated synthesis [J]. Microporous and Mesoporous Materials, 2005, 78:255-263.
[49] Zhang X, Zhang F, Chan K Y, The synthesis of large mesopores alumina by microemulsion templating,their characterization and properties as catalyst support [J]. Materials Letters, 2004, 58:2872-2877
[50] Zhang X, Zhang F, Chan K Y, Synthesis and characterization of amino-functionalized mesostructured cellular foams with large mesopores using microemulsion templating [J]. Scripta Materialia, 2004, 51:343-347.
[51] Gugliotti L A, Feldheim D L, Eaton B E et al, RNA-Mediated Metal-Metal Bond Formation in the Synthesis of Hexagonal Palladium Nanoparticles [J]. Science,2004,304 (5672) :850-852,
[52] Cha J N, Stucky G D, Morse D E et al, Biomimetic synthesis of ordered silica structures mediated by block copolypeptides [J]. Nature,2000,403 (6767) :289-292.
[53]. Pedroni V, Schulz P C, Gscchaider De Ferreira M E et al, A chitosan-templated monolithic siliceous mesoporous-macroporous material [J]. Colloid Polymer Science,,2000,278: 964-971.
[54] Faiardo H V, Martins A O, De Almeid R M et al, Synthesis of mesoporous Al_2O_3 macrospheres using the biopolymer chitosan as a template: A novel active catalyst system for CO_2 reforming of methane [J]. Materials Letters, 2005, 59:3963-3967.
[55] Yang P D, Zhao D Y, Margolese D 1 et al. Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks [J]. Nature 1998, 396:152-155.
[1] Zhang L, Zhu Y, He Y et al, Preparation and performances of mesoporous TiO_2 film photocatalyst supported on stainless steel [J]. Applied Catalysis B: Environmental 2003, 40:287-292
[2] 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,2002, B, 87:122-129
[3] Yun H, Miyazawa K, Honma I et al, Synthesis of semicrystallized mesoporous TiO_2 thin films using triblock copolymer templates [J]. Materials Science and Engineering, 2003, C 23:487-494
[4] Wang Z, Jiang T, Du Y et al, Synthesis of mesoporous titania and the photocatalytic activity for decomposition of methyl orange [J]. Materials Letters, 2006, 60:2493-2496
[5] Xiao J, Peng T, Li R et al, Preparation, phase transformation and photocatalytic activities of cerium-doped mesoporous titania nanoparticles[J]. Journal of Solid State Chemistry, 2006, 179:1161-1170
[6] Mahurin S, Bao L,Yan W et al, Atomic layer deposition of TiO_2 on mesoporous silica[J]. Journal of Non-Crystalline Solids, 2006, 352:3280-3284
[7] 李春燕，李樊强，TiO_2的溶胶—凝胶过程研究[J]．硅酸盐学报，1996，24(3)： 338-341
[8] 王琳，吴忆宁，汪炎，溶胶—凝胶法制备纳米二氧化钛及其性能研究[J]．哈尔滨商业大学学报(自然科学版)，2006，22(3)：76-79
[9] 董素芳，制备纳米二氧化钛凝胶过程中若干因素对凝胶时间的影响[J]．山东理工大学学报(自然科学版)，2005，19(5)：94-97
[1] Imhof A, Pine D J, Ordered macroporous materials by emulsion templating [J].Nature, 1997, 389:948-951
[2] 齐凯，杨振忠，刘正平等，聚苯乙烯模板制备SiO_2三维有序孔材料[J]．科学通报，2000，45：992-994
[3] Fan H, Van Swol F, Lu Y et al, Multiphased assembly of nanoporous silica particles[J]. Journal of Non-Crystalline Solids, 2001, 285: 71-78
[4] Shane Carr C. Shantz D F, Non-ionic-microemulsion mediated growth of zeolite A[J]. Microporous and Mesoporous Materials 2005, 85: 284-292
[5] Axnanda S, Shantz D F, Cationic microemulsion-mediated synthesis of silicalite-1 [J]. Microporous and Mesoporous Materials, 2005, 84: 236-246
[6] Aikawa K, Kanoko K, Tamura T et al, Formation of fractal porous silica by hydrolysis of TEOS in a bicontinuous microemulsion [J]. Colloids and Surface A: Physicochemical and Engineering Aspects, 1999, 150: 95-104
[7] Moriguchi I, Hidaka R. Yamada H et al, Li-intercalation property of mesoporous anatase-TiO_2 synthesized by bicontinuous microemulsion-aided process [J]. Solid State Ionics, 2005, 176: 2361-2366
[8] Antonietti M, Bremser W, Muschenborn D et al, Synthesis and size control of polystyrene latices via polymerization in microemulsion [J]. Macromolecules. 1991, 24: 6636-6643
[9] Wu C, A simple model for the structure of spherical microemulsions [J]. Macromolecules, 1994, 27: 298-299
[10] Maria D A, Luan Z H, Klinowski J, Titanosilicate mesoporous molecular sieves MCM-41: synthesis and characterization [J]. Phys. Chem., 1996, 100: 2178-2182
[11] Jain S, Bates F S. On the origins of morphological complexity in block copolymer surfactants [J]. Science, 2003, 300: 460-464
© 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 |