跳到主要內容

臺灣博碩士論文加值系統

(54.161.24.9) 您好!臺灣時間:2022/01/17 12:54
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果 :::

詳目顯示

我願授權國圖
: 
twitterline
研究生:周孟達
研究生(外文):Meng-Ta Chou
論文名稱:中孔型沸石的晶體形狀之研究
論文名稱(外文):Morphogenesis of Shapes in Mesoporous Molecular Sieves
指導教授:陳郁文陳郁文引用關係
指導教授(外文):Yu-Wen Chen
學位類別:碩士
校院名稱:國立中央大學
系所名稱:化學工程與材料工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:英文
論文頁數:86
中文關鍵詞:麵條狀球形晶體形狀中孔分子篩HMS
外文關鍵詞:HMSMesoporousSpherical ParticlesNoodle-like ParticlesSynthesisMorphologiesMolecular Sieves
相關次數:
  • 被引用被引用:0
  • 點閱點閱:167
  • 評分評分:
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0

HMS是利用1o胺界面活性劑(C12H25NH2, DDA)當作模版與中性醇氧矽(TEOS)以氫鍵結合在室溫下所合成出來的中孔分子篩。本研究改變了許多製備上的條件和配方,包括TEOS加入速度、DDA濃度和醇水比例,合成出均一粒徑的球形HMS和麵條狀的HMS。在鑑定樣品的物理性質上,以X光繞射分析(XRD)鑑定其晶相;由氮吸附、脫附分析測定表面積、孔洞大小及孔洞分布;利用熱重損失分析儀(TGA)做熱分析;藉掃描式電子顯微鏡(SEM)觀察外部形態;最後以穿透式電子顯微鏡了解內部結構。
當TEOS加入的速度愈快,則HMS顆粒愈小且聚集嚴重,但是組織孔洞體積會增加;反之,當TEOS加入的速度愈慢,所得到的顆粒會變大,但是幾乎沒有組織孔洞體積。
在均一粒徑的球形HMS的合成上,隨著DDA的濃度的降低,HMS的孔洞會隨之縮小,且會由小顆粒變成有裂痕的大顆粒,當[DDA]=0.0159 M時,可以得到均一且無裂痕的HMS球形粒子。HMS球形粒子具有很大的表面積(1012 m2/g)和中孔洞(2 nm)。另外,TEOS加入的速度也會影響球形粒子的大小。
麵條狀的HMS是在不含乙醇當共溶劑的條件下所合成出來的,但是大部分仍為小顆粒。這些麵條狀的HMS長度有次微米到數個微米,而直徑約有0.1μm。麵條狀的HMS佔全部樣品的比例並沒有與TEOS的濃度有絕對關係。但在[TEOS]=0.4693 M時,麵條狀的HMS所佔的比例最多;[TEOS]=0.2346 M時,最少;而在[TEOS]=0.0587 M時,發現直徑22μm表面像哈密瓜的HMS球體。


A neutral templating route to mesoporous molecular sieves has been reported by Pinnavaia based on hydrogen bonding interactions and self-assembly between neutral primary amine micelles and neutral inorganic precursors. The effect of cosolvent on the morphology of HMS is still not clear. Hexagonal mesoporous silica (HMS) was prepared at ambient temperature by using dodecylamine (DDA) as the template and tetraethyl orthosilicate (TEOS) as a silica derivative in this study. The properties of HMS were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and N2 adsorption/desorption. The morphology of HMS is usually irregular and small particle. To investigate the morphological change of this HMS material, the samples prepared at various TEOS adding rate, solvent compositions and compositions were studied. With decreasing TEOS adding rate, the sizes of HMS particles increase and the textural porosity reduces. With the concentration of DDA reduces, HMS particles become crackled bigger particles from small particles and the pore size reduces from 2.32nm to 1.72 nm. As [DDA]=0.0159 M, the spherical particles of HMS silicas with uniform size and isolated are obtained. Besides, TEOS adding rate also affects the size of the spheroids. The noodle-like structures are prepared in HMS silicas prepared at R/H ratio=0. These noodle-like structures were about 0.1μm in diameter and about submicrometer to several micrometers in length. In a series of HMS silicas synthesized by various [TEOS], the irregular trends indicated that it is required to prepare the samples under non-alcoholic solution to have non-spherical particles. However, some other parameters may also play a role.


Abstract…………………………………………………………………………i
Table of Contents……………………………………………………………ii
List of Tables………………………………………………………………iv
List of Figures………………………………………………………………v
CHAPTER 1. INTRODUCTION……………………………………………………1
1.1Classification of Porous Materials…………………………1
1.2Synthesis of Mesoporous Materials……………………………1
1.2.1Synthesis and classification of mesoporous materials…1
1.2.2Surfactant templates……………………………………………3
1.2.3Formation mechanism………………………………………………5
1.2.4Classification of hexagonal mesoporous materials………8
1.3Synthesis of Hexagonal Mesoporous Silica (HMS) …………10
1.4Objective and Scope………………………………………………10
CHAPTER 2. LITERATURE REVIEW………………………………………………12
2.1 Synthesis and Characteristics of HMS………………………………12
2.2 Preparation of Mesoporous Structure with a Controlled
Morphology…………………………………………………………………18
CHAPTER 3. EXPERIMENTAL………………………………………………………27
3.1Chemicals………………………………….…………………………27
3.2Synthesis Methods………..……………….………………………27
3.2.1Synthesis of spheroid particles……….………………………27
3.2.2Synthesis of noodle-like particles……………………………27
3.2.3Others samples………………………………………………………28
3.3Characterization……………………………………………………30
3.3.1X-ray diffraction (XRD)……………………………………………30
3.3.2N2 sorption……………………………………………………………30
3.3.3Thermogravimetric analysis (TGA)………………………………30
3.3.4Scanning electron microcopy (SEM)………………………………31
3.3.5Transmission electron microscopy (TEM)………………………31
CHAPTER 4. EFFECTS OF THE ADDITIVES………………………………………32
4.1 Effects of TEOS Adding Rate and Aging Time…………………32
4.2 Effects of the Additives…………………………………………39
CHAPTER 5. MESOPOROUS SILICA SPHERE…………………………………………43
5.1 Effects of the Concentration of DDA……………………………43
5.2 Effects of Stirring Rate…………………………………………51
5.3 Effects of TEOS Adding Rate………………………………………53
CHAPTER 6. MESOPOROUS SILICA of NOODLE-LIKE SHAPE………………………61
6.1 Effects of R/H Volume Ratio………………………………………61
6.2 Effects of the Concentration of TEOS to Noodle-like
Structures……………………………………………………………73
CHAPTER 7. CONCLUSION …………………………………………………………81
REFERENCE……………………………………………………………………………82


Abdel-Fattah, T. M. and Pinnavaia T. J., 〝Tin-Substituted Mesoporous Silica Molecular Sieves (Sn-HMS): Synthesis and Properties as A Heterogeneous Catalyst for Lactide Ring- Oprning Polymerization〞, Chem. Commun., 665-666 (1996)Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K. D.; Chu, C. T-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.; Higgins, J. B. and Schlenker, J. L. 〝A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates〞, J. Am. Chem. Soc. 114, 10834-10843 (1992)Brinker, C. J. and Scherer G. W., 〝SOL-GEL SCIENCE〞(1990)Bruinsma, P. J.; Kim, A. Y.; Liu, J.; Buresh, S., 〝Mesoporous Silica Synthesized by Solvent Evaporation: Spun Fibers and Spray-Dried Hollow Spheres〞, Chem. Mater., 9, 2507-2512 (1997)Cassiers, K.; Van Der Voort, P.; Vansant, E. F., 〝Synthesis of Stable and Directly Usable Hexagonal Mesoporous Silica by Efficuent Amine Extraction in Acidified Water〞, Chem. Commun., 2489-2490 (2000) Chen, C. Y.; Burkett, S. L.; Lin, H. X.; Davis, M. E., 〝Studies on Mesoporous Materials Ⅱ. Synthesis Mechanism of MCM-41〞, Microporous Mater., 2, 27-34 (1993)Di Renzo, F.; Testa, F.; Chen, J. D.; Cambon, H.; Galarneau, A.; Plee, D.; Fajula, F., 〝Textural control of micelle-templated mesoporous silicates:the effects of cosufactants and alkalinilty〞, Microporous and mesoporous material, 28, 437-446 (1999)Firouzi, A.; Monnier, A.; Bull, L. M.; Besier, T.; Sieger, P.; Huo, Q.; Walker, S. A.; Zasadzinski, J. A.; Glinka, C.; Nicol, J.; Margoles, D.; Stucky, G. D., Chemlka, B. F., 〝Cooperative Organization of Inorganic-Surfactant and Biomimetic Assemblies Science〞, 267, 1138-1143 (1995)Fu, Z.; Chen, J.; Yin, D.; Zhang, L.; Zhang, Y., 〝Highly Effectives Cu-HMS Catalyst for Hydroxylation of Phenol〞, Catalysis Letters, 105-108 (2000)Huo, Q.; Feng, J.; Stuck, G. D.; Schuth, F., 〝Preparation of Hard Mesoporous Silica Spheres〞, Chem. Mater., 9, 14-17 (1997)Israelachvili, J. N.; Mitchell, D. J.; Ninham, B. W., J. Chem. Soc., Faraday Trans., 2, 72, 1527 (1976)Kholdeeva, O. A.; Derevyankin, A. Yu.; Shmakov, A. N.; Trukhan, N. N.; Paukshtis, E. A.; Tuel, A.; Romannikov, V. N., 〝Alkene and Thioether Oxidations with H2O2 over Ti-Containing Mesoporous Mesophase catalysts〞, J. Mol. Cata. A: Chem., 158, 417-421 (2000)Khushalani, D.; Ozin, G. A.; Kuperman, A.〝Glycometallate Surfactant. Part1: Non-aqueous Synthesis of Mesoporous Silica〞, J. Mater. Chem., 9, 1483-1489 (1999)Kostova, N. G.; Spojakina, A. A.; Jiratova, K.; Solcova, O.; Dimitrov, L.D.; Petrov, L. A., 〝Hexagonal Mesoporous Silicas with and without Zr as Support for HDS catalysts〞, Catalysis Today, 65, 217-223 (2001)Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C. and Beck, J. S. 〝Ordered Mesoporous Molecular Sieves synthesized by Liquid Crystal Template Mechanism〞, Nature, 359, 710-712 (1992)Lin, H. P. and Mou, C. Y., 〝Tubules-Within-a-Tubule Hierarchical Order Mesoporous Molecular Sieves in MCM-41〞, Science, 273, 9, 765-767 (1996)林弘萍, 〝中孔洞沸石的合成及其晶體形狀的研究〞, 博士學位論文,國立台灣大學化學研究所 (1995)Macquarrie, D. J.; Jackson, D. B.; Tailland, S. and Utting, K. A.〝Organically Modified Hexagonal Mesoporous Silicas (HMS)─Remarkable Effect of Preparation Solvent on Physical and Chemical Properties〞, J. Mater. Chem., 11, 1843-1849 (2001) Monnier, A. Fchuth, Q.; Huo, Q.; Kumar, D.; Margoleses, R. S.; Maxwell, G. D.; Stucky, M.; Krishnamutry, P.; Petroff, A.; Firouzi, M.; Janicke, D.;Chmelka, B. F., Science, 261, 1299 (1993)Mori, Y. and Pinnavaia, T. J.〝Optimizing Organic Functionality in Mesostructured Silica: Direct Assembly of Mercaptopropyl Groups in Wormhole Framework Structures〞, Chem. Mater., 13, 2173-2178 (2001)Ogawa. M., 〝A Simple Sol-gel Route for The Preparation of Silica —surfactant Mesostructured Materials〞, Chem. Commun., 1149-1150 (1996)Pauly, T. R.; Lin, Y.; Pinnavaia, T. J.; Billinge, S. J. L.; Rieker, T. P., 〝Textural Mesoporsity and The Catalytic Activity of Mesoporous Molecular Sieves with Wormhole Framework Structures〞, J. Am. Soc., 121, 8835-8842 (1999)Pauly, T. R. and Pinnavaia, T. J., 〝Pore Size Modification of Mesoporous HMS Molecular Sieves Silicas with Wormhole Framework Structures〞, Chem. Mater., 13, 987-993 (2001)Schacht, S.; Huo, Q.; Voigt-Martin, I. G.; Stuck, G. D.; Schuth, F., 〝Oil-Water Interface Templation of Mesoporous Macroscale Structures〞, Science, 273, 9, 768-770 (1996)Schumacher, K.; Grun, M.; Unger, K. K., 〝Novel Synthesis of Spherical MCM-48〞, Microporous and Mesoporous Materials, 1999, 27, 201-206Tanev, P. T. and Pinnavaia, T. J., 〝A neutral templating route to mesoporous molecular sieves〞, Science, 267, 865-867 (1995)Tanev, P. T. and Pinnavaia, T. J.〝Mesoporous Silicas Molecular Sieves Prepared by Ionic and Neutral Surfactant Templating: A Comparison of Physical Properties〞, Chem. Mater., 8, 2068-2079 (1996)Tanev, P. T.; Ling, Y.; Pinnavaia, T. J.〝Assembly of Mesoporous Lamellar Silicas with Hierarchical Particle Architectures〞, J. Am. Chem. Soc., 119, 8616-8624 (1997)Tollbert, S. H.; Schaffer, T. E.; Jianglin, F.; Hansma, P. K.; Stucky, G.D., 〝A New Phase of Oriented Mesoporous Silicate Thin Films〞, Chem. Mater., 9, 1962-1967 (1997)Tuel, A. and Gontier, S., 〝Synthesis and Characterization of Trivalent Metal Containing Mesoporous Silica Obtained by a Neutral Templating Route〞, Chem. Mater., 8, 114-122 (1996)Ulagappan, N.; Neeral; Raju, B. V. N.; Rao, C. N. R., 〝Prepartion of Lamellar and Hexagonal Forms of Mesoporous Silica and Zirconia by the Neutral Amine Route: Lamellar-Hexagonal Transformation in the Solid State〞, Chem. Commun., 2243-2244 (1996)Yamashita, H.; Yoshizawa, K.; Ariyuki, M.; Higashimoto, S.; Che, M.; Anpo, M., 〝Photocatalytic Reaction on Chromium Containing Mesoporous Silicas Molecular Sieves (Cr-HMS) under Visible Light Irradiation: Decomposition of NO and Partial Oxidation of Propane〞, Chem. Commun., 435-436 (2001)Yang, H.; Kuperman, A.; Coombs, N.; Mamiche-Afara, S.; Ozin, G. A., 〝Synthesis of Oriented Films of Mesoporous Silica on Mica〞, Nature, 379, 22, 703-705 (1996a)Yang, H.; Coombs, N.; Sokolov, I.; Ozin, G. A., 〝Free-Standing and Oriented Mesoporous Silica Films Grown at The Air-Water Interface〞, Nature, 381, 13, 589-592 (1996b)Yang, H.; Coombs, N.; Sokolov, I.; Ozin, G. A., 〝Registered Growth of Mesoporous Silica Films on Graphite〞, J. Mater. Chem., 7, 1285-1290 (1997)Zhang, W.; Froba, M.; Wang, J.; Tanev, P. T.; Wong, J.; Pinnacaia, T. J.〝Mesoporous Titanosilicate Molecular Sieves Prepared at Ambient Temperature by Electrostatic (S+I-, S+X-I+) and Neutral (SoIo) Assembly Pathways: a Comparison of Physical Properties and Catalytic Activity for Peroxide Oxidations〞, J. Am. Chem. Soc., 118, 9164-9171 (1996a)Zhang, W.; Wang, J.; Tanev, P. T.; Pinnacaia, T. J.〝Catalytic Hydroxylation of Benzene over Transition-Metal Substituted Hexagonal Mesoporous Silicas〞, Chem. Commun., 979-980 (1996b)Zhang, W.; Pauly, T. R.; Pinnacaia, T. J.〝Tailoring the Framework and Textural Mesoporous of HMS Molecular Sieves Through an Electrically Neutral (SoIo) Assembly Pathways〞, Chem. Mater., 9, 2491-2498 (1997)
QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top