目錄....................................................Ⅰ 圖索引..................................................Ⅳ 表索引..................................................Ⅷ 第一章緒論..............................................1 1-1溶膠凝膠法...........................................2 1-2以模板製備多孔性材料.................................5 1-2-1界面活性劑模板.....................................6 1-2-2非界面活性劑模板...................................8 1-3研究之目的..........................................10 第二章實驗.............................................11 2-1實驗藥品與儀器......................................12 2-1-1實驗藥品..........................................12 2-1-2儀器..............................................12 2-2多孔性材料之製備....................................13 2-2-1添加模板分子製備多孔性材料........................13 2-2-2添加反應性模板分子製備多孔性材料..................14 2-2-3不添加模板分子製備多孔性材料......................14 2-2-3-1改變pH值及不同鍛燒溫度..........................14 2-2-3-2改變水含量和反應時間 ............................18 2-3儀器分析............................................18 2-3-1孔徑參數之測定....................................18 2-3-2熱重損失測試......................................18 2-3-3玻璃轉移溫度(Tg)測試..............................20 2-3-4紅外線光譜分析....................................20 2-3-5 SEM表面結構分析..................................20 2-3-6 X-ray繞射分析....................................20 2-3-7 TEM表面結構型態..................................20 第三章結果與討論.......................................22 3-1添加模板分子製備多孔性材料..........................23 3-1-1 ASAP表面積、孔洞體積及孔徑大小分佈之分析.........23 3-1-1-1以丙烯酸為模板分子製備多孔性材料................25 3-1-1-2以順丁烯二酸、草酸為模板分子製備多孔性材料......29 3-1-1-3以乳酸為模板分子製備多孔性材料..................35 3-1-1-4四種模板分子製備多孔性材料之比較................39 3-1-2 FTIR分析.........................................39 3-1-3 X-ray繞射分析....................................43 3-1-4 TEM表面結構分析..................................43 3-2添加反應性模板分子製備多孔性材料....................47 3-2-1有機無機混成體之表面積、孔洞體積及孔徑大小分佈....47 3-2-2有機無機混成體熱重損失分析........................53 3-2-3有機無機混成體玻璃轉移溫度探討....................53 3-2-4 FTIR分析.........................................56 3-2-5有機無機混成體表面結構分析........................60 3-3不添加模板分子製備多孔性材料........................64 3-3-1改變pH值及不同鍛燒溫度之結果......................64 3-3-1-1 ASAP表面積、孔洞體積及孔徑大小分佈之分析.......64 3-3-1-2 X-ray繞射分析..................................68 3-3-1-3 TEM表面結構分析................................68 3-3-2改變水含量及反應時間之結果........................68 第四章 結論............................................75 參考文獻...............................................78 圖索引 Fig.1-1 The hydrolysis and condensation of silane.......................3 Fig.1-2 Gel structure for acid and base catalyst reaction...............4 Fig.1-3 Liquid-crystal templating(LCT) mechanism proposed by Beck et al. showing two possible pathways for the formation of MCM-41：(1) liquid-crystal-initiated and (2)silica-initiated.......................................7 Fig.2-1 Synthesis of the porous silica materials by adding template compound via sol-gelprocess.....................................................15 Fig.2-2 Synthesis of the porous silica materials by adding reactive template compound via sol-gel process...........................................16 Fig.2-3 Synthesis of the porous silica materials by adjusting pH value via sol-gel process............................................................17 Fig.2-4 Synthesis of the porous materials by changing reaction time via sol-gel process................................................................19 Fig.3-1 IUPAC classification of adsorption isotherms...................24 Fig.3-2 N2 adsorption－desorption isotherms for the porous silica materials prepared with acrylic acid as the template compound....................26 Fig.3-3 BJH pore size distribution curves derived from the desorption branches for the porous silica materials prepared with acrylic acid as the template compound..........................................27 Fig.3-4 N2 adsorption－desorption isotherms for the porous silica materials prepared with maleic acid as the template compound.....................30 Fig.3-5 N2 adsorption－desorption isotherms for the porous silica materials prepared with oxalic acid as the template compound.....................31 Fig.3-6 BJH pore size distribution curves derived from the desorption branches for the porous silica materials prepared with maleic acid as the template compound..........................................32 Fig.3-7 BJH pore size distribution curves derived from the desorption branches for the porous silica materials prepared with oxalic acid as the template compound..........................................33 Fig.3-8 N2 adsorption－desorption isotherms for the porous silica materials prepared with lactic acid as the template compound.....................36 Fig.3-9 BJH pore size distribution curves derived from the desorption branches for the porous silica materials prepared with lactic acid as the template compound..........................................37 Fig.3-10 The relationship between the a)BET surface area b)Total pore volume and the content of the acrylic acid, maleic acid and oxalic acid........................................................40 Fig.3-11 The relationship between the a)BET surface area b)Total pore volume and the content of the acrylic acid and lactic acid........41 Fig.3-12 IR spectra of (a)SiO2 (b)LAC20 (c)LAC20-600(d)LAC80 (e)LAC80-600....................................................................42 Fig.3-13 Powder XRD pattern of the sample (a) LAC80 (b)AA80(c)MaA80 (d)OA80 after calcinations.....................................................44 Fig.3-14 TEM images for LAC80 after calcinations (a) 105 times (b) 4×105 times..................................................................45 Fig.3-15 N2 adsorption and desorption curves of PMAA/SiO2 hybrid materials with different PMAA weight content after calcinations.......................48 Fig.3-16 Pore diameter distribution of PMAA/SiO2 hybrid materials with different PMAA weight content after calcinations.......................49 Fig.3-17 N2 adsorption and desorption curves of PAA/SiO2 hybrid materials with different PAA weight content after calcinations........................50 Fig.3-18 Pore diameter distribution of PAA/SiO2 hybrid materials with different PAA weight content after calcinations..................................51 Fig.3-19 TGA curves of (a)SiO2gel (b)PMAA-29 (c)PMAA-42 (d)PMAA-59 (e)Pure PMAA...................................................................54 Fig.3-20 TGA curves of (a)SiO2 gel (b)PAA-23 (c)PAA-38 (d)PAA-55 (e)PAA-71 (f)Pure PAA...............................................................55 Fig.3-21 DSC curves of (a) Pure PMAA (b)PMAA-29 (c)PMAA-74.............57 Fig.3-22 DSC curves of (a)Pure PAA (b)PAA-23 (c)PAA-71.................58 Fig.3-23 IR spectra of (a)SiO2 (b)Pure PMAA (c)PMAA-74 (d)PMAA-74-600..59 Fig.3-24 IR spectra of (a)SiO2 (b)PAA-23 (c)PAA-71 (d)PAA-71-600.......61 Fig.3-25 SEM photographs of organic-inorganic hybrid materials before calcinations (a) PMAA-29 (b) PMAA-74 (c) PAA-23 (d) PAA-71......62 Fig.3-26 SEM photographs of organic-inorganic hybrid materials after calcinations (a) PMAA-74 (b) PAA-71....................................63 Fig.3-27 N2 adsorption－desorption isotherms for the porous silica materials prepared at different pH values and calcinations temperature without adding template compounds.....................................................65 Fig.3-28 BJH pore size distribution curves derived from the desorption branches for the porous silica materials prepared at different pH values and calcinations temperature without adding template compounds.............66 Fig.3-29 Powder XRD pattern of (a)pH5-600 (b)pH6-600 (c)pH8-600........69 Fig.3-30 TEM images for pH8-600........................................70 Fig.3-31 N2 adsorption－desorption isotherms for the porous silica materials prepared at different H2O/TEOS ratio and reaction time without adding template compounds..............................................................72 Fig.3-32 BJH pore size distribution curves derived from the desorption branches for the porous silica materials prepared at different H2O/TEOS ratio and reaction time without adding template compounds........................73 表索引 Table3-1 Preparation conditions and the results of the porous silica gels by adding acrylic acid as the template compound...................28 Table3-2 Preparation conditions and the results of the porous silica gels by adding maleic acid and oxalic acid as the template compound....34 Table3-3 Preparation conditions and the results of the porous silica gels by adding lactic acid as the template compound....................38 Table3-4 Preparation conditions of PMAA/SiO2 & PAA/SiO2 hybrid materials and its properties after calcinations......................................52 Table3-5 Preparation conditions and results of the porous silica without adding template compounds.(Effect on pH values and calcinations temperature)..........................................67 Table 3-6 Preparation conditions and results of the porous silica without adding template compounds.(Effect on H2O/TEOS ratio and reaction time)..................................................................74