具羧酸官能基之立方結構中孔洞二氧化矽的合成、鑑定及應用

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研究生：	林于萱 Yu-hsuan Lin
論文名稱：	具羧酸官能基之立方結構中孔洞二氧化矽的合成、鑑定及應用 Synthesis and Application of Carboxylic Acid-Functionalized Cubic Mesoporous Silica Materials
指導教授：	高憲明 Hsien-Ming Kao
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	118
中文關鍵詞：	中孔洞材料、羧酸官能基
外文關鍵詞：	mesoporous silica, Carboxylic acid groups
相關次數：	點閱：12 下載：0
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本論文主要是利用三嵌段共聚高分子Pluronic F127作為模板，將具有羧酸官能基的矽源CES (Carboxyethylsilanetriol sodium salt) 和TEOS (Tetraethyl orthosilicate) 作為共同矽源，在低量酸性條件下以直接共聚合成法進行合成，可得到孔穴狀 (cage) 的孔洞，且其孔洞規則排列為面心立方對稱結構 (Face-centered cubic structure, Fm3m)，也可將羧酸官能基的莫耳比例提高至45%，並利用X-ray 粉末繞射、固態核磁共振光譜、等溫氮氣吸脫附、紅外線光譜儀、熱重分析儀、穿透式電子顯微鏡及掃描式電子顯微鏡等儀器鑑定材料的結構，同時也鑑定官能基含量對孔洞性質的影響。
將上述所合成的中孔洞材料，其簡稱CK-x，x=[CES/(CES+TEOS)]應用在移除廢水中有機染料分子。將CK-x (x=0 - 40) 探討對亞甲基藍的吸附，其pH值愈高且官能基含量提高皆有助於提高吸附量，並且Langmuir 等溫吸附模式比 Freundlich 等溫吸附模式更適合描述CK-x吸附亞甲基藍之的系統。另外也探討四種染料分子Phenosafranine (酚藏花紅)、Methylene blue (亞甲基藍)、Orange II (橘色二號) 和Rhodamine B (羅丹明B)的吸附量，利用不同pH和材料中有無官能基之因素來探討不同染料之最佳吸附環境，並進一步探討吸附動力學。含羧酸官能基之中孔洞材料對於吸附陽離子染料 (酚藏花紅和亞甲基藍) 具有良好的表現，且四種染料吸附動力學皆屬Pseudo-second order模式。

Well-ordered mesoporous silicas CK-x [x=CES/(CES+TEOS)] functionalized with high loadings of carboxylic acid (-COOH) groups, up to 45 mol% of the silicon sites without degradation of ordered structures, have been successfully synthesized via co-condensation of Tetraethyl orthosilicate (TEOS) and Carboxyethylsilanetriol sodium salt (CES) templated with a triblock polymer Pluronic F127 at low HCl concentrations. All these materials have been characterized by powder X-ray diffraction (XRD), nitrogen sorption measurements, solid-state 13C and 29Si MAS NMR spectroscopy, thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The prepared mesoporous CK-x materials have been used as suitable adsorbent for four different dyes (Phenosafranine、Methylene blue、Orange II and Rhodamine B). It was observed that CK-x exhibited an excellent adsorption capacity of cationic molecules. The isotherm models and kinetic models properties were analyzed to describe the adsorption behavior of prepared materials. Langmuir mode and pseudo-second-order kinetics were well-fitted in the simulation of the adsorption behavior of dyes on prepared materials.

中文摘要...............I
Abstract...............II
謝誌...............III
目錄...............IV
圖目錄...............VIII
表目錄...............XI
第一章 緒論...............1
1-1中孔洞二氧化矽簡介...............1
1-2界面活性劑簡介...............4
1-2-1 界面活性劑結構與種類...............4
1-2-2 微胞的形成與結構...............6
1-2-3界面活性劑與矽氧化物的交互作用...............9
1-2-4 共聚高分子 (Block copolymer...............12
1-3 官能基化之中孔洞材料...............15
1-4  KIT-5介紹...............20
1-5 中孔洞材料之吸附的發展及應用...............22
1-6 研究動機與目的...............25
第二章 實驗部分...............26
2-1 實驗藥品...............26
2-2 實驗步驟...............27
2-2-1 合成具羧酸官能基的CK-x-as...............27
2-2-2以硫酸溶液裂解孔洞中的模板...............27
2-2-3 以酸鹼滴定鑑定孔洞材料中的酸當量...............27
2-2-4 染料檢量線之製作...............28
2-2-5  CK-x在不同pH值下吸附亞甲基藍實驗...............29
2-2-6  CK-x在不同反應時間吸附亞甲基藍實驗...............29
2-2-7  CK-30之重複使用性...............29
2-2-8  染料初始濃度對CK-x吸附亞甲基藍實驗...............30
2-2-9  CK-x在不同pH值下及不同反應時間的染料吸附實驗..............30
2-3 實驗設備...............31
2-3-1 實驗合成設備...............    31
2-3-2 實驗鑑定儀器...............    31
2-4 鑑定儀器之原理...............32
2-4-1 同步加速器光源...............32
2-4-2 X射線粉末繞射...............33
2-4-3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定...............34
2-4-4 傅立葉紅外線吸收光譜...............38
2-4-5 紫外光-可見光光譜...............38
2-4-6 熱重分析...............39
2-4-7 穿透式電子顯微鏡...............40
2-4-8 低真空掃描式電子顯微鏡    ...............41
2-4-9 固態核磁共振...............    42
第三章 結果與討論...............49
3-1 合成不同矽源比例的 CK-x...............49
3-1-1 CK-x系列XRD...............49
3-1-2 13C CP/MAS NMR...............51
3-1-3 29Si MAS NMR...............52
3-1-4 等溫氮氣吸脫附...............54
3-1-5 FT-IR紅外線光譜...............58
3-1-6 熱重分析...............60
3-1-7 TEM影像...............62
3-1-8 SEM影像...............64
3-1-9酸鹼滴定...............65
3-1-10表面電位...............67
3-2 CK-x吸附亞甲基藍染料吸附實驗...............68
3-2-1 CK-x在不同pH值下吸附亞甲基藍之效果...............68
3-2-2 CK-x在不同反應時間吸附亞甲基藍之效果...............68
3-2-3 染料初始濃度對CK-x吸附亞甲基藍...............68
3-2-4 等溫吸附模式...............    72
3-2-5 重複使用性...............76
3-3 CK-x對不同染料之吸附影響...............77
3-3-1 不同染料在不同環境下及不同時間的吸附...............77
3-3-2 動力吸附探討...............    81
第四章 結論...............84
第五章 參考文獻...............85
附錄一...............90
附錄二...............92
附錄三...............98

                                

(1)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. J. Am. Chem. Soc. 1992, 114, 10834.
(2)Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature 1992, 359.
(3)IUPAC Pure Apple. Chem 1972, 31.
(4)Raman, N. K. Chem. Mater. 1996, 8.
(5)Hoffmann, F.; Cornelius, M.; Morell, J.; Froba, M. Angew Chem Int Ed Engl 2006, 45, 3216.
(6)Stockholm Surfactants and Polymers in Aqueous Solution; John Wiley: New York, 1997.
(7)Israelachvili, J. N.; Mitchell, D. J.; Ninham, B. W. Biochimica et Biophysica Acta (BBA) - Biomembranes 1977, 470, 185.
(8)Soler-Illia, G. J. d. A. A.; Sanchez, C.; Lebeau, B.; Patarin, J. Chem. Rev. 2002, 102, 4093.
(9)Evans, F. D.; 2nd ed.; VHC: New York, 1999.
(10)Qi, L.; Ma, J.; Chen, H.; Zhao, Z. Colloids Surf., A : Physicochem. Eng. Aspects 1996, 111, 195.
(11)Holmerg, K. Surfactant and Polymers in Aqueous Solution; 2nd ed.; John Wiley & Sons Ltd: Endlang, 2003.
(12)Huo, Q.; Margolese, D. I.; Ciesia, U.; Feng, P.; Gier, T. E.; Sieger, P.; Leon, R.; Petroff, P. M.; Schuth, F.; Stucky, G., D. Nature 1994, 368.
(13)Iler, R. K. The Chemistry of Silica; John Wiley: New York, 1979.
(14)Schubert, U.; Husing, N. Synthesis of inorganic materials, Chapter 4; Wiley-Interscience publications: New York, 2000.
(15)Forster, S.; Antonietti, M. Adv. Mater. 1998, 10.
(16)Chu, B. Langmuir 1995, 11.
(17)Lopes, J. R.; Loh, W. Langmuir 1998, 14, 750.
(18)Almgren, M.; Brown, W.; Hvidt, S. Colloid Polym Sci 1995, 273, 2.
(19)Alexandridis, P.; Holzwarth, J. F.; Hatton, T. A. Macromolecules 1994, 27, 2414.
(20)Evans, D. F. The colloidal domain; VCH: New York, 1999.
(21)Zhao, D.; Huo, Q.; J., F.; Chmelka, B. F.; Stucky, G., D. J. Am. Chem. Soc. 1998, 120, 6024.
(22)Kim, J. M.; Sakamoto, Y.; Hwang, Y. K.; Kwon, Y.-U.; Terasaki, O.; Park, S.-E.; Stucky, G., D. J. Phys. Chem. B 2002, 106, 2552.
(23)Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G., D. Science 1998, 279, 548.
(24)Soler-Illia, G. J. d. A. A.; Crepaldi, E. L.; Grosso, D.; Sanchez, C. Curr. Opin. Colloid Interface Sci. 8 2003, 109.
(25)Kleitz, F.; Choi, S. H.; Ryoo, R. Chem. Commun. 2003, 2136.
(26)Sakamoto, Y.; Kaneda, M.; Terasaki, O.; Zhao, D. Y.; Kim, J. M.; Stuckyk, G.; Shin, H. J.; Ryoo, R. Nature 2000, 408, 11480.
(27)Kleitz, F.; Liu, D.; Anilkumar, G. M.; Park, I.-S.; Solovyov, L. A.; Shmakov, A. N.; Ryoo, R. J. Phys. Chem. B 2003,, 107, 14296.
(28)Kleitz, F.; Solovyov, L. A.; Anilkumar, G. M.; Choi, S. H.; Ryoo, R. Chem. Commun. 2004, 1536.
(29)Yu, C.; Yu, Y.; Zhao, D. Chem. Commun. 2000, 575.
(30)Matos, J. R.; Kruk, M.; Mercuri, L. P.; Jaroniec, M.; Zhao, L.; Kamiyama, T.; Terasaki, O.; Pinnavaia, T. J.; Liu, Y. J. Am. Chem. Soc. 2003, 125, 821.
(31)Stein, A.; Melde, B. J.; Schroden, R. C. Adv. Mater. 2000, 12.
(32)Burkett, S. L.; Sims, S. D.; Mann, S. Chem. Commun. 1996, 1367.
(33)Burleigh, M. C.; Markowitz, M. A.; Spector, M. S.; Gaber, B. P. J. Phys. Chem. B 2001, 105, 9935.
(34)Kao, H. M.; Shen, T. Y.; Wu, J. D.; Lee, L. P. Microporous Mesoporous Mater. 2008, 110, 461.
(35)Hall, S. R.; Fowler, C. E.; Lebeau, B.; Mann, S. Chem. Commun. 1999, 201.
(36)Lei, C.; Shin, Y.; Liu, J.; Ackerman, E. J. J. Am. Chem. Soc. 2002, 124, 11242.
(37)Liu, N.; Assink, R. A.; Brinker, C. J. Chem. Commun. 2003, 370.
(38)Ho, K. Y.; McKay, G.; Yeung, K. L. Langmuir 2003, 19, 3019.
(39)Rosenholm, J. M.; Czuryszkiewicz, T.; Kleitz, F.; Rosenholm, J. B.; Linden, M. Langmuir 2007, 23.
(40)Bruzzoniti, M. C.; Prelle, A.; Sarzanini, C.; Onida, B.; Fiorilli, S.; Garrone, E. Journal of separation science 2007, 30, 2414.
(41)Han, L.; Sakamoto, Y.; Terasaki, O.; Li, Y.; Che, S. J. Mater. Chem. 2007, 17, 1216.
(42)Tsai, C. T.; Pan, Y. C.; Ting, C. C.; Vetrivel, S.; Chiang, A. S.; Fey, G. T.; Kao, H. M. Chem Commun 2009, 5018.
(43)Chen, C. S.; Chen, C. C.; Chen, C. T.; Kao, H. M. Chem Commun 2011, 47, 2288.
(44)Kao, H. M.; Chung, C. H.; Saikia, D.; Liao, S. H.; Chao, P. Y.; Chen, Y. H.; Wu, K. C. Chemistry, an Asian journal 2012, 7, 2111.
(45)Wu, H. Y.; Shieh, F. K.; Kao, H. M.; Chen, Y. W.; Deka, J. R.; Liao, S. H.; Wu, K. C. Chem. Eur. J. 2013, 19, 6358.
(46)Vinu, A.; Miyahara, M.; Mori, T.; Ariga, K. J. Porous Mater. 2006, 13, 379.
(47)Morishige, K.; Yasunaga, H. J. Phys. Chem. C 2007, 111, 9488.
(48)Balasubramanian, V. V.; Srinivasu, P.; Anand, C.; Pal, R. R.; Ariga, K.; Velmathi, S.; Alam, S.; Vinu, A. Microporous Mesoporous Mater. 2008, 114, 303.
(49)Wu, C. Y.; Hsu, Y. T.; Yang, C. M. Microporous Mesoporous Mater. 2009, 117, 249.
(50)Hsu, Y. T.; Chen, W. L.; Yang, C. M. J. Phys. Chem. C 2009, 113, 2777.
(51)Kalita, P.; Sathyaseelan, B.; Mano, A.; Zaidi, S. M.; Chari, M. A.; Vinu, A. Chem. Eur. J. 2010, 16, 2843.
(52)Anand, C.; Srinivasu, P.; Mane, G. P.; Talapaneni, S. N.; Dhawale, D. S.; Wahab, M. A.; Priya, S. V.; Varghese, S.; Sugi, Y.; Vinu, A. Microporous Mesoporous Mater. 2012, 160, 159.
(53)Hata, H.; Saeki, S.; Kimura, T.; Sugahara, Y.; Kuroda, K. Chem. Mater. 1999, 11, 1110.
(54)Feng, X.; Fryxell, G. E.; Wang, L. Q.; Kim, A. Y.; Liu, J.; Kemner, K. M. Science 1997, 276, 923.
(55)Jin, X.; Jiang, M. Q.; Shan, X. Q.; Pei, Z. G.; Chen, Z. Journal of colloid and interface science 2008, 328, 243.
(56)Zhuang, X.; Wan, Y.; Feng, C.; Shen, Y.; Zhao, D. Chem. Mater. 2009, 21, 706.
(57)Duran, C.; Ozdes, D.; Gundogdu, A.; Senturk, H. B. J. Chem. Eng. Data 2011, 56, 2136.
(58)Yang, C. M.; Zibrowius, B.; Schmidt, W.; Schuth, F. Chem. Mater. 2004, 16, 2918.
(59)http://www.nsrrc.org.tw/.
(60)Brunauer, S.; Deming, L. S.; Deming, W. E.; Teller, E., 62.
(61)Gregg, S. J.; Sing, K. S. W. Adsorption, Surface Area and Porosity; 2nd ed.; Academic press: New York, 1982.
(62)Viti, C.; Frezzotti, M. L. Lithos 2001, 55, 125.
(63)http://www.me.ntut.edu.tw.
(64)高憲明 CHEMISTRY（THE CHINESE CHEM. SOC., TAIPEI） 2004, 62, 285~298.
(65)高憲明化學 2009, 第六十六卷第三期, 209.
(66)Wu, C.-Y.; Hsu, Y.-T.; Yang, C.-M. Microporous and Mesoporous Materials 2009, 117, 249.
(67)Espindola-Gonzalez, A.; Martinez-Hernandez, A. L.; Angeles-Chavez, C.; Castano, V. M.; Velasco-Santos, C. Nanoscale research letters 2010, 5, 1408.
(68)Chang, M. Y.; Juang, R. S. Journal of colloid and interface science 2004, 278, 18.
(69)Bhattacharyya, K. G.; Sharma, A. Dyes Pigm. 2005, 65, 51.
(70)Al-Ghouti, M. A.; Khraisheh, M. A. M.; Allen, S. J.; Ahmad, M. N. J. Environ. Manage. 2003, 69, 229.
(71)Abramian, L.; El-Rassy, H. Chem. Eng. J. 2009, 150, 403.
(72)El-Aziz A. Said; Abdel A. M. Aly, A.; M. Abd El-Wahab, M.; A. Soliman, S.; A.Abd El-Hafez, A.; Helmey, V.; N.Goda, M. Resources and Environment 2012, 2, 93.
(73)Li, L.; Liu, S.; Zhu, T. J. Environ. Sci. 2010, 22, 1273.
(74)施超环境化学 ENVIRONMENTAL CHEMISTRY 2013, 第32 卷.
(75)O Shannessy, D. J.; Winzor, D. J. Anal. Biochem. 1996, 236, 275.
(76)Ho, Y. S. Journal of hazardous materials 2006, 136, 681.
(77)Pan, Y. C.; Gavin Tsai, H. H.; Jiang, J. C.; Kao, C. C.; Sung, T. L.; Chiu, P. J.; Saikia, D.; Chang, J. H.; Kao, H. M. The Journal of Physical Chemistry C 2012, 116, 1658.

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