簡易檢索 / 詳目顯示

回結果列表
研究生： 孫碧芸
Bi-Yun Sun
論文名稱： 聚乙烯亞胺(PEI)修飾之官能化磁性奈米吸附劑的製備與應用於環境分析
Preparation of Magnetic Nano-adsorbent Functionalized with Polyethyleneimine and Application for Environmental Analysis
指導教授： 凌永健
Yong-Chien Ling
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 81
中文關鍵詞： 磁性奈米粒子 、有機酸 、無機離子 、環境
相關次數： 點閱：2  下載：0 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • 本研究製備表面修飾有聚乙烯亞胺(PEI)超順磁性奈米吸附劑，利用其奈米級尺寸所表現的大表面積及PEI所具有的化學特性，可以應用於空氣中有機酸及水溶液中的無機陰/陽離子的吸附劑。
    製備方法為首先以化學共沉澱法合成磁性奈米粒子，透過PEI分子做表面官能化修飾，以特性分析確認其表面成功的修飾上PEI分子，BET表面積證實其具有大表面積，屬中等吸附力的吸附劑，且具備超順磁的特性，可提供後續應用為吸附劑時有利的條件。
    於空氣中有機酸的應用，本研究所製備的磁性奈米吸附劑對於有機酸比商業化吸附劑Tenax TA具較佳的吸附及脫附能力。相較於苯環類的化合物，對於有機酸也有較好的選擇性。於水溶液中的無機陰/陽離子的應用，可以同時吸附無機陰離子和陽離子，且在pH 6調態下有最佳的吸附能力，分別沖提無機陰/陽離子時也具有不錯的回收率。本研究所製備的磁性奈米吸附劑可為具有雙重應用價值的吸附劑，結合奈米科技與環境分析，將有助於改善汙染物的分析方法。

    This research prepared magnetic nanoparticles (MNPs) surface modified with polyethyleneimine (PEI), demonstrated their use as adsorbent in gas and liquid phase. MNPs possess the characteristics of high surface area per volume and easy handling by external magnetic field. These novel properties are of great interest for researches from a wide range of disciplines. Both polar groups (amine) and apolar groups (ethylene) are present on the macromolecular chains of PEI, which enable MNPGAPEI to adsorb compounds like organic acids. PEI is a water-soluble polymeric amine and with many nitrogen atoms on the chains, which can produce very strong chelating action for inorganic cations. Besides, PEI is a cationic polyelectrtolyte in aqueous solutions, so there is a strong electrostatic interaction with negatively charged species like inorganic anions. The dual features of PEI permit MNPGAPEI as a universal adsorbent for both inorganic cations and anions.
    MNPGAPEI were demonstrated as adsorbents for carboxylic acids (analytes are acetic acid, propionic acid, butanoic acid, valeric acid and iso-valeric acid), inorganic cation (Pb), and anion (As). FT-IR and zeta potential analysis were used to verify the surface functional group. Results demonstrated that organic acids were effectively adsorbed onto 50-mg of MNPGAPEI packed in a glass sorbent tube. MNPGAPEI show better adsorption and desorption ability for organic acids than Tenax TA. Optimal desorption temperature and time was 225 ℃ and 6 min, respectively. MNPGAPEI show better selectivity toward organic acid than benzene-like compounds.
    In aqueous solution, MNPGAPEI possess dual affinity toward both caions (Pb) and anions (As) at pH 6. Desorption study of inorganic cation or anion shows good recoveries. It is expected that the MNPGAPEI could be used as a novel and functional solid adsorbent material for trapping carboxylic acids from atmosphere and inorganic cations and anions from aqueous sample.

    第一章 緒論 1 1.1 奈米材料與奈米技術 1 1.2 磁性奈米材料 3 1.2.1 磁性奈米粒子的製備方法 4 1.2.2 磁性奈米粒子的表面修飾 6 1.3 空氣中有機酸及水體中無機陰/陽離子之分析現況 7 1.3.1空氣中的有機酸 7 1.3.1.1 現行採樣及分析方法 8 1.3.1.2 固體吸附劑的選擇 9 1.3.2 水體中的無機陰/陽離子 11 1.3.2.1 無機陰/陽離子的吸附劑 12 1.4 研究動機與目的 13 第二章 利用化學共沈澱法製備磁性奈米粒子及其表面修飾 22 2.1 實驗方法 22 2.1.1 試劑與儀器 22 2.1.2 化學共沈澱法製備磁性奈米粒子 23 2.1.3 利用聚乙烯亞胺（PEI）修飾磁性奈米粒子 24 2.1.4 特性分析 24 2.2 結果與討論 29 2.3結論 33 第三章 PEI修飾之官能化磁性奈米吸附劑應用於環境分析 42 3.1 PEI修飾之官能化磁性奈米吸附劑/熱脫附氣相層析質譜儀應用於空氣中有機酸之測定 42 3.1.1 實驗方法 42 3.1.1.1 試劑 42 3.1.1.2 標準氣體配製 42 3.1.1.3 吸附管的製備 43 3.1.1.4 幫浦採樣方式 44 3.1.1.5 熱脫附氣相層析質譜儀分析系統 44 (1)氣相層析質譜儀 44 (2)冷凍濃縮熱脫附儀 45 3.1.2 結果與討論 46 3.1.2.1 吸附劑效能確認 46 (1)空白測試 46 (2) 吸附能力測試及比較 46 (3) 熱脫附條件最佳化條件測試 48 (4) 選擇性測試 49 3.1.2.2 分析方法確效 50 (1) 檢量線建立 50 (2) 方法偵測極限 50 (2) 精密度及準確度 50 3.1.2.3 空氣真實樣品分析 51 3.1.3 結論 52 3.2 PEI修飾之官能化磁性奈米粒子吸附劑應用於吸附無機陰/陽離子 53 3.2.1實驗方法 53 3.2.1.1試劑、儀器與溶液配製 53 3.2.1.2 吸附及沖提無機陰/陽離子的實驗流程 54 3.2.1.3 反向滴定實驗方法 55 3.2.2 結果與討論 55 3.2.2.1 反滴定之表面官能基種類探討 55 3.2.2.1 吸附性質 56 (1) pH值對吸附性質的影響 56 3.2.2.2 脫附性質 57 (1) 陽離子沖提液 57 (2) 陰離子沖提緩衝液 57 3.2.2.3混合無機陰離子和陽離子的沖提 58 3.2.3 結論 59 第四章 結論 77 第五章 參考文獻 78

    1. Tartaj, P.; Morales, M. D.; Veintemillas-Verdaguer, S.; Gonzalez-Carreno, T.; Serna, C. J., The preparation of magnetic nanoparticles for applications in biomedicine. Journal of Physics D-Applied Physics 2003, 36, (13), R182-R197.
    2. Ma, M.; Wu, Y.; Zhou, H.; Sun, Y. K.; Zhang, Y.; Gu, N., Size dependence of specific power absorption of Fe3O4 particles in AC magnetic field. Journal of Magnetism and Magnetic Materials 2004, 268, (1-2), 33-39.
    3. 李昆峰, 磁性奈米粒子於生醫領域之應用. 科儀新知 2006, 28, (1), 61-69.
    4. Lu, A. H.; Salabas, E. L.; Schuth, F., Magnetic nanoparticles: Synthesis, protection, functionalization, and application. Angewandte Chemie-International Edition 2007, 46, (8), 1222-1244.
    5. Masciangioli, T.; Zhang, W. X., Environmental technologies at the nanoscale. Environmental Science & Technology 2003, 37, (5), 102A-108A.
    6. 高逢時, 奈米科技. 科學發展 2005, 386, 66-71.
    7. The Offensive Odor Control Law in Japan. http://www.env.go.jp/en/ 2005.
    8. Chebbi, A.; Carlier, P., Carboxylic acids in the troposphere, occurrence, sources, and sinks: A review. Atmospheric Environment 1996, 30, (24), 4233-4249.
    9. Willig, S.; Lacorn, M.; Claus, R., Development of a rapid and accurate method for the determination of key compounds of pig odor. Journal of Chromatography A 2004, 1038, (1-2), 11-18.
    10. 加藤龍夫, 惡臭之機器測定. 復漢出版社: 台南, 1992.
    11. Michulec, M.; Wardencki, W.; Partyka, M.; Namiesnik, J., Analytical techniques used in monitoring of atmospheric air pollutants. Critical Reviews in Analytical Chemistry 2005, 35, (2), 117-133.
    12. 2-1-6 Gholson, A. R., Evalation of aluminum canisters for collection and storage of air toxics. Anal. Chem. 1990, 62, 1899-1902.
    13. 行政院勞工安全衛生所(IOSH), 行政院勞委會標準分析參考方法5010 醋酸. 1994.
    14. 行政院勞工安全衛生所(IOSH), 行政院勞委會標準分析參考方法RM007A丙酸. 1996.
    15. Dettmer, K.; Engewald, W., Adsorbent materials commonly used in air analysis for adsorptive enrichment and thermal desorption of volatile organic compounds. Analytical and Bioanalytical Chemistry 2002, 373, (6), 490-500.
    16. MacLeod G, A. J., Comparative assessment of the artefact background on thermal desorption of Tenax GC and Tenax TA. J. Chromatogr. A 1986, 355, 393-398.
    17. 黃弈孝，黃瑞琪, 熱脫附被動式採樣器(Tenax TA)之評估研究. 行政院勞工委員會勞工安全衛生研究所計畫報告，2000 IOSH 89-A105.
    18. Cao, X. L.; Hewitt, C. N., Evaluation of Tenax-GR adsorbent for the passive sampling of volatile organic compounds at low concentrations. Atmospheric Environment Part a-General Topics 1993, 27, (12), 1865-1872.
    19. Leboda, R.; Lodyga, A.; Gierak, A., Carbon adsorbents as materials for chromatography .1. Gas chromatography. Materials Chemistry and Physics 1997, 51, (3), 216-232.
    20. Brown, R. H., What is the best sorbent for pumped sampling thermal desorption of volatile organic compounds? Experience with the EC sorbents project. Analyst 1996, 121, (9), 1171-1175.
    21. Greenberg, J. P.; Guenther, A.; Zimmerman, P.; Baugh, W.; Geron, C.; Davis, K.; Helmig, D.; Klinger, L. F., Tethered balloon measurements of biogenic VOCs in the atmospheric boundary layer. Atmospheric Environment 1999, 33, (6), 855-867.
    22. EPA, U. S., Determination of volatile organic compounds in ambient air using active sampling onto sorbent tubes. Compendium Method TO-17 1999.
    23. Cutter, G. A., Kinetic controls on metalloid speciation in seawater. Marine Chemistry 1992, 40, (1-2), 65-80.
    24. 李世裕, 水源被砷或汞污染時對健康的影響. http://www.sekada.com/, 2008
    25. Choong, T. S. Y.; Chuah, T. G.; Robiah, Y.; Koay, F. L. G.; Azni, I., Arsenic toxicity, health hazards and removal techniques from water: an overview. Desalination 2007, 217, 139-166.
    26. An, F. Q.; Gao, B. J., Chelating adsorption properties of PEI/SiO2 for plumbum ion. Journal of Hazardous Materials 2007, 145, (3), 495-500.
    27. 奈米時代-實現與夢想. 中國輕工業出版社.
    28. 凌永健, 曾新華, 徐明聖, 陳思偉, 陳仁焜, 劉人銪, 蕭文修, 周姿君, 異味氣體之監測. 科儀新知 2005, 26, (5), 6-23.
    29. Koziel, J. A.; Spinhirne, J. P.; Lloyd, J. D.; Parker, D. B.; Wright, D. W.; Kuhrt, F. W., Evaluation of sample recovery of malodorous livestock gases from air sampling bags, solid-phase microextraction fibers, Tenax TA sorbent tubes, and sampling canisters. Journal of the Air & Waste Management Association 2005, 55, (8), 1147-1157.
    30. 莊萬發, 香臭氣味控制應用. 復漢出版社: 台南, 1995.
    31. Cao, G. E. F. G., Environmental Applications of Nanomaterials. Imperial College Press: London, 2007.
    32. 行政院環境保護署飲用水全球資訊網, 飲用水水質標準. 2008.
    33. http://www.sunnywin.com.tw/tw/02/01.htm. 2008
    34. Robins, R. G., The aqueous chemistry of arsenic in relation to hydrometallurgical processes. Impurity Control Disposal, Proc. 15th CM Annual Hydrometallurgy Meeting 1985, 1-1 -1-26.
    35. 楊家銘, 奈米製作與量測專題：奈米孔洞材料之物理吸脫附分析. 科儀新知 2005, 26, (第六期), 32-38.
    36. Lin, C. L.; Lee, C. F.; Chiu, W. Y., Preparation and properties of poly(acrylic acid) oligomer stabilized superparamagnetic ferrofluid. Journal of Colloid and Interface Science 2005, 291, (2), 411-420.
    37. 唐秋莎, 新型納米基因載體的製備、表征及體外實驗. 功能材料 2007, 38, 1268-1272.
    38. McBain, S. C.; Yiu, H. H. P.; El Haj, A.; Dobson, J., Polyethyleneimine functionalized iron oxide nanoparticles as agents for DNA delivery and transfection. Journal of Materials Chemistry 2007, 17, (24), 2561-2565.
    39. Katsoyiannis, I. A.; Zouboulis, A. I., Removal of arsenic from contaminated water sources by sorption onto iron-oxide-coated polymeric materials. Water Research 2002, 36, (20), 5141-5155.
    40. Yang, R. T., Adsorbent : fundamentals and applications. John Wiley & Sons, Inc.: New Jersey 2003.
    41. Ngomsik, A. F.; Bee, A.; Draye, M.; Cote, G.; Cabuil, V., Magnetic nano- and microparticles for metal removal and environmental applications: a review. Comptes Rendus Chimie 2005, 8, (6-7), 963-970.

    無法下載圖示 全文公開日期 本全文未授權公開 (校內網路)
    全文公開日期 本全文未授權公開 (校外網路)

    QR CODE