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研究生:林宗範
論文名稱:磁性中孔洞孔殼材料之製備及其應用於水樣品中鄰苯二甲酸酯類檢測之研究
論文名稱(外文):Preparation of magnetic core mesoporous shell material and it's application on the determination of phthalates in aqueous samples.
指導教授:徐永源徐永源引用關係
學位類別:碩士
校院名稱:國立高雄師範大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:79
中文關鍵詞:磁性中孔洞孔殼材料
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本研究以CTAB做為模板基、TEOS做為矽源,製備Fe3O4@nSiO2@mSiO2的磁性孔殼結構吸附劑,且利用微波輔助去除模板基。並將所得吸附劑應用於萃取水樣品中鄰苯二甲酸酯類,再結合氣相層析質譜儀做為偵測儀器。

實驗所得粉末經由傅立葉轉換紅外光光譜儀(FT-IR)、熱重分析儀(TGA)、氮氣等溫吸附/脫附儀(BET)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM) 、超導量子干涉磁量儀(SQUID)等鑑定其特性。鑑定得知實驗所得孔殼吸附劑粉末粒徑大小約為500 nm,比表面積為155.5 cm2/g,外層孔洞體積為0.14 cm3/g,孔洞直徑為37.07 nm,磁性為56 emu/g。

實驗結果指出,使用甲醇做為模板基去除劑,在微波條件80℃、Ramp To Temperature、Ramp Time 10分鐘、Hold Time 1小時、Power 600w、Stirring Mode之下可以快速移除Fe3O4@nSiO2@mSiO2上之CTAB模板基,經過熱重分析儀在150~350℃之加溫過程中,重量損失為2.4%。  
  在萃取過程中,使用5 mg的少量吸附劑,並在20分鐘內完成萃取,所得偵測極限介於3.02~3.75μg/L 、相相關係數皆在0.991以上,相對標準偏差則在1.1%以下,回收率分別為52.3%、73.3%、80.0%、80.8%,且吸附劑經過重複5次萃取後,其吸附能力仍維持在85%以上。
  本研究成功利用微波加熱取代傳統冷凝迴流方法去除CTAB模板基,合成出二氧化矽結合四氧化三鐵的磁性中度孔洞殼層吸附劑,結合氣相層析質譜儀的高靈敏度及穩定的再現性,有效應用於萃取水樣品中鄰苯二甲酸酯類化合物並測量其含量。

We develop a novel method which prepares magnetic core mesoporous shell material with microwave-assisted removal of template and combine this material with gas chromatography-mass spectrometry. This method is used to determine four common phthalate in aqueous samples.
In this study, we confirm the various properties of magnetic powder by FT-IR, TGA, BET, SEM, TEM, SQUID. The diameter of magnetic powder is about 500 nm, the BET surface and total pore volume and pore diameter were calculated to be 155.5cm2/g and 0.14cm3/g and 37.07 nm. The magnetic property is 56 emu/g.
The result indicate that using methanol to be extraction solvent in the process of microwave heating. It could remove CTAB template quickly when the condition is 80℃, ramp To temperature, ramp Time 10 min, hold Time 1 hour、Power 600w、stirring mode. At150℃~350℃,the mass losing is 2.4%.
In the process of extraction phthalate, using 5 mg powder and completion of the experiment in 20 min. The LOD, R2, RSD, is 3.02~3.75μg/L, 0.9914~0.9987,0.98~1.11 %.
In our work, a novel method of extraction CTAB template was developed, the method of magnetic core mesoporous shell material combine with gas chromatography-mass spectrometry resulting high sensitivity and reproducibility. This can be widely used to detect for phthalate in aqueous samples.

目錄
摘要.............................................................................................................................I
Abstract...................................................................................................................III
目錄.........................................................................................................................IV
表目錄.................................................................................................................. VII
圖目錄....................................................................................................................IX
第一章、緒論..........................................................................................................1
1-1 Fe3O4磁性粒子介紹........................................................................................2
1-1-1 Fe3O4簡介............................................................................................2
1-1-2 Fe3O4合成方法介紹…........................................................................2
1-2 SiO2形成中度孔殼結構…..............................................................................3
1-2-1 SiO2簡介..............................................................................................3
1-2-2 溶膠凝膠法(sol-gel) ...........................................................................4
1-2-3 磁性孔殼結構應用.............................................................................5
1-3鄰苯二甲酸酯類..............................................................................................7
1-3-1 鄰苯二甲酸酯類簡介.........................................................................7
1-3-2 鄰苯二甲酸酯類對人體的影響.........................................................8
1-3-3 鄰苯二甲酸酯類性質.........................................................................9
1-4 微波輔助合成...............................................................................................15
1-4-1 微波發展歷史...................................................................................15
1-4-2 微波原理簡介...................................................................................15
1-4-3 微波特性簡介...................................................................................17
1-4-4 微波裝置...........................................................................................17
1-4-5 微波加熱與傳統加熱比較...............................................................18
1-5 氣相層析質譜儀...........................................................................................20
1-5-1氣相層析法原理簡介.........................................................................20
1-5-2 注射口與進樣...................................................................................21
1-5-3 管柱與烘箱溫度...............................................................................21
1-5-4 偵測器...............................................................................................22
1-5-5 電子撞擊游離法(Electron Impact Ionization,EI) ...........................25
第二章、實驗.......................................................................................................24
2-1 儀器與器材...................................................................................................24
2-1-1實驗用儀器設備.................................................................................24
2-1-2實驗用器材.........................................................................................25
2-2 藥品...............................................................................................................26
2-3 實驗方法.......................................................................................................27
2-3-1 Fe3O4@nSiO2@mSiO2製備步驟.......................................................28
2-3-1-1 Fe3O4製備步驟.......................................................................28
2-3-1-2 Fe3O4@nSiO2製備步驟..........................................................28
2-3-1-3 Fe3O4@nSiO2@mSiO2製備步驟...........................................29
2-3-1-4 一般冷凝迴流去除CTAB模板基.........................................30
2-3-1-5 微波加熱去除CTAB模板基.................................................30
2-3-2 特性鑑定實驗...................................................................................31
2-3-2-1傅立葉轉換紅外光光譜儀(FT-IR).........................................31
2-3-2-2熱重分析儀(TGA)...................................................................31
2-3-2-3氮氣等溫吸附/脫附儀(BET)..................................................31
2-3-2-4掃描式電子顯微鏡(SEM) ......................................................32
2-3-2-5穿透式電子顯微鏡(TEM) .....................................................32
2-3-2-6超導量子干涉磁量儀(SQUID)...............................................32 2-3-3藥品配置.............................................................................................................33
2-3-3-1 鄰苯二甲酸酯類標準溶液配置............................................33
2-3-3-2 鄰苯二甲酸酯類標準混合溶液配置....................................33
2-3-3-3 鄰苯二甲酸酯類標準混合水溶液配置................................33
2-3-3-4 檢量線標準溶液配置............................................................34
2-3-3-5 檢量線標準水溶液配置........................................................34
2-3-3-6 真實水樣品............................................................................34
2-3-4檢量線確立.........................................................................................35
2-3-4-1直接進樣檢量線.....................................................................35
2-3-4-2方法檢量線.............................................................................35
2-3-5 萃取吸脫附實驗...............................................................................36
2-3-5-1 不同吸附劑克數比較............................................................37
2-3-5-2 不同脫附時間比較................................................................37
2-3-5-3 不同濃度鄰苯二甲酸紙類水溶液比較................................37
2-3-5-4 不同熱食容器之鄰苯二甲酸酯類偵測................................38
2-3-5-5 飲用水中鄰苯二甲酸酯類偵測............................................38
2-3-6 電子撞擊游離法氣相層析質譜儀之條件設定...............................39
第三章、結果與討論.......................................................................................40
3-1 磁性孔殼吸附劑特性鑑定結果...................................................................40
3-1-1 FT-IR光譜圖......................................................................................40
3-1-2 TGA熱重分析圖................................................................................43
3-1-3氮氣等溫吸附/脫附儀(BET)測量孔洞大小.....................................49
3-1-4顯微鏡(SEM、TEM)觀察粒子大小與形狀.......................................49
3-1-5超導量子干涉磁量儀(SQUID)測量磁性..........................................58
3-2 萃取實驗.......................................................................................................60
3-2-1 不同吸附劑克數...............................................................................60
3-2-2 不同吸附時間...................................................................................61
3-2-3 於不同濃度中吸附效果比較...........................................................64
3-2-4 重複吸脫附實驗並觀察其重複利用情形.......................................65
3-3 檢量線...........................................................................................................66
3-3-1 直接進樣檢量線...............................................................................66
3-3-2 方法檢量線.......................................................................................69
3-4 真實樣品測量...............................................................................................72
第四章、結論.......................................................................................................74
參考文獻...............................................................................................................76























表目錄
表一、鄰苯二甲酸丁酯之特性..................................................................10
表二、鄰苯二甲酸丁酯苯甲酯之特性..................................................11
表三、鄰苯二甲酸二(2-乙基己基)酯之特性.....................................12
表四、鄰苯二甲酸二辛酯之特性.............................................................13
表五、台灣食品藥物管理局之塑化劑每日耐受量表..................14
表六、歐盟法規之塑膠材料中塑化劑含量最大限值表.............14
表七、實驗用藥品.............................................................................................24
表八、實驗用儀器.............................................................................................25
表九、實驗用器材.............................................................................................26
表十、GC升溫設定圖.....................................................................................39
表十一、TGA各項參數實驗結果表......................................................48
表十二、表面積及孔洞大小與孔洞直徑表.......................................49
表十三、重複萃取實驗百分比結果表..................................................66
表十四、直接進樣之四種鄰苯二甲酸酯類之線性關係與偵測極限及線性相關係數表...............................................................................69
表十五、磁固相萃取四種鄰苯二甲酸酯類之線性關係與偵測極限及線性相關係數表...............................................................................72
表十六、磁固相萃取方法測得各水樣品中鄰苯二甲酸酯類之含量表.....................................................................................................................73










圖目錄
圖一、磁性孔殼吸附劑合成步驟圖..........................................................7
圖二、去除CTAB示意圖................................................................................7
圖三、鄰苯二甲酸丁酯之結構圖.............................................................10
圖四、鄰苯二甲酸丁酯苯甲酯之結構圖.............................................11
圖五、鄰苯二甲酸二(2-乙基己基)酯之結構圖...............................12
圖六、鄰苯二甲酸二辛酯之結構圖.......................................................13
圖七、波長頻率圖.............................................................................................15
圖八、分子偶極矩感應磁場圖..................................................................16
圖九、實驗用微波儀器圖.............................................................................17
圖十、傳統加熱示意圖..................................................................................19
圖十一、微波加熱示意圖.............................................................................19
圖十二、氣相層析儀構造簡圖..................................................................20
圖十三、總實驗流程圖..................................................................................27
圖十四、萃取實驗流程圖.............................................................................36
圖十五、Fe3O4 IR圖.........................................................................................41
圖十六、Fe3O4@檸檬酸 IR圖...................................................................41
圖十七、Fe3O4@nSiO2 IR圖.......................................................................42
圖十八、Fe3O4@nSiO2@mSiO2 IR圖....................................................42
圖十九、未去除模板基之Fe3O4@nSiO2@mSiO2重量損失一次微分圖...............................................................................................................43
圖二十、未去除模板基之Fe3O4@nSiO2@mSiO2...........................44
圖二十一、冷凝迴流加熱去除模板基之Fe3O4@nSiO2@mSiO2
.....................................................................................................................................44
圖二十二、以Acetone做為去除溶劑之Fe3O4@nSiO2@mSiO2
.....................................................................................................................................46
圖二十三、以Ethanol做為去除溶劑Fe3O4@nSiO2@mSiO2
.....................................................................................................................................46
圖二十四、以Methanol做為去除溶劑Fe3O4@nSiO2@mSiO2
.....................................................................................................................................46
圖二十五、微波加熱時間一小時之Fe3O4@nSiO2@mSiO2
.....................................................................................................................................47
圖二十六、微波加熱時間二小時之Fe3O4@nSiO2@mSiO2
.....................................................................................................................................48
圖二十七、微波加熱時間三小時之Fe3O4@nSiO2@mSiO2
.....................................................................................................................................48
圖二十八、Fe3O4 SEM圖...........................................................................50
圖二十九、Fe3O4 SEM圖...........................................................................50
圖三十、Fe3O4@nSiO2 SEM圖...............................................................51
圖三十一、Fe3O4@nSiO2 SEM圖..........................................................51
圖三十二、Fe3O4@nSiO2@mSiO2 SEM圖.......................................52
圖三十三、Fe3O4@nSiO2@mSiO2 SEM圖.......................................52
圖三十四、Fe3O4@nSiO2@mSiO2 SEM圖.......................................53
圖三十五、Fe3O4 TEM圖........................................................................53
圖三十六、Fe3O4@nSiO2 TEM圖..........................................................54
圖三十七、Fe3O4@nSiO2@mSiO2 TEM圖......................................54
圖三十八、Fe3O4@nSiO2@mSiO2 TEM圖......................................55
圖三十九、Fe3O4@nSiO2@mSiO2 TEM圖......................................55
圖四十、Fe3O4@nSiO2@mSiO2 TEM圖............................................56
圖四十一、Fe3O4@nSiO2@mSiO2 TEM圖......................................56
圖四十二、Fe3O4@nSiO2@mSiO2 TEM圖......................................57
圖四十三、Fe3O4與Fe3O4@nSiO2@mSiO2 磁滯曲線圖............58
圖四十四、Fe3O4@nSiO2@mSiO2 於水溶液中搖晃混合圖....59
圖四十五、Fe3O4@nSiO2@mSiO2 以磁鐵蒐集圖.........................59
圖四十六、使用不同份量吸附劑萃取鄰苯二甲酸酯類圖.......60
圖四十七、過程中震盪不同時間以萃取鄰苯二甲酸酯類圖..61
圖四十八、過程中震盪不同時間以萃取DBP圖............................62
圖四十九、過程中震盪不同時間以萃取BBP圖............................62
圖五十、過程中震盪不同時間以萃取DEHP圖.............................63
圖五十一、過程中震盪不同時間以萃取DNOP圖.......................63
圖五十二、磁性吸附劑物於不同濃度鄰苯二甲酸酯類混合水溶液萃取效果圖...............................................................................................64
圖五十三、重複萃取實驗結果圖.............................................................65
圖五十四、DBP直接進樣檢量線圖.......................................................67
圖五十五、BBP直接進樣檢量線圖.......................................................67
圖五十六、DEHP直接進樣檢量線圖...................................................68
圖五十七、DNOP直接進樣檢量線圖...................................................68
圖五十八、DBP方法檢量線圖..................................................................70
圖五十九、BBP方法檢量線圖..................................................................70
圖六十、DEHP方法檢量線圖...................................................................71
圖六十一、DNOP方法檢量線圖.............................................................71
圖六十二、水樣品中四種鄰苯二甲酸酯類含量圖.......................73

參考文獻

[1] 賴麗瑩,談環境賀爾蒙(上)(下),環境檢驗月刊(1999),第21頁。
[2] 廖建森,張.袁紹英,環境賀爾蒙-塑膠添加物(鄰苯二甲酸酯類)之環境流布,環境檢驗雙月刊(2001),第35卷,第12-16頁。
[3] 林彥宏,Preparation and magnetic properties of Fe3O4-SiO2 core-shell nanoparticles,東海大學碩士論文(2003),第24頁。
[4] Meng, JianHua, Yang, GuiQin, Yan, LeMei, Wang, Xiu,Yu,Synthesis and characterization of magnetic nanometer pigment Fe3O4,Dyes and Pigments(2005),109-113。
[5] 蔡信行、孫光中,奈米科技導論,新文京開發出版股份有限公司(1994),第206-208頁與第353-354頁。
[6] 張安華、劉陵崗、李進典、張火成、薛中興、蔣作群、賴紹榮、陳振漢、朱光馨、徐曼珈、王盛時,實用奈米技術,新文京開發出版股份有限公司(1995),第85、94、98-100、103、222、223頁。
[7] K.T. Wu, P.C. Kuo, Y.D Yao, E.H Tsai,Magnetic and Optical Properties of Fe3O4 Nanoparticle Ferro fluids Prepared by Co precipitation Technique,Ieee Transactions on magnetic(2001),2651-2653。
[8] X.Z. Li, L. Wang, R.M. Liao,Layer-by-layer deposition of luminescent polymeric microgel films on magnetic Fe3O4@SiO2 nanospheres for loading and release of ibuprofen,Powder Technology(2013),235,103-109。
[9] Z.L. Liu, Y.J. Liu, K.L. Yao, A.H. Ding, J. Tao. X. Wang,Synthesis and Magnetic Properties of Fe3O4 Nanoparticles,Journal of Materials Synthesis and processing(2002),83-87。
[10] Jeong, Jing-Ryul, Shin,Sung-Chul,Lee , Seung-Jun, Kim,Jong-Duk,Magnetic properties of superparamagnetic γ-Fe2O3 nanoparticles reparedby coprecipitation technique,Journal of Magnetism and Magnetic Materials (2005),5-9。
[11] X.Z. Li, Lin Wang, R.M. Liao,Layer-by-layer deposition of luminescent polymeric microgel films on magnetic Fe3O4@SiO2 nanospheres for loading and release of ibuprofen,Powder Technology(2013),235,103-109。
[12] 張川修、許祐川、楊家銘,以奈米鑄造法製備三維規則中孔洞材料之簡介,國立清華大學化學系(2008) ,第六十六卷第二期。
[13] Y.H. Deng, D.W. Qi, C.H. Deng, X.M. Zhang, and D.Y. Zhao,Superparamagnetic High-Magnetization Microspheres with an Fe3O4@SiO2,Journal of the American Chemical Society(2008),130,28-29。
[14] Kim, J. Lee, J. E.; Lee, J. Yu, J. H. Kim, B. C. An, K. Hwang, Y. Shin, C. H. Park, J. G. Kim, J. Hyeon, T. J. Am, Chem. Soc( 2006), 128, 688-689。
[15] Lin, Y. S.; Wu, S. H.; Hung, Y.; Chou, Y. H.; Chang, C.; Lin, M. L.; Tsai, C. P.; Mou, C. Y. Chem,Mater(2006), 18, 5170-5172。
[16] Giri, S.; Trewyn, B. G.; Stellmaker, M. P.; Lin, V. S. Y. Angew. Chem.,Int. Ed( 2005), 44, 5038-5044。
[17] Zhao, W. R.; Gu, J. L.; Zhang, L. X.; Chen, H. R.; Shi. J. L. J. Am. Chem. Soc(2005), 127, 8916-8917。
[18] Y.H. Deng, D.W. Qi, C.H. Deng, X.M. Zhang, and D.Y Zhao,Superparamagnetic High-Magnetization Microspheres with an Fe3O4@SiO2,Journal of the American Chemical Society(2008),130,28-29。
[19] Z.B. Li , Danni Huang, C.F. Fu, B.W. Wei, W.J. Yu, C.H. Deng,, X.M. Zhang,Preparation of magnetic core mesoporous shell microspheres with C18-modified interior pore-walls for fast extraction and analysis of phthalates in water samples.,Journal of Chromatography A(2011),6232-6239。
[20] European Food Safety Authority, Opinion of the Scientific Panel on with Food(AFC) on a request from the Commission related to (DBP、BBP、DEHP) for use in food contact material. ,The EFSA Journal(2005),242,1-17。
[21] Magdic,S., Pawliszyn,JB.,Analysis of organochlorine pesticides using solid-phase microextraction.,J.Chromatogr.A(1996),732。
[22] Sarman,M:Read ,W.A.;Castle,L;Gilber,J.,Level of di-(2-ethyhexyl)phthalate and total phthalate ester in milk,cream,butter and cheese.,Food Additives and Contaminants。
[23] Ma,L.L.; Chu,S.G; Xu,X.B.,Organic contamination in the greenhouse soils from Beijing suburbs.,China.J.Environ.Monit(2003),5(5),786-790。
[24] Li,X.;Zeng,Z,Chen.;Xu,Y.,Determination of phthala acid ester plasticizer in plastic by ultrasonic solvent extraction combine with solid-phase microextraction using calix arene fiber.,Talanta(2004),63,1013-1019。
[25] 許道平,分析樣品前處理技術-微波萃取法。Journal of Chinese Chemical Society(1988),56,285-294。
[26] CEM,CEM Coporation-Innovators in Microwave Technology for Synthetic Chemistry ,Life Sciences, Analytical and Process Control(2012),1-79。
[27] Kingston,H.K., Jassie,L.B., Introduction to microwave sample preparation :theory and practice. American Chemical(1988)
[28] Scott Brian J, Wirnsberger Gernot, Stucky Galen D. ,Chem Mater (2001),13,3140–3150。
[29] T.L. Lai , Y.Y. Shu , Ya-Chu Lin , W.N. Chen , C.B. Wang,Rapid removal of organic template from SBA-15 with microwave assisted extraction,Materials Letters(2009),
[30] Kleitz Freddy, Schmidt Wolfgang, Schüth Ferdi. Microporous Mesoporous Mater (2003),65,1–29。
[31] Kawi Sibudjing, Lai MW.,Chem Commun (1998),13,1407–1408。
[32] Skoog,D.A., Holler,F.J., Crouch,S.R.,Principles of Instrumental Analysis.,Gas Chromatography(2007)。

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