臺灣博碩士論文加值系統

A layered double hydroxide (LDH) material was prepared and coated onto the surface of glassy fiber as a sorbent of solid phase microextraction (SPME) to collect halo-phenols in aqueous samples by headspace sampling for GC-ECD analysis.
The LDH material was prepared by mixing magnesium nitrate and aluminum nitrate in water homogeneously and adjusted the pH to 10, then reflux for 24 hrs at 100 oC. After washing with water to neutral and then by alcohol, the LDH was formed posterior to dry in an oven. The SPME-LDH sorbent was prepared by dip-coating a glassy fiber into a mixed solution of LDH and silicone adhesive several times and dried vertically. The effectiveness of LDH fiber preparation was identified their functional groups by FT-IR, and the surface was observed with SEM.
A headspace sampling of halo-phenols from 10 mL aqueous sample in a 20 mL sampling-vial was examined. Factors affecting the sampling such as the pH and temperature of sample, stir-rate, salting-out effect, and extraction time were optimized. Results indicated that the sampling was optimal at pH 2.0, 30% NaCl addition, 1000 rpm stirring at 60 oC for 35 min. For desorption and analysis by GC-ECD, detections are linear in 0.05 - 7.5, 0.01 - 1.5, and 0.005 - 7.5 μgL-1 for trichlorophenol, tetrachlorophenol, tribromophenol and pentachlorophenol, respectively, with correlation coefficients (R2) in 0.9960 - 0.9978. Detection limits are in 1.3 - 14.6 ngL-1 and method detection limits are in 4.4 - 48.5 ngL-1.
The method was used to analyze four halophenols in river water and in farm-soil samples, and no residuals of halophenols was found. When spiked standards in samples and analyzed by the method, the recoveries of halophenols were in 86.6 - 98.3% with RSD in 2.4 - 7.4 %, and in 86.6 - 98.5 % with RSD in 2.8 - 7.7 %, respectively.
The prepared LDH absorbent for SPME sampling with advantages of easy preparation, thermal stability, low-costs, high-enrichment, no carry-over, and no organic solvent required. Thus, it is a simple, rapid, sensitive, inexpensive, and eco-friendly sample preparation method.

目錄
摘要 i
Abstract iii
目錄 iv
表目錄 viii
圖目錄 ix
第一章 緒論 1
1. 1前言 1
1. 2鹵酚類化合物之概述 2
1. 3鹵酚類化合物之樣品前處理技術回顧 3
1.3.1液相-液相萃取法 5
1.3.2固相萃取技術 8
1.3.3超臨界流體萃取 12
1. 4固相微萃取技術之概述 14
1. 5 層狀雙氫氧化合物之介紹 21
1.5.1層狀雙氫氧化合物之概述 21
1.5.2層狀雙氫氧化合物之製備 23
1.5.3合成層狀雙氫氧化合物的影響因素 24
1.5.4層狀雙氫氧化合物之應用 25
1.6研究目的 26
第二章 研究方法 27
2. 1藥品、實驗器材與儀器設備 27
2.1.1藥品 27
2.1.2器材 28
2.1.3儀器設備 29
2. 2藥品配置 30
2.2.1緩衝溶液之配置 30
2.2.2鹵酚類化合物標準品儲存溶液之配製 31
2.2.3鹵酚類化合物範圍濃度溶液之配製 32
2.2.4河水之取樣及處理 32
2.2.5添加分析物於河水之配製 33
2.2.6土壤之取樣及處理 33
2.2.7添加分析物於土壤水溶液之配製 33
2. 3玻璃裝置之矽烷化 34
2. 4儀器裝置操作之參數 35
2.4.1氣相層析之參數設定 35
2.4.2 LDH塗覆熔融矽纖吸附相固相微萃取法之最佳化參數 35
2. 5實驗方法及流程 36
2.5.1 LDH吸附材料之製備條件及萃取流程 36
2.5.2 LDH材料特性之檢測 36
2.5.3 LDH吸附相固相微萃取條件 38
2. 6方法可行性之評估 40
2.6.1儀器檢量線製作 40
2.6.2方法檢量線製作 41
2.6.3固相微萃取法LDH吸附相製備之穩定性與再現性測試 41
2. 7真實樣品之分析與回收率 42
2.7.1河水樣品分析 42
2.7.2河水樣品之回收率測定 42
2.7.3土壤樣品分析 42
2.7.4土壤樣品之回收率測定 42
第三章 結果與討論 44
3. 1層狀雙氫氧化合物特性測試之結果 46
3.1.1層狀雙氫氧化合物之SEM圖 46
3.1.2層狀雙氫氧化合物之IR圖譜 46
3.1.3層狀雙氫氧化合物之比面積與一般孔洞大小分析 50
3. 2 GC-ECD方法之確立 50
3. 3有無修飾LDH之熔融矽纖維固相微萃取比較 51
3. 4固相微萃取之最佳化 51
3.4.1水樣品pH值之選擇 51
3.4.2無機鹽類添加量之選擇 58
3.4.3磁石攪拌子轉速之選擇 60
3.4.4萃取溫度之選擇 60
3.4.5萃取時間之選擇 62
3. 5方法可行性評估與真實樣品之測定 65
3.5.1標準品之儀器校正曲線與偵測極限 65
3.5.2經前處理方法之校正曲線與偵測極限 66
3.5.3真實樣品之測定 69
3.5.4 LDH吸附相之穩定性與再現性 76
3.5.6 方法濃縮倍率 79
3.5.7自製LDH塗覆熔融矽纖維萃取與其他萃取方法比較 79
第四章 結論 82
第五章 參考文獻 83

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