新穎鋁金屬有機骨架複合材在有機磷農藥萃取研究

Extraction of organophosphorus pesticides using the novel aluminum based metal organic framework composites

陳進學(Chin-Hsueh Chen)

指導教授 ： 劉婉舲 ； 林嘉和

中原大學/理學院/化學研究所/碩士(2018年)

https://doi.org/10.6840/cycu201800843

摘要

本論文利用鋁與2,6-萘二羧酸進行合成新穎鋁金屬有機骨架(MIL-68-NDC)，研究中探討MIL-68-NDC合成條件(金屬與配位基比例、加熱方法、清洗方法或加熱溫度)並進行材料鑑定，實驗結果發現，MIL-68-NDC經合成條件優化後，其粉末式X光繞射圖具有和MIL-68-NDC之理論計算值一致的主要結構訊號，氮氣吸脫附儀測得MIL-68-NDC具有三角窗口與六角窗口之孔徑，其孔徑大小為11.2 Å和18.8 Å，表面積1912 m2/g。隨後，我們將合成成功之MIL-68-NDC與活性碳混摻形成複合材料，進行有機磷農藥之萃取，藉由優化萃取步驟(不同溶劑測試、改變溶劑濃度等)提升對有機磷農藥之回收率，其最佳萃取結果為81.2～94.5%，其偵測極限為0.009～0.018 ppm，同日間之回收率為79.6～90.3% (RSD = 0.21～1.44%)，異日間之回收率為81.1～90.6% (RSD = 0.33～1.75%)，以及材料批與批之回收率為79.7～93.3% (RSD = 0.63～1.94%)，由此可見，此萃取材料具備良好的再現性與穩定性，在材料耐受性測試，經萃取50次之回收率為80.7～93.7% (RSD = 0.91～1.39%)，與第一次萃取回收率無顯著差異，故此材料可多次使用，降低實驗成本，最後我們將此萃取方法應用在實際樣品(農田水、洗菜水)，其回收率分別為85.8～98.7% (RSD = 0～0.6%)和82.3～95.4% (RSD = 0.1～0.8)。由上述實驗結果可知，本研究所開發新型態鋁金屬有機骨架材料(MIL-68-NDC)與活性碳混摻後，可調整材料性質以提升萃取效果，且此材料製備容易、成本低廉、萃取效率高且可重複多次使用，於萃取材料的發展極具潛力。

關鍵字

金屬有機骨架 ； 有機磷農藥 ； 固相微萃取

並列摘要

In this study, a novel aluminum metal-organic framework (MIL-68-NDC) was synthesized that was constructed with aluminum metal ion and 2,6-naphthalene dicarboxylic acid. The syn-thetic conditions were optimized such as the ratio of metal and ligand, heating methods, clean-ing methods or heating temperature. From the results, the powder X-ray diffraction (PXRD) patterns of experimental MIL-68-NDC were similar to the simulated pattern of MIL-68-NDC, and MIL-68-NDC has the triangular window and hexagonal window pores, the pore size is 11.2 Å and 18.8 Å, respectively, the surface area was 1912 m2/g. Subsequently, MIL-68-NDC were mixed with activated carbon (AC) and applied to ophosphorus pesticide extraction. The recovery of organophosphorus pesticides was im-proved by optimizing the extraction conditions (solvent types, solvent concentration) and the best extraction recovery was 81.2 to 94.5%, the limit of detection was 0.009 to 0.018 mgL 1, the intra-day recovery was 79.6 to 90.3% (RSD = 0.21 to 1.44%), the inter-day recovery was 81.1 to 90.6% (RSD = 0.33 to 1.75%) and the re-covery of batch to batch was 79.7 to 93.3% (RSD = 0.63 to 1.94%) that demonstrated a good reproducibility and stability for the composites. Furthermore, the composites could be used 50 times at least, the recovery of the 50th time was 80.7~93.7% (RSD = 0.91~1.39%), similar to the 1st extraction efficiency. Thus, the developed composites could reduce the cost. Finally, the material was applied to real samples (farmland water and washing vegetable water) determina-tion, and the recovery was 85.8 to 98.7% (RSD = 0 to 0.6%) and 82.3 to 95.4% (RSD = 0.1 to 0.8), respectively.
In this study, the extraction efficiency was enhanced by adjusting the material property that was mixed with MIL-68-NDC and AC. The ease preparation, cheap, high extraction perfor-mance and reusability were obtained from the incorporation materials. In the future, it has a greate potential in extracted materials field.

並列關鍵字

MOF ； organophosphorus pesticides ； solid phase microextraction

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