金屬有機骨架複合材料於親水與疏水性化合物之萃取研究

Metal-Organic Framework Composites for the Extraction of Hydrophobic and Hydrophilic Compounds.

李芳瑜(Fang-Yu Li)

指導教授 ： 林嘉和 ； 劉婉舲

中原大學/理學院/化學研究所/碩士(2018年)

https://doi.org/10.6840/cycu201800324

摘要

本論文探討聚苯乙烯(polystyrene,PS) 結合金屬有機骨架 (metal-organic frameworks, MOFs)複合材料之合成條件，並將其應用為固相微萃取 (solid phase microextraction, SPME)之吸附劑，主要進行疏水性的多環芳香烴化合物 (polycyclic aromatic hydrocarbons, PAHs)及親水性的非類固醇類抗發炎藥物 (non-steroidal anti-inflammatory drugs, NSAIDs)萃取，討論不同MOFs對親疏水性化合物之萃取效果。
首先，使用硫酸（H2SO4）後修飾PS核心合成不同的MOFs @ PS複合材料，隨後生長MOF納米材料。本研究的第一部分，合成單苯環之配位基Terephthalic acid (H2BDC)之MIL-53(Al，探討聚苯乙烯(polystyrene, PS)、MIL-53(Al)以及MIL-53(Al)@PS複合材料對於親水性分析物-非類固醇類抗發炎藥物萃取效能差異，結果顯示MIL-53(Al)@PS複合材料對NSAIDs的萃取效果最為優異，推測PS為單苯環，π-π作用力較弱，MIL-53(Al)具有孔洞性及較高的表面積，而有較好的回收率；MIL-53(Al)@PS複合材料具有疏水性材料PS球以及具備孔洞及高比表面積的MIL-53 (Al)，因此吸附能力提升外，由於複合材料的性質也可以將萃取物完全脫附，故回收率佳。隨後，以雙苯環之配位基1,4-Naphthalenedicarboxylic acid (1,4-NDC)合成之Al-1,4-NDC代替MIL-53 (Al)，並進行非類固醇類抗發炎藥物萃取應用，Al-1,4-NDC及Al-1,4-NDC@PS複合材料對NSAIDs的萃取回收率分別為78.8%~82.5%及93.0%~98.9%，此部分說明，具有雙苯環結構的MOFs有較強的π-π作用力，吸附效果優於MIL-53(Al)，Al-1,4-NDC@PS複合材料具備疏水性材料，亦使分析物容易脫附，故回收率較高。
第二部分研究，進一步探討Al-1,4-NDC以及Al-1,4-NDC@PS複合材料對於疏水性分析物﹣多環芳香烴化合物萃取效能差異，結果顯示PS、Al-1,4-NDC及Al-1,4-NDC@PS複合材料對PAHs的萃取回收率分別為37.7 %~59.0 %、60.8 %~82.9 % 以及60.0%~96.4%，於疏水性分析物的萃取中，複合材料依舊提供最佳的回收率。
因此，本研究所開發之複合材，以MOF改善原始PS吸附效能外，MOF與PS的結合使萃取物更能完全脫附，故此兩種材料的結合不僅在親水性分析物有好的萃取效果，於疏水性分析物亦有良好效率。

關鍵字

金屬有機骨架；複合材料；固相微萃取；多環芳香烴；非類固醇類抗發炎藥物

並列摘要

In this study, the applications of polystyrene and metal-organic frameworks (MOFs@PS) composite materials in solid phase microextraction (SPME) are discussed. Several parameters affecting the extraction efficiency of different MOFs@PS in SPME application were also investigated.
First, different MOFs@PS composites were synthesized via post modification of PS core using sulfuric acid (H2SO4) and subsequently grown the MOF nanomaterials. Herein, a terephthalic acid based aluminum MOF, MIL-53(Al), was synthesized onto the PS core (MIL-53(Al)@PS) and applied in the extraction of hydrophilic analytes NSAIDs. To make a useful comparison, the extraction efficiency of polystyrene (PS), and pristine MIL-53(Al) were also investigated. The results showed that the extraction recoveries for NSAIDs using MIL-53(Al)@PS composite was found higher compared to its counterpart. Due to the structure of PS, which contains one aromatic ring, the adsorption behavior of the NSAIDs via π-π interaction was found weaker. Meanwhile, the presence of MIL-53(Al), which exhibits high porosity, large surface area, further enhanced the extraction efficiency for NSAIDs. On the other hand, another MOF, aluminum 1,4-naphthalenedicarboxylic acid (Al-1,4-NDC), was grown onto the PS core (Al-1,4-NDC@PS) and applied in SPME of NSAIDs. The results showed that the extraction recoveries for NSAIDs using Al-1,4-NDC and Al-1,4-NDC@PS were in the range of 78.8 %-82.5 % and 93.0 %-98.9 %, respectively. Comparing this result suggests that Al-1,4-NDC@PS, which contains bicyclic benzene rings, exhibited better extraction performance than to that of the MIL-53(Al)@PS due to its high π-π interaction sites. The enhanced efficiency of Al-1,4-NDC@PS composite also showed the ease of elution for NSAID analytes with high recoveries.
Second, further investigation on the potential of Al-1,4-NDC@PS composites in SPME of hydrophobic polyaromatic hydrocarbons (PAHs) was conducted. The results showed that the extraction recoveries for PAHs using PS, Al-1,4-NDC and Al-1,4-NDC@PS composites were in the range of 37.7 %-59.0 %, 60.8 %-82.9 % and 60.0%-96.4%, respectively. These results also proved that the Al-1,4-NDC@PS composite could be useful in the extraction of hydrophobic analytes. Finally, the successful preparation of MOFs@PS composites demonstrated their potential as adsorbent for both hydrophilic and hydrophobic analytes.

並列關鍵字

metal-organic frameworks, MOFs；Composites ；non-steroidal anti-inflammatory drugs, NSAIDs；polycyclic aromatic hydrocarbons, PAHs

參考文獻

參考文獻

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