金屬有機骨架:金屬、配位基種類於萃取多環芳香烴之影響

蕭舒映

doi:10.6840/cycu201600367

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金属有机骨架:金属、配位基种类於萃取多环芳香烃之影响

Metal-Organic Frameworks: the Effect of the Types of Metal and Ligand on the Extraction of Polycyclic Aromatic Hydrocarbons

萧舒映 , 硕士　　导师：黄悉雅　　

繁体中文 DOI： 10.6840/cycu201600367

金属有机骨架；多环芳香烃；配位基效应；金属效应；萃取； Metal-Organic Frameworks ； Polycyclic Aromatic Hydrocarbons

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摘要 │ 参考文献 (65) │ 国际计量

摘要〈TOP〉

本论文探讨以金属有机骨架(metal-organic frameworks, MOFs)材料，制备金属有机骨架-高分子(MOF-polymer)管柱，作为固相微萃取(solid phase microextraction, SPME)之吸附剂，进行9种多环芳香烃(polycyclic aromatic hydrocarbons, PAHs)萃取，探讨MOF之配位基及金属种类对於萃取之效果。
　　第一部分研究，比较不同配位基1,4-benzenedicarboxylate (BDC)、4, 4'-biphenyldicarboxylate (BPDC)及2,6-naphthalenedicarboxylate (2,6-NDC)所合成之MOF。实验首先以BDC合成的MOF，MIL-101-(Cr)及MIL-53-(Al)，进行PAHs之萃取，由於PAHs结构是由二个或以上芳香环相互键结形成之碳氢化合物，可藉由MOF中配位基与PAHs间形成的π-π作用力达到吸附目的。结果显示MIL-101-(Cr) 与MIL-53-(Al)对PAHs的萃取回收率分别为23.61%~66.87%与56.32%~78.84%，推测BDC结构为单苯环，因此π-π作用力较弱，但MIL-53-(Al)具呼吸效应，能有效增益对PAHs之吸附，而有较好的回收率。
　　以BPDC、2,6-NDC合成的MOF，DUT-5及DUT-4，对PAHs之萃取回收率分别为21.53%~69.35%及25.51~70.93%，说明具双苯环结构的MOF相较於MIL-101-(Cr)有较好的萃取能力，此外，由於DUT-5之双苯环配位基(BPDC)为单键可旋转之结构，导致PAHs在吸附过程可能因DUT-5配位基之双苯环间单键旋转而不共平面，较不容易产生π-π作用力，造成吸附效果不佳。而DUT-4配位基为共平面之双苯环结构，有利於PAHs以平面的方式进行吸附，产生较强之π-π作用力故得更好之吸附效果。
　　第二部分研究，为以相同配位基1,4-naphthalenedicarboxylate (1,4-NDC)，但不同金属来源所合成一系列构型相同之1,4-NDC系列的MOF，讨论不同金属之MOF对於PAHs萃取之差异，分成不同过渡金属元素及不同硼族金属元素作比较。在所测试过渡金属元素(Ｖ、Cr、Fe)中，依据原子半径大小排列V为最大，Cr次之，Fe为最小，对PAHs之萃取回收率分别为，60.56%~100.05%、28.31~95.14%及19.39%~89.28%，说明当金属原子半径越大回收率越好，所建构的孔洞也相对较大，较有利於9种PAHs进入孔洞中，与配位基上的双苯环形成更有利的π-π作用力，且藉由理论计算了解PAHs在不同过渡金属元素之MOFs中之吸附行为，计算後的吸附能量趋势能符合实际萃取中的回收率结果，搭配电子密度图对於MOF吸附PAHs前後之变化，成功发现吸附PAHs後，金属V电子密度改变最为明显Cr次之，Fe为最小。
　　以不同硼族金属元素(Al、Ga、In)讨论，依据原子半径大小排列In为最大，Ga次之，Al为最小，对PAHs之萃取回收率分别为，16.78%~76.85%、23.15~79.81%及61.82%~78.11%，说明当金属原子半径越大所建构的孔洞也相对较大，较有利於大尺寸(五环)PAHs进入孔洞中，与配位基上的双苯环形成更有利的π-π作用力，并发现当中心金属的电子亲和力越大时(Al > Ga > In)，可大幅度的提升前六个尺寸小的PAHs回收率，藉由理论计算了解PAHs在不同硼族元素之MOFs中之吸附行为，计算後的吸附能量趋势也符合实际萃取中的回收率结果，搭配电子密度图对於MOF吸附PAHs前後之变化，成功发现吸附PAHs後，金属Al电子密度改变最为明显Ga次之，In为最小。

并列摘要〈TOP〉

In this study, metal organic frameworks-polymer (MOF-polymer) columns, which were synthesized with metal-organic frameworks (MOFs) materials and used as adsorbent in solid-phase microextraction of nine polycyclic aomatic hydrocarbons (PAHs). The extraction of PAHs was investigated based on the effect of ligand and metal types.
For the first part of the study, the MOFs were synthesized with different ligands, 1,4-benzenedicarboxylate (BDC), 4,4'-biphenyldicarboxylate (BPDC) and 2,6-naphthalenedicarboxylate (2,6-NDC), were discussed. Firstly, the PAHs were extracted using BDC-based MOFs, MIL-101- (Cr) and MIL-53- (Al). Due to the structure of PAHs, which composed of two or more aromatic hydrocarbon rings, the adsorption is based on the π-π interactions between the ligand of MOFs and PAHs. The results showed that the extraction recoveries of PAHs for MIL-101- (Cr) and MIL-53-(Al) are in the range of 23.61-66.87% and 78.84-56.32%, respectively. It suggests that the BDC structure is a monocyclic benzene ring. Therefore, the π-π interaction is rather weak whereas the breathing effect of MIL-53-(Al) can effectively enhance the adsorption ability of PAHs with extraction higher recoveries. Meanwhile, the extraction recoveries of PAHs were in the range of 21.53-69.35% and 25.51 - 70.93% for the MOF synthesized with BPDC (DUT-5) and 2,6-NDC (DUT-4), respectively. The MOFs with bicyclic benzene ring structure demonstrated better extraction efficiency compared to that of the MIL-101-(Cr). Furthermore, due to the rotatable single bond structure of bicyclic benzene ring ligand (BPDC) of DUT-5, the rotation occurs at non-co-plannar position causing its difficulty to form a π-π interaction during the adsorption process. In contrast, the ligand of DUT-4, which is co-planar bicyclic benzene ring structure, favors the adsorption at co-planar position to form a stronger π-π interaction, which improves the adsorption efficiency.
The second part of the study involve several MOFs, which were built using the same ligand, 1,4-naphthalenedicarboxylate (1,4-NDC), but with different central metal were utilized to extract PAHs. Transition metal elements and Boron group elements were separately compared. For transition metal elements (V, Cr, Fe), in which the largest atomic radius is V followed by Cr and Fe as the smallest, the extraction recoveries of PAHs were in the range of 60.56-100.05%, 28.31-95.14% and 19.39-89.28%, respectively. The results showed that better recoveries could be obtained when larger atomic radius is utilized. Besides, the constructed pore sizes are relatively larger, which favors the nine PAHs to pass through the pore of MOFs and form a stronger π-π interaction between the bicyclic benzene ring and the PAHs. Based on theoretical calculation, the adsorption behavior of PAHs with different transition metal element of MOFs showed similar trends of adsorption energy and matched with the results of actual extraction recoveries. Furthermore, the change of electron density maps of MOFs before and after PAHs extraction showed that the electron density of V demonstrated an obvious change followed by Cr and Fe. Different boron metal elements (Al, Ga, In), which were discussed based on the size of the atomic radius in which the largest was In followed by Ga and Al as the smallest, showed that extraction recoveries of PAHs were in the range of 16.78-76.85%, 23.15-79.81% and 61.82-78.11%, respectively. The results depict that the greater the metal atom radius the larger the constructed pore size, thereby favoring the nine PAHs to pass through the pore and form a stronger π-π interaction with the ligand. Furthermore, we found that the small size six PAHs recoveries could largely be enhanced when the central metal has greater electron affinity (Al> Ga> In). Based on theoretical calculation, we found that the adsorption behavior of PAHs with different transition metal element of MOFs afforded similar results with that of the adsorption energy after calculation and matched with the actual extraction recoveries. Furthermore, the change of electron density maps of MOFs before and after PAHs extractions showed an obvious change for Al followed by Ga and In.

参考文献 ( 65 ) 〈TOP〉

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引用含有DOI的文献

DOI可强化引用精确性、增强学术圈连结，并给予使用者跨平台的良好使用经验，目前在全世界已有超过五千万个对象申请DOI。 如想对DOI的使用与概念有进一步了解，请参考 （ ） 。

DOI可强化引用精确性、增强学术圈连结，并给予使用者跨平台的良好使用经验，目前在全世界已有超过五千万个对象申请DOI。如想对DOI的使用与概念有进一步了解，请参考（）。