Preparation and properties of dibenzothiophene molecularly imprinted functionalized MOF199 adsorbent
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摘要: 结合分子印迹技术，MOF199为基体，以二苯并噻吩（DBT）为模板分子，甲基丙烯酸（MAA）为功能单体，制备了新型表面分子印迹聚合物材料MOF@SMIP。采用SEM、BET、FT-IR等对其结构和形貌进行表征，在模拟油样中进行吸附评测，吸附平衡时间为1.5 h。MOF@SMIP对DBT吸附量为130.73 mg/g较MOF199吸附量37.79 mg/g有很大提升，同时MOF@SMIP吸附量对比MOF@NIP吸附量（57.13 mg/g）优势明显，印记因子fimp为2.29。吸附行为遵循伪一阶动力学模型说明吸附主要为物理过程。选择性吸附实验表明，MOF@SMIP对目标分子DBT表现出比对结构类似物苯并噻吩（BT）和联苯更高的亲和力，吸附DBT对干扰物BT和联苯的相对选择系数k'分别达到2.55和2.14。Abstract: Combined with molecular imprinting technology, a novel surface molecularly imprinted polymer material MOF@SMIP was prepared, using MOF199 used as matrix, dibenzothiophene (DBT) as template molecule and methacrylic acid (MAA) as functional monomer. The structure and morphology were characterized by SEM, BET, FT-IR, etc. The adsorption behavior was evaluated using a simulated oil sample. The adsorption equilibrium time was 1.5 h. The MOF@SMIP adsorption capacity for DBT (130.73 mg/g) was higher than that for the MOF199 (37.79 mg/g), while the MOF@SMIP adsorption capacity (57.13 mg/g) was comparable to the MOF@NIP adsorption capacity. The obvious advantage is that the imprint factor fimp is 2.29. Adsorption behavior follows the pseudo-first-order kinetic model, indicating that the adsorption is primarily a physical process. The selective adsorption experiments showed that the MOF@SMIP exhibited a higher affinity for the target molecule DBT than the structural analog benzothiophene (BT) and biphenyl. The relative selection coefficient k' of the adsorbed DBT to the interferent BT and biphenyl was 2.55 and 2.14, respectively.
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Key words:
- MOFs /
- molecular imprinting /
- dibenzothiophene /
- functional monomer
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图 1 MOF199(a)、KMOF199(b)、MOF@SMIP(c)红外光谱谱图
Figure 1 Infrared spectrum of MOF199 (a), KMOF199 (b), MOF@SMIP (c)
图 2 MOF199 (a)和MOF@SMIP((b)、(c)、(d))的SEM照片
Figure 2 SEM images of MOF199 (a) and MOF@SMIP ((b), (c), (d))
图 3 MOF199、MOF@NIP和MOF@SMIP的氮气吸附-脱附等温曲线和粒径分布图
Figure 3 Nitrogen adsorption-desorption isotherms and particle size distribution of MOF199, MOF@NIP and MOF@SMIP
图 4 MOF@SMIP、MOF@NIP、MOF199对同一浓度DBT溶液的吸附动力学曲线
Figure 4 MOF@SMIP, MOF@NIP, MOF199 for the same concentration of DBT solution adsorption kinetics curve
图 5 MOF@SMIP对DBT、BT和联苯干扰物的吸附选择性
Figure 5 Adsorption selectivity of MOF@SMIP towards DBT against BT and biphenyl interferents
表 1 MOF199、MOF@NIP和MOF@SMIP的比表面积和多孔参数
Table 1 Specific surface area and porosity parameters of MOF199, MOF@NIP and MOF@SMIP
Adsorbent Specific surface area A/(m2·g-1) Specific pore volum v/(mL·g-1) Most accessible aperture d/nm MOF199 524.39 0.2942 2.42 MOF@NIP 301.98 0.1444 2.07 MOF@SMIP 364.16 0.1763 2.18 
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表 2 MOF@SMIP和MOF@NIP对DBT的吸附动力学参数
Table 2 Adsorption kinetic parameters of DBT by MOF @ SMIP and MOF @ NIP
Sample Qe，exp/
(mg·g-1)Psedo-first-order Psedo-second-order Qe，cal/(mg·g-1) k1/min-1 R2 Qe，cal/(mg·g-1) k2/(g·mg-1·min-1) R2 MOF@SMIP 130.73 131.49 0.0787 0.9780 147.77 0.00068 0.9272 MOF@NIP 57.13 56.77 0.0595 0.9914 64.98 0.00115 0.9872
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表 3 MOF@SMIP和MOF@NIP的吸附选择性
Table 3 Adsorption selectivity of MOF@SMIP and MOF@NIP
Adsorbate MOF@SMIP MOF@NIP Qe/(mg·g-1) Kd/(L·g-1) k Qe/(mg·g-1) Kd/(L·g-1) k k′ DBT 124.86 0.2548 42.32 0.079 BT 44.73 0.1176 2.17 35.67 0.093 0.850 2.55 Biphenyl 30.24 0.0980 2.60 29.01 0.065 1.22 2.14
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