氨基化MIL-101表面印迹聚合物的制备及其吸附行为

研究了金属有机骨架材料MIL-101表面印迹聚合物的制备方法及其吸附行为。以MIL-101为载体，先通过化学修饰氨基制备了ED-MIL-101材料，再以京尼平苷为模板，甲基丙烯酸为功能单体，二乙烯基苯为交联剂，表面接枝京尼平苷分子印迹聚合物制备了MIPs@MIL-101印迹聚合物。通过傅里叶红外光谱（FTIR）、X射线衍射光谱（XRD）、扫描电镜（SEM）对聚合物进行结构表征，测试了聚合物的等温吸附及吸附动力学性能，探讨了聚合物的固相萃取性能。红外光谱及XRD衍射分析表明了MIL-101氨基化修饰及表面接枝复合材料的成功制备。吸附动力学研究表明当分子印迹聚合物用于吸附京尼平苷时，可在270min内达到吸附平衡。当温度为298K、308K、318K、328K时，印迹聚合物对模板的吸附量分别为55.94mg/g、46.16mg/g、38.98mg/g、31.47mg/g。吸附热ΔH为26.997kJ/mol。分子印迹固相萃取杜仲提取物中的京尼平苷时，总回收率达95.0%。

Preparation of a surfacially imprinted polymer based on metal organic framework MIL-101 as support and its adsorption behavior

In present work, a surfacially imprinted polymer based on metal organic framework MIL-101 as the support was prepared and its adsorption behavior explored. Firstly, MIL-101 was chemically modified by using ethidene diamine as modifier to obtain ED-MIL-101. Secondly, a surface-imprinting technique was used to prepare MIPs@MIL-101 polymer with geniposide as the template, methacrylic acid as the functional monomer, divinylbenzene as the cross-linker by adopting a surface grafting technique. The molecularly imprinted polymers obtained was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The adsorption dynamics and therodynamics behaivors were tested and the solid phase extraction performance for this polymer evaluated. The adsorption kinetics study showed that when the MIP is used for geniposide, the adsorption equilibrium can reach within 270 minutes. When the temperature was set at 298K, 308K, 318K, 328K, the adsorption capacity for the MIPs toward the template was 55.94mg/g, 46.16mg/g, 38.98mg/g and 31.47mg/g, respectively, with an enthalpy value of ΔH=26.997kJ/mol. This MIP can be used as sorbent for the solid phase extraction of geniposide from crude extract of Eucommia ulmoides, with a total recovery of 95.0%.