基于明胶/壳聚糖双功能单体离子印迹聚合物的制备及用于重金属离子的选择性吸附研究

Ion imprinted polymers can selectively recognize metal ions and have many superior characteristics such as ease of preparation, highly effective adsorption and ease of recycling. Thus, these polymers are regarded as one of the most potential sorbents to remove the heavy metal ions from industrial wastewater. Because of the absence of active groups in metal ions, the choice of functional monomer is very important for the preparation of ion imprinted polymers. However, the limited active groups of traditional functional monomers may lead to the non-compatibility of adsorption capacity and selectivity of ion imprinted polymers. Thus, these polymers have not provided sufficient competitive advantages over materials used in pollution control to warrant their practical application. Based on the abundant active groups and specific space structure of gelatin, ion imprinted polymers with high adsorption capacity, excellent selectivity and reproductivity are synthesized using cadmium ion (lead ion) as the template and gelatin/chitosan as the functional monomers. The selective recognition ability and ion imprinted mechanisms of imprinted polymers are then investigated. Subsequently, they are used as the sorbents for the purification and recycling treatment of heavy metal ions in industrial wastewater to prove the feasibility for practical application. This study provides the theoretical basis for the preparation of specific imprinted polymers using the compounds with very few active groups as the template. Furthermore, it can be used for the pollution treatment and resources recycling of wastewater containing heavy metals, which reveals great scientific value and exciting perspective of practical application in the future.

离子印迹聚合物可以选择性识别金属离子，具有高效吸附、反复利用、制备简便的优势，已成为重金属污染治理的理想吸附剂之一。由于金属离子缺乏活性基团，功能单体的选择成为印迹聚合物制备的关键。而常规功能单体活性基团偏少，制备的印迹聚合物存在吸附容量和选择性不能兼顾的问题，难以发挥印迹技术的优势。本研究借助明胶蛋白丰富的活性基团和特殊的空间结构，拟分别采用镉离子和铅离子为模板，明胶蛋白/壳聚糖为双功能单体，制备出吸附容量高、选择性和重现性好的离子印迹聚合物，系统探讨印迹聚合物的选择性识别性能及印迹机理，并将其作为吸附剂实现工业废水中重金属离子的高效净化处理和选择性回收，初步论证其实际应用价值。本研究不仅为活性基团偏少的化合物制备特异性印迹聚合物提供一种新思路，而且实现了重金属污染废水的高效治理和资源回收，具有较高的科研价值和市场应用前景。

按照项目总体要求，以明胶蛋白/壳聚糖为双功能单体，制备吸附容量高、选择性和重现性好的离子印迹聚合物，实现重金属离子的高效净化处理。围绕上述任务，课题组系统开展（1）明胶蛋白/壳聚糖为双功能单体，京尼平为交联剂的蜂窝状离子印迹聚合物的制备，实现对重金属离子的高效吸附和选择性识别。（2）提出一种明胶蛋白/壳聚糖/聚乙烯亚胺为功能单体，谷氨酰胺转氨酶为交联剂的新型合成体系，制备出绿色环保的重金属吸附剂；（3）制备出聚乙烯亚胺修饰的明胶海绵，实现污水灌溉锅中重金属离子的高效去除；（4）以普通滤纸作为支撑材料，通过表面自由基聚合技术可控制备离子印迹薄膜，并结合催化动力学光谱法，实现镉离子的快速检测；（5）以明胶的三股螺旋骨架为载体, 借助丰富的功能基团，制备出明胶/二氧化锰复合材料，实现污水和地表水中重金属离子的高效去除。项目组完成了申请书提出的设想，论证富含多种功能基团的明胶能够增强离子印迹聚合物的去除效果和选择性识别能力，并在此基础上提出一种新型离子印迹制备方法和酶交联体系，并结合功能纳米复合材料，在生活饮用水、工业污水和地表水以及污水灌溉过程中重金属去除方面开展了实际应用。基于研究成果，获得了2016年国家自然科学基金面上项目，发表SCI论文2篇，投稿4篇。