功能化有序多孔材料的设计合成及其对重金属离子的吸附性能研究

Adsorption is one of the most effective heavy metal wastewater treatment methods. It is especially suitable for low-concentration wastewater and advanced wastewater treatment. However, the heavy metal adsorbents currently available feature several limitations, including poor selectivity, difficulties in regeneration, short service lives, and difficulties in heavy metal recovery, etc. To address these issues, this project aims to design and syntheze two types of novel functionalized ordered porous materials for heavy metal adsorption. The double diallylalkylamine-type reticulated porous materials were synthesized by free radical polymerization, which have functional groups at their mesh nodes that could strongly adsorb heavy metals. The block copolymer-type ordered porous materials were synthesized through preparation of block copolymers using living/controlled free radical polymerization and subsequent treatment by a process called collective osmotic shock (COS). Then, the porous materials were functionally modified according to the characteristics of different heavy metal ions to improve their selective adsorption performance for the target heavy metal ions. Through studies of the effect of preparation conditions on the microstructure, and the effect of microstructure on adsorption perfermance, the relationships between the microstructures of the materials and process control parameters, as well as those between the microstructures formed and adsorption properties, were revealed. The results of these analyses can help establish methods for the controllable preparation, functionalization, and microstructural control of ordered porous materials. This project provides a theoretical basis and guidance for the design, large-scale preparation, structural control, and application of novel ordered porous materials for heavy metal wastewater treatment.

吸附法是重金属废水处理最有效的方法之一，特别适合于低浓度废水和废水的深度处理，但现有的吸附剂存在选择性差、难以再生、使用寿命短、所吸附的重金属难以回收等问题。本项目拟设计合成两类新型功能化有序多孔重金属吸附材料：通过自由基聚合制备双二烯丙基烷基胺型网状多孔材料，其网孔节点具有对重金属离子有较强作用的功能基；采用可控活性自由基聚合法合成系列嵌段共聚物，通过共渗透振动法（COS）制备嵌段共聚物型有序多孔材料。然后，针对不同重金属离子的特点对有序多孔材料进行功能化改性，进一步提高其对目标重金属离子的选择吸附性能。通过研究制备条件对材料微结构、材料微结构对吸附性能的影响，揭示材料微结构形成与材料制备过程控制参数、材料微结构与吸附性能间的关系规律，建立有序多孔材料的可控制备、功能化和微结构调控的方法，为新型高效有序多孔材料的设计、规模化制备与结构调控，以及在重金属废水处理中的应用提供理论基础和指导。

吸附法是一种重要的重金属离子分离富集方法，因其操作简单、效率较高、成本较低等优点，在重金属废水处理中获得日益广泛的应用。吸附法处理重金属废水的关键在于吸附剂的性能。本项目设计合成了系列具有新结构和功能的重金属吸附材料。首先设计合成了3类双二烯丙基烷基胺型网状多孔材料，考察了其对重金属离子的吸附性能。结果表明，合成的网状多孔材料对重金属离子具有优异的吸附效果和洗脱再生性能，是一类具有推广应用前景的重金属离子吸附材料。其次，研发了一种活性炭可控氧化方法，制备的改性活性炭螯合基团主要分布在表面上，内部保持活性炭原有的孔道结构，使之兼具优异的去除重金属和有机污染物的能力。第三，设计合成了系列新型介孔硅酸钙材料，包括巯基化和氨基化硅酸钙以及介孔硅酸钙与氧化石墨烯、介孔硅酸钙负载纳米零价铁、活性炭负载介孔硅酸钙、纤维素负载介孔硅酸钙和固体磁性硅酸钙(Fe3O4)等复合吸附材料，探讨了材料结构与性能的关系，考察了其对Pb2+、Cd2+、Cu2+、Cr3+、Ni2+、Mn2+和Zn2+等重金属离子的吸附性能、吸附热力学和动力学特征，并探讨了吸附作用机理。所制备的介孔硅酸钙吸附材料对重金属离子具有优异的吸附性能；对重金属离子的吸附是一个吸热、熵增的自发过程，包括物理吸附、化学吸附（特别是表面络合）和离子交换吸附机理，以化学吸附为主。此外，探索了材料对重金属吸附能力提高和对实际重金属废水中有机污染物去除的方法，合成了螯合剂、磁性固体螯合吸附材料、聚氨酯水凝胶和具有光催化降解的Ag@AgCl-胶原纤维复合材料。. 本项目研究完成，可为重金属离子的吸附处理提供若干性能优良的吸附材料，为其进一步开发、应用和改进提供了理论基础和技术支撑，并为新型高效重金属吸附材料的设计合成提供借鉴。