在众多对废水的处理方法中，吸附法由于具有操作简便、性价比高等特点而被广泛应用。天然或人工合成的微纳米粉体材料（如黏土矿物、金属-有机框架材料(MOFs)）具有独特的小尺寸效应和表面与界面效应，表现出了良好的吸附性能。但是，在吸附完成之后，将这些微纳米级的粉体材料从水体中分离却十分困难，极易造成二次污染，严重限制了微纳米材料在印染废水处理中的实际应用。

针对如何在充分发挥微纳米材料吸附性能的同时改善其固液分离特性这一关键问题，本文通过原位的化学交联反应将两种纳米粉体材料（MOFs和天然纳米黏土矿物）引入到可以高度溶胀的水凝胶三维网络结构之中，制备出有机/无机复合凝胶吸附材料，并同时研究了其对于水体中典型有机染料的去除行为和固液分离性能。本研究获得的研究成果如下：

1、以具有极强稳定性和良好吸附性的UiO-66纳米颗粒作为吸附功能组分，通过水溶液自由基聚合反应制备出聚丙烯酰胺/UiO-66 (简称为PAM/UiO-66) 复合凝胶吸附剂，并通过FTIR、SEM和XRD等表征方法验证了PAM/UiO-66的成功制备。

以阴离子染料甲基橙（MO）作为模型染料，研究了PAM/UiO-66复合凝胶的吸附行为。分别考察了吸附剂用量、MO溶液初始pH值、接触时间和MO溶液的初始浓度等因素对于吸附过程的影响；分析了PAM/UiO-66复合凝胶对于MO的吸附动力学和吸附热力学特征。同时评估了PAM/UiO-66复合凝胶的固液分离特性和循环使用性能。结果表明：PAM/UiO-66复合凝胶中的UiO-66能够充分发挥其吸附特性；拟二级动力学可较好地描述PAM/UiO-66复合凝胶对于MO的吸附过程，吸附等温线符合Langmuir模型，计算得到的最大吸附量为52.13mg/g。得出该吸附过程是一个吸热的自发过程。PAM/UiO-66复合凝胶颗粒良好地沉降于水底，表现出了优异的固液分离特性和循环使用性能。

2、为了降低复合吸附剂的成本，同时减少对于石油基小分子单体的依赖，以天然一维纳米矿物凹凸棒黏土（ATP）作为无机功能组分，通过天然普鲁兰多糖的原位化学交联制得了普鲁兰/凹凸棒黏土复合（简称为PU/ATP ）凝胶材料。

研究了PU/ATP复合凝胶对于阳离子染料结晶紫(CV)的吸附行为。研究结果表明，PU/ATP复合凝胶中的ATP能够有效发挥其吸附功能。对于低浓度的CV染料溶液，PU/ATP复合凝胶表现出了良好的去除效果。拟二级动力学模型可更好地描述该吸附动力学过程，吸附等温线符合Langmuir模型，计算得到的最大吸附量为13.13mg/g。吸附热力学结果表明，PU/ATP复合凝胶对于CV的吸附是一个放热的自发过程。毫米级的PU/ATP复合凝胶颗粒具有优异的沉降特性，表现出了良好的固液分离特性和循环使用性能,重复使用5次之后的吸附量仍可到达初始吸附量的 83.86%。

3、为了进一步提升凹凸棒黏土（ATP）基复合凝胶的吸附性能，在凹凸棒黏土（ATP）作为无机功能组分的基础上，通过2-丙烯酰胺-2-甲基丙磺酸（AMPS）和 生物基单体衣康酸（IA）的自由基共聚反应制得了聚(2-丙烯酰胺-2-甲基丙磺酸-co-衣康酸) （简称P(AMPS-co-IA)/ATP）复合凝胶。

研究了P(AMPS-co-IA)/ATP复合凝胶对于阳离子染料结晶紫(CV)的吸附行为。研究结果表明，P(AMPS-co-IA)/ATP复合凝胶中对于低浓度的CV染料溶液，表现出了良好的去除效果。三种动力学模型都与该吸附动力学过程较为符合，吸附等温线符合Langmuir模型，计算得到的最大吸附量为512.82 mg/g。吸附热力学结果表明，P(AMPS-co-IA)/ATP复合凝胶对于CV的吸附是一个放热的自发过程。毫米级的P(AMPS-co-IA)/ATP复合凝胶颗粒具有良好的沉降特性，表现出了优异的固液分离特性和循环使用性能,重复使用5次之后的吸附量仍可到达109.51 mg/g。

Among various wastewater treatment methods, adsorption method is widely used because its simple operation, low cost and high performance. Natural or synthetic micro-nano powder materials (such as clay minerals, metal-organic frameworks (MOFs)) have unique small size effects, surface and interface effects, and exhibit good adsorption properties. However, after completing the adsorption of dyes in the water body, it is often to use filtration or centrifugation to separate these micro-nano-scale powder materials from the water body. The separation process is difficult and easy to cause secondary pollution, which seriously limits the practical application of micro-nano materials in dye wastewater treatment.

How to fully exploit the adsorption properties of micro-nano materials and improve their solid-liquid separation properties is the key issue, in this paper, two nano-powder materials (MOFs and natural nano-clay minerals) were introduced into the solid-liquid separation through in-situ chemical cross-linking reaction. In the highly swollen hydrogel three-dimensional network structure, organic/inorganic composite gel adsorbents were prepared, and their removal behavior for typical organic dyes in water was studied, in order to provide a useful reference for the development of new adsorption materials based on micro-nano powders. The specific work carried out is as follows:

1. UiO-66 nanoparticles with extremely strong stability and good adsorption as adsorption functional materials,Polyacrylamide/UiO-66 (referred to as PAM/UiO-66) composite gel adsorption was prepared by aqueous solution radical polymerization. The successful preparation of PAM/UiO-66 was verified by FTIR, SEM and XRD characterization methods.         

Using the anionic dye methyl orange (MO) as a model dye, the adsorption behavior of PAM/UiO-66 composite gels was studied. The effects of adsorbent dosage, the initial pH valu, contact time and initial concentration of MO solution on the adsorption process were investigated respectively.The adsorption kinetics and adsorption thermodynamic characteristics of PAM/UiO-66 composite gel for MO were analyzed. At the same time, the solid-liquid separation characteristics and recycling performance of PAM/UiO-66 composite gel were evaluated. The results show that: UiO-66 in PAM/UiO-66 composite gel can give full play to its adsorption properties; pseudo-second-order kinetics can describe the adsorption process of PAM/UiO-66 composite gel for MO well, and the adsorption isotherm According to the Langmuir model, the calculated maximum adsorption capacity was 52.13 mg/g. The adsorption process is an endothermic spontaneous process. Millimeter-sized PAM/UiO-66 composite gel particles settled on the bottom of the water naturally, showing good solid-liquid separation characteristics and recycling performance.

2.In order to reduce the cost of composite adsorbents and reduce the dependence on petroleum-based small-molecule monomers, the natural one-dimensional nano-mineral attapulgite (ATP) was used as the inorganic functional component, The pullulan/attapulgite composite (referred to as PU/ATP) gel material was prepared by in situ chemical cross-linking of natural pullulan polysaccharide.

Based on the successful preparation, the adsorption behavior of PU/ATP composite gel for the cationic dye crystal violet (CV) was studied. The results show that the ATP in the PU/ATP composite gel can effectively exert its adsorption function. For low-concentration CV dye solutions, the PU/ATP composite gel showed a good removal effect. The pseudo-second-order kinetic model can better describe the adsorption kinetic process, the adsorption isotherm conforms to the Langmuir model, and the calculated maximum adsorption capacity is 13.13 mg/g. The adsorption thermodynamic results indicated that the adsorption of CV on the PU/ATP composite gel was an exothermic spontaneous process. The millimeter-scale PU/ATP composite gel particles have excellent sedimentation characteristics, showing good solid-liquid separation characteristics and recycling performance. After repeated use for 5 times, the adsorption capacity can still reach 83.86% of the initial adsorption capacity.

3. In order to further improve the adsorption performance of attapulgite (ATP)-based composite gels, on the basis of attapulgite (ATP) as an inorganic functional component, AMPS and P(AMPS-co-IA)/ATP composite gels were prepared by the free-radical copolymerization of the biobased monomer itaconic acid (IA).

The adsorption behavior of the cationic dye crystal violet (CV) on the P(AMPS-co-IA)/ATP composite gel was studied. The results showed that the P(AMPS-co-IA)/ATP composite gel exhibited a good removal effect for low-concentration CV dye solutions. The three kinetic models are in good agreement with the adsorption kinetic process, the adsorption isotherm is in accordance with the Langmuir model, and the calculated maximum adsorption capacity is 512.82 mg/g. The adsorption thermodynamic results indicated that the adsorption of CV on the P(AMPS-co-IA)/ATP composite gel was an exothermic spontaneous process. The millimeter-scale P(AMPS-co-IA)/ATP composite gel particles have good sedimentation characteristics, showing excellent solid-liquid separation characteristics and recycling performance, and the adsorption capacity can still reach 109.51 mg/g after repeated use for 5 times.

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