二硫化钼材料用于去除水中重金属铅的效率与机理研究

随着工业与城市化的蓬勃发展，人们对水资源的消耗也日益增长，而与此同时，水资源的污染问题也愈发突出。重金属铅（Pb）是一种在世界范围内广泛存在的蓄积性毒物，水环境中的铅会对人体健康和生态环境造成巨大威胁。吸附是目前工业除铅的常用处理方案。相较于传统材料来说，二硫化钼等二维材料对铅离子（Pb(II)）的亲和性更高，因此寻求或制备高效的二维纳米材料用于铅离子的去除成为备受关注的问题。但是，国内外对于二维材料去除重金属的研究大多只关注吸附剂的短期添加对体系中铅离子含量的影响，而忽略在此过程中吸附剂的稳定性及是否会对水质造成二次污染。此外，对于络合态铅，其在工业废水中更为常见、也更难以去除，但针对该形态的处理工艺并没有得到足够重视和研发。因此，本文使用二硫化钼（MoS₂）作为Pb(II)的吸附剂和过氧化氢（H₂O₂）的活化剂，实现不同水环境体系中游离和络合态铅的高效去除。

对于出水水质要求高的生活饮用水，研究采用超声辅助的电化学剥离法，制备鸟苷酸（GMP）负载的2H相电化学剥离的二硫化钼纳米片（E-MoS₂）。通过批量实验测试了纳米片的吸附性能（吸附容量和吸附动力学）以及环境因子（pH和共存离子）的影响。实验结果表明，E-MoS₂能迅速去除体系中的Pb(II)，处理效果不受钙、镁两种天然水体常见的二价离子影响，且吸附容量相比于MoS₂粉末来说得到了显著的提升。为了探究MoS₂二维材料的稳定性，研究选取了水热制备和化学剥离的二硫化钼纳米材料作为对比，通过稳定性实验和15天吸附容量对比实验来测试材料的氧化速率。实验证明，在保证优良吸附性能的同时，E-MoS₂还展现出了极高的化学稳定性，这对于饮用水处理来说有极大的优势。研究借助XRD、XPS、SEM-EDS等分析手段对实验中的二硫化钼材料进行了形貌、结构和性质表征，既检验和评估了材料的吸附性能及机理，也对铅和材料在体系中的化学转化过程进行了较为深入的探究。研究表明，吸附是E-MoS₂除铅的唯一机理；此外，其极高的化学稳定性可能源于GMP与E-MoS₂表面分子间的相互作用和E-MoS₂材料晶体的完整性。

对于工业废水中难以通过吸附去除的络合态铅，研究采用产量大、价格低廉的二硫化钼粉末，设计了MoS₂粉末/H₂O₂体系。通过批量实验以及试剂浓度梯度实验来确定反应的最佳配比和pH，以及最佳条件下体系的反应效率。实验证明，这种体系在较广的pH范围内保持稳定优异的性能。研究通过自由基淬灭实验和电子自旋共振波谱仪（EPR）分析，确定了主要活性自由基为·OH和O₂^∙-。并借助XRD、XPS、SEM-EDS等测试手段分析了体系的除铅机理。研究提出，体系可能的反应机制是MoS₂粉末活化H₂O₂产生自由基使得Pb-EDTA被氧化降解，从而将络合态铅转化为与MoS₂粉末亲和度高的离子态铅，随即一部分被MoS₂表面吸附，一部分与MoS₂氧化产生的钼酸根离子结合生成钼酸铅析出。

With the rapid development of industry and urbanization, the consumption of water resources is also increasing. At the same time, the problem of water pollution is becoming more and more prominent. Lead (Pb) is a kind of accumulative toxicant that spreads all over the world, which is a great threat to human health and ecological environment. Adsorption is a common treatment method for industrial lead removal. Compared with traditional materials, two-dimensional materials such as molybdenum disulfide (MoS₂) have higher affinity for lead ions (Pb(II)), so seeking or preparing efficient two-dimensional nanomaterials for lead ion removal has become a concern. However, most of the studies on the removal of heavy metals by two-dimensional MoS₂ materials only focus on the influence of short-term addition of adsorbents on the content of lead ions in the system, while ignoring the stability of adsorbent and whether it will cause secondary pollution to water quality in this process. In addition, complexed lead is more common in industrial wastewater and more difficult to remove, however, the treatment for complexed lead has not received enough attention. Therefore, MoS₂ was used as an adsorbent of Pb(II) and an activator of hydrogen peroxide (H₂O₂) to achieve efficient removal of free and complex lead in different water environment systems.

For drinking water with high effluent quality requirements, 2H phase of molybdenum disulfide nanosheets coated with guanylate acid (GMP) (E-MoS₂) were prepared by ultrasonically-assisted electrochemical exfoliation. Through batch experiments, the adsorption properties (adsorption capacity and adsorption kinetics) of the nanosheets and the influence of environmental factors (pH and co-existing ions) were tested. The experimental results show that the removal of Pb(II) in the system is quite quickly, and the treatment efficiency is not affected by calcium and magnesium, which are two common divalent ions in natural water. In addition, the adsorption capacity of E-MoS₂ is significantly improved compared with bulk MoS₂. In order to explore the stability of MoS₂ two-dimensional materials, hydrothermal and chemically exfoliated MoS₂ nanomaterials were selected for comparison. Through the stability experiment and 15-day adsorption capacity comparison experiment, the oxidation rate of the materials was tested. The experimental results show that, while ensuring excellent adsorption performance, E-MoS₂ also shows high chemical stability, which has great advantages for drinking water treatment. By means of XRD, XPS, SEM-EDS and other analysis methods, the morphology, structure and properties of MoS₂ in the experiment were characterized, which not only tested and evaluated the adsorption performance of the materials, but also deeply explored the chemical transformation and removal mechanism of lead and materials in the system. The results show that adsorption is the only mechanism existing in the removal of lead by E-MoS₂, and its high chemical stability may be due to the defect-free structure of E-MoS₂ and the molecular interaction between GMP and the surface of E-MoS₂.

Bulk MoS₂ /H₂O₂ system was designed by using bulk MoS₂ with high yield and low price to remove the complex lead from industrial wastewater. Batch experiments were carried out to determine the optimal reagent ratio and pH of the reaction, and test the reaction efficiency of the system under the best conditions. The results show that the system has stable and excellent performance in a wide range of pH. The main active radicals in the system were ·OH and O∙-2. XRD, XPS, SEM-EDS and other characterizations were used to analyze the mechanism of lead removal. The possible reaction mechanism of the system is that MoS₂ powder activated H₂O₂ to produce ·OH and O∙-2 which leads Pb-EDTA oxidization, thus transforming the complex lead into ionic lead with high affinity with MoS₂ powder. Then part of the ionic lead is adsorbed on the surface of MoS₂, and part of it is combined with molybdate ions produced by the oxidation of MoS₂ to produce lead molybdate precipitation.

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