新型吸附材料的制备及对重金属离子和染料吸附性能研究

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英文题名：Preparation of Novel Materials for the Adsorption of Heavy Metal Ions and Dyes 作者：师兰 论文级别：博士 学科专业名称：应用化学 中文关键词：重金属离子 ; 染料 ; 纳米复合材料 ; 吸附剂 ; 磁分离 ; 光催化剂 英文关键词：Heavy metal ions ; organic dyes ; nanocomposite materials ; adsorbents ; magnetic 英文关键词：separation ; photocatalyst 学位年度：2014 导师：甘树才 学科代码：081704 学位授予单位：吉林大学 论文提交日期：2014-04-01

摘要

随着现代工业的迅猛发展，工厂排放大量含重金属离子和染料的废水，给生态系统和人类健康带来日益严重的污染和危害。如果不及时有效地治理这些污染物，将直接威胁人类生存。如何更好地处理污水是当前烝待解决的问题。本论文选题研究制备新型磁性纳米复合材料和金属氧化物材料，探究其吸附重金属离子和吸附（或光催化降解）有机染料的性能，具体成果如下：
     1.采用三步法成功制备了透明质酸（HA）功能化的磁性纳米粒子（Fe3O4@SiO2-HA)，并首次应用于对铜离子吸附研究。实验结果表明，Fe3O4@SiO2-HA纳米粒子单分散性较好，具有球形外貌和清晰的核壳结构。合成的Fe3O4@SiO2-HA粒子具有超顺磁性，可以利用外加磁场对其进行分离和收集。实验讨论了Cu（II）离子初始浓度和溶液pH值对吸附效率的影响，同时也研究了Fe3O4@SiO2-HA的吸附等温线和动力学机制。当Cu（II）离子的初始浓度为30mg/L时，合成的Fe3O4@SiO2-HA在除去水中Cu（II）离子的最佳pH值为6.8。最佳实验条件下，Fe3O4@SiO2-HA对Cu（II）离子的最大吸附量为13.5mg/g。吸附等温线研究结果表明，Fe3O4@SiO2-HA的吸附Cu（II）离子过程遵循Freundlich吸附等温方程；Fe3O4@SiO2-HA对Cu（II）离子的吸附行为用拟二级动力学模型拟合结果较好。
     2.以属于多糖类的田菁胶为碳源，采用水热法成功制备了磁性含碳多糖纳米粒子（Fe3O4@CPS），并对样品进行了多项表征和吸附性能研究。合成的Fe3O4@CPS纳米粒子具有球形外貌和明显的核壳结构。实验探讨了吸附剂用量、吸附质初始浓度、溶液pH值、吸附时间等对Fe3O4@CPS吸附重金属离子效率的影响。对Fe3O4@CPS的吸附机理进行了探究分析。重金属离子初始浓度在50-250mg/L范围内，Fe3O4@CPS对Cd（II）、Cu（II）、Pb（II）离子的最大吸附容量分别达到50.1mg/g，27.5mg/g和23.4mg/g。Fe3O4@CPS对重金属离子具有不同程度的吸附容量是因为吸附剂和重金属离子之间存在软硬酸碱（HSAB）作用。Fe3O4@CPS纳米粒子具有超顺磁性，可使该粒子在水溶液中具有较好的可回收性。吸附/解吸循环实验结果表明，Fe3O4@CPS循环使用3次后，对Cd（II）、Cu（II）、Pb（II）离子的解吸率分别高达96.7%，91.2%和87.6%以上。
     3.采用氧化聚合法成功制备了聚巴比妥酸功能化的磁性纳米粒子（PBA-MNPs），并对其进行了各种表征和吸附性能研究。测试结果显示，PBA-MNPs具有球形外貌，平均粒径为327nm，且由粒径小于15nm小颗粒堆积组成。在50mg/L–300mg/L初始浓度范围内，PBA-MNPs对Pb（II）和Cu（II）离子的最大吸附容量分别是130.5mg/g和95.2mg/g。吸附-脱附循环实验结果表明，PBA-MNPs经过循环使用三次后，该材料对Cu（II）和Pb（II）离子的解吸效率分别可达到87.1%和82.7%，说明PBA-MNPs在重金属离子的分离和收集方面具有很好的应用价值。
     4.结合沉淀法和焙烧法成功制备了氧化铝（Al90-600）。探讨了反应温度对氧化铝形貌的影响。结果显示，在90oC下合成的Al90-600具有层级中空结构和320.6m2/g的大比表面积，预示着该材料具有优良的吸附特性。利用合成的Al90-600作吸附剂，探讨了其对水中的刚果红（CR）和甲基橙（MO）有机染料的吸附效率。对于Al90-600而言，吸附CR的最佳溶液pH值是5.0。Al90-600对CR和MO的实验得到的饱和最大吸附容量分别为826.4mg/g和26.0mg/g，与Langmuir公式计算得到的理论最大吸附容量值835.0mg/g和25.5mg/g相类似，表明层级中空结构的Al90-600更有利于吸附CR。这是因为材料吸附能力不仅与材料比表面积有关，还与材料结构和吸附质分子量大小有关。
     5.利用均匀沉淀和焙烧相结合法成功制备了层级中空结构的氧化锌（Z-400）。用合成的Z-400对刚果红（CR）进行了吸附和光催化降解试验。实验探讨了影响吸附和光降解效果的一些因素及其吸附和光催化降解理论的机制。为了评价Z-400吸附/光催化降解CR的效率，相同实验条件下进行了商业ZnO和TiO2P25吸附/光催化降解CR的平行实验。等温线研究表明，Langmuir吸附等温线更好的描述Z-400吸附CR的过程，而商业ZnO和TiO2P25的吸附过程更符合Freundlich吸附等温线。最佳实验条件下，Z-400，商业ZnO和TiO2P25对CR的最大吸附容量分别是97.0mg/g，41.5mg/g和7.2mg/g；光催化降解实验结果显示，光催化反应2时Z-400对CR的光降解率可达到65%以上，而TiO2P25和商业ZnO对CR的光降解率分别是41%和31%。相比于两种商业产品，Z-400对CR有更好的吸附和光催化降解能力。
With the rapid development of modern industry, factories always discharge effluentcontaining heavy metal ions and dyes, which can bring about serious environmentalthreats and serious hazards to ecosystem and human health, respectively, due to theirtoxicity. If not promptly and effectively remove those toxic contaminants will directlythreaten human survival. Therefore, it is urgent to effectively deal with the wastewatercontaining toxic heavy metal ions and dyes. In this thesis, a series of novel magneticnanocomposite materials were synthesized and their adsorption performances towardheavy metal ions and photocatalysis performances toward organic dyes wereinvestigated. The details are as follows:
     1. The hyaluronic acid (HA) functionalized magnetic nanoparticles(Fe3O4@SiO2-HA) were synthesized and firstly used as adsorbent for potentialapplication in water treatment. Fe3O4@SiO2-HA nanoparticles have uniform sizes,legible spherical shapes and obvious core-shell structures. The Fe3O4@SiO2-HAnanoparticles have super-paramagagnetic property, which can make thesenanoparticles easily separated by an external magnetic force after adsorptionaccomplished. Effects of Cu (II) ions initial concentration and aqueous pH value onthe adsorption efficiency have been discussed. The adsorption isotherms and kineticshave also been investigated. The results showed that the optimum pH value for Cu (II)uptake studies was selected as6.8. The maximum adsorption capacity of thesynthesized Fe3O4@SiO2-HA was found to be13.5mg/g. Freundlich isotherm modelgave better fittings the adsorption equilibrium data. Kinetic experiments clearlyindicated that adsorption process of copper ions on the Fe3O4@SiO2-HA was followedpseudo-second-order kinetic models.
     2. Magnetic carbonaceous polysaccharide nanoparticles (Fe3O4@CPS) weresynthesized through hydrothermal process by using sesbania gum (SG) served ascarbon resource, and their structure, morphology, and component were characterizedsubsequently. Fe3O4@CPS nanoparticles have legible spherical shapes and obvious core-shell structures. Effects of adsorbent dosage, initial concentration, pH value andadsorption time on the adsorption capacity for heavy metal ions have been discussed.The adsorption isotherms and kinetics have also been investigated subsequently.When the initial concentration of heavy metal ions varing from50mg/L to250mg/L,the maximum adsorption capacities of Fe3O4@CPS towards Cd (II), Cu (II) and Pb (II)ions were found to be50.1mg/g,27.5mg/g, and23.4mg/g, respectively. Thedifference in adsorption capacities can be well explained because the “hard” metalions (Cd (II) and Cu (II)) had a higher complexation affinity than the “soft” metal ions(Pb (II)). Magnetism study displayed that Fe3O4@CPS nanoparticlas havesuper-paramagnetic property and strong magnetic response at room temperature,which can make these nanoparticles easily separated by applying the externalmagnetic force. The results showed that the Fe3O4@CPS have above91.2%for Cu(II),96.7%for Cd (II) and87.6%for Pb (II) ion desorption efficiency after theregeneration process.
     3. Poly(barbituric acid) functionalized magnetic nanoparticles (PBA-MNPs) weresynthesized through one-step oxidation polymerization method. Their microstructure,morphology, and functional groups were characterized in detail. The nanoparticleshave spherical shape. These spherical functional particles were formed by smallerspherical agglomerates of dimension~15nm. The synthesized PBA-MNPs used asadsorbents for potential application in water treatment. When the initial concentrationof adsorbates varing from50mg/L to300mg/L, the PBA-MNPs nanoparticles havethe adsorption capacities toward Cu (II) and Pb (II) ions were95.2mg/g and130.5mg/g, respectively. Recycling adsorption/desorption experiments revealed that thePBA-MNPs shown above87.1%for Cu (II) and82.7%for Pb (II) ions desorptionefficiency after the three regeneration cycle process. PBA-MNPs showed potentialapplication as recyclable adsorbent for heavy metal ions.
     4. A facile sol-gel method and sequential calcination treatment was utilized tofabricate alumina (Al90-600) with hierarchical hollow structure and high surface area.The as-prepared Al90-600was characterized by a series of measurement. Effect ofreaction temperature on the morphology of alumina was studied. The as-obtainedAl90-600exhibited a large BET surface area of320.6m2/g and expected that willpresent excellent adsorption behavior towards organic dyes. The as-obtained Al90-600was used as adsorbents for Congo red and Methyl orange removal. The results showed that the optimum pH value for CR uptake studies was selected as5.0. Todescribe how adsorbate molecules interact with the adsorbent surface, the adsorptionisotherms and kinetics were applied to analysis equilibrium adsorption data. Themaximum adsorption capacities of Al90-600obtained from the equilibrium adsorptionvalue were found to be CR (835.0mg/g) and MO (26.0mg/g), which are nearly closeto the adsorption capacity of adsorbent calculated from Langmuir adsorption isotherm.The adsorption experimental results showed that the maximum adsorption capacity ofCR by Al90-600was much higher than the maximum adsorption capacity for the MO.This is indicated that the as-synthesized Al90-600with hierarchical hollow structuremay is beneficial for enhancing adsorption intensity relatively large organic molecule.This is indicated that the adsorption capacity of an adsorbent is not only determinedby the specific surface area of materials, but correlated with structure and themolecular size distribution of adsorbate molecule.
     5. A facile homogeneous precipitation method and sequential calcination treatmentwas utilized to fabricate zinc oxide (Z-400) with hierarchical hollow structure. Theprepared Z-400can be utilized as efficient adsorbent/photocatalyst for CR removal.The factors affecting the adsorption/photocatalytic degradation capacity towards CRand the corresponding mechanisms were investigated in detail. In order to evaluate theadsorption/photocatalysis efficiency of Z-400, the removal experiments of CR withTiO2P25and commercial ZnO were also selected as the reference under the identicalreaction conditions. The adsorption data of the Z-400were well fitted with theLangmuir model, whereas for those of the TiO2P25and commercial ZnO, simulationwith the Freundlich model was better than those with Langmuir model. The maximumsorption capacity (qm) of Z-400, commercial ZnO and TiO2P25toward CR were97.0mg/g,41.5mg/g and7.2mg/g, respectively. The photocatalytic result showed that thedegradation percentiles of each sample were65%for Z-400,41%for TiO2P25, and31%for commercial ZnO within2h irradiation time. Based on the experimentalresults, Z-400is combined adsorbent and catalyst materials for removal of CR fromwaterbodies.

引文

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