【作者】 王婷；

【导师】 刘大欢；

【作者基本信息】 北京化工大学 ， 化学工程与技术， 2022， 硕士

【摘要】 不论是污水中存在的有害离子还是汽车燃油产生的尾气都严重的危害环境和人类健康,有效脱除存在的有害污染物对人类的发展具有十分重要的意义。本论文采用吸附脱除的方法去除水体环境中的有害离子以及模型油中的噻吩。金属-有机骨架材料（metal-organic frameworks,MOFs）拥有丰富的官能团,根据特定需求可人为进行目标结构的调节和设计,在吸附分离领域已展现出了巨大的优势。本论文主要研究了铝基和锆基MOFs通过一步还原法制备了含银纳米颗粒的衍生材料,该制备将Ag⁺的还原与负载一步实现,方法简单高效,继而实现了对卤素离子以及模型油中噻吩的吸附脱除。具体工作如下:1.合成了金属-有机骨架材料CAU-1-（OH）₂,通过一步氧化还原法以该材料为还原前驱体制备了MOF衍生的新材料Ag⁰/C-NP。相比于其他银纳米颗粒的制备方法,该方法将银在材料中的负载以及通过添加还原剂或在高温环境中热还原的步骤结合起来。基于硝酸银与MOF材料羟基之间特定的氧化还原反应,银离子可被还原为零价的银纳米颗粒且成功的负载在材料中,制备的银颗粒尺寸为5-10纳米左右,该材料对污水中存在的溴离子具有良好的吸附脱除效果,对溴离子的吸附容量可达177.4 mg g^-1。此外,吸附动力学表明吸附剂在1 h左右达到对溴离子的吸附平衡、共存无机盐的存在表明制备的Ag⁰/C-NP具有良好的抗离子干扰能力。2.合成了MOF材料UiO-66-（OH）₂,该材料拥有高密度的羟基-OH官能团以及具有优异的稳定性,利用该材料制备了Ag⁰-Ui O-66-（OH）₂,一步还原法之后新制备的材料仍然可以保持原始Ui O-66-（OH）₂的骨架结构,还原生成均匀分布的银颗粒约为5-10纳米,与碘离子之间有强烈的相互作用。最大吸附量为531.98 mg g^-1,吸附动力学表明该材料在1 h左右达到对碘离子的吸附平衡,共存盐的存在表明该材料具有优异的抗离子干扰能力。此外该材料对碘离子不可逆的吸附脱除可以避免放射性碘的泄露,对其深埋处理从而不会有造成二次污染的危害。3.前文通过一步氧化还原法由金属-有机骨架材料UiO-66-（OH）₂与硝酸银制备的新型吸附剂Ag⁰-Ui O-66-（OH）₂具有丰富的Ag活性位点,基于酚羟基的均匀分布,使还原负载的Ag在材料中具有均匀的分布,基于银元素具有空轨道,噻吩具有π电子以及硫原子的孤对电子对都能与银有较强的相互作用,从而能够提高Ag⁰-Ui O-66-（OH）₂对噻吩的吸附量,对噻吩的吸附量为116.04 mg g^-1,对噻吩的脱除大约在150 min达到平衡,制备的新型吸附剂在噻吩的脱除方面具有应用前景。更多还原

【Abstract】 Whether it is the harmful ions in the sewage or the exhaust gas produced by the fuel,both of them seriously damage to the development of environment and human health,so it is extremely significant for us to find a meaningful strategy to removal of them.In this thesis,harmful ions and thiophene in the simulated oils have been removed by using the method of adsorption.Benefit from the rich and diverse functional groups,metal-organic frameworks（MOFs）can be adjusted and designed artificially according to the specific requirements,showing great advantages in the field of adsorption and separation.The preparation of silver nanoparticle-containing derived carbon materials and composites by aluminum-based and zirconium-based MOFs through a one-step reduction method was proposed in this work.The reduction and loading of Ag0 can be realized in one step.The method is simple and efficient,thereby realizing the extraordinarily effective adsorption and removal of halide ions and thiophene.The research contents are as follows:1.CAU-1-（OH）₂was synthesized and MOF-derived Ag⁰/carbon nanoparticle（Ag⁰/C-NP）was prepared by using the metal-organic framework as a reduction precursor.Compared with other preparation methods of silver nanoparticles doped materials,the method combined the loading of silver in the materials with the steps of reduction by adding reducing agent or at high temperature.Silver ions can be reduced and successfully loaded in the materials based on the specific redox reaction between silver nitrate and hydroxyl groups.The synthesized Ag⁰/C-NP is composed of the carbon-based matrix and Ag nanoparticles with a uniform size of 5-10 nm.The synthetic material exhibits an excellent adsorption capacity of 177.4 mg g^-1.Besides,adsorption can be reached equilibrium at 1 h,Ag⁰/C-NP have a good anti-interference ability.2.UiO-66-（OH）₂,which has a high density hydroxy-OH functional groups and highly stability,was synthesized and Ag⁰-Ui O-66-（OH）₂was prepared by using this material.The integral framework of the resulting material（Ag⁰-Ui O-66-（OH）₂）was found to be complete after this reaction.The size of silver nanoparticles which reduced is about 5-10 nm.Silver,which ascribes to soft acid can interact with soft bases,iodide.The obtained material exhibits a high adsorption capacity of iodide(531.98 mg g^-1).Adsorption can reach equilibrium at 1 h and Ag⁰-Ui O-66-（OH）₂have a good anti-interference ability in the condition of co-exist ions.Besides,the irreversible adsorption of iodide in Ag⁰-Ui O-66-（OH）₂is meaningful,which promoting the deep burial treatment of this radioactive substance,and avoids secondary pollution caused.3.The novel adsorbent Ag⁰-UiO-66-（OH）₂prepared from UiO-66-（OH）₂and silver nitrate by one-step redox method has abundant Ag active sites.The obtained Ag has a good distribution in the materials due to the well-dispersed hydroxyl groups.The empty orbital of Ag has a strong interaction with theπelectron of thiophene or the lone pair of sulfur atom,which can increase the adsorption capacity of thiophene.The adsorption amount of thiophene for116.04 mg g^-1,adsorption can reach equilibrium at 150 min.更多还原