磁性纳米粒子的制备及其在重金属离子处理中的应用

重金属离子污染已成为当前最重要的环境问题之一,建立有效去除和监测重金属离子的方法具有重大意义。磁性纳米粒子(MNPs)除了具有纳米粒子的体积小、表面积大、活性位点高等特点外,其本身具有的磁学特性使MNPs在分离科学领域具有独特的优势。近年来,MNPs在环境分析领域的应用逐渐增多,尤其是在重金属离子的处理方面。该文综述了共沉淀法、微乳液法、溶剂热法和热分解法等几种常见的磁性纳米粒子合成方法,重点讨论了磁性纳米粒子在常见重金属离子如Cu(Ⅱ)、Pb(Ⅱ)、Cr(Ⅵ)、Hg(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)处理中的应用,并对该领域的发展前景进行了展望。     

凹凸棒土应用于重金属离子吸附剂的研究

以新型无机矿物材料凹凸棒土作为吸附剂处理废水中的重金属离子。通过扫描电镜、红外光谱及等温吸附-脱附曲线对凹凸棒土进行了表征,并阐述了凹凸棒土对重金属离子的可能吸附机理。在室温下,分别将0.05 g凹凸棒土投入初始质量浓度为500 mg.L-1的Cu(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)和Cr(Ⅵ)的溶液中,凹凸棒土对上述离子的平衡吸附量分别高达99、56、117、198 mg.g-1。结果表明,用凹凸棒土吸附废水中的重金属离子切实可行、经济有效。     

还原态氧化石墨烯的制备及其对重金属离子的吸附性能

通过乙二胺（EDA）对氧化石墨烯（GO）进行还原制备了还原态氧化石墨烯（RGO）,利用红外光谱、拉曼光谱、热重分析和扫描电子显微镜等技术对制得的RGO进行了表征。 考察了RGO复合材料在静态吸附条件下对Pb(Ⅱ)、Cd(Ⅱ)、Cu(Ⅱ)和Mn(Ⅱ)金属离子的吸附性能。 结果表明,该吸附材料对上述4种重金属离子在25 ℃时的静态饱和吸附量分别为396.6、115.3、54.2和38.6 mg/g。 吸附于RGO上的Pb(Ⅱ)可用0.05 mol/L HCl溶液进行洗脱,再生后的RGO重复使用3次时吸附量能达到首次吸附量的85%。     

综合化学实验：磁性金属有机骨架材料的合成及对铅的吸附

设计了一个综合实验——磁性金属有机骨架材料的合成及对铅的吸附。先合成四氧化三铁,再通过氨基修饰制备磁性金属有机骨架吸附材料。考察了此材料对铅的吸附性能,铅的浓度用火焰原子吸收光谱法测定。通过实验加深了学生对物理化学课程中吸附动力学等相关内容的理解,同时巩固了学生对仪器分析课程中的原子吸收光谱法的相关内容的掌握。     

功能化碳质材料的制备及其对水中重金属的去除

重金属污染是目前最为严峻的环境问题之一,我国的重金属污染问题尤为突出。活性炭、纳米碳管和石墨烯等环境友好型碳质材料由于其比表面积大,吸附能力强等优点而被应用于水中重金属的去除,而进行官能团功能化改性后其吸附效果可以明显提高。本文重点阐述了活性炭、纳米碳管、石墨烯及生物质炭等碳质材料的巯基化(-SH)、氨基化(-NH₂)等功能化改性方法及其应用,考察了功能化碳质复合材料对水中重金属离子的去除效果和影响因素,最后展望了功能化碳质复合材料对水中重金属污染物去除研究的发展方向。     

Heavy Metal Removal from Synthetic Solutions with Magnetic Beads Under Magnetic Field

The aim of this study is to prepare magnetic beads which can be used for the removal of heavy metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate‐vinyl imidazole) [m‐poly(EGDMA‐VIM)] beads were produced by suspension polymerization in the presence of magnetite Fe₃O₄ nano‐powder. The specific surface area of the m‐poly(EGDMA‐VIM) beads was found to be 63.1 m²/g with a size range of 150–200 µm in diameter and the swelling ratio was 85%. The average Fe₃O₄ content of the resulting m‐poly(EGDMA‐VIM) beads was 12.4%. The maximum binding capacities of the m‐poly(EGDMA‐VIM) beads were 32.4 mg/g for Cu²⁺, 45.8 mg/g for Zn²⁺, 84.2 mg/g for Cd²⁺and 134.5 mg/g for Pb²⁺. The affinity order on mass basis is Pb²⁺>Cd²⁺>Zn²⁺>Cu²⁺. Equilibrium data agreed well with the Langmuir model. pH significantly affected the binding capacity of the magnetic beads. Binding of heavy metal ions from synthetic wastewater was also studied. The binding capacities were 26.2 mg/g for Cu²⁺, 33.7 mg/g for Zn²⁺, 54.7 mg/g for Cd²⁺ and 108.4 mg/g for Pb²⁺. The magnetic beads could be regenerated up to about 97% by treating with 0.1 M HNO₃. These features make m‐poly(EGDMA‐VIM) beads a potential candidate for support of heavy metal removal under magnetic field.     

功能化MOFs及MOFs/聚合物复合膜在有机染料和重金属离子吸附分离中的应用

全球工业的发展带来了严重的水污染问题,对含各类有机和无机污染物工业废水的处理也成为了重要研究课题。金属-有机骨架(Metal-Organic Frameworks, MOFs)化合物由于其大比表面积、高孔隙率、有序孔道结构及可调节孔道物理化学性质、热稳定性高、易于合成和丰富的开放活性位点等特点,在诸多领域得到广泛应用,其中在固相吸附/分离领域,特别是吸附水中污染物方面展现出良好应用前景。通过合成后改性、使用含取代基配体原位合成、与特定功能材料复合等方法实现MOFs功能化,可有效增加MOFs材料的吸附活性位点,提高吸附性能和吸附选择性。与MOFs颗粒相比较,MOFs/聚合物复合膜结合了MOFs颗粒的结构与物理化学特性以及聚合物薄膜优秀的分离/载体性能,在有机染料及重金属离子的吸附中表现出优秀的吸附/分离性能。本文重点综述了以染料和重金属离子为代表的有机、无机污染物的吸附去除为目标的MOFs功能化方法,以及MOFs/聚合物复合膜的制备方法,并对未来研究方向和研究前景进行展望。     

明胶-环氧聚醚胺交联膜的合成及其对重金属离子的吸附性能

首先利用聚乙二醇二缩水甘油醚(PEO-DE)、聚二甲基硅氧烷二缩水甘油醚(PDMSDE)与无水哌嗪以1∶1∶1的物质的量之比反应合成环氧封端的聚醚胺(ePEA),然后将ePEA分散在水相中与明胶混合,浇铸固化成膜。利用红外光谱(FT-IR)、X射线衍射(XRD)、示差扫描量热法(DSC)和原子吸收光谱(AAS)等手段研究了明胶-环氧聚醚胺交联膜的结构和离子吸附性能。结果表明,与纯明胶膜相比,交联膜中的环氧聚醚胺与明胶之间出现了新的化学交联结构,在水溶液中的稳定性提高;交联膜对Cu2+、Pb2+、Cd2+均有一定的吸附作用,并且吸附能力随着ePEA含量的增加而增加;吸附过程符合二级动力学模型和Langmuir等温模型。     

Oxidized Biomass and Its Usage as Adsorbent for Removal of Heavy Metal Ions from Aqueous Solutions

Nowadays, very coarse wool fibers are considered waste biomass and are discarded at random or burned. Therefore, it is of actual interest to valorize coarse wool fibers as utile products. In this sense, we report herein an environmentally-friendly process for the preparation of a new material based on oxidized wool fibers and designed for efficient adsorption of heavy metals from wastewater. The morphology and the structure of the obtained product were characterized by scanning electron microscopy (SEM) coupled with an X-ray energy-dispersive module (EDX) and by Fourier-transform infrared spectroscopy (FTIR). Likewise, the performances of the oxidized wool fibers for the adsorption of heavy metal cations (Cu²⁺, Cd²⁺, Pb²⁺) from aqueous solutions were tested. The adsorption kinetics data were analyzed by applying the pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models. The equilibrium of the adsorption process was investigated by using the Freundlich and Langmuir isotherm models. According to the Langmuir isotherms registered at 300 K, the maximum adsorption capacities of the oxidized wool were found to increase from Cu²⁺ (9.41 mg/g) and Cd²⁺ (10.42 mg/g) to Pb²⁺ (30.71 mg/g). Consequently, the removal efficiency of metal ions was found to vary in the range of 96.8–99.7%. The thermodynamic parameters (e.g., enthalpy, entropy, and Gibbs free energy) were calculated and discussed.     

聚苯胺及其复合物对重金属离子的高效吸附性能

基于国外最新文献,系统总结了近年来聚苯胺及其复合物的制备方法及其重金属离子吸附性能,重点分析了吸附性能特征,指出聚苯胺及其复合物具有吸附下限浓度低、达到吸附平衡快以及解吸附性能优异等特点.填充有聚苯胺颗粒的吸附柱在动态处理初始浓度为83 ng/L的汞离子溶液时,经一次吸附与解吸循环操作后,汞离子的富集倍数可达120倍.应用于冷原子吸收光谱的待测样品的浓缩与富集,可以将汞的测试下限拓展到0.05 ng/L.聚苯胺及其复合物在痕量重金属离子的高效富集与灵敏探测等方面展示了广阔的应用前景.     

磁性壳聚糖复合微球的制备及其Cu~(2+)吸附性能

以球磨后的粉煤灰磁珠(MS)颗粒为磁核,通过溶胶凝胶法和反相微乳液法依次包覆SiO_2和壳聚糖(CS),制备了MS@SiO_2@CS磁性微球。利用扫描电镜及能量色散谱仪、热重分析仪、红外光谱仪、X射线衍射仪、振动样品磁强计对所得样品的结构和磁性进行了系统表征。结果表明,磁珠颗粒表面实现了逐层包覆,较均匀的分散于壳聚糖基体中,MS@SiO_2@CS微球的比饱和磁化强度可达7.04 emu·g~(-1)。Cu~(2+)离子吸附实验表明,所得磁性壳聚糖微球对Cu~(2+)具有良好的吸附能力,最大吸附量可达11.08 mg·g~(-1);而且可通过磁选法高效固液分离。吸附动力学研究表明,MS@SiO_2@CS微球对Cu~(2+)离子的吸附符合准二级动力学模型,以化学吸附为主。     

Highest and Fastest Removal Rate of PbII Ions through Rational Functionalized Decoration of a Metal–Organic Framework Cavity

To overcome the challenge of developing a multipurpose adsorbent for effective removal of toxic and carcinogenic Pb^II ions from aqueous solutions, a made-for-purpose functional group (N¹,N²-di(pyridine-4-yl)oxalamide) was rationally designed and incorporated into the cavities of a Zn metal–organic framework (MOF), namely, TMU-56. Large enough pore size along with high densities of strong metal chelating sites lead not only to the highest uptake capacity for Pb^II ions, but also the fastest removal rate that has ever been reported for functionalized MOFs, occurring in just 20 s. Moreover, high concentrations of lead ions favor the ion exchange reaction, resulting in a high degree of metal exchange. In addition, TMU-56 can be a practical adsorbent because of its notable performance in the simultaneous removal of several toxic and carcinogenic heavy metals from wastewater, which has rare precedence.     

Rapid Screening of Lipase Inhibitors in Scutellaria baicalensis by Using Porcine Pancreatic Lipase Immobilized on Magnetic Core–Shell Metal–Organic Frameworks

As for ligand fishing, the current immobilization approaches have some potential drawbacks such as the small protein loading capacity and difficult recycle process. The core–shell metal–organic frameworks composite (Fe₃O₄-COOH@UiO-66-NH₂), which exhibited both magnetic characteristics and large specific surface area, was herein fabricated and used as magnetic support for the covalent immobilization of porcine pancreatic lipase (PPL). The resultant composite Fe₃O₄-COOH@UiO-66-NH₂@PPL manifested a high loading capacity (247.8 mg/g) and relative activity recovery (101.5%). In addition, PPL exhibited enhanced tolerance to temperature and pH after immobilization. Then, the composite Fe₃O₄-COOH@UiO-66-NH₂@PPL was incubated with the extract of Scutellaria baicalensis to fish out the ligands. Eight lipase inhibitors were obtained and identified by UPLC-Q-TOF-MS/MS. The feasibility of the method was further confirmed through an in vitro inhibitory assay and molecular docking. The proposed ligand fishing technique based on Fe₃O₄-COOH@UiO-66-NH₂@PPL provided a feasible, selective, and effective platform for discovering enzyme inhibitors from natural products.     

磁性碳包铁纳米粒子在重金属元素检测分离富集中的应用

以氩电弧等离子体法制备的碳包铁纳米粒子为固相萃取材料,采用等离子体原子发射光谱法(ICP-AES)系统研究了该材料对Cr、Ni、Cd、Pb离子的吸附性能,并确定了最佳吸附和洗脱条件。实验结果表明:当pH值为8.0～9.0时,分析物均可被碳包铁纳米粒子定量吸附;采用酸性溶液(pH=1.0～2.0)可将吸附在碳包铁纳米粒子上的金属离子完全脱附。该法对Cr、Ni、Cd、Pb的检出限分别为3.6、4.1、1.1、9.8μg/L,Cr、Ni、Cd的线性范围为1～500μg.L-1,Pb的线性范围为10～1 000μg.L-1,线性相关系数均大于0.999。方法用于自来水中Cr、Ni、Cd、Pb离子的测定,回收率可达到93%～105%;碳包铁纳米粒子对Cr、Ni、Cd、Pb离子的吸附量分别为3.6、4.8、6.3、2.1 mg/g。     

磁性壳聚糖复合微球的制备及其Cu2+吸附性能

以球磨后的粉煤灰磁珠（MS）颗粒为磁核,通过溶胶凝胶法和反相微乳液法依次包覆SiO₂和壳聚糖（CS）,制备了MS@SiO₂@CS磁性微球。利用扫描电镜及能量色散谱仪、热重分析仪、红外光谱仪、X射线衍射仪、振动样品磁强计对所得样品的结构和磁性进行了系统表征。结果表明,磁珠颗粒表面实现了逐层包覆,较均匀的分散于壳聚糖基体中,MS@SiO₂@CS微球的比饱和磁化强度可达7.04 emu·g^-1。Cu²⁺离子吸附实验表明,所得磁性壳聚糖微球对Cu²⁺具有良好的吸附能力,最大吸附量可达11.08 mg·g^-1;而且可通过磁选法高效固液分离。吸附动力学研究表明,MS@SiO₂@CS微球对Cu²⁺离子的吸附符合准二级动力学模型,以化学吸附为主。     

Removal of Chromium(III) and Cadmium(II) Heavy Metal Ions from Aqueous Solutions Using Treated Date Seeds: An Eco-Friendly Method

The aim of the research was to prepare low-cost adsorbents, including raw date pits and chemically treated date pits, and to apply these materials to investigate the adsorption behavior of Cr(III) and Cd(II) ions from wastewater. The prepared materials were characterized using SEM, FT-IR and BET surface analysis techniques for investigating the surface morphology, particle size, pore size and surface functionalities of the materials. A series of adsorption processes was conducted in a batch system and optimized by investigating various parameters such as solution pH, contact time, initial metal concentrations and adsorbent dosage. The optimum pH for achieving maximum adsorption capacity was found to be approximately 7.8. The determination of metal ions was conducted using atomic adsorption spectrometry. The experimental results were fitted using isotherm Langmuir and Freundlich equations, and maximum monolayer adsorption capacities for Cr(III) and Cd(II) at 323 K were 1428.5 and 1302.0 mg/g (treated majdool date pits adsorbent) and 1228.5 and 1182.0 mg/g (treated sagai date pits adsorbent), respectively. It was found that the adsorption capacity of H₂O₂-treated date pits was higher than that of untreated DP. Recovery studies showed maximal metal elution with 0.1 M HCl for all the adsorbents. An 83.3–88.2% and 81.8–86.8% drop in Cr(III) and Cd(II) adsorption, respectively, were found after the five regeneration cycles. The results showed that the Langmuir model gave slightly better results than the Freundlich model for the untreated and treated date pits. Hence, the results demonstrated that the prepared materials could be a low-cost and eco-friendly choice for the remediation of Cr(III) and Cd(II) contaminants from an aqueous solution.     

Screening Metal–Organic Frameworks for Separation of Binary Solvent Mixtures by Compact NMR Relaxometry

Metal–organic frameworks (MOFs) have great potential as an efficient alternative to current separation and purification procedures of a large variety of solvent mixtures—a critical process in many applications. Due to the huge number of existing MOFs, it is of key importance to identify high-throughput analytical tools, which can be used for their screening and performance ranking. In this context, the present work introduces a simple, fast, and inexpensive approach by compact low-field proton nuclear magnetic resonance (NMR) relaxometry to investigate the efficiency of MOF materials for the separation of a binary solvent mixture. The mass proportions of two solvents within a particular solvent mixture can be quantified before and after separation with the help of a priori established correlation curves relating the effective transverse relaxation times T_2eff and the mass proportions of the two solvents. The new method is applied to test the separation efficiency of powdered UiO-66(Zr) for various solvent mixtures, including linear and cyclic alkanes and benzene derivate, under static conditions at room temperature. Its reliability is demonstrated by comparison with results from ¹H liquid-state NMR spectroscopy.     

金属有机骨架材料MIL-101及其改性材料去除环境污染物的研究进展

目前我国水环境以及空气面临着严峻的污染形势,许多危害人身体健康的污染物亟待治理。 金属有机骨架作为目前新兴的多孔材料,具有高孔隙率、高比表面积、结构可调性以及不饱和金属位点等特点。 这使得金属有机骨架材料具有一定的环境污染物去除能力。 围绕对苯二甲酸铬金属有机骨架材料(MIL-101)及其功能化修饰的改性材料的结构信息展开,总结了材料的主要合成方法,对功能化修饰的方法和原理进行分析,重点分析了这种材料在环境污染物去除等方面的应用研究进展,包括它在重金属离子、农药、抗生素、有机染料、碘离子等污染物的吸附处理领域的应用, 以及在污染物的监测和环境风险预警方面的应用潜力。 指出了材料在制备成本、反复利用次数、污染物后续处理等方面仍然存在的问题。