功能化金属有机骨架材料去除饮用水污染物的研究进展

金属有机骨架(MOFs)材料是一类以过渡金属为中心、含杂原子的有机物为配体、通过配位作用形成的周期性网络多孔晶体材料。与其他的多孔材料相比,MOFs配体种类繁多,比表面积极大,孔径大小可调控且具有特殊(饱和或不饱和)的金属位点,在气体存储、催化、吸附与分离等领域有广阔的应用前景。近年来,功能化MOFs对污染物的富集和去除成为学者关注的热点。这是由于通过对MOFs进行功能化修饰,能够改变MOFs的孔径大小、表面带电性质等物化性质,从而实现对目标物更高效的吸附。该文综述了近年来功能化MOFs对饮用水污染物吸附的研究进展,包括饮用水污染物的类型及危害、功能化MOFs的制备方法以及去除饮用水污染物的应用,并对今后的发展前景进行了展望。     

Oil/Water Separation with Selective Superantiwetting/Superwetting Surface Materials

The separation of oil from oily water is an important pursuit because of increasing worldwide oil pollution. Separation by the use of materials with selective oil/water absorption is a relatively recent area of development, yet highly promising. Owing to their selective superantiwetting/superwetting properties towards water and oil, superhydrophobic/superoleophilic surfaces and underwater superoleophobic surfaces have been developed for the separation of oil/water‐free mixtures and emulsions. In this Review, after a short introduction to oil/water separation, we describe the principles of materials with selective oil/water absorption and outline recent advances in oil/water separation with superwetting/superantiwetting materials, including their design, their fabrication, and models of experimental setups. Finally, we discuss the current state of this new field and point out the remaining problems and future challenges.     

Fluorous metal-organic frameworks with superior adsorption and hydrophobic properties toward oil spill cleanup and hydrocarbon storage

We demonstrate that fluorous metal-organic frameworks (FMOFs) are highly hydrophobic porous materials with a high capacity and affinity to C(6)-C(8) hydrocarbons of oil components. FMOF-1 exhibits reversible adsorption with a high capacity for n-hexane, cyclohexane, benzene, toluene, and p-xylene, with no detectable water adsorption even at near 100% relative humidity, drastically outperforming activated carbon and zeolite porous materials. FMOF-2, obtained from annealing FMOF-1, shows enlarged cages and channels with double toluene adsorption vs FMOF-1 based on crystal structures. The results suggest great promise for FMOFs in applications such as removal of organic pollutants from oil spills or ambient humid air, hydrocarbon storage and transportation, water purification, etc. under practical working conditions.     

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。     

多孔有机聚合物在水处理中的应用

多孔有机聚合物是一类由纯有机基团构成的新型材料。 近年来,多孔有机聚合物在吸附水中污染物方面引起了人们的兴趣。 本文简要地介绍了几种多孔有机聚合物吸附水中污染物最近的研究进展,并对其吸附机理、影响因素和研究前景进行了总结与展望。     

Highly Porous Hydroxyapatite/Graphene Oxide/Chitosan Beads as an Efficient Adsorbent for Dyes and Heavy Metal Ions Removal

Dye and heavy metal contaminants are mainly aquatic pollutants. Although many materials and methods have been developed to remove these pollutants from water, effective and cheap materials and methods are still challenging. In this study, highly porous hydroxyapatite/graphene oxide/chitosan beads (HGC) were prepared by a facile one-step method and investigated as efficient adsorbents. The prepared beads showed a high porosity and low bulk density. SEM images indicated that the hydroxyapatite (HA) nanoparticles and graphene oxide (GO) nanosheets were well dispersed on the CTS matrix. FT-IR spectra confirmed good incorporation of the three components. The adsorption behavior of the obtained beads to methylene blue (MB) and copper ions was investigated, including the effect of the contact time, pH medium, dye/metal ion initial concentration, and recycle ability. The HGC beads showed rapid adsorption, high capacity, and easy separation and reused due to the porous characteristics of GO sheets and HA nanoparticles as well as the rich negative charges of the chitosan (CTS) matrix. The maximum sorption capacities of the HGC beads were 99.00 and 256.41 mg g⁻¹ for MB and copper ions removal, respectively.     

Recent advances on hydrogels based on chitosan and alginate for the adsorption of dyes and metal ions from water

In contemporary times, water resources have become increasingly scarce and suffer from anthropogenic pollution sources with an organic and inorganic origin that are products of industrial, agricultural, and everyday waste. Contamination with heavy metals and dyes in wastewater is considered a risk for water sources that can leak into underground and surface sources, leading to increased biological and chemical contamination. The pollutant removal process is performed by adsorption treatment methods, which is the most common method, and it is considered an effective method with a high and economical removal rate.In this review, we discuss the use of biobased hydrogel adsorbents in the removal of organic dyes and metal ions from water. The literature indicates that hydrogels exhibit rapid absorption kinetics and a dye removal absorption capacity that can reach more than 100 mg/g and sometimes more than 2000 mg/g, with a metal adsorption capacity ranging from 38 mg/g to more than 440 mg/g. These results are discussed and compared by taking into account hydrogel materials that contain biopolymers such as alginate, chitosan or both. In general, absorption depends mainly on biobased materials, which have a natural origin and can be utilized to synthesize hydrogels to remove pollutants, dyes and heavy metals. Chitosan and alginate are prominent materials for this use and they can be incorporated with other components to obtain hydrogels or nanocomposite materials with different efficacies to remove dyes and metal ions.     

铁基金属-有机骨架及其复合物高级氧化降解水中新兴有机污染物

新兴有机污染物(Emerging organic contaminants,EOCs)是对人体健康及生态环境具有潜在或实质威胁的新型化学污染物。由于其被频繁使用且能在水生生态系统中持久性存在而对水生生物健康和安全造成严重威胁,故引起大众越来越多的关注。以活性污泥法为代表的传统水处理工艺通常不足以消除这些新兴有机污染物。为高效去除新兴有机污染物,基于新材料的高级氧化技术是最主要的深度处理技术之一。铁基金属-有机骨架(Fe-MOFs)及其复合物在诸多领域得到了广泛的应用,特别是在催化氧化去除水中有机污染物方面展现出良好的应用前景。通过合成方法改进、合成后改性以及与特定功能材料复合等方法可有效提升Fe-MOFs及其相关材料的吸附性能、增强其光吸收特性和促进载流子有效分离等。本文重点综述了Fe-MOFs及其复合物高级氧化(光催化、类芬顿和硫酸根自由基($SO_{4}^{-·}$)介导的氧化)去除水中新兴有机污染物的研究进展,并探讨了未来研究所面临的机遇和挑战。     

高效集水仿生超浸润材料的研究进展

有效地收集空气中的雾气是缓解缺水危机的一种方法.近年来,可雾水收集的仿生超浸润材料受到了广泛的关注.通过进一步研究雾水收集过程中的液滴动态运输行为,为设计并构筑多功能仿生超浸润材料提供指导.本综述详细地总结了自然界典型的雾水收集现象,并对液滴在不同润湿性材料表面的动态运输行为进行了分类.从单一仿生到多重仿生出发,系统介...     

Surface Modification of Graphene Oxides by Plasma Techniques and Their Application for Environmental Pollution Cleanup

Graphene oxides (GOs) have come under intense multidisciplinary study because of their unique physicochemical properties and possible applications. The large amount of oxygen‐containing functional groups on GOs leads to a high sorption capacity for the removal of various kinds of organic and inorganic pollutants from aqueous solutions in environmental pollution cleanup. However, the lack of selectivity results in difficulty in the selective removal of target pollutants from aqueous solutions in the presence of other coexisting pollutants. Herein, the surface grafting of GOs with special oxygen‐containing functional groups using low‐temperature plasma techniques and the application of the surface‐modified GOs for the efficient removal of organic and inorganic pollutants in environmental pollution are reviewed. This paper gives an account of our research on the application of GO‐based nanomaterials in environmental pollution cleanup, including: (1) the synthesis and surface grafting of functional groups on GOs, summarizing various types of low‐temperature plasma techniques for the synthesis of graphene/GOs; and (2) the application of graphene/GOs and their composites for the efficient removal of organic and inorganic pollutants from aqueous solutions, including the interaction mechanism according to recently published results.     

多孔有机聚合物吸附分离水体系中有机污染物研究和应用进展

有机物对水体的污染严重威胁生态环境安全和人类健康。 如何有效控制和消除水体系中的有机污染物是当前全球性热点问题之一,基于多孔材料的高效吸附是处理水体有机污染的有效方法。 多孔有机聚合物(Porous Organic Polymers,POPs)具有比表面积高、物理化学稳定性好、易修饰等特点,作为新型吸附剂在处理水体系有机污染方面具有广阔的应用前景。 本文综述了近10年来新型多孔有机聚合物对水体系中有机溶剂、农药与杀虫剂、有机染料等污染物的吸附分离研究进展。     

衍生多孔碳材料在固相微萃取中的应用研究进展

固相微萃取是一种集采样、萃取、富集和进样于一体的样品前处理技术,其萃取效果与涂层材料密切相关。多孔碳材料具有比表面积大、多孔结构可控、活性位点多和化学稳定性好等优点,广泛应用于电池、超级电容器、催化、吸附和分离等领域,也是一种热门的用作固相微萃取探针的涂层材料。衍生多孔碳材料因种类丰富、可设计性强被广泛研究,研究主要集中在对衍生多孔碳材料的结构优化方面。但是衍生多孔碳材料在固相微萃取中的应用还存在如下问题:(1)共价有机框架衍生多孔碳材料的制备已取得较大进展,但将其应用于固相微萃取领域的研究仍较少;(2)有待进一步明确制备出的衍生多孔碳材料用作固相微萃取涂层表现出优异提取能力的机理;(3)有待进一步深入研究将衍生多孔碳材料用作固相微萃取涂层以实现对不同物理化学性质污染物的广谱高灵敏度分析。文章综述了近3年衍生多孔碳材料在固相微萃取中的应用研究,并展望了未来衍生多孔碳材料在固相微萃取中的研究前景。引用文献共56篇,主要来源于Elsevier。     

Photocatalytic degradation of organic pollutants by MOFs based materials: A review

Metal-organic frameworks (MOFs) are currently popular porous materials with research and application value in various fields. Aiming at the application of MOFs in photocatalysis, this paper mainly reviews the main synthesis methods of MOFs and the latest research progress of MOFs-based photocatalysts to degrade organic pollutants in water, such as organic dyes, pharmaceuticals and personal care products, and other organic pollutants. The main characteristics of different synthesis methods of MOFs, the main design strategies of MOFs-based photocatalysts, and the excellent performance of photocatalytic degradation of organic pollutants are summarized. At the end of this paper, the practical application of MOFs, the current limitations of MOFs, the synthesis methods of MOFs, and the future development trend of MOFs photocatalysts are explained.     

Metal Nanoparticles Supported on Biomass‐Derived Hierarchical Porous Heteroatom‐Doped Carbon from Bamboo Shoots: Design,Synthesis and Applications

Heteroatom‐doped porous carbon derived from biomass have recently received increasing attention due to their unique properties such as high electrical conductivity, large specific surface area, high porosity, and easy availability, which are appealing materials for versatile applications in catalysis, energy, separation and adsorption, and life sciences as well. On the basis of our previous work in this field, we summarized in this account our recent progress on design, synthesis of metal (e. g., Pd, Co) nanoparticles supported heteroatom‐doped hierarchical porous carbon material derived from bamboo shoots and their applications for important organic transformations, including chemoselective semihydrogenation of alkynes, hydrosilylation of alkynes, cascade synthesis of benzofurans from terminal alkynes and iodophenols, selective hydrogenation of functionalized nitroarenes to form anilines, imines, and formamides. Finally, the current state and future challenges in this field are discussed. We hope this account could shed light on the rational design of novel non‐noble metal based heterogeneous catalysts derived from biomass for efficient and sustainable organic transformations.     

新型芳香三嗪超交联多孔聚合物去除水溶液中甲基橙

Organic dyes, especially the harmful cationic dye methyl orange (MO), are emerging pollutants. The development of new materials for their efficient adsorption and removal is thus of great significance. Porous organic polymers (POPs) such as hyper-cross-linked polymers, covalent organic frameworks, conjugated microporous polymers, and polymers with intrinsic microporosity are a new class of materials constructed from organic molecular building blocks. To design POPs both with good porosity and task-specific functionalization is still a critical challenge. In this study, we have demonstrated a simple one-step method for the synthesis of the hyper-cross-linked aromatic triazine porous polymer (HAPP) via the Friedel-Crafts reaction. The resultant porous polymer was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, elemental analysis (EA), thermo-gravimetric analysis (TGA), solid-state ¹³C nuclear magnetic resonance (¹³C NMR), and nitrogen adsorption-desorption isotherms. The results show that HAPP is a rough, irregular morphology, porous organic polymer that is amorphous in nature. The novel polymer showed high Brunauer-Emmett-Teller surface area (of up to 104.36 m²∙g⁻¹), porosity, and physicochemical stability. Owing to the presence of N heteroatom pore surfaces in the network, the material exhibited a maximum adsorption capacity of 249.3 mg∙g⁻¹ for MO from aqueous solutions at room temperature. This is higher than that of some reported porous materials under the same conditions. To explain this phenomenon more clearly, theoretical quantum calculations were performed via the DFT method using Gaussian 09 software and Multiwfn version 3.4.1. It is performed to analyze the properties and electrostatic potential (ESP) of the HAPP monomer and MO. The results indicated that the N heteroatom of HAPP can easily develop strong interactions with MO, supporting the efficient adsorption of MO. The parameters studied include the physical and chemical properties of adsorption, pH, contact time, and initial concentrations. The percentage of MO removal increased as the pH was increased from 2 to 4. The optimum pH required for maximum adsorption was found to be 5.6. Adsorption kinetics data were modeled using the pseudo-first-order and pseudo-second-order models. The results indicate that the second-order model best describes the kinetic adsorption data. The adsorption isotherms revealed a good fit with the Langmuir model. More importantly, the HAPP can be regenerated effectively and recycled at least five times without significant loss of adsorption capacity. Therefore, it is believed that HAPPs with hierarchical porous structures, high surface areas, and physicochemical stability are promising candidates for the purification and treatment of dyes in solution.     

Current Trends in the Application of Nanomaterials for the Removal of Pollutants from Industrial Wastewater Treatment—A Review

In the recent decades, development of new and innovative technology resulted in a very high amount of effluents. Industrial wastewaters originating from various industries contribute as a major source of water pollution. The pollutants in the wastewater include organic and inorganic pollutants, heavy metals, and non-disintegrating materials. This pollutant poses a severe threat to the environment. Therefore, novel and innovative methods and technologies need to adapt for their removal. Recent years saw nanomaterials as a potential candidate for pollutants removal. Nowadays, a range of cost-effective nanomaterials are available with unique properties. In this context, nano-absorbents are excellent materials. Heavy metal contamination is widespread in underground and surface waters. Recently, various studies focused on the removal of heavy metals. The presented review article here focused on removal of contaminants originated from industrial wastewater utilizing nanomaterials.     

离子型共价有机框架材料的制备及对染料吸附性能的研究

茜素红(Alizarin Red,AR)作为蒽醌类染料中的重要组成,由于其具有优异的特性,在染料和酸碱指示剂等方面被广泛使用。但是AR具有毒性高、结构复杂以及化学需氧量(COD)值大等原因,使其成为了主要污染物之一,去除水体中的茜素红染料污染物已经成为了目前亟待解决的问题。共价有机框架材料作为一种新型的多孔有机材料,由于其具有比表面积大,孔径均一和可设计的独特优势,已经广泛应用吸附和分离等方面。因此,以三醛基间苯三酚和溴化乙锭为构筑单元,通过水热的方法合成一种二维离子型共价有机框架材料(TpEB-COF)。对制备的TpEB-COF进行相关表征,包括X射线衍射仪(XRD),扫描电镜(SEM)和能量色散谱仪(EDS)等。然后将制备的TpEB-COF作为固体吸附剂,将其应用对水中AR的吸附,研究了不同吸附时间和不同pH值对吸附过程的影响。实验结果证明制备的离子型共价有机框架材料具有良好的晶型结构。同时,对实验数据分析表明,离子型共价有机框架材料对于茜素红的吸附符合准二级动力学方程和Langmuir吸附模型,吸附效率为82.8%,最大吸附量为828 mg g-1。本研究不仅为共价有机框架材料的设计和合成奠定坚实的基础,而且拓展了离子型共价有机框架材料的应用范围,促进共价有机框架材料的发展。     

金属有机骨架材料在吸附分离大气污染物中的应用

大气污染问题是关系人民生命健康和经济社会和谐发展的重大问题.因此需要开发高效的吸附材料用于大气污染物的吸附和分离.金属有机骨架材料(MOFs)是一类新型的多孔材料,该材料具有结构多样、孔结构有序、大比表面积和高孔隙率等结构特点.MOFs通过调节有机配体的长度和官能团调节孔径和孔道尺寸,并进行功能化修饰在孔道中引入功能性...     

Applications of Carbon-Based Materials in Activated Peroxymonosulfate for the Degradation of Organic Pollutants: A Review

In recent years, water pollution has posed a serious threat to aquatic organisms and humans. Advanced oxidation processes (AOPs) based on activated peroxymonosulfate (PMS) show high oxidation, good selectivity, wide pH range and no secondary pollution in the removal of organic pollutants in water. Carbon-based materials are emerging green catalysts that can effectively activate persulfates to generate radical and non-radical active species to degrade organic pollutants. Compared with transition metal catalysts, carbon-based materials are widely used in SR-AOPs because of their low cost, non-toxicity, acid and alkali resistance, large specific surface area, and scalable surface charge, which can be used for selective control of specific water pollutants. This paper mainly presents several carbon-based materials used to activate PMS, including raw carbon materials and modified carbon materials (heteroatom-doped and metal-doped), analyzes and summarizes the mechanism of activating PMS by carbon-based catalysts, and discusses the influencing factors (temperature, pH, PMS concentration, catalyst concentration, inorganic anions, inorganic cations and dissolved oxygen) in the activation process. Finally, the future challenges and prospects of carbon-based materials in water pollution control are also presented.     

2D MOFs-based Materials for the Application of Water Pollutants Removing: Fundamentals and Prospects

Water quality can have serious impacts on human health. One crucial issue of water pollution seriously affects our safety due to the continually emerging of discovered anthropogenic pollutants. The water treatment technologies are persistent improvement to adapt such new contaminants, which accelerates the evolution of materials science to explore solving the problems. Metal-organic Frameworks (MOFs) as the significant porous and multi-dimensional networks has been concerned for toxic pollutant elimination, especially probed the applications of outstanding layered 2D skeletons MOFs-based materials. The emphases of this review highlight the 2D MOFs-based materials used in water remediation and treatment strategies including adsorption and catalysis methods. Further, the prospects and challenges of 2D MOFs-based materials for water treatments applications would be surveyed meticulously for the future research and development.