Environmental application of three-dimensional graphene materials as adsorbents for dyes and heavy metals: Review on ice-templating method and adsorption mechanisms

The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.     

聚烯丙基氯化铵调控的中空多孔磷酸八钙超结构及其对Pb(Ⅱ)的吸附特性

环境友好、价格低廉且易于批量化生产的矿物基吸附剂在环境污染物去除方面越来越显现出其优越性,但以往的研究多集中于晶相的矿物吸附剂,有关亚稳相的研究相对较少.因此,本文通过仿生矿化的方法,以聚烯丙基氯化铵（PAH）作为生长调节剂,在气相扩散过程中成功制备了由超薄纳米片构筑的中空、多孔磷酸八钙（Octacalcium Phosphate,OCP）微球.结果发现,制备的吸附剂具有较高的比表面积和孔隙率,且高分辨电镜图片显示其具有一定的非晶纳米区域,并对重金属离子Pb（II）表现出优越的吸附特性.吸附实验证明,OCP/PAH对Pb（Ⅱ）的吸附符合Langmuir等温吸附模型和准二级吸附动力学模型,最高吸附量可达1644.74 mg·g^-1.该亚稳相矿物吸附剂出色的重金属吸附性能,为开发新型矿物吸附剂提供了新思路.     

共价有机骨架复合材料去除水体中重金属离子的研究进展

共价有机骨架复合材料（covalent organic framework composites,COFs）是由轻元素C、O、N、B等以强共价键结合而成的一类具有二维或三维晶体结构的新兴多孔聚合物材料.由于它们具有孔道有序可调、比表面积大、孔隙率高、结构稳定及官能团丰富可进行后修饰等优点,在污染物吸附去除领域受到了广泛关注.本文总结了COFs复合材料的最新合成策略（"自下而上"、合成后修饰和混合合成策略）和COFs复合材料在水体中去除重金属离子方面的研究进展,并对其应用前景进行了展望.近年来,运用吸附方式从环境水体中去除重金属离子在环境治理领域颇受关注.COFs复合材料作为一种新型多孔结晶材料,具有优异的吸附性能,可从水溶液中有效去除重金属离子,因此具有广阔的应用前景.COFs复合材料吸附重金属离子的方式由化学吸附和物理吸附组成,且化学吸附占主导地位.现有的COFs复合材料合成方法因其存在时间较长、成本较高及产率较低等缺点,阻碍了其在环境分析领域中的实际应用,为增加效率、节约成本及实现工业化生产,迫切需要进一步开发合成COFs及复合材料的更多新方法.      

Novel eco-friendly spherical porous adsorbent fabricated from Pickering middle internal phase emulsions for removal of Pb(II) and Cd (II)

Spherical porous materials prepared from the emulsion template used in the water treat-ment have displayed a vast prospect,as the high surface area,abundant porous structure,convenient operation and excellent adsorption performance.But the tedious fabrication process,high consumption of organic solvent and surfactant limited the application widely.Herein,a facile and eco-friendly spherical porous adsorbent (SPA) is fabricated from the green surfactant-free (corn oil)-in-water Pickering medium internal phase emulsions (Pick-ering MIPEs) via the convenient ion crosslinking procedure.The Pickering MIPEs synergis-tically stabilized with the semi-coke (SC),which is the natural particle produced from the shale oil distillation,and sodium alginate (SA) has excellent storage and anti-coalescence stability.The as-prepared porous adsorbent possessed the abundant pore structure,which provided favorable conditions for effective mass transfer in adsorption,and could be tuned by varying the SA dosage.The saturation adsorption capacities of Pb(Ⅱ) and Cd(Ⅱ) can be achieved with 460.54 and 278.77 mg/g within 45 min at 25℃,respectively.Overall,this study supplied a viable and eco-friendly route for fabricating the spherical porous adsorbent with a tunable porous structure for heavy metal ion wastewater.     

Review on heterogeneous oxidation and adsorption for arsenic removal from drinking water

The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.     

功能化多孔材料对CO_2的吸附分离研究进展

功能化多孔材料拥有优越的CO_2吸附和存储性能,在燃煤电厂、玻璃炉窑、水泥厂、钢铁厂等高耗能工矿企业采用CO_2吸附技术,对CO_2减排、减缓温室效应具有重要意义。随着研究的不断深入,新型CO_2吸附材料呈现出廉价、易获取、高吸附率等趋势,当前研究重点集中在介孔硅、金属有机框架、沸石、活性炭、聚合物等的表面功能化。总结了上述典型吸附剂功能化的最新成果,重点介绍多孔吸附材料的功能化方法、吸附机理与吸附动力学的研究进展,并提出多孔材料对CO_2的吸附分离的研究空间和发展趋势。     

Effect of biomass addition on the surface and adsorption characterization of carbon-based adsorbents from sewage sludge

Sewage sludge with the additive corn cob was used as prescusor to prepare sludge-based carbon adsorbents by pyrolysis method. And then, the carbonizated products were activated with potassium hydroxide. The mixing ratio of the corn cob to sewage sludge was investigated. The surface area and pore size distribution, elemental composition, surface chemistry structure and the surface physical morphology were determined and compared. The results demonstrated that the addition of corn cob into the sewage sludge sample could effectively improve the surface area (from 287 to 591 m 2 /g) and the microporosity (from 5% to 48%) of the carbon based adsorbent, thus enhancing the adsorption behavior. The sulfur dioxide adsorption capacity was measured according to breakthrough test. It was found that the sulfur dioxide adsorption capacity of the adsorbents was obviously enhanced after the addition of the corn cob. It is presumed that not only highly porous adsorbents, but also a high metallic content of these materials are required to achieve good performances.     

碳纳米管基复合吸附剂的制备及其吸附性能

为了解决碳纳米管(CNTs)在吸附水中污染物时易聚集、难分离的问题,本文采用静电自组装技术将碳纳米管固定化在具有微米级粒径的碳酸钙颗粒表面,设计制备了壳-核结构的CNTs基复合吸附剂.实验考查了不同碳纳米管分散体系对复合吸附剂制备的影响,并采用Zeta电位、拉曼光谱、扫描电镜等手段对复合吸附剂的制备过程和结构进行表征,探讨了制备的碳纳米管基复合吸附剂对菲的吸附性能.结果发现,复合吸附剂对菲的吸附能力随CNTs载量的增加而增大,CNTs标化的吸附系数则随CNTs载量的增加而下降,碳纳米管是复合吸附剂的主要吸附位点.     

Insight into the adsorption of tetracycline onto amino and amino–Fe functionalized mesoporous silica: Effect of functionalized groups

In order to study the influences of functionalized groups onto the adsorption of tetracycline (TC), we prepared a series of amino and amino–Fe^3 + complex mesoporous silica adsorbents with diverse content of amino and Fe^3 + groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction, Fourier transform infrared spectrometer and N₂ adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe^3 + groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe^3 + increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe^3 + content increased from 3.93% to 8.26%, the Q_max of the adsorbents increased from 102 to 188 mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications.     

Mesoporous carbon adsorbents from melamine-formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), elemental(CHN) analysis, Fourier transform infrared(FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO_2 capture.The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO_2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO_2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO_2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO_2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.     

Mesoporous carbon adsorbents from melamine–formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental (CHN) analysis, Fourier transform infrared (FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO₂ capture. The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO₂ adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO₂ adsorption capacity among the synthesized adsorbents. Breakthrough time and CO₂ equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO₂ system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.     

Efficient nitrogen doped porous carbonaceous CO2 adsorbents based on lotus leaf

In this work, the waste biomass lotus leaf was converted into N-doped porous carbonaceous CO₂ adsorbents. The synthesis process includes carbonization of lotus leaf, melamine post-treatment and KOH activation. For the resultant sorbents, high nitrogen content can be contained due to the melamine modification and advanced porous structure were formed by KOH etching. These samples were carefully characterized by different techniques and their CO₂ adsorption properties were investigated in detail. These sorbents hold good CO₂ adsorption abilities, up to 3.87 and 5.89 mmol/g at 25 and 0°C under 1 bar, respectively. By thorough investigation, the combined interplay of N content and narrow microporous volume was found to be responsible for the CO₂ uptake for this series of sorbents. Together with the high CO₂ adsorption abilities, these carbons also display excellent reversibility, high CO₂/N₂ selectivity, applicable heat of adsorption, fast CO₂ adsorption kinetics and good dynamic CO₂ adsorption capacity. This study reveals a universal method of obtaining N-doped porous carbonaceous sorbents from leaves. The low cost of raw materials accompanied by easy synthesis procedure disclose the enormous potential of leaves-based carbons in CO₂ capture as well as many other applications.     

Comparison study of phosphorus adsorption on different waste solids: Fly ash, red mud and ferric–alum water treatment residues

The adsorption of phosphorus(P) onto three industrial solid wastes(fly ash, red mud and ferric–alum water treatment residual(FAR)) and their modified materials was studied systematically via batch experiments. Compared with two natural adsorbents(zeolite and diatomite), three solid wastes possessed a higher adsorption capacity for P because of the higher Fe, Al and Ca contents. After modification(i.e., the fly ash and red mud modified by FeCl_3 and FARs modified by HCl), the adsorption capacity increased, especially for the modified red mud, where more Fe bonded P was observed. The P adsorption kinetics can be satisfactorily fitted using the pseudo-second-order model. The Langmuir model can describe well the P adsorption on all of the samples in our study. p H and dissolved organic matter(DOM) are two important factors for P adsorption. Under neutral conditions, the maximum adsorption amount on the modified materials was observed. With the deviation from pH 7, the adsorption amount decreased, which resulted from the change of P species in water and surface charges of the adsorbents. The DOM in water can promote P adsorption, which may be due to the promotion effects of humic-Fe(Al) complexes and the pH buffer function exceeds the depression of competitive adsorption.     

树脂基固态胺吸附材料的选择性CO2吸附性能

基于简单的湿浸渍法将聚乙烯亚胺(PEI)有效负载到多孔树脂(HP20)中,制备获得树脂基固态胺吸附材料,并探究了PEI负载量(30%~60%)、吸附温度(30~90℃)和压力(2~100kPa)对材料CO₂吸附性能的影响.研究表明树脂基固态胺吸附材料的最佳PEI负载量为50%,过量的PEI会致使材料CO₂吸附容量和胺基利用效率的显著降低.所筛选的材料在较低或较高的CO₂分压范围内均能展现出优异的CO₂吸附性能,在30℃下的CO₂吸附容量达到3.06~3.78mmol/g,表明该材料在不同CO₂分压的多种碳捕集应用中均有着较好的适用性.此外,树脂基固态胺吸附材料的CO₂/CH₄和CO₂/N₂选择性在2~100kPa的压力范围内分别有262~5858和708~11551,在各类传统或新兴的固体吸附材料中处于较高水平.     

MOFs材料在废水污染物吸附治理中的应用研究进展

介绍了国内外MOFs材料吸附去除废水中各种污染物的研究进展,主要针对重金属离子(Hg²⁺、U⁶⁺、Cr⁶⁺、Cd²⁺、Pb²⁺、Co²⁺、Sb⁵⁺、Sr²⁺)及类金属离子(As³⁺、As⁵⁺)、有机污染物(染料分子、芳香化合物)等的去除,分析了MOFs及改性MOFs材料对废水中污染物的吸附性能;展望了MOFs材料在废水污染物吸附治理中的应用前景,提出高稳定性及具有催化性质的MOFs材料是用于废水中污染物吸附治理的理想材料。     

吸附法去除水中抗生素研究进展

随着社会经济的快速发展,抗生素被越来越多地应用于生产生活中,抗生素污染已成为亟须解决的环境问题。吸附法是一种去除抗生素简单、高效、经济的方法。综述了环境领域应用较为广泛的抗生素吸附材料,主要包括碳材料、矿物材料、金属骨架材料及水凝胶、气凝胶、磁性纳米材料、分子印迹材料等新型材料等,并比较了这些吸附材料各自的优缺点。同时,对利用吸附法去除抗生素的机理和吸附动力学行为进行了讨论。综合评价吸附材料的二次污染及环境风险,开发吸附材料的回收利用和安全处置方法,是未来吸附材料研发的重点。     

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes

Iron oxide(FeO)coated by natural organic matter(NOM)is ubiquitous.The associations of minerals with organic matter(OM)significantly changes their surface properties and reactivity,and thus affect the environmental fate of pollutants,including nutrients(e.g.,phosphorus(P)).In this study,ferrihydrite/goethite-humic acid(FH/GE–HA)complexes were prepared and their adsorption characteristics on P at various p H and ionic strength were investigated.The results indicated that the Fe O–OM complexes showed a decreased P adsorption capacity in comparison with bare Fe O.The maximum adsorption capacity(Q_(max))decreased in the order of FH(22.17 mg/g)FH-HA(5.43 mg/g)GE(4.67 mg/g)GE-HA(3.27 mg/g).After coating with HA,the amorphous FH–HA complex still showed higher P adsorption than the crystalline GE–HA complex.The decreased P adsorption observed might be attributed to changes of the Fe O surface charges caused by OM association.The dependence of P adsorption on the specific surface area of adsorbents suggests that the Fe O component in the complexes is still the main contributor for the adsorption surfaces.The P adsorptions on Fe O–HA complexes decreased with increasing initial p H or decreasing initial ionic strength.A strong dependence of P adsorption on ionic strength and p H may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the Fe O component and P.Therefore,previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils,especially in humic-rich areas.     

碘化阶层孔氧化硅纳米球对水中典型有机氯污染物的吸附性能研究

采用共缩聚法,成功地原位合成了碘改性的阶层多孔氧化硅纳米球（SiO₂-I）,研究了其基于卤键作用对典型有机氯污染物六六六的吸附性能,并考察了改性剂I-硅烷含量和pH值对吸附效果的影响.实验结果表明,该纳米材料对六六六表现出优异的吸附富集性能,吸附速率快,60 min内对六六六的去除率为71.6%,240 min内达到吸附平衡,去除率可达98.3%,最大吸附量为178.6 mg·g^-1;吸附动力学符合拟二级动力学模型;碘物种的加入提高了阶层多孔氧化硅的吸附速率和吸附效率.另外,为了便于纳米吸附材料的分离,本研究对SiO₂-I纳米球进行了磁性化.研究发现,磁性化修饰后,SiO₂-I纳米材料仍然保留对六六六优异的吸附富集性能,240 min时的吸附去除率达90.3%.     

挥发性有机物(VOCs)吸附材料的研究进展

目前,我国面临严重的挥发性有机物（VOCs）污染问题。吸附法是研究与应用最为广泛的VOCs治理技术。主要介绍了吸附净化VOCs原理和几种常见的VOCs吸附材料,包括活性炭、新型多孔炭材料、沸石分子筛、黏土基吸附剂、金属有机框架和介孔硅。详述了各吸附材料的VOCs吸附能力和优缺点,判断了其应用价值,并指出了为提升大规模工业化应用潜力,后续研发的VOCs吸附材料应满足高吸附量、高疏水性、高热稳定性和再生能力强4个特征。     

氨三乙酸酐改性纤维素对Cd~(2+)的吸附性能

本实验采用氨三乙酸酐改性玉米秸秆纤维素和苎麻纤维素,制备了两种改性纤维素吸附剂NTAA-CS及NTAA-RF,并研究了这两种吸附剂对水中Cd2+的吸附性能.通过元素分析、FTIR及SEM分析发现,纤维材料表面成功引入了氨三乙酸分子中的酯键和氨基基团.在改性纤维素吸附剂投加量为2 g·L-1,Cd2+的初始浓度为200 mg·L-1,p H值为4.0时,NTAA-CS和NTAA-RF对Cd2+的去除率分别为82.6%和90.2%.吸附实验结果表明:改性纤维素吸附剂对Cd2+的吸附是一个快速过程,吸附的最佳p H范围为4.0~7.0.吸附等温线用Langmuir方程的拟合效果优于Freundlich方程.经过5次吸附再生,吸附剂仍可以保持较大的吸附容量.这些结果表明,NTAA-CS和NTAA-RF在去除重金属废水中有较大的应用前景.