Adsorption of graphene oxide/chitosan porous materials for metal ions

Porous graphene oxide/chitosan（PGOC） materials were prepared by a unidirectional freeze-drying method.Their porous structure,mechanical property and adsorption for metal ions were investigated.The results show that the incorporation of graphene oxide（GO） significantly increased the compressive strength of the PGOC materials.The saturated adsorption capacity of Pb²⁺ increased about 31%,up to 99 mg/g when 5 wt%GO was incorporated These biodegradable,nontoxic,efficient PGOC materials will be a potential adsorbent for metal ions in aqueous solution.     

A Layered Chitosan/Graphene Oxide Sponge as Reusable Adsorbent for Removal of Heavy Metal Ions

Along with the growing severity of environment problem and energy crisis, it is inevitable to develop novel materials, which are contributed to the removal of hazardous pollutants from contaminated water. Herein, we reported a fhcile method for the preparation of free-standing chitosan/graphene oxide(CS/GO) composite sponges with low density, where CS/GO mixtures were first synthesized by tlie homogeneous reaction of chitosan and graphene oxide in aqueous acetic acid solution;then CS/GO sponges were obtained by lyophilizing the suspension, which were prefrozen at -20 ℃ and in liquid nitrogen successively. The obtained layered sponge showed good water- driven shape memory effect and was a good adsorbent of Co^2+ and Ni^2+ witli a large adsorption capacity of 224.8 and 423.7 mg/g, respectively. Importantly, the successive adsorption-desorption studies employing CS/GO sponge indicated that the composite could be regenerated by HC1 solution and reused in more than five cycles with regeneration efficiency beyond 80%. Also, the resultant sponge was explored as an exceptionally adsorbent for the removal of organic dye(e.g., methylene blue, MB).     

磁性壳聚糖/Fe3O4/氧化石墨烯吸附剂的制备及其多染料吸附性能

为了提高壳聚糖的多染料吸附性能并使其便于固液分离,采用共沉淀法制备了壳聚糖、磁铁矿纳米颗粒、氧化石墨烯复合磁性吸附剂(CS/Fe₃O₄/GO)。系统的结构表征显示,CS包覆的Fe₃O₄磁性纳米颗粒均匀地分布在GO的表面。CS/Fe₃O₄/GO具有高达42.5 emu·g-1的室温铁磁性,因此可在外加磁场中实现高效固液分离。研究表明,CS/Fe₃O₄/GO对亚甲基蓝(MB)、甲基橙(MO)和刚果红(CR)等多种染料具有良好的吸附性能,溶液的pH、初始浓度和吸附时间对其多染料吸附性能具有显著影响。在最佳条件下,CS/Fe₃O₄/GO对MB、MO和CR的吸附量分别达到210.6、258.6和308.9 mg·g-1。CS/Fe₃O₄/GO具有优异的循环利用性能,经5次循环后仍能保留90%以上的原始吸附量。采用吸附等温线和吸附动力学对...     

磁性壳聚糖/Fe3O4/氧化石墨烯吸附剂的制备及其多染料吸附性能

为了提高壳聚糖的多染料吸附性能并使其便于固液分离,采用共沉淀法制备了壳聚糖、磁铁矿纳米颗粒、氧化石墨烯复合磁性吸附剂(CS/Fe₃O₄/GO)。系统的结构表征显示,CS包覆的Fe₃O₄磁性纳米颗粒均匀地分布在GO的表面。CS/Fe₃O₄/GO具有高达42.5 emu·g^-1的室温铁磁性,因此可在外加磁场中实现高效固液分离。研究表明,CS/Fe₃O₄/GO对亚甲基蓝(MB)、甲基橙(MO)和刚果红(CR)等多种染料具有良好的吸附性能,溶液的pH、初始浓度和吸附时间对其多染料吸附性能具有显著影响。在最佳条件下,CS/Fe₃O₄/GO对MB、MO和CR的吸附量分别达到210.6、258.6和308.9 mg·g^-1。CS/Fe₃O₄/GO具有优异的循环利用性能,经5次循环后仍能保留90%以上的原始吸附量。采用吸附等温线和吸附动力学对CS/Fe₃O₄/GO的多染料吸附性能进行了拟合分析,并详细讨论了其吸附机理。     

Preparation of an Anti-Aggregation Silica/Zinc/Graphene Oxide Nanocomposite with Enhanced Adsorption Capacity

Nanomaterials play a significant role in adsorption treatment of dye wastewater, but irreversible aggregation of nanoparticles poses a significant problem. In this work, nanomesoporous zinc-doped silicate (NMSZ) was prepared by an in situ method. To prevent agglomeration, NMSZ was covalently bonded to graphene oxide (GO) sheets to form a nano-silica/zinc/graphene oxide composite (GO-NMSZ), aimed at removal of cationic dye methylene blue (MB). For comparison, undoped mesoporous silica (MS) was also synthesized and modified to obtain a silica/graphene oxide composite (GO-MS). The materials were characterized by powder XRD, SEM, FTIR spectroscopy, TEM, nitrogen sorption, and X-ray photoelectron spectroscopy (XPS). Preservation of the oxygen-containing groups of GO in the composites led to higher adsorption capacities. The best GO-NMSZ composite exhibited an enhanced adsorption capacity of 100.4 mg g⁻¹ for MB compared to those of undoped GO-MS (80.1 mg g⁻¹) and nongrafted NMSZ (55.7 mg g⁻¹). The nonselective character of GO-NMSZ is demonstrated by effective adsorption of anionic dye Congo red (127.4 mg g⁻¹) and neutral dye isatin (289.0 mg g⁻¹). The adsorption kinetics, adsorption isotherms, and a thermodynamic study suggested that MB adsorption occurs by chemisorption and is endothermic in nature.     

金负载氧化石墨烯/PDPB复合材料用于同步去除六价铬离子和苯酚

近年来,电镀和染料行业工业废水中排放的有机污染物和重金属离子严重危害着环境.构建无机-有机新型纳米材料用于光催化去除重金属离子和有机污染物受到了广泛的关注.共轭聚合物因其低廉的制造成本,快速的电子传送能力,优秀的电化学性能和高的机械性能,它们作为一类新能源材料已经快速发展起来.Remita等使用软模板方法制备的一种共轭聚合物聚1,4-二苯基丁二炔(PDPB)在可见光下对苯酚表现出较好的去除率.然而,聚合物PDPB的一些缺陷限制了其应用,比如高的疏水特性和快速的光生电子-空穴复合.因此,我们引入氧化石墨烯(GO)和金纳米粒子来提高PDPB的光催化活性.通过简单的机械搅拌和光还原方法制备了Au-GO/PDPB复合材料.通过TEM,XRD,XPS,固体紫外和光电流测试等技术对催化剂进行了一系列表征,结果发现氧化石墨烯作为优秀的电子传送基地,金纳米粒子作为电子捕获剂,在空间上实现了电子空穴的空间隔离,从而大大提高了Au-GO/PDPB复合材料对于六价铬离子和苯酚的同步光去除的光催化活性.XPS表征和TEM图像表明了GO和Au纳米粒子的存在.其PDPB有着纳米纤维的结构,宽度在20 nm左右,长度在几个微米.当复合了氧化石墨烯后,可以明显看出氧化石墨烯的形态,进一步光还原负载金纳米粒子,同样可以在TEM图中观察到金纳米粒子的存在,其直径在10 nm左右.之后通过光催化同步去除六价铬离子和苯酚来探究Au-GO/PDPB复合材料的活性,结果表明所制备的Au-GO/PDPB比纯的PDPB有着增强的光催化活性在同步光去除六价铬离子(Cr(VI))和苯酚中.更进一步地是,我们同样确定了GO和Au纳米离子的最佳负载量,结果发现,Au1-GO2/PDPB复合材料(金的负载量为1 wt%,氧化石墨烯的负载量为2 wt%)在所有催化剂中有着最好的光催化活性,其在4 h内对苯酚的去除率达到49.4%,相应的对于六价铬离子的还原率达到了77.4%.我们的研究提供了一种构建有机-无机杂化复合材料的方法,其在太阳光下对于有机污染物和重金属离子的同步去除有着高的光催化活性.     

GO-SWCNT Buckypapers as an Enhanced Technology for Water Decontamination from Lead

Water decontamination is an important challenge resulting from the incorrect disposal of heavy metal waste into the environment. Among the different available techniques (e.g., filtration, coagulation, precipitation, and ion-exchange), adsorption is considered the cheapest and most effective procedure for the removal of water pollutants. In the last years, several materials have been tested for the removal of heavy metals from water, including metal-organic frameworks (MOFs), single-walled carbon nanotubes (SWCNTs), and graphene oxide (GO). Nevertheless, their powder consistency, which makes the recovery and reuse after adsorption difficult, is the main drawback for these materials. More recently, SWCNT buckypapers (SWCNT BPs) have been proposed as self-standing porous membranes for filtration and adsorption processes. In this paper, the adsorption capacity and selectivity of Pb²⁺ (both from neat solutions and in the presence of other interferents) by SWCNT BPs were evaluated as a function of the increasing amount of GO used in their preparation (GO-SWCNT buckypapers). The highest adsorption capacity, 479 ± 25 mg g⁻¹, achieved for GO-SWCNT buckypapers with 75 wt.% of graphene oxide confirmed the effective application of such materials for cheap and fast water decontamination from lead.     

A new efficient adsorbent in the preconcentration studies of the Cr(III) and Fe(III) ions

In this study, the imine‐graphene hybrid material (HM) was used as an adsorbent for removal of Fe(III) and Cr(III) metal ions from the drinking waters. The adsorbent material (HM) was prepared at three steps. At the first step, the graphite was oxidized by Hummer's method for preparation of graphene oxide (GO), in the second step, the silanization derivative (GO‐APTES) was obtained from the reaction of the 3‐(trimethoxysilyl) propylamine and GO. In the final step, the hybrid material (HM) was synthesized from the reaction of the 3,5‐diiodosalicylaldehyde and GO‐APTES. The chemical structures of three materials GO, GO‐APTES and HB were characterized by using the FT‐IR, XRD, EDX, SEM, TEM and UV‐vis methods. Thermal properties of the materials GO, GO‐APTES and HB were investigated by TGA/DTA methods in the 25–1000°C temperature range. Adsorption and desorption studies of the hybrid material toward Fe(III) and Cr(III) metal ions were investigated using the Batch method. The effect of pH, contact time, temperature, concentration on the adsorption properties of the hybrid material were investigated by ICP‐OES. The Fe(III) and Cr(III) ions have the maximum adsorption at the pH 7. The adsorption capacity decreases with the increase in pH values because above pH 9 the adsorption decreases due to the precipitation of metal hydroxide.     

Fabrication of macroporous polystyrene/graphene oxide composite monolith and its adsorption property for tetracycline

Macroporous polystyrene microsphere/graphene oxide(PS/GO) composite monolith was first prepared using Pickering emulsion droplets as the soft template. The Pickering emulsion was stabilized by PS/GO composite particles in-situ formed in an acidic water phase. With the evaporation of water and the oil phase(octane), the Pickering emulsion droplets agglomerated and combined with each other, forming a three-dimensional macroporous PS/GO composite matrix with excellent mechanical strength. The size of the macrospores ranged from 4 mm to 20 mm. The macroporous PS/GO composite monolith exhibited high adsorption capacity for tetracycline(TC) in an aqueous solution at p H 4–6. The maximum adsorption capacity reached 197.9 mg g 1at p H 6. The adsorption behaviour of TC fitted well with the Langmuir model and pseudo-second-order kinetic model. This work offers a simple and efficient approach to fabricate macroporous GO-based monolith with high strength and adsorption ability for organic pollutants.     

Porous graphene oxide-based carbon artefact with high capacity for methylene blue adsorption

A three-dimensional porous graphene oxide (PGO) material prepared by hydrothermal method was selected to adsorb methylene blue (MB), which demonstrates a high MB adsorption capacity, up to 1100 mg g^?1 in alkaline solution at room temperature. The influences of different pore structures and different contents of oxygen-containing functional groups on MB adsorption behaviors were studied in detail, which indicated that the high MB adsorption capacity is mainly ascribed to the synergistic effect of the large number of oxygen-containing functional groups and the interconnected 3D porous network. Moreover, based on the investigation on the adsorption kinetics and the effect of pH value on MB adsorption, we propose a two-step adsorption kinetics for PGO, which involved in two interactions between MB molecular and porous graphene oxide-based carbon: electrostatic force and π-π stacking. Besides, the calculation of the activation energies indicates that chemisorption dominates the adsorption for PGO in comparison with physisorption for three-dimensional porous graphene materials which has low adsorption capacity because of the removal of functional groups. The results are of great significance for the design and environmental applications of PGO as a promising adsorbent material for water purification.     

原位沉析法制备磁性氧化铁羟基磷灰石/壳聚糖棒材

首先通过化学沉淀法制备磁性氧化铁羟基磷灰石(Fe3O4/HA),然后以壳聚糖(CS)为基体,利用原位沉析法将Fe3O4/HA与CS复合,制得磁性Fe3O4/HA/CS复合材料.经XRD、粒径分布和PPMS测试,结果表明了Fe3O4/HA复合物的生成.系统研究了磁性Fe3O4/HA/CS棒材力学性能的影响因素,最终确定Fe3O4与HA质量比为3∶17,磁性Fe3O4/HA与CS质量比为9∶91时,棒材的力学性能最优,弯曲强度可达到87.0 MPa,弯曲模量1.57 GPa.     

Enhanced and selective adsorption of mercury ions on chitosan beads grafted with polyacrylamide via surface-initiated atom transfer radical polymerization

Enhanced and selective removal of mercury ions was achieved with chitosan beads grafted with polyacrylamide (chitosan-g-polyacrylamide) via surface-initiated atom transfer radical polymerization (ATRP). The chitosan-g-polyacrylamide beads were found to have significantly greater adsorption capacities and faster adsorption kinetics for mercury ions than the chitosan beads. At pH 4 and with initial mercury concentrations of 10-200 mg/L, the chitosan-g-polyacrylamide beads can achieve a maximum adsorption capacity of up to 322.6 mg/g (in comparison with 181.8 mg/g for the chitosan beads) and displayed a short adsorption equilibrium time of less than 60 min (compared to more than 15 h for the chitosan beads). Coadsorption experiments with both mercury and lead ions showed that the chitosan-g-polyacrylamide beads had excellent selectivity in the adsorption of mercury ions over lead ions at pH < 6, in contrast to the chitosan beads, which did not show clear selectivity for either of the two metal species. Mechanism study suggested that the enhanced mercury adsorption was due to the many amide groups grafted onto the surfaces of the beads, and the selectivity in mercury adsorption can be attributed to the ability of mercury ions to form covalent bonds with the amide. It was found that adsorbed mercury ions on the chitosan-g-polyacrylamide beads can be effectively desorbed in a perchloric acid solution, and the regenerated beads can be reused almost without any loss of adsorption capacity.     

氧化石墨烯/壳聚糖微球吸附-电感耦合等离子体质谱法测定地质样品中痕量钽EI北大核心CSCD

建立了氧化石墨烯/壳聚糖微球吸附-电感耦合等离子体质谱法测定地质样品中痕量Ta的方法。合成了氧化石墨烯/壳聚糖微球,将其应用于地质样品中痕量Ta的分离富集,采用电感耦合等离子体质谱对富集后的试液进行测定。对氧化石墨烯含量、配体种类和浓度、pH、吸附时间、吸附剂用量等吸附条件和洗脱剂类型、体积、洗脱时间等洗脱条件进行了优化,在优化的条件下,对地质样品标准物质进行测定,Ta的方法检出限为2.0 ng/g,富集倍数为26.7倍。     

Adsorption of Cu(II) on porous chitosan membranes functionalized with histidine

The ability of chitosan to form complexes with bivalent metal ions has been broadly explored in the literature. The present work investigates the influence of functionalization of macroporous chitosan membranes with histidine on their ability to remove copper ions from aqueous solution in the range of pH 4–6. The maximum adsorption capacity for Cu(II) ion was 2.5 mmol metal/g pristine chitosan membranes. Under this condition, no influence of membrane porosity was observed. However, for membranes with immobilized histidine, the porosity was shown to be a factor that affects the maximum adsorption capacity, with values ranging from 2.0 to 3.0 mmol metal/g chitosan. These results indicate that the immobilization of histidine on porous chitosan membranes presents synergy with porosity in the ability to complex Cu(II) ions. This synergy may be negative or positive, depending on the initial membrane porosity.     

Humic Acid Removal by Combining the Magnetic Property of Maghemite with the Adsorption Property of Nanosized Hydroxyapatite

Maghemite incorporated hydroxyapatite (HAP) nanocomposite was prepared by in situ precipitation of the calcium phosphate phase in an iron oxide colloidal suspension. The resultant nanocomposite was characterized by x-ray diffraction, Fourier transform infrared spectrometer, transmission electron microscope, N₂ adsorption analysis, and vibrating sample magnetometry. The potential of HAP/γ-Fe₂O₃ nanocomposite for HA adsorption from aqueous solution was evaluated by batch experiments and adsorption kinetic tests. HA adsorption amount on the adsorbent decreased with increasing solution pH and the presence of KNO₃ and alkali-earth metal ions resulted in enhanced HA adsorption. HA adsorption onto HAP/γ-Fe₂O₃ nanocomposite could be well described by Freundlich and Sips models, while HA adsorption process on the adsorbent obeyed pseudo-second-order kinetics and the adsorption rates decreased with increasing initial HA concentration. This study showed that the HAP/γ-Fe₂O₃ nanocomposite could be used as an efficient and magnetically separable adsorbent for the removal of HA from aqueous solution. Subsequent studies demonstrated that the HA-loaded HAP/γ-Fe₂O₃ nanocomposite could be further applied for the highly efficient adsorption of methylene blue (MB) and separated from the medium by a simple magnetic process.     

The morphology modulation of graphene to produce wrinkles and folds for effective electrochemical determination of Hg(II)

A highly efficient electrode material, three-dimensional reduced graphene oxide with varying wrinkles and folds (WRGO), applicable for electrochemical determination of Hg(II) was obtained by treating graphene oxide (GO) with KOH aqueous solution. After alkaline etching, the relatively flat graphene was altered and its self-aggregation was significantly alleviated, producing more wrinkles and folds, which provided more active adsorption sites for heavy metal ions. WRGO-5 modified electrode system herein offers a highest sensitivity of (31.83 μAμM⁻¹) and a lowest LOD of (16.28 nM). Moreover, the electrode sensor possesses good stability and reproducibility.     

Graphene Oxides Prepared by Hummers’, Hofmann’s,and Staudenmaier’s Methods: Dramatic Influences on Heavy‐Metal‐Ion Adsorption

Graphene oxide (GO), an up‐and‐coming material rich in oxygenated groups, shows much promise in pollution management. GO is synthesised using several synthetic routes, and the adsorption behaviour of GO is investigated to establish its ability to remove the heavy‐metal pollutants of lead and cadmium ions. The GO is synthesised by Hummers’ (HU), Hofmann’s (HO) and Staudenmaier’s (ST) methodologies. Characterisation of GO is performed before and after adsorption experiments to investigate the structure–function relationship by using Fourier‐transform infrared spectroscopy and X‐ray photoelectron spectroscopy. Scanning electron microscopy coupled with elemental detection spectroscopy is used to investigate morphological changes and heavy‐metal content in the adsorbed GO. The filtrate, collected after adsorption, is analysed by inductively coupled plasma mass spectrometry, through which the efficiency and adsorption capacity of each GO for heavy‐metal‐ion removal is obtained. Spectroscopic analysis and characterisation reveal that the three types of GO have different compositions of oxygenated carbon functionalities. The trend in the affinity towards both Pb^II and Cd^II is HU GO>HO GO>ST GO. A direct correlation between the number of carboxyl groups present and the amount of heavy‐metal ions adsorbed is established. The highest efficiency and highest adsorption capacity of heavy‐metal ions is achieved with HU, in which the relative abundance of carboxyl groups is highest. The embedded systematic study reveals that carboxyl groups are the principal functionality responsible for heavy‐metal‐ion removal in GO. The choice of synthesis methodology for GO has a profound influence on heavy‐metal‐ion adsorption. A further enrichment of the carboxyl groups in GO will serve to enhance the role of GO as an adsorbent for environmental clean‐up.     

Preparation of silver/graphene/polymer hybrid microspheres and the study of photocatalytic degradation

Three-dimensional silver/graphene/polymer hybrid microspheres were prepared to depress the aggregation of two-dimensional graphene. Graphene oxide (GO) sheets were successfully wrapped on the surface of amine-functionalized polystyrene-poly (glycidyl methacrylate) (PS-PGMA) microspheres (～3 μm in diameter) to form graphene oxide/amino-microsphere (GO/AMS) core–shell structure. Subsequently, the wrapped GO sheets were reduced by using hydrazine hydrate as the reducing agents, meanwhile decorated with silver nanoparticles on the wrinkled surface to form Ag-rGO/AMS hybrid microspheres with monodisperse distributions in shape and diameter. The resulting materials were characterized by power X-ray diffraction, scanning electron microscope, Raman spectra, and ultraviolet–visible (UV–vis) absorption spectra. Since Ag nanoparticles behave surface plasmon resonance effect and rGO structure can improve the separation of photogenerated electrons and holes, the Ag-rGO/AMS composites present good photocatalytic activities for the degradation of methylene blue (MB) as 93 % MB were degraded after 2.5 h under irradiation.     

Graphene oxide-based two-dimensional molecular brush for efficient removal of lead and copper ions from water media

In this study, graphene oxide (GO)-based two-dimensional molecular brush was fabricated by grafting polyacrylamide onto GO nanosheets for efficient removal of Pb²⁺ and Cu²⁺ from water media. Owing to the rich oxygen and nitrogen functional groups in the composites, the synthetic GO two-dimensional molecular brush can get the maximum adsorption capacity of 268.4 mg/g for Pb²⁺ and 127.2 mg/g for Cu²⁺, respectively. Moreover, the interspaces between the stacked two-dimensional molecular brushes provide fast pathways for the diffusion of heavy metal ions. As a result, GO-based two-dimensional molecular brush can reach the adsorption equilibrium within 60 min. These results indicated that the synthetic GO-based two-dimensional molecular brush is a promising adsorbent to separate heavy metal ions from water media.     

GO/PVA nanocomposites with significantly enhanced mechanical properties through metalion coordination

In this study, a simple and efficient way is demonstrated to create strong interfacial interaction between graphene oxide(GO) filler and poly(vinyl alcohol)(PVA) matrix through metal ion coordination. The coordination bonding provides efficient load transfer during the tensile process, and enhances the mechanical properties of the nanocomposites significantly. After being coordinated with Cu(Ⅱ) ions, GO/PVA composites show much higher Young's moduli and yield stresses than pure PVA and noncoordinated GO/PVA. UV–vis and FTIR spectra are performed to confirm the successful coordination between GO and PVA. Ethylene diamine tetraacetic acid disodium salt(EDTA-2 Na) is used to confirm the important role of coordination in enhancing the composites. This research provides a new approach to manufacture polymer-matrix nanocomposites with significantly improved mechanical performances.