Removal of copper(II) from an aqueous solution with copper(II)‐imprinted chitosan microspheres

Ion‐imprinted chitosan (CS) microspheres (MIPs) were prepared with Cu(II) as a template and epichlorohydrin as a crosslinker for the selective separation of Cu(II) from aqueous solution. The microspheres showed a higher adsorption capacity and selectivity for the Cu(II) ions than nonimprinted chitosan microspheres (NMIPs) without a template. The results show that the adsorption of Cu(II) on the CS microspheres was affected by the initial pH value, initial Cu(II) concentration, and temperature. The kinetic parameters of the adsorption process indicated that the adsorption followed a second‐order adsorption process. Equilibrium experiments showed very good fits with the Langmuir isotherm equation for the monolayer adsorption process. The maximum sorption capacity calculated from the Langmuir isotherm was 201.66 mg/g for the Cu–MIPs and 189.51 mg/g for the NMIPs; these values were close to the experimental ones. The selectivity coefficients of Cu(II) and other metal ions on the NMIPs indicated a preference for Cu(II). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Zeolite X/chitosan hybrid microspheres and their adsorption properties for Cu(II) ions in aqueous solutions

The preparation of zeolite X/chitosan (CS) hybrid microspheres for efficient removal of Cu(II) ions by an impregnation-gelation-hydrothermal synthesis technique is reported here. Characterizations by various techniques indicate that the microspheres show porous structures and intimate interaction between zeolite and CS. The adsorption experiments are performed to evaluate the adsorption capacity of zeolite X/CS hybrid microspheres and comparisons are made with binderless zeolite X microspheres, pure CS microspheres and mechanical mixed zeolite X/CS microspheres. The effects of Cu(II) solution concentration and the pH are investigated. The results indicate that zeolite X/CS hybrid microspheres with the zeolite content of 60 wt% show the highest adsorption capacity, which is 90 mg/g at the initial Cu(II) concentration of 10 mg/L and 150.4 mg/g at Cu(II) concentration of 500 mg/L. The adsorption capacity increases with increasing initial pH and reaches a maximum at pH 5.5 in the range of 0–6.0. The equilibrium adsorption data are well described by the Langmuir isotherm model, exhibiting a maximum adsorption capacity of 152.0 mg/g, and the kinetic data are well fitted with the pseudo-second-order equation. Complete removal of Cu(II) ions can be obtained even at very low concentrations. The microspheres show high adsorption capacity and efficiency for Cu(II) ions, exhibiting potential practical application in the treatment of water pollution of heavy metal ions.     

Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads

The adsorption of Cu(II) ions onto chitosan and cross-linked chitosan beads has been investigated. Chitosan beads were cross-linked with glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. Batch adsorption experiments were carried out as a function of pH, agitation period, agitation rate and concentration of Cu(II) ions. A pH of 6.0 was found to be a optimum for Cu(II) adsorption on chitosan and cross-linked chitosan beads. Isotherm studies indicate Cu(II) can be effectively removed by chitosan and cross-linked chitosan beads. Adsorption isothermal data could be well interpreted by the Langmuir equation. Langmuir constants have been determined for chitosan and cross-linked chitosan beads. The experimental data of the adsorption equilibrium from Cu(II) solution correlated well with the Langmuir isotherm equation. The uptakes of Cu(II) ions on chitosan beads were 80.71 mg Cu(II)/g chitosan, on chitosan-GLA beads were 59.67 mg Cu(II)/g chitosan-GLA, on chitosan-ECH beads were 62.47 mg Cu(II)/g chitosan-ECH and on chitosan-EGDE beads were 45.94 mg Cu(II)/g chitosan-EGDE. The Cu(II) ions can be removed from the chitosan and cross-linked chitosan beads rapidly by treatment with an aqueous EDTA solution and at the same time the chitosan and cross-linked chitosan beads can be regenerated and also can be used again to adsorb heavy metal ions.     

Thiocarbohydrazide‐modified chitosan as anticorrosion and metal ion adsorbent

To explore the application of chitosan (CS) derivatives in anticorrosion and adsorption, thiocarbohydrazide‐modified chitosan (TCHECS) derivative was synthesized and characterized. The preliminary electrochemical measurements of the behaviors of 304 steel and Cu sheets in 2% HAc (v/v) containing TCHECS, chitosan (CS), and hydrazine cross‐linked epoxy‐N‐phthaloylchitosan (HECS) had been performed. The short‐term electrochemical tests show that the new compound can act as a mixed‐type metal anticorrosion inhibitor; its inhibition efficiency is 88% when the concentration was 30 mg/L. The preliminary adsorption studies for sorbents TCHECS and HECS on a metal ion mixture aqueous solution were also performed. The results show that TCHECS can absorb As (V), Ni (II), Cu (II), Cd (II), and Pb (II) efficiently at pH 9; the removal of the As (V), Ni (II), Cu (II), Cd (II), and Pb (II) are around 55.6–99.9%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40671.     

壳聚糖/聚丙烯酸水凝胶的制备及对Cu2 和Cd2 的吸附性能

以丙烯酸(AA)和壳聚糖(CS)为原料,N,N''-亚甲基双丙烯酰胺(MBA)为交联剂,利用辉光放电电解等离子(GDEP)技术在水溶液中一步引发制备壳聚糖/聚丙烯酸(CS/PAA)水凝胶。采用FT-IR、XRD和SEM对水凝胶的结构和形貌进行表征,考察了溶液pH、吸附时间和初始浓度对Cu2 和Cd2 吸附的影响,探讨了水凝胶的重复利用性。结果表明,丙烯酸成功接枝到壳聚糖链上,水凝胶呈现多孔的三维网络结构,CS/PAA对Cu2 和Cd2 的吸附符合Langmuir 吸附等温式和准二级动力学模型,由Langmuir 模型得到的最大理论吸附量为161.8和327.9 mg/g,该水凝胶在EDTA-4Na溶液中具有良好的再生和重复利用性。     

Adsorption of lanthanum by magnetic alginate‐chitosan gel beads

BACKGROUND: The risk of environmental pollution is aggravated by the increasing application of considerable amounts of rare earth elements in advanced materials. This paper reports the preparation of novel magnetic alginate–chitosan gel beads and their application for adsorption of lanthanum ions from aqueous solution. RESULTS: Stable magnetic alginate–chitosan gel beads with average diameter 0.85 ± 0.05 mm were prepared by loading iron oxide nanoparticles onto a combined alginate and chitosan absorbent. The performance of the prepared beads for the adsorption of lanthanum ions from aqueous solution was tested. It was found that various parameters, such as aqueous pH, contact time, metal ion concentration, ion strength and temperature, have an effect on the adsorption. Adsorption equilibrium was reached in 10 h and the maximum uptake capacity was 97.1 mg g^?1. From the analysis of pH, FTIR and XPS data, it is proposed that lanthanum adsorption proceeds through mechanisms of cation exchange, electrostatic interaction and surface complexation, with the oxygen atoms the main binding sites. In addition, lanthanum ions could be selectively separated from coexisting base metal ions such as Pb (II), Cd (II), Co (II), Ni (II) and Cu (II) in the aqueous solution. CONCLUSION: The prepared magnetic alginate–chitosan gel beads exhibit high uptake capacity and selectivity for lanthanum sorption, and thus can be used for adsorptive recovery of lanthanum from aqueous solutions. Copyright © 2010 Society of Chemical Industry     

Effect of a non-ionic surfactant on skin-retention of cationic minoxidil microparticles suspended in an anionic surfactant solution

The effect of Brij 78, a nonionic surfactant, on the interactions between cationic minoxidil (MXD) microparticles and sodium lauryl ether sulfate (SLES) in an aqueous phase was investigated. Cationic MXD microparticles were prepared by high pressure homogenization, where distearyldimethylammonium chloride (DSDMAC) was used as a cationic dispersant. The positive surface charge of MXD microparticles was neutralized at the equimolar ratio of SLES/DSDMAC and became negative in the presence of excess amount of SLES, whether Brij 78 was included in the MXD suspensions or not. On the other hand, when nonionic surfactant was included in the suspension so that the molar ratio of Brij 78/DSDMAC was 0.063: 1, the suspension of the cationic microparticles was stable in terms of turbidity change even in the presence of excess amount of SLES. It means that while electrostatic interactions between DSDMAC and SLES were occurring, the aggregation of cationic MXD microparticles was prevented with the aid of Brij 78. Due to the cationic microparticle-stabilizing effect of Brij 78 in the presence of the anionic surfactant, the substantivity of the cationic MXD microparticles having Brij 78 was about two times higher than that of the microparticles without the nonionic surfactant.     

Anti-fog chitosan/sodium lauryl ether sulfate films

The aim of this study was the preparation and characterization of hydrophobic–hydrophilic chitosan films obtained through interaction between the cationic biopolymer, chitosan (CH), with sodium lauryl ether sulfate (SLES), an anionic surfactant, which has also nonionic surfactant properties. The chitosan flat films were obtained at different concentrations of SLES, in the range of 0.02–0.1 M, where spherical capsules were also obtained. The wettability, quantified by the values of contact angle, indicated the hydrophobic character of the films. The significant values of swelling capacity in water, and in 1 % acetic acid solution confirmed the hydrophilic character of the obtained films. Weight loss of CH/SLES films after 24 h, in water and 1 % acetic acid solution was less than 3 % for the all samples. The structure of CH/SLES complex was determined by FTIR spectroscopy method. The morphology of CH/SLES film surfaces determined by atomic force microscopy showed a film surface with nanoroughness structure, determined by the SLES self-assembled nanostructures. The obtained CH/SLES films are transparent and have anti-fogging properties, compared with CH/sodium lauryl sulfate film, which is also transparent but, it gets fogged when coming in contact with warm air.     

Preparation,characterization, and adsorption properties of chitosan microspheres crosslinked by formaldehyde for copper (II) from aqueous solution

The chitosan microspheres crosslinked by formaldehyde were prepared by spray drying method and used as an adsorbent for copper (II) from aqueous solution. A batch adsorption system was applied to study the adsorption of copper (II) from aqueous solution by chitosan microspheres. The maximum adsorption capacity of the chitosan microspheres for copper (II) was 144.928 mg/g at pH 6.0. Langmuir adsorption model was found to be applicable in interpreting the adsorption process. To elucidate the adsorption mechanism, the chitosan microspheres before and after copper (II) adsorption were further characterized by Fourier transform infrared spectra, zeta potential analysis, and scanning electron microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adsorption of cadmium (II) and copper (II) ions from aqueous solution using chitosan composite

The binary chitosan/silk fibroin composite synthesized by reinforcement of silk fibroin fiber into the homogenous solution of chitosan in formic acid was used to investigate the adsorption of two metals of Cu(II) and Cd(II) ions in an aqueous solution. The binary composite was characterized by Fourier transform infrared and scanning electron microscopy. The optimum conditions for adsorption by using a batch method were evaluated by changing various parameters such as contact time, adsorbent dose, and pH of the solution. The experimental isotherm data were analyzed using the Freundlich and Langmuir equations, indicated to be well fitted to the Langmuir isotherm equation under the concentration range studied, by comparing the correlation co‐efficient. Adsorption kinetics data were tested using pseudo‐first‐order and pseudo‐second‐order models. Kinetics studies showed that the adsorption followed a pseudo‐second‐order reaction. Due to good performance and low cost, this binary chitosan/silk fibroin composite can be used as an adsorbent for removal of Cu(II) and Cd(II) from aqueous solutions. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Adsorption of Cu(II) and Ni(II) using a Novel Xanthated Carboxymethyl Chitosan

Removal of Cu(II) and Ni(II) from aqueous solutions by a novel xanthated carboxymethyl chitosan (XCC) was investigated. XCC obtained was characterized by FTIR, SEM, EDX, and XRD. The adsorption ability of chitosan and XCC toward Cu(II) and Ni(II) was compared. The effect of pH (2.0–7.0), contact time (5–60 min), and adsorption isotherms on adsorption were also investigated. It was observed that the modified chitosan XCC showed a remarkable increase in Cu(II) and Ni(II) adsorption as compared to chitosan and displayed a quick adsorption performance. Further, The Langmuir isotherm was found to provide the best correlation of the experimental data and the adsorption capacity obtained from the Langmuir model was 174.2 mg/g and 128.4 mg/g for Cu(II) and Ni(II), respectively. FTIR and UV spectra suggested that the amino groups, carboxyl groups, and xanthate groups of XCC participated in the adsorption.     

Effect of heparin coating on epichlorohydrin cross-linked chitosan microspheres on the adsorption of copper (II) ions

Epichlorohydrin cross-linked chitosan microspheres (CS) and chitosan–heparin polyelectrolyte complex microspheres (CSH) were used in the adsorption of copper (II) ions in aqueous solution. The chitosan microspheres were prepared by the phase inversion method. The use of a cross-linking agent improved the resistance to acidic medium. Polyelectrolyte complex microspheres were prepared by impregnating heparin in cross-linked chitosan microspheres. The microspheres were characterized by IR, TGA and DSC. A study on the effect of the pH on the adsorption of copper (II) ions showed that the optimum pH for both CS and CSH microspheres was 6.0. From a kinetic evaluation, it could be established that the adsorption equilibrium was achieved after 8 h for CS and 25 h for CSH microspheres. The adsorption isotherms were interpreted using Langmuir and Freundlich mathematical models. The results revealed that experimental data of CS was best adjusted by Langmuir model, with maximum capacity of surface saturation equal to 39.31 mg g⁻¹. On the other hand, Langmuir and Freundlich models provided a good fit for adsorption by CSH and the adsorption capacity was 81.04 mg g⁻¹. The interactions between copper (II) ions and both CS and CSH were confirmed by electron paramagnetic resonance spectroscopy, which revealed the formation of a square-planar complex with tetrahedral distortion on the surface of the adsorbents.     

Microwave preparation and copper ions adsorption properties of crosslinked chitosan/ZSM molecular sieve composites

A novel chitosan‐based composite (CTS/ZSM) made of chitosan and ZSM molecular sieve was prepared under microwave irradiation and was used for the removal of Cu (II) ions from aqueous solution. The composites were characterized by FTIR spectra, XRD spectra, and thermogravimetric analysis. The effects of the ZSM content, amount of glutaraldehyde and pH value on adsorption properties of Cu (II) ions by CTS/ZSM were discussed in detail. Contrast with crosslinked chitosan (CCTS), the CTS/ZSM had higher adsorption capacity for Cu (II). Kinetic studies showed that the adsorption of Cu (II) onto CTS/ZSM composite had low correlation coefficients for the pseudo‐first and ‐second order model and intraparticle diffusion model. The equilibrium process was better described by the Langmuir than Freundlich isotherm model. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Macroporous chitosan/carboxymethylcellulose blend membranes and their application for lysozyme adsorption

The adsorption of lysozyme was investigated with novel macroporous chitosan (CS)/carboxymethylcellulose (CMC) blend membranes. The CS/CMG blend membranes were prepared by a simple solution‐blending method with glutaraldehyde as a crosslinking agent for CS and with silica particles as porogens. The CS/CMC blend membranes were insoluble in aqueous media when the CMC concentration in the membranes did not exceed 30 mol %. The protein adsorption on these membranes from aqueous solutions containing different amounts of lysozyme at different pHs was investigated in batch systems. The results showed that the lysozyme adsorption capacity had a maximum at pH 9.2, and this indicated that the CS/CMC blend membranes could act as cation‐exchange membranes. Moreover, the blend membranes showed the best adsorption properties for lysozyme when the CMC concentration was 20 mol %. In addition, the lysozyme adsorption capacity of the blend membranes increased with an increase in the initial lysozyme concentration and the adsorption temperature. The maximum adsorption capacity of the macroporous CS/CMC blend membranes was as high as 240 mg/g (170 mg/mL), and more than 95% of the adsorbed lysozyme was desorbed in a pH buffer at 11.8. The blend membranes also demonstrated good reusability after several adsorption–desorption cycles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1267–1274, 2005     

Preparation and characterization of chitosan/Cu(II) affinity membrane for urea adsorption

We used silica particles as a porogen to prepare macroporous chitosan membranes and subsequently prepared macroporous chitosan/Cu(II) affinity membranes for urea adsorption. The morphology, porosity, Cu(II) adsorption capacity, and swelling ratio of the macroporous membrane were measured. SEM photographs show the pores in the membrane dispersed uniformly, a feature that didn't change much after the adsorption of Cu(II). The porosity of the membrane had a maximum value when the silica/chitosan ratio was about 12. The Cu(II) adsorption capacity in the membrane leveled off when the initial concentration of CuSO₄ solution exceeded 5 × 10^?2 mol/L. The macroporous chitosan/Cu(II) affinity membrane was successfully used for urea adsorption. The maximum urea adsorption capacity was 78.8 mg/g membrane, which indicates that the membrane has a great potential for hemodialysis for urea removal. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1108–1112, 2003     

Preparation and characterization of porous chitosan–tripolyphosphate beads for copper(II) ion adsorption

Porous chitosan–tripolyphosphate beads, prepared by the ionotropic crosslinking and freeze‐drying, were used for the adsorption of Cu(II) ion from aqueous solution. Batch studies, investigating bead adsorption capacity and adsorption isotherm for the Cu(II) ion, indicated that the Cu(II) ion adsorption equilibrium correlated well with Langmuir isotherm model. The maximum capacity for the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, deduced from the use of the Langmuir isotherm equation, was 208.3 mg/g. The kinetics data were analyzed by pseudo‐first, pseudo‐second order kinetic, and intraparticle diffusion models. The experimental data fitted the pseudo‐second order kinetic model well, indicating that chemical sorption is the rate‐limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process. This study explored the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, and used SEM/EDS, TGA, and XRD to examine the properties of adsorbent. The use of porous chitosan–tripolyphosphate beads to adsorb Cu(II) ion produced better and faster results than were obtained for nonporous chitosan–tripolyphosphate beads. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of complexing agents on liquid‐phase adsorption and desorption of copper(II) using chitosan

The effect of complexing agents on adsorption and desorption of Cu(II) from aqueous solutions using chitosan was investigated. Three complexing agents were used including EDTA (ethylenediaminetetraacetic acid), citric acid, and tartaric acid. It was shown that the isotherm data could be fitted by the Langmuir equation under a limited concentration range. Furthermore, the adsorption processes were analyzed by an intraparticle diffusion model and the rate parameters of intraparticle diffusion for Cu(II) adsorption could be correlated with the initial Cu(II) concentrations. Finally, the desorption of Cu(II) and its complexes from the loaded chitosan was tested using complexing agent solutions. Under comparable conditions, tartaric acid solution gave the best desorption efficiency. © 1999 Society of Chemical Industry     

Synergistic removal of Cu(II) and nitrazine yellow dye using an eco‐friendly chitosan‐montmorillonite hydrogel: Optimization by response surface methodology

A comprehensive feasibility study on adsorption of Cu(II) and a water‐soluble nitrazine yellow (NY) dye by chitosan‐montmorillonite (CS‐MMT) hydrogel as the biosorbent was investigated as a function of biosorbent dosage, initial concentration, pH, temperature, and the presence of salts. Box–Behnken methodology was applied to optimize the adsorption experiments. Maximum adsorption values were determined as 132.74 mg/g and 144.41 mg/g at pH = 5.0, for Cu(II) and NY dye, respectively. Equilibrium isotherms of Langmuir and Freundlich were analyzed by the non‐linear regression model. The equilibrium data were well described by Freundlich model and the adsorption process well fitted pseudo‐second order kinetics. The enthalpy change of adsorption (ΔH°) were calculated as ?3.78 kJ/mol and ?5.75 kJ/mol for Cu(II) and NY dye, respectively, indicating that the adsorption processes were exothermic. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43664.     

Removal of Reactive Blue 21 onto magnetic chitosan microparticles functionalized with polyamidoamine dendrimers

Chitosan/poly(amidoamine) (MCS/PAMAM) microparticles were prepared as magnetic adsorbents for removal of Reactive Blue 21 (RB 21) dye from aqueous solution. Characterization of these particles was carried out using scanning electron microscopy, Fourier transform-infrared spectroscopy, X-ray diffractometry and vibrating sample magnetometry. The results indicate that the magnetic chitosan microparticles (MCS) were functionalized with PAMAM dendrimers and maintained its intrinsic magnetic properties. The effects of initial pH, adsorbent dose, initial concentration, contact time and temperature on adsorption were investigated. Kinetic studies showed that the dye adsorption process followed a pseudo-second-order kinetic model but that the adsorption rate was also influenced by intraparticle diffusion. Equilibrium adsorption isotherm data indicated a good fit to the Langmuir isotherm. The maximum adsorption capacities obtained from the Langmuir model were 555.56, 588.24, 625.00 and 666.67 mg g⁻¹ at 303, 313, 323 and 333 K, respectively. The thermodynamic parameters revealed the feasibility, spontaneity and endothermic nature of the adsorption. Recycling experiments confirmed the relative reusability of the adsorbent.     

Simultaneous removal of copper and zinc ions by low cost natural snail shell/hydroxyapatite/chitosan composite

In this work, the snail shell/hydroxyapatite/chitosan composite was prepared as adsorbent. The adsorption potential of the composite was studied for simultaneous sorption behavior of Zn(Ⅱ) and Cu(Ⅱ) ions in a batch system. Chitosan and hydroxyapatite(HAP) were extracted from shrimp shell and bone ash,respectively, so this is a low cost natural composite. To prepare the composite, chitosan was dissolved in acetic acid, then HAP and snail shell powders were added to the chitosan solution. The morphology and characterization of the composite was studied by SEM and EDX analysis. Atomic adsorption was used to measure the amount of the ions. Experimental parameters were optimized with Design Expert Software and five parameters such as the concentration of ions, p H, adsorbent amount and contact time were studied at room temperature. Optimized value for the parameters of Zn(Ⅱ) and Cu(Ⅱ) concentrations, p H, adsorbent dose, and contact time were 3.01 mg·L~(-1), 5.5, 0.02 g and 95 min, respectively. The adsorption isotherms for Zn(Ⅱ) and Cu(Ⅱ) showed Langmuir and Tempkin, respectively. Kinetic and equilibrium studies showed the experimental data of Zn(Ⅱ) and Cu(Ⅱ) ions were best described by the pseudo-second-order model. Studies on thermodynamic show the adsorption process were physical and spontaneous.