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.     

Removal of cadmium(II) cations from an aqueous solution with aminothiourea chitosan strengthened magnetic biochar

An aminothiourea chitosan modified magnetic biochar composite (TMBC) was prepared for the efficient removal of Cd(II) from wastewater. The synthesized materials were characterized, and the detailed adsorption mechanisms and thermodynamics were studied. The adsorption experiments revealed that TMBC had a higher affinity for Cd(II) than the magnetic biochar composite, raw biochar, and other carbon‐based adsorbents did. The Cd(II) adsorption process fit the pseudo‐second‐order kinetic model, and the maximum adsorption capacities on the basis of the Langmuir model were 93.72, 121.9, and 137.3 mg/g at 298, 308, and 318 K, respectively. The practical efficacy of the adsorbent was also tested with a real mine water. The metal‐ion‐loaded TMBC could be conveniently collected by a magnet and could be easily regenerated with adsorption efficiencies up to 84% after five adsorption–desorption cycles. The as‐prepared TMBC might be a promising adsorbent for the treatment of heavy‐metal‐ion‐contaminated water or highly mineralized mine water. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46239.     

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     

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     

Removal of chromium (VI) from aqueous solutions using quaternized chitosan microspheres

In this study, quaternized chitosan microspheres (QCMS) were prepared and its Cr(VI) removal potential was investigated. Batch experiments were conducted to examine kinetics, adsorption isotherm, pH effect, and thermodynamic parameters. Equilibrium was attained within 50 min and maximum removal of 97.34% was achieved under the optimum conditions at pH 5. Adsorption data for Cr (VI) uptake by the QCMS were analyzed according to Langmuir, Freundlich, and Temkin adsorption models. The maximum uptake of Cr(VI) was 39.1 mg·g^-1. Thermodynamic parameters for the adsorption system were determinated at 293 K, 303 K, 313 K and 323 K. (ΔH°=16.08 kJ·mol^-1;ΔG°=-5.84 to -8.08 kJ·mol^-1 and ΔS°=74.81 J·K^-1·mol^-1). So the positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption.ΔG° values obtainedwere negative indicating a spontaneous adsorption process. The kinetic process was described by a pseudo-second-order rate equation very well. The results of the present study indicated that the QCMS could be considered as a potential adsorbent for Cr (VI) in aqueous solutions.     

Removal of Cr(VI) from aqueous solution using amino‐modified Fe3O4–SiO2–chitosan magnetic microspheres with high acid resistance and adsorption capacity

A novel, bioadsorbent material of polyethylenimine‐modified magnetic chitosan microspheres enwrapping magnetic silica nanoparticles (Fe₃O₄–SiO₂–CTS‐PEI) was prepared under relatively mild conditions. The characterization results indicated that the adsorbent exhibited high acid resistance and magnetic responsiveness. The Fe₃O₄ loss of the adsorbent was measured as 0.09% after immersion in pH 2.0 water for 24 h, and the saturated magnetization was 11.7 emu/g. The introduction of PEI obviously improved the adsorption capacity of Cr(VI) onto the adsorbent by approximately 2.5 times. The adsorption isotherms and kinetics preferably fit the Langmuir model and the pseudo‐second‐order model. The maximum adsorption capacity was determined as 236.4 mg/g at 25°C, which was much improved compared to other magnetic chitosan materials, and the equilibrium was reached within 60 to 120 min. The obtained thermodynamic parameters revealed the spontaneous and endothermic nature of the adsorption process. Furthermore, the Cr(VI)‐adsorbed adsorbent could be effectively regenerated using a 0.1 mol/L NaOH solution, and the adsorbent showed a good reusability. Due to the properties of good acid resistance, strong magnetic responsiveness, high adsorption capacity, and relatively rapid adsorption rate, the Fe₃O₄–SiO₂–CTS‐PEI microspheres have a potential use in Cr(VI) removal from acidic wastewater. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43078.     

Oxidative coupling of 2,6‐dimethylphenol catalyzed by copper(II) complexes in aqueous solution

The oxidative coupling reaction of 2,6‐dimethylphenol (DMP) with H₂O₂ catalyzed by four copper(II) complexes was investigated in Tris‐HNO₃ buffer solution at 25°C. The kinetics of formation of diphenoquinone (DPQ, 4‐(3,5‐dimethyl‐4‐oxo‐2,5‐cyclohexadienylidene)‐2,6‐dimethyl‐2,5‐cyclohexadienone) from DMP was studied in detail. The kinetic parameters k₂ and K_m were obtained in the pH range of 6.0–9.0. The copper(II) complexes exhibited the optimal catalytic activity at around pH 7.0. The pH effect was reasonably explicated by the catalytic kinetic model suggested in this work. The catalytic mechanism was discussed. The deprotonized associated radical LCu^I(OH^?)‐^?OOH was suggested as the possible predominant species to oxidize DMP. The C? C and C? O coupling products were analyzed and the ratio of poly (2,6‐dimethyl‐1,4‐phenylene ether) (PPE) to DPQ was also evaluated. Both in weak acidic (pH < 6.5) and in alkaline aqueous solution (pH > 8) were suitable to the C? O coupling reaction in our catalytic systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Removal of copper (II) and phenol from aqueous solution using porous carbons derived from hydrothermal chars

The feasibility of hydrothermal char (HTC), a byproduct from biomass hydrothermal liquefaction for bio-oil production, as raw material for preparation of porous carbons was investigated in the present study. The resultant HTC-derived porous carbons were characterized and utilized as adsorbents for copper (II) and phenol removal from aqueous solution. Compared with porous carbons using pyrolytic char as precursor, the HTC-derived porous carbons exhibited unique textural features, e.g., narrow pore size distribution, high surface area and large pore size. In addition, FT-IR analysis confirmed that substantial amount of ketene groups existed on the surface of the HTC-derived porous carbons. As the adsorbents, the copper (II) adsorption onto HTC-derived carbons was strongly affected by the pH value of the solution in comparison with phenol adsorption. The carbons derived from pinewood and rice husk HTC exhibited high adsorption capacity of 83.88 and 39.30 mg/g for phenol and 25.18 and 22.62 mg/g for copper (II), respectively. The adsorption data for copper (II) and phenol onto the carbon adsorbents could be well described by Langmuir and Freundlich models. In comparison with pinewood sawdust HTC-derived carbon, the adsorption onto rice husk HTC-derived carbon preferentially followed Freundlich model due to the presence of silica on the surface.     

Melamine‐based microporous polymer for highly efficient removal of copper(II) from aqueous solution

In this study, we investigated the ability of a melamine‐based microporous polymer network as an adsorbent for removal of copper(II) species from aqueous solutions. A designed Schiff based network (SNW) with high specific surface area was synthesized using melamine and terephthalaldehyde monomers at 180 °C for 3 days followed by a freeze‐drying process. The porous structure of the material was confirmed by SEM analysis and CO₂ adsorption/desorption studies at 77.3 K. The adsorption character of the SNW polymer for various metal salts, namely Pb(II), Fe(II), Hg(II), Zn(II), Ni(II) and Cd(II), was investigated and a specific sorption behaviour against Cu(II) salts was observed. The role of pH and contact time was examined and the highest adsorption capacity for Cu(II) was found as 92% with pH 3.5 at the end of 300 min. As evidenced by XRD and Fourier transform infrared spectral analysis, the sorption mechanism is attributed to the coordination system formed between amino groups in the porous structure and Cu(II) ions. Reusability of the system was also demonstrated by applying four cycles without any significant loss of activity. © 2016 Society of Chemical Industry     

Removal of nickel(II) from aqueous solution by carbon nanotubes

Single‐walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs) were oxidized by NaClO solutions and were employed as sorbents to study sorption characteristics of nickel(II) from aqueous solution. The surface properties of CNTs such as functional groups, total acidic sites and negatively charged carbons were greatly improved after oxidation, which made CNTs become more hydrophilic and resulted in sorption of more Ni²⁺. The amount of Ni²⁺ sorbed onto oxidized CNTs increased with a rise in agitation speed, initial Ni²⁺ concentration and solution pH in the range 1–8, but decreased with a rise in CNT mass and solution ionic strength. The sorption mechanisms are complicated and appear attributable to electrostatic forces and chemical interactions between the Ni²⁺ and the surface functional groups of the CNTs. The oxidized SWCNTs and MWCNTs have shorter equilibrium time and better Ni²⁺ sorption performance than the oxidized granular activated carbon, suggesting that both NaClO oxidized CNTs are efficient Ni²⁺ sorbents and that they possess good potential applications in water treatment. Copyright © 2006 Society of Chemical Industry     

Removal of Cd(II), Hg(II), and Pb(II) ions from aqueous solution using p(HEMA/chitosan) membranes

An interpenetration network (IPN) was synthesized from 2‐hydroxyethyl methacrylate (HEMA) and chitosan, p(HEMA/chitosan) via UV‐initiated photo‐polymerization. The selectivity to different heavy metal ions viz Cd(II), Pb(II), and Hg(II) to the IPN membrane has been investigated from aqueous solution using bare pHEMA membrane as a control system. Removal efficiency of metal ions from aqueous solution using the IPN membranes increased with increasing chitosan content and initial metal ions concentrations, and the equilibrium time was reached within 60 min. Adsorption of all the tested heavy metal ions on the IPN membranes was found to be pH dependent and maximum adsorption was obtained at pH 5.0. The maximum adsorption capacities of the IPN membrane for Cd(II), Pb(II), and Hg(II) were 0.063, 0.179, and 0.197 mmol/g membrane, respectively. The adsorption of the Cd(II), Hg(II), and Pb(II) metal ions on the bare pHEMA membrane was not significant. When the heavy metal ions were in competition, the amounts of adsorbed metal ions were found to be 0.035 mmol/g for Cd(II), 0.074 mmol/g for Hg(II), and 0.153 mmol/g for Pb(II), the IPN membrane is significantly selective for Pb(II) ions. The stability constants of IPN membrane–metal ions complexes were calculated by the method of Ruzic. The results obtained from the kinetics and isotherm studies showed that the experimental data for the removal of heavy metal ions were well described with the second‐order kinetic equations and the Langmuir isotherm model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Removal of Congo red from aqueous solution using a chitosan/organo‐ montmorillonite nanocomposite

To further improve the adsorption capacity of chitosan (CTS), a series of novel chitosan/organo‐montmorillonite nanocomposites (CTS/OMMT) were synthesized and the adsorption abilities for Congo red (CR) investigated in this study. The nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the results indicated that an exfoliated nanostructure was formed in CTS/OMMT nanocomposites. Compared with the adsorption capacity of OMMT (192.4 mg g^?1), CTS/OMMT with an amount of cetyltrimethylammonium bromide equal to 0.75 CEC of MMT and molar ratio of CTS to OMMT of 1:10 exhibited the higher adsorption capacity (290.8 mg g^?1). The adsorption behaviours of OMMT and CTS/OMMT showed that the adsorption kinetics and isotherms were in good agreement with a pseudo‐second‐order equation and the Langmuir equation, respectively. The IR spectra revealed that a chemical interaction occurred between CTS/OMMT and CR. The adsorption capacity of CTS/OMMT nanocomposite was higher than that of other absorbents; this study suggested that the CTS/OMMT nanocomposite could be used as an adsorbent to remove CR dye from aqueous solution. Copyright © 2007 Society of Chemical Industry     

Adsorption of Cd(II), Pb(II), and Ag(I) in aqueous solution on hollow chitosan microspheres

Cross‐linked chitosans synthesized by the inverse emulsion cross‐link method were used to investigate adsorption of three metal ions [Cd(II), Pb(II), and Ag(I)] in an aqueous solution. The chitosan microsphere, was characterized by FTIR and SEM, and adsorption of Cd(II), Pb(II), and Ag(I) ions onto a cross‐linked chitosan was examined through analysis of pH, agitation time, temperature, and initial concentration of the metal. The order of adsorption capacity for the three metal ions was Cd²⁺ > Pb²⁺ > Ag⁺. This method showed that adsorption of the three metal ions in an aqueous solution followed the monolayer coverage of the adsorbents through physical adsorption phenomena and coordination because the amino (? NH₂) and/or hydroxy (? OH) groups on chitosan chains serve as coordination sites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Removal of boron from aqueous solution by composite chitosan beads

Various metal-oxide nanoparticles and chitosan were blended to form new adsorbents (M-Oxide-CTS) for removing boron from aqueous solutions in a batch system. The maximum boron adsorption capacity (q = 7.8 mg/g) was reached at pH = 4 within 5 min. Calculations based on Langmuir, Freundlich, and Dubinin–Radushkevich models showed the heterogeneous and physical nature of boron adsorption on M-Oxide-CTS. Modeling of the thermodynamic date indicated the nonspontaneous and exothermic process. The pseudo-second-order model adequately described the boron adsorption on M-Oxide-CTS. Desorption by means of alkaline solution at pH = 12 was carried out successfully.     

Removal of perchlorate from aqueous solution using protonated cross-linked chitosan

Protonated cross-linked chitosan was used to remove perchlorate from aqueous solution. Adsorption isotherms, the effects of pH and co-existing anions on the adsorption process, proper actual contact time in the adsorption column and the regeneration ability of the adsorbent were investigated. The equilibrium data fitted well with Langmuir and Freundlich isotherm models, and the maximum monolayer adsorption capacity was 45.455 mg g^?1. To balance the protonated degree of the amino groups and the effect of the ion competing on adsorption capacity, the optimal pH value was determined to be about 4.0. Column adsorption results indicated that the proper actual contact time was 8.1 min and the effluent perchlorate could be steadily kept below 24.5 μg L^?1 up to about 95 bed volumes with the influent perchlorate of 10 mg L^?1. The presence of other anions weakened the perchlorate adsorption, especially the high valence anion such as sulfate. The adsorbents could be well regenerated by sodium hydroxide solution with pH 12 and reused at least for 15 cycles. Electrostatic attraction as well as physical force was the main driving force for perchlorate adsorption.     

Removal of Pb(II) from solution using cellulose‐containing materials

The potential of cheap cellulose‐containing natural materials such as coir, jute, sawdust and groundnut shells for removal for Pb(II) from aqueous solution of lead nitrate was assessed before and after modifying them with a monochlorotriazine type of dye. The materials showed enhanced adsorption capacity of Pb(II) due to the specific dye loading. This was attributed to chelation and an ion exchange mechanism. The maximum cation uptake values obtained were 0.127, 0.087, 0.090, and 0.106 mmol g^?1 for coir, sawdust, jute and groundnut shell in their dyed forms, respectively. The kinetics of both undyed and dyed coir was analysed and the second order rate equation was observed to provide the best correlation of the experimental data. Adsorption isotherm models were developed. The best fit was obtained in the Langmuir model. When subjected to repeated adsorption–desorption cycles, with an intermediate step of mild sodium hydroxide treatment, both dyed and undyed coir retained its adsorptive capacity even after five cycles of reuse. Copyright © 2004 Society of Chemical Industry     

Removal of trace boron from aqueous solution using iminobis-(propylene glycol) modified chitosan beads

In this paper, a new boron chelating chitosan based polymer with multi-hydroxyl iminobis (propylene glycol) (IBPG) functions was prepared. A cross-linked chitosan (CCTS) with 2.70 mmol g⁻¹ amine content was modified with excess amount of glycidol at pH 7 and boron chelating resin with IBPG functions (4.60 mmol g⁻¹) was obtained. The boron chelating ability of the resulting resin was investigated under different experimental conditions (pH, foreign ions). This prepared material was evaluated by FT–IR spectra and UV spectra analysis. The IBPG modified CCTS resin was demonstrated to have a boron loading capacity of 2.2 ± 0.05 mmol g⁻¹ within 45 min. Desorption and resin regeneration studies were carried out to determine the effectiveness of the synthesized resin with HCl and NaOH respectively. The adsorption test indicated that the chitosan based chelating resin with IBPG functions exhibited higher selectivity of boron (2.05 mmol g⁻¹) in the presence of foreign ions especially Fe(III).     

Interaction of microcrystalline chitosan with Ni(II) and Mn(II) ions in aqueous solution

The protonation constant of the NH₂ function was determined by the method of Katchalsky and Spitnik and by the SUPERQUAD fitting procedure. Samples with higher concentrations of chitosan indicated aggregations of polymer chains, which led to a loss in the effective concentration of the ligand (L). It followed, as a result of potentiometric titrations, that an excess of L of microcrystalline chitosan (MCCh) with a deacetylation degree of 0.90 was a complexing agent toward the metal (M), which was Ni(II) or Mn(II). Species ML and ML₂ were accepted by SUPERQUAD for both of the M's, where coordination occurred via the amino nitrogen. For Ni(II), however, the hydroxyl oxygen may also have been an electron‐pair donor at lower excesses of MCCh and, by that, made possible the formation of five‐membered chelate rings in the hydroxyl deprotonated MLH_‐1 species. The evaluated formation constants were compared with the values known until now for monomeric D ‐glucosamine. Additional confirmation of the M–L interaction was determined by the spectrophotometric titration of a Ni(II)–MCCh solution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2572–2577, 2005     

Selective solid-phase extraction of trace Pb(II) from aqueous solution using Pb(II)-ion imprinted polymer

In this work, we synthesized several ions imprinted polymers based on the inclusion of 8-hydroxyquinoline, vinyl benzoic acid, and diazoaminobenzene as ligands into the polymer matrix to complex with lead ions. Besides, to optimize various parameters for the selective extraction and enrichment of lead ions using the best synthesized imprinted polymers, the selectivity of the chosen inorganic ions was investigated. These investigations indicated that the synthesized imprinted polymer particles have good potential for selective enrichment of lead ions compared with other heavy metal ions, and the selectivity of lead ion-imprinted polymers for lead ion was higher than non-imprinted polymer.