A modified cellulose adsorbent for the removal of nickel(II) from aqueous solutions

A series of adsorption studies was carried out on a glycidyl methacrylate‐ modified cellulose material functionalised with imidazole (Cellulose‐g‐GMA‐Imidazole) to assess its capacity in the removal of Ni(II) ions from aqueous solution. The study sought to establish the effect of a number of parameters on the removal of Ni(II) from solution by the Cellulose‐g‐GMA‐Imidazole. In particular, the influence of initial metal concentration, contact time, solution temperature and pH were assessed. The studies indicated a Ni(II) uptake on the Cellulose‐g‐GMA‐Imidazole sorbent of approximately 48 mg g^?1 of nickel from aqueous solution. The adsorption process fitted the Langmuir model of adsorption and the binding process was mildly endothermic. The kinetics of the adsorption process indicated that nickel uptake occurred within 400 min and that pseudo‐second order kinetics best describe the overall adsorption process. Nickel(II) adsorption, recovery and re‐adsorption studies indicated that at highly acidic pH values the adsorbent material becomes unstable, but in the range pH 3–6, the adsorbent is stable and shows limited but significant Ni(II) recovery and re‐adsorption capability. Copyright © 2006 Society of Chemical Industry     

Dithiocarbamate functionalized Al(OH)3‐polyacrylamide adsorbent for rapid and efficient removal of Cu(II) and Pb(II)

Heavy metal ions such as Cu²⁺ and Pb²⁺ impose a significant risk to the environment and human health due to their high toxicity and non‐degradable characteristics. Herein, Al(OH)₃‐polyacrylamide chemically modified with dithiocarbamates (Al‐PAM‐DTCs) was synthesized using formaldehyde, diethylenetriamine, carbon disulfide, and sodium hydroxide for rapid and efficient removal of Cu²⁺ and Pb²⁺. The synthesized adsorbent was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis, scanning electron microscopy–energy dispersive X‐ray spectroscopy analysis, and transmission electron microscope measurements. Al‐PAM‐DTCs showed rapid removal of Cu²⁺ (<30 min) and Pb²⁺ (<15 min) with high adsorption capacities of 416.959 mg/g and 892.505 mg/g for Cu²⁺ and Pb²⁺ respectively. Al‐PAM‐DTCs also had high capacities in removing suspended solids and metal ions simultaneously in turbid bauxite suspensions. FTIR, thermodynamic study, and elemental mapping were used to determine the adsorption mechanism. The rapid, convenient, and effective adsorption of Cu²⁺ and Pb²⁺ indicated that Al‐PAM‐DTCs has great potential for practical applications in purification of other heavy metal ions from aquatic systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45431.     

Removal of Cu(II) from aqueous solutions by chelating starch derivatives

Two chemically modified starch derivatives, crosslinked amino starch (CAS) and dithiocarbamates modified starch (DTCS), were prepared and used for the removal of Cu(II) from aqueous solutions. CAS was found to be effective for the adsorption of Cu(II), which tended to form a stable amine complex. Adsorption of Cu(II) onto DTCS was higher than that onto CAS. Experiments showed that the adsorption processes of Cu(II) on both CAS and DTCS were endothermic, and followed Freundlich isothermal adsorption. For both adsorbents, dynamic modeling of their adsorption showed that the first‐order reversible kinetic model described the adsorption process. The adsorption rate constants of CAS and DTCS were 1.578 and 10.32 h^?1, respectively. From the results of the thermodynamic analysis, free energy ΔG, enthalpy ΔH, and entropy ΔS of the adsorption process were calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3881–3885, 2004     

Thiourea modified hyper‐crosslinked polystyrene resin for heavy metal ions removal from aqueous solutions

A hyper‐crosslinked resin chemically modified with thiourea (TM‐HPS) was synthesized, characterized, and evaluated for the removal of heavy metal ions (Pb²⁺, Cd²⁺, and Cu²⁺) from aqueous solutions. The structural characterization results showed that a few thiourea groups were grafted on the surface of the resin with a big BET surface area and a large number of narrow micropores. Various experimental conditions such as pH, contact time, temperature, and initial metal concentration of the three heavy metal ions onto TM‐HPS were investigated systematically. The results indicated that the prepared resin was effective for the removal of the heavy metal ions from aqueous solutions. The isotherm data could be better fitted by Langmuir model, yielding maximum adsorption capacities of 689.65, 432.90, and 290.69 mg/g for Pd²⁺, Cd²⁺, and Cu²⁺, respectively. And the adsorption kinetics of the three metal ions followed the pseudo‐second‐order equation. FTIR and XPS analysis of TM‐HPS before and after adsorption further revealed that the adsorption mechanism could be a synergistic effect between functional groups and metal ions and electrostatic attraction, which may provide a new insight into the design of highly effective adsorbents and their potential technological applications for the removal of heavy metal ions from aqueous solutions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45568.     

Polymeric hydrogels obtained using a redox initiator: Application in Cu(II) ions removal from aqueous solutions

Poly(acrylic acid‐co‐acrylamide) hydrogels were prepared via free‐radical solution polymerization, crosslinked with ethylene‐glycol‐dimethacrylate, potassium persulfate/ammonium bisulfite as the initiator, and applied in the removal of Cu(II) ions from aqueous solutions. Molar ratios of acrylamide/acrylic acid moieties and the amount of crosslinking agent were varied to determine the swelling capacities of hydrogels and maximum metal uptake. Polymerization kinetics was investigated by ¹H‐NMR. Hydrogel physicochemical properties were characterized by nitrogen sorption measurements, elemental analysis, FTIR, and X‐ray photoelectron spectroscopy (XPS). Swelling results indicated that hydrogels were swollen up to 27,500%. Hydrogels showed equilibrium Cu(II) adsorption capacities of 211.7 mg g^?1 and fast kinetics (～20 min). Langmuir isotherm fitted adsorption equilibrium data. FTIR and XPS results helped in elucidating the presence of monodentate copper complex on the surface of hydrogels. A simple synthesis route of hydrogels using the redox initiator suggests the potential application in the removal of toxic metals from aqueous streams. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39933.     

Imidazole modified acrylate-containing photocured hydrogels for the efficient removal of malachite green dye from aqueous solutions

In this work, we aimed to prepare a simple and an efficient adsorbent for the removal of toxic, cationic dye; malachite green (MG). We reviewed many previous studies and designed our adsorbent based on the rationale that (1) acidic groups containing monomers which are capable of making hydrogen bonds (or electrostatic interactions) with MG are very effective in adsorption and (2) π-π stacking enhances the adsorption capacity. We first synthesized an imidazole-acrylate adduct and used it for the preparation of photocured hydrogels. The imidazole-acrylate adduct was characterized by H NMR and FTIR spectroscopy. The effect of experimental conditions on the MG adsorption properties of the hydrogels such as the effect of pH, time and MG concentration were also investigated. Under the optimum conditions (pH = 6 and 220 min contact time) at room temperature, the maximum adsorption capacity was found as high as 714.28 mg/g. The results showed that the adsorption process of the optimum hydrogel, which can be used 4 times without a significant loss in its adsorption capacity, fits the Langmuir isotherm model. The hydrogel adsorbent displayed good selectivity and reusability.     

Adsorption of Hg(II) in aqueous solutions using mercapto‐functionalized alkali lignin

A novel adsorbent for Hg(II), mercapto‐functionalized alkali lignin (AL‐SH) was synthesized by Friedel–Crafts alkylation reaction and nucleophilic substitution reactions. The adsorbent was characterized by the techniques of Fourier transform‐infrared spectroscopy (FT‐IR), elementary analysis and thermogravimetric analysis, and N₂ adsorption techniques. The effect of various parameters on Hg(II) adsorption process such as initial pH, contact time, ionic strength, initial Hg(II) concentration, temperature, and adsorbent dosage were investigated in detail through batch static experiments. The results indicated that the adsorption process of Hg(II) on AL‐SH was mainly dependent on the pH and the optimal pH value was at pH ranging from 4.0 to 6.0. The adsorption process was found to follow pseudosecond‐order kinetics and the main process was chemical adsorption, which equilibrated at 8 h. The adsorption isotherm was better described by Langmuir and Temkin isotherm equations compared to Freundlich isotherm equation and the maximum adsorption capacity obtained was 101.2 mg g^?1 (pH = 4.0, 20°C, initial Hg(II) concentration was 200 mg L^?1). The thermodynamic parameters of and were positive while was negative, revealed that the adsorption of Hg(II) onto AL‐SH was a spontaneous and endothermic process with increased entropy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40749.     

Polyethylenimine-modified sugarcane bagasse cellulose as an effective adsorbent for removing Cu(II) from aqueous solution

Polyethylenimine-modified sugarcane bagasse cellulose (SBCMP), as a new adsorbent, was synthesized by the reaction of polyethylenimine (PEI) with sugarcane bagasse cellulose and glutaraldehyde. The adsorption of Cu(II) by SBCMP was pH-dependent, and the higher removal efficiency of Cu(II) appeared in the range of pH 3.0–6.0. The adsorption isothermal data fitted well with the Langmuir model, and the maximum adsorption capacity of SBCMP was up to 107.5 mg/g. The adsorption kinetics was best described by the pseudo-second-order kinetic. The adsorption of Cu(II) by SBCMP was unfavorable at high temperatures, and thermodynamic analyses implied that the adsorption of Cu(II) by SBCMP was an exothermic reaction. Fourier transform infrared spectroscopy (FT-IR) combined with X-ray photoelectron spectroscopy (XPS) revealed that Cu(II) adsorption on SBCMP mainly controlled by the nitrogen atoms of  NH group in PEI. The results of regeneration cycles showed that SBCMP was suitable for reuse in the adsorption of Cu(II) from aqueous solution. These experimental results suggested that SBCMP is expected to be a new biomass adsorbent with high efficiency in removing Cu(II) from wastewater.     

Adsorption and desorption of copper(II) from solutions on new spherical cellulose adsorbent

An investigation was conducted on the adsorption and desorption of copper(II) from aqueous solutions with a new spherical cellulose adsorbent containing the carboxyl anionic group. Various factors affecting the adsorption were optimized. The adsorption of Cu²⁺ ions on the adsorbent was found to be dependent on the initial time and pH, the concentration, and the temperature. The adsorption process follows both Freundlich and Langmuir adsorption isotherms and was found to be endothermic (ΔH = 23.99 kJ/mol). The Cu²⁺ ions adsorbed on the adsorbent can be recovered with a NaOH or HCl aqueous solution. The maximum percentage of recovery is about 100% when 2.4 mol/L HCl solution is used. In addition, only 7.2% of the adsorption capacity is lost after 30 replications of the adsorption and desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 478–485, 2002; DOI 10.1002/app.10114     

Adsorption of Cu(II) ions from aqueous solutions using ion exchange resins with different functional groups

The extraction of heavy metals from industrial effluents using efficient adsorbents is crucial for wastewater treatment and beneficial for metal recycling. In this study, the removal of Cu(II) from an acidic solution by commercial resins Dowex G-26 and Puromet™ MTS9570 was investigated. The influences of contact time, solution concentration, pH, temperature, and a resin dosage on the adsorption process were studied with batch technique. The optimum adsorption conditions were obtained at a concentration of 1100 mg/L Cu, contact time of 30 min, pH 3.5, and resin dosage of 0.025 g/ml for the removal of 99.9% and 90% of copper ions by G-26 and MTS9570, respectively. The experimental data of copper adsorption were analyzed using the Langmuir, Freundlich, and Temkin isotherm models. The highest metal uptakes of 41.67 and 37.70 mg/g were observed for Dowex G-26 and MTS9570, respectively. It was found that both resins had higher adsorption capacities than the substances reported in the literature. The adsorption kinetic studies showed that the copper adsorption process could be better described by the pseudo-second order model. Adsorption occurs spontaneously under endothermic conditions, which indicates the endothermic nature of the process.     

Methamidophos removal from aqueous solutions using a super adsorbent based on crosslinked poly(vinyl alcohol) hydrogel

This study describes the absorption of methamidophos (MMP) from aqueous solution by crosslinked poly(vinyl alcohol) (PVA) hydrogel synthesized using malic acid (MA) as a crosslinker (CLPHMA). The prepared hydrogels were characterized by FTIR spectroscopy, scanning electron microscopy, and the thermal properties were studied by using thermal gravimetric analysis. Also, the swelling index as a function of PVA:MA composition and pH were studied. An in silico rational study, which involved all‐atom molecular dynamics simulations of PVA:MA systems in proportions 10:2, 10:4, and 10:6 was performed. The in silico studies concluded that the more suitable crosslinking degree for MMP pesticide removal is with the 20% (wt %) of crosslinker (CLPHMA‐20). The experimental analysis of MMP removal with CLPHMA was performed as well. It was found that the prepared CLPHMA‐20 had a great efficiency to recover around 86% of MMP from their solutions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45964.     

Hg(II) removal from HCl solutions using a tetraalkylphosphonium ionic liquid impregnated onto Amberlite XAD‐7

Extractant impregnated resins (EIRs) were prepared by impregnation of Amberlite XAD‐7 with tetraalkylphosphonium chloride ionic liquid (IL). The EIRs were tested for the sorption of Hg(II) in HCl solutions. Mercury is bound on the EIR through an ion exchange mechanism involving chloroanionic species and the IL. The effect of HCl concentration and IL content is studied and the sorption isotherms are obtained in 1 M HCl solutions: the sorption capacity linearly increases with IL loading up to 100 mg Hg L^?1. A little fraction of the IL immobilized on the resin (about 40 mg IL g^?1) is tightly bound to the polymer limiting its reactivity with metal ions. The uptake kinetics are mainly controlled by intraparticle diffusion. At high IL loading the kinetics are slowed down, while the temperature has a limited impact. Nitric acid can be used for desorbing mercury and recycling the EIR for at least five cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41086.     

Significantly improving the Cu2+ removal performance of conducting polymer-based adsorbent from aqueous solution through cross-linking modification

Through cross-linking modification of poly(o-phenylenediamine) (PoPD) to increase the adsorption active sites, the Cu²⁺ adsorption capacity of PoPD was improved significantly. According to FT-IR, XRD, SEM and BET results, both PoPD and the cross-linked PoPD had porous or surface-adhesive porous morphology with a typical mesoporous character, the specific surface area of the latter was increased obviously from the former. Both of them showed excellent Cu²⁺ adsorption capabilities with the maximum adsorption q^exp_max of 76.51 and 85.49 mg·g⁻¹, and the corresponding removal ratios of 60.21% and 68.39%, respectively. The adsorption capacity was increased to its 1.54 times with pentaerythritol tris[3-(1-aziridinyl)propionate] (cross-linking agent-III) as cross-linking agent at pH = 5 and 25°C. Because temperature could affect the adsorption behavior of materials and the adsorption process is endothermic with ΔG < 0, the process should be accompanied by spontaneous chemical changes. The XRD, SEM–EDX mapping and XPS results showed that Cu²⁺ was successfully removed from the aqueous solution. Additionally, the adsorption was mainly based on the cation-π interaction and the formation of Cu-N bonds.     

Removal of concentrated heavy metal ions from aqueous solutions using polymers with enriched amidoxime groups

Particulate and fibrous adsorbents with enriched amidoxime groups were synthesized by using a novel monomer N,N′‐dipropionitrile acrylamide. The adsorption properties of amidoximated poly(N,N′‐dipropionitrile acrylamide) [poly(DPAAm)] particles and a nonwoven fabric grafted with the same for UO₂²⁺, Pb²⁺, Cu²⁺, and Co²⁺ at high concentrations were investigated by batch process. Metal ion adsorption studies were conducted from metal ion solutions with different initial concentrations (100–1500 ppm). It was shown that particulated amidoximated poly(DPAAm) has higher adsorption capacity than amidoximated nonwoven fabrics for all metal ions, especially for uranyl ions. The results of the adsorption studies showed that the interaction between UO₂²⁺ and amidoximated groups agree with the Langmuir‐type isotherm. From the Langmuir equation, the adsorption capacities were found as 400 mg UO₂²⁺/g dry amidoximated poly(DPAAm) and 250 mg UO₂²⁺/g dry amidoximated graft polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1705–1710, 2004     

Preparation of Fe3O4/poly(l‐glutamic acid) microspheres and their adsorption of Cu(II) ions

Fe₃O₄/poly(l ‐glutamic acid) (P‐l ‐Glu) magnetic microspheres were synthesized in an l ‐glutamic acid solution by coprecipitation and a dehydration condensation reaction and were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and ζ‐potential measurement. P‐l ‐Glu was coated on the surface of Fe₃O₄ microspheres. The average particle diameter of Fe₃O₄/P‐l ‐Glu was 388 nm and dispersed homogeneously in water. The adsorption of Cu(II) ions on Fe₃O₄/P‐l ‐Glu was further studied. The effect of different pH values and reaction times on the adsorption of Fe₃O₄/P‐l ‐Glu was discussed. The adsorption equilibrium was reached in 40 min, and the maximum adsorption for Cu(II) ions was more than 500 mg/g; this value occurred at pH 8 in water. The adsorption dynamic process fit the Freundlich isotherms well, and the adsorption kinetics followed the adsorption mechanism of the pseudo‐second‐order equation, which was the main complexation reaction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43730.     

Polymer‐grafted banana (Musa paradisiaca) stalk as an adsorbent for the removal of lead(II) and cadmium(II) ions from aqueous solutions: kinetic and equilibrium studies

This study examined the effectiveness of a new adsorbent prepared from banana (Musa paradisiaca) stalk, one of the abundantly available lignocellulosic agrowastes, in removing Pb(II) and Cd(II) ions from aqueous solutions. The adsorbent (PGBS‐COOH) having a carboxylate functional group at its chain end was synthesized by graft copolymerization of acrylamide on to banana stalk, followed by functionalization. Batch adsorption experiments were carried out as a function of solution pH, ionic strength, contact time, metal concentration, adsorbent dose and temperature. A pH range of 5.5–8.0 was found to be effective for the maximum removal for both Pb(II) and Cd(II). Metal uptake was found to decrease with increase in ionic strength due to the expansion of the diffuse double layer and, more importantly, the formation of some chloro complexes (since NaCl was used in the adjustment of ionic strength), which do not appear to be adsorbed to the same extent as cations [M²⁺ and M(OH)⁺]. The kinetic studies showed that an equilibrium time of 3 h was needed for the adsorption of Pb(II) and Cd(II) on PGBS‐COOH and adsorption processes followed a pseudo‐second‐order equation. The Langmuir isotherm model fitted the experimental equilibrium data well. The maximum sorption capacity for Pb(II) and Cd(II) ions was 185.34 and 65.88 mg g^?1, respectively, at 30 °C. The thermodynamic parameters such as changes in free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were derived to predict the nature of adsorption. The isosteric heat of adsorption was found to be independent of surface coverage. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC‐50, for comparison. Synthetic wastewater samples were treated with the adsorbent to demonstrate its efficiency in removing Pb(II) and Cd(II) ions from industrial wastewaters. Acid regeneration was tried for several cycles with a view to recovering the sorbed metal ions and also restoring the sorbent to its original state. Copyright © 2005 Society of Chemical Industry     

Hyperbranched polyglycerol/poly(acrylic acid) hydrogel for the efficient removal of methyl violet from aqueous solutions

Hydrogels were synthesized from hyperbranched polyglycerol (HPG) and acrylic acid through free‐radical polymerization with HPG as the crosslinker. The HPG/poly(acrylic acid) (PAA) hydrogel could absorb cationic dyes in aqueous solutions because of the existence of a porous structure and the large numbers of hydroxyl and carboxylic groups. With methyl violet chosen as a model compound, the HPG/PAA hydrogel reached a maximum adsorption of 394.12 mg/g at a feed concentration of 1 g/L. The highest removal ratio of 98.33% was observed at a feed concentration of 50 mg/L. The effects of the pH, contact time, and feed concentration on the dye adsorption were investigated. The dye adsorption data fit well with the pseudo‐second‐order and Langmuir models. We believe that the HPG/PAA hydrogels could perform well in appropriate applications in the removal of cationic dyes from aqueous solutions because of their high adsorption capacity and environmental friendliness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42951.     

Phosphorylated cellulose/electrospun chitosan nanofibers media for removal of heavy metals from aqueous solutions

Contamination of water resources by toxic heavy metals has significant impacts on environmental and human health. Their removal from aqueous media is essential to ensure water sustainability and to provide safe freshwater availability to population. Electrospun chitosan (CS) nonwoven mats are efficient at removing heavy metals from aqueous media. However, they suffer from low permeability and low-mechanical strength. They are also unable to remove contaminants in a nonselective way. A bilayer sorbent media made of a porous phosphorylated cellulose substrate covered by electrospun CS nanofibers was developed to overcome those weaknesses. The hydrophilic composite shows good water permeability and mechanical strength with appropriate thermal and chemical characteristics. Adsorption tests with Cd(II) indicate that pseudo-second order and Langmuir models best fitted experimental data, with a maximum adsorption capacity of 591 mg/g at 25°C. Adsorption with multielement samples containing Cr(VI), Cu(II), Cd(II), and Pb(II) also reveal their capability to remove them in a selective way. This mechanically resistant, hydrophilic, and permeable adsorbent media was able to capture both cationic and anionic metallic contaminants.     

Investigation of adsorption behaviors of Cu(II), Pb(II), and Cd(II) from water onto the high molecular weight poly (arylene ether sulfone) with pendant carboxyl groups

Three types of high molecular weight polyarylether adsorbents with different molar ratios of carboxyl and phenylene were designed and synthesized through direct polycondensation in mixture solvents. The as‐prepared polymers were characterized by FTIR, ¹H‐NMR, TGA, DSC, SEM, EDS, and GPC in order to study the regularity of polymeric adsorption/thermostability performances. Because of the highest molar ratio of carboxyl and phenylene, PAES‐C‐Na presented the highest adsorption capacity of Cu²⁺ compared to PAESK‐C‐Na and PAES; therefore, PAES‐C‐Na was opted to study the impacts of adsorbent dosage, pH, contact time, and initial concentration on the adsorption of Pb²⁺ and Cd²⁺. Moreover, a kinetic analysis revealed that the adsorption process followed pseudo‐second‐order model, while the thermodynamic experimental data properly fitted with the Freundlich model. The multi‐component competitive adsorption capacity followed the order Pb²⁺ > Cu²⁺ > Cd²⁺. Additionally, the regeneration tests indicated that PAES‐C‐Na still possessed the excellent adsorption capacity after several recycles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41984.