Surface modification of macroporous glycidyl methacrylate based copolymers for selective sorption of heavy metals

Two samples of macroporous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), poly(GMA-co-EGDMA), were synthesized by suspension copolymerization and modified with amines. Initial poly(GMA-co-EGDMA), and the samples modified with ethylene diamine [poly(GMA-co-EGDMA)-en], diethylene triamine [poly(GMA-co-EGDMA)-deta] and triethylene tetramine [poly(GMA-co-EGDMA)-teta], were characterized by mercury porosimetry, FTIR spectroscopy and elemental analysis. The most pronounced increase of specific surface area (75%) was observed for poly(GMA-co-EGDMA)-teta sample with smaller particles (D < 150 μm). The Cu(II) sorption was rapid, depending on porosity of amino-functionalized samples and ligand type. For poly(GMA-co-EGDMA)-deta and poly(GMA-co-EGDMA)-teta sorption half time required to reach 50% of total sorption capacity, t _1/2, were around 3 min. Sorption capacities for Cu(II), Co(II), Cd(II) and Ni(II) as well as for Cr(VI), Co(II), Cd(II) and Ni(II) ions were determined under competitive conditions as a function of pH, ligand type and porosity at room temperature. The results indicate selectivity of poly(GMA-co-EGDMA)-deta for Cu(II) over Cd(II) of 3:1 and for Cu(II) over Ni(II) and Co(II) of 6:1. The decrease in particle size of poly(GMA-co-EGDMA)-teta caused the increase of sorption capacities for all metal ions. At pH 1.8 the selectivity of poly(GMA-co-EGDMA)-teta with smaller particles for Cr(VI) over Ni(II), Co(II) and Cd(II) ions was 8.5:1.     

Templated synthesis of mesoporous aluminas by <Emphasis Type="Italic">graft</Emphasis> copolymer and their CO<Subscript>2</Subscript> adsorption capacities

Mesoporous aluminas were synthesized via a sol–gel process by templating an amphiphilic graft copolymer, PVC–g–POEM, consisting of a poly(vinyl chloride) (PVC) backbone and poly(oxyethylene methacrylate) (POEM) side chains. The mesoporous structures of aluminas with large surface areas were confirmed by X-ray diffraction, transmission electron microscopy, and nitrogen adsorption/desorption analysis. Aluminas synthesized with PVC–g–POEM graft copolymer exhibited higher CO₂ adsorption capacities (0.7 mol CO₂/kg sorbent) than aluminas synthesized without graft copolymer (0.6 mol CO₂/kg sorbent). The adsorption capacity of alumina strongly depends on its structure and calcination temperature; amorphous (400 °C) > γ phase (800 °C) > α phase (1000 °C).     

Competitive adsorption of Cu(II) and Cd(II) ions on spray-dried chitosan loaded with Reactive Orange 16

Chitosan microspheres cross-linked with glutaraldehyde and containing the reactive dye Orange 16 (RO 16) as a chelating agent were obtained by spray drying technique. These microspheres (CHS-RO 16) were characterized by FTIR, TGA, DSC, SEM and EDX analyses, and tested for metal adsorption. The new adsorbent was used in batch experiments to evaluate the adsorption of Cu(II) and Cd(II) ions in single and binary metal solutions. In single metal solutions, the maximum adsorption capacity for Cu(II), obtained by Langmuir model, was close to 1.69 mmol Cu g^? 1; this means the double of the adsorption capacity for Cd(II) (i.e. 0.80 mmol Cd g^? 1). Adsorption isotherms for binary solutions showed that the presence of Cu(II) decreased Cd(II) adsorption due to a significant competition effect. On the other hand, Cu(II) adsorption hardly changed when the initial concentration of Cd(II) increased: the new adsorbent was selective to Cu(II) against Cd(II). The metal ions were efficiently desorbed from chitosan-RO 16 with aqueous solutions of H₂SO₄.     

Effect of γ-irradiation on the structure of poly(ethyl acrylate-co-hydroxyethyl methacrylate) copolymer networks for biomedical applications

The effect of the sterilization process by γ-irradiation on the structure of poly(ethyl acrylate-co-hydroxyethyl methacrylate) copolymer networks, P(EA-co-HEMA) is studied for a broad dose range (7, 15, 25 and 50 kGy) and copolymer composition interval (0, 0.3, 0.5, 0.7 and 1 weight fraction of HEMA in the copolymer). γ-irradiation promotes chain scission in PHEMA homopolymer but induces new crosslinking points in PEA homopolymer. Both effects are present in the copolymers, with a net result that depends on composition. For copolymers with high HEMA fractions chain scission predominates, while, as the amount of EA in the copolymer increases, the situation changes and the net effect turns out to be an increase in the number of elastically active chains. Further, γ-irradiation strengthens the γ relaxation in PHEMA homopolymer, what suggest that the number of interchain hydrogen bonds decreases. FTIR spectroscopy reveals no oxidation as a consequence of the sterilization process.     

Synthesis,characterization, and antimicrobial activity of poly(GMA-co-EGDMA) polymer decorated with silver nanoparticles

Composite consisting of silver nanoparticles coordinated to poly(GMA-co-EGDMA) macroporous copolymer was prepared by attachment of amino group to the poly(GMA-co-EGDMA) in the reaction with ethylene diamine, and consequent reduction of silver ions with amino groups at elevated temperature. The infrared measurements indicated that surface of silver nanoparticles is passivated through the coordination of the lone pair on the N atom of the imine present in the skeleton of the poly(GMA-co-EGDMA) copolymer. The inductively coupled plasma atomic emission, UV–Vis reflection spectroscopy, X-ray diffraction, and transmission electron microscopy measurements revealed the high content (52 wt%) of well-separated silver nanoparticles in the size range of 5–10 nm onto composite. Antimicrobial efficiency of composite was tested against Gram-negative bacteria E. coli, Gram-positive bacteria S. aureus, and fungus C. albicans in wide concentration range of composite. The composite ensured almost maximum reduction of both bacteria, while the fungi reduction reached 96.5 %.     

Design of microencapsulated phase change material by one-step swelling polymerization in Pickering emulsion

Microencapsulated phase change materials (MePCMs) based on swelling polymerization in Pickering emulsion were demonstrated. Monodisperse poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) P(GMA-co-HEMA) particles were prepared by dispersion polymerization. The introduction of hydrophilic monomer HEMA endowed the obtained particles with suitable surface hydrophilicity for stabilizing Pickering emulsion. MePCMs with PGMA–polystyrene interpenetrating composite shell were formed when non-crosslinked particles were employed as stabilizer, while MePCMs with particles-embedded shell were prepared with crosslinked particles as Pickering stabilizer. Phase change property, thermal stability and thermal reliability of two kinds of MePCMs were investigated by TGA, FT-IR, DSC and cycling test. The temperature of 10% weight loss of MePCMs with interpenetrating shell was 11 °C higher than that of MePCMs with particles-embedded shell. After cycling test, the percentage of leached core materials from MePCMs with interpenetrating shell was approximately one-third of that from MePCMs with particles-embedded shell. The results showed that MePCMs with an integral shell presented better thermal stability, tightness and thermal reliability than MePCMs with particles-embedded shell. The research developed a simple process for MePCMs with excellent performance.     

The influence of different porogens with halogen substituents on the pore structure of polydivinylbenzene beads

Polydivinylbenzene (PDVB) beads with high surface area and porosity were prepared via suspension polymerization in the presence of solvents with halogen substituents as porogens. The porogens employed in the present work were p-dichlorobenzene, chlorobenzene, bromobenzene, benzyl chloride, and tetrachloroethane. The porogens were used in a 1/1 volume ratio with divinylbenzene (DVB). As predicted from previous knowledge of porogen with halogen substituents possessing strong capacity to construct porosity, the surface area of PDVB beads prepared with the above porogens reached 647.1–744.6 m² g⁻¹, which mainly depended on the difference of solubility parameter of the porogens and PDVB networks. The smaller the difference, the larger the surface area of PDVB beads was. Overall, research results of the present study indicated that in comparison with other types of porogen, solvent with halogen substituent could generate larger surface area and construct higher porosity in PDVB beads.     

Adsorption of platinum(IV) and palladium(II) from aqueous solution by thiourea-modified chitosan microspheres

The chitosan microparticles were prepared using the inverse phase emulsion dispersion method and modified with thiourea (TCS). TCS was characterized by scanning electron microscope (SEM), the Fourier transform infrared (FT-IR) spectra, sulfur elemental analysis, specific surface area and pore diameter. The effects of various parameters, such as pH, contact time, initial concentration and temperature, on the adsorption of Pt(IV) and Pd(II) by TCS were investigated. The results showed that the maximum adsorption capacity was found at pH 2.0 for both Pt(IV) and Pd(II). TCS can selectively adsorb Pt(IV) and Pd(II) from binary mixtures with Cu(II), Pb(II), Cd(II), Zn(II), Ca(II), and Mg(II). The adsorption reaction followed the pseudo-second-order kinetics, indicating the main adsorption mechanism of chemical adsorption. The isotherm adsorption equilibrium was well described by Langmuir isotherms with the maximum adsorption capacity of 129.9 mg/g for Pt(IV) and 112.4 mg/g for Pd(II). The adsorption capacity of both Pt(IV) and Pd(II) decreased with temperature increasing. The negative values of enthalpy (ΔH°) and Gibbs free energy (ΔG°) indicate that the adsorption process is exothermic and spontaneous in nature. The adsorbent was stable without loss of the adsorption capacity up to at least 5 cycles and the desorption efficiencies were above 95% when 0.5 M EDTA–0.5 M H₂SO₄ eluent was used. The results also showed that the preconcentration factor for Pt(IV) and Pd(II) was 196 and 172, respectively, and the recovery was found to be more than 97% for both precious metal ions.     

Poly(hydroxyethyl methacrylate) nanobeads containing imidazole groups for removal of Cu(II) ions

Poly(hydroxyethyl methacrylate) (PHEMA) nanobeads with an average size of 300 nm in diameter and with a polydispersity index of 1.156 were produced by a surfactant free emulsion polymerization. Specific surface area of the PHEMA nanobeads was found to be 996 m²/g. Imidazole containing 3-(2-imidazoline-1-yl)propyl(triethoxysilane) (IMEO) was used as a metal-chelating ligand. IMEO was covalently attached to the nanobeads. PHEMA-IMEO nanobeads were used for the removal of copper(II) ions from aqueous solutions. To evaluate the degree of IMEO loading, the PHEMA nanobeads were subjected to Si analysis by using flame atomizer atomic absorption spectrometer and it was estimated as 973 µmol IMEO/g of polymer. The PHEMA nanobeads were characterized by transmission electron microscopy and fourier transform infrared spectroscopy. Adsorption equilibrium was achieved in about 8 min. The adsorption of Cu²⁺ ions onto the PHEMA nanobeads was negligible (0.2 mg/g). The IMEO attachment into the PHEMA nanobeads significantly increased the Cu²⁺ adsorption capacity (58 mg/g). Adsorption capacity of the PHEMA-IMEO nanobeads increased significantly with increasing concentration. The adsorption of Cu²⁺ ions increased with increasing pH and reached a plateau value at around pH 5.0. Competitive heavy metal adsorption from aqueous solutions containing Cu⁺, Cd²⁺, Pb²⁺ and Hg²⁺ was also investigated. The adsorption capacities are 61.4 mg/g (966.9 µmol/g) for Cu²⁺; 180.5 mg/g (899.8 µmol/g) for Hg²⁺; 34.9 mg/g (310.5 µmol/g) for Cd²⁺ and 14.3 mg/g (69 µmol/g) for Pb²⁺. The affinity order in molar basis is observed as Cu²⁺ > Hg²⁺ > Cd²⁺ > Pb²⁺. These results may be considered as an indication of higher specificity of the PHEMA-IMEO nanobeads for the Cu²⁺ comparing to other ions. Consecutive adsorption and elution operations showed the feasibility of repeated use for PHEMA-IMEO nanobeads.     

Biosorption of cadmium(II), zinc(II) and lead(II) by Penicillium simplicissimum: Isotherms, kinetics and thermodynamics

The isotherms, kinetics and thermodynamics of Cd(II), Zn(II) and Pb(II) biosorption by Penicillium simplicissimum were investigated in a batch system. The effects of pH, initial metal ions concentration, biomass dose, contact time, temperature and co-ions on the biosorption were studied. Adsorption data were well described by both the Redlich–Peterson and Langmuir model. Chemical ion-exchange was found to be an important process based on free energy value from Dubini–Radushkevich isotherm for all metal ions. The results of the kinetic studies of all metal ions at different temperature showed that the rate of adsorption followed the pseudo second-order kinetics well. The thermodynamics constants ΔG°, ΔH° and ΔS° of the adsorption process showed that biosorption of Cd(II), Zn(II) and Pb(II) ions on Penicillium simplicissimum were endothermic and spontaneous.     

Synthesis of crosslinked poly(styrene-<Emphasis Type="Italic">co</Emphasis>-divinylbenzene-<Emphasis Type="Italic">co</Emphasis>-sulfopropyl methacrylate) nanoparticles by emulsion polymerization: Tuning the particle size and surface charge density

We have synthesized highly charged, crosslinked poly (styrene-co-divinylbenzene-co-sulfopropyl methacrylate) copolymer colloidal particles using emulsion polymerization. The effects of concentration of the emulsifier and the initiator on the particle size and the charge density of the colloidal particles are studied. Colloidal particle size is highly dependent upon the concentration of the emulsifier and the initiator. The colloidal particle diameter decreases with increasing concentration of the emulsifier and increases with increasing concentration of the initiator in the polymerization mixture. Number of particles, surface charge density and charges per particle are also functions of both the emulsifier and the initiator concentration. The surface charge density and the number of charges per sphere increase with increasing particle diameter. These copolymer colloid particles self assemble readily and diffract visible light. Polymer hydrogel imbibed with these colloids shows the light diffraction.     

Comparative adsorption of Cu(II), Zn(II), and Pb(II) ions in aqueous solution on the crosslinked chitosan with epichlorohydrin

The crosslinked chitosans synthesized by the homogeneous reaction of chitosan in aqueous acetic acid solution with epichlorohydrin were used to investigate the adsorptions of three metals of Cu(II), Zn(II), and Pb(II) ions in an aqueous solution. The crosslinked chitosan characterized by 13CNMR, SEM, and elemental analysis, and the effects of pH and anion on the adsorption capacity were carried out. The dynamical study demonstrated that the adsorption process was followed the second-order kinetic equation. The results obtained from the equilibrium isotherms adsorption studies of three metals of Cu(II), Zn(II), and Pb(II) ions by being analyzed in three adsorption models, namely, Langmuir, Freundlich, and Dubinnin-Radushkevich isotherm equations, indicated to be well fitted to the Langmuir isotherm equation under the concentration range studied, by comparing the linear correlation coefficients. The order of the adsorption capacity (Qm) for three metal ions was as follows: Cu2+>Pb2+>Zn2+. This technique for syntheses of the crosslinked chitosans with epichlorohydrin via the homogeneous reaction in aqueous acetic acid solution showed that the adsorptions of three metal ions in aqueous solution were followed the monolayer coverage of the adsorbents through physical adsorption phenomena.     

Adsorption and desorption characteristics of lindane, carbofuran and methyl parathion on various Indian soils

Adsorption and desorption characteristics of three insecticides on four Indian soils were studied. Insecticides used were representative of organochlorine, organophosphate, and carbomate groups. The order of adsorption of pesticides on soils was: lindane > methyl parathion > carbofuran. Compost soil had shown the maximum adsorption capacity. The order of adsorption capacity of various soils were: compost soil > clayey soil > red soil > sandy soil. Adsorption isotherms were better fitted to Freundlich model and K_f values increased with increase in organic matter content of the soils. Thermodynamic parameters indicated favorable adsorption of all the three pesticides in four different soils. Adsorption was exothermic in nature. Distilled water desorbed 30–60% of adsorbed pesticides whereas; organic solvents were able to affect 50–80% of sorbed pesticides. Clay content and organic matter played a significant role in pesticide adsorption and desorption processes. Hysteresis effect was observed in red, clayey and compost soils. Hysteresis effect increased with increase in organic matter and clay content of the soils.     

Preparation of a novel zwitterionic graphene oxide-based adsorbent to remove of heavy metal ions from water: Modeling and comparative studies

A novel zwitterionic graphene oxide-based adsorbent was first synthesized in a multistep procedure including the successive grafting of bis(2-pyridylmethyl)amino groups (BPED) and 1,3-propanesultone (PS) onto graphene oxide (GO) sheets. Then, the as-prepared materials were used as adsorbent for the removal of metal ions from aqueous solutions. The influence of solution pH, contact time, metal ion concentration, and temperature onto the adsorption capacity of the zwitterionic GO-BPED-PS adsorbent was investigated and compared with the GO-BPED adsorbent. In particular, it was shown that the maximum adsorption capacities of the GO-BPED-PS adsorbent were as high as 4.174 ± 0.098 mmol.g^?1 for the Ni(II) ions and 3.902 ± 0.092 mmol.g^?1 for the Co(II) ions under optimal experimental conditions (metal ion concentration = 250 mg.L^?1, pH = 7 and T = 293 K). In addition, the adsorption behaviors of Ni(II) and Co(II) ions onto both the GO-BPED and GO-BPED-PS adsorbents fitted well with a pseudo-second-order kinetic model and a Jossens isotherm model. Moreover, adsorption thermodynamics of Ni(II) and Co(II) ions have been studied at various temperatures and confirmed the exothermic adsorption nature of the adsorption process onto the GO-BPED-PS adsorbent. Furthermore, the zwitterionic GO-BPED-PS adsorbent retained good adsorption properties after recycling 18 times which is much better than the conventional adsorbents.     

Purification of yeast alcohol dehydrogenase by using immobilized metal affinity cryogels

In this study, poly(2-hydroxyethyl methacrylate–glycidylmethacrylate) [poly(HEMA–GMA)] cryogels were prepared by radical cryocopolymerization of HEMA with GMA as a functional comonomer and N,N′-methylene-bisacrylamide (MBAAm) as a crosslinker. Iminodiacetic acid (IDA) functional groups were attached via ring opening of the epoxy group on the poly(HEMA–GMA) cryogels and then Zn(II) ions were chelated with these structures. Characterization of cryogels was performed by FTIR, SEM, EDX and swelling studies. These cryogels have interconnected pores of 30–50 μm size. The equilibrium swelling degree of Zn(II) chelated poly(HEMA–GMA)-IDA cryogels was approximately 600%. Zn(II) chelated poly(HEMA–GMA)-IDA cryogels were used in the adsorption of alcohol dehydrogenase from aqueous solutions and adsorption was performed in continuous system. The effects of pH, alcohol dehydrogenase concentration, temperature, and flow rate on adsorption were investigated. The maximum amount of alcohol dehydrogenase adsorption was determined to be 9.94 mg/g cryogel at 1.0 mg/mL alcohol dehydrogenase concentration and in acetate buffer at pH 5.0 with a flow rate of 0.5 mL/min. Desorption of adsorbed alcohol dehydrogenase was carried out by using 1.0 M NaCI at pH 8.0 phosphate buffer and desorption yield was found to be 93.5%. Additionally, these cryogels were used for purification of alcohol dehydrogenase from yeast with a single-step. The purity of desorbed alcohol dehydrogenase was shown by silver-stained SDS–PAGE. This purification process can successfully be used for the purification of alcohol dehydrogenase from unclarified yeast homogenates and this work is the first report about the usage of the cryogels for purification of alcohol dehydrogenase.     

Use of rice straw as biosorbent for removal of Cu(II), Zn(II), Cd(II) and Hg(II) ions in industrial effluents

Adsorption experiments were carried out using waste rice straw of several kinds as a biosorbent to adsorb Cu(II), Zn(II), Cd(II) and Hg(II) ions from aqueous solutions at room temperature. To achieve the best adsorption conditions the influence of pH and contact time were investigated. The isotherms of adsorption were fitted to the Freundlich equation. Based on the experimental data and Freundlich model, the adsorption order was Cd(II) > Cu(II) > Zn(II) > Hg(II) on the rice straw. This quick adsorption process reached the equilibrium before 1.5 h, with maximum adsorptions at pH 5.0. Thermodynamic aspects of the adsorption process were investigated. The biosorbent material was used in columns for the removal of ions Cu, Zn, Cd and Hg of real samples of industrial effluent and its efficiency was studied.     

Effect of competitive ions on the arsenic removal by mesoporous hydrous zirconium oxide from drinking water

Adsorption properties of 302-type commercially available hydrous zirconium oxide (302-HZO) towards arsenic and some competitive anions and cations have been studied under batch and column conditions. Due to amphoteric properties, anion exchange performance of hydrous zirconium oxide is pH dependent. Media exhibits high affinity towards arsenic in a broad pH range, with high adsorption capacity at pH < 8. It was shown that silicate and phosphate ions are arsenic's main competitors affecting media adsorption capacity. Presence of transition metal cations in <1 ppm does not affect 302-HZO capacity on arsenic, whereas alkaline-earth cations improve arsenic removal. The possibility for significant increase of 302-HZO adsorption capacity on arsenic at pH > 8 by using “solid acidifier” technique is discussed. Results of 302-HZO field trials are presented.     

Kinetics and thermodynamic of adsorption of chromium(VI) from aqueous solution using puresorbe

This paper deals with an investigation on coir-based adsorbent, puresorbe, in the removal of chromium(VI) from the aqueous solutions. The adsorption of chromium(VI) was carried out by varying the parameters such as agitation time, metal concentration, adsorbent dose, temperature and pH. The experimental isotherm data were analyzed using Langmuir, Freundlich and Redlich and Peterson isotherms. Adsorption followed second order rate expression for the particle size 250–500 μm at pH 2. The monolayer adsorption capacity is 76.92 mg chromium(VI) per gram of puresorbe. Thermodynamic parameters show the endothermic nature of chromium(VI) adsorption. Desorption study carried out using distilled water adjusted to pH of 2–10, suggests that chemisorption might be the mode of adsorption.     

Adsorption characteristics of heavy metal ions onto a low cost biopolymeric sorbent from aqueous solutions

In this study, the adsorption conditions of Cu(II), Pb(II) and Cd(II) metal ions onto sporopollenin have been studied. The different variables effecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration and temperature have been investigated. Adsorption isotherms correlated well with the Freundlich type adsorption isotherm and adsorption capacities were found to be 0.0195, 0.0411 and 0.0146 mmol g(-1) for Cu(II), Pb(II) and Cd(II) metal ions, respectively. Experimental data were also evaluated to find out kinetic characteristics of the adsorption process. Adsorption processes for three target heavy metal ions were found to follow pseudo-second order type adsorption kinetics. Intraparticle diffusion was found to take part in adsorption processes but it could not be accepted as the primary rate-determining step. The mean free energies of adsorption (E) were found to be between 8 and 16 kJ mol(-1) for the metal ions studied and therefore adsorption mechanism for the adsorbent was explained as an ion-exchange process. But it was observed that chelating effect is also playing an important role in the adsorption of metal ions onto sporopollenin. Thermodynamic parameters, DeltaH degrees , DeltaS degrees and DeltaG degrees were also calculated from graphical interpretation of the experimental data. Standard heats of adsorption (DeltaH degrees ) were found to be endothermic and DeltaS degrees values were calculated to be positive for the adsorption of Cu(II), Pb(II) and Cd(II) ions onto the adsorbent. Negative DeltaG degrees values indicated that adsorption process for these three metal ions onto sporopollenin is spontaneous.     

Dispersion of chitosan on perlite for enhancement of copper(II) adsorption capacity

Chitosan coated perlite beads were prepared by drop-wise addition of slurry, made of chitosan dissolved in oxalic acid and perlite, to an alkaline bath (0.7 M NaOH). The beads that contained 32% chitosan enhanced the accessibility of OH and amine groups present in chitosan for adsorption of copper ions. The experiments using Cu(II) ions were carried out in the concentration range of 50-4100 mg/L (0.78-64.1 mmol/L). Adsorption capacity for Cu(II) was pH dependent and a maximum uptake of 104 mg/g of beads (325 mg/g of chitosan) was obtained at pH 4.5 when its equilibrium concentration in the solution was 812.5 mg/L at 298 K. The XPS and TEM data suggested that copper was mainly adsorbed as Cu(II) and was attached to amine groups. The adsorption data could be fitted to one-site Langmuir adsorption model. Anions in the solution had minimal effect on Cu(II) adsorption by chitosan coated perlite beads. EDTA was used effectively for the regeneration of the bed. The diffusion coefficient of Cu(II) onto chitosan coated beads was calculated from the breakthrough curve and was found to be 2.02 x 10(-8) cm(2)/s.