Designed multifunctionalized magnetic mesoporous microsphere for sequential sorption of organic and inorganic pollutants

A novel magnetic microsphere with thiol-functionalized mesoporous shell was fabricated by using a colloidal chemical method and cationic surfactants (CTAB) as structure-directing agents. As a high performance adsorbent, these microspheres were examined for environmental protection applications to adsorb and remove toxic phenolic compounds and heavy metal ions, sequentially, in aqueous solution. The prepared nanocomposite microspheres were mesoporous and magnetizable, with a diameter of 350-400 nm, a high surface area of 913.14 m²/g, a pore size of 2.48 nm, and a saturation magnetization of 33.9 emu/g. These multifunctional microspheres showed excellent adsorptive capability towards toxic phenolic compounds and heavy metal ions (Hg²⁺, Pb²⁺). The cation micelle made of CTAB in the mesopores has great attractive power to phenolic compounds and the adsorption capacity was as high as 144.78 mg/g for 4-methyl-2,6-dinitrophenol. The thiol-functionalized magnetic mesoporous microsphere (TMMM) which had adsorbed phenolic compounds can further adsorb metal ions after removing CTAB. The adsorption capacity was 185.19 mg/g for Hg²⁺ and 114.7 mg/g for Pb²⁺. The TMMM can be easily removed from solution by an external magnetic field. These results suggest that this kind of nanocomposites is potentially useful materials for effectively adsorbing and removing different dangerous pollutants in aqueous solution.     

Binding of several heavy metal ions by polyaspartyl polymers and their application to some Chinese herbal medicines

Water‐insoluble polyaspartyl polymers were synthesized by using water as medium instead of organic medium. Taking Ca²⁺ as a reference, the binding of several heavy‐metal ions, including Pb²⁺, Cd²⁺, Hg²⁺, Cr³⁺, Cu²⁺, and Mn²⁺, by polyaspartyl polymers was studied. The experimental results revealed that polyaspartate is an excellent binding agent for the investigated heavy‐metal ions. These cation ions were bound to polyaspartate polymer by the same mechanism as Pb²⁺, which can be explained by ion exchange model. Since polyaspartate has a protein‐resembling structure that is sensitive to trace heavy metal, it was used to remove some trace heavy‐metal elements in Chinese herbal medicines. It was found that polyaspartate material was an effective agent for the removal of Pb²⁺, Cd²⁺, and Hg²⁺ ions from glycyrrhizin, angelica, and gynostemma pentaphyllum. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

DNA‐loaded porous polyethersulfone particles for environmental applications II. Utilization

DNA‐loaded porous polyethersulfone (PES) particles are fabricated using a liquid–liquid phase separation technique. The particles are then used for environmental applications. Both the DNA‐loaded porous PES particles and the DNA‐loaded PES porous particle column could accumulate and remove DNA intercalating pollutants, such as ethidium bromide, acridine orange, endocrine disruptors, and heavy metal ions. The microsphere column shows more high removal efficiency. These results proved that the DNA‐loaded porous particles have the potential to serve as absorbents for environmental applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1674–1678, 2005     

Preparation of porous and hollow Mn2O3 microspheres and their adsorption studies on heavy metal ions from aqueous solutions

Mn₂O₃ microspheres are prepared and used as adsorbent for removal of heavy metal ions. Morphology and structure of Mn₂O₃ microspheres are analyzed by SEM, TEM, XRD, XPS and N₂ sorption technique. Effects of adsorbent concentration, ion concentration and agitation time on adsorption behavior are investigated. Adsorption isotherm and kinetics are also studied. The results show Mn₂O₃ microspheres have well-developed porous and hollow structure, demonstrating good potential on removal of heavy metal ions. Adsorption data fit better with Freundlich isotherms than Langmuir isotherms. Kinetic studies indicate adsorption behavior is described by pseudo-second-order kinetic model, and intra-particle diffusion plays a significant role.     

Grafting of tea waste with polyacrylic acid and its potential applications

The indigenous materials such as tea waste were exploited as antimicrobial adsorbent for removing heavy metal ions. It was well known that tea waste was characterized with biodegradability and environmental-friendly product. Grafting copolymerization of acrylic acid onto tea waste was carried out using gamma radiation. The effects of solvent, dose and feeding concentration of acrylic acid have been investigated to achieve the optimum conditions. Grating (%) ranged from 30 to 70 for DMSO and H₂O, respectively. The grafted tea waste was characterized by Fourier transform infrared (FTIR) spectroscopy, swelling study, scanning electron microscopy (SEM) and energy dispersive spectrometry X-rays (EDS). The grafted samples were used in waste water treatment to remove heavy metal ions (Cr³⁺, Pb²⁺ and Hg²⁺). The highest adsorption capacity was 35 and 200 mg/g of Hg⁺² ions for ungrafted and grafted samples, respectively. The results showed that the selectivity among these metal ions is different onto tea waste-graft-polyacrylic acid. The grafted tea waste samples, which complexed with Cr³⁺, Pb²⁺ and Hg²⁺ ions, were found to have antimicrobial features. Therefore, they could be used as adsorbent in removing heavy metal ions with antimicrobial features as well.

     

Ion exchange properties of carboxylated bagasse

Bagasse fibers were chemically modified with the aim to prepare lignocellulosic materials that have the ability to remove heavy metal ions from waste water. Three different reactions were used for the modification: etherification using monochloroacetic acid, esterification using succinic anhydride, and oxidation using sodium periodate and sodium chlorite. Bagasse was crosslinked using epichlorohydrin before chemical modification to avoid loss of its constituents during the chemical modification or application. The structure of the prepared derivatives was proofed using Fourier transform infrared and chemical methods. The ability of the prepared bagasse cation exchangers to adsorb heavy metal ions (Cu²⁺, Ni²⁺, Cr³⁺, Fe³⁺), on a separate basis or in a mixture of them, at different metal ion concentration was tested. Thermal stability of the different bagasse derivatives was studied using thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1399–1404, 2006     

Congo red attached poly(EGDMA–HEMA) microspheres as specific sorbents for removal of cadmium ions

Poly[ethyleneglycoldimethacrylate (EGDMA)–hydroxyethylmethacrylate (HEMA)] microspheres (150–200 μm in diameter) were produced by suspension copolymerization of EGDMA and HEMA in an aqueous medium. Toluene was included in the formulations in order to produce water-swellable microspheres. Poly(vinyl alcohol) and benzoyl peroxide were used as stabilizer and initiator, respectively. Congo red was chemically attached to the microspheres as a metal chelating ligand for specific adsorption of heavy metal ions. These sorbents were characterized by an optical microscopy and a FTIR. Adsorption/desorption of cadmium (Cd²⁺) ions from aqueous solutions on these sorbents were investigated in batch equilibrium experiments by using an atomic absorption spectroscopy with a graphite furnace atomizer. The maximum cadmium adsorption on to the dye-attached microspheres (i.e., by complex formation) was about 18.3 mg Cd²⁺ ions/g polymer, which was observed at pH 6.8. While adsorption onto the plain poly(EGDMA–HEMA) microspheres (i.e., nonspecific adsorption) was about 0.93 mg Cd²⁺ ions/g polymer at the same conditions. More than 90% of the adsorbed cadmium was desorbed in 1 h by using 2M NaCl as an eluant. The resorption capacity of the sorbent did not significantly decrease during repeated sorption–desorption cycling. © 1996 John Wiley & Sons, Inc.     

Application of jojoba wax bound to polyethylene membranes and hollow fibers in ion‐exchange and pervaporation processes

Chlorosulfonated polyethylene membranes and hollow fibers were reacted with allylic amino jojoba to bind the wax chemically to the polymer. The modified membranes and hollow fibers were then tested in the ion‐exchange and pervaporation processes, respectively. The jojoba‐bound polyethylene membranes were selective in preventing transfer of divalent ions such as Ca²⁺ and Mg²⁺, while monovalent ion such as K⁺ and Na⁺ could penetrate the membranes. The flux of the monovalent ions depended on the amount of jojoba bound to the polymer, which acted as a barrier to the ions (the monovalent ions could be eluted by acid washing). The concentration of ions (in the range of 0.05–1.0 N) in the feed solution had little effect on the flux. Preliminary results of pervaporation of a dioxane/water mixture through hollow fibers made of jojoba‐bound chlorosulfonated polyethylene show separation of the dioxane from the water with a separation factor of 6. This technique can be applied to remove residual organic solvents in the purification of industrial waste water. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 763–768, 2001     

Understanding polymer morphology. Arthur E. Woodward. Carl Hanser Verlag,Munich, 1995. pp. ix + 130, price DM38.00. ISBN 3-446-17431-1

An investigation was undertaken regarding the adsorption of heavy metal ions (CrO^2?₄ or Pb²⁺) and phenol from solution with a highly crosslinked amphoteric starch containing the phosphate anionic group and the tertiary amine cationic group. The adsorption process was found to be dependent on initial pH and concentration for both metal ions, and to be concentration-independent for the phenol organic substance. The adsorption follows the Langmuir adsorption isotherm for CrO^2?₄, and the Freundlich adsorption isotherm for Pb²⁺. The adsorption mechanism confirms that the Na⁺ of the sodium phosphate group and the Cl^? of the tertiary amine group are used to exchange Pb²⁺ and CrO^2?₄ ions, respectively, and the tertiary amine group is used to adsorb phenol.     

Spectroscopic and thermal studies of poly[(N‐vinylimidazole)‐co‐(maleic acid)] hydrogel and its quaternized form

BACKGROUND: In this study, poly[(N‐vinylimidazole)‐co‐(maleic acid)] (poly(VIm/MA)) hydrogels were prepared by γ‐irradiation of ternary mixtures of N‐vinylimidazole–maleic acid–water using a ⁶⁰Co γ‐source. Spectroscopic and thermal analyses of these hydrogels as a function of protonation showed that the results are consistent with the existence of an H‐bridged complex when the imidazole rings are partially protonated. Finally, the efficiency and binding trends of Cu²⁺, Co²⁺, Cd²⁺ and Pb²⁺ ions with both protonated and unprotonated poly(VIm/MA) hydrogels were determined. RESULTS: Gelation of 90% was reached at around 180 kGy dose at the end of irradiation. The poly(VIm/MA) hydrogels synthesized were further protonated in HCl solutions with different concentrations. Hydrogels originally showed 450% volumetric swelling; this ratio reached 1900% after protonation at pH = 5.0. Fourier transform infrared spectral changes in the ⁺N? H stretching region (3200–3600 and 1173 cm^?1) and the ring mode deformation at 915 cm^?1 are consistent with the formation of an H‐bridged complex between the protonated and unprotonated imidazole rings upon partial protonation. Similar changes were obtained from NMR spectra of both the protonated and unprotonated forms of the hydrogels. CONCLUSION: Protonated and unprotonated hydrogels have been used in heavy metal ion adsorption studies for environmental purposes. Adsorption decreased with decreasing pH value due to the protonation of the VIm ring. The adsorption of Me²⁺ ions decreased in the order Cu²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺, which is related to the complexation stability as well as the ionic radius of the metal ions. These results show that P(VIm/MA) hydrogels can be used efficiently to remove heavy metal ions from aqueous solutions. However, the protonated form is a bad choice for heavy metal ion adsorption due to electrostatic repulsion forces; it can nevertheless be assumed to be a good choice for anion adsorption from environmental waste water systems. Copyright © 2007 Society of Chemical Industry     

Poly(itaconic acid)-assisted ultrafiltration of heavy metal ions’ removal from wastewater

The complexation–ultrafiltration technique has been introduced as a capable system to remove heavy metals ions from wastewater. This method needs a water-soluble polymer; therefore, in this paper we synthesized super water-soluble poly(itaconic acid) (PITA) and employed it in polymer-assisted ultrafiltration process to remove Pb(II) ions from synthetic wastewater solutions. The itaconic acid can be produced from different agricultural products and is a green and eco-friendly material. Factors influencing the removal of the metals ions including poly(itaconic acid) concentration, pH and permeate flux were investigated. The results showed that the maximum percentage of metal ion removal was obtained in the basic pH (pH > 7). The flux test was performed by 200 mg/L of poly(itaconic acid) and after 60 min, the flux of membrane was 33.4 L/m²h. The simultaneously selective removal ability of the poly(itaconic acid) for adsorption of different metal ions (Pb²⁺, Sn²⁺, Cu²⁺, Zn²⁺, and Cd²⁺) was also studied. The trend of rejection was Pb²⁺ > Cu²⁺ > Sn²⁺ > Zn²⁺ > Cd²⁺. The highest rejection of Pb(II) ions was achieved as 86%. Generally, the results of this research demonstrated that poly(itaconic acid) (with two carboxyl groups on its repeating unit) is more effective in removing heavy metals ions from wastewater in comparison with customary polymers.

     

Preparation of Ferrocene-Based Coordination Polymer Microspheres and Their Application in Hydrogen Storage

In this article, a functional ferrocene-based metalloligand has been synthesized and used as the building block to assemble novel coordination polymer microspheres. Specifically, this metalloligand was coordinated with two different types of metal ions (Co²⁺ and Mn²⁺) to fabricate two different but isostructural microspheres under solvothermal conditions. To deepen our understanding of the formation process of the coordination polymer microspheres, a growth mechanism has been proposed based on the morphology change of these spheres throughout the whole reaction process. Furthermore, the prepared multi disperse microspheres, in the form of hollow spheres with high thermostability, can be applied to store hydrogen for their promising hydrogen uptake capacity (1.84wt% for CPM-1 and 1.00 wt% for CPM-2 at 163 K under 5 MPa). Moreover, the different adsorption enthalpies of these two materials that relevant to the varied hydrogen uptake capacity have been calculated, compared and explained.     

Chelating polymer bearing triazolylazophenol moiety as the functional group

The chelating polymer-bearing triazolylazophenol moiety as the functional group was synthesized, its metal adsorption properties for 6 divalent heavy metal ions; Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ were investigated. The capacity of the polymer for Cu²⁺ achieved 8.7 mEq/g in pH 5.3 solution. The polymer showed remarkable color changes from orange to red violet or blue violet with its chelations to the heavy metal ions. The metal adsorption rates of the polymer were rapid in performing complete capacity saturation of heavy metal ions in about 30 min. The capacities varied little the presence of alkali or alkaline earth metal ions in solutions. The perfect elimination of metals from the polymer–M²⁺ chelates were performed with mineral acid solutions. The metal ions; Cu²⁺ and Ni²⁺ in plating-process solutions were effectively removed by the chelating polymer, and the polymer can be practically used for the removal of these ions from waste water.     

Heavy metals removal from solution by polyaniline/palygorskite composite

Batch adsorption experiments were carried out to remove heavy metal ions such as Cu (II), Ni (II), Cd (II), and Cr (VI) from single‐metal solutions using a polyaniline/palygorskite (PP) composite. Different parameters affecting the adsorption capacity such as contact time and pH of the solution have been investigated. The structural characteristics of the PP composite were studied in this work. Atomic absorption spectroscopy was used for the measurement of heavy metal contents, and the adsorption capacity (q_e) calculated were 114 mg Cu (II) g^?1, 84 mg Ni (II) g^?1, 56 mg Cd (II) g^?1, and 198 mg Cr (VI) g^?1 under optimal conditions. The removal of the metal ions from solutions was assigned to chelation, ionic exchange, and electrostatic attraction. Data from this study proved that the novel organic/inorganic composite presents great potential in the recovery and elimination of noble or heavy metal ions from industrial wastewater. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Micellar thin-layer chromatographic separation of heavy metal cations: Effect of organic and inorganic additives on migration behavior

The migration behavior of heavy metal cations on cellulose layers using aqueous micellar, hydro-organic, and water-organic-surfactant mobile phases was investigated. Anionic, cationic, and nonionic surfactant systems were examined over a 0.001–5% concentration range. Brij-35, a nonionic surfactant capable of forming charged complexes with some metal ions, was identified as the best surfactant. The effect of the presence of organic additives, such as dimethylsulfoxide, dimethylformamide, methanol and acetone, on the mobility of metal ions was also studied. Acetone was found to be the most effective additive at 10% concentration with 3% Brij. Quantitative determination of UO₂ ²⁺ by spectrophotometry after preliminary thin-layer chromatographic (TLC) separation from Fe³⁺ and Hg²⁺ was also performed. A maximal recovery of 93% was obtained. This TLC method is rapid, with development times averaging 2 min.     

Metal‐chelated polyamide hollow fibers for human serum albumin separation

We modified microporous polyamide hollow fibers by acid hydrolysis to amplify the reactive groups and subsequent binding of Cibacron Blue F3GA. Then, we loaded the Cibacron Blue F3GA‐attached hollow fibers with different metal ions (Cu²⁺, Ni²⁺, and Co²⁺) to form the metal chelates. We characterized the hollow fibers by scanning electron microscopy. The effect of pH and initial concentration of human serum albumin (HSA) on the adsorption of HSA to the metal‐chelated hollow fibers were examined in a batch system. Dye‐ and metal‐chelated hollow fibers had a higher HSA adsorption capacity and showed less nonspecific protein adsorption. The nonspecific adsorption of HSA onto the polyamide hollow fibers was 6.0 mg/g. Cibacron Blue F3GA immobilization onto the hollow fibers increased HSA adsorption up to 147 mg/g. Metal‐chelated hollow fibers showed further increases in the adsorption capacity. The maximum adsorption capacities of Co²⁺‐, Cu²⁺‐, and Ni²⁺‐chelated hollow fibers were 195, 226, and 289 mg/g, respectively. The recognition range of metal ions for HSA from human serum followed the order: Ni(II) > Cu(II) > Co(II). A higher HSA adsorption was observed from human serum (324 mg/g). A significant amount of the adsorbed HSA (up to 99%) was eluted for 1 h in the elution medium containing 1.0M sodium thiocyanide (NaSCN) at pH 8.0 and 25 mM ethylenediaminetetraacetic acid at pH 4.9. Repeated adsorption–desorption processes showed that these metal‐chelated polyamide hollow fibers were suitable for HSA adsorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3346–3354, 2002     

Multifunctional humate-based magnetic sorbent: Preparation,properties and sorption of Cu (II), phosphates and selected pesticides

The magnetic sorbents with various contents of humic acids (ca. 6.6–15.5%) were prepared by a simple co-precipitation procedure from Fe²⁺/Fe³⁺ salts and a commercially available alkaline humate concentrate. The sorbents were able to remove heavy metal cations (Cu²⁺) from waters with the sorption capacity ranging from 0.006 to 0.25 mmol/g in dependence on the content of humic acids. An ability to remove some organic compounds (triazine and organophosphate pesticides) was also demonstrated. In both cases, the presence of humic acids in the sorbents plays a crucial role in the sorption process – whereas the sorption of metal cations was attributed to the presence of acidic functional groups, the sorption of (less polar) organic compounds was attributed to the presence of glassy-state polymeric domains in the iron-humate matrix. The iron-humate sorbents were effective also in the removal of inorganic phosphorus (phosphate anions) from water. In this case, however, the removal efficiency decreased with increasing content of humic acids in the sorbent. Although the saturation magnetization decreased proportionally with increasing content of humic acids, it remained still sufficiently high for all the examined sorbents to facilitate their effective separation in magnetic field.     

Poly(hydroxamic acid) ligand from palm-based waste materials for removal of heavy metals from electroplating wastewater

Heavy metals pollutants are nonbiodegradable and their bioaccumulation results in detrimental environmental consequences. Therefore, it is important to effectively remove toxic heavy metal waste from industrial sewage. Thus, the main goal of this research is to synthesize an ideal cellulose-based adsorbent from palm-based waste materials (agro waste) in order to be utilized in real-life practical applications with low cost as such removing common toxic heavy metals from industrial effluents. A poly(methyl acrylate) grafted palm cellulose was synthesized via a free-radical initiation process, followed by an oximation reaction to yield poly(hydroxamic acid) ligands. The adsorption capacity (q_e) of poly(hydroxamic acid) ligands for metal ions such as copper (Cu²⁺), iron (Fe³⁺), and lead (Pb²⁺) were 325, 220, and 300 mg g⁻¹, respectively at pH 6. In addition, the X-ray photoelectron spectrometry results are to be proved the binding of metal ions, for instance, Cu(II) ions showed typically significant BEs of 932.7 and 952.0 eV corresponding to the Cu2p3/2 and Cu2p1/2 species. The heavy metal ions adsorption followed a pseudo-first-order kinetic model pathway. The adsorption capacity (q_m) is also derived from the Langmuir isotherm linear plot, which does not showed good correction coefficients. However, the results were correlated to the Freundlich isotherm model, where the R² value showed significance (>0.98), indicating that multiple layer adsorption occurs on the synthesized ligand. The synthesized polymeric ligand is an excellent adsorbent for the removal of heavy metals from the industrial wastewater. In addition, the metal analysis results showed that about 98% removal of copper and iron ions from electroplating wastewater including lead, nickel, and chromium can be removed up to 85–97%.     

Adsorption of heavy-metal ions (Pb2+, Cu2+) on perm-lotion-treated human hair

Removal of toxic heavy metal ions from environmental and biological systems is important, but the use of commercially available heavy metal adsorbents is complicated by the need for specific pretreatment steps. We chose to study human hair treated with perm lotion as a heavy metal adsorbent because it is readily available and contains a large number of sulfur atoms for strong coordination to heavy metal ions. The optimal pH of adsorption by perm lotion-treated human hair was 4.16, which was slightly higher than the isoelectric point (pI) of the hair. The maximum removal ratio at pH 4.16 was 88.5% for a 50 ppm Cu²⁺ solution, and 96.79% for a 50 ppm Pb²⁺ solution. Almost 90% of the Pb²⁺ was removed from a 120 ppm Pb²⁺ solution. The perm-lotion-treated human hair was a cation-selective adsorbent.     

Structural Insights for the Stronger Ability of Shrimp Ferritin to Coordinate with Heavy Metal Ions as Compared to Human H-Chain Ferritin

Although apoferritin has been widely utilized as a new class of natural protein nanovehicles for encapsulation and delivery of nutraceuticals, its ability to remove metal heavy ions has yet to be explored. In this study, for the first time, we demonstrated that the ferritin from kuruma prawns (Marsupenaeus japonicus), named MjF, has a pronouncedly larger ability to resist denaturation induced by Cd²⁺ and Hg²⁺ as compared to its analogue, human H-chain ferritin (HuHF), despite the fact that these two proteins share a high similarity in protein structure. Treatment of HuHF with Cd²⁺ or Hg²⁺ at a metal ion/protein shell ratio of 100/1 resulted in marked protein aggregation, while the MjF solution was kept constantly clear upon treatment with Cd²⁺ and Hg²⁺ at different protein shell/metal ion ratios (50/1, 100/1, 250/1, 500/1, 1000/1, and 2500/1). Structural comparison analyses in conjunction with the newly solved crystal structure of the complex of MjF plus Cd²⁺ or Hg²⁺ revealed that cysteine (Cys) is a major residue responsible for such binding, and that the large difference in the ability to resist denaturation induced by these two heavy metal ions between MjF and HuHF is mainly derived from the different positions of Cys residues in these two proteins; namely, Cys residues in HuHF are located on the outer surface, while Cys residues from MjF are buried within the protein shell. All of these findings raise the high possibility that prawn ferritin, as a food-derived protein, could be developed into a novel bio-template to remove heavy metal ions from contaminated food systems.