Synthesis of magnetic Fe3O4@SiO2-(-NH2/-COOH) nanoparticles and their application for the removal of heavy metals from wastewater

In this work, Fe₃O₄@SiO₂-(-NH₂/-COOH) nanoparticles were synthesized for the removal of Cd²⁺, Pb²⁺ and Zn²⁺ ions from wastewater. The results of characterization showed that Fe₃O₄@SiO₂-(-NH₂/-COOH) was superparamagnetic with a core–shell structure. The surface of Fe3O4 was successfully coated with silica and modified with amino groups and carboxyl groups through the use of a silane coupling agent, polyacrylamide and polyacrylic acid. The dispersion of the particles was improved, and the surface area of the Fe3O4@SiO2-(-NH2/-COOH) nanoparticles was 67.8 m²/g. The capacity of Fe₃O₄@SiO₂-(-NH₂/-COOH) to adsorb the three heavy metals was in the order Pb²⁺ > Cd²⁺ > Zn²⁺, and the optimal adsorption conditions were an adsorption dose of 0.8 g/L, a temperature of 30°C and concentrations of Pb²⁺, Cd²⁺ and Zn²⁺ below 120, 80 and 20 mg/L, respectively. The maximum adsorption capacities for Pb²⁺, Cd²⁺ and Zn²⁺ were 166.67, 84.03 and 80.43 mg/g. The adsorption kinetics followed a pseudo-second-order model and Langmuir isotherm model adequately depicted the isotherm adsorption process. Thermodynamic analysis showed that the adsorption of the three metal ions was an endothermic process and that increasing the temperature was conducive to this adsorption.     

Mechanism of Hg(II), Cd(II) and Pb(II) ions sorption from aqueous solutions by Aspergillus niger spores

ABSTRACT

Recent work has focused on the removal of Pb²⁺, Hg²⁺, and Cd²⁺ by using an organ of Aspergillus niger – spores, which were spherical particles with small diameter (2 µm) characterized by negative charge. Results shown that the biosorption of Pb²⁺, Hg²⁺, and Cd²⁺ from aqueous solutions using spores was analyzed at varying biosorbent dosages, pH levels, contact times and initial heavy metal concentrations. The maximum biosorption capacities of Pb²⁺, Hg²⁺, and Cd²⁺ were 23.9, 27.2, and 21.5 mg/g at a natural pH with the initial concentration were 30 mg/L, respectively. The sequence of biosorption capacity for cationic heavy metals was Pb²⁺>Cd²⁺>Hg²⁺. Spores exhibited a short biosorption equilibrium time of 60 min at a pH range of 4.0–6.0, and the main biosorption mechanism was electronic attraction, ion exchanges and complexation(involved in C = C, C-H, C-O, N-H), the data fit well in the pseudo-second-order kinetic equation and the Freundlich isotherm. In addition, Spores can grow on many kinds of moist agriculture waste without any added nutrition. The results showed that spores could be considered as a potential biosorbent for the removal of cationic heavy metals from aqueous solutions.     

2-Mercaptoimidazole Covalently Bonded to a Silica Gel Surface for the Selective Separation of Mercury(II) from an Aqueous Solution

Abstract

Silica gel with a specific surface area of 365 m²·g^?1 and an average pore diameter of 60 Å was chemically modified with 2-mercaptoimidazole. The degree of functionalization of the covalently attached molecule, (≡SiO)₃(CH₂)₃—MI, where MI is the 2-mercaptoimidazole bound to the silica surface by a propyl group, was 0.58 mmol·g^?1. In individual metal adsorption experiments from aqueous solutions by the batch procedure, the affinity order was Hg^II « Cd^II > Cu^II ～ Zn^II ～ Pb^II > Mn^II at solution pHs between 4 and 7. Due to the high affinity by the sulfur atom, Hg^II is strongly bound to the functional groups. When solution containing a mixture of Hg^II, Cd^II, Cu^II, Zn^II, Pb^II, and Mn^II ions was passed through a column packed with the adsorbent, Hg^II was the only one whose adsorption and elution was not affected by the presence of other ions.     

Removal of heavy‐metal ions by magnetic beads containing triazole chelating groups

The aim of this study was to prepare magnetic beads that could be used for the removal of heavy‐metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [m‐poly(EGDMA–VTAZ)] beads were produced by suspension polymerization in the presence of a magnetite Fe₃O₄ nanopowder. The specific surface area of the m‐poly(EGDMA–VTAZ) beads was 74.8 m²/g with a diameter range of 150–200 μm, and the swelling ratio was 84%. The average Fe₃O₄ content of the resulting m‐poly(EGDMA–VTAZ) beads was 14.8%. The maximum binding capacities of the m‐poly(EGDMA–VTAZ) beads from aquous solution were 284.3 mg/g for Hg²⁺, 193.8 mg/g for Pb²⁺, 151.5 mg/g for Cu²⁺, 128.1 mg/g for Cd²⁺, and 99.4 mg/g for Zn²⁺. The affinity order on a mass basis was Hg²⁺ > Pb²⁺ > Cu²⁺ > Cd²⁺> Zn²⁺. The binding capacities from synthetic waste water were 178.1 mg/g for Hg²⁺, 132.4 mg/g for Pb²⁺, 83.5 mg/g for Cu²⁺, 54.1 mg/g for Cd²⁺, and 32.4 mg/g for Zn²⁺. The magnetic beads could be regenerated (up to ca. 97%) by a treatment with 0.1M HNO₃. These features make m‐poly(EGDMA–VTAZ) beads potential supports for heavy‐metal removal under a magnetic field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and adsorption selectivity for Hg(II) and Ag(I) of chelating resin immobilizing benzothiazolyl group on crosslinked polystyrene via hydrophilic sulfur‐containing PEG spacer

A new chelating resin incorporating 2‐mercaptobenzothiazole (MBZ) into macroporous chloromethylated polystyrene via hydrophilic spacer of polyethylene glycol containing sulfur was synthesized. The resin was characterized by elementary analysis and infrared spectra. The adsorption capacity of the resin for Ag⁺, Hg²⁺, Cu²⁺, Zn²⁺, and Pb²⁺ as a function of pH was determined. The effects of interference ions, such as Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺, on percent recovery were also investigated. The results showed that the resin could effectively remove Hg²⁺ and Ag⁺ from solutions containing a large excess of Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. In column operation, it was observed that Hg²⁺ and Ag⁺ in trace quantities were effectively removed from binary metal ions. The percent recovery of the resin for Hg²⁺ and Ag⁺ was >98.6% and >97.5%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5034–5038, 2006     

Complexation of poly(vinylpyrrolidone) and gelatin with some transition metal chlorides in aqueous solution

Complexation of poly(vinylpyrrolidone) and gelatin with certain metal chlorides (HgCl₂, CdCl₂, CoCl₂, and ZnCl₂) have been investigated by viscosimetric and spectrophotometric techniques in aqueous solutions. While the change in intrinsic viscosity, [η], of poly(vinylpyrrolidone) has shown a discontinuity with a concentration of metal chlorides, gelatin showed a steady decrease with increasing metal chloride concentration. The decreasing order of effectiveness of cations in complex formation is Hg²⁺ > Cd²⁺ > Co²⁺ > Zn²⁺ for poly(vinylpyrrolidone) and Zn²⁺ > Co²⁺ > Cd²⁺ > Hg²⁺ for gelatin solutions. It has been suggested that the poly(vinylpyrrolidone)/metal cation interaction is a charge-controlled reaction, and gelatin/metal cation is a covalent coordination in character. A similar metal cation effect has been observed for poly(vinylpyrrolidone) by UV-VIS spectrophotometry. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 891–895, 1998     

Synthesis and characterization of a new guar gum 4‐hydroxybenzoic acid resin and its use for the separation of heavy metal ions in industrial effluents

Hydroxybenzoic acid group has been incorporated onto guar gum by modified Porath's method of functionalization of polysaccharides. The newly synthesized guar gum 4‐hydroxybenzoic acid (GHBA) resin was characterized by Fourier‐transform infrared spectroscopy, elemental analysis, ion‐exchange capacity, column reusability, and physicochemical properties. The distribution coefficient (K_d) values and effect of pH on chelation of these metal ions using batch method were studied. The separations of mixture of Fe²⁺, Zn²⁺, Cu²⁺, Cd²⁺, and Pb²⁺ metal ions on GHBA resin on the basis of their distribution coefficient at various pH were also achieved using column chromatography. The effect of experimental parameters such as pH, treatment time, agitation speed, temperature, adsorbent dose, initial metal ion concentration, and flow rate on the removal of metal ions has been also studied. GHBA resin is effective adsorbents for the removal of different toxic metal ions from aqueous solutions and follows the order: Fe²⁺ > Zn²⁺ > Cu²⁺ > Cd²⁺ > Pb²⁺. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Binding of heavy metal ions by formaldehyde-polymerized peanut skins

Peanut skin, when treated with formaldehyde to polymerize tannins, is a highly efficient substrate for removal of many heavy metal ions from aqueous waste solutions. The ions Ag¹⁺, Cd²⁺, Cr⁶⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, as well as Ca²⁺ and Mg²⁺, were contacted with formaldehyde-treated peanut skin. Quantitative removal could be achieved with Ag¹⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺, and Zn²⁺. Capacity of the substrate for ions was promising for Pb²⁺ (2.1 meq/g substrate), Cu²⁺ (3.0 meq/g), and Cd²⁺ (1.3 meq/g). Sorption from a solution containing Cd²⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, on a packed column of formaldehyde-treated peanut skin indicated that Hg²⁺, Pb²⁺, and Cu²⁺ were rapidly and completely bound to the packing, while Cd²⁺, Ni²⁺, and Zn²⁺ were poorly bound until the preferred ions had been removed from solution.     

Biomass grafted with polyamic acid for enhancement of cadmium(II) and lead(II) biosorption

In this study, a simple method was used to prepare modified biomass to improve its adsorption capacity for Cd²⁺ and Pb²⁺. The modified biomass of baker’s yeast was obtained by grafting polyamic acid, which was prepared via the reaction of pyromellitic dianhydride (PMDA) and lysine, onto the surface of glutaraldehyde-pretreated biomass at 50 °C for 3 h. The presence of polyamic acid on the biomass surface was verified by Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS), the morphologies of the biomass before and after modification were observed by microscope. Due to the high density of the carboxyl and amide groups on the biomass surface, the uptake for Cd²⁺ and Pb²⁺ showed a significant increase. According to Langmuir adsorption isotherm, the maximum uptake for Cd²⁺ and Pb²⁺ were 95.2 and 204.5 mg g⁻¹, which were 15- and 11-fold for that obtained on the uncontaminated biomass. The kinetics for Cd²⁺ and Pb²⁺ adsorption followed the pseudo-second-order model. The results of FTIR and XPS revealed that carboxyl, amide, and hydroxyl groups on the biomass surface were involved in the adsorption of Cd²⁺ and Pb²⁺.     

Adsorption characteristics of metal ions by CO2-fixing Chlorella sp. HA-1

Single and binary metal systems were employed to investigate the removal characteristics of Pb²⁺, Cu²⁺, Cd²⁺, and Zn²⁺ by Chlorella sp. HA-1 that were isolated from a CO₂ fixation process. Adsorption test of single metal systems showed that the maximum metal uptakes were 0.767 mmol Pb²⁺, 0.450 mmol Cd²⁺, 0.334 mmol Cu²⁺ and 0.389 mmol Zn²⁺ per gram of dry cell. In the binary metal systems, the metal ions on Chlorella sp. HA-1 were adsorbed selectively according to their adsorption characteristics. Pb²⁺ ions significantly inhibited the adsorption of Cu²⁺, Zn²⁺, and Cd²⁺ ions, while Cu²⁺ ions decreased remarkably the metal uptake of Cd²⁺ and Zn²⁺ ions. The relative adsorption between Cd²⁺ and Zn²⁺ ions was reduced similarly by the presence of the other metal ions.     

Treatment of industrial wastewater using zeolitite and sepiolite,natural microporous materials

This work investigates the ability of natural microporous materials, such as a zeolite-rich tuff (zeolitite) and a modulated phyllosilicate (sepiolite), to remove heavy-metal ions from simulated inorganic polluted industrial wastewater. Fixed beds of sepiolite and zeolitite were percolated by a solution of Co²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ (concentration of each cation, 2 ? 10^?3 N; total concentration, 10^?2 N) and were regenerated with a 2 ? 10^?3 N Na⁺ solution. The order of decreasing affinity was, for sepiolite: Cu²⁺ > Zn²⁺ > Cd²⁺ > Pb²⁺ ? Co²⁺, and, for zeolitite: Pb²⁺ “Cd²⁺ > Cu²⁺ > Zn²⁺ > Co²⁺. After regeneration with Na⁺ solution, a fraction of the retained heavy metals was quickly released by the beds as follows: sepiolite, Co²⁺ ? Pb²⁺ > Cd²⁺ > Zn²⁺ > Cu²⁺; zeolitite, Cd²⁺ > Cu²⁺ ? Zn²⁺ > Co²⁺ > Pb²⁺. XRD and DTA-TGA analyses examined structural changes in the natural and final materials.     

Chromogenic sensing of Cu(II) by imino linked thiacalix[4]arene in mixed aqueous environment

Thiacalix[4]arene based imino receptors 4–5 carrying azophenol appendage have been synthesized and studied for their binding abilities towards different metal ions (Li⁺, Na⁺, K⁺, Cd²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺ and Hg²⁺). Receptor 4 showed selective chromogenic sensing for Cu²⁺ ions in mixed aqueous conditions (THF:H₂O, 9:1 v/v).     

New hydrogel containing sulfur compound prepared by γ irradiation and its application for metal recovery

A new hydrogel that contains sulfur is prepared by radiation polymerization and its application for recovery of Hg²⁺, Pb²⁺, Cd²⁺, and Cu²⁺ ions is discussed. The metal hydrogel complexes are isolated and characterized by using different spectroscopic techniques (UV‐visible, IR, NMR, and mass), thermal analysis (TGA and DSC) measurements, and SEM. Also, the mode of complexation is determined using IR and NMR spectroscopy. The scanning electron micrographs show that the hydrogel has a great ability to recover the metal ions in the following order: Hg²⁺ > Cd²⁺ > Pb²⁺ > Cu²⁺. TGA thermograms are used to investigate the mechanism of thermal decomposition. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 955–966, 2000     

Synthesis and Metal‐ion Binding Properties of New N2S4O2‐ and N2S5O2‐Donor Macrocycles

Abstract

Synthetic procedures for new mixed‐donor macrocycle compounds were reported. The macrocyclic compounds were used in solvent extraction metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Pb²⁺, and Co²⁺. The metal picrate extractions were investigated at 25±0.1°C with the aid of UV‐visible spectrometry. It was found that 6,7,9,10,12,13,23,24‐octahydro‐19H,26Hdibenzo[h,t](1,4,7,13,16,22,10,19) dioxatetrathiadiazasiclotetracosine‐20,27(21H,28H)‐dione showed selectivity towards Ag⁺, Hg²⁺, and Cd²⁺ among the other metals. The extraction constants (Log K_ex) and complex compositions were determined for the Ag⁺ and Hg²⁺ complexes for this compound and 9,10,12,13,23,24,26,27,29,30‐decahydro‐5H,15H‐dibenzo‐[h,w][1,4,7,13,16,19,25‐,10,22] dioxapentathiadiazacycloheptacosine‐6,16(7H,17H)‐dione.     

Poly (acrylic acid-co-acryloyl tetrasodium thiacalix[4]arene tetrasulfonate) grafted dextrin: new supper metal ion adsorbing hydrogels

Dextrin as a biodegradable natural polymer has hydrophilic nature that capable to increase the swelling properties and biodegradability of the synthetic hydrogels. This study describes the synthesis of a poly (acrylic acid-co-acryloyl tetrasodium thiacalix[4]arene tetrasulfonate) grafted dextrin superabsorbent hydrogels (ADA) via solution polymerization. The effects of acryloyl tetrasodium thiacalix[4]arene tetrasulfonate (ACSTCA) dose (20–60) on swelling properties of the hydrogels were studied. The synthesized hydrogels were characterized by FTIR, TGA, DMTA and rheometry. The metal ion removal capacity of the gels was investigated by atomic absorption for Cd²⁺, Pb²⁺, and Hg²⁺. The tendency of metal ions adsorption decreased in the order of Pb²⁺>Cd²⁺>Hg²⁺. The effect of key operating parameters including ACSTCA content, contact time, adsorbent dosage, solution pH, and crosslinker density was experimentally studied on Pb²⁺ adsorption from aqueous solution. The equilibrium data was analyzed using Langmuir and Freundlich adsorption isotherms. Our experimental data are in best agreement with Freundlich isotherms, and adsorption of metal cation onto hydrogel followed a pseudo second-order kinetic model. According to the thermodynamic parameters, the adsorption of Pb²⁺ occurred spontaneously. The hydrogels could be regenerated after releasing heavy metal ions, and reused 5 times with less than 7 % loss of adsorption capacity.     

Characterization and adsorption behavior of newly synthesized sodium bis(2-ethylhexyl) sulfosuccinate–cerium (IV) phosphate (AOT–CeP) cation exchanger

A new cationic exchange material, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with cerium (IV) phosphate (AOT–CeP) has been synthesized. The characterization of the ion exchanger was performed by using infra red spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo gravimetric analysis/differential thermo gravimetric analysis (TGA/DTA/DTG) and elemental analysis. The ion exchange properties like ion exchange capacity, elution and concentration behavior of AOT–CeP were determined by taking the material into a column and elution of H⁺ was done by NaNO₃. The thermal stability of the ion exchanger was studied by determining ion exchange capacity after heating to different temperatures for one hour. The adsorption studies on AOT–CeP demonstrated that the material is selective for Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions. AOT–CeP was found to be effective for the separation of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of alkali metals/alkaline earth metals. This cationic exchanger was also effective for the removal of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of acid and other transition metal ions. Thus, AOT–CeP can be used for the removal of these ions from the waste water during its treatment.     

Synthesis,characterization, and Pb2+ ion sensing application of hexa‐armed dansyl end‐capped poly(ε‐caprolactone) star polymer with phosphazene core

Novel hexa‐armed dansyl end‐capped poly(ε‐caprolactone) (PCL) star polymer with phosphazene core ( P2 ) was prepared via ring opening polymerization (ROP) and esterification reactions. P2 showed dual fluorescence emission when excited at 328 nm in acetonitrile : water (6 : 4) due to twisted intramolecular charge transfer (TICT) between dimethylamino and naphthalene units in the dansyl moiety. TICT emission band (A band) in the emission spectra red‐shifted with increasing solvent polarity. P2 responded to the addition of Pb²⁺, Hg²⁺, Co²⁺, Cd²⁺, Mn²⁺, and Zn²⁺ metal ions by decreasing TICT emission band with slight bathochromic shifts. The highest quenching efficiency was observed for Pb²⁺ ion with Stern–Volmer constant of 324.74M^?1. The Stern–Volmer plot for Pb²⁺ was rather linear with the increasing concentration of the quencher, indicating a dynamic (collisional) quenching mechanism. Stern–Volmer constants for Hg²⁺, Co²⁺, Cd²⁺, Mn²⁺, and Zn²⁺ ions were found to be 212.33, 189.21, 36.24, 20.84, and 20.69, respectively. Besides, the highest quenching efficiency (94.24%) was attained in the presence of Pb²⁺, suggesting that P2 could be employed as a potential Pb²⁺ chemical probe. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42380.     

Chelation ion‐exchange properties of copolymer resin derived from 4‐hydroxyacetophenone,oxamide, and formaldehyde

A copolymer (4‐HAOF) prepared by condensation of 4‐hydroxyacetophenone and oxamide with formaldehyde in the presence of an acid catalyst proved to be a selective chelating ion‐exchange copolymer for certain metals. Chelating ion‐exchange properties of this copolymer were studied for Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Hg²⁺ ions. A batch equilibrium method was employed in the study of the selectivity of metal‐ion uptake involving the measurements of the distribution of a given metal ion between the copolymer sample and a solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe³⁺ ions than for Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Ni²⁺, and Hg²⁺ ions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 787–790, 2003     

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.     

1-(Pyridin-2-yl) Imine Functionalized Silica Gel: Synthesis,Characterization, and Preliminary Use in Metal Ion Extraction

A new silica gel material covalently bonded with 1-(pyridin-2-yl) imine (SiNPn) was synthesized and well characterized by elemental analysis, FT–IR, ¹³C NMR of the solid state, nitrogen adsorption-desorption isotherm, BET surface area, B.J.H. Pore sizes, thermogravimetry curves (TGA), and scanning electron microscope (SEM). The new chelating surface exhibits good chemical and thermal stability. The adsorption capabilities of this new system towards toxic metal ions (Hg²⁺, Cd²⁺, Pb²⁺, and Zn²⁺) were investigated using the batch method. The percentage limits of extraction were determined by atomic absorption measurements.