Highly efficient removal of toxic lead ions from aqueous solutions using a new magnetic metal‐organic framework nanocomposite

A magnetic metal‐organic framework (MOF) nanocomposite was successfully prepared by a new and green strategy through reasonable design. Magnetic MOF of Fe₃O₄‐NHSO₃H@HKUST‐1 nanocomposite use for removal of lead ions as an environmental pollutant. The experimental results indicated that the nano adsorbent of Fe₃O₄‐NHSO₃H@HKUST‐1 can removed lead ions under optimum operational conditions. The dosage of the nanocomposite, pH of the sample solution, and contact time were obtained to be 10 mg, 7.0, and 90 min, respectively, while the initial concentration of Pb(II) ions of 400 mg/L was used. A kinetic study indicated that a pseudo‐second‐order model agreed well with the experimental data. The isotherm experiments revealed that the Langmuir model attained better fits to the equilibrium data than the Freundlich model. The maximum adsorption capacity of the adsorbent for the removal of lead under the optimum operational conditions of pH 7.0 and temperature 25°C was found to be 384.6 mg/g. The thermodynamic parameters indicate that the adsorption of lead is spontaneous and endothermic. The magnetic MOF nanocomposite could be recovered easily and reused many times without significant loss of its nano‐adsorbent activity. The proposed method is simple, eco‐friendly, low cost, and efficient in the removal of lead ions from aqueous solutions.     

Optimization of adsorption parameters for Fe (III) ions removal from aqueous solutions by transition metal oxide nanocomposite

Manganese oxide nanocomposite (Mn₂O₃/Mn₃O₄) was prepared by sol-gel technique and used as an adsorbent. Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and Field Emission Scanning Electron Microscopy (FE-SEM) were used to characterize the adsorbent. The response surface methodology (RSM) was employed to evaluate the effects of solution pH, initial Fe (III) ions concentration, adsorbent weight, and contact time on the removal ratio of the Fe (III) ions. A total of 27 adsorption experimental runs were carried out employing the detailed conditions designed based on the Box-Behnken design (BBD). Results showed that the pH of the solution and initial Fe (III) ions concentration were the most significant parameters for Fe (III) ions removal. In process optimization, the maximal value of the removal ratio of Fe (III) was achieved as 95.80%. Moreover, the corresponding optimal parameters of adsorption process were as: contact time?=?62.5?min, initial Fe (III) concentration?=?50?mg/L, adsorbent weight?=?0.5?g, and pH?=?5. The experimental confirmation tests showed a strong correlation between the predicted and experimental responses (R²?=?0.9803). The fitness of equilibrium data to common isotherm equations such as Langmuir, Freundlich, and Temkin were also tested. The sorption isotherm of adsorbent was best described by the Langmuir model. The kinetic data were analyzed using pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich kinetic models. The adsorption kinetics of Fe (III) ions were well fitted with the pseudo-second-order kinetic model.     

Removal of Chromium(III) and Cadmium(II) Heavy Metal Ions from Aqueous Solutions Using Treated Date Seeds: An Eco-Friendly Method

The aim of the research was to prepare low-cost adsorbents, including raw date pits and chemically treated date pits, and to apply these materials to investigate the adsorption behavior of Cr(III) and Cd(II) ions from wastewater. The prepared materials were characterized using SEM, FT-IR and BET surface analysis techniques for investigating the surface morphology, particle size, pore size and surface functionalities of the materials. A series of adsorption processes was conducted in a batch system and optimized by investigating various parameters such as solution pH, contact time, initial metal concentrations and adsorbent dosage. The optimum pH for achieving maximum adsorption capacity was found to be approximately 7.8. The determination of metal ions was conducted using atomic adsorption spectrometry. The experimental results were fitted using isotherm Langmuir and Freundlich equations, and maximum monolayer adsorption capacities for Cr(III) and Cd(II) at 323 K were 1428.5 and 1302.0 mg/g (treated majdool date pits adsorbent) and 1228.5 and 1182.0 mg/g (treated sagai date pits adsorbent), respectively. It was found that the adsorption capacity of H₂O₂-treated date pits was higher than that of untreated DP. Recovery studies showed maximal metal elution with 0.1 M HCl for all the adsorbents. An 83.3–88.2% and 81.8–86.8% drop in Cr(III) and Cd(II) adsorption, respectively, were found after the five regeneration cycles. The results showed that the Langmuir model gave slightly better results than the Freundlich model for the untreated and treated date pits. Hence, the results demonstrated that the prepared materials could be a low-cost and eco-friendly choice for the remediation of Cr(III) and Cd(II) contaminants from an aqueous solution.     

Thiol-functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> microspheres with superparamagnetism and their adsorption properties for Au(III) ion separation

Thiol-functionalized Fe₃O₄/SiO₂ microspheres (Fe₃O₄/SiO₂-SH) with high saturation magnetization (69.3 emu g^–1), superparamagnetism, and good dispersibility have been prepared by an ethylene glycol reduction method in combination with a modified Stöber method. The as-prepared composite magnetic spheres are characterized with fourier transform infrared spectroscopy (FT-IR), zeta potential, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and superconducting quantum interference magnetometer, and tested in separation of Au(III) ions from aqueous solutions. The data for Au(III) adsorption on Fe₃O₄/SiO₂-SH are analyzed with the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models, and the pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetics models. The adsorption behaviors of Au(III) on Fe₃O₄/SiO₂-SH follow the Langmuir isotherm model, and the adsorption process conforms to the pseudo-second-order kinetic model. The maximum adsorption capacity of Au(III) on Fe₃O₄/SiO₂-SH is 43.7 mg g^–1. Acetate anions play an important role yet Cu(II) ions have little interference in the adsorption of Au(III) on the adsorbent. A satisfactory recovery percentage of 89.5% is acquired by using an eluent with 1 M thiourea and 5% HCl, although thiols have a high affinity to Au(III) ions based on the hard-soft acid-base (HSAB) theory by Pearson.     

One-Pot Synthesis of Novel Amino-Functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Hybrid Microspheres for Cu(II) Removal from Aqueous Solutions

In this work, we report the development of novel amino-functionalized Fe₃O₄ hybrid microspheres adsorbent from a facial and one-step solvothermal route by using FeCl₃·6H₂O as a single iron source and 3-aminophenoxy-phthalonitrile as ource of amino groups. During solvothermal process, the nitrile groups of 3-aminophenoxy-phthalonitrile would bond with the Fe₃O₄ through the phthalocyanine cyclization reaction to form the amino-functionalized Fe₃O₄ magnetic nano-material, which was confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermo-gravimetric analyzer (TGA). From the scanning electron microscope (SEM) and transmission electron microscopy (TEM) observation, the resulting monodispersed amino-functionalized Fe₃O₄ hybrid microspheres with the diameters of 180–200 nm were synthesized via the self-assembly process. More importantly, as-prepared Fe₃O₄ nano-materials with abundant amino groups exhibited high separation efficiency when they were used to remove the Cu(II) from aqueous solutions. Furthermore, the adsorption isotherms of Fe₃O₄ nano-material for Cu(II) removal fitted the Langmuir isotherm model, in which the calculated maximum adsorption capacity could increase from 5.51 to 16.25 mg g^–1 at room temperature. This work demonstrated that the amino-functionalized Fe₃O₄ magnetic nano-materials were promising as efficient adsorbents for the removal of heavy metal ions from wastewater in low concentration.     

3‐D graphene‐supported mesoporous SiO2@Fe3O4 composites for the analysis of pesticides in aqueous samples by magnetic solid‐phase extraction with high‐performance liquid chromatography

Three‐dimensional graphene‐supported mesoporous silica@Fe₃O₄ composites (mSiO₂@Fe₃O₄‐G) were prepared by modifying mesoporous SiO₂‐coated Fe₃O₄ onto hydrophobic graphene nanosheets through a simple adsorption co‐condensation method. The obtained composites possess unique properties of large surface area (332.9 m²/g), pore volume (0.68 cm³/g), highly open pore structure with uniform pore size (31.1 nm), as well as good magnetic separation properties. The adsorbent (mSiO₂@Fe₃O₄‐G) was used for the magnetic solid‐phase extraction of seven pesticides with benzene rings in different aqueous samples before high‐performance liquid chromatography. The main parameters affecting the extraction such as adsorbent amount, volume of elution solvent, time of extraction and desorption, salt effect, oscillation rate were investigated. Under the optimal conditions, this method provided low limits of detection (S/N = 3, 0.525–3.30 μg/L) and good linearity (5.0–1000 μg/L, R² > 0.9954). Method validation proved the feasibility of the developed adsorbent, which has a high extraction efficiency and excellent enhancement performance for pesticides in this study. The proposed method was successfully applied to real aqueous samples, and satisfactory recoveries ranging from 77.5 to 113.6% with relative standard deviations within 9.7% were obtained.     

Magnetic iron(III)‐based framework composites for the magnetic solid‐phase extraction of fungicides from environmental water samples

We adopted a facile hydrofluoric acid‐free hydro‐/solvothermal method for the preparation of four magnetic iron(III)‐based framework composites (MIL‐101@Fe₃O₄‐COOH, MIL‐101‐NH₂@Fe₃O₄‐COOH, MIL‐53@Fe₃O₄‐COOH, and MIL‐53‐NH₂@Fe₃O₄‐COOH). The obtained four magnetic iron(III)‐based framework composites were applied to magnetic separation and enrichment of the fungicides (prochloraz, myclobutanil, tebuconazole, and iprodione) from environmental samples before high‐performance liquid chromatographic analysis. MIL‐101‐NH₂@Fe₃O₄‐COOH showed more remarkable pre‐concentration ability for the fungicides as compared to the other three magnetic iron(III)‐based framework composites. The extraction parameters affecting enrichment efficiency including extraction time, sample pH, elution time, and the desorption solvent were investigated and optimized. Under the optimized conditions, the standard curve of correlation coefficients were all above 0.991, the limits of detection were 0.04–0.4 μg/L, and the relative standard deviations were below 10.2%. The recoveries of two real water samples ranged from 71.1–99.1% at the low spiking level (30 μg/L). Therefore, the MIL‐101‐NH₂@Fe₃O₄‐COOH composites are attractive for the rapid and efficient extraction of fungicides from environmental water samples.     

Removal of Lead(II), Cadmium(II), and Arsenic(III) from Aqueous Solution Using Magnetite Nanoparticles Prepared by Green Synthesis with Box–Behnken Design

Two types of magnetite (Fe₃O₄) nanoparticles were investigated as adsorbents for the simultaneous removal of Pb(II), Cd(II), and As(III) metal ions from aqueous solution. Magnetite nanoparticles were prepared by two synthesis procedures, both using water as solvent, and are referred to as conventional Fe₃O₄ nanoparticles and green Fe₃O₄ nanoparticles. The latter used Citrus limon (lemon) aqueous peel extract as the surfactant. Box–Behnken experimental design was used to investigate the effects of parameters such as initial concentration (20–150?mg?L^?1), pH (2–9), and biomass dosage (1–5?g?L^?1) on the removal of Pb(II), Cd(II), and As(III) ions. The optimum parameters for removal of the studied metal ions from aqueous solutions, including the initial ion concentration (20?mg?L^?1), pH (5.5) and adsorbent dose (5?g?L^?1), were determined. The pseudosecond-order model exhibited the best fit for the kinetic studies, while adsorption equilibrium isotherms were best described by Langmuir and Freundlich models. The optimum conditions were applied for the treatment wastewater. The removal efficiencies of Pb(II), Cd(II), and As(III) using the conventional and green synthesized Fe₃O₄ nanoparticles were 59.4?±?4.3, 18.7?±?1.9 and 17.5?±?1.6, and 98.8?±?5.6, 46.0?±?1.3, and 48.2?±?2.6%, respectively. These results demonstrate the potential of magnetite nanoparticles synthesized using C. limon peel extract as highly efficient adsorbents for the removal of Pb(II), Cd(II), and As(III) ions from aqueous solution.     

Validation of a Monte Carlo HPGe detector model against irradiated foil gamma-ray spectroscopy measurements

In order to separate and pre-concentrate uranium from aqueous phase, a novel silica-based adsorbent was prepared by impregnating nalidixic acid (HNA) into a macroreticular silica/polymer composite support (SiO₂-P) with a mean diameter of 60 μm. Adsorption behavior of uranium from aqueous solution onto the adsorbent was studied. Experimental results indicated that HNA/SiO₂-P showed strong adsorption for uranium in a wide range of pH from 3.5 to 10.0, and the maximum adsorption capacity was 35.4 mg g⁻¹. In addition, HNA/SiO₂-P exhibited good selectivity for U(VI) and showed weak or bare adsorption affinity to foreign ions. Kinetic and isotherm of uranium adsorption were in accordance with the pseudo-second-order kinetic model and Langmuir isotherm adsorption model, respectively. Moreover, U(VI) sorption was found to be an endothermic reaction and spontaneous under experimental state. The synthesized adsorbent showed an admirable stability at lower pH values in aqueous solution.

     

Adsorptive removal of malachite green and Rhodamine B dyes on Fe3O4/activated carbon composite

This study demonstrates the adsorption experiments of toxic dyes malachite green (MG) and Rhodamine B (RB) on Fe₃O₄-loaded activated carbon (AC). AC, which is known to be a high-capacity adsorbent, was aimed to be easily separated from aqueous media by loading it with Fe₃O₄. Fe₃O₄-loaded AC was prepared by the coprecipitation method and named magnetic activated carbon (M-AC), and the produced M-AC was characterized by x-ray diffraction (XRD), thermogravimetric analysis (TGA), and pH_pzc analyses. MG and RB adsorption by the M-AC was performed separately by batch technique and the effects of adsorbent amount, solution pH, and initial dye concentration on the adsorption were explored. Maximum removal efficiencies were found to be 96.11% for MG and 98.54% for RB, and the Langmuir isotherm model was the most fitted isotherm model for the adsorption. The kinetic and thermodynamic studies showed that the adsorption proceeded via the pseudo-second-order kinetic model and endothermic in-nature for both dyes.     

A novel green synthesis of Fe3O4 magnetic nanorods using Punica Granatum rind extract and its application for removal of Pb(II) from aqueous environment

We described a novel and eco-friendly approach to remove toxic heavy metal of Pb(II) by using dimercaptosuccinic acid (DMSA) anchored Fe₃O₄ magnetic nanorods (MNRs) which were synthesized via facile method utilizing Punica Granatum rind extract which was a non toxic waste material. The DMSA@Fe₃O₄ MNRs were characterized by X-ray diffraction (XRD), Fourier transformed infrared analysis (FT-IR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), nitrogen adsorption and desorption techniques, and vibrating sample magnetometer (VSM). These DMSA@Fe₃O₄ MNRs have been used for the removal of Pb(II) from aqueous solution. The adsorption isotherm data fitted well with Langmuir isotherm and Freundlich model, the monolayer adsorption capacity was found to be 46.18 mg/g at 301 K. The experimental kinetic data fitted very well with the pseudo-second-order model. The results indicate that the biogenic synthesized DMSA@Fe₃O₄ MNRs act as significant adsorbent material for removal of Pb (II) from aqueous environment.     

Removal of Cd(II) from Micro-Polluted Water by Magnetic Core-Shell Fe3O4@Prussian Blue

A novel core-shell magnetic Prussian blue-coated Fe₃O₄ composites (Fe₃O₄@PB) were designed and synthesized by in-situ replication and controlled etching of iron oxide (Fe₃O₄) to eliminate Cd (II) from micro-polluted water. The core-shell structure was confirmed by TEM, and the composites were characterized by XRD and FTIR. The pore diameter distribution from BET measurement revealed the micropore-dominated structure of Fe₃O₄@PB. The effects of adsorbents dosage, pH, and co-existing ions were investigated. Batch results revealed that the Cd (II) adsorption was very fast initially and reached equilibrium after 4 h. A pH of 6 was favorable for Cd (II) adsorption on Fe₃O₄@PB. The adsorption rate reached 98.78% at an initial Cd (II) concentration of 100 μg/L. The adsorption kinetics indicated that the pseudo-first-order and Elovich models could best describe the Cd (II) adsorption onto Fe₃O₄@PB, indicating that the sorption of Cd (II) ions on the binding sites of Fe₃O₄@PB was the main rate-limiting step of adsorption. The adsorption isotherm well fitted the Freundlich model with a maximum capacity of 9.25 mg·g⁻¹ of Cd (II). The adsorption of Cd (II) on the Fe₃O₄@PB was affected by co-existing ions, including Cu (II), Ni (II), and Zn (II), due to the competitive effect of the co-adsorption of Cd (II) with other co-existing ions.     

Cetyltrimethylammonium bromide-coated magnetite nanoparticles as highly efficient adsorbent for rapid removal of reactive dyes from the textile companies’ wastewaters

The utilization of modified magnetite nanoparticles (Fe₃O₄ NPs) with a cationic surfactant (cetyltrimethylammonium bromide (CTAB)) as an efficient adsorbent was successfully carried out to remove reactive black 5 (RBBA), reactive red 198 (RRR) and reactive blue 21 (RTB) dyes from aqueous solutions. First, a reactor was designed to be simple, repeatable and efficient in its synthesis of Fe₃O₄ NPs via co-precipitation method. Then, an orthogonal array design (OAD), four factor-four level (4⁴) matrix was applied to assign affecting factors on removing of the dyes from aqueous solutions. The obtained results from ANOVA showed that the amount of CTAB and NaCl% significantly affect the adsorption of RBBA, RRR and RTB dyes. The sorption kinetics of the dyes were best described by a second-order kinetic model, suggesting chemisorptions mechanism. Also, dye adsorption equilibrium state data were fitted well to the Langmuir isotherm rather than Freundlich isotherm. Also, the maximum monolayer capacity, q_max, obtained from the Langmuir was 312.5, 163.9 and 556.2 mg g^-1 for RBBA, RRR and RTB, respectively. The obtained results in the present study indicated that the CTAB-coated Fe₃O₄ NPs can be an efficient adsorbent material for removal of reactive dyes form aqueous solutions.     

Facile synthesis of Fe3O4@C hollow nanospheres and their application in polluted water treatment

Nanostructured carbon-based materials, such as carbon nanotube arrays have shown respectable removal ability for heavy metal ions and organic dyes in aqueous solution. Although the carbon-based materials exhibited excellent removal ability, the separation of them from the aqueous solution is difficult and time-consuming. Here we demonstrated a novel and facile route for the large-scale fabrication of Fe₃O₄@C hollow nanospheres, with using ferrocene as a single reagent and SiO₂ as a template. The as-prepared Fe₃O₄@C hollow nanospheres exhibited adsorption ability for heavy metal ions and organic dyes from aqueous solution, and can be easily separated by an external magnet. When the as-prepared Fe₃O₄@C hollow nanospheres were mixed with the aqueous solution of Hg²⁺ within 15 min, the removal efficiency was 90.3%. The as-prepared Fe₃O₄@C hollow nanospheres were also exhibited a high adsorption capacity (100%) as the adsorbent for methylene blue (MB). In addition, the as-prepared Fe₃O₄@C hollow nanospheres can be used as the recyclable sorbent for water treatment via a simple magnetic separation.     

Adsorption of antimony using amino-functionalized magnetic MIL-101(Cr): Optimization by response surface methodology

Amino-functionalized magnetic MIL-101(Cr) was prepared via a one-step solvothermal method, characterized, and applied in adsorptive Sb(III) removal. The effects of solution pH, adsorbent dosage, and coexisting substances on the adsorption of Sb(III) by MIL-101(Cr)–NH₂/MnFe₂O₄ were studied. The adsorption kinetics were analyzed using pseudo-first order, pseudo-second order, intraparticle diffusion, and Elovich models, while Freundlich and Langmuir isotherm models were used to fit the experimental data. The pseudo-second-order kinetic model provided the best fit for the kinetic data. The maximum adsorption capacity of MIL-101(Cr)–NH₂/MnFe₂O₄ for Sb(III) was 91.07 ​mg/g, as calculated using the Langmuir adsorption isotherm model. Thermodynamic analysis revealed that the adsorption of antimony onto MIL-101(Cr)–NH₂/MnFe₂O₄ is spontaneous and endothermic, while response surface optimization revealed that the optimal conditions for Sb(III) adsorption by MIL-101(Cr)–NH₂/MnFe₂O₄ are an adsorbent loading of 222.55 ​mg/L, a pH of 4.5, and a temperature of 294.59 ​K. The predicted adsorption capacity of MIL-101(Cr)–NH₂/MnFe₂O₄ for Sb(III) is only a 1.8% deviation from the actual value. Furthermore, MIL-101(Cr)–NH₂/MnFe₂O₄ exhibits strong magnetism, allowing it to be separated from wastewater using a magnet. Finally, a preliminary economic analysis showed that the cost of treating a ton wastewater containing 25 ​mg/L antimony using this composite would be 26.24 USD. Thus, MIL-101(Cr)–NH₂/MnFe₂O₄ is promising for treatment of Sb(III)-containing wastewater.     

Cost‐efficient magnetic nanoporous carbon derived from citrus peel for the selective adsorption of seven insecticides

A magnetic solid‐phase extraction adsorbent that consisted of citrus peel‐derived nanoporous carbon and silica‐coated Fe₃O₄ microspheres (C/SiO₂@Fe₃O₄) was successfully fabricated by co‐precipitation. As a modifier for magnetic microspheres, citrus peel‐derived nanoporous carbon was not only economical and renewable for its raw material, but exerted enormous nanosized pore structure, which could directly influence the type of adsorbed analytes. The C/SiO₂@Fe₃O₄ also possessed the advantages of Fe₃O₄ microspheres like superparamagnetism, which could be easily separated magnetically after adsorption. Integrating the superior of biomass‐derived nanoporous carbon and Fe₃O₄ microspheres, the as‐prepared C/SiO₂@Fe₃O₄ showed high extraction efficiency for target analytes. The obtained material was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and the Brunauer–Emmett–Teller method, which demonstrated that C/SiO₂@Fe₃O₄ was successfully synthesized. Under the optimal conditions, the adsorbent was selected for the selective adsorption of seven insecticides before gas chromatography with mass spectrometry detection, and good linearity was obtained in the concentration range of 2–200 μg/kg with the correlation coefficient ranging from 0.9952 to 0.9997. The limits of detection were in the range of 0.03–0.39 μg/kg. The proposed method has been successfully applied to the enrichment and detection of seven insecticides in real vegetable samples.     

Facile synthesis of Fe3O4/MoS2 nanohybrid for solid phase extraction of Ag(I) and Pb(II): kinetic,isotherm and thermodynamic studies

Recently, MoS₂ with abundant electron density in its structure attracted more attention as an adsorbent for environmental remediation. However, hard manipulation of target solution owing to high dispersibility in aqueous media restricts its application as adsorbent. Preparation of Fe₃O₄/MoS₂ nanohybrid can solve this problem. Also, this nanohybrid improves adsorption capacities of target ions. In this work, Fe₃O₄ nanoparticles, MoS₂ nanosheets and hybrid of these two were synthesised and then characterised by X-ray diffraction, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, Fourier transforms infrared spectra, Brunauer–Emmett–Teller surface area and vibrating sample magnetometer. Subsequently, adsorption of Ag(I) and Pb(II) ions from aqueous solution by these three adsorbents was examined in detail and compared with each other while the adsorption conditions including the pH value, contact time, dosage of sorbent, elution conditions and interfering ions have been optimised. According to obtained results, prepared nanohybrid showed enhanced adsorption capacities for both ions relative to naked Fe₃O₄ and MoS₂. The limits of detection for Ag(I) and Pb(II) were calculated as 0.49 µg L^?1 and 2.7 µg L^?1, respectively, and the relative standard deviation percentages (n = 5) for Ag(I) and Pb(II) were 2.8%, and 3.0%, respectively. Furthermore, the preconcentration factors were 300 and 75 for Ag(I) and Pb(II) ions, respectively. Moreover, kinetic studies showed that pseudo-second-order model can better describe target analytes adsorption properties by every three adsorbents. Regeneration of the adsorbents was performed with HCl/thiourea mixture.     

Humic Acid Removal by Combining the Magnetic Property of Maghemite with the Adsorption Property of Nanosized Hydroxyapatite

Maghemite incorporated hydroxyapatite (HAP) nanocomposite was prepared by in situ precipitation of the calcium phosphate phase in an iron oxide colloidal suspension. The resultant nanocomposite was characterized by x-ray diffraction, Fourier transform infrared spectrometer, transmission electron microscope, N₂ adsorption analysis, and vibrating sample magnetometry. The potential of HAP/γ-Fe₂O₃ nanocomposite for HA adsorption from aqueous solution was evaluated by batch experiments and adsorption kinetic tests. HA adsorption amount on the adsorbent decreased with increasing solution pH and the presence of KNO₃ and alkali-earth metal ions resulted in enhanced HA adsorption. HA adsorption onto HAP/γ-Fe₂O₃ nanocomposite could be well described by Freundlich and Sips models, while HA adsorption process on the adsorbent obeyed pseudo-second-order kinetics and the adsorption rates decreased with increasing initial HA concentration. This study showed that the HAP/γ-Fe₂O₃ nanocomposite could be used as an efficient and magnetically separable adsorbent for the removal of HA from aqueous solution. Subsequent studies demonstrated that the HA-loaded HAP/γ-Fe₂O₃ nanocomposite could be further applied for the highly efficient adsorption of methylene blue (MB) and separated from the medium by a simple magnetic process.     

Adsorption of Cl<Superscript>−</Superscript> ions on γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> oxide from nitrate solutions

The adsorption of chloride ions on γ-Fe₂O₃ oxide (maggemite) from nitrate solution is studied using the method of potentiometric titration and an ion-selective electrode. The specific character of adsorption is determined. It is shown that the maggemite surface coverage with Cl^? ions increases with increasing concentration of ions in the solution, decreasing pH value, and increasing potential. The adsorbability of ions changes drastically in the pH range about pH₀ (γ-Fe₂O₃)6.2. It is found that the adsorption of chloride ions from neutral nitrate solution exponentially increases in the potential range from 0.1 to 1.0 V. The type of adsorption isotherm and the adsorption parameters are determined. It is found that, in the absence of external polarization, the concentration dependences of adsorption of Cl^? ions are complex-shaped, and their initial portions are described by the Langmuir isotherm. Further increase of adsorption is explained by the penetration of Cl^? ions inwards the oxide.     

Phosphate uptake behavior of layered rare earth hydroxides l-RE(OH)3 (RE = Sm,Gd, Er,and Y) from water

The use of rare earths (REs) provides various advantages for removal and recovery of phosphate from water because they have high affinity to form stable complexes with phosphates even at low concentrations. Very low solubility of rare earth phosphate REPO₄ in water was expected to induce a high phosphate adsorption rate and capacity. In this study, layered rare earth hydroxides, l-RE(OH)₃ (RE = Sm, Gd, Er, and Y), have been employed to remove or recover phosphate from aqueous solution. This layered polymorph of l-RE(OH)₃, which is composed of hydroxocation layers, exhibited a high point of zero charge (pH_pzc > 10) and significantly enhanced adsorptive ability for phosphates over a wide pH range. The isotherm and kinetics of phosphate adsorption on l-RE(OH)₃ were explained dominantly by the Langmuir isotherm model and pseudo-second-order kinetic model, respectively. A strong dependence of isotherm and kinetic parameters on RE demonstrated that the adsorption of phosphate on l-RE(OH)₃ is a chemisorption dominated process involving the replacement of –OH by phosphate ion to be included into the coordination polyhedra of RE. The desorption of phosphate from l-RE(OH)₃ was slow but the desorption efficiency for all RE members was higher than 97% in a 1.0 M NaOH solution after 4 days at room temperature. Considering high capacity and stability as well as no significant interference in recovery of phosphate from waters containing common competing anions, this rare earth adsorbent series is proposed as a promising alternative for efficient and sensitive phosphate recovery from natural and wastewaters.