Kinetic Study of the Photoexcited Triplet State of Free Base Porphyrins by EPR

An electron paramagnetic resonance (EPR) study of the photoexcited triplet state of four free base porphyrins is presented. The zero field splitting parameters (ZFS) |D| and |E| were calculated from the EPR spectra of the porphyrins dissolved in n-octane matrices at 80°K. |D| = 0.0359 cm^?1, |E| = 0.0079 cm^?1 for tetra phenyl porphyrin (H₂ TPP), |D| = 0.0432 cm^?1, |E| = 0.0037 cm^?1 for tetra (per-fluoro) phenyl porphyrin H₂T (per-F) PP, |D| = 0.0366 cm^?1, |E| = 0.0078 cm^?1 for tetra (para-chloro) phenyl porphyrin H₂T(P-Cl)PP, |D| = 0.0369 cm^?1, |E| = 0.0076 cm^?1 for tetra (para-methyl) phenyl porphyrin H₂T(P-Me)PP. The transient behavior of the EPR signal intensities in the last two porphyrins is discussed. The depopulation rate constants of the triplet sublevels k_p, the ratio between the population rate constants A_p (at zero field, p = x,y,z), and the spin lattice relaxation rate W within the triplet manifold, were calculated. k_x = (12 ± 2) × 10² sec^?1, k_y = (0.5 ± 0.1) × 10² sec^?1, k_z = (1.2 ± 0.4) × 10² sec^?1, A_x:A_y:A_z ? 0.63:0.01:0.33, W = (0.4 ± 0.1) × 10⁴ sec^?1 for H₂T(P-Cl)PP, k_x = (7 ± 2) × 10² sec^?1, k_y = (4 ± 1) × 10² sec^?1, k_z = (1.5 ± 0.5) × 10² sec^?1, A_x:A_y:A_z ? 0.56:0.31:0.13, W = (1.7 ± 0.4) × 10³ sec^?1 for H₂T(P-Me)PP.     

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.     

Iminodiacetic acid‐containing polymer brushes grafted onto silica gel for preconcentration and determination of copper(II) in environmental samples

Silica gel has been modified by silylation with 3‐mercaptopropyltrimethoxysilane followed by graft polymerization of dimethylacrylamide and (N,N‐bis‐carboxymethyl)amino‐3‐allylglycerol‐co‐dimethylacrylamide, synthesized via the reaction of allyl glycidyl ether with iminodiacetic acid. The sorbent, poly(AGE/IDA‐co‐DMAA)‐grafted silica gel, has been characterized by FTIR, elemental analysis, thermogravimetric analysis (TGA), FT‐Raman, and scanning electron microscopy and studied for the preconcentration and determination of trace amounts of Cu(II) ion in environmental water samples. The optimum pH value for quantitative sorption of Cu(II) in batch mode was 5.5 and desorption was achieved, using 0.5 mol L^?1 nitric acid. The sorption capacity of functionalized sorbent is 32.3 mg g^?1. The chelating sorbent was reused for 15 sorption–desorption cycles without any significant change in sorption capacity. The profile of copper uptake by the sorbent reflected good accessibility of the chelating sites in the poly(AGE/IDA‐co‐DMAA)‐grafted silica gel. Scatchard analysis demonstrated homogeneous nature of binding sites. The equilibrium adsorption data of Cu(II) on modified sorbent were analyzed by Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.0665, 4.26, and 8.34, respectively, at pH 5.5 and 20°C. Adsorption isotherms were analyzed at different temperatures to obtain free energy, enthalpy, and entropy of adsorption. The method was applied for Cu(II) determination in sea water samples. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Separation and adsorption properties of poly styrene‐graft‐ethyl methacrylate copolymer for zinc,copper, and cobalt ions in water samples

In this article, separation and adsorption properties of poly styrene‐graft‐ethyl methacrylate copolymer for zinc, copper, and cobalt ions in water samples were investigated. For this aim, some experimental and analytical parameters such as solution pH, sample flow rate, type of eluting agent, and sample solution volume were optimized. The adsorbed metal ions on polymeric resin were eluted with 5 ml of 2 mol l^?1 HNO₃ and they were determined by flame atomic absorption spectrometry. In optimized conditions, the adsorption capacities for Zn, Cu, and Co were obtained as 6.8, 5.2, and 7.5 mg g^?1, respectively. The detection limits were calculated as 0.82 μg l^?1 for Zn, 1.24 μg l^?1 for Cu, and 0.68 μg l^?1 for Co from standard deviation of the blank (50 ml, pH 5.8) measurements 10 replicates. The relative standard deviation of recoveries for seven replicate analyses of Zn, Cu, and Co ions (50 ml of 0.10 mg l^?1) were found as 2.4, 2.8, and 1.5%, respectively. The accuracy of method was checked with certified reference material (NIST SRM 1643e, trace elements in water) and the developed method was successfully applied to tap water, commercial drinking water, and mineral water samples. POLYM. ENG. SCI., 54:1555–1559, 2014. © 2013 Society of Plastics Engineers     

Synthesis and spectroscopic characterization of N-substituted thiosemicarbazone complexes

Complexation between Co(II), Ni(II), and Cu(II) with some 3,4-hexanedione bis[N-substituted thiosemicarbazones] has been investigated. The ligands release the two hydrazine hydrogens during the complex formation and act as binegative tetradentate (N₂S₂) except [Cu(H₂Hx4M)Cl₂] and [Cu(H₂Hx4Et)Cl₂]2H₂O in which the ligands behave as neutral tetradentate. The magnetic moments and electronic spectra provide information about the geometry of the complexes, which is supported by calculating the ligand field parameters for the Co(II) complexes. Most Ni(II) complexes are diamagnetic, indicative of a square-planar structure. The bands observed in Nujol are shifted to higher energies in dimethylformamide (DMF) solution, suggesting a weak interaction with the solvent. The ESR spectra of the complexes in solid and DMF solution exhibit axial symmetric g-tensor parameters with g _|>g _⊥>2.0023. The molecular parameters of [Ni(Hx4M)] have been calculated theoretically by semiempirical PM3 method. Also, the electronic transitions were calculated theoretically and found approximately similar to those recorded experimentally.     

Hydrothermal synthesis and characterization of copper containing crystalline silicate mesoporous materials from gel mixture

Novel copper-containing crystalline silicate mesoporous materials (SCMM) have been synthesized by the hydrothermal treatment of slurries of silicon–magnesium–copper hydroxide precipitates along with quaternary ammonium salt. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed a house-of-cards type structure consists of very thin platy silicates. Nitrogen adsorption–desorption isotherms of calcined material show that it has a high surface area (550 m² g⁻¹) and porosity properties. Pore characteristics are similar to that of MCM-41 and FSM-16, and fine-tuning of the pore size was achieved easily by modulating the synthesis temperature. Identification and the location of copper species in Cu-SCMM were done by X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR), respectively. ESR data of air-dried Cu-SCMM consist of clearly defined g_||=2.34, A_||=140×10⁻⁴ cm⁻¹ and g=2.08 at room temperature and g_||=2.34, A_||=160×10⁻⁴ cm⁻¹ and g=2.10 at 77 K. The resulting material exhibited superior catalytic activity towards the hydrogenation of α–β unsaturated aldehyde in supercritical carbon dioxide.     

Studies on the activation of hydrogen peroxide for color removal in the presence of a new Cu(II)-polyampholyte heterogeneous catalyst

In this work we describe the application of a new non-soluble and non-porous complex with copper ion based on ethylene glycol diglycidyl ether (EGDE), methacrylic acid (MAA) and 2-methylimidazole (2MI) in the decolorization of an azo dye Methyl Orange (MO) as a model pollutant at room temperature.The complex with copper ion was studied by ESR and SEM and was tested as a heterogeneous catalyst for H₂O₂ activation. A possible mechanism of interaction involves the production of hydroxyl radicals (confirmed by ESR), dioxygen and water.The Cu(II)-polyampholyte/H₂O₂ system acted efficiently in the color removal of MO. The adsorption and oxidative degradation of the azo-based dye followed pseudo-first-order kinetic profiles, and the rate constant for degradation had a second-order dependence on copper ion content in the mixture.A removal of MO higher than 90% was achieved in 20 min at pH 7.0, combining 0.8 mM of complexed copper ions in the mixture with 24 mM hydrogen peroxide.The dye adsorbed on the polyampholyte following a L4-type isotherm with 4.9 μmol g⁻¹ maximum loading capacity and 3.1 μM dissociation constant for the first monolayer.     

Pilot plant biosorption in an integrated contact–settling system: application to Cu(II) removal by anaerobically digested sludge

Surplus biological sludge can be used as a low‐cost adsorbent in the removal of heavy metal from wastewater. A three‐zone contact–settling pilot plant was designed and operated to maintain continuous sludge–metal solution contact and subsequent separation of solid–liquid phases, all in the same vessel. Mild agitation was used to ensure good contact between Cu(II) and sludge without impairing solid–liquid separation. Heavy metal removal efficiency was largely unaffected by an increase in the Cu/sludge feed ratio as long as metal binding sites in the sludge remained unsaturated. Maximum metal uptake (75 mg Cu(II) g^?1 of total solids in the sludge) was found for Cu/sludge feed ratios ≥ 90 mg Cu(II) g^?1 of total solids. Pilot plant metal sorption uptake at different operational conditions correlated well with the calculated values from batch equilibrium adsorption isotherms. The amount of Cu(II) adsorbed on sludge influenced the degree of clarification due to the flocculating effect of Cu(II). Under operational conditions, a high degree of heavy metal removal and efficient clarification were achieved. Pilot plant operation at a Cu/sludge feed ratio around 90 mg Cu(II) g^?1 of total solids allowed efficient use of the biosorbent and high heavy metal removal efficiency in addition to a good quality metal‐free effluent in terms of low total suspended solids content. © 2001 Society of Chemical Industry     

Adsorption and desorption behaviour of Pb(II) on a natural kaolin: equilibrium,kinetic and thermodynamic studies

BACKGROUND: Pb(II) is common in both waste‐waters and gas emissions. In developing countries, public health problems have been reported concerning Pb(II) pollution, so that stringent measures are required to deal with it. MAJOR RESULTS: The adsorption and desorption behaviour of Pb(II) has been investigated on a natural Chinese kaolin. Several factors, including initial concentration, pH, equilibration time, dosage and temperature correlated positively with Pb(II) adsorption. The Pb(II) adsorption capacity of natural kaolin was 165.117 mg g^?1. A kinetic study shows that Pb(II) adsorption on purified kaolin equilibrates within 35 min. The enthalpy changes of Pb(II) adsorption on purified kaolin were 63.683, 20.488 and 21.371 kJ mol^?1 with entropy changes 262.250, 112.210 and 105.120 J mol^?1 K^?1 for solutions containing 50, 100 and 200 mg L^?1 Pb(II) respectively, indicating an endothermic and spontaneous adsorption process. The desorption of Pb(II) from kaolin was difficult with more than 85% Pb(II) removal. Based on X‐ray diffraction (XRD) analysis, the Pb(II) adsorption on natural and purified kaolin was attributed mainly to the magnesite component and complexation with the mineral surface. CONCLUSIONS: Natural kaolin exhibits a satisfactory performance for adsorption of Pb(II) from aqueous solution. The optimum conditions for adsorption were: ionic strength = 0.01 mol L^?1; pH ≥ 7.2; dosage = 10 g L^?1; temperature = 25 °C; duration ≥ 16 h (C_i = 80 mg L^?1); and the optimum conditions for desorption were ionic strength = 0.1 mol L^?1 and pH ≤ 5.0. Copyright © 2009 Society of Chemical Industry     

Reactive red 120 and NI(II) derived poly(2‐hydroxyethyl methacrylate) nanoparticles for urease adsorption

Non‐porous poly(2‐hydroxyethyl methacrylate) [p(HEMA)] nanoparticles were prepared by surfactant free emulsion polymerization. The p(HEMA) nanoparticles was about 200 nm diameter, spherical form, and non‐porous. Reactive Red 120 (RR 120) was covalently attached to the p(HEMA) nanoparticles and Ni(II) ions were incorporated to attach dye molecules. Urease was immobilized onto RR120‐Ni(II) attached p(HEMA) nanoparticles via adsorption. The maximum urease adsorption capacity of RR120‐Ni(II) attached p(HEMA) nanoparticles was 480.01 mg g^?1 nanoparticles at pH 7.0 in phosphate buffer. It was observed that urease could be repeatedly adsorbed and desorbed without significant loss in adsorption amount. K_m values were 21.50 and 34.06 mM for the free and adsorbed enzyme. The V_max values were 4 U for the free enzyme and 3.3 U for the adsorbed enzyme. The optimum pH was 25 mM pH 7 phosphate buffer for free and adsorbed enzyme. The optimum temperature was determined at 35°C and 55°C for the free and adsorbed enzyme, respectively. These findings show considerable promise for this material as an adsorption matrix in biotechnological applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39757.     

Adsorption of bismuth(III) by bayberry tannin immobilized on collagen fiber

The adsorption behavior of collagen fiber‐immobilized bayberry tannin towards Bi(III) at acidic pH values was investigated. The adsorption capacity of the adsorbent towards Bi(III) was 0.348 mmol g^?1 at 303 K, and increased with the rise in temperature. The adsorption isotherms of Bi(III) were in the shape of so‐called type II isotherms and could be described by an empirical equation, ln q_e = k + (1/n)C_e, which implies that chemical adsorption is predominant at lower concentrations of Bi(III) and that physical adsorption is involved at higher concentrations. The adsorption kinetics of Bi(III) on the immobilized bayberry tannin could be well described by the pseudo‐second‐order rate model, and the adsorption capacities calculated by the model were almost the same as those determined by actual measurements. The adsorbent could be regenerated by using 0.02 mol dm^?3 ethylenediaminetetraacetic acid (EDTA) solution after adsorption of Bi(III). The adsorption selectivity of the immobilized bayberry tannin towards Bi(III) in a Cu(II)–Bi(III) binary solution in acidic medium was remarkable. Therefore, it is strongly suggested that the immobilized bayberry tannin could be applied to the removal of Bi(III) from crude Cu(II) samples under proper conditions. Copyright © 2006 Society of Chemical Industry     

Removal of Copper(II) and Zinc(II) from Aqueous Solutions Using a Lignocellulosic-Based Polymeric Adsorbent Containing Amidoxime Chelating Functional Groups

In this study, the adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto amidoximated polymerized banana stem (APBS) has been investigated. Infrared spectroscopy was used to confirm graft copolymer formation and amidoxime functionalization. The different variables affecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration, and temperature have been investigated. The optimum pH for maximum adsorption was 10.5 (99.99%) for Zn²⁺ and 6.0 (99.0%) for Cu²⁺ at an initial concentration of 10 mg L^?1. Equilibrium was achieved approximately within 3 h. The experimental kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models and are well fitted with pseudo- second-order kinetics. The thermodynamic activation parameters such as ΔG^o, ΔH^o, and ΔS^o were determined to predict the nature of adsorption. The temperature dependence indicates an exothermic process. The experimental isotherm data were well fitted to the Langmuir model with maximum adsorption capacities of 42.32 and 85.89 mg g^?1 for Cu(II) and Zn(II), respectively, at 20°C. The adsorption efficiency was tested using industrial effluents. Repeated adsorption/regeneration cycles show the feasibility of the APBS for the removal of Cu(II) and Zn(II) ions from water and industrial effluents.     

Efficient removal of Cu(II) using amino‐functionalized superparamagnetic nanoparticles prepared via SI‐ATRP

An amino‐functionalized nano‐adsorbent (DETA‐MNPs) was prepared by a process involving: (1) synthesis of superparamagnetic Fe₃O₄ nanoparticles; (2) introduction of amino groups after which ATRP initiator was anchored; (3) grafting of glycidyl methacrylate (GMA) via SI‐ATRP; and (4) ring‐opening reaction of epoxy groups with diethylenetriamine (DETA). The nano‐adsorbent was characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM) and applied to remove Cu(II) in batch experiments. The effects of pH, Cu(II) concentrations, solution ionic strength, and contact time were investigated. The results show that the DETA‐MNPs are spherical with cubic spine structure, high saturation magnetization (41.9 emu g^?1), and an average diameter of 10 nm. The maximum Cu(II) adsorption capacity achieves 83.33 mg g^?1 at pH 5.0 by Langmuir model. The adsorption process is highly pH‐dependent and reaches equilibrium within 20 min. Furthermore, the DETA‐MNPs exhibit excellent dispersibility and reusability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42859.     

Affinity microspheres and their application to lysozyme adsorption: Cibacron Blue F3GA and Cu(II) with poly(HEMA-EGDMA)

Lysozyme adsorption onto Cibacron Blue F3GA attached and Cu(II) incorporated poly(2-hydroxyethyl methacrylate–ethylene glycol dimethacrylate) [poly(HEMA-EGDMA)] microspheres was investigated. The microspheres were prepared by suspension polymerization. Various amounts of Cibacron Blue F3GA were attached covalently onto the microspheres by changing the initial concentration of dye in the reaction medium. The microspheres with a swelling ratio of 65%, and carrying different amounts of dye (between 1.4 and 22.5 µmol/g⁻¹) were used in the lysozyme adsorption studies. Lysozyme adsorption on these microspheres from aqueous solutions containing different amounts of lysozyme at different pH values was investigated in batch reactors. The lysozyme adsorption capacity of the dye–metal chelated microspheres (238.2 mg g⁻¹) was greater than that of the dye-attached microspheres (175.1 mg g⁻¹). The maximum lyzozyme adsorption capacities (q_m) and the dissociation constant (k_d) values were found to be 204.9 mg g⁻¹ and 0.0715 mg ml⁻¹ with dye-attached and 270.7 mg g⁻¹ and 0.0583 mg ml⁻¹ with dye–metal chelated microspheres, respectively. More than 90% of the adsorbed lysozyme were desorbed in 60 min in the desorption medium containing 0.5 M KSCN at pH 8.0 or 25 mM EDTA at pH 4.9. © 1999 Society of Chemical Industry     

Enhanced copper removal from aqueous solution by hydrous TiO2/zeolite composite

ABSTRACT

Hydrous titanium dioxide was impregnated on the surface of zeolite to obtain a kind of hydrous TiO₂/zeolite (HTiO₂/ZFA) adsorbent using the hydrothermal method. HTiO₂/ZFA was characterised by scanning electron microscopy combined with energy-dispersive spectrometer, X-ray diffraction, Fourier transform infrared, particle size distribution; and the pH of zero point charge measurement and its performance for Cu(II) adsorption were investigated. It was shown that Ti was not inserted into the skeleton of ZFA and hydrous TiO₂ loaded on the surface was amorphous. The pHzpc of HTiO₂/ZFA decreased to pH 5.5 from pH 6.5 of ZFA. Cu(II) adsorption was favoured in a pH range of 3.0–6.0, and 90% copper could be removed in first 30?min for 60?mg?L^–1 Cu(II) solution. The Langmuir isotherm model could well describe the adsorption isotherm data and the maximal Cu(II) adsorption capacity reached 251.9?mg?g^–1. Moreover, the HTiO₂/ZFA could be desorbed by HCl solution for further use, which implied an effective application in wastewater treatment.     

Effect of pH on microbial hydrogen fermentation

The influence of initial pH of the culture medium on hydrogen production was studied using sucrose solution and a mixed microbial flora from a soybean‐meal silo. Hydrogen production was not observed at pH values of 3.0, 11.0 and 12.0 but low production was observed at pH values 5.0 and 5.5. The pH of the experimental mixture decreased rapidly and produced hydrogen gas within 30 h. Methane was not detected at initial pH values between 6.0 and 10.0. The sucrose degradation efficiency increased as the initial pH value increased from 3.0 to 9.0. The maximum sucrose degradation efficiency of 95% was observed at pH 9.0. The maximum specific production yields of hydrogen, VFAs and alcohols were 126.9 cm³ g^?1 sucrose (pH of 9.0), 0.7 gCOD g^?1 sucrose (pH of 8.0) and 128.7 mgCOD g^?1 sucrose (pH of 9.0), respectively. The relationship between the hydrogen ion concentration and the specific hydrogen production rate has been mathematically described. The best kinetic parameters on the specific hydrogen production rate were K_OH = 1.0 × 10^?7 mol dm^?3 and K_H = 1.1 × 10^?4 mol dm^?3 (r² = 0.86). The maximum specific hydrogen production rate was 37.0 cm³ g^?1 VSS h^?1. © 2002 Society of Chemical Industry     

Local Symmetry of Cu2+ Ions in Sodium Silicate Glasses from Data of EPR Spectroscopy

Sodium silicate glasses with a constant ratio of oxide concentrations (mol %) SiO₂/Na₂O = 2.4 and with copper ions introduced in the form of CuO (from 1 to 10 mol %) are studied by the EPR method. The shape and width of the EPR line of copper ions are analyzed, and the spin-Hamiltonian parameters g _||, g , A _||, and A are determined by simulating the EPR spectrum and comparing the simulated and experimental spectra. The EPR spectrum of copper ions (1 mol %) is characterized by the parameters g _|| = 2.35, g = 2.065, A _|| = 135 × 10^–4 cm^–1, A = 7 × 10^–4 cm^–1, and H = 25 G. An analysis of this spectrum shows that the nearest environment of the Cu²⁺ ion has the shape of an elongated octahedron. The EPR spectrum of the sodium silicate glass containing 10 mol % Cu is a superposition of the spectrum of an octahedral complex (g _|| = 2.35, g = 2.075, A _|| = 135 × 10^–4 cm^–1, H = 40 G) and the spectrum of a cluster (g _|| = 2.35, g = 2.15, A _|| = 135 × 10^–4 cm^–1, H = 50 G).     

Evaluation of biosorbents for Cu removal from wastewater in the presence of EDTA

BACKGROUND: This paper evaluates the use of several biosorbents for Cu removal from aqueous solutions in the absence and presence of ethylenediaminetetraacetic acid (EDTA). The objective was to determine the applicability of the sorption process after conventional physicochemical wastewater treatment, or as primary treatment, replacing the physicochemical process. RESULTS: Fixed‐bed experiments were performed at Cu influent concentrations of 2 and 20 mg dm^?3 and EDTA doses between 0 and 10 mg dm^?3. At low Cu concentration without EDTA, Cu uptake capacity followed the order Posidonia oceanica > chitosan > chitin > Scharlau AC > Darco AC, with a maximum, at C/C₀ = 0.2, of 23.2 mg g^?1. In the presence of EDTA, Cu was detected in the effluent from the beginning of the operation, except for the activated carbons and chitosan at low EDTA doses. At higher EDTA doses, the activated carbons showed the best performance. Uptakes at Cu concentration of 20 mg dm^?3 without EDTA were 51.6 (Posidonia oceanica) and 41.4 mg g^?1 (chitosan) at C/C₀ = 0.2. CONCLUSION: A sequence of one fixed bed with Posidonia oceanica followed by another with Scharlau AC should be an alternative to Cu precipitation, with Cu effluent concentration lower than 0.5 mg dm^?3 for more than 350 pore volumes. Copyright © 2007 Society of Chemical Industry     

Investigation of α‐iron oxide‐coated polymeric nanocomposites capacity for efficient heavy metal removal from aqueous solution

In the present study, PS@α‐Fe₂O₃ nanocomposites were prepared by chemical microemulsion polymerization approach and the ability of magnetic beads to remove Cu(II) ions from aqueous solutions in a batch media was investigated. Various physico‐chemical parameters such as pH, initial metal ion concentration, temperature, and equilibrium contact time were also studied. Adsorption mechanism of Cu²⁺ ions onto magnetic polymeric adsorbents has been investigated using Langmuir, Freundlich, Sips and Redlich–Petersen isotherms. The results demonstrated that the PS@α‐Fe₂O₃ nanocomposite is an effective adsorbent for Cu²⁺ ions removal. The Sips adsorption isotherm model (R² > 0.99) was more in consistence with the adsorption isotherm data of Cu(II) ions compared to other models and the maximum adsorbed amount of copper was 34.25 mg/g. The adsorption kinetics well fitted to a pseudo second‐order kinetic model. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated from the temperature dependent sorption isotherms, and the results suggested that copper adsorption was a spontaneous and exothermic process. POLYM. ENG. SCI., 55:2735–2742, 2015. © 2015 Society of Plastics Engineers     

Batch and fixed‐bed column adsorption of Cu(II), Pb(II) and Cd(II) from aqueous solution onto functionalised SBA‐15 mesoporous silica

Functionalised SBA‐15 mesoporous silica with polyamidoamine groups (PAMAM‐SBA‐15) was successfully prepared with the structure characterised by X‐ray diffraction, nitrogen adsorption–desorption, Fourier transform infrared spectra and thermogravimetric analysis. PAMAM‐SBA‐15 was applied as adsorbent for Cu(II), Pb(II) and Cd(II) ions removal from aqueous solution. The effects of the solution pH, adsorbent dosage and metal ion concentration were studied under the batch mode. The Langmuir model was fitted favourably to the experimental data. The maximum sorptive capacities were determined to be 1.74 mmol g^?1 for Cu(II), 1.16 mmol g^?1 for Pb(II) and 0.97 mmol g^?1 for Cd(II). The overall sorption process was fast and its kinetics was fitted well to a pseudo‐first‐order kinetic model. The mean free energy of sorption, calculated from the Dubinin–Radushkevich isotherm, indicated that the sorption of lead and copper, with E > 16 kJ mol^?1, followed the sorption mechanism by particle diffusion. The adsorbent could be regenerated three times without significant varying its sorption capacity. A series of column tests were performed to determine the breakthrough curves with varying bed heights and flow rates. The breakthrough data gave a good fit to the Thomas model. Maximum sorption capacity of 1.6, 1.3 and 1.0 mmol g^?1 were found for Cu(II), Pb(II) and Cd(II), respectively, at flow rate of 0.4 mL min^?1 and bed height of 8 cm, which corresponds to 83%, 75% and 73% of metallic ion removal, respectively, which very close to the value determined in the batch process. Bed depth service time model could describe the breakthrough data from the column experiments properly. © 2012 Canadian Society for Chemical Engineering