Chitosan functionalized with 2[-bis-(pyridylmethyl) aminomethyl]4-methyl-6-formyl-phenol: equilibrium and kinetics of copper (II) adsorption

The complexation agent 2[-bis-(pyridylmethyl) aminomethyl]-4-methyl-6-formyl-phenol (HL) was immobilized in chitosan in order to obtain a new adsorbent material to be employed in studies on adsorption and pre-concentration of Cu(II). The chitosan modified by the complexation agent was characterized by infrared spectroscopy, DSC and TGA. The studies were conducted as a function of the pH of the medium and the mechanism of Cu(II) adsorption in the solid phase was analyzed utilizing several kinetic models. The parameters for the adsorption of Cu(II) ions by chitosan-HL were determined with a Langmuir isotherm, the maximum saturation capacity of the monolayer being 109.4 mg of Cu(II) per gram of polymer. Electron paramagnetic resonance spectroscopy revealed that Cu^II ions coordinate to the donor atoms of the HL ligand anchored to the surface of the polymer forming a stable chelate complex in the solid state.     

Synthesis of cross-linked poly(4-vinylpyridine) and its copolymer microgels using supercritical carbon dioxide: Application in the adsorption of copper(II)

Compared with conventional precipitation polymerization method, cross-linked poly(4-vinylpyridine) (P4VP) and its microgels copolymerized with α-methacrylic acid (MAA) were synthesized through a new route of stabilizer-free polymerization in supercritical fluids. The yellow, dry, fine powders were directly obtained from precipitation polymerization of 4-vinylpyridine in supercritical carbon dioxide (scCO₂) at pressures ranging from 70.0 to 230 bar, using N,N′-methylenebisacrylamide as cross-linker. The effects of the reaction pressure, cross-linker ratio, initiator concentration, and reaction time were investigated. The capacity of this microgel for adsorption of copper(II) was also studied. At higher cross-linker concentrations, a high yield of the cross-linked P4VP microgel was generated in scCO₂, and its particle size was less than 300 nm. Polymerization of cross-linked P4VP in scCO₂ was extremely sensitive to the density of the continuous phase. The adsorption followed the Langmuir isotherm. The adsorption capacities of cross-linked P(4VP-co-MAA) and cross-linked P4VP were 47.2 and 26.9 mg g⁻¹, respectively.     

Calcined tetrabutylammonium kaolinite and montmorillonite and adsorption of Fe(II), Co(II) and Ni(II) from solution

Kaolinite and montmorillonite were modified with tetrabutylammonium (TBA) bromide, followed by calcination. The structural changes were monitored with XRD, FTIR, surface area and cation exchange capacity measurements. The modified clay minerals were used for adsorption of Fe(III), Co(II) and Ni(II) ions from aqueous solution under different conditions of pH, time and temperature. The uptake of the metal ions took place by a second order kinetics. The modified montmorillonite had a higher adsorption capacity than the corresponding kaolinite. The Langmuir monolayer capacities for the modified kaolinite and montmorillonite were Fe(III): 9.3 mg g^− 1 and 22.6 mg g^− 1; Co(II): 9.0 mg g^− 1 and 22.3 mg g^− 1; and Ni(II): 8.4 mg g^− 1 and 19.7 mg g^− 1. The modified kaolinite interacted with Co(II) in an endothermic manner, but all the other interactions were exothermic. The decrease of the Gibbs energy in all the cases indicated spontaneous adsorption.     

Kinetics of the dissolution of copper(ii) oxide in acidified ascorbic acid solution

The zero order kinetics of the dissolution of CuO in ascorbic acid solution, acidified with HCl, was followed by measuring the absorbance of the coloured solution formed at 750 nm. From the variation of the logarithm of the rate constant with the reciprocal of the absolute temperature, an activation energy of 36 kJ mol^-1 was calculated. The infrared spectrum of a solid isolated from the reaction mixture was compared with the spectrum of ascorbic acid. A tentative mechanism of the reaction is suggested.     

Least square-support vector (LS-SVM) method for modeling of methylene blue dye adsorption using copper oxide loaded on activated carbon: Kinetic and isotherm study

A multiple linear regression (MLR) model and least square support vector regression (LS-SVM) model with principal component analysis (PCA) was used for preprocessing to predict the efficiency of methylene blue adsorption onto copper oxide nanoparticle loaded on activated carbon (CuO-NP-AC) based on experimental data set achieved in batch study. The PCA-LSSVM model indicated higher predictive capability than linear method with coefficient of determination (R²) of 0.97 and 0.92 for the training and testing data set, respectively. Firstly, the novel nanoparticles including copper oxide as low cost, non-toxic, safe and reusable adsorbent was synthesized in our laboratory with a simple and routine procedure. Subsequently, this new material properties such as surface functional group, homogeneity and pore size distribution was identified by FT-IR, SEM and BET analysis. The methylene blue (MB) removal and adsorption onto the CuO-NP-AC was investigated and the influence of variables such as initial pH and MB concentration, contact time, amount of adsorbent and pH, and temperature was investigated. The results of examination of the time on experimental adsorption data and fitting the data to conventional kinetic model show the suitability of pseudo-second order and intraparticle diffusion model. Evaluation of the experimental equilibrium data by Langmuir, Tempkin, Freundlich and Dubinin Radushkevich (D-R) isotherm explore that Langmuir is superior to other model for fitting the experimental data in term of higher correlation coefficient and lower error analysis.     

Synthesis of cadmium(II) hydroxide, cadmium(II) carbonate and cadmium(II) oxide nanoparticles; investigation of intermediate products

Sonochemical and hydrothermal routes have been used in different conditions for preparation of CdCO₃ and Cd(OH)₂ nanoparticles at air and inert atmospheres, respectively. The CdO nanoparticles were obtained by heating of CdCO₃ and Cd(OH)₂ nanoparticles at 400 °C. Powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) microscopy have been used to characterize the nanoparticles. The XRD results of intermediate products showed that the origin of CdCO₃ is CO₂ from air atmosphere.     

Recent studies in adsorption of Pb(II), Zn(II) and Co(II) using conventional and modified materials:a review

ABSTRACT

Heavy metal contamination and its detrimental effects on human health and environment have been a worldwide concern. Over the years, various technologies have been adapted to tackle this problem. Adsorption is still considered to be one of the most feasible and cost-effective methods for treating wastewater contaminated with heavy metals. Adsorbents such as activated carbon, clay, zeolites and silica have been studied extensively in the past. Modification of these conventional adsorbents and the synthesis of nonconventional adsorbents such as nanocomposites and metal organic frameworks (MOF’s) have been the main focus of study in recent times. This review article attempts to present a detailed account of various adsorbents and their removal efficiencies for the treatment of wastewater contaminated with lead(II), zinc(II) and cobalt(II) in the current decade. Influence of various parameters, adsorption isotherms and kinetics best described for their removal have also been reviewed in detail. It is observed that most of the adsorbents followed pseudo second order kinetics suggestive of a chemisorption process. After conducting a thorough review of more than 120 recently published papers, it can be inferred that nanomaterials and nanocomposites have shown excellent adsorption capacity for removal of these heavy metals.     

Water purification of removal aqueous copper (II) by as-grown and modified multi-walled carbon nanotubes

This study compares aqueous copper (II) adsorbed onto as-grown and modified carbon nanotubes (CNTs), using H₂SO₄ and H₂SO₄/KMnO₄ processes. H₂SO₄ and H₂SO₄/KMnO₄ modifications reduced pH_iep and Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed that some functional groups were formed on modified CNTs. The adsorption capacity of copper (II) onto modified CNTs was greater than that of as-grown CNTs, especially at pH 6. The results demonstrate that the modified processes increased the adsorption capacity because the functional groups were generated on the modified surfaces of the CNTs. Additionally, the adsorption capacity of copper (II) onto as-grown and modified CNTs both increased with temperature, and the results indicated that the Langmuir isotherm fitted the experimental data well. Simulation results indicated that the ΔH⁰ values of as-grown, H₂SO₄-modified CNTs and H₂SO₄/KMnO₄-modified CNTs were 4.83, 14.37 and 29.92 kJ/mol, respectively. Based on ΔH⁰, the adsorption of Cu²⁺ onto H₂SO₄/KMnO₄-modified CNTs is suggested to proceed simultaneously by physisorption and chemisorption but that onto as-grown and H₂SO₄-modified CNTs may proceed only by physisorption.     

Arsenic adsorption mechanism on clay minerals and its dependence on temperature

In the present study, the As(V) removal efficiency of different clay minerals was investigated as a function of solution pH, time, As(V) concentration, and temperature. Arsenic mobility was also investigated by determining the As(V) released from the loaded samples by leaching with various aqueous solutions. The kinetics of adsorption was observed to be fast and reached equilibrium within 3 h. As(V) adsorption on studied clays was pH dependent and maximum adsorption was achieved at pH 5.0. The maximum adsorption capacity was calculated by fitting the Langmuir equation to the adsorption isotherms and found to be 0.86, 0.64, and 0.52 mg As(V)/g of kaolinite, montmorillonite, and illite, respectively. The negative effect of temperature on As(V) adsorption showed the interactions to be exothermic. Based on the results, it was found that among the studied clay minerals, kaolinite was the best As(V) adsorbent and montmorillonite had strong retention capacity. The electrokinetic behavior of kaolinite and montmorillonite was modified in the presence of As(V), indicating that adsorption involves inner sphere surface complexation and strong specific ion adsorption.     

Thermostabilizing effect of copper(II) bromide on poly(ethylene oxide) in their binary blends

Thermoanalytical (thermogravimetry, differential thermogravimetry, and differential thermal analysis) and structural (IR spectroscopy, light microscopy, etc.) methods were employed to estimate the thermal behavior of binary blends of poly(ethylene oxide) (PEO) with copper(II) bromide (CuBr₂) of various concentrations under the conditions of a broad temperature interval. Solid residues obtained after heating the blends at different characteristic stages of the thermal destruction were also studied. CuBr₂ introduced in concentrations of 5–10% exhibited a significant thermostabilizing effect on PEO in an air medium, regardless of the mode of the blend preparation. No data about the formation of crystallizing complexes or new compounds prepared from the starting materials on heating the blends were obtained within the concentration range studied (0.1–40% CuBr₂). An assumption for the formation of associations between the oxygen atoms of PEO and the metal ion, which obstruct the thermal oxidation processes to a certain degree, were made in order to explain the antioxidative mechanism of action of the inorganic salt. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3324–3330, 1999     

Batch adsorptive removal of copper ions in aqueous solutions by ion exchange resins: 1200H and IRN97H

The removal of copper from aqueous solution by ion exchange resins, such as 1200H and IRN97H, is described. Effect of initial metal ion concentration, agitation time and pH on adsorption capacities of ion exchange resins was investigated in a batch mode. The adsorption process, which is pH dependent, shows maximum removal of copper in the pH range 2–7 for an initial copper concentration of 10 mg/L. The experimental data have been analyzed by using the Freundlich, Langmuir, Redlich-Peterson, Temkin and Dubinin-Radushkevich isotherm models. The batch sorption kinetics have been tested for a first-order, pseudo-first order and pseudo-second order kinetic reaction models. The rate constants of adsorption for all these kinetic models have been calculated. Results showed that the intraparticle diffusion and initial sorption into resins of Cu(II) in the ion exchange resins was the main rate limiting step. The uptake of copper by the ion exchange resins was reversible and thus has good potential for the removal/recovery of copper from aqueous solutions. We conclude that such ion exchange resins can be used for the efficient removal of copper from water and wastewater. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Cationic conjugated polyelectrolyte-based fluorometric detection of copper(II) ions in aqueous solution

A series of water-soluble cationic polyfluorene copolymer containing 2,2′-bipyridine moieties (PFP-P_1-3) in the backbone were designed and synthesized as the fluorescent probes for Cu²⁺ ions. In the absence of the Cu²⁺ ion, the PFP-P₂ exhibits strong fluorescence emission in aqueous solution. Upon adding the Cu²⁺ ion, the PFP-P₂ coordinates to Cu²⁺ ions through weak N?Cu interactions, and its fluorescence is efficiently quenched by the Cu²⁺ ion with a Stern-Volmer constant (K_sv) of 1.44 × 10⁷ M⁻¹. The new method has high sensitivity with a detection limit of 20 nM. The minor interference from other heavy metal ions clearly shows that the PFP-P₂ can be used as the Cu²⁺ ion probe with good selectivity.     

Nickel(Ⅱ) removal from water using silica-based hybrid adsorbents:Fabrication and adsorption kinetics

A series of novel silica-based hybrid adsorbents were prepared by the crosslinking reaction of N-[3-(trimethoxysilyl)propyl] ethylene diamine(TMSPEDA) with epichlorohydrin(ECH) via a sol–gel process.Fourier transform infrared(FTIR) spectra confirmed that the reaction occurred.TGA curves showed that the thermal stability of these hybrid adsorbents reached as high as 180 °C.As a typical example,the adsorption performance of nickel(II) ions onto an adsorbent(the volume ratio of TMSPEDA and ECH was 4:1) was explored.It was found that the adsorption of nickel(II) ions onto this adsorbent followed the Lagergren pseudo-second-order kinetic model.The investigation of the adsorption mechanism demonstrated that nickel(II) adsorption was chiefly controlled by diffusion–chemisorption,suggesting that more diffusion processes were involved in the adsorption of nickel(II) ions onto this type of adsorbents.Desorption experiment indicates that these hybrid adsorbents can be regenerated.These findings reveal that this type of silica-based hybrid adsorbent is promising in the separation and recovery of nickel(II) ions from Ni-containing wastewater or contaminated water.     

Regeneration of spent bleaching earth and its adsorption of copper (II) ions from aqueous solutions

This study was designed to provide a comprehensive investigation into heat and acid reactivation of spent bleaching earth (SBE) and adsorption of Cu(II) ions from aqueous solutions. Heat treatment was the master variable in SBE regeneration. Dilute acid treatment did not constitute an effective SBE reactivation protocol for this purpose. Solvent extraction of residual oil using excess methylethyl ketone followed by heating at 370 °C was, therefore, the most effective reactivation procedure. Highly adsorptive materials with > 98% removal of Cu(II) ions from solution were obtained. Thus, > 80% Cu adsorption was reversible at SBE silicate sites because of their higher proportion in the adsorbent.     

Synthesis and characterization of carbon/AlOOH composite for adsorption of chromium(VI) from synthetic wastewater

In this work, flake like carbon/AlOOH composite has been synthesized and evaluated as a new adsorbent for the removal of Cr(VI) from synthetic wastewater. Different characterization tools such as, SEM, EDAX, XRD and XPS were performed to characterize the composite material. Batch adsorption studies for Cr(VI) removal were performed under the influence of various operational parameters such as solution pH, contact time, initial solution concentration and temperature. Results obtained revealed that adsorption of Cr(VI) onto carbon/AlOOH composite followed the pseudo-second order kinetics and Freundlich isotherm model. Thermodynamic results suggests that adsorption of Cr(VI) onto carbon/AlOOH composite was spontaneous and endothermic in nature.     

Two-dimensional (2D) Ti3C2Tx MXene nanosheets with superior adsorption behavior for phosphate and nitrate ions from the aqueous environment

With the advancement of modern industries and metropolitan areas, negative environmental impacts such as eutrophication have become serious issues obstructing the usage of water sources in many countries. In this study, two-dimensional (2D) MXene materials were employed for the adsorptive removal of phosphate and nitrate ions from waters. The adsorption parameters of the sorption system including reaction time, solution pH, background ions, and reusability, were evaluated in batch experiments. Material characterization techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, Fourier transform infrared spectroscopy, thermal gravimetric analysis, Brunauer–Emmett–Teller analysis, and high-resolution transmission electron microscopy were performed. The mechanism of removing phosphate and nitrate was clearly described by various kinds of interactions such as electrostatic interactions, and the complexation was significant to elucidate the adsorption mechanism. The adsorption data for phosphate and nitrate update was determined using different isotherms and kinetic models. Reusability and field studies on the MXenes were also conducted. The above findings demonstrate that 2D MXenes could act as promising adsorbents for the elimination of toxic ions from water/wastewater.     

Kinetics of ligand exchange reaction of Cu(II)-ammine complex with poly(vinyl alcohol) in aqueous solution

The kinetics of the ligand exchange reaction of the Cu(II)-ammine complex with poly(vinyl alcohol) (PVA) has been studied by a stopped-flow method at pH 9–10, at μ=0.1 (NH₄Cl) and at 25°C. The reaction is initiated by the formation of unstable [Cu(NH₃)₃]²⁺ by the attack of H⁺ on Cu(II)-ammine complex, and proceeds through the mixed complex {[Cu(NH₃)₃(O?PVA)]²⁺}. This step may be rate-determining, followed by a rapid reaction. Finally, the Cu(II) ion is taken up by PVA. The rate is given by d[Cu(II)?PVA]/dt=k[H⁺]{[Cu(NH₃)₄]²⁺}[PVA]/[NH₄Cl], where k=k₁ + k′₂[H⁺], k₁=4.25× 10s^?1 and k′₂=5.20× 10¹¹l mol^?1s^?1.     

Kinetics and thermodynamics of Cu(II) adsorption on oil shale wastes

The oil shale waste material, retorted shale, was utilized as an adsorbent for Cu(II) removal from aqueous solution. The kinetics and thermodynamic adsorption was investigated during a series of batch adsorption experiments. The removal efficiency was controlled by solution pH, temperature, initial ion concentration and contact time. Two simple kinetic models, pseudo-first-and second-order, were used to investigate the adsorption mechanisms. The pseudo-second-order chemical reaction kinetics provides the best correlation with the experimental data. Langmuir and Freundlich models were used to fit the equilibrium data, which showed that Langmuir best-fitted these data. Thermodynamic parameters such as free energy, enthalpy and entropy were calculated to predict the nature of the adsorption process.     

Synthesis of novel copper ion-selective material based on hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate)

A novel hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate) using a double-imprinting approach for the Cu²⁺ selective separation from aqueous medium was prepared. In the imprinting process, both Cu²⁺ ions and surfactant micelles (cetyltrimethylammonium bromide – CTAB) were employed as templates. The hierarchically imprinted organic polymer named (IIP-CTAB), single-imprinted (IIP-no CTAB) and non-imprinted (NIP-CTAB and NIP-no CTAB) polymers were characterized by SEM, FTIR, TG, elemental analysis and textural data from BET (Brunauer–Emmett–Teller) and BJH (Barrett–Joyner–Halenda). Compared to these materials, IIP-CTAB showed higher selectivity, specific surface area and adsorption capacity toward Cu²⁺ ions. Good selectivity for Cu²⁺ was obtained for the Cu²⁺/Cd²⁺, Cu²⁺/Zn²⁺ and Cu²⁺/Co²⁺ systems when IIP-CTAB was compared to the single-imprinted (IIP-no CTAB) and non double-imprinted polymer (NIP-CTAB), thereby confirming the improvement in the polymer selectivity due to double-imprinting effect. For adsorption kinetic data, the best fit was provided with the pseudo-second-order model for the four materials, thereby indicating the chemical nature of the Cu²⁺ adsorption process. Cu²⁺ adsorption under equilibrium was found to follow dual-site Langmuir–Freundlich model isotherm, thus suggesting the existence of adsorption sites with low and high binding energy on the adsorbent surface. From column experiments 600 adsorption–desorption cycles using 1.8 mol L⁻¹ HNO₃ as eluent confirmed the great recoverability of adsorbent. The synthesis approach here investigated has been found to be very attractive for the designing of organic ion imprinted polymer and can be expanded to the other polymers to improve performance of ion imprinted polymers in the field of solid phase extraction.     

Copper (hydr)oxide modified copper electrode for electrocatalytic oxidation of hydrazine in alkaline media

Stable copper (hydr)oxide modified copper electrode was prepared by cyclic voltammetry in 0.1 M NaOH solution in the potential range of −300 to 800 mV. In the first cycle the oxidation peaks of copper were observed but in the second and next cycles, they were omitted and a clean background was obtained. This indicates that an irreversible electrochemical transformation has been achieved during the first cycle and a stable layer of hydr(oxide) formed on the surface of the copper electrode. This layer protects the electrode from corrosion. This electrode can be used for electrochemical studies in the potential range of −300 to 800 mV without any interfering effects by the oxidation peaks of copper. The modified electrode was used for electrocatalytic oxidation of hydrazine. Results showed that on the bare copper electrode the oxidation peak of 10 mM hydrazine appear at 380 mV while on the copper (hydr)oxide modified copper electrode, it appear at 260 mV. About 120 mV negative shift of the peak potential indicated the catalytic activity of (hydr)oxide layer for hydrazine. The kinetic parameters were investigated by using cyclic voltammetry and chronoamperometry.