Chitosan modified with Reactive Blue 2 dye on adsorption equilibrium of Cu(II) and Ni(II) ions

This study aimed at immobilizing Reactive Blue 2 (RB 2) dye in chitosan microspheres through nucleophilic substitution reaction. The adsorbent chemical modification was confirmed by Raman spectroscopy and thermogravimetric analysis. This adsorption study was carried out with Cu(II) and Ni(II) ions and indicated a pH dependence, while the maximum adsorption occurred around pH 7.0 and 8.5, respectively. The pseudo second-order kinetic model resulted in the best fit with experimental data obtained from Cu(II) (R = 0.997) and Ni(II) (R = 0.995), also providing a rate constant, k₂, of 4.85 × 10⁻⁴ and 3.81 × 10⁻⁴ g (mg min)⁻¹, respectively, thus suggesting that adsorption rate of metal ions by chitosan-RB 2 depends on the concentration of ions on adsorbent surface, as well as on their concentration at equilibrium. The Langmuir and Freundlich isotherm models were employed in the analysis of the experimental data for the adsorption, in the form of linearized equations. Langmuir model resulted in the best fit for both metals and maximum adsorption was 57.0 mg g⁻¹ (0.90 mmol g⁻¹) for Cu(II) and 11.2 mg g⁻¹ (0.19 mmol g⁻¹) for Ni(II). The Cu(II) and Ni(II) ions were desorbed from chitosan-RB 2 with aqueous solutions of EDTA and H₂SO₄, respectively.     

Heavy metals uptake from aqueous solutions and industrial wastewaters by humic acid-immobilized polymer/bentonite composite: Kinetics and equilibrium modeling

This study explored the feasibility of utilizing a novel adsorbent, humic acid-immobilized-amine-modified polyacrylamide/bentonite composite (HA-Am-PAA-B) for the adsorption of Cu(II), Zn(II) and Co(II) ions from aqueous solutions. The FTIR and XRD analyses were done to characterize the adsorbent material. The effects of pH, contact time, initial adsorbate concentration, ionic strength and adsorbent dose on adsorption of metal ions were investigated using batch adsorption experiments. The optimum pH for Cu(II), Zn(II) and Co(II) adsorption was observed at 5.0, 9.0 and 8.0, respectively. The mechanism for the removal of metal ions by HA-Am-PAA-B was based on ion exchange and complexation reactions. Metal removal by HA-Am-PAA-B followed a pseudo-second-order kinetics and equilibrium was achieved within 120 min. The suitability of Langmuir, Freundlich and Dubinin-Radushkevich adsorption models to the equilibrium data was investigated. The adsorption was well described by the Langmuir isotherm model. The maximum monolayer adsorption capacity was 106.2, 96.1 and 52.9 mg g^?1 for Cu(II), Zn(II) and Co(II) ions, respectively, at 30 °C. The efficiency of HA-Am-PAA-B in removing metal ions from different industry wastewaters was tested. Adsorbed metal ions were desorbed effectively (97.7 for Cu(II), 98.5 for Zn(II) and 99.2% for Co(II)) by 0.1 M HCl. The reusability of the HA-Am-PAA-B for several cycles was also demonstrated.     

High surface area-activated carbon from Glycyrrhiza glabra residue by ZnCl2 activation for removal of Pb(II) and Ni(II) from water samples

A high-surface-area activated carbon was prepared by chemical activation of Glycyrrhiza glabra residue with ZnCl₂ as active agent. Then, the adsorption behavior of Pb(II) and Ni(II) ion onto produced activated carbon has been studied. The experimental data were fitted to various isotherm models. According to Langmuir model, the maximum adsorption capacity of Pb(II) and Ni(II) ions were found to be 200 and 166.7 mg g⁻¹, respectively, at room temperature. Kinetic studies showed the adsorption process followed pseudo second-order rate model. High values of intra-particle rate constants calculated shows the high tendency of activated carbon for removal of Pb(II) and Ni(II) ions.     

Simultaneous preconcentration of Cd(II), Cu(II) and Pb(II) on Nano-TiO2 modified with 2-mercaptobenzothiazole prior to flame atomic absorption spectrometric determination

Nano-TiO₂ modified with 2-mercaptobenzothiazole (MBT) was investigated as a new adsorbent for preconcentration of Cd(II), Cu(II) and Pb(II). The metal ions are adsorbed onto nano-TiO₂-MBT, eluted by nitric acid and determined by flame atomic absorption spectrometry. The parameters affecting the adsorption were investigated. Under optimized conditions, the calibration curves were linear in the range of 0.2–25.0, 0.2–20.0, and 3.0–70.0 ng mL⁻¹ for cadmium, copper and lead, respectively. The limits of detection for Cd(II), Cu(II) and Pb(II) were 0.12, 0.15 and 1.38 ng mL⁻¹, respectively. The method was applied to determination of Cd(II), Cu(II) and Pb(II) in water and ore samples.     

Cadmium biosorption by a glyphosate-degrading bacterium,a novel biosorbent isolated from pesticide-contaminated agricultural soils

In this study, biosorption of cadmium (II) ions from aqueous solutions by a glyphosate degrading bacterium, Ochrobactrum sp. GDOS, was investigated in batch conditions. The isolate was able to utilize 3 mM GP as the sole phosphorous source, favorable to bacterium growth and survival. The effect of different basic parameters such as initial pH, contact time, initial concentrations of cadmium ion and temperature on cadmium uptake was evaluated. The adsorption process for Cd (II) is well fitted with Langmuir adsorption isotherm. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. Maximum metal uptake q_max was obtained as 83.33 mg g⁻¹. The sorption process of cadmium onto the Ochrobactrum sp. GDOS biomass followed second-order rate kinetic (R² = 0.9986). A high desorption efficiency was obtained in pH 2. Reusability of the biomass was examined under successive biosorption–desorption cycle repeated thrice. The characteristics of the possible interactions between biosorbent and metal ions were also evaluated by scanning electron microscope (SEM), Fourier transform infrared (FT-IR) and X-ray diffraction analysis.     

Effect of heparin coating on epichlorohydrin cross-linked chitosan microspheres on the adsorption of copper (II) ions

Epichlorohydrin cross-linked chitosan microspheres (CS) and chitosan–heparin polyelectrolyte complex microspheres (CSH) were used in the adsorption of copper (II) ions in aqueous solution. The chitosan microspheres were prepared by the phase inversion method. The use of a cross-linking agent improved the resistance to acidic medium. Polyelectrolyte complex microspheres were prepared by impregnating heparin in cross-linked chitosan microspheres. The microspheres were characterized by IR, TGA and DSC. A study on the effect of the pH on the adsorption of copper (II) ions showed that the optimum pH for both CS and CSH microspheres was 6.0. From a kinetic evaluation, it could be established that the adsorption equilibrium was achieved after 8 h for CS and 25 h for CSH microspheres. The adsorption isotherms were interpreted using Langmuir and Freundlich mathematical models. The results revealed that experimental data of CS was best adjusted by Langmuir model, with maximum capacity of surface saturation equal to 39.31 mg g⁻¹. On the other hand, Langmuir and Freundlich models provided a good fit for adsorption by CSH and the adsorption capacity was 81.04 mg g⁻¹. The interactions between copper (II) ions and both CS and CSH were confirmed by electron paramagnetic resonance spectroscopy, which revealed the formation of a square-planar complex with tetrahedral distortion on the surface of the adsorbents.     

Adsorption of an acid dye onto coal fly ash

In this study, we found the raw coal fly ash (CFA) that had not been subjected to any pretreatment process had superior adsorbing ability for the anionic dye Acid Red 1 (AR1) than did two modified coal fly ashes (CFA-600 and CFA-NaOH). The adsorption capacities followed the order CFA > CFA-600 > CFA-NaOH, and they each increased upon increasing the temperature (60 °C > 45 °C > 30 °C). The adsorptions of AR1 onto CFA, CFA-600, and CFA-NaOH all followed pseudo-second-order kinetics. The isotherms for the adsorption of AR1 onto the raw and modified coal fly ashes fit the Langmuir isotherm quite well; the adsorption capacities of CFA, CFA-600, and CFA-NaOH for AR1 were 92.59–103.09, 32.79–52.63, and 12.66–25.12 mg g^?1, respectively. According to the positive values of ΔH° and ΔS°, these adsorptions were endothermic processes. The ARE and EABS error function methods provided the best parameters for the Langmuir isotherms and pseudo-second-order equations, respectively, in the AR1–CFA adsorption system.     

Influence of anion induced proton abstraction on Cu(II) adsorption by alginic acid

Alginic acid (AA) synthesized by acidification of commercial sodium alginate was investigated for its Cu(II) adsorption efficiency in the presence of different counter ions. The results of batch adsorption studies indicated an adsorption of 169.86 mg/g of Cu(II) by AA in the presence of acetate ions, however, it significantly decreased in the presence of chloride (126.36 mg/g), sulphate (115.24 mg/g) and nitrate (113.28 mg/g) as counter ions. This can be accounted to the tendency of conjugate base (anion) to abstract proton from AA, which determines the extent of deprotonation of carboxylic acid. The FTIR and TGA/DTA studies support the difference in the coordination of carboxylate to Cu(II) in the presence of various counter anions. Acetate showed strong chelate coordination between Cu(II) and AA, whereas in the presence of Cl⁻, NO₃⁻ and SO₄^2 −, Cu(II) was complexed by weak bridging coordination with AA.     

Adsorption Behavior of Rhodamine B on UiO-66

The adsorption characteristics of UiO-66 (a Zr-containing metal–organic framework formed by terephthalate) for Rhodamine B (RhB), such as isotherms, kinetics and thermodynamics, were investigated systematically. The batch adsorption data conform well to the Langmuir and Freundlich isotherms. The adsorption kinetics of UiO-66 for RhB can be well described by the pseudo first-order model, and the adsorption thermodynamic parameters ΔG₀, ΔH₀ and ΔS₀ at 273 K are − 6.282 kJ·mol^− 1, 15.096 kJ·mol^− 1 and 78.052 J·mol^− 1·K^− 1, respectively. The thermodynamic analyses show that the adsorption process of RhB on UiO-66 is more favorable at higher temperatures. UiO-66 can be regenerated by desorbing in DMF solution with ultrasonic for 1 h. UiO-66 can keep good performance for at least six cycles of sorption/desorption.     

Adsorption of methylene blue from aqueous solution onto multiporous palygorskite modified by ion beam bombardment: Effect of contact time,temperature, pH and ionic strength

Our previous work has reported that an inorganic nano-network of palygorskite with multiporous structure can be fabricated from rigid nano-rods by ion beam bombardment and has better adsorption capability than nano-rods. Here, this dispersed modified nano adsorbent was characterized by Fourier Transform Infrared (FTIR) spectroscopy and Scanning Electron Microscope (SEM). The adsorption property of methylene blue (MB) onto this adsorbent was investigated. It was found that the adsorption capacity increased with contact time, pH, MB initial concentration, respectively, and then reached an equilibrium. Moreover, the effect of pH on the adsorption was strongly determined by zeta potential. The adsorption kinetics of MB was dominated by the pseudo-second-order reaction model, and the adsorption isotherms fit the Freundlich isotherms better than the Langmuir isotherms. Three temperatures (293 K, 303 K, 313 K) were set for describing the thermodynamic parameters (ΔH^θ, ΔS^θ, and ΔG^θ), which indicated that the adsorption was spontaneous and exothermic. Lastly, the mechanism of the influence of ionic strength on the adsorption was discussed.     

Copper(II) azide complexes of [Cu(acac)(N3)(dpyam)] and [Cu(μ-N3-κN1)(C2N3-κN1)(dpyam)]2: Synthesis,crystal structure and magnetism

Two new compounds, [Cu(acac)(N₃)(dpyam)] (1), (acac = acetylacetonate; dpyam = di-2-pyridylamine) and [Cu(μ-N₃-κ^N1)(C₂N₃- κ^N1) (dpyam)]₂ (2), have been synthesized and characterized by single-crystal X-ray diffraction and magnetic analyses. Compound 1 is a mononuclear compound in which each of two independent Cu(II) ions is penta-coordinated with a distorted square pyramidal geometry with distortion parameters τ = 0.21 and 0.16. In contrast, compound 2 is an azido-bridged dinuclear compound with monodentate dicyanamide anions and the Cu(II) ions display a distorted trigonal bipyramidal geometry with τ = 0.73 and end-on azido bridges providing an equatorial–axial position between the metal ions. The EPR spectra of powdered samples for 1 and 2 have also been investigated. Magnetic susceptibility measurements of compound 2 reveal a very weak ferromagnetic interaction between the Cu(II) ions with a J value of +5.8 cm⁻¹.     

Preparation and characterization of magnetic chelating resin based on chitosan for adsorption of Cu(II), Co(II), and Ni(II) ions

Cross-linked magnetic chitosan–diacetylmonoxime Schiff’s base resin (CSMO) was prepared for adsorption of metal ions. CSMO obtained was investigated by means of scanning electron microscope (SEM), FTIR, ¹H NMR, wide-angle X-ray diffraction (WAXRD), magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of cross-linked magnetic CSMO resin toward Cu²⁺, Co²⁺ and Ni²⁺ ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetics was evaluated utilizing the pseudo-first-order and pseudo-second-order. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 95 ± 4, 60 ± 1.5, and 47 ± 1.5 mg/g for Cu²⁺, Co²⁺ and Ni²⁺ ions, respectively. Cross-linked magnetic CSMO displayed higher adsorption capacity for Cu²⁺ in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded cross-linked magnetic CSMO were regenerated with an efficiency of greater than 84% using 0.01–0.1 M ethylendiamine tetraacetic acid (EDTA).     

Adsorption of chromate and para-nitrochlorobenzene on inorganic–organic montmorillonite

Batch studies of chromate and para-nitrochlorobenzene (p-NCB) on montmorillonite modified by poly(hydroxo aluminium) ions (Al) and cetyl trimethylammonium bromide (CTMAB) are reported. The amounts adsorbed decreased in the order Al-CTMA-mont > CTMA-mont > Al-mont > montmorillonite. Adsorption of chromate on Al-CTMA-mont reached a maximum at pH = 4 while p-NCB was pH independent. The adsorption kinetics could be described by the pseudo-second-order model. The adsorption rates for chromate and p-NCB were 9.73 and 5.78 mg g^? 1 min^? 1, respectively. The adsorption capacity of chromate and p-NCB on Al-CTMA-mont calculated by the Langmuir model was 2.3 × 10^? 4 and 2.2 × 10^? 4 mol/g, the values of the adsorption energy of the Dubinin-Radushkevitch (D-R) model were 13.9 and 7.8 kJ/mol. These results implied that the chromate adsorption proceeded as chemisorption, mainly by ion exchange whereas p-NCB was bound by van der Waals forces.     

Adsorption thermodynamics and kinetics of Cr(VI) on KIP210 resin

Series of resin selection experiments were carried out and the KIP210 strong base anion exchange resin was confirmed to have the maximum equilibrium adsorption capacity to remove Cr(VI) from wastewater. The adsorption thermodynamics and kinetics of Cr(VI) on KIP210 resin were investigated completely and systematically. The static experiments were performed to study the effects of various parameters, such as shaking speed, resin dosage and pH during the adsorption process. The results indicate that the effect of external diffusion is eliminated at 160 rpm, the best pH value is 3.0 and the removal percentage of Cr(VI) increases with the increase of the resin dosage. The adsorption of Cr(VI) on KIP210 agrees well with the Langmuir isotherm and the adsorption parameters of thermodynamics are ΔH = 26.5 kJ mol⁻¹, ΔS = 126.7 J mol⁻¹ K⁻¹ and ΔG < 0. It demonstrates that the adsorption of Cr(VI) on KIP210 is a spontaneously endothermic physisorption process. Moreover, the adsorption process can be described well by a pseudo-second-order kinetic model and the activation energy is 30.9 kJ mol⁻¹. The kinetic analysis showed that the adsorption rate is controlled by intraparticle diffusion. The resin is successfully regenerated using the NaOH solutions.     

Kinetic and thermodynamic studies on the removal of Cu(II) ions from aqueous solutions by adsorption on modified sand

Studies on the removal of copper by adsorption on modified sand have been investigated. The adsorbent was characterized by XRD, FTIR and SEM. Removal of Cu was carried out in batch mode. The values of thermodynamic parameters namely ΔG⁰, ΔH⁰ and ΔS⁰ at 25 °C were found to be −0.230 kcal⁻¹ mol⁻¹, +4.73 kcal⁻¹ mol⁻¹ and +16.646 cal K⁻¹ mol⁻¹, respectively. The process of removal was governed by pseudo second order rate equation and value of k₂ was found to be 0.122 g mg⁻¹ min⁻¹ at 25 °C. The resultant data can serve as baseline data for designing treatment plants at industrial scale.     

The effects of the surface oxidation of activated carbon,the solution pH and the temperature on adsorption of ibuprofen

A commercial microporous–mesoporous granular activated carbon was modified by oxidation with either H₂O₂ in the presence or absence of ultrasonic irradiation, or NaOCl or by a thermal treatment under nitrogen flow. Raw and modified materials were characterized by N₂ adsorption–desorption measurements at 77 K, Boehm titrations, pH measurements and X-ray photoelectron spectroscopy. Ibuprofen adsorption kinetic and isotherm studies were carried out at pH 3 and 7 on raw and modified materials. The thermodynamic parameters of adsorption were calculated from the isotherms obtained at 298, 313 and 328 K. The pore size distribution of carbon loaded with ibuprofen brought out that adsorption occurred preferentially into the ultramicropores. The adsorption of ibuprofen on pristine activated carbon was found endothermic, spontaneous (ΔG° = −1.1 kJ mol⁻¹), and promoted at acidic pH through dispersive interactions. All explored oxidative treatments led mainly to the formation of carbonyl groups and in a less extent to lactonic and carboxylic groups. This then helped to enhance the adsorption uptake while decreasing adsorption Gibbs energy (notably −7.3 kJ mol⁻¹ after sonication in H₂O₂). The decrease of the adsorption capacity after bleaching was attributed to the presence of phenolic groups.     

Spectroscopic studies on bis(1-amidino-O-alkylurea) copper(II) sulfate complexes where alkyl = methyl,ethyl, n-propyl or n-butyl: EPR evidence for binuclear complexes

Four new Cu(II) Complexes viz. [Cu(II)(1-amidino-O-methylurea)₂]SO₄·2H₂O (1), [Cu(II)(1-amidino-O-ethylurea)₂](SO₄)₂·2H₂O (2), [Cu(II)(1-amidino-O-n-propylurea)₂] SO₄·2H₂O (3), [Cu(II)(1-amidino-O-n-butylurea)₂]₂(SO₄)₂·2H₂O (4) have been synthesized and characterized. EPR spectrum of complex 4 at RT consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) of 0.0485 cm^?1 and a half-field signal (ΔMs = ±2) at ca. 1600 G, revealed formation of binuclear complex (S = 1). Whereas EPR spectrum of complex 2 in DMSO showed a mixture of mononuclear and binuclear complex in the ratio 0.75:1.0 with ZFS of 0.0385 cm^?1. From the temperature dependence of the EPR signal intensity, the isotropic exchange-interaction constant J was evaluated.     

ESR,solid-state 31P MAS NMR,and UV–vis–NIR studies on linear CuI CuII CuI trinuclear species: Crystal structure of bis-μ-salicylato (2−)-1:2 κ4O; 2:3 κ4O-tetrakis (triphenylphosphine-1κ2P, 3κ2P)-tricopper(I,II, I), [(PPh3)2Cu]2(μ-o-OC6H4COO)2Cu

A novel neutral mixed-valence Cu(I)Cu(II)Cu(I) linear trinuclear copper metallomacrocycle [(PPh₃)₂Cu]₂[μ-o-OC₆H₄COO]₂Cu (3) has been synthesized and characterized. Compound 3 consists of two Cu(I) ions and one Cu(II) ion which are bridged by two salicylate (2^?) ligands, and the external copper(I) atoms are coordinated by four terminal triphenylphosphines. The essentially localized mixed-valence [Cu(I)Cu(II)Cu(I)] formulation for 3 was determined on the basis of X-ray crystallography, solid-state ³¹P MAS NMR, and ESR spectroscopy. The solid-state ³¹P MAS NMR spectra of 3 is reported, affording δ[P(2)] = ?1.7 ppm with ¹J[Cu(I), P] = 1330 Hz and δ[P(1)] = ?3.4 ppm with ¹J[Cu(I), P] = 1600 Hz. UV–vis–NIR spectral measurement demonstrates the Robin–Day class II behavior of the mixed-valence compound 3 with a weak copper–copper interaction.     

Adsorption separation of vinyl chloride and acetylene on activated carbon modified by metal ions

This work mainly involved the adsorption separation of vinyl chloride and acetylene on modified activated carbons. Six metal ions with different hardness were loaded on activated carbon respectively. The effect of metal ions on the adsorption separation performance of vinyl chloride and acetylene was investigated. The experimental results shown that the separation factor of C₂H₃Cl to C₂H₂ over modified activated carbon followed the order: Al(III)/AC > Mg(II)/AC > Fe(III)/AC > AC > Zn(II)/AC ≈ Cu(II)/AC > Ag(I)/AC. The effect of the hardness of metal ions on the adsorption capacity of C₂H₂ was more remarkable than that of C₂H₃Cl, thus the separation factor of C₂H₃Cl to C₂H₂ increased with the rising of absolute hardness of the metal ions.     

Introduction of copper nanoparticles in chitosan matrix as strategy to enhance chromate adsorption

In this study, copper nanoparticles (CuNPs) were incorporated to chitosan (CHI) matrix as strategy to enhance the chromate adsorption by CHI membrane. The CuNPs were synthesized using NaBH₄ as the reducing agent. Dispersive X-ray Absorption Spectroscopy (DXAS) was used to monitor the in situ reduction of Cu(II). The influence of the presence of CuNPs on the hygroscopic behavior was also evaluated. DXAS technique showed that the adsorbed Cu(II) was reduced to Cu(I) (63%) and Cu(0) (37%) species, at the end of the reduction reaction (using NaBH₄, after ∼30 min). The hygroscopic behavior of the proposed sorbent was more influenced by CuNPs when the water vapor adsorption was conducted under synthetic air atmosphere. A decrease in the energy of interaction among the water molecules adsorbed on the monolayer was observed. The chromate adsorption study has shown a higher equilibrium concentration of adsorbed chromium species when the CHI membrane containing CuNPs was used as sorbent. The CuNPs offered a second active adsorption site, which was characterized by a higher coefficient of affinity (12 L mmol⁻¹, against 0.18 L mmol⁻¹ reported for CHI). The enhanced adsorption of chromium in the presence of CuNPs was associated to the redox reaction between the CuNPs and chromate anions.