TEOS as an improved alternative for chitosan beads cross‐linking: A comparative adsorption study

In this work the use of tetraethoxysilane (TEOS) for cross‐linking of chitosan hydrogel beads was studied at the level of 1 mmol TEOS per gram of chitosan. They were compared with glutaraldehyde and epichlorohydrin cross‐linked beads. The hydrogels were characterized by FTIR, SEM, water content, nitrogen content, and their point of zero charge. The performance of the anionic dye Remazol Black (RB) and the cationic Cd(II) adsorptions was assessed in order to characterize the sorbate–sorbent interaction. Adsorption experimental data were analyzed using two‐ and three‐parameter isotherm models along with the evaluation of mean adsorption energy and standard free energy. The adsorption was observed to be pH dependent. The uptake rate of RB and Cd(II) showed that the three type of beads followed a similar kinetic behavior. For both sorbates the TEOS cross‐linked beads showed the higher maximum adsorption capacity, followed by epichlorohydrin and glutaraldehyde cross‐linked beads. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41005.     

Preparation and characterization of porous chitosan–tripolyphosphate beads for copper(II) ion adsorption

Porous chitosan–tripolyphosphate beads, prepared by the ionotropic crosslinking and freeze‐drying, were used for the adsorption of Cu(II) ion from aqueous solution. Batch studies, investigating bead adsorption capacity and adsorption isotherm for the Cu(II) ion, indicated that the Cu(II) ion adsorption equilibrium correlated well with Langmuir isotherm model. The maximum capacity for the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, deduced from the use of the Langmuir isotherm equation, was 208.3 mg/g. The kinetics data were analyzed by pseudo‐first, pseudo‐second order kinetic, and intraparticle diffusion models. The experimental data fitted the pseudo‐second order kinetic model well, indicating that chemical sorption is the rate‐limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process. This study explored the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, and used SEM/EDS, TGA, and XRD to examine the properties of adsorbent. The use of porous chitosan–tripolyphosphate beads to adsorb Cu(II) ion produced better and faster results than were obtained for nonporous chitosan–tripolyphosphate beads. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adsorption of Pb2+ and Cd2+ onto a Novel Activated Carbon‐Chitosan Complex

A novel activated carbon‐chitosan complex adsorbent (ACCA) was prepared via the crosslinking of glutaraldehyde and activated carbon‐(NH₂‐protected) chitosan complex under microwave irradiation. The surface morphology of this adsorbent was characterized. The adsorption of ACCA for Pb²⁺ and Cd²⁺ was investigated. The results demonstrate that ACCA has higher adsorption capacity than chitosan. The adsorption follows pseudo first‐order kinetics. The isotherm adsorption equilibria are better described by Freundlich and Dubinin‐Radushkevich isotherms than by the Langmuir isotherm. The adsorbent can be recycled. These results have important implications for the design of low‐cost and effective adsorbents in the removal of heavy metal ions from wastewaters.     

A novel lead ion‐imprinted chelating nanofiber: Preparation,characterization, and performance evaluation

A novel Pb(II) ion‐imprinted chelating nanofibers (nIIP), synthesized by combining electrospinning with surface ion imprinting technique, was reported in this study. nIIP was characterized with Fourier transmission infrared spectrometry and scanning electron microscopy, respectively. The performance of nIIP for Pb(II) sorption was conducted through a batch adsorption experiments. Experimental data showed that adsorption capacity of nIIP was much higher than that of non‐ion imprinted chelating acrylic microfibers (mNIP) derived from commercial available acrylic microfibers, and adsorption behaviors agreed well with pseudo‐second‐order kinetic and Langmuir isotherm model. The values of Gibbs free energy change derived from experimental data suggested that the adsorption Pb(II) on nIIP is spontaneous and favorable at high temperature. In addition, nIIP had the highest selectivity among three tested fibrous adsorbents for Pb(II) from binary metal solution, the selectivity coefficients for Pb(II) from binary metal solution of Pb(II)/Cu(II), Pb(II)/Ni(II), and Pb(II)/Cd(II) onto nIIP were 47, 101, and 162, respectively. Besides, a forty adsorption/desorption cycles revealed that nIIP was a promising recyclable adsorbent. In conclusion, the novel nIIP is a highly effective adsorbent for enrichment and separation of Pb(II) in the presence of competitive ions in aqueous solution, and it is potential to be applied for recovering metals from heavy metal polluted industrial wastewater such as Pb(II)/Cd(II), Pb(II)/Ni(II), and Pb(II)/Cu(II) polluted wastewater. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41507.     

Adsorption of aluminium from wastewater by chitin and chitosan produced from silkworm chrysalides

Chitin, extracted from silkworm chrysalides, was employed for the production of a high‐purity and porous chitosan, as observed by scanning electron microscopy. Chitin and the chitosan produced from it were also analysed using ¹³C NMR spectroscopy to show the efficiency of deacetylation. The extracted chitin was investigated as an adsorbent material for aluminium removal from textile wastewater, by the column chromatographic method. After the treatment, the residual aluminium was lower than the limitation criterion of 0.2 mg L^?1. The isotherms of adsorption on chitin and chitosan surfaces were investigated and the best fits were observed using the Freundlich isotherm. At pH 5.0, the maximum adsorption capacity was 21.3 mg of aluminium per gram of chitosan over 70 h of experiments. Copyright © 2006 Society of Chemical Industry     

Studies on the synthesis and properties of hydroxyl azacrown ether‐grafted chitosan

The chitosan hydroxyl azacrown ether was synthesized by reaction of hydroxyl azacrown ether with epoxy‐activated chitosan. The C₂ amino group in chitosan was protected from the reaction between benzaldehyde and chitosan to form N‐benzylidene chitosan. After reaction with epichlorohydrin and azacrown ether, reacting O‐aryl mesocyclic diamine‐N‐benzylidene chitosan and dilute ethanol hydrochloride solution to obtain novel chitosan‐azacrown ether bearing hydroxyl removed the Schiff base. Its structure was confirmed with elemental analysis, FTIR spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. Its static adsorption properties for Ag(I), Cd(II), Pb(II), and Cr(III) were also investigated. The experimental results showed that the hydroxyl azacrown ether grafted chitosan has good adsorption capacity and high selectivity for Ag(I) in the coexistence of Pb(II) and Cd(II), the selectivity coefficients of hydroxyl azacrown ether chitosan were K_Ag(I)/Pb(II) = 32.34; K_Ag(I)/Cd(II) = 56.12. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1838–1843, 2001     

Comparative studies of Oryza sativa L. husk and chitosan as lead adsorbent

The adsorption capacity of two low‐cost adsorbents, Oryza sativa L. husk and chitosan, was studied. Lead solution was used as the adsorbate. The effect of initial lead concentration, pH, temperature, weight of adsorbent, particle size and contact time on lead uptake was investigated. It was found that the isotherm data were well described by the Freundlich isotherm for both adsorbents. The adsorption capacities of rice husk and chitosan were 5.69 and 8.31 mg g^?1, respectively. It was shown that chitosan was more effective than rice husk. Copyright © 2005 Society of Chemical Industry     

Facile preparation of magnetic chitosan modified with thiosemicarbazide for adsorption of copper ions from aqueous solution

In this study, magnetic chitosan modified with thiosemicarbazide (TSC‐Fe₃O₄/CTS) was facilely synthesized with glutaraldehyde as the crosslinker, and its application for removal of Cu(II) ions was investigated. The as‐prepared TSC‐Fe₃O₄/CTS was characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray powder diffraction (XRD), and scanning electron microscopy (SEM). The results showed that TSC‐Fe₃O₄/CTS has high adsorption capacity and selectivity towards Cu(II) ions. Adsorption experiments were carried out with different parameters such as pH, solution temperature, contact time and initial concentration of Cu(II) ions. The adsorption process was better described by the pseudo‐second‐order model. The sorption equilibrium data was fitted well with the Langmuir isotherm model and the maximum adsorption capacity toward Cu(II) ions was 256.62 mg/g. The thermodynamic parameters indicated that the adsorption process of Cu(II) ions was exothermic spontaneous reaction. Moreover, this adsorbent showed excellent reusability and the adsorption property remained stable after five cycles. This adsorbent is believed to be one of the promising and favorable adsorbent for the removal of Cu(II) ions from aqueous solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44528.     

Fabrication of a copolymer flocculant and application for Cr(VI) removal

A copolymer flocculant (CATCS) derived from starch and chitosan was fabricated and used as eco‐friendly adsorbent for removal of Cr(VI) from aqueous solution. The CATCS flocculant was characterized by scanning electron microscope, thermogravimetic analysis, and Fourier transform infrared spectroscopy. The effects of CATCS dosage, initial Cr(VI) concentration, pH, and reaction time on removal of Cr(VI) were discussed. The results showed CATCS removed Cr(VI) effectively and the adsorption isotherm agreed well with the Freundlich isotherm and R–P isotherm models. The enthalpy change (ΔH) of the process was 16.75 kJ/mol suggesting the existence of chemisorption and the reaction was endothermic. Moreover, the negative free energy change (ΔG) indicated the adsorption process was feasible and spontaneous. The positive entropy change (ΔS) showed there was an increase of disorder in the system during the adsorption process. The adsorption kinetics results showed that the adsorption could be described by the pseudo‐second‐order kinetics mechanism. The activation energy (E_a) of the adsorption reaction was 29.16 kJ/mol. POLYM. ENG. SCI., 56:1213–1220, 2016. © 2016 Society of Plastics Engineers     

Studies of adsorption of alkaline trypsin by poly(methacrylic acid) brushes on chitosan membranes

Poly(methacrylic acid)‐grafted chitosan membranes (chitosan‐g‐poly(MAA)) were prepared in two sequential steps: in the first step, chitosan membranes were prepared by phase‐inversion technique and then epichlorohydrin was used as crosslinking agent to increase its chemical stability in acidic media; in the second step, the graftcopolymerization of methacrylic acid onto the chitosan membranes was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan‐g‐poly(MAA) membranes were first used as an ion‐exchange support for adsorption of trypsin from aqueous solution. The influence of pH, equilibrium time, ionic strength, and initial trypsin concentration on the adsorption capacity of the chitosan‐g‐poly(MAA) membranes have been investigated in a batch system. Maximum trypsin adsorption onto chitosan‐g‐poly(MAA) membrane was found to be 92.86 mg mL^?1 at pH 7.0. The experimental equilibrium data obtained for trypsin adsorption onto chitosan‐g‐poly(MAA) membranes fitted well to the Langmuir isotherm model. The adsorption data was analyzed using the first‐ and second‐order kinetic models, and the experimental data was well described by the second‐order equation. More than 97% of the adsorbed trypsin was desorbed using glutamic acid solution (0.5M, pH 4.0). In addition, the chitosan‐g‐ poly(MAA) membrane prepared in this work showed promising potential for various biotechnological applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(2‐hydroxyethylmethacrylate)/chitosan dye and different metal‐ion‐immobilized interpenetrating network membranes: Preparation and application in metal affinity chromatography

Composite membranes were synthesized with 2‐hydroxyethylmethacrylate and chitosan (pHEMA/chitosan) via an ultraviolet‐initiated photopolymerization technique in the presence of an initiator (α,α′‐azobisisobutyronitrile). The interpenetrating network (IPN) membranes were improved by the immobilization of dye molecules via hydroxyl and amino groups on the membrane surfaces from the IPNs. A triazidine dye (Procion Green H‐4G) was covalently immobilized as a ligand onto the IPN membranes. The protein showed various affinities to different chelated metal ions on the membrane surfaces that best matched its own distribution of functional sites, resulting in a distribution of binding energies. In support of this interpretation, two different metal ions, Zn(II) and Fe(III), were chelated with the immobilized dye molecules. The adsorption and binding characteristics of the different metal‐ion‐chelated dye‐immobilized IPN membranes for the lysozyme were investigated with aqueous solutions in magnetically stirred cells. The experimental data were analyzed with two adsorption kinetic models, pseudo‐first‐order and pseudo‐second‐order, to determine the best fit equation for the adsorption of lysozyme onto IPN membranes. The second‐order equation for the lysozyme–dye–metal‐chelated IPN membrane systems was the most appropriate equation for predicting the adsorption capacity for all the tested adsorbents. The reversible lysozyme adsorption on the dye‐immobilized and metal‐ion‐chelated membranes obeyed the Temkin isotherm. The lysozyme adsorption capacity of the pHEMA/chitosan dye, pHEMA/chitosan dye–Zn(II), and pHEMA/chitosan dye–Fe(III) membranes were 2.54, 2.85, and 3.64 mg cm^?2, respectively. The nonspecific adsorption of the lysozyme on the plain pHEMA/chitosan membrane was about 0.18 mg cm^?2. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1843–1853, 2003     

Thiocarbohydrazide‐modified chitosan as anticorrosion and metal ion adsorbent

To explore the application of chitosan (CS) derivatives in anticorrosion and adsorption, thiocarbohydrazide‐modified chitosan (TCHECS) derivative was synthesized and characterized. The preliminary electrochemical measurements of the behaviors of 304 steel and Cu sheets in 2% HAc (v/v) containing TCHECS, chitosan (CS), and hydrazine cross‐linked epoxy‐N‐phthaloylchitosan (HECS) had been performed. The short‐term electrochemical tests show that the new compound can act as a mixed‐type metal anticorrosion inhibitor; its inhibition efficiency is 88% when the concentration was 30 mg/L. The preliminary adsorption studies for sorbents TCHECS and HECS on a metal ion mixture aqueous solution were also performed. The results show that TCHECS can absorb As (V), Ni (II), Cu (II), Cd (II), and Pb (II) efficiently at pH 9; the removal of the As (V), Ni (II), Cu (II), Cd (II), and Pb (II) are around 55.6–99.9%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40671.     

Removal of Copper (II) and Nickel (II) Ions from Aqueous Solutions by a Composite Chitosan Biosorbent

Abstract

A composite chitosan biosorbent (CCB) was prepared by coating chitosan on to ceramic alumina. The adsorption characteristics of the sorbent for copper and nickel ions were studied under batch equilibrium and dynamic flow conditions at pH 4.0. The equilibrium adsorption data were correlated with Langmuir, Freundlich, and Redlich‐Peterson models. The ultimate monolayer capacities, obtained from Langmuir isotherm, were 86.2 and 78.1 mg/g of chitosan for Cu(II) and Ni(II), respectively. In addition, dynamic column adsorption studies were conducted to obtain breakthrough curves. After the column was saturated with metal ions, it was regenerated with 0.1 M sodium hydroxide. The regenerated column was used for a second adsorption cycle.     

Removal of copper(II) from an aqueous solution with copper(II)‐imprinted chitosan microspheres

Ion‐imprinted chitosan (CS) microspheres (MIPs) were prepared with Cu(II) as a template and epichlorohydrin as a crosslinker for the selective separation of Cu(II) from aqueous solution. The microspheres showed a higher adsorption capacity and selectivity for the Cu(II) ions than nonimprinted chitosan microspheres (NMIPs) without a template. The results show that the adsorption of Cu(II) on the CS microspheres was affected by the initial pH value, initial Cu(II) concentration, and temperature. The kinetic parameters of the adsorption process indicated that the adsorption followed a second‐order adsorption process. Equilibrium experiments showed very good fits with the Langmuir isotherm equation for the monolayer adsorption process. The maximum sorption capacity calculated from the Langmuir isotherm was 201.66 mg/g for the Cu–MIPs and 189.51 mg/g for the NMIPs; these values were close to the experimental ones. The selectivity coefficients of Cu(II) and other metal ions on the NMIPs indicated a preference for Cu(II). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and adsorption properties for metal ions of mesocyclic diamine‐grafted chitosan‐crown ether

A new type of grafted chitosan‐crown ether was synthesized using mesocyclic diamine crown ether as the grafting agent. The C2 amino group in chitosan was protected from the reaction between benzaldehyde and chitosan to form N‐benzylidene chitosan (CTB). After reaction with mesocyclic diamine crown ether of the epoxy propane group to give mesocyclic diamine‐N‐benzalidene chitosan (CTBA), the Schiff base was removed in a dilute ethanol hydrochloride solution to obtain chitosan‐crown ether (CTDA). Its structure was confirmed by FTIR spectra analysis and X‐ray diffraction analysis. Its static adsorption properties for Pb(II), Cu(II), Cd(II), and Cr(III) were studied. The experimental results showed that the grafted chitosan‐crown ether has high selectivity for the adsorption of Cu(II) in the presence of Pb(II), Cu(II), and Cd(II) and its adsorption selectivity is better than that of chitosan. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1255–1260, 2000     

Hexafunctional poly(propylene glycol) based hydrogels for the removal of heavy metal ions

Two types of degradable poly(propylene glycol) (PPG) hydrogels that are suitable for the absorption of heavy metals have been presented. The PPG‐O‐P(O)Cl₂ fragments obtained by treating hexafunctional PPG with phosphorous oxychloride (POCl₃) react with 1,3‐propanediamine (PDA; Gel‐1 ) or PDA together with 1,2‐ethanedithiol ( Gel‐2 ), to yield cross‐linked and water‐swellable hydrogels in a one‐pot method. This protocol for the fabrication of PPG hydrogels exhibits promising advantages over prior methods including a short reaction time, mass‐production, easy separation, and high yield. A series of heavy metal ions were employed to test the adsorptive properties of the hydrogels. Gel‐2 shows better adsorption capacity than Gel‐1 for all the metal ions and the metal ions adsorption efficiency of the two types of hydrogels is in the order of Fe(III) > Pb(II) > Cd(II) > Zn(II) > Cu(II) > Ni(II) > Co(II) > Hg(II). The amounts of metal ions adsorbed increases with metal ion concentration and hydrogel dosage, but decreases with temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40610.     

Preparation of a surface molecular‐imprinted adsorbent for Ni2+ based on Penicillium chrysogenum

A new chitosan molecular‐imprinted adsorbent was prepared from the mycelium of waste biomass. The results showed that an adsorbent using Penicillium chrysogenum mycelium as the core material was better than one derived from peanut coat. The adsorption capacity of the surface‐imprinted adsorbent for Ni²⁺ was enhanced by increasing the chitosan concentration in the imprinting process. Epichlorohydrin was better than glutaraldehyde as a cross‐linking agent; the optimal imprinted Ni²⁺ concentration for preparing the surface‐imprinted adsorbent was 2 mg (Ni²⁺) g^?1 of mycelium. The adsorption capacity of the surface‐imprinted adsorbent was 42 mg g^?1 (at 200 mg dm^?3 initial metal ions concentration) and twice that of the mycelium adsorbent. The surface‐imprinted adsorbent can be reused for up to 15 cycles without loss of adsorption capacity. Copyright © 2005 Society of Chemical Industry     

Walnut shell supported nanoscale Fe0 for the removal of Cu(II) and Ni(II) ions from water

The walnut shell supported nanoscale zero‐valent iron (walnut‐nZVI) was prepared from sodium borohydride, iron(II) chloride tetrahydrate, and walnut shell by liquid phase chemical reduction and characterized by FTIR, TEM, and XRD. The composites were tested as adsorbent for the removal of Cu(II) or Ni(II) ions. The equilibrium data were analyzed by the Langmuir, Freundlich, Dubinin–Radushkevich, which revealed that Langmuir isotherm was more suitable for describing Cu(II) and Ni(II) ions adsorption than the other two isotherm models. The results indicated that the maximum adsorption capacity was higher than some other modified biomass waste adsorbents under the proposed conditions, were 458.7, 327.9 mg g^?1 for Cu(II) or Ni(II). The adsorption kinetics data indicated that the adsorption fitted well with the pseudo‐second‐order kinetic model. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43304.     

Adsorption of Hg(II) in aqueous solutions using mercapto‐functionalized alkali lignin

A novel adsorbent for Hg(II), mercapto‐functionalized alkali lignin (AL‐SH) was synthesized by Friedel–Crafts alkylation reaction and nucleophilic substitution reactions. The adsorbent was characterized by the techniques of Fourier transform‐infrared spectroscopy (FT‐IR), elementary analysis and thermogravimetric analysis, and N₂ adsorption techniques. The effect of various parameters on Hg(II) adsorption process such as initial pH, contact time, ionic strength, initial Hg(II) concentration, temperature, and adsorbent dosage were investigated in detail through batch static experiments. The results indicated that the adsorption process of Hg(II) on AL‐SH was mainly dependent on the pH and the optimal pH value was at pH ranging from 4.0 to 6.0. The adsorption process was found to follow pseudosecond‐order kinetics and the main process was chemical adsorption, which equilibrated at 8 h. The adsorption isotherm was better described by Langmuir and Temkin isotherm equations compared to Freundlich isotherm equation and the maximum adsorption capacity obtained was 101.2 mg g^?1 (pH = 4.0, 20°C, initial Hg(II) concentration was 200 mg L^?1). The thermodynamic parameters of and were positive while was negative, revealed that the adsorption of Hg(II) onto AL‐SH was a spontaneous and endothermic process with increased entropy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40749.     

Novel batch reactor design for the adsorption of arsenate on chitosan

BACKGROUND: The sorption of arsenate, a poison of acute toxicity found in natural waters, onto chitosan, a biosorbent derived from waste seafood shells has been studied. A batch adsorber design model was developed to determine how much chitosan adsorbent is required to reduce the arsenate concentration in solutions to the WHO standard of 10 µg L^?1. RESULTS: A series of batch kinetic experiments has been carried out at different initial pH values. The initial arsenate sorption appears to be completed after 30 min, however, a steady reversible reaction takes place resulting in the desorption of arsenate over 48 h. These phenomena in the batch kinetic data have been correlated simultaneously using the newly developed pseudo‐first order reversible model. Two batch reactor design models have been developed and compared. The first model is a conventional approach based on the equilibrium isotherm capacity equation. A second batch adsorption reactor design is based on the principle of contacting time required, t_max, for the chitosan to achieve its maximum adsorption capacity, q_max. The practical outcome from the second batch adsorber model results in a saving in adsorbent mass per batch of approximately 39.4%, 96.2% and 92.3% chitosan adsorbent at pH conditions of 3.5, 4.0 and 5.0, respectively. CONCLUSION: The adsorbent cost and handling costs are reduced in the second batch adsorber model. There is also a significant savings in the batch turnaround time required in the batch adsorber design when the design is based on the maximum adsorption capacity rather than the equilibrium adsorption capacity. Copyright © 2010 Society of Chemical Industry