Activated carbon from bacterial cellulose as an effective adsorbent for removing dye from aqueous solution

ABSTRACT

Novel activated carbon (AC) derived from bacterial cellulose (BC-AC) was produced by phosphoric acid activation at a carbonization temperature of 500 °C. BC-AC possesses mesoporous structures of 2.3 nm in diameter, porosity of 1.0 cm³/g and surface area of 1734 m²/g with high thermal stability between 100 and 500 °C. BC-AC could be used as an effective adsorbent for removing methylene blue (MB) from aqueous solutions with the maximum adsorption capacity of 505.8 mg/g. BC-AC presented physisorption and the adsorption of MB was most likely to be a monolayer adsorption. The Redlich–Peterson model displayed the best fit with the experimental data.     

Improved synthesis of a branched poly(ethylene imine)‐modified cellulose‐based adsorbent for removal and recovery of Cu(II) from aqueous solution

This study focuses on an improved synthesis of a branched poly (ethylene imine) (PEI)‐modified cellulose‐based adsorbent (Cell‐g‐PGMA‐PEI). We aim to improve the adsorbent capacity by reducing side reaction of epoxide ring opening during graft copolymerization of glycidyl methacrylate (GMA) onto cellulose which increases the content of epoxy groups, anchors to immobilize branched PEI moieties. FTIR spectra provided the evidence of successful graft copolymerization of GMA onto cellulose initiated by benzoyl peroxide (BPO) and modification with PEI. The amount of epoxy groups of Cell‐g‐PGMA was 4.35 mmol g^?1 by epoxy titration. Subsequently, the adsorption behavior of Cu(II) on cell‐g‐PGMA‐PEI in aqueous solution has been investigated. The data from the adsorption kinetic experiments agreed well with pseudo‐second‐order model. The adsorption isotherms can be interpreted by the Langmuir model with the maximum adsorption capacity of 102 mg g^?1 which was largely improved compared with the similar adsorbent reported. The dynamic adsorption capacity obtained from the column tests was 119 mg g^?1 and the adsorbent could be regenerated by HCl of 0.1 mol L^?1. Results indicate that the novel pathway for the synthesis of Cell‐g‐PGMA‐PEI exhibits significant potential to improve the performance of adsorbents in removal and recovery of Cu(II) from aqueous solution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hydroxyethyl cellulose hydrogel modified with tannic acid as methylene blue adsorbent

This work developed an effective way to improve the methylene blue (MB) adsorption performance of cellulose-based hydrogel by modified with tannic acid (TA). HEC-co-p(AA-AM)/TA hydrogel was synthesized by grafting of acrylic acid (AA) and acrylamide (AM) onto hydroxyethyl cellulose (HEC), followed by modified with TA. Fourier transform infrared spectroscopy manifested that AA and AM were successfully grafted onto the hydrogel, and TA was immobilized in the hydrogel. Field emission scanning electron microscope demonstrated that the hydrogel after TA modification had a homogeneous pore structure. Brunauer-Emmett-Teller (BET) surface areas, total pore volume, and average pore diameters of the hydrogel are 11.821 m² g⁻¹, 0.0641 cm³ g⁻¹, and 2.538 nm, respectively. The high swelling ratio (1179.2 g g⁻¹ in deionized water) was in favor of the MB adsorption. The results of the adsorption experiments illustrated that HEC-co-p(AA/AM) hydrogel had excellent MB adsorption performance. As the pH increases, the electrostatic attraction is enhanced, and the adsorption capacity is improved. The adsorption process was more fit with pseudo-second-order kinetics, and the maximum adsorption capacity (3438.27 mg g⁻¹) was determined by Langmuir model. Thermodynamic studies suggested that the adsorption process is spontaneous, exothermic, and entropy reduction. X-ray photoelectron spectroscopy analysis confirmed that MB molecules were reacted with the oxygen atoms in hydroxyl and carboxyl groups by ion-exchange. High reusability demonstrated that the hydrogel could be a potential candidate for removal cationic dye from industrial effluents.     

Fabrication of natural cellulose microspheres via electrospraying from NaOH/Urea aqueous system

Regenerated cellulose microspheres (RCM) with controllable sizes and architectures are prepared via electrospraying from environmental‐friendly NaOH/Urea aqueous system. The particle size and shape of RCM is mainly dependent on the interplay among the electrical force, surface tension, and viscous force. Particle size can be reduced to a certain extent by increasing voltage and decreasing surface tension, electrode spacing, solution concentration, degree of polymerization, and flow rate. The deformation of droplets, which is peculiarly prone to occur for low viscosity and long electrode spacing, results in elongated spheres, tear‐shaped particles, wedge‐shaped particles, and banding shaped particles besides micorspheres. The sophericity and uniformity of particles generally become worse as a result of the deformation of droplets. RCM possess good porosity and large specific surface area after regeneration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40656.     

Removal of Cd2+, Cu2+, Ni2+, and Pb2+ ions from aqueous solutions using tururi fibers as an adsorbent

This work investigates the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ ions from aqueous solutions using tururi fibers as an adsorbent under both batchwise and fixed‐bed conditions. It was found that modification of the tururi fibers with sodium hydroxide increased the adsorption efficiencies of all metal ions studied. The fractional factorial design showed that pH, adsorbent mass, agitation rate, and initial metal concentration influenced each metal adsorption differently. The kinetics showed that multi‐element adsorption equilibria were reached after 15 min following pseudo‐second‐order kinetics. The Langmuir, Freundlich, and Redlich–Peterson models were used to evaluate the adsorption capacities by tururi fibers. The Langmuir model was found to be suitable for all metal ions. Breakthrough curves revealed that saturation of the bed was reached in 160.0 mL with Cd²⁺ and Cu²⁺, and 52.0 mL with Ni²⁺ and Pb²⁺. The Thomas model was applied to the experimental data of breakthrough curves and represented the data well. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40883.     

Removal of cadmium(II) cations from an aqueous solution with aminothiourea chitosan strengthened magnetic biochar

An aminothiourea chitosan modified magnetic biochar composite (TMBC) was prepared for the efficient removal of Cd(II) from wastewater. The synthesized materials were characterized, and the detailed adsorption mechanisms and thermodynamics were studied. The adsorption experiments revealed that TMBC had a higher affinity for Cd(II) than the magnetic biochar composite, raw biochar, and other carbon‐based adsorbents did. The Cd(II) adsorption process fit the pseudo‐second‐order kinetic model, and the maximum adsorption capacities on the basis of the Langmuir model were 93.72, 121.9, and 137.3 mg/g at 298, 308, and 318 K, respectively. The practical efficacy of the adsorbent was also tested with a real mine water. The metal‐ion‐loaded TMBC could be conveniently collected by a magnet and could be easily regenerated with adsorption efficiencies up to 84% after five adsorption–desorption cycles. The as‐prepared TMBC might be a promising adsorbent for the treatment of heavy‐metal‐ion‐contaminated water or highly mineralized mine water. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46239.     

Microcrystalline cellulose as reactive reinforcing fillers for epoxidized soybean oil polymer composites

Microcrystalline cellulose (MCC) and its oxidized product dialdehyde cellulose (DAC) were introduced as the reinforcing filler in epoxidized soybean oil (ESO) thermosetting polymer. The composites comprising up to 25 wt % cellulose fillers were obtained via a solution casting. The reinforcing effects of the cellulose were evaluated by microstructure analysis, dynamic mechanical analysis, and tensile and thermal stability tests. The results showed that at the same filler concentration, DAC led to higher stretching strength, modulus, and break elongation than MCC. The 5 wt % DAC loading in ESO polymer exhibits the highest toughness and thermal stability due to the good dispersion and interfacial interaction between DAC and ESO polymer matrix. The increased storage modulus and glass transition temperature also indicate the cellulose fillers impart stiffness to the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42488.     

Regenerated cellulose aerogel: Morphology control and the application as the template for functional cellulose nanoparticles

This article focuses on controlling the morphology of regenerated cellulose aerogel (RCA) and its application as a template for the preparation of functional cellulose nanoparticles (FCNPs). RCA is prepared by lyophilizing cellulose hydrogel which is fabricated through a sol–gel method in sodium hydroxide (NaOH)/urea aqueous solution. The morphology of RCA is adjusted by varying the gelation temperature and time. With the gelation temperature and time increasing, lamellar RCA transforms into strings of cellulose nanoparticles. Subsequently, RCA with the morphology of "strings of nanoparticles" is modified through the bulk condensation of l -lactic acid and RCA. Eventually, the prepared functionalized RCA (FRCA) is dispersed in an organic solvent to obtain purified FCNPs. The results demonstrate that single FCNP can be obtained by dispersing FRCA in dimethyl sulfoxide. Moreover, the prepared FCNPs have uniform size, good thermal-stability, and increasing hydrophobicity, which are ideal candidates for polymer composites in terms of fillers.     

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.     

Preparation and characterization of transparent cellulose films using an improved cellulose dissolution process

Effective dissolution of cellulosic macromolecules is the first predominant step to prepare functional bio‐based materials with desirable properties. In this study, we developed an improved dissolution process using a freeze‐drying pretreatment to promote the dissolution of cellulose. Rheological measurements of cellulose solutions and physicochemical characterization of regenerated cellulose films (scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis) were performed. Cellulose solution prepared from 5% microcrystalline cellulose (w:v) in the solvent exhibits a Newtonian fluid character while cellulose solutions at higher concentrations show a pseudo‐plastic fluid behavior. Results from physicochemical characterization indicate that a freeze‐drying pretreatment step of cellulose leads to a complete dissolution at 5% concentration while only part of cellulose is dissolved at 10% and 15% concentrations. The results obtained indicated that the use of a freeze‐drying pretreatment step under mild conditions lead to a complete dissolution of cellulose at 5% concentration. The cellulose films prepared from 5% concentration exhibited desirable properties such as good optical transparency, crystallinity, and thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44871.     

Nanocomposites of ethylene vinyl alcohol copolymer with thermally resistant cellulose nanowhiskers by melt compounding (II): Water barrier and mechanical properties

In the present work, the crystallinity and crystalline morphology, thermal stability, water barrier, and mechanical properties of ethylene vinyl alcohol copolymer (EVOH) nanocomposites prepared by melt compounding and incorporating both plant (CNW) and bacterial cellulose nanowhiskers (BCNW) are reported. An improvement in the water barrier performance was observed, that is, 67% permeability drop, only for the microcomposite sample incorporating 2 wt % of bacterial cellulose fibrils. No significant differences in the water‐barrier properties of the nanocomposites generated through the two studied preincorporation methods were observed despite the fact that an excellent dispersion was observed in the previous study. On the other hand, direct melt‐mixing of the freeze‐dried nanofiller with EVOH resulted in increased water permeation. The aggregation of the filler in the latter nanocomposite was also ascribed to the detrimental effect on the mechanical properties. Interestingly, by using the precipitation method, an increase in the elastic modulus and tensile strength of ～36 and 22%, respectively, was observed for a 3 wt % BCNW loading, which was thought to coincide with the percolation threshold. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

All-cellulose composites prepared by partially dissolving cellulose using NaOH/thiourea aqueous solution

All-cellulose composites (ACCs) were prepared by partially dissolving cellulose in the filter paper using NaOH/thiourea aqueous solution. The effects of dissolution time, thiourea ratio, and temperature on the properties of ACCs were investigated. ACCs were characterized by scanning electron microscope, attenuated total reflectance Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and tensile tests. The results revealed that the fibers in ACCs were tightly intertwined. The crystalline form of cellulose in ACCs was transformed from type I to type I/II mixture, and the crystallinity decreased from 77.32 to 51.40%. The tensile strength of ACCs was remarkably improved to 23.16 MPa. The results confirmed ACCs had a high potential for practical applications in the packaging field.     

Phosphorylated cellulose/electrospun chitosan nanofibers media for removal of heavy metals from aqueous solutions

Contamination of water resources by toxic heavy metals has significant impacts on environmental and human health. Their removal from aqueous media is essential to ensure water sustainability and to provide safe freshwater availability to population. Electrospun chitosan (CS) nonwoven mats are efficient at removing heavy metals from aqueous media. However, they suffer from low permeability and low-mechanical strength. They are also unable to remove contaminants in a nonselective way. A bilayer sorbent media made of a porous phosphorylated cellulose substrate covered by electrospun CS nanofibers was developed to overcome those weaknesses. The hydrophilic composite shows good water permeability and mechanical strength with appropriate thermal and chemical characteristics. Adsorption tests with Cd(II) indicate that pseudo-second order and Langmuir models best fitted experimental data, with a maximum adsorption capacity of 591 mg/g at 25°C. Adsorption with multielement samples containing Cr(VI), Cu(II), Cd(II), and Pb(II) also reveal their capability to remove them in a selective way. This mechanically resistant, hydrophilic, and permeable adsorbent media was able to capture both cationic and anionic metallic contaminants.     

Evaluation of new chemically modified coconut shell adsorbents with tannic acid for Cu (II) removal from wastewater

The adsorption of Cu (II) from aqueous solutions using coconut shell modified powder was investigated in batch experiments. The surface charge of the adsorbent was determined. The points of zero charge (PZC) of the adsorbents (pH_PZC) were 4.5, 2.0, and 2.0 to raw coconut (RC), raw coconut alkalized (RCA), and coconut shell modified with tannic acid (TCA) adsorbent, respectively. Batch experiments were performed under kinetic and equilibrium conditions. The kinetic data were analyzed using a pseudo second‐order, and Elovich equation. Adsorption equilibrium data were investigated using the Langmiur, Freundlich, Temkin, and Dubinin–Raduschevich (D–R) isotherm models. It has been found that chemically modified coconut shell (TAC) affected performance when compared with unmodified coconut shell (RC). Kinetic studies showed that the adsorption followed a pseudo‐second‐order rate model. Biosorption kinetics of Cu(II) on the adsorbent TCA was rapid such that almost 90% of Cu(II) were adsorbed within 80 min. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40744.     

Bio‐sorbents from cassava waste biomass and its performance in removal of Pb2+ from aqueous solution

Cassava xanthogenate and their derivatives, as adsorbents to remove Pb²⁺ from aqueous solution, are studied based upon orthogonal factorial design. The structural and thermal properties, adsorption performance as well as equilibrium‐kinetics are comprehensively investigated with multiple tools, such as Fourier transform infrared spectroscopy, thermal gravimetric analysis (TGA), and UV–visible spectrum technique. The influence of multiple parameters, including initial Pb²⁺ concentrations, compositions, pH values, and temperatures, on the adsorption performance is emphasized. The crosslinked cassava xanthogenate serves as an effective bio‐sorbent to remove Pb ions from aqueous solution, allowing regeneration in dilute acid solution. The findings in this study are beneficial for the development of adsorbents from cassava waste biomass and may contribute to environment recovery in “nature‐to‐nature” manner. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39780.     

Poly(vinyl alcohol)/quaternized lignin composite absorbent: Synthesis,characterization and application for nitrate adsorption

A new poly(vinyl alcohol) (PVA)/quaternized lignin composite absorbent (PVA/QL) was synthesized from modified lignin and PVA, crosslinked by glutaraldehyde. As‐prepared absorbent was characterized by IR, DSC, SEM BET, and DMA. Effects of shaking time, absorbent dose, initial pH, and temperature on NO₃^? removal from aqueous solution by the absorbent were comprehensively investigated. The results show that the PVA/QL absorbent comprises quaternary ammonium groups in the form of ether bond. The composite absorbent exhibits remarkable network structure with large numbers of connected holes. The mechanical strength of the absorbent is enhanced by combining of PVA with modified lignin and crosslinkage of glutaraldehyde. The effect of pH on adsorption of NO₃^? is apparent and appropriate pH is 2.0. The adsorption process is endothermic, and determined to be consistent with the Langmuir isotherm. Furthermore, it is found that the quaternary ammonium structure and network structure in the surface of PVA/QL are the key factors to remove nitrate. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of treelike and rodlike carboxymethylated nanocellulose and their effect on carboxymethyl cellulose films

In this work, carboxymethyl cellulose (CMC) with low substitution degree, followed by different posttreatments, was applied to prepare treelike CMC nanofibrils (CMCNFs) and rodlike CMC nanocrystals (CMCNCs), and their performance in CMC composite film was evaluated simultaneously. From transmission electron microscopy results, it was found that the treelike CMCNCFs exhibited a lager aspect ratio compared to the rodlike CMCNCs. As for reinforcing CMC film, 4 wt% was the best adding amount, at this time, the tensile strength of CMC/CMCNFs and CMC/CMCNCs composite films was increased by 72.1% and 47.3%, respectively. Moreover, adding these nanofillers to CMC also could enhance the thermal stability of composite films slightly, while the transmittance of composite films was reduced at the same time. In addition, CMC/CMCNFs film was designed as a packaging box to determine its performance. Therefore, this study could reveal the differences of properties for composites with different types of nanocellulose and provide a foundation for further application of nanocellulose.     

Bifunctional cellulose derivatives for the removal of heavy‐metal ions and phenols: Synthesis and adsorption studies

In this article, we report a study of the design and synthesis of a bifunctional cellulose derivative on the removal of phenols and heavy‐metal ions in wastewater treatment. A radical polymerization was performed in an ionic liquid, 1‐allyl‐3‐methylimidazolium chloride, to graft two monomers, butyl methacrylate and 4‐vinyl pyridine, on the backbone of cellulose. The effects of the five reaction conditions on the yield of final products were evaluated. The grafted celluloses were characterized by means of Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Adsorption experiments were carried out on the cellulose‐g‐poly(butyl methacrylate‐co‐4‐vinyl pyridine) to evaluate the capacity of the removal of 2,4‐dichlorophenol (2,4‐DCP) and Cu(II) in water. The adsorption isotherms were measured at five temperatures and interpreted by a Langmuir model of adsorption. The thermodynamics of the adsorption suggested that the binding process was mildly exothermic for Cu(II) and endothermic for 2,4‐DCP. Kinetic studies were interpreted with a pseudo‐second‐order adsorption model. The process of the adsorption of 2,4‐DCP could be described overall by the model, whereas the adsorption of Cu(II) involved two processes. This was due to adsorption both on the surface and inside the adsorbent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41830.     

Effect of dimethyl sulfoxide on synthesis of thermoplastic cellulose‐Graft‐poly(l‐lactide) copolymer using ionic liquid as reaction media

In this study, ring‐opening graft polymerization of l ‐lactide onto cellulose was carried out homogeneously in ionic liquid (IL)/dimethyl sulfoxide (DMSO) co‐solvent as a reaction media. Through the effective control of high viscosity and steric hindrance caused by the interaction between the IL and the hydroxyl group of cellulose by adding DMSO as a co‐solvent, cellulose‐graft‐poly(l ‐lactide) (Cell‐g‐PLLA) copolymer with higher substitution efficiency was successfully prepared, at relatively low concentration of l ‐lactide. The maximum values of molar substitution, degree of lactyl substitution, and degree of polymerization of poly(l ‐lactide) in the copolymer were 3.76, 1.74, and 2.16, respectively, determined by ¹H‐NMR. The prepared cell‐g‐PLLA copolymers showed thermal plasticization with a glass transition temperature of 155°C. In addition, the thermal processibility could be improved as the amount of grafted PLLA in the copolymer increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41331.