Radiation synthesis of graphene oxide/composite hydrogels and their ability for potential dye adsorption from wastewater

A high yield of graphene oxide (GO) was chemically synthesized from graphite powder utilizing adjusted Hummer's method. The contents of acidic functional groups in GO were determined using potentiometric titration. Composite hydrogels dependent on graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid)/polyvinyl alcohol (GO/PAMPS/PVA) were synthesized utilizing a ⁶⁰Co gamma irradiation source at different doses. The synthesized graphene oxide and composite hydrogels were portrayed via X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared analysis. The morphology of composite hydrogels was characterized by scanning electron microscope. The gel % and swelling % for the prepared hydrogel demonstrated that the swelling % of hydrogel increased with raising AMPS content. Whereas the increment of GO and increasing the irradiation dose lead to a reduction in the swelling %. The influences of pH, GO percentage, initial dye concentration, the adsorbent dosage, contact time, and temperature on the adsorption of basic blue 3 dye were evaluated and the adsorption capacity was 194.6 mg/g at optimum conditions; pH = 6, GO/PAMPS/PVA composite hydrogels with 5 wt% of GO, initial dye concentration = 200 mg/L, adsorbent dose = 0.1 g, solution volume = 50 mL after 360 min at room temperature (25°C). The adsorption of dye onto the GO/PAMPS/PVA composite hydrogels follows Pseudo-second-order adsorption kinetics, fits the Freundlich adsorption isotherm model.     

Removal of methylene blue from aqueous solutions by poly(2-acrylamido-2-methylpropane sulfonic acid-co-itaconic acid) hydrogels

In this study, removal of methylene blue (MB) from aqueous solution by poly(AMPS-co-IA) hydrogels was examined by batch equilibration technique. The effects of monomer ratio, concentration of initiator and crosslinker, pH, adsorption time, initial dye concentration and adsorption temperature on the removal of MB were studied. The results show that the removal of MB was highly effected by preparation conditions of hydrogel. The maximum removal was observed at 10/90 IA/AMPS monomer ratio, 1.0% KPS, and 10.0% MBAAm concentrations. Removal of MB was strongly affected by pH. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were applied. It was concluded that adsorption of MB on hydrogel followed pseudo-second-order kinetics. It was found that the adsorption isotherm of the MB fit Langmuir-type isotherms. From the Langmuir equation, the adsorption capacity was found as 1,000 mg/g for MB dye. Thermodynamic parameters suggest that the adsorption is a typical physical process, spontaneous, and exothermic in nature. Ten adsorption—desorption cycles demonstrated that the hydrogels were suitable for repeated use without considerable change in adsorption capacity. The results revealed that this hydrogels have potential to be used as an adsorbent for the removal of MB from aqueous solution.     

Cellulose-graft-polyacrylamide/hydroxyapatite composite hydrogel with possible application in removal of Cu (II) ions

Cellulose-graft-polyacrylamide/hydroxyapatite composite hydrogels of different weight ratios were prepared through a suspension polymerization method. Physical and chemical characteristics of the composite were investigated by Fourier transform infrared spectroscopy and scanning electron microscopy. The swelling behaviors of the composite hydrogels were investigated under varying conditions of time, temperature and pH. The optimized swelling capacity in standard conditions was found to be 5197% per gram of the hydrogel. The prepared hydrogel has the potential to be used for ion adsorption in water treatment. Such a possibility was examined through adsorption of copper (II) ions from an aqueous solution. The effects on adsorption of varying the time, pH, and initial concentration of copper (II) solution as well as some thermodynamic parameters were also investigated. The maximum adsorption capacity was found to be 175 mg per gram of composite hydrogel in dried state. The mechanism of adsorption was well presented using a pseudo-second-order kinetic model. Finally, the mercury-loaded hydrogel was regenerated without losing its original activity and stability.     

Uptake of Pb2+ Using N-Vinyl Imidazole Based Uniform Porous Hydrogels

The uniform porous and continuous phase lead (II) adsorbent hydrogel, was prepared by copolymerizing 2-hydroxyethyl methacrylate (HEMA), acrylic acid (AAc), and N,N′-methylenebisacrylamide (MBAAm), with n-vinyl imidazole (VIM). A series of hydrogels, including different ratios of VIM, were prepared by photopolymerization and characterized. The influence of the uptake conditions such as pH, functional monomer percent, contact time, initial feed concentration, and foreign metal ions on the metal ion binding capacity of hydrogel, were also tested. The selective chelation of heavy metal ions from synthetic wastewater was also studied. The affinity order on molar basis was observed as follows: Pb (II) > Zn (II) > Cd (II). Chelation behavior of heavy metal ions could be modelled using both the Langmuir and Freundlich isotherms and it was seen that the Langmuir isotherm model was the best fit for the adsorption of Pb (II) ions in P(VIM/AAc/HEMA) hydrogel. Moreover, the limits of detection and the quantification values were determined. Regeneration of the hydrogels was easily performed with 1 M HCl and the same hydrogel can be reused five times almost without any loss of adsorption capacity. All these features make P(VIM/AAc/HEMA) hydrogels potential candidate adsorbent for heavy metal removal.     

Removal of malachite green from aqueous solution by zinc oxide nanoparticle loaded on activated carbon: Kinetics and isotherm study

In this research, a novel adsorbent, zinc oxide nanoparticle loaded on activated carbon (ZnO-NP-AC) was synthesized by a simple, low cost and efficient procedure. Subsequently, this novel material was characterizated and identified by different techniques such as Brunauer, Emmett and Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) analysis. Unique properties such as high surface area (>603 m²/g) and low pore size (<61 Å) and average particle size lower than 100 Å in addition to high reactive atom and presence of various functional groups make it possible for efficient removal of malachite green (MG). In batch experimental set-up, optimum conditions for quantitative removal of MG by ZnO-NP-AC was attained following searching effect of variables such as adsorbent dosage, initial dye concentration and pH. Optimum values were set as pH of 7.0, 0.015 g of ZnO-NP-AC at removal time of 15 min. Kinetic studies at various adsorbent dosage and initial MG concentration show that maximum MG removal was achieved within 15 min of the start of every experiment at most conditions. The adsorption of MG follows the pseudo-second-order rate equation in addition to interparticle diffusion model (with removal more than 95%) at all conditions. Equilibrium data fitted well with the Langmuir model at all amount of adsorbent, while maximum adsorption capacity was 322.58 mg g⁻¹ for 0.005 g of ZnO-NP-AC.     

Resin-loaded cationic hydrogel: A new sorbent for recovering of grapefruit polyphenols

This paper presents a study of the recovering of polyphenols from grapefruit biowastes through extraction and batch adsorption process using novel resin-loaded cationic hydrogel. To prepare adsorbent, 2-(dimethylamino) ethyl methacrylate (DMAEMA) monomer was polymerized by free radical mechanisms in presence of resin particles and then tertiary amino groups on PDMAEMA residue were quaternized using methyl iodide. The developed adsorbent was then characterized by FTIR, SEM, XRD, and Brunauer, Emmet, and Teller analysis. The resin-loaded cationic hydrogel displayed an enhanced affinity for binding with polyphenols at pH value of 10 due to the strong electrostatic attraction between positively charged adsorbent surface and solute molecules. The adsorption capacity of 60 (mg-naringin-g^?1-adsorbent) was obtained when the other experimental conditions were chosen as follows: initial polyphenol concentration; 0.13?g?mL^?1, contact time; 30?min, temperature; 25°C. On the other hand, the adsorbent consisting solely of resin particles shown lower affinity for polyphenols. The adsorption results revealed that the resin-loaded cationic hydrogels exhibited significant improvement in the recovery of polyphenols from grapefruit peels through integrated extraction–adsorption process.     

Swelling and auramine-<Emphasis Type="Italic">O</Emphasis> adsorption of carboxymethyl cellulose grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels

Carboxymethyl cellulose (CMC) grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels were prepared for adsorptive removal of auramine-O (as a cationic dye model) from wastewater. For the synthesis of nanocomposite hydrogel by free radical polymerization method, potassium persulfate (KPS), methyl methacrylate (MMA), N,N′-methylene bisacrylamide (MBA) and Cloisite 30B were used as initiator, monomer, cross-linker and nano-filler, respectively. The nanocomposite hydrogels were characterized by FTIR, TGA, SEM and XRD techniques. The FTIR results showed that the monomer was grafted onto carboxymethyl cellulose chains successfully. Swelling behavior of nanocomposite hydrogel as a function of KPS, MBA, MMA concentration and CMC/Cloisite 30B weight ratio was studied by Taguchi method using Minitab 16 software. According to ANOVA results, the most effective factor of equilibrium swelling of nanocomposite hydrogel was CMC/Cloisite 30B weight ratio. Addition of Cloisite 30B to hydrogel up to a certain amount improved swelling, though its high amount decreased swelling. The effects of pH and ionic strength on swelling of optimum hydrogels were investigated. Maximum swelling of nanocomposite hydrogel occurred at pH 7.0. The kinetic data of adsorption fitted well to pseudo-second-order model. The best isotherm for investigation of adsorption mechanism was Langmuir model suggesting the formation of a monolayer on the adsorbent surface. FTIR results, before and after auramine-O adsorption, showed that complexation is the main mechanism of adsorption. High adsorption capacity of nanocomposite hydrogels made them more efficient in wastewater treatment application.     

荔枝皮吸附水中孔雀绿的响应曲面法研究

采用Box-Behnken响应曲面优化设计对荔枝皮吸附去除水中染料孔雀绿（MG）的影响因素（如吸附时间、吸附剂用量、pH值）进行研究,建立了去除率和上述因素之间的二次多项式模型,得到荔枝皮吸附孔雀绿的最佳吸附条件为：温度25℃、吸附时间122.31min、吸附剂用量2.81g/L、pH=6.75、MG浓度为100mg/L,最优条件下荔枝皮对孔雀绿的吸附去除率可以达99.75%。用Langmuir和Freundlich方程对吸附等温线进行拟合,其中Langmuir方程拟合效果最好,其最大吸附量为142.86mg/g,且吸附过程符合假二次动力学模型。此外,热力学结果表明,荔枝皮对孔雀绿的吸附属于自发的吸热过程。结合吸附-解吸循环实验和对吸附的FT-IR表征,表明荔枝皮是一种极具潜力的高效的吸附剂,能有效去除水中的孔雀绿离子。     

Swelling and dye adsorption study of novel superswelling [Acrylamide/N-vinylpyrrolidone/3(2-hydroxyethyl carbamoyl) acrylic acid] hydrogels

Summary Super swelling acrylamide (Am)/N-vinylpyrrolidone (NVP)/3-(2-hydroxyethyl carbamoyl) acrylic acid (HECA) hydrogels were prepared by free radical polymerization of quaternary mixtures of Am, NVP, HECA and water. The hydrogels were used in experiments on swelling, diffusion and adsorption of some water-soluble monovalent cationic dyes such as Crystal Violet (CV), Malachite Green (MG) and Methylene Blue (MB). In the experiment of the adsorption of dyes from their aqueous solutions type-S adsorption isotherm were found. The diffusion of water within the hydrogel was found to have non Fickian character. The uptake of dyes within the hydrogel increased in the following order: MG > MB > CV. The binding ratio of the hydrogel/dye systems was gradually increased with the increase of HECA content in the AAm/NVP/HECA hydrogel.     

Comparative study of PEO and PVA hydrogels for removal of methylene blue dye from wastewater

In this study, poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO) hydrogels were synthesized and evaluated as adsorbent for dye removal from wastewater using methylene blue (MB) in aqueous solution as probe. PEO samples were photochemically prepared by varying irradiation time (1–16 h), while PVA samples were synthetized with different concentration of glutaraldehyde (GA) (0.03–0.48%). The obtained hydrogels were obtained through the analysis of a swelling test, scanning electron microscopy, and adsorption studies. PEO hydrogels adsorption capacity was dependent on the irradiation time, while the PVA hydrogel adsorption capacity reduces with GA concentration. Both hydrogels demonstrated a Langmuir isotherm adsorption model at the equilibrium and pseudo‐second order kinetic fits properly. pH studies showed that when pH reaches 12, the adsorbed MB amount is close to 8 and 2 times higher than pH = 2 both hydrogels. Photochemical preparation of hydrogels shows an easier way of tuning their properties in order to maximize dye removal. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45043.     

Removal of Mercury (II) from Aqueous Solution using Chitosan-graft-Polyacrylamide Semi-IPN Hydrogels

Chitosan-graft-polyacrylamide semi-interpenetrating polymer network (IPN) superabsorbent hydrogel was prepared via UV irradiation and N, N′-methylene-bis-acrylamide was used as crosslinker. The product was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM). The hydrogels were observed to exhibit as much as 2580.2% swelling under optimum reaction conditions. The hydrogel is an efficient selective sorbent for the removal of mercuric ions (Hg(II)) from aqueous solutions. The mercury sorption capacity under non-buffered conditions is achieved around 9.98 mmol · g^?1 (or 2001.8 mg (mercury)/g (hydrogel)) via the colorimetric method. The kinetic data were fitted to the pseudo second order model. Furthermore, the influence of pH, hydrogel dose, and initial mercury concentration on adsorption capacity of the semi-IPN hydrogel was evaluated. Also, the isothermal adsorption equilibrium data was described using the Langmuir model. Finally, the mercury loaded hydrogel was regenerated without losing its original activity and stability.     

Single and Binary Adsorption of Food Dyes on Chitosan/Activated Carbon Hydrogels

The removal of dye contaminants from water is an important issue and different adsorbents have been developed for this purpose. Here, chitosan hydrogel, scaffold‐chitosan hydrogel, and scaffold‐chitosan hydrogel with activated carbon were developed and used in the adsorption of food blue 2 and food red 17, from single and binary aqueous systems. The adsorbents presented good mechanical properties, high efficiency, high adsorption capacity, and fast kinetics for single and binary systems. Chitosan hydrogel presented excellent reusability capacity and can be reused for five cycles. The use of these hydrogels enables the application of adsorbent materials with three‐dimensional frameworks for dye adsorption in single or binary systems.     

UV-induced synthesis of chitosan-<Emphasis Type="Italic">g</Emphasis>-polyacrylamide semi-IPN superabsorbent hydrogels

Superabsorbent hydrogels of chitosan-g-polyacrylamide with N,N′-methylene-bis-acrylamide as a crosslinker were prepared via UV irradiation in the absence of photoinitiator under homogeneous conditions. The product was characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy to confirm the formation of hydrogels. The transparent hydrogels have been observed to exhibit as much as 2987% swelling in acidic solution. In addition, the hydrogel which hydrolyzed for 6 h (0.24 × 10³ min) can have a water uptake of 106 times its weight (5300% swelling for 0.5 g hydrogel). The effect of several variables such as time, temperature, pH, acrylamide/chitosan ratio, crosslinker amount, and different media was explored. Finally, the prepared hydrogel have been used in adsorption of Zn(II) ions from water with high removal efficiency (0.636 meq g⁻¹ or 20.8 mg g⁻¹) at pH = 7. The experimental data of the adsorption equilibrium from Zn(II) solution fit well with the pseudo-second-order model.     

Adsorption of Ag (I) Ions from Aqueous Solutions Using Photocured Thiol-Ene Hydrogel

In this present work, we reported the adsorption and recovery studies of a P(Penta3MP4/PEG-DA/HEMA) thiol-ene based hydrogel. Real-time infrared spectroscopy technique was used to identify the photopolymerization kinetics of thiol-ene based formulations. The chemical composition and surface morphology of hydrogels were also characterized. The influence of the adsorption conditions such as pH, hydrogel formulations, contact time, initial metal ion concentration, and foreign metal ions on the metal ion binding capacity of hydrogel, were tested. Both the Langmuir and Freundlich isotherm models were applied to the method. The reusability of the hydrogels and the usability of the hydrogels for preconcentration studies were also investigated. The analytical parameters of the method were calculated and the recovery of silver ions from waste radiographic films was also applied to the hydrogels.     

A novel nonchemical approach to the expansion of halloysite nanotubes and their uses in chitosan composite hydrogels for broad‐spectrum dye adsorption capacity

A novel method based on cryoscopic expansion of halloysite nanotubes via frozen water molecules entrapped in their lumens and subsequent lyophilization was described. Detailed analyses confirmed that the inner and outer diameters as well as the surface area of the nanotubes could be efficiently increased without disturbing the inherent tubular structure. The benefits of cryo‐expanded nanotubes for the enhancement of chitosan hydrogel performances were discussed. The composite hydrogels, depending on their compositions and morphologies, exhibited significantly enhanced swelling and mechanical properties compared with neat chitosan hydrogel. This effect was even more pronounced in the hydrogels containing cryo‐expanded halloysite nanotubes. Although neat chitosan is a selectively good adsorbent for anionic dyes, in the presence of a small amount of cryo‐expanded halloysite, the resultant composite hydrogel can establish a relatively high adsorption capacity for anionic and cationic dyes as a broad‐spectrum dye adsorbent. POLYM. COMPOS., 37:2770–2781, 2016. © 2015 Society of Plastics Engineers     

N-vinylpyrrolidone/acrylic acid/2-acrylamido-2-methylpropane sulfonic acid based hydrogels: Synthesis,characterization and their application in the removal of heavy metals

In this work, the synthesis of N-vinylpyrrolidone/acrylic acid/2-acrylamido-2-methylpropane sulfonic acid (NVP/AAc/AMPS) based hydrogels by UV-curing technique was studied and their swelling behavior, heavy metal ion recovery capabilities were investigated. The structures of hydrogels were characterized by FT-IR analysis and the results were consistent with the expected structures. Thermal gravimetric analysis of hydrogels showed that the thermal stability of hydrogel decreases slightly with incorporation of AMPS units into the structure. In addition, the morphology of the dry hydrogel sample was examined by SEM. According to swelling experiments, hydrogels with higher AMPS content gave relatively higher swelling ratio compared to neat hydrogel. These hydrogels were used for the separation of Cd(II), Cu(II) and Fe(III) ions from their aqueous solutions. The influence of the uptake conditions such as pH, time and initial feed concentration on the metal ion binding capacity of hydrogel was also tested. The selectivity of the hydrogel towards the different metal ions tested was Cd(II) > Cu(II) > Fe(III). It was observed that the specific interaction between metal ions and ionic co-monomers in the hydrogel affected the metal binding capacity of the hydrogel. The recovery of metal ions was also investigated in acid media.     

ZnO/Cassava Starch-Based Hydrogel Composite for Effective Treatment of Dye-Contaminated Wastewater

Industrial expansion has increased the discharge of contaminated wastewater. Wastewater can be treated by adsorption with petroleum-based hydrogels but the materials are not biodegradable and therefore cause secondary toxic waste. In this work, hydrogel composites are prepared based on non-biodegradable polyacrylamide and biodegradable materials of cassava starch (CS) and poly(vinyl alcohol). The effect of CS content on the porous structure is studied. The highest water absorption capacity of 74 g g⁻¹ is obtained from a hydrogel 30 wt% of CS. Within 4 h, the hydrogel effectively adsorbs the cationic dyes methylene blue (MB) and crystal violet, and the anionic dyes congo red and reactive orange. The maximum adsorption capacity toward MB is 993 mg g⁻¹. Experimental data indicate a monolayer adsorption via chemisorption. Silica-coated ZnO photocatalyst particles are synthesized via a sol–gel method and coated on the outer surface of the hydrogel. Under sunlight, the hydrogel composite degrades almost 90% of adsorbed dye. The hydrogel composite is capable of effective photodegradation for at least three cycles under artificial UV irradiation and four cycles under sunlight, but adsorption capacity remains higher than 80% at the eighth cycle. The hydrogel composite also shows antibacterial activities, indicating an additional beneficial property for industrial wastewater treatment.     

Poly (acrylic acid-co-acryloyl tetrasodium thiacalix[4]arene tetrasulfonate) grafted dextrin: new supper metal ion adsorbing hydrogels

Dextrin as a biodegradable natural polymer has hydrophilic nature that capable to increase the swelling properties and biodegradability of the synthetic hydrogels. This study describes the synthesis of a poly (acrylic acid-co-acryloyl tetrasodium thiacalix[4]arene tetrasulfonate) grafted dextrin superabsorbent hydrogels (ADA) via solution polymerization. The effects of acryloyl tetrasodium thiacalix[4]arene tetrasulfonate (ACSTCA) dose (20–60) on swelling properties of the hydrogels were studied. The synthesized hydrogels were characterized by FTIR, TGA, DMTA and rheometry. The metal ion removal capacity of the gels was investigated by atomic absorption for Cd²⁺, Pb²⁺, and Hg²⁺. The tendency of metal ions adsorption decreased in the order of Pb²⁺>Cd²⁺>Hg²⁺. The effect of key operating parameters including ACSTCA content, contact time, adsorbent dosage, solution pH, and crosslinker density was experimentally studied on Pb²⁺ adsorption from aqueous solution. The equilibrium data was analyzed using Langmuir and Freundlich adsorption isotherms. Our experimental data are in best agreement with Freundlich isotherms, and adsorption of metal cation onto hydrogel followed a pseudo second-order kinetic model. According to the thermodynamic parameters, the adsorption of Pb²⁺ occurred spontaneously. The hydrogels could be regenerated after releasing heavy metal ions, and reused 5 times with less than 7 % loss of adsorption capacity.     

Removal of Lead and Cadmium Ions from Aqueous Solutions Using Sulphur and Oxygen Donor Ligand Bearing Hydrogels

A new thiourea and urea functional monomers were synthesized. A series of hydrogels were prepared by photopolymerization. The hydrogels were used for the removal of Pb(II) and Cd(II) ions from aqueous solutions. The influence of the uptake conditions such as the pH, the time, and the initial feed concentration on the metal ion binding capacity of hydrogel was tested. The selectivity of the hydrogels towards the different metal ions was also tested. The adsorption isotherm models were applied. The limits of detection and quantification were calculated. The usability of the hydrogels for preconcentration studies were also investigated.     

Nickel and copper removal study from aqueous solution using new cationic poly[acrylamide/N,N‐DAMB/N,N‐DAPB] super absorbent hydrogel

A new cationic poly[acrylamide/N,N‐diallyl morpholinium bromide/N,N‐diallyl piperidinium bromide] super absorbent hydrogels (H1–H7) were prepared via microwave irradiated free radical cyclopolymerization using different composition. By the swelling study, hydrogel H1 is found to bear good swelling properties amongst all prepared hydrogels. The hydrogel H1 has been characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM), and TGA analysis. A batch system was applied to study the adsorption of Ni(II) and Cu(II) from aqueous solutions by hydrogel H1. The effect of treatment time, pH of the medium, amount of adsorbent doses, and initial feed concentration of metal ion on adsorption of Ni(II) and Cu(II) from their solution were also investigated. Adsorption of Ni(II) and Cu(II) increases with the increase in treatment time, adsorbent doses, and initial feed concentration and decreases with the increase in pH of the medium. The desorption of metal ions were carried out using 1N HCl and 0.5N H₂SO_4. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011