Removal of dyes from water by conducting polymeric adsorbent

Chemically synthesized conducting polyaniline (PANI) was investigated as adsorbent for its possible application in the removal of organic dyes, such as methylene blue (MB) and procion red (PR) from their aqueous solution. PANI adsorbent behaves as a charged surface upon post‐synthesis treatment of the polymer with acid and base. The adsorbent thus treated shows a high selectivity for the removal of dyes in the adsorption process. The Langmuir adsorption isotherm was used to represent the experimental adsorption data. The cationic dye, MB can be preferentially removed by the base‐treated PANI while the anionic dye, PR is predominately removed by the acid‐treated one. These observations were further evidenced from the measurements of molar conductance and pH of the dye solutions employed for adsorption. The finding can be explained considering the electrostatic nature of adsorption coupled with the morphology of the PANI surface thus treated. Copyright © 2004 John Wiley & Sons, Ltd.     

Enhanced Photocatalytic Degradation of Synthetic Dyes and Industrial Dye Wastewater by Hydrothermally Synthesized G–CuO–Co<Subscript>3</Subscript>O<Subscript>4</Subscript> Hybrid Nanocomposites Under Visible Light Irradiation

To enhance the degradation of colour and chemical oxygen demand using photocatalytic activity, Graphene–CuO–Co₃O₄ hybrid nanocomposites were synthesized using an in situ surfactant free facile hydrothermal method. The photocatalytic degradation of synthetic anionic dyes, methyl orange (MO) and Congo red (CR), and industrial textile wastewater dyes under visible light irradiation was evaluated. The synthesized nanocomposite was characterized structurally and morphologically using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, high-resolution transmission electron microscope, and Fourier transform infrared spectroscopy. Evaluation of the colour indicated complete removal at 15 min of irradiation for the MO and CR dyes, with 99% degradation efficiency. The reaction time for the primary effluent wastewater dye was 60 min for 81% dye removal. In contrast, a longer reaction time was required to meet the national discharge regulation for the raw wastewater dye, 300 min for 60% dye removal. The mechanism for dye degradation using the Graphene–CuO–Co₃O₄ hybrid nanocomposite was elucidated using the Langmuir–Hinshelwood model, and the rate constant and half-life of the degradation process were calculated. The results demonstrate that photocatalytic degradation using a hybrid nanocomposite and visible light irradiation is a sustainable alternative technology for removing colour from wastewater dye.     

羧基化石墨烯对4种离子型染料的吸附脱色

合成的羧基化石墨烯（G-COOH）用FT-IR进行表征,并对G-COOH用于水溶液中甲基紫、中性红、灿烂黄和茜素红4种离子型染料的吸附性能进行了研究。 考察了吸附剂用量、吸附时间、初始浓度以及溶液pH值等条件对吸附效果的影响。 同时,研究了甲基紫染料的脱附性能,结果表明,用NaOH/EtOH混合溶液洗脱甲基紫,洗脱率可达88.2%,洗脱后的G-COOH可再利用。 从热力学角度探讨得出,G-COOH对阳离子染料甲基紫和中性红的吸附行为能够较好的符合Langmuir等温吸附模型,而对阴离子染料灿烂黄和茜素红的吸附行为则能够较好的符合Freundlich等温吸附模型,计算的吸附参数表明,G-COOH对4种染料的吸附过程容易进行。 动力学研究表明,G-COOH对4种离子型染料的吸附行为均能较好的符合准二级吸附模型。 该实验研究表明,在处理染料废水时,G-COOH为相当优异的吸附剂。     

Adsorption study for removal of Congo red anionic dye using organo-attapulgite

The organo-attapulgite was prepared using hexadecyltrimethylammonium bromide (HTMAB) with equation equivalent ratio of HTMAB to CEC of attapulgite added and then used as adsorbent for the removal of Congo red (CR) anionic dye from aqueous solution. Adsorbent characterizations were investigated using infrared spectroscopy and X-ray diffraction. The effects of contact time, temperature, pH and initial dye concentration on organo-attapulgite adsorption for CR were investigated. The results show that the amount adsorbed of CR on the organo-attapulgite increase with increasing dye concentration, temperature, and by decreasing pH. The adsorption kinetics was studied with the pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and the rate constants were evaluated. It was found that the adsorption mechanisms in the dye/organo-attapulgite system follow pseudo-second-order kinetics with a significant contribution of film diffusion. Equilibrium data fitted perfectly with Langmuir isotherm model compared to Freundlich isotherm model, and the maximum adsorption capacity was 189.39 mg g⁻¹ for the adsorbent. Kinetic and desorption studies both suggest that chemisorption should be the major mode of CR removal by the organo-attapulgite. The results indicate that HTMAB-modified attapulgite could be employed as low-cost material for the removal of Congo red anionic dye from wastewater.     

Polyethyleneimine-grafted polyphosphazene microspheres for rapid and efficient capture of anionic dyes from wastewater

Developing novel adsorbent to capture organic contaminants from wastewater rapidly and efficiently is highly desirable for waste treatment and environmental restoration. Herein, we reported a new amino-rich spherical adsorbent (PZS-PEI) for highly-efficient uptake of anionic dyes from aqueous solution. The PZS-PEI adsorbent was fabricated through a two-step process including synthesis of PZS-Cl microspheres via room temperature polymerization of hexachlorocyclotriphosphazene with bis(4-hydroxyphenyl) sulfone and subsequent surface grafting reaction of PZS-Cl microspheres using branched polyethyleneimine (PEI). The microstructure of as-obtained PZS-PEI microspheres was fully characterized by scanning electron microscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, zeta potential, and N₂ adsorption test. The adsorption performance of the PZS-PEI microspheres towards organic dyes was evaluated through carrying out a series of studies including various influence factor analysis, adsorption isotherm, kinetics, and thermodynamics. Results show that the PZS-PEI adsorbent owned good adsorption selectivity towards anionic dyes, and the maximum adsorption capacities for methyl orange (MO), acid chrome blue K, eosin-Y reached 190.29, 152.90, and 92.34 mg/g at 25 °C, respectively. In addition, the uptake behavior of organic dye by the PZS-PEI adsorbent conformed to Freundlich isotherm and pseudo-second order kinetic model, and the adsorption process followed a three-stage intraparticle diffusion mode with an endothermic and spontaneous characteristic. Electrostatic interaction and hydrogen bonding were responsible for the highly-efficient adsorption of the PZS-PEI adsorbent towards typical anionic dye MO.     

Equilibrium and fractal-like kinetic studies of the sorption of acid and basic dyes onto watermelon shell (<Emphasis Type="Italic">Citrullus vulgaris</Emphasis>)

In the present study, batch experiments were used to determine adsorption characteristics of Watermelon Shell Biosorbent (WSB) for the uptake of anionic and cationic dyes from aqueous solution. Various factors such as initial dye concentration, adsorbent dosage, pH, contact time and temperature were systematically investigated and discussed. WSB was characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy and Fourier Transform Infrared Spectroscopy. The adsorption kinetics was best described by Elovich and Diffusion-Chemosorption models for Basic red 2 (BR2) (cationic dye) and Orange G (OG) (anionic dye) respectively. However, the fractional time index “α” and non-integer “n” order by Fractal-like pseudo-first order kinetic affirmed that the mechanism of interaction of both dyes with WSB was by chemical reaction. The applicability of four adsorption isotherm models for the present system was tested. The equilibrium data were found to be well represented by the Extended Langmuir isotherm equation. The monolayer adsorption capacity of WSB for BR2 and OG adsorption was found to be 125 and 27 mg/g, respectively. The effect of temperature on the adsorption process was also investigated and the values of thermodynamic parameters ΔG°, ΔH° and ΔS° revealed that the adsorption system was spontaneous.     

Quartzite an efficient adsorbent for the removal of anionic and cationic dyes from aqueous solutions

Quartzite obtained from local source was investigated for the removal of anionic dye congo red (CR) and cationic dye malachite green (MG) as an adsorbent from aqueous solution in batch experiment. The adsorption process was studied as a function of dye concentration, contact time, pH and temperature. Adsorption process was described well by Langmuir and Freundlich isotherms. The adsorption capacity remained 666.7 mg/g for CR dye and 348.125 mg/g for MG dye. Data was analyzed thermodynamically, ΔH⁰ and ΔG⁰ values proved that adsorption of CR and MG is an endothermic and spontaneous process. Adsorption data fitted best in the pseudo-first order kinetic model. The adsorption data proved that quartzite exhibits the best adsorption capacity and can be utilized for the removal of anionic and cationic dyes.     

Characterization and Mechanism Elucidation of Dye Adsorption Using Cuprous Selenide Nanoparticles from Aqueous Solutions

The removal of cationic dyes, methylene blue(MB) and rhodamine B(RB), and anionic dyes, methyl or-ange(MO) and eosin Y(EY), from aqueous solutions by adsorption using Cu₂Se nanoparticles(Cu₂SeNPs) was studied. The effects of the initial pH values, adsorbent doses, contact time, initial dye concentrations, salt concentrations, and operation temperatures on the adsorption capacities were investigated. The adsorption process was better fitted the Langmuir equation and pseudo-second-order kinetic model, and was spontaneous and endothermic as well. The adsorption mechanism was probably based on the electrostatic interactions and π-π interactions between Cu₂SeNPs and dyes. For an adsorbent of 0.4 g/L of Cu₂SeNPs, the adsorption capacities of 23.1(MB), 22.9(RB) and 23.9(EY) mg/g were achieved, respectively, with an initial dye concentration of 10 mg/g(pH=8 for MB and pH=4 for RB and EY) and a contact time of 120 min. The removal rate of MB was still 70.4% for Cu₂SeNPs being reused in the 5th cycle. Furthermore, the recycled Cu₂SeNPs produced from selenium nanoparticles adsorbing copper were also an effective adsorbent for the removal of dyes. Cu₂SeNPs showed great potential as a new adsorbent for dyes removal due to its good stability, functionalization and reusability.     

Fabrication of flexible graphene oxide paper-like adsorbent doped with magnetite nanoparticles for removal of dyes

Organic dyes are used in many industries, e.g., textile, cosmetics and food. Hence, contamination of organic dyes to water sources is a critical issue. To reduce water pollution by organic dyes, we propose a paper-like adsorbent with a practical and economical production procedure. Subsequently, a flexible adsorbent was produced using a one-step approach by vacuum filtration of graphene oxide (GO) and iron oxide nanoparticles (Fe₃O₄-NPs) containing dispersion through a membrane and quoted as GO/Fe₃O₄ paper. For comparison, GO paper was also prepared using the same procedure. Both papers were characterized using UV–VIS absorption spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, electron diffraction X-ray analysis, X-ray photoelectron spectroscopy, and powder X-ray diffraction techniques. At the steady-state conditions, GO/Fe₃O₄ and GO papers were performed as adsorbent for cationic dyes of methylene blue, neutral red, and anionic dyes of methyl orange and fluorescein. In general, the removal efficiency of GO/Fe₃O₄ paper was higher than that of GO paper for adsorption of all dyes and this adsorbent revealed satisfactory adsorption properties for cationic dyes when compared to anionic dyes.

     

Adsorption of tartrazine from an aqueous solution by octadecyltrimethylammonium bromide-modified bentonite: Kinetics and isotherm modeling

A modified bentonite was prepared at different surfactant (ODTMA) loadings through ion exchange. The obtained organobentonite adsorbent materials were then used for the removal of an anionic dye, tartrazine, from an aqueous solution. The bentonite was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and Brunauer- Emmett-Teller (BET) method. The modification of organophilic bentonite by ODTMA increases the basal spacing d₀₀₁ from 24.1 to 39.1 Å when the cation exchange capacity increases from 1 to 4. The increase in the spacing, due to the basic organic modifications, was confirmed by the results of thermogravimetric analysis, Fourier transform infrared spectroscopy, and BET. The effects of contact time, initial concentration, and solution pH onto an adsorbed amount of tartrazine were investigated. To predict adsorption isotherm, the experimental data were analyzed using the Langmuir and Freundlich isotherm equations. It was determined that the isotherm data were fitted to the Langmuir isotherm. The adsorption process was also found to follow a pseudo-second-order kinetic model.     

Polypyrrole-coated cotton textile as adsorbent of methylene blue dye

Pollution caused by organic dyes is of serious environmental and health concern to the population. Dyes are widely used in textile coloring applications. In the present work, cotton textile was coated with a conducting polymer, polypyrrole (PPy), in situ during the oxidative polymerization of pyrrole. The resulting materials were utilized as easily separated and recyclable adsorbent for the removal of methylene blue (MB) as a model of cationic dyes in alkaline solutions. It showed also some affinity to remove Acid Green 25 as an anionic dye in acidic medium. The adsorption was assessed by monitoring the decrease in dye concentration by UV–Visible absorption spectroscopy. The influence of various parameters such as initial dye concentration, contact time, pH, temperature, and adsorbent dose on the adsorption process was studied. The pseudo-second-order kinetic model and Freundlich isotherm model were found to describe the adsorption process. The thermodynamic study revealed that the adsorption of MB by PPy was feasible, spontaneous, and exothermic process. Investigation of the substrate regeneration revealed that PPy deposited on cotton textile can be reused for dye adsorption several times with good efficiency and it allows for the recovery of MB for recycling purposes.     

Gold Nanoparticles Loaded on Activated Carbon as Novel Adsorbent for Kinetic and Isotherm Studies of Methyl Orange and Sunset Yellow Adsorption

In this research, a novel adsorbent gold nanoparticle loaded on activated carbon (Au-NP-AC) was synthesized by a low cost in a routine protocol. Subsequently, this novel material characterization and identification are followed by different techniques such as th eBruner–Emmet–Teller (BET) theory, scanning electron microcopy, and transmission electron microscopy analysis. Unique properties such as high BET surface area (>1229.55 m²/g) and low pore size (<22.46 Å) and average particle size lower than 48.798 Å in addition to high reactive atom and presence of various functional groups make it possible for efficient removal of sunset yellow (SY) and methyl orange (MO). Generally, the influence of variables including amount of adsorbent, initial dyes concentration, contact time, temperature on dyes removal percentage has great effect on removal percentage that their influence was optimized. The kinetic of proposed adsorption processes efficiently followed, pseudo-second-order and intra-particle diffusion approach. The equilibrium data of the removal strongly follow the Langmuir monolayer adsorption with high adsorption capacity in a short amount of time. This novel adsorbent by small amount (0.01 g) really is applicable for removal of high amount of both dyes (MO and SY) in short time (<18 minutes). Equilibrium data fitted well with the Langmuir model at all amount of adsorbent, while maximum adsorption capacity for MO 161.29 mg g^?1 and for SY 227.27 for 0.005 g of Au-NP-AC.     

A versatile amphiprotic cotton fiber for the removal of dyes and metal ions

Adsorption is an efficient method to combat the important issues of water pollution caused by dyes and metal ions. However, due to the surface charge diversity of pollutants, there is a pressing need to develop an all-round, efficient, cheap and environmentally friendly adsorbent. To this end, this work synthesized an amphiprotic adsorbent based on cotton fibers, which were chemically modified with a cationic monomer (3-chloro-2-hydroxypropyl trimethyl ammonium chloride) and anionic monomer (2-acrylamide-2-methyl propane sulfonic acid) respectively. The resultant amphiprotic cotton (AP-cotton) can cope with both of anionic and cationic pollutants. Its adsorption behavior as influenced by the pH value, adsorption time and initial concentration of various adsorbates was investigated. The results demonstrate that the adsorption equilibrium was reached within 4 h for Congo red (CR) and methylene blue (MB), 2 h for Cu²⁺ and 3 h for Pb²⁺, respectively. Adsorption kinetics showed that the adsorption rate was well fitted with the pseudo-second-order rate model, and the best adsorption isotherms fitted the Langmuir model. The Langmuir maximum adsorption capacities were 175.1 mg/g for CR, 113.1 mg/g for MB, 88.9 mg/g for Cu²⁺ and 70.6 mg/g for Pb²⁺, respectively, and the adsorption capacities could be maintained above 90 % after six regenerations. The all-round adsorption capacity and good regeneration performance of AP-cotton benefited from its hollow, flat-banded structure and amphiprotic characteristic. Therefore, AP-cotton exhibited a much better application potential compared with many other reported adsorbents based on natural materials.     

Facile synthesis of bioglass nanospheres for the adsorption of cationic and anionic dyes from aqueous solution

A novel adsorbent, bioglass nanospheres (BGN), has been prepared by a facile process. The BGN were spheres with an amorphous structure and a relatively high specific surface area, as indicated by SEM, transmission electron microscopy, BET, FTIR, and XRD. This paper was aimed at evaluating the adsorption behavior of this new material for the adsorptive removal of cationic (methylene blue, neutral red) and anionic (congo red) dyes from aqueous solution. The effects of the initial dye concentration, contact time, solution pH, and temperature were investigated. The adsorption kinetics showed that the adsorption behavior followed the pseudo-second-order kinetic model. The adsorption isotherm fit well to the Langmuir model. Thermodynamic analyses showed that the adsorption was physisorption, and it was also a spontaneous and endothermic process. The BGN exhibited a good reusability after five consecutive cycles for cationic dyes. In addition, the possible adsorption mechanism was also proposed based on the above experimental results.     

Adsorption and kinetic studies of cationic and anionic dyes on pyrophyllite from aqueous solutions

The adsorption of cationic Methylene Blue (MB) and anionic Procion Crimson H-EXL (PC) dyes from aqueous medium on pyrophyllite was studied. Changes in the electrokinetics of pyrophyllite as a function of pH were investigated in the absence and presence of multivalent cations. The results show that pyrophyllite in water exhibits a negative surface charge within the range pH 2-12. Pyrophyllite is found to be a novel adsorbent for versatile removal of cationic and anionic dyes. The negative hydrophilic surface sites of pyrophyllite are responsible for the adsorption of cationic MB molecules. The adsorption of anionic PC dye is possible after a charge reversal by the addition of trivalent cation of Al. Nearly 2 min of contact time are found to be sufficient for the adsorption of both dyes to reach equilibrium. The experimental data follow a Langmuir isotherm with adsorption capacities of 70.42 and 71.43 mg dye per gram of pyrophyllite for MB and PC, respectively. For the adsorption of both MB and PC dyes, the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.     

Bio-adsorption of dyes from aqueous solution by powdered excess sludge (PES): Kinetic,isotherm, and thermodynamic study

Over 30 million tons of excess sludge is discharged from rural municipal sewage plants annually in China and it is predicted that this figure will keep increasing. However, most of the excess sludge is dumped in landfills except for minor applications. In this study, based on low-cost and recycling waste, the excess sludge was used to adsorb organic dyes from aqueous solution after being directly dewatered. The powdered excess sludge (PES) presents selective adsorption property to cationic dyes. Statics batch adsorption experiments of malachite green (MG) on PES were performed to evaluate the effects of pH, adsorbent dosage, and initial MG concentration. Results revealed that the bio-adsorption equilibrium of MG on the PES can be quickly achieved at 30 min with maximum percentage adsorption of 84% at pH 7, initial dye concentration of 20 mg L^?1, and adsorbent dosage of 1.5 g L^?1. Moreover, the adsorption kinetics follows a pseudo-second-order pathway, and the equilibrium adsorption data could be described well by the Langmuir isotherm equation. Intra-particle diffusion is not the only rate-controlling step in the entire adsorption process. The adsorption process is endothermic, spontaneous, and random. PES can be used as a low-cost adsorbent for refractory cationic organic dye in effluent.     

Usage of Biogenic Apatite (Fish Bones) on Removal of Basic Fuchsin Dye from Aqueous Solution

The contamination with toxic dyes is the most important problem facing all over the world for water sources, environment and living beings. Therefore, in present study, the removal of fuchsin dye from aqueous environment was investigated using fish bones as source of biogenic apatite to the best removal efficiency. The removal efficiency of the adsorbent was investigated as a function of contact time and initial dye concentration. The highest removal capacity was found to 14.75 mg/g. The experimental data generally exhibit a good compliance with the pseudo-second-order equation. Langmuir and Freundlich models were also applied to experimental equilibrium data to find the best adsorption isotherm. Weber-Morris and Urano-Tachikawa models were used to calculate diffusion constants. The results were showed that fish bones can be effectively used as a sorbent for the removal of basic dyes from aqueous solutions.     

镁铝二元水滑石的焙烧产物对染料废水酸性红88的吸附

研究了镁铝水滑石的焙烧产物(LDO)对阴离子染料废水酸性红88(AR88)的吸附特征。分别考察了染料的初始浓度、吸附剂投加量、初始pH值、反应温度和竞争离子等因素的影响,并用XRD、红外光谱对水滑石以及吸附前后的LDO进行了表征。实验结果表明：LDO对高浓度的AR88具有良好的去除效果,在15 ℃、pH=10～11下,1.0 g·L^-1的LDO对浓度为2 000 mg·L^-1的AR88的去除率可高达99.95%,吸附容量为1 999.0 mg·g^-1。经4次回收重复利用的LDO对AR88的去除率仍为90%以上。     

Fabrication of PANI@Fe–Mn–Zr hybrid material and assessments in sono-assisted adsorption of methyl red dye: Uptake performance and response surface optimization

In recent decades, industrial wastewater discharge containing toxic or hazardous manufactured dyes has risen tremendously, creating a serious environmental threat. A new hybrid adsorbent, [email protected]–Mn–Zr synthesized by mixing Fe–Mn–Zr metal oxide composite with polyaniline (PANI), was used to study methyl red (MR) dye removal from aqueous solution. The adsorption process was observed to be influenced by the sonication time, dose of [email protected]–Mn–Zr, and initial concentration of MR dye. At an initial MR dye concentration of 25 mg/L, 0.25 g/L of [email protected]–Mn–Zr dose, 15 min of sonication, and pH 7.0, the maximum MR dye adsorption efficiency of 90.34% was achieved. Kinetic analysis was performed using five different kinetic models, which shows that the pseudo-second-order kinetic model had the best fit among the five models. The Langmuir isotherm best fits the adsorption experiments at pH 7.0, yielding a significant MR dye uptake capacity of 434.78 mgg^?1. The most significant adsorption mechanisms that have been observed in uptake of MR dye onto [email protected]–Mn–Zr were electrostatic attraction, π-π bond interactions and hydrogen bonding. Response surface optimization study was performed for optimizing the experimental conditions from which maximum dye removal of 98.19% was obtained at contact time of 12 min, initial MR dye concentration of 15 mg/L and [email protected]–Mn–Zr dose of 0.4 g/L. Use of real wastewater and water samples suggest that there is only 6–19% reduction in the dye removal efficiency as compared to the blank or controlled experiments conducted with deionized water.