Facile synthesis of mesoporous magnesium oxide–graphene oxide composite for efficient and highly selective adsorption of hazardous anionic dyes

Mesoporous magnesium oxide–graphene oxide composite (MGC) has been synthesized using a facile post-immobilization method by mixing pre-synthesized magnesium oxide (MgO) with graphene oxide (GO). MgO used for fabrication of the composite has been synthesized using an environment-friendly method involving gelatin as a template. XRD, Raman and EDX analyses have confirmed the presence of MgO and GO in the composite. FTIR and SEM analyses of synthesized MGC have further elucidated the surface functionalities and morphology, respectively. Using N₂ adsorption–desorption isotherm, BET surface area of MGC has been calculated to be 55.9 m² g^?1 and BJH analysis confirmed the mesoporous nature of MGC. The application of synthesized MGC as a selective adsorbent for various toxic anionic dyes has been explored. Batch adsorption studies have been carried out to investigate the influence of different adsorption parameters on the adsorption of two anionic dyes: indigo carmine (IC) and orange G (OG). The maximum adsorption capacities exhibited by MGC for IC and OG are 252.4 and 24.5 mg g^?1, respectively. Plausible mechanism of dye adsorption has been explained in detail using FTIR analysis. In a mixture of cationic and anionic dyes, MGC selectively adsorbs anionic dyes with high separation factors, while in binary mixtures of anionic dyes, both dyes are adsorbed efficiently. Thus, MGC has been shown to be a potential adsorbent for the selective removal of anionic dyes from wastewater.

     

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.     

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.     

Effective removal of anionic dyes from aqueous solutions by novel polyethylenimine-ozone oxidized hydrochar (PEI-OzHC) adsorbent

The adsorption behavior of the anionic dyes Remazol Brilliant Blue R (RBBR) and Reactive Black 5 (RB5) from aqueous solutions by polyethylenimine ozone oxidized hydrochar (PEI-OzHC) was investigated. The adsorption capacities of both dyes increased with functionalization of PEI in the hydrochar adsorbent. The results of surface characterization (FTIR, BET, TGA, elemental analysis, and SEM) showed that PEI modification greatly enhanced the adsorbent surface chemistry with a slight improvement of adsorbent textural properties. In addition, the adsorption kinetics data showed an excellent adsorption efficiency as reflected in the high removal percentages of the anionic dyes. The Isotherm results indicated that RBBR and RB5 dye adsorption occurred via monolayer adsorption, and chemisorption was the rate-controlling step. The PEI-OzHC adsorbent possesses higher maximum Langmuir adsorption capacity towards RBBR (218.3 mg/g) than RB5 (182.7 mg/g). This increase in adsorption capacity is attributed to the higher number of functional groups in RBBR that interact with the adsorbent. This study reveals the potential use of adsorbents derived from pine wood hydrochar in municipal as well as industrial wastewater treatment. Furthermore, surface chemistry modification is proven as an effective strategy to enhance the performance of biomass-derived adsorbents.     

Superabsorbent amphoteric nanohydrogels: Synthesis,characterization and dyes adsorption studies

The goal of the present research is to remove high percentage of cationic and anionic dyes such as,Neutral Red, Safranin O and Indigo Carmine from aqueous solutions by poly(NIPAAm/N,Ndiallylpyrrolidinium bromide/AA) superabsorbent amphoteric nanohydrogels synthesized using the inverse microemulsion polymerization method. Effect of various parameters such as, treatment time,initial dye concentration, p H and adsorbent dose were investigated. Furthermore, kinetics and isotherms adsorption models were applied to determine the maximum adsorption and mechanism for adsorption,which shows that adsorption obeyed the pseudo-second order kinetics. From the results, removal of dyes within the nanohydrogel was found to be in the order: AB-74 BR-2 BR-5.     

Fast and highly efficient removal of anionic organic dyes with a new Cu modified nanoclinoptilolite

Adsorption of anionic dyes onto most of zeolites with net negative charge may be restricted. In this article, a natural nanoclinoptilolite was modified with Cu and the obtained nanomaterial was used as an effective adsorbent for removal of methyl red as an anionic model azo dye up to 90% in 20 min.This new adsorbent was characterized utilizing X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. Also, effects of methyl red concentration, mass of sorbent and pH on the removal percent were examined. Moreover, the adsorption mechanism was investigated by plotting the Langmuir and Freundlich adsorption isotherms. The results showed that the data can be fitted with both models. The most adsorption capacity obtained from Langmuir isotherm was about 200 mg/g. Moreover, the Cu modified nanoclinoptilolite was successfully employed for adsorption of another anionic dye, bromothymol blue. The results confirmed that this new adsorbent can be effectively applied for removing of anionic dyes from waste waters.     

Chemical and biological treatment of waste water with a novel silver/ordered mesoporous alumina nanocomposite

One of the serious problems in the present century is chemical and biological pollution of the environment. Nanocomposites are multiphase solid materials that have been used as adsorbent of pollutants such as dyes, pesticides, anions and etc. in the last decades. In this study, a novel nanocomposite including silver nanoparticles and ordered mesoporous alumina (OMA) has been synthesized and used for the removal of dyes pollutants (methyl orange, bromothymol blue and reactive yellow) from aqueous solution. The characterization of synthesized nanocomposite has been performed by TEM, N₂ adsorption/desorption, XRD and energy dispersive X-ray spectroscopy analysis. The adsorption kinetic and equilibrium data have been obtained by UV–vis spectroscopy. The results show that the silver/OMA nanocomposite (Ag/OMA nanocomposite) is good adsorbent for the removal of anionic dyes from aqueous solution, and also this nanocomposite has a biocidal action against both Gram-negative and Gram-positive bacteria.     

石墨烯基吸附剂的设计及其对水中抗生素的去除

抗生素的大量使用,所带来的环境污染问题受到广泛关注。吸附法因去除效率高、普遍适用性强,呈现出广阔的应用前景,开发新型吸附剂是高效能吸附处理的关键。近年来石墨烯优良的物理和化学性质以及吸附性能,使其成为重要的抗生素吸附剂。由于石墨烯自身的局限性以及对石墨烯吸附剂处理效能和稳定性的要求,基于石墨烯设计开发了多种石墨烯基吸附材料。而目前基于水体中抗生素的石墨烯基复合材料的设计、合成及其吸附作用机制缺乏相关的系统性综述。本文综述了目前水体中抗生素的危害,针对石墨烯基复合吸附材料中,广泛关注的磁性石墨烯吸附剂、聚合物/石墨烯吸附剂、三维石墨烯凝胶和石墨烯/生物炭吸附剂的设计和制备方法进行了总结和概述,并阐述了石墨烯基吸附材料对水体中抗生素的主要吸附作用机制。最后,本文对石墨烯基吸附材料去除水体中抗生素未来的发展方向进行了展望。     

Non-functionalized oil palm waste-derived reduced graphene oxide for methylene blue removal: Isotherm,kinetics, thermodynamics,and mass transfer mechanism

The discharge of colored effluents from industries is one of the significant sources of water pollution. Therefore, there is a growing demand for efficient and low-cost treatment methods. An adsorption process with reduced graphene oxide (rGO) synthesized using a novel double carbonization and oxidation method from the natural precursor of oil palm empty fruit bunch (OPEFB) as adsorbent is a promising approach for addressing the problem. In this study, OPEFB biochar was mixed with ferrocene with a ratio of 5:1 (m/m) and oxidized under nitrogen flow at a temperature of 300 °C for 20 min, which resulted in 75.8 wt% of yield. The potential of the synthesized rGO as an effective adsorbent for dye removal from water and wastewater was explored using methylene blue (MB) as a model. Several factors were investigated, including adsorbent dosage, initial concentration, contact time, and pH, to obtain the optimum adsorption condition through batch studies. The physical and chemical characteristics of the rGO in terms of functional groups, surface morphology, elemental composition, and crystallinity phase were determined through characterization. The nonlinear isotherms were appropriated using several error functions to describe the adsorption isotherm with a maximum adsorption capacity of 50.07 mg/g. The kinetic study demonstrates that MB’s adsorption fits the PFO kinetic model and agrees with Bangham’s interpretation of pore diffusion. The adsorption mechanism was found to be physisorption on the multilayer heterogeneous surface of the rGO involving π-π interaction, hydrophobic association, and electrostatic interaction. The thermodynamics study showed that the process was spontaneous and exothermic. The mass transfer mechanism study shows that the adsorption is controlled by intraparticle diffusion and involves complex pathways. The study found that the novel non- functionalized rGO could remove cationic dyes from water and wastewater.     

An electrokinetic study on a synthetic adsorbent of crystalline calcium silicate hydrate and its mechanism of endotoxin removal

A synthetic, disposable adsorbent of crystalline calcium silicate hydrate, LRA product by Advanced Minerals Corp., has been found highly effective for endotoxin removal from aqueous solutions. Endotoxin removal by this adsorbent is greatly enhanced by the addition of an electrolyte, such as NaCl or Tris-HCl. The electrophoretic method has been used to study the mechanism of endotoxin adsorption. In many cases, adding the electrolyte increases the magnitude of negative zeta potential of the adsorbent in water, while endotoxin adsorption reduces the magnitude. It is hypothesized that ion-exchange between monovalent cations from the aqueous phase and Ca2+ ions near the surface of the adsorbent shift zeta potential of the adsorbent to the more negative direction. It is further hypothesized that endotoxins form cationic species through binding between its phosphate groups and Ca2+ ions dissolved from the adsorbent. The adsorption of endotoxins in the form of cationic species is enhanced by the increased negative zeta potential of the adsorbent when an electrolyte is added.     

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.

     

The use of freshwater fish scale of the species Leporinus elongatus as adsorbent for anionic dyes

Fish scale of the species Leporinus elongatus was tested as an adsorbent for anionic Remazol dyes. Characterization has suggested that hydroxyl, phosphate, amides I, II, and III, and carbonate groups are the potential sites of adsorption. From solution calorimetry, values of thermal effects, Q _int, and amount of dye that interacts, n _int, were determined. The adsorption order observed was Yellow-dye/scale?>?Red-dye/scale?>?Blue-dye/scale. The Q _int and n _int data were successfully adjusted to the Langmuir isotherm model. The dyes removals by fish scale are exothermic processes (from ?83 to ?199?kJ?mol^?1) with negative entropies and are thermodynamically spontaneous. The thermodynamic results suggest that the interactions at scale/anionic dye interfaces occur mainly by surface reactions. It was finding that fish scale is a new and suitable sorbent material for recovery and biosorption/adsorption of anionic dyes from aqueous solutions.     

Rapid removal of anionic organic dye from contaminated water using a poly(3-aminobenzoic acid/graphene oxide/cobalt ferrite) nanocomposite low-cost adsorbent via adsorption techniques

This research study aims to remove hazardous anionic azo dyes (Congo red (CR)) from aqueous solutions via a simple adsorption method using a poly(3-aminobenzoic acid/graphene oxide/cobalt ferrite) nanocomposite (P3ABA/GO/CoFe₂O₄) as a novel and low-cost nanoadsorbent, as synthesized by a simple and straightforward polymerization method. Typically, 3-aminobenzoic acid (3ABA), as monomer, was chemically polymerized with graphene oxide (GO) and cobalt ferrite (CoFe₂O₄) in an aqueous acidic medium containing an ammonium persulfate initiator. The adsorbent P3ABA/GO/CoFe₂O₄ nanocomposite was characterized using various techniques such as Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, energy-dispersive analysis by X-ray and Brunauer–Emmett–Teller, vibrating sample magnetometer, and zeta potential techniques. These techniques confirmed the interaction between the poly(3-aminobenzoic acid) with GO and CoFe₂O₄ due to the presence of π-π interactions, hydrogen bonding, and electrostatic forces. Herein, the removal efficiency of dye from aqueous solution by the adsorbent was studied according to several parameters such as the pH of the solution, dye concentration, dosage of adsorbent, contact time, and temperature. The adsorption of the dye was fitted using a Langmuir model (R² between 0.9980 and 0.9995) at different temperatures, and a kinetic model that was pseudo-second order (R² = between 0.9993 and 0.9929) at various initial concentrations of CR dye. In addition, the data revealed that the P3ABA/GO/CoFe₂O₄ nanocomposite exhibited a high adsorption capacity (153.92 mg/g) and removal for CR dye (98 %) at pH 5. Thermodynamic results showed the adsorption process was an endothermic and spontaneous reaction. It was found that, in terms of reusability, the P3ABA/GO/CoFe₂O₄ adsorbent can be used for up to six cycles. In this study, P3ABA/GO/CoFe₂O₄ nanocomposites were found to be low cost, and have an excellent removal capability and fast adsorption rate for CR from wastewater via a simple adsorption method. Moreover, this adsorbent nanocomposite could be simply separated from the resultant solution and recycled.     

Fast and sensitive dye-sensor based on fluorescein/reduced graphene oxide complex

We report on a fast, sensitive, label-free, and general dye-sensor platform for synthetic organic dyes detection by competitive adsorption on reduced graphene oxide (rGO) against a fluorescent dye (FD). Fluorescein (Fl) as fluorescence indicator and a cationic dye methylene blue (MB) as model analyte were employed to investigate the analytical feature of this assay platform. An anionic dye sunset yellow FCF (SY) was chosen as a comparison analyte to test the generality of this strategy. Results show that rGO can bind Fl and quench the fluorescence by fluorescence resonance energy transfer (FRET), while MB can displace Fl quickly from the Fl/rGO complex by competitive adsorption, inducing the fluorescence recovery which provides a quantitative readout for MB. Besides, this design was simply based on the competitive adsorption of rGO between dye and FD, and can be generally applied to other dyes for label-free detection. The fluorescence enhancement efficiency (FEE) is proportional to the dye concentration over the range of 7.60-420.00 ng mL(-1) MB and 7.28-400.25 ng mL(-1) SY, respectively. The linear regression equations were calculated as FEE(MB) = 0.0192c(MB)- 0.3103 for MB and FEE(SY) = 0.0142 c(SY)- 0.0427 for SY, with the detection limits of 1.03 and 1.15 ng mL(-1), respectively. The MB in waste water and SY in an orange-flavored sports drink sample were assayed with satisfactory results.     

The adsorption of dyes used in the textile industry on mesoporous materials

An adsorbent material made with a silica lamellar mesoporous material treated with chitosan has been proved to be useful to adsorb both anionic and cationic dyes used in the textile industry. The two tested dyes Tectilon Blue (anionic) and Rhodamine B (cationic) have different adsorption kinetics reflecting a complex mechanism of the phenomenon. Furthermore, the adsorption capacity and interaction strength of Tectilon Blue is higher than those of Rhodamine B. Tectilon Blue molecules are situated with the molecular plane perpendicular to the adsorbent surface, whilst that of the Rhodamine B molecule is flat and parallel to the surface. The differences may be attributed to the different regions of the adsorbent surface on which the dyes are adsorbed because of their different electric charge.     

Design and green synthesis of 1-(4-ferrocenylbutyl)piperazine chemically grafted reduced graphene oxide for supercapacitor application

In this paper, we report the green synthesis of 1-(4-ferrocenylbutyl)piperazine chemically grafted rGO (P.Fc/rGO) as a battery-type supercapacitor electrode material. For this purpose, initially, the ability of the aqueous Damson fruit extract is investigated in the reduction reaction of graphene oxide (GO). 1-(4-ferrocenylbutyl)piperazine (P.Fc) is synthesized via nucleophilic substitution reaction of piperazine with as-synthesized 4-chlorobutylferrocene. In continue, P. Fc is incorporated to GO by ring-opening reaction of epoxide groups on the GO surface. In the next step, the modified reduction method by aqueous Damson fruit extract was used to prepare the P.Fc/rGO from P.Fc/GO. The prepared materials were characterized by various techniques including FT-IR, Uv–vis, XRD, SEM, EDX, and BET. N₂ adsorption–desorption data of P.Fc/rGO nanocomposite shows that the surface area is 37.746 m² g⁻¹. The capability of P.Fc/rGO nanocomposite for using as an energy storage electrode material in battery-type supercapacitor was examined by investigation of its electrochemical behavior by CV, EIS, and GCD measurements. The charge storage capacity of 1,102 mAh g⁻¹ is achieved at 2.5 A g⁻¹. This nanocomposite shows 89% retention of charge storage capacity after 2000 CV cycles.     

Synthesis and characterization of hexagonal boron nitride used for comparison of removal of anionic and cationic hazardous azo-dye: kinetics and equilibrium studies

The purpose of this study was to compare the adsorption behavior of cationic and anionic dyes onto a hexagonal boron nitride (hBN) nanostructure that was rich in a negative charge. Herein, the hBN nanostructure was synthesized using boric acid as a precursor material. The characteristic peaks of the hBN nanostructure were performed using Fourier transform infrared (FT-IR) and Raman spectroscopies. The morphology and the particle size of hBN nanostructure were determined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). During the studies, various essential adsorption parameters were investigated, such as the initial dye concentration, pH of the dye solution, adsorbent dose, and contact time. Under optimal conditions, the removal of 42.6% Metanil yellow (MY) and 90% Victoria blue B (VBB) from aqueous solution was performed using a 10-mg hBN nanostructure. Furthermore, the equilibrium studies showed that the Freundlich isotherm model fitted well for the removal of MY. However, the Langmuir isotherm model fitted well for the removal of VBB. Moreover, according to the results obtained from the kinetic studies, while the first-order kinetic model was suited for the adsorption of the MY, the second-order kinetic model was found to well fit for the adsorption of VBB.     

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.     

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.