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.     

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.     

Graphene Oxide Nanosheets at the Water–Organic Solvent Interface: Utilization in One‐Pot Adsorption and Reactive Extraction of Dye Molecules

Graphene oxide (GO) is amphiphilic in nature, due to its structure, which consists of hydrophilic oxygen‐containing functional groups and a hydrophobic basal plane of polyaromatic benzene rings. Due to this amphiphilicity, GO can create stable bubbles at water–organic solvent interfaces. In this study, the formation of bubbles at aqueous–organic interfaces in the presence of GO is investigated with different organic solvents. Bubble formation and transfer of GO from water to the organic phase is more prominent in aromatic solvents compared to aliphatic solvents, due to π–π interactions. Maximum transfer of GO from the aqueous to the organic phase is achieved at pH 2, and decreases with rising pH of the aqueous phase. Based on this property, and the ability of GO to adsorb cationic and anionic dye molecules, its application as a carrier for reactive extraction of cationic and anionic dye molecules is explored in toluene, kerosene, and carbon tetrachloride at pH 2 and 25 °C. The kinetics of the adsorption of the dyes onto GO nanosheets that takes place in the aqueous phase is also evaluated with different models, and a pseudo‐second‐order (linear) model is found to be the best fit. The adsorption isotherm data are also analyzed with different isotherm models. The electrostatic interaction and π–π interaction between the dye molecules and GO nanosheets leads to dye extraction of up to 98.2 % using this technique. The dye extraction is maximum in toluene and at low dye concentration.     

Competitive Adsorption removal of Congo red and Rhodamine B over alkaline membrane from in situ polymerization of Gemini cationic molecule

An alkaline membrane with full interpenetrating network (Full-IPN) with positive charge groups of uniform distribution was prepared as adsorbent for removal of Rhodamine B (RB) and Congo red (CR) in single and binary dye systems. Compared with single dye system, in binary dye systems a synergistic effect is due to the interaction between RB (cationic dyes) and CR (anionic dyes), which will impede the adsorption of CR or RB. Moreover, under the same experimental conditions, the magnitude of CR removal is better than that of RB in binary dye systems and that in the single system. The aforementioned phenomenon has resulted from one CR molecule bound to one RB molecule; the RB–CR binding occurred spontaneously, and the main binding forces between CR and RB were hydrogen bond and van der Waals interactions. Pseudo-second-order rate equation and Freundlich adsorption isotherm are with the better fit in single and binary dye systems for fitting the kinetic data. The results of ΔG, ΔH and ΔS revealed that the adsorption process for single and binary systems is endothermic and spontaneous. The electrostatic interaction between the dye and the quaternized ammonium groups present in membrane was identified as a major mechanism of the adsorption process.     

Mechanism of TiO2-assisted photocatalytic degradation of dyes under visible irradiation: photoelectrocatalytic study by TiO2-film electrodes

Photoelectrocatalytic degradation of various dyes under visible light irradiation with a TiO(2) nanoparticles electrode has been investigated to reveal the mechanism for TiO(2)-assisted photocatalytic degradation of dyes. The degradation of both cationic and anionic dyes at different biases, including the change in the degradation rate of the dyes and the photocurrent change with the bias potential, the degraded intermediates, the voltage-induced adsorption of dyes, the accumulation of electrons in the TiO(2) electrode, the effect of various additives such as benzoquinone (BQ) and N,N-dimethyl aniline (DMA), and the formation of active oxygen species such as O(2)(*-) and H(2)O(2) were examined by UV-visible spectroscopy, HPLC, TOC, and spin-trap ESR spectrometry. It was found that the dyes could controllably interact with the TiO(2) surface by external bias changes and charging of dyes. The cationic dyes such as RhB and MG underwent efficient mineralization at negative bias, but the N-dealkylation process predominated at positive bias under visible light irradiation. The discolorations of the anionic dyes SRB and AR could not be accelerated significantly at either negative or positive bias. At a negative bias of -0.6 V vs SCE, O(2)(*-) and dye(*+) were formed simultaneously at the electrode/electrolyte interface during degradation of cationic RhB. In the case of anionic dyes, however, it is impossible for the O(2)(*-) and dye cationic radical to coexist at the electrode/electrolyte surface. Experimental results imply both the superoxide anionic radical and the dye cationic radical are essential to the mineralization of the dyes under visible light-induced photocatalytic conditions.     

Adsorption of xanthene dyes by lysozyme crystals

Adsorption characteristics of cross-linked lysozyme crystals of different morphologies (tetragonal, orthorhombic, triclinic and monoclinic) were examined using four anionic dyes (fluorescein, eosin, erythrosin, and rose bengal), one zwitterionic dye (rhodamine B), and one cationic dye (rhodamine 6G). The adsorption isotherms were of the Langmuir type for all examined systems with the exception of rhodamine B adsorption by monoclinic crystals. The weakest adsorption was observed for the cationic dye, rhodamine B, whereas dianionic dyes, eosin, rose bengal, and erythrosin were strongly adsorbed on the protein surface. The adsorption capacities of the crystals for the dyes were found to depend on both charge and hydrophobicity of the dye, reflecting the heterogeneous character of the lysozyme pore surface. The adsorption affinity of the crystals for the dyes was a function of the dyes' hydrophobicity. Furthermore, the crystal morphology was identified as an additional factor determining capacity and affinity for dye adsorption. Differences between crystals prepared in the presence of the same precipitant were lower than between morphologies prepared with different precipitants.     

Cationic Zr-based metal-organic framework via post-synthetic alkylation for selective adsorption and separation of anionic dyes

Adsorption and separation of toxic organic dyes are of great importance in wastewater treatment and dye recycling. In this work, cationic metal-organic framework MIL-140C–2NMe⁺ with triangular hydrophobic channels was prepared in which methyl groups were added to the pyridyl sites of the ligand [2,2'-bipyridine]-5,5'-dicarboxylic acid (H₂bpydc) via post-synthetic alkylation reaction. MIL-140C–2NMe⁺ can be used as an efficient adsorbent for the selective adsorption and separation of anionic dyes in the aqueous mixture of cationic/anionic dyes. Specifically, the adsorption capacities of MIL-140C–2NMe⁺ for anionic methyl orange can reach 310 mg/g in 10 min. With a facile doctor-blading process, we have also polymerized the MIL-140C–2NMe⁺ nanocrystals and polyvinylidene fluoride (PVDF) polymer to fabricate a flexible and self-supporting mixed matrix membrane (MMM), which can selectively capture and separate the anionic organic dyes from the binary dye mixtures.     

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.     

Bifunctional Cage‐Type Cubic Mesoporous Silica SBA‐1 Nanoparticles for Selective Adsorption of Dyes

Bifunctional SBA‐1 mesoporous silica nanoparticles (MSNs) with carboxylic acid and amino groups (denoted as CNS‐10‐10) have been successfully synthesized, characterized, and employed as adsorbents for dye removal. Adsorbent CNS‐10‐10 shows high affinity towards cationic and anionic dyes in a wide pH range, and exhibits selective dye removal of a two‐dye mixture system of cationic methylene blue and anionic eosin Y. By changing the pH of the medium, the selectivity of the adsorption behavior can be easily modulated. For comparison purposes, the counterparts, that is, pure silica SBA‐1 MSNs (CS‐0) and those with either carboxylic acid or amino functional groups (denoted as CS‐10 and NS‐10, respectively) were also prepared to evaluate their dye‐adsorption behaviors. As revealed by the zeta‐potential measurements, the electrostatic interaction between the adsorbent surface and the dye molecule plays an important role in the adsorption mechanism. Adsorbent CNS‐10‐10 can be easily regenerated and reused, and maintains its adsorption efficiency up to 80 % after four cycles.     

Hydrophobic effect for anionic dye - cationic surfactant interaction in aqueous and mixed solvent

Abstract

The interaction between anionic dyes [Reactive Orange 122 (R.O 122), Reactive Blue 19 (R.B 19), Reactive Violet 5 (R.V 5) and Acid Green 20 (A.G 20)] with cationic surfactant cetyltrimethylammoniun bromide (CTAB) has been investigated by spectrophotometry and conductance technique. The used dyes are characterized by tautomeric behavior which affects the mechanism of the interaction. Various parameters such as dye structure, surfactant composition, solvent composition, temperature and pH of the medium were studied. The spectral data were applied for calculating the binding constant between dye and surfactant (K_b), fraction of micellization (?_mic), and standard free energy change of binding (ΔG°_b) in 0,10,20 and 30 v/v % acetonitile (AN). Conductance technique was constructed to estimate the ion pairing constant (K_a) at different temperatures and v/v % AN. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for ion pair formation were evaluated. The role of hydrophobic and electrostatic effect on dye-surfactant interaction was discussed.     

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.     

Aggregation and adsorption of reactive dyes in the presence of an anionic surfactant on mesoporous aminopropyl silica

A surface tension technique was used to determine the critical aggregation concentration (cac) of a yellow and a red dye in relation to the presence of the anionic surfactant sodium dodecylbenzene sulfonate (DBS) and to temperature changes in buffered aqueous solutions. The cac values of the yellow dye increase from 25 to 45 degrees C (from 41.37 to 50.32 mg L-1) and decrease from 45 to 55 degrees C (from 50.32 to 38.72 mg L-1). The cac values for the red dye/DBS aggregates decrease (from 124.52 to 88.50 mg L-1) from 25 to 55 degrees C. Adsorption of the two dyes onto a mesoporous aminopropyl silica (Sil-NH2) was also studied. The adsorption of the yellow dye increases with an increase in temperature from 25 to 55 degrees C. In the presence of DBS the adsorption on Sil-NH2 for the yellow dye decreases, and for the red dye increases from 25 to 55 degrees C. Adsorptions occurred below and above the cac of the anionic dyes/DBS aggregates. Adsorption of the dyes onto Sil-NH2 fitted well to the Langmuir, Freundlich, and Redlich-Peterson adsorption models. However, in the presence of DBS, only the Freundlich model fit the experimental adsorption data at low dye concentrations (less than 400 mg L-1). In this case, the Redlich-Peterson model was only fitted to the red dye adsorption data. The magnitude of the Dubinin-Radushkevich energetic parameters (E, from 7.00 to 15.00 kJ mol-1) indicates that the adsorption of the dyes onto Sil-NH2, in the absence and in the presence of DBS, is controlled by water adsorbed/dye in solution ion-exchange interactions. It is observed that the values of DeltaadsH are positive for both dyes and the values are quite similar to each other. The exception is the adsorption of the yellow dye in the presence of DBS, which is slightly exothermic. The DeltaadsG values are all negative. However, the interactions of the dyes with Sil-NH2 silica are more spontaneous in the presence of the surfactant. The positive adsorption entropy values (DeltaadsS) for the interaction of the dyes suggest that entropy is a driving force of the dye adsorptions. However, the entropic contribution is higher for the adsorptions in the presence of DBS. It was suggested that the chemical structures of the dyes play an important role in the formation of the dye/DBS aggregates and in dye adsorption onto the aminopropyl silica.     

Terpyridine-based smart organic-inorganic hybrid gel as potential dye-adsorbing agent for water purification

A terpyridine-based organic-inorganic hybrid gelator possessing triethoxylsilane moiety was synthesized and its adsorption capacity for aromatic dyes in the absence and the presence of metal ions such as Zn²⁺ and Cu²⁺ was measured by UV-vis spectroscopy. From aqueous solutions of dyes, the hybrid gel, in the absence of metal ions, adsorbed 97.4% for basic blue 41, 94.2% for crystal violet, and 41.5% for bromocresol green. When metal ion was present, the adsorption capacity of dried hybrid gel 1 for the anionic dye bromocresol green significantly increased due to the enhanced electrostatic interaction between cationic gel and anionic dye. Thus, this hybrid gel can efficiently adsorb various toxic dyes in water.     

Kinetic and calorimetric study of the adsorption of dyes on mesoporous activated carbon prepared from coconut coir dust

Mesoporous activated carbon has been prepared from coconut coir dust as support for adsorption of some model dye molecules from aqueous solutions. The methylene blue (MB) and remazol yellow (RY) molecules were chosen for study of the adsorption capacity of cationic and anionic dyes onto prepared activated carbon. The adsorption kinetics was studied with the Lagergren first- and pseudo-second-order kinetic models as well as the intraparticle diffusion model. The results for both dyes suggested a multimechanism sorption process. The adsorption mechanisms in the systems dyes/AC follow pseudo-second-order kinetics with a significant contribution of intraparticle diffusion. The samples simultaneously present acidic and basic sites able to act as anchoring sites for basic and acidic dyes, respectively. Calorimetric studies reveal that dyes/AC interaction forces are correlated with the pH of the solution, which can be related to the charge distribution on the AC surface. These AC samples also exhibited very short equilibrium times for the adsorption of both dyes, which is an economically favorable requisite for the activated carbon described in this work, in addition to the local abundance of the raw material.     

Kinetic and equilibrium adsorption of methylene blue and remazol dyes onto steam-activated carbons developed from date pits

Steam-activated carbons DS2 and DS5 were prepared by gasifying 600 °C-date pits carbonization products with steam at 950 °C to burn-off = 20 and 50%, respectively. The textural properties of these carbons were determined from the nitrogen adsorption at ?196 °C. The chemistry of the carbon surface was determined from the surface pH and from neutralization of the surface carbon–oxygen groups of basic and acidic type. The kinetic and equilibrium adsorption of MB and RY on DS2 and DS5 was determined at 27 and 37 °C and at initial sorption solution pH 3–7.DS2 and DS5 have expanded surface area, large total pore volume and contain both micro and mesoporosity. They have on their surface basic and acidic groups of different strength and functionality. This enhanced the sorption of the cationic dye (MB) and of the anionic dye (RY). The adsorption of MB and RY on DS2 and DS5 involves intraparticle diffusion and followed pseudo-second order kinetics. The adsorption isotherms were applicable to the Langmuir isotherm and high monolayer capacities for MB and RY dyes were evaluated indicating the high efficiencies of the carbons for dye adsorption.     

pH DEPENDENCE OF SENSITIZED PHOTOOXIDATION IN MICELLAR ANIONIC AND CATIONIC SURFACTANTS, USING THIAZINES DYES

Abstract— Our study of the kinetics of sensitized photooxidation, as a function of pH in anionic micellar systems using cationic dyes as sensitizers, shows that adsorption of the dye slows the protonation step of his triplet state. This observation has important implicaticins in interpretation of results in the so-called photodynamic effect in biological systems: using cationic dyes as sensitizers the rate of photooxidation for the same pH is different depending whether or not the medium allows adsorption of the dye.     

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.