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.     

Optimization of methylene blue removal from aqueous solutions using activated carbon derived from coffee ground pyrolysis: A response surface methodology (RSM) approach for natural and cost-effective adsorption

This study aimed to examine the impact of operational factors on the adsorption capacity of methylene blue (MB) using a natural and cost-effective adsorbent, activated carbon from coffee grounds (CAP). The three-factor Box-Behnken design of the response surface methodology (RSM) was employed to optimize this economically viable process with maximum efficiency. Through extensive experiments, the factors influencing the adsorption process were identified, their interactions were measured, and a mathematical model was developed. The experiment evaluated the quantity of MB adsorbed by CAP based on pH (2.5–10), initial MB concentration (10–100 mg/L), and CAP adsorbent amount (0.05–0.1 g/L). The results revealed that both concentration and mass significantly influenced the decoloration enhancement. Optimal conditions for achieving a 91 % degradation efficiency were determined as 0.05 g/L adsorbent weight, 100 mg/L dye concentration, and pH 2.5, with a desirability score of approximately 0.986, aligning closely with the predictions of the BBD model. In conclusion, this research addresses a research gap by demonstrating the high effectiveness of the CAP adsorbent in removing dyes from textiles.     

Removal of basic dye methylene blue from aqueous solutions using sawdust and sawdust coated with polypyrrole

This research deals with the application of wood sawdust obtained from walnut and its polypyrrole (PPy) coated form for the removal of methylene blue (MB) from aqueous solutions. MB, a typical cationic dye, was used as a test probe. Coating of sawdust was carried out chemically via direct addition of chemical oxidant (FeCl₃) on the sawdust which was previously soaked in monomer solution (0.2 M pyrrole). Adsorption experiments were carried out using both batch and fixed bed column systems. The effects of different system variables such as adsorbent dose, initial dye concentration, pH of test solution, contact time and breakthrough curves were studied. In order to find out the possibility of reuse, desorption study was also carried out in this investigation. It was found that both SD and PPy/SD are efficient and cost-effective adsorbents for the removal of MB dye from aqueous solutions. The collected data in this research indicate that compared with PPy/SD, adsorption of MB by SD is not a very pH dependent process, at least from pH 4 to 10. Higher sorption percentage of MB is obtained for PPy/SD at alkaline pHs.     

Cellulose nanocrystals as promising adsorbents for the removal of cationic dyes

Cellulose nanocrystals (CNCs) prepared from cellulose fibre via sulfuric acid hydrolysis was used as an adsorbent for the removal of methylene blue (MB) from aqueous solution. The effects of pH, adsorbent dosage, temperature, ionic strength, initial dye concentration were studied to optimize the conditions for the maximum adsorption of dye. Adsorption equilibrium data was fitted to both Langmuir and Freundlich isotherm models, where the Langmuir model better described the adsorption process. The maximum adsorption capacity was 118 mg dye/g CNC at 25 °C and pH 9. Calculated thermodynamic parameters, such as free energy change (ΔG = ?20.8 kJ/mol), enthalpy change (ΔH = ?3.45 kJ/mol), and entropy change (ΔS = 0.58 kJ/mol K) indicates that MB adsorption on CNCs is a spontaneous exothermic process. Tunability of the adsorption capacity by surface modification of CNCs was shown by oxidizing the primary hydroxyl groups on the CNC surface with TEMPO reagent and the adsorption capacity was increased from 118 to 769 mg dye/g CNC.     

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.     

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.     

Adsorption studies on the removal of Vertigo Blue 49 and Orange DNA13 from aqueous solutions using carbon slurry developed from a waste material

Waste material (carbon slurry), from fuel oil-based generators, was used as adsorbent for the removal of two reactive dyes from synthetic textile wastewater. The study describes the results of batch experiments on removal of Vertigo Blue 49 and Orange DNA13 from synthetic textile wastewater onto activated carbon slurry. The utility of waste material in adsorbing reactive dyes from aqueous solutions has been studied as a function of contact time, temperature, pH, and initial dye concentrations by batch experiments. pH 7.0 was found suitable for maximum removal of Vertigo Blue 49 and Orange DNA13. Dye adsorption capacities of carbon slurry for the Vertigo Blue 49 and the Orange DNA13 were 11.57 and 4.54 mg g(-1) adsorbent, respectively. The adsorption isotherms for both dyes were better described by the Langmuir isotherm. Thermodynamic treatment of adsorption data showed an exothermic nature of adsorption with both dyes. The dye uptake process was found to follow second-order kinetics.     

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.     

Numerical investigations of response surface methodology for organic dye adsorption onto Mg-Al LDH -GO Nano Hybrid: An optimization,kinetics and isothermal studies

We developed Mg-Al LDH intercalated with NO₃^- decorated Graphene Oxide nanohybrid with positive cationic textile dye adsorption, such as methylene blue. Contact time, initial dye concentration, and pH were among the independent variables used in the study. The Response Surface Model (RSM) was used to optimise and describe the interdependencies of the different variables. The method was evaluated using the Box-Behnken design (BBD). A second-order polynomial model was used to understand the experimental results, and the effectiveness of the chosen model was verified by its strong agreement in determination coefficient values. The adsorption results suited the best for the Langmuir isotherm than the D-R and Freundlich isotherms, resulting in efficient adsorption of 187.62 ?mg/g, proving LDH-GO is an effective dye adsorbent. Simultaneously, the kinetics were based on the pseudo-second-order model, and additional kinetic factors such as Elovich, pseudo-first-order, and intra-particular diffusion were examined. According to Thermodynamic studies, the adsorption process is spontaneous, which is exothermic and characterised by increased randomness. According to a regeneration test, even after four cycles, 37% of the removal efficiency for MB can be achieved. Based on this report, these materials can be used as an adsorbent to remove the dye.     

Utilization of Waste Biomass (Kitchen Waste) Hydrolysis Residue as Adsorbent for Dye Removal: Kinetic,Equilibrium, and Thermodynamic Studies

Kitchen waste hydrolysis residue (KWHR), which is produced in the bioproduction process from kitchen waste (KW), is usually wasted with potential threats to the environment. Herein, experiments were carried out to evaluate the potential of KWHR as adsorbent for dye (methylene blue, MB) removal from aqueous solution. The adsorbent was characterized using FT-IR and SEM. Adsorption results showed that the operating variables had great effects on the removal efficiency of MB. Kinetic study indicated pseudo-second-order model was suitable to describe the adsorption process. Afterwards, the equilibrium data were well fitted by using Langmuir isotherm model, suggesting a monolayer adsorption. The Langmuir monolayer adsorption capacity was calculated to be 110.13 mg/g, a level comparable to some other low-cost adsorbents. It was found that the adsorption process of MB onto KWHR was spontaneous and exothermic through the estimation of thermodynamic parameters. Thus, KWHR was of great potential to be an alternative adsorbent material to improve the utilization efficiency of bioresource (KW) and lower the cost of adsorbent for color treatment.     

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.     

Review on recent advances of carbon based adsorbent for methylene blue removal from waste water

The growth in textile and printing industries proven detrimental to the aquatic environment as the industrial waste containing dye seeped into the ecosystem. A high concentration of dye in water possess negative impacts on water ecosystem and harmful to human health. Removal of methylene blue (MB) dye from industrial waste via adsorption pathway has been widely investigated that promised high efficiency of MB removal. This review will summarize researches published from 2008 to 2019 on the removal of MB using carbon adsorbent with focus will be given on the synthesis and modification of carbon-based materials, and the structural properties influencing the performance of MB adsorption. Summary on the type of material used for the synthesis of carbon materials (activated carbon and biochar) will be included from utilization of the naturally occurring carbon sources such as polymers, biomasses and biowastes, and also sucrose and hydrocarbon gases. Modification of carbon materials such as chemical activation and physical activation; surface grafting to form functionalized surfaces; deposition with metal and magnetic nanoparticles via impregnation; and manufacturing of carbon composites will be discussed on the effects to promote MB adsorption and desorption. Another type of carbon adsorbents such as porous carbon; graphitic carbons including graphite, graphene, graphene oxide, and carbon nitride (g-C₃N₄); and finally nanocarbon in the form of nanotube, nanorod and nanofiber; will be included in the review with details on the synthesis method and the correlation between structural properties and adsorption activity. The regeneration process to increase the life cycle of carbon adsorbent will also be discussed based on two regeneration pathway i.e. a thermal degradation and desorption on MB. Finally the thermodynamics, kinetics, and the adsorption models of MB on carbon adsorbent will be discussed in this review.     

Adsorption of reactive dyes on titania-silica mesoporous materials

This paper presents a study on the adsorption of two basic dyes, methylene blue (MB) and rhodamine B (RhB), from aqueous solution onto mesoporous silica-titania materials. The effect of dye structure, adsorbent particle size, TiO(2) presence, and temperature on adsorption was investigated. Adsorption data obtained at different solution temperatures (25, 35, and 45 degrees C) revealed an irreversible adsorption that decreased with the increment of T. The presence of TiO(2) augmented the adsorption capacity (q(e)). This would be due to possible degradation of the dye molecule in contact with the TiO(2) particles in the adsorbent interior. The adsorption enthalpy was relatively high, indicating that interaction between the sorbent and the adsorbate molecules was not only physical but chemical. Both Langmuir and Freundlich isotherm equations were applied to the experimental data. The obtained parameters and correlation coefficients showed that the adsorption of the two reactive dyes (MB and RhB) on the adsorbent systems at the three work temperatures was best predicted by the Langmuir isotherm, but not in all cases. The kinetic adsorption data were processed by the application of two simplified kinetic models, first and second order, to investigate the adsorption mechanism. It was found that the adsorption kinetics of methylene blue and rhodamine B onto the mesoporous silica-titania materials surface under different operating conditions was best described by the first-order model.     

Partially carboxymethylated cotton dust waste for sorption of textile wastewater coloured with the cationic dye Basic Blue 41 as a model: synthesis,regeneration and biodegradability

The removal of residual dyes in coloured textile wastewaters is mandatory, and a significant portion of the dyes used are cationic. Textile factories mainly process cotton yarns, and 8 % of this virgin feedstock is lost as cotton dust waste (CDW). Using factorial experimental design, this dust was derivatised with monochloroacetic acid (MCAA) to produce a partially carboxymethylated cellulose (CM^?-CDW) with NaOH, MCAA and isopropanol for the retention of Basic Blue 41 dye (BB 41) (column and batch), and biodegradability was investigated. The dye retention efficiency was examined with additional experiments varying the initial concentration, contact time and addition of salts. Heteronuclear multiple bonding correlation-nuclear magnetic resonance confirmed the covalent insertion of CM^? groups in the cellulosic fibres. The selected matrix provided a dye sorption of 58.33 (column) and 64.50 mg/g (batch). The Langmuir isotherm was a good fit to the sorption data. The efficiency of uptake of BB 41 was predominantly dictated by the concentration of alkali in the matrix synthesis. Biodegradability by cellulases was similar when using uncharged and dye-charged matrices. The latter were fully regenerated by washing in dilute acid. Retention was proportional to the initial dye concentration and the contact time required to reach equilibrium, which was longer for higher dye concentrations. The addition of 10 mmol/l NaCl decreased BB 41 retention by 50 %. Therefore, CM^?-CDW proved effective for the removal of the cationic dye BB 41 and thus represents an important alternative in the treatment of coloured textile effluents.     

The removal of textile dyes by diatomite earth

The adsorption of some textile dyes by diatomite was investigated using Sif Blau BRF (SB), Everzol Brill Red 3BS (EBR), and Int Yellow 5GF (IY). Adsorption of these textile dyes onto diatomite earth samples was studied by batch adsorption techniques at 30 degrees C. The adsorption behavior of textile dyes on diatomite samples was investigated using a UV-vis spectrophotometric technique. The effect of particle size of diatomite, diatomite concentration, the effect of initial dye concentrations, and shaking time on adsorption was investigated. Adsorption coverage over the surface of diatomite was studied using two well-known isotherm models: Langmuir's and Freundlich's. These results suggest that the dye uptake process mediated by diatomite has a potential for large-scale treatment of textile mill discharges. According to the equilibrium studies, the selectivity sequence can be given as IY > SB > EBR. Values of the removal efficiency of the dyes ranged from 28.60 to 99.23%. These results show that natural diatomite holds great potential to remove textile 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.     

Mechanistic insights into methylene blue removal via olive stone-activated carbon: A study on surface porosity and characterization

Global attention is increasingly focused on the adverse health and environmental impacts of textile dyes, marking the necessity for effective and sustainable dye remediation strategies in industrial wastewater. This study introduces a novel, eco-friendly activated carbon produced from olive stones (OLS), a readily available by-product of the olive oil industry. The OLS was chemically activated with H₃PO₄ and KOH, creating two materials: OLS-P and OLS-K, respectively. These were then utilized as cost-effective adsorbents for the removal of methylene blue (MB) dye. The activated materials were characterized via X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), iodine number, and pHpzc analysis, with the zero-point charge determined as approximately pH 1 for OLS-P and pH 8 for OLS-K. Batch adsorption experiments conducted at various temperatures revealed that adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Temperature was found to significantly impact adsorption performance, with OLS-K demonstrating a substantial increase in adsorption capacity (q_e) from 6.27 mg/g at 23˚C to 94.7 mg/g at 32 ˚C. Conversely, OLS-P displayed a decrease in q_e from 16.78 mg/g at 23 ˚C to 3.67 mg/g at 32 ˚C as temperature increased. The study highlights the potential of KOH-treated olive stones as a promising, cost-efficient adsorbent for methylene blue remediation from wastewater.     

Enhanced adsorption performance of a novel Fe‐Mn‐Zr metal oxide nanocomposite adsorbent for anionic dyes from binary dye mix: Response surface optimization and neural network modeling

A novel adsorbent, Fe‐Mn‐Zr metal oxide nanocomposite was synthesized and investigated for removal of methyl orange (MO) and eosin yellow (EY) dyes from binary dye solution. The magnetic nanocomposite has shown surface area of 143.01 m²/g and saturation magnetization of 15.29 emu/g. Optimization was carried out via response surface methodology (RSM) for optimizing process variables, and optimum dye removal of 99.26% and 99.55% were obtained for MO and EY dye, respectively with contact time 62 min, adsorbent dose 0.45 g/l, initial MO concentration 11.0 mg/l, and initial EY concentration 25.0 mg/l. A feed forward back propagation neural network model has shown better prediction ability than RSM model for predicting MO and EY dye removal (%). Adsorption process strictly follows Langmuir isotherm model, and enhanced adsorption capacities of 196.07 and 175.43 mg/g were observed for MO and EY dye, respectively due to synergistic effects of physicochemical properties of trimetal oxides. Surface adsorption and pore diffusions are the mechanisms involved in the adsorption as revealed from kinetic studies.     

Selective and effective adsorption of methyl blue by barium phosphate nano-flake

We report the synthesis of barium phosphate (BP) nano-flake and its adsorption behavior to methyl blue (MB) in aqueous solution. The as-obtained BP nano-flake revealed pure rhombohedral crystal structure. The adsorption capacity of MB onto BP reached 1500mgg(-1). The adsorption equilibrium results fitted well with the Freundlich isotherm model. The adsorption process took less than 30min to reach equilibrium. The adsorption kinetics was elucidated by the pseudo-second-order kinetic equation. It followed 2-stage and 3-stage intra-particle diffusion models for the low and high concentration of dye solutions, respectively. The adsorption of MB using the BP nano-flake was highly selective, compared with the adsorption of other dyes. The interactions between MB and BP were mainly the ionic interaction and hydrogen bonds, which were confirmed by the X-ray photoelectron spectroscopic results and the density functional theory calculations. The BP nano-flake revealed less than 5% decrease in adsorption amount when it was recycled and reused five times. The present work shows that the BP nano-flake is promising for practical applications in MB removal from aqueous solutions.     

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.