Optimizing adsorptive removal of malachite green and methyl orange dyes from simulated wastewater by Mn‐doped CuO‐Nanoparticles loaded on activated carbon using CCD‐RSM: Mechanism,regeneration, isotherm,kinetic, and thermodynamic studies

In the present work, Mn‐doped CuO‐NPs‐AC was prepared by a simple method, characterized using various techniques such as FESEM, EDX, XRD, PSD, and pH_pzc and finally used for the adsorption of malachite green (MG) and methyl orange (MO) in a number of single and binary solutions. A series of adsorption experiments were conducted to investigate and optimize the influence of various factors (such as different pH, concentration of MG and MO, adsorbent mass, and sonication time) on the simultaneous adsorption of MG and MO using response surface methodology. Under optimal conditions of pH 10, adsorbent dose of 0.02 g, MG concentration of 30 mg L^?1, MO concentration of 30 mg L^?1, and sonication time of 4.5 min at room temperature, the maximum predicted adsorption was observed to be 100.0%, for both MG and MO, showing that there is a favorable harmony between the experimental data and model predictions. The adsorption isotherm of MO and MG by Mn‐doped CuO‐NPs‐AC could be well clarified by the Langmuir model with maximum adsorption capacity of 320.69 mg g^?1 and 290.11 mg g^?1 in the single solution and 233.02 mg g^?1 and 205.53 mg g^?1 in the binary solution by 0.005 g of adsorbent mass for MG and MO, respectively. Kinetic studies also revealed that both MG and MO adsorption were better defined by the pseudo‐second order model for both solutions. In addition, the thermodynamic constant studies disclosed that the adsorption of MG and MO was likely to be influenced by a physisorption mechanism. Eventually, the reusability of the Mn‐doped CuO‐NPs‐AC after six times showed a reduction in the adsorption percentage of MG and MO.     

Synthesis and characterization of antibacterial chromium iron oxide nanoparticle‐loaded activated carbon for ultrasound‐assisted wastewater treatment

The aim of this study was to evaluate the surface adsorption capacity of CrFeO₃ nanoparticle‐loaded activated carbon (CrFeO₃‐NPs–AC) for the removal of a cationic dye (methyl violet, MV). CrFeO₃‐NPs were hydrothermally synthesized and loaded on AC followed by characterization using X‐ray diffraction, field‐emission scanning electron microscopy and energy‐dispersive and Fourier transform infrared spectroscopies. The CrFeO₃‐NPs were tested for in vitro antibacterial activities against Gram‐positive (Staphylococcus aureus) and Gram‐negative (Pseudomonas aeruginosa) bacteria. Minimum inhibitory and minimum bactericidal concentrations of CrFeO₃‐NPs–AC were obtained to be 50 and 100 μg ml^?1, respectively, against S. aureus and 25 and 50 μg ml^?1 against P. aeruginosa. These results indicated the antibacterial properties of CrFeO₃‐NPs–AC. To investigate the adsorption process, several systematic experiments were designed by varying parameters such as adsorbent mass, pH, initial MV concentration and sonication time. The adsorption process was modelled and the optimal conditions were determined to be 0.013 g, 7.4, 15 mg l^?1 and 8 min for adsorbent mass, pH, MV concentration and sonication time, respectively. The real experimental data were found to be efficiently explained by response surface methodology and genetic algorithm model. Kinetic studies for MV adsorption showed rapid sorption dynamics described by a second‐order kinetic model, suggesting a chemisorption mechanism. Then, the experimental equilibrium data obtained at various concentrations of MV and adsorbent masses were fitted to conventional Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Dye adsorption equilibrium data were fitted well to the Langmuir isotherm. From the Langmuir model, the maximum monolayer capacity was calculated to be 65.67 mg g^?1 at optimum adsorbent mass.     

Zinc oxide nanorod‐loaded activated carbon for ultrasound‐assisted adsorption of safranin O: Central composite design and genetic algorithm optimization

This paper focuses on the development of an effective methodology to obtain the optimum ultrasonic‐assisted removal of a dye, safranin O (SO), under optimum conditions that maximize the removal percentage, using ZnO nanorod‐loaded activated carbon (ZnO‐NRs‐AC) in aqueous solution. Central composite design coupled with genetic algorithm was used for parameter optimization. The effects of variables such as pH, initial dye concentration, mass of ZnO‐NRs‐AC and sonication time were studied. The interactive and main effects of these variables were evaluated using analysis of variance. The structural and physicochemical properties of the ZnO‐NRs‐AC adsorbent were investigated using field emission scanning electron microscopy and X‐ray diffraction. Adsorption equilibrium data were fitted well with the Langmuir isotherm and the maximum monolayer capacity was found to be 32.06 mg g^?1. Studies of the adsorption kinetics of the SO dye showed a rapid sorption dynamic with a ^pseudo‐second‐order kinetic model, suggesting a chemisorption mechanism.     

Optimization of cadmium adsorption from aqueous solutions by functionalized graphene and the reversible magnetic recovery of the adsorbent using response surface methodology

Novel functionalized graphene adsorbent was prepared and characterized using different techniques. The prepared adsorbent was applied for the removal of cadmium ions from aqueous solution. A response surface methodology was used to evaluate the simple and combined effects of the various parameters, including adsorbent dosage, pH, and initial concentration. Under the optimal conditions, the cadmium removal performance of 70% was achieved. A good agreement between experimental and predicted data in this study was observed. The experimental results revealed of cadmium adsorption with high linearity follow Langmuir isotherm model with maximum adsorption capacity of 502 mg g^?1, and the adsorption data fitted well into pseudo‐second order model. Thermodynamic studies showed that adsorption process has exothermic and spontaneous nature. The recommended optimum conditions are: cadmium concentration of 970 mg L^?1, adsorbent dosage of 1 g L^?1, pH of 6.18, and T = 25 °C. The magnetic recovery of the adsorbent was performed using a magnetic surfactant to form a noncovalent magnetic functionalized graphene. After magnetic recovery of the adsorbent both components (adsorbent and magnetic surfactant) were recycled by tuning the surface charges through changing the pH of the solution. Desorption behavior studied using HNO₃ solution indicated that the adsorbent had the potential for reusability.     

Simultaneous removal of Cu2+ and Cr3+ ions from aqueous solution based on Complexation with Eriochrome cyanine‐R and derivative spectrophotometric method

TiO₂ nanoparticles deposited on activated carbon (TiO₂–NP–AC) was prepared and characterized by XRD and SEM analysis. Subsequently, simultaneous ultrasound‐assisted adsorption of Cu²⁺ and Cr³⁺ ions onto TiO₂‐NPs‐AC after complexation via eriochrome cyanine R (ECR) has been investigated with UV–Vis and FAA spectrophotometer. Spectra overlapping of the ECR‐Cu and ECR‐Cr complex was resolve by derivative spectrophotometric technique. The effects of various parameters such as initial Cu²⁺ (A) and Cr³⁺ (B) ions concentrations, TiO₂‐NPs‐AC mass (C), sonication time (D) and pH (E) on the removal percentage were investigated and optimized by central composite design (CCD). The optimize conditions were set as: 4.21 min, 0.019 mg, 20.02 and 13.22 mg L^?1 and 6.63 for sonication time, TiO₂–NP–AC mass, initial Cr³⁺ and Cu²⁺ ions concentration and pH, respectively. The experimental equilibrium data fitting to Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models show that the Langmuir model is a good and suitable model for evaluation and the actual behavior of adsorption process and maximum adsorption capacity of 105.26 and 93.46 mg g^?1 were obtained for Cu²⁺ and Cr³⁺ ions, respectively. Kinetic evaluation of experimental data showed that the adsorption processes followed well pseudo second order and intraparticle diffusion models.     

Effective removal of 2,4,6‐trinitrophenol over hexagonal metal–organic framework NH2‐MIL‐88B(Fe)

A nanostructured organic–inorganic framework, hexagonal NH₂‐MIL‐88B, has been prepared through a facile one‐pot reflux reaction and then it was characterized using various techniques. The as‐prepared sample with high specific surface area (414 m² g^?1) showed excellent adsorption for 2,4,6‐trinitrophenol (TNP) in the liquid phase. Detailed studies of the adsorption kinetics, adsorption mechanism, adsorption isotherm, activation energy and various thermodynamic parameters were conducted. The adsorption mechanism of NH₂‐MIL‐88B for TNP may be ascribed to hydrogen bond interaction, and the complexation between ─OH in TNP and unsaturated Fe(III) on the surface of NH₂‐MIL‐88B. The maximum adsorption capacity of NH₂‐MIL‐88B for TNP based on the Langmuir isotherm was 163.66 mg g^?1. The as‐prepared NH₂‐MIL‐88B adsorbent seems to be a promising material in practice for TNP removal from aqueous solution.     

Comparative study of acid yellow 119 adsorption onto activated carbon prepared from lemon wood and ZnO nanoparticles loaded on activated carbon

Activated carbon from lemon wood (AC) and ZnO nanoparticles loaded on activated carbon (ZnO‐NP‐AC) were prepared and their efficiency for effective acid yellow 199 (AY 199) removal under various operational conditions was investigated. The dependence of removal efficiency on variables such as AY 199 concentration, amount of adsorbent and contact time was optimized using response surface methodology and Design‐Expert. ZnO nanoparticles and ZnO‐NP‐AC were studied using various techniques such as scanning electron microscopy, X‐ray diffraction and energy‐dispersive X‐ray analysis. The optimum pH was studied using one‐at‐a‐time method to achieve maximum dye removal percentage. Small amounts of the proposed adsorbents (0.025 and 0.025 g) were sufficient for successful removal of AY 199 in short times (4.0 and 4.0 min) with high adsorption capacity (85.51 and 116.29 mg g^?1 for AC and ZnO‐NPs‐AC, respectively). Fitting the empirical equilibrium data to several conventional isotherm models at optimum conditions indicated the appropriateness of the Langmuir model with high correlation coefficient (0.999 and 0.978 for AC and ZnO‐NPs‐AC, respectively) for representation and explanation of experimental data. Kinetics evaluation of experiments at various time intervals revealed that adsorption processes can be well predicted and fitted by pseudo‐second‐order and Elovich models. This study revealed that the combination of ZnO nanoparticles and AC following simple loading led to significant improvement in the removal process in short adsorption time which was enhanced by mixing the media via sonication.     

Surface‐initiated atom transfer radical polymerization of a new rhodanine‐based monomer for rapid magnetic removal of Co(II) ions from aqueous solutions

The present study reports synthesis and characterization of a new acrylamide‐based monomer containing rhodanine moiety, N‐3‐amino‐thiazolidine‐4‐one‐acrylamide (ATA). Poly(ATA)‐grafted magnetite nanoparticles (poly(ATA)‐g‐MNPs) were prepared using surface‐initiated atom transfer radical polymerization of the monomer on Fe₃O₄ nanoparticles. The grafted nanoparticles were characterized by Fourier transform infrared analysis, scanning electron microscopy, X‐ray diffraction, and vibrating sample magnetometry. The amount of the grafted polymer was 209 mg g⁻¹, as calculated from thermogravimetric analysis experiment. The capability of poly(ATA)‐g‐MNPs to remove Co(II) cations was shown under optimal conditions of contact time, pH, adsorbent dosage, and initial Co(II) concentration. About 86% of the Co(II) cations were removed over 7 minutes. The adsorption kinetics obeyed the pseudo–second‐order kinetic equation, and the Langmuir isotherm model best described the adsorption isotherm with a maximum adsorption capacity of 3.62 mg g⁻¹. The thermodynamic investigation showed spontaneous nature of the adsorption process (ΔG = −2.90 kJ mol⁻¹ at 25°C ± 1°C). In addition, the poly(ATA)‐g‐MNPs were regenerated by simply washing with an aqueous 0.1M HCl solution. The study of the reusability of the prepared magnetic sorbent revealed that the sorbent can be reused without a significant decrease in the extraction efficiency and be recovered by 95.4% after 7 cycles. These findings suggest that the grafted nanoparticles are stable and reusable adsorbent and can be potentially applied to water treatment in efficient removal of Co(II) cations.     

Nitrate removal from aqueous solution using watermelon rind derived biochar-supported ZrO2 nanomaterial: Synthesis,characterization, and mechanism

Recently, biochar has attracted tremendous research interest for environmental applications. In this study, biochar-derived watermelon rind (WM) was produced via optimal pyrolysis at 500 °C for 2 h, and then improved the adsorption capacity by Zirconium oxide nanoparticles (ZrO₂ NPs). The WM@ZrO₂ was characterized using X-ray diffraction (XRD), Scanning electron microscopic - Energy-dispersive X-ray spectroscopy (SEM-EDS), and Fourier transform infrared (FTIR). The adsorptive capacities of synthesized ZrO₂ NPs were investigated for nitrate as a function of pH, adsorbent dosage, contact time, initial adsorbate concentration, and pyrolysis temperature in the batch experiment. The results showed that a Langmuir isotherm and a pseudo-second-order kinetics model were the best-fit for experimental nitrate data in its non-linear form as correlation coefficients (R²) were 0.985 and 0.998, respectively. The maximum adsorption capacity for the Langmuir isotherm model was 15.196 mg g^?1. The proposed mechanism, including electrostatic attraction and ligand exchange, played a dominant role in nitrate adsorption. After testing with the real domestic wastewater, the removal of nitrate for WM@ZrO₂ was achieved at 78 %, which was equivalent to the adsorption capacity of 8.1 mg g^?1 of adsorbent. Overall, the WM@ZrO₂ is proposed as a promising, effective, and environmentally friendly adsorbent in removing nitrate from an aqueous solution.     

Yolk–shell microspheres assembled from Preyssler‐type NaP5W30O11014− polyoxometalate and MIL‐101(Cr) metal–organic framework: A new inorganic–organic nanohybrid for fast and selective removal of cationic organic dyes from aqueous media

Novel inorganic–organic yolk–shell microspheres based on Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate and MIL‐101(Cr) metal–organic framework (P₅W₃₀/MIL‐101(Cr)) were synthesized by reaction of K_12.5Na_1.5[NaP₅W₃₀O₁₁₀], Cr(NO₃)₃·9H₂O and terephthalic acid under hydrothermal conditions at 200°C for 24 h. The as‐prepared yolk–shell microspheres were fully characterized using various techniques. All analyses confirmed the incorporation of the Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate into the three‐dimensional porous MIL‐101(Cr) metal–organic framework. The results revealed that P₅W₃₀/MIL‐101(Cr) demonstrated rapid adsorption of cationic methylene blue (MB) and rhodamine B (RhB) with ultrahigh efficiency and capacity, as well as achieving rapid and highly selective adsorption of MB from MB/MO (MO = methyl orange), MB/RhB and MB/RhB/MO mixtures. The P₅W₃₀/MIL‐101(Cr) adsorbent not only exhibited a high adsorption capacity of 212 mg g^?1, but also could quickly remove 100% of MB from a dye solution of 50 mg l^?1 within 8 min. The effects of some key parameters such as adsorbent dosage, initial dye concentration and initial pH on dye adsorption were investigated in detail. The equilibrium adsorption data were better fitted by the Langmuir isotherm. The adsorption kinetics was well modelled using a pseudo‐second‐order model. Also, the inorganic–organic hybrid yolk–shell microspheres could be easily separated from the reaction system and reused up to four times without any change in structure or adsorption ability. The stability and robustness of the adsorbent were confirmed using various techniques.     

Multi‐responses optimization of simultaneous adsorption of methylene blue and malachite green dyes in binary aqueous system onto Ni:FeO(OH)‐NWs‐AC using experimental design: derivative spectrophotometry method

In this research, response surface methodology (RSM) approach using Central Composite Design (CCD) coupled by derivative spectrophotometry method was applied to develop mathematical model and optimize process parameters for simultaneous adsorption of methylene blue (MB) and malachite green (MG) from aqueous solution using Ni:FeO(OH) ‐ NWs‐AC. The optimal conditions to adsorption of MB and MG in binary mixture solution from aqueous solution were found at pH 8.0, MB concentration 20 mg L^‐1, MG concentration 20 mg L^‐1, adsorbent dosage 0.033 g and contact time 40 min. At these conditions, high adsorption efficiency (99.39% and 100.0% for MB and MG, respectively) was achieved. Among experimental equilibrium, Langmuir isotherm model fitted well with maximum monolayer adsorption capacity of 28.6 and 29.8 mg g^‐1 for MB and MG, respectively. The adsorption kinetic data followed pseudo second‐order kinetics for MB and MG dyes.     

A novel green biosorbent from chitosan modified by sodium phytate for copper (II) ion removal

A novel kind of adsorbent bead was prepared from chitosan (CS) by ionic‐linked with sodium phytate (SP) and then covalent cross‐linked with epichlorohydrin (ECH) by nonsolvent‐induced phase separation. The structure of the beads was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The adsorption properties of the beads for Cu(II) ions under different adsorption conditions were investigated. The maximum adsorption capacity of Cu(II) ions was 177.1 mg g⁻¹ at the conditions of pH of 5.2, temperature of 50°C, and initial Cu(II) ion concentration of 728.3 mg L⁻¹. The adsorption isotherm of Cu(II) ions on the CS/SP/ECH beads was well correlated with the Langmuir isotherm model, and the whole adsorption process could be better followed the pseudo‐second‐order kinetic model. Moreover, the CS/SP/ECH beads still exhibited good adsorption capacity even after the 15th regeneration cycles.     

Glutaraldehyde cross-linked epoxyaminated chitosan as an adsorbent for the removal and recovery of copper(II) from aqueous media

A novel glutaraldehyde cross-linked epoxyaminated chitosan (GA-C-ENCS) prepared through chemical modification was used as an adsorbent for the removal and recovery of Cu(II) from aqueous media. The adsorbent was characterized by FTIR, SEM-EDS, ESR, TG/DTG, BET-surface area and potentiometric titration. The Cu(II) adsorption process, which was pH dependent showed maximum removal at pH 6.0. Adsorption equilibrium was achieved within 3 h. The adsorption of Cu(II) followed a reversible-first-order kinetics. The equilibrium data were evaluated using the Langmuir, Freundlich and Dubinin–Radushkevich isotherm models. The best interpretation for the equilibrium data was given by the Dubinin–Radushkevich isotherm. The adsorption capacity of the adsorbent increased from 3.11 to 3.71 mmol g⁻¹ when the temperature was increased from 20 to 50 °C. The complete removal of 20.7 mg L⁻¹ Cu(II) from electroplating industry wastewater was achieved by 0.4 g L⁻¹ GA-C-ENCS. Regeneration experiments were tried for four cycles and the results indicate a capacity loss of <7.0%.     

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.

     

Preparation of ferric nitrate–graphene nanocomposite and its adsorption of arsenic(V) from simulated arsenic‐containing wastewater

Ferric nitrate–graphene (FG) nanocomposites synthesized via the equivalent‐volume impregnation method were used for the removal of As(V) species from simulated arsenic‐containing wastewater. Effects of various factors were assessed, such as the reaction temperature, solution pH, adsorbent dosage, and reaction time. The results indicated that the As(V) removal efficiency was as high as 99%, and the concentration of arsenic‐containing wastewater after FG treatment was as low as 9.4 μg L^–1 as a result of the optimal absorption capacity and maximum specific surface area (171.766 m²/g) of this material. The equilibrium adsorption capacity of FG for As(V) was achieved in approximately 20 min, and the maximum adsorption capacity was calculated to be 112.4 mg g^–1 by Langmuir adsorption isotherm, which was higher than that of other adsorbents such as manganese‐incorporated iron(III) oxide–graphene (14.42 mg g^–1). Moreover, the removal efficiency of As(V) can be maintained above 95% under acidic and alkaline conditions. Brunauer–Emmett–Teller analysis showed that the modified FG pore structure was regular. Based on the characterizations by X‐ray diffraction, X‐ray photoelectron spectroscopy, and Fourier transform infrared, the products on the surface of the used FG were Fe(OH)₃, FeAsO₄, and other compounds, and As(V) was mainly removed by the formation of insoluble compounds and coprecipitation.     

Synthesis and characterization of SnO2/(NH4)2‐SnCl6 nanocomposites loaded on activated carbon and its application for adsorption of methylene Blue and Orange G

The present study deals with the synthesis and characterization (FE‐SEM, particle size distribution, XRD and point of zero charge) SnO₂/(NH₄)₂‐SnCl₆ nanocomposites loaded on activated carbon (SnO₂/(NH₄)₂‐SnCl₆‐NCs‐AC) and its subsequent application for the simultaneous removal of Methylene Blue (MB) and Orange G (OG) from aqueous solution. Response surface methodology (RSM) based on central composite design (CCD) give trend of influencing responses with respect to five parameters such as contact time (X₁), OG concentration (X₂), MB concentration (X₃), adsorbent mass (X₄) and pH (X₅). In later stage following recognition of significant variables and interaction, quadratic model generated which are able to predict the dyes removal in different conditions. Justification and selection of significant terms was conducted based on analysis of variance and Fisher's F‐test Optimal value of contact time, OG concentration, MB concentration, adsorbent mass and pH were set at 4.0 min, 10 mg l^?1, 20 mg L^?1, 0.015 g and 6.0, respectively, which lead to achievement of best experiment removal percentage of 97.0 and 99.5% OG and MB respectively, from their binary solutions. The whole experimental data follow pseudo‐first‐order and pseudo‐second‐order rate equations. The fitting experimental data to more available conventional model like Langmuir, Freundlich, Temkin and Dubinin‐Radushkevich isotherm models revel more ability of Langmuir model (with R² > 0.997) for explanation of system in equilibrium. The adsorption efficiency remained high even after the five cycle of reuse (99.76% and 95.56% for MB and OG, respectively).     

Analysis of the role of various biochar in the remediation of heavy metals in contaminated water and its kinetics study

Biochar prepared from agricultural wastes has gained great attention as a cost-effective treatment for metal-contaminated water. In this study, the effectiveness of corn cob and sugarcane bagasse-derived biochar for metals (Pb, Ni, and Cu) removal from an aqueous medium was examined following their physical, chemical, and structural characterization. Batch sorption experiments were carried out by employing the Langmuir and Freundlich equations. The results indicated that separation factor (R_L) values lay in the range of 0 and 1 representing the productive adsorption. The optimum dosage for metal adsorption can be recommended as 30 g L^?1. The optimum adsorption conditions were found at 6.5 and 5.5 pH, 1.5 g adsorbent dose, and at 180 min equilibrium time, for both corn cob and sugarcane bagasse biochars. At pH 6.5, adsorption capacities of Pb, Ni, and Cu were found maximum i.e., 11.34, 15.71, and 11.96 mg kg^?1 for corn cob and 8.96, 15.46, and 12 mg kg^?1, for sugarcane bagasse biochars, respectively. The metal adsorption kinetics was analyzed via four different types of the pseudo-second-order kinetic model. Moreover, the corn cob biochar showed a more pronounced activity in the removal of metals compared to sugarcane bagasse biochar. Hence, it was concluded that corncob and sugarcane bagasse-derived biochars could be utilized as economical bio-adsorbents for the heavy metals removal from wastewater.