Adsorption properties of amine modified lignin-hydrogel composite for uranyl ions: Theoretical and experimental insights

A new modified material was synthesized and characterized as ethylene diamine modified (EA) Polyacrylamide (PAA)-Lignin (L). The adsorption features of EA modified PAA-L were studied for uranyl ions. The characterization experiments were evaluated by FT-IR spectroscopic techniques, scanning electron microscopy (SEM), and PZC analysis. Adsorption of UO₂²⁺ ions as a function of concentration, pH, temperature, and time of adsorption were studied. The adsorption phenomenon of UO₂²⁺ ions onto PAA-L-EA from aqueous medium was successfully evaluated by various equilibrium models such as Langmuir, Freundlich, and Dubinin-Radushkevich (DR). The (Qe) maximum adsorption capacity values for Langmuir model was calculated as 0.792 kg mol^?1 by using experimental data. The constant values of thermodynamic parameters such as (ΔG°), (ΔH°) and (ΔS°) were calculated and it has observed that the mechanism of adsorption was found compatible with endothermic and spontaneous owing to increasing disorderliness at solution/solid system. The adsorption mechanism is compatible with Elovich and intraparticle diffusion models. The power of the interaction between modified lignin and uranyl ?on was explained in the light of Hard and Soft Acid-Base Principle.     

Preparation and adsorption properties of crosslinked polystyrene-supported low-generation diethanolamine-typed dendrimer for metal ions

Two novel chelating resins, polystyrene supported G1.0 diethanolamine-typed dendrimer (PS-DEA) and G2.0 diethanolamine-typed dendrimer (PS-(DEA)₂), were prepared by anchoring low-generations diethanolamine-typed dendrimer into crosslinked polystyrene in this paper. Fourier transform-infrared spectra (FTIR), scanning electron microscopy (SEM) and elemental analysis were employed to character their structures. The results of adsorption for metal ions showed that the resins had good adsorption capacities for Cu²⁺, Ag⁺ and Hg²⁺, especially PS-DEA for Cu²⁺. The adsorption kinetics and adsorption isotherms of PS-DEA for Cu²⁺ and PS-(DEA)₂ for Hg²⁺ were studied. The results showed that the adsorption kinetics of the two resins can be modeled by pseudo second-order rate equation wonderfully and Langmuir and Freundlich equations could well interpret the adsorption of PS-(DEA)₂ for Hg²⁺ and PS-DEA for Cu²⁺, respectively. The adsorption mechanism of the resins for Cu²⁺ was confirmed by X-ray photoelectron spectroscopy (XPS).     

Kinetics, thermodynamic and chromatographic behaviour of the uranyl ions sorption from aqueous thiocyanate media onto polyurethane foams

The retention profile of uranyl ions from aqueous thiocyanate media by polyether-type based polyurethane foams (PUFs) has been studied to gain more information regarding the mechanism of extraction. The effect of pH, shaking time, surfactant type, extraction media, temperature and analyte concentration on the retention of uranyl ions onto PUFs has been studied. It has been found that, the sorption of uranyl ions involved in the formation of a ternary complex ion associate of uranyl ion, thiocyanate and PUFs is highly dependent on these parameters. The kinetics and thermodynamics of the uranyl ions sorption have been studied in more detail. The dependency of the extraction on the parameters can be explained via a “solvent extraction,” mechanism. However, owing to the complex nature of the PUFs a dual-mode sorption mechanism involving both absorptions related to “solvent extraction” and an added component for “surface adsorption” may be operated simultaneously. Attempts for quantitative retention and recovery of the uranyl ions in tap and industrial waste water samples by the proposed PUFs columns has been carried out and satisfactory results have been obtained. The cellular structure of the PUF sorbent offer unique advantages over a conventional bulk type sorbents in rapid, versatile effective separation and/or preconcentration of uranyl ions.     

Application of Brazilian kaolinite clay as adsorbent to removal of U(VI) from aqueous solution: Kinetic and thermodynamic of cation-basic interactions

The compound N¹-[3-(trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route. The modified and natural kaolinite samples were characterized by transmission electron microscopy, scanning electron microscopic, X-ray diffraction, and nuclear magnetic nuclei of ²⁹Si and ¹³C. The well-defined peaks obtained in the ¹³C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The kinetic parameters analyzed by the Lagergren and Elovich models gave a good fit for a pseudo-second order reaction with k₂ values 16.0 and 25.1 mmol g⁻¹ min⁻¹ ranges for natural and modified kaolinite clays, respectively. The energetic effects caused by metal ion adsorption were determined through calorimetric titrations.     

Field-portable ratiometric fluorescence imaging of dual-color label-free carbon dots for uranyl ions detection with cellphone-based optical platform

Under the public spotlight, uranyl (UO₂²⁺) ions has attracted considerable attention for the extreme radioactive and chemical toxicity to ourselves and our environment. Herein, we present a simple and effective ratiometric fluorescence imaging method for the visualizing and quantitative detection UO₂²⁺ ions by cellphone-based optical platform. The sensing solution was prepared by mixing label-free red carbon dots (r-CDs) and blue carbon dots (b-CDs) together with a fixed photoluminescence intensity ratio of 4:1. When UO₂²⁺ ions were added, the fluorescence of r-CDs can be selectively quenched, while the fluorescence of b-CDs remains stable without spectral changes. With the gradually increase the amounts of UO₂²⁺ ions, the different response of dual-color CDs resulted in a signification color evolution from deep red to dark purple under the ultraviolet (UV) light illumination. Then, a cellphone-based optical platform was constructed for directly imaging the color change of the samples, and the built-in Colorpicker APP quickly output the red, green and blue (RGB) channel values of these images within one second. Interesting, there was a linear relationship between the ratio of red and blue (R/B) channel values and UO₂²⁺ ions concentration from 0 μmol/L to 30.0 μmol/L (R² = 0.92804) with the detection limit of ∼8.15 μmol/L (signal-to-noise ratio of 3). In addition, the optical platform has also been applied to the quantification of UO₂²⁺ ions in tap water and river water sample. With the advantage of low-cost, portable, easy to operation, we anticipate that this method would greatly improve the accessibility of UO₂²⁺ ions detection even in resource-limited areas.     

Sterculia foetida fruit shell based activated carbon for the effective removal of industrial effluents

In this work, Sterculia foetida fruit shells were used for the preparation of activated carbon and utilized for the removal of industrial effluent methylene blue is described. The carbon materials were prepared by washing the shells with water, dried in sunlight and subjected to heating at 700 ​°C in a muffle furnace to get the carbon material. This is divided into three portions, one is used as pristine and two portions were subjected to physical activation using steam and chemical activation using K₂CO₃. The impurities were removed by treatment with NaOH (0.1 ​M) and subsequently with HCl (0.1 M). Turbostatic structure was determined by XRD and the specific surface area was determined using BET showed 4, 1017 and 596 ​m²/g as the surface areas. Using these activated carbon materials, we have achieved 93% removal of methylene blue, found in industrial effluents.     

Field-portable ratiometric fluorescence imaging of dual-color label-free carbon dots for uranyl ions detection with cellphone-based optical platform

Under the public spotlight, uranyl (UO₂²⁺) ions has attracted considerable attention for the extreme radioactive and chemical toxicity to ourselves and our environment. Herein, we present a simple and effective ratiometric fluorescence imaging method for the visualizing and quantitative detection UO₂²⁺ ions by cellphone-based optical platform. The sensing solution was prepared by mixing label-free red carbon dots (r-CDs) and blue carbon dots (b-CDs) together with a fixed photoluminescence intensity ratio of 4:1. When UO₂²⁺ ions were added, the fluorescence of r-CDs can be selectively quenched, while the fluorescence of b-CDs remains stable without spectral changes. With the gradually increase the amounts of UO₂²⁺ ions, the different response of dual-color CDs resulted in a signification color evolution from deep red to dark purple under the ultraviolet (UV) light illumination. Then, a cellphone-based optical platform was constructed for directly imaging the color change of the samples, and the built-in Colorpicker APP quickly output the red, green and blue (RGB) channel values of these images within one second. Interesting, there was a linear relationship between the ratio of red and blue (R/B) channel values and UO₂²⁺ ions concentration from 0 μmol/L to 30.0 μmol/L (R² = 0.92804) with the detection limit of ~8.15 μmol/L (signal-to-noise ratio of 3). In addition, the optical platform has also been applied to the quantification of UO₂²⁺ ions in tap water and river water sample. With the advantage of low-cost, portable, easy to operation, we anticipate that this method would greatly improve the accessibility of UO₂²⁺ ions detection even in resource-limited areas.     

Green synthesis of loofah-based biosorbent via radiation grafting for effective removal of methylene blue

A new loofah-based biosorbent with high adsorption capacity for cationic dye was synthesized by a one-step co-radiation grafting method. The successful grafting of sodium 4-vinylbenzene sulfonate (SSS) onto loofah sponge (LFs) through electron beam radiation can significantly improve the remove capacity of methylene blue in wastewater. The biosorbent with a 409.67 mg/g of uptake capacity for methylene blue (MB), was higher than most of the loofah based adsorbents reported. FT-IR, elemental analysis, XRD, SEM and TG were used to analyze the changes in the functional group composition, element content, morphology, thermal stability of the obtained biosorbent. The pH, contact time, temperature and the effect of dosage on adsorption were also investigated. The results showed that the adsorption behavior well accorded with the pseudo-second-order kinetic and Langmuir adsorption model, which proved that the adsorption was a single-layered and chemisorption process. The thermodynamic parameters suggested a spontaneous and endothermic process. XPS analysis confirmed a potential adsorption mechanism was based on hydrogen bond interaction, electrostatic interaction and π-π stacking. Additionally, the adsorbent owned outstanding reusability, which could be reused five times with a slight reduction of removal rate. Overall, this research enriches the MB trapping agent and provides a new methods for the reuse of waste natural loofah sponge, and it will be a valuable research with the advantages of low cost and less environmental pollution.     

Experimental and theoretical evaluation of synthetized cobalt oxide for phenol adsorption: Adsorption isotherms,kinetics, and thermodynamic studies

Water pollution by phenolic composites is considered a major environmental problem. Therefore, their removal by adsorption is of great practical importance. In this paper, the synthesized cobalt oxide Co₃O₄ was used as an adsorbent for the adsorption of phenol in an aqueous medium. A DFT calculation has been carried out to determine the sites accountable for the interactions in phenol molecule, and molecular dynamics (MD) simulations were used to understand the mechanism of interaction between phenol molecule and Co₃O₄ surface. The developed adsorbent was characterized by physicochemical methods including XRD, SEM, FT-IR, and BET. The maximum adsorption capacity was observed at pH = 4 with an adsorbed amount of 8.10 mg/g and (R = 98 %). Furthermore, to probe the adsorption action of the phenolic emulsion on the cobalt oxide face, theoretical simulations based on MD (molecular dynamics) and DFT (viscosity functional proposal) were performed. The DFT results verified the chemisorption ascendancy while the MD simulations indicated an increased trade of Co₃O₄ with phenol in the presence of detergent due to water-bridged H- bonds.     

Super-assembled highly compressible and flexible cellulose aerogels for methylene blue removal from water

Physical adsorption is a common method to solve the contamination of methylene blue in dyeing wastewater. As a kind of adsorption material, cellulose aerogels with high porosity and surface areas have great potential application in methylene blue removal. However, the week hydrogen bonding between cellulose nanofibers making the cellulose aerogels with the poor mechanical properties and can be easily destroyed during adsorption. Hence, the preparation of cellulose aerogels with high mechanical strength is still a great challenge. Here, we report a robust super-assembly strategy to fabricate cellulose aerogels by combining cellulose nanofibers with PVA and M-K10. The resulting cellulose aerogels not only has a robust chemically cross-linked network, but also has strong H-bonds, which greatly enhance the mechanical properties. The resulting cellulose aerogels possess a low density of 19.32 mg/cm3.Furthermore, the cellulose aerogel shows 93% shape recovery under 60% strain(9.5 k Pa under 60% strain)after 100 cycles, showing excellent mechanical property. The adsorption capacity of cellulose aerogel to methylene blue solution of 20 mg/L is 2.28 mg/g and the adsorption kinetics and adsorption isotherms have also been studied. Pseudo-second-order kinetic model and Freundlich isotherm model are more acceptable for indicating the adsorption process of methylene blue on the cellulose aerogel. Thus, this compressible and durable cellulose aerogel is a very prospective material for dyeing wastewater cleanup.     

Dye and its removal from aqueous solution by adsorption: A review

In this review article the authors presented up to-date development on the application of adsorption in the removal of dyes from aqueous solution. This review article provides extensive literature information about dyes, its classification and toxicity, various treatment methods, and dye adsorption characteristics by various adsorbents. One of the objectives of this review article is to organise the scattered available information on various aspects on a wide range of potentially effective adsorbents in the removal of dyes. Therefore, an extensive list of various adsorbents such as natural materials, waste materials from industry, agricultural by-products, and biomass based activated carbon in the removal of various dyes has been compiled here. Dye bearing waste treatment by adsorption using low cost alternative adsorbent is a demanding area as it has double benefits i.e. water treatment and waste management. Further, activated carbon from biomass has the advantage of offering an effected low cost replacement for non-renewable coal based granular activated carbon provided that they have similar or better adsorption on efficiency. The effectiveness of various adsorbents under different physico-chemical process parameters and their comparative adsorption capacity towards dye adsorption has also been presented. This review paper also includes the affective adsorption factors of dye such as solution pH, initial dye concentration, adsorbent dosage, and temperature. The applicability of various adsorption kinetic models and isotherm models for dye removal by wide range of adsorbents is also reported here. Conclusions have been drawn from the literature reviewed and few suggestions for future research are proposed.     

Preparation of crosslinked polystyrene-supported ethylenediamine via a S-containing spacer and adsorption properties towards metal ions

Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg²⁺ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg²⁺ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg²⁺ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg²⁺, Cu²⁺ and Ag⁺ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR.     

Progress and challenges in molecularly imprinted polymers for adsorption of heavy metal ions from wastewater

Molecularly imprinted polymers (MIPs), prepared by the interaction forces such as forming covalent or non-covalent bonds by crosslinkers and initiators, are new types of specific recognition polymers with particular cavities. This is an ideal class of materials for wastewater treatment because of the particular holes left by the elution process. This review discusses the development process, classification, synthesis principles, systems, and polymerization methods of MIPs. At the same time, the adsorption mechanism of Copper (Cu), Mercury (Hg), Chromium (Cr), Silver (Ag), and Lead (Pb) in the MIPs technique are studied. Finally, some suggestions and prospects for the future development of MIPs are also put forward.     

Fabrication of SiO2/CuFe2O4/polyaniline composite: A highly efficient adsorbent for heavy metals removal from aquatic environment

A novel multifunctional of SiO₂/CuFe₂O₄/polyaniline composite was synthesized through the interaction between silica (SiO₂), copper iron oxide (CuFe₂O₄), and polyaniline (PANI) as starting materials. SiO₂/CuFe₂O₄/polyaniline composite was characterized for morphology, crystallinity, textural properties, and utilised for the removal of Fe(II), Mn(II), and Cu(II) from synthetic wastewater solutions. The roles of solution pH (2.0–6.0), interaction time (15–420 min), initial ion concentration (50–700 mg/L), and solution temperature (30–50 °C) in the adsorption process were investigated. The adsorption capacities of SiO₂/CuFe₂O₄/PANI for the tested metal ions were high compared to SiO₂, CuFe₂O_4, and polyaniline. Equilibrium studies indicated that Fe(II) and Mn(II) adsorption were compliant with the Langmuir model, while the Freundlich equation described the removal of Cu(II) ions. The maximum Langmuir capacities were up to 285.71, 416.67, and 454.55 mg/g for Cu(II), Fe(II), and Mn(II), respectively. The pseudo-first-order kinetic model fitted well the metal ions removal data. The rate-controlling step reflected the involvement of surface and inner pore diffusion (intraparticle) processes. Electrostatic attractions and chelation were mainly responsible for the binding of metals ions onto SiO₂/CuFe₂O₄/PANI. The selectivity of the studied ions was governed mainly by the hydrated ionic radii and the composite adsorption active sites. SiO₂/CuFe₂O₄/PANI can be easily reused with a slight decrease (around 2–3%) in metal removal efficiency after four successive regeneration cycles.     

Recent advances on hydrogels based on chitosan and alginate for the adsorption of dyes and metal ions from water

In contemporary times, water resources have become increasingly scarce and suffer from anthropogenic pollution sources with an organic and inorganic origin that are products of industrial, agricultural, and everyday waste. Contamination with heavy metals and dyes in wastewater is considered a risk for water sources that can leak into underground and surface sources, leading to increased biological and chemical contamination. The pollutant removal process is performed by adsorption treatment methods, which is the most common method, and it is considered an effective method with a high and economical removal rate.In this review, we discuss the use of biobased hydrogel adsorbents in the removal of organic dyes and metal ions from water. The literature indicates that hydrogels exhibit rapid absorption kinetics and a dye removal absorption capacity that can reach more than 100 mg/g and sometimes more than 2000 mg/g, with a metal adsorption capacity ranging from 38 mg/g to more than 440 mg/g. These results are discussed and compared by taking into account hydrogel materials that contain biopolymers such as alginate, chitosan or both. In general, absorption depends mainly on biobased materials, which have a natural origin and can be utilized to synthesize hydrogels to remove pollutants, dyes and heavy metals. Chitosan and alginate are prominent materials for this use and they can be incorporated with other components to obtain hydrogels or nanocomposite materials with different efficacies to remove dyes and metal ions.     

An evaluation of coal fly ash as an adsorbent for the removal of methylene blue from aqueous solutions: kinetic and thermodynamic studies

Abstract

In this study the effect of the dose and particle size of the adsorbent, initial dye concentration, initial pH, contact time and temperature were investigated for the removal of by means of fly ash (FA) methylene blue (MB) from an aqueous solution. The FA dose was found to be 2.0?g and the under 270 mesh sized particles were found to be effective particles for adsorption. The adsorption process reached its maximum value at 0.5?mg/L dye concentration and attained equilibrium within 10?minutes. The adsorption isotherm was found to follow the Langmuir model. The estimated adsorption free energy (ΔG^o), enthalpy change (ΔH^o), and entropy change (ΔS^o) for the adsorption process were ?37.77?kJ mol^?1, ?13.44?kJ mol^?1 and 122 J mol^?1 K^?1 respectively at 298 K. The maximum adsorption capacity is 0,12?mg g^?1 at 298 K and 0,07?mg g^?1 at 398 K. The adsorption process was exothermic, feasible and spontaneous. The positive value of ΔS^o shows the affinity of FA for MB while the low value of ΔG^o suggests a physical adsorption process.     

Synthesis of polyacrylamide-bound hydroquinone via a homolytic pathway: Application to the removal of heavy metals

Polyacrylamide (PAAm) was chemically modified with hydroquinone (HQ) via a homolytic route. A degree of modification of approximately 58% was obtained under optimal reaction conditions: time of 6 h, and [modifier]/[acrylamide] molar ratio of 5. PAAm and its modified form HQ–PAAm were characterized by UV–visible spectroscopy, FT–IR spectroscopy, ¹³C NMR spectroscopy, DSC, TGA, XRD, and SEM. A relatively lower molecular weight of the corresponding hydroquinone-functionalized form was measured. The glass transition temperature of the modified polymeric material was lower than that of the pristine one: 78.82 °C for HQ–PAAm versus 161.19 °C for PAAm. A study of Cu(II) adsorption by the cross-linked PAAm and HQ–PAAm resins was conducted by varying the following parameters: pH, time, temperature, ionic strength, sorbent mass, and initial Cu(II) concentration. The adsorption capacity of Pb(II) and Cd(II) by the different resins and their corresponding extents of desorption were estimated. The optimal conditions for metal ion uptake by polyacrylamide and its modified resin were: pH = 5.4, time = 120 min, temperature = 45 °C. The sorption extent by the modified resin was in the order Pb(II) > Cu(II) > Cd(II). The desorption of the experimented metallic ions from the resins exceeded 97%. A new way of cross-linking PAAm and its modified form is described herein.     

Activated carbon blended with grape stalks powder: Properties modification and its application in a dye adsorption

In this study, activated carbon was blended with grape stalks powder to adsorb methylene blue (MB) dye with various concentrations from a wastewater. For this purpose, five independent variables involving pH (2–13), contact time (5–270 min), grape stalks powder dosage (0.1–10 g/l), methylene blue initial concentration (20–300 mg/l), and activated carbon dosage (0.1–10 g/l) for methylene blue adsorption were studied. The Central Composite Design (CCD) under Response Surface Methodology (RSM) was applied to estimate the independent variables effects on the methylene blue adsorption. The pseudo- first order, pseudo-second order, Elovich and intraparticle diffusion models were employed to study the adsorption kinetics and isotherm. The Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models were applied to investigate the adsorption isotherm. It was concluded that the intraparticle diffusion isotherm and pseudo-second order kinetic models could show the best results. Furthermore, some data such as physical adsorption (by analyzing FTR and applying some standard equations) and mean free energy (E) were discovered in this research. Finally, activated carbon blended with grape stalks powder as an effective bio-adsorbent for the methylene blue reduction from a wastewater was introduced.     

Aminoalkylbis(phenolate) [O,N,O] donor ligands for uranyl(VI) ion coordination: Syntheses,structures, and extraction studies

The syntheses of five new aminoalkylbis(phenolate) ligands (as hydrochlorides) and their uranyl complexes are described. The reaction between uranyl nitrate hexahydrate and phenolic ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminopropane) · HCl], H₂L1 · HCl, forms a uranyl complex [UO₂(HL1)₂] · 2CH₃CN (1). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminobutane) · HCl], H₂L2 · HCl, forms a uranyl complex with a formula [UO₂(HL2)₂] · 2CH₃CN (2). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methyl benzyl)-1-aminohexane) · HCl], H₂L3 · HCl, yields a uranyl complex with a formula [UO₂(HL3)₂] · 2CH₃CN (3) and the ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-cyclohexylamine) · HCl], H₂L4 · HCl, yields a uranyl complex with a formula [UO₂(HL4)₂] (4). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-benzylamine) · HCl], H₂L5 · HCl, forms a uranyl complex with a formula [UO₂(HL5)₂] · 2MeOH (5). The molecular structures of 1, 2′ (2 without methanol), 3, 4 and 5 were verified by X-ray crystallography. The complexes 1–5 are neutral zwitterions which form in a molar ratio of 1:2 (U to L) in the presence of a base (triethylamine) and bear similar mononuclear, distorted octahedral uranyl structures with the four coordinating phenoxo ligands forming an equatorial plane and resulting in a centrosymmetric structure for the uranyl ion. In uranyl ion extraction studies from water to dichloromethane with ligands H₂L1 · HCl–H₂L5 · HCl, the ligands H₂L2 · HCl and H₂L4 · HCl are the most effective ones.