Langmuir Isotherm Research Articles

A facile and green synthesis of corn cob-based graphene oxide and its modification with corn cob-K2CO3 for efficient removal of methylene blue dye: Adsorption mechanism, isotherm, and kinetic studies

In recent years, the treatment of synthetic dyes has become an environmental concern. In this study, a single step calcination process was used to develop the inventive, simple, and inexpensive adsorbent CC-GO/CC-K2CO3 composite. The composite was employed for the treatment of methylene blue (MB), a cationic dye. Several characterization methods including powder XRD, FTIR, XPS, BET, FESEM, EDX, Raman, and HRTEM techniques were utilized for the analysis of the composite. The surface area and mean pore diameter of CC-GO/CC-K2CO3 were 32.651 m2 g−1 and 3.71 nm, respectively. The adsorption experiment showed that optimal parameters for the removal of MB dye are at an adsorbent dose of 60 mg, initial dye concentration of 80 mg/L, contact time of 150 min, and pH value of 12 at room temperature. Under optimized conditions, CC-GO evidences a removal efficiency of 70.34 ± 1.36 % while after incorporation with CC-K2CO3 the removal capacity sharply increases up to 98.10 ± 0.4 %. Kinetic and isotherm models were used to analyze the removal rate constant and equilibrium adsorption capacity under various adsorption environments. The adsorption study was found to follow the models of pseudo-second order kinetic and Freundlich isotherm. The CC-GO/CC-K2CO3 composite has the maximum adsorption capacity (MAC) of 160.77 mg/g established by the Langmuir isotherm. The prepared composite has demonstrated the capacity to be recycled up to three times with a gradual decrease in its adsorption behavior, exhibiting removal efficiency of 61.66 ± 2.04 %.A cost estimation study of the composite was also performed to assess its cost effectiveness.

Biosorption of Cr(VI) by Theobroma cacao pericarp.

This paper reports a comprehensive study of Theobroma cacao pericarp (TCP) residues, which has been prepared, characterized, and tested as an inexpensive and efficient biosorbent of Cr(VI) from aqueous solutions. The maximum adsorption capacity of TCP obtained at optimal conditions (pH = 2, dose = 0.5g L-1, C0 = 100mg L-1) was qmax = 48.5mgg-1, which is one of the highest values reported by the literature. Structural and morphological characterization has been performed by FTIR, SEM/EDX, and pHPZC measurements. FTIR analysis revealed the presence of O-H, -NH, -NH2, C = H, C = O, C = C, C-O, and C-C functional groups that would be involved in the Cr(VI) biosorption processes. The experimental equilibrium data of biosorption process were successfully fitted to non-linear Langmuir (R2 = 0.95, χ2 = 11.0), Freundlich (R2 = 0.93, χ2 = 14.8), and Temkin (R2 = 0.93, χ2 = 14.7) isotherm models. Kinetics experimental data were well adjustment to non-linear pseudo-2nd (R2 = 0.99, χ2 = 2.08)- and pseudo-1st-order kinetic models (R2 = 0.98, χ2 = 2.25) and also to intra-particle Weber-Morris (R2 = 0.98) and liquid film diffusion (R2 = 0.99) models. These results indicate that Cr(VI) biosorption on heterogeneous surfaces as well as on monolayers of TCP would be a complex process controlled by chemisorption and physisorption mechanisms. The thermodynamic results indicate that the Cr(VI) biosorption on TCP is a feasible, spontaneous, and endothermic process. TCP can be regenerated with NaOH and reused up to 3 times.

Synthesis of magnetic chitosan-composite biochar and its removal of copper ions (Cu2+) and methylene blue (MB) dye from aqueous solutions.

This study presents the synthesis and evaluation of a magnetic chitosan-modified biochar (M-BC-CS) composite, developed from waste maize straw, for the efficient removal of copper ions (Cu2+) and methylene blue (MB) dye from aqueous solutions. The composite was characterized using advanced techniques such as SEM, BET, FTIR, XPS, and XRD, confirming its enhanced surface area, porosity, and magnetic properties. The study is aimed at investigating the optimal conditions for adsorption of Cu2+ and MB by M-BC-CS through analysis of the influence of diverse adsorbent dosages, pH levels, reaction times, and initial solution concentrations. The findings demonstrated that the equilibrium duration for the adsorption of Cu2+ and MB by M-BC-CS was 60min, resulting in corresponding equilibrium adsorption quantities of 54.42mg/g and 67.23mg/g, respectively. To elucidate the adsorption mechanism, the present investigation applied the pseudo-second-order kinetic model and the Langmuir isotherm. The outcomes suggested that the adsorption process is attributable to single molecular layer chemisorption. XPS and FTIR analysis determined that ion exchange and electrostatic interactions are the predominant mechanisms responsible for the simultaneous adsorption of Cu2+ and MB, and a competitive relationship exists between these mechanisms. In addition, M-BC-CS exhibited exceptional magnetic separation performance, enabling effortless and effective separation when exposed to an external magnetic field. Furthermore, the results demonstrated that M-BC-CS has good reusability and high adsorption capacity also in real wastewater, thus emphasizing its potential as a promising adsorbent for the elimination of Cu2+ and MB from aqueous solutions.

2-(4-fluorobenzyl)Chromeno[2,3-c]Pyrozol-3(2H)-One as Copper Corrosion Inhibitor in HNO3: Gravimetric and Quantum Chemical Investigation Methods

The use of organic compounds as corrosion inhibitors has become a principal means of protecting metal equipment in industrial applications. This work therefore set out to evaluate the inhibiting properties of 2-(4-fluorobenzyl)chromeno[2,3-c] pyrozol-3(2H)-one for copper corrosion in 1M nitric acid solution. These properties were investigated using gravimetric method and quantum chemical calculations. Inhibition efficiency increased with temperature, inhibitor concentration and immersion time. Adsorption of this molecule on copper surface occurs according to Langmuir isotherm, while the thermodynamic parameters of absorption and kinetics prove that adsorption is spontaneous and dominated by chemisorption. Quantum chemical parameters derived from density functional theory (DFT) revealed that there is a strong interaction based on electronic exchange between the inhibitor and copper. Global and local reactivity parameters such as highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy, energy gap, Fukui functions and dual descriptor were used to understand the molecule-metal interface and to design more appropriate organic corrosion inhibitors. Theoretical results proved to be consistent with the experimental data obtained.

Exploring the dyeing potential of annatto dye on linen substrate: An inquiry into the effects of different mordants

AbstractThis study aimed to compare the dyeing capacity of annatto dye on linen textile substrates under the influence of different mordants, such as ferrous sulphate, alum, chitosan, and poly(diallyldimethylammonium chloride) (PDDACl). Annatto dye was extracted in an alcoholic medium, and the concentrations of the dye compounds bixin and norbixin were determined using ultraviolet‐visible spectrophotometry. Dyeing experiments were conducted with 10% and 20% weight of material (s.p.m.) concentrations, both on mordant‐treated substrates and on substrates pre‐bleached only. The colour evaluation indicated better colour yields for substrates pretreated with alum and PDDACl, with colour strength (K/S) values of 41.14 and 38.74, respectively, for dyeing with 20% s.p.m. However, these substrates exhibited the highest colour deviation (∆E) values in washing and lightfastness tests. The substrate pretreated with ferrous sulphate and the substrate pre‐bleached only showed K/S values of 25.99 and 18.68, respectively, with the ferrous sulphate‐treated substrate exhibiting the lowest ∆E values in washing and lightfastness tests among all evaluated substrates. Chitosan‐cationised samples showed the lowest colour yield, with a K/S of 12.51. Regarding washing and lightfastness, the pre‐bleached only substrate and the chitosan‐pretreated substrate displayed intermediate ∆𝐸 values. The dyeing kinetics of pre‐bleached substrates exhibited pseudo‐first‐order behaviour, while for ferrous sulphate‐pretreated samples, pseudo‐second‐order behaviour was observed. Langmuir's adsorption model was suitable for pre‐bleached substrate dyeing and ferrous sulphate‐pretreated sample dyeing in adsorption isotherms. However, for mordanted samples, higher adsorption intensity was observed.

Efficient phosphate removal from water using ductile cast iron waste: a response surface methodology approach.

Water scarcity is a critical issue worldwide. This study explores a novel method for addressing this issue by using ductile cast iron (DCI) solid waste as an adsorbent for phosphate ions, supporting the circular economy in water remediation. The solid waste was characterized using XRD, XRF, FTIR, and particle size distribution. Wastewater samples of different phosphate ion concentrations are prepared, and the solid waste is used as an adsorbent to adsorb phosphate ions using different adsorbent doses and process time. The removal percentage is attained through spectrophotometer analysis and experimental results are optimized to get the optimum conditions using Design Expert V13. The pseudo-second order (PSO) kinetics model and Langmuir isotherm were fitted with the experimental results with maximum adsorption capacity (qmax = 0.28mg/g). The thermodynamic analysis indicated that this adsorption process was spontaneous based on the negative value of Gibbs free energy (∆G). Additionally, the positive values of enthalpy (∆H) indicated the endothermic nature of this adsorption system. It was able to reach the highest adsorption percentage of 98.9 (%) for phosphate ions from aqueous solutions using response surface methodology (RSM) with optimum conditions of 10mg/L phosphate ion concentration, pH = 8, normal room temperature, 9min adsorption, and 0.5g/L adsorbent dosage.

Highly efficient and sustainable polyacrylic acid-polyacrylamide double-network hydrogels prepared by cross-linking of waste residues for heavy metals ions removal

In this paper, an adsorbent composite called S-PEMR, which consists of electrolytic manganese residues (EMR)- silicate minerals-based polyacrylic acid-polyacrylamide double-network hydrogels, has been developed. The successful synthesis was confirmed by the characteristic peaks of COO, amide I, CO, -CH2, C-N group vibration in FTIR spectra as well as amorphous carbon in XRD patterns. This composite tackles the issue of harnessing EMR, which consists of layered silicate minerals and additional elements. These elements have potential value but are difficult to be effectively and safely utilized. It was observed that the adsorption process agreed with the quasi-secondary model and the Langmuir isotherm, the adsorption process is controlled by a chemisorption mechanism with the occurrence of electron sharing or electron transfer (establishment of covalent bonds) between the S-PEMR and the adsorbate. The S-PEMR was found to be recyclable up to four times. In the initial experiment, the concentrations of Ni, Cu, Cd, and Pb in a natural wastewater were recorded as 645.84, 906.21, 378.15, and 8.29 μg/L, respectively. The composites used in the study exhibited high removal efficiency for Ni (42.06 %), Cu (93.14 %), Cd (89.68 %), and Pb (77.02 %). The S-PEMR can be recycled up to four times with only a moderate reduction in adsorption performance. The removal mechanism primarily involved chelation or coordination, ion exchange, functional groups containing elements such as O and N, as well as the interaction of Si-O and Al-O with the heavy metal ions. This research establishes S-PEMR as a highly effective adsorbent for removing harmful contaminants from water.

Tuning of Particle Size of Zeolitic Imidazolate Framework-7 via Rapid Synthesis Duration for CH4 Adsorption

In this work, zeolite imidazolate framework-7 (ZIF-7) nanoparticles are synthesized via a solvothermal method and rapid synthesis durations of 1 h and 3 h. The effect of the synthesis duration on the structural properties of ZIF-7 was characterized by XRD and FESEM analyses. Subsequently, CH4 single gas adsorption over ZIF-7 nanoparticles was examined using the volumetric method at room temperature and pressure ranging from 2 to 9 bar. The results showed that the synthesized ZIF-7 adsorbents were highly crystalline with a well-defined and homogeneous particle size distribution of 50–60 nm. It was found that increasing the synthesis duration from 1 h to 3 h did not amend the structure and morphology of the resultant samples significantly, mainly due to the short synthesis duration. Meanwhile, the CH4 adsorbed by ZIF-7 nanoparticles increased with rising pressure for both samples, and the ZIF-7 nanoparticles synthesized at 3 h showed a greater adsorption capacity than that of 1 h, mainly due to its higher crystallinity and well-developed pore structure. The ZIF-7 synthesized at 3 h demonstrated an adsorption capacity up to 2.2 mol/kg, which was higher than those values reported in the literature for micron-sized ZIF-7 samples. The CH4 gas adsorption behavior of ZIF-7 nanoparticles synthesized at 1 h and 3 h were well predicted by the Langmuir isotherm model, with coefficients of determination, R2, of 0.9994 and 0.9982, respectively.

Process optimization of victoria blue dye removal using polypyrrole-encapsulated zirconium oxide: Mechanistic pathway and economic assessment

In this study, an organometallic composite, namely a polypyrrole-encapsulated zirconium oxide (ZrO2/PPy) nanocomposite, was developed and used to eliminate Victoria blue dye (VB) from water system. Specific surface area of the ZrO2/PPy obtained from BET study was observed to be 61.822 m2/g. Solution pH of 7.0, ZrO2/PPy nanocomposite dose of 0.8 g/L, sonication period of 40 min and initial VB dye concentration of 50 mg/L were chosen as optimal test parameters, at which 86.23 (±1.15) % of VB dye elimination was observed. The VB dye uptake process follows pseudo-second-order kinetic model and Langmuir isotherm model, with the later providing the maximum VB dye adsorption capacity of ZrO2/PPy nanocomposite as 238.09 mg/g. Thermodynamics study suggests the spontaneous (ΔGo< 0) and endothermic (ΔHo> 0) nature of the adsorption study. Food processing wastewater causes maximum hindrance (∼20 (±0.90) % −25 (±1.03) %) in the VB dye uptake process while the presence of phosphate (PO43−) ions can create highest interference (∼17 (±0.93) % −19 (±1.08) %) in the VB dye uptake process. At the optimum test parameter values (adsorbent dose: 1.3 g/L, initial VB dye concentration: 20 mg/L, sonication period: 70 min) as suggested by response surface methodology (RSM), maximum VB dye elimination of ∼96 % was observed. Electrostatic attraction, π–π interaction and hydrogen bond formation are amongst the major uptake mechanisms. Regeneration study indicates ∼19 (±1.36) % of decrease in VB dye elimination (%) after fifth cycle of reuse. The lab scale and industrial scale fabrication expense of 1.0 kg of ZrO2/PPy nanocomposite were obtained as 75.74 and 22.20 USD, respectively. The findings of this study suggest the potential of ZrO2/PPy nanocomposite as an effective and economically viable adsorbent to eliminate VB dye from wastewater.

Elucidating capabilities of the ZIF-8-Zn metal organic framework as an adsorbent for COD removal of gas refinery wastewater under mild operating conditions

The chemical oxygen demand (COD) of gas refinery wastewater containing discharged ethanolamines and an extent of hydrocarbons was highly reduced utilizing ZIF-8-Zn metal organic framework adsorbent. The mesoporous adsorbent was initially synthesized through hydrothermal method and characterized via FT-IR, XRD, SEM, TEM, EDX, Zeta potential and BET analysis methods. The COD reduction of the wastewater was then followed with effects of pH (5.5–11.5), adsorbent concentration (0.2–2.5 g/L) and contact time (15–110 min). The response surface methodology (RSM) was employed for design of experiments, modelling and optimization of the process. Amazingly, 98.6 % COD reduction was achieved under mild operating conditions of pH 8.3, adsorbent concentration of 1.5 g/L and temperature of 293.2 K after 63 min contact time. A quadratic equation satisfactorily correlated the COD variations versus involved parameters. The data were also precisely correlated with the extended Langmuir isotherm and the mixed 1, 2-order kinetic model implying mono-layer adsorption of the multicomponent adsorbates through physisorption mechanism because of dominant electrostatic interactions. The results of thermodynamic analysis were also consistent with findings. The maximum adsorption capacity of 972.20 mg/g as well as nice reusability in five sequential cycles proved the promising capability of the adsorbent for decontaminating of the gas refinery wastewater.

Synthesis and evaluation of an environmentally friendly phosphorus-free and nitrogen-free polymer as a scale and corrosion inhibitor

Polyepoxysuccinic acid (PESA) was modified by glycidyl (Gly) to obtain a phosphate-free and nitrogen-free polymer (Gly-PESA), and its scale and corrosion inhibition properties were studied.The effects of Gly-PESA concentration, calcium ion concentration and temperature to scale inhibition performance were studied by static scale inhibition method. The corrosion inhibition performance of Gly-PESA was studied by static weight-loss method. The morphology and structure of calcium scale and steel surface were characterized by spectroscopic and microscopic methods. The scale inhibition efficiency of Gly-PESA for CaCO3 and CaSO4 was 98.06% and 92.6%, respectively. Under the same experimental conditions, the scale inhibition effect of Gly-PESA was obviously better than that of PESA. Gly-PESA could effectively inhibit the growth of CaCO3 and CaSO4 crystals and cause their crystal lattice distortion or crystal dispersion. The corrosion inhibition efficiency of Gly-PESA for carbon steel was 78.17%. The adsorption of Gly-PESA on the surface of the steel test piece followed Langmuir adsorption isotherm, and formed a protective film, which increased the corrosion resistance of the steel test piece, thus effectively protecting the steel test piece. Therefore, Gly-PESA was a green scale and corrosion inhibitor, which solved the problem of environmental pollution.

Experimental and theoretical simulations to examine the influence of nonionic surfactant on the corrosion control of mild steel in hydrochloric acid

The increasing demand for corrosion prevention strategies that are both effective and sustainable is part of the research the background. Nonionic surfactants offer a potential replacement for traditional corrosion inhibitors. These surfactants are well-known for their low toxicity and biodegradability. The research involved conducting experimental tests (such as weight loss, polarization and impedance spectroscopy) and theoretical computations to investigate the role of nonionic surfactant (polyoxyethylene (7) tribenzyl phenyl ether) (PETPE) in controlling the corrosion of mild steel in hydrochloric acid (1.0 M HCl) environment. The results of the study demonstrated that PETPE exhibited significant corrosion inhibition properties for mild steel in HCl solution. The inhibition efficiency of PETPE was found to increase with increasing PETPE concentration. PETPE is an excellent corrosion inhibitor because it significantly reduces the rate of corrosion, as seen by the notable inhibition efficiency result (95.4%) at a relatively low dose of PETPE (100 ppm). Thermodynamic studies were used to discuss the fundamental mechanisms that control PETPE-acid interactions. The adsorption process followed Langmuir adsorption isotherm, indicating a monolayer adsorption of the PETPE on the mild surface. Theoretical computations confirm the strong inhibition behavior of PETPE. The innovative feature of this research is its comprehensive strategy, which integrates experimental studies and theoretical simulations to evaluate the impact of PETPE on the corrosion control of mild steel in hydrochloric acid. The combined effort has the ability to supply valuable knowledge into the mechanisms of corrosion that will lead to the establishment of powerful corrosion control strategies.

Fabrication of surface functionalized QCM sensor for BTX detection at ambient conditions

Developing optimized gas sensors for detecting low concentrations of Benzene, Toluene, and Xylene (BTX) in ambient conditions is advantageous for health and environment monitoring applications. This study reports on the feasibility of using Quartz Crystals Microbalance (QCM) coated by Tungsten Oxide (WO3) to detect BTX compounds. A WO3 layer was deposited on the QCM surface using DC magnetron sputtering. Optical Profilometry (OP), Scanning Electron Microscopy (SEM), and X-ray Diffraction (XRD) were employed to analyze sensor surface morphology and structure. Adsorption properties were studied through the Langmuir adsorption isotherm. Thermal stability was evaluated by thermogravimetric analysis. The response to BTX vapours was investigated using a laboratory-designed gas-sensing setup in ambient conditions. The optimized film thickness was 200.81 ± 0.39 nm for 540 s of sputtering. XRD pattern confirms the amorphous nature, and SEM images of WO3 show the granular microstructure with 200 nm diameter. The developed sensor shows the highest sensitivity for xylene (5.10 ± 0.08 Hz/ppm), followed by toluene (5.69 ± 0.22 Hz/ppm) and benzene (3.36 ± 0.24 Hz/ppm). The limit of detection for BTX was 1.48 ppm, 0.79 ppm, and 0.33 ppm, respectively. The sensor exhibited faster response times of 30 s, 32 s, and 43 s for BTX, respectively. Repeatability of 99 % and reproducibility of 98 % were observed for BTX vapours. The fabricated WO3-coated QCM sensor can detect BTX vapour at room temperature with high sensitivity and response time. Thus, it can play a significant role in detecting BTX in the workplace for health and environment monitoring systems.

Selective separation and recovery of rare-earth elements (REEs) from acidic solutions and coal fly ash leachate by novel TODGA-Impregnated organosilica media

Rare-earth elements (REEs) are essential in a wide range of applications including magnets and satellite technology, with demand driven by geopolitical factors. While multiple techniques exist for REE recovery including solvent extraction and selective precipitation, solid–liquid extraction offers key advantages in selectivity, scalability, and recyclability. N, N, N′, N′-tetraoctyl diglycolamide (TODGA) is a tridentate ligand widely used in solvent extraction, but the incorporation in a solid support to separate individual lanthanides from acid solutions remains largely unexplored. A novel TODGA-organosilica sorbent material was developed and tested to evaluate recovery of 17 elements (REEs and thorium) in terms of selectivity, kinetics, and equilibrium isotherms in 0.01 to 15.9 M nitric acid. Characterization of the new sorbent was performed before and after sorption using FTIR, XPS, and SSA techniques to help elucidate sorption mechanisms and limiting variables. REE adsorption increased from 1.26 mg g−1 to 10 mg g−1 with nitric acid concentrations of 0.01 M and 15.9 M, respectively. TODGA-organosilica exhibits high selectivity towards heavy REEs (Dy to Lu), with minimal sorption of lighter REEs (Ce to Gd). Batch adsorption experiments confirm pseudo-second-order kinetics and a Langmuir adsorption isotherm with TODGA binding to REEs in a 3:1 complex. A packed bed column study confirmed the high selectivity of TODGA-impregnated organosilica towards heavy REEs and a proof-of concept experiment with coal fly ash leachate shows high selectivity for REEs over Al, Fe, and Ca present in several orders of magnitude higher concentrations. Fractionation was observed where loading cycle effluent contained 84 % light REEs while strip cycle effluent contained 80 % heavy REEs. More than 90 % of loaded REEs were successfully stripped with water as the stripping agent.

Effect of Incorporated Transition Metals on the Adsorption Mechanisms of Radioactive Cesium in Prussian Blue Analogs

Extensive efforts were made to remove radioactive cesium (137Cs) from the environment, with Prussian blue analogs (PBAs) emerging as highly selective and efficient materials for 137Cs removal. However, limited studies systematically compared Cs+ adsorption across different transition metals in PBA. This study investigates the influence of the choice of transition metal ion (Co, Cu, Fe, Mn, Ni, Zn) on Cs+ adsorption mechanisms and efficiency. PBAs were synthesized and characterized based on their specific surface area, ion exchange capacity, lattice parameter, and defect sites (as indicated by water molecule content). Cs+ adsorption mechanisms varied significantly with transition metals. In CoFe and FeFe PBAs, ion exchange with K+ dominated, while CuFe and MnFe PBAs, with more defect sites primarily used ion exchange between H+ and Cs+. NiFe and ZnFe exhibited enhanced Cs+ adsorption under light irradiation, likely due to their light-absorbing properties facilitating a reduction reaction. The Langmuir adsorption isotherm was applied to model the adsorption behavior, confirming that each performance of PBA depends on the transition metal used. These findings suggest that PBAs with various transition metals can efficiently remove 137Cs under diverse environmental conditions by using distinct adsorption mechanisms.

Supercritical Methane Adsorption Characteristics and Pore Structure Characteristics of Deep Middle Rank Coal

Abstract In order to accurately analyze the adsorption characteristics, pore structure, and fractal law of deep middle rank coal, high-pressure isothermal adsorption tests based on magnetic levitation high-pressure thermobalance and pore structure tests based on mercury intrusion method were carried out on coal samples collected from typical kilometer level deep wells. The fractal law of sponge model was studied. The results showed that: a. The weight method adsorption test showed “excess adsorption” phenomenon with the increase of equilibrium pressure, and the modified Gibbs surface excess adsorption theory was in line with the Langmuir adsorption model; b. The distribution of macropore volume in deep middle rank coal accounts for a dominant proportion of 57.44% to 62.47%, and the proportion of microporous specific surface area reaches 72.96% to 74.27%, indicating that microporous adsorption capacity is the strongest; c. The pore structure parameters and adsorption constants exhibit strong nonlinear characteristics.

Porous chitosan quaternary ammonium salt hydrogel embedded with Cu, Ni and Pd nanoparticles for efficient coupled adsorption-catalytic reduction of methylene blue and 4-nitrophenol

Anthropogenic wastewater generation and water pollution can have negative impacts on public health and ecosystems. However, most materials do not have both adsorptive and catalytic properties, so the design and development of sustainable and multifunctional materials is essential for wastewater treatment. Herein, composite hydrogel (PHG) containing [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (SBMA) and chitosan quaternary ammonium salts (HACC) were prepared for wastewater treatment. The adsorption capacities of the PHG hydrogels for nickel (NiII), copper (CuII), and palladium (PdII) ions were 158.68, 182.99, and 229.78 mg/g, respectively. The adsorption process is consistent with the Langmuir adsorption model and quasi-secondary kinetics. For further application of adsorbed metal ions, NaBH4 was selected for in situ reduction to prepare hydrogel-based catalysts cemented with metal nanoparticles (Ni-, Cu- and Pd-NPs), respectively. The PHG-Pd catalysts demonstrated significant catalytic efficiency in reducing 4-nitrophenol and methylene blue, and Kapp were 0.307 and 0.365 min−1, respectively. Among them, the activation parameters for the reduction of 4-NP over PHG-Pd catalyst were calculated as Ea = 36.27 kJ/mol, ΔH# = 33.72 kJ/mol and ΔS# = −259.68 J/(mol·K). This study is expected to provide insights into the design of multifunctional adsorption catalysts for the removal of dyes and nitro compounds from wastewater.

Gel-type resin loaded with nano-hydrated ferric oxide for the removal of anions from papermaking wastewater

The main anions in papermaking wastewater are sulfate and chloride. In this paper, a strongly basic gel-type anion exchange resin (201×7) loaded with 20 ~ 200nm hydrated ferric oxide was prepared by dispersion impregnation with ethanol. The modified resin enhances the ability to remove sulfate by complexation of ligands to cause sulfate to form outer and inner sphere complexes on hydrated ferric oxide. The modified resin was dependent on acidic conditions, and the maximum exchange capacity for sulfate was enhanced by 14.2% under the optimal pH, exchange time, and ion concentration conditions. Competitive exchange experiments showed that the removal effect of the modified resin on chloride was almost unchanged under different chloride, sulfate ratios, and the degree of improvement of the removal effect on sulfate decreased from 9.5 ~ 5.5% with the increase of chloride ratio. The removal of sulfate by the modified resin was consistent with the proposed secondary kinetics and Langmuir adsorption model. In addition, the modified resin maintained 88% reuse after four desorption-adsorption cycles and achieved a regeneration rate of 93.1% after was eluted with HCl and reloaded with hydrated ferric oxide. The expected removal effect was well achieved when the resin was applied to the actual wastewater treatment. The above results indicate that the hydrated ferric oxide modification can improve the ability of the 201×7 resin to remove sulfate from water, and is a promising method for removing anions from papermaking wastewater.

Adsorption and removal of herbicide paraquat from aqueous solutions via novel bimetal organic framework: Kinetics, equilibrium and statistical surface modeling

This study examines the adsorption and removal of the herbicide paraquat in relation to a bimetal organic framework known as the Terbium/Palladium Metal-Organic Framework (Tb/Pd-MOF). Analysis of N2 adsorption/desorption isotherms, which were used to assess the properties of the Tb/Pd-MOF, revealed that the absorption of paraquat on Tb/Pd-MOF resulted in a reduction in pore volume, pore size, and surface area. Specifically, the pore volume decreased from 8.25 to 5.68 cm3/g, the pore size decreased from 11.34 nm to 8.92 nm, and the surface area decreased from 1456.61 to 1262.82 m2/g. The pore radius also decreased from 0.96 nm to 0.58 nm. Tb/Pd-MOF’s functional groups were identified through FT-IR, and the structure of the compound was confirmed using XPS. Various adsorption parameters including temperature, adsorbent dosage, pH, paraquat concentration, and contact time were studied. Density functional theory (DFT) was used to understand the electrical properties, reactivity, and morphology of paraquat. Results from the DFT analysis revealed that the electrophilic and nucleophilic attack sites aligned with the molecular orbitals (HOMO and LUMO) and MEP outcomes. The study found that Tb/Pd-MOF demonstrated a significant absorption capacity for paraquat, with adsorption data consistent with the Langmuir isotherm and pseudo-second-order kinetic models. The paraquat adsorption capability of Tb/Pd-MOF was determined to be 574.8 mg/g. Furthermore, chemisorption was identified as the primary form of adsorption, as indicated by the adsorption energy of 26.98 kJ·mol−1. The optimal conditions for achieving a high adsorption capacity were identified as pH 8 and 0.02 g of Tb/Pd-MOF. The temperature-dependent changes in the thermodynamic parameters ΔG°, ΔH°, and ΔS° indicated that the paraquat absorption onto Tb/Pd-MOF occurred spontaneously, was endothermic, and involved random processes. To optimize the absorption process, Response Surface Methodology and Box-Behnken design (RSM, BBD) were employed. These techniques enabled effective removal of paraquat from the Tb/Pd-MOF material. During chemisorption, the adsorbate and adsorbent form chemical bonds, while aromatic rings are involved in π-π bonding. Additionally, pore-filling occurs when the adsorbate fills the pores of the adsorbent, and electrostatic interactions result from the attraction or repulsion of charges between the adsorbate and adsorbent. As a means of eliminating paraquat from wastewater, Tb/Pd-MOF demonstrates significant potential due to its diverse absorption processes and high capacity for adsorption.

Fabrication of mango-leaf biowaste mediated green magnetite (Fe3O4@MBE NPs) and modified EDTA/Fe3O4@MBE NCs for enhanced heavy metals sequestration: Characterisation, simulation modelling, mechanism, cost-effectiveness and electroplating wastewater performance

This work reports biogenic green fabricated novel magnetite nanoparticles (Fe3O4@MBE NPs) coated with mango-leaf biowaste extract and modified disodium ethylenediamine tetra-acetate (EDTA) functionalised nanocomposite (EDTA/Fe3O4@MBE NCs). Several approaches were used to characterise them, and their applicability as nanoadsorbents was exhaustively investigated in batch mode sequestration of Cd(II), Ni(II), and Zn(II) from synthetic solutions. The Brunauer Emmett and Teller’s surface areas of Fe3O4@MBE and EDTA/Fe3O4@MBE was determined to be 47.73 and 43.95 m2/g, respectively, with average porous diameters of 10.36 and 7.44 nm, revealing mesoporosity. EDTA/Fe3O4@MBE NCs exhibit soft ferromagnetism with a saturation magnetisation of 40.67 emu/g. Further, EDTA modification creates carboxyl and amino sites, improving adsorption performance. Adsorption was pH dependent, with optimal sequestration at 40 mg/L divalent metal ions, 0.5 g/L nanoadsorbent dosage, and 75 min of reaction duration at 27 °C. Among the simulation models employed, the Langmuir isotherm, pseudo second order kinetic, and Elovich kinetic were the best fitted and offered the highest capability to explain the adsorption process. The Langmuir monolayer adsorption capacity (qmax) of 147.06, 129.87, and 117.65 mg/g for Cd(II), Ni(II), and Zn(II) by EDTA/Fe3O4@MBE, respectively, were significantly higher than Fe3O4@MBE (120.48, 102.04, and 95.24 mg/g). The best-suited kinetics precisely describe chemisorption as the primary rate-limiting phase in divalent metal ions adsorption. Thermodynamics approved the endothermic nature and feasibility of divalent metals adsorption, with modest improvement in efficacy at higher temperatures. The ability of EDTA/Fe3O4@MBE to form stable surface complexes with divalent metals enhances adsorption even in the presence of other co-existing ionic species. EDTA/Fe3O4@MBE NCs magnetic separability, improved sequestration upto five recycles, and regenerability of ≥89.07 % demonstrate its cost-effectiveness in heavy metals sequestration. Finally, practicality study confirmed that EDTA/Fe3O4@MBE nanoadsorbent provides a practical and economically efficient option for heavy metals sequestration from electroplating wastewater; thus, it contributed towards UN-2030, SDG No-6.