Facile synthesis and characterization of a magnetic biosorbent derived from sodium alginate and activated graphite schist: Experimental and statistical physics analysis for Mn(VII) remediation.

H2O2-modified graphite schist (GS) and sodium alginate (SA) interface was loaded by Fe3O4 nanoparticles (MNPs) to prepare a magnetic biosorbent that was employed in removing Mn(VII) from solutions. The prepared GS/SA/MNPs adsorbent was investigated using a variety of techniques, including elemental mapping, TEM, XPS, FTIR, FESEM, EDX, XRD, XPS, and zeta potential. An experimental study supported by statistical physics calculations was carried out to obtain a new outline of the Mn(VII) uptake mechanism. The classical Freundlich and the statistical physical double-layer models adequately described the Mn(VII) uptake process at pH 3.0 and a temperature of 25-55 °C. The removed number of Mn ions (such as Mn+7 and Mn+2) per GS/SA/MNPs active site ranged from 0.70 to 0.84, indicating a mixed adsorption orientation driven by surface complexation and attraction forces mechanisms. The adsorption energies (∆E) calculated by the double-layer model ranged from 18.79 to 24.94 kJ/mol, suggesting that the interaction between Mn(VII) and GS/SA/MNPs was controlled by physical forces. Increasing the adsorption capacity at saturation (Qsat) from 333.14 to 369.52 mg/g with temperature proposed an endothermic capture process. Thermodynamic functions clarified the viability and spontaneity of Mn(VII) uptake on the GS/SA/MNPs adsorbent.

Sodium alginate-modified alkali-activated eggshell/Fe3O4 nanoparticles: A magnetic bio-based spherical adsorbent for cationic dyes adsorption.

Herein, a mixture of eggshell (ES) and magnetite nanoparticles (MNPs) was alkali-activated using NaOH/Na2SiO3 solution and then, impregnated with sodium alginate (SA) to prepare a magnetic bio-based adsorbent (namely SAAES/SA/MNPs) for the decontamination of water containing basic dyes, in particular, methylene blue (MB) and crystal violet (CV). The physicochemical properties of magnetic spheres of SAAES/SA/MNPs were characterized using XRD, FTIR, FESEM, EDX, elemental mapping, TEM, and zeta potential techniques. Dye adsorption equilibrium was studied experimentally at pH 8.0 and 25-55 °C, and a statistical physics multilayer model was applied to understand the removal mechanism of these dyes including the adsorption orientations on the adsorbent surface. The number of adsorbed dye molecules per functional group (n) of this bio-based adsorbent ranged from 0.70 to 0.91, indicating the presence of vertical and horizontal adsorption orientations for these organic molecules at all tested solution temperatures. The calculated saturation adsorption capacities (Qsat) were 332.57-256.62 mg/g for CV and 304.47-240.62 mg/g for MB, and an exothermic adsorption was observed for both adsorbates. The estimated adsorption energies (∆E) were < 25 kJ/mol, confirming that the SAAES/SA/MNPs-dye interactions were governed by physical forces as electrostatic interactions. This bio-based adsorbent was effectively regenerated using ethanol and it can be reused showing a removal of 71 and 74 % of MB and CV, respectively, after fourth adsorption-desorption cycles. Overall, the results of this article suggest the attractive performance of SAAES/SA/MNPs for removing basic dyes from aqueous solutions, thus highlighting the promising potential of this magnetic bio-based adsorbent for sustainable wastewater treatment at an industrial level.

Employ a Clay@TMSPDETA hybrid material as an adsorbent to remove textile dyes from wastewater effluents.

A grafting of N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMSPDETA) on natural clay was carried out to obtain an organic-inorganic hybrid clay material that was applied as an adsorbent to the uptake of Reactive Blue 19 (RB-19) and Reactive Green 19 (RG-19) dyes from aqueous wastewaters. This research demonstrates the effect of TMSPDETA contents on amino-functionalized clay materials' hydrophobic/hydrophilic behavior. The resultant material was utilized to uptake reactive dyes in aqueous solutions. The clay@TMSPDETA hybrid material was characterized by isotherm of adsorption and desorption of nitrogen, FTIR, elemental analysis, TGA, pHpzc, total acidity, total basicity groups, and hydrophilic balance. The hybrid samples were more hydrophilic than the pristine clay for ratios from 0.1 up to 0.5 due to adding amino groups to the pristine clay. FTIR spectra suggest that TMSPDETA was grafted onto the clay. The hybrid material presents a surface area 2.17-fold (42.7 m2/g) lower than pristine clay (92.7 m2/g). The total volume of pores of hybrid material was 0.0822 cm3/g, and the pristine clay material was 0.127 cm3/g, corresponding to a diminution of the total pore volume (Vtot) of 1.54 times. The kinetic data followed the pseudo-second-order (PSO) model for RB-19 and RG-19 reactive dyes. The equilibrium data were better fitted to the Liu isotherm model, displaying a Qmax as 178.8 and 361.1 mg g-1 for RB-19 and RG-19, respectively, at 20.0 °C. The main mechanism of interactions of the reactive dyes with the hybrid clay is electrostatic interaction. The clay@TMSPDETA has a very good effect on treating synthetic dye-textile wastewater. The removal percentage of simulated wastewater was up to 97.67% and 88.34% using distilled water and plastic industry wastewater as the solvents, respectively. The clay@TMSPDETA-0.1 could be recycled up to 5 cycles of adsorption and desorption of both dyes, attaining recoveries of 98.42% (RB-19) and 98.32% (RG-19) using 0.1 M HCl + 10% ethanol.

Repurposing carbonate-based waste for producing an innovative binder: optimization and characterization.

This study reports the full recycling of dolomite waste (DW) in the fabrication of a novel cementitious material through a facile and eco-efficient method. The proposed technique includes mixing different alkali-activators (i.e., NaOH and Na2SiO3) with DW powder, followed by curing at room temperature. Based on the alkali-activator type, sodium oxide concentration, and curing time, the formulated mixtures yield a wide range of compressive strengths. When DW powder is mixed with different contents of NaOH (2.5, 5, and 7.5 wt.% Na2O), the resulting hardened materials exhibited modest compressive strengths (less than 11 MPa) due to the formation of the gaylussite Na2CO3·CaCO3·5H2O phase. Concerning the other chemical activator (Na2SiO3), a significant improvement in the compressive strengths of the resulted hardened materials was detected. This was ascribed to the formation of calcium silicate hydrate, with a high binding capacity, through the exchange reaction between Na2SiO3 and CaCO3 inside DW. The sample activated with Na2SiO3 (silica modulus of 1.5) equivalent to Na2O of 7.5 wt.% offered the highest 90-day compressive strength (34 MPa). At silica modulus lower or higher than 1.5, a noticeable decrease in the performance of the hardened materials was observed, which could be attributed to the alter in binding phase composition. Overall, the present work presented a new approach in utilizing the available and low cost carbonate-based wastes as main precursors in the family of promising alkali-activated materials.

Mesoporous Silicas Obtained by Time-Controlled Co-Condensation: A Strategy for Tuning Structure and Sorption Properties.

Mesoporous silicas synthesized by the co-condensation of two and three different silica monomers were synthesized by varying the time intervals between the addition of individual monomers, while the total time interval was kept constant. This resulted in different structural properties of the final silicas, particularly in their porosity and local ordering. One of the obtained samples exhibited an unusual isotherm with two hysteresis loops and its total pore volume was as high as 2.2 cm3/g. In addition, to be thoroughly characterized by a wide range of instrumental techniques, the obtained materials were also employed as the adsorbents and release platforms of a diclofenac sodium (DICL; used here as a model drug). In the case of DICL adsorption and release, differences between the samples were also revealed, which confirms the fact that time control of a monomer addition can be successfully used to fine-tune the properties of organo-silica materials.

Dual-functional marine algal carbon-based materials with highly efficient dye removal and disinfection control.

The design and simple, green preparation of dual-functional materials for the decontamination of both hazardous dyes and pathogenic microorganisms from wastewater remain challenging currently. Herein, a promising marine algal carbon-based material (named C-SA/SP) with both highly efficient dye adsorptive and antibacterial properties was fabricated based on the incorporation of sodium alginate and a low dose of silver phosphate via a facile and eco-friendly approach. The structure, removal of malachite green (MG) and congo red (CR), and their antibacterial performance were studied, and the adsorption mechanism was further interpreted by the statistical physics models, besides the classic models. The results show that the maximum simulated adsorption capacity for MG reached 2798.27 mg/g, and its minimal inhibit concentration for Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was 0.4 mg/mL and 0.2 mg/mL, respectively. The mechanistic study suggests that silver phosphate exerted the effects of catalytic carbon formation and pore formation, while reducing the electronegativity of the material as well, thus improving its dye adsorptive performance. Moreover, the MG adsorption onto C-SA/SP showed vertical orientation and a multi-molecular way, and its adsorption sites were involved in the adsorption process with the increase of temperature. Overall, the study indicates that the as-made dual-functional materials have good applied prospects for water remediation.

Utilization of Foamed Glass as an Effective Adsorbent for Methylene Blue: Insights into Physicochemical Properties and Theoretical Treatment.

This study reports a potential approach for the valorization of glass waste (GW) that is mainly composed of amorphous silica to prepare lightweight foamed glass (FG). The preparation of FG was achieved by mixing sodium hydroxide with GW powder followed by sintering at a temperature of 800 °C. As-synthesized FG was characterized and applied as an effective adsorbent for the removal of hazardous organic water contaminants, in particular, methylene blue (MB) dye. FG exhibited porosity of 91%, bulk density of 0.65 g/cm3, compressive strength of 4 MPa, and thermal conductivity of 0.27 W/m·K. Theoretical treatment indicated that a monolayer model with one energy site was the best in fitting the removal of MB molecules. The number of MB molecules per active site (n) ranged from 2.20 to 1.70, suggesting vertical orientation and a multi-molecular adsorption mechanism. The density of FG receptor sites (DM) increased with the temperature, and this parameter played a vital role in the adsorption process. The adsorption capacity (Qsat) increased from 255.11 to 305.58 mg/g, which signifies endothermic interactions. MB adsorption on FG was controlled by physical forces such as electrostatic interactions (i.e., the adsorption energies were <20 kJ/mol). The results of this study prove the feasibility of glass waste as an effective and low-cost adsorbent for water remediation.

Effective removal of Cr(VI) and methyl orange by nano magnetite loaded starch/muscovite biocomposite: Characterization, experiments, advanced modeling, and physicochemical parameters interpretation.

Magnetite nanoparticles (MNPs) synthesized from heated basalt were used to support a biocomposite prepared from muscovite (Mus) and carbohydrate polymer starch (St). The developed Mus/St/MNPs composite was characterized by XRD, FTIR, FESEM, TGA, DSC, and Zeta potential techniques. This multifunctional composite showed outstanding adsorption properties for hexavalent chromium (Cr(VI)) and methyl orange (MO) removal at 25-55 °C and pH 3.0. The adsorption isotherms were fitted to Langmuir model for Cr(VI) and Freundlich equation for MO. To understand microscopically these systems and to analyze their adsorption geometry and interactions mechanism, three statistical physics models were utilized. Theoretical calculations indicated that Cr(VI) ions were adsorbed on composite surface presenting a combination of horizontal and vertical positions, while the aggregated MO molecules displayed a non-parallel adsorption orientation and multi-interactions mechanism. The saturation adsorption capacity increased from 243.37 to 371.59 mg/g for Cr(VI) and 409.29 to 457.62 mg/g for MO at 25 and 55 °C (i.e., endothermic interactions). Cr(VI) and MO adsorption on Mus/St/MNPs was controlled by van der Waals forces, hydrogen bonding, and electrostatic interactions where the calculated adsorption energies were 12.5-30.62 kJ/mol. The utilized adsorbent was easily reactivated and reused several times where regenerated Mus/St/MNPs composite showed nearly 79 % of Cr(VI) and 85 % of MO adsorption capacities even after the fourth adsorption-desorption cycle. This study contributes to understand the physicochemical factors of Cr(VI) and MO adsorption on multifunctional adsorbents like MNPs/carbohydrate polymers/aluminosilicates interface.

Composite of methyl polysiloxane and avocado biochar as adsorbent for removal of ciprofloxacin from waters.

Two carbon composite materials were prepared by mixing avocado biochar and methyl polysiloxane (MK). Firstly, MK was dissolved in ethanol, and then the biochar was added at different times. In sample 1 (R1), the time of adding biochar was immediately after dissolving MK in ethanol, and in sample 2 (R2), after 48 h of MK dissolved in ethanol. The samples were characterized by nitrogen adsorption/desorption measurements obtaining specific surface areas (SBET) of 115 m2 g-1 (R1) and 580 m2 g-1 (R2). The adsorbents were further characterized using scanning electron microscopy, FTIR and Raman spectroscopy, adsorption of vapors of n-heptane and water, thermal analysis, Bohem titration, pHpzc, and C H N elemental analysis. R1 and R2 adsorbents were employed as adsorbents to remove the antibiotic ciprofloxacin from the waters. The t1/2 and t0.95 based on the interpolation of Avrami fractional-order were 20.52 and 246.4 min (R1) and 14.00 and 157.6 min (R2), respectively. Maximum adsorption capacities (Qmax) based on the Liu isotherm were 10.77 (R1) and 63.80 mg g-1 (R2) for ciprofloxacin. The thermodynamic studies showed a spontaneous and exothermic process for both samples, and the value of ΔH° is compatible with physical adsorption.

New insights into the selective adsorption mechanism of cationic and anionic dyes using MIL-101(Fe) metal-organic framework: Modeling and interpretation of physicochemical parameters.

In the current study, iron-based metal organic framework (MOF) MIL-101(Fe) was successfully prepared via a facile solvothermal method. The as-synthesized MIL-101(Fe) was characterized by XRD, FE-SEM, FTIR, TGA and zeta potential techniques, and then employed as an adsorbent for methyl orange (MO) and methylene blue (MB) dyes. The adsorbed quantities of MO (1067 to 831 mg/g) were higher than those of MB (402 to 353 mg/g) indicating the high selectivity of MIL-101(Fe) towards the anionic dye at all temperatures (20-60 °C). Adsorption processes of MO and MB followed the pseudo-second order kinetics and the Langmuir equilibrium model. The interaction mechanism at a molecular level was analyzed and deeply interpreted via the advanced multilayer adsorption model. Steric parameters indicated that MO molecular aggregation (n) was 0.95-1.33 thus signifying the presence of multi-docking and multi-interactions mechanisms. The aggregated number of MB was superior to unity (i.e., n = 1.17-1.78) suggesting a vertical adsorption position and a multi-interactions mechanism at all operating temperatures. The density of MIL-101(Fe) active sites (DM = 77.33-52.38 mg/g for MB and 149.91-107.07 for MO) and the total adsorbed dye layers (Nt = 3.12-2.49 for MB and 5.36-3.67 for MO) resulted in improving the adsorption capacities of MO dye. The adsorption energies ranged from 8.89 to 33.73 kJ/mol and they displayed that MO and MB uptake processes were exothermic controlled by physical interactions at all temperatures. Regeneration results indicated that this adsorbent can be reutilized without a significant loss in its removal efficiency after five adsorption-desorption cycles. Overall, the adsorption capacity, chemical stability, and regeneration performance of MIL-101(Fe) support its application as a very promising adsorbent for the removal of organic hazardous pollutants from water.

Chitosan/activated coal composite as an effective adsorbent for Mn(VII): Modeling and interpretation of physicochemical parameters.

Chitosan was impregnated into porous activated coal to produce a multifunctional chitosan/activated coal (Cs/Ac) composite. The resulted Cs/Ac was characterized and utilized as a cost-effective adsorbent for Mn(VII) at altered temperatures (i.e., 25, 35, and 45 °C). The adsorption results were fitted to classical as well as advanced statistical physics models. The Freundlich equation described well the achieved experimental data at all temperatures. Enhancing the Langmuir adsorption capacity from 203.26 to 224.03 mg/g with temperature indicated that Mn(VII) adsorption was an endothermic process. Steric, energetic and thermodynamics data of the double layer model with two energy sites (i.e., the best fit statistical model) were completely interpreted. The number of Mn(VII) per adsorption site (n) was between 0.76 and 0.92 suggested the presence of multi-docking and multi-interactions mechanisms. The active sites density (NM) of the Cs/Ac decreased with improving temperature. Energetically, Mn(VII) uptake by Cs/Ac was governed by physical interactions (i.e., adsorption energy <40 kJ/mol). Macroscopically, the interaction between Mn(VII) and Cs/Ac was spontaneous. Overall, modification of the Ac by the used marine biomass (Cs) produced a promising Mn(VII) adsorbent and also, the application of physical analysis offered a deep interpretation for the adsorption mechanism.

Insights Into the Mn(VII) and Cr(VI) Adsorption Mechanisms on Purified Diatomite/MCM-41 Composite: Experimental Study and Statistical Physics Analysis.

In this study, a purified diatomite (PD) with a concentration of diatom frustules more than 92% SiO2 was utilized to synthesize a composite of MCM-41 silica under hydrothermal conditions. The as-synthesized PD/MCM-41 composite was characterized and tested as an adsorbent for the removal of Cr(VI) and Mn(VII) ions from aqueous solution. Results of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR) revealed that the diatom frustules of the PD were coated with MCM-41 mesoporous silica. Experimental isotherms of Cr(VI) and Mn(VII) adsorption were fitted to classical and advanced statistical physics models at 25°C-55°C and pH 3. The Langmuir model estimated monolayer adsorption capacities ranging from 144.1 to 162.2 mg/g for Cr(VI) and 166.2 to 177.0 mg/g for Mn(VII), which improved with increasing the solution temperature. Steric and energetic parameters obtained from a monolayer adsorption model with one adsorption site was utilized to explain the adsorption mechanism at a microscopic level. The number of Cr(VI) and Mn(VII) ions adsorbed on PD/MCM-41 active site (n) were 1.25-1.27 for Cr(VI) and 1.27-1.32 for Mn(VII), thus suggesting multi-interaction mechanisms. The density of PD/MCM-41 active sites (D M) was a key parameter to explain the adsorption of these heavy metals. The adsorbed quantities were maximum at 55°C, thus obtaining 102.8 and 110.7 mg/g for Cr(VI) and Mn(VII), respectively. Cr(VI) and Mn(VII) adsorption energies ranged from 18.48 to 26.70 kJ/mol and corresponded to an endothermic adsorption with physical forces. Entropy, free enthalpy, and internal energy associated to the adsorption of Cr(VI) and Mn(VII) ions were calculated, thus indicating that the removal of these pollutants was spontaneous. Overall, this article offers new interpretations for the Cr(VI) and Mn(VII) adsorption mechanisms on PD/MCM-41 composite, which are relevant to contribute to the development of effective water treatment processes.

Experimental and Theoretical Studies of Methyl Orange Uptake by Mn-Rich Synthetic Mica: Insights into Manganese Role in Adsorption and Selectivity.

Manganese-containing mica (Mn-mica) was synthesized at 200 °C/96 h using Mn-carbonate, Al-nitrate, silicic acid, and high KOH concentration under hydrothermal conditions. Mn-mica was characterized and tested as a new adsorbent for the removal of methyl orange (MO) dye from aqueous solutions. Compared to naturally occurring mica, the Mn-mica with manganese in the octahedral sheet resulted in enhanced MO uptake by four times at pH 3.0 and 25 °C. The pseudo-second order equation for kinetics and Freundlich equation for adsorption isotherm fitted well to the experimental data at all adsorption temperatures (i.e., 25, 40 and 55 °C). The decrease of Langmuir uptake capacity from 107.3 to 92.76 mg·g-1 within the temperature range of 25-55 °C suggested that MO adsorption is an exothermic process. The role of manganese in MO selectivity and the adsorption mechanism was analyzed via the physicochemical parameters of a multilayer adsorption model. The aggregated number of MO ions per Mn-mica active site ( n ) was superior to unity at all temperatures signifying a vertical geometry and a mechanism of multi-interactions. The active sites number (DM) of Mn-mica and the total removed MO layers (Nt) slightly changed with temperature. The decrease in the MO adsorption capacities (Qsat = n·DM·Nt) from 190.44 to 140.33 mg·g-1 in the temperature range of 25-55 °C was mainly controlled by the n parameter. The results of adsorption energies revealed that MO uptake was an exothermic (i.e., negative ΔE values) and a physisorption process (ΔE < 40 kJ mol -1). Accordingly, the adsorption of MO onto Mn-mica was governed by the number of active sites and the adsorption energy. This study offers insights into the manganese control of the interactions between MO ions and Mn-mica active sites.

A Novel Nanocomposite of Activated Serpentine Mineral Decorated with Magnetic Nanoparticles for Rapid and Effective Adsorption of Hazardous Cationic Dyes: Kinetics and Equilibrium Studies.

A widely distributed mineral, serpentine, obtained from Wadi Ghadir (Eastern Desert in Egypt) was studied as a potential naturally and abundantly available source for the synthesis of an efficient adsorbent for aquatic remediation applications. A novel nanocomposite was synthesized after the exfoliation of the layered structure of serpentine by hydrogen peroxide treatment (serpentine (SP)), followed by decoration with magnetic Fe3O4 nanoparticles (MNP). The goal behind the utilization of the latter phase was to increase the environmental remediation capability and to incorporate magnetic properties at the final adsorbent, toward a better separation after the use. The fabricated composite (MNP/SP) was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). The composite's potential adsorption application toward the removal of two cationic dyes, methylene blue (MB) and malachite green (MG), was investigated. The observed adsorption kinetics was fast, and the highest uptake was observed at pH = 8, with the capacities to reach 162 and 176 mg g-1 for MB and MG, respectively, values significantly higher than various other materials tested against these two cationic dyes. Compared to hydrogen peroxide-treated serpentine, the removal efficiency of the composite was higher by 157 and 127% for MB and MG, respectively. The MB and MG were adsorbed because of the favorable electrostatic interactions between MNP/SP active sites and the cationic dyes. The close value capacities suggest that the difference in chemistry of the two dyes does not affect the interactions, with the later occurring via the dyes' amine functionalities. With increasing ionic strength, the adsorption of the studied basic dyes was slightly decreased, suggesting only partial antagonistic ion effect. The sorbent can be easily regenerated and reused without significant deterioration of its adsorption efficiency, which makes MNP/SP a promising adsorbent for the removal of hazardous pollutants from aquatic environments.

Enhancing adsorption capacity of Egyptian diatomaceous earth by thermo-chemical purification: Methylene blue uptake.

In the current study, calcination and thermo-chemical methods were applied in treatment of the processed diatomite fraction (<45 µm), which containing nearly 82.6 wt.% of the raw Egyptian diatomaceous earth. The untreated and modified diatomite fractions were characterized by optical microscopy (OM), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Thermo-chemical purification produced the highest concentration of diatom frustules (>92% SiO2) without blocking impurities and created SiOSi active sites. These fractions were tested for Methylene blue (MB) adsorption at different pH solutions (2.0-10.0). The purified diatomite via thermo-chemical treatment (PD) gave the greatest adsorption capacity for MB compared to the untreated (UD) and calcinated (CUD) diatomite fractions. Effects of experimental parameters such as MB concentration (60-200 mg L-1), contact time (5-480 min), adsorbent mass (50-250 mg) and temperature (30-55 °C) on MB uptake were investigated. Linear and non-linear forms of Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models indicated that Langmuir model with a maximum adsorption capacity (qmax=105.03mgg-1) fitted well the adsorption data. The chemical nature of MB uptake was revealed by the values of mean free energy E=8.655kJ/moland correlation coefficient of the pseudo-second-order model (R2=0.9997). The calculated thermodynamic parameters (ΔH0, ΔG0 and ΔS0) indicated that the removal of MB is spontaneous and endothermic.