organo acid-activated clays for water treatment as removal agent of Eosin-Y: Properties, regeneration, and single batch design absorber.

Organoclays have been proposed as efficient removal agents for colored wastewater treatment. In this study, organo-acid-activated clays were investigated for their ability to remove eosin Y dye molecules. Firstly, the clay was acid activated using sulfuric solution at 90 °C for overnight. Secondly, the resulting materials were treated by hexadecyltetramethylammonium bromide solutions to obtain organo-acid-activated clays. Several techniques were used, such as X-ray diffraction, carbon hydrogen nitrogen analysis, silicon-29 and carbon-13 solid-state nuclear magnetic resonance, and nitrogen adsorption isotherms. The cation exchange capacity values were reduced and the specific surface area values increased from 80.1 m2/g to 183.2 m2/g during the acid activation process. The resulting organo-acid-activated clays had a similar expansion of interlayer spacing of 3.90 nm with less intercalated hexadecyltetramethylammonium surfactants, ranging from 0.80 mmol/g to 1.22 mmol/g; 13C solid NMR indicated that the intercalated surfactants exhibited different degree of conformation. Many factors, including the solid dose, solution pH, amount of intercalated surfactants, and starting eosin-Y concentrations, were studied in relation to the removal capabilities of organo acid-activated clays. Based on the Langmuir model, the removal capacity of the organo acid-activated clays ranged from a minimum of 43.5 mg/g to a maximum of 79.3 mg/g, dependent on the surfactant quantities and acid activation degree. , and the pH. The removal percentage of eosin-Y was increased from 50.5 % to 80.8 % by treating the organo acid-activated clay with HCl solution before the removal procedure. Regeneration and reuse of two selected organo acid-activated clays were carried out for seven successive cycles, and a reduction in the initial efficiency was in the range of 26.4 %-30.1 %. However, for organoclay (without acid activation), approximately 52.1 % efficiency was maintained. Using the Langmuir model and mass balance equations, a single-stage adsorber design was suggested for different dye volumes at a constant starting concentration.

Radical Mediated Rapid In Vitro Formation of c-Type Cytochrome.

A cytochrome c552 mutant from Thermus thermophilus HB8 (rC552 C14A) was reported, where the polypeptide with replaced Cys14 by alanine, overexpressed in the cytosol of E. coli. The apo-form of the C14A mutant (apo-C14A) without the original prosthetic group was obtained by simple chemical treatments that retained compact conformation amenable to reconstitution with heme b and zinc(II)-protoporphyrin(IX), gradually followed by spontaneous formation of a covalent bond between the polypeptide and porphyrin ring in the reconstituted apo-C14A. Further analysis suggested that the residual Cys11 and vinyl group of the porphyrin ring linked through the thiol-ene reaction promoted by light under ambient conditions. In this study, we describe the kinetic improvement of the covalent bond formation in accordance with the mechanism of the photoinduced thiol-ene reaction, which involves a thiyl radical as a reaction intermediate. Adding a radical generator to the reconstituted C14A mutant with either heme-b or zinc(II) porphyrin accelerated the bond-forming reaction, which supported the involvement of a radical species in the reaction. Partial observation of the reconstituted C14A in a dimer form and detection of sulfuryl radical by EPR spectroscopy indicated a thiyl radical on Cys11, a unique cysteinyl residue in rC552 C14A. The covalent bond forming mediated by the radical generator was also adaptable to the reconstituted apo-C14A with manganese(II)-protoporphyrin(IX), which also exhibits light-mediated covalent linkage formation. Therefore, the radical generator extends the versatility of producing c-type-like cytochrome starting from a metallo-protoporphyrin(IX) and the apo-C14A instantaneously.

Enhancement Properties of Zr Modified Porous Clay Heterostructures for Adsorption of Basic-Blue 41 Dye: Equilibrium, Regeneration, and Single Batch Design Adsorber.

Zirconium porous clay heterostructures (Zr-PCH) were synthesized using intercalated clay minerals by zirconium species with different contents of zirconium. The presence of zirconium and silica species was confirmed by X-ray diffraction, X-ray fluorescence, and magic-angle spinning nuclear magnetic resonance. The insertion of zirconium improved the thermal stability, the specific surface area with a maximum of 950 m2/g, and the acidity concentration of 0.993 mol of protons per g of solid. These materials were used to adsorb the basic blue-41 from aqueous solution. The adsorption efficiency was examined at different conditions, with a maximum adsorbed amount of 346 mg/g as estimated from Langmuir model. This value was dependent on zirconium content in the PCHs. The adsorption process was found to be favorable and spontaneous. The efficiency of the spent materials was maintained after five reuse cycles with a decrease by 15% of the original value for a particular Zr-PCH material with a Zr content of 6.82%. Single stage batch adsorber was suggested using the mass balance equation and Langmuir isotherm model. The amount of PCH materials required depended on the target percentage of adsorption at specific volume and initial concentration of the basic-blue-41 dye solution.

Al and Zr Porous Clay Heterostructures as Removal Agents of Basic Blue-41 Dye from an Artificially Polluted Solution: Regeneration Properties and Batch Design.

The removal of Basic Blue-41 dye molecules was carried out by using two doped porous clay heterostructures by aluminum (Al) or zirconium (Zr) species. The proposed method of synthesis showed its efficiency, starting from Al or Zr intercalated hydrolyzed species, prior to its reaction with dodecylamine (C12 amine) and tetraethyl orthosilicate (TEOS) as a silica source. The intercalated precursors and their porous clay heterostructures (PCH) derivatives were characterized by different techniques. Solid NMR technique proved the presence of Al species into the intercalated silica between the clay sheets, and in addition to Si in different environments within the PCH materials. The Zr-PCH material exhibited a higher surface area and pore volume compared to its Al-PCH counterpart, with a mesoporous character for both materials. A maximum removed amount of 279 and 332 mg/g was achieved and deduced from the Langmuir equation. The regeneration tests revealed that the removal efficiency of Zr-PCH was retained after five regeneration runs, with a loss of 15% of the original value; meanwhile, the Al-PCH lost 45% of its efficiency after only three cycles. A single-stage batch design was proposed based on the Langmuir isotherm parameters. The increase of the removal capacity of Zr-PCH led to the reduction of the required amounts for the target removal of BB-41 dye compared to Al-PCH.

Highly Efficient Methylene Blue Dye Removal by Nickel Molybdate Nanosorbent.

Removing methylene blue (MB) dye from aqueous solutions was examined by the use of nickel molybdate (α-NiMoO4) as an adsorbent produced by an uncomplicated, rapid, and cost-effective method. Different results were produced by varying different parameters such as the pH, the adsorbent dose, the temperature, the contact time, and the initial dye concentration. Adsorbent dose and pH had a major removal effect on MB. Interestingly, a lower amount of adsorbent dose caused greater MB removal. The amount of removal gained was efficient and reached a 99% level with an initial methylene blue solution concentration of ≤160 ppm at pH 11. The kinetic studies indicated that the pseudo-second-order kinetic model relates very well with that of the obtained experimental results. The thermodynamic studies showed that removing the MB dye was favorable, spontaneous, and endothermic. Impressively, the highest quantity of removal amount of MB dye was 16,863 mg/g, as shown by the Langmuir model. The thermal regeneration tests revealed that the efficiency of removing MB (11,608 mg/g) was retained following three continuous rounds of recycled adsorbents. Adsorption of MB onto α-NiMoO4 nanoparticles and its regeneration were confirmed by Fourier transform infrared spectroscopy (FTIR) analysis and scanning electron microscopy (SEM) analysis. The results indicated that α-NiMoO4 nanosorbent is an outstanding and strong candidate that can be used for removing the maximum capacity of MB dye in wastewater.

Iron Molybdate Fe2(MoO4)3 Nanoparticles: Efficient Sorbent for Methylene Blue Dye Removal from Aqueous Solutions.

The present study investigated iron molybdate (Fe2(MoO4)3), synthesized via a simple method, as a nanosorbent for methylene blue (MB) dye removal from aqueous solutions. Investigations of the effects of several parameters like contact time, adsorbent dose, initial dye concentration, temperature and pH were carried out. The results showed that MB removal was affected, significantly, by adsorbent dose and pH. Interestingly, lower values of adsorbent dose resulted in the removal of higher amounts of MB. At the optimum pH, the removal efficiency of 99% was gained with an initial MB concentration of ≤60 ppm. The kinetic study specified an excellent correlation of the experimental results with the pseudo-second-order kinetics model. Thermodynamic studies proved a spontaneous, favorable and endothermic removal. The maximum amount of removal capacity of MB dye was 6173 mg/g, which was determined from the Langmuir model. The removal efficiency was shown to be retained after three cycles of reuse, as proven by thermal regeneration tests. The presence and adsorption of the dye onto the Fe2(MoO4)3 nanoparticle surface, as well as the regeneration of the latter, was ascertained by scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). These findings are indicative that the investigated nanosorbent is an excellent candidate for the removal of MB in wastewater.

Physicochemical characteristics and photocatalytic performance of TiO2/SiO2 catalyst synthesized using biogenic silica from bamboo leaves.

In this work, TiO2/SiO2 composite photocatalysts were prepared using biogenic silica extracted from bamboo leaves and titanium tetraisopropoxide as a titania precursor via a sol-gel mechanism. A study of the physicochemical properties of materials as a function of their titanium dioxide content was conducted using Fourier transform infrared spectroscopy, a scanning electron microscope, a diffuse reflectance ultraviolet-visible (UV-vis) spectrophotometer, and a gas sorption analyzer. The relationship between physicochemical parameters and photocatalytic performance was evaluated using the methylene blue (MB) photocatalytic degradation process under UV irradiation with and without the addition of H2O2 as an oxidant. The results demonstrated that increasing the TiO2 helps enhance the parameters of specific surface area, the pore volume, and the particle size of titanium dioxide, while the band gap energy reaches a maximum of 3.21 eV for 40% and 60% Ti content. The composites exhibit photocatalytic activity with the MB degradation with increasing photocatalytic efficiency since the composites with 40 and 60% wt. of TiO2 demonstrated the higher degradation rate compared with TiO2 in the presence and absence of H2O2. This higher rate is correlated with the higher specific surface area and band gap energy compared with those of TiO2.

Eosin Removal by Cetyl Trimethylammonium-Cloisites: Influence of the Surfactant Solution Type and Regeneration Properties.

The effect of the counteranion of hexadecyltrimethylammonium salts on the physico-chemical properties of organoclays was investigated, using a selected natural clay mineral with a cation exchange capacity of 95 meq/100 g. The uptake amount of C16 cations was dependent on the hexadecyltrimethylammonium (C16) salt solution used, the organoclay prepared from C16Br salt solution exhibited a value of 1. 05 mmole/g higher than those prepared from C16Cl and C16OH salt solutions. The basal spacing of these organoclays was in the range of 1.81 nm to 2.10 nm, indicating a similar orientation of the intercalated surfactants, and could indicated that the excess amount of surfactants, above the cation exchange capacity of 0.95 meq/g could be adsorbed on the external surface of the clay mineral sheets. These organoclays were found to be stable in neutral, acidic, and basic media. The thermal stability of these organoclays was carried out using thermogravimetric analysis and in-situ X-ray diffraction (XRD) techniques. The decomposition of the surfactant occurred at a maximum temperature of 240 °C, accompanied with a decrease of the basal spacing value close to 1.42 nm. The application of these organoclays was investigated to remove an acidic dye, eosin. The removal amount was related to the initial used concentrations, the amount of the surfactants contents, and to the preheated temperatures of the organoclays. The removal was found to be endothermic process with a maximum amount of 55 mg of eosin/g of organoclay. The value decreased to 25 mg/g, when the intercalated surfactants were decomposed. The reuse of these organoclays was limited to four regeneration recycles with a reduction of 20 to 30%. However, noticeable reduction between 35% to 50% of the initial efficiency, was achieved after the fifth cycle, depending of the used organoclays.

Application of Organo-Magadiites for the Removal of Eosin Dye from Aqueous Solutions: Thermal Treatment and Regeneration.

Na-magadiite exchanged with cetyl-trimethylammonium cations provided organophilic silicate materials that allowed for the effective removal of the acidic dye "eosin". The organic cations were intercalated into the interlayer spacing of the layered silicate via an exchange reaction between the organic cations from their bromide salt and the solid Na-magadiite at room temperature. Different techniques were used to characterize the effect of the initial concentration of the surfactant on the structure of the organo-magadiites. The C, H, and N analysis indicated that a maximum of organic cations of 0.97 mmol/g was achieved and was accompanied by an expansion of the basal spacing of 3.08 nm, with a tilted angle of 59° to the silicate layers. The conformation of the organic surfactants was probed using solid-state 13C, finding mainly the trans conformation similar to that of the starting cetyl trimethylammonium bromide salt (C16TMABr). Thermal gravimetric analysis was carried out to study the thermal stability of the resulting organo-magadiites. The intercalated surfactants started to decompose at 200 °C, with a mass loss percentage of 8% to 25%, depending on the initial loading of the surfactant, and was accompanied by a decrease of the basal spacing from 3.16 nm to 2.51 nm, as deduced from the in situ X-ray diffraction studies. At temperatures below 220 °C, an expansion of the basal spacing from 3.15 to 3.34 nm occurred. These materials were used as a removal agent for the anionic dye eosin. The maximum amount of the dye removed was related to the organic cation content and to the initial concentration of eosin, with an improvement from 2.5 mg/g to 80.65 mg/g. This value decreased when the organo-magadiite was preheated at temperatures above 200 °C. The regeneration tests indicated that an 85% removal efficiency was maintained after six cycles of use for the organo-magadiite using Ci of 200 mg/L.

Removal Properties of Anionic Dye Eosin by Cetyltrimethylammonium Organo-Clays: The Effect of Counter-Ions and Regeneration Studies.

The organo-clays (OCs) were prepared by a cation exchange reaction between surfactant (cetyltrimethylammonium, C16TMA) from different counterions (Bromide, Chloride, and Hydroxide). The effect of the counterions was investigated on the physico-chemical properties of the prepared organo-clays. The highest uptake of organic cations (1.60 mmol/g) was achieved using cetyl trimethylammonium bromide solution and the lowest value (0.93 mmol/g) was obtained after modification with cetyl trimethylammonium hydroxide solution starting from the same initial ratio of mmol/g of clay greater than 2.40. The arrangement of C16TMA cations within the interlayer space was assumed to be perpendicular with a tilt angle of 32° to the plane of clay sheets instead of being parallel to the clay surface using C16TMAOH solution at the same ratio. Different techniques were used to characterize these materials. The thermal stability of these organ-clays was investigated using an in-situ X-ray diffraction (XRD) technique. The decomposition of the surfactant moiety occurred at temperatures higher than 215 °C and was accompanied with a shrinkage of the basal spacing value to 1.42 nm. These materials were applied in the removal of an acid dye "eosin." The removed amount of eosin depended on the initial concentrations and the content of surfactants in the organo-clays. The removal of eosin was found to be an endothermic process. The maximum amount of 90 mg/g was achieved. The preheated treatment temperature of two selected OCs did affect the removal properties of eosin. A progressive reduction was observed at temperatures higher than 200 °C. The regeneration of spent OCs was studied and acceptable removal efficiency was maintained after 4 to 6 cycles depending on the used initial concentrations.

Molybdenum Trioxide: Efficient Nanosorbent for Removal of Methylene Blue Dye from Aqueous Solutions.

Nano Molybdenum trioxide (α-MoO3) was synthesized in an easy and efficient approach. The removal of methylene blue (MB) in aqueous solutions was studied using this material. The effects of various experimental parameters, for example contact time, pH, temperature and initial MB concentration on removal capacity were explored. The removal of MB was significantly affected by pH and temperature and higher values resulted in increase of removal capacity of MB. The removal efficiency of Methylene blue was 100% at pH = 11 for initial dye concentrations lower than 150 ppm, with a maximum removal capacity of 152 mg/g of MB as gathered from Langmuir model. By comparing the kinetic models (pseudo first-order, pseudo second-order and intraparticle diffusion model) at various conditions, it has been found that the pseudo second-order kinetic model correlates with the experimental data well. The thermodynamic study indicated that the removal was endothermic, spontaneous and favorable. The thermal regeneration studies indicated that the removal efficiency (99%) was maintained after four cycles of use. Fourier Transform Infrared (FTIR) and Scanning Electron Microscopy (SEM) confirmed the presence of the MB dye on the α-MoO3 nanoparticles after adsorption and regeneration. The α-MoO3 nanosorbent showed excellent removal efficiency before and after regeneration, suggesting that it can be used as a promising adsorbent for removing Methylene blue dye from wastewater.

Modified Nigella Sativa Seeds as a Novel Efficient Natural Adsorbent for Removal of Methylene Blue Dye.

The aim of this work was to investigate the use of modified nigella sativa seeds (MNS) for removing of methylene blue (MB) dye from aqueous solution. The nigella sativa (NS) seeds have been pre-treated at different temperatures and periods of time. The maximum adsorption of MB was achieved using NS sample washed with distilled water pre-heated at 65 °C for one hour, then ground to 250 µm particle size (MNS-4). Different parameters were modified to optimize the removal process of MB using MNS-4, such as contact times, temperatures, initial dye concentrations, adsorbent doses, and pH of the solution. MNS-4 exhibited a removal efficiency of 99% for initial dye concentrations greater than 800 ppm at pH value of 11. The kinetic study indicated that the removal process follows the pseudo second order model. The removal was spontaneous, endothermic and favorable, and this was indicated by the thermodynamic study. Maximum removal capacity was 194 mg/g as deduced from Langmuir model. The removal efficiency was maintained after four recycle uses. The modified nigella sativa seeds were characterized before, and after adsorption and regeneration by Fourier Transform infrared (FTIR) and scanning electron microscopy (SEM). The data suggested that nigella sativa seeds could be a prospective agent for removing MB from wastewater.

Exfoliation properties of acid-activated montmorillonites and their resulting organoclays.

The intercalation process of acid-treated montmorillonite clays by a cationinc surfactant (decyltrimethylammonuium) from a hydroxide solution was affected by the temperature of acid activation. Although the cation exchange capacity of the treated clay at 90 degrees C (0.74 mequiv g(-1)) was lower compared to that treated at room temperature (0.84 mequiv g(-1)), the uptaken amount of the surfactant (1.24 mmol g(-1)) and thus the basal spacing (3.83 nm) were higher. These values depended on the initial loading concentrations. However, when the clay was treated at room temperature, the uptaken amounts of surfactant (0.81 mmol g(-1)) and the basal spacing (2.20 nm) were lower. These values were independent of the initial loading concentration. The higher basal spacing (3.83 nm) was also affected by the type of the exchange medium and the washing solution by a mixture of ethanolic solutions. The intercalation of the surfactants occurred in two different ways, and was related to exfoliation properties of the acid activated clays. The intercalated surfactant exhibited different conformations in the interlayer space and different thermal stability.

Effect of the acid activation levels of montmorillonite clay on the cetyltrimethylammonium cations adsorption.

For the first time, the intercalation properties of acid-activated montmorillonites treated at different acid/clay (w/w) ratios with a cationic surfactant cetyltrimethylammonium (C16TMA) hydroxide are reported. The acid activation causes a reduction in the number of cation exchange sides and, hence improves the exfoliation of the silicate sheets at higher pH values. The basal spacing increases significantly from 1.54 to 3.80 nm, and is related to the acid activation extent. The acid activated clays with acid/clay ratios above 0.2 intercalated significant amounts of C16TMA cations with a basal spacing of 3.8 nm compared to the non acid activated montmorillonite with a basal spacing of 2.10 nm. The 13C CP/MAS NMR indicates that the intercalated surfactants exhibit a significant degree of gauche conformation in the acid-activated clays. According to in-situ powder XRD, an increase of the basal spacing to 4.08 nm is observed at intermediate temperatures of 50-150 degrees C for organoclay with basal spacing of 3.80 nm, at higher temperatures above 300 degrees C, the decomposition of the surfactant occurs and the basal spacing decreases to a value of about 1.4 nm, with the persistence of a reflection at 3.8 nm for clay at a higher acid/clay ratio of 0.5.