Temperature effects on iodine adsorption on organo-clay minerals: II. Structural effects

Smectites and vermiculites modified with hexadecylpyridinium (HDPy⁺), hexadecyltrimethylammonium (HDTMA⁺), benzethonium (BE⁺) and dipyridinododecane (DPyDD²⁺) cations exhibit high adsorption capabilities for the anionic radionuclide ¹²⁵I⁻ (Part I of this article). In some cases, exposure to higher temperature decreased the anion adsorption. To clarify the mechanisms of temperature dependence of the investigated organo-clay minerals, structural properties and thermal stabilities were examined by in situ powder X-ray diffraction (XRD), thermogravimetry (TG), thermocalorimetry (DTA) and FTIR spectral analyses.The organic cations HDPy, HDTMA and BE form bilayers, pseudotrimolecular layers and paraffin-type structures. The basal spacings of DPyDD-smectite and DPyDD-vermiculite were more or less unchanged in comparison to the original clay minerals (1.4 nm). It is assumed that the anion adsorption is due to the uptake of organic cations in an excess of the CEC, predominantly in the interlayer spaces as ion pairs.The decreasing iodide adsorption with increasing temperature is probably due to conformational changes of the alkyl chains, which are most pronounced for DPyDD-vermiculite at 60 °C (1.48→1.20 nm). Additionally, dehydration reactions, which occur at distinct temperatures for the organo-vermiculites (HDPy, 71; HDTMA, 57, 72; BE, 61; DPyDD, 41 °C), may be another reason for a decrease in iodide adsorption. The thermal decomposition of the organic cation starts at 200 °C. The HDPy, HDTMA and DPyDD-smectites and the HDTMA and BE-vermiculites show a high thermal stability with the basal spacing remaining constant up to 150 °C, which recommends the use for anion retention in engineered barriers for heat-producing waste.     

Adsorption of difenzoquat on montmorillonite: model calculations and increase in hydrophobicity

The adsorption of difenzoquat (DZ) on montmorillonite was studied at a wide range of concentrations and ionic strengths. Up to difenzoquat loadings of 0.4 mmol/g clay, all the added cation were adsorbed. Maximal adsorbed amounts exceeded slightly the cation exchange capacity (CEC) of the clay (0.8 mol_c/kg). The adsorbed amounts did not change upon increasing the concentration of NaCl in the medium to 500 mM. An adsorption model that combines electrostatic equations with specific binding in a closed system could adequately predict the adsorbed amounts of DZ, even at high ionic strength. Simultaneous adsorption of the divalent cationic herbicide diquat (DQ) and DZ was also determined and the predictions of the model were adequate for total loadings up to the CEC of the clay. At higher loads the model adequately predicts the DZ adsorbed, but underestimates the amounts of DQ adsorbed. The influence of adsorbed DZ on the hydrophobicity of montmorillonite was tested by using the hydrophobic herbicide pendimethalin (PM). The adsorption isotherm of PM on crude montmorillonite is of the S type, indicating very low adsorption at low added amounts, and increasing affinity after part of the surface is covered with the hydrophobic molecules. Adsorption of PM on montmorillonite saturated with DZ up to 80% of the CEC showed a C behavior, indicating a partition mechanism between the solvent and the adsorbent even at low added amounts. The enhanced hydrophobicity of DZ–montmorillonite was also demonstrated in qualitative experiments in a mixed chloroform–water environment: whereas the crude clay mineral stayed in the water phase, DZ–montmorillonite concentrated in the chloroform phase.     

Improved efficiency of a divalent herbicide in the presence of clay, by addition of monovalent organocations

A severe decrease in efficacy of contact herbicides such as diquat (DQ) is caused by dust accumulated on the weeds. Such inactivation was explained by the adsorption of herbicides on dust particles. As a result of this inactivation, the rates of pesticides needed for efficient pest control are usually larger than the recommended rates, which increases the expenses, and pose a real danger to the environment and to the ecological balance of watersheds. We proposed the hypothesis that the addition of a monovalent organic cation to the herbicide formulation might improve the efficacy by lowering the amount of herbicide that is inactivated by the sorption to clay minerals. This hypothesis was tested on lettuce and pepper plants dusted with clay, using the commercial formulation of diquat (“Reglone”) and adding the monovalent organic cations acriflavin (AF) and mepiquat (MQ). We observed that a clay mineral with a high cation exchange capacity (CEC), such as montmorillonite, reduced the herbicidal activity of DQ more than a lower CEC clay as sepiolite. However, addition of 5–20 mM concentrations of AF or MQ may overcome the influences of a clay dust on the activity of a cationic herbicide. Such addition allowed the obtainment of good herbicidal results with less than 1/3 of the normal used amount of herbicide. The results of our research point out to a mechanism that may lower the needed doses of contact herbicides, due to a competitive adsorption on the clay–dust particles between the pesticide and monovalent organic cations that leaves more herbicide available to act on the weed.     

Reduction of photodegradation and volatilization of herbicides in organo-clay formulations

The use of commercially available emulsifiable concentrate (EC) formulations of alachlor and metolachlor may be an environmental hazard because of their volatilization to the atmosphere and photodecomposition, which requires increased applied amounts. The objectives of this study were to develop organo-clay based formulations which would be less volatile and better protected from photodegradation. Bioassays have shown that the use of organo-clay formulations improves photoprotection, reduces volatilization and maintains herbicidal activity in the soil under laboratory and field conditions. Largest adsorption of herbicides by organo-clays correlates with an optimal reduction of photodecomposition and volatilization. It appears that the role of the organic cation, e.g., benzyltrimethylammonium (BTMA) is to enhance the adsorption of the non-polar herbicides to the organo-clay complex, whereas the actual photoprotection is mainly provided by the clay.     

Vapor Adsorption of Volatile Organic Compounds Using Organically Modified Clay

Abstract

Organically modified clay was used to adsorb volatile organic compounds from a gaseous phase. The organoclay was prepared by adsorbing hexadecyltrimethylammonium (HDTMA) on the surface of montmorillonite particles. Two volatile organic compounds (VOCs), chlorobenzene and trichloroethylene, were adsorbed to the organoclay using a fixed adsorption bed. The adsorption was carried out at various inlet concentrations of gaseous VOCs in a carrier gas (nitrogen). The adsorption behavior of VOCs was investigated using natural clay and two types of organoclays, which had different HDTMA loadings. Adsorption breakthrough curves were obtained, and the adsorption data were modeled with two adsorption isotherms. Desorption of VOCs was also conducted using pure nitrogen, and the desorption profiles were fitted with two different theoretical models. It was found that the organoclay possesses significant adsorption capacity towards VOCs and the uptake depends on the degree of HDTMA loading on clay surface.     

Dicamba adsorption–desorption on organoclays

The adsorption–desorption of the herbicide dicamba (pK_a=1.9, water solubility, 6.5 g kg⁻¹) by organoclays (OCls) was studied at different concentrations and pH levels. Two smectites (SAz and SWy), varying in surface properties, were reacted with amounts of different alkylammonium cations [octadecyl(C18)-, hexadecyl-trimethyl(HDT)- and dioctadecyldimethyl(DOD)ammonium] equal to 50% or 100% of the clays' CEC. Adsorption isotherms of dicamba on diverse OCl were some of L-type and others of S-type, but both resulted in sigmoid form when extended to higher concentration. Adsorption was greater for OCls with high-layer charge, basal spacing, alkylammonium size and organocation saturation close to CEC. Dicamba adsorption by OCls seems to involve hydrophobic and polar interactions for which the availability of interlayer room between organocations is very important. Adsorption data at different pH levels and two different concentrations (0.05 and 1 mM) indicated that molecular dicamba is the main adsorbing species, especially at high concentration. Desorption isotherms were reversible, except in OCls with primary alkylammonium (C18) and largest quaternary (DOD), for which there were moderate hysteresis as a result of stronger polar contribution in the primary alkylammonium and the difficulty for diffusion in the case of the quaternary, bulky OCl. The treatment of an artificially dicamba-contaminated soil with highly adsorptive OCls rendered a dramatic decrease in the CaCl₂-released- or mobile dicamba, suggesting these OCls as potential immobilising agents. The amount of herbicide immobilised by the OCl was partially extractable with methanol/CaCl₂ solution, suggesting its biovailability and hence, its possible combination with bioremediation technique.     

Adsorption of chromate from aqueous solutions by HDTMA-modified clinoptilolite,glauconite and montmorillonite

Adsorption of chromate on natural clinoptilolite (Cp), glauconite (Gl), and montmorillonite (Mt) treated with hexadecyl trimethylammonium (HDTMA) bromide at amounts equivalent to 1.0 and 2.0 of their cation-exchange capacities (CEC) was investigated by batch study. In the case of the Cp and Gl, adsorption of HDTMA took place on the zeolite and clay mineral surfaces only and thus relates to the external CEC (ECEC). The amount of chromate removed from the solution by the organo-silicates continuously decreased with increasing pH in the range 1.3–10. The highest values were obtained at pH between 1.3 and 6, and decreased rapidly above pH 6. At an initial chromate concentration of 6.25 mmol/L, its amounts bound to the Cp, Gl and Mt modified using 1.0 CEC loadings of the surfactant were 47, 102, and 168 mmol/kg, respectively. When amount of HDTMA used was equivalent to 2.0 CEC of the silicate, these values increased to 182, 240, and 285 mmol/kg, respectively. The results obtained suggest that the surfactant molecules, bound beyond the CEC to the external surfaces of the Cp and Gl, show a greater chromate adsorption ability in comparison with such molecules located in the interlayer spaces of the Mt. It is also evident that an excess of the surfactant, not adsorbed on the silicate surfaces, participated in the removal of chromate from the solution by formation of a precipitate of alkylammonium chromate.     

Removal of cationic dye from aqueous solution by adsorption onto crosslinked poly(4-vinylpyridine/crotonic acid) and its N-oxide derivative

In this study, crosslinked poly(4-vinylpyridine/crotonic acid) [poly(4-VPy/CrA)] and its N-oxide derivative were synthesized to compare the adsorption of cationic methylene blue (MB) dye on these materials. The adsorptive removal of MB from aqueous solution onto adsorbents was studied by using column adsorption method. Experimental results showed that MB was removed more effective by poly(4-VPy/CrA)–N-oxide than poly(4-VPy/CrA) resins. The percentage removal of MB increased with pH, and it was observed that basic pH was favorable for the adsorption of MB. The adsorption capacity for poly(4-VPy/CrA)–N-oxide resin was found to 19.96 mg/g. It was found that the adsorption isotherm of the MB-fitted Langmuir-type isotherm. For the adsorption of MB, the pseudo-second-order chemical reaction kinetics provides the best correlation with the experimental data. Ten adsorption–desorption cycles demonstrated that the resins were suitable for repeated use without considerable change in adsorption capacity.     

Adsorption of tannic acid on chitosan-montmorillonite as a function of pH and surface charge properties

Chitosan, a natural biopolymeric cation, is a candidate to modify montmorillonite for the adsorption of anions. As an anionic organic pollutant the adsorption of tannic acid was studied. Because of protonation/deprotonation reactions of both chitosan-montmorillonite and tannic acid, the adsorption process is strongly pH-dependent. The objective of this work is to characterize the pH dependency of adsorption in combination with surface charge determinations.Montmorillonite was modified with different amounts of chitosan, corresponding to 20–1000% of the cation exchange capacity (CEC). The deacetylation degree of chitosan was determined by polyelectrolyte titration and was found to be 74%. The uptake of chitosan was determined by the C-content. The interlayer expansion was investigated by X-ray powder diffraction. The adsorption capacity for tannic acid was investigated with the batch technique at pH 3, 4, 5 and 8. As a measure for the adsorption properties, the electrokinetic surface charge was determined with a particle charge detector.The uptake of chitosan by montmorillonite is up to 152% (1.69 mol_c kg^− 1) of the CEC. The resulting anion exchange capacity of chitosan-montmorillonite calculated from C-content is 0.43 mol_c kg^− 1. At low loadings with chitosan (24.7 and 49.5% uptake), a monolayer is formed in montmorillonite. At an uptake of 96.8%, a bilayer structure is observed, which becomes more dominant at higher loadings. On the external surface, a monolayer of chitosan was formed. From pH 4 to 8, the surface charge of all modified montmorillonites is with − 9 to 8 mmol_c kg^− 1 close to the point of zero charge. The maximal adsorption capacity for tannic acid is found with 240 g kg^− 1 (0.14 mol_c kg^− 1) at pH 4. The adsorption process fits in well with the Freundlich isotherm. At lower as well as higher pH values the adsorption capacity decreases up to about 25%. Most probably the exchange sites in the interlayer do not contribute to the adsorption of tannic acid. The observed surface charge is lower than the adsorbed amount of tannin. It is thought that tannin is adsorbed also by van der Waals forces besides ionic forces.     

Organo-clay formulations of pesticides: reduced leaching and photodegradation

Adsorption of organic cations on several clay minerals is reviewed with an emphasis on the effect of ionic strength and modeling. The clay exchanged with suitable organic cations forms a basis for ecologically acceptable formulations of herbicides with reduced leaching, ground water contamination and enhanced weed control efficacy. Incomplete neutralization of the clay surface charge by an organic cation may be advantageous in achieving maximal adsorption of hydrophobic herbicides. One conclusion from these studies is that optimization of clay-based herbicide formulations requires a selection of structurally compatible organic cations preadsorbed on the clay at optimal coverage. New experimental results are presented for alachlor formulations, which significantly reduce herbicide leaching under conditions of heavy irrigation. We were able to demonstrate that organo-clay formulations of alachlor and metolachlor can increase crop yields in a 1-year field experiment. The photostabilization of pesticides is reviewed and improved organo-clay formulations of the herbicides trifluralin and norflurazon are described. A pillared clay, nanocomposite micro- and/or meso porous material, was effective in reducing leaching and in conferring photostabilization, without added organic cations.     

Removal of methylene blue from aqueous solutions by poly(2-acrylamido-2-methylpropane sulfonic acid-co-itaconic acid) hydrogels

In this study, removal of methylene blue (MB) from aqueous solution by poly(AMPS-co-IA) hydrogels was examined by batch equilibration technique. The effects of monomer ratio, concentration of initiator and crosslinker, pH, adsorption time, initial dye concentration and adsorption temperature on the removal of MB were studied. The results show that the removal of MB was highly effected by preparation conditions of hydrogel. The maximum removal was observed at 10/90 IA/AMPS monomer ratio, 1.0% KPS, and 10.0% MBAAm concentrations. Removal of MB was strongly affected by pH. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were applied. It was concluded that adsorption of MB on hydrogel followed pseudo-second-order kinetics. It was found that the adsorption isotherm of the MB fit Langmuir-type isotherms. From the Langmuir equation, the adsorption capacity was found as 1,000 mg/g for MB dye. Thermodynamic parameters suggest that the adsorption is a typical physical process, spontaneous, and exothermic in nature. Ten adsorption—desorption cycles demonstrated that the hydrogels were suitable for repeated use without considerable change in adsorption capacity. The results revealed that this hydrogels have potential to be used as an adsorbent for the removal of MB from aqueous solution.     

Adsorption of diquat, paraquat and methyl green on sepiolite: experimental results and model calculations

Adsorption of the divalent organic cations paraquat (PQ), diquat (DQ) and methyl green (MG) on sepiolite was determined experimentally and investigated with an adsorption model. The largest amounts of DQ, PQ and MG adsorbed were between 100% and 140% of the cation exchange capacity (CEC) of sepiolite. In previous experiments with monovalent organic cations (dyes), the largest amounts of dyes adsorbed were about 400% of the CEC of sepiolite. Consequently, it was proposed that most of this adsorption was to neutral sites of the clay. The large differences between the adsorption of these divalent organic cations and the monovalent dyes may indicate that there is almost no interaction between DQ, PQ and MG and the neutral sites of sepiolite. This assumption was confirmed by infrared (IR) spectroscopy measurements, that did not show changes in the peaks arising from the vibrations of external Si---OH groups of the clay when the divalent organic cations were added. Adsorption results were compared with calculations of an adsorption model that combines the Gouy–Chapman solution and specific binding in a closed system. The model considers cation adsorption on neutral sites of the clay, in addition to adsorption to mono- or divalent negatively charged sites, forming neutral or charged complexes. The model could adequately simulate the adsorption of the divalent organic cations DQ and PQ when added alone, and could yield good fit for the competitive adsorption experiment between the monovalent dye methylene blue and DQ. In competitive adsorption experiments, when total cationic charges exceeded the CEC, monovalent organic cations were preferentially adsorbed on the clay at the expense of the divalent cations.     

Computerized Solution of the Dynamic Sorption Process for a Ternary System in a Heterophase Medium

A mathematical model equation for the ternary adsorption–reaction process was developed and illustrated for the catalytic dehydrogenation of cyclohexane to benzene with the adsorption of hydrogen atoms as a monomolecular species on platinum–rhenium/alumina catalyst in inert and active carrier gases using pulse and continuous flow techniques. An optimization routine of the Nelder–Mead simplex method was used to estimate the surface reaction rate constant and adsorption equilibrium constant at different temperatures. These constants were then used to determine activation energies and adsorption equilibrium energies for cyclohexane dehydrogenation in inert (argon, helium) and active (hydrogen) carrier gases using pulse and continuous flow techniques. Numerical solutions for the ternary adsorption–reaction scheme were compared with the binary adsorption–reaction case where hydrogen adsorption is ignored. The predicted results for the ternary adsorption–reaction revealed that hydrogen adsorption during cyclohexane dehydrogenation is significant.     

Cation exchange capacity methodology II: A modified silver–thiourea method

The silver–thiourea method for the determination of the cation exchange capacity (CEC) has been critically examined. The chemical instability of the exchange solution used causes silver sulphide precipitation on the walls of tubes resulting in a loss of the index cation. This produces misinterpretation and yields usually in an overestimation of the CEC. Furthermore, when expandable clay minerals are investigated excess adsorption occurs leading to unreliable CEC results dependent on solution/solid ratio and ionic strength of the exchange solution. A modified silver–thiourea method is proposed, which uses a chemically more stable exchange solution, eliminating silver sulphide precipitation and substantially lowering excess adsorption, which is abolished by additional washings. The results are comparable to the ammonium acetate method.     

Photostabilization of Beauveria bassiana conidia using anionic dyes

Microbial biocontrol agents, which are selective and non-polluting measures for controlling insect pests, are sensitive to environmental factors, notably solar UV radiation. To overcome the constraint of photoinstability and provide adequate field performance, the photostabilizing potential of organo-clay matrices was studied. The clay mineral surfaces were modified by adsorption of chitosan, a polycationic biopolymer. The positively charged clay–chitosan complexes served for adsorption of potent photoprotective anionic dyes. A variety of clay–chitosan–dye matrices were prepared and examined as to their potential to photostabilize UV-irradiated fungal conidia of the entomopathogen Beauveria bassiana. The matrices were composed of palygorskite, montmorillonite, bentonite and kaolinite and of 6 anionic dyes: Acid Yellow 25 (AY), Chrysophenine G (Chrys.), Direct Yellow 50 (DY), Mordant Blue (MB), Fast Green (FG) and Naphthol Yellow S (NYS). The adsorption isotherms of dyes and their level of adsorption to the organo-clays were established. Clay–chitosan complexes per se were able to bestow significant measures of photoprotection, apparently due to their UV light scattering property. High and relatively consistent levels of photostabilization were observed with clay–chitosan matrices containing Chrys., AY, NYS and DY following prolonged irradiation. Depending on the clay-based matrix, MB and FG provided less persistent photostabilization levels. In contrast to the other clay–chitosan complexes, the high photoprotection bestowed by kaolinite–chitosan per se obscured to a great extent any contribution of the anionic dyes. Apparently, the photostabilization of the clay-based matrices is a combination of UV light scattering capacity of clay minerals and the UV screening effect due to the adsorbed dyes.     

Adsorption of gaseous SO2 and structural changes of montmorillonite

Several montmorillonite samples after adsorption of gaseous SO₂ were analyzed to evaluate structural and textural changes. The equilibrium adsorption of the SO₂ gas was measured at 25 °C and 0.1 MPa. The samples were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), swelling index (SI), pH measurements, and N₂ adsorption–desorption isotherms. SO₂ adsorption increased with the specific surface area of montmorillonite. SO₂ retention decreased pH of the dispersed samples from 6 to 1 and released interlayer and octahedral cations from the structure, which increased the specific BET surface area and specific micropore surface similar to that of acid-activated montmorillonite.     

Liquid phase oxidation of dibenzothiophene with alumina-supported vanadium oxide catalysts: An alternative to deep desulfurization of diesel

Alumina-supported vanadium oxide catalysts were prepared by different methods as thermal spreading, incipient wetness impregnation of ammonium metavanadate and sol–gel synthesis of alkoxide precursors, with different vanadium loadings, in order to increase the performance in oxidative desulfurization (ODS) of dibenzothiophene. The catalysts were characterized by several techniques: X-ray diffraction, UV–vis DRS, Raman spectroscopy, FT-IR of adsorbed pivalonitrile, and TPR. As additional experimental techniques, SEM–EDX and N₂ adsorption–desorption were applied, to obtain elemental analyses and textural properties. Results evidenced the presence of different superficial V species, which depend on both vanadium loading and preparation method, while significant differences in ODS activity were observed due to the catalysts preparation method.     

Influence of ethanol addition on the modification of montmorillonite by hexadecyl trimethylammonium bromide

Although modification of montmorillonite (MMT) with cationic surfactants has been studied extensively, the influence of the reaction medium has not been investigated systematically. The present paper reports the influence of ethanol on the modification of MMT using hexadecyl trimethylammonium bromide (HDTMA-Br). Wide angle X-ray diffraction (WAXD) and thermogravimetric analysis (TGA) were used to characterize the organically modified montmorillonite (OMMT). The addition of ethanol had little influence on the cation exchange, but affected greatly on the intercalation of the surfactant ion pairs into the interlayer space when HDTMA exceed the cation exchange capacity (CEC) of MMT. The increase of the ethanol/water ratio increased the critical micelle concentration (CMC) of HDTMA-Br solution. The intercalation of HDTMA ion pairs proceeded when the HDTMA concentration was above the CMC. It was confirmed that both of basal spacing and organic fraction followed sigmoid functions for OMMT prepared with excess HDTMA-Br amount and various surfactant concentrations under different CMC.     

Adsorption of Organic Phenojs onto Dual Organic Cation Montmorillonite from Water

Abstract

Single- and multicomponent competitive adsorptions were carried out in a batch reactor to investigate the removal of three toxic organic phenols, 2-chlorophenol, 3-cyanophenol, and 4-nitrophenot, using organically modified montmorillonite. To study the removal capacity of phenolic contaminants dissolved in aqueous solution, two organic cations, tetramethylammonium (TMA) and hexadecyltrimethylammonium (HDTMA), were exchanged for the metal cations on the montmorillonite to the extent of about 40 and 45% of the cation-exchange capacity (CEC) of the montmorillonite, respectively, resulting in a surface property change from hydrophilic to organophilic. From the experimental results it was observed that adsorption affinity on TMA/HDTMA–montmorillonite is in the order 2-chlorophenol > 4-nitrophenol > 3-cyanophenol. The Langmuir and the Redlich–Peterson models were used to analyze the single component adsorption equilibria. On the other hand, the IAST and LCM models were used to predict the multicomponent competitive adsorption equilibria. These models yielded favorable representations of both individual and competitive adsorption behaviors.     

Removal of heavy metal ions by dithiocarbamate-anchored polymer/organosmectite composites

In this study, the dithiocarbamate-anchored polymer/organosmectite composites were prepared for the removal of heavy metal ions (lead, cadmium and chromium) from aqueous media containing different amounts of these ions (50–750 ppm) and at different pH values (2.0–8.0). Initially, the modification of the natural smectite minerals was performed by treatment with quartamin styrene and chloromethylstyrene. Then, modified smectite nanocomposites were reacted with carbondisulfide, in order to incorporate dithiocarbamate functional groups into the nanolayer of organoclay. The dithiocarbamate-anchored nano-composites have been characterized by FTIR and used in the adsorption–desorption process. The maximum adsorptions of heavy metal ions onto the dithiocarbamate-anchored polymer/organosmectite composites from their solution was 170.7 mg g^− 1 for Pb(II); 82.2 mg g^− 1 for Cd(II) and 71.1 mg g^− 1 for Cr(III). Competition between heavy metal ions (in the case of adsorption from mixture) yielded adsorption capacities of 70.4 mg g^− 1 for Pb(II); 31.8 mg g^− 1 for Cd(II) and 20.3 mg g^− 1 for Cr(III). Desorption of the heavy metal ions from composite was studied in 0.5 M NaCl and very high desorption rates, greater than 93%, were achieved in all cases. Adsorption–desorption cycles showed the feasibility of repeated uses of this nanocomposite.