Fluoride adsorption on γ − Fe2O3 nanoparticles
© Jayarathna et al. 2015
Received: 30 October 2014
Accepted: 11 July 2015
Published: 24 July 2015
Fluoride contamination of groundwater, both anthropogenic and natural, is a major problem worldwide and hence its removal attracted much attention to have clean aquatic systems. In the present work, removal of fluoride ions from drinking water tested using synthesized γ-Fe2O3 nanoparticles.
Nanoparticles were synthesized in co-precipitation method. The prepared particles were first characterized by X-ray diffraction (XRD) and Transmission Electron Microscope (TEM). Density functional theory (DFT) calculations on molecular cluster were used to model infrared (IR) vibrational frequencies and inter atomic distances.
The average size of the particles was around 5 nm initially and showed a aggregation upon exposure to the atmosphere for several hours giving average particle size of around 5–20 nm. Batch adsorption studies were performed for the adsorption of fluoride and the results revealed that γ-Fe2O3 nanoparticles posses high efficiency towards adsorption. A rapid adsorption occurred during the initial 15 min by removing about 95 ± 3 % and reached equilibrium thereafter. Fluoride adsorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at lower pH. Fourier transform infrared spectroscopy (FT-IR) was used for the identification of functional groups responsible for the adsorption and revealed that the direct interaction between fluoride and the γ-Fe2O3 particles.
The mechanism for fluoride removal was explained using the dehydoxylation pathway of the hydroxyl groups by the incoming fluoride ion. FT-IR data and other results from the ionic strength dependence strongly indicated that formation of inner-spherically bonded complexes. Molecular clusters were found to be good agreement with experimental observations. These results show direct chemical interaction with fluoride ions.
Keywordsγ-Fe2O3 nanoparticles Fluoride FTIR Adsorption and removal High efficiency DFT Molecular modeling Gaussian 09
Fluorine is a naturally occurring element in minerals, geochemical deposits and natural water systems and that enters into food chains through either drinking water or eating plants and cereals . Elevated concentrations of fluoride in soil and ground water arising from both natural and anthropogenic activities harm living beings around the world including Sri Lanka. Chemical weathering of some fluoride containing minerals leads to fluoride enrichment in soils and ground water. Discharge of fluoride from some industries, for example semiconductors, steel, etc. are among the main anthropogenic sources of fluoride pollution .
Removal of fluoride from water is one of the most important issues due to the effect on human health and environment. But as a necessary dilute element in human body fluoride in drinking water may be beneficial or detrimental depending on its concentration. Namely, dietary intake of fluoride with the concentration of 1 mg/L can prevent particularly skeletal and dental problems . When the fluoride concentration is above this level, it leads to many bone diseases, mottling of teeth and lesions of the endocrine glands thyroid, liver and other organs. Owing to these adverse effects of fluoride, World Health Organization (WHO) accepted the drinking water with fluoride concentration of 1.5 mg/L . In the literature, it was reported that many countries have regions where the water containing more than 1.5 mg/L of fluoride including north central province in Sri Lanka .
Recently, removal of fluoride from ground water and wastewater has been paid high attention in literature and different materials and methods have been tested. The mostly tested methods are adsorption [6–9], ion exchange , precipitation [10, 11], Donna dialysis , electrolysis  and nanofiltration [10, 12].
Among these methods, adsorption is the most widely used method for the removal of fluoride from water. Though these techniques have been extensively used in worldwide, but due to high cost, that methods are not suitable for field application .
Therefore, in recent years considerable attention has been devoted to the study of different types of low-cost and effective materials such as different clays, spent bleaching earths, alum sludge, red mud etc. in this approach, a large number of low-cost materials have been examined for the fluoride removal [5, 13–15]. However, to date, adsorbent of magnetic nanoparticles were reported very little, if any, to removal of fluoride from water solution where as magnetic nanoparticles adsorbent with excellent controllable properties can be developed for separation and removal ions from even very dilute aqueous solutions as the nanoparticles usually undergo modification of its geometric and electronic properties compared to bulk systems leading different pathways for the adsorption of molecules or atoms. Further, if the particles or the adsorbent possess magnetic properties then the main advantage is that the adsorbent can be easily separated using the external magnetic field and will be reused [16–20].
The most important solid surfaces for fluoride adsorption in water are the surfaces of Iron and Aluminum hydroxides, for example magnetite and gibbsite. In turn, adsorption of ions on hydroxide surfaces can affect the pH by influencing adsorption of protons. In the case of fluoride, adsorption of the negative ions enhances proton adsorption and tends to increase the pH. Although the amount of background electrolyte ions involved in this adsorption is generally minimal relative to the amount present in the solution. These effectively uncouple the adsorption of protons and fluoride and make the adsorption of fluoride at variable pH a multi-component process [21, 22].
The electronic and optical properties and the chemical reactivity of small clusters are completely different from the known properties of bulk or at extended surfaces. To overcome such difficulties, complex quantum mechanical models are required to predict the properties with particle size, and typically well defined conditions are needed to compare experiment results with theoretical predictions. The most important techniques in computational modeling are ab-initio, semi-empirical and molecular mechanics [23, 24].
Density functional theory (DFT) is a one of the newest approaches in computational modeling. In this method, the energy of the molecule and all of its derivative values depend on the determination of the wavefunction. Even though the wavefunction does not exist as a physically, observable property of an atom or a molecule, the mathematical determination of the wavefunction (within the atomic and molecular orbitals) is a good predictor of energy and other actual properties of the molecule .
Where, T s is the kinetic energy of the non-interacting system; the second term is the nuclear attraction energy and the third is the classical coulomb self-energy; the last term is the E xc energy. Each of these terms is a function of the function ρ, the electron density, which is itself a function of the three positional coordinates (x, y, and z) .
In this work, simple chemical method was used to synthesize magnetic iron oxide nanoparticles and employed to remove fluoride from solutions. Effects of pH and the background electrolyte were studied in the batch process. The FTIR spectroscopy was mainly used to characterize the systems in order to understand the adsorption mechanism of fluoride ions on the nanoparticles. Molecular modeling of the adsorbate-adsorbent interaction is very important to understand the surface complexation. Density functional theory, a type of ab-initio methods, applied to examine the atomistic and molecular level understanding of fluoride-γ-Fe2O3 interactions.
All the chemicals used were in analytical grade.
Ferromagnetic iron oxide nanoparticles were synthesized by using modified co-precipitation of ferrous and ferric ions in alkaline medium . Briefly an aqueous solution of Fe ions with molar ratio Fe(II)/Fe(III) = 0.5 was prepared by dissolving 3.25 g FeCl3 and FeCl2.4H2O powder in 60 mL of aqueous HCl acid (50 mL deionized water + 10 mL of 1 M HCl) solution. The resulting solution was added drop wise in to 100 mL of 1 M of NaOH solution under vigorous stirring. After all the Fe ions solution was added, the reaction mixture was stirred further to prevent coagulation of particles. Then, obtained colloidal solution was centrifuged at 2500 rpm, and precipitate was washed with deionized water with several times. Finally, precipitate was dried under normal atmospheric conditions.
Characterization of iron oxide particles
Iron oxide particles were characterized by an X-ray diffraction (XRD) with an X-ray diffractometer equipped with a copper anode generating Cu Kα radiation (λ-1.5406 Ả). The surface structure, size and morphology were investigated by Transmission Electron Microscope (TEM). Fourier transform-infrared spectroscopy (Nicolet 6700 FT-IR) was also conducted on the particles. The surface area of iron oxide nanoparticles was estimated as 16.5 ± 2.5 m2/g according to Sears’ method, comparable with literature (20.40 m2/g) .
Batch adsorption studies were conducted by contacting 10 g/L suspension of iron oxide particles with 20 mL of fluoride solution at varying concentrations (10–100 ppm) in polystyrene high-density tubes shaking for a 12 h, which had been shown in preliminary study to ensure equilibration to be reached. Temperature of adsorption test was ~25 0C while the pH of the reaction mixture was adjusted in range of 2–12 using 0.1 M NaOH or 0.1 M HNO3. After shaking, the suspension was subjected for centrifugation and final fluoride ion concentration of the suspension was measured with a specific fluoride ion selective electrode (Orion 9409BN) by using an Orion EA960 auto-titrator. FTIR measurements in DRIFT mode were done on the residue solids obtained from each experiment in order to get insights into the mechanism of the fluoride adsorption on the iron oxide particles.
Where, m is the scale factor obtained from the slope of the plot, and v is the calculated frequencies for selected theory/basis set.
Results and discussion
Characterization of nanoparticles: XRD and TEM
Measurements on fluoride adsorption
Effect of pH of the solution on fluoride removal in different ionic strength
After characterizing the particles with ZPC the effect of pH on the adsorption of Fluoride was investigated. Fluoride adsorption by iron oxide was found to be strongly pH dependent. Adsorption amount decreased with increasing pH up to 4.5 and then remain more or less constant in the pH range of 6.0–10.0 and also that the adsorption remains almost constant regardless of ionic strength, but decreased slightly after pH >10.0. This may indicate the formation of inner-spherically bonded complexes [31, 35].
These results indicate that the adsorbent exhibits a commendable removal capacity in wide range of pH. At lower pH, below pHzpc, most of the surface sites are positively charged and attract negatively charged fluoride easily by electrostatic interaction. However, at very high pH, the removal capacity decreases due to the competition between hydroxide and fluoride ions in this medium .
It has also been observed that the removal of fluoride is very rapid in the first 15 min and then reaches a maximum. The percent fluoride removal after 15 min was found to be 95% at the pH 3.6 to 6. The change in the rate of removal might be due to the fact that initially all adsorbent sites were vacant and the solute concentration gradient is high. After 15 min, the fluoride uptake rate by adsorbent had been decreased due to the decrease in number of adsorbent sites. This removal percentage is remarkably higher than the systems reported earlier by using different types of clays . This nature might be due to the modification of particles geometrically and electronically due to its nano size and also the high surface area of the small particles leads high affinity towards adsorption.
FTIR measurements on the bare and fluoride adsorbed particles
Solid line in Fig. 3 shows the FTIR spectrum of fluoride adsorbed iron oxide nanoparticles. Adsorption bands at above 3000 cm-1 are well resolved now in comparison with the spectrum of bare-iron oxide. The IR absorption bands between 3300 and 3600 cm-1 are due to surface bound OH groups having their characteristic isolated nature. Indeed, a negative band at around 1620 cm-1 appeared and another band appeared at 1660 cm-1, revealing the presence of characteristic absorption bands for unbound surface water layer. The spectra shown in Fig. 3 are expanded to three different spectral regions in order to see the changes clearly and the following section deals with the major changes observed in the IR spectra upon the fluoride adsorption.
Calculated bond parameters for Fe2(OH)6(H2O)4, Fe2(OH)5(H2O)4F and Fe2(OH)4(H2O)4F2 clusters
Computed bond distances Å
Cluster models were applied assuming the adsorption process is local phenomena. Such a model describing the surface adsorption sites can give important insights about the structure of the surface complexation. However, two ferrous atoms-hydroxide octahedral cluster (Fe2(OH)6(H2O)4) implemented as a basis of γ-Fe2O3 because this fragment is large enough to describe the fluoride adsorption and to avoid any complex time consuming calculation steps.
According to the calculated IR spectra of the Fe2(OH)6(H2O)4, Fe2(OH)5(H2O)4F and Fe2(OH)4(H2O)4F2 clusters, spectra show higher wavenumber shifting for Fe2(OH)5(H2O)4F and Fe2(OH)4(H2O)4F2 clusters. It is good indication for decreases of hydrogen bond strength for fluoride adsorbed clusters.
Magnetic γ − Fe2O3 nanoparticles were synthesized by the co-precipitation method and this work confirmed that magnetic γ − Fe2O3 nanoparticles possess remarkably high efficiency for the removal of fluoride from drinking water and wastewater. The removal of fluoride capacity was 3.65 mg/g and it is strongly depended on initial pH of solution and the removal level is high as 95% of the removal occurs in acidic to neutral pH. FTIR measurements indicated the formation of inner-spherically bonded complexes and the removal of outer-sphere water molecules paved the way to appear isolated OH groups in the IR spectra upon the adsorption of fluoride and that the data helped us to predict the mechanism for the adsorption. Computational chemistry is very useful tool for studying surface reactions when used in combination with a variety of experimental techniques. Density Functional Theory (DFT) can reproduce the structure and vibration frequencies of bulk γ-Fe2O3 and these methods were also applied to predict the surface structure.
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