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MedBioTech J. 2019; 3(1): 05-09 |5 MBTJ, 3(1): 005-009, 2019 Evaluation of modified montmorillonite clay with magnetite nanoparticles Reza Laksian * , Mahboobe Rezaei Soil Science Department, Faculty of Agriculture, University of Birjand, Iran Received: 19 December 2018 Accepted: 08 February 2019 Published: 01 March 2019 Abstract Iron oxide nanoparticles play an important role in decontamination of a large number of environmental pollutants, such as solvents, chlorinated pesticides, and so on. The magnetic and catalytic properties of iron oxide nanoparticles are widely used. The main problem of iron nanoparticles is instability and their high tendency to agglomerate. In order to solve this problem, a modified montmorillonite clay with magnetite nanoparticles was prepared. The properties of prepared clay were investigated by X-ray diffraction and scanning electron microscopy. The results of X-ray diffraction showed that powerful peak of the first order (d001) tended to smaller angles of 2θ in modified clays with magnetite nanoparticles compared to the primary cluster of montmorillonites, so the gap between the layers and as a result, surface of prepared nanocomposite is increased. In scanning electron microscopy images of modified montmorillonite clay with magnetite nanoparticles was observed that magnetite nanoparticles are dispersed in the surface and between layers of clay and their aggregation was very reduced, which led to an increase in the surface of the nanocomposite. A significant increase in the surface of this nanocomposite can increase its ability to remove pollutants from the environment. Keywords: Montmorillonite; Magnetite Nanoparticles; X-ray Diffraction; Scanning Electron Microscope How to cite the article: R. Laksian, M. Rezaei, Evaluation of modified montmorillonite clay with magnetite nanoparticles, Medbiotech J. 2019; 3(1): 005-009, DOI: 10.22034/mbt.2019.80824. 1. Introduction Nanoparticles play a role in the microbial biomass preservation, activity and stability of the enzymes due to their small size, high surface area, crystalline shape, unique network order, and high reactivity [3,5,10]. One of the main problems of iron nanoparticles is that they cannot be stable separately and they accumulate in the long time [8, 9, 12]. It has been reported that storage of nanoparticles on polymer [11], pores of silica [2] and zeolites [1] are effective methods to reduce the accumulation of used nanoparticles. In some studies, to address this problem, iron nanoparticles have been kept on surface of activated carbon [6]. But in 2010, Lee et al., used mineral clay which are abundant, environmentally friendly, and much cheaper than carbon to preserve nanoparticles and * Corresponding author email: [email protected] they reported that the combination of surfactant and minerals clay caused to solve this problem and could be very useful and widely used in agriculture and the environment [7]. Minerals of type 1: 2 montmorillonite phyllosilicates are di-octahedral with layer load of 0.4-0.2 with high hydration degree, surface level, cation exchange capacity, water holding capacity and absorption power. So, they considered as important ingredient in the clay minerals. Montmorillonite is an abundant, inexpensive miner with great qualities that is very important in agriculture, the environment, industry and engineering. It seems that nanocomposites formed from combination of montmorillonite clay and magnetite nanoparticles can be very effective in removing pollutants in the environment. The aim of this study

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Page 1: Evaluation of modified montmorillonite clay with magnetite ... · iron oxide nanoparticles are widely used. The main problem of iron nanoparticles is instability and their high tendency

M e d B i o T e c h J . 2 0 1 9 ; 3 ( 1 ) : 0 5 - 0 9 |5

MBTJ, 3(1): 005-009, 2019

Evaluation of modified montmorillonite clay with

magnetite nanoparticles

Reza Laksian*, Mahboobe Rezaei

Soil Science Department, Faculty of Agriculture, University of Birjand, Iran

Received: 19 December 2018 Accepted: 08 February 2019 Published: 01 March 2019

Abstract Iron oxide nanoparticles play an important role in decontamination of a large number of environmental pollutants, such as solvents, chlorinated pesticides, and so on. The magnetic and catalytic properties of iron oxide nanoparticles are widely used. The main problem of iron nanoparticles is instability and their high tendency to agglomerate. In order to solve this problem, a modified montmorillonite clay with magnetite nanoparticles was prepared. The properties of prepared clay were investigated by X-ray diffraction and scanning electron microscopy. The results of X-ray diffraction showed that powerful peak of the first order (d001) tended to smaller angles of 2θ in modified clays with magnetite nanoparticles compared to the primary cluster of montmorillonites, so the gap between the layers and as a result, surface of prepared nanocomposite is increased. In scanning electron microscopy images of modified montmorillonite clay with magnetite nanoparticles was observed that magnetite nanoparticles are dispersed in the surface and between layers of clay and their aggregation was very reduced, which led to an increase in the surface of the nanocomposite. A significant increase in the surface of this nanocomposite can increase its ability to remove pollutants from the environment.

Keywords: Montmorillonite; Magnetite Nanoparticles; X-ray Diffraction; Scanning Electron Microscope

How to cite the article: R. Laksian, M. Rezaei, Evaluation of modified montmorillonite clay with magnetite nanoparticles, Medbiotech J. 2019; 3(1): 005-009, DOI: 10.22034/mbt.2019.80824.

1. Introduction Nanoparticles play a role in the microbial biomass preservation, activity and stability of the enzymes due to their small size, high surface area, crystalline shape, unique network order, and high reactivity [3,5,10]. One of the main problems of iron nanoparticles is that they cannot be stable separately and they accumulate in the long time [8, 9, 12]. It has been reported that storage of nanoparticles on polymer [11], pores of silica [2] and zeolites [1] are effective methods to reduce the accumulation of used nanoparticles. In some studies, to address this problem, iron nanoparticles have been kept on surface of activated carbon [6]. But in 2010, Lee et al., used mineral clay which are abundant, environmentally friendly, and much cheaper than carbon to preserve nanoparticles and

*Corresponding author email: [email protected]

they reported that the combination of surfactant and minerals clay caused to solve this problem and could be very useful and widely used in agriculture and the environment [7]. Minerals of type 1: 2 montmorillonite phyllosilicates are di-octahedral with layer load of 0.4-0.2 with high hydration degree, surface level, cation exchange capacity, water holding capacity and absorption power. So, they considered as important ingredient in the clay minerals. Montmorillonite is an abundant, inexpensive miner with great qualities that is very important in agriculture, the environment, industry and engineering. It seems that nanocomposites formed from combination of montmorillonite clay and magnetite nanoparticles can be very effective in removing pollutants in the environment. The aim of this study

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was to construct modified montmorillonite with natural and low-cost magnetite nanoparticles.

2. Experimental section

2.1 Materials

Sodium montmorillonite clay used in this study was prepared from the United States with 95% purity and 725 m2 / g specific surface area. The cation exchange capacity (CEC) of montmorillonite clay was determined using Ammonium acetate method at 89.9 cu m / kg soil. In this study, the prepared montmorillonite clay was named MM. The used chemical materials in this study were laboratory grade for solutions preparation and distilled water and water without ion was used for washing. The used nanoparticles in this study were from Nutrino Co. with a 99% purity. Initial studies were carried out to ensure the crystalline size, chemical composition and phase of the nanoparticles. The average actual particle diameter was estimated 43.15 nm by particle measurement device and diagram of a particle diameter distribution was prepared (figure 1).

Figure 1. Nanomagnite particle diameter distribution

X-ray diffractogram is shown in Figure 2 and interpreted by X’pert software, and the visible

peaks are related to crystalline screens 220, 311, 222, 400, 422, 511, 440, 620, 533, 444, 642, 731, due to correspondence of these plates peaks of and their diffraction angles with the card number (19-0629), the Joint Committee of the Pearl Dispersion Standard, magnetite property of the particles was confirmed. Figure 3 shows the scanning electron microscopic images of nanoparticles, which characterizes the particle morphology.

2.2 Preparation of modified montmorillonite clays with magnetite nanoparticles

To prepare the modified montmorillonite clays with magnetite, nanoparticles magnetite nanoparticles were firstly added to distilled water and a cationic colloidal solution (magnetite hydrocele) with a pH of about 4 was prepared. To prepare montmorillonite coated with nanoparticles, a suspension of 1 g of clay montmorillonite was prepared per 20 ml of water, and magnetite hydrocele was added to the volume equivalent to the montmorillonite suspension.

Figure 2. X-ray (XRD) diffractogram of magnetite nanoparticles

Figure 3. Scanning Electron Microscope (FESEM) of magnetite nanoparticles in different magnifications

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The suspension was stirred for 30 minutes with a magnetic stirrer. The supernatant solution was centrifuged for 5 minutes at 4000 rpm and the colorless property of supernatant solution was evaluated. The supernatant solution was discard and the magnetite hydrocele was re-added. The solid material was isolated and dried in a vacuum at 40 ° C (Yuan et al., 2119). In this study, the prepared clay by using magnetite nanoparticles was named NMM. Prepared samples were stored in the desiccator for further experiments.

2.3 Prepared clay specification

The properties of the prepared materials depend on their shape and size. The distance of inter layers of clay was determined by X-ray diffraction (XRD) and X’pert software. The X-ray diffraction device was a Philips MPD-pert'X system. X-ray diffractometry spectra were in the range of 2° -40 ° and the target lamp was copper with an λ radiation of 1.54 ° A (K∝Cu). Accelerating voltage of 40 kW and beam current of 30 mm were used in these experiments. The scan speed angle, θ, was adjusted at a rate of 1 ° / min. Structural and morphological characteristics were determined by scanning electron microscopy (FESEM). So, for imaging Tscan II-Vega model of scanning electron microscopy were used.

3. Results and discussion

3.1 Characteristics of prepared clay

Figure 4 is the X-ray diffractogram (XRD) of clay montmorillonite (MM) and according to the figure, the inter-layer distance of the first layer peak (d001) of this clay is 11 angstroms.

Figure 4. X-ray diffractogram of Sodium Montmorillonite (MM)

According to the X-ray diffractogram (figure 5), it was observed that the modified clay with magnetite nanoparticles (NMM) has the inter-layer of the first peak (d001) of 17.51 Angstrom.

The effect of adding nanoparticles on the interlayer of clays has been studied by some researchers. Yan

et al., In 2009, developed a nanocomposite with montmorillonite clay and iron nanoparticles, and observed that the inter-layer of the first peak (d001) of primary montmorillonite was 17.51 Angstrom, which increased with magnetite nanoparticles up to 15.8 angstroms [16]. Lee et al. in 2010, converted montmorillonite clay to organic clay with hexadecyltrimethylammonium cationic surfactant and then added zero-strength iron nanoparticles to clay and prepared nanocomposite of organic clay-iron-nanoparticles and by examining X-ray diffractograms, they observed the inter-layer distance of montmorillonite clay was 14.8 Å, which increased to 15.1 Å after converting to nanocomposite. In 2014, Wu et al. reported in a similar experiment with montmorillonite clay modifying by Hexadecyltrimethylammonium bromide and zero-strength iron nanoparticles, the inter-layer distance of the first clay peak was increased up to 15 angstroms.

Figure 5. X-ray diffractogram of modified clay with Magnetite Nanoparticles (NMM)

In figure 6, morphology of sodium montmorillonite clay (MM) has been shown in various magnifications. As seen in the figure, montmorillonite has more massive form and silicate layers are not detectable at high magnification. The integrated structure and low porosity of the clay in these images are clearly visible.

In figure 7, the morphology of modified clay with magnetite nanoparticles (NMM) has been shown in various magnifications. In these images, magnetite nanoparticles are observable that disperse on the surface and between layers of the clay. Therefore, the preparation of this nanocomposite has been addressed the weakness point of the instability of nanoparticle and their high tendency to accumulate or to crack down. As a result, the surface area of this nanocomposite increased significantly, which is a very important parameter in the removal of environmental pollutants.

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Figure 6. Scanning Electron Microscopy (FESEM) of Clay Sodium Montmorillonite (MM) in different magnifications

Figure 7. Scanning electron microscopy (FESEM) of modified clay with magnetic nanoparticles (NMM) in different magnifications

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