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Green Hulls Extract Medium: Magnetic Properties and Characterization. Mohammad .... Solution B: a mixture of walnut green hull extract in amino ethanol (2 ..... amidoalkyl-2-naphthol derivatives using barium phosphate nano- powders. Chin.
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Green Synthesis of NiFe2O4/Fe2O3/CeO2 Nanocomposite in a Walnut Green Hulls Extract Medium: Magnetic Properties and Characterization Mohammad Reza Mohammad Shafieea, Mahboubeh Kargara, Mina Sadat Hashemia and Majid Ghashang*a,b a

Department of Chemistry, Faculty of Sciences, Najafabad Branch, Islamic Azad University, P.O. Box: 517; Najafabad, Esfahan, Iran; bAdvanced Materials Research Center, Najafabad Branch, Islamic Azad University, Najafabad, Iran Please provide corresponding author(s)

photograph Abstract: A green method for the synthesis of NiFe2O4/Fe2O3/ CeO2 nanocomposite was explored by size should be 4" x 4" inches using a walnut green hull extract. Walnut green hulls are rich cellulose compounds which make it a good candidate to synthesize nanoparticle due to acting as chelating agents. The as prepared samples were characterized by XRD, FE-SEM, EDX, VSM techniques. The nanoparticles show uniform dispersed and the thickness ranges from 60 to 140 nm. The effect of different extract concentrations on the morphology, crystal growth, particle size and magnetic properties of the samples was investigated. The method has the advantages of cost-effective, non-toxic, and use of walnut green hull extract as an environmentally friendly medium.

Keyword: Green synthesis, nanocomposite, NiFe2O4/Fe2O3/ CeO2, walnut green hull extract. Received: February 21, 2015

Revised: March 18, 2015

1. INTRODUCTION The magnetic materials based on the spinel ferrites with the general formula of MFe2O4 have been shown excellent potential for application in electronic, catalysis, magnetic storage devices and various fields of medicine such as immunoassays, hyperthermia therapy and magnetic resonance imaging due to their noticeable electrical and magnetic properties [1-3]. Currently, magnetic nanocomposites have attracted more attention as they could provide a platform of innovative in chemistry, physics and medicine, which are not found in the single-phase nanostructures. Magnetic nanocomposites are currently the subject of research interest because of their potential application in catalysis, bioprocessing, electronic, and magneto-optical devices [1-4]. There are several advantages to use of ferrites nanocomposites instead of their spinel structures as they are stable and can improve catalytic properties, magnetic, magnetooptic and mechanical properties [4]. Generally, several synthetic methods have been expressed for the synthesis of magnetic nanocomposites, including co-precipitation [5], solvo-thermal [6], deposition [7], hydrothermal precipitation [8] and sol-gel method [9]. Nevertheless, some of these preparation strategies are expensive and involve complicated process and also the use of environmentally malignant chemicals and organic solvents which are poisonous and *Address correspondence to this author at the Advanced Materials Research Center, Najafabad Branch, Islamic Azad University, Najafabad, Iran; Tel: +98-3142291004; Fax: +98-3142291016; E-mail: [email protected]

1573-4137/16 $58.00+.00

Accepted: May 2, 2016

causes to a large quantity of wastes inserted into water sources and environments [5-9]. The advantages of green chemistry have led to the development of an eco-friendly approach for the synthesis of magnetic nanocomposites. The use of environmentally benign materials like plant extract for the synthesis of magnetic nanocomposites offers the advantages of environmentally friendly and compatibility for pharmaceutical applications [10-22]. Black walnut hull extract is unquestionably a safe, green and environmentally friendly media, interested for herbalists and medicines. The presence of juglone on the Black walnut hull extract causes a variety of pharmacological properties such as antibacterial, antiviral, antiparasitic, and fungicide. It can be used as a skin wash to treat ringworm, yeast and candida infections [23-26]. The walnut trees are abundant in Iran and are a good candidate to be used for our scientific investigation. To the best of our knowledge, Black walnut hull was not used before for the preparation of nanostructured materials. Utilization of Black walnut hull not only provides a low cost and easily available material for the synthesis of nano-materials, but also it would help the environmental pollution. The present investigation describes the synthesis, characterization and magnetic properties of NiFe2O4/Fe2O3/CeO 2 nanocomposite prepared by a green biosynthesis method using walnut green hull extract for the first time.

© 2016 Bentham Science Publishers

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2. EXPERIMENTAL 2.1. Physical Measurements Phase identification was carried out for the asprecipitated and heat treated samples by an X-ray Diffraction (XRD) method with a Rigaku D-max C III, X-ray diffractometer using Ni-filtered Cu K radiation. Field Emission Scanning Electron Microscope (FESEM) images were obtained on HITACHI S-4160. The compositional analysis was done by energy dispersive X-ray (EDS, Kevex, Delta Class I). The magnetic measurements were performed by a Lake Shore 7300 vibrating sample magnetometer (VSM) system. 2.2. Plant Material and Extraction Walnut green hulls (150 g) were washed in running tap water, and then mixed with distilled water (800 mL) up to 3h on the magnetic stirrer at reflux condition. A small amount of the brown extract was used for the synthesis. 2.3. Synthesis of NiFe2O4/Fe2O3/CeO2 Nanocomposite Ferric chloride hexahydrate (FeCl3.6H2O), nickel chloride hexahydrate (NiCl2.6H2O) and cerium nitrate hexahydrate (Ce(NO3)3.6H2O) were purchased from Merck Company (Aldrich) and used without further purication. NiFe2O4/Fe2O3/CeO2 nanocomposites were prepared by the following experimental progression: two different solutions were prepared. Solution A: a mixture of NiCl2.6H2O (1 mmol), FeCl3.6H2O (2 mmol) and CeNO3.6H2O (1 mmol) dissolved in the 60 mL of distillate water. Solution B: a mixture of walnut green hull extract in amino ethanol (2 mL). It was noted that the amount of walnut green hull extract is 50 mL (in sample 1), 100 mL (in sample 2), and 150 mL (in sample 3). Also, it was noted that sample 4 was prepared without walnut green hull extract. Then Solution B was added drop-wise into the solution A under constant stirring for about 2h to gain homogenous mixture and the obtained mixture with PH = 9 was stirred at room temperature for another 15 min. The resultant brown precipitates were ltered, washed with distilled water and absolute ethanol and dried at room temperature. Moreover, the precipitates were then calcinated slowly up to 600 °C in an electric furnace using alumina crucibles and maintained at the stable mentioned temperature for 2h. After calcination, the obtained products of brown NiFe2O4/Fe2O3/CeO2 nanocomposite were stored in airtight container for further analysis. 3. RESULTS AND DISCUSSIONS The NiFe2O4/Fe2O3/CeO2 nanocomposite has been synthesized via a green co-precipitation method in a walnut green hull extract medium. Green co-precipitation method is an economical, non-toxic, and generally leads to the formation of uniform nanostructures. Walnut consists of three main parts: meat, woody skin and green skin. Green skin consists of cellulose, hemicelluloses and lignin. Cellulose is a linear, crystalline homo polymer with repeating units of Glucose strung together by

Fig. (1). The XRD patterns of NiFe2O4/Fe2O3/CeO2 nanocomposite: with (a) 50 mL, (b) 100 mL, and (c) 150 ml walnut green hull extract; (d) with 100 mL deionized water.

beta-glucosidic linkages. The existence of cellulose compounds in walnut green hull makes it a good candidate for the synthesis of nanomaterial because of the ability of cellulose compounds to act as chelating agents [27]. This method is cost-effective, non-toxic, eco-friendly, and generally leads to the formation of crystalline nanostructures with a collection of shapes. In addition, the effect of various amounts of extract has been investigated on morphology, crystal-size, and magnetic properties of the samples by using X-ray diffraction (XRD), eld emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), and VSM. The XRD patterns of NiFe2O4/Fe2O3/CeO2 nanocomposite prepared in different conditions, including various volumes of walnut green hull extract (0, 50, 100, and 150 mL) are shown in Figure 1. All the XRD profiles could be easily indexed according to the mixture of the cubic structure of NiFe2O4 (space group Fd-3m; JCPDS 074-1913), rhombohedral Fe2O3 (space group R-3c; JCPDS 074-1913), and Cubic phase of CeO2 (space group Fd-3m; JCPDS 074-1913). It can be observed that the presence of walnut green hull extract does have a small impact on the crystal structure of the nanocomposite. Nevertheless, the trace of hexagonal phase FeO with lattice parameters  = b =2.5740 Å, c = 5.1720 Å (JCPDS 049-1447) has been observed in sample 1 and 4. Comparsion of both the samples 2 and 4 in Figure 2 shows

Green Synthesis of NiFe2O 4/Fe 2O3/CeO 2 Nanocomposite in a Walnut

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Fig. (2). Energy dispersive X-ray spectrums of NiFe2O4/Fe2O3/CeO2 nanocomposite: with (a) 50 mL, (b) 100 mL, and (c) 150 ml walnut green hull extract; (d) with 100 mL deionized water.

the effect of green extract on the morphology and crystallinity samples. Sample 4 shows sharper peak. The sharp peaks denote the higher particle size and the better crystallinity. By enhancing the amount of extract, the peaks of XRD become wider, showing either decrease in the size of particle or the crystallinity. The energy dispersion spectroscopy (EDS) analysis was been selected to examine the chemical composition of NiFe2O4/Fe2O3/CeO2nanocomposite (Fig. 2). Peaks of Ni, Fe, Ce, and O elements in the sample without any trace of other additives or pollutions were observed. To investigate the effect of the extract concentration on the morphology of the products, FESEM images of nanocomposites were taken and shown with two magnifications in Figure 3a-h. When the amount of extract was 50 mL, the particles were large and agglomerated together in Fig. 3a and 3b. By increasing the amount of extract as a chelating agent to 100 and 150 ml, the size of particles decreased and become homogenous as shown in Figure 3c-f, respectively. On the other hand, comparing sample 2 and 4, with and without extract, Figure 3c, d and Figure 3g,h show that the amount of extract has an important role in forming more uniform particle size in the media. Because the chemical structure in walnut green hull extract have made enough space between the particles when they are forming in the initial solution. The size of particles in Table 1.

Hysteresis loop (Sq) and magnetic properties of NiFe2O4/Fe2O3/CeO2 nanocomposite formed at various amounts of the extract have been shown in Figure 4. According to Fig. 4 and Table 1, it can be observed that Ms and H c depend on the size of particle effectively. Both Ms and Hc are relatively low for the samples obtained without green walnut hull extract (Fig. 4d), which attributed to the size of the particle being larger than the samples that formed in 100 mL amount of green walnut hull extract because the crystalline size, morphology, and calcination temperature considerably influenced the magnetic properties [28]. On the other hand, hysteresis loop (Sq) has been decreased by increasing the amount of extract which contains lower particles. Both saturation magnetization and coercivity increased due to particle size. The magnetization properties including both saturation magnetization and coercivity versus particle size plots are shown in Figure 5. As shown, the values of Hc and Ms decrease by increasing the particle size. Therefore, the results specify that the increasing of green walnut hull extract is a good strategy to synthesize NiFe2O4/Fe2O3/CeO2 nanocomposite with outstanding magnetic properties. In comparison NiFe2O4/Fe2O3/CeO2 nanocomposite with NiFe2O4 nanoparticle has a higher saturation magnetization which is probably due to existence of CeO2 as an isolator between magnetic particles and prevent to make agglomerated particles [29].

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Table 1. Determine the size of the nanoparticle and magnetic properties of all samples (particle size was determined by statistical design from FE-SEM photographs) Sample Number

Fig. (3). FE-SEM images8 of samples with (a) and (b) with 50 mL extract; (c) and (d) with 100 mL extract; (e) and (f) with 150 mL extract; (g) and (h) with 100 mL deionized water.

0.165

3.3

89

20

47

50

1

0.143

4.3

101

30

32

100

2

0.142

4.7

104

33

27

150

3

0.17

2.9

97

17

51

100 water (without extract)

4

Fig. (5). Particle size dependence of the Hc and Ms values.

around 27-51 nm according to FESEM images because of cellulose compound in green walnut hulls. The increasing amount of extract makes the smaller particle, hereby the amount of 150mL of extract make an appropriate nanoparticle with suitable magnetic properties. Clearly, the smaller the nanoparticles the lower the magnetic loops and bigger the saturation magnetic. The method has the advantages of costeffective, non-toxic, use of green walnut hull extract as an environmentally friendly method. CONFLICT OF INTEREST The authors confirm that this article content has no conflict of interest. ACKNOWLEDGMENTS

Fig. (4). VSM curves of NiFe2O4/Fe2O3/CeO2 nanocomposite prepared in (a), (b), (c), 50, 100 and 150 ml walnut green hull extract respectively ; (d) 100 mL deionized water.

We are thankful to the Islamic Azad University, Najafabad Branch research council for partial support of this research. REFERENCES

CONCLUSION

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