Научная статья на тему 'SYNTHESIS AND STUDY OF STRUCTURES OF MAGNETITE FE3O4 NANOPARTICLES IN POLYETHYLENE GLYCOL MEDIUM'

SYNTHESIS AND STUDY OF STRUCTURES OF MAGNETITE FE3O4 NANOPARTICLES IN POLYETHYLENE GLYCOL MEDIUM Текст научной статьи по специальности «Нанотехнологии»

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Azerbaijan Chemical Journal
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MAGNETITE / NANOPARTICLES / POLYETHYLENE GLYCOL / CO-PRECIPITATION METHOD / POLYMER

Аннотация научной статьи по нанотехнологиям, автор научной работы — Humbatova S.F.

Synthesis of magnetite Fe3O4 nanoparticles functionalized with polyethylene glycol was carried out by co-precipitation method using a very small amount of organic substances to obtain a highly monodisperse form of nanoparticles, and the structure of obtained Fe3O4 nanoparticles was studied by physical methods. During the synthesis of magnetic Fe3O4 nanoparticles surrounded by a polymer, it has been determined that by adjusting the amount of used polymer, the nature of the precipitating agent, the concentration of the initial precursors and the temperature it was possible to synthesize and stabilize monodisperse Fe3O4 nanoparticles with a high degree of purity, uniform in size

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Текст научной работы на тему «SYNTHESIS AND STUDY OF STRUCTURES OF MAGNETITE FE3O4 NANOPARTICLES IN POLYETHYLENE GLYCOL MEDIUM»

AZERBAIJAN CHEMICAL JOURNAL № 4 2022

ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)

UDC 544.23.02/.03;544.25.02/.03

SYNTHESIS AND STUDY OF STRUCTURES OF MAGNETITE Fe3O4 NANOPARTICLES

IN POLYETHYLENE GLYCOL MEDIUM S.F.Humbatova

M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan

seadet.humbetova@inbox.ru Received 05.05.2022 Accepted 14.06.2022

Synthesis of magnetite Fe3O4 nanoparticles functionalized with polyethylene glycol was carried out by co-precipitation method using a very small amount of organic substances to obtain a highly monodisperse form of nanoparticles, and the structure of obtained Fe3O4 nanoparticles was studied by physical methods. During the synthesis of magnetic Fe3O4 nanoparticles surrounded by a polymer, it has been determined that by adjusting the amount of used polymer, the nature of the precipitating agent, the concentration of the initial precursors and the temperature it was possible to synthesize and stabilize monodisperse Fe3O4 nanoparticles with a high degree of purity, uniform in size.

Keywords: magnetite, nanoparticles, polyethylene glycol, co-precipitation method, polymer.

doi.org/10.32 73 7/0005-2531-2022-4-60-65 Introduction

Recently, study of Fe3O4 colloidal and composite systems with magnetic properties is of great interest. Natural and synthetic polymer composites containing nanoparticles are widely used in microelectronics, in the delivery of drug systems during the treatment of various diseases, in the creation of nanocomposites that are used as efficient catalysts in various chemical processes, and in the production of nano-composite structures that absorb electromagnetic waves [1-9]. The analysis of the literature data shows that a large number of studies on the stabilization of magnetite Fe3O4 nanoparticles by various synthesis methods have been conducted and are still ongoing. Natural and synthetic based polymers containing polar functional groups are especially applied in maintaining the long-term stability of any nanopar-ticle, regardless of its nature [10-12].

Polymers containing electron-donating groups are situated among the most commonly used polymers for this purpose, because the arrangement of chemical functional groups with electron density around positively charged metal atoms and oxides and the formation of boundaries with other nanoparticles is the main factor [13-16].

Fe3O4 nanoparticles are applied for surface modifications in biomedicine. On the

one hand, modification increases their chemical stability, and, on the other hand, improves their biocompatibility [17-21].

Modern literature data show that the production of Fe3O4 nanocomposites using natural and synthetic polymers is currently one of the promising directions.

The results of synthesis of Fe3O4 nanoparticles carried out in polyethylene glycol (PEQ) medium and investigation of their structures studied by several physical methods are given in the presented research.

Experimental part

Materials

PEQ having a chemical purity of 97% used as a stabilizer and was purchased from Fluka. Polymer was used without purification. All other chemical reagents were chemically pure and purchased from Fluka.

Synthesis of Fe3O4 nanoparticles

The synthesis of PEQ-functionalized magnetite Fe3O4 nanoparticles was carried out by co-precipitation method, obtaining a highly monodisperse form of nanoparticles. 5 ml of PEQ is added to 50 ml of salt solution con-

3+ 2+

taining Fe and Fe cations in a molar ratio of 2:1 and intensively mixed a few minutes. Then 10 mmol NaOH solution was added in order to keep the solution pH around 10. The reaction is

continued under uninterrupted stirring for 30 min. The formation of a black precipitate proves the formation of nanoparticles. The resulting black precipitate is separated by the decantation method and washed several times with distilled water. In order to completely

3+ 2+

remove unreacted Fe and Fe salts from Fe3O4 nanoparticles, the nanoparticles are separated from the main mass by centrifugation and washed several times with distilled water. The particles are sonicated for 10 minutes, then poured into a Petri dish and dried for 24 hours.

Characterization

Advance D8 (Bruker) X-ray diffracto-meter was used for the XRD analysis of the composite. The chemical shift of the functional groups was confirmed by Fourier transform infrared spectroscopy (FTIR). The surface morphology of the nanocomposite was studied by a scanning electron microscope (SEM, JSM-6390, Japan). The amount of elements in the

61

composite was determined for dry samples by a German-made Elemental Analyzer (GmbH, Hanau, Germany).

Results and discussion

A simple scheme of covering magnetite Fe3O4 nanoparticles with PEQ macromolecule after synthesis is shown below.

The synthesis reaction of magnetite Fe3O4 nanoparticles was performed according to the following chemical reactions:

Fe3+ + 3OH- ^ Fe(OH)3 Fe(OH)3 ^ FeOOH + H2O Fe2 + 2OH- ^ Fe(OH)2

2FeOOH + Fe(OH)2 ^ Fe3O4 + 2H2O

Characteristic diffraction peaks for magnetite oxide are observed in the XRD spectrum of PEQ magnetite Fe3O4 nanoparticle composites obtained from the synthesis reaction carried out at different temperatures.

o[-CH2-CH2o-Jn -H

I

h

Functionalization of h FesO4 h-

PEQ-400

PEQ-400-Fes04

Fig. 1. Schematic representation of magnetite nanoparticles surrounded with PEQ-400.

• Fe304 U (*-Fe203

Ö « ~ 1Î » As [ I (422) K ! k (d)

, I A (c)

3

0 lîl, o*» CN O .»k. 0 1 (b)

*

* * 0 *# X. * K. (a)

20 30 40 50 60 70

20 n

Fig. 2. XRD spectra of PEQ-Fe3O4 nanocomposites.

According to the XRD analysis of magnetic nanoparticles, the main peaks 30.1 (220), 35.6 (311), 39.42 (400), 57.32 (511), and 62.74 (440) for the nanocomposite obtained at 20 °C belong to Fe3O4 nanocrystal. Crystallite sizes were calculated according to Debye-Scherer formula related to the peak with the maximum intensity. From the XRD diffractograms and the XRD results of analyses of the obtained samples at different temperatures it is clear that the synthesized nanoparticles are Fe3O4 with a spinel structure:

30.18° (220); 35.64° (311); 39.48° (222); 43.31° (400); 53.48° (422); 57.4° (511); 62.75° (440) for 30°C.

30.21° (220); 35.71° (311); 39.53° (222); 43.38° (400); 53.54° (422); 57.46° (511); 62.78° (440) for 40°C.

30.26° (220); 35.78° (311); 39.59° (222); 43.42° (400); 53.61° (422); 57.48° (511); 62.82° (440) for 50°C.

The dimensions of the crystalline phase were calculated according to the peak with the maximum intensity according to the Debye-Scherer formula, and the dimensions of

magnetite nanoparticles according to the obtained nanocomposites are given in the Table below.

As can be seen, the increase in temperature during the synthesis of nanoparticles causes to slightly increase the size of magnetite Fe3O4 nanoparticles. When the temperature increases, the flexibility of the macromolecule chain increases, and as a result, the nanoparticles are not covered ideally by the polymer. Also, the internal energy of the particles increases, which leads to their partial aggregation.

FTIR spectra of all magnetite Fe3O4 nanoparticle samples taken at different temperatures were studied (Figure 3).

Observation of characteristic bands of OH bonds at 3514-3334 cm-1 indicates that magnetite Fe3O4 nanoparticles are surrounded by polymer macromolecule. An intensive peak at 667-420 cm-1 characterizes the Fe-O bond. In addition, the visible bands at 2362-2360 cm-1 and 1454-1412 cm-1 area of the spectrum are related to C-H and C-C bonds, which once again proves the presence of a polymer chain around magnetite Fe3O4 nanoparticles.

Dependence of nanoparticle sizes of magnetite Fe3O4 surrounded with PEQ on temperature

Reaction temperature, 0C Size of crystalline phase, nm According to SEM, surface size of the particles, nm Lattice parameter, (a) A

20 37.24 38.52 8.384

30 39.43 43.65 8.388

40 41.26 47.71 3.392

50 50.28 56.23 3.393

■ i ■ i

4000 2500 1000

Wavenumber(cm"')

Fig. 3. FTIR spectra of PEQ- Fe3O4 nanocomposites at different temperatures.

Thus, these chemical bonds are not observed in the spectrum of pure magnetite Fe3Ö4. Most importantly, the peak at 1124-1093 cm-1 corresponds to the Fe-O-C bond, which indicates the bond between PEQ and Fe3O4 nanoparticles.

A scanning electron microscope (SEM) was also used to analyze the size and structure of Fe3O4 particles. During the scanning process, the accelerating voltage of electrons was 15 kV, and the working distance was 4.5 mm. The presence of PEQ macromolecule is very important in the stabilization of nanoparticles during SEM analysis. In the presence of PEQ, the nanoparticles are completely covered, which is evident when comparing SEM images with images of pure Fe3O4 nanoparticles (Figure 4).

Fig. 4. SEM micrographs of pure Fe3O4 powder and PEQ-Fe3O4 nanocomposite.

As can be seen from Figure 4, the morphology of the PEQ-encapsulated magnetite Fe3O4 nanoparticles is different because they

are covered by the polymer phase. Observation of globules characteristic of macromolecular chains in SEM microimages proves that nanoparticles are fully covered. It has been determined that the average size of nanoparticles synthesized in the presence of PEQ is 26-55 nm depending on temperature.

The energy dispersive spectrum of magnetite Fe3O4 nanoparticles surrounded by PEQ was also studied during the research (Figure 5). It can be seen from the results that the observation of characteristic diffractions for elements C and H in the composition indicates that the macromolecule is actively involved in the process.

Fig. 5. Energy dispersive spectrum of Fe3O4 magnetic nanoparticles.

Thus, it has been determined that in order to obtain a nanocomposite with stable properties, it is necessary to stabilize nanoparticles in their obtaining process. In order to weaken the agglomeration and control the size of the particles, it is necessary to choose the optimal parameters of the precipitation process - temperature, pH, mixing rate of the solution, stabilizing polymer macromolecule. It has been found that by adjusting the amount of used polymer, the nature of the precipitating agent, the density of the initial precursors and the temperature during the synthesis of Fe3O4 nanoparticles with magnetic properties surrounded by a polymer, it is possible to synthesize and stabilize monodisperse Fe3O4 nanoparticles with a high degree of purity, uniform in size.

Conclusion

Thus Fe3O4 nanoparticles were synthesized in the presence of PEQ. The broad peaks in the FTIR spectrum characterize the interaction between Fe3O4 nanoparticles and the functional groups in the polymers. As can be seen from the SEM images, the morphology of the magnetite Fe3O4 nanoparticles surrounded by PEQ is different from that of pure Fe3O4 because it is covered with a polymer phase. Observation of globules characteristic of macromolecular chains in SEM microimages proves that nanoparticles are fully covered. It has been shown that the average size of nanoparticles synthesized in the presence of PEQ is 26-55 nm depending on temperature.

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POLiETiLENQLiKOL MÜHiTiNDO MAQNETiT Fe3O4 NANOHiSSOCiKLORlNiN SiNTEZi УЭ

QURULU§LARININ TODQiQi

S.F. Hümbatova

Polietilenqlikol ila funksionalla§dmlan maqnetit Fe3O4 nanohissaciklarinin sintezi so-gökdürma üsulu ila üzvi maddalardan gox az miqdarda istfada etmakla nanohissaciklarin yüksak monodispers formasini alda etmakla yerina yetirilmiij va alinmi§ Fe3O4 nanohissaciklarinin qurulu§lari müxtalif fiziki üsullarla tadqiq edilmi§dir. Müayyan olunmu§dur ki, polimerla ahata olunmu§ maqnit xassali Fe3O4 nanohissaciklarinin sintezi zamani istifada olunan polimerin miqdanni, gökdürücü agentin tabiatini, ilkin prekursorlann qatiligini va temperaturu tanzimlamakla yüksak tamizlik daracasina malik, ölgülarina göra bircins va monodispers Fe3O4 nanohissaciklarini sintez etmak va stabilla§dirmak olar.

Agar sözlzr: maqnetit, nanohissaciklar, polietilenqlikol, so-gökdürm3, polimer

СИНТЕЗ И ИССЛЕДОВАНИЕ СТРУКТУРЫ НАНОЧАСТИЦ МАГНЕТИТА Fe3O4 В СРЕДЕ ПОЛИЭТИЛЕНГЛИКОЛЯ

С.Ф.Гумбатова

Синтез наночастиц магнетита Fe3O4, функционализированных полиэтиленгликолем, осуществляли методом соосаждения с использованием очень малого количества органических веществ, для получения высоко-монодисперсной формы наночастиц, и структуры полученных наночастиц Fe3O4 изучали различными физическими методами. Было установлено, что, регулируя количество используемого полимера, природу осадителя, концентрацию исходных прекурсоров и температуру при получении наночастиц Fe3O4 с магнитными свойствами, окруженных полимером, можно синтезировать и стабилизировать однородные по размеру и монодисперсные наночастицы Fe3O4 с высокой степенью чистоты.

Ключевые слова: магнетит, наночастицы, полиэтиленгликоль, метод соосаждения, полимер.

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