Superparamagnetic Fe3O4 nanoparticles, synthesis and surface modification

doi:10.1016/j.mssp.2015.05.035

Materials Science in Semiconductor Processing

Volume 39, November 2015, Pages 641-648

https://doi.org/10.1016/j.mssp.2015.05.035 Get rights and content

Abstract

Magnetite nanoparticles have been synthesized through a co-precipitation of iron (Fe³⁺ and Fe²⁺), and were characterized using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and superconducting quantum interference device magnetometer (SQUID). The particles have been modified by several types of stabilizers such as polyethylene glycol (PEG 4000), sodium citrate, and ethylenediaminetetraacetic acid (Na₂H₂Y·2H₂O). These nanoparticles are nearly spherical with an average diameter 12 nm. The capping agents have been successfully anchored to the surface, as revealed by the absorption bands in infrared, and the adsorbed quantities are evaluated by TGA analysis. Magnetization of these magnetic nanoparticles was almost zero at room temperature in the absence of an applied magnetic field, indicating their superparamagnetic behavior. Such NPs magnetite could serve as a magnetic core to an eventual core-shell structure when coated with various materials.

Introduction

Materials science has always been at the heart of the physico-chemical science. It is the basis of many major scientific revolutions in various fields such as electronics, automotive, aerospace, nanoscience, medicine, catalysis, emulsion paints and cosmetics, renewable energy, sustainable development, sensors etc. It is commonly defined that a hybrid material, is an organomineral system for which a combination of the unique properties of both organic and inorganic components is obtained. Generally, the inorganic component provides mechanical, thermal, magnetic and electrical properties while the organic component provides elastic, optical, electrochemical and biological properties with a facility of implementation, notably as thin layers. With an infinite choice of their formulations, the potential of hybrid materials is immense.

Recent developments in the scientific world have been increasingly interested in nanotechnology for the last two decades. Thus, in today׳s world of “all green” and sustainable energy, the interest to develop new functional materials is not only important but also strategic. Research in the field of materials science continues to grow in the main purpose of providing new materials with various applications, mainly dedicated to environmental and biomedical fields. Furthermore, magnetic nanomaterials constitute nowadays an interesting axis of development due to the properties they offer. Their chemical functionalization is a major tool in the coupling of their final properties.

The iron oxide nanoparticles (Fe₃O₄ NPs) present an interesting potential in the fields of biochemical sensors and nanoelectronics in addition to data storage. Eventually, functionalized magnetic nanoparticles are studied for targeted therapy in medicine [1], [2], [3], [4]. These nanotechnologies defy the challenge that lies within the cancer through the development of cleverly shaped nano-objects, using highly promising approaches, unfolded by researchers experimenting on nanoparticles that can destroy brain tumors using photodynamic therapy [5], [6]. Other researchers are striving to create intelligent vehicles, capable of carrying anticancer drugs to be delivered into the tumor [7], [8]. Thus, by targeting the tumor precisely, we can significantly reduce the side effects of chemotherapy.

Furthermore, a multitude of studies incorporating superparamagnetic iron oxide within a wide variety of organic materials were intensively reported in the literature [9], [10], [11], [12], [13], [14], [15]. Most of these authors have encapsulated the mineral Fe₃O₄ in a polymer shell in order to obtain a nanostructures “core–shell” with a promising superparamagnetic property. The potential applications of such materials are numerous: photocatalysis [16], [17], [18], heavy metal ion pollution [19], [20], immunological test [21], extraction of phenolic compounds [13], [22], magnetic resonance imaging and drug delivery [23], [24], [25], [26], proteins separation[27], magnetic storage media, improving the efficiency of energy conversion in the solar cells [28], rechargeable lithium batteries and photoelectrochemical solar cells using nanomaterial׳s electrodes [29].

Moreover, different authors have been interested in the development of magnetic or luminescent nanoparticles based on cobalt, lanthanum, and phosphorus [30], [31], [32]. They point out that the use of a combination of solvents and/or capping agents such as oleic acid, trioctylphosphine, polymeric chains of polyvinyl pyrollidone or sodium oleate enables better control of the size and shape of the synthesized nanoparticles. This will reduce the magnetic dipolar interactions in order to re-disperse them in aqueous or organic media.

The main purpose of this article is to prepare magnetite nanoparticles using the coprecipitation technique of ferrous and ferric salts. It is proposed to study the behavior of different protective agents on the surface of synthesized NPs, in order to better understand the state of association between these protective molecules and groups naturally existing on the surface of magnetite. The choice of modifiers was limited to sodium citrate, sodium ethylenediaminetetraacetate and PEG polyethylene glycol. Indeed, the first two have carboxylates functional groups which are known to have the ability to connect with the transition metal ions such as ferrous and ferric ions to the surface of the magnetite. Their anchoring surface should bring a change of the state of the iron oxide surface with a resultant repulsion to prevent aggregation. Polyethylene glycol is a water soluble polymer that should bind to the surface via its hydroxyl groups and eventually enhance particles repulsion via its carbon chains. Stabilization of NPs is recommended in order to manipulate them when they are mostly disaggregated to facilitate their further encapsulation in various shells. Finally, the superparamagnetic properties of the obtained stabilized particles will be assessed.

Section snippets

Chemicals

Iron (III) chloride hexahydrate (FeCl₃·6H₂O), iron (II) chloride tetrahydrate (FeCl₂·4H₂O), aqueous ammonia (25%), and hydrochloric acid (37% aqueous solution) were purchased from Sigma-Aldrich. Trisodium citrate and Triton X-100 $(M w = 625 g / mol)$ were purchased from Sigma-Aldrich and polyethylene glycol PEG 4000 $(M w = 4000 g / mol)$ , disodium ethylenediaminetetraacetic salt (Na₂H₂Y·2H₂O) also called EDTA, supplied by Fluka were used as capping agents.

Synthesis of Fe₃O₄ nanoparticles

Fe₃O₄ nanoparticles were synthesized by

X-ray diffraction

The crystal orientation of the magnetic particles was investigated through XRD measurements. The average crystallite size is calculated using the Debye–Sherrer equation: $D = k λ / β \cos θ$ where $k = 0.95$ is Sherrer׳s constant, λ is the X-ray wavelength, β is the full width at half-maximum, and θ is the Bragg diffraction angle. Fig. 1 shows the XRD patterns of pure Fe₃O₄ nanoparticles, citrate – coated Fe₃O₄, PEG 4000 – coated Fe₃O₄ and EDTA – coated Fe₃O₄. Compared to bulk magnetite, the peaks at (111),

Conclusion

In this work, magnetite nanoparticles have been synthesized and stabilized using different agents. Stabilizers were deposited on the particles׳ surface in the aim of an eventual encapsulation. The particles have been fully characterized using different methods, in particular XRD measurements reveal a good crystalline structure which corresponds to the inverse spinel lattice, despite the addition of stabilizers. It was noticed that there were interactions between the stabilizers and the surface

Acknowledgments

This work was financially supported by the research council of Saint-Joseph University (Grant number ESIB16) and the CEDRE (Grant number 12SCIL20/F22) program. The Authors gratefully acknowledge Professor Antoine Samrani for his valuable help.

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Superparamagnetic Fe3O4 nanoparticles, synthesis and surface modification

Abstract

Introduction

Section snippets

Chemicals

Synthesis of Fe3O4 nanoparticles

X-ray diffraction

Conclusion

Acknowledgments

J. Formos. Med. Assoc.

Carbohydr. Polym.

Cancer Treat. Rev.

Biomaterials

Mater. Sci. Eng. C

J. Alloy. Compd.

Mater. Sci. Eng. B

J. Phys. Chem. Solids

J. Magn. Magn. Mater.

J. Chromatogr. A

Colloids Surfaces A: Physicochem. Eng. Asp.

Int. J. Biol. Macromol.

Appl. Surface Sci.

Mater. Res. Bull.

Detect. Assoc. Equip.

Chem. Eng. J.

Chem. Eng. J.

Eng. Asp.

J. Chromatogr. A

J. Magn. Magn. Mater.

Powder Technol.

Superparamagnetic Fe₃O₄ nanoparticles, synthesis and surface modification

Synthesis of Fe₃O₄ nanoparticles