Colloids and Surfaces A: Physicochem. Eng.

Aspects 336 (2009) 130–134

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Colloids and Surfaces A: Physicochemical and Engineering Aspects
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Facile synthesis of magnetic iron oxide nanoparticles using 1-methyl-2-pyrrolidone as a functional solvent
Chen Qin a , Chen Li a , Yizhe Hu a , Jianfeng Shen a , Mingxin Ye a,b,∗
a b

Department of Materials Science, Fudan University, Shanghai 200433, PR China The Key Laboratory of Molecular Engineering of Polymer, Ministry of Education, China

a r t i c l e

i n f o

a b s t r a c t
Magnetic nanoparticles were generated by thermal decomposition of ferric triacetylacetonate in the presence of 1-methyl-2-pyrrolidone, a functional solvent. The particle size and shape could be varied by altering reaction parameters. For example, with the addition of oleic acid surfactant, smaller particles were produced. In addition, step elevation of reaction temperature was in favor of regular particle morphology. The obtained iron oxide nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis and vibrating sample magnetometer. All of the experimental evidences supported that we succeeded in synthesizing monodisperse iron oxide nanoparticles via a facile and effective route. Moreover, when the oleic acid was added, 1-methyl-2-pyrrolidone and oleic acid possibly forms an intercalated monolayer on the particle surface. © 2008 Elsevier B.V. All rights reserved.

Article history: Received 26 September 2008 Received in revised form 10 November 2008 Accepted 17 November 2008 Available online 28 November 2008 Keywords: Facile Synthesis Iron oxide nanoparticles Functional solvent

1. Introduction Magnetic nanoparticles have been among the appealing research topics of nanoscience due to their unique properties and potential applications [1–4]. Although there are several kinds of interesting magnetic nanoparticles, iron oxide particles – magnetite (Fe3 O4 ) and its oxidized form maghemite ( -Fe2 O3 ) – have attracted more attention because they are non-toxic and less susceptible to changes due to oxidation. These facts make this kind of nanoparticles one of the most studied materials for biomedical applications. For all applications, synthetic techniques providing precise control over nanocrystal grain size are crucial in that they permit engineering of the magnetic properties. The classical synthetic techniques of iron oxide nanoparticles have relied on the coprecipitation of Fe2+ and Fe3+ ions by a base. The disadvantage of these aqueous solution syntheses is that the pH value of the reaction mixture has to be adjusted in both the synthesis and purification steps, and the process toward monodisperse nanoparticles smaller than 20 nm has only very limited success [5]. Other techniques such as microemulsion, ultra sound irradiation and laser pyrolysis, have been developed for producing iron oxide nanoparticles. However,

∗ Corresponding author at: Department of Materials Science, Fudan University, No. 220, Hadan Road, Shanghai 200433, China. Tel.: +86 21 55664095; fax: +86 21 65642622. E-mail address: (M. Ye). 0927-7757/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2008.11.040

nanoparticles obtained by above-mentioned approaches may be poorly crystalline and the size uniformity is hard to control [6]. In recent years, an alternative method based on the thermal decomposition of organic iron precursors has been demonstrated to be very successful in the preparation of iron oxide nanoparticles with controllable size and high quality. Rockenberger’ group published a study of -Fe2 O3 nanocrystals prepared by thermal decomposition of pentacarbonyliron [Fe(CO)5 ] in hot surfactants [7]. Sun and co-workers reported that the thermolysis of ferric triacetylacetonate [Fe(acac)3 ] can make monodisperse Fe3 O4 nanoparticles [8]. Some other research groups demonstrated that FeCup3 [Cup: C6 H5 N(NO)O− ] could be used as a starting material to form -Fe2 O3 nanoparticles [9–11]. Rather than adopting commonly used nonpolar high-boilingpoint solvents, we have focused our study on 1-methyl-2pyrrolidone which can serve as a coordinating solvent in addition to a high-temperature reaction medium. Moreover, comparing to different ethers in many cases, 1-methyl-2-pyrrolidone has no peroxide formation and is less dangerous. In this work, we report a one-pot synthesis of monodisperse iron oxide nanoparticles by thermal decomposition of Fe(acac)3 in the presence of 1-methyl-2pyrrolidone. Oleic acid (OA) was added as a competitive surfactant to find its influence. The heating procedures were also changed to examine how the temperature affected the formation of magnetic nanoparticles. We characterized the products in term of their magnetic properties, their particle morphology, surfactant coverage and interaction at the particle surface by vibrating sample magnetometer (VSM), X-ray diffraction (XRD), transmission electron

696 1.5 h.710 1.523 2. 1 h microscopy (TEM).C. After cooled to room temperature.39 3.80◦ 17. 39-1346).705 1.092 1. 1. possibly Fe3 O4 in the core and -Fe2 O3 on the surface.02◦ s−1 in the 2 ranging from 25◦ to 75◦ .39 Total volume of 1-methyl-2-pyrrolidone (ml) 50 50 50 Temperature 131 194 ◦ C. Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). Qin et al. / Colloids and Surfaces A: Physicochem. labeled MN1. 19-0629 for Fe3 O4 (see Table 2).967 2. (B) MN2 = 3:1. the particle size and shape would be varied by altering different reaction parameters. The whole process was carried out under a nitrogen atmosphere. Sample MN1 MN2 MN3  17. 1 h 194 ◦ C. By the current synthetic approach.953 2.527 2.1. 204 ◦ C. the mixture was treated with a 3-fold volume excess of ethanol under air to yield a black precipitate. (4 0 0).8 nm with a standard deviation of 1. When there was no addition of OA. Aspects 336 (2009) 130–134 Table 1 Magnetic nanoparticles synthesized via different processes. while the morphology of samples was observed by TEM using a JEOL 2010F.0152 0. 2A was about 16.0140 D311 (nm) 16.6 nm.154056 nm). 1 h 194 ◦ C. 1. For comparison the synthesis was carried out by the similar preparation processes but with different parameters. the initial deep red-brown color of the solution changed to dark brown.476 of these particles. 0.  is the diffraction angle.0086 0. a typical synthesis yielding iron oxide nanocrystals is described.612 1. Fig. Therefore. With the experimental evidence. The process of dropping was completed in 5 min and the stirring was continued for another 1 h. We believe that these well-organized self-assemblies will allow further applications in many technological fields such as high area density data storage.41 g Fe(acac)3 was dissolved in 20 ml purified 1-methyl-2-pyrrolidone and added dropwise into the 1-methyl-2-pyrrolidone/OA solution under vigorous stirring. 1 shows XRD patterns of nanoparticles synthesized from reaction mixtures. ˇ is the full width at half maximum intensity of the peak and D is the particle size. X-ray diffraction patterns of samples with different molar ratios of OA to Fe(acac)3 : (A) MN1 = 0:1.78 17.607 1. to examine their roles critical to the sizeand shape-guiding processes. hkl 220 311 400 422 511 440 Fe3 O4 2.972 2. (3 1 1). The positions were assigned to the (2 2 0).484 MN2 2.715 1. Crystal structure information was obtained using a Rigaku D/max.089 1. In other words. d-spacing values of all diffraction peaks in Fig.41 1.3 .89 ˇ cos  (1) where is the wavelength (0.481 -Fe2 O3 2. were listed in Table 1. Magnetic measurement was operated in air at room temperature by using a home-made VSM. The crystal domain sizes of magnetic nanocrystals could be calculated from line broadenings by the Scherrer’s formula [12]: D≈ 0.B X-ray diffract meter with Cu K radiation ( = 1.54056 Å) at a scanning rate of 0.41 Mass of OA (g) 0 3. (4 2 2).518 2.532 2.531 2. 3. The particle size yielding from the above equation in the (3 1 1) reflection was listed in Table 3. Table 2 Comparison of d-spacing values of the synthesized iron oxide nanocrystals with standard JCPDS Fe3 O4 and -Fe2 O3 data. MN2 and MN3.946 2. Sample MN1 MN2 MN3 Mass of Fe(acac)3 (g) 1.616 1.41 1.5 10. especially on the surface Fig. (C) MN3 = 3:1 with an additional heating procedure. Composition and microstructure of the thermolysis products Both XRD and TEM measurements were performed to obtain structure information of the resulting magnetic nanoparticles. The average size was in close agreement with the value estimated by Table 3 The size of magnetic nanocrystals calculated by Scherrer’s formula. easily oxidized to -Fe2 O3 by the atmospheric O2 during the washing and drying processes. TGA was conducted with Netzsch TG 209 that was fitted to a nitrogen purge gas from 30 ◦ C to 600 ◦ C at 10 ◦ C/min heating rate.608 1. (5 1 1) and (4 4 0) reflections of the inverse spinel structure of -Fe2 O3 (JCPDS no.099 1. FTIR Spectroscopy data were collected on a NEXUS 670 spectrometer. which could be collected either by centrifugation.610 1.478 MN3 2. 1 are well consistent with data from the JCPDS no. Experimental In the following. It should be noted that the standard XRD patterns of -Fe2 O3 and Fe3 O4 are alike. 30 ml purified 1-methyl-2-pyrrolidone containing 3. At room temperature. Three different samples. the spectra were recorded by signal averaging of 32 scans at a resolution of 2 cm−1 in the range of 4000–500 cm−1 .703 1. However. The resulting black powder was washed several times by acetone and dried in a vacuum oven at 60 ◦ C overnight. larger particle size calculated from the statistical results shown in Fig. Eng.967 2. 2. During this thermolysis process.095 1. Results and discussion 3.092 1.72◦ ◦ ˇ (rad) 0. we concluded that these samples were mixture of -Fe2 O3 and Fe3 O4 . our data suggest that the nanoparticles are monodisperse and the synthetic route does not require a size-selection procedure.485 MN1 2.7 9. the initial synthesized Fe3 O4 .39 g oleic acid was heated to 194 ◦ C. such as the addition of oleic acid and the heating procedure.

Scherrer’s formula.1 ± 1. This suggests that step elevation of reaction temperature was in favor of regular particle morphology. Otherwise the shape of nanoparticles was not spheriform but irregular. Qin et al. Aspects 336 (2009) 130–134 Fig. (B) MN2. which could be ascribed to that when the OA surfactant was adsorbed on the iron oxide particles. The inserted pictures are corresponding particle size histograms. 3. smaller particles (9.2 ± 2. It is indicated that each individual particle is nearly a single crystal. 3. FTIR spectra of purified 1-methyl-2-pyrrolidone. The atomic lattice fringes in Fig. Sample MN3 (Fig. 2B could demonstrate that the particles are also crystalline. / Colloids and Surfaces A: Physicochem. Characterization of nanoparticle surfaces The surface chemical structure of the magnetic nanocrystals and their capping were characterized by FTIR spectroscopy and Fig.132 C. This sample was even larger in size (11. and (C) MN3. Once the OA surfactant was added. the number of accessible sites for further crystal growth was reduced. Eng. The acquisition of larger particles was consistent with the Ostwald ripening process during which large crystals grow even larger at the expense of smaller nanocrystals [14]. 2. leading to termination of crystal growth [13]. TEM images of (A) MN1. .1 nm) were produced (Fig. iron oxide nanoparticles and pure oleic acid.2. 2B).2 nm) and possessed more homogeneous shape than that obtained by simply refluxing the reaction mixture at 194 ◦ C for 1 h. 2C) was achieved by refluxing the reaction mixture at 204 ◦ C for 1 h after an initial treatment at 194 ◦ C for 30 min.

but two additional vibrational bands appear at around 1530 cm−1 and 1430 cm−1 in both spectra MN2 and MN3. the weight losses were due to the desorption and subsequent evaporation of the 1methyl-2-pyrrolidone. hysteresis loops were recorded at room temperature. it further supports that the OA does not completely displace 1-methyl-2-pyrrolidone and possibly forms an intercalated layer on the particle surface (Fig. 3. was in great excess in comparison with OA under current preparative condition. which is characteristic of the OA dimer form [16]. Since this band remains in spectra MN2 and MN3. the mass profile exhibits a well defined decrease over a temperature range of 260–400 ◦ C. For sample MN1. TGA. Fe nanoparticles whose surface is capped with 1-methyl-2-pyrrolidone or a monolayer consisting of both 1-methyl-2-pyrrolidone and oleic acid. 4.4% at T < 180 ◦ C. it can be deduced that the 1-methyl-2-pyrrolidone molecules bound to the particle surface are partially replaced by OA. more than 20% mass losses were observed by other research groups [20. 3. This is because 1-methyl-2-pyrrolidone. revealing a different pattern from that observed for MN1. In Fig. 6.0% and 14. the amount of water release corresponds to ∼3. 5. For the sample MN2. organic shell and solvent residues. Schematic drawing of 1-methyl-2-pyrrolidone. Heating curves for (A) sample MN1 and (B) sample MN2. In both cases. Therefore. sample MN1 and sample MN2 have 11. The FTIR measurements also reveal that the vibrational band C O shifts from 1680 cm−1 for pure 1-methyl-2-pyrrolidone to 1650 cm−1 for sample MN1. respectively. / Colloids and Surfaces A: Physicochem. . a coordinating solvent. 6 shows the room-temperature magnetization curves Fig. Both samples display y a similar massloss profile below 260 ◦ C. we could determine the relative composition of iron oxide core. Aspects 336 (2009) 130–134 133 Fig. Qin et al. All of these results support that the carboxylic acid from OA is bound to the particle surface. Fig. oleic acid. The band peak at 1710 cm−1 is attributed to the carbonyl (C O) stretching mode. For the sample MN1. the characteristic peaks centered at 585 cm−1 in all spectra of magnetic particles can be ascribed to lattice absorption of magnetite [15]. Such changes are assigned to the formation of either a monodentate or bidentate complex between the carboxylic acid and Fe on the surface of the iron oxide nanoparticles [17. This band is not observed in the spectra of magnetic samples. and the mass loss decreased more intensely as the temperature above 270 ◦ C.21]. with initial losses for water or solvent residues and subsequently organic shell degradation. Based on TGA measurements. Magnetic hysteresis loops measured at room temperature for samples MN1 and MN2.8% mass loss for organic shell. a scenario which needs further investigation. according to FTIR results. 4.C. Eng. the weight reductions are attributed to quantitative mass loss of OA and 1-methyl-2pyrrolidone. We believe that there is some competition between 1-methyl-2-pyrrolidone and OA to coordinate with iron particles. significant mass losses were detected in the heating from 270 ◦ C to 430 ◦ C. Fig.18]. 5). For sample MN2. respectively. For OA coated iron oxide nanoparticles. which indicates that the O from C O coordinates with Fe on the surface of the magnetic nanocrystallites [19].3. Magnetic properties In a preliminary investigation of magnetic properties of these nanoparticles. As depicted in Fig. curves A and B show the degradation of samples MN1 and MN2. During the temperature range of 180–700 ◦ C.

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