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Materials Research Bulletin 62 (2015) 217221

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Materials Research Bulletin


journal homepage: www.elsevier.com/locate/matresbu

Short communication

Hydrothermal synthesis of superparamagnetic Fe3O4 nanoparticles


with ionic liquids as stabilizer
Xiao-Di Liu * , Hao Chen, Shan-Shan Liu, Li-Qun Ye, Yin-Ping Li
College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang, Henan 473061, China

A R T I C L E I N F O A B S T R A C T

Article history: Superparamagnetic Fe3O4 nanoparticles have been successfully synthesized under hydrothermal
Received 25 June 2014 condition with the assistant of ionic liquid 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl). The
Received in revised form 17 October 2014 structure and morphology of the sample have been investigated by X-ray diffraction (XRD), X-ray
Accepted 8 November 2014
photoelectron spectra (XPS), transmission electron microscopy (TEM), and high-resolution TEM
Available online 11 November 2014
(HRTEM), and the results indicate that the as-synthesized inverse spinel Fe3O4 nanoparticles have an
average diameter of about 10 nm and exhibit relatively good dispersity. More importantly, it is found that
Keywords:
[C16mim]Cl acts as stabilizer for the Fe3O4 nanoparticles by adsorbing on the particles surfaces to prevent
A. Magnetic materials
B. Chemical synthesis
the agglomeration. In addition, the obtained superparamagnetic Fe3O4 nanoparticles have a saturation
B. Magnetic properties magnetization of 67.69 emu/g at 300 K.
2014 Elsevier Ltd. All rights reserved.

1. Introduction possessing 1-alkyl-3methlyimidazolium cation ([Cnmim]+) have


gained much attention for their favorable physico-chemical
Fe3O4 nanoparticles (NPs), as one kind of the most important properties, and they have served as reactants, solvents, and
magnetic materials, have been widely applied in biomedicine, templates in the fabrication of nanomaterials [1214]. ILs can be
magnetic storage devices, ferrouids, and separation processes due manufactured to be hydrophobic or hydrophilic by designing their
to their excellent magnetic properties [1,2]. The magnetic property of structures; furthermore, the low surface tensions of ILs are
Fe3O4 NPs strongly depends on their sizes, and Fe3O4 NPs with benecial to improve the stability of the as-formed nanomaterials.
diameters between 3 and 15 nm possess superparamagnetic In these regards, some imidazolium-based ILs have been chosen as
property [3]. Most recently, superparamagnetic magnetic materials stabilizers to prepare dispersible nanomaterials [1517]. For
have attracted much attention in the biomedical eld such as drug example, Dupont et al. have synthesized stable transition-metal
delivery and magnetic resonance imaging (MRI) [4]. To date, several NPs (23 nm in size) by reduction of transition-metal compounds
synthesis processes, including hydrothermal/solvothermal tech- dissolved in [Bmim]PF6. Therefore, it is reasonable to conceive that
nique, solgel route, and co-precipitation method, have been ILs with special cations and anions can be employed as stabilizers
developed to synthesize Fe3O4 NPs [2,57]. In the synthesis, Fe3O4 to improve the monodispersity of Fe3O4 NPs.
NPs tend to agglomerate for their large surface energy and Herein, we have developed a novel and effective hydrothermal
magnetization, which would seriously affect the applications; method for the fabrication of superparamagnetic Fe3O4 NPs. IL
therefore, several stabilizers such as surfactants and polymer 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl) have
matrixs have been used to improve the dispersity of Fe3O4 NPs been used as stabilizer in the synthetic system. The effect of
[4,8,9]. However, the nal products would possess relatively low [C16mim]Cl on the morphology of product have been investigated
saturation magnetizations for the nonmagnetic layers [10]. Thus, it is in details.
still a challenge to explore novel routes for the fabrication of Fe3O4
NPs with both good dispersity and excellent magnetic property. 2. Material and methods
Ionic liquids (ILs) are organic salts with low melting points and
consist of predominantly ionic species [11]. Most recently, ILs 2.1. Materials

All chemicals were analytical-grade and used without further


* Corresponding author. Tel.: +86 377 63525056; fax: +86 377 63513540. purication. [C16mim]Cl was prepared according to the literature
E-mail addresses: liuxiaodiny@126.com, didi899@126.com (X.-D. Liu). procedures [18].

http://dx.doi.org/10.1016/j.materresbull.2014.11.022
0025-5408/ 2014 Elsevier Ltd. All rights reserved.
218 X.-D. Liu et al. / Materials Research Bulletin 62 (2015) 217221

2.2. Synthesis of Fe3O4 NPs

In a typical synthesis, FeCl24H2O (0.15 mmol) and


C6H5Na3O72H2O (0.30 mmol) were dissolved into deionized water
(7.5 mL) with magnetic stirring until a clear solution was obtained.
Then, [C16mim]Cl (0.4 g) and N2H4H2O (2.5 mL) were added to the
solution. After it was stirred for 5 min, the solution was transferred
and sealed in a teon-lined stainless steel autoclave with a capacity
of about 20 mL. The autoclave was sealed and maintained at 150  C
for 12 h. The products were separated by centrifugation, washed by
deionized water and anhydrous ethanol, and then dried in a
vacuum at 60  C for 5 h. Finally black powder was obtained.

2.3. Instruments and characterizations

The phase compositions of the product were characterized by


X-ray diffraction (XRD) on a Rigaku D/max 2500V/PC X-ray
diffractometer (Cu Ka, l = 1.54056 ) with a 2u range between
20 and 80 . The generator voltage was 40 kV, the current was
40 mA and the step velocity was 8 /min. The X-ray photoelectron
spectra (XPS) data was characterized using PHI-1600 ESCA X-ray
photoelectron spectroscopy with Mg Ka as radiation. The sizes and
structures of the products were performed by a Hitachi H-
7650 transmission electron microscopy, which were operated at an
accelerating voltage of 100 kV and 200 kV, respectively. The
magnetic studies were performed on a Quantum Design MPMS-
XL-7 SQUID susceptometer and a vibrating sample magnetometer
(VSM, LDJ-9600, USA).

3. Results and discussions


Fig. 1. (a) XRD pattern of the obtained Fe3O4 NPs; (b) Fe2p peaks in the XPS
3.1. Characterization results of the Fe3O4 NPs spectrum of the Fe3O4 NPs.

Fig. 1a depicts the XRD pattern of Fe3O4 NPs. All of the


diffraction peaks are indexed as face-centered cubic Fe3O4 with the assigned to Fe2p1/2 and Fe2p3/2, are consistent with the values
lattice parameters of a = 8.381 , which matches well with the reported for Fe3O4 in the literature; furthermore, no satellite peak
reported values (JCPDS No. 75-0033). No peaks corresponding to around 719.0 eV is identied, indicating the absence of g -Fe2O3 in
impurities are detected, showing the high purity of the sample. The the sample [21].
mean crystallize size of Fe3O4 NPs is calculated to be about 10.5 nm TEM image (Fig. 2a) gives a general view of the as-synthesized
based on Scherrer formula. Fe3O4 has an inverse spinel structure Fe3O4 NPs. It can be clearly seen that the sample is quasi-round NPs
similar to that of g -Fe2O3; therefore, XRD result cannot provide and has a mean diameter of about 10 nm, consisting with the XRD
enough evidence to conrm the formation of Fe3O4 [19]. Thus, we result. In the HRTEM image taken at a typical particle (Fig. 2b), the
employ XPS, which is sensitive to the iron valence state, to Fe3O4 nanoparticle has a d-spacing of about 0.255 nm, correspond-
distinguish these two different phases [20]. As shown in the XPS ing to the lattice spacing of the (3 11) plane in cubic Fe3O4;
spectra of Fe2p in Fe3O4 (Fig. 1b), the peaks at 724.1 and 710.5 eV, moreover, its corresponding fast Fourier transform (FFT) pattern

Fig. 2. (a) TEM image of the as-synthesized Fe3O4 NPs; (b) HRTEM image of a typical Fe3O4 NPs with the electron beam incident along the [0 0 1] direction, and the inset of (a)
is its FFT pattern.
X.-D. Liu et al. / Materials Research Bulletin 62 (2015) 217221 219

(the inset in Fig. 2a) has a highly symmetrical dotted lattice,


exhibiting the single-crystal nature of the Fe3O4 NPs.

3.2. Formation mechanism of the Fe3O4 NPs

It is well-known that the isotropic growth of particles is


governed by their isotropic unit cell structure, and thus, leads to
spherical or near-spherical shapes [13,22]. Fe3O4 has an inverse
spinel structure based on Fd-3m space group. In the crystal
structure of cubic Fe3O4 (Fig. 3a), the O atoms form a fcc closed
packing and the Fe atoms occupy interstitial tetrahedral sites and
octahedral sites, symbolized as [Fe3+]A[Fe2+Fe3+]BO4, in which the
A (tetrahedral sites) are occupied by Fe3+ ions, and the B
(octahedral sites) by equal numbers of Fe2+ and Fe3+ ions [2].
Thereby, the as-formed Fe3O4 nuclei are easy to present quasi-
round morphology for its isotropic crystal structure.
Once the Fe3O4 NPs are formed, they have a strong tendency to
form aggregates owing to their high surface energy and strong
magnetic dipoledipole interaction [23]. Fortunately, [C16mim]Cl
can be used to stabilize these particles. We consider that the Fig. 4. TEM image of Fe3O4 NPs synthesized without the assistant of [C16mim]Cl.
possible reasons mainly involve two aspects. Firstly, the isoelectric
point of Fe3O4 is discovered to be pI = 6.46.8 and the surface of
Fe3O4 is charged negatively at pH > 6.8; therefore, cationic carried out a control experiment, in which [C16mim]Cl is not used
surfactants can hardly adsorbed to the surface of Fe3O4 NPs at and other reaction parameters remain unchanged. Finally, as
pH < 6.5 [2426]. In the synthesis, the pH value is measured to be shown in Fig. 4, the obtained Fe3O4 NPs are prone to aggregate with
about 12.1, so the cations of [C16mim]Cl could adsorb on the each other. In addition, ILs could be reused in a simple process, so
particles surfaces and hinder the agglomeration of the Fe3O4 NPs in the employment of IL as stabilizer is favorite from the viewpoints
the solution (shown in Fig. 3b). Secondly, ILs show polar features, of environmental protection and economy, especially in large-scale
but they have lower surface tensions compared with water [27]. As synthesis [29].
to imidazolium-based ILs with the same anions, the surface
tension decreased with the increase of alkyl chain length of 3.3. Magnetic properties of the Fe3O4 NPs
[Cnmim]+. In the experiment, the surface tension of the complex
solvent is between 35 and 40 mN m1 against water (73 mN m1), When the size of the Fe3O4 NPs is below a critical value, each
which is good for improving the stability of the product [28]. In nanoparticle becomes a single magnetic domain and shows
there regards, the dispersibility of the sample could be improved. superparamagnetic behavior when the temperature is above the
In order to further substantiate the effect of [C16mim]Cl, we have blocking temperature (TB) [30]. As to a single domain particle, the
magnetic anisotropy energy (Ku), which is required to overcome
the energy barrier of reversing the magnetization from one stable
magnetic conguration to another, is proportional to the particle
volume,
KV
Ku /
kB T
where K is the anisotropy constant of the particle, V is the particle
volume, kB is Boltzmanns constant, and T is temperature. When
the particle size is sufciently small, the thermal energy can
overcome its anisotropy energy and change the direction of

Fig. 3. (a) Crystal structure of cubic Fe3O4; (b) adsorption of [C16mim]+ on the
surfaces of the Fe3O4 NPs. Fig. 5. Zero-eld-cooled (ZFC) and eld-cooled (FC) curves for the Fe3O4 NPs.
220 X.-D. Liu et al. / Materials Research Bulletin 62 (2015) 217221

Fig. 6. Hysteresis loop of the Fe3O4 NPs at 300 K, and the inset is the corresponding hysteresis loop on a large scale.

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