Applied Surface Science 253 (2006) 2611–2617

www.elsevier.com/locate/apsusc

Oleic acid coating on the monodisperse magnetite nanoparticles

Ling Zhang, Rong He, Hong-Chen Gu *
Institute for Micro and Nano Science and Technology, Shanghai Jiaotong University, 200030 Shanghai, China
Received 15 March 2005; received in revised form 27 December 2005; accepted 15 May 2006
Available online 23 June 2006

Abstract
Monodisperse magnetite nanoparticles provide a more factual model to study the interface interactions between the surfactants and magnetic
nanoparticles. Monodisperse magnetite nanoparticles of 7 and 19 nm coated with oleic acid (OA) were prepared by the seed-mediated high
temperature thermal decomposition of iron(III) acetylacetonate (Fe(acac)3) precursor method. Fourier transform infrared spectra (FTIR) and X-ray
photoelectron spectroscopy (XPS) reveal that the OA molecules were adsorbed on the magnetic nanoparticles by chemisorption way. Analyses of
transmission electron microscopy (TEM) shows the OA provided the particles with better isolation and dispersibility. Thermogravimetric analysis
(TGA) measurement results suggest that there were two kinds of different binding energies between the OA molecules and the magnetic
nanoparticles. The cover density of OA molecules on the particle surface was significantly various with the size of magnetite nanoparticles.
Magnetic measurements of the magnetite nanoparticles show the surface coating reduced the interactions among the nanoparticles.
# 2006 Elsevier B.V. All rights reserved.

PACS: 73.20

Keywords: Monodisperse; Magnetite nanoparticles; Oleic acid; Chemisorption

1. Introduction Oleic acid (OA) is a commonly used surfactant to stabilize

the magnetic nanoparticles synthesized by the traditional
Magnetic nanoparticles have been of great interests because coprecipitation method, and some studies [12,13] have proved
of their extensive applications in high-density data storage, that the strong chemical bond formed between the carboxylic
biochemistry, hyperthermia, in vivo drug delivery, MR contrast acid and the amorphous iron and amorphous iron oxide
reagent [1–7]. To apply magnetic nanoparticles in various nanoparticles. However, it is hardly to know the interaction
potential fields, it is very important to control the size and between the single nanoparticle and surfactant from the
shape, and to keep the thermal and chemical stability by surface ‘‘compositive’’ results given by these kinds of size and shape
modification [8]. This modification generally will play a key widely dispersed nanoparticles systems. For the nanoparticles
role on the properties and applications of the magnetic with different sizes, the surface effects are significantly various
nanoparticles in bio-solutions or tissue environments [9]. The due to the difference of volume fraction of surface atoms within
magnetic structure of the surface layer usually is greatly the whole particle. Excitingly, the chemical routes of synthesis
different from that in the body of nanoparticle, and the monodisperse magnetic nanoparticles by thermal decomposi-
magnetic interactions in the surface layer could have a notable tion method have obtained outstanding results [14–17]. These
effect on the magnetic properties of nanoparticles [10,11]. monodisperse nanoparticles coated with OA may provide a
Understanding the interaction between the surfactant and the factual system to get the exact information of the interaction
nanoparticle is critical and essential to synthesis and and adsorption model at the interface. In the present work,
application of nanoparticles. monodisperse Fe3O4 nanoparticles with diameter of 7 and
19 nm were synthesized by the seed-mediated high temperature
thermal decomposition of iron(III) acetylacetonate (Fe(acac)3)
precursor method. The chemical structure of the surfactant
* Corresponding author. Tel.: +86 21 62933731; fax: +86 21 62804389.
adsorbed on the magnetite nanoparticles has been identified,
E-mail addresses: [email protected] (L. Zhang), and the model of OA molecules adsorbed on the nanoparticles
[email protected] (H.-C. Gu). surface was discussed.

0169-4332/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2006.05.023

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2612 L. Zhang et al. / Applied Surface Science 253 (2006) 2611–2617

2. Experimental 2.4. Fourier transform infrared spectra (FTIR)

Magnetite nanoparticles were prepared according to the FTIR spectra of the nanoparticles were collected on a Bruker
Sun’s method [16]. Such nanoparticles then serve as seeds to spectrometer. The sample powders were ground with KBr and
grow larger nanoparticles in the seed-mediated growth process. compressed into a pellet whose spectra were record. A drop of
It is worth to note that the OA as the surfactant added in the neat OA was mixed with KBr and compressed into a pellet at
reaction mixture before the Fe3O4 nuclei produced, but not as 20000 psi, and the spectra were recorded as a reference.
usual way that the surfactant was modified after the Fe3O4
synthesised [18–20]. 2.5. X-ray photoelectron spectroscopy (XPS)
In a typical synthesis, Fe(acac)3 (2 mmol), 1,2-hexade-
canediol (10 mmol), benzyl ether (20 ml), oleic acid XPS analyses were performed with an ESCALAB-MK (VG
(6 mmol), and oleylamine (6 mmol) were mixed and Company). Photoemission was stimulated by a monochro-
magnetically stirred under a flow of nitrogen. The mixture mated Al Ka radiation (1486.6 eV) with the operating at 12 kV
was heated to 200 8C for 30 min and then, under a blanket of and a 0.10 eV/step interval. Binding energies of spectra were
nitrogen, heated to reflux (298 8C) for another 30 min. The referenced to the C 1s binding energy set at 284.6 eV. The
black–brown mixture was cooled to room temperature by samples powders were pressed to a pellet, and then the pellet
removing the heat source. After addition of ethanol and was put into the entry-load chamber to pump for 4 h.
centrifuging, the monodisperse 7 nm Fe3O4 nanoparticles
were obtained. 2.6. Thermogravimetric analysis (TGA)
Such 7 nm Fe3O4 nanoparticles dispersed in hexane were
used as seeds to grow larger Fe3O4 nanoparticles in the Thermogravimetric analysis was carried out for powder
Fe(acac)3 precursors solution. The mixture were first heated to samples (5 mg) with a heating rate of 10 8C/min using a
100 8C for 30 min to remove hexane, then to 200 8C for 1 h and Perkin-Elmer TGA 7 thermogravimetric analyzer in a synthetic
keep at reflux (298 8C) for 1 h before being cooled down to N2 atmosphere up to 800 8C.
room temperature. Following the workup procedures described
in the synthesis of 7 nm Fe3O4 nanoparticles, the 19 nm Fe3O4 2.7. Magnetic property measurement
nanoparticles were obtained.
In order to perform the characterization of the sample, the The magnetic measurements were performed with a
as-synthesized magnetite nanoparticles were washed several Quantum Design PPMS magnetometer and a vibrating sample
times by ethanol to get rid of the ‘‘free’’ surfactant molecules magnetometer (VSM) (Lakeshore 7300) for the as-synthesis
and then were collected for drying to powder. To confirm the samples dispersed in octane and powders at room temperature,
dryness of the samples, the samples were heated to 150 8C at a respectively.
rate of 10 8C/min and maintained at that temperature for 2 h. If
no mass loss (0.2%) was detected, we assumed that there was 3. Results and discussion
no remaining solvent in the sample.
XRD patterns in Fig. 1 reveal the nanocrystal nature of the
2.1. Powder X-ray diffraction (XRD) two samples. The position and relative intensity of all peaks

XRD were recorded on a Rigaku Dmax-r C X-ray

diffractometer using Cu Ka ration (l = 1.540 Å) operated at
40 KV and 100 mA.

2.2. Transmission electron microscopy (TEM)

The particle morphology, size and structure of the Fe3O4

were determined by Philips CM120 transmission electron
microscopy operating at 80 kV. The two samples dispersed in
the hexane were drop-cast onto the 300-mesh Formvar-covered
copper grids separately.

2.3. High-performance particle sizer (HPPS)

Hydrodynamic diameter of magnetite nanoparticles were

measured with a HPPS (Malvern Instrument, l = 632.8 nm,
T = 25 8C). The concentration of each sample was 3 mg Fe3O4/ Fig. 1. The XRD diffraction pattern of (a) 7 nm seeds of as-synthesized Fe3O4
ml hexane. nanoparticles; (b) Fe3O4 nanoparticles with diameter of 19 nm.
 L. Zhang et al. / Applied Surface Science 253 (2006) 2611–2617 2613

the surface of the nanoparticles was a combination of

molecules bonded symmetrically and molecules bonded at
an angle to the surface [22]. A strong adsorption at 1050 cm 1
arises from C–O single bond stretching. These results revealed
that oleic acid were chemisorbed onto the Fe3O4 nanoparticles
as a carboxylate.
Combined with previous studies of carboxylates, the
interaction between the carboxylate head and the metal atom
was categorized as four types: monodentate, bridging
(bidentate), chelating (bidentate), and ionic interaction
[21,23]. The wavenumber separation, D, between the
nas(COO–) and ns(COO–) IR bands can be used to distinguish
the type of the interaction between the carboxylate head and the
metal atom. The largest D (200–320 cm 1) was corresponding
to the monodentate interaction and the smallest D (<110 cm 1)
was for the chelating bidentate. The medium range D (140–
190 cm 1) was for the bridging bidentate. In this work, the D
(1639–1541 = 98 cm 1) was ascribed to chelating bidentate,
where the interaction between the COO– group and the Fe atom
Fig. 2. FTIR spectra of (a) pure oleic acid; (b) Fe3O4 nanoparticles coated with was covalent (as showed in Scheme 1).
oleic acid. The XPS spectra of C 1s, Fe 2p core level give a further
proof for the chemical structure of the OA coated Fe3O4
match well with standard Fe3O4 powder diffraction data, nanoparticles in Fig. 3. Two C 1s peaks posited at 284.6 and
indicating that each sample is Fe3O4 crystal. 287.4 eV for 7 nm Fe3O4 nanoparticles, and 284.6 and
To understand the adsorption mechanism of the OA on the 288.3 eV for 19 nm Fe3O4 nanoparticles. Peak at 284.6 eV
surface of Fe3O4 nanoparticles, Fourier transform infrared was ascribed to the carbon atoms in the aliphatic chain (C–C),
measurements were carried out on the pure oleic acid and the and peaks at 287.4 and 288.3 eV belonged to the carboxylate (–
composite Fe3O4 nanoparticles coated with OA. Fig. 2 shows COO ) moiety, which were consistent with the data obtained
the typical FTIR spectrum of the pure oleic acid (a), and Fe3O4 from carboxylateds in the previous literature [24]. C 1s peak
nanoparticles coated with oleic acid (b). In curve (a), two sharp corresponded to carboxylic carbon (–COOH), which posited at
bands at 2924 and 2854 cm 1 were attributed to the 290 eV, did not appear in the spectrum, indicating the absence
asymmetric CH2 stretch and the symmetric CH2 stretch, of free acid on the coated Fe3O4 nanoparticles. The bonding
respectively. The intense peak at 1710 cm 1 was derived from energies at 710.8 eV were the characteristic peak from Fe 2P3/2
the existence of the C O stretch, and the band at 1285 cm 1 core level electrons. The Fe 2p1/2 peaks at 724.1 eV for 7 nm
exhibited the presence of the C–O stretch. The O–H in-plane and 725.0 eV for 19 nm Fe3O4 nanoparticles were attributed to
and out-of-plane bands appeared at 1462 and 937 cm 1, the carboxylate–Fe bond. The XPS results substantiate to the
respectively. In the curve (b), the asymmetric CH2 stretch and FTIR data, indicating the formation of chemical bonds
the symmetric CH2 shifted to 2922 and 2852 cm 1, respec- between the iron oxide substrate and the oxygen atoms of
tively. The surfactant molecules in the adsorbed state were the carboxylic acid.
subjected to the field of the solid surface. As a result, the Fig. 4 shows TEM images of magnetite nanoparticles coated
characteristic bands shifted to a lower frequency region which with OA. The sizes of faceted particles were 7 nm for seeds,
indicated that the hydrocarbon chains in the monolayer 19 nm for the nanoparticles synthesized by seed-mediated
surrounding the nanoparticles were in a closed-packed, growth method. Each particle was separated from its neighbors
crystalline state [21]. It is worth to note that the C O stretch by the organic ligands absorbed on the particles. It can be seen
band of the carboxyl group, which was present at 1710 cm 1 in that the intervals of each neighboring Fe3O4 nanoparticles were
the curve (a), spectrum of the pure liquid oleic acid, was absent uniform.
in the curve (b), spectrum of the coated nanoparticles. And Dynamic laser scattering (DLS) had been performed as an
there appeared two new bands at 1541 and 1639 cm 1, which additional method to determine the particle size and distribu-
were characteristic of the asymmetric nas(COO–) and the tion. Fig. 5 gives the HPPS results of the as-synthesis samples.
symmetric ns(COO–) stretch, instead. This result can be It is evident that this hydrodynamic diameter was larger than
explained that the bonding pattern of the carboxylic acids on the size determined from TEM. The value of the hydrodynamic

Scheme 1. Chelating bidentate interaction between the COO– group of oleic acid and the iron atom.
2614 L. Zhang et al. / Applied Surface Science 253 (2006) 2611–2617

Fig. 3. XPS spectra obtained from the oleic acid coated Fe3O4 nanoparticles: (a) C 1s core level of 19 nm particles; (b) C 1s core level of 7 nm particles; (c) Fe 2p core
level of 19 nm particles; (d) Fe 2p core level of 7 nm particles.

diameter was composed of size of the OA (2 nm) molecule attributed the results to two kinds of bonding of the
and the magnetite nanoparticle (Dhydrodynamic = DTEM + phosphonate group on the Fe surface but rather a bilayer
2 nm + 2 nm). The TEM and HPPS analysis showed the size structure. Two types of bonding pattern on the surface was also
and shape of as-synthesized Fe3O4 nanoparticles was homo- suggested by Spencer and co-workers [26] for phosphate coated
genous. It indicated the marco-characterization may truly Ta2O5 and Hiroshi et al. [27] for HCOOCH3 adsorbed on MgO
reflect the single nanoparticles information in this mono- surface. In this case, it is interesting to find that the ratio of the
disperse system. first weight loss to the second weigh loss was about 0.4:1 for
TGA derivative curves show two distinct transitions for both both 7 and 19 nm Fe3O4 nanoparticles (Table 1). We think that
sizes samples between room temperature and 600 8C in Fig. 6. there were two possible reasons to explain the constant ratio of
The transition temperatures and the corresponding percentage two kinds of weight loss. First, in generally, the different
weight losses were summarized in Table 1. It is clear from the surface shows different adsorption activity [28]. The as-
data that two desorption processes occured in the coated synthesized Fe3O4 nanoparticle was terminated by (1 1 1) faces
nanoparticles in the vicinity of 260 and 380 8C both in 7 and and (1 0 0) faces and the ratio of two faces may keep constant
19 nm nanoparticles. These different desorption processes were for both 7 and 19 nm Fe3O4 nanoparticles; second, the OA may
explained by the bilayer or quasi-two-layers adsorbed models be bonded with two states of iron ion. We plan to perform
on the particles surface previously [18,19]. But Gedanken and further study to confirm the detailed mechanism to explain the
co-workers [25] found that the TGA of phosphate coated phenomenon. Consider the results from TGA HPPS, we
amorphous ferric oxide particles was double-stepped, and they confirm that there was a single oleic acid molecule layer
 L. Zhang et al. / Applied Surface Science 253 (2006) 2611–2617 2615

Fig. 5. HPPS results of 7 nm (- - -), 19 nm (—) Fe3O4 nanoparticles.

the balancing of Van der Waals energies and osmotic pressure.

More surfactant molecules adsorbed on the smaller size
particles increased the osmotic pressure (repulsion force) to
balance the increasing Van der Waals energies (attraction)
resulted from smaller size. The cover density comparison
among various sizes of nanoparticles is meaningful for
interpreting the solution of nanoparticles coated with surfac-
tant. We find that the larger Fe3O4 nanoparticles were rather
hard to re-disperse in the solvent after drying treatment but the
smaller size of nanoparticles were well re-dispersed after the
drying. Vastly differing coverage density would represent
different surface environments and therefore will introduce
uncertainty to the magnetic response of nanoparticles after the
surface modification.
Fig. 7 displays the magnetization of coated Fe3O4
nanoparticles with different sizes which were dispersed in
the solution or powder states at room temperature. In Fig. 7(b),
the nature of the curves in both case show no coercivity,

Fig. 4. TEM images of magnetite nanoparticles: (a) 7 nm seeds of as-synthe-

sized Fe3O4 nanoparticles; (b) Fe3O4 nanoparticles with diameter of 19 nm.

adsorbed on the surface of the Fe3O4 nanoparticle, but the OA

molecule adsorbed by two kinds of bonding energy.
Table 1 shows the surfactant adsorption amount decreased
with the size of the Fe3O4 nanoparticles increasing. For 7 nm
nanoparticles, the total amount was 25.1%, whereas as for
19 nm it was 6.5%. Based on the above single layer adsorption
model, the cover density of OA molecular chemisorbed on the
particle surface could be calculated from the TGA results. The
cover density was 98% with the 7 nm nanoparticles, but
dramatically decreased to 62% with diameter of 19 nm. The
cover densities on the nanoparticle surfaces were decreased
with the increasing of the nanoparticles sizes. This sharp Fig. 6. TGA results: derivative of the weight loss as function of temperature for
difference between the two sizes of particles may result from oleic acid coated Fe3O4 nanoparticles.
2616 L. Zhang et al. / Applied Surface Science 253 (2006) 2611–2617

Table 1
Results and analysis based on TGA cures in Fig. 6
Sample size (nm) TGA
First weight loss Second weight loss
Derivative Weight Derivative Weight Total Packing
peak (8C) loss (%) peak (8C) loss (%) loss (%) density (%) *
7 261 7.5 382 17.6 25.1 98.0
19 256 1.9 391 4.6 6.5 62.0
*
Packing density was calculated by total loss/coated surfactants  100%, which it supposed that the area of the head of the oleic acid and oleic amine is 24 Å.

suggesting the superparamagnetic nature of the particles. 4. Conclusions

However, the coercivity was appeared in the curve in Fig. 7(a).
This phenomenon can explain that magnetic interactions Monodisperse magnetite nanoparticles coated with OA
between the particles should exist in these two samples since provided a factual system to get the exact information about the
the particles have not been isolated in a matrix or fluid [29]. interaction and adsorption model at interface. Study shows the
Consequently, the coated OA molecules on the particles surface adsorption of OA molecules on the nanoparticles were by
can protect the Fe3O4 nanoparticles and reduce the interaction chemisorption in all cases, and the OA molecular coated on the
between the particles in the non-polar solution. particles surface with a single layer structure. Furthermore, the
two distinct of surfactant desorbed on the particle surface
implied that there were two kinds of different binding energies
between the OA molecular and the particle surface. The total
adsorption amount and cover density of OA molecular on the
Fe3O4 nanoparticles surface decreased sharply with the
increase of the sizes of the particles. Coated OA molecules
can reduce the interactions between the Fe3O4 nanoparticles.

Acknowledgments

The authors are grateful to the 863 Hi-Tech Research and

Development Program (2002AA302210) and Shanghai Nano
Program (0249 nm071) for financial support.

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