Journal of Colloid and Interface Science 297 (2006) 660–664

www.elsevier.com/locate/jcis

Synthesis of Ag–Fe3 O4 heterodimeric nanoparticles

Ling Zhang, Yong-Hua Dou, Hong-Chen Gu ∗
Institute for Micro and Nano Science and Technology, Shanghai Jiaotong University, Shanghai, 200030, People’s Republic of China
Received 30 September 2005; accepted 4 November 2005
Available online 9 December 2005

Abstract
We report a general synthetic method for construction of size-controlled Ag–Fe3 O4 heterodimeric nanoparticles using the Fe3 O4 nanoparticles
as the seeds. The Ag–Fe3 O4 heterodimeric nanoparticle can be controlled by tuning the size of the Fe3 O4 seed and reaction conditions for
synthesis of the Ag nanoparticles grown on it. The as-synthesized nanoparticles can be readily converted into aqueous-soluble form with newly
introduced functional groups on the surface of Ag–Fe3 O4 heterodimeric nanoparticles.
© 2005 Elsevier Inc. All rights reserved.

Keywords: Heterostructure; Magnetite; Nanoparticles; Nanostructure; Silver

1. Introduction To construct the functional heterostructure nanoparticles, we

With the rapid development of applications of nanomateri-
als, which range from electrooptics, magnetism, and catalysis
to biomedicine [1–6], nanocomposites that contain two or more
different nanoscale functionalities are attractive candidates for
advanced nanomaterials. Dimer or oligomers heterostructures
composed of individual components with different nanoscale
properties may give rise to a combination of unique proper-
ties [7]. The nonsymmetric structure may facilitate introduc-
tion of an anisotropic distribution of different surface functional
groups. Recently, there have been a few reports about construct-
ing bifunctional dimer nanoparticles with two different inor-
ganic compositions. γ -Fe2 O3 –CdSe/ZnS nanocomposite par-
ticles were obtained by quantum dots bound to the surface of
thiol-modified magnetic beads [8]. FePt–CdS, γ -Fe2 O3 /II–VI
nanocomposites were synthesized by direct addition of sulfur
and metal reagents to the magnetic nanoparticle reaction mix-
ture [7,9]. Dumbbell-like Au–Fe3 O4 nanoparticles were syn-
thesized using decomposition of Fe(CO)5 on the surface of
the Au nanoparticles [10]. Ag–Fe3 O4 , Ag–Au nanocomposites
were formed at a liquid–liquid interface [11].
* Corresponding author. Fax: +86 21 62804389.
E-mail address: hcgu@sjtu.edu.cn (H.-C. Gu).
0021-9797/$ – see front matter © 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.11.009
choose silver (Ag) and magnetite (Fe3 O4 ) nanoparticles as the
building blocks because (a) Ag and Fe3 O4 have unique proper-
ties (e.g., surface plasmon resonance and superparamagnetism,
respectively) in nanoscale; (b) both Ag and Fe3 O4 nanopar-
ticles are biocompatible and have low cytotoxicity [12,13];
(c) the surface chemistry properties are different but comple-
mentary for Ag and Fe3 O4 nanoparticles (e.g., thiolate ligand
(–SH) coordinating to Ag and carboxyl ligand (–COOH) to
Fe3 O4 ).
Here we report on a new and easy method for synthesiz-
ing Ag–Fe3 O4 heterodimeric nanoparticles with Ag and Fe3 O4
in nanometer contact. The heterodimer structure was formed
through epitaxial growth of Ag on the Fe3 O4 seeds in non-
polar solution. The size of the Fe3 O4 seeds can be tuned
with the modified method of Sun et al. [14], and the size
of Ag nanoparticles can be controlled by the reaction con-
ditions [15].The as-synthesized nanoparticles can be readily
converted into aqueous-soluble form with newly introduced
functional groups on the surface of Ag–Fe3 O4 heterodimeric
nanoparticles. Although the synthetic method for Ag–Fe3 O4
heterodimeric nanoparticles at the liquid–liquid interface is in-
genious [11], our work results in an important method for ob-
taining a mass of heterostructure nanoparticles in one experi-
ment, and provides promising materials for the application in
catalysts and biomedicine.
 L. Zhang et al. / Journal of Colloid and Interface Science 297 (2006) 660–664
2. Experimental
2.1. Materials
Iron(III) acetylacetonate (Fe(acac)3 , 99.9%), silver acetate
(Ag(ac), 99.9%), 1,2-hexadecanediol (C14 H29 CH(OH)CH2 –
(OH), 90%), oleylamine (C9 H18 =C9 H17 NH2 , 70%), oleic acid
(C9 H18 =C8 H15 COOH, 99%), phenyl ether (C12 H10 O, 99%),
mercaptosuccinic acid (HOOCCH2 CH(SH)COOH, 97%), and
D -glucuronic acid (C6 H10 O7 , 98%) were purchased from
Aldrich, and other solvents (toluene, hexane, and ethanol) were
purchased from Shanghai Reagent Company, and used as re-
ceived.
2.2. Synthesis
The synthetic route for constructing heterodimers is straight-
forward and controllable. Fe3 O4 nanoparticles were synthe-
sized using a modified protocol [14]. Briefly, 0.706 g of Fe-
(acac)3 (2 mmol) was mixed in 20 ml of phenyl ether with 2 ml
of oleic acid (∼6 mmol) and 2 ml of oleylamine (∼6 mmol)
under argon atmosphere with vigorous stirring. A quantity of
2.067 g 1,2-hexadecanediol (8 mmol) was added into the solu-
tion. The solution was heated to 210 ◦ C and refluxed for 0.5 h.
After cooling to room temperature, ethanol was added into
the solution. A dark-brown precipitate was separated by cen-
trifuging, followed by washing with ethanol. The 9-nm Fe3 O4
nanoparticles were easily dispersed in hexane. And these Fe3 O4
nanoparticles were used as seeds to synthesize 12-nm nanopar-
ticles by the same method.
The construction of Ag–Fe3 O4 (6–12 nm) heterodimeric
nanoparticles involved an initial synthesis of Fe3 O4 nanopar-
ticles as seeds and a subsequent reduction of Ag(ac) in the
presence of the seeds. In a typical synthesis, 48 mg of Fe3 O4
nanoparticles (12 nm), 50 mg of Ag(ac), and 9 mmol of oley-
lamine were added into 40 ml toluene. Under argon and with
vigorous stirring, the reaction solution was heated to 80 ◦ C and
was kept at this temperature for 8 h. After cooling down to
room temperature, ethanol was added into the solution. A dark-
yellow material was precipitated and separated by centrifuging.
The precipitated product was washed with ethanol and redis-
persed in toluene. In order to observe the kinetic growth of the
Ag–Fe3 O4 heterodimer, a small aliquot of the reaction mixture
was removed at 2 h of reaction, quenched from the reaction with
ethanol, and redispersed in toluene for further analysis.
Mixture of 12-nm Ag nanoparticles and 9-nm Fe3 O4 nano-
particles were obtained under same conditions except that the
reaction was designed at 100 ◦ C for 8 h. The 4–9 nm Ag–
Fe3 O4 heterodimeric nanoparticles were obtained using the
9-nm Fe3 O4 nanoparticles as the seeds and the reaction was
designed at 60 ◦ C for 15 h.
By dissolving 50 mg (0.30 mmol) of Ag(ac) in 7.5 mmol
(2.5 ml) of oleylamine and by injecting the solution quickly into
50 ml of refluxing hexane for 8 h, 6-nm Ag nanoparticles were
obtained. The solution was cooled to room temperature and was
concentrated to about 15 ml in a rotary evaporator. A quantity
661
of 200 ml of ethanol was added to yield a black solid, which
was dissolved in 50 ml of toluene.
2.3. Characterization
The morphology, size, and structure of the Ag–Fe3 O4 het-
erodimeric nanoparticles were determined by JEOL 2010 trans-
mission electron microscopy (TEM) and JEOL 2100 high-
resolution TEM (HRTEM) operating at 200 kV. The surface
plasmon resonance was measured by a UNICAM UV300 UV–
vis spectral instrument. X-ray diffraction (XRD) was recorded
on a Rigaku Dmax-r C X-ray diffractometer using CuKα ra-
diation (λ = 1.540 Å) operated at 40 kV and 100 mA. The
samples were deposited from their toluene dispersions onto
Si substrates and dried under ambient conditions. The mag-
netic measurements were performed with a Quantum Design
PPMS magnetometer for the as-synthesized samples’ powders
at 300 K.
3. Results and discussion
The growth process of Ag–Fe3 O4 heterodimeric nanopar-
ticles were characterized by TEM (Figs. 1a–1c). As the reac-
tion proceeds, the size and uniformity of the Ag nanoparticles
grown on the Fe3 O4 seeds increased, and the unattached small
Ag nanoparticles presented at 2 h (in Fig. 1b) disappeared at
8 h (in Fig. 1c). The final Ag–Fe3 O4 (6–12 nm) heterodimeric
nanoparticles were obtained at 8 h with size distribution well.
This indicates that the Ostwald ripening (in which larger parti-
cles grow at the cost of the smaller ones) process occurs in the
reaction, and no new Ag nuclei were formed subsequently be-
cause of the low reaction temperature and precursor concentra-
tion. High-resolution TEM (HRTEM) analysis provided more
detailed structural information of the Ag–Fe3 O4 heterodimeric
nanoparticles. Fig. 1d shows a typical HRTEM image of Ag–
Fe3 O4 heterodimeric nanoparticles in Fig. 1c. The correspond-
ing right pictures of Fourier transform of the lattice image gives
diffractogram spots for Fe3 O4 nanoparticles and diffractogram
rings for Ag nanoparticles, indicating Fe3 O4 being a single
crystal, but the Ag nanoparticles twinned.
Fig. 2 shows the representative XRD patterns of the Ag–
Fe3 O4 (6–12 nm) heterodimeric nanoparticles. The positions
and relative intensities of all diffraction peaks matched with
standard Fe3 O4 (Fd-3m) and Ag (Fm-3m) powder diffraction
data, indicating that the synthesis yielded crystalline Fe3 O4
and Ag.
Fig. 3 shows the UV–vis spectra of the several samples re-
dispersed in toluene solution. In contrast to the largely silent
feature in the visible region of the Fe3 O4 seeds (Fig. 3c), the
Ag–Fe3 O4 heterodimeric nanoparticles show a surface plas-
mon resonance band at 419 nm (Fig. 3b, d), and the peaks
become clearer with the reaction process. This band is shifted
to higher wavelength in comparison with pure Ag nanoparticles
(412 nm, in Fig. 3a) with the same size, synthesized according
to Hiramatsu and Osterloh [15]. Similar surface plasmon reso-
nance band red shift phenomena were reported for Au–Fe3 O4
nanocomposite [10,16]. They could result from charge transfer
662 L. Zhang et al. / Journal of Colloid and Interface Science 297 (2006) 660–664

Fig. 1. TEM images of (a) Fe3 O4 seeds; (b, c) Ag–Fe3 O4 heterodimeric nanoparticles prepared at 80 ◦ C for 2 and 8 h, respectively; (d) HRTEM image of the
Ag–Fe3 O4 heterodimeric nanoparticle.

Fig. 3. UV–vis spectra of (a) Ag nanoparticles; (b, d) Ag–Fe3 O4 heterodimeric

Fig. 2. X-ray diffraction patterns of Ag–Fe3 O4 (6–12 nm) heterodimeric nanoparticles prepared at 80 ◦ C for 2 and 8 h, respectively; (c) Fe3 O4 nanopar-
nanoparticles with representative index on typical peaks. ticles.
 L. Zhang et al. / Journal of Colloid and Interface Science 297 (2006) 660–664
Fig. 4. TEM images of (a) Ag–Fe3 O4 heterodimeric nanoparticles prepared at
60 ◦ C for 15 h; (b) Ag and Fe3 O4 nanoparticles prepared at 100 ◦ C for 8 h.
between the Ag nanoparticle and the Fe3 O4 nanoparticle in the
heterodimer structure [17]. The Ag–Fe3 O4 heterodimer nano-
structure tuning the surface plasmon resonance band red shift
could open the door to construction of advance materials.
The mechanism of formation of the Ag–Fe3 O4 heterodime-
ric nanoparticles was further systematically studied by tuning
the reaction temperature at 60, 80, and 100 ◦ C. When the reac-
tion temperature was designed at 60 or 80 ◦ C, the Ag–Fe3 O4
heterodimer structure was obtained in both reactions. Fig. 4a
shows the Ag–Fe3 O4 (4–9 nm) heterodimeric nanoparticles
synthesized at 60 ◦ C for 15 h using the 9 nm Fe3 O4 nanopar-
ticles as seeds. When the reaction temperature increased to
100 ◦ C, unattached ∼12-nm Ag nanoparticles appeared in the
solution instead of the heterostructure. Fig. 4b shows that the
black spherelike Ag nanoparticles mixed with light-colored and
faceted Fe3 O4 nanoparticles (Ag has a higher electron density
and allows fewer electrons to transmit). These experimental re-
sults can be explained on the basis that at low temperature,
Ag reduction was so slow that the Fe3 O4 nanoparticle seed
663
Fig. 5. Hysteresis loops of (a) Fe3 O4 and (b) Ag–Fe3 O4 heterodimeric nano-
particles measured at 300 K.
Fig. 6. TEM images of Ag–Fe3 O4 heterodimeric nanoparticles dispersed in
deionized water.
was used as the nucleus for the Ag nanoparticle to grow on
it; moreover, the large lattice mismatch between the Ag (fcc,
a = 4.08 Å) and Fe3 O4 (fcc, a = 8.40 Å) could result in non-
symmetric heterodimer structure forming instead of centrosym-
metric core/shell type structure. On the other hand, at high tem-
perature, the reaction system supplied more thermal energy, in
favor of the Ag nuclei forming independently and quickly [17].
So the final products contained the mixture of individual Ag
and Fe3 O4 nanoparticles.
Fig. 5 shows the hysteresis loops of Ag–Fe3 O4 (6–12 nm,
curve a) heterodimeric nanoparticles and Fe3 O4 (∼12 nm,
curve b) nanoparticles measured at 300 K. The Ag–Fe3 O4
heterodimeric nanoparticles show similar hysteresis loop with
the Fe3 O4 nanoparticles. This indicates that the as-synthesized
Ag–Fe3 O4 heterodimeric nanoparticles show superpara-
magnetism at 300 K (more magnetic property study is in pro-
gress).
664 L. Zhang et al. / Journal of Colloid and Interface Science 297 (2006) 660–664
The substantial difference between the two blocks in the
heterostructure provides different surface chemistry properties.
The exchange of thiol groups with amine groups is favored
on silver surfaces [15,18], which facilitated the hydrophobic
Ag–Fe3 O4 heterodimeric nanoparticle changing to hydrophilic.
The as-synthesized Ag–Fe3 O4 heterodimeric nanoparticle dried
powders were redispersed in mercaptosuccinic acid aqueous so-
lution (10 mg/ml) to form an “emulsion-like” solution. The
thiol groups exchanged with the amine groups from the Ag sur-
face, which is a stronger ligand to coordinate with Ag. With
the magnetic separation, a brown sediment was obtained. The
proper amount of D-glucuronic acid dissolved in ethanol was
added to react with the above sediment and sonicated for 5 min
to yield a clear solution. After the centrifugation, the brown
sediment was redispersed in deionized water, forming a stable
solution (at least for 1 month). The TEM image (Fig. 6) shows
the Ag–Fe3 O4 heterodimeric nanoparticles redispersed well in
deionized water after the ligand exchange.
4. Conclusions
In conclusion, an easy and controllable method for con-
structing Ag–Fe3 O4 heterodimeric nanoparticles in solution has
been developed, and the size of individual blocks of the het-
erodimer is controlled by regulating the synthetic conditions.
The heterostructure with two distinct surfaces and properties
offers more application areas for nanomaterials. For example,
with Ag, one can use it as a real-time probe and live cell im-
age [2,12]; with Fe3 O4 , it has been used as magnetic resonance
imaging or hyperthermia therapy reagent [13,19,20]. The Ag–
Fe3 O4 heterodimer will link both of the above work together.
Furthermore, the Ag–Fe3 O4 heterodimeric nanoparticles, con-
sidering the superparamagnetism of Fe3 O4 , used as cata-
lyst could overcome the difficulty in recovering nanoparticle-
supported asymmetric catalysts by settling or filtration, allow-
ing their widespread application.
Acknowledgments
This work was supported by the 863 Hi-Tech Research
and Development Program (2002AA302210) and the Shanghai
Nano Program (0249nm071).
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