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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 10779
www.rsc.org/materials PAPER
Facile one-step synthesis of plasmonic/magnetic core/shell nanostructures and
their multifunctionality†
Yunxia Zhang,* Hualin Ding, Yanyan Liu, Shusheng Pan, Yuanyuan Luo and Guanghai Li*
Received 1st December 2011, Accepted 27th March 2012
DOI: 10.1039/c2jm16293h
Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H

A very simple protocol, which involves the chemical reduction of AgNO3 and Fe(NO3)3 with ethylene
glycol as reducing agent, has been developed for synthesizing Ag@Fe3O4 core/shell nanostructures in
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which the silver nanoparticle core was covered by a thicker layer of the Fe3O4 nanoparticle shell. The
obtained Ag@Fe3O4 core/shell nanostructures simultaneously possess both strong magnetic
responsiveness and tunable plasmonic properties. The plasmonic properties of the composite
nanospheres are profoundly influenced by the high dielectric constant of the outer Fe3O4 shell layer and
could be conveniently modulated over a broad spectral range spanning from the ultraviolet to near-
infrared (NIR) regions (789 nm) by simply altering the thickness of the Fe3O4 shell. The localized
surface plasmon resonances of the core/shell nanocomposites red-shifted with increasing thickness of
the Fe3O4 shell. The morphology transformation of the Ag/Fe3O4 nanocomposites from core/shell
structures with a continuous dense coating to flower-like nanostructures also allows the tuning of their
plasmonic properties to be blue-shifted (to 510 nm). Catalytic degradation of rhodamine 6G (R6G)
experiments show that the Ag/Fe3O4 composite nanostructures exhibit high catalytic activity by sodium
borohydride. Due to the efficient optical response through localized surface plasmon resonances, the
catalytic performance from the silver core and external magnetic manipulation from the Fe3O4 shell,
such multifunctional nanoparticles will provide an opportunity for simultaneous optical detection and
catalytic reduction with the additional benefit of relatively facile recovery and regeneration.

1. Introduction nanomaterials hold significant promise for a diverse number of

Recently, there has been an increasing need towards the inte-
gration of multiple materials into a single hybrid nanostructure.
The attraction of multicomponent nanostructures is that
multiple functionalities can be incorporated into a single nano-
system for specific applications by the marriage of two or more
different materials.1–6 Moreover, the close coupling between
different components on the nanoscale may significantly improve
the overall performance of the nanostructured system and even
generate entirely novel synergetic properties that are unachiev-
able in the individual components. Such multifunctional
Key Laboratory of Material Physics, Anhui Key Laboratory of
Nanomaterials and Nanotechnology, Institute of Solid State Physics,
Chinese Academy of Sciences, Hefei, 230031, P.R. China. E-mail:
yxzhang@issp.ac.cn; ghli@issp.ac.cn
† Electronic supplementary information (ESI) available: XRD (Fig. S1)
and EDS (Fig. S2) spectrum of Ag@Fe3O4 core/shell nanostructures;
TEM image (Fig. S3) and UV/Vis spectrum (Fig. S4) of Fe3O4
nanoshells; UV-visible absorption spectra of R6G after adding Ag@
Fe3O4 nanostructures for 60 min in the absence of NaBH4 (Fig. S5)
and in the absence of the as-prepared samples (Fig. S6); Magnetic
hysteresis loop of Ag@Fe3O4 nanoflowers with Ag/Fe ratio of 0.30 at
300 K (Fig. S7); XRD pattern (Fig. S8) and line profiles (Fig. S9) of
Au@Fe3O4 samples; and UV/Vis spectra (Fig. S10) of Au@Fe3O4 NPs
at different reaction times. See DOI: 10.1039/c2jm16293h
applications, e.g. electronic, optical and magnetic devices,
multimodal biological detection and in the magnetic field-assis-
ted delivery of biomolecules and SPR-derived heating and
treatment of tumors. For example, multifunctional hybrid
nanoparticles consisting of Au, Fe3O4, and PbS or PbSe combine
magnetic, plasmonic, and semiconducting properties, and the
properties of each component within the hybrids can be effec-
tively adjusted by the conjugating components, aided by the
coherent interfaces between them.7
As one of the hybrid nanomaterials, magnetic-core gold/silver-
shell nanoparticles have captured particular attention, owing to
the combined functions of magnetic and optical properties from
the two components, which can lead to exciting opportunities for
integrated imaging, diagnosis, targeted drug delivery, and ther-
apeutics. A few examples for such magnetic-core gold–shell
nanomaterials have been reported that combine the NIR optical
properties of gold with magnetic properties.8–15 Successful
synthetic protocols include surface immobilization onto pre-
formed magnetic cores and the subsequent reduction of gold salts
by an external reducing agent10 and a seed-mediated growth
route, which involved the preparation of nanoparticles of one
material, and then using them as nucleation seeds to deposit the
other components.11 However, the reported nanocomposites are

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also far from optimal: they neither show sufficient response to
external magnetic fields nor display a strong and precisely
controllable plasmon band in the NIR; in addition, they form
irreversible aggregates during the shell formation.12 Besides the
magnetic oxide@metal configuration, the inverse system, a gold/
silver core and a magnetic shell, is also an interesting system for
practical applications. Nanocomposites based on a metal@-
magnetic oxide configuration can overcome the aforementioned
disadvantages, in which the oxide shells act as physical barriers
to protect the Au cores from irreversible aggregation.16 The
coating of metallic nanoparticles with a shell of magnetic mate-
rial is rather challenging, and only a few reports about
Au@Fe3O4,17 Ag@Fe3O418 or Au@MnO19 nanoparticles
Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H
demonstrate this possibility.
Compared with these complicated and sub-economic methods,
it is highly attractive and of great significance to develop a facile,
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reliable, inexpensive, and scalable strategy to fabricate size-
tunable metal/Fe3O4 core/shell nanostructures by using
a nontoxic solvent and reagents under mild conditions and to
explore their potential applications from both scientific and
applicable perspectives. In this communication, we demonstrate
a convenient one-step solvothermal strategy of Ag@Fe3O4 core/
shell nanostructures via in situ reduction of AgNO3 and
Fe(NO3)3 using ethylene glycol as the reducing agent. The overall
procedure is simple and readily scaled-up because it does not
require high temperature calcination or any other complicated
steps. Unlike the conventional multi-step syntheses where sepa-
ration and purification of the samples are usually the most-time-
consuming steps, the high superparamagnetic responsiveness of
Ag@Fe3O4 particles made the separation and purification be
completed efficiently within one or two minutes by applying an
external magnet, which largely simplifies the cleaning and puri-
fication processes.
2. Experimental
2.1 Synthesis of Ag@Fe3O4 core/shell nanospheres
The synthesis of Ag@Fe3O4 core/shell nanospheres was carried
out by a simple solvothermal approach according to a previous
report for Fe3O4 nanospheres with some modification and
extension.20 In a typical procedure, Fe(NO3)3$9H2O (4 mmol)
was dissolved in ethylene glycol (EG, 40 mL) to form a clear
solution, followed by the addition of sodium acetate (NaAc,
35 mmol) and AgNO3 (0.59 mmol). The mixture was stirred
vigorously until all the reactants were fully dissolved. The
obtained suspension was then transferred to a 50 mL Teflon-
lined stainless-steel autoclave and heated at 200
C for 4–24 h.
The autoclave was allowed to cool down to room temperature
naturally. Finally, the black precipitate was magnetically
collected and rinsed thoroughly with deionized water and abso-
lute ethanol, followed by drying under vacuum at 60
C for 24 h.
2.2 Characterization
The phase structure and purity of the as-synthesized products
were examined by X-ray diffraction (XRD), using a Rigaku
D/Max gA X-ray diffractometer with Cu-Ka radiation (l ¼

The size and morphology were determined using
1.5405 A).
a JEOL-2010 high-resolution transmission electron microscope
10780 | J. Mater. Chem., 2012, 22, 10779–10786
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at 200 kV. Energy dispersive spectroscopy was recorded to
determine the composition of the products. The UV/vis/NIR
absorbance spectra were measured using a Shimadzu UV 3600
spectrophotometer with a MPC-3100 Integrating sphere
attachment over a wavelength range from 240 to 1200 nm. The
products were dispersed in ethanol for absorption experiments.
Magnetic measurements were carried out using a super-
conducting quantum interference device magnetometer (SQUID
MPMS5, Quantum Design Inc.).
2.3 Catalytic reduction of R6G dye molecules
The reduction of R6G solution was carried out in a quartz
cuvette and monitored using UV-vis spectroscopy at room
temperature. To study the catalytic activity, 2 mg of the Ag/
Fe3O4 nanospheres powder was added to 5 mL of aqueous R6G
solution (1  105 M). 0.2 mL of fresh NaBH4 (0.1 M) solution
was then added to the above solution. Changes in the concen-
tration of the R6G solution were monitored by examining the
variations in the maximal absorption of the R6G solution at
526 nm. After the catalytic reaction was completed, the catalysts
were separated by an external magnetic field.
3. Results and discussion
3.1 Synthesis and characterization of Ag@Fe3O4
nanostructures
This one-step synthetic method for silver core/magnetite shell
structures was achieved by exposing a mixture of AgNO3 and
Fe(NO3)3 precursors to the reducing agent at the same time,
where the core Ag nanoparticles (NPs) can be formed first,
supported by the fact that the primary reaction involved the
reduction of silver nitrate with ethylene glycol at around
160
C.21 Then, these preformed Ag NPs served as the in situ
seeds for the successive catalytic reduction, leading to the growth
Fig. 1 (a) and (b) SEM and TEM images of the as-prepared Ag@Fe3O4
core/shell nanostructures obtained at 200
C for 24 h; (c) TEM image of
a single Ag@Fe3O4 particle and the corresponding EDS elemental
mappings of Ag, Fe and O; (d) line profiles of Ag (blue), Fe (green), and
O (red) recorded along the red line shown in (c).
This journal is ª The Royal Society of Chemistry 2012

of outer Fe3O4 NP shells (the increased reaction temperature of
200
C is necessary for the production of Fe3O4.20). Under the
present solvothermal treatment, the core/shell structure is also
determined by controlled kinetic factors such as the reduction
rates of Ag+ and Fe3+. It is important that the reduction rate of
the Ag+ ion is greater than that of formation of the Fe3O4 shell.
The basic concept of this one-step synthesis of the Ag@Fe3O4
core/shell NPs is to take advantage of the difference in reduction
potentials between the two soluble metal salts (EAg /Ag ¼ +
+ 0.799 eV vs. the standard hydrogen electrode (SHE);
EFe /Fe ¼ +0.77 eV vs. SHE), where a suitable reducing agent is
3+ 2+
essential. Since the standard potential of Ag+/Ag0 is higher than
that of Fe3+/Fe2+, the reduction rate of Ag+ to Ag0 is faster than
Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H
that of Fe3+ to Fe2+ and Ag cores are initially formed. Then,
owing to the presence of Ag NPs as seeds, Fe3O4 NPs are formed
and deposited outside the surface of the Ag NPs. The formation
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of core/shell structures is illustrated in Scheme 1. It should be
noted that the Ag@Fe3O4 core/shell nanostructures obtained in
our experiments are obviously different from the previous report
by J.-S. Chen et al.,22 in which Ag and Fe3O4 primary particles
are randomly distributed.
The scanning electron microscope (SEM) image in Fig. 1(a)
shows that the as-prepared samples are composed of many nearly
monodisperse spherical particles with a diameter of about
200 nm. From the magnified image in the inset of Fig. 1(a), one
can see that the surfaces of these nanospheres are not smooth and
are composed of many small NPs. Fig. 1(b) shows the typical
transmission electron microscope (TEM) image of the resulting
composite particles. The apparent contrast between the inner
core and outer shell suggests the formation of core/shell struc-
tures. The Ag particles appear black and the Fe3O4 are light
colored in the image because Ag has a higher electron density and
allows fewer electrons to be transmitted. The silver NP core has
nearly a uniform size of about 70 nm and the shells are composed
of many tiny NPs with a thickness of ca. 60 nm. The XRD
pattern of the as-synthesized Ag@Fe3O4 nanocomposites (see
Fig. S1, ESI†) has two series of Bragg reflections corresponding
to the diffractions from Fe3O4 (JCPDS card No. 19-0629) and
cubic phase silver (JCPDS card No. 04-0783), respectively. To
further determine the composition of the samples, energy-
dispersive spectroscopy (EDS) was performed on an individual
composite particle. The spectrum in Fig. S2† shows only Ag, Fe
and O peaks in addition to the Cu and C peaks from the copper
grid and C film, respectively. The elemental composition was also
confirmed from the EDS-mapping of a single nanosphere in
Scheme 1 Illustration of the synthesis procedure of Ag@Fe3O4 core/
shell nanostructures.
This journal is ª The Royal Society of Chemistry 2012
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Fig. 1(c) where the red spots (silver) correspond to the blacker
and the central areas and lighter areas are composed of Fe (blue)
and O (green), which confirmed the localization of Ag atoms in
the core and Fe, O atoms in the shell of the Ag/Fe3O4 nano-
structures. In addition, the line profile microanalysis across
a single core was used to get information on the relative locations
of Ag and Fe3O4 in the nanostructures. As shown in Fig. 1(d),
obvious different distribution patterns of Ag, Fe and O are
observed: Fe and O signals are distributed over the entire
structure and the signals in the center are a little lower than those
in the peripheral part, as expected; the Ag signal appears only in
the central region of the particle where the silver core is located.
Thus, based on the relative positions of these peaks, the central
area corresponds to Ag, surrounded by iron oxide on the outside.
These results proved that the shell is iron oxide, and the core is
predominantly silver, and Ag@Fe3O4 core/shell nanostructures
have been successfully fabricated.
A careful choice of the experimental conditions is crucial to
achieve the optimal size of the Ag core and thickness of the Fe3O4
shell, which will maintain an optical activity and impart
a significant magnetic response. By controlling the experimental
conditions such as the hydrothermal reaction time, the thickness
of the Fe3O4 shell can be modulated. For example, a silver core of
60  5 nm in diameter and a Fe3O4 shell thickness of about 55 
2 nm can be obtained once the solvothermal reaction was con-
ducted for only 4 h (see Fig. 2(a)). On the other hand, as seen in
Fig. 2(b), the diameter of the silver core and the thickness of the
Fe3O4 shell can grow up to about 70  5 and 62  2 nm,
respectively, by simply prolonging the reaction time to 8 h while
keeping the other synthetic conditions fixed. From Fig. 2(b), one
can see that the crystallinity of the Fe3O4 NPs is highly improved
and the corresponding particles sizes increase with the prolong-
ing of reaction time via an Ostwald ripening process. If the
reaction time was further extended, the growth of the Fe3O4 shell
would be processed continuously, and then a thicker Fe3O4 shell
was achieved. After 24 h (Fig. 1(b)), the size of the silver core and
Fe3O4 shell increase to about 90 and 70 nm, respectively.
Although the shell thickness can be controlled by the reaction
time, there was no straightforward linear correlation between
sphere size and changes in reaction time due to the complexity of
the growth process as described in the system of MFe2O4 ferrite
microspheres.20
Similarly, the mild synthetic method reported here also
permits other types of synthetic architectures. For example,
increasing the molar ratio of Ag/Fe precursors, well-faceted and
much larger Fe3O4 crystallites were formed on the surface of the
Fig. 2 TEM images of Ag@Fe3O4 core/shell nanostructures with an Ag/
Fe ratio of 0.15 at different reaction times: (a) 4 and (b) 8 h.
J. Mater. Chem., 2012, 22, 10779–10786 | 10781

Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H
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Fig. 3 TEM images of flower-like Ag@Fe3O4 core/shell nanostructures
at 200
C for 8 h with an Ag/Fe ratio of (a) 0.30; (b) 0.60.
Ag seeds, resulting in a flower-like Ag/Fe3O4 nanostructure.
Fig. 3(a) shows the TEM images of such flower-like nano-
structures with the faceted Ag core being 20–45 nm in diameter
and the Fe3O4 petals have an average size of 20 nm, which
demonstrates clearly the multi-nucleation of iron oxide on the
faceted Ag seeds. As seen in Fig. 3(b), such Ag@Fe3O4 nano-
flowers become more irregular with increasing the Ag/Fe ratio to
0.6. With a low ratio of Ag/Fe precursors (0.15), the resultant
nanostructures have a spherical shape composed of a silver core
and dense Fe3O4 nanoparticles (Fig. 2), whereas with a higher
ratio of Ag/Fe precursors (0.3 or 0.6), loosely aggregated Fe3O4
shells around the silver core are formed (Fig. 3), which is
different from the result reported by Jianfang Wang et al.23 It is
noteworthy that regardless of their exact sizes and morphologies,
the Fe3O4 NPs in the hybrid nanostructures always grow
heterogeneously on the silver seeds, and no unattached Fe3O4
NPs are observed. The controllable size and morphology of the
Ag@Fe3O4 nanostructures will lead to tunable optical
properties.
3.2 Optical properties of Ag@Fe3O4 nanostructures
The scattering in a turbid environment has significant influences
on the measurement of absorption spectra. An integrating sphere
spectroscopy has been confirmed to be an effective method for
overcoming scattering-dependence problems.24–26 In our experi-
ments, the quartz cuvette holder loaded with the sample was
placed outside the sphere similar to the approach described by
M. N. Merzlyak et al.26 Using such an external integrating sphere
mode, the as-obtained spectra will be much closer to the true
absorption spectrum of the sample, in which the effect of scat-
tering was greatly reduced. The exact position of the plasmon
resonance band of noble metal colloids depends strongly on the
particle size and shape, as well as the medium (dielectric prop-
erties) surrounding them. Thus, the coating of silver NPs with
a dielectric material leads to a shift of the surface plasmon
resonance (SPR) frequency. Since the refractive index of Fe3O4 is
higher (2.42) than that of silver (0.399) or ethanol (ca. 1.359), the
10782 | J. Mater. Chem., 2012, 22, 10779–10786
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Fig. 4 UV/vis/NIR spectra of Ag@Fe3O4 nanostructures: (a) at
different reaction times ((1) 4 h, (2) 8 h; and (3) 24 h); (b) with different
molar ratios of Ag/Fe precursors ((1) 0.15; (2) 0.30; (3)0.60).
presence of an Fe3O4 shell should strongly affect the plasmon
band position of silver. The unique characteristics of the
Ag@Fe3O4 core/shell geometry enable the tuning of the plas-
monic resonance by controlling the coating thickness of the
Fe3O4 shell around the silver core. As shown in Fig. 4(a), one can
see that the dipole plasmon of the as-obtained Ag@Fe3O4
spherical particles after solvothermal treatment for 4 h at 200
C
has red-shifted to 712 nm (curve 1) as compared with the pure
silver colloids. In addition to the dipole resonance, a distinct
quadrupole resonance peak at 392 nm was also observed, which
might be caused by the larger size of the Ag nanoparticles. The
quadrupole mode was theoretically and experimentally observed
for 50–150 nm spherical particles.27 When the reaction time was
prolonged to 8 h, both the diameter of the Ag core and the
thickness of the Fe3O4 shell increase, the SPR peaks red-shift to
longer wavelengths (i.e. 764 and 427 nm, curve 2 in Fig. 4(a)), and
an obvious NIR absorption is observed. By further increasing the
reaction time to 24 h, the dipole and quadrupole resonances red-
shift to 789 and 439 nm (curve 3 in Fig. 4(a)), respectively. There
are two reasons for the red-shift of the absorption spectra, one is
the increased particle dimension and another is the encapsulation
attributed to the dielectric constant of the surrounding matrix.
For the silver particles with a size of 50–100 nm, the size effect is
not high enough to lead to a shift of the dipole resonance from
390 nm to 712 nm (or longer wavelength). The contribution from
the larger refractive index of the surrounding dielectric Fe3O4
should come into effect. Based on these analyses, it is considered
that the increase both in the size of the Ag core and the thickness
of the Fe3O4 shell is responsible for the shift of the SPR wave-
length from the ultraviolet to the NIR region. The observed
plasmon resonance shift can be understood by Mie scattering
theory.28 Similar phenomena were also observed in Au@SiO2,29
Au@SnO2,30 Au@TiO231 and Au@Fe3O432 core/shell
This journal is ª The Royal Society of Chemistry 2012
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nanocrystal systems, in which the coverage of shell materials
possessing a higher refractive index encapsulating the Au cores
led to a red-shift in the SPR position of Au.
The Ag/Fe3O4 nanocomposites obtained at different Ag/Fe
molar ratios also showed a certain shifting of the SPR peaks.
Significantly, the peak position of the dipole resonance could be
blue-shifted from 764 nm to 510 nm with the increasing molar
ratio of the Ag/Fe precursor (shown in Fig. 4(b)). When the
molar ratio of Ag/Fe is about 0.15, the dipole and quadrupole
resonance modes are situated at 764 and 427 nm (curve 1),
respectively. However, the quadrupole resonance mode basically
disappears and only one SPR peak appears at 536 nm (curve 2)
when the molar ratio of Ag/Fe increased to 0.30, and this SPR
Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H
526 nm, a characteristic absorption band of R6G. After a small
amount of Ag@Fe3O4 catalysts were added, the color of the R6G
solution gradually faded with the reaction time. Fig. 5(a) and (b)
display the time-dependent absorption spectra of the R6G
solution upon the addition of NaBH4 for the as-prepared
Ag@Fe3O4 nanospheres and Ag/Fe3O4 nanoflowers, respec-
tively. Obviously, the absorption spectra of R6G suffers
a gradual decrease in the peak intensity with the peak shape and
position remaining almost unchanged after the two catalysts had
been added, indicating the reduction of the R6G dyes. As the
reaction proceeds, the orange red R6G solution gradually
becomes colorless, indicating the complete reduction of R6G.
From Fig. 5, only 34% of R6G could be reduced within 5 min at

peak further shifts to 510 nm (curve 3) when the molar ratio of room temperature and it took 30 min to complete the reduction
Ag/Fe increased to 0.60. One of the important reasons is the of about 90% of R6G for the Ag@Fe3O4 nanospheres catalyst;
obvious decrease in both the size of the silver core and the for the Ag/Fe3O4 nanoflower catalyst, about 80% of R6G could
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thickness of the Fe3O4 shell in the Ag/Fe3O4 nanoflowers, be reduced within 5 min and over 98% of R6G was degraded
compared with Ag@Fe3O4 spherical nanostructures, which may after 20 min. The catalytic results reveal that the as-synthesized
induce the SPR blue-shifting of the Ag/Fe3O4 nanocomposites. Ag/Fe3O4 nanoflowers show higher catalytic performance than
Another reason for affecting the SPR peak position is the lack of
a uniform Fe3O4 coating around the silver cores in the flower-like
Ag/Fe3O4 nanostructures. This is supported by the fact that the
morphologies of the Ag/Fe3O4 nanocomposites changed from
the core/shell structures with a continuous and uniform Fe3O4
coating to flower-like structures with only partial Fe3O4 domains
loosely surrounding the silver core with increasing Ag/Fe ratio.
As shown in Fig. 3, there are some regions in which silver
particles are directly exposed to the surrounding environment
without Fe3O4 coverings. Since the refractive index of the
surrounding medium (ethanol) is lower than that of Fe3O4, the
decrease in the dielectric constant of the surrounding matrix
might bring about the blue-shift of the SPR peaks. It is necessary
to mention here that the SPR peaks of these flower-like nano-
structures still show a red-shift in comparison with the pure silver
colloids. The above results demonstrate that the SPR peaks of
the Ag/Fe3O4 nanocomposites can be conveniently tuned over
a broad spectral range spanning from the ultraviolet to the NIR
not only by simply controlling the reaction time but also the
molar ratio of the Ag/Fe precursors.
For comparison, the Ag@Fe3O4 core/shell nanospheres were
further treated with a 0.25 M NaCl aqueous solution for a day at
room temperature in order to dissolve the silver core particles,
following the procedure of D.Y. Zhao et al.33 The resulting
particles were washed thoroughly with deionized water to
remove unreacted ions. The TEM image (Fig. S3†) revealed them
to be hollow particles without Ag cores, which confirmed the
porosity of the iron oxide shells. This resulted in the disappear-
ance of the absorption bands at 427 and 764 nm that were
derived from the plasmonic absorption of the silver nanocrystal
cores (Fig. S4†), which means the complete dissolution of the
silver cores by chloride ions.

3.3 Catalytic properties of Ag@Fe3O4 nanostructures
The catalytic performance of the Ag@Fe3O4 nanostructures was
investigated by employing the reduction of R6G dye, which was
conducted in the presence of NaBH4 as a model system. The
kinetic process of the reduction reaction was evaluated by
monitoring the intensity of the absorption peak located at
Fig. 5 (a) and (b) Time dependent absorption spectra for the catalytic
reduction of R6G by NaBH4 in the presence of the as-prepared
Ag@Fe3O4 nanospheres and nanoflowers, respectively. The arrows mark
the increase of reaction time. (c) The corresponding kinetic degradation
plots of R6G for Ag@Fe3O4 catalysts, I0 is the initial absorption intensity
of R6G at 526 nm, and I is the absorption intensity of R6G at 526 nm
after different reaction times. [R6G] ¼ 1.0  105 M; [Catalyst] ¼
0.4 g L1; [NaBH4] ¼ 0.1 M.

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the Ag@Fe3O4 spherical nanoparticles, which may be attributed
to their lower resistance to mass transfer from the thinner Fe3O4
shell. As control experiments, the maximum absorption peak of
R6G decreased a little when the Ag/Fe3O4 sample was dispersed
in the stock solution of R6G for 60 min in the absence of NaBH4
(see Fig. S5†), which may be attributed to the absorbance of the
Ag/Fe3O4 nanostructures. Without the addition of catalysts, the
R6G can only be reduced by NaBH4 by about 15% even after
120 min (as shown in Fig. S6†), indicating that the Ag@Fe3O4
catalysts play an important role in the reduction of R6G dye.
Since the concentration of borohydride largely exceeds the
concentration of R6G, pseudo-first-order kinetics can be applied
to evaluate the catalytic activity. Based on the curve in Fig. 5(c),
the rate constants are 0.1139 and 0.22 min1 for the Ag@Fe3O4
Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H
nanospheres and nanoflowers, respectively. Hence, the kinetic
reaction rate constant of the latter is larger than that of the other
nanomaterials (e.g. 0.11 min1 for the silver-coated ZnO nano-
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wire arrays)34 for the catalytic reduction of R6G. The ratio of the
rate constant to the total weight of catalyst used (2 mg) is
0.949 s1 g1 and 1.83 s1 g1 for the Ag@Fe3O4 nanospheres and
nanoflowers, respectively, which are closer to the reported ratio
for Ag–NP/C composites (1.69 s1 g1)35 and much higher than
silver NPs supported on halloysite nanotubes (0.087 s1 g1)36
and Ag-NP-doped hollow poly(N-isopropylacrylamide) spheres
(0.014 s1 g1).37 Compared with Ag nanoparticles decorated on
the surfaces of other supports, the as-prepared Ag@Fe3O4
nanocomposites have some additional advantages: firstly, the
Fe3O4 protective coatings can effectively stabilize the Ag nano-
particles and prevent the reduction in activity due to coagulation;
secondly, the loss of Ag nanoparticles due to frictional or other
mechanical forces can be avoided also; more importantly, the
catalysts can be recovered efficiently from the reaction solution
by applying an external magnet with the additional benefit of
relatively facile recovery and regeneration.
To study the reusability of the as-obtained catalysts, the used
catalysts were quickly separated from reaction mixtures with an
experiment magnet and rinsed with deionized (DI) water for the
next cycle of catalysis. Similar to the above reduction process, the
recycled catalysts were redispersed in 5 mL of aqueous R6G
solution (1  105 M) and mixed with 0.2 mL of fresh NaBH4
(0.1 M) solution. After reaction for 30 min, the solution was
measured using UV-vis spectroscopy. The procedure was
repeated 7 times. No obvious increase in the absorption intensity
of the final R6G solution was detected, that is, no visible decrease
in the catalytic performance was demonstrated after eight
successive reactions. We thus believe that the Ag@Fe3O4 nano-
composites obtained by our reported strategy are promising
recyclable catalysts in the reduction of R6G.
3.4 Magnetic properties of Ag@Fe3O4 nanostructures
In addition to the unique optical and catalytic properties asso-
ciated with the Ag domains, the as-obtained Ag/Fe3O4 nano-
composites also exhibit superparamagnetic properties because of
the existence of outer Fe3O4 shells. The magnetic properties of
the as-prepared Ag@Fe3O4 core/shell nanostructures were
investigated using a superconducting quantum interference
device (SQUID) magnetometer. The plots of magnetization
versus magnetic field (M–H loop) at room temperature are
10784 | J. Mater. Chem., 2012, 22, 10779–10786
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Fig. 6 (a) Magnetic hysteresis loops of Ag@Fe3O4 core/shell nano-
structures with an Ag/Fe ratio of 0.15 at 300 K; the inset is the temper-
ature dependence of the magnetization in FC and ZFC modes.
Photographs of the Ag@Fe3O4 particle suspension in water before (b)
and after (c) magnetic separation by an external magnet.
illustrated in Fig. 6(a). The M–H loops show that all the samples
have a rather strong magnetization and that the saturation
magnetization of the Ag@Fe3O4 nanospheres obtained after 4, 8
and 24 h is about 50, 58, 65 emu g1, respectively, which are
smaller than that of the bulk magnetite (90 emu g1).38 This
reduction can be understood to be the result of spin canting39 due
to spin frustration and lattice strain in small particles relative to
the bulk, which is especially manifested at the particle’s surface,40
and this effect will become dominant with decreasing particle
size. The decrease in magnetic moment of these Ag@Fe3O4
nanospheres could be also ascribed to the incorporation of
a diamagnetic Ag component in the nanocomposites that dilutes
the magnetic response of the Fe3O4 components. On the other
hand, the saturated mass magnetizations of those Ag@Fe3O4
nanospheres increased with prolonged reaction time, which is
consistent with their better crystallinity and the larger size of the
Fe3O4 particles. No obvious remanence or coercivity is observed
at room temperature in the magnetization curve of the
Ag@Fe3O4 nanospheres, indicating that they exhibit a super-
paramagnetic behavior. The inset in Fig. 6(a) shows the
temperature dependence of the magnetization for the field cooled
(FC) and zero field cooled (ZFC) curves of the Ag@Fe3O4
nanospheres obtained at 200
C for 24 h under applied magnetic
fields of 100 Oe, indicating that the blocking temperature is
above room temperature. Similarly, the Ag@Fe3O4 nanoflowers
also have rather strong magnetization with a saturation
magnetization of 50.7 emu g1 (see Fig. S7†). The strong
magnetic responsivity of these core/shell nanoparticles was also
revealed by the fact that they were easily attracted by an external
magnetic field. Fig. 6(b) shows a digital photograph of the
Ag@Fe3O4 nanospheres dispersed in water. When a cylindrical
NdFeB permanent magnet was placed besides the wall of a vial
containing the suspension, the particles were quickly attracted to
the walls of the vials within seconds, leaving the remaining liquid
colorless and transparent as shown in Fig. 6(c), which also proves
that the Ag and iron oxide are bound together and that no free
Ag particles exist.
3.5 Synthesis of Au@Fe3O4 nanostructures
This facile protocol described above was also employed to
prepare Au@Fe3O4 core/shell nanostructures (Fig. 7(a)), simply
by replacing AgNO3 with HAuCl4. A distinct contrast of the core
and shell can be observed clearly, and the dark cores are Au and
This journal is ª The Royal Society of Chemistry 2012

Fig. 7 (a) TEM image of the as-prepared Au@Fe3O4 core/shell nano-
spheres; (b) TEM image of a single Ag@Fe3O4 particle and the corre-
sponding EDS elemental mappings of Au, Fe and O.
Published on 23 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16293H
the gray shells are Fe3O4. Fig. S8† shows the XRD pattern of the
as-obtained products, from which it can be observed that cubic-
phase Au and Fe3O4 with an inverse spinel structure were
Downloaded by Pennsylvania State University on 26 May 2012
formed. The EDS mapping results (Fig. 7(b)) and line elemental
EDS data (see ESI, Fig. S9†) across a single nanosphere further
confirm that the Au atoms are located in the core and the Fe, O
atoms occur in the shell of the Au/Fe3O4 nanostructures. These
Au@Fe3O4 core/shell hybrid particles also exhibit super-
paramagnetic properties and tunable optical properties that
correspond to the SPR of the Au nanoparticles (ESI, Fig. S10†).
4. Conclusions
In summary, multifunctional Ag@Fe3O4 core/shell nano-
structures have been fabricated through a simple one-step sol-
vothermal process. Our studies demonstrate that both the
plasmonic properties of the silver core and the strong magneti-
zation of the magnetite shell are retained in such multifunctional
nanostructures. More specifically, the size and morphology of
these multifunctional hybrid nanoparticles can be modulated
simply by controlling the reaction time and the molar ratio of
Ag/Fe precursors, which can effectively tune both the magnetic
and plasmonic properties, and the SPR can be adjusted over
a broad range from the ultraviolet to NIR range. Apart for the
tunable plasmon resonance shift, the Ag@Fe3O4 composite
spheres also exhibit significant catalytic activity towards the
reduction of R6G by sodium borohydride. By using this novel
and general method, diverse noble metals can be successfully
incorporated into Fe3O4 nanospheres to form core/shell nano-
composites. Combining tunable optical properties, a strong
magnetic response, and superior stability, these multifunctional
nanomaterials may open up many exciting opportunities in
biomedical applications, such as integrated imaging, diagnosis,
targeted delivery, therapeutics and great potential applications in
catalysis, photovoltaics, plasmonics, and optics.
Acknowledgements
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (Grant Nos.
50802095, 11004197) and the National Basic Research Program
of China (Grant No. 2007CB936601).
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