pubs.acs.

org/Langmuir
© 2009 American Chemical Society

Preparation, Characterization, and Catalytic Activity of Core/Shell

Fe3O4@Polyaniline@Au Nanocomposites
Shouhu Xuan,†,§ Yi-Xiang J. Wang,‡ Jimmy C. Yu,† and Ken Cham-Fai Leung*,†
†
The Center of Novel Functional Molecules, Department of Chemistry, The Chinese University of Hong Kong,
Shatin, NT, Hong Kong SAR, ‡Department of Diagnostic Radiology and Organ Imaging, Prince of Wales
Hospital, The Chinese University of Hong Kong, Shatin, NT, Hong Kong SAR, and §Department of Materials
Science and Engineering, China Jiliang University, Hangzhou, 310018, People’s Republic of China

Received April 23, 2009. Revised Manuscript Received June 28, 2009

We report a new method to synthesize magnetically responsive Fe3O4@polyaniline@Au nanocomposites. The

superparamagnetic Fe3O4@polyaniline with well-defined core/shell nanostructure has been synthesized via an ultra-
sound-assisted in situ surface polymerization method. The negatively charged Au nanoparticles with a diameter of about 4
nm have been effectively assembled onto the positively charged surface of the as-synthesized Fe3O4@polyaniline core/shell
microspheres via electrostatic attraction. The morphology, phase composition, and crystallinity of the as-prepared
nanocomposites have been characterized by transmission electron microscopy (TEM) and powder X-ray diffraction
(XRD). The central Fe3O4 cores are superparamagnetic at room temperature with strong magnetic response to externally
applied magnetic field, thus providing a convenient means for separating the nanocomposite from solution. As-prepared
inorganic/organic nanocomposite can be used as a magnetically recoverable nanocatalyst for the reduction of a selected
substrate.

1. Introduction various core/shell architectures based on Fe3O4 are important

In recent years, core/shell-structured composite materials, 1 research subjects. Studies on the modular synthesis of the mag-
which combine with the advantageous properties of both materials netic core/shell composite materials with unique size- and shape-
of the core and the shell, have attracted increasing interest to dependent properties are of great interest and are actively being
materials scientists due to their unique physicochemical properties pursued.
and great potential applications in the areas of electronics, photo- The most common method to synthesize magnetic core/shell
nics, catalysis, biotechnology, and nanotechnology.2 These specific composite materials was coating Fe3O4 particles with functional
core/shell structures which possess the ability to be modified with shells. Among these shell materials, polyaniline (PANI) has received
different charges, functions, or reactive moieties on the surface with more attention for its unique electrical property.5 Recently,
enhanced stability and compatibility provide an avenue for the Fe3O4@PANI nanocomposite has become a popular material for
synthesis of complex composite materials. Alternatively, various applications in electrical-magnetic shields, electrochemical display
types of bifunctional or trifunctional core/shell materials, such as devices, and microwave absorbing materials.6 Several methods have
electronic/optical, electronic/catalytic, magnetic/electronic, etc., been developed to synthesize Fe3O4@PANI nanocomposite.7 Wan
could be technically obtained.3 et al.7a studied a series of PANI-containing nanomagnets which was
Magnetite (Fe3O4), which is a common ferrite possessing a prepared by chemical polymerization. Deng et al.7b reported the
cubic inverse spinel structure, has been widely studied because of preparation of PANI/Fe3O4 nanoparticles with core/shell structure
their potential applications as ferrofluids, catalysts, biological via an in situ polymerization of aniline monomer in aqueous
assays, chemical sensors, and electrophotographic developers.4 solution, which contained Fe3O4 nanoparticles and surfactants.
With respect to these properties, the design and synthesis of Besides the spherical morphology, other types of Fe3O4@PANI
nanocomposite such as Y-junction structure can also be selectively
prepared by using in situ self-assembly of water-soluble Fe3O4
*Corresponding author: Tel þ852 26096342; Fax þ852 26035057; e-mail nanoparticles.8 The as-prepared composite particles are shown to
[email protected]. be superparamagnetic, wherein they serve as ideal candidates for
(1) Caruso, F. Adv. Mater. 2001, 13, 11–22.
(2) (a) Li, X.; Wan, M. X.; Wei, Y.; Shen, J. Y.; Chen, Z. J. J. Phys. Chem. B biomedical applications, such as enzyme immobilization, nucleic
2006, 110, 14623–14626. (b) Roca, M.; Haes, A. J. J. Am. Chem. Soc. 2008, 130, acid extraction, cancer diagnosis, biosensors, and drug delivery.9
14273–14279. (c) Yi, D. K.; Lee, S. S.; Ying, J. Y. Chem. Mater. 2006, 18, 2459–2461. However, most of these nanoparticles result in fluctuations in size
(d) Feng, X.; Mao, C.; Yang, G.; Hou, W.; Zhu, J. J. Langmuir 2006, 22, 4384–4389. (e)
Salgueirio-Maceira, V.; Correa-Duarte, M. A.; Spasova, M.; Liz-Marzan, L. M.; Farle,
M. Adv. Funct. Mater. 2006, 16, 509–514. (5) (a) Zhang, L. J.; Wan, M. X. J. Phys. Chem. B 2003, 107, 6748–6753. (b)
(3) (a) Xi, Y.; Zhou, J.; Guo, H.; Cai, C.; Lin, Z. Chem. Phys. Lett. 2005, 412, 60– Liang, L.; Liu, J.; Windisch, C. F.; Exarhos, G. J.; Lin, Y. Angew. Chem., Int. Ed. 2002,
64. (b) Mangeney, C.; Bousalem, S.; Connan, C.; Vaulay, M.; Bernard, S.; Chehimi, M. 41, 3665–3668.
M. Langmuir 2006, 22, 10163–10169. (6) Lu, X. F.; Yu, Y. H.; Chen, L.; Mao, H. P.; Gao, H.; Wang, J.; Zhang, W. J.;
(4) (a) The Iron Oxides; Cornell, R. M., Sehwertmann, U., Eds.; VCH: Weinheim, Wei, Y. Nanotechnology 2005, 16, 1660–1665.
Germany, 1996.(b) Keane, M. A. J. Catal. 1997, 166, 347–355. (c) Geus., J. W. Appl. (7) (a) Wan, M. X.; Li, W. C. J. Polym. Sci., Part A: Polym. Chem. 1997, 35,
Catal. 1986, 25, 313–333. (d) Martin, B. R.; Dermody, D. J.; Reiss, B. D.; Fang, M. M.; 2129–2136. (b) Deng, J. G.; He, C. L.; Peng, Y. X.; Wang, J. H.; Long, X. P.; Li, P.; Chan,
Lyon, L. A.; Natan, M. J.; Mallouk, T. E. Adv. Mater. 1999, 11, 1021–1025. (e) Huo, L.; A. S. C. Synth. Met. 2003, 139, 295–299. (c) Deng, J.; Ding, X.; Zhang, W.; Peng, Y.;
Li, W.; Lu, L.; Cui, H.; Xi, S.; Wang, J.; Zhao, B.; Shen, Y.; Lu, Z. Chem. Mater. 2000, Wang, J.; Long, X.; Li, P.; Chan, A. S. C. Polymer 2002, 43, 2179–2184.
12, 790–794. (f) Matijevic, P. E.; Hench, L. L.; Ulrich, D. B. Colloid Science of (8) Xia, H. B.; Cheng, D. M.; Xiao, C. Y.; Chan, H. S. O. J. Mater. Chem. 2005,
Composites System Science of Ceramic Chemical Processing; Wiley: New York, 15, 4161–4166.
1986; p 463. (9) Lee, G.; Kim, J.; Lee, J. H. Enzyme Microb. Technol. 2008, 45, 466–472.

Langmuir 2009, 25(19), 11835–11843 Published on Web 08/24/2009 DOI: 10.1021/la901462t 11835
Article Xuan et al.

whereas they had a nonuniform magnetite fraction in each nano- has been synthesized via a simple ultrasound-assisted in situ
sphere due to nanoscale clustering of magnetic particles. In order to surface polymerization method. Although it has been reported
achieve steady and reproducible applications, it is therefore of great that the dedoped PANI can be used as reductant for the gene-
interest to prepare well-dispersed Fe3O4@PANI nanocomposite ration of Au nanoparticles from Au metal salts,16 a method which
with defined core/shell nanostructure. utilizes electrostatic attractions was employed to immobilize the
Additionally, a rational combination of the above magnetic presynthesized Au nanoparticles onto the Fe3O4@PANI core/
core/shell particles together with other functional materials (noble shell microspheres. The negatively charged Au nanocatalysts,
metals, semiconductor, etc.) would result in multicomponent which possess an average diameter about 4 nm, can be effectively
nanocomposites with integrated and stable optical, catalytic, assembled onto the positively charged surface of the as-synthe-
electrical, and magnetic properties.10 These species of nanocom- sized Fe3O4@PANI core/shell microspheres. To the best of our
posite exhibited promising application in many areas.11 Various knowledge, this is the first report about the synthesis of mono-
complex structures, such as Fe3O4@SiO2@PABI-Tb, Fe3O4 disperse Fe3O4@PANI@Au nanocomposites with defined core/
@SiO2@Au, Fe3O4@SiO2@CdTe, Fe3O4@SiO2(FITC), etc.12 shell nanostructure. The central magnetite cores are superpara-
have been successfully prepared. A significant amount of work magnetic at room temperature with strong magnetic response to
has been reported using the Fe3O4@inorganic@shell type three- externally applied magnetic fields, thus providing a convenient
component composite particles. However, the study of the means for separating the nanocomposite from solution. Addi-
Fe3O4@polymer@shell three-component composites is rare, tionally, such nanocomposite can be used as a magnetically
which may be attributed to the synthetic difficulties of the recoverable catalyst for the reduction of rhodamine B (RhB) with
Fe3O4@organic shell composite particles. Very recently, Wang NaBH4. In a parallel comparison to the Fe3O4@SiO2@Au
et al.13 reported the synthesis of Fe3O4@PAH@Au multifunc- catalyst, the Fe3O4@PANI@Au nanoparticle is a more effective
tional nanoparticles, which display both magnetism and near- catalyst which can also be recycled for repeated catalyzes.
infrared absorption. Xu’s group14 has also successfully prepared
Fe3O4@PPy@Au nanocomposite which exhibited excellent elec- 2. Experimental Section
trocatalytic properties for ascorbic acid. Additionally, Yu et al.15
prepared Fe3O4@Au/PANI nanocomposites by in situ polymeri- Materials. Ferric chloride hexahydrate, sodium acrylate,
sodium acetate, hydrogen tetrachloroaurate hydrate, ethylene
zation in the presence of mercaptocarboxylic acid. However,
glycol, trisodium citrate, tetraethyl orthosilicate (TEOS), 3-ami-
many of these multifunctional magnetic nanocomposites do not nopropyltriethoxysilane (APTES), rhodamine B (RhB), sodium
possess monodispersity with well-defined core/shell nanostruc- borohydride, absolute ethanol (EtOH), ammonium peroxodisul-
tures, which confined their properties and applications. There- fate (APS), and poly(vinylpyrrolidone) (PVP; 30 kDa) were
fore, the construction of monodisperse Fe3O4@polymer@shell purchased from Aldrich. All chemicals were of analytical grade
composite particles with well-defined core/shell nanostructure is a and used without further purification. Aniline was also obtained
pressing need for the study of their physicochemical properties. from Aldrich and was distilled at a reduced pressure before use.
On the basis of the above considerations, one could combine Doubly deionized water was used through out the synthetic
the collective advantages of Fe3O4, PANI, and Au nanoparticle to processes. The sonicator was operated at 35 kHz using an Elma
fabricate multifunctional materials with well-defined core/shell TI-H-5 apparatus.
structures, sharing good stability, solvent compatibility, optical Synthesis of Fe3O4 Microspheres. The magnetic Fe3O4
microspheres were prepared through a solvothermal reaction.
property, catalytic activity, and magnetic separability. However,
Briefly, FeCl3 3 6H2O (1.08 g), sodium acrylate (3.0 g), and sodium
the study of the Fe3O4@PANI@Au microspheres with well- acetate (3.0 g) were dissolved in ethylene glycol (40 mL) with
defined core/shell nanostructure has not been reported, which magnetic stirring at room temperature for 2 h. The homogeneous
mostly correspond to the difficulty to synthesize Fe3O4@PANI yellow solution was then transferred to a Teflon-lined stainless-
particles with defined core/shell structure, and thus further steel autoclave (container volume=80 mL) and sealed to heat at
confine the synthesis of the Fe3O4@PANI@Au core/shell com- 200 °C. After a reaction for 10 h, the autoclave was cooled to room
posite particles. temperature. The supernatant of the mixture was discarded. The
In this paper, a novel method for the synthesis of magnetically obtained Fe3O4 particle suspension was washed successively with
responsive Fe3O4@PANI@Au nanocomposites with monodis- H2O and EtOH three times and then dried in vacuum for 12 h at
perse core/shell nanostructure is reported. The superparamag- room temperature.
netic Fe3O4@PANI with well-defined core/shell nanostructure Synthesis of Fe3O4@PANI Nanocomposite with Core/
Shell Nanostructures. In a typical procedure, PVP (50 mg) and
Fe3O4 microspheres (10 mg) were dispersed in H2O (12.5 mL)
(10) (a) Kim, J.; Lee, J. E.; Lee, J.; Jang, Y.; Kim, S. W.; An, K.; Yu, J. H.; under ultrasonication at room temperature. After 30 min, aniline
Hyeon, T. Angew. Chem., Int. Ed. 2006, 45, 4789–4793. (b) Sacanna, S.; Philipse, (1.2 10-3, 1.6 10-3, or 2.0 10-3 M) in the presence of
A. P. Langmuir 2006, 22, 10209–10216. (c) Chen, M.; Kim, Y. N.; Lee, H. M.; Li, C.;
Cho, S. O. J. Phys. Chem. C 2008, 112, 8870–8874. (d) Yang, H.; Jiang, W.; Lu, Y.
concentrated HCl (25 μL) was added into the mixture at room
Mater. Lett. 2007, 61, 2789–2793. (e) Nagao, D.; Yokoyama, I.; Yamauchi, N.; temperature. The solution was shaken for 12 h at room tempera-
Matsumoto, H.; Kobayashi, Y.; Konno, M. Langmuir 2008, 24, 9804–9808. (f) Lu, Z.; ture. Then, H2O (10 mL) was added to the mixture, followed by
Qin, Y.; Fang, J.; Sun, J.; Li, J.; Liu, F.; Yang, W. Nanotechnology 2008, 19, 055602. ultrasonication (1 h at room temperature). After an hour, an
(11) Stoeva, S. I.; Huo, F.; Lee, J. S.; Mirkin, C. A. J. Am. Chem. Soc. 2005, 127,
15362–15363.
aqueous solution of APS (0.3 g of APS in 10 mL of H2O) was
(12) (a) Yu, S. Y.; Zhang, H. J.; Yu, J. B.; Wang, C.; Sun, L. N.; Shi, W. D. added into the above mixture instantly to start the oxidative
Langmuir 2007, 23, 7836–7840. (b) Ji, X.; Shao, R.; Elliott, A. M.; Stafford, R. J.; polymerization under ultrasonic irradiation, and the reaction was
Esparza-Coss, E.; Bankson, J. A.; Liang, G.; Luo, Z. P.; Park, K.; Markert, J. T.; Li, allowed to proceed for 2 h at room temperature. After the
Chun. J. Phys. Chem. C 2007, 111, 6245–6251. (c) Lu, C. W.; Hung, Y.; Hsiao, J. K.;
Yao, M.; Chung, T. H.; Lin, Y. S.; Wu, S. H.; Hsu, S. C.; Liu, H. M.; Mou, C. Y.; Yang,
reaction, the precipitate was magnetic separated and washed
C. S.; Huang, D. M.; Chen, Y. C. Nano Lett. 2007, 7, 149–154. successively with H2O and EtOH three times. The final product
(13) Wang, L. Y.; Bai, J. W.; Li, Y. J.; Huang, Y. Angew. Chem., Int. Ed. 2008,
47, 2439–2442.
(14) Zhang, H.; Zhong, X.; Xu, J. J.; Chen, H. Y. Langmuir 2008, 24, 13748–
13752. (16) (a) Wang, J.; Neoh, K. G.; Kang, E. T. J. Colloid Interface Sci. 2001, 239,
(15) Yu, Q. Z.; Shi, M. M.; Cheng, Y. N.; Wang, M.; Chen, H. Z. Nanotechnol- 78–86. (b) Tseng, R. J.; Huang, J.; Ouyang, J.; Kaner, R. B.; Yang, Y. Nano Lett. 2005,
ogy 2008, 19, 265702. 5, 1077–1080.

11836 DOI: 10.1021/la901462t Langmuir 2009, 25(19), 11835–11843

Xuan et al. Article

was dried in vacuum for 12 h at room temperature to obtain the

desired Fe3O4@PANI core/shell nanocomposite.
Synthesis of Fe3O4@PANI@Au Nanocomposites. An
electrostatic attraction method was employed for the immobiliza-
tion of Au nanoparticles onto the Fe3O4@PANI core/shell micro-
spheres to form the Fe3O4@PANI@Au microspheres. First, in
order to induce positive charges at the surface of the Fe3O4
@PANI microspheres, acetic acid solution (0.1 mL) was added
into the ethanolic dispersion of Fe3O4@PANI (10 mg/mL, 1 mL)
at room temperature and then sonicated at room temperature for
1 h. Subsequently, an aqueous solution of Au nanoparticles with
an average diameter of 4 ( 1 nm was prepared according to
literature procedures.17 In brief, an aqueous solution (20 mL)
containing HAuCl4 (2.5 10-4 M) and trisodium citrate (2.5
10-4 M) was prepared in a conical flask. Then, cold NaBH4
solution (0.6 mL, 0.1 M) was added with vigorous stirring. The
solution turned pink immediately after the addition of NaBH4,
Figure 1. XRD diffraction patterns of the as-prepared Fe3O4 (a),
indicating the Au nanoparticle formation. The freshly prepared Fe3O4@PANI (b), Fe3O4@PANI@Au (c), and Fe3O4@SiO2@Au
Au nanoparticles solutions were used within 2-5 h after prepara- (d) microspheres.
tion. Finally, the solution of positively charged Fe3O4@PANI
microspheres (1 mL) was added to the Au solution under sonica- magnetic particles are hydrophilic while polymers are hydropho-
tion at room temperature for 30 min. The Au nanoparticles were bic. In our previous report,18 Fe3O4@PANI microspheres with
electrostatically attracted on the surface of the Fe3O4@PANI blackberry-like morphology have been successfully obtained by
nanocomposites; thereby, the resultant Fe3O4@PANI@Au pro- using an in situ surface polymerization method. However, a
duct was removed from the solution by applying an external
modification of the Fe3O4 microsphere cores is inevitable before
magnetic field, rinsed successively with H2O and EtOH three
times, and then dispersed in H2O for the characterization of PANI coating, which renders a complex synthetic route. More-
catalytic properties. over, a more uniform PANI coating apart from the rough
Catalytic Properties of the Fe3O4@PANI@Au Nano- blackberry-like morphology should be obtained. Therefore, a
composites. The reduction of RhB by NaBH4 was chosen as a facile method must be developed to directly coat a uniform PANI
model reaction for the efficiency testing of the Au-immobilized layer onto Fe3O4 particles without prior surface modification.
nanoparticle. A given amount of the magnetic catalysts were It has been reported that the coating of colloids with PANI
added into a solution with RhB (20 mL, 5 10-5 mol/L), in which shells is strongly influenced by the sign of charges of the
the volume of the mixture was adjusted to 40 mL with H2O. After materials.19 Since PANI chains are positively charged in the
that, an aqueous solution of NaBH4 (1 mL, 0.4 mol/L) was reaction solution, uniform PANI shells can be successfully
rapidly injected at room temperature with stirring. The color of obtained when negatively charged templates such as PSA are
the mixture gradually vanished, indicating the reduction of the used.20 Therefore, in order to coat a uniform PANI layer on to the
RhB dye. Changes in the concentration of RhB were monitored
Fe3O4 core, carboxylate-functionalized Fe3O4 microspheres were
by examining the variations in the maximal UV/vis absorption at
554 nm. After the catalytic reaction was completed, the nanoca- used as the core template.
talysts were separated by externally applied magnetic field and Herein, carboxyl group functionalized Fe3O4 microspheres
then repeated for the catalytic reaction. The recyclability of the were synthesized through a solvothermal method in ethylene
nanoparticle catalysis was determined by measuring the maximal glycol using FeCl3 3 6H2O as the sole iron source. Sodium acrylate
UV/vis absorption of RhB at the end of each catalytic degradation was used in the reaction system, which served both as base and
reaction. surface modification agent. The XRD pattern of the as-synthe-
Characterization. X-ray powder diffraction patterns (XRD) sized product is shown in Figure 1a, which can be indexed to face-
of the products were obtained on a Japan Rigaku DMax-γA center-cubic phase of Fe3O4 (JCPDS Card No. 19-629). Accord-
rotation anode X-ray diffractometer equipped with graphite ing to the Scherrer equation,21 the average crystallite size which is
monochromatized Cu KR radiation (λ=1.541 78 Å). Transmis- calculated based on the XRD pattern (311) is ∼7.5 nm. Repre-
sion electron microscopy (TEM) photographs were taken on a
sentative TEM images of the as-synthesized Fe3O4 particles are
FEI CM120 microscope at an accelerating voltage of 120 kV. X-
ray photoelectron spectra (XPS) were measured on a photoelec- shown in Figure 3d. Clearly, the diameter of the spherical micro-
tron spectrometer using Mg KR radiation. Infrared (IR) spectra sphere is about 170 nm. The microsphere is an assembly of many
were recorded in the wavenumbers ranging from 4000 to 500 cm-1 small Fe3O4 nanocrystals, which agrees well with the observed
with a Nicolet Model 759 Fourier transform infrared (FT-IR) broad X-ray diffraction lines. Figure 2a presents the typical FTIR
spectrometer using a KBr wafer. Thermogravimetric (TG) ana- spectrum of the Fe3O4 microspheres. The bands appeared at 590,
lyses were conducted with a Netzsch STA 409C thermoanalyzer 1450, and 3400 cm-1 are related to the Fe-O vibration, the CH2
instrument. The magnetic properties (M-H curve) were evaluated bending mode, and the O-H stretching vibrations, respectively.22
on a BHV-55 vibrating sample magnetometer (VSM). UV/vis The two bands located at 1550 and 1405 cm-1 correspond to
spectra were obtained using a UV-365 spectrophotometer. the COO- antisymmetrical vibration and COO- symmetric
3. Results and Discussion
(18) Xuan, S. H.; Wang, Y. X. J.; Leung, K. C.-F.; Shu, K. Y. J. Phys. Chem. C
3.1. Synthesis of Monodisperse Fe3O4@PANI Micro- 2008, 112, 18804–18809.
(19) Lu, Y.; McLellan, J.; Xia, Y. N. Langmuir 2004, 20, 3464–3470.
spheres with Well-Defined Core/Shell Nanostructure. To (20) (a) Ding, K. L.; Miao, Z. J.; Liu, Z. M.; An, G. M.; Xie, Y.; Tao, R. T.; Han,
date, the effective coating of Fe3O4 particles with natural or B. X. J. Mater. Chem. 2008, 18, 5406–5411. (b) Kim, B. J.; Oh, S. G.; Han, M. G.; Im,
synthetic polymers is still a challenge since the surfaces of S. S. Polymer 2002, 43, 111–116.
(21) Klug, H. P.; Alexander, L. E. X-ray Diffraction Procedures for Polycrystal-
line and Amorphous Materials; Wiley: New York, 1962; pp 491-538.
(17) Jana, N. R.; Gearheart, L.; Murphy, C. J. J. Phys. Chem. B 2001, 105, 4065– (22) Xuan, S. H.; Hao, L. Y.; Jiang, W. Q.; Gong, X. L.; Hu, Y.; Chen, Z. Y.
4067. J. Magn. Magn. Mater. 2007, 308, 210–213.

Langmuir 2009, 25(19), 11835–11843 DOI: 10.1021/la901462t 11837

Article Xuan et al.

First, the water-soluble carboxylic acid-functionalized Fe3O4

microspheres were dispersed in an aqueous solution. Then, the
aniline monomers were added and partly reacted with the sur-
face carboxylic acid groups to give the -COO-H3Nþ- ion pairs.
The adsorption of aniline onto the particle surface results in a
close proximity. It is believed that the initial polymerization of
aniline under this circumstance is favorable.25 Once the aniline
nucleation is generated, the polymerization takes place preferen-
tially and continuously on the particle’s surface rather than in
solution.18 Eventually, the monodisperse, well-defined Fe3O4-
@PANI core/shell structure is formed. TEM images permit the
comparison of the particle morphology between the Fe3O4
particles (Figure 3d) and the Fe3O4@PANI microspheres
(Figure 3a-c). As shown in Figure 3a, the as-prepared Fe3O4-
@PANI nanocomposites were well dispersed on the copper grid
Figure 2. FTIR spectra of the as-prepared Fe3O4 (a), Fe3O4- without large aggregations. Figure 3b shows the TEM image of
@PANI (b), Fe3O4@PANI@Au (c), and Fe3O4@SiO2 (d) micro- Fe3O4@PANI nanocomposites with a higher resolution; it is clear
spheres. that the composite particles are constituted of two distinct
components: a black core of Fe3O4 and a gray shell of PANI.
No obvious changes in size or shape of the Fe3O4 cores are
observed; thereby a well-defined Fe3O4@PANI core/shell struc-
ture is successfully achieved. Figure 3c shows the TEM image of a
single Fe3O4@PANI particle with a typical core/shell nanostruc-
ture. The Fe3O4 core is well wrapped by the coating layer, and the
average thickness of the PANI coating shell is about 25 nm.
Moreover, there exists a clear interface between the PANI shell
and the Fe3O4 core (Figure 3c), indicating a tight encapsulation.
For the XRD spectrum of Fe3O4@PANI nanocomposites
(Figure 1b), the major peaks are similar to the pristine Fe3O4
particles (Figure 1a), revealing that the as-prepared core/shell
composites consist of the Fe3O4 component. Because of the
relatively thin layer and amorphous crystallinity of the PANI
prepared under this in situ polymerization method, no obvious
diffraction peak for the PANI is observed. Figure 2b shows the
typical FTIR spectrum of the as-prepared Fe3O4@PANI com-
posites. The characteristic peaks at approximately 1591, 1315,
1177, and 820 cm-1 are similar to that of the pure PANI sample,
which further support that the PANI shell is successfully coated
on the Fe3O4 microspheres’ surface.18
In our system, both the ultrasonic irradiation treatment and
usage of PVP are particularly important for the synthesis of the
Figure 3. TEM images of the as-prepared Fe3O4@PANI (a-c) monodisperse Fe3O4@PANI core/shell nanoparticles. The nega-
and Fe3O4 (d) microspheres.
tively charged Fe3O4 microspheres are in favor of coating by
vibration, indicating the bidentate bonding of the carbonyl positively charged PANI; however, the major problem regarding
groups to the surface Fe atoms.23 Additionally, a weak band the coating of PANI onto the Fe3O4 microspheres is that the
appeared at 1710 cm-1 is attributed to the CdO stretching mode polymerization is required to perform in acidic condition. As the
of the residue carboxylic acid groups, which form dimer pairs and carboxyl-functionalized Fe3O4 microspheres are easily to form
sideway chains with hydrogen bonds.24 Although large amounts aggregates in acidic solution, it has resulted in large conglomera-
of carboxylate groups are coordinated strongly to the iron tion which responds to the strong hydrogen-bonding interaction
cations, there are still many polymer chains located on the between PANI and Fe3O4 microspheres during the polymeri-
particles’ surface with uncoordinated residue carboxylic acid zation process. Once the coating process was performed under
groups. All these results indicate that carboxyl functionalized mechanical stirring without the usage of PVP surfactant, only
Fe3O4 microspheres have been successfully obtained. Therefore, PANI encapsulated, large Fe3O4 microspheres aggregates were
it is noteworthy that uniform PANI layer can be directly observed (Figure 4a). Therefore, PVP macromolecules were
coated onto the as-prepared carboxylic acid-functionalized added into the reaction solution in order to stabilize the Fe3O4
Fe3O4 microspheres. microspheres. Figure 4b represents the typical TEM image of the
The preparation of the Fe3O4@PANI microspheres with Fe3O4@PANI nanocomposites which were synthesized with the
defined core/shell nanostructure using the ultrasonic-assisted use of PVP. It is clear that all the Fe3O4 microspheres are
in situ polymerization method can be divided into several steps. well wrapped in the PANI coating layer. However, the Fe3O4-
@PANI core/shell particles are still terribly linked with the PANI
layers which indicate that the addition of PVP surfactant was
(23) Lin, C. L.; Lee, C. F.; Chiu, W. Y. J. Colloid Interface Sci. 2005, 291, 411–
420.
(24) Ge, J.; Hu, Y.; Biasini, M.; Dong, C.; Guo, J.; Beyermann, W. P.; Yin, Y. (25) Zhu, C. L.; Chou, S. W.; He, S. F.; Liao, W. N.; Chen, C. C. Nanotechnol-
Chem.;Eur. J. 2007, 13, 7153–7161. ogy 2007, 18, 275604.

11838 DOI: 10.1021/la901462t Langmuir 2009, 25(19), 11835–11843

Xuan et al. Article

cores was fixed, the average thickness of the PANI was from 7 to
15 and 25 nm (Figure S1) by changing the concentration of the
aniline monomer from 1.2 10-3 to 1.6 10-3 and 2.0 10-3 M,
respectively.
3.2. Synthesis of Well-Dispersed Fe3O4@PANI@Au
Core/Shell Nanocomposite. It has been reported that PANI
and its derivatives can act as reactive templates for polymer-
supported gold nanoparticles, which will facilitate the synthetic
procedures for polymer-supported gold nanoparticles within one
step.27 Very recently, Guo’s group28 has reported that well-
defined gold nanoparticles with tunable size and morphology
can be supported by the shells of hollow microspheres of poly-
(o-phenylenediamine) (PoPD), a derivative of PANI. The synth-
esis relies on a method from which the hollow microspheres of
PoPD act as both reductant and template/stabilizer. In our
experiment, the as-prepared Fe3O4@PANI microspheres can
also be used as the reactive template to synthesize the Fe3O4-
@PANI@Au nanocomposites from Au(III) salt. However, the
sizes of the as-prepared Au nanoparticles which are supported on
Fe3O4@PANI microspheres are not uniform. Therefore, direct
Figure 4. TEM images of the as-prepared Fe3O4@PANI without immobilization of presynthesized Au nanoparticles via electro-
PVP surfactant by mechanical stirring (a), with PVP surfactant by static interactions could be employed to synthesize the mono-
mechanical stirring (b), without PVP surfactant by ultrasonic disperse Fe3O4@PANI@Au nanocomposites.
irradiation (c), and with PVP surfactant by ultrasonic irradiation For the synthesis of the Fe3O4@PANI@Au nanocomposites,
(d). All other synthetic parameters were the same.
amine groups on the Fe3O4@PANI microspheres’ surface were
insufficient to prevent the Fe3O4 aggregation. It has been reported protonated such that the citrate-coated, negatively charged Au
that ultrasound has been widely used in chemical reactions, seeds could be immobilized by electrostatic interactions.29 When
dispersion, emulsifying, crushing, and polymerization because the Fe3O4@PANI nanocomposites with a shell thickness of 25
the ultrasonic cavitation can generate high local temperatures and nm were introduced into the Au colloid solution, Fe3O4@PA-
high local pressure.26 Hence, in the present study, the ultrasonic NI@Au composite microspheres were formed by virtue of multi-
irradiation technique was employed to prepare the Fe3O4@PANI ple electrostatic interactions. As shown in Figure 6a, Fe3O4-
core/shell microspheres. The TEM image of the Fe3O4@PANI @PANI@Au nanocomposites with well-defined core/shell nano-
nanocomposites which were synthesized under ultrasonication structure are well-dispersed on the copper grid. From the TEM
without PVP surfactant (Figure 4c) shows that all the Fe3O4 image with a higher resolution (Figure 6b), clearly, all the Fe3O4
particles are well encapsulated in the PANI latex without large cores (dark) are wrapped by the composite PANI (gray) coating
aggregates. This is because the ultrasonic irradiation can effec- layer. Furthermore, there is another dark line-like coating on the
tively break down the aggregation of the Fe3O4 microspheres. PANI surface, which can be indexed to be Au nanoparticles.
However, it is also noticed that some particles are lightly Figure 6c shows a representative TEM image of a single Fe3O4-
agglomerated by the coalescence of the PANI shell. To solve this @PANI@Au core/shell microspheres. It is clear that all the Au
problem, the PVP surfactant was added into the reaction system nanoparticles are homogeneously located on the Fe3O4@PANI
so that the monodisperse Fe3O4@PANI microspheres with core/ particles’ surface. No individual nanoparticles are found in the
shell nanostructure were successfully obtained (Figure 4d). solution, indicating that the adsorption of the noble metal
Under the intense dispersion and stirring effects offered by the nanoparticles takes place completely. The TEM image with
ultrasonic irradiation, Fe3O4 microspheres were well dispersed in higher resolution (Figure 6d) shows that all the Au nanoparticles
the reaction system. After the addition of an oxidant (APS), the (4 ( 1 nm) are uniform in size and well-dispersed on the surface
polymerization of aniline begins. The hydrogen bond and co- without forming large aggregates. Compare to the TEM image of
ordinative interactions between the carboxylic acid-functiona- the preprepared Au nanoparticles and the immobilized Au
lized Fe3O4 microspheres and the PANI chains favor the nanoparticles, it is obvious that the immobilization process does
absorption of PANI on the surface of Fe3O4, thereby leading to not affect the size of the Au nanoparticles (Figures S2 and S3).
the formation of the PANI-encapsulated Fe3O4 composite parti- Moreover, these hybrid composite structures are stable and not
cles. Because of the fast polymerization reaction, large amounts of disintegrated even after a sonication for 2 h.
PANI nucleates appeared and favored to aggregate together to Figure 7 shows the UV-vis absorption spectra of the as-
form large particles, which further lead to large Fe3O4@PANI prepared colloidal gold solution (a) and the gold solution after
agglomerates by coalescence of the PANI shell. With the presence immobilization on the Fe3O4@PANI microspheres after mag-
of PVP surfactant, once PANI nucleation was generated, the netic separation (b). The characteristic UV-vis absorption peak
grains might be stabilized by the PVP molecules. Therefore, large of the citrate-stabilized colloidal Au nanoparticles appears at
and irregular PANI particles often caused by the linkage of 518 nm. A dramatic decrease in the intensity at 518 nm is observed
nearby Fe3O4@PANI microspheres would be avoided. Finally, after the Au nanoparticle deposition, indicating that all of the Au
a homogeneous, continuous, and uniform PANI shell was formed
on the surface of the Fe3O4 core. In this process, various (27) (a) Feng, X. M.; Mao, C. J.; Yang, G.; Hou, W. H.; Zhu, J. J. Langmuir
thicknesses of PANI shell were obtained by varying the aniline 2006, 22, 4384–4389. (b) Gao, Y.; Chen, C. A.; Gau, H. M.; Bailey, J. A.; Akhadov, E.;
monomer concentrations (Figure 5). When the amount of Fe3O4 Williams, D.; Wang, H. L. Chem. Mater. 2008, 20, 2839–2844.
(28) Han, J.; Liu, Y.; Guo, R. Adv. Funct. Mater. 2009, 19, 1112–1117.
(29) Fang, C. L.; Qian, K.; Zhu, J.; Wang, S.; Lv, X.; Yu, S. H. Nanotechnology
(26) Suslick, K. S. Science 1990, 247, 1439–1445. 2008, 19, 125601.

Langmuir 2009, 25(19), 11835–11843 DOI: 10.1021/la901462t 11839

Article Xuan et al.

Figure 5. TEM images of the as-prepared Fe3O4@PANI core/shell nanocomposite with the PANI shell thickness of 0 (a-c), 7 (d-f), 15
(h-j), and 25 nm (k-m), which were prepared at a concentration of aniline in reaction system with 0, 1.2 10-3, 1.6 10-3, and 2.0 10-3 M,
respectively.

Figure 7. UV-vis absorption spectra of the as-prepared colloidal

Au solution (a) and the Au solution after immobilization on the
Fe3O4@PANI microspheres after magnetic separation (b). Inset
shows the photographs of the colloidal Au solution (1), reaction
solution (2), and after magnetic separation (3).

Figure 6. TEM images of the as-prepared Fe3O4@PANI@Au

nanocomposite with core/shell nanostructure with different mag-
nifications.

nanoparticles are adsorbed effectively on the PANI surface. The

absorption intensity of the Au colloid is not affected by the
magnetic separation. A fraction of the Au nanoparticles in
solution that can be deposited on PANI is up to 98%
(calculated by UV adsorption), which is further supported by
the TG analysis (Figure S4). Moreover, the color transformation
from red to colorless after the immobilization reaction also
indicates the success of effective immobilization (inset of
Figure 7). The compositions of the Fe3O4@PANI@Au compo-
sites were investigated by XRD. In comparison to the XRD
diffraction of the Fe3O4@PANI (Figure 1b), three additional Figure 8. EDX spectra of the as-prepared Fe3O4@PANI@Au
peaks at 38°, 43°, and 65°, which represent the Bragg reflections composite with core/shell structure.
from (111), (200), and (200) planes of Au, are observed, showing
clearly the existence of Au nanoparticles in the Fe3O4@PA- shows that the elemental compositions of the nanocomposites are
NI@Au composites (Figure 1c). The EDX result in Figure 8 Fe, C, O, and Au, which agrees with the XRD analysis. All the

11840 DOI: 10.1021/la901462t Langmuir 2009, 25(19), 11835–11843

Xuan et al. Article

Figure 9. XPS spectroscopy of the as-prepared Fe3O4@PA-

NI@Au core/shell composites. Inset shows the enlarged area
corresponded to the Fe element.
Figure 10. TEM images of the as-prepared Fe3O4@SiO2@Au
above results indicate that Au nanoparticles were well-immobi- with core/shell nanocomposite with different magnification (a-c)
and the high-magnification TEM image of the as-prepared
lized onto the Fe3O4@PANI microspheres to form the mono- Fe3O4@PANI@Au (d).
disperse Fe3O4@PANI@Au composites.
XPS has often been used for the surface characterization of UV/vis absorption spectroscopy with no appreciable of bypro-
various materials, and unambiguous results are readily obtained duct formation.
when various surface components contain unique elemental In agreement with previous results,30 the reduction of RhB, if it
markers. To further analyze the PANI/Au composite shell in occurs at all, is insignificant in the absence of Au nanoparticles.
the Fe3O4@PANI@Au system, XPS (Figure 9) was employed to Without the Au catalyst, the reduction of RhB does not proceed
examine the composition of the Fe3O4@PANI@Au particles’ even with large excess of NaBH4, as evidenced by an absorption
surface. It is clear that the elemental contents of the surface are C, spectrum with the major peak located at 554 nm;a characteristic
O, N, and Au. The binding energy at 710.20 eV for Fe 2p3 cannot absorption band of RhB. Additionally, when RhB solutions were
be detected, which further supports that all the Fe3O4 cores in the tested for NaBH4 reduction in the presence of Fe3O4@PANI
composite are confined within a shell of PANI/Au, in agreement composite spheres, the color of the RhB dyes remained un-
with the above TEM and XRD analyses. changed. That is, the peak at 554 nm was still observed, indicating
In this case, the PANI has served as a better support for noble that the RhB was not reduced. However, when catalytic amounts
metal nanoparticle dispersion with strong affinity and more of our Fe3O4@PANI@Au composite catalyst are introduced into
effectively in suppressing agglomeration and aggregation of Au the RhB solutions, the absorption at 554 nm decreases gradually,
nanoparticles during the immobilization process. In a parallel indicating that the reduction of RhB occurs spontaneously. This
experiment, amine-functionalized Fe3O4@SiO2 core/shell micro- evidence confirms that the Fe3O4@PANI@Au composite has a
spheres with a shell thickness of 25 nm (Figure S5) were employed good catalytic performance. Since the concentration of the
to investigate the immobilization efficiency. Figure 10 shows the Fe3O4@PANI@Au catalyst is relatively low, light scattering that
TEM images of the Fe3O4@SiO2@Au microspheres which were is caused by the carrier colloids does not interfere with the
synthesized using the previously described method with amine- absorption measurements. Figure 11 shows the UV/vis absorp-
functionalized Fe3O4@SiO2 microspheres as the catalyst support. tion spectra of the RhB dyes during their catalytic reductions with
In comparison to the Fe3O4@PANI@Au nanocomposite Fe3O4@PANI@Au. Evidently, the maximal absorption (λmax =
(Figure 6), although most of the Au nanoparticles were well 554 nm) of the dyes gradually decreases in time, indicating the
located on the core/shell particles’ surface (Figure 10a, Figure reduction of the RhB dyes. The catalytic reduction of the dyes
S6), some large aggregates of Au nanoparticles are also clearly proceeds successfully, wherein no deactivation or poisoning of the
observed (Figure 10b). Further investigations demonstrate that the catalyst is observed. The rate of the catalyzed reduction of the
Au nanoparticles which immobilized on the Fe3O4@SiO2 micro- dyes increases with increased concentrations of the magnetic
spheres are less stable (Figure 10c) than those immobilized on the composite catalyst (Figure 12).
Fe3O4@PANI microspheres (Figure 10d) under ultrasonic treat- Clearly, the as-prepared Fe3O4@PANI@Au composite cata-
ment. Thus, these results suggest that the Fe3O4@PANI micro- lyst can be efficiently recovered and recycled in the reaction
sphere serves as a better catalyst support than the Fe3O4@SiO2. mixtures by magnetic separation. As an example, when the
3.3. Catalytic Properties of the As-Prepared Fe3O4@- composite spheres are dispersed in water to give a black suspen-
PANI@Au Core/Shell Nanocomposites. Metallic gold cata- sion, upon applying an external magnetic field, the black powder
lysts usually possess high activity and selectivity.28 The is readily harvested within 5 min; thereby the solution becomes
immobilization of Au nanoparticles with magnetic support may transparent. As a recyclable catalyst, another important factor;
render them a practical recyclable nanocatalyst. By way of an the renewable catalytic activity;was also investigated by per-
example, we employ the Fe3O4@PANI@Au nanocomposites for forming the RhB reductions five times using the recycled compo-
the catalytic reduction of rhodamine B dye in the presence of site nanocatalysts. The catalytic activity of the recycled composite
NaBH4 as a model system as well as to demonstrate the recycl- nanocatalysts was tested five times with magnetic separations.
ability and repeated catalytic activities of our Fe3O4@PANI@Au
nanocomposites. One of the advantages for the reduction of (30) (a) Jiang, Z. J.; Liu, C. Y.; Sun, L. W. J. Phys. Chem. B 2005, 109, 1730–
RhB with NaBH4 is that the reaction is easily monitored by 1735. (b) Jana, N. R.; Sau, T. K.; Pal, T. J. Phys. Chem. B 1999, 103, 115–121.

Langmuir 2009, 25(19), 11835–11843 DOI: 10.1021/la901462t 11841

Article Xuan et al.

Figure 13. Conversion of RhB in five successive cycles of reduc-

Figure 11. UV-vis absorption spectra of RhB during the reduc- tion and magnetic separation with two types of catalysts: Fe3O4@-
tion catalyzed by Fe3O4@PANI@Au composite microspheres. PANI@Au and Fe3O4@SiO2@Au. [RhB] = 2.5 10-5 mol/L,
[RhB] = 2.5 10-5 mol/L, [NaBH4] = 1 10-2 mol/L, [Au]0 = [NaBH4] = 1 10-2 mol/L, [Au]0 = 6.25 10-5 mol/L.
2.5 10-5 mol/L. The arrows mark the increase of reaction time,
showing the gradual reduction of RhB with Fe3O4@PANI@Au
catalyst.

Figure 14. M-H curve of the Fe3O4@PANI@Au composite at

room temperature.
Figure 12. Plot of conversion (C, %) of RhB versus time (t, min) at
different concentrations of Au nanocatalysts: (a) [Au]0 = 2.5 nanocatalyst exhibited much higher stability in various chemical
10-5 mol/L, (b) [Au]0 = 3.13 10-5 mol/L, (c) [Au]0 = 3.75 and physical environments.
10-5 mol/L, (d) [Au]0 = 6.25 10-5 mol/L. [RhB] = 2.5 It has been experimentally demonstrated that metal nanopar-
10-5 mol/L and [NaBH4] = 1 10-2 mol/L keep constant. ticles have high catalytic activities for hydrogenation, hydrofor-
UV/vis absorption spectroscopy was employed to monitor the mylation, carbonylation, and so forth. In our system, with the
changes in absorbance at 554 nm. Figure 13 shows the conversion Au nanocatalyst, the RhB was reduced to give its leuco form
for each run which was measured by UV/vis spectroscopy. For (Figure S8).32 The Au nanoparticles which are supported on
Fe3O4@PANI@Au, the reduction of RhB drops slightly after Fe3O4@PANI microspheres serve as an electron relay in the
each cycle (Figure 13a), and it decreased gradually in subsequent system for an oxidant and a reductant, and electron transfer
runs to 89% at run 5. TEM micrographs (Figure S7) revealed occurs via the supported Au nanoparticles.30 In the reaction, the
many large Au nanoparticles exist in the Fe3O4@PANI@Au nucleophile NaBH4 can donate electrons to Au nanoparticles,
catalysts after 5 runs. This could have led to the reduced catalytic and the electrophile RhB dyes would capture electrons from Au
activity after multiple recycling processes. However, the reduction nanoparticles. Therefore, in such reaction, the rate of catalytic
ratio drops rapidly in the following reaction cycles when the reaction should be determined by the concentration of the
Fe3O4@SiO2@Au nanocomposite (Figure 13b) was employed as catalyst.
the catalyst (only keep 40% conversion). The catalytic results The magnetic properties of the composite nanocatalysts have
reveal that the as-synthesized Fe3O4@PANI@Au nanocatalyst been investigated using a VSM. Figure 14 shows a hysteresis loop
show higher catalytic performance than the Fe3O4@SiO2@Au, of typical Fe3O4@PANI@Au nanocomposites measured by
which may be partly caused by the effective contact between sweeping the external field between -1 and 1 T at room
PANI and Au nanocatalysts. Moreover, in this catalytic reaction, temperature. The magnetization curve shows no remanence or
the relatively high concentration of NaBH4 slowly etches the silica coercivity at room temperature, suggesting the superparamag-
surfaces, which lead to the gradual detachment of Au nanopar- netic character. Superparamagnetism is the responsiveness to an
ticles from the support surface and dramatically reduced their applied magnetic field without retaining any magnetism after
catalytic activity.31 Therefore, compared to the Fe3O4- removal of the applied magnetic field. With the superparamag-
@SiO2@Au catalyst that has been studied, Fe3O4@PANI@Au netic property, capillary blockage by aggregations formed by

(32) (a) Kr€uger, U.; Memming, R. Ber. Bunsen-Ges. Phys. Chem. 1974, 78, 670–
(31) Ge, J. P.; Zhang, Q.; Zhang, T. R.; Yin, Y. D. Angew. Chem., Int. Ed. 2008, 678. (b) Li, Y. X.; Lu, G. X.; Li, S. B. J. Photochem. Photobiol. A: Chem. 2002, 152,
47, 8924–8928. 215–228.

11842 DOI: 10.1021/la901462t Langmuir 2009, 25(19), 11835–11843

Xuan et al. Article

residual magnetism after removal of the applied field will be to form the Fe3O4@PANI@Au composite microspheres. These
avoided. The saturated mass magnetization is estimated to be Au-immobilized nanocomposites exhibit excellent catalytic prop-
29.7 emu/g. Therefore, the as-prepared Fe3O4@PANI@Au erties as the demonstration on the reduction of RhB with NaBH4
nanocatalyst can be easily separated from the reaction solution in comparison to the Fe3O4@SiO2@Au nanocatalyst. Most
by applying a relatively low magnetic field gradient, which importantly, these results offer a powerful platform to construct
renders the catalyst cost-effective and promising for various other multicomponent composite spheres, which are likely found
applications. many potential catalytic and biomedical applications derived
from their rational combination of magnetic properties with
4. Conclusions surface plasmon resonance, luminescence, or catalysis.
In summary, we have demonstrated a simple, reproducible, and
facile method of preparing core/shell Fe3O4@PANI@Au nano- Acknowledgment. The authors acknowledge the support from
composites. On the basis of the carboxyl-functionalized Fe3O4 a Strategic Investments Scheme and Direct Grant of Research
microspheres, PANI shell with various thicknesses from 7 to 15 (2060336 and 2041339) administrated by The Chinese University
and 25 nm can be directly coated on the cores to form the of Hong Kong as well as The Research Grants Council of
monodisperse Fe3O4@PANI microspheres with well-defined Hong Kong (CUHK401709).
core/shell nanostructure. By means of the electrostatic interac-
tions between positively charged PANI coating and citrate-stabi- Supporting Information Available: Experimental details,
lized Au nanoparticles, plentiful Au nanoparticles with ∼4 nm in TEM, TGA and EDX data. This material is available free
size are well assembled onto the surface of Fe3O4@PANI carriers of charge via the Internet at http://pubs.acs.org.

Langmuir 2009, 25(19), 11835–11843 DOI: 10.1021/la901462t 11843