Journal of Colloid and Interface Science 356 (2011) 107110

Contents lists available at ScienceDirect

Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Photoluminescent Fe3O4/carbon nanocomposite with magnetic property

Xiaodie He a, Yang Liu a,b,, Haitao Li a, Hui Huang a,b, Jinglin Liu b, Zhenhui Kang a,b,, Shuit-Tong Lee a,c
a

Institute of Functional Nano & Soft Materials, Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou, Jiangsu 215123, China
Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China
c
Center of Super-Diamond and Advanced Films (COSADF), City University of Hong Kong, Hong Kong SAR, China
b

a r t i c l e

i n f o

Article history:
Received 3 November 2010
Accepted 24 December 2010
Available online 1 January 2011
Keywords:
Composites
Magnetic materials
Luminescence
Magnetic properties

a b s t r a c t
Fe3O4/carbon nanocomposite has been prepared by a facile chemical method, and characterized by X-ray
diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, fourier transform infrared spectroscopy and scanning electron microscopy. The uorescent and magnetic properties of the sample were investigated by uorescence spectroscopy and vibrating-sample magnetometer, respectively.
The results indicate that the Fe3O4/carbon nanocomposite exhibit good photoluminescent (emission
ranging from 425 to 550 nm) and strong magnetic (saturation magnetization of 44.2 emu/g) properties.
2011 Elsevier Inc. All rights reserved.

1. Introduction
Magnetic and photoluminescent nanoparticles are of particular
importance due to their widely potential applications in current
science and technology [14]. It is expected that the combination
of magnetic and uorescent properties in one nanocomposite will
greatly enhance its versatile properties and open up potential
applications in biological imaging, cell tracking, magnetic bioseparation, information technology and environmental science [57].
To date, many magnetic-uorescent nanocomposites have been reported, including silica-based, dye functionalized magnetic nanoparticles and quantum dots (QDs) based magnetic nanoparticle
composites [8]. However, the introduction of traditional QDs
(CdS etc.) would lead to the health and enviroment concerns;
dye molecules are likely to be bleached due to their low photochemical stability. On the other hand, the synthetic approaches
to their preparation also suffer from the complicated multi-step
process and quenching of uorescent entity by the magnetic core
[8]. Therefore, the design and synthesis of environmental and biological benign nanomaterials with magnetic-uorescent properties
are still an urgent challenge.
Due to their biocompatibility, excellent conductivity and facile
surface functionalization, the uorescent carbon nanoparticles
offer great potential applications in biomedical imaging and photocatalysis [9,25]. The emergence of uorescent carbon nanoparticles
make the biological benign magnetic-uorescent nanomaterials
Corresponding authors. Address: Institute of Functional Nano & Soft Materials,
Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow
University, Suzhou, Jiangsu 215123, China. Fax: +86 512 6588 2846.
E-mail addresses: yangl@suda.edu.cn (Y. Liu), zhkang@suda.edu.cn (Z. Kang).
0021-9797/$ - see front matter 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2010.12.075

being a reality: magnetic Fe3O4 and uorescent carbon nanoparticle in one entity will endow the nanocomposite both strong magnetic and stable uorescent properties.
Carbon is an ideal candidate for outside coating material owing
to its ease of functionalization, its reduction of the magnetic coupling between individual magnetic metal particles and stability
in acid or alkali, which may protect the encapsulated materials
from environmental degradation [10]. Moreover, the carbon material in the composite can improve the electronic conductivity and
the surface area of Fe3O4 nanoparticles [11]. It is reported that
the magnetic carbon microspheres (Fe3O4@C) have been synthesized by the hydrothermal reaction of Fe3O4 microspheres and glucose in water [12]. However, these microspheres lack uorescent
properties. Here, we report a facile chemical method for synthesizing magnetic-uorescent Fe3O4/carbon nanocomposite. The fabrication details, characterization, feasibility and performance of the
Fe3O4/carbon nanocomposite are described in the following
sections.
2. Materials and methods
2.1. Materials
Glucose, FeCl3 and FeSO4
7H2O, ethanol (analytical purity, Beijing Chemical Reagent Factory). They were used as received. All
the aqueous solutions were prepared using de-ionized water.
2.2. Methods
Synthesis of carbon nanoparticles: Glucose was rst dissolved
in water (100 mL) to form a clear solution. Then, the solution

108

X. He et al. / Journal of Colloid and Interface Science 356 (2011) 107110

was placed in a 20 mL Teon-sealed autoclave and maintained at

180 C for 4 h. After that, the obtained reddish-brown solution
was centrifuged and washed three times with double-distilled
water and alcohol, and nally dried in a vacuum oven at 70 C to
remove the residual solvent.
Synthesis of Fe3O4/carbon nanocomposite: The newly prepared
carbon nanoparticles were dispersed in water with the aid of ultrasonication to give a 20 wt.% carbon suspension. FeCl3 (1.62 g) and
FeSO4
7H2O (5.56 g) were dissolved in carbon suspension under
N2 protection and vigorous stirring for 3 h. After that, 45 mL of
1 mol/L NaOH was added dropwise into the resulting solution,
and the mixture was vigorously stirred for 2 h. The suspension
was then isolated by ltration, and cleaned by three cycles of centrifugation/washing/redispersion in water and alcohol. Finally, the
as-prepared product was isolated from the mixture by external
magnetic eld.
The morphology, structure and composition of Fe3O4/carbon
nanocomposite were further investigated by X-ray diffraction
(XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), FTIR spectroscopy, and scanning electron
microscopy (SEM).
3. Results and discussion
Recently, with glucose as precursor, a microwave pyrolysis approach to synthesize FCNPs has been reported [13]. In this communication, we report a general and facile method for the synthesis of
magnetic-uorescent Fe3O4/carbon nanocomposite. The synthesis
was done via sequential two-step reaction as follows (see Scheme
1): the rst step is the hydrothermal treatment of glucose at 180 C
to obtain the uorescent carbon nanoparticles (FCNPs); the followed one is the formation of Fe3O4 nanoparticles in as-prepared
carbon nanoparticles (absorbtion of Fe2+/Fe3+ in carbon nanoparticles and then alkaline treatment) to obtain Fe3O4/carbon nanocomposite. In our experiment, the FCNPs (300 nm) prepared in the
rst step show strong photoluminescence (PL) with different excitation wavelengths, and the PL spectra are shown in Fig. S1 (see
EIS). The nal Fe3O4/carbon nanocomposite possesses both magnetic and uorescent properties, coming from the Fe3O4 nanoparticles and carbon materials, respectively.
Typical XRD patterns of the as-prepared Fe3O4/carbon nanocomposite (red line) and Fe3O4 (black line) samples are presented
in Fig. 1a. For the XRD pattern of Fe3O4/carbon nanocomposite,
the diffraction peaks at 30.1 (200), 35.4 (311), 43.0 (400), 53.7
(422), 57.2 (511) and 62.6 (440) are consistent with the standard
X-ray data of the Fe3O4 magnetite phase (JCPDS no.19-0629). The
broad peak near 20 with a relatively low intensity is attributed
to amorphous carbon [14]. Fig. 1b shows the XPS pattern of
Fe3O4/carbon nanocomposite. The appearance of the characteristic
peaks of Fe2p (711.1 eV) and O1s is typical for iron oxide, while the
peaks ascribe to C1s at expected positions further indicate the existence of carbon. The peak at 148 eV is attributed to Si2s, coming
from the substrate (silicon wafer). As known, XPS mainly reveals
the information of the surface with a depth of 0.110 nm [15]. In
our experiment, only a weak peak of corresponding Fe2p was detected by XPS characterization, which may be due to the embedding of Fe3O4 nanoparticles in FCNPs.

Scheme 1. Fabrication of Fe3O4/carbon nanocomposite via two-step chemical

reaction process.

The morphology and structure of the as-prepared Fe3O4/carbon

nanocomposite were investigated by TEM and SEM. SEM image of
Fe3O4/carbon nanocomposite is shown in Fig. S2, from which we
can see that all the particles present a spherical shape, and the
diameter of the nanocomposite is about 300 nm (see EIS). The inset
photograph shows the TEM image of the as-prepared Fe3O4/carbon
nanocomposite. Obviously, the spherical Fe3O4 nanoparticles with
diameter about 510 nm have been embedded in FCNPs, which is
consistent with the result of XPS.
The UVvis absorption and PL spectra of the as-prepared Fe3O4/
carbon nanocomposite are shown in Fig. 2. The absorption spectrum (1blue line) exhibits a full absorption band in the visible range
of 400700 nm, which corresponds to the absorption of Fe3O4
nanoparticles [16]. The absorption band ranging from 300 to
400 nm is comparable to those previously reported for the carbon
dots [17]. The peak at 250300 nm represents the typical absorption of an aromatic pi system, which is similar to that of polycyclic
aromatic hydrocarbons [18]. The extended conjugation in the
structure of carbon leads to the red shift of the pp transition
[19]. This result further indicates that the as-prepared nanocomposite is a composite of carbon and Fe3O4. As shown in Fig. 2, the
PL spectra of Fe3O4/carbon nanocomposite are broad and dependent on excitation wavelengths (the emission peak ranges from
425 to 550 nm). Comparing the PL spectra of Fe3O4/carbon nanocomposite with that of FCNPs (Fig. S1), the Fe3O4/carbon and FCNPs
have similar PL properties. It should be noted that the PL of the
Fe3O4/carbon composite should come from the carbon nanoparticles or the interface between Fe3O4 nanoparticles and carbon, because the Fe3O4 nanoparticles are not photoluminescent. Further
control experiments show that the expected PL spectra (Fig. S3,
see EIS) can still be observed after the Fe3O4/carbon nanocomposite samples were treated by the HCl solution (to remove the Fe3O4
nanoparticles). Therefore, we can conclude that the PL properties
of the as-prepared Fe3O4/carbon nanocomposite are attributed to
the presence of FCNPs. The structure of carbon nanoparticles was
characterized by TEM and HRTEM (Fig. S5). As shown, there is no
discernible lattice structures on the HRTEM image, indicating that
the resultant carbon nanoparticles are amorphous. Thus, the observed luminescence emission may be due to the presence of surface functional groups and surface energy traps that become
emissive upon stabilization as a result of the surface passivation,
for which a widely accepted mechanism for luminescence emission is the radiative recombination of excitations [9,17].
To study the magnetic properties, the magnetization curves of
the as-prepared Fe3O4/carbon nanocomposite were measured at
room temperature by a vibrating-sample magnetometer. It can
be seen from Fig. 3 that the saturation magnetization of the as-prepared Fe3O4/carbon nanocomposite is 44.2 emu/g. The decrease of
the saturation magnetization of the as-prepared nanocomposite
compared to the bulk magnetite (84 emu/g) [20] would be attributed to the existence of the carbon. The hysteresis loop at room
temperature gives a negligible coercivity, indicating the superparamagnetic behavior. With increasing the applied eld from 0 to
8000 Oe, the magnetization increases sharply, and the magnetization is nearly saturated at about 2000 Oe. Further experiments
show that the as-prepared Fe3O4/carbon nanocomposite is effective in magnetic separation. As shown in the inset photographs
in Fig. 3, a color change from black to transparent was observed
when an external magnetic eld was applied for 510 min. After
removal of the magnet, the Fe3O4/carbon nanocomposite can be
easily redispersed in water with slight hand shaking.

1
For interpretation of color in Fig. 2, the reader is referred to the web version of
this article.

X. He et al. / Journal of Colloid and Interface Science 356 (2011) 107110

109

Fig. 1. (a) XRD patterns of Fe3O4/carbon nanocomposite (red line) and Fe3O4 (black line); (b) full XPS pattern of the as-prepared Fe3O4/carbon nanocomposite (silicon wafer as
substrate). The inset image is the corresponding XPS pattern of Fe2p. (For interpretation of the references to colour in this gure legend, the reader is referred to the web
version of this article.)

Fig. 2. UVvis absorption and PL spectra (with different excitation: 300, 350, and
400 nm) of the as-prepared Fe3O4/carbon nanocomposite.

groups. The FeO vibration is detected at around 570 cm 1, which

is consistent with the previously reported results [21]. Based on
the above results, it is can be concluded that the presence of carbon
not only provides PL active center but also enhances their dispersibility and prevents the nanocomposites from aggregating in water.
We can expect that a better carbon sources (i.e. fructose, sucrose or starch), other additives (i.e. acid, alkali or different ionic
liquids) or more suitable reaction conditions (i.e. ultrasonic power,
reaction temperature, microwave reaction) may further optimize
the present reaction process and improve the photoluminescent/
magnetic properties of the Fe3O4/carbon nanocomposite. Notably,
this kind of Fe3O4/carbon nanocomposite will bring a new way
for hosting many other applications including separating materials,
drug delivery systems, bio-imaging and data storage etc. The existence of carbon also make them suitable for further functionalization by the attachment of another species (metal, oxide, organic,
polymeric, etc.) to construct multi-functional novel hybrids with
excellent catalytic, magnetic, conductive, optical and electronical
properties [2225].
4. Conclusions
In summary, the Fe3O4/carbon nanocomposite (300 nm) has
been prepared by a two-step chemical route. The as-prepared
Fe3O4/carbon nanocomposite exhibits both magnetic (44.2 emu/g
of saturation magnetization) and uorescent (emission peak ranging from 425 to 550 nm) properties, coming from the Fe3O4 nanoparticles and carbon materials, respectively. The Fe3O4/carbon
nanocomposite combining both magnetic and uorescent properties in one entity is expected to hold promise in potential biomedical uses, including biological imaging, cell tracking, magnetic
bioseparation, bio- and chemo-sensoring.
Acknowledgments

Fig. 3. Magnetization curves of the Fe3O4/carbon nanocomposite. The inset

photograph: (a) the aqueous solution of the Fe3O4/carbon nanocomposite; (b) the
separation of the Fe3O4/carbon nanocomposite with external magnetic eld.

The FTIR spectrum (Fig. S4, see EIS) was used to identify the
functional groups of the Fe3O4/carbon nanocomposite. The broad
characteristic band from 3600 to 3100 cm 1 should be assigned
to OH stretching vibration arising from hydroxyl groups on nanoparticles [9]. The two peaks around 1700 and 1615 cm 1 are attributed to the stretching vibration mode of C@O, COOH group and
aromatic ring structures, respectively [9]. The peaks in the range
of 10001300 cm 1 including the COH stretching and OH bending vibrations [9], imply the existence of large numbers of hydroxyl

This work was supported by the National Basic Research

Program (973 Program) (No. 2010CB934500), the National Natural
Science Foundation of China (Nos. 20801010, 20803008, 21073127,
21071104), A Foundation for the Author of National Excellent Doctoral Dissertation of PR China (FANEDD) (No. 200929), and
Research Grants Council of Hong Kong SAR (Grant No. CityU5/
CRF/08).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jcis.2010.12.075.

110

X. He et al. / Journal of Colloid and Interface Science 356 (2011) 107110

References
[1] S.Y. Lian, Z.H. Kang, E.B. Wang, M. Jang, Ch.W. Hu, L. Xu, Solid State Commun.
127 (2003) 605608.
[2] S.Y. Lian, E.B. Wang, Z.H. Kang, Y.P. Bai, L. Gao, M. Jiang, C.W. Hu, L. Xu, Solid
State Commun. 129 (2004) 485490.
[3] Z.H. Kang, Y. Liu, C.H.A. Tsang, D.D.D. Ma, X. Fan, N.B. Wong, S.T. Lee, Adv.
Mater. 21 (2009) 661664.
[4] T. Hyeon, Chem. Commun. (2003) 927934.
[5] F. Bertorelle, C. Wilhelm, J. Roger, F. Gazeau, C. Menager, V. Cabuil, Langmuir 22
(2006) 53855391.
[6] A.G.J. Tibber, B.G. deGrooth, J. Greve, P.A. Liberti, G.J. Dolan, L.W.M.M.
Terstappen, Nat. Biotechnol. 17 (1999) 12101215.
[7] T.J. Yoon, J.S. Kim, B.G. Kim, K.N. Yu, M.H. Cho, J.K. Lee, Angew. Chem., Int. Ed.
44 (2005) 10681071.
[8] S.A. Corr, Y.P. Rakovich, Y. Gunko, Nanoscal. Res. Lett. 3 (2008) 87104.
[9] X.M. Sun, Y.D. Li, Angew. Chem., Int. Ed. 43 (2004) 597601;
L. Cao, X. Wang, M.J. Meziani, F. Lu, H. Wang, P.G. Luo, Y. Lin, B.A. Harruff, L.M.
Veca, D. Murray, S.-Y. Xie, Y.-P. Sun, J. Am. Chem. Soc. 129 (2007) 11318
11319;
R.L. Liu, D.Q. Wu, S.H. Liu, Q. Li, K. Koynov, W. Knoll, Angew. Chem., Int. Ed. 48
(2009) 45984601;
B.R. Selvi, D. Jagadeesan, B.S. Suma, G. Nagashankar, M. Arif, K.
Balasubramanyam, M. Eswaramoorthy, T.K. Kundu, Nano Lett. 8 (2008)
31823188.
[10] G.X. Zhu, X.W. Wei, S. Jiang, J. Mater. Chem. 17 (2007) 23012306.

[11] C.L. Bian, Q.X. Zeng, H.Y. Xiong, X.H. Zhang, S.F. Wang, Bioelectrochemistry, in
press.
[12] Z.F. Wang, H.S. Guo, Y.L. Yu, N.Y. He, J. Magn. Magn. Mater. 302 (2006) 397
404.
[13] H. Zhu, X.L. Wang, Y.L. Li, Z.J. Wang, F. Yang, X.R. Yang, Chem. Commun. (2009)
51185120.
[14] L.B. Luo, S.H. Yu, H.S. Qian, J.Y. Gong, Chem. Commun. (2006) 793795.
[15] J.F. Moulder, W.F. Stickle, P.E. Sobol, Handbook of X-ray Photoelectron
Spectroscopy, Perkin-Elmer Corporation, Eden Prairie, MN, 1992.
[16] R.D. Waldron, Phys. Rev. 99 (1955) 17271735.
[17] Y.P. Sun, B. Zhou, Y. Lin, W. Wang, K.A.S. Fernando, P. Pathak, M.J. Meziani, B.A.
Harruff, X. Wang, H.F. Wang, P.J.G. Luo, H. Yang, M.E. Kose, B.L. Chen, L.M. Veca,
S.Y. Xie, J. Am. Chem. Soc. 128 (2006) 77567757.
[18] S.Y. Xie, R.B. Huang, L.S. Zheng, J. Chromatogr., A 864 (1999) 173177.
[19] Y. Liu, Y. Chu, L.K. Yang, Mater. Chem. Phys. 98 (2006) 304308.
[20] S. Ahmad, U. Riaz, A. Kaushik, J. Alam, J. Inorg. Organomet. Polym. 19 (2009)
355360.
[21] X. Liang, X. Wang, J. Zhuang, Y.T. Chen, D.S. Wang, Y.D. Li, Adv. Funct. Mater. 16
(2006) 18051813.
[22] D.B. Mawhinney, V. Naumenko, A. Kuznetsova, J.T. Yates, J. Liu, R.E. Smalley, J.
Am. Chem. Soc. 122 (2000) 23832384.
[23] Z.H. Kang, E.B. Wang, L. Gao, S.Y. Lian, M. Jiang, C.W. Hu, L. Xu, J. Am. Chem.
Soc. 125 (2003) 1365213653.
[24] Z.H. Kang, E.B. Wang, B.D. Mao, Z.M. Su, L. Gao, L. Niu, H.Y. Shan, L. Xu, Appl.
Catal., A 299 (2006) 212217.
[25] H.T. Li, X.D. He, Z.H. Kang, H. Huang, Y. Liu, J.L. Liu, S.Y. Lian, C.H.A. Tsang, X.B.
Yang, S.T. Lee, Angew. Chem., Int. Ed. 49 (2010) 44304434.