Sensors and Actuators B 221 (2015) 1084–1093

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Graphene oxide wrapped Fe3 O4 @Au nanohybrid as SERS substrate

for aromatic dye detection
Guihong Ding a , Shi Xie a , Yongmei Zhu b , Ying Liu a , Li Wang a,∗ , Fugang Xu a,∗
a
College of Chemistry and Chemical Engineering, Jiangxi Normal University, People’s Republic of China
b
Analytical and Testing Center of Jiangxi Normal University, Nanchang 330022, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: An active surface-enhanced Raman scattering (SERS) substrate composed of graphene oxide (GO)
Received 18 February 2015 wrapped gold nanoparticles (AuNPs) decorated-magnetic sphere Fe3 O4 (GO wrapped Fe3 O4 @Au hybrid)
Received in revised form 11 July 2015 was prepared and used for aromatic dye detection. The hybrid was characterized by SEM, EDX, XRD,
Accepted 17 July 2015
UV–visible spectroscopy and Raman spectroscopy. This hybrid showed high activity for SERS detec-
Available online 21 July 2015
tion of aromatic dye due to the synergistic interaction among GO nanosheet, AuNPs and Fe3 O4 sphere.
The dosages of AuNPs and GO were optimized to achieve a high sensitivity. The unique GO wrapped
Keywords:
Fe3 O4 @Au hybrid has several advantages (such as high adsorption to target dye molecules, low noise
Surface enhanced Raman scattering
Graphene oxide
response and high SERS enhancement ability) as SERS substrate over previously reported Fe3 O4 and
Aromatic dye molecule AuNPs co-decorated GO sheet. Finally, the hybrid was successfully used for SERS detection of aromatic
Enhancement substrate dye pollutant malachite green (MG) and nile blue A (NBA) even at concentration down to 1 nM and
Malachite green 0.1 nM, respectively. Potential of this substrate for multiplex detection of dye mixture (MG and NBA),
and practical detection of MG in real sample were also evaluated. Our results suggested that the hybrid
of GO wrapped Fe3 O4 @Au can be used as an efficient SERS platform for aromatic dye detection.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction [7–9]. Although these modifications enhance the capture ability

Surface-enhanced Raman scattering (SERS), as a non-
destructive, ultrasensitive and powerful analytical technique,
has exhibited attractive applications in environmental monitoring,
chemical and biological sensing, and biomedical imaging [1]. These
unique properties and applications of SERS are closely related to
highly active enhancement substrates. Traditionally, silver (Ag) or
gold (Au) nanomaterials with various size, shape, and assembled
structures have been proved to be active SERS substrates [2]. How-
ever, single component Au or Ag nanostructure is not enough for
sensitive detection sometimes [3], and modification or integration
of Au or Ag with other materials is needed. For example, aromatic
dyes are a large group of environmental pollutants, and SERS has
been proved to be a powerful and practical tool for their detection
[4–6]. However, many aromatic pollutants show poor affinity to
the enhancement substrate. One widely used approach to achieve
the sensitive detection of aromatic pollutants by SERS is to modify
the Au or Ag enhancement substrate with functional molecules,
such as calixarenes, viologen dication and cyclodextrin derivatives
∗ Corresponding authors. Tel.: +86 791 88120861; fax: +86 791 88120861.
E-mail addresses: lwang@jxnu.edu.cn (L. Wang), fgxu@jxnu.edu.cn (F. Xu).
of these substrates to aromatic molecules, the preparation of the
functional molecules and the modified substrates is complex and
high-cost due to the involvement of complicated organic synthesis
(e.g., calixarenes) or expensive reagents (e.g., viologen dication).
Moreover, it is tedious to perform centrifugation, which aims to
concentrate the Au or Ag nanoparticles and thus achieve high
sensitivity. Therefore, it is highly desirable to develop a facile,
economic, and wieldy SERS substrate for the detection of aromatic
dye pollutant.
Recently, graphene and graphene derived materials, such as
graphene oxide (GO) and reduced graphene oxide (RGO), have
been shown to be promising SERS substrates due to their abil-
ity to generate strong chemical enhancement [10–13]. In addition,
graphene can reduce the “SERS background” or quench molecule
fluorescence to improve the Raman signal-to-noise ratio [14,15].
Furthermore, the large surface area and interconnected sp2 net-
work of graphene or GO give it the ability to undergo ␲–␲
stacking with aromatic molecules, thus greatly enhance its absorp-
tion ability to aromatic dyes [16,17]. Compared with graphene,
GO can be produced in a high yield, low cost and more available
way, and thus provides a better chance for practical applications.
Moreover, GO possesses sufficient active oxygen sites and highly
negative surface charge, which can notably enhance its electrostatic

http://dx.doi.org/10.1016/j.snb.2015.07.074
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 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093
absorption to positive aromatic dyes [18,19]. Due to these advan-
tages of graphene or GO, it was found graphene–metal hybrid
exhibits higher SERS enhancement effect compared to the individ-
ual component [18,20–24]. For most graphene–metal composite,
metal nanoparticles are decorated on both sides of GO or graphene
sheet, forming a metal–GO–metal sandwiched structure, which
may produce large background from GO [20–24], leading to low
signal to noise ratio. This is not good for sensitive SERS detection.
Besides, many papers reported two-component graphene–metal as
SERS substrate, but few involve ternary component hybrid for SERS
analysis, which may bring additional advantages, such as higher
sensitivity, easy separation and concentration effect.
Magnetic nanoparticles such as Fe3 O4 have been successfully
applied to various applications, such as separation of biomolecules,
magnetic field assisted transport, medical imaging via magnetic
field control, and heterogeneous catalysis [25]. In analytical sci-
ence, magnetic particle-incorporated SERS substrates have been
widely used for selective enriching target molecules and separat-
ing substrate from matrix, which greatly improve the detection
limit, simplify the detection procedure, and facilitate the cycle use
of the substrate [26]. The examples and recent advances about
Fe3 O4 based SERS substrate can be found in a recent published
review by Yang [27]. Very recently, Chen reported a Fe3 O4 and
AuNPs co-decorated GO sheet as substrate for in situ SERS detec-
tion and catalytic reduction of 4-nitrophenol (4-NP) [28]. However,
as a SERS substrate, the Fe3 O4 and Au co-decorated GO brings large
background noise from GO and low signal to noise ratio as those
previous reports [20–24]. Besides, the separation of the composite
needs a long time magnetic force attraction. Thus a different struc-
ture should be developed to achieve sensitive detection of target
molecules with facile magnetic separation.
In this study, a new ternary nanohybrid composed of Fe3 O4
magnetic sphere, gold nanoparticles (AuNPs) and GO nanosheet
assembled in a unique GO wrapped gold nanoparticle-decorated
Fe3 O4 (Fe3 O4 @Au) structure was prepared and its potential as an
active SERS substrate for aromatic dye detection was investigated
(Scheme 1). Fe3 O4 @Au was first prepared by loading AuNPs onto
silanized Fe3 O4 spheres, and then it was wrapped by GO sheet. Mag-
netic Fe3 O4 facilitates the concentration of target molecules and
quickly separation of the hybrid substrate from sample solution
within one minute. AuNPs are employed to produce enormous elec-
tromagnetic enhancement, and GO could promote the absorption
ability of the hybrid to aromatic molecules and provide additional
charge transfer enhancement. The agents used for preparation of
GO and Fe3 O4 are very cheap, and no complex organic synthesis or
expensive functional molecules are needed. Considering the eco-
nomic preparation, easy separation and high SERS activity, it is
believed that the ternary hybrid GO wrapped Fe3 O4 @Au should
have great promise in SERS monitoring of aromatic dye pollutants
through carefully tailing its component to achieve a synergistic
effect.
2. Experimental
2.1. Reagents
Ferric chloride (FeCl3 ·6H2 O), chloroauric acid tetrahydrate
(HAuCl4 ·4H2 O), sodium citrate, ethylene glycol (EG, 98%),
unhydrous sodium acetate (NaAc), polyethylene glycol (PEG,
MW.10000), and 3-aminopropyltriethoxysilane (APTES, 97%) were
purchased from Shanghai Sinopharm Chemical Reagent Co. Ltd.
(Shanghai, China). Graphite (325 mesh) was purchased from Alfa
Aesar. Raman probe and target analytes including crystal violet
(CV), malachite green (MG), and nile blue A (NBA) were purchased
from aladdin reagent company (Shanghai, China). All reagents are
1085
of analytical grade and used without further purification. All solu-
tions are prepared with deionized water purified by a Millipore-Q
System (18.2 M cm), except that with special notification.
2.2. Apparatus
Scanning electron microscopy (SEM) images were captured
using an S-3400 scanning electron microscope equipped with
an energy-dispersive X-ray (EDX) analyzer (Hitachi, Japan). The
absorption spectra were measured using a U-3900H UV-vis spec-
trophotometer (Hitachi, Japan). Powder X-ray diffraction (XRD)
patterns were collected on a D8 advance (Bruker, Germany) diffrac-
tion meter using Cu K␣ radiation at  = 0.154 nm operating at 40 kV
and 40 mA with step size 4◦ /min. Zeta potentials of various mate-
rials were measured with a Zetasizer Nano ZS (Malvern, Britain)
using an He–Ne laser at a wavelength of 632.8 nm. Raman spec-
tra were acquired on a LABRAM-HR Raman system with a 633 nm
He–Ne laser (Horiba, Jobin-Yvon, France).
2.3. Materials preparation
2.3.1. Preparation of Fe3 O4 and amine-functionalized Fe3 O4
Magnetic Fe3 O4 spheres were prepared according to Li’s method
with some modification [29]. In a typical experiment, FeCl3 ·6H2 O
(0.90 g) was dissolved in EG (14 mL) to form a clear solution, fol-
lowed by the addition of NaAc (1.2 g) and PEG (0.1 g). The mixture
was stirred vigorously for 30 min and then sealed in a Teflon-
lined stainless-steel autoclave (25 mL capacity). The autoclave was
heated to and maintained at 200 ◦ C for 8 h and allowed to cool to
room temperature. The black product was washed several times
with ethanol and dried at 60 ◦ C in an electric oven.
The Fe3 O4 (174 ± 15 nm) was grafted with amine group through
its reaction with APTES. Magnetic spheres (30 mg Fe3 O4 ) was mixed
with silane reagent (1 mL APTES, 97%) in 20 mL anhydrous ethanol.
This mixture was sonicated for 5 min and then reacted for 6 h under
mechanical stirring at room temperature (∼25 ◦ C). The product was
magnetically seperated and redispersed in 15 mL water to produce
2 mg/mL silanized Fe3 O4 suspension.
2.3.2. Preparation of AuNPs and Fe3 O4 @Au composites
Gold nanoparticles (AuNPs) were synthesized by reduction of
HAuCl4 with sodium citrate [30]. Briefly, 50 mL of 1 mM HAuCl4 was
heated to boiling and reacted with 5 mL of 38.8 mM sodium citrate
under refluxing with vigorous stirring. After 10 min, the heating
mantle was removed, and stirring was continued for an additional
15 min. The final volume of AuNPs suspension was tuned to 50 mL.
Thus prepared AuNPs show an absorption maximum at 520 nm
with a particle size of 13 ± 3 nm.
To decorate Fe3 O4 with AuNPs, 1 mL silanized Fe3 O4 (2 mg/mL)
was mixed with certain amount (2–10 mL) of as-prepared AuNPs
(∼0.2 mg/mL Au), and water was added to tune the total volume
to 12 mL. The mixture was mechanically stirred for 3 h to adsorb
AuNPs onto Fe3 O4 . The product Fe3 O4 @Au was magnetically sepa-
rated and redispersed in 1 mL water.
2.3.3. Preparation of GO and GO wrapped Fe3 O4 @Au hybrid
The GO nanosheet was prepared according to a modified Hum-
mers’ method. Details of the preparation can be found in our
previous work [31]. For the preparation of GO wrapped Fe3 O4 @Au
hybrid, 1 mL of the above prepared Fe3 O4 @Au composite was mixed
with different volumes (0.25–2 mL) of 0.5 mg/mL GO, and then
water was added to tune the total volume to 12 mL. This mixture
was reacted for 6 h under mechanical stirring, and finally sepa-
rated and redispersed in 1 mL water. Except special instruction,
GO wrapped Fe3 O4 @Au hybrid prepared from Fe3 O4 1 mL 2 mg/mL,
1086 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093
Scheme 1. The main procedure for preparation of GO wrapped Fe3 O4 @Au hybrid and its application for SERS detection of dyes.
AuNPs 4 mL 0.2 mg/mL, and GO 0.5 mL 0.5 mg/mL was used for cor-
responding characterizations and SERS detection.
2.3.4. Sample preparation for SERS analysis
The stock solution of aromatic dye CV, MG, or NBA with concen-
tration of 10−4 M was prepared in ethanol. These stock solutions
were step-by-step diluted with water to prepare various concen-
trations of analytes (from 10−5 M to 10−10 M).
For SERS measurement, 100 ␮L of nanomaterials (Fe3 O4 ,
Fe3 O4 @Au, or GO wrapped Fe3 O4 @Au) were incubated with 100 ␮L
target molecules solution for 3 h. These materials were magneti-
cally separated, dropped on silicon slide and dried in air for SERS
measurements. The laser power was about 2 mW and the integra-
tion time is 10 s. The spot size of the laser beam is about 2 ␮m.
The GO wrapped Fe3 O4 @Au hybrids composed of same amount of
Fe3 O4 but different AuNPs or GO dosage were also prepared for
SERS analysis in order to investigate effects of dosage of AuNPs
or GO on the SERS performances. Both of the materials prepara-
tion and SERS analysis procedure performed in the same way as
noted above. More than five SERS spectra were recorded from dif-
ferent positions of one sample, and the averaged SERS result was
presented.
2.3.5. Procedure for real sample detection
The water samples were obtained from a local lake. The impu-
rities of the collected water samples were filtered by 0.45 ␮m filter
film and then stored at room temperature. Then, both of the SERS
spectra of the pre-treated lake water and the lake water spiked
with malachite green (MG, an aromatic dye, pollutant and illegal
fungicide in fishery) were recorded by the general SERS analysis
procedure.
3. Results and discussion
3.1. Preparation of Fe3 O4 , Fe3 O4 @Au, and GO wrapped Fe3 O4 @Au
In this study, magnetic sphere Fe3 O4 was used as suppor-
ting substrate to fabricate SERS active hybrid in order to achieve
easy separation of enhancement substrate and simple concentra-
tion of analyte to magnify SERS signal with the help of external
magnetic force. Fig. 1 shows the SEM images of Fe3 O4 sphere,
Fe3 O4 @Au composite, and GO wrapped Fe3 O4 @Au hybrid. Basi-
cally, the magnetic Fe3 O4 particles exhibit a spherical morphology
with an average diameter of 174 ± 15 nm (Fig. 1a and b). Element
analysis demonstrates that this material is mainly composite of Fe
and O (inset of Fig. 1b). These Fe3 O4 spheres are grafted with amine
group through its reaction with APTES to endow the magnetic
particles with positive surface charge (zeta potential = 15.3 mV
shown in Table 1). Citrate reduced and capped Au NPs (zeta
Table 1
Zeta potential of GO, amine group functionalized Fe3 O4 , Fe3 O4 @Au composite, and
GO wrapped Fe3 O4 @Au hybrid.
Materials Zeta potential (mV)
GO sheet −52.0
Au NPs −40.3
Fe3 O4 sphere 15.3
Fe3 O4 @Au 2.21
GO wrapped Fe3 O4 @Au −12.0
potential = −40.3 mV, Table 1) are then decorated onto the Fe3 O4
spheres through electrostatic interaction. As shown in Fig. 1c,
the morphology of Fe3 O4 does not change after its integra-
tion with AuNPs. Further magnified image Fig. 1d clearly shows
that small AuNPs are successfully adsorbed onto Fe3 O4 to form
Fe3 O4 @Au nanocomposite (zeta potential = 2.21 mV, Table 1). Ele-
ment analysis further confirms the presence of Au in the composite
(inset of Fig. 1d). This composite is further mixed with GO (zeta
potential = −52 mV, Table 1) suspension to produce GO wrapped
Fe3 O4 @Au hybrid (zeta potential = −12 mV, Table 1) through elec-
trostatic interaction. Fig. 1e shows that lots of spherical particles
interlaced with film-like matter pile on the silicon substrate. Fur-
ther magnified image shows that a thin film wraps around the
Fe3 O4 @Au composite (Fig. 1f). EDS investigation shows that the
content of element C increases compared with that of Fe3 O4 @Au
composite due to the incorporation of GO in the hybrid (inset of
Fig. 1f). All these results indicate the formation of GO wrapped
Fe3 O4 @Au hybrid (Fig. 1f).
The crystal structures of these materials were characterized by
XRD and the results are listed in Fig. 2. The XRD spectrum of Fe3 O4
displays diffraction peaks with 2 at 30.2◦ , 35.6◦ , 43.3◦ , 53.6◦ , 57.3◦ ,
62.7◦ and 74.4◦ (black curve of Fig. 2a), corresponding to the (2 2 0),
(3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0) and (5 3 3) planes of pure cubic
spine crystal structure of magnetite Fe3 O4 , respectively [30] (JCPDS
card No. 19-0629). Compared with Fe3 O4 , several new peaks at 2
of 38.5◦ , 44.6◦ , 64.8◦ , and 77.7◦ appear for Fe3 O4 @Au (blue curve
of Fig. 2a). These peaks correspond to the (1 1 1), (2 0 0), (2 2 0),
(3 2 2) plane of face-centered cubic phase of gold, implying the
successful adsorption of AuNPs on Fe3 O4 sphere. For GO wrapped
Fe3 O4 @Au (red curve of Fig. 2a), the diffraction peaks are similar
to that of Fe3 O4 @Au, and no obvious diffraction peak of GO (pink
curve of Fig. 2a) is observed, which indicates the stacking of GO
sheet remains disordered [32].
UV–vis absorption spectroscopy was also applied to confirm the
preparation process of these materials (Fig. 2b). Magnetic Fe3 O4
spheres exhibit a weak peak at 240 nm and a broad peak at about
700 nm (black curve), which is similar to previous work by Zhai
[33]. For Fe3 O4 @Au, a new peak at about 535 nm appears (red
curve). The red-shift of the absorption peak indicates that AuNPs
 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093 1087

Fig. 1. SEM images of as-prepared Fe3 O4 (a, b), Fe3 O4 @Au (c, d), GO wrapped Fe3 O4 @Au (e, f). Inset of (a) shows the size distribution of Fe3 O4 spheres; insets of b, d, and f
show the element analysis of corresponding materials.

Fig. 2. XRD (a) and UV–vis absorbance spectra (b) of GO, Fe3 O4 , Fe3 O4 @Au, and GO wrapped Fe3 O4 @Au (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of the article.).
1088 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093
Fig. 3. (a) SERS spectra of CV obtained on Fe3 O4 , Fe3 O4 @GO, Fe3 O4 @Au, and GO wrapped Fe3 O4 @Au. (b) SERS intensities of the main peak of CV obtained from different
materials.
displayed some aggregation after it adsorbed on Fe3 O4 spheres. This
is consistent with the SEM results (Fig. 1d). After the encapsulation
of Fe3 O4 @Au with GO, enhanced absorbance at about 240 nm is
observed (blue curve), which implies the presence of GO. The peak
for Au NPs still exists, but slightly red-shifts and broadens com-
pared with that of Fe3 O4 @Au, indicating some aggregation happens
among Fe3 O4 @Au composites after they interacted with GO. Such
aggregation may produce more SERS hot spots, which are vital
for the efficient electromagnetic enhancement of SERS signal. The
results obtained here further confirm the formation of Fe3 O4 @Au
and GO wrapped Fe3 O4 @Au hybrid.
3.2. SERS activity of Fe3 O4 , Fe3 O4 @Au, and GO wrapped
Fe3 O4 @Au
This study aims to develop an active and wieldy SERS substrate
for the facile and sensitive detection of aromatic pollutant in water,
so the SERS enhancement activities of these materials were inves-
tigated using an aromatic dye crystal violet (CV) as a probe. Fig. 3a
shows the SERS spectra of 1 ␮M CV obtained from these materi-
als. No SERS signal of CV obtains on Fe3 O4 (black curve), so Fe3 O4
has no direct contribution to enhance the SERS signal of CV. Sev-
eral weak diffraction peaks of CV at 424 cm−1 , 526 cm−1 , 800 cm−1
and 1174 cm−1 are obtained on Fe3 O4 @GO, which is mainly due to
the chemical enhancement of GO (green curve) and the enhanced
adsorption of CV on GO. Typical SERS spectrum of CV is obtained on
Fe3 O4 @Au (blue curve) mainly due to the electromagnetic enhance-
ment of decorated AuNPs. Strong SERS signal and distinct scattering
peaks of CV are observed on the GO wrapped Fe3 O4 @Au hybrid
(red curve). The peak 445 cm−1 can be assigned to the vibration of
Phenyl-C-phenyl out-of-plane antisymmetric bending [34,35]. The
band at 920 cm −1 is from the ring skeletal vibrations; the band
at 1179 cm−1 and 1375 cm−1 are attributed to C–H in-plane bend-
ing vibrations and N-phenyl stretching, respectively. The bands at
1586 and 1620 cm−1 are assigned to ring C–C stretching [36,37].
The SERS intensity of several main peaks of CV enhances at least 5
fold compared with that obtained on Fe3 O4 @Au (Fig. 3b), demon-
strating the importance of GO in amplifying the SERS response.
GO could enhance SERS signal through two approaches: promot-
ing absorption of CV, and directly enhancing SERS signal. First, GO
with large surface area, negative surface charge (Table 1) and sp2
network structure greatly facilitates the absorption of CV onto the
enhancement substrate through electrostatic interaction and ␲–␲
stacking [16–19]. Thus the amount of molecules in the effective
enhancement region increases, which leads to an enhanced SERS
signal. The enhanced absorption of the hybrid to CV was confirmed
by UV–vis spectra (Fig. 4a). CV solution was incubated with one of
these materials for 3 h, after that, the material was separated by
magnetic force, and the UV–vis spectrum of residual CV solution
was recorded to estimate the absorption ability of these materi-
als to CV (Fig. 4). Compare with pure CV solution (black curve),
the absorbance intensity for CV gradually decreases after it incu-
bated with Fe3 O4 (red curve), or Fe3 O4 @Au (blue curve). A much
more obvious decrease was observed after CV incubated with GO
wrapped Fe3 O4 @Au (green curve). The absorption ratio of CV after
it incubated with materials to that of CV before it incubated with
material gradually decrease from no material to Fe3 O4 , Fe3 O4 @Au,
GO wrapped Fe3 O4 @Au (Fig. 4b). That demonstrates GO wrapped
Fe3 O4 @Au hybrid has the strongest absorption ability to CV. As
the amine functionalized Fe3 O4 bearing positive surface charge
(Table 1), it is reasonable that it shows weak absorption to pos-
itive dye molecule CV due to electrostatic repulsion. Decoration
of Fe3 O4 with negatively charged AuNPs reduces the repulsion
between material and CV (Zeta potential changed from 15.3 mV
of Fe3 O4 to 2.1 mV of Fe3 O4 @Au shown in Table 1), thus its adsorp-
tion towards CV slightly increases. After the integration with GO,
the surface charge of the hybrid shifts from positive to negative
(Table 1), which greatly facilitates its adsorption to the positively
charged CV. Moreover, GO with large area and aromatic structure
also enhance its adsorption to aromatic molecules such as CV, and
this property of GO has been widely used to remove dye pollutant
from water [19], and confirmed by UV–vis results obtained here. In
addition, GO can enhance the SERS signal through charge transfer
mechanism [10–13], which makes direct contribution to amplify
the SERS signal. All these factors including enrichment of target
molecules by GO, electromagnetic enhancement by AuNPs, chemi-
cal enhancement by GO, and concentrating analyte by Fe3 O4 work
together and lead to greatly enhanced SERS signal.
3.3. Optimization of the usage of AuNPs and GO
As illustrated above, both AuNPs and GO play important role in
amplifying the SERS signal. Thus we tried to use different amount of
AuNPs or GO to prepare the GO wrapped Fe3 O4 @Au hybrid in order
to achieve high detection sensitivity. The hybrids with the same
amount of Fe3 O4 but different AuNPs or GO dosage were used for
SERS detection following the procedure noted in the experimental
Section 2.3.4. From Fig. 5a and b, it can be seen, the SERS response
for 1 ␮M CV increases as the volume of AuNPs increases from
0 mL to 4 mL (the dosage of GO was fixed at 0.5 mL of 0.5 mg/mL
GO suspension). The growing SERS signal can be attributed to the
increased hot spots as the dosage of AuNPs increases. However,
 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093 1089

Fig. 4. (a) UV–vis absorption of pristine CV solution (10−6 M, black line), and the absorption of CVs after it incubated with (abbreviate as a.i.w.) Fe3 O4 (red line), Fe3 O4 @Au
composite (blue line), and GO wrapped Fe3 O4 @Au hybrid (green line). (b) Absorption ratio of CV after CV solution incubated with material Aa.i.w. to that before CV solution
incubated with material Ab.i.w (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.).

SERS signal of CV decreases when more AuNPs is added. That
may be due to the serious aggregation and sedimention of the
composite caused by too much AuNPs. Therefore, 4 mL of AuNPs
(0.2 mg/mL) was used to prepare Fe3 O4 @Au nanocomposite. Thus
prepared Fe3 O4 @Au was used to fabricate GO wrapped Fe3 O4 @Au
hybrid, and the dosage of GO on SERS activity of the hybrid was
investigated. Fig. 5c and d shows 0.5 mL GO (0.5 mg/mL) wrapped
Fe3 O4 @Au exhibits the strongest SERS signal. As discussed above,
GO could enrich aromatic molecules on the substrate and enhance
SERS signal through charge transfer mechanism. Thus SERS signal
of CV increases as the volume of GO increases from 0 to 0.5 mL.
However, too much GO could arouse large background signal from
the D and G bands of GO, and weaken the electromagnetic enhance-
ment of AuNPs as the distance between AuNPs and target molecules
increases due to the wrapped GO sheet. Finally, 1 mL 2 mg/mL Fe3 O4
decorated with 4 mL 0.2 mg/mL AuNPs, and then wrapped by 0.5 mL
0.5 mg/mL GO was used to form the highly active GO wrapped
Fe3 O4 @Au hybrid for subsequent SERS measurement. The resultant

Fig. 5. The effect of different dose of AuNPs (a) or GO (c) on the SERS response of GO wrapped Fe3 O4 @Au for 1 ␮M CV in water. Dosage of Fe3 O4 : 1 mL, 2 mg/mL. (b, d) SERS
intensities of the main peaks of CV obtained from GO wrapped Fe3 O4 @Au prepared in the presence of different dosage of Au (b) or GO (d).
1090 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093

Fig. 6. SERS spectra of MG (a) or NBA (c) with different concentrations obtained on GO wrapped Fe3 O4 @Au hybrid. (b, d) Corresponding SERS intensities of main peaks of
MG (b) or NBA (d) at different concentrations.

GO wrapped Fe3 O4 @Au has an element molar ratio of 18/1.5/13/60

for Fe:Au:C:O revealed by EDX analysis.

3.4. GO wrapped Fe3 O4 @Au as substrate for SERS Detection of

aromatic pollutant

Using CV as a probe molecule, it has been demonstrated that

the GO wrapped Fe3 O4 @Au hybrid exhibited high adsorption abil-
ity and efficient SERS enhancement effect to aromatic molecules.
Here, its performance as SERS active substrate was further tested
using other aromatic dye molecules. First, malachite green (MG)
was chosen as an example. Malachite green is an aromatic dye,
which has been used illegally as a fungicide and parasiticide in
aquaculture because of its high efficiency and low cost [38]. Since
MG and its derivative are suspected carcinogenic and mutagenic
agents [38,39], it is of significant importance to develop rapid, accu-
rate, and economic methods for determination of MG in water and
aquatic products. SERS has been proved a promising tool to achieve Fig. 7. SERS spectra of single NBA, single MG or their mixture obtained on GO
this object [40]. Fig. 6a shows the SERS signal of different concen- wrapped Fe3 O4 @Au hybrid.
trations of MG obtained on GO wrapped Fe3 O4 @Au. Characteristic
peaks of MG can be clearly observed at 100 nM concentration.
The prominent peaks of malachite green at 1621 cm−1 , 1370 cm−1
and 1171 cm−1 in the Raman spectrum were caused by ring C–C still distinguishable at concentration of 1 nM (Fig. 6a). Thus this GO
stretching, N-phenyl stretching, and in-plane modes of C–H bend- wrapped Fe3 O4 @Au hybrid can be used as a low cost and highly
ing, respectively. The medium bands at 1398 cm−1 , 1220 cm−1 , active SERS substrate for sensing of MG in water. Similar results
916 cm−1 were attributed to N-phenyl stretching, C–H rocking and are obtained for another aromatic dye nile blue A (NBA) (Fig. 6c and
C–H out-of-plane bending, respectively [40]. As the concentration d). The lowest detectable concentration for NBA is 0.1 nM on this
of MG decreases, the peak intensity gradually decreases (Fig. 6a GO wrapped Fe3 O4 @Au enhancement substrate. These results indi-
and b). Compared with the blank signal, some scattering peaks of cate that the hybrid substrate can be used for detection of different
MG including 445 cm−1 , 796 cm−1 , 916 cm−1 , and 1180 cm−1 are aromatic dyes.
 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093
Fig. 8. (a) SERS signal of MG with different concentration spiked in lake water obtained on GO wrapped Fe3 O4 @Au hybrid. (b) Corresponding SERS intensities of main peaks
of MG with different concentration in water sample.
Previously, Chen prepared Fe3 O4 and AuNPs co-decorated
graphene sheet as SERS substrate for detection and in situ study
the catalytic reduction of 4-nitrophenol (4-NP) [28]. Here, it is noted
that our new hybrid is different from these reported by Chen, espe-
cially in the arrangement of the component Fe3 O4 , Au and GO or
reduced GO. To demonstrate the different performances of our sub-
strate and the reference reported substrate, we also prepared the
substrate following the procedure reported by Chen, and then study
its adsorption ability to dyes and SERS activity for dye detection.
For convenience Chen’s substrate is denoted as co-decorated sub-
strate GO–Fe3 O4 –Au, and our substrate is denoted as GO wrapped
Fe3 O4 @Au. As shown in Fig. S1 in supporting information, the co-
decorated substrate displays poor adsorption ability to the same
concentration of dye molecules. Besides, for the same 10−5 M dyes
MG or NBA, co-deposited substrate displays low sensitivity, less
characteristic peaks of dyes, and large background signal, which
result in a low signal to noise ratio and thus high detection limit
(10−5 to 10−6 M) for these dyes detection. Compared with the
results obtained on this co-decorated substrate, our GO wrapped
Fe3 O4 @Au shows much enhanced adsorption ability to dyes (Fig. 4),
and higher sensitivity and greatly lower detection limit (10−9 to
10−10 M, Fig. 6). So, it is clearly indicated that the arrangement of
the GO wrapped Fe3 O4 @Au hybrid has significant influence on the
properties of the final substrate. The main reasons for the differ-
ent performance can be ascribed to the following aspects. First,
the large surface area of GO was occupied by Fe3 O4 and AuNPs
in the reference reported substrate, and the substrate has few neg-
ative charged functional groups due to the capping agent PEG, so
its adsorption ability to dyes sharply decreases; for our substrate
Fe3 O4 @Au@GO, the GO sheet wraps around Fe3 O4 @Au, so unique
properties of GO including the large surface area, sp2 structure
and negative surface charge can be well retained, which greatly
facilitate the adsorption to dyes (Fig. 4). Second, co-depositing
Au directly on GO leads to formation of Au–GO–Au sandwiched
structure, which leads to high background signal of GO, thus high
noise and low signal to noise ratio is obtained on the co-deposited
substrate (Fig. S1). Consequently, high detection limit is obtained
using the co-decorated substrate for molecule detection. For our
substrate, Fe3 O4 @Au was wrapped by GO, and few Au–GO–Au
sandwiched structure formed. As a result, the background noise
is lower than that of the co-deposited substrate; the decorated
AuNPs could provide strong electromagnetic enhancement and
thus high sensitivity and low detection limit is achieved. Moreover,
our approach is more convenience to tune the particle size of these
components, which is more flexible for different study purpose.
Finally, our substrate needs much shorter time (within 1 min) to
separate by magnetic force than that co-deposited substrate (about
1091
5 min). Thus, our substrate is a new designed substrate, which is
different not only in structure, but also in performance from the
reported one.
As many dye molecules coexist in environment, the simulta-
neous detection of different dye molecules is important for practical
analysis. Here, the multiplex detection ability of GO wrapped
Fe3 O4 @Au hybrid was tested by measuring its response to aro-
matic mixture in water. Aromatic dye 1 ␮M NBA was mixed with
1 ␮M MG in water. The mixture was incubated with GO wrapped
Fe3 O4 @Au for 3 h, and then hybrid was separated by magnetic force
for SERS measurement. Fig. 7 shows the SERS spectrum of the dye
mixture obtained on the Fe3 O4 @Au@GO hybrid. Compared with
the individual spectrum of NBA or MG (Fig. 7), several character-
istic peaks for NBA and MG are observed from the SERS spectrum
of their mixture. That indicates this hybrid substrate has a great
potential for selective and multiplex detection of aromatic dyes.
Similar to previous result [41], the SERS intensity of each molecule
in the mixture decreases compared with that from single compo-
nent solution, which can be ascribed to the competitive adsorption
between these two dyes on GO wrapped Fe3 O4 @Au.
To illustrate the practical application of the GO wrapped
Fe3 O4 @Au hybrid in real sample analysis, SERS signal of MG in real
lake water sample was also recorded. As can be seen in Fig. 8, the
SERS signal of MG in water sample is similar to that of MG in pure
water solution, except that the intensity decreases. The SERS inten-
sity of MG gradually decreases as the concentration of MG decrease
from 1000 nM to 10 nM (Fig. 8a and b). The lowest detectable con-
centration of MG is about 10 nM, which is higher than that obtained
in pure aqueous solution. The decreased SERS intensity and higher
detectable concentration may be due to the complex of the real
water sample, in which co-existed matter may affect the adsorption
of MG onto the GO wrapped Fe3 O4 @Au substrate.
4. Conclusion
In summary, a ternary hybrid composed of GO wrapped AuNPs-
decorated-Fe3 O4 spheres was prepared as a highly active SERS
substrate for the sensitive detection of aromatic dye pollutant.
This hybrid material combines the magnetic separation and con-
centration of Fe3 O4 sphere, the electromagnetic enhancement of
AuNPs, and the high adsorption and charge transfer enhancement
effect of GO toward aromatic molecules, thus produces largely
amplified SERS response. The unique structure of GO wrapped
Fe3 O4 @Au has several advantages over previously reported co-
decorated structure. The substrate with high sensitivity and easy
handling properties has great potential for aromatic dye analysis.
Our results demonstrate that rational combination of plasmonic
1092 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093
nanoparticle with magnetic sphere and graphene derived material
can be an alternative way to fabricate highly active substrates for
SERS analysis.
Acknowledgements
This work is financially supported by Natural Science Founda-
tion of Jiangxi Province (20132BAB213012), Science Foundation
of Jiangxi Provincial Department of Education (GJJ14263 and
GJJ13247), and Research Funds of Jiangxi Normal University (no.
4506 and no. 4304).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2015.07.074
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Biographies
Guihong Ding received her science bachelor in chemistry in 2012 from Gannan
Normal College, China. She is working for her master’s degree in Jiangxi Normal
University, China. Her research interests are nano-materials and their applications
in SERS analysis.
Shi Xie is working for her master’s degree in Jiangxi Normal University, China. Her
research interests are designing nano-materials for SERS analysis.
 G. Ding et al. / Sensors and Actuators B 221 (2015) 1084–1093
Yongmei Zhu is a Senior Experimentalist in the analytical and testing center of
Jiangxi Normal University. Her research interest is Raman spectroscopy and its
application in material science.
Ying Liu is working for her master’s degree in Jiangxi Normal University, China. Her
research interests are nano-materials and their applications in sensors.
Li Wang received her PhD in analytical chemistry from the Changchun Institute of
Applied Chemistry, Chinese Academy of Science, China. She is currently working as
1093
a Professor at Jiangxi Normal University. Her current research interest is focused on
nanomaterials based sensors.
Fugang Xu received his PhD degree in analytical chemistry from the Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences, China. He joined
Jiangxi Normal University as a faculty member in 2012. His research interests include
synthesis of nanomaterials, electrochemical sensors, and SERS analysis.