Applied Surface Science 316 (2014) 22–27

Contents lists available at ScienceDirect

Applied Surface Science

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

In situ green synthesis of silver–graphene oxide nanocomposites by

using tryptophan as a reducing and stabilizing agent and their
application in SERS
Biwen Yang 1 , Zhiming Liu 1 , Zhouyi Guo, Wen Zhang, Mingming Wan, Xiaochu Qin,
Huiqing Zhong ∗
MOE Key Laboratory of Laser Life Science & SATCM Third Grade Laboratory of Chinese Medicine and Photonics Technology, South China Normal University,
Guangzhou, Guangdong 510631, PR China

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

Article history: Silver–graphene oxide (Ag–GO) nanocomposites were in situ fabricated rapidly through a green one-pot
Received 1 April 2014 method by using tryptophan (Trp) as a reducing and stabilizing agent. The morphologies of synthesized
Received in revised form 30 June 2014 Ag–GO nanocomposites were characterized by UV–vis absorption spectroscopy, transmission electron
Accepted 6 July 2014
microscopy (TEM), and micro-Raman system. The results indicated silver nanoparticles (Ag NPs) with
Available online 30 July 2014
spherical size were well dispersed on the surface of graphene oxide (GO). The role of pH has been explored
to obtain optimum reaction conditions during the growth process. Raman signals of GO were greatly
Keywords:
enhanced after Ag NPs loaded on its surface. More importantly, the synthesized Ag–GO nanocomposites
Tryptophan
Silver–graphene oxide composites
exhibited excellent surface-enhanced Raman scattering (SERS) activity as SERS substrates to detect crystal
Surface-enhanced Raman scattering violet (CV) in aqueous solution, and the enhancement factor (EF) from the intensity of the vibrational
mode at 1621 cm−1 was calculated to be 1.6 × 105 .
© 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction have been intensively investigated for formation of GO-MNPs for

Since Geinn and Novoselov first acquired single-layer samples
from graphite in 2004, graphene, a flat monolayer of carbon atoms
closely packed into a 2-dimensional honeycomb lattice, has drawn
significant attention due to its fascinating properties and potential
application [1–3]. Graphene oxide (GO) is a common and important
derivative of graphene, which is generally known as a precursor
for the achievement of large-scale graphene by chemical reduc-
tion or thermal annealing treatment [4,5]. GO is oxygenated with
phenolic, carboxyl, and epoxide groups on the planes and edges,
making it convenient for further chemical modification and func-
tionality [6,7]. Compared to graphene, these oxygenated groups
make GO to show good hydrophilic and dispersion ability both in
water and polar organic solvents [8,9]. The high specific surface of
GO would greatly improve the loading capacities [10]. Therefore,
GO is thought to be a promising multifunctional building block
for graphene oxide-metal composites (GO-MNPs) [11–13]. Until
now, series of noble metal nanoparticles, especially gold and silver,
∗ Corresponding author. Tel.: +86 20 85211920 8721; fax: +86 20 85211428.
E-mail addresses: zhonghq@scnu.edu.cn, 408539118@qq.com (H. Zhong).
1
These authors contributed equally to this work.
further application in catalysis [14], electrochemical [15], microbi-
cide [16], and surface-enhanced Raman scattering (SERS) [17]. The
wet chemical methods with used for the fabrication of GO-MNPs
are mainly self-assembled methods [18,19] and in situ methods
[20,21]. The advantage of in situ fabrication of GO-MNPs is sim-
ple and efficient [22–24]. However, a large number of reducing and
surfactants/stabilizing agent used in this strategy are toxic (such as
hydrazine and sodium borohydride), and the procedure of the fab-
rication is always complicated. Therefore, it is still necessary and
some methodological challenges to large-scale synthesis GO-MNPs
by chemical reduction method with green agents and convenient
route.
The Trp has amino group, hydroxyl and aromatic rings (chemi-
cal structure of Trp no shown). Therefore, Trp can be adsorbed on
the surface of GO and form stably dispersed in water as a precur-
sor for the subsequent reduction reaction, because affinity GO will
toward condensing molecules through the stacking and electro-
static interaction [25–27]. It is crucial that using Trp as a reducing
and stabilizing agent will not induce any environmental problem
during the process of formation. The SERS as one of the most pow-
erful spectroscopic techniques for chemical or biochemical analysis
has gained increasing attention because of its high sensitivity, capa-
bility, and specificity [28]. It has been generally accepted that the

http://dx.doi.org/10.1016/j.apsusc.2014.07.084
0169-4332/© 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
 B. Yang et al. / Applied Surface Science 316 (2014) 22–27
Fig. 1. A scheme to illustrate the preparation of Ag–GO composites via in situ chemical reduction of silver nitrate by Trp.
mechanism of Raman enhancement is caused by a combination of
electromagnetic and chemical effects. Electromagnetic mechanism
(EM) is based on the enhancement of the local electromagnetic
field, while chemical mechanism (CM) is based on charge transfer
between molecule and metal. There is substantial evidence indicat-
ing that the SERS effect is dominated by the strong electromagnetic
field enhancement due to the excitation of the localized surface
plasmon resonance (LSPR) on the metal surface. In general, the elec-
tromagnetic SERS enhancement factor is considered to contribute
enhancement factors on the order of 1012 , while the chemical SERS
enhancement factor is usually 101 –102 [29]. Thus, the practical
applications of SERS technique depend strongly on the LSPR prop-
erties of the nanostructured noble metal. To apply SERS in routine,
SERS substrates with large enhancement factor and good repro-
ducibility are essential. Previous investigations suggest that noble
metallic nanostructure taking advantage of the EM is often selected
to fabricate SERS substrates for detecting molecules, especially sil-
ver nanoparticles that have been well studied in recent years [30].
In addition, Ling et al. [31] and Yu et al. [32] have demonstrated that
graphene can use as a new type of surface enhanced Raman scatter-
ing substrate following the chemical enhancement mechanism. The
building block of graphene and graphene oxide not only improves
the stability and biocompatibility of the encapsulation Ag NPs, but
also adds the SERS substrates with the capability of controllability
[33,34]. In this work, a facile, convenient, environment-friendly and
low-cost method was used to synthesize water-dispersible Ag–GO
composites with tryptophan (Trp) as a reducing and stabilizing
agent (Fig. 1). Under alkaline conditions, we researched that differ-
ent pH how to influence the Ag–GO synthesizing. More importantly,
we have demonstrated that the fabricated Ag–GO composites show
dramatic SERS activity as SERS substrates to detect the probe
molecule of crystal violet (CV) in water.
2. Experimental
2.1. Materials
GO was purchased from Shanghai Yifan Graphite Co., Ltd. The
GO aqueous solution was prepared by dissolving commercial solid
GO in distilled water with sonication for several hours. Tryptophan,
23
silver nitrate (AgNO3 ), sodium hydroxide (NaOH) and CV were
obtained from Sinopharm Group Chemical Reagent Co., Ltd and
were used as-received unless otherwise stated. All chemicals were
used without further purification. Double distilled water was used
as the solvent throughout the experiments.
2.2. Preparation of Ag–GO composites
We prepared the aqueous solution of the GO with a concen-
tration of 0.5 mg mL−1 , stored at room temperature. Trp aqueous
solution with a concentration of 5 mM was freshly prepared before
the experiment. In a typical experiment, the Ag–GO composites
were prepared according to the following two steps: (1) prepa-
ration of Trp–GO suspension; typically, 0.8 mL of 0.5 mg mL−1 GO
were dispersed into 2.8 mL double distilled water, after shaking
several times, 0.4 mL of 5 mM Trp aqueous solution were added
into above GO aqueous solution under ultrasonic irradiation about
10 min. (2) 2 M NaOH aqueous solution was dripped into the mix-
ture solution to adjust the pH to 12.0. After that, 20 ␮L of 200 mM
AgNO3 was added into the dispersion. At last, the glass bottle was
put into a water bath at 60 ◦ C, during which Ag–GO composites
were synthesized. Interestingly, at different pH, Ag NPs absorbed on
GO with different sizes and shapes could be obtained. To investigate
the influence of pH on the formation of Ag–GO nanocomposites, dif-
ferent amounts of NaOH with 2 M were added into the same mixed
solution of GO, Trp, and AgNO3 . The products were centrifuged and
washed with double distilled water several times to remove the
unreacted Trp and redispersed in water for characterization and
further applications.
2.3. Preparation of Ag colloid
Ag NPs were prepared by in situ reduction of AgNO3 at the pH of
12.0 with the use of Trp as reducing and stabilizing agent. In order
to adjust the pH of solution to 12.0, a certain amount of 2 M NaOH
aqueous solution was dripped into 4 mL of 0.5 mM Trp aqueous
solution. After that, 20 ␮L of 200 mM AgNO3 aqueous solution was
added into the mixture solution and the mixture solution was kept
in a water bath at 60 ◦ C for approximately 30 min.
24 B. Yang et al. / Applied Surface Science 316 (2014) 22–27

Fig. 2. UV–vis absorption of aqueous dispersions of Trp, GO, Trp–GO, and Ag–GO composites (a), the right inset shows a picture of the solutions of synthesized Trp, GO,
Trp–GO, GO–Ag (from left to right); and UV–vis absorption spectra of the solution prepared for Ag–GO composites at different pH (b) (the right inset are corresponding
pictures of different pH (9, 10, 11, 12, and 13) composites (from right to left)).

2.4. SERS experiments
The SERS experiments, CV was chosen as the probe molecule.
Soaking was used to absorb the molecule on the surface of Ag–GO
composites. 50 ␮L of CV aqueous solutions with concentration of
2 × 10−8 M was mixed with 50 ␮L of as-prepared Ag–GO compos-
ites. After shaking several times, the mixture was allowed to stay
for 3 h at room temperature to reach the adsorption equilibrium for
direct SERS detection in liquid environment.
2.5. Characterization
Transmission electron microscopy (TEM) was used for charac-
terization of Ag–GO composites shape and size. Typical images
were acquired by using a JEOL JEM-2100 (HR) with an accelerat-
ing voltage of 200 kV by dropping an aqueous solution of Ag–GO
composites on carbon-coated copper grids and drying in ambient
conditions. The optical properties of Ag–GO composites were char-
acterized using a NanoDrop ND-1000 UV–Vis spectrophotometer.
SERS spectra were collected using Renishaw InVia Micro-Raman
system (Renishaw Inc., New Mills, UK) at the excitation wavelength
of 514.5 nm by an Ar+ laser.
3. Results and discussion
3.1. Characterization of Ag–GO composites
3.1.1. UV–vis spectra analysis
The synthesized Ag–GO composites were firstly characterized
by UV–vis absorption spectra (Fig. 2(a)). It was found that a band
centered at 278 nm which coincide with the Trp absorption band
due to the excitation of –* transitions in the indole group of the

Fig. 3. TEM images of the Ag–GO composites at different pH: 10 (a); 11 (b); 12 (c) and 13(d).
 B. Yang et al. / Applied Surface Science 316 (2014) 22–27
Fig. 4. Raman spectra of GO and SERS Ag–GO composites (a), and Raman spectra of CV adsorbed on the substrates of GO, Ag colloid, and Ag–GO composites, respectively (b).
molecule. And the UV–vis absorbance spectrum of GO showed two
absorption peaks at 230 nm, which corresponds to the –* transi-
tions of the aromatic C C bonds, and 300 nm, which is attributed to
the n–* transitions of the C C bonds. Meanwhile, the absorbance
peak of Trp at 278 nm was broadened and the center was blue
shift to 270 nm, as the presence of n–* interaction between the
aromatic rings of Trp and GO sheets (as shown in Fig. 2(a)). After
the addition of AgNO3 into the suspension of Trp-GO, there was
a new absorbance band centered at 412 nm, which is assigned to
the optical signatures of colloidal Ag, indicating the formation of
Ag nanoparticles [35]. The spontaneous formation of Ag nanoparti-
cles can also be attributed to the direct redox reaction between Trp
and Ag+ . The Ag+ is reduced to metallic Ag by the indole group of
Trp, which is evidenced by the disappearance of the superimposed
absorbance bands of Trp–GO around 278 nm [36]. Indeed, Trp as
an essential aromatic amino acid has been successfully used as a
reducing and stabilizing agent for the synthesis of Ag nanoparticles
and Au nanoparticles [37,38]. Meanwhile, the production of well-
dispersed Ag–GO was visibly observed from a distinct color change
from faint yellow to brown yellow (Fig. 2(a)). It is well known
that pH is an important parameter in the synthesized procedure
of composites. To determine the influence of pH in the strategy of
preparation Ag–GO hybrids, different amounts of NaOH were added
into the same mixed solution of GO–Trp to adjust the pH. Fig. 2(b)
displays the UV–vis absorption spectra of the final products when
the pH at 9.0, 10.0, 11.0, 12.0, and 13.0. It can be seen, with the
increasing of pH from 9.0 to 11.0 (Fig. 2(b)), there is a significant
increase in the intensity of the absorption band, as well as the nar-
rowing of the size distribution. This phenomenon indicates that the
presence of NaOH facilitates the deposition of Ag NPs on the sur-
face of GO. We obtained the maximum intensity of the absorption
band of Ag NPs at 12.0(as shown in Fig. 2(b) pH 12). However, the
position of absorption band appeared red shift. Further increasing
the pH of the composites causes the intensity decrease (as shown
in Fig. 2(b) pH 13). This might be that the formation of AgOH is at
such condition, in which less silver source can be consumed during
the growth process. At the other hand, the production of Ag–GO
from different pH (9, 10, 11, 12, and 13) was visibly observed from
a distinct color change from light color to deep color (Fig. 2(b) from
left to right).
3.1.2. TEM analysis
Fig. 3 illustrates the representative TEM images of the formed
Ag–GO composites at different pH (10, 11, 12, and 13). From
Fig. 3(a–d), it was clearly observed that the surface of GO sheets
was modified by the nanosized Ag NPs. Most of the synthesized Ag
NPs absorbed on the GO exhibit spherical shape, which displays a
good combination between Ag NPs and GO. In the Fig. 3(c), the size
of Ag NPs is estimated to be 20–30 nm. Meanwhile, the arrange-
ment of the Ag NPs on the GO was not very closely, therefore, there
25
were still some blanks between the Ag NPs for the enrichment of
the probe molecules. The TEM images further confirm the ability of
GO nanosheets to anchor dispersive Ag NPs on their surface. And
it was found that pH 12 is the optimum condition for synthesizing
Ag–GO (there results are in accordance with above UV–vis results).
3.2. SERS activity of Ag–GO composites
3.2.1. Raman spectra of GO and SERS of Ag–GO composites
Fig. 4(a) shows the Raman spectra of GO before and after the
Ag NPs absorbed on its surface. Two characteristic D and G bands
at around 1350 cm−1 and 1600 cm−1 were observed. The D band
provides the information of the breathing mode of -point, and the
G band relates to the tangential stretching mode of E2g phonon of
sp2 carbon atom [39]. It is noticed that the intensities of these two
bands were enhanced dramatically after the decoration of Ag NPs
on the surface of GO, and the proportion of D and G bands did not
change significantly. This excellent SERS activity is attributed to a
short-range chemical effect between Ag NPs and GO.
3.2.2. GO-Ag hybrids as a SERS substrate for CV
To evaluate the SERS activity of the as-synthesized Ag–GO com-
posites, The GO and Ag NPs were also used as substrate of the
Raman probe molecule CV, respectively. As shown in Fig. 4(b), a
strong SERS spectrum of 2 × 10−8 M CV was achieved with the addi-
tion of Ag–GO hybrids. The main vibrations of CV shown in the
SERS spectrum were confirmed according to the reported work
[40]. The prominent peaks of CV at 1587 cm−1 and 1621 cm−1
which are assigned to aromatic C C stretching mode; the band
at 915 cm−1 is attributed to aromatic skeletal vibration mode; the
band at 1179 cm−1 is related to C H bending mode; and the band
at 1368 cm−1 is due to the N-phenyl stretching mode; and some
other weak bands such as 809 cm−1 , 1298 cm−1 , 1445 cm−1 and
1538 cm−1 , are also obtained in the spectrum. As a contrast, the
SERS intensities of the CV on GO or Ag NPs reduced was much
lower than that on the Ag–GO composites, especially for GO sub-
strate, there was no recognizable Raman bands of CV but only two
characteristic bands, G and D bands, which are the characteristic
bands of GO. The great enhancement of the SERS signal of CV on
Ag–GO composites can be attributed to be both the high coverage
density of Ag NPs on the surface of GO and the appropriate interval
between neighboring Ag NPs. Thus, the excellent Raman scattering
enhancement abilities of both GO and Ag NPs.
Additionally, we estimated the enhancement ability of Ag–GO
hybrids quantitatively by calculating the enhancement factor (EF)
of CV molecule adsorbed on the substrate. The EF values using the
following expression (1):
ISERS Nbulk
EF = (1)
IRaman Nsurface
26 B. Yang et al. / Applied Surface Science 316 (2014) 22–27
Fig. 5. SERS spectra of CV with different concentrations by using Ag–GO composites as the SERS substrates (a): (A) 5 × 10−8 M, (B) 5 × 10−9 M, (C) 1 × 10−10 M; and (b) SERS
dilution series (from 1 × 10−10 M to 5 × 10−7 M) of CV in water based on the peak located at 1621 cm−1 .
where ISERS and IRaman stand for the intensities of the same vibra-
tional mode in the SERS and normal Raman spectra, respectively.
These data can be directly obtained from the experiment. Nbulk
and Nsurface are the number of CV molecules illuminated by the
laser focus spot under normal Raman and SERS condition, respec-
tively. They were calculated on the basis of the estimation of the
concentration of the surface species or bulk sample and the corre-
sponding sampling area [25,41]. Suppose the molecules on the film
were assumed to be 2 × 10−4 mol L−1 × 8 ␮L × NA /100 mm2 (the
surface area of the substrate is 10 mm × 10 mm), namely, 9.6 × 1012
molecules mm−2 . The laser spot has a 1 ␮m diameter and the
surface area is about 7.9 × 10−7 mm2 , so Nsurface had a value of
7.6 × 106 . Tacking the laser spot (1 ␮m diameter), the penetration
depth (about 2 ␮m), the molecular weight of CV (407.98 g mol−1 )
and the density of the solid CV (0.83 g cm−3 ) into account, Nbulk had
a value of 1.93 × 109 in the detected solid sample area. All spectra
were normalized for acquisition time and laser power. The EF from
the intensity of the vibrational mode at 1621 cm−1 was calculated
to be 1.6 × 105 for Ag–GO hybrids.
To further verify the ability of detection, SERS spectra of CV with
different concentrations (1 × 10−10 M, 5 × 10−9 M, and 5 × 10−8 M)
were also detected, as shown in Fig. 5(a). It can be seen that
the intensity of the SERS spectra increased with the increas-
ing concentrations of CV. The SERS intensity of the vibration
located at 1621 cm−1 . The concentration of CV was also plotted in
Fig. 5(b), while revealed a linear SERS response from 1 × 10−10 M to
5 × 10−7 M of CV. Hence, the as-prepared Ag–GO composites could
be an excellent SERS substrate for detection of CV molecules in
water. Considering that the as-prepared nanohybrids have a high
enhancement effect, they can be used as a potential SERS sensor to
detect environmentally harmful substances.
4. Conclusions
In conclusion, we have developed a facile, environment-
friendly, and one-pot strategy to synthesize Ag–GO composites by
using of Trp as a reducing and stabilizing agent. The pH of the
mixture plays an important role in the preparation procedure. The
resultant of Ag–GO composites indeed shows excellent SERS activ-
ity as SERS substrates to detect CV molecules in water.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Nos. 31300691, 61335011, 61275187, &
81071790), Specialized Research Fund for the Doctoral Program of
Higher Education of China (Nos. 20114407110001, 200805740003,
& 20134407120003), the Natural Science Foundation of Guangdong
Province (9251063101000009) and the cooperation project in
industry, education and research of Guangdong province and
Ministry of Education of PR China (2011A090200011).
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