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Investigation of Graphene/Ag Nanocomposites Synthesis Parameters for Two

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Investigation of Graphene/Ag Nanocomposites Synthesis

Parameters for Two Different Synthesis Methods
a a a
Zafer Çiplak , Nuray Yildiz & Ayla Çalimli
a
Department of Chemical Engineering, Ankara University, Ankara, Turkey
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To cite this article: Zafer Çiplak, Nuray Yildiz & Ayla Çalimli (2015) Investigation of Graphene/Ag Nanocomposites Synthesis
Parameters for Two Different Synthesis Methods, Fullerenes, Nanotubes and Carbon Nanostructures, 23:4, 361-370, DOI:
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 Fullerenes, Nanotubes and Carbon Nanostructures (2014) 23, 361–370
Copyright © Taylor & Francis Group, LLC
ISSN: 1536-383X print / 1536-4046 online
DOI: 10.1080/1536383X.2014.894025

Investigation of Graphene/Ag Nanocomposites Synthesis

Parameters for Two Different Synthesis Methods
ZAFER ÇIPLAK, NURAY YILDIZ and AYLA ÇALIMLI
Department of Chemical Engineering, Ankara University, Ankara, Turkey

Received 6 August 2013; accepted 23 December 2013

Downloaded by [Ankara Universitesi] at 22:52 14 September 2014

Graphene/Ag nanocomposites were prepared with two different approaches; (i) sequential reduction of graphene oxide and silver
nitrate (AgNO3), (ii) simultaneous reduction of graphene oxide and AgNO3 with hydrazine hydrate. The effect of synthesis
parameters such as AgNO3 amount, concentration of AgNO3 solution, reducing agent amount, concentration of reducing agent
solution, on the mean size and particle size distribution of Ag nanoparticles deposited on graphene nanosheets were examined. The
structure and morphology of the prepared nanocomposites were characterized with Fourier transform infrared spectrophotometer
(FTIR), UV-visible spectra, scanning electron microscope (SEM), transmission electron microscope (TEM), and Raman spectra.
Based on experimental data shown in this work Ag nanoparticles with smaller sizes (3.04 § 0.64 nm) and narrower size range (2–
6 nm, approximately % 90) that homogenously deposited on graphene nanosheets were obtained by simultaneous reduction method,
compared to sequential reduction method.
Keywords: graphene, Ag nanoparticles, nanocomposites

Introduction graphene nanosheets so that they can prevent agglomeration

of the graphene nanosheets (5, 24, 25). Among the other
Graphene is a two-dimensional sp2-bonded carbon material metallic nanoparticles, Ag nanoparticles have good electronic
that has a honeycomb crystal lattice structure. It is the build- and catalytic properties but also antibacterial activity
ing block of the graphitic materials and has attracted signifi- (26, 27). There are many reports about preparing graphene/
cant attention because of its unique properties. Graphene has silver nanocomposites. Xu et al. (28) synthesized graphene/
high surface area, high electrical and thermal conductivity, Ag nanocomposite through sequential reduction of graphene
and excellent mechanical and chemical stability (1–4). oxide and AgNO3 with excess hydrazine. The composite
Because of this superior properties, it has wide range of exhibited surface-enhanced Raman scattering activity and
potential applications such as transparent conductive electro- better electrochemical properties. Tien et al. (5) prepared gra-
des (5), biosensors and electrochemical sensors (6, 7), and phene/Ag film through a two-step reduction with sodium
energy storage systems like supercapacitors, Li ion batteries, borohydride and ethylene glycole. The resulting film was
fuel cells, and photovoltaics (8–15). both highly transparent and electrically conductive therefore
There are three main methods for preparing graphene, it may be a promising material for use in transparent conduc-
known as mechanical exfoliation of graphite, chemical vapor tive films. Li et al. (29) synthesized graphene/Ag heterostruc-
deposition (CVD) and chemical reduction of oxidized graph- ture with deposition of Ag nanoparticles on graphene oxide
ite. Among them, chemical reduction is an easy, scalable, and by reduction of AgNO3 at room temperature, than reducing
low cost way to prepare graphene nanosheets (3, 4). graphene oxide with sodium borohydride. Liu et al. (30, 31)
Metallic nanoparticles have high electrical conductivity prepared graphene/Ag nanocomposites for enzymless hydro-
and catalytic activity. These properties are beneficial for gen peroxide detection. They reduced AgNO3 that added
enhancing the performances of graphene and graphene-based into graphene dispersion by poly[(2-ethyldimethylammo-
nanocomposites for applications of biosensors and electro- nioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)]
chemical sensors or energy storage systems (16–23). They (PQ11) and aniline. The nanocomposite exhibited good cata-
also play the role of spacers to increase the distance between lytic activity toward the reduction of H2O2. Nowadays there
is an increasing attention on graphene and graphene oxide-
based silver nanoparticle nanocomposites and their antibac-
Address correspondence to Nuray Yildiz, Department of Chemi- terial properties. Shen et al. (32) prepared graphene/Ag
cal Engineering, Ankara University, Ankara, Turkey. E-mail: nanocomposites through reducing graphene oxide and
nyildiz@[Link] AgNO3 with mixed reducing agents. Xu et al. (33) synthe-
Color versions of one or more of the figures in this article can be sized graphene/Ag nanocomposite by reducing AgNO3
found online at [Link]/lfnn. added into graphene-poly(sodium 4-styrenesulfonate) (PSS)
 362 Ç iplak et al.

solution. Yuan et al. used an environment friendly method to and AgNO3. In this procedure, AgNO3 solution (10–40 mM)
prepare graphene/Ag nanocomposite (34). They used sodium was added into the synthesized graphene dispersion at differ-
citrate as a reducing and stabilizing agent. These studies ent mass ratios of AgNO3/graphite oxide (0.125–1). The mix-
showed that the silver nanoparticles embedded inside the gra- ture was stirred at room temperature for 1 hour. After that,
phene nanosheets retain their antibacterial activity. The syn- NaBH4 (5–400 mM) solution with different AgNO3/NaBH4
ergistic effect arising from the adsorption properties of molar ratios (0.125–0.5) was added slowly into the above
graphene nanosheets and antibacterial properties of silver mixture under vigorous stirring to reduce silver ions. The
nanoparticles make this nanocomposite as a promising mate- reduction mixture was stirred for 1 h at room temperature
rial in biomedical field. (20). (ii) The nanocomposites were prepared by simultaneous
In this study, we synthesized graphene/silver nanocompo- reduction of graphene oxide and AgNO3 with hydrazine
sites using two different routes; (i) sequential reduction of hydrate. In this procedure, 50 mL of GO mixture was pre-
graphene oxide and AgNO3 (ii) simultaneous reduction of pared as specified above. Then, AgNO3 solution (5–40 mM)
graphene oxide and AgNO3 with hydrazine hydrate. It is the was added into this mixture and stirred for 1 hour. Hydrazine
first detailed study to investigate the effect of various parame- hydrate solution (0.1–14 M) with different mass ratios of
ters on the structure and morphology of graphene/Ag nano- hydrazine hydrate/graphite oxide (0.7–2.1) was added to
composites and size and size distribution of Ag nanoparticles. GO/AgNO3 mixture to reduce both GO and AgNO3. At
Among this parameters, the effect of concentration and last, the above mixture was put in an oil bath (»95 C) and
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amount of reducing agents on graphene/Ag nanocomposite stirred for 24 hours. For both routes, the final graphene/
were first time investigated in this study for two different syn- AgNPs solutions were filtered and washed with water using
thesis methods. an average pore size of 0.22 mm filter. The final graphene/Ag
nanocomposite was dried in a vacuum oven at 50 C for
24 hours.
Experimental Section

Chemicals Characterization
Graphite oxide (Gr O) (30 mm thickness, 500 mm mean Infrared spectra were obtained by a Fourier transform infra-
diameter) was purchased from Grafen Kimya Sanayi Sti. red spectrophotometer in the range between 400 and
(Turkey). Hydrazine hydrate (50–60% w/w), polyvinylpyrol- 4000 cm¡1 (Schimadzu FTIR 8400-S). UV-visible spectra
lidone (PVP, powder, mean Mw: 29000) ammonia (28% w/ were recorded in the range between 200 and 700 nm (Schi-
w), and silver nitrate (AgNO3, 99,5%) were purchased from madzu UV 1601). The morphologies of the nanocomposites
Sigma-Aldrich, Germany. Sodium borohydride was pur- and EDX analysis were observed by scanning electron micro-
chased from Merck, (Germany). Deionized water (resistivity scope (SEM) (FEI QUANTA 400 F high resolution field
18 MV cm) was used for preparation of all aqueous solu- emission SEM) and transmission electron microscope (TEM)
tions obtained from aquaMAXTM-ultra ultrawater purifica- images taken by a Fei Tecnai G2 Spirit Bio (TWIN) operated
tion system. at an accelerating voltage of 80 kV. The samples for TEM
analysis were prepared by placing a drop of the solution sam-
ple onto a copper grid covered with carbon. Raman spectra
Preparation of Graphene of the samples were recorded with Thermoscientific DXR
Graphene nanosheets were prepared by reducing of graphene Raman microscope by using 633 nm excitation wavelength.
oxide using hydrazine hydrate as a reducing agent. First,
25 mg of Gr O was added into 50 mL of deionized water,
the pH of the mixture was adjusted to 10 with ammonia, and Results and Discussion
then the mixture was sonicated for 1 hour (Elmasonic S 70
H, 150 W, 47 kHz). After sonication, unexfoliated graphite Synthesis and Characterization of Graphene
oxide was removed by centrifugation for 30 min at 3000 rpm Figure 1 shows the FTIR spectra of GO and graphene (rGO)
and graphene oxide (GO) was obtained. 200 mg of PVP was synthesized in the presence of PVP. In the FTIR spectrum of
added to above brown solution and stirred continuously for GO, because of extensive oxidation, GO has a strong and
12 hours. Following that, hydrazine hydrate was added to broad O H stretching vibration band at 3410 cm¡1, car-
the above solution and vigorously stirred for a few minutes boxyl CHO stretching band at 1721 cm¡1,O H deformation
(20). Finally, this solution was put in an oil bath (»95 C) and vibration band at 1404 cm¡1 and C O stretching vibration
stirred for 24 hours. After the reduction reaction, the stable at 1087 cm¡1. As expected, due to the reduction reaction by
black graphene dispersion (reduced graphene oxide, rGO) hydrazine hydrate these characteristic bands of GO are rela-
was obtained. tively weaker or completely removed in the FTIR spectra of
graphene. This results indicates that rGO was successfully
obtained after reduction reaction (19, 32).
Preparation of Graphene/AgNPs
UV-visible spectra of GO and graphene are shown in
Graphene/Ag nanocomposites were synthesized with two Figure 2. There are two characteristic absorption bands in
different routes (i) sequential reduction of graphene oxide the UV-visible spectra of GO. The absorption band centered
 Investigation of Graphene/Ag Nanocomposites Synthesis Parameters for Two Different Synthesis Methods 363
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Fig. 1. FTIR spectrum of graphene oxide and graphene.

at 232 nm is attributed to p ! p* transitions of aromatic within graphene nanosheets is restored via reduction reac-
C C bonds. The shoulder centered at 298 nm is correspond- tion. Similar results were also obtained by Yu et al. (26) and
ing to n ! p* transitions of CHO bonds. After the reduction Xu et al. (28)
reaction with hydrazine hydrate, the absorbance in the whole
spectra increases, also the absorption peak at 232 redshifts to
269 nm and the other absorption band at 298 nm is Synthesis of Graphene/Ag Nanocomposite
completely removed. The UV-visible spectra results demon-
strate that the oxygen containing functional groups on the Subsequent Reducing Method
surface of GO are mostly removed and electronic conjugation For the nanocomposites synthesized with subsequent reduc-
ing method, the effect of synthesis parameters such as mass
ratio of AgNO3/Gr O, the concentration of AgNO3 added
on graphene dispersion, the concentration of NaBH4 used as
a reducing agent and AgNO3/NaBH4 molar ratios on size
and size distribution of Ag nanoparticles deposited on gra-
phene nanosheets was investigated.
First, graphene/Ag nanocomposites were prepared by
using different AgNO3/Gr O mass ratios at constant
AgNO3 concentration (40 mM), NaBH4 concentration
(150 mM), and AgNO3/NaBH4 molar ratio (1/4) to investi-
gate the effect of AgNO3 dosage on nanoparticle formation.
UV-vis spectra of graphene/Ag composites prepared by
using different AgNO3/Gr-O mass ratios are shown in Fig-
ure 3. In the UV-visible spectra of graphene/Ag nanocompo-
sites, besides the characteristic UV-vis absorption band of
graphene, a new absorption band occurs at about 405 nm.
This band arises from the surface plasmon resonance (SPR)
Fig. 2. UV-vis spectra of graphene oxide and graphene. absorption band of silver nanoparticles and shows the
 364 Ç iplak et al.

constant AgNO3/Gr-O mass ratio (1:2), NaBH4 concentra-

tion (150 mM), and AgNO3/NaBH4 molar ratio (1:4)]. For
graphene/Ag nanocomposite samples prepared at 40 mM
AgNO3 aqueous dispersion, SPR band of silver nanoparticles
occurs at 406 nm. Decreasing in AgNO3 concentration from
40 mM to 20 mM causes that SPR band maxima blueshifts
to 398 nm, this can be attributed to decrease in silver nano-
particle size. In addition, the SPR band intensity increases
and band width narrows significantly, this indicates more Ag
nanoparticles with narrower particle size distribution are
obtained. At lower AgNO3 concentration (10 mM), the SPR
band intensity is very weak and SPR band maxima redshifts
significantly. This indicates formation of fewer nanoparticles
having larger sizes. Besides, in these spectra, a shoulder
occurs at 350 nm, this band presents polydispersity of the size
and shape of the prepared Ag nanoparticles as stated by Das
et al. (35). Figure 6(b) presents UV-vis spectra of graphene/
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Ag nanocomposites prepared by using different concentra-

Fig. 3. UV-vis spectra of graphene/Ag nanocomposites prepared tions of reducing agent solution (5, 25, 150, 200, 400 mM
with different AgNO3/Gr-O (1:1, 1:2, 1:4, 1:8) mass ratios [at NaBH4 aqueous solutions). Graphene/Ag nanocomposite
constant AgNO3 concentration (40 mM), NaBH4 concentration synthesized at low concentration of NaBH4 aqueous disper-
(150 mM), and AgNO3/NaBH4 molar ratio (1:4)]. sion (5 mM) has a SPR band at 417 nm. When the NaBH4
concentration increases to 25 mM, SPR band maxima of sil-
formation of Ag nanoparticles. While at low AgNO3/Gr O ver nanoparticles blueshifts to 406 nm. In addition, SPR
ratios (1:8 and 1:4) a weak SPR band occurs, the SPR band band intensity of this sample increases significantly. The SPR
intensity enhances by increasing content of AgNO3 (1:2 and band maxima of the samples obtained by using 150 and
1:1) in the graphene dispersion. This indicates that Ag nano- 200 mM NaBH4 shifts to a shorter wavelength (398 nm).
particles are synthesized at higher AgNO3/Gr O ratios. These results indicate that smaller-sized Ag nanoparticles are
SEM images of graphene/Ag composites prepared at dif- obtained at high concentration in comparison to the sample
ferent AgNO3/Gr O mass ratios are shown in Figure 4. synthesized at low concentration of NaBH4 aqueous solution
SEM images indicate that the Ag nanoparticles are deposited (5 mM). For further increase in NaBH4 concentration
on curled and wrinkled graphene nanosheets. At high (400 mM), a change doesn’t observe in SPR band maxima,
AgNO3/Gr O ratio (1:1), bigger nanoparticles forms and however, SPR band intensity decreases dramatically. This is
agglomerations increase significantly (Figure 4(a)). Decreas- attributed to fewer Ag nanoparticles forms at this condition.
ing in the AgNO3 dosage (1:2), results in formation of many In our knowledge, there hasn’t been any study in the literature
silver nanoparticles deposited on graphene nanosheets. They that investigates the effect of NaBH4 solution concentration
are well dispersed and separated from each other (Figure 4 on the preparation of graphene/Ag nanocomposite. Figure 6
(b)). At low AgNO3/Gr O ratio (1:4), silver nanoparticles (c) shows UV-vis spectra of graphene/Ag nanocomposite
can be barely seen on graphene nanosheets (Figure 4(c)). samples prepared at different AgNO3/NaBH4 molar ratios
Yuan et al. also found that high dosages of AgNO3 cause (1:1, 1:2, 1:4, 1:8). At low amount of reducing agent [AgNO3/
agglomerations of Ag nanoparticles deposited on graphene NaBH4 (1:1)], SPR band of Ag nanoparticles doesn’t
nanosheets (34). EDX spectra of the sample prepared at observed, suggesting that AgNO3 doesn’t reduce and the Ag
AgNO3/Gr O mass ratio (1:2) are presented in Figure 4(d). nanoparticles don’t form at this condition. After NaBH4
EDX spectra indicate that graphene nanosheets are deco- amount increases [AgNO3/NaBH4 (1:2)], a relatively weak
rated with Ag nanoparticles. and broad SPR band forms at 418 nm. At AgNO3/NaBH4
Figure 5(a) shows TEM image of graphene/Ag nanocom- molar ratio (1:4), the intensity of the SPR band increases,
posite sample prepared at AgNO3/GO (1:2). This image band width becomes narrower significantly, and SPR band
shows Ag nanoparticles are successfully deposited on gra- maxima blueshifts to 396 nm. These results indicate that
phene nanosheets as supported by SEM and EDX analysis. smaller particles with high concentration and narrower parti-
Figure 5(b) shows that more than 80% of this nanoparticles cle size range are obtained at this condition. At high amount
fall in the size range of 3–14 nm, and the mean particle diam- of reducing agent, SPR band intensity decreases again and
eter is 4.96 § 1.65 nm. band maxima redshifts to 416 nm which can be attributed to
Second, the other important parameters such as, the effect the formation of more agglomerated Ag nanoparticles. This
of AgNO3 aqueous solution concentration, reducing agent result is consistent with the study reported by Lee et al. (36).
solution concentration, and AgNO3/NaBH4 ratio on the size Figure 7(a) and (b) shows the TEM image of graphene/
and size distribution of silver nanoparticles embedded gra- Ag nanocomposite prepared by using 200 mM NaBH4 solu-
phene sheets was carried out. Figure 6(a) shows the UV-vis tion. As seen in Figure 7(a) and (b), well dispersed spherical
spectra of graphene/Ag nanocomposite samples synthesized Ag nanoparticles are deposited on graphene sheets homoge-
at different AgNO3 concentrations [40, 20, 10 mM) (at nously, the size range of Ag nanoparticles (approximately
 Investigation of Graphene/Ag Nanocomposites Synthesis Parameters for Two Different Synthesis Methods 365
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Fig. 4. SEM images of graphene/Ag composites prepared by using different AgNO3/Gr-O mass ratios (a) 1:1, (b) 1:2, (c) 1:4, and (d)
EDX spectra of the composite synthesized at AgNO3/GO mass ratio (1:2).

80%) are between 3 and 8 nm and the mean particle diameter other hand, 200 mM of NaBH4 concentration seems the best
is 5.19 § 1.04 nm. concentration for the synthesis of graphene/Ag nanocompo-
Mean size and size distributions of Ag nanoparticles of site due to the presence of highest amount of Ag nanopar-
graphene/Ag nanocomposites prepared with different ticles with low sizes and more homogenously coverage of
NaBH4 concentrations are presented in Table 1. A dramatic graphene nanosheets. More increase in the reducing agent
change is not observed in particle size distributions for sam- concentration causes that mean particle size increases and
ples obtained at 5, 25, 150, and 200 mM NaBH4. On the particle size range widens significantly.
 366 Ç iplak et al.
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Fig. 6. UV-vis spectra of graphene/Ag nanocomposites prepared

with (a) 10–40 mM AgNO3 aqueous solutions [at constant
AgNO3/Gr-O mass ratio (1:2), NaBH4 concentration
(150 mM), and AgNO3/NaBH4 molar ratio (1:4)], (b) 5–
Fig. 5. (a) TEM image and (b) particle size distribution of gra- 400 mM NaBH4 aqueous solutions [at constant AgNO3/Gr-O
phene/Ag composite synthesized at AgNO3/Gr-O (1:2). mass ratio (1:2), AgNO3 concentration (20 mM), and AgNO3/
NaBH4 molar ratio (1:4)], (c) obtained at different molar ratios
of AgNO3/NaBH4 1:1–1:8 [at constant AgNO3/Gr-O mass
Raman spectra are a powerful tool to characterize carbo-
ratio (1:2), AgNO3 concentration (20 mM) and NaBH4 concen-
naceous materials. Raman spectra of synthesized GO, gra-
tration (200 mM)].
phene, and graphene/Ag nanocomposites are presented in
Figure 8. As seen in Figure 8, in the Raman spectra of GO,
the band at 1585 cm¡1 is called G band, this band arise from concentration of hydrazine hydrate solution (0.1–14 M) as a
the first-order scattering of the E2g mode. The band at reducing agent and mass ratio of hydrazine hydrate/Gr-O
1330 cm¡1 is the D band that is corresponded to decrease of (0.7–2.1) on size and size distribution of Ag nanoparticles
the size of in plane sp2 domains as a result of extensive oxida- deposited on graphene nanosheets were studied by applying
tion of graphene nanosheets. GO and graphene have both D simultaneous reducing method.
and G bands. After reduction reaction, D/G intensity ratio Figure 9(a) shows UV spectra of graphene/Ag nanocom-
(ID/IG) of graphene increases from 1.184 to 1.386. This posites synthesized at different AgNO3 (5, 10, 20, and
increase is due to formation of new graphitic domains that 40 mM) concentrations [at constant AgNO3/Gr O mass
are numerous in number and smaller in size with respect to ratio (1:2), hydrazine hydrate/Gr-O (1.4), and hydrazine
the ones present in graphene oxide. In the Raman spectra, hydrate concentration (14 M)]. The sample obtained at
graphene/Ag nanocomposite intensity of this bands increase 40 mM AgNO3 aqueous solution has SPR band maxima at
significantly. This increase is attributed to surface-enhanced 416 nm. When the concentration of AgNO3 decreases to
Raman scattering (SERS) effect of Ag nanoparticles that 20 mM, the place of the SPR band maxima doesn’t change,
arise from the intense local electromagnetic fields of Ag nano- however, the intensity of the band increases significantly.
particles (29, 37, 38). Further decreasing in AgNO3 concentration (10 mM) results
in a shoulder occurring at 350 nm that presents polydispersity
of the size and shape of synthesized Ag nanoparticles.
Simultaneous Reducing Method Besides, SPR band maxima redshifts to 421 nm, the intensity
In this study, another synthesis route to obtain graphene/Ag of the SPR band reduces and SPR band width widens signifi-
nanocomposites is simultaneous reducing method. The cantly. This shows fewer and larger Ag nanoparticles with
effect of concentration of AgNO3 solution (5–40 mM), the wider particle size distribution forms at this condition. At
 Investigation of Graphene/Ag Nanocomposites Synthesis Parameters for Two Different Synthesis Methods 367
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Fig. 8. Raman spectra of graphene oxide, graphene, and gra-

phene/Ag nanocomposite [synthesized at constant AgNO3/
Gr-O mass ratio (1:2), 20 mM AgNO3, 200 mM NaBH4, and
AgNO3/NaBH4 molar ratio (1:4)].

Fig. 7. (a) TEM image (b) particle size distribution of graphene/

Ag nanocomposite prepared at 200 mM NaBH4 aqueous solu-
tion at constant 1:2 AgNO3/Gr-O mass ratio and 20 mM
AgNO3 concentration.

low AgNO3 concentration (5 mM), SPR band is very weak

and this indicates fewer Ag nanoparticles occur at this condi-
tion in comparison to higher concentrations of AgNO3. In
addition, the SPR band maxima of the samples synthesized
by simultaneous reducing method redshifts with respect to
the samples synthesized by sequential reducing method. This
difference may be due to the change of the size or shapes of
Ag nanoparticles or differences of dielectric environment and
electron density of Ag nanoparticles synthesized by these two
distinct methods (29). Figure 9(b) presents UV-vis spectra of

Table 1 Mean particle size and particle size distributions of Ag

nanoparticles of Graphene/Ag nanocomposites that are pre-
pared with different NaBH4 concentrations
Fig. 9. UV-vis spectra of graphene/Ag nanocomposites synthe-
AgNO3 Mean particle Particle size sized at (a) 5–40 mM AgNO3 aqueous solutions [at constant
concentration (mM) size (nm) distribution AgNO3/Gr-O mass ratio (1:2), hydrazine hydrate/Gr-O mass
ratio (1.4), and hydrazine hydrate concentration (14 M)], (b)
5 4.26 § 1.46 2–8 nm (70%) 0.1–14 M hydrazine hydrate aqueous solutions [at constant
25 4.56 § 1.44 2–8 nm (82%) AgNO3/Gr-O mass ratio (1:2), AgNO3 concentration (20 mM),
150 4.83 § 1.23 3–8 nm (80%) and hydrazine hydrate/Gr-O mass ratio (1.4)], (c) different
200 5.19 § 1.04 3–8 nm (85%) hydrazine hydrate/GO mass ratios (0.7–2.1) [at constant
400 24.13 § 9.93 3–8 nm (10%) AgNO3/Gr-O mass ratio (1:2), AgNO3 concentration (20 mM),
6–52 nm (98%) and hydrazine hydrate concentration (14 M)].
 368 Ç iplak et al.

graphene/Ag nanocomposite samples synthesized at different SPR band of Ag nanoparticles weakens and redshits to higher
hydrazine hydrate concentrations (0.1, 1, 14 M). The SPR wavelength (435 nm). In literature, there hasn’t been another
band of Ag nanoparticles isn’t observed at dilute hydrazine study yet to investigate the effect of hydrazine hydrate
hydrate solution (0.1 M), which indicates the Ag nanopar- amount on the synthesis of graphene/Ag nanocomposite.
ticles aren’t synthesized by hydrazine hydrate reduction at TEM images of graphene/Ag nanocomposite sample
this condition. When concentration increases to 1 M, a weak prepared by using 20 mM AgNO3 solution are presented in
and broad SPR band is observed and it indicates fewer Ag Figure 10(a). As shown in Figure 10(a), despite the existence
nanoparticles occur. After the hydrazine hydrate concentra- of some larger particles, most of the Ag nanoparticles are
tion increases to 14 M, the SPR band intensity becomes very small and well dispersed homogenously on graphene sheets.
strong with respect to more dilute reducing agent solutions. The large Ag nanoparticles may be formed due to the aggre-
Figure 9(c) shows UV-vis spectra of graphene/Ag nanocom- gative growth of the small particles during reducing process.
posites prepared by using different hydrazine hydrate/Gr-O The size range of Ag nanoparticles mostly (approximately
mass ratios (0.7, 1.4, 2.1), with keeping the other parameters 90%) distribute between 2 and 6 nm, and the mean particle
constant. The characteristic absorption band for graphene size diameter is 3.04 § 0.64 nm [Figure 10(b)].
isn’t observed at low amount of reducing agent, this result Table 2 shows the mean size and size ranges of Ag nano-
indicates that the reduction doesn’t occur at this condition. particles for graphene/Ag nanocomposite samples synthe-
On the other hand a weak SPR band is observed at 435 nm, sized with different AgNO3 concentrations. The sample
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which indicates formation of Ag nanoparticles. After the prepared by using 20 mM AgNO3 solution has the narrowest
hydrazine hydrate/Gr O mass ratio increases to 1.4, the particle size range with smallest particle sizes. It is observed
characteristic graphene band near 268 nm forms and a clear that, at below or above 20 mM AgNO3 concentration, larger
and intensive SPR band of Ag nanoparticles blueshifts to particles with wider particle size distribution are obtained.
416 nm. At high hydrazine hydrate/Gr O mass ratio (2.1),
similar to sequential reducing method by NaBH4 reduction,
Comparison of Synthesis Methods and Effect
of Synthesis Parameters
In this study, some important synthesis parameters that
effected graphene/Ag nanocomposite structure and particle
size distribution of synthesized Ag nanoparticles on graphene
nanosheets were examined. At low AgNO3 dosage [AgNO3/
Gr-O (1:4))] fewer Ag nanoparticles forms, at high AgNO3
dosage [AgNO3/Gr O (1:1)] agglomerated bigger Ag nano-
particles are obtained. On the other hand, for AgNO3/
Gr O (1:2) sample, numerous Ag nanoparticles well dis-
persed on graphene nanosheets are obtained by applying sub-
sequent reducing method. For both synthesis methods at
20 mM AgNO3 solution concentration, highest fractions of
smaller nanoparticles with narrower particle size distributions
are obtained. In addition, well-dispersed spherical Ag nano-
particles are deposited on graphene sheets more homoge-
nously at 20 mM AgNO3 concentration for both methods.
For graphene/Ag nanocomposite synthesized by sequential
reduction method, 85% of Ag nanoparticles have particle size
between 3 and 8 nm with mean particle size 5.19 § 1.04 nm.
However, by applying simultaneous reducing method at
20 mM AgNO3 concentration, the portion of smaller size

Table 2 Mean particle size and particle size distributions of Ag

nanoparticles of Graphene/Ag nanocomposites that are pre-
pared with different AgNO3 concentrations by using simulta-
neous reducing method
AgNO3 Mean particle Particle size
concentration (mM) size (nm) distribution

10 19.42 § 11.65 2–8 nm (25%)

Fig. 10. (a) TEM image and (b) particle size distribution of gra-
2–34 nm (82%)
phene/Ag nanocomposite prepared at 20 mM AgNO3 aqueous
20 3.04 § 0.64 2–6 nm (90%)
solution according to simultaneous reducing method [at constant
40 9.10 § 5.81 2–8 nm (56%)
AgNO3/Gr-O mass ratio (1:2), hydrazine hydrate/Gr-O mass
4–22 nm (83%)
ratio (1.4), and hydrazine hydrate concentration (14 M)].
 Investigation of Graphene/Ag Nanocomposites Synthesis Parameters for Two Different Synthesis Methods 369

nanoparticles increases and particle size distribution narrows 7. Shao, Y., Wang, J., Wu, H., Liu, J., Aksay, I. A., and Lin, Y.
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by sequential and simultaneous reduction methods. During W., Yang, Q. H., and Kang, F. (2012) Could graphene construct an
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on morphology and structure of nanocomposites and size and hybrid materials and devices for biosensing. Adv. Drug Deliver.
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sequential reducing method due to obtainment of narrower capacitance of polypyrrole-based nanocomposites. Synth. Met.,
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Authors would like to thank Ankara University Scientific 21. Shan, C., Yang, H., Han, D., Zhang, Q., and Ivaska, A. (2010)
Research fund (Grant No.: 12B4343013) for their financial Graphene/AuNPs/chitosan nanocomposites film for glucose bio-
support in this work. sensing. Biosens. Bioelectron., 25: 1070–1074.
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