Article

pubs.acs.org/Langmuir

Migration of Silver Nanoparticles from Silver Decorated Graphene

Oxide to Other Carbon Nanostructures
K. A. Shiral Fernando,*,† Venroy G. Watson,† Xifan Wang,† Nicholas D. McNamara,† Mary C. JoChum,‡
Dylan W. Bair,‡ Barbara A. Miller,† and Christopher E. Bunker‡
†
Energy Technology and Materials Division, University of Dayton Research Institute, Dayton, Ohio 45469, United States
‡
Propulsion Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433-7103, United States
*
S Supporting Information

ABSTRACT: Decoration of graphene oxide (GO) sheets with Ag nanoparticles has

been demonstrated using a simple sonication technique. By changing the ratio
between Ag-decorated-GO and GO, a series of Ag-decorated-GO samples with
different Ag loadings were synthesized. These Ag-decorated-GO samples were
characterized using transmission electron microscopy (TEM), X-ray diffraction
(XRD) spectroscopy, thermal gravimetric analysis (TGA), and differential scanning
calorimetric (DSC) techniques. TEM analysis showed that Ag nanoparticles were
evenly distributed on GO sheets, and the size analysis of the particles using multiple
TEM images indicated that Ag nanoparticles have an average size of 6−7 nm. TEM
analysis also showed that Ag nanoparticles migrated from Ag-decorated-GO to later-
added GO sheets. In XRD, all the Ag-decorated GO samples showed the
characteristic peaks related to GO and face-centered-cubic (fcc) Ag. Thermal analysis
showed peaks related to the combustion of graphitic carbon shifted to lower
temperatures after GO sheets were decorated with Ag nanoparticles. In addition, further experiments performed using Ag-
decorated-GO and multiwalled carbon nanotubes (MWNTs) confirmed that Ag nanoparticles migrated from Ag-decorated-GO
to later-added carbon nanotubes without a noticeable coalescence of Ag nanoparticles.

■ INTRODUCTION
Much recent effort has gone into research of metal-decorated
carbon nanostructures because these nanostructures possess
very attractive featues.1−6 As a result, a wide range of metal-
decorated carbon nanostructures have been prepared that
exhibit promising applications in nanotechnology and nano-
biotechnology.2,3,7−11 For example, Sun and co-workers
demonstrated that metal-decorated carbon nanoparticles
might be used to convert carbon dioxide to fuel and split
water in order to produce hydrogen in the presence of light.2,8
Silver is widely known for its antimicrobial activity, and
therefore, Ag-decorated carbon supports are used in biomedical
applications, such as in wound dressing and medical
catheters.12,13 Ruiz et al. have reported that GO was highly
biocompatible with bacterial and mammalian cells, with no
cytotoxicity, and that in fact GO promotes bacterial and
mammalian cell growth by enhancing cell attachment and
proliferation, while Ag-decorated-GO inhibits the growth of
bacterial cells.7 In this paper, we present the preparation and
characterization of Ag-decorated-GO samples with different Ag
concentrations/loadings using simple sonochemical methods
that mix different ratios of Ag-decorated-GO and GO. GO was
prepared using a modified Hummers method.14−16 This
method involves the chemical oxidation of graphite to produce
highly exfoliated graphene sheets that contain a large amount of
oxygen functional groups (epoxides, alcohols, ketones, carbon-
yls, and carboxylic groups).17−23 The oxygen functional groups
on the GO surface have a major role in the nucleation and
growth of Ag nanoparticles.25−42 For example, Pasricha et al.
reported that oxygen functional groups act as nucleation sites
for formation and anchoring of metal nanoparticles.42 In
addition, metal (Ag and Au) nanoparticles can interact with
GO sheets through physisorption, electrostatic interactions, and
charge-transfer interactions.42 Furthermore, this study shows
that Ag nanoparticles migrate from Ag-decorated-GO to later-
added GO and produce a new Ag-decorated-GO sample with
less Ag content. The microscopy characterization shows that Ag
nanoparticles are evenly distributed without any noticeable
ripening effect or coalescence. To the best of our knowledge,
this is the first report showing migration of metal nanoparticles
from one carbon nanostructure to another (inter). However,
Lu et al. have reported that, at elevated temperatures (>100
°C), small Ag nanoparticles moved on GO surface to form
larger Ag nanoparticles.51 Lu et al. observed that the
coalescence of Ag nanoparticles happened in same GO sheet
(intra), and they did not report any Ag nanoparticles migration
between GO sheets (inter). They speculated that two possible
mechanisms, Oswald ripening and particles coalescence, are
likely to have been responsible for the ripening process.51
Received: June 20, 2014
Revised: August 21, 2014

© XXXX American Chemical Society A dx.doi.org/10.1021/la502401n | Langmuir XXXX, XXX, XXX−XXX

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Figure 1. TEM images for Ag-GO samples with different Ag loadings.
■ RESULTS AND DISCUSSION
GO was prepared by oxidation of natural graphite powder using
a modified Hummers method.14−16 Graphite consists of
stacked graphene layers with a plane distance of 0.335
nm.17,43 The severe oxidation process in a modified Hummers
method separates these stacked graphene layers and introduces
many oxygen-containing functional groups, as noted be-
fore.17−23 GO powder readily exfoliates into individual or
few-layers-thick nanosheets in polar solvents (water, DMF,
ethanol, etc.) upon a simple sonication forming a suspension
that is stable for a long period of time. In addition, it has been
reported that metal ions could be adsorbed on GO nanosheets
because these oxygen functional groups provide reactive sites
for nucleation and growth of metal nanoparticles.24−42 Both
GO and silver acetate are readily soluble in DMF, and so DMF
was used as the solvent in our Ag decoration of GO reactions.
In addition, Pastoriza-Santos and co-workers have reported that
DMF is a mild reducing agent that reduces silver acetate to
silver nanoparticles easily at elevated temperatures.44 Fur-
thermore, DMF has a desired vapor pressure and viscosity,
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which are important properties to use in a sonochemical
reaction.
Controlling the Ag Content of GO. A 33 wt % Ag loaded
sample was prepared by mixing 50 mg of GO with 25 mg of
silver acetate in DMF and sonicated for 20 min. The same
experiment was repeated five more times to obtain a sufficient
amount of 33 wt % Ag-decorated-GO stock sample. The other
Ag-decorated-GO samples with different Ag loadings (20, 15,
10, and 5 wt %) were synthesized by changing the ratio
between 33 wt % Ag-decorated-GO and GO. In synthesis the
precise ratio between 33 wt % Ag-decorated-GO and GO was
sonicated in DMF for an hour in a bath sonicater. The
reproducibility of this experiment was performed by replicating
above experiments multiple times in the same conditions.
These Ag-decorated-GO samples (33−5 wt %) were
characterized using TEM, XRD, and simultaneous TGA/DSC
analysis.
TEM analysis was performed to determine morphology,
extent of nanoparticle decoration, and size distribution of Ag
nanoparticles. TEM samples were prepared by dropping the
dispersions of GO and Ag-decorated-GO samples in
Langmuir
isoproponol onto carbon-coated or plain copper TEM grids
and then drying at room temperature. As seen in Figure 1a, GO
has a typical flaky structure that is a few layers thick and has a
wrinkled surface. Ag-decorated-GO with different Ag loadings
(33−5%) are shown in Figure 1b−f. Ag nanoparticles appear as
dark dots and are evenly decorated on GO sheets in each
sample. The population of Ag nanoparticles on GO surface
decreases from 33 wt % sample to 5 wt % sample, as expected.
For Ag-decorated-GO samples with different Ag loadings, we
did not observe in TEM the areas where Ag nanoparticles are
agglomerated or larger undecorated areas of GO. The size
analysis of Ag nanoparticles on GO surface was performed
using multiple TEM images of each Ag-decorated-GO. The size
analysis of Ag nanoparticles using TEM showed an average size
of 6−7 nm, with a size distribution of 1−22 nm, as shown in
Figure 2a−e.
Figure 2. Size distributions of Ag nanoparticles on GO for 33 (a), 20
(b), 15 (c), 10 (d), and 5 wt % (e).
XRD analysis was performed to determine the crystallinity of
GO and Ag-decorated-GO samples, as shown in Figure 3. In
XRD analysis, GO exhibits a carbon (002) diffraction peak at
2θ value in the range of 10°−12°, which is considerably lower
than the diffraction peak of graphite at 2θ value of ∼26°.45−47
GO shows a lower 2θ value in XRD because the vigorous
oxidation process during GO synthesis introduces oxygen
functional groups and water molecules between graphene
layers; therefore, GO has a higher interlayer distance. The
interlayer distance of graphene sheets of GO is ∼0.709−0.804
nm, and the interlayer distance of graphene sheets of graphite is
∼0.335 nm.17,43,45 In XRD, all the Ag-decorated-GO samples
show the characteristic peaks related to GO and face-centered-
cubic (fcc) Ag, which are well matched to ICDD card data. In
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Figure 3. XRD analysis of the GO and Ag-decorated-GO samples.
addition to GO peak and fcc Ag peaks, a broad peak appeared
at a 2θ value of 24°, which is related to reduced graphene oxide
(r-GO). Qui et al. reported a similar observation of a new broad
peak appearing at 2θ value of ∼24° after GO was decorated
with Pt nanoparticles, and later they identified it as a r-GO
peak.28 The observation of the peak at 2θ value of ∼24°
indicates GO is partially reduced during the sonochemical
reaction. The intensity ratio between XRD peak of GO and Ag
peaks increases when Ag percentage decreases, as expected.
Therefore, 33 wt % Ag-decorated-GO sample has the lowest
intensity and 5 wt % Ag-decorated-GO sample has highest
intensity of GO peak. Simultaneously, 33 wt % Ag-decorated-
GO sample has the highest intensity and 5 wt % Ag-decorated-
GO sample has the lowest intensity of fcc Ag peak.
In addition, TGA and DSC analyses were performed using a
simultaneous TGA/DSC instrument at a temperature range
from 25 to 800 °C to obtain the Ag loading and thermal
behavior of Ag-decorated-GO samples, as shown in Figure 4. It
has been reported that Ag nanoparticles are stable in air up to
∼1000 °C, and therefore, in thermal analysis, Ag nanoparticles
are not oxidized.48,49 In DSC analysis, GO and Ag-decorated-
GO samples showed two exothermic peaks, with the first peak
centered at ∼222 °C and the second peak centered at 578 °C.
The first peak is related to the removal of oxygen functionality
from GO surface, and the second peak is related to the
combustion of graphene sheets.17,50 The intensity of the first
peak at ∼222 °C depends on the Ag content of sample. A 33 wt
% Ag-decorated-GO sample has the lowest intensity for the first
peak because it has the highest percentage of Ag loading, while
a 5 wt % sample has the highest intensity for first peak because
it has the lowest percentage of Ag loading. As noted before, the
oxygen functional groups on the surface of GO act as
nucleation sites for formation and anchoring of the metal
nanoparticles. Therefore, the highest Ag loaded sample has the
lowest amount of free oxygen functional groups and the lowest
Ag loaded sample has the highest amount free oxygen
functional groups. As a result, the 33 wt % Ag-decorated-GO
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Figure 4. DSC (a) and TGA (b) traces for GO and Ag-decorated-GO samples with different Ag loadings.

sample showed the lowest intensity for the first peak at ∼222 and increase the interlayer distance further. Subsequently, Ag-
°C and the 5 wt % Ag-decorated-GO showed the highest decorated-GO samples have a larger surface area than regular
intensity for the same peak. This DSC results provide direct GO to absorb heat from heating source. Therefore, the
evidence that nucleation and the growth of Ag nanoparticles combustion of Ag-decorated-GO samples occurs at a lower
occurred in oxygen functional groups of GO surface. The temperature than regular GO. In TGA, weight loss between 25
second peak at 578 °C of GO, which is related to the and 100 °C is attributed to the removal of water between
combustion of carbon of graphene sheets, is shifted to lower graphene sheets of GO. Then, there are two regions of
temperature for all the Ag-decorated-GO samples. A 33 wt % noticeable weight loss: from 150 to 250 °C and 550 to 600 °C.
Ag-decorated-GO has the highest shift, while 5 wt % Ag- The former is attributed to the removal of oxygen functional
decorated-GO has the lowest shift of the carbon combustion groups from GO surface while the latter is related to the
peak, as shown in Table 1. The exact reason behind this carbon combustion of graphitic carbon sheets of GO. The two weight
loss regions in TGA correlate well with two exothermic peaks
Table 1. Actual Ag Content, Average Nanoparticle Size from observed in DSC. As noted before, Ag nanoparticles are stable
TEM and the Position of Carbon Combustion Peak from in air up to ∼1000 °C without making their oxide. As GO is
DSC for Ag-Decorated-GO Samples Synthesized by completely burned out before ∼600 °C, TGA analysis could be
Changing the Ratio between 33 wt % Ag-Decorated-GO and utilized to determine the Ag content of Ag-decorated-GO
GO samples (Table 1). Ag loading of Ag-decorated-GO samples
that were obtained from TGA showed a good agreement with
actual Ag loading av size from position of carbon
sample from TGA (wt %) TEM (nm) combustion peak calculated values.
GO 578
Migration of Ag Nanoparticles. In the synthesis of Ag-
33 wt % Ag-GO 32 6 418 decorated-GO samples with different Ag loadings, a 33 wt %
20 wt % Ag-GO 15 7 457 Ag-decorated-GO sample was used as a starting material, and it
15 wt % Ag-GO 12 7 461 was mixed with GO to obtain desired Ag loading. In order to
10 wt % Ag-GO 8 6 478 synthesize new Ag-decorated-GO samples with different Ag
5 wt % Ag-GO 5 7 499 loading, Ag nanoparticles should leave the 33 wt % Ag-
decorated-GO sample and migrate to later-added GO. TGA,
DSC, and XRD analyses show the presence of Ag in newly
combustion peak shift to a lower temperature is not yet synthesized Ag-decorated-GO samples. Nevertheless, these
understood. However, we speculate this could likely be due to characterization techniques do not provide any information
three effects. First, Ag behaves as a catalyst and catalyzes the about the migration of Ag nanoparticles from 33 wt % Ag-
combustion of graphitic carbon. Second, silver is an excellent decorated-GO to later-added GO. Therefore, these techniques
conductor, absorbing heat and passing to graphene sheets cannot be utilized to characterize the migration and distribution
efficiently, and thus the combustion of GO occurs at lower of Ag nanoparticles. Microscopic techniques, especially TEM,
temperature in the presence of Ag nanoparticles on GO sheets. are useful to characterize the distribution of Ag nanoparticles
Third, it has already been published that metal nanoparticles on GO sheets. As shown in Figure 1, all the newly prepared Ag-
intercalate between graphene sheets during the metal decorated-GO samples show that Ag nanoparticles are evenly
decoration of GO,28 so metal nanoparticles behave as spacers distributed on GO surface. The content of Ag nanoparticles on
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GO surface of each sample depends on ratio between 33 wt %

Ag-decorated-GO and GO used during synthesis. A 5 wt % Ag-
decorated-GO sample has the lowest content of Ag nano-
particles, while 33 wt % Ag-decorated-GO has the highest
content of Ag nanoparticles.
Even though TEM analysis confirms that Ag nanoparticles
are evenly distributed in newly synthesized Ag-decorated-GO
samples with less Ag loading, we need further investigation to
confirm the migration of Ag nanoparticles from 33 wt % Ag-
decorated-GO to later-added GO because later-added GO has
the similar morphology to GO with Ag nanoparticles.
Therefore, a couple of new experiments were designed to
confirm the migration of Ag nanoparticles from Ag-decorated-
GO to later-added GO. The first experiment was designed to
determine whether the migration of Ag nanoparticles from Ag-
decorated-GO to GO is continuous. In this experiment, 10 wt
% Ag-decorated-GO sample was synthesized from 20 wt % Ag-
decorated-GO sample instead from 33 wt % Ag-decorated-GO
sample, as shown in Figure 5. Analysis of this sample confirmed
that successive migration of Ag nanoparticles occurred and that
10 wt % Ag-decorated-GO can be synthesized from 20 wt %
Ag-decorated-GO sample. As noted before, size analysis was
performed using multiple TEM images of 10 wt % Ag-
decorated-GO sample, and it indicated the average size of Ag
nanoparticles is ∼10 nm with a size distribution of 1−20 nm. In
addition to TEM analysis, this sample was analyzed by XRD
and simultaneous TGA/DSC. These characterizations showed
that there were no meaningful differences between the 10 wt %
Ag-decorated-GO samples synthesized from 20 or 33 wt % Ag-
decorated-GO. Therefore, this experiment has proved the
successive migration of Ag nanoparticles from Ag-decorated-
GO to later-added GO.
The second experiment was designed by adding MWNTs to
33 wt % Ag-decorated-GO sample instead of GO because in
TEM the tubular structure of MWNTs can be easily
differentiated from GO sheets. A 33 wt % Ag-decorated-GO
sample was mixed with MWNTs in DMF and sonicated similar
to previous Ag-decorated-GO synthesis experiments. TEM
analysis of product (Ag-decorated-GO-MWNTs) indicated
both GO and MWNTs are evenly decorated with Ag
nanoparticles, as shown in Figure 6. Size distribution analysis
was performed to evaluate the size distribution of Ag
nanoparticles on MWNTs and GO. Analysis of particles Figure 5. TEM analysis to prove the migration of Ag nanoparticles
revealed the average size of Ag nanoparticles on both GO and from Ag-decorated- GO to GO is not limited to one time. The
MWNTs surfaces are ∼6−7 nm, with a size distribution of 1− successive migration of Ag nanoparticles occurs between Ag-
24 nm. These numbers are well matched with an average size decorated-GO to GO.
and a size distribution of Ag nanoparticles obtained for our
previous Ag-decorated-GO samples. Therefore, this experiment from Ag-decorated-GO to later-added GO or MWNTs is not
confirms that Ag nanoparticles are migrating from Ag- clear at this point. We speculate that sonochemistry activates
decorated-GO to later-added MWNTs without any noticeable some of the silver nanoparticles that are attached to GO
ripening or damage of particles. Similar to this, Ag nanoparticles surface, so silver nanoparticles release to DMF solution. Later-
should migrate from 33 wt % Ag-decorated-GO to later-added added GO and MWNTs also have reactive sites, including
GO in the synthesis of 5−20 wt % Ag-decorated-GO samples. defect sites and oxygen functional groups. Therefore, Ag
To the best of our knowledge, no papers have been published nanoparticles in DMF solution can attach to the surface of
related to the migration of metal nanoparticles from one carbon later-added GO or MWNTs. We should note here that the
substrates to another (inter). However, as mentioned before, simple mixing of 33 wt % Ag-decorated-GO with GO or
Lu et al. reported that, in elevated temperatures, Ag MWNTs in the absence of aforementioned experimental
nanoparticles, especially smaller ones, moved on same GO conditions (in DMF and sonication) did not show any silver
sheet (intra) and agglomerated to form larger nanoparticles.51 presence on later-added GO or MWNTs. Therefore, sonication
In addition, there are other reports of the migration, and a solvent (DMF) are essential for migration of Ag
coalescence, and agglomeration of small metal nanoparticles nanoparticles from one carbon substrate to another. In the
to form larger metal nanoparticles in a same GO sheet.51−55 synthesis of Ag-decorated-GO samples (20−5 wt %), the 33 wt
The exact mechanism of the migration of Ag nanoparticles % Ag-decorated-GO sample was mixed with GO and sonicated
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Figure 6. TEM analysis to show the migration of Ag nanoparticles from Ag-decorated-GO to MWNTs: acid-treated MWNTs (a), 33 wt % Ag-
decorated-GO (b), and 20 wt % Ag equivalent Ag-decorated-GO-MWNTs (c).
in a round-bottom flask. In this reaction both Ag-decorated-GO
and later-added GO are in close proximity in DMF solvent.
Sonication provides the required kinetic energy to mix and
collide Ag-decorated-GO with later-added GO. Therefore, Ag
nanoparticles might also migrate from Ag-decorated-GO to
later-added GO because of these rapid collisions.
It has been reported in the literature that synthesis of Ag and
other metal nanoparticles using passivation agents to prevent
agglomerations and then attaching these passivated-metal
nanoparticles to GO and other carbon nanostructures via
covalent bonds or weak intermolecular interactions such as
π−π stacking, hydrophobic, and electrostatic interactions.3,56
The nature of chemical interaction between GO and Ag
nanoparticles is completely different in these samples compared
to our Ag-decorated-GO. Our Ag nanoparticles do not have a
passivation agent, and therefore, Ag nanoparticles are directly
attached to the surface of GO or any other carbon
nanostructures. This migration of metal nanoparticles between
nanostructures is significant because this method might be
utilized to introduce metal nanoparticles to the substrates that
are inherently difficult to functionalize with metal nanoparticles.
GO, carbon nanoparticles, and purified carbon nanotubes are
easy to functionalize with metal nanoparticles because they
have oxygen functional groups on the surface. As noted before,
these oxygen functional groups provide platforms for
nucleation and growth of metal nanoparticles. Metal nano-
particles do not agglomerate because the nucleation and growth
of metal nanoparticles happens in distinct places on these
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nanostructures. However, the materials and substrates that do
not have defects and functional groups cannot be decorated
with metal nanoparticles easily because of the absence of
nucleation centers. Therefore, migration of metal nanoparticles
might be useful in decorating the substrates and materials with
metal nanoparticles that do not possess nucleation centers.
■ CONCLUSIONS
GO was successfully decorated with Ag nanoparticles in DMF
using sonochemistry. The loading of Ag nanoparticles on GO
surface was controlled by mixing 33% Ag-decorated-GO with
known amounts of GO. TEM analyses revealed that GO
surfaces are evenly decorated with Ag nanoparticles in all the
Ag-decorated-GO samples prepared in this study. Size analysis
using TEM indicated an average size of 6−7 nm, with a size
distribution of 1−22 nm. Simultaneous TGA and DSC analysis
of GO and Ag-decorated-GO samples with different Ag
loadings indicated that the carbon combustion peak of GO at
∼578 °C shifted to lower temperature after Ag nanoparticles
were added to GO surfaces. Further experiments performed
using MWNTs confirmed that Ag nanoparticles migrated from
Ag-decorated-GO to later-added MWNTs.
■
EXPERIMENTAL SECTION
Materials. Silver acetate (99.99%), ammonium persulfate,
phosphorus pentoxide, potassium permanganate, multiwall carbon
nanotubes (MWNTs), sulfuric acid, hydrochloric acid, 13.3 M nitric
acid (>69%), and N,N-dimethylformamide (DMF) (99.6%) were
Langmuir
purchased from Sigma-Aldrich. Graphite powder was obtained from
Asbury Carbon (grade 3805). Dialysis tubes (MWCO ∼ 6000−8000)
and reagent ethanol (90%) were also purchased from Fisher Scientific.
All the solvents were used as received without any further treatment or
purification.
Synthesis of Graphene Oxide. Graphene oxide was synthesized
by using modified Hummers method. H2SO4 (10 mL) was heated at
80 °C in a 500 mL round-bottom flask, and then (NH4)2S2O8 (0.9 g)
and P2O5 (0.9 g) were added. The mixture was stirred well until all the
reagents were dissolved well and make a homogeneous solution.
Graphite powder was introduced to the flask, and the mixture was
allowed to heat for 4.5 h at 80 °C and then cooled down to room
temperature. The reaction mixture was diluted with 250 mL of
deionized water and kept for 12 h. The mixture was filtered, and a
solid residue in filter paper was washed repeatedly with water and
dried in an oven for overnight. The solid residue was added to H2SO4
(40 mL) in a 500 mL round-bottom flask and cooled in an ice bath.
KMnO4 (5 g over 40 min) was added to the mixture while the
temperature was kept <10 °C. Upon achieving a color change from
black to greenish brown, the mixture was kept at 35 °C for 2 h. Then
the mixture was diluted with 85 mL of water. Ice bath was used to
maintain the inside temperature of the mixture below 35 °C during
this water addition. After the temperature reached room temperature,
the flask was heated at 60 °C overnight. 250 mL of water was added to
the mixture and kept another 5 h at ∼60 °C. Then the mixture was
poured into a beaker, and 10 mL of aqueous H2O2 was added after
mixture was reached room temperature. Effervescence and a color
change to yellow were observed. The reaction mixture was allowed to
sit for 12 h, after which the transparent supernatant was removed, and
H2SO4 (5 wt %)−H2O2 (0.5 wt %) and a solution of HCl (10 wt %)
were used to repeatedly wash the sediment. The washing with water
was performed repeatedly until the sample did not show layers
separation. Then, the sample was transferred to dialysis tubes, which
were kept in a deionized filled water beaker for 7−10 days, and water
was changed once a day. The final product was recovered as a black
flaky powder after water was removed by rotary evaporation.
Acid Treatment of MWNTs. 500 mg of MWNTs was added to a
2.6 M solution of 250 mL of nitric acid and refluxed for 24 h. Upon
completion of refluxing, the mixture was cooled to room temperature,
centrifuged, and washed with deionized water many times until the pH
of supernatant was neutral. Then, the recovered sample was washed
with acetone several times to remove water. Nitrogen was blown over
the sample to remove acetone, and a final product was recovered as a
black powder.
Sonochemical Synthesis of Ag-Decorated-GO with 33 wt %
Ag Loading. 50 mg of GO, 15 mL of DMF, and 25 mg of silver
acetate were mixed in a sonication flask (Sonics Inc., Suslick flask).
The mixture was sonicated using a horn sonicator at 1-s-on and 1-s-off
at 37% amplitude for 20 min. After sonication, the mixture turned to a
black solution, and the final temperature was measured as ∼90 °C.
After cooling to room temperature, the solution in a sonication flask
was transferred to a round-bottom flask. Then, DMF was removed
using a rotary evaporator, leaving a black powder in the round-bottom
flask. In order to remove any unreacted Ag acetate and loosely bound
Ag nanoparticles, the sample needed to be washed with water and
ethanol. For this purpose, the sample was transferred to centrifuge
tubes and washed with water and ethanol five times. Ethanol was dried
by blowing nitrogen across the surface of the solution, and a final
product was recovered as a black powder. This synthesis procedure
was repeated multiple times to synthesize enough Ag-decorated-GO
for experiments that are discussed in this article.
Synthesis of Ag-Decorated-GO Sample with 20 wt % Ag
Loading. In a round-bottom flask, 30.77 mg of Ag-decorated-GO (33
wt % Ag loading) and 19.23 mg of GO were mixed with 15 mL of
DMF and sonicated for 1 h in a bath sonicator. Upon completion of
sonication, DMF was removed from sample using a rotary evaporator.
Then, the sample was transferred to centrifuge tubes and washed with
ethanol 5 times. The final product was recovered as a black powder
with 46 mg yield after blowing nitrogen across the surface of the
sample.
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Synthesis of Other Ag-Decorated-GO with 15, 10, and 5 wt
% Ag Loading. These Ag-decorated-GO samples were synthesized in
the same way as described in 20 wt % Ag-decorated-GO synthesis
procedure. In these reactions, the weight ratio between GO and Ag-
decorated-GO were changed to obtain the new Ag-decorated-GO
samples with desired Ag loadings.
Successive Dilution of 33 wt % Ag-Decorated-GO To Obtain
20 and 10 wt % Ag-Decorated-GO. First, the 20 wt % Ag-
decorated-GO sample was synthesized in the same way as described
earlier. In the preparation of 10 wt % Ag-decorated-GO sample, 20 wt
% Ag-decorated-GO (25 mg) was mixed with GO in DMF (15 mL)
and sonicated for 1 h. The recovery and cleaning procedures were
performed in the same way as stated in previous synthesis procedures.
Synthesis of 20 wt % Ag-GO-MWNTs. In a round-bottom flask,
9.13 mg of MWNT and 15.38 mg of 33 wt % Ag-decorated-GO were
mixed with 15 mL of DMF and sonicated in a bath sonicator for 1 h.
Cleaning and recovery of the sample were performed in the same way
as described in the previous synthesis procedures.
Measurements. Transmission electron microscopy (TEM) images
were obtained using a Hitachi H-7600 operated at 100−120 kV.
Samples for TEM were prepared in butanol and drip spotted on
copper grids coated with carbon. X-ray diffraction (XRD) studies were
performed using a Bruker D8-Advance equipped with a Cu Kα source
and a Sol-X detector. Observed XRD patterns were identified with the
ICDDS crystallographic database. The mass and energetic behavior of
the samples as a function of temperature were determined using
thermogravimetric analysis (TGA) and differential scanning calorim-
etry (DSC) on a TA Q600. The solid sample was heated in an opened
alumina pan from room temperature to 800 °C at 10 °C/min with air
flow rate kept at 100 mL/min. A PerkinElmer 400F equipped with a
continuous 785 nm laser was used to record the Raman spectrum over
a wavenumber ranging from 100 to 3000 cm−1 by placing the solid
sample on a glass slide in the sample holder for analysis.
■
ASSOCIATED CONTENT
*
S Supporting Information
Experimental details and Figures S1−S6. This material is
available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail Shiral.Fernando@udri.udayton.edu (K.A.S.F.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the continued support of
Dr. Michael Berman of AFOSR for fundamental fuels and
energy research. Additional support was provided by the AFRL
Fuels and Energy Branch and the Nanoenergetics Program.
The authors also thank Prof. Ya-Ping Sun for helpful
discussions.
■
REFERENCES
(1) McNamara, N. D. Sonochemical synthesis and characterization of
metal nanoparticle-decorated carbon supports. Master of Science
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