DOI: 10.1002/slct.
201600157 Communications
z Materials Science inc. Nanomaterials & Polymers
Improved and A Simple Approach For Mass Production of
Graphene Nanoplatelets Material
Mr. Duong Duc La,[a] Suresh Bhargava ,[a, b] and Sheshanath V. Bhosale *[a, b]
Graphene has become the most studied nanomaterial of the
past decade, due to its unique electronic properties which are
essential for various applications such as electronics, sensors,
transistors, batteries, as well as conducting polymer compo-
sites. There are several report outlined to prepare few layers of
graphene nanoplatelets, however, few of them suffer from few
drawbacks such as use of toxic reagents (oleum) tedious meth-
od and also suffer from production of defect free graphene.
Herein, we describe mass production of graphene nano-
platelets (GNPs) by exfoliation of natural graphite flakes in sin-
gle step using sodium persulfate and sulphuric acid at room
temperature followed by washing with dry acetone. The pro-
duced GNPs (~ 100 %) are tens of microns in diameter with
thickness are about 10–20 nm. We have also evaluated role of
water for exfoliation of graphite. The formed GNPs were con-
firmed by SEM, TEM, and AFM microscopy.
Graphene is a nanomaterial has attracted significant interest in
recent years due to its potential applications in many inter-
disciplinary areas in physics, chemistry and engineering.[1–6] Gra-
phene possesses a range of useful properties such as thermal
conductivity and mechanical stiffness and may challenge
graphite itself in its broad range of applications.[2] The in-
dividual graphene scaffolds have excellent electronic properties
which are essential for various applications such as sensors,
transistors, batteries, as well as conducting polymer composites
for solar cells.[7,8]
This has led to many studies attempting to develop techni-
ques to create single layer graphene. Three general routes have
been employed, which include (i) mechanical peeling, (ii) epi-
taxial graphene growth and (iii) solution-based reduction of
graphene oxide. Mechanical peeling can repeatedly produce
single graphene sheets of up to 10 mm in planar size. Where as
the epitaxial method produces graphene by treatment of sili-
con carbide wafers at high temperatures.[9,10] It is important to
[a] M. D. D. La, Prof. S. Bhargava , Dr. S. V. Bhosale
School of Applied Sciences
RMIT University
GPO Box 2476, Melbourne, VIC-3001, Australia
E-mail: sheshanath.bhosale@rmit.edu.au
[b] Prof. S. Bhargava , Dr. S. V. Bhosale
Centre for Advance Materials and Industrial Chemistry
RMIT University
GPO Box 2476, Melbourne, VIC-3001, Australia
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/slct.201600157
ChemistrySelect 2016, 5, 949 – 952
note that these two techniques are extremely time consuming
and can only produce very small amounts of graphene with the
quality depending on the type of substrate employed. The
third method is the solution-based approach, which has
emerged as a promising route to produce large quantities of
graphene.[11–13] Commonly in this approach graphite oxide (GO:
a product from oxidation of graphite) is used as a medium to
obtain stable graphene dispersion in a solvent.[14] Another sol-
ution based approach is the conversion of graphite to graphite
intercalation compounds (GICs), in which intercalation expands
graphite and lessens the adhesive forces between the con-
stituent graphene layers, thereafter, GIC’s are introduced into a
liquid and upon sonication or microwave heating afford par-
tialy exfoliated graphite.[15–19] However, both these methods suf-
fer drawbacks such as oxidation of graphite to produce GO re-
sults in diminished performance of its excellent electrical
properties and ultimately becomes an electrical insulator due
to formation of distorted sp3-hybridized geometry.[20] For the
GICs technique describe previously is mechanical one, not
chemical, therefore the degree of delamination is very low and
can often be inconsistent. The use and application of graphene
is hampered by the lack of efficient process for its mass pro-
duction and also time consuming and very costly. Therefore
there is a need to develop a simple and straight forward meth-
od to produce graphene of consistent quality, and in bulk
quantity.
Herein, we describe a simple technique for synthesis of gra-
phene nanoplatelets (GNPs) and few-layer graphene (Gfew-layer)
in quantitative yield with the flakes being about tens of micron
in size. Typically, 1 g of natural graphite flakes (from Press-
olGmbh, with particles size > 100 mesh) was dispersed in
80 mL of sulphuric acid (98 %) thereafter 6 g of sodium persul-
fate (Na2S2O8) was added and reaction mixture gently stirred for
3 h at room temperature, followed by direct filtration, washing
with dry acetone (3x10 mL) and Milli-Q water (5 mL), dried at
60 oC in open air gave a quantitative yield of GNPs (Figure 1).
The method described herein avoids the use of expensive
reagents and toxic oleum,[21] avoids conversion of graphene
back to graphite,[22] and uses of a simple stirring method (saves
two third of the time required in the conventional method) as
shown in Figure 2. Furthermore, the filtrated solution contain-
ing H2SO4 and Na2S2O8 could possiblbly be reused for the
graphite exfoliation, allowing for a more “green” approach. The
method developed in this study is a simple, efficient and faster
than conventional method (Figure 2)[23] for production of mass
GNPs from natural graphite.
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Figure 1. Synthetic route of the graphene nanoplatelets from graphite flakes.
Figure 2. Comparision of the standard method (obtained from Journal of Life
Cycle Assessment 2014 19, 1226)[23] and method described in this work.
The formation of GNPs was confirmed by scanning electron
microscopy (SEM) as shown in Figure 3. Figure 3 A, shows typi-
cal nature of graphite flakes with a thick lateral structure. How-
ever, GNPs retained their expanded exfoliated states confirmed
by SEM imaging as showin in Figure 3B and 3C. The low-magni-
fication image (Figure 3B) of GNPs shows a very consistent
crumpled and wrinkled morphology with lateral size of 10–50
mm, which indicate that the GNPs only contain a few graphene
layers in each stack, such morphology has also been reported
by Müllen group.[24] The high-magnification image of GNPs
shows semitransparency to the electron beam, which clearly
show GNPs with less than 10–40 layers in the stack (Fig-
ure 3C).[25–27] Thethermogravimetric analysis (TGA) data is
shown in Figure 3D, typically, the GNPs exhibit a 2.3 % weight
loss in the 120–230 oC temperature intervals and this weight
loss is typical for graphene oxide and attributed to decom-
position of some oxygen functionalities along with the loss of
trapped water. The weight loss of about 2 % after 230 oC is at-
ChemistrySelect 2016, 5, 949 – 952
Communications
Figure 3. SEM images of (A) natural graphite flakes, (B and C) GNPs and Gfew-
, respectively, and (D) TGA of GNPs at 20 oC min 1 in air atmosphere.
layer
tributed to the loss of intercalated H2SO4, Na + , S2O82 within
the GNPs.
Figure 4 and S1 shows a AFM images of the GNPs. The aver-
age height and thickness ratio of GNPs gained from AFM image
Figure 4. Topographic AFM image of graphene nanoplatelets and the height
profile taken across the white line on the AFM image.
is ~ 18 nm, which is about 36 layers of a graphene as shown in
Figure 4. The synthesised GNPs are not uniformly flat due to
their wrinkled morphology, therefore leads to the top graphene
layers “jumping” out of Si wafer surface.[21]
The X-ray-diffraction (XRD) analysis of GNPs only shows a
broad peak at about 26.5o (Figure 5 A and Figure S2). The
broad peak as compared to graphite (sharp peak observed for
graphite) between 25–288 2q angle areas indicative of less or-
derly structure, which is consistent with SEM image (Figure 3C).
The XRD comparison clearly shows that 002 diffraction signals
950  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 5. (A) XRD spectrum of graphite flakes (Black) and graphene nano-
platelets (Red); (B) TEM image of GNPs; and XPS spectra of GNPs: (C) survey
scan and (D) C 1 s.
of the GNPs are significantly broader and weaker compared to
that of graphite flakes (Figure 5 A). These results clearly indicate
that although GNPs hold multilayered flakes, the ordered inter-
layer structure, of constituent graphene layers as seen in graph-
ite is no longer exists.
The morphology of GNPs was further confirmed by trans-
mission electron microscopy (TEM) analysis. TEM images clearly
shows that the formed GNPs have a wrinkled structure with
corrugation and scrolling which is typical to graphene (Fig-
ure 5B and S3).[21,22,24–27] The semitransparency of GNPs ob-
served in TEM images also confirms that the GNPs comprise
very few layers of graphene, overlaid side by side.
Furthermore, the quality of the as-fabricated GNPs was con-
firmed by X-ray photoelectron spectroscopy (XPS) as shown in
Figure 5C. A survey scan of GNPs, confirms the appearance of
Na + , Sulfur and O trapped between GNPs layers with 86 % of
Carbon, 13 % of Oxygen, 0.7 % of Sulfur and 0.3 % of Sodium.
This atomic ratio is in good agreement with EDS data with
atomic percentage of C and O are 89 % and 11 % respectively.
The C 1 s spectrum (Figure 5D) shows only one peak of binding
energy at 284.5 eV, which is corresponds to C C bonds indicat-
ing the final product is pure GNPs. The absence of peaks at
285.5 eV or 286.6 eV indicates that there is no oxidized carbon
species existed in obtained Graphene NPs.
In an earlier report by Tour group[22] suggested that the wa-
ter has an influence in exfoliating graphite when ammonium
persulfate/sulphuric acid intercalation compounds were used.
With this method they observed that the formation of graphite
intercalation compounds is reversible upon washing with wa-
ter. In another report they have also suggested that use of
oleum as a dehydrating agent within the reaction would over-
come this issue and increase the yield of GNPs in nearly quanti-
tative yield.[21] From these two reports it is clear that water
plays a significant role in exfoliation of graphite flakes.
ChemistrySelect 2016, 5, 949 – 952
Communications
We therefore investigated the effects of various amount of
water content in H2SO4 for the exfoliation of graphite as shown
in Figure 6 (A E). SEM and optical images (glass vial) exhibit a
Figure 6. SEM image of GNPs obtained from exfoliation of graphite flakes
with different concentration of H2SO4: (A) 80 %, (B) 90 %, (C) 95 %, (D) 98 %,
(E) 100 % (H2SO4 98 % + oleum 65 % SO3 free), and (F) TEM image of gra-
phene nanoplatelets synthesized from H2SO4 100 %.
slight expansion of graphite flakes when > 2 % H2O content in
H2SO4 is used. However, the graphitic structures are similar for
GNPs obtained from H2SO4 of both 98 % and 100 % (Figure 6D
and 6E). Figure 5F displays the TEM image of few layers GNPs
obtained from 100 % H2SO4, which is similar to GNPs obtained
from H2SO4 98 % (Figure 5B). Although water appears to have
an effect on exfoliation of graphite, the revese reaction does
not occurs when sodium perfate is used as a intercalator.[27]
This phenomenon can be explained by the participant of Na +
ion in intercalation[28] and subsequently exfoliation of graphite
flakes overcome the hydrophobic force of 2 % H2O, the main
factor preventing exfoliation when ammonium persulfate was
used.[21] From this experiment, we concluded that there is no
need to use expensive and toxic oleum for exfoliation of graph-
ite (see ESI Figure S4). It is important point to note that after
exfoliation direct quenching and washing with water should be
avoided otherwise shrinking/aggregated graphene will be pro-
duced (see ESI Figure S5).[21]
In conclusion, we have developed a new, and efficient
method for the mass production of graphene nanoplatelets
(GNPs) with later size of ~ 10-20 nm thick. The method de-
scribed is very simple and avoids toxic reagents for the pro-
duction of defect free and few-layered GNPs. Importantly, no
chemical oxidation of graphite occurs when sodium persulfate/
sulphuric acid is used for mass production of GNPs.
Supporting Information
Supporting Information include details of experimental, XRD
and microscopiy analysis.
Acknowledgements
This work was financially support by the Australian Research
Council under a Future Fellowship Scheme (FT110100152). The
951  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

authors acknowledge the facilities, and the scientific and techni-
cal assistance, of the Australian Microscopy & Microanalysis Re-
search Facility at RMIT University.
Keywords: Graphene · Sodium persulfate · Graphene
nanoplatelets · Graphite exfoliation · Sulphuric acid
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Submitted: February 29, 2016
Accepted: April 7, 2016
952  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim