JOM, Vol. 67, No.

12, 2015
DOI: 10.1007/s11837-015-1522-5
2015 The Minerals, Metals & Materials Society

Graphite to Graphene via Graphene Oxide: An Overview

on Synthesis, Properties, and Applications

D.P. HANSORA,1 N.G. SHIMPI,2 and S. MISHRA1,3,4

1.Department of Nanoscience & Technology, University Institute of Chemical Technology,

North Maharashtra University, Jalgaon 425001, Maharashtra, India. 2.Department of
Chemistry, University of Mumbai, Kalina, Santacruz East, Mumbai 400098, Maharashtra, India.
3.e-mail: profsm@live.com. 4.e-mail: profsm@rediffmail.com

This work represents a state-of-the-art technique developed for the prepara-

tion of graphene from graphitemetal electrodes by the arc-discharge method
carried out in a continuous flow of water. Because of continuous arcing of
graphite-metal electrodes, the graphene sheets were observed in water with
uniformity and little damage. These nanosheets were subjected to various
purification steps such as acid treatment, oxidation, water washing, cen-
trifugation, and drying. The pure graphene sheets were analyzed using Ra-
man spectrophotometry, x-ray diffraction (XRD), field emission-scanning
electron microscopy (FE-SEM), and tunneling electron microscopy (TEM).
Peaks of Raman spectra were recorded at (13001400 cm1) and (1500
1600 cm1) for weak D-band and strong G-band, respectively. The XRD pat-
tern showed 85.6% crystallinity of pure graphite, whereas pure graphene was
66.4% crystalline. TEM and FE-SEM micrographs revealed that graphene
sheets were overlapped to each other and layer-by-layer formation was also
observed. Beside this research work, we also reviewed recent developments of
graphene and related nanomaterials along with their preparations, proper-
ties, functionalizations, and potential applications.

knowledge of the topic. Research on graphene has

INTRODUCTION
Nanotechnology has been blossoming for more
than two decades as its importance increases.118
Nowadays, graphene emerges as a rising star and
new paradigm of relativistic condensed-matter
physics and material science. The discovery of gra-
phene is an important addition as a worlds thinnest
material. Its derivatives play a significant key role
in modern scientific life.19 The fundamental break-
throughs toward the physical understanding of
graphene and graphite were routed in the 1940s
and 1950s.20,21
Discovery and History of Carbon Nanomate-
rials
The word graphene originates from the Greek
word graphein, which means to write. Earlier re-
search on preparation and fundamental properties
of nanocarbons (e.g., epitaxial graphene films,
nanoribbons, and nanopatches) provides a basic
been successfully capitalized after its discovery in
2004 by Novoselov et al.19 (see also Refs. 20, 22, 23).
Graphene is an intriguing material for highly con-
trolled systems, e.g., evolution from two-dimen-
sional (2-D) to three-dimensional (3-D) topology
having new properties. These 3-D materials can be
engendered by the substituting the carbon atoms
with selected heteroatoms or entire functional
groups.19,21,2428
Graphene is composed of a single-layer hybrid
nanosheet of sp2 or multiple layers of carbon atoms.
These carbon atoms are densely packed into ben-
zene rings stripped of their hydrogen atoms. This
2-D material has exceptional characteristics like
electronic and high crystal quality. Its short history
has already shown a cornucopia of new physics and
potential applications. Graphene is the basic struc-
tural parent of all carbon allotropes, as shown in
Fig. 1. These carbon allotropes include graphite,
fullerenes, nanorings, nanobuds, single-walled car-
bon nanotubes (SWCNTs), double-walled carbon

(Published online July 3, 2015) 2855

2856
nanotubes (DWCNTs), and multiwalled carbon
nanotubes (MWCNTs).1921 There are mainly three
types of graphene sheets: single layer, bilayer, and
few layers (<10). Kuilla et al.25 reported about sin-
gle-layer graphene sheets and other 2-D crystals.
Graphene is considered as a conducting nanofiller
with a one-atom-thick planar sheet of sp2 bonded
carbon atoms packed in a honeycomb crystal lat-
tice.29 Graphene has been researched due to its
exceptional physical properties, chemical tenability,
and potential for various applications.30
Types of Graphene-Related Nanomaterials
Graphene-related carbon nanomaterials28,31,32
are (I) doped graphene and derived graphene
nanoribbons (GNRs), (II) graphene oxide (GO), (III)
graphane, (IV) florographene, (V) graphyne and
graphdiyne, (VI) graphone, and (VII) porous gra-
phene. Graphene is characterized as a zero band
gap semimetal in which conduction and valence
bands meet at the Dirac point. The band gap can be
tuned by doping and cutting the 2-D graphene into
one-dimensional GNRs.20,33 GO is an oxide-func-
tionalized derivative of graphene, which has re-
ceived tremendous interest of scientists. GO is a
hydrophilic material because it possesses excellent
water dispersity. It can adhere to interfaces because
of lower interfacial energy. GO is used as a surfac-
tant for the emulsification of organic solvents in
water. It can be used for the dispersion of insoluble
graphite and CNTs in water. This ability opens
opportunities for developing functional hybrid
materials of graphene and other P-conjugated sys-
tems.33,34 Graphane is hydrogenated derivative of
Fig. 1. (a) Graphene as honeycomb lattice of carbon atoms. (b) Graphite as a stack of graphene layers. (c) Fullerene (C60) molecules of wrapped
graphene through the introduction of pentagons on the hexagonal lattice. (d) CNTs as rolled-up cylinders of graphene sheets. (e) DWCNT as two
concentric nanotubes. (f) MWCNTs as multiconcentric nanotubes. [Images (a, cf) reproduced with permission of Shigeo Maruyama, University
of Tokyo (http://www.photon.t.u-tokyo.ac.jp/maruyama/agallery/agallery.html). Image (b) was reproduced with permission of Dmitri Kope-
liovich, SubsTech (Substaces Technologies, http://www.substech.com)].
Hansora, Shimpi, and Mishra
graphene and a theoretical nonmagnetic semicon-
ductor with an energy gap formed by hydrogena-
tion. Graphane is extended 2D polymer of carbon. It
is newly invented hydrocarbon with stoichiometry
formula unit of CH as shown in Fig. 2a. Graphane
adds wealth to the carbon-based materials, showing
its great potential in nanoelectronics and hydrogen
storage applications. The hydrogen atoms alternate
directions along with the graphane sheet and
transform the carbon lattice from sp2 to sp3
hybridization. Graphane can also be converted back
into a graphene sheet through an annealing pro-
cess. Florographene is another important structural
derivative of graphene with a stoichiometric for-
mula unit of CF. Florographene has a similar geo-
metric structure and sp3 bonding configuration to
graphane with each carbon bonded to one fluorine
atom. Florographene can be used as a superior solid
lubricant for batteries under extreme conditions.
Graphyne and graphdiyne (Fig. 2b and c) are new
forms of non-natural carbon allotropes. These
nanocarbon allotropes have shown interest better
than graphene due to their unique structures, and
electronic and intriguing properties. Graphyne is a
one-atom-thick planar sheet of sp and sp2 bonded
carbon atoms arranged in a crystal lattice. Gra-
phyne is another form of graphene, and it has
acetylenic linkages connecting the hexagons of
graphene. Graphone (Fig. 2d) is predicted as a
semihydrogenated (50%) derivative of graphene
with C2H as stoichiometric formula.32 Hydrogen
atoms are attached to one side of the carbon sheet. It
is also a mixture of hybridized sp2 and sp3 carbon
atoms. Porous graphene is a new class of light-
weight material. It can be described as a distributed
Graphite to Graphene via Graphene Oxide: An Overview on Synthesis, Properties, and Applications
Fig. 2. Structure of (a) graphene [Reproduced by permission from Ref. 60. 2014 IOP Publishing], (b) graphyne [extracted from http://forum.
nasaspaceflight.com/index.php?topic=28157.0], (c) graphdiyne [Reproduced with permission from Ref. 61. Royal Society of Chemistry 2014],
and (d) graphone.
inherent structure within the covalent p-electronic
framework of graphene.
Present Scenario of Graphene-Related Carbon
Materials
The focus of scientists has moved toward more
complex systems like modified graphene and 3-D
systems based on the assembly of graphene sheets.
Graphene is the latest sensation with unusual
properties such as the half-integer quantum Hall
effect and ballistic electron transport.19 This 2-D
material is expected to consist of single layer, but
considerable interest has been observed in investi-
gating two-layer and few-layer graphenes. The re-
search has led to next-generation graphene-based
nanomaterials. These next-generation graphene
nanomaterials include modified graphene (carbon
atoms replaced by N, B, S, or P) and architectures of
3-D graphenes (e.g., nanospheres, nanocapsules,
nanopapers, and nanolayers).24,29 Graphene has
attracted both academic and industrial interests
because it can improve properties of composites at
low filler content.
In this article, we describe the continuous syn-
thesis of graphene from graphitemetal electrodes
by arc-discharge method carried out in continuous
flow of water. These graphene sheets were purified
before their characterization and testing. This arti-
cle also reviews about types of graphene-related
nanomaterials, various synthesis methods, func-
tionalization, properties and applications of gra-
phene, and its derivatives.
EXPERIMENTAL
Materials
Research-grade (turbostratic and pyrolytic grade)
graphite electrodes with high orientation and car-
bon electrodes were purchased from M/s Schurtz
Carbon Electrodes Pvt. Ltd. (Gandhinagar, Gujarat,
India). Different metal (tungsten, carbon, and cop-
per) electrodes were used from scrap materials.
Demineralized (DM) water was used as a continu-
2857
ous flowing medium for uniform dispersion of gra-
phitic nanostructured sheets. An ice-bath was used
for cooling purpose. Hydrochloric acid (HCl) was
received from S.D. Fine-Chem Limited (Mumbai,
India) and used as such for purification of graphene
sheets.
Synthesis Method
Graphene has been synthesized by various meth-
ods like (I) catalytic chemical vapor deposition
(CCVD) or microwave CVD,2025,2830,33,3539 (II) arc-
discharge method,20,28,29 (III) micromechanical exfo-
liation,19,20,23,25,29,30,33,37,4043 (IV) epitaxial growth
on SiC,2025,28,29,33,37,39 (V) chemical reduc-
tion,20,25,33,34,37,41,43,44 (VI) thermal reduction,20,22,28
(VII) liquid phase exfoliation,20,22,29,30,4043 and (VIII)
unzipping of CNTs,38 and (IX) gas phase microwave
plasma reactor.20
GO can be synthesized from oxidation of graphite
by various methods like Brodie, Staudenmaier, and
Hummers. The Brodie and Staudenmaier methods
involve combining the oxidants like KClO3 with
HNO3, whereas the Hummers method involves
combination of KMnO4 and H2SO4. GO was pre-
pared by a chemical reduction method using
reducing agents like hydrazine, hydroquinone, so-
dium borohydride, and ascorbic acid.30,31,34,44 Gra-
phyne was synthesized using dehydrobenzo
annulene and graphdyne (graphyne with acetylene
group) was synthesized on copper substrates via a
cross-coupling reaction using hexaethynyl benzene.
Graphone was synthesized by applying pressure on
to boron, nitrogen and hydrogenated graphene
sheets so that nitrogen could pick hydrogen from
graphene sheet. On releasing of pressure, the
dehydrogenated graphene sheet was formed with all
hydrogen atoms on the one side. Graphane was
synthesized for the first time by annealing of gra-
phene crystals at 573 K in an argon atmosphere for
duration of 4 h. These crystals were exposed to cold
hydrogen plasma and then a hydrogen and argon
mixture was allowed to pass at low pressure for 2 h.
A scalable method for hydrogenation of graphene is
2858
also reported.32 This method includes thermal
exfoliation of GO without a plasma source and in
the presence of hydrogen atmosphere at 493823 K
and 600015,000 kPa pressure. This process pro-
duced quantity in gram of graphane. Thus, it can be
a potential candidate for mass production.31,32,45
Figure 3 shows synthesis methods of graphene
and their derivatives along with their applications.
Graphene sheets are classified according to the
synthesis techniques used as per the available data
of patents filed, published, and granted.36 Figure 4
illustrates a pie chart that shows emerging tech-
niques such as ion implantation, electrochemical
deposition, arc-discharge, self-assembly, and laser
irradiation. Based on this analysis, it can be said
that substantial patenting steps have been directed
toward the development of various methods. These
methods include CVD, mechanical, and liquid phase
exfoliation of graphite and chemical exfoliation of
GO. Other dominant techniques are epitaxial
growth, chemical synthesis and unzipping of CNTs.
All above mentioned methods have significant
Fig. 3. Synthesis methods of graphene and their derivatives along with their applications (Reproduced from Ref. 36 with permission from
CKMNT.
Hansora, Shimpi, and Mishra
potential for large scale production of graphene at
an affordable cost.36
The state-of-the-art technique for the production
of graphene nanosheets is described in this article.
Graphene sheets were developed by a continuous
arc-discharge method in flowing water, which is
shown in Fig. 5ad.
Construction and Working of Arc-Discharge
Setup
The arc-discharge setup was designed using var-
ious parts with provision of continuous flow of
water.35,36,4042 These parts include a sealed cham-
ber of a horizontal tubular reactor, an ice-cooling
bath, a direct current (DC) dual-power supply cir-
cuit, cathodeanode electrodes, a cathodeanode
junction, and an interelectrode gap variation
assembly. A cylindrical graphite rod was used as a
cathode, while metal (carbon, copper, and tungsten)
rods were used as an anode individually. The
diameter and length measurements of anodecathode
Graphite to Graphene via Graphene Oxide: An Overview on Synthesis, Properties, and Applications
Fig. 4. Segmentation of graphene synthesis methods (Reproduced from Ref. 36 with permission from CKMNT.
electrodes were kept to be (0.01 m 9 0.005 m). These
anodecathodes were connected to DC power supply.
A DC power supply was designed with current
range of 0150 A and voltage range of 040 V. This
range was sufficient for continuous arc-struck with
inter electrode gap of 13 mm between the anode
and cathode. A horizontal tubular reactor was made
from transparent acrylic tube to visualize the actual
arc-struck process between electrodes. This tube
has dimensions of 0.3 m diameter and 1.2 m length.
A provision of inlet and outlet was kept for water
circulation. Figure 5a shows a schematic diagram of
arc-discharge setup. Figure 5b shows arc-struck
process and carbon deposition between cathode and
anode. Figure 5c shows photographic image of
interelectrode gap assembly and ice bath, while
Fig. 5d shows a photograph of an actual arc-struck
process, graphene deposition, and a DC supply
machine.
Synthesis Procedure
As mentioned above, Fig. 5d shows an arc-struck
process between anodecathode with the interelec-
trode gap of 13 mm. The cathode was kept sta-
tionary, whereas the anode was adjustable and kept
moving toward the cathode by adjusting slide of
interelectrode gap variation assembly. The elec-
trodes were brought continuously into contact by
maintaining gaps of 13 mm during the arc-dis-
charge process. The intensity of the arc was stable
and no twinkling was observed. The temperature at
the electrodes edge was higher than that in the
2859
central region during the arc-discharge process.
Initial values of current and voltage were kept same
throughout experiment. The time of soot generation
was kept at 2 h. This can also be made continuous
for 24 h production in a single day. The water level
was maintained (2 L) by controlling the inlet and
outlet flow of water. The arc-discharge setup was
positioned accurately to keep a steady and contin-
uous flow of water at rate of 1 mL min1. The
temperature of the viscous carbon clustered solution
was controlled using a cooling bath. There is less
damage in liquid environments owing to the better
cooling capacity of water.46,47
The carbon powder was developed continuously
during the arc-struck process, which gets dispersed
in flowing water. After completion of the arc-dis-
charge process, carbon nanostructured materials
were collected three ways: (I) soot was dissolved in
crude continuously coming out from reactor, (II)
from the cathode surface, and (III) most of the soot
was observed to be settled down and deposited in
the inner wall of tubular reactor. After the comple-
tion of arc-discharge, most of the soot was con-
densed near the wall of chamber. The settled and
deposited soot was in the form of a continuous,
thick, cloth-like film. The discharge produced in
cake-shape graphitic carbonaceous material de-
posited on the cathode surface.48 The crude was
collected continuously from the outlet flow of water.
It took 1 h to spend a 0.05 m anode rod to yield
0.002 kg of soot, so 0.048 kg of soot can be produced
in 1 day. The crude sample containing graphitic
carbon nanostructured material and metallic
impurities was subjected to purification steps.
2860 Hansora, Shimpi, and Mishra

Fig. 5. (a) Schematic view of experimental arc-discharge setup technique. Photographic representation of (b) batch and (c) continuous process.
(d) Magnified view of arc struck and carbon soot deposition.

Purification Procedure distilled water and then dispersed in ethanol. The

pure and metal-free graphitic nanosheets were fil-
Obviously, it was necessary to purify the crude
tered using Millipore (0.28 lm) filter paper and
solution because it was a mixture of cotton-like
collected on the surface of it. The overall purifica-
soot and impurities. These materials were observed
tion steps are illustrated in schematic cum photo-
to have a web-like appearance of amorphous gra-
graphic representation as shown in Fig. 6.
phitic carbon nanoparticles, graphene sheets,
Graphitic nanosheets were observed in agglomer-
tubular structures, and metallic particles if any.
ated form before sonication. A cross-sectional view
Purification of carbonaceous materials can be done
of this crude droplet shows that carbon soot was
by various steps like high-temperature hydrogen
atomized uniformly after ultrasonication. The
treatment, hydrothermal treatment, microfiltra-
ultrasonication is a simple way to de-agglomerate
tion, solvent extraction, acid treatment, and air
the chemically reacted carbon nanostructures with
oxidation. Gas-phase purification, microwave acid
organic materials.52 This crude was again soni-
digestion, and high-temperature annealing are
cated in concentrated HCl and rinsed with distilled
well-known purification methods, but these could
water. Pure crude solution was mixed with DM
affect the structural integrity of the carbon
water and then proceeded to centrifugation step.
nanostructured materials.4951 Graphene sheets
This separated graphene was oxidized in air at
were purified by a novel method. Graphitic na-
453 K for a 12-h drying cycle. Then, oxidation and
nosheets (GS) base viscous crude was first soni-
drying steps were carried out to remove the
cated in 35% HCl at 323 K for a duration of
amorphous carbon.
30 min. Then, the sample was washed with
Graphite to Graphene via Graphene Oxide: An Overview on Synthesis, Properties, and Applications
Fig. 6. Purification steps of graphene showing schematic cum photographic representation.
Characterization
A Raman spectrophotometer is a useful tool for
the analysis of chemical bonding, nature of disorder,
diameter of nanotube, and defects in graphitic na-
nosheets materials. Raman spectra were recorded
on Horiba JY Lab RAM HR800 micro-Raman spec-
trophotometer (Horiba, Japan) with 632.8 nm laser
excitation (HeNe laser). An x-ray diffraction anal-
ysis of pure graphene sheets was conducted on D8
Advance x-ray diffractometer (Bruker AXS, Karl-
sruhe, Germany) with CuKa1 radiation
(k = 1.5404 A) within the 2h range of 20 to 80o. The
surface morphology of pure graphene sheets was
studied by S-4800, field emission-scanning electron
microscopy (FE-SEM) (Hitachi, Tokyo, Japan). Pure
graphene was dispersed in acetone by ultrasound
treatment of 10 min to form a holey carbon film.
Pure graphene sheets were subjected to a gold
coating and mounted on specimen tub before view-
ing in SEM. The exact size and shape of graphene
sheets were studied by CM200, tunneling electron
microscopy (TEM) (Philips, Amsterdam, the
Netherlands) at a resolution of 2.4 A and operating
voltage of 20200 kV. Pure graphene sheets were
dispersed in water and kept in a conventional
2861
ultrasonic bath for 10 min. This sonicated crude
droplet of colloidal suspension was dried and then
put on a holey electron microcopper grid of the
microscope specimen.
RESULTS AND DISCUSSION
Raman Spectra
Raman spectroscopy was used to study optical
phonon spectrum and Raman spectrum of pure
graphene. Raman spectra can be used to determine
the quality of graphene. Raman spectra are also
used to determine the number of layers for n-layer
graphene (for n up to 5) from the shape, width, and
position of the 2-D peak. The shifting and splitting
of Raman modes can be useful for analyzing a
mechanical strain in graphene. The intensity ratio
of the D- and G-peaks is used to study metrics of
disorder in graphene. The disorder in graphene
could be in the form of charged impurities arising
from ripples, edges, presence of domain boundaries,
and others.22,30
Figure 7ac shows that the peaks are distributed in
two bands, i.e., a very weak D-band (13001400 cm1)
2862
Fig. 7. Raman spectrum of graphitic nanocarbon structures syn-
thesized using anode-cathode (a) graphitegraphite, (b) copper
graphite, and (c) tungstengraphite.
and a strong G-band (15001600 cm1). A Raman
spectrum of graphene indicates a peak at 1580 cm1
for a G-band, which shows the evidence of single-lay-
ered graphene.22,29 A peak is observed at 1350 cm1
for D-band indicating the presence of amorphous
carbon.22,50 This is because of the first-order zone
boundary phonons and defect-free graphene. But de-
fected graphene still exists.30,40 A 2-D peak is observed
at 26502700 cm1 due to optical vibration of carbon-
graphite electrode. The 2-D peak at 2700 cm1 is
caused by in-plane optical vibration and second-order
zone boundary phonons. Defects in graphene may oc-
cur due to the oxidation step during purification
strategy.46
X-ray Diffraction (XRD)
Figure 8a and b shows XRD patterns of graphitic
raw material and graphitic carbon nanosheets. The
peaks are indexed to the reflections of hexagonal
graphite. Figure 8a shows 2h at 26.3, which indi-
cates that the graphite is crystalline material and
crystallinity was reported to be 85.6%. Figure 8b
shows the XRD pattern, which indicates amorphous
nature of graphitic carbon nanosheet and its crys-
tallinity was reported to be 66.4%. A diffraction of
pure graphite is clearly seen which confirms the
presence of crystalline material.
FE-SEM
Typical SEM micrographs (Fig. 9) show the sur-
face morphology of pure graphene sheets. Struc-
tural degradation is observed in the graphitic
microstructure. The microstructured materials
were found randomly in large form and long gra-
phitic nanostructured sheets. In fact, several mor-
phologies and different microstructures were also
observed despite the small surface of the electrode.
Hansora, Shimpi, and Mishra
Fig. 8. XRD patterns of (a) graphite and (b) graphene nanosheet.
A compact globular material was observed on the
outer surface layer of cylindrical periphery. The
temperature in this region was low because of the
direct cooling liquid environment.46 The damage
was less in water medium, owing to the better
cooling capacity of water.49
TEM
TEM micrographs in Fig. 10 show nanostructures
of graphene sheet. The TEM study revealed that
most multilayered graphene sheets22,40,42 were
overlapped to each other. Hence, the texture of
sheets is highly crystalline with least defect due to
effect of ultrasonication and centrifugation steps.40
The morphologies of graphitic carbonaceous na-
nosheets look like a form of wrinkled sheets. The
carbon was no longer deposited at the surface of
cathode on applying voltage greater than 22 V, but
fine a powder appeared to be dispersed in the water.
For lower voltage, mainly amorphous carbon was
deposited on the wall of reactor. So we can say that
nanoporous carbon is the main resulting product of
the process.46
VARIOUS POSSIBLE FUNCTIONALIZATION
Forefront research on graphene is mainly pushed
by active materials, which has progressed to next-
generation graphene-related nanomaterials. These
materials are divided into two main categories24,30:
chemically modified graphene (CMG) and 3-D gra-
phene architectures (3DG). In CMG materials, car-
bon atoms of graphene sheets are replaced by other
atoms of N, B, S, or P, or by entire functional
groups. In 3DG materials, graphene or CMG sheets
were assembled together to form 3-D interconnected
Graphite to Graphene via Graphene Oxide: An Overview on Synthesis, Properties, and Applications
Fig. 9. FE-SEM micrographs of graphene sheets synthesized by arc-struck (a) carboncarbon, (b) carboncopper, and (c) carbontungsten
electrodes.
networks or highly complex nano-objects. Graphene
sheets can be functionalized by chemical and elec-
trochemical surface modification,25,29,53 which give
CMG and 3DG nanomaterials.
Chemical Modification of Surface
Pristine graphene materials are unsuitable for
intercalation with polymer chains because bulk gra-
phene has a pronounced tendency to agglomerate in
a polymer matrix. Chemical functionalization of
graphene related nanomaterial is an attractive tar-
get because it can tune its stability, electronic, and
magnetic properties, and it can improve the solubil-
ity, processibility, and interactions with organic
polymers. Doping of graphene-related nanomaterial
is done for tuning their different properties. Doping
can be done by various techniques.31 Graphene can
be organochemically modified by different ap-
proaches25,28,29,45 such as the reduction of GO,
covalent modification of graphene, noncovalent
functionalization of graphene, nucleophilic substitu-
tion, diazonium salt coupling, and adsorption of me-
tal. The reduction of GO is carried in a stabilized
medium; e.g., KOH-treated GO can be modified with
hydroxyl, epoxy, or carboxylic acid groups. Covalent
modification of graphene is done by using lithium
reagents, isocynates, and di-isocynates to reduce
2863
hydrophilic character of GO, e.g., chitosan function-
alized GO and CNT33,54,55 for biological and medical
applications. GO nanoplatelets also can be function-
alized by polysodium styrene sulfonate, which is an
example of noncovalent functionalization.33,45
Amine-modified GO is an example of nucleophilic
substitution. GO can be reduced by hydrazine and
treated by aryl diazonium salts, which is example of
di-azonium salt coupling. Atoms of transition metals
like Ti and Fe can be anchored to adsorb on the
surface of GO. Derivatives of graphane can be fab-
ricated by changing the substrate atoms (C, Si, Ge,
and P) and the surface atoms (H, OH, NH2, He, Li,
Fe, Mn, all VII A group elements).45
Electrochemical Modification of Surface
A colloidal suspension of graphene can be pre-
pared from electrochemically modified graphite.25
In this 30-min electrochemical reaction, a commer-
cial graphite electrode was used as a cathode and
immersed in a phase-separated mixture of water
and imidazolium-based ionic liquids. A constant
potential of 1020 V was applied across the elec-
trodes so ionic liquid functionalized graphene sheets
can be precipitated from the anode. A homogeneous
dispersion of 1 mg mL1 was prepared by ultra-
sonication process using functionalized and dried
2864
Fig. 10. TEM micrographs of overlapped multilayer graphene nanosheets at resolution of (a) 500, (b) 200, and (c) 100 nm, respectively and
wrinkled graphene nanosheets at resolution of (d) 200, (e) 100, and (f) 50 nm, respectively.
graphene sheets in DMF. These types of graphene
dispersions show a Tyndall effect.41
pp Interaction
It is reported that graphene can be modified by
considering the pp interaction between the p orbi-
tals of graphene and poly (iso-propyl acrylamide) in
the presence of water.25 Water-dispersible graphene
can be produced by ultrasonication in an ice bath.
Another example of an pp interaction is graphene
with pyrene derivative soluble in DMF.29 Graphene
can be incorporated with metals nanoparticles. This
may keep graphene sheets in deaggregated form
during the reduction of GO.29
VARIOUS CHARACTERISTIC PROPERTIES
Graphene is preferable as conductive nanofiller
owing to remarkable and excellent properties. These
characteristic properties include high surface area,
aspect ratio, tensile strength, thermal conductivity
and electrical conductivity, EMI shielding ability,
flexibility, transparency, and low coefficient of
thermal expansion. These intrinsic properties have
generated enormous interest for the preparation of
graphenium devices such as high speed and radio
frequency logic devices, thermally and electrically
conducting nanocomposite materials, ultrathin car-
bon films, electronic circuits, sensors, and trans-
parent and flexible electrodes for displays and solar
Hansora, Shimpi, and Mishra
cells. Graphene sheets have shown characteristic
properties, which are listed in the next sections.
Morphology and Structure
The graphene honeycomb lattice is composed of
two equivalent sublattices of carbon atoms bonded
together with r-bonds. Each carbon atom in the
lattice has p orbital that contributes to a delocalized
network of electrons. Apart from intrinsic corru-
gations, graphene in real 3-D space can have de-
fects like topological shapes (pentagons, heptagons,
or their combination), vacancies, adatoms, edges,
cracks, and adsorbed impurities.30 It is reported
that when half of the carbon atoms are hydro-
genated to form graphone, strong r bonds are
formed between the carbon and hydrogen atoms.
These r bonds disrupt the usual p bonding network
of metallic and nonmagnetic 2-D graphene sheets
and cause the electrons on the unbonded carbon-
hydrogen atoms, which make it localized and un-
paired.32
Electronic
Graphene is a zero band gap 2-D semiconductor
material. As a consequence of the graphenes
structure, the first Brillouin zone has two equiva-
lent points known as Dirac points where a band
crossing occurs. A tight-binding interaction with a
Graphite to Graphene via Graphene Oxide: An Overview on Synthesis, Properties, and Applications
Table I. Comparison of properties of various materials
Materials Tensile strength
Graphene 130 10 GPa
CNT 60150 GPa
Nanosized steel 1769 MPa
Plastic (HDPE) 1820 MPa
Rubber (Natural rubber) 2030 MPa
Fiber (Kevlar) 3620 MPa
Reproduced with permission from Ref. 25. Elsevier Science Ltd., U.K.
first neighbor provides the dispersion relation to the
electrons near the Dirac points.19,26,2830,33,56 Gra-
phyne nanoribbons have band gaps in the semi-
conductor range of 0.591.25 eV and widths of one
repeat unit to eight repeat units. Graphyne has a
strain free value of 0.47 eV, which can act as very
attractive semi conductive material.32
Mechanical
Mechanical properties (youngs modulus, elastic
modulus, and fracture strength) can be studied from
molecular dynamics. Youngs modulus of defect-free
graphene was reported to be 1 TPa and the frac-
tural strength was reported to be 130 GPa. The
elastic modulus of chemically modified graphene
was reported of 0.25 TPa. The maximum elastic
modulus and fracture strength of GO platelets pa-
per were reported as 32 GPa and 120 GPa,
respectively. Graphdiyne is a softer material than
either graphyne or graphene, and it has plane
stiffness of 120 N m1 (=Youngs modulus of
375 GPa).22,30,32,33
Optical
The high-frequency conductivity for Dirac fer-
mions in graphene has been stated to be a constant
that is shown in Eq. A1 of Appendix A. The optical
transmittance (T) and reflectance (R) are shown in
Eq. A2 of Appendix A. The expression of (T) and (R)
in terms of fundamental constants that does not
directly involve material parameters to determine
the structure and electronic properties of graphene.
The complex dielectric property of graphyne is a
function of energy adsorbed for an electric field
parallel and perpendicular to the graphyne
sheet.22,30,32 The optical properties of GNRs are
independent of their edge shapes and widths. These
unique properties make GNR a suitable candidate
for various applications in optical and optoelectronic
devices.34
2865
Thermal
conductivity Electrical
(W m21 K21) at room conductivity
temperature (S m21)
(4.84 0.44) 9 103 to (5.30 0.48) 9 103 7200
3500 30004000
56 1.35 9 106
0.460.52 Insulator
0.460.142 Insulator
0.04 Insulator
Thermal
Thermal conductivity (j) of graphene is domi-
nated by phonon transport, which is also known as
diffusive conduction at high temperatures and bal-
listic conduction at low temperatures. A thermal
conductivity of suspended monolayer graphene is
reported to be 6000 W m1 K1, which is higher
than that of graphitic carbon. The thermal conduc-
tivity of CVD growth graphene is reported to be
2500 W m1 K1 at 900 K and 1400 W m1 K1
at 1046 K. The heat capacity of graphene is reported
to be 29.32 0.23 J mol1 K1, which is 14.8%
greater than the graphene.22,30,33,45,57
Magnetic
Magnetism in sp2 hybridized carbon materials
has been controversial because of the possible con-
tamination with magnetic impurities. Paramag-
netism and certain other magnetic features
including spin-glass behavior and magnetic
switching phenomena were observed in nano-
graphite particles.29
Electrical and Electrochemical
Graphene and carbon nanoparticles with a few
layers showed semiconducting or insulating behav-
ior with little change in their resistance in the
temperature range of 100373 K. The resistivity
was found to increase sharply below 50 K. But this
might decrease if the graphene is heated to high
temperatures; e.g., GNRs and a palladium sheet
sandwiched between graphene sheets can be used
as an electrode material for supercapacitors because
of its superconducting nature.29,32
Surface and Sensing
Single-layer graphene sheet has a large surface
area 2600 m2 g1. Surface areas of different few
layer graphene samples were reported in the range
of 2701550 m2 g1. GNRs are also useful for
2866
Table II. Various applications of graphene sheet based on its resistance range
Sr. no. Resistance range (X cm2)
1 550450
2 450350
3 350220
4 22030
5 0.530
adsorption of different gas molecules such as CO,
CO2, NO, NO2, O2, N2, and NH3.29,45,55
Toxicity
A toxicological effect of CNTs and graphene
nanomaterial is discussed in terms of cytotoxicity on
the basis of their size.22,54 Table I shows a chart on
the mechanical, thermal, and electrical properties of
graphene compared with CNT, steel, plastic, rubber,
and fiber. The tensile strength of graphene is ob-
served to be the same or slightly more than CNT but
it is still much higher than steel, Kevlar, HDPE,
and natural rubber. It is clearly seen from Table I
that the thermal and electrical conductivity of gra-
phene sheets are higher than all these materials.
Polymer and graphene nanocomposites showed
superior mechanical, thermal, gas barrier, electri-
cal, and flame-retardant properties compared with
the neat polymer.
VARIOUS APPLICATIONS
As illustrated in Table II, the fascinating of prop-
erties graphene and their derivatives enable them to
be used in many potential applications, which are
shown below based on their electrical resistance.
GraphenePolymer Nanocomposites
Exfoliated graphene or graphite nanoplatelets
and their functionalized derivatives can be incor-
porated in polymers like PMMA, PS, PVA, PET, PP,
PVDF, PAni, PC, PU, polyester, silicone, and foam.
Polymergraphene nanocomposites have shown
dramatic improvements in their thermal, electrical,
and mechanical properties such as thermal stabil-
ity, electrical conductivity, elastic modulus, and
tensile strength. But these improvements are due to
the low filler content, large interfacial area, and
high aspect ratio of filler, which is required for
achieving a percolation.21,22,25,28,30,33,38
GrapheneMetal Hybrid Nanocomposites
Graphenemetal hybrid nanocomposites have
attractive properties that make them ideal tem-
plates. These graphene-based nanocomposites can
be prepared by incorporating metal nanoparticles
like Au, Ag, Pd, Pt, Ni, and Cu. Depending on type
of the anchored nanoparticle, the graphenemetal
nanocomposites are used in the applications of
Hansora, Shimpi, and Mishra
Applications
Touch screen
Smart electronic window
Flexible liquid crystal device
Flexible organic light-emitting diode
Solar cell
catalysis, electrochemical sensing, and surface-en-
hanced Raman scattering. Graphene-based tem-
plates have been synthesized using various kinds of
semiconductor nanomaterials such as ZnO, NiO,
Cu2O, TiO2, SnO2, MnO2, RuO2, Fe2O3, Fe3O4,
Co3O4, CdS, and CdSe. These graphene nanocom-
posites can be useful in energy, electronics, and
optics applications as Li-ion batteries, supercapaci-
tors, and solar cells.22,28,33
Field-Effect Transistors (FETs)
Graphene is a suitable material for metallic
transistor applications. The graphene carriers are
bipolar with electrons and holes that can be tuned
by a gate electrical field due to a unique band
structure. A graphene quantum-dots-based single-
electron transistor was made using the electron
beam lithography technique. GNRs prepared from
unzipped CNTs by plasma etching and chemical
oxidization methods are potential production tech-
niques for future graphene FET devices. Graphene
derivatives are better materials, which can be used
as super capacitors than silicon-based ones because
graphene derivatives possess band gap and semi-
conductor properties.19,23,28,30,32,33,45,57,58
Sensors
A monolayer graphene sheet has the ability to
sense a variety of gases and biomolecules. Its sens-
ing ability is based on a large specific surface area
and a change in conductance as a function of surface
adsorption. As molecules adsorb into the graphenes
surface, adsorption experiences a charge transfer
with the graphene sheet as a donor or acceptor. This
changes the fermi level, electrical resistance, and
carrier density of graphene due to which chemical
sensing occurs. A large body of research has sug-
gested that monolayer and functionalized graphene
are promising candidates to detect a variety of gas
molecules of LPG, ammonia and CO, organic va-
pors, protein molecules, and DNA. The large elastic
region of graphyne and graphdyne has the ability to
strain and relax to its original shape by releasing
strain without permanent deformation. This en-
ables resilient electromechanical coupling, which is
required in high-temperature sensing. Graphane is
also used in the application of biosensing due to its
electrochemical oxidation.2628,30,32,33,45,55,59
Graphite to Graphene via Graphene Oxide: An Overview on Synthesis, Properties, and Applications
Transparent Conductive Films (TCFs)
Graphene materials are promising candidates for
TCFs because of their high carrier mobility, elec-
trical conductivity, and optical transmittance in the
visible range of the spectrum. The optical trans-
mittance (transparency) of chemically modified
graphene is reported to be 83% at a wavelength of
1000 nm. Disordered films of randomly stacked
multilayered graphene platelets have shown 75%
transmittance at wavelength of 550 nm. GO-based
TCF show 87% transmittance at a wavelength of
550 nm. Graphene base TCFs have been used as
electrodes for dye-sensitized solar cells, liquid crys-
tal devices, and organic light-emitting diodes.28,38
Clean Energy Devices
Graphene is a promising electrode material due to
its high theoretical surface area and electron
transferability along its 2-D surface. Graphene-
based electrodes are used as rechargeable lithium-
ion batteries and electrochemical double-layer
capacitors. Graphene nanocomposites can form a
conducting 3-D network due to the uniform disper-
sion of silicon particles and reconstitution of gra-
phene platelets, which are important aspects for the
high storage capacities. Chemically modified gra-
phene sheets have the potential to act as an elec-
trode material for ultracapacitors. Lithium-doped
graphane was used for hydrogen adsorption and its
storage applications.30,32,45
Memory and Photovoltaic Devices
Graphene-related nanomaterials have also been
used in memory devices, transparent electrodes,
electron acceptors, and light adsorbers because of
their good electronic properties, transparency, and
large specific surface area.33
CONCLUSION
Intensive investigations on graphene during the
past several years have shown increasing efforts to
search for new graphene-related functional materi-
als. This paper endeavors to sum up state-of-the-art
techniques and the current status on graphene and
their derivatives which have been predominated in
the field of functionalized graphene. Graphene has
shown its potential as a technological material be-
cause of its good electronic conduction, easy func-
tionalization and a versatile nanoscale design.
These characteristics are useful in the applications
of fuel cell electrodes, supercapacitors, and batter-
ies. Finally, graphene has been proven as advanced
functional material that can be used in many
potential applications.
A considerable cost-effective yield of graphene
sheets and carbon nanostructured materials can be
obtained by facile, cheapest, simple, and continuous
arc-discharge under the flow of water. This method
also shows a possibility of mass production of carbon
2867
nanostructured material by arc-discharge setup.
This requires a DC power supply and a metalgra-
phite electrode without any accessories such as
pumps, seals, water-cooled vacuum chambers, and
gas purging systems. The system is adaptable in a
continuous manner without interruptions. The
continuous arc-discharge technique was found to be
very effective compared with other reported tech-
niques. This method is more suitable, cheaper, and
easier to implement for the large-scale production
and efficient formation of graphitic nanosheets be-
cause of its superior controllability and optional
conditions. Carbon nanostructures could be pro-
duced with high yields after effective control by
optimizing the shape of graphite electrodes, catalyst
concentration, and electric parameters. Based on
this strategy, the continuous arc-discharge tech-
nique can be used for the efficient formation of
carbon nanostructures with a high production rate
and yield.
ACKNOWLEDGEMENT
The authors are thankful to Council of Scientific
and Industrial Research (CSIR), New Delhi, India
(Project No.: 02(0023)/11/EMRII) for providing
financial assistance to carry out this research work.
APPENDIX A
The high-frequency conductivity for Dirac fer-
mions in graphene has been given by the following
expression (Eq. A1).
 2
pe
(A1)
2h
For normal incidence light, optical4 transmittance
(T) and reflectance (R) are expressed as
   
1 2 1
T 1 and R (A2)
2pa 4p2 a2 T
where a = (2pe2/hc)  (1/137), e is the electron
charge, c is the light speed, and h is Plancks con-
stant; the opacity is (1  T)  (pa)  2.3%.
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