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Journal of the Taiwan Institute of Chemical Engineers

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

Review on graphene and its derivatives: Synthesis methods and

potential industrial implementation
Xin Jiat Lee a, Billie Yan Zhang Hiew a, Kar Chiew Lai a, Lai Yee Lee a,∗, Suyin Gan a,
Suchithra Thangalazhy-Gopakumar a, Sean Rigby b
a
Department of Chemical and Environmental Engineering, University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih, Selangor, Malaysia
b
Department of Chemical and Environmental Engineering, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom

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

Article history: Graphene and its derivatives have gained significant attention of late due to their remarkable physico-
Received 15 March 2018 chemical properties. This review focuses firstly on the synthesis methods of graphene and its derivatives
Revised 27 October 2018
along with their attributes and characterization techniques. This is followed by a discussion of the po-
Accepted 31 October 2018
tential industrial implementation of the synthesis routes. The potential industrial implementation of the
Available online xxx
graphene synthesis methods are reviewed using the key criteria of cost, process condition, yield, scalabil-
Keywords: ity, product quality and environmental impact. The literature data supported that synthesis routes such
Graphene as oxidative exfoliation-reduction, liquid-phase exfoliation and chemical vapor deposition have the poten-
Graphene oxide tial to be commercialized due to their ability to produce large amount of high quality graphene. Further
Reduced graphene oxide development is necessary to overcome barriers such as environmental concerns and the high graphene
Characterization cost.
Synthesis methods
© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction rated graphene composite exhibited excellent electrochemical per-

The discovery of graphene by Andre Geim and Konstantin
Novoselov in 2004 has motivated the scientific community to ex-
plore extensively the potential applications of this material [1].
Graphene is commonly referred as a two dimensional (2D) sheet-
like material with sp2 hybridized carbon atoms configured in a
hexagonal or honeycomb-like structure and its thickness is equiv-
alent to an atom diameter [2]. Furthermore, graphene is made up
of pure carbon whereby each carbon atom is covalently bonded to-
gether in the same planar and the monolayer graphene sheets are
linked by van der Waals forces.
Along with its derivatives, particularly graphene oxide (GO) and
reduced graphene oxide (rGO), graphene materials have been stud-
ied in various fields due to the presence of aromatic ring, free
π -π electron and reactive functional groups. A number of com-
prehensive reviews have documented the remarkable performance
of graphene materials [3–6]. For instance, Zhao et al. [7] devel-
oped an S-doped graphene sponge for the removal of Cu2+ with a
high adsorption capacity of 228 mg/g which was 40 times greater
than activated carbon. In energy storage application, Li and co-
workers [8] have reported that a well-controlled pyrene deco-
∗
Corresponding author.
E-mail address: lai-yee.lee@nottingham.edu.my (L.Y. Lee).
formance with a specific capacitance of 310.7 F/g and capaci-
tance retention of 99% after 15,0 0 0 cycles at a current density
of 1.5 A/g in a three-electrode system. Mechanical properties en-
hancement by graphene material has been proven in Yang’s work
[9]. From this work, the addition of 0.54 wt% graphene nanoplates
into pure Al matrix significantly increased the yield strength and
tensile strength by 228% and 93% after extrusion, respectively, and
the strengthening mechanism could be described by the modified
shear-lag model. As such, graphene and its derivatives are consid-
ered as a frontier material for future technology advancement.
The number of graphene related research articles and patents
has increased rapidly in the past 5 years suggesting the blooming
era of graphene and the statistics are expected to increase in the
upcoming years [4,6]. Therefore, mass production of graphene at
commercial level is imminent to accommodate the high graphene
demand in future market. At present, the graphene synthesis
methods can be classified into two groups, namely top-down
method and bottom-up method. The top-down approach involves
the structural breakdown of precursor such as graphite followed
by the interlayer separation to produce graphene sheets. Some ex-
amples of this method include mechanical exfoliation, oxidation–
reduction of GO, liquid phase exfoliation and arc discharge. Mean-
while, the bottom-up technique such as chemical vapor deposition,
epitaxial growth and total organic synthesis utilize carbon source
gas to synthesize graphene on a substrate.

https://doi.org/10.1016/j.jtice.2018.10.028
1876-1070/© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028
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Fig. 1. Structures of pristine graphene (a) and its graphene oxide derivatives based on Hofmann (b), Ruess (c), Scholz-Boehm (d), Nakajima-Matsuo (e), Lerf-Klinowski (f)
and Szabo (g) models [21].
Despite the rapid developments in graphene synthesis meth-
ods, a cost effective method for mass production of high qual-
ity graphene remains scarce thus limiting the potential implemen-
tation of graphene at industrial scale. Hence, this review paper
encompasses the synthesis methods of graphene and its deriva-
tives from an engineering perspective, aiming to establish their
feasibility and identify the current challenges faced in upscaling
the production of graphene and its derivatives. The paper starts
off by firstly discussing the attributes and characterization meth-
ods of graphene and its derivatives. Synthesis methods are sub-
sequently discussed followed by an evaluation of the potential
industrial implementation of the synthesis methods. The evalua-
tion is based on a sustainability assessment methodology devel-
oped by the Institution of Chemical Engineers. The final section
of the paper concludes the key findings of this review and high-
lights the most feasible synthesis methods for future industrial
implementation.
2. Attributes of graphene and its derivatives
Graphene has emerged as one of the most interesting carbon
nanomaterials since its successful isolation from graphite in 2004
[1]. It is an atom thick layer with a honeycomb framework com-
prising two equivalent sub-lattices carbon atoms linked together
via carbon-carbon sigma (σ ) bond of 0.142 nm long [10] as shown
in Fig. 1(a). As a 2D planar single sheet of sp2 hybridized carbon,
graphene is the basic building block of other allotropes of car-
bon such as fullerene (0D), CNT (1D) and graphite (3D) [11]. This
thinnest carbon material bears unique characteristics such as ex-
ceptionally high specific surface area (up to 2630 cm2 /g), intrinsic
electron mobility (up to 20 0,0 0 0 cm2 /Vs), Young’s modulus (up to
1.0 TPa), thermal conductivity (up to 50 0 0 W/mK), optical trans-
mittance (up to 97.7%), chemical stability and quantum Hall ef-
fect at ambient temperature [12,13]. Additionally, graphene is 200
times stronger than steel making it one of the strongest materi-
als ever tested [14]. Due to its amazing features, graphene is used
in a wide spectrum of applications, prominently in photonic, elec-
tronic, biomedical and environmental pollution control as biosen-
sor, drug carrier, energy storage, polymer nanocomposite and ad-
sorbent [5,13,15].
Graphene mainly consists of pure carbon element, but its edge
and basal plane present different electrochemical characteristics.
Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028
[m5G;November 23, 2018;18:13]
Graphene edge has a greater specific capacitance, rate of elec-
tron motion and catalytic power as compared to graphene basal
plane [16]. Pristine graphene can be synthesized and presented
in single-, bi- and few-layer graphene. Meanwhile, GO which is
a graphene derivative, is rich in oxygenous functional groups. It
has hydroxyl and epoxide groups on its basal plane, and car-
boxylic, ketone and aldehyde groups on its layer edge. Hence,
GO is a compound structurally rich in carbon, hydrogen and oxy-
gen. Since there are different methods to synthesize GO, its non-
stoichiometric structure and composition are highly dependent
on the production step [17]. Therefore, several structures of GO
have been proposed, namely the Hofmann, Ruess, Scholz-Boehm,
Nakajima-Matsuo, Lerf-Klinowski and Szabo models [18] as illus-
trated in Fig. 1(b)–(g). The Lerf-Klinowski molecular structure is
widely accepted as the role model of GO based on its compre-
hensive analysis by solid-state nuclear magnetic resonance and X-
ray diffraction [19]. Due to the oxidation process, the presence of
defects, impurities, structural disorder, wrinkle, crack, fragmenta-
tion and other structural attributes are possible, and these may af-
fect the electronic, optical and adsorption properties of GO. Thus,
GO can be further processed into another graphene derivative
known as reduced graphene oxide (rGO). The transformation of
GO to rGO can be achieved through chemical or physical reduc-
tion. Through reduction process, the oxygenous functional groups
in the GO are eliminated to form rGO with a carbon to oxy-
gen (C/O) ratio of 8:1–246:1 [20]. Within the adsorption field,
graphene, GO and rGO are gaining popularity lately as precur-
sors for adsorbent development for utilization in heavy metals
decontamination [5].
3. Characterization methods for graphene and its derivatives
In most research on graphene materials, properties such as
morphological, textural, surface chemistry and other physicochemi-
cal attributes have been investigated. Scanning electron microscopy
(SEM) is a technique used for examining the morphology of
graphene and its derivatives. In this analysis, highly energetic elec-
trons are applied to produce SEM images of the sample. The
graphene material is placed on a silicon wafer of specific thickness
for SEM scanning and the number of layers can be estimated based
on the color depth [22].
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Atomic force microscopy (AFM) can be used to measure the
thickness, surface roughness and other morphological features of
graphene and its derivatives. Liu et al. [23] studied the adsorption
and desorption of U(VI) on GO of different sizes. The size distribu-
tions of larger GO (LGO) and smaller GO (SGO) were reported to
be 2–5 and 0.1–0.3 μm, respectively. From AFM, both LGO and SGO
shared similar average thickness of 1–2 nm which is in agreement
with other literature data. However, this technique has difficulty
in scanning bulky material and only provides topographical im-
ages. It is unable to accurately distinguish the number of layers of
graphene [24]. The measured thickness of a single layer graphene
by AFM varied between 0.4–1.7 nm which differs substantially from
the theoretical thickness of 0.34 nm. The discrepancy is due to the
surface interactions, image feedback settings and surface chem-
istry. Cameron et al. [25] modified the AFM probe and adopted
a new AFM imaging mode to accurately determine the thickness
of graphene by reducing the error from within 0.1–1.3 nm to 0.1–
0.3 nm.
Transmission electron microscope (TEM) is commonly used to
analyze graphene due to its ability to image the material at
atomic level. In TEM, a very high voltage of electron is transmitted
through the thin sample and the signal produced is further ana-
lyzed. TEM is used to identify the extent of defects, vacancy, dislo-
cations and Stone-Wales rotation of graphene [26,27]. High resolu-
tion TEM (HRTEM) can be used to determine the thickness, num-
ber of layers and cross-sectional view of folded graphene sheets
at different locations. In TEM images, monolayer graphene sheets
are displayed as transparent sheets while multi-layered graphene
sheets are shown as multiple dark lines when the folded graphene
sheets are placed parallel to the electron beam. In addition, the
typical hexagonal crystalline nature of graphene can be identi-
fied by selected area electron diffraction (SAED) pattern from TEM
analysis. Fig. 2 illustrates the TEM image and SAED pattern for
boron doped GO (BR-GO) developed by Singh et al. [28]. From their
work, GO exhibited a wrinkled and undulated structure whereas
BR-GO had a thin flexible sheet-like structure with more corruga-
tions than GO. Furthermore, the BR-GO was observed to contain
highly crystalline boron doped graphene islands separated by dis-
ordered regions using HRTEM. According to the SAED pattern, the
0.33 nm interplanar spacing of BR-GO corresponded to graphene
(002) planes thereby confirming the polycrystalline structure of
BR-GO [28].
The crystallinity, atomic arrangement and crystal size can be
investigated by X-ray diffraction (XRD) or X-ray crystallography.
A crystalline material can be classified by its orderly and con-
tinuously repeating arrangement in the atomic planes. A unique
diffraction pattern is formed when X-rays are emitted on a crys-
talline material from the XRD [26]. Additionally, the distance be-
tween the atomic planes can be calculated by the Bragg’s Law. Each
crystalline material has a unique XRD pattern which can be used as
a fingerprint reference for material identification. In graphite XRD
pattern, a distinctive peak can be observed at 2θ = 26.66° which is
related to the (0 0 2) basal plane. Upon oxidation of graphite, its
crystal structure is altered. The produced GO has a characteristic
peak at 2θ = 9.18° and the interlayer spacing increases from 3.34
(graphite) to 9.62 Å. The reduction of GO to rGO can also be con-
firmed by XRD analysis. The absence of the characteristic peak of
GO at 11.5° and the formation of new peak at around 26.5° indicate
the successful reduction of GO [29].
Raman spectroscopy is an essential analytical technique for
graphene characterization. The carbon material has distinctive Ra-
man peaks known as D-, G- and 2D-peaks at approximately 1350,
1580 and 2700 cm−1 , respectively. Generally, the G-peak refers to
the tangential stretching (E2g ) mode of highly oriented pyrolytic
graphite whereas the D-peak represents the disorder in sp2 hy-
bridized carbon atoms (lattice distortion) and the 2D-peak is the
Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028
[m5G;November 23, 2018;18:13]
3
second order Raman scattering process. The intensity ratio of D-
peak to G-peak (ID /IG ) can be used to determine the degree of
disorder in the graphene sample. In Zhao et al. [30]’s work, the
ID /IG ratio for GO and magnetic Fe3 O4 /graphene composite were
0.85 and 1.11, respectively. The difference in ID /IG was attributed
to the incorporation of a large amount of new graphitic domains
and the increase in disorder during functionalization [30]. Mean-
while, the intensity ratio of 2D-peak to G-peak (I2D /IG ) can be
used to evaluate the quality of graphene. A large I2D /IG and in-
significant D-peak indicate that the quality of graphene is high. Li
et al. [31] reported that graphene produced by CVD had a higher
I2D /IG as compared to that synthesized by mechanical exfoliation,
suggesting that CVD was conducive for producing high quality
graphene.
Fourier transform infrared spectroscopy (FTIR) is a method used
for the determination of chemical functional groups in graphene
and its derivatives. Typically, graphite has characteristic peaks at
3430 and 1610 cm−1 corresponding to O–H stretching of adsorbed
water and skeletal vibration from graphitic domains of aromatic
C = C, respectively. In comparison to the graphite spectrum, the
GO spectrum has new peaks at 1785 and 1707 cm−1 (due to
C = O stretching of carbonyl and carboxylic groups, respectively)
and 1105 cm−1 (assigned to C–O stretching) indicating the exis-
tence of oxygenous functional groups in the sample. Moreover, the
peak shift from 1610 (in graphite spectrum) to 1625 cm−1 (in GO
spectrum) shows the successful incorporation of oxygenous func-
tional groups into graphite after oxidation. The rGO spectrum re-
portedly displayed a relatively low peak intensity at 3430 cm−1
and disappearance of peaks at 1785, 1707 and 1105 cm−1 which
suggested the occurrence of reduction of GO [32].
X-ray photoelectron spectroscopy (XPS) is commonly used to
determine the relative amount of carbon (C), oxygen (O) and other
functional groups present in graphene materials [33]. It is relatively
accurate in determining the amount of C and O in the graphene
sample, particularly GO, as it is difficult to fully dehydrate GO
[34]. XPS also provides information on the local binding environ-
ment of a certain species for better understanding of the sur-
face chemistry of the carbon material [35]. Liang and co-workers
[36] have characterized nitrogen (N) doped graphene oxide aero-
gel using XPS. From their work, the full spectra of C 1s, N 1s and
O 1s were detected at peaks ∼284.6, ∼400 and ∼532 eV, respec-
tively. GO portrayed four distinctive peaks at 284.4, 286.3, 288.1
and 289.0 eV at core level C 1s spectra, corresponding to sp2 hy-
bridized graphitic carbon, C–OH, C = O and O–C = O configurations,
respectively. Additional peaks at 285.8 and 287.4 eV implied that
the doping of N atom has been achieved. Upon further inspection,
four kinds of N atom were doped, namely amine groups (389.9 eV),
protonated N or graphitic N (401.6 eV), pyrrolic N (399.7 eV) and
amide bond (400.7 eV). The amide bond could be due to the
C–NH2 bond in tetraethylenetetramine with carboxylic groups
of GO [36].
Brunauer-Emmett-Teller (BET) surface area analysis is an ad-
vanced technique employed to determine the specific surface area
and pore size distribution of graphene and its derivatives. Gener-
ally, graphene has a large theoretical specific surface area which
provides surface interactions between graphene and other mate-
rials. The specific surface area of graphene has been extensively
investigated and the experimental results have been reported to
vary within 30 0–10 0 0 m2 /g. The variation could be attributed to
the distinct structures and layers of the graphene nanosheets syn-
thesized by different methods [37]. For instance, the graphene pro-
duced via thermal exfoliation at high temperature consisted of
single- and multi-layer structures which resulted in a high specific
surface area of 940 m2 /g [38]. Meanwhile, the graphene treated
by chemical modification possessed a moderate surface area of
705 m2 /g [39].
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4 X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

Fig. 2. TEM images of GO (a, b), HRTEM images of BR-GO (c, d) and SAED pattern of BR- GO (e). Reprinted with permission by Elsevier [28].

4. Synthesis methods of graphene and its derivatives
In order to be successfully applied in industry, graphene should
be produced at a cost competitive to that of current materials. It is
of great challenge to develop synthesis processes with the follow-
ing attributes: cost effective, highly reliable and scalable produc-
tion as well as high product yield and quality [40,41]. Hence, the
following discussion on the synthesis methods focuses mainly on
these attributes. The mechanisms of synthesis and detailed charac-
terization of graphene have been reported elsewhere in the litera-
ture [15,26,42].
The synthesis of graphene can be performed by two main ap-
proaches: top-down (destruction) and bottom-up (construction)
methods [43,44] as illustrated in Fig. 3. The top-down meth-
ods such as mechanical exfoliation [1], arc discharge [45], ox-
idative exfoliation-reduction [46,47], liquid-phase exfoliation (LPE)
[48,49] and unzipping of CNT [45,50] usually isolate and delami-
nate the layers of graphite into single-, bi- and few-layer graphene.
These methods destroy larger precursors such as graphite and
other carbon-based precursors to form nano-sized graphene. Gen-
erally, some top-down methods are highly scalable and pro-
duce high quality products, but have difficulties in forming prod-
ucts with consistent properties, low yield and rely heavily on
the finite graphite precursor. The bottom-up methods synthe-
size graphene and its derivatives using other carbon sources
apart from graphite. These methods construct graphene materi-
als from atomic-sized precursors. The bottom-up methods include
chemical vapor deposition (CVD) [51,52], epitaxial growth [53,54],
substrate-free gas-phase synthesis (SFGP) [55], template route
[56] and total organic synthesis [42]. Even though the bottom-up
methods produce graphene products with almost defect-free and
large surface area, they often involve high production cost and so-
phisticated operational setup.
4.1. Mechanical exfoliation
Mechanical exfoliation can be categorized based on directional
routes such as normal force and shear force vectors (Fig. 4). One
of the recent studies on the normal force synthesis route is the
peeling of graphite using advanced machinery of ultra-sharp single
crystal diamond wedge [57]. This method eliminates the need for
manual operation, and saves time and labor cost. Another method
uses a three-roll mill machine, an established technique in rubber
industry, to produce graphene of 1.13–1.41 nm [58,59]. The major
drawback of this method is the cost of adhesives such as polyvinyl
chloride (PVC) and the purification of graphene from the adhesive.
The removal of PVC was achieved by heating in a muffle furnace
at 500 °C for 3 h [59]. Thus, residue PVC elimination could lead to
high energy consumption and hence high production cost. The two
approaches, however, still lack in-depth synthesis and parametric
studies.
The shear force-based methods such as ball milling and fluid
dynamic methods have been gaining much attention recently.
Ball milling which is commonly used in grinding minerals, ce-
ramic, cement and fertilizer, utilizes grinding media in the form
of balls to generate the mechanical force via impact and attrition,

Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
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Fig. 3. Synthesis methods of graphene [43].

Fig. 4. Mechanical exfoliation of graphene based on different mechanical routes

[58].

exfoliating graphite to form graphene flakes. This technique fa-

cilitates exfoliation and fragmentation of graphite to graphene of
nano-size thickness [58], mixing between graphene and compos-
ite materials [60] and even functionalization of graphene [61]. The
quality of graphene produced by ball milling synthesis is controlled
by process parameters such as grinding media type, time, matrix,
speed and precursor initial size [62]. Exfoliation of graphene using
ball milling is a time consuming process. The reaction time for the
process could vary from 24 to 48 h which is undesirable for large-
scale production. Notwithstanding the suitability of ball milling for
batch and continuous processes, this undesirable factor needs to
be resolved to ensure scalability.
4.2. Arc discharge
Arc discharge, a conventional technology used for preparation
of fullerene [63] and CNT [64], has been found to be highly adapt-
able for graphene synthesis [45]. As shown in Fig. 5, the reac-
tion chamber consists of an anode (carbon precursor) and a cath-
ode (graphite rod) which are submerged either in a gas or liquid
medium. The applied electrical current dissociates the medium to
generate a high temperature plasma reaching up to 3727–5727 °C,
sufficient to sublime the precursor [65]. The synthesis of graphene
has been investigated under different inert gas conditions which is
Fig. 5. Arc discharge system for graphene synthesis (a) and shutter used to control
exposure time of substrate to carbon flux from the arc (b) [68].
generally expensive due to the use of vacuum equipment [66]. To
address this issue, low cost graphene was prepared by using an air
medium in the arc discharge, instead of a H2 /He medium, by Wang
et al. [67]. The graphene production reached several tens of grams
per day and the product had a number of layers varying between 2
and 10 nanosheets. However, this synthesis method required pre-
cise high air pressure to ensure the growth of graphene. A fur-
ther attempt to reduce the cost of production was demonstrated
in the work by Li et al. [66] where graphene was produced from
petroleum asphalt in a water arc discharge system. This synthesis
method was considered cost effective due to the water medium
used. Furthermore, the use of asphalt, a carbon-rich material, en-
able an inexpensive raw material to be used [66]. The high preci-
sion required in process control and the energy intensive nature of
arc discharge synthesis could hinder the scalability of the graphene
production. However, arch discharge could produce graphene at
an affordable cost given the emerging improvements observed
recently.

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Fig. 6. Graphite oxidation route schemes [69,72].
4.3. Oxidative exfoliation-reduction
Most GO are synthesized by oxidative exfoliation of graphite
followed by reduction to graphene sheets or rGO. There are four
main routes for GO synthesis which include those of Brodie, Stau-
denmaier, Hofmann and Hummers. Fig. 6 shows the reaction path-
ways of these methods which occur at temperatures below 100 °C
[46,69]. The relatively low synthesis temperature is desirable to
maintain low production cost. However, toxic gases such as nitro-
gen dioxide (NO2 ) and dinitrogen tetroxide (N2 O4 ) are generated
by these methods [41,70]. Thus, process safety and environmen-
tal costs need to be considered during process scale-up. Currently,
the Hummers method is widely used for synthesis of GO as it is a
comparatively fast and safe process. Moreover, it does not generate
explosive gases such as chlorine dioxide (ClO2 ) and acidic fog with
the use of potassium permanganate (KMnO4 ) and sodium nitrate
(NaNO3 ) instead of potassium perchlorate (KClO4 ) and nitric acid
(HNO3 ) [71]. Over the years, modification of the Hummers method
has introduced a greener approach to producing GO [40]. For in-
stance, the improved Hummers method has eliminated the use of
NaNO3 to synthesize GO, thereby decreasing the production cost
and environmental protection cost [71].
The oxidation of graphite increases the distance between the
graphite layers from 0.335 to 0.625 nm, or greater, due to the in-
corporation of graphite intercalation compounds [73]. Thus, the in-
terlayer van der Waals force is weakened during the carbon sheet
displacement and subsequent exfoliation by sonication in suitable
solvents can produce well dispersed single-, bi- and few-layer GO
[73]. GO is highly hydrophilic due to the presence of oxygenous
functional groups, hence it can be dispersed in different solutions
such as water, ethylene glycol, N-methyl-2-pyrrolidone (NMP) and
tetrahydrofuran (THF) [74,75].
GO possesses a disrupted sp2 bonding and to restore its hon-
eycomb lattice, reduction methods are often utilized. As indicated
in Fig. 3, chemical, thermal and electrochemical processes are the
main methods for GO reduction. Most of the oxygenous functional
Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028
[m5G;November 23, 2018;18:13]
groups such as carbonyl, hydroxyl and carboxylic in GO are elim-
inated during reduction. However, a complete reduction of GO to
produce pure graphene is still not achievable [20,76]. The resulting
rGO usually has high resemblance to pristine graphene, but with
a certain degree of defects and dimension differences. The quality
of rGO is governed by reductant type and process conditions such
as reduction time, temperature, pressure and voltage. Furthermore,
the C/O ratio gives an indication of the suitability of the reducing
agent in GO reduction [46]. A large C/O ratio suggests a high de-
gree of de-oxygenation resulting in a higher quality of rGO.
In chemical reduction of GO, hydrazine (N2 H4 ) is commonly
used to reduce the oxygen content of GO. However, N2 H4 is rel-
atively expensive and toxic, and these limit its large-scale ap-
plication. As such, a greener approach was initiated to substi-
tute toxic N2 H4 used in GO reduction [77,78]. A wide range of
reduction agents such as borohydrides, aluminium hydride, hydro-
halic acid, sulfur-based reagents, nitrogen-based reagents, oxygen-
based reagents, metal-acid, metal-alkaline, amino acid, plant ex-
tracts, microorganisms, proteins and hormones were used [46].
The chemical reduction generated high C/O using zinc/hydrochloric
acid (33.5) [79], benzyl alcohol (30) [80], thionyl chloride (8.48)
[81], caffeic acid (7.15) [82], sodium borohydride (6.9) [83] and
baker’s yeast (5.9) [84], but safety concerns, additional chemical
cost, environment pollution and lengthy synthesis time need to be
considered during process scale-up. Therefore, alternative meth-
ods such as thermal reduction [85] and hydrothermal reduction
[86] of GO have been increasingly examined by researchers. The
major issues associated with thermal reduction are the high tem-
perature incurring high operation cost and the release of CO2 ,
a well-known greenhouse gas. In contrast, hydrothermal reduc-
tion has been shown to reduce GO to rGO at lower temperatures
and thus has lower energy requirement [87]. Electrochemical re-
duction of GO has garnered attention because of its rapid reduc-
tion, cost effectiveness, environmentally friendliness and facileness.
More importantly, it employs less toxic reductants as compared to
chemical reduction. Other GO reduction processes reported in the
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Fig. 7. (Top) LPE of graphite with addition of naphthalene, includes mixing, exfoliation, centrifugation and vacuum filtration steps. (Bottom) Exfoliation of graphite using
π -π stacking interaction with naphthalene [93].
literature include microwave, photothermal, photocatalytic, sono-
chemical, laser and plasma treatment [88,89].
The synthesis of GO by oxidative exfoliation of graphite and fur-
ther reduction to rGO are associated with low production cost and
high yield. However, the rGO suffers from relatively low surface
area, poor electronic conductibility, low solubility and irreversible
restacking of sheets due to van der Waals attraction [90]. Further-
more, there are uncertainties with the synthesis process such as
chemical composition variation from the oxidation and reduction
processes, batch-to-batch reproducibility and generation of perma-
nent defects during the oxidation process [40]. Even so, the ad-
vantages of high scalability and low operation cost outweigh the
shortcomings of this method.
4.4. Liquid-phase exfoliation (LPE)
LPE, one of most widely used synthesis methods for graphene
production, was first introduced in 2008 [91]. There are three main
steps in LPE synthesis: (i) disperse graphite in a suitable solvent,
(ii) exfoliate and (iii) purify the final products [92] as shown in
Fig. 7 [93].
Since LPE exfoliates graphite by overcoming van der Waals
force, the selection of a suitable solvent is dependent on the liquid
properties such as surface energy, surface tension, Hildebrand sol-
ubility and Hansen solubility parameters [43,58]. Aqueous or non-
aqueous solvents with surface energies within 70–80 mJ/m2 or sur-
face tension within 40–50 mJ/m2 are ideal for graphite exfoliation.
This is due to their similar surface energies to graphite which re-
sults in a smaller mixing enthalpy and thus easier exfoliation pro-
cess [58]. Over 40 types of solvent were studied in LPE of graphene
by Hernandez et al. [94]. The obtained information not only could
be used to produce high concentration of graphene products in a
very small volume of solvent, but also to scale-up the process by
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[m5G;November 23, 2018;18:13]
7
selecting less expensive, less hazardous and more stable solvents
for graphene dispersion.
Apart from solvent selection, the modulation of sonication also
plays a crucial role to provide appropriate cavitational effects for
exfoliation of graphite to generate single-layer graphene. Low-
frequency ultrasound (20–100 kHz) can cause physical modifica-
tions to graphite solid such as fragmentation effect, shock wave,
well-mixing effect and mass transport [95]. Although LPE is a
promising method for graphene synthesis, several studies indicated
that sonication could produce defects on its edges and basal planes
[96]. Defects on the graphene products could be avoided by opti-
mizing the effects of sonication time, temperature and intensity,
an area of research which is lacking in the literature. These infor-
mation are particularly important for the design of sonication re-
actor [58]. While LPE exhibits certain disadvantages, this process
is highly versatile in product synthesis and functionalization, and
produces high quality graphene [97].
4.5. Unzipping of carbon nanotube (CNT)
Unrolling or unzipping of CNT involves cutting of the cylindri-
cal structure to lay flat the carbon sheet into single, bi- or few-
layer graphene. Generally, unzipping of CNT requires a high strain
rate (108 –10 /s) to break the C–C bond either in axial or longitudi-
nal direction [98]. Furthermore, this method is applicable to both
single-walled CNT (SWCNT) and multi-walled CNT (MWCNT) re-
sulting in different number of layers of graphene sheet and these
products are termed as graphene nanoribbon (GNR). Numerous
unzipping methods were investigated to produce graphene and
derivatives from CNT such as chemical attack [99], plasma etching
[100], intercalation and exfoliation [101] and metal-catalyzed cut-
ting [102] as shown in Fig. 8. The chemical unzipping of CNT starts
with H2 SO4 treatment followed by KMnO4 oxidation to fracture
the axial-directional C–C bond [99]. The yield of graphene from
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Fig. 8. (a) Unzipping of MWCNT by treatment with H2 SO4 and KMnO4 to form GNR [99]. (b) Etching of CNT partially embedded in a polymer film by Ar plasma [100]. (c)
Insertion of alkali-metal atoms between concentric cylinder of MWCNT to peel off graphene sheet [101]. (d) Cutting along CNT length by catalytic metal nanoparticles acting
as scissors. Image from Thess et al. [102].

this method was low with significant amount of precursor being
destroyed [103]. To improve yield, intercalation of MWCNT was
performed with a chemical medium (oxalic acid) before chemical
unzipping. Oxalic acid (0.38 nm) has a compatible size with the in-
terlayer spacing within MWCNT (0.34 nm), thus ensuring that ox-
alic acid molecules can be easily intercalated in the lattice space
between MWCNT layers [104].
In plasma etching, CNT is embedded in a polymer film such as
poly-methyl methacrylate (PMMA), and the matrix of PMMA/CNT
is further peeled off in KOH before being exposed to argon (Ar)-
based plasma [100]. This would lead to longitudinal fracture of the
C–C bond of CNT. This method can produce graphene with smooth
edges and narrow size distributions (10–20 nm) [100].
Intercalation and exfoliation present another option for CNT un-
zipping by introducing lithium (Li) and ammonia (NH3 ) to the
carbon structure. The strong stress induced by foreign molecules
within the cylindrical structure of CNT breaks the internal tube
wall resulting in layers of graphene [101]. Other metal nanopar-
ticles such as Ni, cobalt (Co) and Cu were reportedly used to
break the H–H and the C–C bonds of the MWCNT [105]. Further-
more, this method avoids the usage of aggressive oxidants such as
KMnO4 , KClO4 , H2 SO4 and HNO3 [106]. Despite much interest in
this method, unzipping of CNT structure utilizes expensive precur-
sors and chemicals.
4.6. Chemical vapor deposition (CVD)
CVD decomposes hydrocarbon gases (such as methane (CH4 ),
acetylene (C2 H2 ), ethylene (C2 H4 ) and hexane (C6 H14 )) and other
biomass materials to grow graphene sheet on metallic catalysts
(such as Cu and Ni films) at elevated temperatures (650–10 0 0 °C)
[107,108]. Upon contacting the hot surface of metal catalyst, the
carbon precursor dissociates into free carbon and hydrogen atoms.
The carbon atom then diffuses through the surface and the bulk
of metal catalyst, and subsequently forms graphene sheet on the
metal surface upon reaching the carbon solubility limit [109,110].
To improve the CVD processes, substrates such as glass, silicon,
quartz, silicon oxide, sapphire and boron nitride were used for
graphene synthesis and the mechanisms were detailed in the work
of Chen et al. [111].
CVD can produce high quality graphene with low defects, highly
interconnected structure and large surface area [108]. However,
it has disadvantages such as high production cost, low through-
put, further purification to remove residue catalyst and transfer of
graphene to other substrates [112]. To overcome these setbacks,
many researchers have focused on optimizing the synthesis con-
ditions at lower temperature and ambient pressure, without com-
promising the quality of graphene [107,113]. For instance, Kalita et
al. [114] were able to synthesize graphene coating at 450 °C us-
ing surface wave plasma enhanced CVD (PECVD). This procedure
significantly lowered the growth temperature and deposition time
(< 5 min) which subsequently enhanced the overall synthesis and
scalability of the process [42]. The setup of conventional CVD can
be modified into PECVD as shown in Fig. 9 [115].
CVD alone is still considered immature for commercializa-
tion as much improvement in the synthesis process is required
with regard to production cost and yield. In order to be feasi-
ble at commercial scale, CVD should be further developed along

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Fig. 9. (a) Remote radiofrequency PECVD system. (b) Illustration of the c-PECVD procedure. (c) Atomic force microscopy (AFM) images of a peel-off graphene flake before
(left) and after (right) c-PECVD. (d) Plots of the experimental results as a function of temperature (T) and H2 content at 48, 90 and 300 mTorr. (e, f) AFM images of peel-off
graphene flakes after activation of the edges with H2 plasma (250 mTorr, 500 °C) for 20 min (left columns), followed by CH4 + H2 plasma CVD (30% H2 , 300 mTorr, 550 °C)
for 80 min (e, right column) or CH4 + H2 plasma CVD (20% H2 , 300 mTorr, 600 °C) for 40 min (f, right column). The height profile across the red line in the AFM in (f) is
shown below the AFM image. Scale bars (c, e, f): 500 nm [115].

with other technologies such as thermal-based and plasma-based

CVD.

4.7. Epitaxial growth

Graphene can also be prepared by thermal decomposi-

tion (120 0–160 0 °C) of hexagonal substrate (silicon carbide
(SiC)) under vacuum or inert condition [116] as shown in
Fig. 10. High temperature treatment causes silicon (Si) to
sublimate (Si melting point = 1100 °C), leaving excessive C
atoms to aggregate and form an sp2 hybridized network
which induce graphene growth [116]. This process is known
as epitaxial growth of graphene on SiC [112,117]. However,
the graphene produced by this method lacks homogeneity
[117]. A novel exothermic reaction between SiC and polyte-
trafluoroethylene (PTFE) has been reported [118]. However, an
environmental concern was raised due to the release of tetraflu-
oroethylene (C2 F4 ) during synthesis albeit the production of high Fig. 10. Growth on SiC. Gold and grey spheres represent Si and C atoms, respec-
tively. At elevated temperature, Si atom evaporates (arrow), leaving a carbon-rich
quality graphene (< 1 wt% of O) and simple operation. Based on surface which forms graphene sheet [121].
current synthesis condition, epitaxial growth of graphene would
be expensive due to the energy intensive process and limited
size of commercial SiC substrate [112]. Furthermore, the epi-
taxial growth can produce different polar faces such as Si-face 4.8. Substrate-free gas-phase (SFGP)
or C-face which hinder the graphene product quality [42,119].
Si-face graphene formation is preferred as it ensures homogeneous SFGP is a relatively new method for synthesis of graphene ma-
growth of graphene [119]. Using this method, the number of terials through gas phase reaction without the presence of any
layers of graphene which depends on heating temperature can substrates (Fig. 11) [122]. An aerosol mixture of liquid ethanol
be easily modulated [119]. So far, this synthesis method is still and Ar gas is transferred to a microwave-generated plasma at
under review as data on the growth mechanisms and interaction atmospheric condition. Graphene is formed when the ethanol
between graphene and the substrate is still scarce [120]. droplets are vaporized and dissociated in the plasma region over

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Fig. 11. Synthesis of graphene sheets. (a) Schematic of the atmospheric pressure microwave plasma reactor used to synthesize graphene. (b) Photograph of graphene sheets
dispersed in methanol. (c) A typical transmission electron microscopy (TEM) image of graphene sheets freely suspended on a lacey carbon TEM grid. Homogeneous and
featureless regions (indicated by arrows) indicate regions of monolayer graphene. Scale bar represents 100 nm [122].

a time scale of 1 s [123]. Approximately 2 mg/min of graphene was
reportedly produced by this process from 164 mg/min of ethanol
feed [127]. Dato and Frenklach [124] investigated the influence
of different carbon precursors using this method. It was found
that isopropyl alcohol and dimethyl ether precursors could yield
graphene nanosheet. However, the product required further mor-
phological characterization and removal of unwanted amorphous
materials [124]. The findings also suggested that SFGP might be
similar to soot formation mechanism enabling the use of cheaper
precursors [124]. Nevertheless, this method lacks comprehensive
parametric studies and more research is required to establish the
mechanism of SFGP. Overall, SFGP has a high potential for scal-
ing to commercial level as it can produce clean and high quality
graphene.
and produced high quality and stable single-layer graphene with
0.6 nm thickness using non-hazardous reagents [127].
A soft-hard template approach was developed recently to fab-
ricate graphene on silica substrate as shown in Fig. 12 [56].
This method replaced the carbon source with pyrene and assem-
bled the matrix material with cetyl trimethyl ammonium bromide
(CTAB) and tetramethoxysilane (TMOS) to form a sandwich-like
SiO2 /CTAB/pyrene with CTAB as the soft template and SiO2 as the
hard template. Thermal treatment was carried out under inert con-
dition at 900 °C for 2 h to obtain the graphene sandwiched be-
tween the soft-hard templates. In view of commercialization, this
method is less desirable due to the tedious washing step and the
potential in destroying the produced graphene permanently during
template removal [125].

4.10. Total organic synthesis

4.9. Template route
Graphene synthesis based on one-dimensional metal, oxide or
polymeric templates was reported to produce graphene deriva-
tive with high throughput, good quality and well defined structure
[125]. The template method was initiated by Wei et al. [126]. It
involved CVD template growth starting with physical vapor depo-
sition (PVD) to produce ZnS ribbon as the template for graphene
growth with CH4 as the carbon source. The residue ZnS nanobelt
was etched with HCl. Another template route for graphene synthe-
sis is the self-assembly of graphene on a lamellar meso–structured
silica template as the carbon source which was derived from
a pyrrole moiety-containing surfactant [127]. The pyrrole moiety
was polymerized and carbonized into individual nanosheet in in-
ert condition. This method was highly controllable and gave high
yield (in gram scale) of graphene under mild operating conditions,
In total organic synthesis, graphene is fabricated based on
the unique properties of polycyclic aromatic hydrocarbons (PAHs).
PAHs are often described as 2D graphene segment composed of all
sp2 carbons due to their structural size which is between molec-
ular and macromolecular phases [128]. Furthermore, PAHs can be
easily modified with suitable aliphatic chains to tailor the prod-
uct solubility [129]. The key step of this process is to select suit-
able precursors to deliver high yield and quality graphene via a
simple reaction route. The 2D GNR fabricated by total organic
synthesis was reported to have lengths up to 12 nm and the reac-
tion conditions are illustrated in Fig. 13 [130]. However, the qual-
ity of graphene might be affected by the limited size range of
PAHs which would decrease the graphene solubility and forma-
tion of side reactions resulting from increased molecular weight
[92,131]. These shortcomings were resolved by Yan et al. [132] as

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Fig. 12. Synthesis of graphene film by soft-hard template approach [56].

Fig. 13. Synthesis of GNR. Reaction conditions: (a) 4-bromophenylboronic acid, Pd(PPh3 )4 , aliquot 336, K2 CO3 , toluene, 80 °C, 24 h, 93%. (b) (i) n-BuLi, THF, −78 °C, 1 h; (ii)
2-isopropoxy-4,4,5,5-tetramethyl[1,3,2]dioxaborolane, rt, 2 h, 82%. (c) compound 1, Pd(PPh3 )4 , aliquot 336, K2 CO3 , toluene/H2 O, reflux, 72 h, 75%. (d) FeCl3 , CH2 Cl2 /CH3 NO2 ,
25 °C, 48 h, 65% [130].

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Fig. 14. World production of graphite (1900 – 2015) [134].
the derived graphene showed stable dispersibility despite its large
size. Total organic synthesis showed good progress in graphene
synthesis, but the occurrence of side reactions and precise para-
metric control have hindered its commercial application.
4.11. Comparison of graphite and other feedstock for graphene
synthesis
The type of feedstock would greatly affect the economic feasi-
bility of graphene (and its derivatives) synthesis as its mass pro-
duction would require continuous supply of the carbon precur-
sor [40]. Graphite is the most common feedstock for top-down
graphene synthesis. It is relatively inexpensive as it is abundant in
nature. Fig. 14 illustrates the increase in graphite demand from the
year 1900 to 2015, with worldwide production reaching 1190 thou-
sand metric tons (MT) in 2015 [133]. The production of graphite
is expected to increase due to the increase in demand for battery
manufacture in the future [133].
The grade of graphite is dependent on its flake size and car-
bon content, and the price range of graphite is as follows: amor-
phous powder with 80–85% carbon ($430–480/MT), fine crystalline
form with 90% carbon ($750–800/MT), medium crystalline form
with 90% carbon ($950–10 0 0/MT), large crystalline form with 90%
carbon ($1150–1200/MT) and synthetic form with 99.95% carbon
($70 0 0–20,0 0 0/MT) according to a U.S. Geological Survey [135].
The price of graphite tends to be higher with better grade (higher
flake size and carbon content) and the current graphite supply
is sufficient for graphene synthesis. As nanotechnology is still re-
garded as a niche field, the graphite demand for graphene synthe-
sis would have less impact on the market price and production
cost [135]. Therefore, future development of graphene using top-
down process will not be affected by the availability and cost of
graphite.
Apart from graphite feedstock, more sustainable precursors
have been tested in both top-down and bottom-up processes for
graphene synthesis. For instance, biomass materials were studied
as the feedstock for oxidative exfoliation instead of graphite, and
asphalt was explored as the starting material in arc discharge syn-
thesis to reduce the overall production cost of graphene [66,124].
Biomass feedstock such as wood, leaf, bagasse, fruit, newspa-
per, bone and cow dung have been used to replace high qual-
ity graphite which is commonly used in oxidative exfoliation-
reduction process [136]. Typically, the biomass was required to
undergo incomplete burning for 5 days followed by heating
at 450 °C for 24 h. The carbonized precursor was then graphi-
tized using iron (III) chloride (FeCl3 ) solution and dried gradu-
ally for a week followed by oxidative exfoliation-reduction syn-
thesis. The preparation of the precursor was time consuming and
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[m5G;November 23, 2018;18:13]
required complicated and precise control of process parameters.
Nonetheless, this method provides a feasible option for the syn-
thesis of graphene derivatives, namely GO and rGO.
Conventionally, CVD utilizes fossil-based hydrocarbon products
such as benzene (C6 H6 ), xylene (C8 H10 ), toluene (C7 H8 ), methanol
(CH3 OH) and ethanol (C2 H5 OH) for graphene synthesis [137]. Al-
ternative carbon precursors such as agricultural, food and animal
wastes were used to replace fossil-based hydrocarbons to minimize
cost and eliminate usage of toxic raw materials [137]. Since the
global production of plastic has reached a significant amount of
299 million tons in 2013 [138], plastic waste obtained from pack-
aging industries is also a possible precursor as it mainly consists
of polyethylene (PE) and polystyrene (PS) which are carbon rich
materials [139]. Hexagonal graphene crystals with 0.5 nm thickness
were successfully fabricated on polycrystalline Cu foil using solid
waste plastic as the carbon source [139]. Takami et al. [140] also
produced graphene film using PMMA polymer film as the carbon
source under Ar or Ar/H2 condition. Thus, using plastic waste as a
carbon source can be an alternative way to reduce the waste vol-
ume and provide low cost feedstock for graphene synthesis [141].
Furthermore, Ruan et al. [142] studied the growth of graphene us-
ing cookies, chocolate, grass, dog feces and cockroach legs as the
precursors, annealed at 1050 °C in a flow of Ar: H2 of 5:1 and us-
ing Cu foil as the support. Graphene used directly without purifi-
cation was successfully produced. Based on recent developments,
Fig. 15 shows the possible precursors for synthesis of graphene
and its derivatives through oxidative exfoliation-reduction and CVD
methods. As observed, various precursors are readily available from
nature and industrial wastes which could significantly reduce the
production cost.
5. Potential industrial implementation of graphene synthesis
methods
Within the last two decades, much research has been con-
ducted to explore feasible synthesis routes for mass production
of graphene [143–145]. As previously discussed in Section 4, each
synthesis method would generate a graphene product of specific
characteristics and the scalability potential of the process is lim-
ited by the synthesis conditions, feedstock availability and cost,
as well as other factors. Several sustainability assessment method-
ologies have been applied to evaluate the performance of synthe-
sis processes which include the Global Reporting Initiative, Ameri-
can Institute of Chemical Engineers Sustainability Index, Institution
of Chemical Engineers Sustainable Development Progress Metrics
(IChemE SDPM) and Green Chemistry [146].
In this section, the graphene synthesis methods are examined
by the IChemE SDPM for their potential industrial implementation
[147]. The IChemE metrics cover three important aspects applied as
the primary indicators in process evaluation, namely environment,
economic and social indicators. The environmental indicators focus
on the use of resources (such as energy, material, water and land)
and the impacts on the environment (such as atmospheric, aquatic
and land) due to emissions, effluents and wastes generated by
the process. Meanwhile, the economic indicators cover the profit
gained, value-added and taxes paid, and investment made while
the social indicators consider the employment situation, health and
safety at work, and impacts to the society [147]. Nevertheless, not
all the suggested metrics are applicable in every case, but the key
indicators have to be selected from environmental, economic and
social aspects in order to give a balanced view on the process eval-
uation [146].
Based on the IChemE guidelines, six key indicators were iden-
tified for the present assessment on the graphene synthesis
methods, and these are: (i) cost (precursor cost and operating
cost), (ii) scalability potential, (iii) product quality, (iv) process
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Fig. 15. Carbon precursors for synthesis of graphene and its derivatives.
condition (process safety and complexity), (v) yield and (vi) en-
vironment (use of hazardous chemicals). The results are illustrated
by the radar charts in Fig. 16 whereby a preference score (0 = none
or not available, 1 = low, 2 = average and 3 = high) is assigned to
each key indicator for each synthesis method. The most promising
synthesis method for commercialization would be indicated by the
highest total score [4,148].
Fig. 16 portrays that each synthesis method had different char-
acteristics in terms of cost, scalability, product quality, process
condition, yield and environment indicators. Mechanical exfolia-
tion has been reported to be inexpensive due to its simple opera-
tion and low cost feedstock requirement such as graphite. It forms
graphene product of different sizes and irregular shape [149]. How-
ever, this synthesis route is considered labor intensive for produc-
tion of single-layer graphene and its yield is very low which may
increase the overall operating cost [4,13]. As such, this method was
rated by an average score in cost, process condition and prod-
uct quality and a low score in scalability and yield as shown in
Fig. 16(a). Hence, mechanical exfoliation method requires further
process improvement before its commercialization can be realized.
SFGP is able to produce high quality graphene in a continu-
ous operation [122–124,150], thus it is rated the highest preference
score for yield and scalability (Fig. 16(b)). However, it is currently
not ready for commercialization due to the lack of parametric and
mechanism studies [151]. Although this method could effectively
produce graphene, the requirement of specialized equipment such
as microwave plasma reactor and the formation of few-layered
graphene resulted in a low preference score for cost and product
quality [124,150]. Additionally, the number of layers is hard to con-
trol and multi-layered graphene is not preferred in electronic ap-
plications [150]. Therefore, this synthesis method requires further
exploration before it can be applied at industrial-scale.
Total organic synthesis is highly versatile in producing high
yield graphene, but it has several constraints which hinder its
upscaling. In particular, precision control and extensive reaction
steps contributed to the low preference score in cost and pro-
cess condition. Furthermore, challenges such as the handling of
hazardous PAH, difficulty in maintaining dispersibility and occur-
rence of structural distortion have led to the low preference score
in product quality, process condition and environment as depicted
in Fig. 16(c) [6,152].
Template route has a low preference score in cost, scalability,
product quality and process condition (Fig. 16(d)) due to the po-
tential destruction of graphene product during the tedious purifi-
cation steps and additional cost associated with the destruction of
the sacrificial template at the end of the synthesis process [5,150].
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13
As shown in Fig. 16(e), the use of relatively expensive feedstock
such as CNT is unfavorable in large-scale graphene production as
this will incur high operating cost. The graphene quality produced
through the unzipping of CNT route is highly dependent on the
type of CNT (such as SWCNT and MWCNT) and the plasma etching
time. Hence, this synthesis method still requires further study to
improve the graphene yield and other CNT unzipping parameters
for industrial application [150,153].
Plasma operation in arc discharge method requires high volt-
ages in delivering high temperature process condition to synthe-
size graphene. This has raised process safety concerns and in-
curred higher operating cost compared to other synthesis meth-
ods as reflected by the low preference score for process condition
and cost in Fig. 16(f) [13,24]. The graphene produced by arc dis-
charge has been reported to exhibit multi-layer feature and the
number of graphene layer formed was hard to control, thus lim-
iting the potential industrial production of high quality graphene
[13].
The potential application of epitaxial growth in industry is gen-
erally limited by the strict operating conditions and the use of spe-
cial equipment such as high temperature, ultrahigh vacuum, in-
ert condition and utilization of single-crystal substrate [144,150].
These have resulted in the low preference score for commercial-
ization in terms of cost, scalability, process condition and yield as
displayed in Fig. 16(g).
Based on the total preference score, oxidative exfoliation-
reduction (16 points, Fig. 16(h)), CVD (13 points, Fig. 16(i)) and LPE
(16 points, Fig. 16(j)) demonstrated high commercialization poten-
tial due to their relatively high graphene yield and product qual-
ity, as evident by the wide use of the graphene produced by these
methods in various research fields such as wastewater treatment,
polymer reinforcement, energy storage and biosensors [149,154–
157]. Oxidative exfoliation-reduction is considered as the most vi-
able route as it offers mass production of rGO sheets from graphite
feedstock at a relatively low cost and approximately 80% of mono-
layer rGO sheets could be generated by this process [150,158,159].
However, the resulting product may not be pure due to the de-
formation of hexagonal carbon chains which in turn can affect its
thermal, mechanical and electrical properties. Graphene material
produced by this method has been utilized as precursor in ad-
sorbent development, drug delivery and composite reinforcement
[160-162]. Toxic chemicals such as hydrazine, borohydrides and
aluminium hydride have been used as the reducing agents in ox-
idative exfoliation-reduction method, thereby limiting the environ-
ment indicator preference score in the process evaluation. Recently,
green reducing agents such as bacteria, plant extract and yeast,
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14 X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

Fig. 16. Process evaluation of graphene synthesis: (a) mechanical exfoliation, (b) SFGP, (c) total organic synthesis, (d) template route, (e) unzipping of CNT, (f) arc discharge,
(g) epitaxial growth, (h) oxidative exfoliation-reduction, (i) CVD and (j) LPE. Preference score: 0 = none or not available, 1 = low, 2 = average and 3 = high.

Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028
JID: JTICE
ARTICLE IN PRESS
X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx
have also been investigated to minimize the harmful effects of us-
ing the toxic chemicals for GO reduction [158,163,164].
CVD has garnered global interest in graphene commercial-
ization due to the high quality of graphene produced and
the flexibility in tailoring graphene derivatives. The amount of
graphene synthesized by this method depends on the size of sub-
strate [4,24]. However, this technique is costly in comparison to
oxidative exfoliation-reduction as the process cost is constrained
by the size of substrate, precursor type and energy cost. Moreover,
the scalability of CVD is hindered by the difficulty in transferring
the graphene product developed on the substrate (Fig. 16(i)). The
product transferring step is challenging as structural defects and
impurities could be introduced to the final product if mishandled
[144]. The high quality graphene produced by CVD is highly favor-
able in electronic and optical applications, but is not well suited
for applications requiring bulk quantity such as polymer compos-
ites [144].
Owing to its high versatility and cost effectiveness in produc-
ing good quality graphene, LPE has good potential for commer-
cialization. The use of cheap feedstock, straightforward operation
and use of environmentally friendly chemicals are the main ad-
vantages of LPE which support its potential industrial implemen-
tation [165,166] (Fig. 16(j)). The graphene produced by LPE has
lesser structural defects, thus many applications such as biosen-
sors, energy storage and functional devices employed this tech-
nique to produce graphene [149,167]. However, several challenges
hinder the process scale-up and these include a lack of informa-
tion on commercial reactor set-up, high operating cost and lower
yield as compared to other synthesis methods [168].
In summary, oxidative exfoliation-reduction, CVD and LPE have
high potential for industrial implementation and this is supported
by their good performance in relation to the IChemE SDPM. Since
each of the synthesis methods has distinctive benefits, the selec-
tion of a suitable synthesis route should also be based on the fi-
nal application of the graphene product [6,13,150]. For instance,
in applications requiring large quantities of graphene feedstock
such as in adsorbents development and polymer reinforcement, it
would be appropriate to select the oxidative exfoliation-reduction
[144,151]. LPE and CVD methods could benefit industrial sectors
such as electronic, optical and biosensors in producing sufficient
graphene [144,157].
6. Conclusions
Graphene and its derivatives have gained attention with their
superior physicochemical properties such as high specific sur-
face area as well as excellent chemical and thermal stability
which facilitate applications in various fields. The synthesis meth-
ods of graphene and its derivatives have been reviewed com-
prehensively. Through the IChemE SDPM assessment, oxidative
exfoliation-reduction, CVD and LPE have been demonstrated to
possess high potential for industrial implementation. The selection
of a suitable synthesis route should also be based on the final ap-
plication of the graphene product. Nonetheless, challenges such as
environmental risks as well as the high cost of graphene and its
derivatives need to be overcome before full commercialization for
different applications can be realized.
Acknowledgments
This research was supported by the Ministry of Higher Edu-
cation (MOHE), Malaysia under the Fundamental Research Grant
Scheme (FRGS/1/2015/SG06/UNIM/02/1).
Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028
[m5G;November 23, 2018;18:13]
15
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Please cite this article as: X.J. Lee, B.Y.Z. Hiew and K.C. Lai et al., Review on graphene and its derivatives: Synthesis methods and potential
industrial implementation, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2018.10.028