Journal of Industrial and Engineering Chemistry 83 (2020) 449–458

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Journal of Industrial and Engineering Chemistry

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

Preparation of synthetic graphite from waste PET plastic

Seunghyun Koa , Yeon Ju Kwona,b , Jea Uk Leea,c , Young-Pyo Jeona,c,*
a
Carbon Industry Frontier Research Center, Korea Research Institute of Chemical Technology (KRICT), 141, Gajeong-ro, Yuseong-gu, Daejeon, 34114, Republic of
Korea
b
School of Chemical Engineering, Sungkyunkwan University (SKKU), 2066, Seobu-ro, Jangan-gu, Suwon, 16419, Republic of Korea
c
Advanced Materials and Chemical Engineering, University of Science and Technology (UST), 217, Gajeong-ro, Yuseong-gu, Daejeon, 34113, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: The development of new technologies for converting waste plastics into value-added products is
Received 26 June 2019 attracting widespread attention because of the global plastic waste crisis. In this study, we present a
Received in revised form 3 December 2019 novel route for the upcycling of waste plastics, wherein synthetic graphite is prepared from a waste
Accepted 16 December 2019
polyethylene-terephthalate (PET) bottle through a facile and scalable method. PET was successfully
Available online 23 December 2019
converted to graphite via a synthetic method of pyrolysis at 900
C followed by boron-assisted catalytic
graphitization at 2400
C. This technique overcame the intrinsic non-graphitizable property of PET and
Keywords:
yielded graphite showing high crystallinity with the maximum crystallite size of 20.9 nm in Lc and the
Plastic waste
Polyethylene terephthalate
d(002) spacing of 3.373 Å. In particular, it showed a much higher degree of graphitization (80.6%) than that
Graphitization (68.9%) derived from a well-known AR mesophase pitch (Mitsubishi). In addition, via a microwave-
Graphite assisted liquid-phase exfoliation, the PET-derived graphite was successfully exfoliated as graphene sheets
Graphene with the average lateral size of 410 nm. We expect that our work can guide the innovative upcycling of
waste plastics to invaluable synthetic graphite, which has many potential applications such as anode
materials in secondary batteries and fillers for carbon composites, and may serve as an alternative source
for graphene production.
© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction Upcycling is any technique that transforms waste materials into

Rapidly increasing plastic waste is becoming a major threat to
living organisms on earth. As of 2015, a cumulative total of 6.3
billion metric tons (MT) of plastic waste had been generated, but
only 9% recycled [1]. Of the rest of the plastic waste, 79% has been
landfilled or discarded in the ocean while 12% has been incinerated
[1,2], causing serious environmental contamination. Polyethylene
terephthalate (PET) is one of the most commonly used plastics,
mainly applied as containers for various liquids and foods because
of its affordability, transparency, and good mechanical properties.
The estimated amount of PET consumption has exceeded 24
million MT per year and continues to increase [3]. This contributes
a significant volume of plastic waste. Hence, new innovative
technologies for the post-utilization of PET and other plastic
wastes are in high demand to maximize their utility and avoid
landfilling or incineration.
* Corresponding author at: Carbon Industry Frontier Research Center, Korea
Research Institute of Chemical Technology (KRICT), 141, Gajeong-ro, Yuseong-gu,
Daejeon, 34114, Republic of Korea.
E-mail address: ypjeon@krict.re.kr (Y.-P. Jeon).
more valuable products [4]. Recently, many studies on upcycling of
waste PET into various valuable carbon materials, including
activated carbons (ACs), carbon spheres, carbon sheets, and
nanostructured carbons, have been reported. The main constituent
of PET is carbon with 62.5 wt%; it is free of inorganic components
[5], making it a good source for the preparation of carbon
materials. Many attempts for the conversion of PET into ACs have
been reported [6–9]. Mendoza-Carrasco et al. prepared ACs
through physical and chemical activation methods [6]. Bratek
et al. converted PET into AC through carbonization followed by CO2
activation; the AC showed hydrogen storage capability and
applicability as a supercapacitor electrode [7]. The application of
PET-derived AC as a sensing platform was also suggested [8]. The
preparation of porous carbons other than ACs from PET, such as
porous carbon sheets [10] and mesoporous carbons [11–13], has
also attracted significant attention. Regarding nanocarbons, the
conversion of PET into graphene-like materials [5,14], nanotubes
[15,16], and other nanostructured carbons has been attempted.
Unfortunately, previous studies have been limited to the
conversion of PET into carbon materials with disordered (amor-
phous or turbostratic) structures or nanostructured carbons, rather
than the highly ordered graphite structure. Graphite is of great

https://doi.org/10.1016/j.jiec.2019.12.018
1226-086X/© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
450 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
research interest and widely used industrially because of the
properties arising from its unique crystal structure. In the graphite
structure, sp2-hybridized carbon atoms are covalently bonded and
arranged hexagonally in a planar condensed ring system that forms
two-dimensional (2D) layers. The layers are stacked parallel to
each other and held together with loose van der Waals forces.
Because of this structural feature, graphite is a good conductor of
heat and electricity and shows a high regular stiffness and
strength. It sustains these properties at temperatures reaching
~3600
C with almost no thermal expansion. These special
properties permit many uses in mechanical, nuclear, aerospace,
and chemical applications. In particular, because of its high energy-
storage capacity and stable cycle life, graphite is the most
commonly used anode material for rechargeable lithium-ion
batteries [17] since the first commercialization of such batteries
in the early 1990s [18]. Research on PET conversion to graphitic
structures is limited because of the non-graphitizable nature of
PET. The non-graphitizability suppresses the structural evolution
to graphite during graphitization processes, which are usually
performed at temperatures above 1800
C under inert atmos-
pheres [19]. Through the conventional graphitization process,
graphite cannot be obtained from PET. Therefore, the graphitiza-
tion of PET remains a significant challenge.
In this study, we attempted to convert PET waste to graphite. A
PET bottle was used as the starting material and successfully
converted to graphite with a well-developed crystal structure. The
synthetic method involved the pyrolysis of PET under an inert
atmosphere and subsequent catalytic graphitization in the
presence of boron (Fig. 1). Moreover, we performed liquid-phase
exfoliation on the resultant graphite and successfully obtained
graphene sheets. The intrinsic non-graphitizability of the PET was
overcome by the boron-induced catalytic graphitization. The
addition of boron to carbon fibers improves the mechanical and
thermal properties of the carbon fibers, as has been reported
previously [20,21]. This is because of the catalytic effect of boron on
graphitization [19,22,23]. Boron-induced catalytic graphitization
has been used to prepare high-performance carbon materials from
various carbon sources such as phenolic resin [24,25], polyimide
[26], glucose [27], coke [28], and bituminous coal [29,30].
However, the catalytic effect of boron has not previously been
used for the graphitization of PET or other plastic wastes. To the
best of our knowledge, we report the first use of boron for the
graphitization of plastic waste and the first successful conversion
of PET to graphite.
Fig. 1. Schematic for preparation of graphite and graphene from PET plastic.
Experimental
Preparation of synthetic graphite from waste PET
A PET water bottle (Jejusamdasoo, Jejuprovince Development
Co., Republic of Korea) was used as a starting material. It was cut
into pieces measuring 10 mm  10 mm and subsequently
carbonized and graphitized.
For carbonization, 10 g of the PET flakes were placed in a tube-
type furnace and heated to 900
C at a ramping rate of 5
C/min and
held for 1 h. To create an inert atmosphere, N2 gas was flowed
through the furnace throughout heat treatment. The carbonaceous
material obtained through this process showed the carbon yield of
19.0% and was named wPET-C9.
For catalytic graphitization, wPET-C9 was ground and sieved
into powder of <250 mm in particle size. Then, the wPET-C9
powder was mixed with amorphous boron powder (Sigma-
Aldrich, 1 mm in average particle size) with various mixing ratios
of 0, 1, 2, 3, 4, and 5 wt%. The mixtures were graphitized in a box-
type furnace (ThermVac Engineering, Republic of Korea) equipped
with graphite heating elements. Heat treatment was performed at
2400
C for 1 h under flowing helium gas. The ramping rate was
15
C/min. These graphitization processes produced six samples of
the series wPET-Bx-G24 (0–5% boron), where x indicates the
amount of boron added. All the samples exhibited similar
graphitization yields of 86.0  0.6% without distinct variations
according to the boron content.
For direct graphitization, 1 g of the PET flakes was placed in the
same box-type furnace described above under the same conditions
but without any additives. The thus-prepared product was named
wPET-DG24 and showed the carbon yield of 17.1%.
Preparation of graphene from PET-derived graphite
Graphene was prepared from wPET-B5-G24 via microwave-
assisted liquid phase exfoliation. For expansion of graphite, 1 g of
wPET-B5-G24 was placed in a 100 mL flask, and 40 mL of sulfuric acid
(95%, Samchun Chemicals) and 12 mL of fuming nitric acid
(95%, Samchun Chemicals) were separately added. After stirring
for 24 h at ambient temperature, the mixture was poured slowly into
deionized (DI) water and vacuum-filtered, yielding a solid sample.
This solid was washed using DI water several times and dried at 60
C
for 24 h. The acid-treated graphite was sealed in a glass vial and
purged with Ar for 2 h. The vial was then heated in a microwave oven
 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
(MD-203CC, 60 Hz, LG Electronics) for 6 s. The expanded graphite
flakes were then suspended in N-methyl-2-pyrrolidone (NMP)
(99.5%, Samchun Chemicals) with the concentration of 3.33 mg/mL.
The resulting suspension was then exfoliated in an ultrasonicator
(JAC-3010, U1TECH, Republic of Korea) for 3 h. The obtained
dispersion was centrifuged for 5 min at 5000 rpm. The final
graphene powder was collected by vacuum filtration.
Material characterization
X-ray diffraction (XRD) was conducted using a Rigaku D/Max-3C
diffractometer equipped with a rotating anode and a Cu Kα radiation
source (l = 1.5418 Å); the samples were scanned in the 2u range
10–90
with a step size of 0.02
. Thermal gravimetric analysis (TGA)
and differential scanning calorimetry (DSC) were performed using a
SDT Q600 (TA Instruments) under N2 flow with a heating rate of
5
C/min. Fourier transform infrared spectroscopy (FTIR) was
conducted with Bruker ALPHA-T. X-ray photoelectron spectroscopy
(XPS) data were recorded using an AXIS NOVA spectrometer (Kratos
Analytical Ltd., United Kingdom) with a monochromatic Al Kα
source at a power of 150 W (15 KeV, 12 mA). Scanning electron
microscopy (SEM) images were obtained using a CX-200 (COXEM).
Atomic force microscopy (AFM) characterization was performed
using a Bruker Nanoscope in the tapping mode with a scan size of
2 mm and total scan time of 10 h. TEM images were obtained using
an F-200s model (FEI Talos).
Results and discussions
Crystallinity and thermal behavior of waste PET
Firstly, the crystallinity of the waste PET used in this study was
examined by XRD. PET has a triclinic crystal structure; when
analyzed by XRD, it shows three characteristic peaks at 18
, 23.4
,
and 25.8
in its XRD pattern, corresponding to the (010), (110),
and (100) crystal planes, respectively [31]. Fig. 2(a) shows the
XRD pattern of the waste PET sample used in this study. One large
peak appears at 25.6
, corresponding to the (100) plane. The
deconvolution of this peak, as shown in the inset, reveals two
peaks at 18.1
and 22.9
with low intensities. These peaks
correspond to the (010) and (110) planes, respectively. This
demonstrates that the PET used in this study has a triclinic
structure with low crystallinity.
Fig. 2(b) shows the thermal behavior and stability of the waste
PET as measured by DSC/TGA. The DSC curve shows the heat flow
upon heating at temperatures reaching 800
C. The endothermic
peak at 250
C indicates the melting of PET. A subsequent
endothermic peak shows that PET decomposition begins at
360
C, with the peak maximum at 417
C. After decomposition,
Fig. 2. (a) XRD pattern of PET; inset shows deconvolution of (100) peak. (b) TGA and DSC curves of PET.
451
residual matter shows progressive carbonization. The TGA curve
shows that the decomposition produces 17.3 wt% residue, and the
subsequent carbonization produces finally 13.4 wt% carbon. Other
plastics comprising only carbon and hydrogen cannot undergo
carbonization; instead, they decompose completely and vaporize
without producing any carbonaceous matter. As examples, the
TGA/DSC results of polystyrene (PS) and low-density polyethylene
(LDPE) are depicted in Fig. S1 in the Supplementary material. They
showed complete decomposition under heating to 800
C and
produced almost 0 wt% residue. However, the presence of oxygen
in the PET structure allows PET to withstand decomposition to a
certain extent and experience carbonization, because the oxygen
atoms in PET are present as ester groups serving as chemical
linkages.
Structural change of the waste PET upon carbonization and
graphitization
In order to identify the crystal structure developed after
carbonization, wPET-C9 (produced by heat-treatment of waste PET
at 900
C for 1 h) was analyzed using XRD. Fig. 3(a) presents the
obtained XRD pattern of wPET-C9. It shows three broad peaks at
22.7
, 43.6
, and 79.2
, corresponding to the (002), (100), and (110)
crystal planes of the graphite structure, respectively. All peaks are
low in intensity with large peak widths, consistent with typical
diffraction patterns of amorphous carbons [32,33]. This indicates
that heat-treatment of PET at 900
C produces carbon with
amorphous structure.
To investigate its graphitizability, PET was directly heat-treated
at 2400
C for 1 h. Fig. 3b shows an XRD pattern of the resulting
product, denoted wPET-DG24. No distinctive differences are
observed compared to the pattern of wPET-C9, except for slightly
higher intensities of the (002) and (100) peaks and the appearance
of a very low-intensity (004) peak. This showed that graphite
structure is not obtained from PET even through heat-treatment at
temperatures beyond 1800
C. Normally, graphitizable carbons
progressively undergo development of graphite structures at
temperatures above 1800
C. Mesophase pitch is a well-known
graphitizable carbon source capable of graphitization at such
temperatures. Using mesophase pitch (AR pitch, Mitsubishi Gas
Chemical), synthetic graphite was prepared via heat-treatment at
2400
C for 1 h and its XRD pattern was depicted in Fig. 3(c). It is
seen that its diffraction pattern is quite different from that of wPET-
DG24. It had a pattern with a high signal-to-noise, and is consistent
with that of natural graphite (Kanto Chemical Co. Inc.) depicted in
Fig. 3(d), suggesting synthetic graphite had graphite structure.
However, in the case of wPET-DG24, the characteristic features in
diffraction pattern of graphite structure were not observed, and
thereby confirming that it still remained to be amorphous
452 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
Fig. 3. XRD patterns of carbon products obtained after heat-treatment of PET at (a) 900
C (wPET-C9) and (b) 2400
C (wPET-DG24). XRD patterns of (c) synthetic graphite and
(d) natural graphite. The synthetic graphite is prepared by heat-treatment at 2400
C of mesophase pitch, a well-known graphitizable carbon precursor.
structure. This indicates graphite cannot be obtained from PET via
conventional graphitization process.
The non-graphitizable property of PET likely arises from the
presence of oxygen atoms in the PET structure. PET contains 33 wt
% oxygen in its polymer structure. Heat treatment in the presence
of oxygen induces the oxidation of organic materials at temper-
atures above 180
C [34]. This causes crosslinking within their
molecular structures between oxygen-containing groups, which
fixes the molecular structures [35,36] and prevents the liquid-
phase carbonization necessary for graphitization [37]. Many
organic species solidify and undergo carbonization without
liquid-state carbonization when they are heated beyond a certain
temperature; the subsequent dehydrogenation and condensation
reactions yield polycyclic aromatic hydrocarbons (PAHs) and
consequently carbonaceous materials. Some organic species
undergo liquid-phase carbonization before solid-phase carboni-
zation. During the liquid-phase carbonization, reactions similar to
those occurring in solid-phase carbonization yield PAHs, but the
liquid phase permits the molecular rearrangement of PAHs,
thereby producing highly oriented graphite-like structures. Such
graphite-like structures are advantageous for crystal growth
without significant PAH migration or rotation, thus enabling
graphitization. Meanwhile, because PET skips liquid-phase
carbonization and directly begin solid-phase carbonization due
to the crosslinking by oxygen containing groups, highly oriented
structures are not formed and disordered structures are main-
tained even after graphitization treatment.
Graphitization of waste PET
Graphite has a structure of two-dimensional carbon planes
composed of hexagonal rings; each plane is one graphene layer,
and graphite is an orderly stack of graphene layers along the
direction perpendicular to the graphene plane [38]. Thus,
graphitization can be expressed as the increase in size of the
individual carbon layers and the increase in number of the carbon
layers. The consequences of graphitization are evident from XRD
analysis [39–41]. The most common feature is the (002) diffraction
peak appearing at~26
, which is attributed to the stacking of carbon
layers; the diffraction intensity strengthens as the number of layers
increases. The growth of individual carbon layers along the in-
plane direction is apparent through a change in the (110) peak at
~77
. This peak is broader at the beginning and becomes sharper as
graphitization progresses. In addition, two peaks of (100) and (101)
appear as a single peak at ~43
when the crystallinity is low; the
peaks gradually separate as the crystallinity increases. Other peaks
including (004) and (112) also appear as evidence of graphitization.
After the catalytic graphitization, these changes are distinc-
tively observed in the XRD patterns of the PET-derived products.
Fig. 4 shows the XRD patterns of products obtained after boron-
assisted catalytic graphitization (wPET-B0-G24 to wPET-B5-G24).
The (002) reflection peak is dramatically increased in intensity and
decreased in width as the boron addition amount increases from
0 wt% (wPET-B0-G24) to 5 wt% (wPET-B5-G24), suggesting
increases in the number of stacked graphene layers. In addition,
the insets of Fig. 4 show the gradual separation of the peak near 43

into two different peaks of (100) and (101), as well as the
appearance of a new peak at ~83.3
corresponding to the (112)
plane. The (110) peak at around 77.2
becomes very sharp and
narrow, suggesting the growth of individual graphene layers along
the in-plane direction as well. All these changes in the XRD
patterns and the corresponding crystal growths indicate the
evolution of the graphite structure. Comparison with the diffrac-
tion patterns of synthetic graphite and natural graphite, depicted
at the bottom of the patterns (like those presented in Fig. 3),
confirms that the graphitization of wPET-B5-G24 has progressed
well, with a similar crystallinity to both synthetic graphite and
natural graphite.
 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
Fig. 4. XRD patterns of PET-derived products obtained after heat treatment at
2400
C according to boron addition amount. Insets: magnified images of 40–60

and 75–90
regions. For easy comparison, XRD patterns of synthetic graphite and
natural graphite are added at the bottom of the patterns.
To quantify the crystallinity, the crystallite sizes of Lc and La
were calculated using the Scherrer equation. Lc is the measure of
crystallite size along the c-axis in graphite structure (perpendicu-
lar to the graphene layers), and La is along the a-axis (in-plane
direction). Fig. 5(a) shows the resulting values plotted against the
amount of boron addition. When graphitized without boron
(wPET-B0-G24), the crystallite sizes are 2.1 nm and 4.3 nm for Lc
and La, respectively. However, as the amount of boron increases,
the values for Lc and La are rapidly increased, consequently
reaching 20.9 nm and 31.1 nm, respectively, in wPET-B5-G24. These
values are comparable to those of synthetic graphite and natural
graphite. The calculated Lc values of synthetic graphite and natural
graphite are 25.6 nm and 21.0 nm, respectively; the La values are
44.1 nm and 45.3 nm, respectively. This shows that the crystal
growths of wPET-B5-G24 along both the c- and a-axes progress to
an extent comparable to those of natural graphite and synthetic
graphite.
Fig. 5. (a) Crystallite sizes of Lc and La calculated based on XRD patterns of PET-derived carbons as a function of boron content. (b) Degree of graphitization of wPET-DG24,
wPET-B5-G24, synthetic graphite, and natural graphite.
453
Based on the model given by Maire and Mering [42,43], the
degree of graphitization is calculated using the following equation:
0:3440  dð002Þ
Degree of graphitization ð%Þ ¼  100 ð1Þ
0:3440   0:3354 
where 0.3440 and 0.3354 are the d-spacings of the fully non-
graphitized carbon and the ideal graphite crystal, respectively. This
formula defines the fully non-graphitized carbon as turbostratic
carbon with the d(002) spacing of 0.3440 nm; therefore, carbons
with much poorer crystallinities than turbostratic carbon can show
negative values in the degrees of graphitization. The calculated
degrees of graphitization of wPET-DG24, wPET-B5-G24, synthetic
graphite, and natural graphite are presented in Fig. 5(b). The
sample obtained by direct graphitization from PET (wPET-DG24)
exhibits the degree of graphitization of 42%. This is far less than
that of the fully non-graphitized structure defined by the formula,
indicating that the evolution of the graphite structure does not
progress at all during the direct graphitization without both
carbonization process and boron catalyst, yielding a very poor
crystallinity. Meanwhile, wPET-B5-G24 obtained after the boron-
induced catalytic graphitization shows the significantly higher
value of 80.6%, indicative of a high-quality graphite structure.
Notably, this value is comparable to that of natural graphite
(89.5%), and more significantly, it is much higher than that of
synthetic graphite (68.9%) derived from the well-known graphi-
tizable carbon source of mesophase pitch.
Fig. 6 shows TEM images of wPET-C9, wPET-DG24, and wPET-
B5-G24. In Fig. 6(a), wPET-C9 shows crystallites of a few
nanometers in lateral size forming clusters of several stacked
layers; the clusters lack regular orientation, indicating an
amorphous carbon structure. Similarly, wPET-DG24 (Fig. 6b)
shows no ordered structure; it remains amorphous even after
graphitization heat treatment. However, wPET-B5-G24 clearly
shows a graphite structure with parallel stacks of graphene layers
and a higher degree of orientation compared to those of the former
two samples.
Mechanism of PET graphitization
Non-graphitizable carbons, after heat-treatment at graphitiza-
tion temperatures, generally exhibit complicated (002) diffraction
peaks, which can be separated into three components of A
(amorphous), T (turbostratic), and G (graphitic) [44]. Turbostratic
454 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
Fig. 6. TEM images of (a) wPET-C9, (b) wPET-DG24, and (c) wPET-B5-G24.
carbon is intermediate between amorphous and graphitic carbon
[45], with irregularly stacked layers and interlayer (002) spacings
of approximately 0.344 nm. The (002) spacing of ideal graphite is
0.335 nm; increases in structural disorder cause increases in this
value. We hypothesized that the PET-derived carbons would
exhibit similar tendencies with these three different structures,
and attempted deconvolution of the (002) peaks in their XRD
patterns. However, we could not obtain good peak fitting results
using only these three components, probably due to the presence
of residual alkyl side chains. Therefore, we introduced another
component to the (002) peak deconvolution, which was the
g-component corresponding to the stacking of alkyl side chains.
Such a g-component is frequently used in the structural analysis of
asphaltene molecules that are common in heavy aromatic oils
[46–48]. Asphaltene molecules comprise PAHs and long alkyl side
chains; the presence of these alkyl chains yields one peak at
approximately 20
in XRD patterns, offering important structural
information related to the structure of alkyl chains. With the
g-component in the (002) peak deconvolution of the XRD patterns
of PET-derived carbons, we obtained peak fittings with good
coherences. The presence of g-components in PET-derived carbons
implies that they contain residual alkyl side chains as well as PAHs,
even after graphitization. The presence of these alkyl chains was
confirmed by FTIR spectral analysis of wPET-B0-G24 (Fig. S2,
Supplementary material). The spectra showed groups of peaks at
3000–2800 cm1, attributed to sp3 aliphatic C H bond stretching
involving both CH2  and CH3 [49]. In particular, the peak at
2924 cm1 assigned to  CH2  was more intense than the others,
indicating the presence of long alkyl chains in the structure of
wPET-B0-G24.
The deconvolution results are presented in Fig. 7. Firstly, the
deconvolution of the (002) peak for wPET-B0-G24 (Fig. 7a) shows
g-, A-, and T-components at 21.10
, 25.29
, and 25.90
, respectively.
The A- and g-components form a large portion of the wPET-B0-G24
(002) peak, while the T-component has a small contribution and no
G-component is observed. This implies that wPET-B0-G24 mainly
comprises amorphous carbon with long aliphatic chains and no
graphite. Upon the addition of boron, noticeable changes are found.
Fig. 7(b) shows the deconvolution result for wPET-B1-G24, wherein
the intensities of the A- and g-components are significantly
decreased compared to those of wPET-B0-G24, while the intensity
of T-component is increased and a G-component appears at 26.35
as
a very sharp peak. This tendency is confirmed with the samples
produced with higher boron contents. As the boron content
increases, the intensities of the T- and G-components are rapidly
increased, accompanying continuous decreases in the intensities of
the g-and A-components.
To observe these changes in more detail, the relative intensities
of each component are plotted as a function of boron content
(Fig. 8a), where the relative intensities are obtained by dividing
each intensity by the sum of all components. For the A- and
g-components, their intensities are steadily decreased as the
boron content increases. They show relative intensities of 63% and
22% for 0 wt% boron; these are finally decreased down to 5% and 2%
for 5 wt% boron, respectively. This accompanies the continuous
and rapid increase in the intensity of the G-component, which is
initially 0% for 0 wt% boron and finally reaches 65% for 5 wt% boron.
However, the T-component shows a different tendency; it shows a
steady increase in intensity to 49% for 3 wt% boron and then a
decrease to 29% for 5 wt% boron.
Fig. 8(b) shows the (002) interlayer spacing values of the four
components plotted against the boron content. As mentioned
above, the (002) spacing reflects the degree of graphitization in
carbon materials. Spacing values for the g-component are
somewhat larger than those of the other three components, with
a decrease from 4.207 to 4.047 Å for 0–5 wt% boron, respectively.
 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458 455

Fig. 7. Deconvolutions of (002) peaks on XRD patterns of (a) wPET-B0-G24, (b) wPET-B1-G24, (c) wPET-B2-G24, (d) wPET-B3-G24, (e) wPET-B4-G24, and (f) wPET-B5-G24.

Fig. 8. (a) Relative intensities of g (aliphatic), A (amorphous), T (turbostratic), and G (graphitic) structural components as a function of boron content. (b) (002) interlayer
spacing of the structural components as a function of boron content.

Similarly, the spacing values for the A- and T-components show
decreasing tendencies with values from 3.519 Å and 3.437 Å (0 wt%
boron) to 3.490 Å and 3.416 Å (5 wt% boron), respectively. These
indicate gradual improvements in the crystallinities of the g-, A-,
and T-components. Meanwhile, the spacing of the G-component
remains nearly constant for all compositions with the average
value of 3.373 Å. This indicates no increase in crystallinity, but only
an increase in the relative prevalence of the G-component. These
results yielded further insight into the mechanism of structural
change from a disordered structure to graphite.
It is likely that the boron-assisted development of graphite
structure in the current study was governed by two mechanisms.
The first is due to doped boron. Boron atoms readily diffuse into
disordered carbon structures through crystal defects and substi-
tute for carbon atoms at lattice positions [50,51]. This doped boron
removes crystal defects and relaxes lattice distortion by diffusion
456 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
into the carbon lattice [52], which possibly enables the rearrange-
ment of adjacent layers and the formation of new sp2 bonds,
consequently inducing gradual improvements in the crystallinity
of disordered carbon. The increased prevalence of the turbostratic
structure represented by the T-component in Fig. 8(a) was
attributed to the doped boron. Boron diffused into the amorphous
structure during the graphitization of the PET-derived carbons and
facilitated the elimination of defects involving sp3 carbons, thus
causing the conversion of amorphous structures with aliphatic
chains to turbostratic structures.
However, the formation of graphite structure probably occurred
differently. It would be very difficult to form graphite only through
the diffusion of doped boron. Graphitizable carbon or soft carbon
that can be graphitized at high temperatures comprises crystallites
that are small in size but well-oriented in a certain direction,
exhibiting a structure similar to that of graphite. Thus, when
graphitizable carbon is heat-treated at high temperatures above
2000
C, connections between the crystallites form with long-
range ordering through dehydrogenative condensation reactions,
thus yielding the graphite structure. In other words, even before
graphitization, soft carbon already possesses crystallites that are
well-aligned in a manner similar to that found in graphite, and
graphitization treatment only serves to connect them. Meanwhile,
with non-graphitizable carbon or hard carbon, the orientation is
not well-aligned but random; thus, regardless of the applied heat,
long-range ordering cannot be created and graphite cannot form.
For the graphitization of such hard carbon, both the alignment of
crystallites within the disordered structure and their connection
are required. However, boron doped in crystal lattice does not
cause the alignment of all crystallites. Instead, it only removes
partial crystal defects such as sp3 carbon atoms and lattice
vacancies. Therefore, another mechanism must occur in the
conversion of non-graphitizable carbon to graphite.
XPS results provide support for this second mechanism. The
high-resolution XPS spectra of the C 1s regions for the boron-
doped samples are shown in Fig. 9. A distinct peak shift of sp2
carbon towards lower binding energies is observed with increasing
boron content. For pristine carbon without boron, the peak located
at 284.3 eV is ascribed to sp2 carbon [53–55], but it is moved to
284.0 eV with 1% boron. As the boron content increases, the sp2
carbon peak is further shifted towards lower energies, finally
reaching 283.8 eV for 5 wt% boron. This peak shift is due to
substitutional doping of boron in the carbon lattice [55–57]. This
supports the first mechanism of the structural development by the
diffusion of doped boron. In addition to this peak, a new peak
Fig. 9. High-resolution C 1s XPS spectra of wPET-B0-G24, wPET-B1-G24, wPET-
B2-G24, wPET-B3-G24, wPET-B4-G24, and wPET-B5-G24.
appears near 282.0 eV and is increased in intensity as the boron
content is increased, which is ascribed to the formation of the B4C
phase. Although boron readily forms a solid solution with carbon
occupying substitutional sites, it also readily forms the B4C phase.
B4C is highly effective in promoting the graphitization of
disordered carbons [24,58]. When a disordered carbon is heat-
treated at graphitizable temperatures in the presence of B4C, the
carbon is dissolved and enter into the B4C phase and reprecipitated
as graphite instead of disordered carbon [24]. This is because
graphite is thermodynamically more stable than disordered
carbon. In this mechanism, the disordered structure collapses
entirely to allow the formation of a new and more stable graphite
structure, regardless of the graphitizability of the precursor
carbon. In the same way, in the present study, the appearance
of the B4C phase during the graphitization of the PET-derived
carbons was observed, which could have caused the transition
from disordered carbon to graphite.
Exfoliation of PET-derived graphite
In order to examine whether the PET-derived graphite could be
used as a graphene source, wPET-B5-G24 was exfoliated into
graphene sheets through a microwave-assisted liquid-phase
exfoliation method. Before exfoliation, it was expanded by
chemical treatment with sulfuric acid and fuming nitric acid
under concomitant microwave radiation. Fig. 10(a) and (b) show
SEM images of the pristine and expanded forms of wPET-B5-G24,
respectively. The acid treatment followed by microwave irradia-
tion clearly expands the wPET-B5-G24, which exhibits a pleated
morphology with spacing between separated sheets. The expand-
ed wPET-B5-G24 was then immersed in NMP to induce the
intercalation of solvent molecules in the separated sheets and
subsequently exfoliated by ultrasonication treatment, which, in
turn, yielded PET-derived graphene sheets. A TEM image of thus
prepared graphene sheets is shown in Fig. 10(c, d). It exhibits a flat
and transparent morphology; some are partly wrinkled and curled
due to the thinness and flexibility of the resulting graphene sheets.
In terms of lateral size, the average size was 410 nm with the
maximum of about 1.2 mm. The topographic profile measured by
AFM is shown in Fig. 10(e), which demonstrates the layer thickness
of approximately 4.8 nm sheets, corresponding to few-layered
graphene. All these microscope data clearly show that the wPET-
derived graphite is capable of expansion by acid and exfoliation
into few-layered graphene sheets, like common graphite. In
addition, we examined applicability of the resulting graphene
sheets by fabricating into a graphene paper and measuring its
sheet resistance. To fabricate a graphene paper, we applied the
vacuum filtration method that is a well-known method widely
used when fabricating a graphene paper [59]. Following this
method, graphene samples with bad quality normally produce
uneven papers showing many wrinkles or cracks on its surface.
However, in the case of wPET-derived graphene sheets sample, it
showed very good quality, producing a paper with very even
surface without being wrinkled or cracked; its photo image is
shown in Fig. S2 (Supplementary material). As to the measurement
of sheet resistance, it showed an average value of 41.1 V/& as
shown in Fig. 10(f). For the comparison, we also applied the very
same procedure to natural graphite-derived graphene sheets.
Notably, the natural graphite-derived one showed almost the same
value of 41.8 V/&, indicating that wPET-derived graphite sheets
sample has the same performance with that of natural graphite-
derived one in terms of electrical property. Thus, it was
demonstrated that the wPET-derived graphene has a high potential
in applications like electrical devices showing good processability
and good electrical property compatible to that of natural graphite-
derived one.
 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
Fig. 10. SEM images of (a) pristine and (b) expanded wPET-B5-G24. (c, d) TEM images and (e) AFM image of graphene sheets derived from wPET-B5-G24. (f) Sheet resistance of
wPET-B5-G24 graphene sheets and natural graphite-derived graphene sheets.
Conclusion
In the current study, we introduced a new route for the
upcycling of PET waste, wherein synthetic graphite was success-
fully prepared through a facile and scalable method. The synthetic
method included the pyrolysis and carbonization of PET under an
inert atmosphere and subsequent graphitization in the presence of
boron as a catalyst. This method overcame the non-graphitizability
of PET and yielded graphite with high crystallinity comparable to
that of natural graphite. Furthermore, the thus-prepared PET-
derived graphite was effectively expanded and exfoliated into
graphene sheets. The PET-derived graphite presented here possibly
has many potential applications for various purposes, such as
anode materials in secondary batteries and fillers for carbon
composites materials, and may serve as an alternative source for
graphene production. While the current study only investigated
the utilization of PET, we assume that the conversion of other
heavily used plastics such as PE, PP, and PS is also plausible with the
457
proper treatments. Related studies are currently in progress in our
group. We expect that our work present here can guide the
innovative upcycling of waste plastics.
Conflict of interest
The authors declare that they have no conflict of interest.
Acknowledgments
This work was supported by the Korea Evaluation institute of
Industrial Technology through Development of Core Industrial
Technology (10082582, Development of petroleum-based high
quality mesophase pitch and high yield mesophase pitch for
premium carbon materials) and Synthetic Graphite Development
Project (20006642, Development of high quality precursors for
premium grade synthetic graphite) funded by Ministry of Trade,
Industry and Energy (MOTIE, Korea).
458 S. Ko et al. / Journal of Industrial and Engineering Chemistry 83 (2020) 449–458
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.jiec.2019.12.018.
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