Applied Surface Science 476 (2019) 539–551

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Applied Surface Science

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

Full Length Article

Molten salt conversion of polyethylene terephthalate waste into graphene T

nanostructures with high surface area and ultra-high electrical conductivity
⁎
Ali Reza Kamali , Jigang Yang, Qiang Sun
Energy and Environmental Materials Research Centre (E2MC), School of Metallurgy, Northeastern University, Heping District, Shenyang 110819, China

A R T I C LE I N FO A B S T R A C T

Keywords: The pollution caused by the accumulation of plastic products is a serious emerging threat to the nature and to us.
PET Here, we first report on the structural and thermokinetic characterization of the plastic bottle material. It was
Molten salt found that the pyrolysis of polyethylene terephthalate in air leads to the formation of an amourphose carbon
Electrical conductivity with an exceptional thermal oxidation resistance, based on which an effective and scalable molten salt strategy
Thermal oxidation
for green conversion of plastic bottles into a highly conductive nanostructured carbon is proposed. In this
Graphitization
process, no complicated equipment or protective gas is required. The nanostructured carbon consisted of crys-
talline graphitic nanosheets with a thickness of less than 10 nm; and an ultra-high electrical conductivity of 1150
S m−1 at a low bulk density of 1 g cm−3, with an estimated production cost about US $6 kg−1. These char-
acteristics are attractive for various applications including conductive additives to electronic devices. In the light
of the fact that the plastic pollution crisis cannot be appropriately resolved without the involvement of short
term economic motivations, the proposed molten salt method may provide a sufficient economic driving force
towards the use of PET wastes as valuable raw materials, hence protecting the environment.

1. Introduction
Plastics, with an annual production of over 300 million tons, have
increasingly been employed for a large variety of structural applications
in the modern life, owing to their low production cost, durability, low
density, high chemical resistance and dimensional stability [1]. Poly-
ethylene terephthalate ((C10H8O4)n, PET) is the most commonly used
plastic, often employed as containers for bottled liquids and other food
products due to its affordable cost, excellent mechanical properties,
barrier properties and clarity. Its radiation resistant properties are also
accountable for applications as insulator and nuclear track detector in
nuclear plants and devices [2].
In fact, the constant increasing demand for bottled water has
boosted the annual consumption of plastic bottles to somewhere around
500 billion across the world. Whilst only around 9% of virgin plastics
are recycled in new water bottles, around 80% of the used bottles find
themselves in landfills or in the oceans. The latter is estimated to be
hundreds of millions of tones, adding up their microscopic plastic
content to be ingested by birds, fish and other organisms, and even-
tually by mankind who eat these creatures, creating a serious global
waste management and environmental crisis, perhaps with the same
level of consequences as are currently experienced by the climate
change. The current trend will result in a global used plastic accumu-
lation of about 12,000 million tons in 20 years time [3–8]. Considering
the fact that the natural degradation of PET takes a long time, probably
over the course of several hundreds of years [9], its recycling or con-
version has received an increasing worldwide attention. For instance,
converting PET wastes into short fibers used for the strain hardening of
cementitious composites [10], roadway pavement materials [11] and
oil sorbent agents [12] have shown promising results. Also, being hy-
drocarbons, plastics have high caloric values [13], and therefore have
widely been considered as a potential feedstock for producing H2 and
syngas [14–16].
On the other hand, owing to its high carbon content of about 45 at%
and also the lack of inorganic components, PET can be considered a
viable source of high purity solid carbon materials [17]. It is worth
mentioning that, particularly, carbon materials with high surface area
and conductivity are of great importance due to their increasing ap-
plications in various demanding fields such as energy storage systems
[18–20], conductive composites [21], solar energy harvesting [22],
conductive inks [23], and environmental applications [24]. For the
qualitative and quantitative evaluation of such carbon materials, a
combination of techniques including electron microscopy, conductivity
measurements as well as X-ray diffraction and Raman spectroscopy are

⁎
Corresponding author at: Energy and Environmental Materials Research Centre (E2MC), School of Metallurgy, Northeastern University, Heping District, Shenyang
110819, China.
E-mail address: ali@smm.neu.edu.cn (A.R. Kamali).

https://doi.org/10.1016/j.apsusc.2019.01.119
Received 27 November 2018; Accepted 15 January 2019
Available online 16 January 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
A.R. Kamali et al.
often used, within which the latter has been widely employed as a
powerful method, since it provides explicit insights into the layer
structure, crystallinity and defects. Particularly, the ratio of the in-
tensity of Raman bands ID/IG and I2D/IG in graphite-based materials
correspond to the density of defects and the quality of graphene flakes,
respectively [25,26], and therefore to the conductivity of the material
[27,28]. Generally speaking, a lower ID/IG value can be measured in
graphene-based materials with higher values of I2D/IG and electrical
conductivity. For instance, reduced graphene oxide (RGO) materials
with an ID/IG value of 1.55, 1.19 and 1.02 exhibited an I2D/IG value of
0.01, 0.07 and 0.14, and an electrical conductivity of 69, 133 and 166 S
m−1, respectively [29].
PET has been used as the carbon source to prepare a variety of
carbonaceous materials [30–39]. It is known that the high temperature
pyrolysis of PET under N2 and subsequent activation under steam, CO2,
and/or KOH [30–34], and also treatment of PET under a protective
atmosphere in various equipment such as arc discharge [35], chemical
vapor deposition [36,37] and autoclave [38,39] reactor leads to the
formation of amorphous carbon materials with an ID/IG value of greater
than unity, and a very weak Raman 2D band. Such carbon materials
inevitably suffer from low electrical conductivity, highly limiting their
possible applications, and hence the viability of PET as the carbon
source. It is an unfortunate, since there are an increasing amount of
waste plastic bottles which can be considered as low cost carbon
sources. It is not to mention that the transformation of hazardous plastic
wastes to valuable useful materials can be accompanied with a highly
positive environmental impact.
The so called molten salts, which are ionic liquids with a melting
point typically above 200 °C, have historically been used as the elec-
trolyte in the industrial scale electrolytic production of aluminum with
an annual production of more than 50 Mt [40], and other metals in-
cluding lithium [41] and magnesium [42]. The molten salt electrolytic
preparation of other metals/intermetallics such as Ti [43], W [44], U
[45], Ni [46] and TiAl3 [47] as well as nanodiamonds [48,49] and
graphitic carbon nanostructures [50–54] have been developed in the
recent 20 years. The latter was reviewed recently [55].
A part from the electrolytic applications, molten salts have the
prospect of being commercially viable as the heat transfer fluid and
energy storage media [56] in nuclear reactors [57] and solar power
towers [58], due to the advantages of simplicity and cost-effectively
[59]. The other emerging application of molten salts is based on their
capability to act as a diffusion-enhancing medium to promote chemical
reactions [60–62]. For instance, Li et al. [61] reported that the dis-
solution of SrO in molten KCl enhances the diffusion of ionic species
Sr2+ and O2− to the surface of TiO2 particles immersed in the melt,
leading to the facile synthesis of Sr3Ti2O7. We have reported that the
hydrolysis of molten LiCl leads to the formation of O2−. The reaction of
O2− and Li+ with Nb2O5 particles added to the melt promoted the
ultrafast formation of LiNbO3, much faster than solid state synthesis
methods [62]. We have also reported that the exposure to the molten
salt media can enhance the crystallinity of graphitic materials [63].
These observations imply that molten salts might be able to act as the
graphitization medium to improve the quality of plastic-derived car-
bons. Considering that NaCl is the cheapest salt and one of the most
abundant natural materials, here, molten NaCl-assisted pyrolysis of PET
is proposed for the green and cost-effective preparation of a carbon
nanomaterial possessing a combination of interesting properties such as
high surface area (522 m2 g−1), a low value of Raman ID/IG (0.47) and a
high value of Raman I2D/IG (0.52). These characteristics resulted in an
impressive electrical conductivity of 1150 S m−1 obtained under a
compressive pressure of about 6 MPa corresponding a bulk density of
about 1 g cm−3. The single step molten salt process employed here
could produce the highest quality plastic-derived carbon material
which has been reported so far, to the best of our knowledge.
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Applied Surface Science 476 (2019) 539–551
2. Experimental
2.1. Preparation of nanostructured carbon using PET precursor
A plastic water bottle was cut into small pieces (around 10 × 5 mm)
using a scissor. 9.83 g of plastic pieces was placed into an alumina
crucible with an approximate internal diameter and height of 50 mm
and 100 mm, respectively. Then, 50.80 g sodium chloride (NaCl,
Aladdin C111533, purity 99.5%) was added to the crucible. The cru-
cible was placed into a resistance furnace and heated in the air atmo-
sphere of the furnace at 10 °C min−1 to 1300 °C, and then immediately
cooled down with an approximately same heating rate to the room
temperature. The black solid mixture of solidified salt and carbon
product was placed in sufficient amount of distilled water, in which the
salt was dissolved. The carbon product (1.15 g) was then recovered
from the suspension by vacuum filtration using a filter paper, and
drying in air at 80 °C overnight.
2.2. Characterization methods
Electron microscopy evaluations were carried out using a Nova
Nano-SEM 450 equipped with energy dispersive x-ray analyzer (EDX)
and a 200 kV FEI Tecnai F20 field emission gun high resolution TEM
(HRTEM). X-ray diffraction (XRD) patterns were recorded on a Philips
1710 X-ray diffractometer (XRD) with Cu K-alpha radiation
(k = 1.54 Å) at a step size and a dwell time of 0.05 2θ and 5 s, re-
spectively. The XRD patterns were then analyzed using the X'Pert High
Score Plus program. Raman spectroscopy was conducted using a
Renishaw 1000 Ramanscope with a He–Ne ion laser of a wavelength of
633 nm (red, 1.96 eV). Thermal gravimetric analysis (TGA) and differ-
ential scanning calorimetry (DSC) were carried out simultaneously
using a thermal analyzer model SDT-Q600 equipped with alumina
crucibles at a heating rate of 40 °C min−1 under a constant air flow rate
of 100 ml min−1 through the sample chamber.
Brunauer–Emmett–Teller (BET) surface area analysis was performed by
recording nitrogen adsorption/desorption isotherms using a static vo-
lumetric technique with a Micromeritics TriStar 3000 V6.04 A analyser
at −196 °C. The electrical conductivity measurement was conducted by
compressing 0.5 g of the carbon material into an acrylic tube
(ID = 20.05 mm, H = 45.37 mm) using a brass piston (D = 20.05 mm,
H = 85.36 mm) on a copper holder. The carbon powder was compacted
under different pressure values up to about 6 MPa using a hydraulic
press. At different pressures, various values of electric current in the
range 0.16–3 A was conducted between the brass piston and the copper
holder, and the corresponding potentials were recorded using the four-
probe DC method at 20 °C. The electrical resistivity of compressed
carbon powder was calculated using the equation:
ρ = (S × V)/(I × H) (1)
where ρ is the resistivity (μΩ m), S is the surface area of the acrylic
tube’s hole (mm2), V is the potential difference (mV), I is the current (A)
and H is the height of the compressed powder (mm). The value of
electrical conductivity was calculated as the reciprocal of electrical
resistivity.
The electrochemical capacitance performance of the as-produced
carbon product was evaluated using a three-electrode system, in which
the working electrode was prepared by mixing the carbon materials
with 10% conductive carbon (SP45 with a BET surface area of 45 m2
g−1) and 10% binder (polytetrafluoroethylene, PTFE). The mixture was
loaded on a Ni plate of 1.2 cm in diameter, with a mass loading of
3.3 mg cm−2. The electrolyte was 6 M KOH. A platinum wire and a
saturated calomel electrode (Hg/HgCl in saturated KCl) were employed
as the counter and the reference electrode, respectively. Cyclic vol-
tammetry (CV) and galvanostatic charge–discharge measurements were
performed to evaluate the electrochemical performance of the carbon
product.
A.R. Kamali et al.
Fig. 1. XRD Pattern of the PET plastic bottle heated overnight at 260 °C. The
diffraction peaks are indexed to crystalline PET (anorthic) structure.
3. Results and discussion
3.1. Structural characterization of the PET precursor
The XRD diffraction pattern recorded on small pieces of a water
bottle is shown in Fig. S1, representing a low crystalline PET structure.
The low crystalline PET material was heated in a resistance furnace at
260 °C, above the melting point of PET, overnight. After cooling down
to the room temperature, the heat treated material obtained, in form of
white color large irregular shaped crystalline particles, was subjected to
XRD analysis (Fig. 1). The diffraction peaks observed in the pattern can
be indexed according to the crystalline PET anorthic structure. The
most intense (1 0 0) reflection peak is observed at 2θ = 26.00°. The
SEM morphology of the crystalline PET is shown as the inset in Fig. 1, in
which a large size particle with dimensions in excess of 0.5 mm, sharp
edges and smooth surfaces can be observed.
The EDX analysis of the crystalline PET (Fig. S2) demonstrated a
C:O value of 1.8, which is smaller than the theoretical value of atomic
C:O ratio of the repeat unit for PET (2.5). Gonzalez et al. [64] measured
the C:O ratio of the virgin and plasma-treated PET to be 3 and 1.7,
respectively using XPS analysis. The higher value of C:O measured on
the virgin PET was attributed to the presence of surface contaminations.
On the other hand, the lower value of C:O in plasma treated PET was
explained by the presence of more CeO and C]O bonds on the surface
of PET induced by the plasma treatment. In our case, the lower value of
C:O ratio observed based on the EDX analysis can be attributed to the
surface electron irradiation of PET occurred during the microscopy.
These observations confirm that the crystallization of PET occurred
during its solidification from melt, and that the plastic bottle was made
of pure PET. Such material with high carbon content and no inorganic
component is an attracting source for the preparation of solid carbon
materials.
3.2. Themokinetic characterization of the PET precursor
The TGA and DSC thermograms recorded on a small number of PET
pieces in the temperature range from 25 to 900 °C under a flow of air
can be seen in Fig. 2. Three endothermic events can be distinguished in
the DSC curve observed. The first endothermic peak at 254.1 °C is at-
tributed to the melting of PET. The second endothermic peak observed
at 466.8 °C is due to the decomposition of PET, which is accompanied
by a mass reduction of 84.17%, according to the TGA curve. The last
endothermic peak at 791.2 °C might be assigned to the minor graphi-
tization of the residual carbon material.
In order to investigate this endothermic peak, small pieces of a PET
plastic was heated in a resistance furnace to 650 °C and 850 °C, and the
black carbon materials obtained were subjected to XRD and SEM ana-
lyses. Fig. 3a exhibits the XRD patterns of the samples. The XRD pattern
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Applied Surface Science 476 (2019) 539–551
Fig.2. DSC and TGA thermograms of the PET sample, heated at the heating rate
of 40 °C min−1 under an air flow of 100 ml min−1.
of the sample heated to 620 °C shows two broad reflections centered at
2θ = 21.2 and 43.4°. The first peak, corresponding to an interplanar
spacing d(0 0 2) of 4.18 Å, can be assigned to the (0 0 2) crystalline planes
in short-range ordered hexagonal arrays of turbostratic carbon [65–67],
which is also called disordered graphite [65] or amorphous carbon
[68], produced by the pyrolysis of PET at 620 °C. The second broad
peak extending from 2θ = 40-45° with a maxima at 43.4° corresponds
to overlapping (1 0 0) and (1 0 1) reflections.
It should be mentioned that in the graphite hexagonal structure
(JCPDS card No. 13-0148), the (0 0 2) reflection appears at the
2θ = 26.6°, indicating an interplanar spacing of 3.35 Å; and the re-
flection peaks (1 0 0) and (1 0 1) appear at the 2θ values of around 42.4
and 44.4°, respectively. The large deviation of d(0 0 2) towards a higher
value in the amorphous carbon material produced in comparison to that
of graphite indicates the poorly crystalline nature of the material
[66–68].
Li et al. [65] identified the turbostratic carbon as a variant of hex-
agonal graphite, in which the (0 0 2) carbon layers may randomly
translate to each other and rotate about the normal of the layers. In the
XRD pattern of PET pyrolyzed at 850 °C (Fig. 3a), the (0 0 2) and the
(1 0 0)/(1 0 1) overlapping diffraction peaks exhibit maxima at the 2θ
value of 25.2° (corresponding to an interlayer spacing value of 3.54 Å)
and 43.2°. The increase in the intensity of the (0 0 2) diffraction peak
and also its shift towards a larger value, in comparison to the sample
prepared at 620 °C, is indicative of the increase in the crystalline order
of the material, hence the occurrence of the graphitization onset.
Ramakrishnan et al. [67] observed the position of the (0 0 2) XRD
reflection in a turbostratic nanocarbon phase at 2θ ∼ 23°. In another
work, Ruz et al. [68] determined the position of (0 0 2) and (1 0 1)
diffraction peaks in the XRD pattern of a turbostratic carbon, produced
using sucrose and zeolite template at 700 °C, to be at 2θ values of
around 20°and 44°, respectively. In their work, by increasing the pro-
cessing temperature to 900 °C, the diffraction peaks became more in-
tense and shifted towards higher angles, and it was attributed to the
increased translational ordering in the carbon sample produced at
higher temperatures [66].
The development of graphitic structures upon pyrolysis of carbo-
naceous materials has been reported. For example, porous graphitic
carbons were successfully obtained by the pyrolysis of wood im-
pregnated with FeCl3 at temperatures as high as 1000–1600 °C. The
corresponding DSC analysis exhibited an endothermic peak at 718 °C,
which was related to the onset of the graphitization process, confirmed
by the presence of the graphite (0 0 2) peak in the XRD pattern of the
sample pyrolized at 850 °C [69]. In this research, the graphitization
occurred was related to the catalytic effect of Fe leading to the for-
mation of FeXCY droplets from which graphitic structures could pre-
cipitate. Nevertheless, a reasonable graphitization was achieved at a
A.R. Kamali et al.
Fig. 3. (a) XRD and (b–d) SEM analysis of the amorphous carbon materials obtained by heating of PET in air to different temperatures of (b) 620 °C and (c and d)
850 °C.
temperature not less than 1600 °C.
Based on these observations, the endothermic peak appeared in the
DSC curve of Fig. 2 at 791.2 °C can be attributed to the onset of the
graphitization of the turbostratic carbon. It can be seen from the TGA
micrograph of Fig. 2 that about 10% of the PET material, equal to about
40% of the total solid carbon still remained at 900 °C, where the ana-
lysis was terminated. According to the results obtained, the pyrolysis of
PET leads to the formation of an amorphous carbon with a high re-
sistance against thermal oxidation in air.
It is known that the intensive oxidation of carbon materials in air
begins at temperatures over 500 °C, depending on the properties of the
carbon material, including its degree of graphitization, particle size and
porosity [70]. Thermal oxidation of highly oriented pyrolytic graphite
was reported by Hahn [71] to occur at 550–950 °C. At temperatures
lower than 875 °C, the oxidation process was found to be dominated by
the formation of pits at defect sites. At higher temperature, however,
the oxidation takes place on both defects and basal planes. It is also
kwon that the rate of oxidation of amorphous carbons is higher than
that of graphitic carbon materials [72]. The inorganic impurities exist
in carbon materials can also act as the oxidation catalyst, decreasing the
oxidation temperature of the material [73–75].
Further information can be obtained from the SEM morphology of
the samples shown in Fig. 3b–d. The SEM micrograph of the carbon
material obtained at 620 °C (Fig. 3b) can be characterized by the pre-
sence of large irregular shaped particles with sharp edges and a size of
up to several hundred micrometers. As seen, despite heating in air,
there are no sign of oxidation on the material, indicating its high oxi-
dation resistance. The EDX analysis of the sample (shown in Fig. S3)
revealed a C:O ratio of 5.2, which is subsequently higher than that of
observed on crystallized PET (1.8, Fig. S2). Nevertheless, the presence
of a relatively high amount of oxygen in the carbon produced at 620 °C
can be a barrier towards further graphitization of the material.
The SEM micrographs of the carbon material obtained at 850 °C
(Fig. 3c and d) show approximately the same features as that observed
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Applied Surface Science 476 (2019) 539–551
on the material obtained at 620 °C, characterized by irregular-shaped
large particles. However, the high magnification images of Fig. 3d show
the presence of small surface pitting holes, which is an indication of the
initial stage of oxidation. A quantity of PET pieces was heated in a
resistance furnace in air to 1100 °C, and no material could be found in
the crucible after cooling down to room temperature, confirming the
occurrence of an intensive oxidation at higher temperatures. Never-
theless, the TGA curve of Fig. 2 and SEM micrographs of Fig. 3 de-
monstrate the very high oxidation resistance of the amorphous carbon
driven from plastics up to temperatures as high as 900 °C, which can be
assigned to its high purity, large particle sizes, low porosity and low
density of surface defects.
This characteristic was employed to develop a green, efficient and
low cost molten NaCl strategy for the conversion of plastic bottles into a
graphitic nanostructured carbon, as explained in the next section. In
this process, no complicated equipment and protective gas is required.
At temperatures below 800 °C, NaCl is in its solid form, but the amor-
phous carbon derived from the plastic resists against oxidation based on
its high oxidation resistance. At higher temperatures, NaCl melts and
protects the carbon material from oxidation. Apart from its protective
role, molten NaCl also greatly promotes the graphitization/exfoliation
of the carbon phase to form a graphene-based nanostructure.
3.3. Molten salt heat treatment of PET
Here we show that the heating of PET with NaCl can lead to the
preparation of highly conductive carbon nanostructures. Fig. 4 shows
the XRD and Raman spectra of the PET-NaCl mixture heated to 1100 °C
and 1300 °C (above the melting point of NaCl, 801 °C) followed by
cooling and washing the NaCl off the product. The XRD pattern of the
black carbon product obtained at 1100 °C reveals the presence of dif-
fraction peaks corresponding to the hexagonal carbon and cubic NaCl.
The latter is the residual of NaCl, which has been remained with the
carbon product even after washing process. On the other hand, the
A.R. Kamali et al.
Fig. 4. (Upper panel) XRD and (down panel) Raman spectrum of the carbon
product obtained by heating of PET with NaCl to 1100 °C and 1300 °C, followed
by cooling and washing process.
(0 0 2) reflection of hexagonal carbon structure appeared at
2θ = 25.13°, representing an interplanar spacing of 3.54 Å. The broad
peak with the maxima at 2θ = 43.18° corresponds to overlapping
(1 0 0) and (1 0 1) reflections of hexagonal carbon.
The Raman spectrum of the carbon product produced by heating the
PET-NaCl mixture to 1100 °C, shown in the lower panel of Fig. 4, pro-
vides information about the graphitic structure of the material. The so-
called defect-induced D band and the G band which correspond to the
stretching vibrations of the basal graphene layers in carbon materials
[25,26] appeared at the Raman shift values of 1372 and 1599 cm−1,
respectively. Moreover, a low intensity 2D band, which is the overtone
of the D band, can be observed at 2703 cm−1. The intensity ratio ID/IG,
that corresponds to the level of defects or inversely to the graphitization
degree of the carbon material [25,26], was measured to be 0.94. Fur-
thermore, the intensity ratio I2D/IG which represents the quality of the
graphene sheets exist in the product is 0.23. Overall, The XRD and
Raman analysis demonstrate the presence of nanocrystalline graphi-
tized domains in the sample.
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Applied Surface Science 476 (2019) 539–551
The SEM morphology of the carbon product produced at 1100 °C is
presented in Fig. 5. Fig. 5a shows the edge of an irregular particle with
mostly smooth surfaces. This morphology seems overall similar to that
observed in the sample prepared by the air heating of PET to 850 °C,
with this difference that a number of graphitization zones are present
on the smooth surface of the carbon material produced in molten NaCl,
particularly on the edges. Fig. 5b clearly shows the presence of graphite
flakes appeared on the edges of the carbon particle. Fig. 5c exhibits a
lower magnification image demonstrating that these graphitization
zones have occasionally developed on the surface of irregular shaped
carbon particles. Some areas were highly crystallized into graphene
nanosheets such as shown in the SEM micrograph of Fig. 5d. This
finding is interesting since it demonstrated that graphitized carbon
nanostructures can be formed by simple heating of PET in NaCl to a
relatively low temperature of 1100 °C.
In order to investigate the effect of temperature, the mixture of PET-
NaCl was heated to 1300 °C by the same heating rate of 10 °C min−1,
and then cooled down to the room temperature. Fig. 6, upper panel-left
side, shows the alumina crucible and the mixture of solidified salt and
carbon product. In order to evaluate the distribution of the carbon
phase in the solidified NaCl, the alumina crucible was broken, by which
the mixture of salt and carbon was easily retrieved from the crucible
(Fig. 6, upper panel-right side). It can be seen that the carbon material
is entirely distributed into the solidified NaCl. This observation de-
monstrates the high dispersability of the carbon product in molten
NaCl. The solid mixture was added to 500 ml distilled water. Upon the
dissolution of NaCl, the carbon material floated on the surface of the
water showing its low density. The suspension obtained was stirred for
20 min and then filtered. The carbon material remained on the filter
paper was then dried overnight. The XRD analysis of the sample ob-
tained (Fig. 4, upper panel), shows the presence of the (0 0 2) peak of
hexagonal graphite at 2θ = 25.9°, representing an interlayer spacing of
3.44 Å. The broad peak with a maxima at 2θ = 42.5°, corresponds to
overlapping (1 0 0) and (1 0 1) reflections. As can be seen, the diffrac-
tion peaks related to NaCl have nearly vanished from the pattern. The
effective salt removal observed can be due to the exfoliated nature of
the sample. The Raman spectrum of the sample (shown in Fig. 4, down
panel) provides interesting information about the quality of the carbon
material produced. The spectrum exhibits a relatively small defect-in-
duced D band at 1364 cm−1, and a sharp and distinguished graphite G
band at 1590 cm−1. The value of ID/IG ratio can be measured from the
spectrum to be low at 0.47. This observation reveals the presence of
crystalline carbon domains with a low defect density. In addition to
this, a symmetric 2D band can also be observed in the spectrum at
2723 cm−1, and the value of I2D/IG ratio was found to be 0.52. These
observations confirm that the carbon product consisted of carbon en-
tities of a few layer graphene [25,26].
3.4. Morphological characterization of the nanostructured carbon product
Fig. 6, down panel, shows the SEM micrographs of the nanos-
tructured carbon material obtained, from which the presence of gra-
phitic layers can clearly be observed. These micrographs, demonstrate
the surface exfoliation of the graphitic structure of the carbon material,
leading to the formation of graphene-like nanosheets. The EDX analysis
recorded on the carbon material (Fig. S4) showed a high C:O atomic
ratio of 28.4.
TEM microscopy (Fig. 7) provided further evidence for the graphi-
tized carbon nanostructure produced. The upper left panel of Fig. 7
exhibits a low magnification image showing the hierarchical mor-
phology of the material consisting of a mixture of nanosheets and
fragmented nanosheets. The upper right panel shows a high magnifi-
cation image taken on the area with the latter morphology, showing the
crystalline fringes of the nanosheets. The fast Fourier transform (FFT)
analysis recorded on a number of sheet fragments indicated in the
figure can be seen as the inset in Fig. 7, upper-right panel. The halo ring
A.R. Kamali et al.
Fig. 5. SEM micrographs of the carbon product obtained by heating of PET with NaCl to 1100 °C.
in the FFT pattern indicates an interplanar spacing of 3.5 Å, corre-
sponding to the (0 0 2) crystalline planes of hexagonal carbon. The
micrograph confirms the nanocrystalline nature of the carbon material
produced in molten NaCl. The down panels in Fig. 7 show high re-
solution TEM images of the carbon sheets exist in the sample with a
high crystalline nanostructure. The FFT pattern recorded on a carbon
sheet, indicated in the down-left panel by black rectangle, exhibits spots
corresponding to the graphitic nanostructure. The down-right panel
shows several graphitic nanosheets, two of which with a thickness of
5.6 nm and 8.5 nm have been identified in the micrograph. The careful
examination of the carbon product revealed that graphitic sheets con-
sisted of 4–20 layers with a thickness of less than 10 nm.
The surface properties of the nanostructured carbon material were
studied through the nitrogen adsorption–desorption technique, and the
recorded isotherm is presented in Fig. S5. According to the IUPAC
classification [76], this curve displays a type-II isotherm and a type-H4
hysteresis loop, suggesting the presence of non-porous or macroporous
surface with narrow, slit like pores and a total pore volume of
0.103 cm3 g−1. The BET surface area of the carbon material was found
to be 522 m2 g−1. The results obtained confirm that the pyrolysis of PET
in molten NaCl leads to the preparation of a nanostructured carbon
consisting of crystalline graphitic nanosheets and sheet fragments with
a thickness of less than 10 nm, and a high surface area.
3.5. Electrical and electrochemical characterization of the nanostructured
carbon product
It should be mentioned that, together with surface area and crys-
tallinity, the electrical conductivity is one of the most important para-
meters which determine the performance of carbon materials in prac-
tical applications such as supercapacitors [77], electromagnetic
shielding [78], catalysts [79], and metal-ion batteries [80]. However, in
carbon materials, usually, the electrical conductivity decreases with the
increase in surface area [77]. The electrical conductivity of the carbon
material produced in this study was evaluated at various compression
pressures using the four probe method. Fig. 8a shows the current-vol-
tage response of the carbon material at different pressures, in the range
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0.01–6.13 MPa, applied to 0.5 g sample, showing a perfect Ohmic re-
sponse. The values of density, calculated by considering the column
height of the compressed powder, and those of electrical conductivity of
the sample were plotted as the function of the pressure applied, and the
result is exhibited in Fig. 8b. As it can be seen, the density of the carbon
powder under a light pressure of 0.10 MPa is 0.10 g cm−3 exhibiting an
electrical conductivity of 12.53 S m−1. By increasing the pressure to
4.14 MPa, the density and conductivity increase considerably to
0.89 g cm−3 and 1071.24 S m−1, respectively. As can be depicted from
the plot, the density increased to 1.04 g cm−3 by a further increase of
pressure to 5.47 MPa, but the corresponding conductivity slightly de-
creased to 1058.43 S m−1. As can be observed from Fig. 8a, the re-
sistance of the sample, indicated by the slope of the I-V curve decreased
from 8.76 mΩ to 6.79 mΩ by the same increase in pressure. The de-
crease in the value of electrical conductivity by the increase of pressure
observed can be explained by the contribution of the reduced column
height of the compressed powder to the value of electrical conductivity
(Eq. (1)). It can be seen that the values of density and conductivity
increased to 1.06 g cm−3 and 1150.15 S m−1 by the increase of the
pressure to 6.13 MPa. The conductivity obtained is rather impressive as
discussed later here.
The electrochemical behavior of the carbon product was evaluated
using a three-electrode system with 6 M KOH as the electrolyte. The CV
profiles, recorded at various scan rates of 5–200 mV s−1, shown in
Fig. 8c, exhibit nearly rectangular shapes, indicating that the carbon
product stores charge mainly via an electrochemical double layer ca-
pacitive mechanism, with a high rate performance and no pseudoca-
pacitive effect. It further confirms the high carbon purity and electrical
conductivity of the sample. Fig. 8d shows the potential-time profiles
measured at different current densities in the range 0.2–20 A g−1. As
can be seen, the discharge time is roughly equal to the charging time,
and the curves are almost isosceles triangle, indicating a high reversi-
bility [81–84].
A.R. Kamali et al.
Fig. 6. Photographs and scanning electron micrographs of products: (Upper panel) the mixture of carbon-solidified NaCl obtained by heating of PET-NaCl mixture to
1300 °C. (Down panel) SEM micrographs of the nanostructured carbon material obtained. The salt content was washed off after cooling down to room temperature.
3.6. Technical and economic evaluation of the process
Fig. 9 shows the schematic illustration of the simple and green
molten salt process proposed here for the preparation of graphitic na-
nostructured carbon from plastic bottles and salt. In this strategy, the
mixture of plastic and NaCl is heated in air to 1300 °C. During the heat
treatment, at about 260 °C, the plastic material melts, and then the melt
becomes pyrolized at about 470 °C to form amorphous carbon particles
with smooth surfaces and sharp edges. This carbon material possesses a
high resistance against oxidation in air and remains stable until the
melting point of NaCl (about 800 °C) is reached. Molten NaCl formed
protects the carbon material from oxidation at higher heating tem-
peratures, and also causes the graphitization of the amorphous carbon.
As shown in Fig. 9, the sign of graphitization/exfoliation appears at
about 1100 °C, preferentially at the edge of amorphous carbon particles.
At 1300 °C, a nanostructured carbon is formed. The carbon product has
interesting characteristics, including high crystallinity, electrical con-
ductivity, purity and surface area. After cooling down to the room
temperature, the solidified salt can be easily washed away from the
carbon product and recycled, enhancing the economic and environ-
mental sustainability of the process.
The capability of molten LiCl in protecting carbon materials against
oxidation was discussed in our earlier study [84]. It was further re-
ported that carbon nanotubes [85] and graphene nanosheets [86,87]
formed by the electrochemical exfoliation of graphite in molten LiCl
and NaCl have a higher degree of crystallinity than the mother graphite,
and it was attributed to the healing of structural defects, the
545
Applied Surface Science 476 (2019) 539–551
improvement of the graphite lattice stacking order and the removal of
impurities from the graphite exposed to the molten salt [84,88]. The
results obtained here demonstrate that molten NaCl can cause graphi-
tization in the amorphous carbon obtained by the pyrolysis of plastic
bottles. This observation can be attributed to the combination of effects
mentioned above.
It is known that the presence of oxygen atoms in amorphous carbons
can be a barrier towards their graphitization, and that the removal
oxygen requires a prolonged heat treatment at very high temperatures
[89]. The comparison of the C:O ratio in the amorphous carbon ob-
tained at 620 °C (5.2) with that of the nanostructured carbon produced
at 1300 °C (28.4) reveals a substantial reduction in the oxygen content
of the carbon material upon the molten salt treatment. This can be at-
tributed to the dissolution of oxygen from the carbon into the molten
salt, which facilitate the graphitization process at such low tempera-
ture.
It should also be mentioned that amorphous carbons obtained by
the pyrolysis of polymeric materials are commonly classified as “non-
graphitizable” carbons. Such carbons are difficult to be converted into
graphite even at temperatures around 3000 °C, due to the existence of a
strong network of oxygen containing cross-links between randomly
oriented crystallites [90,91]. The capability of molten salts to remove
impurities from carbon [84] can be employed to reduce the oxygen
content of non-graphitizable carbons, facilitating their graphitization.
Kim et al. [92] heat treated a non-graphitizable carbon derived from
phenol resin in molten NaOH at 900 °C for 1 h under N2. Thereafter, the
NaOH was washed away at room temperature using HCl, and the
A.R. Kamali et al.
Fig. 7. TEM micrographs of the nanostructured carbon product obtained by heating of PET and NaCl to 1300 °C. The insets in the upper-right and down-left panels
are the FFT analysis recorded on the area indicated by black rectangles in the corresponding TEM micrographs.
graphitization process was conducted at 2800 °C. The removal of gases
and decreasing alkyl groups content of the carbon were explained to be
the possible function of molten NaOH. However, the toxicity of NaOH
and also the acid leaching required may limit the application of this
approach. Furthermore, a high temperature was still required to
achieve the graphitization. In order to reduce the graphitization tem-
perature, Jin et al. [89,93] die pressed an amorphous carbon black
powder into a cylindrical pellet, followed by a consolidation step using
porous nickel foams or graphite containers. The authors reported that
applying a negative potential of −1.7 V on the electrode prepared
immersed in molten CaCl2 at 820 °C would lead to the graphitization of
the amorphous carbon black. This observation was explained based on
the cathodic removal of oxygen from the cathode material, which is
known as the FFC-Cambridge process [46]. Here we have shown that
the graphitization of amorphous carbons may occur by a simple molten
salt heat treatment, without the involvement of high temperature
electrochemical equipment.
It should be mentioned that the improvement of electrical con-
ductivity upon a heat treatment process can be an indication of the
occurrence of the graphitization. This causes due to the development of
the hexagonal stacking structures, facilitating the electron transfer
[94]. The possible dissolution of oxygen from the amorphous carbon in
the molten NaCl, therefore, may play an important role in promoting
the graphitization, owing to the high diffusion rate of oxygen ions in
molten salts [58,59]. The graphitized carbon has then the chance to
become exfoliated in contact with the molten salt to form a
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Applied Surface Science 476 (2019) 539–551
nanostructured carbon, according to our previous observations [84]. As
suggested by Figs. 5 and 9, the graphitization initiates preferentially at
the edges of amorphous carbon particles. This can be attributed to the
higher surface energy and also a greater deal of exposure to the molten
salt in these areas.
Table 1 compares the properties of the graphitic carbon nanos-
tructure produced here with some carbon nanostructures produced by
the state of art methods in the literature. Nanostructured carbon ma-
terials can be produced by variety of methods. One may divide these
methods into two groups, depending whether graphite or non-graphitic
carbon-containing materials are used as the carbon source. Methods
that employ graphite include chemical oxidation and reduction
[95–101,104], liquid phase [102,103] and molten salt [86,87] ex-
foliation of graphite. Synthetic and natural graphite has extensively
been used as the carbon source for the preparation of graphene based
materials mainly by chemical oxidation-exfoliation and subsequent
reduction. Graphite can be chemically oxidized by the use of chemical
agents to produce graphite oxide which can then be exfoliated to pro-
duce graphene oxide (GO). Although it is the most used method of
producing atomically thin sheets of carbon, GO is an insulating mate-
rial, since it is covalently decorated with oxygen-containing functional
groups due to the extensive use of chemicals such as strong acids [105].
The products of this approach can be activated [106] to provide a high
surface area, as high as 3100 m2 g−1 for instance, but the resultant
electrical conductivity of products is rather poor, typically less than 250
S m−1 to values near zero [101,106]. GO can be reduced with reducing
A.R. Kamali et al. Applied Surface Science 476 (2019) 539–551

Fig. 8. Electrical and electrochemical properties of the nanostructured carbon produced by heating of PET with NaCl to 1300 °C. (a) The V-I relationship and (b) the
electrical conductivity and density of the carbon material under various compressive loads applied. (c) The CV profiles, recorded at various scan rates and (d) the
potential-time profiles measured at different current densities for the electrode fabricated using the carbon product.

agents such as hydrazine in order to reduce its oxygen content to graphene sheets caused during the reduction process. Conductivity
achieve reduced graphene oxide (RGO) with an enhanced electrical values obtained can be about 33.7 [95], 700 [96] and 1000 [100] S
conductivity [104]. The electrical conductivity of RGO, however, m−1. More extensive treatments [98] or adding conductive materials
cannot be enhanced considerably duo the structural damage of such as Ag [100] may lead to the further enhancement of electrical

Fig. 9. Schematic representation of the molten salt strategy employed for green conversion of plastic bottles into a highly conductive nanostructured carbon. During
heating in air of the plastic-NaCl mixture, pyrolysis of the plastic occurs leaving an amorphous carbon mixed with solid NaCl behind which is stable until 800 °C, at
which NaCl melts. The molten NaCl then protects the carbon material from oxidation in air, and also promotes its graphitization. At 1100 °C, signs of graphitization/
exfoliation can be observed locally, particularly at the edge of carbon particles. At 1300 °C, a highly conductive and well graphitized nanostructured carbon
consisting of graphene nanosheets is formed. NaCl can be easily recycled and reused in the process.

547
 A.R. Kamali et al.

Table 1
Comparison of the properties of nanostructured carbon produced by the salt treatment of PET with those of common carbon nanostructures including RGO, GO and few layer graphene (FLG) produced by the state of art
methods in the literature, including the values of specific surface area (SA, m2 g−1) and electrical conductivity (EC, S m−1).
Product Carbon source Chemicals Method of production SA EC Ref.

RGO Graphite Three or more chemicals including NaCl, Na2O2, HNO3, Chemical oxidation and reduction 2561 33.7 [95]
HCl, H6N2O, H2SO4, KMnO4, H2O2, (CH3)2NC(O)H – 700–1150 [96]
H2SO4,K2S2O8, P2O5, H2O2 [95–101,104] 40–600 1000 [97]
– 3000–10000 [98]

GO H2SO4, KMnO4 ,NaNO3, HCl Chemical oxidation – 0.0001–250 [101]

FLG Na4P2O7·10H2O, C3H8O Liquid-phase exfoliation – 7.095 × 104 [102]

Graphene nanosheets NaCl, H2 Molten salt exfoliation of graphite 232 2.1 × 105 [87]

Porous carbon GO KOH Microwave irradiation + high temperature activation < 100–3100 500 [106]

Porous graphitic carbon Polymeric Molecular H₈N₂O₈S₂, KOH, N2 Solution treatment + carbonization at 400 ∼ 900 °C under N2, 4073 300 [98]

548
Framework (C₆H₇N, KOH activation at 800 °C
C₆H18O24P6)

Carbon xerogel Resorcinol (C6H6O2) H2CO, Na2CO3, GO scaffold Polycondensation + carbonization at 800 °C + steam activation 600–1600 40–120 [111]
at 800 °C

Carbon xerogel NaOH, GO dopant Polycondensation + gelation + ageing 1600–1700 50–300 [112]

Microporous carbon Pomelo peel KOH, N2 Grinding + pre-carbonization at 700 °C for 1 h under N2 + KOH 1062–2167 10 [113]
Activation

Activated carbon Coconut shells CO2, N2, HCl Drying, crushing, heating under N2 at 900 °C for 1 h, CO2 1300 250 [101]
activation at 900 °C for 5 h, acid washing

Commercial conductive – – – 100–1635 200–1230 [111]

carbon black

Graphene based carbon Plastic bottle, (C10H8O4)n NaCl (reusable) Heat treatment to 1300 °C 522 1150 S m−1 Current
(1.06 g cm−3) study
Applied Surface Science 476 (2019) 539–551
A.R. Kamali et al.
conductivity to values in the range 3000–10000 S m−1.
The exfoliation of graphite by non-oxidizing methods such as liquid-
phase [102,103] or cathodic molten salt exfoliation [86,87] can lead to
relatively higher values of conductivity. Nevertheless, the high con-
ductivity achieved using a graphite precursor is not a surprise since the
graphite raw material used has already been a high value conductive
material, with a conductivity value of often greater than that of the
resultant graphene. For example, the conductivity of synthetic and
natural graphite precursors was measured to be 1.2 × 104 and
2.3 × 104 S m−1 with a surface area of 6 and 7.9 m2 g−1, respectively
[96].
Non-graphitic carbonaceous materials such as polymeric molecular
frameworks [107], resorcinol [108,109] and pomelo peel [110] have
also been used as the carbon source in the fabrication of graphene by
multi-step processes. The electrical conductivity of the carbon products
achieved using non-graphitic precursors, however, is in the range
10–300 S m−1. To the best of our knowledge, the method presented in
this paper, for the first time, offers a very fast and efficient method for
the preparation of carbon nanostructures with a conductivity of greater
than 1100 S m−1 using non-graphitic raw materials. The upscaling of
the process is easy and doesn’t require expensive equipment. Moreover,
the process is green since practically it only uses waste bottles and
electricity to produce the graphene-based materials. The carbon pro-
duct obtained can be positioned within the high quality commercial
conductive carbon materials [111], providing economical motivation
for converting the waste plastic bottles into carbon nanostructures with
a wide use in energy storage devices.
It should also be noticed that PET bottles is made from naphtha
and/or ethane which is a derivative of oil and natural-gas, respectively.
The conversion of the waste plastic into useful carbon applicable in
energy storage devices can provide a perspective in sustainable utili-
zation of fossil fuels. It can be estimated that about 8.5 kg waste plastic
and 30 kWh energy is required for the preparation of 1 kg carbon na-
nostructures in our lab-scale equipment. If we consider the current
average world price of electricity to be about 20 US cents per kWh, it
can be possible to estimate the cost of producing highly conductive
carbon nanostructure from waste bottles to be about US $6 kg−1. The
utilization of more efficient purpose-built industrial heating systems for
continuous-type production can reduce the cost. These characteristics
can make the carbon product attractive for many applications including
as conductive carbon additive in energy storage devices, electrode
materials in supercapacitors and lithium–sulfur cells, hydrogen storage
adsorbents, photocatalysis support material, sorbent, etc., and would,
therefore, provide economic motivations to convert waste water bottles
to conductive carbon for various applications. One possible application
is the electrode material for commercial supercapacitors, as discussed
earlier in this paper. Supercapacitor manufacturers mostly use the ac-
tivated carbon produced from coconut shell due to its moderate con-
ductivity, low cost, and relative availability. However, the conductivity
of carbon materials is known to be a main barrier toward the enhanced
performance of supercapacitors [112,113]. As it can be seen from
Table. 1, despite the multi-step and time consuming production pro-
cedure required, the activated carbon produced from coconut shells
have a conductivity of about 250 S m−1. In contrast, the nanostructured
carbon produced from waste plastic in molten NaCl exhibits a con-
ductivity of about four times greater than that of coconut shell utilizing
a much simpler one step procedure. Apart from conductivity, the price
is another important factor. The cost associated with the commercial
production of active carbon using coconut shells, which is counted as
about half the total materials cost involved in the manufacturing of
supercapacitors, about $15 per kilogram, out-price other possible
competitors, as indicated by Weistein and Dash [114]. The low cost of
producing nanostructured carbon from waste plastic in molten NaCl,
perhaps less than $6 per kilogram, makes the product attractive to be
used in commercial energy storage devices in large scale. Other possible
applications include conductive composites, inks and paints. The
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Applied Surface Science 476 (2019) 539–551
surface area and pore structure of the conductive nanostructured
carbon produced in molten NaCl can be tuned by appropriate activation
methods. This is currently investigated in our lab. The opportunities
involved in the utilization of the carbon derived from waste plastics
would support the environmental protection policies.
4. Conclusions
This study was concerned with the molten salt conversion of plastic
bottles into a highly conductive nanostructured carbon. It was found
that the heat treatment of waste plastic water bottles in air causes the
formation of an amorphous carbon comprising large irregular shaped
particles with sharp edges and a size of up to several hundred micro-
meters, and an exceptionally high resistance against oxidation in air up
to about 900 °C. The high oxidation resistance of the amorphous carbon
material produced was assigned to its high purity, large particle sizes,
low porosity and low density of surface defects. The heat treatment of
the plastic material with NaCl in air to a temperature above the melting
point of the salt led to the formation of a nanostructured carbon con-
taining graphene-based nanosheets with a high conductivity and sur-
face area. The graphitization was found to initiate by the appearance of
locally graphitized areas, particularly around the edge of amorphous
carbon particles at about 1100 °C, and progressed by the increase of
temperature to 1300 °C. In this strategy, molten NaCl protects the
amorphous carbon from oxidation at high temperatures whilst greatly
promotes the graphitization phenomena. The method provides simple,
economical and efficient ways of producing conductive carbon mate-
rials. It can also have a significantly positive environmental impact
through the conversion of almost non-degradable plastic wastes into
high value conductive carbon materials.
Acknowledgements
The financial supports provided by the National Natural Science
Foundation of China (No. 51750110513) and the Fundamental
Research Funds for the Central Universities (No. N172505001 and
N172502003) are greatly appreciated. The authors thank to Kaiyu Xie
for his technical assistance.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2019.01.119.
References
[1] M. Kutz (Ed.), Applied Plastics Engineering Handbook, Processing, Materials and
Applications, second ed., Elsevier, 2017.
[2] K. Chikaoui, M. Izerrouken, M. Djebara, M. Abdesselam, Polyethylene ter-
ephthalate degradation under reactor neutron irradiation, Phys. Chem. 130 (2017)
431–435.
[3] R.C. Thompson, C.J. Moore, F.S. vom Saal, S.H. Swan, Plastics, the environment
and human health: current consensus and future trends, Phil. Trans. R. Soc. B 364
(2009) 2153–2166.
[4] L. Cauwenberghe, C.R. Janssen, Microplastics in bivalves cultured for human
consumption, Environ. Pollut. 193 (2014) 65–70.
[5] T. Galloway, C. Lewis, Marine microplastics, Curr. Biol. 27 (2017) 431–510.
[6] M. Carbery, W. O'Connor, P. Thavamani, Trophic transfer of microplastics and
mixed contaminants in the marine food web and implications for human health,
Environ. Int. 115 (2018) 400–409.
[7] A. Naji, M. Nuri, A. Dick, Vethaak, Microplastics contamination in molluscs from
the northern part of the Persian Gulf, Environ. Pollut. 235 (2018) 113–120.
[8] R. Geyer, J.R. Jambeck, K. Lavender Law, Production, use, and, fate of all plastics
ever made, Sci. Adv. 3 (2017) 1700782.
[9] C. Ioakeimidis, K.N. Fotopoulou, H.K. Karapanagioti, M. Geraga, C. Zeri,
E. Papathanassiou, et al., The degradation potential of PET bottles in the marine
environment: an ATR-FTIR based approach, Sci. Rep. 6 (2016) 23501.
[10] X. Lin, J. Yu, H. Li, J.Y.K. Lam, K. Shih, I.M.L. Sham, C.K.Y. Leung, Recycling
polyethylene terephthalate wastes as short fibers in Strain-Hardening
Cementitious Composites (SHCC), J. Haz. Mater. 357 (2018) 40–52.
[11] M. Gürü, M.K. Cubuk, D. Arslan, S.A. Farzanian, I. Bilici, An approach to the usage
A.R. Kamali et al.
of polyethylene terephthalate (PET) waste as roadway pavement material, J. Haz.
Mater. 279 (2014) 302–310.
[12] J. Saleem, M.A. Riaz, G. McKay, Oil sorbents from plastic wastes and polymers: A
review, J. Haz. Mater. 341 (2018) 424–437.
[13] T. Tomsej, J. Horak, S. Tomsejova, K. Krpec, J. Klanova, M. Dej, et al., The impact
of co-combustion of polyethylene plastics and wood in a small residential boiler on
emissions of gaseous pollutants, particulate matter, PAHs and 1,3,5-triphe-
nylbenzene, Chemosphere 196 (2018) 18–24.
[14] G. Lopez, M. Artetxe, M. Amutio, J. Alvarez, J. Bilbao, M. Olazar, Recent advances
in the gasification of waste plastics. A critical overview, Renew. Sustain. Energy
Rev. 82 (2018) 576–596.
[15] J. Alvarez, S. Kumagai, C. Wu, T. Yoshioka, J. Bilbao, M. Olazar, et al., Hydrogen
production from biomass and plastic mixtures by pyrolysis-gasification, Int. J.
Hydrogen Energy 39 (2014) 10883–10891.
[16] Z. Abu El-Rub, E.A. Bramer, G. Brem, Review of catalysts for tar elimination in
biomass gasification processes, Ind. Eng. Chem. Res. 43 (2004) 6911–6919.
[17] A.A. Aboul-Eneina, A.E. Awadallaha, Production of nanostructured carbon mate-
rials using Fe–Mo/MgO catalysts via mild catalytic pyrolysis of polyethylene
waste, Chem. Eng. J. 354 (2018) 802–816.
[18] J. Ni, Y. Li, Carbon nanomaterials in different dimensions for electrochemical
energy storage, Adv. Energy Mater. 6 (2016) 1600278.
[19] T. Chen, L. Dai, Carbon nanomaterials for high performance supercapacitors,
Mater. Today 16 (2013) 272–280.
[20] M. Notarianni, J. Liu, K. Vernon, N. Motta, Synthesis and applications of carbon
nanomaterials for energy generation and storage, Beilstein J. Nanotechnol. 7
(2016) 149–196.
[21] S. Araby, Q. Meng, L. Zhang, I. Zaman, P. Majewski, J. Ma, Elastomeric composites
based on carbon nanomaterials, Nanotechnology 26 (2015).
[22] S. Jin, G.H. Jun, S. Jeon, S.H. Hong, Design and application of carbon nanoma-
terials for photoactive and charge transport layers in organic solar cells, Nano
Converg. 3 (2016) 8.
[23] F. Hof, K. Kampioti, K. Huang, C. Jaillet, A. Derré, P. Poulin, et al., Conductive inks
of graphitic nanoparticles from a sustainable carbon feedstock, Carbon 111 (2017)
142–149.
[24] M.S. Mauter, M. Elimelech, Environmental applications of carbon-based nano-
materials, Environ. Sci. Technol. 42 (2008) 5843–5859.
[25] A.C. Ferrari, Raman spectroscopy of graphene and graphite: Disorder, electro-
n–phonon coupling, doping and nonadiabatic effects, Solid State Commun. 143
(2007) 47–57.
[26] A.C. Ferrari, D.M. Basko, Raman spectroscopy as a versatile tool for studying the
properties of graphene, Nat. Nanotechnol. 8 (2013) 235–246.
[27] H.C. Lee, W.W. Liu, S.P. Chai, A.R. Mohamed, A. Aziz, C.S. Khe, et al., Review of
the synthesis, transfer, characterization and growth mechanisms of single and
multilayer graphene, RSC Adv. 7 (2017) 15644–15693.
[28] M.S. Dresselhaus, A. Jorio, A.G.S. FilhoI, Defect characterization in graphene and
carbon nanotubes using Raman spectroscopy, Phil. Trans. R. Soc. A 368 (2010)
5355–5377.
[29] M. Mohandoss, S. Sen Gupta, A. Nelleri, T. Pradeep, S.M. Maliyekkal, Solar
mediated reduction of graphene oxide, RSC Adv. 7 (2017) 957–963.
[30] P. Rai, K.P. Singh, Valorization of Poly (ethylene) terephthalate (PET) wastes into
magnetic carbon for adsorption of antibiotic from water: characterization and
application, J. Environ. Manag. 207 (2018) 249–261.
[31] J.B. Parra, C.O. Ania, A. Arenillas, F. Rubiera, J.J. Pis, J.M. Palacios, Structural
changes in polyethylene terepthalate (PET) waste materials caused by pyrolysis
and CO2 activation, Adsorpt. Sci. Technol. 24 (2006) 439–449.
[32] E. Lorenc-Grabowska, M.A. Diez, G. Gryglewicz, Influence of pore size distribution
on the adsorption of phenol on PET-based activated carbons, J. Colloid Interface
Sci. 469 (2016) 205–212.
[33] F. Lian, B. Xing, L. Zhu, Comparative study on composition, structure, and ad-
sorption behavior of activated carbons derived from different synthetic waste
polymers, J. Colloid Interface Sci. 360 (2011) 725–730.
[34] I. Fernandez-Morales, M.C. Almazan-Almazan, M. Perez-Mendoza, M. Domingo-
García, F.J. Lopez-Garzon, PET as precursor of microporous carbons:preparation
and characterization, Micropor. Mesopor. Mater. 80 (2005) 107–115.
[35] A.J. Berkmans, M. Jagannatham, S. Priyanka, P. Haridoss, Synthesis of branched,
nano channeled, ultrafine and nano carbon tubes from PET wastes using the arc
discharge method, Waste Manag. 34 (2014) 2139–2145.
[36] C. Wu, M.A. Nahil, N. Miskolczi, J. Huang, P.T. Williams, Processing real-world
waste plastics by pyrolysis-reforming for hydrogen and high-value carbon nano-
tubes, Environ. Sci. Technol. 48 (2014) 819–826.
[37] M.N.M. Hatta, M.S. Hashim, R. Hussin, S. Aida, Z. Kamdi, A.R. Ainuddin, Synthesis
of carbon nanostructures from high density polyethylene (HDPE) and poly-
ethylene terephthalate (PET) waste by chemical vapour deposition, J. Phys.: Conf.
Ser. 914 (2017) 012029.
[38] V.G. Pol, Upcycling: converting waste plastics into paramagnetic, conducting,
solid, pure carbon microspheres, Environ. Sci. Technol. 44 (2010) 4753–4759.
[39] N.A.E. Essawy, S.M. Ali, H.A. Farag, A.H. Konsowa, M. Elnouby, H.A. Hamad,
Green synthesis of graphene from recycled PET bottle wastes for use in the ad-
sorption of dyes in aqueous solution, Ecotoxicol. Environ. Saf. 145 (2017) 57–68.
[40] H. Alamdari, Aluminum production process: challenges and opportunities, Metals
7 (2017) 133.
[41] G.J. Kipouros, D.R. Sadoway, Toward new technologies for the production of li-
thium, JOM 50 (1998) 24–33.
[42] G. Demirci, I. Karakaya, Collection of magnesium in an Mg–Pb alloy cathode
placed at the bottom of the cell in MgCl2 electrolysis, J. Alloys Compd. 439 (2007)
237–242.
550
Applied Surface Science 476 (2019) 539–551
[43] G.Z. Chen, D.J. Fray, T.W. Farthing, Direct electrochemical reduction of titanium
dioxide to titanium in molten calcium chloride, Nature 407 (2000) 361–364.
[44] R. Abdulaziz, L.D. Brown, D. Inman, S. Simons, P.R. Shearing, D.J.L. Brett, Novel
fluidised cathode approach for the electrochemical reduction of tungsten oxide in
molten LiCl–KCl eutectic, Electrochem. Commun. 41 (2014) 44–46.
[45] L.D. Brown, R. Abdulaziz, R. Jervis, V. Bharath, T.J. Mason, R.C. Atwood,
C. Reinhard, L.D. Connor, D. Inman, D.J.L. Brett, P.R. Shearing, A novel molten
salt electrochemical cell for investigating the reduction of uranium dioxide to
uranium metal by lithium using in situ synchrotron radiation, J. Synchrotron
Radiat. 24 (2017) 439–444.
[46] D. Tang, H. Yin, X. Cheng, W. Xiao, D. Wang, Green production of nickel powder
by electro-reduction of NiO in molten Na2CO3–K2CO3, Int. J. Hydrog. Energy 41
(2016) 18699–18705.
[47] S. Li, X. Zou, K. Zheng, X. Lu, Q. Xu, C. Chen, Z. Zhou, Direct production of TiAl3
from Ti/Al-containing oxides precursors by solid oxide membrane (SOM) process,
J. Alloys Compd. 727 (2017) 1243–1252.
[48] A.R. Kamali, D.J. Fray, Nanocatalytic conversion of CO2 into nanodiamonds,
Carbon 123 (2017) 205–215.
[49] A.R. Kamali, D.J. Fray, Preparation of nanodiamonds from carbon nanoparticles at
atmospheric pressure, Chem. Commun. 51 (2015) 5594–5597.
[50] W.K. Hsu, J.P. Hare, M. Terrones, H.W. Kroto, D.R.M. Walton, P.J.F. Harris,
Condensed-phase nanotubes, Nature 377 (1995) 687.
[51] I.A. Kinloch, G.Z. Chen, J. Howes, C. Boothroyd, C. Singh, D.J. Fray, A.H. Windle,
Electrolytic, TEM and Raman studies on the production of carbon nanotubes in
molten NaCl, Carbon 41 (2003) 1127–1141.
[52] A.R. Dimitrov, G.Z. Chen, I.A. Kinloch, D.J. Fray, A feasibility study of scaling-up
the electrolytic production of carbon nanotubes in molten salts, Electrochim, Acta
48 (2002) 91–102.
[53] A.R. Kamali, D.J. Fray, Electrochemical interaction between graphite and molten
salts to produce nanotubes, nanoparticles, graphene and nanodiamonds, J. Mater.
Sci. 51 (2016) 569–576.
[54] A.R. Kamali, H.K. Kim, K.B. Kim, R.V. Kumar, D.J. Fray, Large scale green pro-
duction of ultra-high capacity anode consisting of graphene encapsulated silicon
nanoparticles, J. Mater. Chem. A 5 (2017) 19126–19135.
[55] A. Rezaei, A.R. Kamali, Green production of carbon nanomaterials in molten salts,
mechanisms and applications, Diamond Relat. Mater. 83 (2018) 146–161.
[56] B. Sánchez, J. Maestre, I.I. Torres, A. Romero, J.M.S. Lizarraga, Molten salt-based
nanofluids as efficient heat transfer and storage materials at high temperatures. An
overview of the literature, Renew. Sust. Energy Rev. 82 (2018) 3924–3945.
[57] G. Zheng, H. Wu, J. Wang, S. Chen, Y. Zhang, Thorium-based molten salt SMR as
the nuclear technology pathway from a market-oriented perspective, Ann. Nucl.
Energy 116 (2018) 177–186.
[58] A. Bonk, S. Sau, N. Uranga, M. Hernaiz, T. Bauer, Advanced heat transfer fluids for
direct molten salt line-focusing CSP plants, Prog. Energy Combust. Sci. 67 (2018)
69–87.
[59] B.C. Du, Y.L. He, Y. Qiu, Q. Liang, Y.P. Zhou, Investigation on heat transfer
characteristics of molten salt in a shell-and-tube heat exchanger, Int. Commun.
Heat Mass 96 (2018) 61–68.
[60] Z. Hu, X. Xiao, H. Jin, T. Li, M. Chen, Z. Liang, Z. Guo, J. Li, J. Wan, L. Huang,
Y. Zhang, G. Feng, J. Zhou, Rapid mass production of two-dimensional metal
oxides and hydroxides via the molten salts method, Nat. Commun. 8 (2017)
15630.
[61] Z. Li, X. Zhang, J. Hou, K. Zhou, Molten salt synthesis of anisometric Sr3Ti2O7
particles, J. Cryst. Growth 305 (2007) 265–270.
[62] A.R. Kamali, D.J. Fray, Preparation of lithium niobate particles via reactive molten
salt synthesis method, Ceram. Int. 40 (2014) 1835–1841.
[63] A.R. Kamali, C. Schwandt, D.J. Fray, Effect of the graphite electrode material on
the characteristics of molten salt electrolytically produced carbon nanomaterials,
Mater. Charact. 62 (2011) 987–994.
[64] E. Gonzalez II, M.D. Barankin, P.C. Guschl, R.F. Hicks, Remote atmospheric-
pressure plasma activation of the surfaces of polyethylene terephthalate and
polyethylene naphthalate, Langmuir 24 (2008) 12636–12643.
[65] Z.Q. Li, C.J. Lu, Z.P. Xia, Y. Zhou, Z. Luo, X-ray diffraction patterns of graphite and
turbostratic carbon, Carbon 45 (2007) 1686–1695.
[66] P. Ruz, S. Banerjee, M. Pandey, V. Sudarsan, P.U. Sastry, R.J. Kshirsagar,
Structural evolution of turbostratic carbon: Implications in H2 storage, Solid State
Sci. 62 (2016) 105–111.
[67] P. Ramakrishnan, S. Shanmugam, Nitrogen-doped carbon nanofoam derived from
amino acid chelate complex for supercapacitor applications, J. Power Sources 316
(2016) 60–71.
[68] N. Subramanian, B. Viswanathan, Nitrogen- and oxygen-containing activated
carbons from sucrose for electrochemical supercapacitor applications, RSC Adv. 5
(2015) 63000–63011.
[69] A. Gutierrez-Pardo, J. Ramírez-Rico, R. Cabezas-Rodríguez, J. Martínez-
Fernandez, Effect of catalytic graphitization on the electrochemical behavior of
wood derived carbons for use in supercapacitors, J. Power Sources 278 (2015)
18–26.
[70] V.Zh. Shemet, A.P. Pomytkin, V.S. Neshpor, High temperature oxidation behavior
of carbon materials in air, Carbon 31 (1993) 1–6.
[71] J.R. Hahn, Kinetic study of graphite oxidation along two lattice directions, Carbon
43 (2005) 1506–1511.
[72] M.Q. Tran, C. Tridech, A. Alfrey, A. Bismarck, M.S.P. Shaffer, Thermal oxidative
cutting of multi-walled carbon nanotubes, Carbon 45 (2007) 2341–2350.
[73] D.W. McKee, D. Chatterji, The catalytic behavior of alkali metal carbonates and
oxides in graphite oxidation reactions, Carbon 13 (1975) 381–390.
[74] A.R. Kamali, C. Schwandt, D.J. Fray, On the oxidation of molten salt
A.R. Kamali et al.
electrolytically produced carbon nanomaterials, Corros. Sci. 54 (2012) 307–313.
[75] A.R. Kamali, G. Divitini, C. Schwandt, D.J. Fray, Correlation between micro-
structure and thermokinetic characteristics of electrolytic carbon nanomaterials,
Corros. Sci. 64 (2012) 90–97.
[76] K.S.W. Sing, D.H. Everrtt, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol,
et al., Reporting physisorption data for gas/solid systems with special reference to
the determination of surface area and porosity, Pure Appl. Chem. 57 (1985)
603–619.
[77] H. Pan, J. Li, Y.P. Feng, Carbon nanotubes for supercapacitor, Nanoscale Res. Lett.
5 (2010) 654–668.
[78] L. Zou, C. Lan, X. Li, S. Zhang, Y. Qiu, Superhydrophobization of cotton fabric with
multiwalled carbon nanotubes for durable electromagnetic interference shielding,
Fiber Polym. 16 (2015) 2158–2164.
[79] B. Weng, Y.J. Xu, What if the electrical conductivity of graphene is significantly
deteriorated for the graphene–semiconductor composite-based photocatalysis?
ACS Appl. Mater. Interfaces 7 (2015) 27948–27958.
[80] N. Nitta, F. Wu, J.T. Lee, G. Yushin, Li-ion battery materials: present and future,
Mater. Today 18 (2015) 252–264.
[81] F. Sun, J. Gao, X. Liu, X. Pi, Y. Yang, S. Wu, Porous carbon with a large surface
area and an ultrahigh carbon purity via templating carbonization coupling with
KOH activation as excellent supercapacitor electrode materials, Appl. Surf. Sci.
387 (2016) 857–863.
[82] Z. Qiu, Y. Wang, X. Bi, T. Zhou, J. Zhou, J. Zhao, et al., Biochar-based carbons with
hierarchical micro-meso-macro porosity for high rate and long cycle life super-
capacitors, J. Power Sources 376 (2018) 82–90.
[83] J. Wang, S. Kaskel, KOH activation of carbon-based materials for energy storage, J.
Mater. Chem. 22 (2012) 23710–23735.
[84] A.R. Kamali, D.J. Fray, Molten salt corrosion of graphite as a possible way to make
carbon nanostructures, Carbon 56 (2013) 121–131.
[85] A.R. Kamali, D.J. Fray, Towards large scale preparation of carbon nanostructures
in molten LiCl, Carbon 77 (2014) 835–845.
[86] A.R. Kamali, Eco-friendly production of high quality low cost graphene and its
application in lithium ion batteries, Green Chem. 18 (2016) 1952–1964.
[87] A.R. Kamali, Scalable fabrication of highly conductive 3D graphene by electro-
chemical exfoliation of graphite in molten NaCl under Ar/H2 atmosphere, J. Ind.
Eng. Chem. 52 (2017) 18–27.
[88] Z. He, L. Gao, X. Wang, B. Zhang, W. Qi, J. Song, et al., Improvement of stacking
order in graphite by molten fluoride salt infiltration, Carbon 72 (2014) 304–311.
[89] X. Jin, R. He, S. Dai, Electrochemical graphitization: an efficient conversion of
amorphous carbons to nanostructured graphites, Chem. Eur. J. 23 (2017)
11455–11459.
[90] P.J.F. Harris, Structure of non-graphitising carbons, Int. Mater. Rev. 42 (1997)
206–218.
[91] K. Jurkiewicz, M. Pawlyta, D. Zygadło, D. Chrobak, S. Duber, R. Wrzalik,
A. Ratuszna, A. Burian, Evolution of glassy carbon under heat treatment: corre-
lation structure–mechanical properties, J. Mater. Sci. 53 (2018) 3509–3523.
[92] D.W. Kim, H.S. Kil, J. Kim, I. Mochida, K. Nakabayashi, C.K. Rhee, et al., Highly
graphitized carbon from non-graphitizable raw material and its formation me-
chanism based on domain theory, Carbon 121 (2017) 301–308.
[93] J. Peng, N. Chen, R. He, Z. Wang, S. Dai, X. Jin, Electrochemically driven trans-
formation of amorphous carbons to crystalline graphite nanoflakes: a facile and
mild graphitization method, Angew. Chem. 129 (2017) 1777–1781.
[94] F.G. Emmerich, Evolution with heat treatment of crystallinity in carbons, Carbon
33 (1995) 1709–1715.
[95] B. Xu, H. Wang, Q. Zhu, N. Sun, B. Anasori, L. Hu, et al., Reduced graphene oxide
551
Applied Surface Science 476 (2019) 539–551
as a multi-functional conductive binder for supercapacitor electrodes, Energy
Storage Mater. 12 (2018) 128–136.
[96] A. Rani, S. Nam, K.A. Oh, M. Park, Electrical conductivity of chemically reduced
graphene powders under compression, Carbon Lett. 11 (2010) 90–95.
[97] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc.
80 (1958) 1339.
[98] V.B. Mohan, R. Brown, K. Jayaraman, D. Bhattacharyya, Characterisation of re-
duced graphene oxide: Effects of reduction variables on electrical conductivity,
Mater. Sci. Eng. B 193 (2015) 49–60.
[99] Y. Zhang, L. Ren, S. Wang, A. Marathe, J. Chaudhuri, G. Li, Functionalization of
graphene sheets through fullerene attachment, J. Mater. Chem. 21 (2011)
5386–5391.
[100] Y. Zhang, S. Wang, L. Li, K. Zhang, J. Qiu, M. Davis, et al., Tuning electrical
conductivity and surface area of chemically-exfoliated graphene through nano-
crystal functionalization, Mater. Chem. Phys. 135 (2012) 1057–1063.
[101] V. Skákalová, P. Kotrusz, M. Jergel, T. Susi, A. Mittelberger, V. Vretenár, et al.,
Chemical oxidation of graphite: evolution of the structure and properties, J. Phys.
Chem. C 122 (208) (2017) 929–935.
[102] J. Zhang, L. Xu, B. Zhou, Y. Zhu, X. Jiang, The pristine graphene produced by
liquid exfoliation of graphite in mixed solvent and its application to determination
of dopamine, J. Colloid Interface Sci. 513 (2018) 279–286.
[103] A. Ciesielski, P. Samorì, Graphene via sonication assisted liquid-phase exfoliation,
Chem. Soc. Rev. 43 (2014) 381–398.
[104] L.G. Guex, B. Sacchi, K.F. Peuvot, R.L. Andersson, A.M. Pourrahimi, V. Ström,
et al., Experimental review: chemical reduction of graphene oxide (GO) to reduced
graphene oxide (rGO) by aqueous chemistry, Nanoscale 9 (2017) 9562–9571.
[105] K.P. Loh, Q. Bao, G. Eda, M. Chhowalla, Graphene oxide as a chemically tunable
platform for optical applications, Nat. Chem. 2 (2010) 1015–1024.
[106] Y. Zhu, S. Murali, M.D. Stoller, K.J. Ganesh, W. Cai, P.J. Ferreira, et al., Carbon-
based supercapacitors produced by activation of graphene, Science 332 (2011)
1537–1541.
[107] J.W.F. To, Z. Chen, H. Yao, J. He, K. Kim, H.H. Chou, et al., Ultrahigh surface area
three-dimensional porous graphitic carbon from conjugated polymeric molecular
framework, ACS Cent. Sci. 1 (2015) 68–76.
[108] G. Ramos-Fernandez, M. Canal-Rodríguez, A. Arenillas, J.A. Menendez,
I. Rodríguez-Pastor, I. Martin-Gullon, Determinant influence of the electrical
conductivity versus surface area on the performance of graphene oxide-doped
carbon xerogel supercapacitors, Carbon 126 (2018) 456–463.
[109] M. Canal-Rodríguez, A. Arenillas, N. Rey-Raap, G. Ramos-Fernandez, I. Martín-
Gullon, J. Angel Menendez, Graphene-doped carbon xerogel combining high
electrical conductivity and surface area for optimized aqueous supercapacitors,
Carbon 118 (2017) 291–298.
[110] F. Sun, L. Wang, Y. Peng, J. Gao, X. Pi, Z. Qu, et al., Converting biomass waste into
microporous carbon with simultaneously high surface area and carbon purity as
advanced electrochemical energy storage materials, Appl. Surf. Sci. 436 (2018)
486–494.
[111] D. Pantea, H. Darmstadt, S. Kaliaguine, C. Roy, Electrical conductivity of con-
ductive carbon blacks: influence of surface chemistry and topology, Appl. Surf. Sci.
217 (2003) 181–193.
[112] L.L. Zhang, X.S. Zhao, Carbon-based materials as supercapacitor electrodes, Chem.
Soc. Rev. 38 (2009) 2520–2531.
[113] X. Geng, L. Li, M. Zhang, B. An, X. Zhu, Influence of reactivation on the electro-
chemical performances of activated carbon based on coconut shell, J. Environ. Sci.
25 (2013) 110–117.
[114] L. Weinstein, R. Dash, Supercapacitor carbons, Mater. Today. 16 (2013) 356–357.