Chemical Engineering Journal xxx (xxxx) xxx

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Impact of temperature on the activity of Fe-Ni catalysts for pyrolysis and

decomposition processing of plastic waste
Dingding Yao a, He Li b, Yanjun Dai c, Chi-Hwa Wang b, *
a
NUS Environmental Research Institute (NERI), National University of Singapore, 138602, Singapore
b
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore
c
School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

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

Keywords: Thermal chemical processing of plastic has been seen as an efficient practice for the disposal and resource uti­
Plastic waste lization facing the current plastic waste problem. A pyrolysis followed by catalytic decomposition process was
Pyrolysis investigated in this work to produce carbon materials from polypropylene plastic over FeNi catalysts. The effects
Catalysis
of both catalysis temperature (600, 700 and 800 ◦ C) and catalyst type on the gaseous yields, as well as the
Carbon materials
physicochemical properties (morphology, porosity, purity and graphitization degree) of the as-obtained carbon
materials were systematically explored. Various technologies including high resolution electron microscopies,
temperature programmed oxidation, Raman, X-ray diffraction were used for full characterizations of the as-
obtained carbons. Results show that the yields of both carbon and hydrogen gas were significantly propor­
tional to the catalysis temperature. In terms of the physiochemical properties of carbon materials, the low
catalysis temperature of 600 ◦ C generated the majority amorphous and disordered carbons, due to the insuffi­
cient decomposition reactions and low catalyst activity. Catalysis temperature higher than 700 ◦ C was necessary
for the successful growth of carbon nanotubes, while further increase in temperature mainly acted on the yield
rather than thermal stability and graphitic degree. High purity multi-walled carbon nanotubes with outer di­
ameters of 20–30 nm and length up to few micrometers were generated with FeNi1 at 800 ◦ C. FeNi1 catalyst
synthesized by sol–gel method displayed higher activity towards the production of high quality carbon materials
than FeNi2 catalyst at any temperature range investigated, due to the porous structure and the uniform
dispersion of metal particles.

1. Introduction Recently, thermal chemical technology has been adopted to convert

With the social industrialization and growing population, the de­
mand and consumption in plastic products have been continuously
increasing due to the diverse applications of plastic material. A recent
report pointed out the global plastics production nearly reached 360
million tonnes in 2018 [1]. However, the huge plastic consumption and
the large stream of plastic waste dumped into environment have been
increasing concerns [2]. Though there has been seen a slight increase in
world plastic waste collecting and recycling rate, existing disposal
methods still much rely on mechanical or energy recovery (incinera­
tion), which involve energy-intensive pretreatment or negative impact
on environment [3,4]. Therefore, developing more efficient methods are
urgently needed to handle waste plastics for an environmental friendly
and sustainable society.
plastic waste into flexible products like hydrogen rich gas, liquid and
solid material [5–7]. Transforming the plastic waste into value-added
products will significantly improve the economy of the overall process
and will further bring more incentives into waste recycling and utili­
zation. Aboul-Enein et al. [8] performed the catalytic pyrolysis of low-
density polyethylene over Fe-Mo/MgO catalyst to synthesize the valu­
able hybrid carbon materials containing nanotubes, nanofibers and
nanosheets. Zheng et al. [9] used the low-cost waste polyethylene to
produce high aspect ratio of carbon nanotube arrays, which then
exhibited good adsorption performance for methylene blue. Wu et al.
[10] reported the production of high value carbon nanotubes from
contaminated waste plastics by a pyrolysis-reforming technology. Car­
bon nanotubes have unique structure with extraordinary physical and
electrical properties, with great pontifical to be used as mechanical

* Corresponding author.
E-mail address: chewch@nus.edu.sg (C.-H. Wang).

https://doi.org/10.1016/j.cej.2020.127268
Received 30 July 2020; Received in revised form 3 October 2020; Accepted 4 October 2020
Available online 8 October 2020
1385-8947/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Dingding Yao, Chemical Engineering Journal, https://doi.org/10.1016/j.cej.2020.127268
D. Yao et al.
reinforcements and electrochemical materials [11]. In a study by Bor­
sodi et al. [12], carbon nanotubes produced from plastic waste were
blended into commercial LDPE. Results showed that the density and
tensile strength were significantly improved by the CNT reinforced
polymer composites. Cai et al. [13] performed a novel catalytic pyrolysis
of waste plastic process to prepare the Fe- and nitrogen- doped carbon
nanotubes as electrocatalyst, which then exhibited remarkable catalytic
activity and even better stability towards oxygen reduction reaction
compared with the commercial Pt/C catalyst. Integrating the synthesis
of carbon nanotubes to the plastic pyrolysis was demonstrated, in a life
cycle assessment case by Ahamed et al [14], to be environmentally
beneficial, in terms of climate change, fossil depletion, human toxicity
and ionizing radiation. The economic feasibility of producing value-
added carbon materials from waste plastics can be further enhanced
by the hydrogen gases produced as by-product, which can be taken as
fuel to provide energy for the reaction system.
Both the catalyst material and processing temperature are extremely
important for the synthesis of carbon materials from plastic. Yang et al.
[15] developed a two-stage fluidized bed system for gasification of waste
plastics, where they found that increasing the temperature of the first-
stage enhanced the degradation of plastic into more carbon precursors
for the following CNTs formation. Additionally, the introduction of Ni-
Cu based catalyst in the second stage improved the yield of carbons.
In a study of thermo-chemical conversion of waste polyethylene pellets,
Liu et al. [16] found that SiO2 supported Fe with large particle size
exhibited higher activity to produce hydrogen and graphitic carbons
than Ni based catalyst. While the most commonly used metal catalysts
for CNTs synthesis were Ni and Fe, recent studies found bimetallic alloys
such as NiCo, NiFe and NiCu were empirically observed to show high
activity, by lowering the activation energy and enhancing the growth
rate [17,18]. Ni, Fe and bimetallic Ni-Fe based catalyst have been pre­
viously studied for the pyrolysis and catalysis of plastic waste [19,20]. It
was found the Ni-Fe catalyst with high Fe to Ni presented outstanding
performance for carbon materials production in both quality and
quantity perspectives. The growth mode of CNTs, as investigated by
Kutteri et al.[21], was also found to be related to the type of 3d transi­
tion metal catalysts. They concluded that tip-grown carbon nanotubes
were selectively produced over Ni-Fe catalyst, while the mixture of tip-
and base-grown carbon nanotubes were more favored over Ni-Co and
Fe-Co catalysts. Operational temperature is another aspect that need to
be carefully controlled for the production of carbon material from
plastic. Veksha et al. [22] performed the pyrolysis and catalytic depo­
sition of different plastic resins at synthesis temperatures of 500 and
800 ◦ C, and concluded that high synthesis temperature yielded more
carbons. The same authors [23] further evaluated the electro-catalytic
performance of those obtained carbon materials for energy-storage
application. They found carbon materials at synthesis temperature of
500 ◦ C displayed more dense edge defects than those synthesized at
800 ◦ C, leading to the relatively high activity of the former as the
electrode material towards oxygen reduction reaction. The literatures
reviewed above encouraged us to use the Fe-Ni bimetallic catalyst to
catalyze pyrolysis of waste plastic for the production of carbon mate­
rials, while the process temperature should also be carefully controlled
for the optimal carbon materials. It was reported that the catalyst syn­
thesis method had significant impact on the catalyst activity with much
difference in metal dispersion and reducibility, which further influenced
the quality of carbon materials [24,25]. In addition, the dependence of
such Fe-Ni catalysts activities on catalysis temperature was also un­
known. As the conversion route of plastic-to-carbon materials involves a
series of consecutive reactions including initial degradation, decompo­
sition, carbon diffusion and precipitation, a comprehensive under­
standing of correlations among operational temperature, catalyst type,
gas composition, and the physicochemical properties of as-obtained
carbon materials will be an important perspective that worth
exploring for efficient utilization of plastic waste resources.
In this work, the effect of operational temperature on the gases
2
Chemical Engineering Journal xxx (xxxx) xxx
products for the non-catalytic and catalytic processing of polypropylene
plastic was firstly investigated. Solid carbon products obtained over
different bimetallic FeNi catalysts were then characterized by various
techniques to determine the impact of catalysis temperature and catalyst
type on the quantity and quality of carbon materials. This work shows a
new opportunity for waste plastic management, as well as a new frontier
for the synthesis of valuable carbon nanotubes from low-cost plastic
material.
2. Materials and methods
2.1. Materials
Polypropylene is one of the most commonly produced plastic glob­
ally and is extensively used to manufacture lunch box, bottles and
storage containers. In this work, polypropylene plastic pellet (Sigma-
Aldrich Pte Ltd.) with the size of 3 mm was used for feedstock as it is,
without any pretreatment.
Catalyst was applied for the catalytic decomposition of volatiles from
plastic pyrolysis, to promote the production of gas and carbon materials.
A type of bimetallic catalyst combining the active Fe and Ni metals was
adopted [19]. To evaluate the effect of catalysis temperature under
different catalyst, two catalyst synthesis methods of sol-gel and con­
ventional wet impregnation were used, with the catalyst named as FeNi1
and FeNi2 respectively. The preparation of FeNi1 catalyst referred to a
previous study [26], where the sol–gel method was optimized for Ni
catalyst by adjusting PH and water amount. Specifically, 20 g of
aluminum-tri-sec-butoxide (ATB) was firstly dissolved in absolute
ethanol and was stirred steadily at 50 ◦ C for around 2.5 h until a
transparent solution was observed. Active metal precursors were pre­
pared by mixing 0.58 g of Ni(NO3)2⋅6H2O and 2.44 g of Fe(NO3)3⋅9H2O
into 5.1 ml of deionized water in order to achieve the active metal
loading at 10 wt% in the final catalyst. Then this solution was added into
ATB solution dropwise and was stirred for 0.5 h at 75 ◦ C. The pH value of
mixed solution was measured in real time and adjusted to 4.8 by adding
nitric acid or ammonium hydroxide. The resultant sample was aged for
another 1 h and dried overnight. The catalyst powder was finally ob­
tained after grinding and a calcination process at 500 ◦ C in air for 3 h.
The synthesis of FeNi2 used a conventional wet impregnation method as
described elsewhere [25]. The preparation started from dissolution of
1.31 g Ni(NO3)2⋅6H2O and 5.47 g Fe(NO3)3⋅9H2O into 100 ml ethanol,
followed by mixing with 9 g alumina powder. The obtained solution was
stirred homogenously for 4 h at 60 ◦ C and was dried overnight. The dried
sample was then ground and heated to 800 ◦ C with heating rate of
10 ◦ C/min and held for 3 h. All chemicals during the synthesis were
obtained from Sigma Aldrich Pte Ltd.
2.2. Experimental system
Experiment was conducted in a two-stage bed system as displayed in
Fig. 1. It generally consists of gas feeding system, heating and reaction
system, liquid and gas collecting system. The reactor has two beds, the
upper for plastic pyrolysis and the lower one for catalytic decomposition
respectively. The temperature of each bed can be controlled and
measured independently. For each experiment, the catalyst (or sand in
the case of non-catalytic experiment) of 0.4 g was loaded in the lower
catalyst bed, and three catalysis temperatures of 600, 700 and 800 ◦ C
were investigated. Nitrogen gas controlled at 100 ml/min by mass flow
meter was supplied as the carrier gas and internal agent for gas yield
calculation. When the temperature of catalyst bed reached the pre­
scribed temperature and kept stable, around 1 g of plastic sample was
then weighed and introduced into upper feedstock bed where the tem­
perature was heated from room temperature to 500 ◦ C at ramp of 15 ◦ C/
min. The evolved gases from reactor went through the condenser and
dryer system, and were finally sampled to be further analyzed by gas
chromatography (GC). The total reaction time for each experiment was
D. Yao et al. Chemical Engineering Journal xxx (xxxx) xxx

were observed by FESEM. Before observation, specimen was coated with

a thin layer of platinum to make it conductive. The inside structure of
carbon product was investigated by high resolution FETEM. The spec­
imen was prepared by dissolving small amount of carbon powders in
ethanol and an ultrasonic dispersion process, followed by placing one
drop of suspension liquid onto carbon coated copper mesh grids. The
thermal stability of produced carbon on the spent catalyst was studied
by temperature programmed oxidation (TPO) method on a DTG-60A
TGA. The oxidation process was programmed from room temperature
to 800 ◦ C at the heating rate of 10 ◦ C/min in air atmosphere and hold at
800 ◦ C for 10 min. The Raman spectrometer was used to study the purity
and graphitization degree of the produced carbon, and the spectrogram
was collected at a laser wavelength of 532 nm with Raman shift from
200 to 3500 cm− 1. In addition, XRD analysis of the fresh and spent
catalysts were conducted on a Bruker D8 Advance instrument operated
at 40 kV and 40 mA using a Cu Kα radiation. Each sample was scanned in
the 2θ range of 10 ~ 85◦ with the step size of 0.02◦ . The specific surface
area of catalysts and the obtained carbon materials were determined by
the Brunauer-Emmett-Teller (BET) method using automated gas sorp­
tion analyzer. The samples were degassed at 300 ◦ C for 6 h before the
Fig. 1. Schematic diagram for the pyrolysis and decomposition processing start of analysis.
of plastic.
3. Results and discussion
around 50 min including the initial heating process and an isothermal
process at the pyrolysis temperature of 500 ◦ C for 20 min to collect all of 3.1. Product distributions and mass balance
the gases evolved. The carrier gas was continued to be supplied until the
reactor cooled down to room temperature to provide the inert atmo­ In order to investigate the effect of catalysis temperature on the
sphere for the solid products inside the reactor. Then solid residues pyrolysis and decomposition of polypropylene, several sets of experi­
including the spent catalyst were taken out and kept in dry boxes for ment were performed: the effect of temperatures 600, 700 and 800 ◦ C on
further analysis. In addition, repeated trials were conducted to deter­ the non-catalytic trails, we well as on the catalytic ones using FeNi1 and
mine the reliability of the reaction system. The mass balance for each FeNi2. Table 2 shows the overall yields and mass balance for each
experiment was also given in results. experiment. It can be seen under the non-catalytic experiment, the
product was rich in liquid while the solid yield was close to zero. In this
work, the solid product came from two parts, one from the residues in
2.3. Analytical methods and product characterizations
the pyrolysis reactor (upper stage) and another one from carbon mate­
rials that deposited on the surface of catalyst after experiment. There­
Table 1 shows all the analytical methods and instruments used in this
fore, in the absence of catalyst, the solid product which was only from
work. The gas composition was measured using GC coupled with a
the pyrolysis stage can be neglected due to the fact the polypropylene
thermal conductivity detector. High purity argon was used as the carrier
was completely volatized at 500 ◦ C [27]. Because of the small amount of
gas. Each gas production can be calculated based on its relative volume
feedstock, it was hard to separate the wax from the condensable gases.
content in the mixed gases together with the content and flow rate of the
Therefore, the liquid products mentioned here included the mixture of
carrier gas. The total gas or liquid yield was determined by the total mass
wax and liquid hydrocarbons. It was observed that the liquid products
of gases or liquid products obtained in relation to the mass of plastic
achieved up to 77.9 wt%, and were almost in the form of white wax at
feedstock. Solid yield was identified as the mass difference between
the minimum temperature studied. Wax are long chain hydrocarbons
fresh and used solid samples divided by the weight of plastic feedstock.
which have carbon number higher than 20. Due to its complexity and
For device maintenance and data reliability, gas chromatography was
difficulty in handling, wax is an undesirable product and the its utili­
calibrated regularly using the two calibration gas mixtures supplied by
zation much relies on the downstream cracking process to get fuels and
Linde Gas Singapore Pte Ltd. Calibration gas #1: H2 8.00%, CO 4.00%,
chemicals [28]. With the temperature rising from 600 to 800 ◦ C, it can
CO2 4.00%, O2 1.00%, CH4 3.00%, balanced by N2; Calibration gas #2:
be seen a significant increase in the gas yield at the expense of liquids,
CH4 2.00%, C2H2 1.00%, C2H4 1.00%, C2H6 1.00%, balanced by N2. The
while the solid yield remained less than 4 wt%. As only thermal
accuracy (relative) was 2% for each gas component. After GC calibra­
decomposition reactions of hydrocarbon volatiles from pyrolysis of
tion, the standard deviation of gas concentration was 0.01%.
polypropylene happened during the non-catalytic trails, it means the
The morphologies of fresh catalyst and the obtained solid product
increased gas yield of 32.0 wt% was attributed to the enhanced thermal
cracking by high temperature. Mass balance was checked for each
Table 1 experiment to ensure the reliability of the reaction system. As shown in
Analysis and instruments. Table 2, mass balance for the non-catalytic experiment was relatively
Type Instrument Producer and origin low, which may due to the difficulty in liquid products colleting as some
Gas chromatography (GC) Clarus 580 PerkinElmer, USA vapors condensed on the wall of reactor. The low mass balance may also
Field emission scanning electron JSM-6700F JEOL, Japan because that pyrolysis of polypropylene decomposed to some hydro­
microscope (FESEM) carbon gases which were hard to be detected by current GC analyzer.
Field emission transmission electron JEM-2100F JEOL, Japan
Compared with the non-catalytic experiment, higher yields of solid and
microscope (FETEM)
Thermo-gravimetric analyzer (TGA) DTG-60A Shimadzu, Japan gases products were observed with the introduction of catalyst. Specif­
Raman spectrometer LabRAM HR800 Horiba, Japan ically, in the presence of FeNi1, the total gas yield was in the range from
X-ray diffractometer (XRD) D8 Advance Bruker, USA 22.0 to 48.5 wt%, while the rising catalysis temperature promoted the
Physisorption Autosorb iQ-MP- Quantachrome gas production. The solid yield was increased by more than three times
AG-AG Instruments, USA
from catalysis temperature of 600 to 800 ◦ C, and reached the maximum

3
D. Yao et al.
Table 2
Results of pyrolysis and catalysis of polypropylene at different catalysis temperature.
Yields (wt%) Non-600 Non-700 Non-800 FeNi1-600
Gas 11.2 30.4 43.2 22.0
Liquid 77.9 56.8 45.5 60.0
Solid 0.4 0.4 4.0 8.0
Mass balance 89.4 87.6 92.7 90.0
of 36.0 wt% among all experiments. The effect of catalysis temperature
on the product yields with FeNi2 was much similar to the case with
FeNi1, except that the gas or solid yield was a little lower than the
former, meaning that catalytic decomposition reactions was more
favored over FeNi1 catalyst.
3.2. Effect of catalysis temperature on gas composition
The productions of hydrogen and carbon, and the gas composition
under different catalysis temperature are shown in Fig. 2. In the absence
of catalyst, hydrogen yield increased from 0.43 to 7.33 mmol/gPP when
temperature increased from 600 to 800 ◦ C. Though the high temperature
lead to a slight increase of carbon deposition in the decomposition stage,
the carbon yield at 800 ◦ C was still around an order of magnitude lower
than that of catalytic counterparts (Fig. 2c and e), indicating that carbon
materials originated from pure thermal cracking could be neglected. It is
reported that transition metal nanoparticles which usually refer to Fe,
Co or Ni are essential for the formation of metal carbides, followed by
carbon diffusion, precipitation and finally the growth of carbon nano­
materials [29]. In this work, the production of carbon materials reached
80 ~ 360 mg/gPP over FeNi1 or 60 ~ 290 mg/gPP over FeNi2 catalyst.
Therefore, it can be concluded that both metal catalyst and proper
temperature were essential conditions for the production of carbon
materials from plastic waste. In terms of gas composition as shown in
Fig. 2b, CH4 took the largest proportion in the gaseous mixture, followed
by H2 and other hydrocarbon gases. The concentrations of hydrogen and
CH4 increased with the temperature, consistent with the reduction in
C2+ gases, as the result of large hydrocarbon gases breaking down into
small ones.
Regarding the gas productions under catalytic process, the produc­
tion of hydrogen was promoted in the presence of catalyst. At 600 ◦ C, the
production of hydrogen was 9.26 mmol/gPP in the presence of FeNi1
catalyst. It was further increased by the rising catalysis temperature, and
reached the maximum of 25.14 mmol/gPP at 800 ◦ C with FeNi1 catalyst.
Hydrogen possessed the highest concentration in the gaseous mixture
for all catalytic experiments as shown in Fig. 2d, while it was the CH4 in
case of non-catalytic one. This could be due to the partially filled 3d
orbitals of catalyst metal which facilitated the decomposition of hy­
drocarbons into hydrogen and carbon atoms as reported in literatures
[21]. It was further demonstrated by the significant increase in the
carbon yields in the presence of catalyst. In addition, high catalysis
temperature favored the catalytic decomposition of large hydrocarbons
into small gases, as was observed in the decrease of C2+ concentration
from 17.93 to 8.23 vol% while an increase in CH4 from 22.06 to 33.12
vol%, when the temperature increased from 600 to 800 ◦ C. The gaseous
products have high content of energy-rich gases like H2 and CH4, which
can be used as fuel in gas-fired engine to provide energy for the pyrolysis
of plastic waste to produce carbon materials.
FeNi2 catalyst displayed the similar trend in terms of the catalyst
activity at different reaction temperatures. The drastic increase in both
H2 yield and carbon deposition can be observed as the temperature
increased from 600 to 800 ◦ C, which was attributed to the endothermic
nature of cracking reactions of hydrocarbons which generated hydrogen
and carbon atoms. Regarding the gas composition, it can be seen from
Fig. 2f as the growing temperature, the concentration of H2 and CH4
slightly increased, while a significant decline of C2+ from 24.43 to 11.39
vol% was observed. For all the operational conditions investigated in
4
Chemical Engineering Journal xxx (xxxx) xxx
FeNi1-700 FeNi1-800 FeNi2-600 FeNi2-700 FeNi2-800
40.0 48.5 21.1 38.6 49.1
30.0 20.0 63.0 32.0 22.0
23.0 36.0 6.0 21.0 29.0
93.0 104.5 90.1 91.6 100.1
this work, repeated trials showed that the standard deviations of
hydrogen yield and carbon deposition were 0.10 ~ 0.80 mmol/gPP and
0.51 ~ 13.35 mg/gPP respectively. It worth noting that when it was at
the same temperature, hydrogen production from FeNi1 was a little bit
higher than that from FeNi2. For example, H2 production was around
21.45 mmol/gPP with FeNi1 at a moderate temperature of 700 ◦ C,
whereas it was only 14.22 mmol/gPP in the presence of FeNi2, indicating
that the former catalyst which was prepared by sol–gel method had
higher activity than the catalyst prepared by impregnation method.
Characterizations of catalyst samples showed that the specific surface
area of FeNi1 and FeNi2 was 212.3 and 90.71 m2/g, respectively. While
the metal loading of these two catalysts remained same (10 wt%), the
difference in catalyst activity may be ascribed to the different porosity
and dispersion of active metals in the catalyst. The more porous nature
of FeNi1 provided larger space for the interactions between reaction
intermediates and active metal sites, which contributed to the higher
activity.
3.3. Carbon materials production with FeNi1 catalyst
SEM images of fresh catalyst particles and the produced carbon
materials are shown in Fig. 3. It can be found the porous structure of the
fresh catalyst in Fig. 3(a). A layer of carbon products was deposited on
the surface of catalyst after experiment, while the density and
morphology of these products varied with the synthesis temperature. At
600 ◦ C, a few flocculent or amorphous fibers were obtained, with the
catalyst surface remained visible. By rising the temperature to 700 or
further to 800 ◦ C, the population density of filamentous carbon was
considerably increased, almost covering the whole catalyst surface.
These filamentous carbons were further investigated by TEM analysis at
high magnifications. Fig. 4(a) shows the morphologies of fresh catalyst
particles, and it can be seen the FeNi particles (dark dots) were uni­
formly dispersed inside the catalyst system, with an average particles
diameter of 15 ~ 20 nm. At synthesis temperature of 600 ◦ C, most
products obtained were amorphous carbon, while only few short carbon
fibers were observed. However, it can be found a high density of carbon
nanotubes grown at the temperature of 700 ◦ C, suggesting that tem­
perature no less than 700 ◦ C was necessary for the effective synthesis of
carbon nanotubes from polypropylene. The multi-walled carbon nano­
tubes were tangled together, making it difficult to identify the diameter
and graphic layers. Some catalyst metals were embedded in the middle
or at the top of tubes, indicating the tip-growth mode of the as-grown
carbon nanotubes with FeNi1 catalyst. Carbon nanotubes produced at
800 ◦ C were more homogeneous, with an external and internal diameter
around 20 ~ 25 and 10 ~ 15 nm, respectively. In addition, the catalyst
particles have changed from spherical in pristine catalyst into conical or
rod-like shape inside the as-grown carbon nanotubes, due to the quasi-
liquid phase of Fe-Ni [20]. Both SEM and TEM observations suggested
that the length of these carbon nanotubes were from hundreds of
nanometers to tens of micrometers. Temperature higher than 800 ◦ C was
not studied in this work, considering the highly energy consumption and
potentially metal particles sintering which may lead to the decrease in
quality of carbon materials [30,31].
Thermal stability of carbon materials was determined by tempera­
ture programmed oxidation analysis, and the plots of weight and de­
rivative weight in relation to oxidation temperature are shown in Fig. 5.
The weight lose between 450 and 700 ◦ C was due to the oxidation of
D. Yao et al. Chemical Engineering Journal xxx (xxxx) xxx

Fig. 2. H2 yield, carbon deposition and gas compositions with (a)-(b) non-catalyst, (c)-(d) FeNi1, and (e)-(f) FeNi2.

5
D. Yao et al. Chemical Engineering Journal xxx (xxxx) xxx

Fig. 3. FESEM analysis of fresh catalyst (a) FeNi1, and spent catalyst (b) FeNi1-600, (c) FeNi1-700, (d) FeNi1-800.

Fig. 4. FETEM analysis of fresh catalyst (a) FeNi1, and carbon materials from (b) FeNi1-600, (c) FeNi1-700, (d) FeNi1-800.

carbon materials while the remaining residue was due to catalyst ma­
terial. Results suggest that carbon products from 600 ◦ C displayed the
lowest yield, while those from high temperature of 800 ◦ C gave the
highest faction. This trend is consistent with the observation by weight
difference of catalyst bed materials before and after experiment as
shown in Table 2, that the production of carbon materials was favored at
high catalysis temperature. The oxidation peaks in derivative weight
plots represent the type of produced carbons, as suggested by reference
[32], that the peak at low oxidation temperature (~520 ◦ C) belongs to
amorphous carbon, while the high oxidation peak (~620 ◦ C) links to
more thermally stable carbon like carbon nanotubes. It can be seen
catalysis temperature of 600 ◦ C generated two oxidization peaks. The
one at around 400 ◦ C may due to the oxidization of heavy hydrocarbons
[33], and the peak around 500 ◦ C was assumed to be related to

6
D. Yao et al. Chemical Engineering Journal xxx (xxxx) xxx

Fig. 5. Temperature programmed oxidation of carbon materials synthesized at different temperature over FeNi1 catalyst.

amorphous carbons. Carbon nanotubes were hardly detected as no
evident peak can be seen around 620 ◦ C. The TPO parameters of the
carbons generated over FeNi1 were summarized in Table 3. Both FeNi1-
700 and FeNi1-800 showed only one degradation step with inflection
temperature around 600 ◦ C, indicating the high crystallinity of carbon
nanomaterials without any amorphous carbon. The onset and end
temperature also moved to high temperatures which was ascribed to
high thermal stability of obtained carbon.
The carbon materials were also studied by Raman spectroscopy,
where the purity and graphitization degree of carbon nanotubes can be
identified from the vibrational modes. As shown in Fig. 6a, the G-band
was associated with the highly ordered graphene layers of carbon
nanotubes, while the D-band was resulted from the impurities in side­
wall structure [34]. ID to IG ratio was therefore used as a quantitative
index to measure the defect density. The Raman spectra of FeNi1-600
was very weak, due to the amorphous nature of the obtained carbon
materials. ID to IG ratio was 1.07 and 0.82 for FeNi1-700 and FeNi1-800
respectively, implying that there were fewer defects in the carbon
nanotubes from the former. The high G’ peak of carbon materials pro­
duced from both 700 and 800 ◦ C indicated that the graphitization degree
were relatively high. Fig. 6b gives the XRD patterns of the fresh and
spent FeNi1 catalysts. The diffraction peaks on fresh catalyst were
almost belong to iron nickel aluminum oxides, as identified by ICDD
#52–1079 with the Fe0.99Ni0.6Al1.1O4 component, implying the inter­
action between active metals Fe/Ni with the alumina support. Iron
aluminum oxides may also exist due to the overlapped pattern. For the
spent catalyst, the diffraction peak at 2θ of 26.23˚was ascribed to the
graphite carbon (0 0 2) as identified by reference #1–075-1621. It can be
seen the peak intensity of the carbon products synthesized at 600˚C was
very weak, whereas it was enhanced significantly at 700 ˚C and was
further intensified at 800˚C, meaning that the graphitization degree of
carbon materials was improved at high synthesis temperature. This was
well aligned with the observations by TPO and TEM that more
homogeneous carbon nanotubes were produced at the maximum tem­
perature investigated. The bimetallic alloy Fe-Ni was identified around
43.50˚according to reference 00–047-1417, implying Fe-Ni alloy was the
active metal composition for the growth of carbon nanotubes. This kind
of bimetallic alloy was reported previously to be more active to generate
carbon nanotubes than monometallic Fe or Ni [17]. In addition,
compared with the iron nickel aluminum oxides as identified from the
fresh catalyst, the bimetallic alloy Fe-Ni in spent catalyst demonstrated
that catalyst has been in situ reduced during the pyrolysis-catalysis
process. The diffraction pattern of catalyst support Al2O3 was also
observed with a broad peak at 66.76˚. The interlayer distance of graphic
layers (d002), and the crystallite size along the c-axis (Lc) of graphic
carbon were determined from the XRD plots, as listed in Table 3. The
d002 values were measured to be 0.345 and 0.346 nm over FeNi1-700
and FeNi1-800 respectively, which are very close to that of desired
graphitic carbon (0.3354 nm). Additionally, the average number of
graphitic layers (N) was calculated by the ratio of Lc to d002 [35]. The N
value increased from 9 to 11 when catalysis temperature increased from
700 to 800 ◦ C, indicating that high temperature contributed to thick
CNTs. It may be due to the fact that high temperature promoted the
decomposition reaction to produce carbon and hence more walls were
formed [36]. Despite the difference in the quality or quantity, Table 3
showed that the specific surface area of carbon materials obtained by
FeNi1 was in the range of 235 ~ 341 m2/g, while it was 104 ~ 139 m2/g
by FeNi2. A slight increase in the specific surface area can be seen as the
increasing temperature. The values were generally higher than those in
literatures, for example 126.1 m2/g in [13] and 44.4 m2/g in [9], where
carbon nanotubes produced by catalytic pyrolysis of waste polyolefin
were used as electro-catalyst and absorbent, respectively. However, the
application and performance of the carbon materials obtained in this
work in different areas will be an interesting topic which needs more
exploration in future work. In addition, the nitrogen adsorp­
tion–desorption isotherms and pore size distribution of the carbon

Table 3
TPO and XRD analysis of as-grown carbon materials on catalysts.
Catalyst- TPO results XRD results Specific surface
temperature area, m2/g
Onset, End, Inflection, Difference, 2 FWHM, d-spacing, Crystallite size, Graphitic layer
◦
C ◦
C ◦
C ◦
C Theta,◦ ◦
d002, nm Lc, nm No., N

FeNi1-600 367 561 453 195 26.29 – – – – 235.15

FeNi1-700 543 650 593 107 25.81 2.48 0.345 3.25 9 303.74
FeNi1-800 552 657 603 105 25.73 2.11 0.346 3.82 11 340.86
FeNi2-600 351 486 422 136 26.14 – – – – 104.89
FeNi2-700 559 667 623 108 26.01 1.93 0.342 4.18 12 138.08
FeNi2-800 550 667 611 117 25.7 1.7 0.346 4.74 14 138.83

7
D. Yao et al. Chemical Engineering Journal xxx (xxxx) xxx

Fig. 6. (a) Raman analysis of carbon materials, (b) XRD pattern of fresh and spent FeNi1 catalyst.

materials were shown in Fig. S1, all the plots displayed the type of IV
isotherm according to the IUPAC classification, implying the meso­
porous structure of the carbon materials.
3.4. Carbon materials production with FeNi2 catalyst
Fig. 7 shows the SEM observations of fresh and spent FeNi2 catalysts.
It can be found the flat and porous surface structure of the fresh FeNi2.
The fracture lines inside particles may due to the calcination process
during the preparation. Quite a lot of flocculent carbons can be seen on
the surface of spent FeNi2 which was operated at 600 ◦ C. However, at
higher temperatures of 700 and 800 ◦ C, very crowed dense of the
entangled filamentous carbons were observed over catalysts. TEM im­
ages in Fig. 8 provide the inner structure of these carbon products. It
shows that FeNi2-600 has various forms of carbons including tubes,
carbon onions, and amorphous carbons. However, the carbon materials
over FeNi2 at the other two catalysis temperatures showed hollow
structure and tangled shape with external diameters from 15 to 50 nm,
with only the difference that those from 700 ◦ C had more impurities. In
addition, compared with FeNi1 which was synthesized by sol gel method
(Fig. 4a), the catalyst particle distribution of the impregnation method
prepared catalyst (Fig. 8a) was less homogeneous, with metal particle
size in the range of 30–100 nm. The diameter of as-obtained carbon
nanotubes was suggested to be highly correlated to the size of catalyst
particle, which explains why the distribution of carbon nanotubes was
more ordered and uniform with FeNi1.
TPO analysis was also performed to determine the type and quality of
the as-obtained carbon materials. The weight loss in Fig. 9, as the result
of combustion of carbon materials, for the FeNi2-600 was only around
10 wt%, which was extremely lower than that of FeNi2-700 and FeNi2-

Fig. 7. FESEM analysis of fresh catalyst (a) FeNi2, and spent catalyst (b) FeNi2-600, (c) FeNi2-700, (d) FeNi2-800.

8
D. Yao et al.
Fig. 8. FETEM analysis of fresh catalyst (a) FeNi2, and carbon materials from (b) FeNi2-600, (c) FeNi2-700, (d) FeNi2-800.
Fig. 9. Temperature programmed oxidation of carbon materials synthesized at different temperature over FeNi2 catalyst.
800 (40 wt%). It agrees with the results in Fig. 2(e) that carbon yield
over FeNi2 catalyst was promoted with the rising temperature. The
derivative profiles showed that a large oxidation peak at 400 ◦ C and a
second small peak around 540 ◦ C were observed for FeNi2-600, which
was due to the combustion of less stable amorphous carbon. The de­
rivative peak moved to high oxidation range above 500 ◦ C for FeNi2-700
and FeNi2-800, implying that with the increase in the catalysis tem­
perature, the fraction of amorphous carbons in the as-obtained carbon
materials was largely decreased. This finding again aligned with the
TEM results that the filamentous carbon nanotubes were dominant
especially at catalysis temperature of 800 ◦ C. The parameters of TPO
plots were summarized in Table 3. The results of carbons from FeNi2-
700 and FeNi2-800 were very similar, indicating the increase of tem­
perature from 700 to 800 ◦ C did not much effect the overall type of
carbon materials. The crystallite properties from XRD analysis of spent
FeNi2 catalyst were also displayed in Table 3. The graphitic layer
9
Chemical Engineering Journal xxx (xxxx) xxx
number and crystallite size of carbon nanotubes increased with the in­
crease of catalysis temperature, which was similar to the case of FeNi1
catalyst as discussed in previous section. It means the high temperature
had an overall thickened effect on the diameter of carbon nanotubes.
For comparison, a number of studies were also performed on the
carbon nanomaterials production from plastic. Jia and colleagues [37]
synthesized the optimum multi-walled carbon nanotubes at a produc­
tion yield of 229 mg/gPE or 220 mg/gPP over a La modified Ni catalyst.
Wang and colleagues [38] investigated the Ni, Ni-Mg and Fe based
cordierite catalyst for the catalytic pyrolysis of polypropylene to
generate carbon nanomaterials. The maximum yield, at around 88 mg/
gPP calculated from TPO profiles, was found to be obtained by Ni cata­
lyst. A group of bimetallic catalysts were invested by Nahil and col­
leagues [39] for catalytic thermal processing of waste polypropylene,
where the yields of carbon nanotubes were in the range from 8 to 23 wt
%. The production yield around 34.39% equivalent to 217 mg/gplastic of
D. Yao et al.
carbon nanotubes was achieved in a study of catalytic conversion of
hard plastics [33]. The yields of carbon nanomaterials from these studies
are much lower than the results obtained in this work.
3.5. Correlations among catalyst, operational temperature and
physiochemical properties of carbon materials
It can be seen, irrespective of the catalyst used, the quantity of car­
bon materials can be considerably improved by the increase of catalysis
temperature. On the one hand, the decomposition reactions was
enhanced by high temperature to generate hydrogen and carbon. On the
other hand, high temperature made the process of carbon dissolution
and precipitation over catalyst particles faster, contributing to the
continuous formation of carbon layers [40,41]. It is worth noting that,
though the yield of carbon was significantly increased by the high
catalysis temperature, the type of carbon nanomaterials were generally
in two categories with boundary at 700 ◦ C. Specifically, carbon mate­
rials obtained at 600 ◦ C were almost amorphous carbon, while the quite
dense carbon nanotubes with very similar carbon thermal stability (by
TPO), purity (by TEM and TPO), as well as graphitization degree (by
Raman) can be found for those at catalysis temperature higher than
700 ◦ C. It is concluded that catalysis temperature of at least 700 ◦ C is
required for the successfully formation of ordered carbon nanotubes.
The reason behind this may because the carbon precursors for the
growth of CNTs was rather insufficient and complicated at low tem­
perature. Fig. 2(b) implies that large molecular hydrocarbon gases took
the majority fraction rather than CH4 in the mixed gases before
encountering with the catalyst particles, whereas the complex carbon
precursors with various C–C intermediates and C–H bonds made the
dissociation and dehydrogenation more difficult to grow graphitic layers
[42,43]. Additionally, as the catalyst in this study was reduced in situ
during the reactions by some reducing gases released from pyrolysis of
polypropylene, the incomplete reduction of catalyst particles due to the
low temperature and insufficient reducing gases make the surface ac­
tivity of FeNi catalyst too low to catalyze the formation of carbon
nanotubes.
In addition, at the same operational conditions, the yields of both
carbon nanotubes and hydrogen, as well as the carbon quality were
lower over the FeNi2 compared with FeNi1. The hydrogen chemisorp­
tion analysis of these two catalysts show that the amount of hydrogen
desorbed was 0.64 and 0.29 mmol/g, for FeNi1 and FeNi2, respectively.
It indicates there were more metallic sites available over FeNi1 for
catalytic decomposition reactions to produce hydrogen and carbon
materials. In addition, the purity and homogeneity of carbon materials
from FeNi1 was slightly higher than those from FeNi2. It was because
FeNi1 had more uniform catalyst particle distribution as observed by
TEM of fresh catalysts. However, both catalysts generated the filamen­
tous carbon nanotubes with high thermal stability and graphitization
degree, as long as the catalysis temperature higher than 700 ◦ C. It
implied that it is the temperature rather than catalyst preparation
method that governed the type of carbon materials (either amorphous or
ordered filamentous carbon nanotubes), though the purity and di­
ameters was related to the dispersion of active metal particles of
catalyst.
4. Conclusions
This work investigated the pyrolysis and catalytic conversion of
polypropylene plastic for the production of high-value carbon materials.
Experiment was conducted in a two-stage reactor system, and the cor­
relations between different catalysis temperatures and the productions
of gas and carbon materials were explored over two FeNi catalysts
prepared by different synthesis method. Results show that non-catalytic
thermal pyrolysis resulted in most liquid products with quite low yield of
gas and negligible solids. The productions of both hydrogen and high
quality carbon nanotubes were promoted over FeNi catalysts by the
10
Chemical Engineering Journal xxx (xxxx) xxx
enhanced catalytic decomposition reactions, when catalysis tempera­
ture increased from 600 to 800 ◦ C. Regarding the physiochemical
properties of carbon materials, a large number of amorphous carbons
can be found at the low catalysis temperature, as a result of the
complicated hydrocarbon gases and the low catalyst activity at this
condition. Catalysis temperature higher than 700 ◦ C generated carbon
materials with the majority carbon nanotubes with much similar prop­
erties of thermal stability and graphitization degree, as observation by
electron microcopy and Raman. XRD analysis suggested the increase of
catalysis temperature thickened the graphitic layers. The FeNi1 catalyst
prepared by sol-gel method showed higher activity to produce carbon
materials with few defects and high uniformity than FeNi2 prepared by
conventional impregnation method.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This research is supported by the National Research Foundation,
Prime Minister’s Office, Singapore under its Campus for Research
Excellence and Technological Enterprise (CREATE) programme No. R-
706-001-102-281.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2020.127268.
References
[1] Plastics – the Facts 2019, Plastic Europe (2019).
[2] R. Geyer, J.R. Jambeck, K.L. Law, Production, use, and fate of all plastics ever
made, Sci. Adv. 3 (2017), e1700782.
[3] C. Cao, C. Bian, G. Wang, B. Bai, Y. Xie, H. Jin, Co-gasification of plastic wastes and
soda lignin in supercritical water, Chem. Eng. J. 388 (2020), 124277.
[4] K. Ragaert, L. Delva, K. Van Geem, Mechanical and chemical recycling of solid
plastic waste, Waste Manage. 69 (2017) 24–58.
[5] A.K. Panda, R.K. Singh, D.K. Mishra, Thermolysis of waste plastics to liquid fuel: A
suitable method for plastic waste management and manufacture of value added
products—A world prospective, Renew. Sustain. Energy Rev. 14 (2010) 233–248.
[6] S. Jung, D. Choi, Y.-K. Park, Y.F. Tsang, N.B. Klinghoffer, K.-H. Kim, E.E. Kwon,
Functional use of CO2 for environmentally benign production of hydrogen through
catalytic pyrolysis of polymeric waste, Chem. Eng. J. 399 (2020), 125889.
[7] I. Barbarias, G. Lopez, J. Alvarez, M. Artetxe, A. Arregi, J. Bilbao, M. Olazar,
A sequential process for hydrogen production based on continuous HDPE fast
pyrolysis and in-line steam reforming, Chem. Eng. J. 296 (2016) 191–198.
[8] A.A. Aboul-Enein, A.E. Awadallah, Production of nanostructured carbon materials
using Fe–Mo/MgO catalysts via mild catalytic pyrolysis of polyethylene waste,
Chem. Eng. J. 354 (2018) 802–816.
[9] Y. Zheng, H. Zhang, S. Ge, J. Song, J. Wang, S. Zhang, Synthesis of Carbon
Nanotube Arrays with High Aspect Ratio via Ni-Catalyzed Pyrolysis of Waste
Polyethylene, Nanomaterials 8 (2018) 556.
[10] 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
Nanotubes, Environ. Sci. Technol. 48 (2014) 819–826.
[11] A. Bazargan, G. McKay, A review - Synthesis of carbon nanotubes from plastic
wastes, Chem. Eng. J. 195–196 (2012) 377–391.
[12] N. Borsodi, A. Szentes, N. Miskolczi, C. Wu, X. Liu, Carbon nanotubes synthetized
from gaseous products of waste polymer pyrolysis and their application, J. Anal.
Appl. Pyrol. 120 (2016) 304–313.
[13] N. Cai, S. Xia, X. Zhang, Z. Meng, P. Bartocci, F. Fantozzi, Y. Chen, H. Chen, P.
T. Williams, H. Yang, Preparation of Iron- and Nitrogen-Codoped Carbon
Nanotubes from Waste Plastics Pyrolysis for the Oxygen Reduction Reaction,
ChemSusChem 13 (2020) 938–944.
[14] A. Ahamed, A. Veksha, K. Yin, P. Weerachanchai, A. Giannis, G. Lisak,
Environmental impact assessment of converting flexible packaging plastic waste to
pyrolysis oil and multi-walled carbon nanotubes, J. Hazard. Mater. 390 (2020),
121449.
[15] R.-X. Yang, S.-L. Wu, K.-H. Chuang, M.-Y. Wey, Co-production of carbon nanotubes
and hydrogen from waste plastic gasification in a two-stage fluidized catalytic bed,
Renewable Energy 159 (2020) 10–22.
D. Yao et al.
[16] X. Liu, Y. Zhang, M.A. Nahil, P.T. Williams, C. Wu, Development of Ni- and Fe-
based catalysts with different metal particle sizes for the production of carbon
nanotubes and hydrogen from thermo-chemical conversion of waste plastics,
J. Anal. Appl. Pyrol. 125 (2017) 32–39.
[17] W.-H. Chiang, R.M. Sankaran, Synergistic Effects in Bimetallic Nanoparticles for
Low Temperature Carbon Nanotube Growth, Adv. Mater. 20 (2008) 4857–4861.
[18] A.A. Aboul-Enein, F.S. Soliman, M.A. Betiha, Co-production of hydrogen and
carbon nanomaterials using NiCu/SBA15 catalysts by pyrolysis of a wax by-
product: Effect of Ni–Cu loading on the catalytic activity, Int. J. Hydrogen Energy
44 (2019) 31104–31120.
[19] D. Yao, C. Wu, H. Yang, Y. Zhang, M.A. Nahil, Y. Chen, P.T. Williams, H. Chen, Co-
production of hydrogen and carbon nanotubes from catalytic pyrolysis of waste
plastics on Ni-Fe bimetallic catalyst, Energy Convers. Manage. 148 (2017)
692–700.
[20] D. Yao, C.-H. Wang, Pyrolysis and in-line catalytic decomposition of polypropylene
to carbon nanomaterials and hydrogen over Fe- and Ni-based catalysts, Appl.
Energy 265 (2020), 114819.
[21] D. Ayillath Kutteri, I.W. Wang, A. Samanta, L. Li, J. Hu, Methane decomposition to
tip and base grown carbon nanotubes and COx-free H2 over mono- and bimetallic
3d transition metal catalysts, Catalysis, Science & Technology 8 (2018) 858–869.
[22] A. Veksha, A. Giannis, V.-W.-C. Chang, Conversion of non-condensable pyrolysis
gases from plastics into carbon nanomaterials: Effects of feedstock and
temperature, J. Anal. Appl. Pyrol. 124 (2017) 16–24.
[23] J. Guo, S. Moo, A. Veksha, W.-D. Oh, A. Giannis, W.D. Chanaka Udayanga, S.-
X. Lin, L. Ge, G. Lisak, Plastic derived carbon nanotubes for electrocatalytic oxygen
reduction reaction: Effects of plastic feedstock and synthesis temperature,
Electrochem. Commun. 101 (2019) 11–18.
[24] D. Yao, H. Yang, H. Chen, P.T. Williams, Co-precipitation, impregnation and so-gel
preparation of Ni catalysts for pyrolysis-catalytic steam reforming of waste plastics,
Appl. Catal. B 239 (2018) 565–577.
[25] D. Yao, H. Yang, Q. Hu, Y. Chen, H. Chen, P.T. Williams, Carbon nanotubes from
post-consumer waste plastics: Investigations into catalyst metal and support
material characteristics, Appl. Catal. B 280 (2021), 119413.
[26] S. Natesakhawat, O. Oktar, U.S. Ozkan, Effect of lanthanide promotion on catalytic
performance of sol–gel Ni/Al2O3 catalysts in steam reforming of propane, J. Mol.
Catal. A: Chem. 241 (2005) 133–146.
[27] Q. Hu, Z. Tang, D. Yao, H. Yang, J. Shao, H. Chen, Thermal behavior, kinetics and
gas evolution characteristics for the co-pyrolysis of real-world plastic and tyre
wastes, J. Cleaner Prod. 260 (2020), 121102.
[28] G. Lopez, M. Artetxe, M. Amutio, J. Bilbao, M. Olazar, Thermochemical routes for
the valorization of waste polyolefinic plastics to produce fuels and chemicals, A
review, Renewable Sustain. Energy Rev. 73 (2017) 346–368.
11
Chemical Engineering Journal xxx (xxxx) xxx
[29] A.-C. Dupuis, The catalyst in the CCVD of carbon nanotubes—a review, Prog. Mater
Sci. 50 (2005) 929–961.
[30] D. Yao, Y. Zhang, P.T. Williams, H. Yang, H. Chen, Co-production of hydrogen and
carbon nanotubes from real-world waste plastics: Influence of catalyst composition
and operational parameters, Appl. Catal. B 221 (2018) 584–597.
[31] Y.-H. Chung, S. Jou, Carbon nanotubes from catalytic pyrolysis of polypropylene,
Mater. Chem. Phys. 92 (2005) 256–259.
[32] D. Xu, Y. Xiong, J. Ye, Y. Su, Q. Dong, S. Zhang, Performances of syngas production
and deposited coke regulation during co-gasification of biomass and plastic wastes
over Ni/γ-Al2O3 catalyst: Role of biomass to plastic ratio in feedstock, Chem. Eng.
J. 392 (2020), 123728.
[33] X. Gou, D. Zhao, C. Wu, Catalytic conversion of hard plastics to valuable carbon
nanotubes, J. Anal. Appl. Pyrol. 145 (2020), 104748.
[34] K.A. Wepasnick, B.A. Smith, J.L. Bitter, D. Howard Fairbrother, Chemical and
structural characterization of carbon nanotube surfaces, Anal. Bioanal. Chem. 396
(2010) 1003–1014.
[35] A.A. Aboul-Enein, A.E. Awadallah, Production of nanostructure carbon materials
via non-oxidative thermal degradation of real polypropylene waste plastic using
La2O3 supported Ni and Ni–Cu catalysts, Polym. Degrad. Stab. 167 (2019)
157–169.
[36] M. Kumar, Y. Ando, Chemical Vapor Deposition of Carbon Nanotubes: A Review on
Growth Mechanism and Mass Production, J. Nanosci. Nanotechnol. 10 (2010)
3739–3758.
[37] J. Jia, A. Veksha, T.-T. Lim, G. Lisak, In situ grown metallic nickel from X-Ni
(X=La, Mg, Sr) oxides for converting plastics into carbon nanotubes: Influence of
metal–support interaction, J. Cleaner Prod. 258 (2020), 120633.
[38] J. Wang, B. Shen, M. Lan, D. Kang, C. Wu, Carbon nanotubes (CNTs) production
from catalytic pyrolysis of waste plastics: The influence of catalyst and reaction
pressure, Catal. Today 351 (2020) 50–57.
[39] M.A. Nahil, C. Wu, P.T. Williams, Influence of metal addition to Ni-based catalysts
for the co-production of carbon nanotubes and hydrogen from the thermal
processing of waste polypropylene, Fuel Process. Technol. 130 (2015) 46–53.
[40] D. Li, L. Dashuai, T. Ling, G. Bo, Synthesis of Multiwalled Carbon Nanotubes on
Stainless Steel by Atmospheric Pressure Microwave Plasma Chemical Vapor
Deposition, Appl. Sci. 10 (2020).
[41] P.T. Williams, Hydrogen and Carbon Nanotubes from Pyrolysis‑Catalysis of Waste
Plastics: A Review, Waste and Biomass Valorization (2020).
[42] M.I. Kairi, M. Khavarian, S.A. Bakar, B. Vigolo, A.R. Mohamed, Recent trends in
graphene materials synthesized by CVD with various carbon precursors, J. Mater.
Sci. 53 (2018) 851–879.
[43] K.A. Shah, B.A. Tali, Synthesis of carbon nanotubes by catalytic chemical vapour
deposition: A review on carbon sources, catalysts and substrates, Mater. Sci.
Semicond. Process. 41 (2016) 67–82.