nanomaterials

Article
Catalytic Preparation of Carbon Nanotubes from
Waste Polyethylene Using FeNi
Bimetallic Nanocatalyst
Kezhuo Li 1 , Haijun Zhang 1, * , Yangfan Zheng 1 , Gaoqian Yuan 1 , Quanli Jia 2 and
Shaowei Zhang 3, *
1 The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology,
Wuhan 430081, China; likezhuo0206@163.com (K.L.); 15671628617@163.com (Y.Z.);
yuangaoqian@126.com (G.Y.)
2 Henan Key Laboratory of High Temperature Functional Ceramics, Zhengzhou University, 75 Daxue Road,
Zhengzhou 450052, China; jiaquanli@zzu.edu.cn
3 College of Engineering, Mathematics and Physical Sciences, University of Exeter, Exeter EX4 4QF, UK
* Correspondence: zhanghaijun@wust.edu.cn (H.Z.); s.zhang@exeter.ac.uk (S.Z.);
Tel.: +86-27-68862829 (H.Z); +44-7710166727 (S.Z.)




Received: 15 July 2020; Accepted: 28 July 2020; Published: 3 August 2020


Abstract: In this work, carbon nanotubes (CNTs) were synthesized by catalytic pyrolysis from waste
polyethylene in Ar using an in-situ catalyst derived from ferric nitrate and nickel nitrate precursors.
The influence factors (such as temperature, catalyst content and Fe/Ni molar ratio) on the formation of
CNTs were investigated. The results showed that with the temperature increasing from 773 to 1073 K,
the carbon yield gradually increased whereas the aspect (length-diameter) ratio of CNTs initially increased
and then decreased. The optimal growth temperature of CNTs was 973 K. With increasing the Fe/Ni
molar ratio in an FeNi bimetallic catalyst, the yield of CNTs gradually increased, whereas their aspect
ratio first increased and then decreased. The optimal usage of the catalyst precursor (Fe/Ni molar ratio
was 5:5) was 0.50 wt% with respect to the mass of polyethylene. In this case, the yield of CNTs reached as
high as 20 wt%, and their diameter and length were respectively 20–30 nm, and a few tens of micrometers.
The simple low-cost method developed in this work could be used to address the environmental concerns
about plastic waste, and synthesize high value-added CNTs for a range of future applications.

Keywords: carbon nanotubes; waste polyethylene; ferric nitrate; nickel nitrate; catalytic pyrolysis

1. Introduction
As a lightweight, waterproof, and corrosion resistant material, plastic is widely used in almost every
aspect of human society, contributing considerably to the economic growth and social sustainability [1].
However, the consistent increase in the accumulation of discarded plastics causes serious pollution to
the environment due to their non-biodegradable nature under ambient conditions [2–4]. Currently,
landfill and incineration are mainly used to dispose plastic waste, but they are becoming less and
less acceptable due to their many demerits, e.g., waste of land and secondary pollution [5,6]. Hence,
exploring a simple, low-cost and sustainable way to recycle plastic waste to form high value-added
products, though very challenging, is of technical importance.
Carbon materials such as graphite, graphene and carbon nanotubes (CNTs) have attracted a lot of
attention [7–16]. Among them, the last one, which possesses excellent properties such as low density,
high tensile strength, high elastic modulus, and high thermal conductivity (>3000 W·m−1 ·K−1 ) [14–16],
is used in the fields of composite materials [17], solar cells [18] and optical devices [19]. CNTs can be
synthesized by arc discharge [20], flame synthesis [21], microwave-assisted synthesis [22], chemical

Nanomaterials 2020, 10, 1517; doi:10.3390/nano10081517 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 1517 2 of 12

vapor deposition [23], and catalytic pyrolysis [24], among which, the last one has proved promising.
With this method, polyolefin, which has a high carbon content, is usually used as the carbon source
because the plastic waste is mostly hydrocarbon polymers [25–30]. This will not only enable the low
cost production of novel CNTs but also address the above-mentioned issues caused by plastic waste
accumulation and the conventional dumping methods.
In the plastic decomposition and carbon deposition process, the catalyst used plays a crucial role, which
determines the morphology and structure of CNTs [31–33]. Conventional catalysts for the preparation
of CNTs mainly include metallic iron, cobalt, nickel, and their compounds [34–36]. And bimetallic and
polymetallic catalysts often perform better compared with monometallic counterparts. For example, by using
Ni(NO3 )2 ·0.6H2 O, Mg(NO3 )2 ·6H2 O and (NH3 )6 Mo7 O24 ·0.4H2 O as catalyst precursors, and PEG200 as
a solvent, Song et al. [25] firstly prepared Ni/Mo/MgO catalyst powders by a combustion method at
923 K, then prepared straight and double-helix multi-wall carbon nanotubes (MWNTs) respectively with
diameters of about 30 and 60 nm from polypropylene powder under the role of the catalysts at 1123 K.
Yang et al. [37] prepared Ni-Cu/MgO and Ni/MgO catalyst powders by sol-gel method from Ni(NO3 )2 ·6H2 O,
Mg(NO3 )2 ·6H2 O and Cu(NO3 )2 ·3H2 O catalyst precursor, then used them to synthesize CNTs via thermal
chemical vapor deposition method. They found that when Ni-Cu/MgO was used as a catalyst, the yield of
CNTs was significantly higher than that used Ni/MgO, indicating that the incorporation of Cu enhanced
the catalytic activity of Ni. By using a similar process, Baba et al. [38] firstly prepared CoO-MoO3 /MgO
catalyst powder from Co(CH3 COO)2 ·4H2 O, Mg(CH3 COO)2 ·4H2 O and (NH3 )6 Mo7 O24 ·4H2 O, then CNTs
with "bamboo-like" structure were successfully formed from ethylene by using the catalyst at 923–1043 K.
The combination of Mo with Co increased the carbon yield by about 20 times. Despite these positive results,
there are still some problems with the catalytic pyrolysis processes, which need to be overcome, including,
e.g., (1) the preparation process of bimetallic catalyst was complex, (2) relatively expensive catalysts were
used and the overall production cost was high, and (3) the yield of CNTs was relatively low.
In addition, it is well known that CNTs prepared using Ni as catalyst have the advantages of
high graphitization degree and good thermal stability, while Fe as catalyst has high catalytic activity
and carbon solubility. Studies have also shown that the FeNi bimetallic catalysts had higher catalytic
activity for catalytic pyrolysis of plastics due to the synergistic effect among components [39,40].
In the present work, CNTs were prepared from low cost waste polyethylene using inexpensive iron
nitrate and nickel nitrate as catalyst precursors via simple catalytic pyrolysis method. The influence
parameters of pyrolysis temperature, catalyst content and Fe/Ni molar ratio on the formation of CNTs
were investigated.

2. Materials and Methods

2.1. Raw Materials

Powdery waste polyethylene (PE, ≥97.0%) was purchased from Shanghai Runwen Material
Co. Ltd. (Shanghai, China). Commercial nickel nitrate (Ni(NO3 )2 ·6H2 O, analytically pure) and ferric
nitrate (Fe(NO3 )3 ·9H2 O, analytically pure) supplied by Shanghai Sinopharm Chem. Co. Ltd. (Shanghai,
China) were used as catalyst precursors. All the reagents were used directly. At the same time, it has
been shown that the use of nitrate or chloride as catalyst precursors has no significant effect on the
formation of CNTs in our previous work [6].

2.2. Sample Preparation

The process of CNTs preparation is as follows: Initially, nickel nitrate and ferric nitrate were
dissolved respectively into 10 mL anhydrous ethanol. Next, they were combined in pairs in different
molar ratios (the molar ratio of Fe/Ni was 10/0, 8/2, 6/4, 5/5, 4/6, 2/8 and 0/10, respectively) at room
temperature (298 K) under vigorous agitation by a magnetic stirrer. The resultant solution was slowly
dripped into the powdery waste polyethylene (the catalyst content was respectively 0.25, 0.50, 0.75 and
1.00 wt% of the weight of polyethylene) along the cup wall via equal volume method. Subsequently,
Nanomaterials 2020, 10, 1517 3 of 12

the waste polyethylene powder loaded with different catalysts precursors was obtained after 12 h
drying at room temperature. Finally, the composite powder was subjected to 2 h heat treatment at 773,
873, 973, and 1073 K (the heating rate was 5 K/min) in an alumina-tube furnace, and the shielding gas
was flowing argon (99.999 vol% purity).

2.3. Sample Characterization

The following equation was used to calculate the yield of carbon after the pyrolysis of waste
polyethylene:
( m2 − m3 ) − m4
C = 1− × 100%
( m1 − m4 )
where, C is residual carbon rate, m1 is the weight of composite powder, m2 is the total weight of
composite powder and alumina crucibles before pyrolysis, m3 is the total weight of composite powder
and alumina crucibles after pyrolysis, m2 –m3 is the weight loss of waste polyethylene precursor before
and after pyrolysis, and m4 is the weight of adding Fe/Ni catalyst theoretically.
Phases in as-prepared samples were analyzed by X-ray powder diffraction (XRD) using a Philips
X’Pert Pro diffractometer (PANalytical, Hillsboro, The Netherlands). The XRD spectra were recorded in
the range from 10◦ to 90◦ (2θ) with a scanning rate of 2◦ /min, at 40 mA and 40 kV, using Cukα radiation
(λ = 0.1542 nm). Microstructure and phase morphologies of as-prepared samples were observed by
means of a scanning electron microscope (SEM; Nova400NanoSEM, 15 kV, Amsterdam, Netherlands),
a transmission electron microscope (TEM; JEM-2100UHRSTEM, 200 kV, Tokyo, Japan) with an energy
dispersive spectrometer (EDS, Penta FET X-3 Si (Li)), and a high-resolution TEM (HRTEM; JEM-3010,
300 kV). N2 adsorption-desorption isotherms were examined on an automatic surface area and pore
size analyzer (Autosorb-1, Quantachrome Instruments, Boynton Beach, FL, USA). The surface area
was calculated from the adsorption branch of the isotherms using non-local density functional theory,
and pore size distribution was calculated using Barrett–Joyner–Halanda model.

3. Results and Discussion

3.1. Effects of Pyrolysis Temperature on the Growth of CNTs

Figure 1 shows XRD patterns of samples obtained at 773–1073 K using 0.50 wt% Fe50 Ni50 (the molar
ratio of Fe/Ni was 5/5) bimetallic catalysts. At 773 K, a broad diffraction peak appeared at around
26◦ (2θ), indicating the formation of graphitic carbon in the sample. Furthermore, at 44.2 and 51.5◦ ,
two weak diffraction peaks were observed, respectively belonging to the (111) and (200) planes of
FeNi3 (ICDD card: No. 03-065-3244). As the pyrolysis temperature increased to 873 K, the peak height
of graphitic carbon increased evidently. With further increasing the pyrolysis temperature to 973 K,
the diffraction peak (about 26◦ ) of graphitic carbon became the sharpest, and well matched to the
characteristic (002) plane of graphite (ICDD card: No. 01-075-1621), revealing the highest graphitization
degree of the carbon. However, the pyrolysis temperature further increasing to 1073 K led to the peak
height of the carbon decreased slightly. The above results suggested that under the test conditions,
973 K was the optimal temperature for CNTs formation.
Presented in Figure 2 are SEM images of samples whose XRD patterns are displayed in Figure 1,
demonstrating significant effects of the temperature on the phase morphology. At 773 K, a relatively
small number of short CNTs were generated (Figure 2a). When the pyrolysis temperature increased to
873 K, the yield and lengths of CNTs increased (Figure 2b). Upon the pyrolysis temperature further
increasing to 973 K, many more CNTs with relatively small diameters of about 20 nm and lengths of a
few tens of micrometers were formed (Figure 2c). However, while the pyrolysis temperature further
increased to 1073 K, thicker and shorter CNTs were obtained, which might be due to the relatively
high temperatures that cause the catalyst particles to aggregate (Figure 2d). The SEM observations
in Figure 2 conclude that the optimal formation temperature of CNTs was at 973 K, which was in
agreement with that suggested by the XRD presented in Figure 1.
 Nanomaterials
Nanomaterials 2020, 2020, 10,
10, x FOR PEER1517 REVIEW 4 of 12 4 of 11

Figure 1. XRD patterns of samples prepared at different pyrolysis temperatures, with 0.50 wt%
Fe50Ni50 bimetallic catalysts.

Presented in Figure 2 are SEM images of samples whose XRD patterns are displayed in Figure
1, demonstrating significant effects of the temperature on the phase morphology. At 773 K, a
relatively small number of short CNTs were generated (Figure 2a). When the pyrolysis temperature
increased to 873 K, the yield and lengths of CNTs increased (Figure 2b). Upon the pyrolysis
temperature further increasing to 973 K, many more CNTs with relatively small diameters of about
20 nm and lengths of a few tens of micrometers were formed (Figure 2c). However, while the
pyrolysis temperature further increased to 1073 K, thicker and shorter CNTs were obtained, which
might be due to the relatively high temperatures that cause the catalyst particles to aggregate (Figure
2d). The SEM
Figureobservations
1. XRD patternsin
of Figure
samples 2 conclude
prepared that the
at different optimal
pyrolysis formation
temperatures, temperature
with 0.50 wt% Fe50of CNTs was
Ni50
Figure 1. XRD patterns
at 973 K, bimetallic
which was of samples prepared at different pyrolysis temperatures,
in agreement with that suggested by the XRD presented in Figure 1.
catalysts.
with 0.50 wt%
Fe50Ni50 bimetallic catalysts.

Presented in Figure 2 are SEM images of samples whose XRD patterns are displayed in Figure
1, demonstrating significant effects of the temperature on the phase morphology. At 773 K, a
relatively small number of short CNTs were generated (Figure 2a). When the pyrolysis temperature
increased to 873 K, the yield and lengths of CNTs increased (Figure 2b). Upon the pyrolysis
temperature further increasing to 973 K, many more CNTs with relatively small diameters of about
20 nm and lengths of a few tens of micrometers were formed (Figure 2c). However, while the
pyrolysis temperature further increased to 1073 K, thicker and shorter CNTs were obtained, which
might be due to the relatively high temperatures that cause the catalyst particles to aggregate (Figure
2d). The SEM observations in Figure 2 conclude that the optimal formation temperature of CNTs was
at 973 K, which was in agreement with that suggested by the XRD presented in Figure 1.

Figure 2. SEM
Figure images
2. SEM of samples
images obtained
of samples with
obtained with0.50
0.50wt%
wt%Fe
Fe5050Ni
Ni5050bimetallic
bimetallic catalysts at:(a)
catalysts at: (a)773
773K,K, (b)
(b)(c)
873 K, 873973
K, (c)
K, 973
andK,(d)
and (d) K.
1073 1073 K.

3.2. Effects of Catalyst Amount on the Growth of CNTs

3.2. Effects of Catalyst Amount on the Growth of CNTs
XRD patterns of the samples fired at 973 K corresponding to different amounts of Fe50 Ni50
XRD patterns
bimetallic of are
catalysts theshown
samples fired 3,
in Figure atindicating
973 K corresponding
that the amounttoofdifferent amounts
catalysts had only a of Fe50Ni50
minor
bimetallic catalysts are shown in Figure 3, indicating that the amount of catalysts had
effect on the phase formation in the product. When 0.25 wt% Fe50 Ni50 bimetallic catalysts was added, only a minor
effecta broad
on thecarbon
phasediffraction
formationpeak
in the product.
appeared When 26
at around ◦
0.25(2θ)
wt% andFetwo
50Niweak
50 bimetallic catalysts
diffraction peaks ofwas added,
FeNi 3
a broad
werecarbon diffraction
also seen. peak appeared
With increasing at around
the catalyst 26°0.50
content to (2θ) andthe
wt%, two weakdiffraction
carbon diffraction peaks
peak of FeNi3
became
weresharper and With
also seen. narrower. With further
increasing increasing
the catalyst the catalyst
content to 0.50content
wt%, to the0.75 wt%, diffraction
carbon the carbon diffraction
peak became
peak almost did not change. When the catalyst content was finally
sharper and narrower. With further increasing the catalyst content to 0.75 wt%, increased to 1.00
thewt%, the carbon
carbon diffraction
diffraction peak decreased significantly. Thus, it can be reasonably concluded that the optimal catalyst
amount required for CNTs formation was 0.50–0.75 wt%.

Figure 2. SEM images of samples obtained with 0.50 wt% Fe50Ni50 bimetallic catalysts at: (a) 773 K, (b)
Nanomaterials 2020, did
peak almost 10, xnot
FORchange.
PEER REVIEW 5 of 11
When the catalyst content was finally increased to 1.00 wt%, the carbon
diffraction peak decreased significantly. Thus, it can be reasonably concluded that the optimal
peak almostamount
catalyst did notrequired
change.for When
CNTsthe catalystwas
formation content was wt%.
0.50–0.75 finally increased to 1.00 wt%, the carbon
diffraction peak decreased significantly. Thus, it can be reasonably concluded that the optimal
Nanomaterials 2020, 10, 1517 5 of 12
catalyst amount required for CNTs formation was 0.50–0.75 wt%.

Figure 3. XRD patterns of samples obtained with various amounts of Fe50Ni50 bimetallic catalysts at
973 K.

Figure
Figure 3. XRD4 gives
Figure SEM
3. XRD
patterns ofimages
samplesofobtained
patterns the samples
of samples obtained whose
with various amounts
with various XRDof Fe50patterns
amounts of Fe50areNi50presented
Ni50 bimetallic catalysts at 973 K. in Figure 3,
bimetallic catalysts at
revealing the generation of CNTs with fine diameters in the samples, and the content of Fe50Ni50
973 K. Figure 4 gives SEM images of the samples whose XRD patterns are presented in Figure 3, revealing
bimetallic catalysts
the generation has
of a great
CNTs influence
with on CNTs
fine diameters yield.
in the As evidenced
samples, and the contentby Figure
of Fe50 Ni4a, an extremely few
50 bimetallic
number catalysts
of CNTshas were detected
a great influence inonthe sample
yield.using 0.25 wt%Figure Fe50Ni4a, bimetallic
extremelycatalysts. However,
of CNTs As evidenced
whose by
50 an few number
Figure 4 gives SEM images the samples XRD patterns are presented in Figure 3,
as the content of the catalyst increased to 0.50 wt%, many
of CNTs were detected in the sample using 0.25 wt% Fe 50 Ni50more CNTs with smaller diameters and
bimetallic catalysts. However, as the
revealing the generation
content of CNTs with to 0.50fine diameters in the samples, and the andcontent of Fe50Ni50
lengths up to aoffew
the catalyst
tens ofincreased
micrometers wt%,
weremany more CNTs
generated with
(Figure smaller
4b). With diameters
the content lengths
of Fe50Ni50
bimetallic catalysts
up to a fewhastensaofgreat influence
micrometers were on CNTs(Figure
generated yield.4b).
AsWithevidenced
the contentbyofFigure
Fe50 Ni504a, an extremely few
bimetallic
bimetallic catalysts further increasing to 0.75 wt%, the CNTs were bent and intertwined despite
number catalysts
of CNTs further
were increasing
detected to 0.75
in the wt%, the
sample CNTs
usingwere bent
0.25was and
wt% intertwined
Fe50Ni despite increase in yield
50 bimetallic catalysts. However,
increase in yield (Figure 4c). When the catalyst content finally increased
(Figure 4c). When the catalyst content was finally increased to 1.00 wt%, short and thick CNTs were to 1.00 wt%, short and
as the content
thick CNTs
formed
of the
were catalyst
and formed
entangledand
increased
entangled
together
to 0.50
together
(Figure 4d).
wt%, many
(Figure
These results
more
4d). These
demonstrated
CNTs with
results
that
smaller
demonstrated
the addition
diameters
of 0.50 wt% that the
and
lengths up Fe
addition to a 50
few
of500.50
Ni wt% tensFe50of
bimetallic Nimicrometers
50 bimetallic
catalysts wereforgenerated
catalysts
was best suitable was of(Figure
CNTs. for4b).
best suitable
the growth the With
growth theof content
CNTs. of Fe50Ni50
bimetallic catalysts further increasing to 0.75 wt%, the CNTs were bent and intertwined despite
increase in yield (Figure 4c). When the catalyst content was finally increased to 1.00 wt%, short and
thick CNTs were formed and entangled together (Figure 4d). These results demonstrated that the
addition of 0.50 wt% Fe50Ni50 bimetallic catalysts was best suitable for the growth of CNTs.

Figure 4.Figure
SEM4. images of samples
SEM images obtained
of samples obtained at 973KKwith
at 973 with various
various amounts
amounts of Fe50of
Ni50Febimetallic
50Ni50 bimetallic

catalysts:catalysts:
(a) 0.25(a) 0.25 wt%,
wt%, (b) 0.50
(b) 0.50 wt%,wt%,
(c)(c) 0.75wt%
0.75 wt% and
and (d)
(d)1.00 wt%.
1.00 wt%.

3.3. Effects of Fe/Ni molar Ratio on the Growth of CNTs

Figure 5 presents XRD patterns of samples fired at 973 K versus the molar ratio of Fe/Ni in FeNi
catalyst
Figure (0.50 wt%
4. SEM was used),
images revealing
of samples the effect
obtained of the
at 973 lattervarious
K with on the amounts
phase composition.
of Fe50Ni50 When iron
bimetallic
only was added as the catalyst, graphite carbon, iron and iron carbide were present as the primary
 Nanomaterials 2020, 10, 1517 6 of 12
Nanomaterials 2020, 10, x FOR PEER REVIEW 6 of 11

3.3. Effects of Fe/Ni molar Ratio on the Growth of CNTs

phases, and when nickel only was used as the catalyst, poorly crystalline graphitic carbon (indicated
Figure 5 presents XRD patterns of samples fired at 973 K versus the molar ratio of Fe/Ni in FeNi
by the broad peak at 26° (2θ)), along with Ni was detected. On the other hand, when the FeNi catalyst
catalyst (0.50 wt% was used), revealing the effect of the latter on the phase composition. When iron
was used, graphitic
only was addedcarbon
as the(ICDD
catalyst, card: No.
graphite 01-075-1621)
carbon, iron and ironbecame thepresent
carbide were dominant crystalline phase,
as the primary
along with phases,
FeNi3 and
(ICDD whencard:
nickel only
No.was used as the catalyst,
03-065-3244) and Fe poorly
2O3 crystalline
(ICDD card:graphitic
No.carbon (indicated byIn addition,
00-001-1053).
the broad peak at 26◦ (2θ)), along with Ni was detected. On the other hand, when the FeNi catalyst was
with the Fe/Ni molar ratio in the catalyst increasing from 2/8 to 8/2, the graphitic carbon initially
used, graphitic carbon (ICDD card: No. 01-075-1621) became the dominant crystalline phase, along
increased but
withthen
FeNi3decreased.
(ICDD card: No.Moreover, the
03-065-3244) andhighest graphitic
Fe2 O3 (ICDD card: No.carbon peakInwas
00-001-1053). seenwith
addition, in the case of
using the catalyst
the Fe/Niwith
molarthe
ratioFe/Ni molarincreasing
in the catalyst ratio of 5/5,
from implying
2/8 to 8/2, thethe highest
graphitic graphitization
carbon degree of the
initially increased
but then decreased. Moreover, the highest graphitic carbon peak was seen in the case of using the
carbon. These results suggested that the Fe/Ni molar ratio of 5/5 was best suitable for the formation
catalyst with the Fe/Ni molar ratio of 5/5, implying the highest graphitization degree of the carbon.
of CNTs. These results suggested that the Fe/Ni molar ratio of 5/5 was best suitable for the formation of CNTs.

Figure 5. XRD patterns of product samples obtained at 973 K for 2 h, using 0.50 wt% Fe or Ni single
Figure 5. XRD patterns of product samples obtained at 973 K for 2 h, using 0.50 wt% Fe or Ni single
metal catalyst and FeNi bimetallic catalyst (Fe/Ni molar ratio between 2/8 and 8/2, in total 0.50 wt%).
metal catalyst and FeNi bimetallic catalyst (Fe/Ni molar ratio between 2/8 and 8/2, in total 0.50 wt%).
Figure 6 shows SEM images of the samples whose XRD patterns are presented in Figure 5, demonstrating
the significant influence of the Fe/Ni molar ratio on the CNTs morphology. A few short and thick CNTs
Figure 6 shows SEM images of the samples whose XRD patterns are presented in Figure 5,
were generated when using 0.50 wt% iron catalyst (Figure 6a), whereas much curved CNTs were formed
demonstrating the significant
and entangled together wheninfluence
using 0.50 of
wt%the Fe/Ni
nickel molar
catalyst (Figure ratio onFe/Ni
6b). With themolar
CNTsratiomorphology.
increasing A few
short and thick CNTs
from 2/8 to 4/6,were generated
there was when
no obvious using
formation 0.50 inwt%
of CNTs iron catalyst
the sample (Figure
(Figure 6c,d). 6a),upon
However, whereas much
increasing the molar ratio of Fe/Ni to 5/5, a large number of CNTs with diameters of 20–30 nm and lengths
curved CNTs were formed and entangled together when using 0.50 wt% nickel catalyst (Figure 6b).
of a few tens of micrometers were formed (Figure 6e). Upon further increasing the Fe/Ni molar ratio to 6/4,
With Fe/Nithinner
molarandratio
longerincreasing from 2/8
CNTs were produced to 4/6, there
and entangled togetherwas
(Figureno6f).obvious formation
Finally, when of CNTs in the
the Fe/Ni molar
sample (Figure 6c & d).
ratio reached 8/2, However,
fewer CNTs withupon increasing
lengths the molar
of a few micrometers andratio of Fe/Ni
diameters of 30–40tonm5/5,
wereaformed
large number of
CNTs with (Figure 6g). According
diameters of 20–30 to the
nmabove
andresults, the optimal
lengths Fe/Ni tens
of a few molar of
ratio for preparation of
micrometers CNTsformed
were should be (Figure 6e).
5/5, which was in agreement with that suggested by the XRD results in Figure 5.
Upon further increasing the Fe/Ni molar ratio to 6/4, thinner and longer CNTs were produced and
entangled together (Figure 6f). Finally, when the Fe/Ni molar ratio reached 8/2, fewer CNTs with
lengths of a few micrometers and diameters of 30–40 nm were formed (Figure 6g). According to the
above results, the optimal Fe/Ni molar ratio for preparation of CNTs should be 5/5, which was in
agreement with that suggested by the XRD results in Figure 5.
 Nanomaterials 2020, 10, 1517 7 of 12
Nanomaterials 2020, 10, x FOR PEER REVIEW 7 of 11

Figure 6. SEM images of product samples obtained at 973 K for 2 h using 0.50 wt% FeNi catalysts with
Figure 6. SEM images of product samples obtained at 973 K for 2 h using 0.50 wt% FeNi catalysts with
different Fe/Ni molar ratio: (a) Fe, (b) Ni, (c) Fe/Ni = 2/8, (d) Fe/Ni = 4/6, (e) Fe/Ni = 5/5, (f) Fe/Ni = 6/4,
different Fe/Ni molar ratio: (a) Fe, (b) Ni, (c) Fe/Ni = 2/8, (d) Fe/Ni = 4/6, (e) Fe/Ni = 5/5, (f) Fe/Ni = 6/4,
and (g) Fe/Ni = 8/2.
and (g) Fe/Ni = 8/2.
Presented in Figure 7 are the effects of Fe/Ni molar ratio in the FeNi catalyst (in total 0.50 wt%) on
thePresented
carbon yield ininFigure 7 are samples
the product the effects of Fe/Ni
obtained molar
at 973 K for ratio in the FeNi
2 h, verifying catalyst
that the carbon(in total
yield 0.50 wt%)
under
onthe
thecircumstance
carbon yield of in the aproduct
using samples
bimetallic catalystobtained
was muchathigher
973 Kthanfor 2that
h, under
verifying that the carbon
the circumstance of yield
using a single metal catalyst. The carbon yield was only about 7 % and
under the circumstance of using a bimetallic catalyst was much higher than that under the8 % when using 0.50 wt%
single metal iron
circumstance and nickel.
of using However,
a single when theThe
metal catalyst. samecarbon
amountyield
of FeNi
was bimetallic
only about catalyst
7 %wasandused,
8 % when
the carbon yield increased significantly. Moreover, with the Fe/Ni molar ratio in
using 0.50 wt% single metal iron and nickel. However, when the same amount of FeNi bimetallic the catalyst increasing
from 2/8 to 8/2, the carbon yield increased from 18 % to 22 %. In addition, the diameter, length and
catalyst was used, the carbon yield increased significantly. Moreover, with the Fe/Ni molar ratio in
carbon yield of as-prepared CNTs using FeNi bimetallic catalysts and corresponding monometallic
the catalyst increasing from 2/8 to 8/2, the carbon yield increased from 18 % to 22 %. In addition, the
counterpart were compared (as shown in Table 1). It shows that the quality (diameter and length) of
diameter, length and carbon yield of as-prepared CNTs using FeNi bimetallic catalysts and
CNTs prepared by present FeNi bimetallic catalysts in this work was better. Although the carbon yield
corresponding monometallic
of samples prepared counterpart
in some literatures were
[39,40] was compared (as shown
higher, however, it should in be
Table 1). It shows
emphasized that thethat the
quality (diameter and length) of CNTs prepared by present FeNi bimetallic catalysts in this work was
better. Although the carbon yield of samples prepared in some literatures [39,40] was higher,
however, it should be emphasized that the length of the CNTs was shorter and the amount of the
catalyst was much higher. At the same time, the yield and quality of CNTs prepared by FeNi
bimetallic catalysts in this work were superior to the corresponding monometallic one. These results
 Nanomaterials 2020, 10, 1517 8 of 12

length of the CNTs was shorter and the amount of the catalyst was much higher. At the same time,
the yield and quality of CNTs prepared by FeNi bimetallic catalysts in this work were superior to the
corresponding monometallic one. These results indicated that the FeNi bimetallic catalysts performed
much better than the single Fe or Ni catalysts in enhancing the carbon yield, and catalyzing the growth
Nanomaterials
of CNTs. 2020, 10, x FOR PEER REVIEW 8 of 11

Figure 7. Carbon yield of product samples prepared at 973 K for 2 h, as a function of Fe/Ni molar ratio
Figurein 7.
theCarbon yield(in
FeNi catalyst oftotal:
product samples prepared at 973 K for 2 h, as a function of Fe/Ni molar ratio
0.50 wt%).
in theTable
FeNi1.catalyst (in total: 0.50 wt%).
Comparison of diameter, length and carbon yield of as-prepared CNTs using FeNi bimetallic
and corresponding single metal as a catalyst.
Table 1. Comparison of diameter, length and carbon yield of as-prepared CNTs using FeNi bimetallic
Catalyst CNTs CNTs Carbon
andRaw
corresponding
Material single metal
Catalyst as a catalyst.
Addition
Temperature
Diameter Length Yield Reference
Type (K)
(wt%) (nm) (µm) (wt%)
Raw PE FeNiCatalyst
0.50 973 CNTsfew tens CNTs
20–30 20
Carbon
This work
Catalyst Fe
PE 0.50 Temperature
973 thick shorter 7 This work Reference
Materia Yield
PEType NiAddition
0.50 （K）
973 Diameter
thick curved Length8 This work
l PE Ni (wt%)0.75 973 (nm) tens (μm)17
30–50 (wt%)
[6]
Mixing plastic FeNi 5.00 1023 10–40 shorter 46 [39]
PE PP FeNi FeNi 0.50 5.00 973
1023 20–30shorterfew tens
20–50 41 20 This work
[40]
PE Fe 0.50 973 PP: polypropylene.
PE: polyethylene; thick shorter 7 This work
PE Ni 0.50 973 thick Curved 8 This work
PE3.4. TEM/HRTEM
Ni Characterization
0.75 of CNTs 973 30–50 tens 17 [6]
Mixing TEM, HRTEM and EDS were used to characterize the morphology and microstructure of CNTs
FeNioptimal conditions
5.00 (973 K/2 h1023 10–40 shorter 46 [39]
plastic
prepared under and 0.50 wt% Fe50 Ni50 bimetallic catalysts). As displayed
PPin Figure 8a,
FeNiCNTs exhibited a clear hollow structure, with a length of a few tens of micrometers
5.00 1023 20–50 shorter 41 [40]
and diameter of 20–30 nm. HRTEM further reveals that the interlayer spacing of CNTs was 0.34 nm,
1 PE: polyethylene; PP: polypropylene.
which was consistent with the standard graphitic interlayer spacing of the (002) plane (0.34 nm),
demonstrating the high crystallinity of the CNTs (Figure 8b). Some nanoparticles of about 10 nm in size
3.4. TEM/HRTEM Characterization
were found at the tips and inside ofofsome
CNTs CNTs (indicated by the white circles in Figure 8a); they were
verified by EDS (Figure 8c) to be FeNi nanoparticles. The above results indicate that FeNi bimetallic
TEM, HRTEM
nanoparticles and
were EDS were
prepared underused to characterize
the experimental the morphology
conditions and acted as aand microstructure
catalyst to catalyze of CNTs
prepared under ofoptimal
the pyrolysis conditions
waste polyethylene (973 K/2
to produce h and
CNTs. 0.50 wt%
Meanwhile, FigureFe Niwell
8a50as 50 bimetallic catalysts). As
as our previous
displayed in proved
work [6] Figurethat
8(a), CNTs
catalyst exhibited
particles alwaysaexisted
clear inside
hollow or atstructure, with a length of a few tens of
the tip of CNTs.
micrometers and diameter of 20–30 nm. HRTEM further reveals that the interlayer spacing of CNTs
was 0.34 nm, which was consistent with the standard graphitic interlayer spacing of the (002) plane
(0.34 nm), demonstrating the high crystallinity of the CNTs (Figure 8b). Some nanoparticles of about
10 nm in size were found at the tips and inside of some CNTs (indicated by the white circles in Figure
8a); they were verified by EDS (Figure 8c) to be FeNi nanoparticles. The above results indicate that
FeNi bimetallic nanoparticles were prepared under the experimental conditions and acted as a
catalyst to catalyze the pyrolysis of waste polyethylene to produce CNTs. Meanwhile, Figure 8a as
 10 nm in size were found at the tips and inside of some CNTs (indicated by the white circles in Figure
8a); they were verified by EDS (Figure 8c) to be FeNi nanoparticles. The above results indicate that
FeNi bimetallic nanoparticles were prepared under the experimental conditions and acted as a
catalyst to catalyze the pyrolysis of waste polyethylene to produce CNTs. Meanwhile, Figure 8a as
well as our2020,
Nanomaterials previous
10, 1517 work [6] proved that catalyst particles always existed inside or at the tip
9 of of
12
CNTs.

Nanomaterials 2020, 10, x FOR PEER REVIEW 9 of 11

Nanomaterials 2020, 10, x FOR PEER REVIEW 9 of 11

Figure 8. TEM and HRTEM images of product samples obtained at 973 K for 2 h using 0.50 wt%
Fe50Ni50 nanocatalyst: (a) TEM image of CNTs, (b) HRTEM image of an individual CNT, and (c) EDS
of the nanoparticles circled in Figure 8a.
8. TEM
Figure 8. TEMandandHRTEM
HRTEMimages of product
images samples
of product obtained
samples at 973atK 973
obtained for 2Kh for
using
2 h0.50 wt%0.50
using Fe50wt%
Ni50
nanocatalyst: (a) TEM image of CNTs, (b) HRTEM image of an individual CNT, and
Fe50Ni50 nanocatalyst: (a) TEM image of CNTs, (b) HRTEM image of an individual CNT, and (c) EDS(c) EDS of the
Nitrogen adsorption-desorption measurements were carried out to determine the specific
nanoparticles circled in Figure 8a.
of the nanoparticles circled in Figure 8a.
surface area and pore size distribution of CNTs prepared under the optimal experimental conditions
(973 K/2 h and
Nitrogen
Nitrogen 0.50 wt% Fe50Ni50measurements
adsorption-desorption
adsorption-desorption bimetallic
measurements catalysts),
were were
carriedascarried
shown
out in Figure
to determine
out 9. Thethe
the specific
to determine CNTs
surface presented a
area
specific
and pore
typical
surface sizeand
type
area distribution
III isotherm
pore sizeofdistribution
CNTs prepared
when the relativeunderpressure
of CNTs the optimal
prepared (P/Pexperimental
under 0) was conditions
between
the optimal 0.1 (973
andK/2
experimental h(Figure
and 0.50 9a), and
1.0conditions
wt%
based Fe
(973 K/250 Ni
on htheand
50 bimetallic
BET model,
0.50 catalysts),
wt% Fe the as
specific
50Ni
shownsurface
50 bimetallic
in Figure 9.
areas of
catalysts), The
asCNTs CNTs presented
shownprepared a
in Figure undertypical
9. The the type
CNTs III
optimal isotherm
presentedexperimental
a
when
typicalthe
conditions relative
type was pressure
III isotherm when
calculated (P/P )139.2
as0thewas between
relative
m2·gpressure 0.1 and 1.0
(P/P
−1. Furthermore, (Figure
0) wasthe
9a),
between
poreand0.1based
and
size on(Figure
1.0 the BET9a),
distribution model,
was and
calculated
the specific
based on the surface areas ofthe
BET model, CNTs prepared
specific surface under the
areas ofoptimal
CNTs experimental
prepared under conditions
thethe wasexperimental
optimal calculated as
using Barrett–Joyner–Halanda model (Figure 9b), it was proved that
2 ·g−1 . Furthermore, the pore size distribution was calculated using Barrett–Joyner–Halanda model
average pore size of the
139.2 m
conditions was calculated as 139.2 m 2 ·g −1 . Furthermore, the pore size distribution was calculated
CNTs prepared was about 11.7 nm.
(Figure 9b), it was proved that themodel
using Barrett–Joyner–Halanda average pore size
(Figure 9b),ofitthe
wasCNTs prepared
proved was average
that the about 11.7 nm.size of the
pore
CNTs prepared was about 11.7 nm.

Figure 9. N2 adsorption-desorption isotherms of CNTs prepared under the optimal experimental conditions.
Figure
Nitrogen9.adsorption/desorption
N2 adsorption-desorption isotherms
isotherms (a) and BJHofpore
CNTssize prepared
distributionunder
profilesthe
(b) optimal experimental
of as-prepared
Figure 9. N2 adsorption-desorption isotherms of CNTs prepared under the optimal experimental
conditions. Nitrogen adsorption/desorption isotherms (a) and BJH pore
CNTs. (2 h catalytic pyrolysis at 973 K with 0.50 wt% Fe Ni bimetallic catalysts). size distribution profiles (b)
conditions. Nitrogen adsorption/desorption isotherms50(a)50 and BJH pore size distribution profiles (b)
of as-prepared CNTs. (2 h catalytic pyrolysis at 973 K with 0.50 wt% Fe50Ni50 bimetallic catalysts).
of as-prepared CNTs. (2 h catalytic pyrolysis at 973 K with 0.50 wt% Fe50Ni50 bimetallic catalysts).
4. Conclusions

4.4.Conclusions
CNTs with a diameter of 20–30 nm and length of a few tens of micrometers were synthesized
Conclusions
by simple catalytic pyrolysis of inexpensive polyethylene in Ar using cheap ferric nitrate and nickel
CNTs
CNTs
nitrate withaaprecursors.
with
as catalyst diameterofof
diameter 20–30
20–30
XRD, nmnm
EDS and
andand length
length
TEM of a of
fewa tens
confirmed few tens
thatof ofbimetallic
micrometers
micrometers
FeNi were were synthesized
synthesized
nanoparticles by
were by
simple
formed catalytic
simple catalytic
in-situ frompyrolysis
pyrolysis
the ferricofof inexpensive
inexpensive
nitrate polyethylene
polyethylene
and nickel in Arin
nitrate catalyst Ar using
using cheap
precursors cheap
ferric
during ferric
thenitrate nitrate and nickel
andprocess,
pyrolysis nickel
nitrate
nitrate
and theyas catalyst
as acted
catalyst precursors.
precursors.
as the XRD,
catalysts toXRD, EDS and
EDSCNTs
produce TEM
and TEM confirmed
from confirmed that FeNi bimetallic
that FeNi
waste polyethylene. nanoparticles
bimetallic
Compared were
tonanoparticles
their single were
formed
formed in-situ from
in-situ
metal counterparts,fromthethe
the ferric
FeNi nitrate
ferric andand
nitrate
bimetallic nickel
catalysts nitrate
nickel
performed catalyst
nitrate
much precursors
catalyst
better. during
precursors
The optimal the pyrolysis
during
condition thethepyrolysis
for
process,
process, and
andofthey
they acted
acted asasthe catalysts
the to produce
catalysts to0.50
produceCNTs from waste
CNTs polyethylene. Compared to their to their
generation CNTs in this work was: using wt% Fe50 Ni50from waste
bimetallic polyethylene.
catalysts, Compared
catalytic pyrolysis
single metal counterparts, the FeNi bimetallic catalysts performed much better. The optimal
single metal counterparts, the FeNi bimetallic catalysts performed much better. The optimal
condition for the generation of CNTs in this work was: using 0.50 wt% Fe50Ni50 bimetallic catalysts,
condition for the generation of CNTs in this work was: using 0.50 wt% Fe50Ni50 bimetallic catalysts,
catalytic pyrolysis 2 h at 973 K. The work reported here could be potentially used to address the
catalytic pyrolysis
current concerns 2 h plastic
about at 973 waste
K. The work
and reported
to convert hereofcould
a range bewaste
plastic potentially
to high used to address the
value-added
current
CNTs. concerns about plastic waste and to convert a range of plastic waste to high value-added
Nanomaterials 2020, 10, 1517 10 of 12

2 h at 973 K. The work reported here could be potentially used to address the current concerns about
plastic waste and to convert a range of plastic waste to high value-added CNTs.

Author Contributions: K.L. did experimental work and wrote the paper; H.Z., S.Z. and Q.J. designed and reviewed
the manuscript and provided some suggestions; Y.Z. did experimental work; G.Y. reviewed the manuscript and
assisted in the experimental work. All authors contributed to and critically reviewed the manuscript. H.Z. and
S.Z. made particularly major contributions to the writing and editing. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was financially supported by National Natural Science Foundation of China (Grant No.
51872210 and 51672194), Program for Innovative Teams of Outstanding Young and Middle-aged Researchers in
the Higher Education Institutions of Hubei Province (T201602), and Key Program of Natural Science Foundation
of Hubei Province, China (Grant/Award Number: 2017CFA004).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Sharuddin, S.D.A.; Abnisa, F.; Daud, W.M.A.W.; Aroua, M.K. A review on pyrolysis of plastic wastes.
Energy Convers. Manag. 2016, 115, 308–326. [CrossRef]
2. Acomb, J.C.; Wu, C.; Williams, P.T. The use of different metal catalysts for the simultaneous production
of carbon nanotubes and hydrogen from pyrolysis of plastic feedstocks. Appl. Catal. B 2016, 180, 497–510.
[CrossRef]
3. Li, G.; Tan, S.; Song, R.; Tang, T. Synergetic effects of molybdenum and magnesium in Ni-Mo-Mg catalysts on
the one-step carbonization of polystyrene into carbon nanotubes. Ind. Eng. Chem. Res. 2017, 56, 11734–11744.
[CrossRef]
4. Bajad, G.; Guguloth, V.; Vijayakumar, R.P.; Bose, S. Conversion of plastic waste into CNTs using Ni/Mo/MgO
catalyst-an optimization approach by mixture experiment. Fullerenes Nanotubes Carbon Nanostruct. 2016, 24,
162–169. [CrossRef]
5. Zhuo, C.; Levendis, Y.A. Upcycling waste plastics into carbon nanomaterials: A review. J. Appl. Polym. Sci.
2013, 131, 39931–39945. [CrossRef]
6. Zheng, Y.; Zhang, H.; Ge, S.; Song, J.; Wang, J.; Zhang, S. Synthesis of carbon nanotube arrays with high
aspect ratio via Ni-catalyzed pyrolysis of waste polyethylene. Nanomaterials 2018, 8, 556. [CrossRef]
7. Ding, D.H.; Chong, X.H.; Xiao, G.Q. Combustion synthesis of B4C/Al2 O3 /C composite powders and their
effects on properties of low carbon MgO-C refractories. Ceram. Int. 2019, 45, 16433–16441. [CrossRef]
8. Tian, C.; Yu, J.; Yuan, L.; Jin, E.; Wen, T.; Jia, D.; Liu, Z. Effect of interfacial reaction behaviour on the clogging
of SEN in the continuous casting of bearing steel containing rare earth elements. J. Alloys Compd. 2019, 792,
1–7. [CrossRef]
9. Chen, Y.; Deng, C.; Wang, X.; Ding, J.; Yu, C.; Zhu, H. Effect of Si powder-supported catalyst on the microstructure
and properties of Si3 N4 -MgO-C refractories. Constr. Build. Mater. 2020, 240, 117964. [CrossRef]
10. Wang, Q.; Li, Y.; Jin, S. Enhanced mechanical properties of Al2 O3 -C refractories with silicon hybridized
expanded graphite. Mater. Sci. Eng. A 2018, 709, 160–171. [CrossRef]
11. Gu, Q.; Ma, T.; Zhao, F.; Jia, Q.L.; Liu, X. Enhancement of the thermal shock resistance of MgO-C slide plate
materials with the addition of Nano-ZrO2 modified magnesia aggregates. J. Alloys Compd. 2020. [CrossRef]
12. Ding, D.; Lv, H.; Xiao, Q. Improved properties of low-carbon MgO-C refractories with the addition of
multilayer graphene/MgAl2 O4 composite powders. Int. J. Appl. Ceram. Technol. 2020, 17, 645–656. [CrossRef]
13. Liu, M.; Huang, T.; Xiong, M. Micro-Nano Carbon Structures with Platelet, Glassy and Tube-Like
Morphologies. Nanomaterials 2019, 9, 1242. [CrossRef] [PubMed]
14. Dresselhaus, M.S.; Dresselhaus, G.; Charlier, J.C.; Hernández, E. Electronic, thermal and mechanical properties
of carbon nanotubes. Philos. Trans. R. Soc. Lond. Ser. A Math. Phys. Eng. Sci. 2004, 362, 2065–2098. [CrossRef]
15. Terrones, M. Carbon nanotubes: Synthesis and properties, electronic devices and other emerging applications.
Int. Mater. Rev. 2013, 49, 325–377. [CrossRef]
16. Zhang, Z.; Dewan, C.; Kothari, S.; Mitra, S.; Teeters, D. Carbon nanotube synthesis, characteristics, and microbattery
applications. Mater. Sci. Eng. B 2005, 116, 363–368. [CrossRef]
17. Kausar, A.; Rafique, I.; Muhammad, B. Review of applications of polymer/carbon nanotubes and epoxy/CNT
composites. Polym.-Plast. Technol. Eng. 2016, 55, 1167–1191. [CrossRef]
Nanomaterials 2020, 10, 1517 11 of 12

18. Jeon, I.; Matsuo, Y.; Maruyama, S. Single-walled carbon nanotubes in solar cells. Top. Curr. Chem. (Cham)
2018, 376, 4–32. [CrossRef]
19. Tan, Y. Chemical sensing applications of carbon nanotube-deposited optical fibre sensors. Chemosensors 2018,
6, 55. [CrossRef]
20. Zhao, T.K.; Ji, X.L.; Jin, W.B.; Yang, W.B.; Li, T.H. Coral-like amorphous carbon nanotubes synthesized by a
modified arc discharge. Fullerenes Nanotubes Carbon Nanostruct. 2017, 25, 359–362. [CrossRef]
21. Sun, B.; Cao, W.; Guo, Y.; Wang, Y.; Luo, J.; Jiang, P. Flame pyrolysis synthesis of self-oriented carbon
nanotubes. AIP Adv. 2013, 3, 56–61.
22. Kure, N.; Hamidon, M.N.; Azhari, S.; Mamat, N.S.; Yusoff, H.M.; Isa, B.M.; Yunusa, Z. Simple
microwave-assisted synthesis of carbon nanotubes using polyethylene as carbon precursor. J. Nanomater.
2017, 2017, 2474267. [CrossRef]
23. Li, Y.; Zhang, X.; Tao, X.; Xu, J.; Chen, F.; Shen, L.; Yang, X.; Liu, F.; Tendeloo, G.V.; Geise, H.J. Single phase
MgMoO4 as catalyst for the synthesis of bundled multi-wall carbon nanotubes by CVD. Carbon 2005, 43,
1325–1328. [CrossRef]
24. Song, J.; Zhang, H.; Wang, J.; Huang, L.; Zhang, S. High-yield production of large aspect ratio carbon
nanotubes via catalytic pyrolysis of cheap coal tar pitch. Carbon 2018, 130, 701–713. [CrossRef]
25. Song, R.; Ji, Q. Synthesis of carbon nanotubes from polypropylene in the presence of Ni/Mo/MgO Catalysts
via combustion. Chem. Lett. 2011, 40, 1110–1112. [CrossRef]
26. Kadapure, S.A.; Arush, K.; Sagar, C.; Shreshtha, S.; Sangeeta, M.; Sukanya, J.; Devdatt, R.T.; Sabhya, S.;
Navya, B.L.; Amit, T. Tertiary recycling of waste plastic using catalytic cracking into crude oil. Energy Sources
Part A 2016, 38, 2942–2948. [CrossRef]
27. Miskolczi, N.; Sója, J.; Tulok, E. Thermo-catalytic two-step pyrolysis of real waste plastics from end of life
vehicle. J. Anal. Appl. Pyrolysis. 2017, 128, 1–12. [CrossRef]
28. Almeida, D.; Marques, M. Thermal and catalytic pyrolysis of plastic waste. Polímeros 2016, 26, 44–51.
[CrossRef]
29. Wu, C.; Wang, Z.; Wang, L.; Williams, P.T.; Huang, J. Sustainable processing of waste plastics to produce high
yield hydrogen-rich synthesis gas and high quality carbon nanotubes. R. Soc. Chem. Adv. 2012, 2, 4045–4047.
[CrossRef]
30. He, M.; Xiao, B.; Hu, Z.; Liu, S.; Guo, X.; Luo, S. Syngas production from catalytic gasification of waste
polyethylene: Influence of temperature on gas yield and composition. Int. J. Hydrog. Energy 2009, 34,
1342–1348. [CrossRef]
31. Zhou, L.-P.; Ohta, K.; Kuroda, K.; Lei, N.; Matsuishi, K.; Gao, L.; Matsumoto, T.; Nakamura, J. Catalytic
functions of Mo/Ni/MgO in the synthesis of thin carbon nanotubes. J. Phys. Chem. B 2004, 109, 4439–4447.
[CrossRef]
32. Liu, W.-W.; Aziz, A.; Chai, S.-P.; Mohamed, A.R.; Hashim, U. Synthesis of single-walled carbon nanotubes:
Effects of active metals, catalyst supports, and metal loading percentage. J. Nanomater. 2013, 110–114.
[CrossRef]
33. Shen, Y.; Gong, W.; Zheng, B.; Gao, L. Ni-Al bimetallic catalysts for preparation of multiwalled carbon
nanotubes from polypropylene: Influence of the ratio of Ni/Al. Appl. Catal. B 2016, 181, 769–778. [CrossRef]
34. Tan, S.-M.; Chai, S.-P.; Liu, W.-W.; Mohamed, A.R. Effects of FeOx , CoOx , and NiO catalysts and calcination
temperatures on the synthesis of single-walled carbon nanotubes through chemical vapor deposition of
methane. J. Alloys Compd. 2009, 477, 785–788. [CrossRef]
35. Ago, H.; Uehara, N.; Yoshihara, N.; Tsuji, M.; Yumura, M.; Tomonaga, N.; Setogucjo, T. Gas analysis of the
CVD process for high yield growth of carbon nanotubes over metal-supported catalysts. Carbon 2006, 44,
2912–2918. [CrossRef]
36. Chai, S.-P.; Sharif., S.H.; Mohamed, A.R. The effect of catalyst calcination temperature on the diameter of
carbon nanotubes synthesized by the decomposition of methane. Carbon 2007, 45, 1535–1541. [CrossRef]
37. Yang, W.; Feng, Y.; Chu, W. Catalytic chemical vapor deposition of methane to carbon nanotubes: Copper
promoted effect of Ni/MgO catalysts. J. Nanotechnol. 2014, 2014, 547030. [CrossRef]
38. Baba, M.S.; Sano, H.; Zheng, G.-B.; Uchiyama, Y. Effect of Mo in Co-Mo/Mgo catalysts on the synthesis yield
and structure of carbon nanotubes. J. Ceram. Soc. Jpn. 2009, 117, 654–658. [CrossRef]
Nanomaterials 2020, 10, 1517 12 of 12

39. Yao, D.; Wu, C.; Yang, H.; Zhang, Y.; Nahil, M.; Chen, Y.; Williams, P.T.; Chen, H. Co-production of hydrogen and
carbon nanotubes from catalytic pyrolysis of waste plastics on Ni-Fe bimetallic catalyst. Energy Convers. Manag.
2017, 148, 692–700. [CrossRef]
40. Cai, N.; Yang, H.P.; Zhang, X.; Xia, S.W.; Yao, D.D.; Bartocci, P.; Fantozzi, F.; Chen, Y.Q.; Chen, H.P.;
Williams, P.T. Bimetallic carbon nanotube encapsulated Fe-Ni catalysts from fast pyrolysis of waste plastics
and their oxygen reduction properties. Waste Manag. 2020, 109, 119–126. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).