Aluminium powder as a reactive template for preparation of carbon flakes from CCl4

Article abstract of DOI:10.1007/s11696-020-01303-1

Abstract: This work presents a simple procedure for the preparation of 2D carbon flakes by a catalyst-free redox reaction in the range of 400–600?°C at atmospheric pressure. Tetrachloromethane (CCl₄) was reduced by aluminium flakes (Al), which also serve as a?template for carbon flakes, for either 60?min or 120?min. Gaseous aluminium chloride (AlCl₃) was released from the?synthesis. According to BET analysis, the prepared carbon flakes exhibit a mesoporous structure with surface area in?the?range of 300–500?m²?g^?1. The 2D morphology and amorphous character was confirmed by XRD, Raman spectra and TEM analyses. In addition, SEM and TEM images revealed the carbon flakes are composed from carbon layers which can be also folded. A?mechanism of their formation was also proposed. At?higher reaction temperature, e.g., 700?°C, 1D carbon nanostructures with worm-like morphology was obtained. Graphic Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s11696-020-01303-1

Chemical Papers
https://doi.org/10.1007/s11696-020-01303-1
ORIGINAL PAPER
Aluminium powder as a reactive template for preparation of carbon
fakes from CCl4
Erik Šimon1,2 · Peter Billik1,3 · Ľubomír Orovčík4 · Štefan Nagy4 · Vlasta Sasinková5 · Martin T. Palou6 ·
Martin Škrátek3 · Veronika Trembošová2,4 · Gustav Plesch1
Received: 10 April 2020 / Accepted: 30 July 2020
© Institute of Chemistry, Slovak Academy of Sciences 2020
Abstract
This work presents a simple procedure for the preparation of 2D carbon fakes by a catalyst-free redox reaction in the
range of 400–600 °C at atmospheric pressure. Tetrachloromethane (CCl4) was reduced by aluminium fakes (Al), which
also serve as a template for carbon fakes, for either 60 min or 120 min. Gaseous aluminium chloride (AlCl3) was released
from the synthesis. According to BET analysis, the prepared carbon fakes exhibit a mesoporous structure with surface area
in the range of 300–500 m2 g−1. The 2D morphology and amorphous character was confrmed by XRD, Raman spectra and
TEM analyses. In addition, SEM and TEM images revealed the carbon fakes are composed from carbon layers which can
be also folded. A mechanism of their formation was also proposed. At higher reaction temperature, e.g., 700 °C, 1D carbon
nanostructures with worm-like morphology was obtained.
Graphic Abstract
Keywords Carbon fakes · CCl4 · Aluminium fakes · Reduction · Mesoporous carbon
Introduction
Two-dimensional (2D) carbon materials, such as graphene
or carbon nanosheets, have received considerable attention
in recent time due to their unique electrical properties, which
make them suitable for application in cutting-edge energy
storage equipment. These 2D materials ofer large surface-
to-volume ratios, continuous conducting pathways through
the electrodes, and facile strain relaxation during battery
operation [Zhu et al. 2011; Huang et al. 2012; Liu et al.
2012; Fan and Shen 2015; Tang et al. 2018].
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11696-020-01303-1) contains
supplementary material, which is available to authorized users.
* Erik Šimon
erik.simon@savba.sk
Extended author information available on the last page of the article
Vol.:(0123456789)
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The last decade has witnessed an immense growth of
preparation methods of carbon materials with 2D morphol-
ogy. They include delaminating, exfoliation [Song et al.
2013], templating processes [Geng et al. 2016], self-assem-
bly [Chen et al. 2013], chemical vapour deposition [Wang
Z et al. 2014b], solvothermal routes [Choi et al. 2014] and
carbonization of biomass [Hou et al. 2017]. However, these
methods are often expensive and require the use of a transi-
tion metal-based catalyst. On the other hand, the templating
method is one of the most used techniques for producing
carbon materials without catalyst. It is suitable for prepara-
tion of carbon with various morphologies including spheres
[Liu et al. 2015], plates [Fan and Shen 2015], rods or other
diferent morphologies [Benzigar et al. 2018]. Two types
of templating methods are usually employed: hard and soft
templating. For hard templating, clay minerals [Santos et al.
2010], zeolites [Kim et al. 2013], silica [Lin et al. 2015], and
metal oxides [Wang Q. et al. 2014] are commonly used as
templates, while a wide range of organic compounds is avail-
able as carbon sources. The main drawbacks of this method
are related to the preparation of these templates and the
use of chemicals such as KOH and HF to remove the tem-
plates [Fan and Shen 2015; Liu et al. 2015; Benzigar et al.
2018]. The soft templating method is based on the process
of self-assembly and does not present the drawbacks of hard
templating. Indeed, this process represents a spontaneous
and reversible organization of molecular units into ordered
structures by van der Waals, capillary, π-π, or hydrogen bond
interactions. Therefore, it is relatively simple and applica-
ble at larger scales, and there is no necessity to remove the
templates. The drawbacks of soft templating involve high
cost, low efectiveness of the process of self-assembly, and
the limited availability of soft templates [Liu et al. 2015;
Benzigar et al. 2018].
Materials and methods
Materials
Tetrachloromethane (CCl4, 99.8%) and aluminium powder
(99.0%) were purchased from Centralchem (Bratislava, Slo-
vakia). The aluminium powder exhibits a fake-shaped mor-
phology and has an active surface of 3.4 m2 g−1 with particle
size ranging from 10 to 70 μm. Argon (purity 99.996%) was
purchased from Messer (Bratislava, Slovakia).
Synthesis of carbon fakes
The synthesis of carbon fakes was performed using 0.2 g of
Al powder and gaseous CCl4. The reaction was performed
in a Classic CZ 4013T tube furnace under atmospheric pres-
sure with a mixture of Ar–CCl4 (molar ratio CCl4:Ar=1:1)
at a fow rate of 20 dm3 h−1. The employed apparatus and
details of laboratory operations are shown in the supplemen-
tary data (Fig. S-1). The reaction of Al powders with CCl4
was performed in the range of 400–700 °C for 60 min and
120 min with a heating rate of 10 °C·min−1. Until reaching
the required temperature, the gas fow contained pure argon.
Then, the samples were heated at the required temperature
in Ar–CCl4 fow. The cooling to ambient temperature was
performed again in pure Ar fow. The obtained product was
dispersed in distilled water, heated to 100 °C, and washed
to remove Cl− anions (test using 0.02 M AgNO3 solution).
Finally, the product was dried at 80 °C for 2 h.
Characterisation of carbon fakes
X-ray difraction (XRD) analysis of the prepared powders
was performed on a Philips PW 1050 difractometer with
Cu-Kα radiation (35 kV, 20 mA). Raman spectra were
measured using a DXR Raman microscope (Thermo Fisher
Scientifc, USA) at room temperature, where the samples
were excited using the 532 nm harmonic of a Nd:YAG laser
(power emission of 5 mW). Raman spectra were analysed
using the OriginPro 9 software, where the G-band and
D-band were deconvoluted by Gaussian ftting and the ratio
of intensities was calculated from D-band and G-band. Scan-
ning electron microscopy (SEM) images were obtained using
a JSM-7600F SEM (Jeol, Japan) operating at 5 kV. Energy
dispersive spectroscopy (EDS) from Oxford Instruments
(England) was used for quantitative chemical analysis and
chemical element mapping of the carbon fakes (operating at
voltage of 10 kV). Transmission electron microscope (TEM)
operating at 100 kV (Jeol 1200EX, Japan) was employed to
characterize the structure of the carbon fakes. The samples
were observed on a Cu mesh grid. The active surface and
To circumvent these difficulties, one possibil-
ity is the reaction of halogen derivatives such as
CH2Cl2, CCl4, and C2Cl4 with alkali metals which serve
as carbon source and reducing agents, respectively [Kuang
et al. 2004; Choi et al. 2014; Chocair et al. 2015; Tang et al.
2016]. Unfortunately, such reactions are highly exother-
mic and potentially explosive. To limit the risks associated
with the reaction, aluminium powder has been suggested as
an alternative reducing agent [Fan et al. 2010; Dong et al.
2015], since it has a satisfactory reduction potential com-
bined to the low cost and sustainability of aluminium.
Therefore, the main goal of this work is to study a sim-
ple catalyst-free procedure for preparation of carbon fakes
from CCl4, using Al powder with fake-shaped morphology,
which acts as reducing agent and template.
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porosity of the prepared samples was determined using an
Autosorb iQ device (Quantachrome Instruments, USA); it
is worth noting that the powders were outgassed overnight
at 130 °C before measurement. Brunauer–Emmett–Teller
(BET) theory was used to investigate the surface area of
the samples. The infuence of synthesis temperature on pore
parameters, adsorption–desorption boundary curves and the
hysteresis loop were studied. The analysis of the particle
size and size distribution of the Al template was carried
out using an Analysette 22 MicroTec Plus machine (Fritsch,
Germany). Thermal analysis of obtained products was per-
formed on SDT 2960 device (TA Instruments, USA) in the
range of 25–900 °C in fowing air at atmospheric pressure
with heating rate of 10 °C·min−1.
D-band G-band
ID/IG
1.17
400 °C, 120 min
1.14
1.16
500 °C, 60 min
600 °C, 60 min
1.27
700 °C, 60 min
1000
1500
2000
2500
3000
Raman shift / cm-1
Fig. 2 Raman spectra of the products obtained from the redox reac-
tion of Al with CCl4 at diferent temperatures
Results and discussion
atoms. This vibration mode does not require the presence
of sixfold rings, and so it occurs on all sp2 sites [Ferrari
and Robertson 2000]. The ratio ID/IG which characterizes
the crystallinity of prepared carbon fakes is also an impor-
tant feature. The intensity ratio at 400 °C, 500 °C, 600 °C
and 700 °C is 1.17, 1.14, 1.16, and 1.27, respectively. By
comparison to the work of Ferrari and Robertson (2000),
this indicates that the obtained products have a signifcant
amorphous character with low degree of graphitization.
In the case of carbon prepared at 700 °C intensity of the
D-band peak is stronger than the G-band peak, while the
ratio ID/IG is about 1.27, thus suggesting the prepared car-
bon materials contain long-range disordered graphitized
carbon [Kuang et al. 2004].
Phase analysis
XRD patterns of the products obtained after reduction of
CCl4 by Al powder at diferent temperatures are shown in
Fig. 1. The heating at 400 °C for 60 min is not enough to
complete the redox reaction, thus requiring longer time
or higher temperature. A broad low-intensive difraction
in the range of 10°–30° (2θ) indicates the formation of
amorphous carbon for samples heated either at 400 °C
for 120 min or 500 °C for 60 min. The Raman spectra
(Fig. 2) show two intensive bands at ~ 1350 cm−1 (labeled
as D-band) and ~ 1580 cm−1 (labeled as G-band). These
bands indicate the presence of amorphous carbon [Chocair
et al. 2015; Dong et al. 2015; Tang et al. 2016]. The peak
at around 1350 cm−1 is associated with defective order
carbon structure (carbon structure with sp3 hybridization
state). The band centered around 1580 cm−1 is associated
with the in-plane bond stretching motion of pairs of C sp2
The EDS and gravimetric measurements indicate also
the presence of small amount of AlCl3 residue in the sam-
ples synthesized at 400 °C, 500 °C and 600 °C. At these
temperatures small amount of AlCl3 remains absorbed
on surface. The complete removal of AlCl3 was achieved
only at 700 °C. In addition, the hygroscopic AlCl3 which
is formed during the synthesis appears as a white coat-
ing on the cold part of the apparatus. Our results indicate
that reduction of CCl4 with Al in the temperature range of
(400–700) °C proceeds according to Eq. (1).
Al
700 °C, 60 min
600 °C, 60 min
500 °C, 60 min
4Al(s) + 3CCl4(g) → 3C(s) + 4AlCl3(g)
(1)
Thermal stability of obtained carbon products was also
investigated by TG and DTA (Fig. S-2). The results show
that the carbon powder undergoes complete oxidation at
600 °C. The small residue which is stable up to 900 °C
consists probably of Al2O3 formed from starting Al fakes.
Representative TG and DTA curves are shown in supple-
mentary data (Fig. S-2).
400 °C, 120 min
(111)
(200)
(220)
400 °C, 60 min
10
20
30
40
50
60
70
2θ (°)
Fig. 1 XRD patterns of the products obtained by the redox reaction
of Al with CCl4 at diferent temperatures
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about 1 μm as shown in Fig. 3c and Fig. 4. These 2D
carbon materials are thicker than those prepared by other
methods (Fan and Shen 2015). Broken 2D carbon struc-
tures (Fig. 3d and Fig. 4) confrm that the carbon fakes
SEM, TEM and EDS analysis of carbon fakes
The morphology of carbon flakes prepared at 400 °C
and 500 °C is shown in Fig. 3. They have a thickness of
Fig. 3 SEM images of carbon fakes a sample prepared at 400 °C (a, b, c) and 500 °C (d) - a cascading fracture is highlighted by red arrow; cor-
rugated surface of the product obtained at 400 °C (e) and 500 °C (f)
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Fig. 4 SEM images of broken carbon fakes prepared at 400 °C (a, b) and 500 °C (c, d)
replicate the shape of the 2D aluminium particles (Fig.
S-3) while leaving voids in the centre of the 2D carbon
particles, which are indicated by arrows. These voids are
due to consumption of aluminium fakes (Sercombe and
Schafer 2006), which acts as a reactive template for the
formation of carbon fakes. In Fig. 3d, it is also possible
to observe a cascading fracture (highlighted by red arrow),
which indicates the presence of carbon layers. In the case
of carbon fakes prepared at 400 °C and 500 °C, the sur-
faces were also corrugated (Fig. 3e, f).
Representative TEM images are shown in Fig. 5 for
samples prepared at 400 °C. Figure 5a, b shows that the
carbon flakes are composed of many layers stacked to
form 2D amorphous structure. This is also confirmed by
electron diffraction (Fig. 5c—insert). The borders of the
layers are highlighted by red arrows. In Fig. 5c, irregular
carbon fragments with sizes of 20–30 nm incorporated
into the flakes can be seen. Their origin is discussed later.
Moreover, the TEM images indicate that the carbon lay-
ers are partially folded (Fig. S-5a highlighted by arrows)
and stacked into irregular formations (Fig. S-5b, d)).
The representative EDS map (Fig. S-6) shows the pres-
ence of homogeneously distributed carbon, oxygen, alu-
minium, and chlorine. Aluminium and chlorine represent
the rest of AlCl3 on the surface of carbon fakes. The pres-
ence of oxygen indicates a residue of surface alumina from
the input Al powder.
The carbon powder prepared at 600 °C consisted of a
mixture of carbon fakes and agglomerates of particles with
1D morphology (Fig. S-4a, b). It is consistent with other
works, where aluminium as a substrate is suitable also for
growth of carbon materials with 1D morphology (Yuan et al.
2008; Esconjauregui et al. 2009). For the carbon products
prepared at 700 °C, only 1D agglomerates and worm-like
morphologies, without clear 2D morphology, were typical
(Fig. S-4c, d). This is caused by the melting of the alumin-
ium template at 660 °C (Binneweis and Milke 2002).
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Fig. 5 TEM images of as-prepared carbon fakes prepared at 400 °C (a–d). Red arrows highlight the borders of the layers
other works using similar method to prepare carbon materi-
als (Table 1). The N2 adsorption and desorption isotherm
curves of the prepared carbon samples are shown in Fig. 6.
These curves exhibit a hysteresis loop, which is character-
istic of the presence of a mesopores with a uniform size
or funnel shape [Rouquerol et al. 2014], thus confrming
that oxidation of Al by CCl4 creates carbon fakes with a
porous structure. The size of the hysteresis loop increases
with temperature up to 500 °C, and then decreases
with increasing temperature at 700 °C. The curves of the
Active surface and porosity
The surface area measurements of the carbon materials show
an increase of active surface with temperature up to 500 °C.
Indeed, the active surfaces of carbon samples prepared
at 400 °C and 500 °C were 311.6 m2 g−1 and 513 m2 g−1,
respectively, while at higher temperatures the surface
area decreases and reaches 229.1 m2 g−1 at 600 °C and
126.0 m2 g−1 at 700 °C. The present work reports carbon
fakes with higher active surface area than that reported in
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Table 1 Comparison of active
Reaction system
Conditions
Active surface, [m2 g˗1]
surface
Al+CCl4
Al+CCl4
K+CCl4
500 °C, 1 h, atmospheric pressure,
513 This work
160 °C, 12 h solvothermal conditions
60 °C, 10 h, solvothermal conditions
Self-assembly process, 700 °C carbonization
226.9 [Dong et al. 2015]
97.2 [Kuang et al. 2004]
2012 [Tang et al. 2016]
K/Na+CCl4
Fig. 6 Adsorption and desorp-
tion isotherm curves of carbon
powders prepared at diferent
temperatures
(a) 400 °C
(b) 500 °C
450
400
350
300
250
200
150
100
50
500
450
400
350
300
250
200
150
100
50
0
0
0,0
0,2
0,4
0,6
0,8
1,0
0,0
0,2
0,4
0,6
0,8
1,0
Relative pressure / P/P0
Relative pressure / P/P0
(c) 600 °C
(d) 700 °C
800
700
600
500
400
300
200
100
0
500
450
400
350
300
250
200
150
100
50
0
0,0
0,2
0,4
0,6
0,8
1,0
0,0
0,2
0,4
0,6
0,8
1,0
Relative pressure / P/P0
Relative pressure / P/P0
adsorption–desorption isotherm are signifcantly closer to
each other than those at other temperatures, due to the sinter-
ing process occurring at that temperature.
under the frst carbon layer leads to formation of further carbon
fragments. Thus, the carbon fakes are formed by layering,
as shown in Fig. 7c, d. The process of layering ends by com-
plete consumption of the aluminium fake-shaped particles,
as shown in Fig. 7d. Finally, voids remain inside the carbon
fakes, where the rest aluminium has been consumed (Fig. 7d).
The formation of folded carbon layers (Fig. S-5b, d) can
be explained by subsequent self-folding of the surface carbon
layer. This process is driven by local strains. Van der Waals
attraction stabilizes the self-folded confguration (Schiepp
et al. 2008). The process of self-folding has been observed
for similar systems with 2D morphology, such as graphene,
MoS2, and WSe2 (Schiepp et al. 2008; Liu et al. 2009; Kim
et al. 2011; Kushima et al. 2015; Zhao et al. 2015).
Formation of carbon fakes
Based on all the previously discussed results, a mechanism
of formation of carbon fakes is suggested. In a frst step,
CCl4 probably decomposes at 400 °C to ·Cl and ·CCl3 radi-
cals (Stern and Uhlig 1952). Free chlorine acts as an oxi-
dant and reacts directly with Al fakes to give AlCl3. Subse-
quently, a cascade of radical reactions may occur, and more
complex halogen carbons are fnally transformed into carbon
fragments (Stern and Uhlig 1952; Archer and Harter 1978).
The overall reaction is given in reaction Eq. (1).
Carbon fragments are formed at various locations on the
aluminium surfaces, where the reaction takes place (Fig. 7).
Simultaneously, AlCl3 gas is released. Subsequently, the frst
superfcial carbon layers are formed by the bonding of car-
bon fragments to each other (Fig. 7b). Further reaction of alu-
minium with halogen derivatives on the aluminium surface
Conclusions
A simple catalyst-free method for preparation of carbon
fakes at atmospheric pressure involving the redox reac-
tion between CCl4 and Al powder has been presented. The
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Fig. 7 Proposed formation
scheme of carbon fakes on the
Al template fakes
lithium-ion batteries. ACS Appl Mater Interfaces 5:9537–9545.
https://doi.org/10.1021/am402368p
surface of aluminium fakes served as a reactive place and
template for formation of carbon fakes. The carbon fakes
were composed of low-crystalline defect graphite. SEM
analysis has revealed voids as a remnant of aluminium fakes
which was consumed and TEM has shown that the carbon
fakes contain folded carbon layers. Carbon fakes prepared
at 400 °C and 500 °C exhibited an active surface area in
the range of 300–500 m2 g−1. Such carbon fakes are highly
promising for applications in cutting-edge energy storage
devices.
Chocair M, Hill MR, Stride AJ (2015) A low temperature reduction
of CCl4 to solid and hollow carbon nanospheres using metallic
sodium. Mater Chem Phys 154:38–43. https://doi.org/10.1016/j.
matchemphys.2015.01.042
Choi HS, Oh JY, Park CR (2014) One step synthesis of sulfur–car-
bon nanosheet hybrids via a solid solvothermal reaction for
lithium sulfur batteries. RSC Adv 4:3684–3690. https://doi.
org/10.1039/C3RA45187A
Dong L, Yan X, Cheng K, Weng W, Han W (2015) Low-temperature
reduction–pyrolysis–catalysis synthesis of carbon nanospheres
for lithium-ion batteries. RSC Adv 5:55474–55477. https://doi.
org/10.1039/C5RA08627B
Acknowledgements This work was supported by the VEGA and
APVV Slovak grant agencies under contract numbers VEGA 1-0739-
16 and APVV-17-0324. This work was also the results of the imple-
mentation of the project Building-up Centre for advanced materials
application of the Slovak Academy of Sciences (ITMS project code
313021T081) which is supported by the Research & Innovation Opera-
tional Programme funded by the ERDF. The authors wish to thank Dr.
Olivier Monfort for valuable discussions.
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interest.
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jurisdictional claims in published maps and institutional afliations.
Song WL, Cao MS, Lu MM, Liu J, Yuan J, Fan LZ (2013) Improved
dielectric properties and highly efcient and broadened bandwidth
Afliations
Erik Šimon1,2 · Peter Billik1,3 · Ľubomír Orovčík4 · Štefan Nagy4 · Vlasta Sasinková5 · Martin T. Palou6 ·
Martin Škrátek3 · Veronika Trembošová2,4 · Gustav Plesch1
1
2
3
4
Department of Inorganic Chemistry, Faculty of Natural
Sciences, Comenius University in Bratislava, Ilkovičova 6,
Bratislava 84215, Slovakia
Institute of Materials and Machine Mechanics, Slovak
Academy of Sciences, Dúbravská Cesta 9, Bratislava 84513,
Slovakia
5
6
Centre of Excellence for Advanced Materials Application,
Slovak Academy of Sciences, Dubravska Cesta 9,
84511 Bratislava, Slovakia
Institute of Chemistry, Slovak Academy of Sciences,
Dúbravská Cesta 9, Bratislava 84538, Slovakia
Department of Materials and Rheology, Institute
of Construction and Architecture, Slovak Academy
of Sciences, Dúbravská Cesta 9, Bratislava 84503, Slovakia
Department of Magnetometry, Institute of Measurement
Science, Slovak Academy of Sciences, Dúbravská Cesta 9,
Bratislava 84104, Slovakia
1 3