Ceramics International 46 (2020) 29271–29281

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Carbon nanostructures based-adsorbent obtained from iron ore tailings T

Giovanni Gomes Guerreiro, Fabrício Vieira de Andrade , Márcio Roberto de Freitas ∗

Universidade Federal de Itajubá - Campus Itabira, Instituto de Engenharias Integradas, Rua Irmã Ivone Drumond, 200 - Distrito Industrial II, 35903-087, Itabira, MG,
Brazil

ARTICLE INFO ABSTRACT

Keywords: In the present work, for the first time in literature, raw iron ore tailings (IOTs) were used as catalysts for the
Iron ore tailings synthesis of carbon nanomaterials (CNMs) by the chemical vapor deposition method (CVD) in a fixed-bed re-
Chemical vapor deposition (CVD) actor. The reaction parameters were optimized using ethanol as the carbon source, and from the best condition,
Carbon nanotubes the synthesis was also carried out using acetone. The characterization of materials showed that both carbon
Emerging contaminants
precursors were able to produce several types of carbon structures: nanometric (MWCNT, CNF) and non-na-
Environmental remediation
nometric (fibers, amorphous carbon). The TEM images, Raman spectroscopy and TGA revealed that the ethanol
led to the growth of more organized structures and less amorphous material. The CNMs from both carbon
sources were used without any purification or functionalization treatment, as adsorbents for the rhodamine B
(cationic) and indigo-carmine (anionic) dyes. The CNMs were able to adsorb only the cationic dye. The ad-
sorption was investigated by the main kinetic models and by adsorption isotherms. Regarding the kinetic study,
the pseudo-second-order model was the best fit to the experimental data, and the intraparticle diffusion model
presented multilinearity for both adsorbents. Concerning the type of isotherm, the data was better adjusted by
the Langmuir model, indicating that the dye adsorption on the CNMs occurred at specific sites.

1. Introduction
Iron ore extraction is one of the most relevant activities for world
socioeconomic development. In Brazilian territory alone, 12.8% of the
total iron ore in the world is mined, of which 64.8% is mined in the
state of Minas Gerais. However, due to the low iron content present in
the ore, it is necessary to benefit it which, besides concentrating the
iron ore, also generates a high volume of tailings [1]. Essentially, iron
ore tailings (IOTs) have been used to fill mining pits or stored in dams,
thus, requiring constant monitoring at high costs. However, recent dam
disruptions throughout the world and the imminence of future disasters
make clear the extent of this problem and highlight the urgency to
propose new forms of reuse for the IOTs [2,3]. In view of this serious
environmental problem, several alternatives have been proposed for the
reuse of IOTs over the years, mainly related to civil construction and
paving [4,5]. However, due to the fact that the IOTs are mainly com-
posed of iron (FexOy) and silicon (SiO2) oxides, it appears to be a ‘ready-
made’ catalyst for the synthesis of carbon nanomaterials (CNMs), the
usage of various iron oxides to synthesize several forms of CNMs is
already widely reported in the literature [6–9]. However, according to
the literature, the usage of the IOTs to synthetize any form of CNM has
not been reported yet. Regarding the use of other tailings, only 07
studies involving the use of red mud (RM) have been found and that is
the main waste of the Bayer process. These articles have motived us to
investigate the usage of IOTs to grow CNMs [3,10–15]. Hence, the
present work proposes in an unprecedented way, the usage of IOT, as a
catalyst for the synthesis of CNMs using the chemical deposition of
(CVD) as the synthesis method, which is considered a simple and eco-
nomical technique capable of producing good quality and has the best
perspectives to become the production method of large-scale CNTs in
the future [16]. The synthesized materials were also employed without
any purification and/or functionalization treatment, as adsorbent of
cationic rhodamine B and anionic indigo carmine dyes, which are
carcinogenic substances and are widely used in the textile and plastic
industries [17,18].
2. Materials and methods
2.1. Characterization of IOTs
As received from Vale S.A., the IOTs were characterized through the
techniques: Raman spectroscopy (iHR550, Horiba Jobin Yvon); X-Ray
Fluorescence (FRX) (model EDX-720, Shimadzu); thermogravimetric
analysis (TGA) (DTG 60, Shimadzu); and scanning electron microscopy

∗
Corresponding author.
E-mail address: fabricio.andrade@unifei.edu.br (F. Vieira de Andrade).

https://doi.org/10.1016/j.ceramint.2020.08.101
Received 19 May 2020; Received in revised form 23 July 2020; Accepted 13 August 2020
Available online 26 August 2020
0272-8842/ © 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
G.G. Guerreiro, et al. Ceramics International 46 (2020) 29271–29281

(SEM) (Quanta FEG 3D, FEI). Where,

2.2. Characterization of CNMs
The CNMs were characterized by thermogravimetric analysis (TGA)
(DTG 60, Shimadzu); Raman spectroscopy (iHR550, Horiba Jobin
Yvon) was used - a 514.5 nm wavelength laser with a power of 5 mW,
performing 10 accumulations of 10 s each; scanning electron micro-
scopy (SEM) (Quanta FEG 3D, FEI); transmission electronic microscopy
(TEM) (Tecnai G2-20 - SuperTwin FEI - 200 kV) in image mode; surface
areas (using BET method) analysis (ASAP 2020Plus, Micromeritics).
2.3. Synthesis of CNMs
qe and qt are the amounts of dye adsorbed per gram of the adsorbent
(mg.g−1) at equilibrium and at time t (min);
Ce is the concentration at equilibrium; C0 is the initial concentra-
tion;
V is the volume of the solution (mL);
m is the mass of the adsorbent (g).
In order to establish the most appropriate correlation with the
curves obtained experimentally, the models of pseudo-first order,
pseudo-second order and intraparticle diffusion were used (Table S2)
[20–22].

2.4.2. Adsorption isotherm experiments

The nanomaterials were synthesized by the CVD method in fixed-
The adsorption isotherms were built using the batch method, thus
bed reactor, using a horizontal oven (Ovens Inti model FT-1200). The
allowing the simultaneous obtaining of several experimental points and
IOTs were used without any purification, as the catalyst for the de-
guaranteeing less dispersion of the results. For that, 10 mg of adsorbent
composition of carbon precursors (acetone and ethanol); the precursors
was added to 10 mL of standard dye solutions of different concentra-
were obtained from the Merck company, and had a minimum purity of
tions (1–30 mg L−1). Duly closed, the erlenmeyrs were placed in a
98%. All syntheses were carried out under argon inert atmosphere
shaker under the same conditions of temperature, pH and agitation as
(99.99% of purity) of the White Martins brand. All mass measurements
in previous experiments. The flasks were kept in agitation until
were performed on an analytical balance (Shimadzu model AY220).
reaching thermodynamic equilibrium (approximately 6 h). After this
Initially, the CNMs were synthesized under 12 different conditions,
period, 3.5 mL aliquots were removed from each solution, centrifuged,
varying three parameters using ethanol as the carbon precursor. Three
and then read on the spectrophotometer. The Langmuir and Freundlich
temperatures were tested (700, 800 and 900 °C), two periods of time
models were used to establish the most appropriate correlation with the
(30 or 60 min) and two flow conditions of the carbon precursor: in the
experimental data (Table S3) [23].
first condition, the flow was maintained throughout the entire synth-
esis, that is, throughout the heating cycle (room temperature to final
temperature), and cooling to room temperature; in the second condi- 3. Results and discussion
tion, the flow was maintained only until the reactor reached the max-
imum temperature (700, 800 or 900 °C). The heating rate used in the 3.1. Characterization of IOTs
first condition was 10 °C.min−1. Later, with the optimized set of
parameters, the synthesis was also carried out using acetone as the 3.1.1. X-ray fluorescence
carbon source. Thus, two carbon nanomaterials were obtained - one Table S4 shows the chemical elements found in the IOTs obtained
synthesized from ethanol (CNM-Et) and the other from acetone (CNM- by X-ray fluorescence spectroscopy (FRX). The chemical characteriza-
Ac). In order to investigate the correlation between the parameter and tion evidenced: SiO2 (50.6%) and Fe2O3 (41.7%) as main constituents
the growth of carbon structures, the yield of the synthesis was calcu- and other components in minor concentrations. This result was ex-
lated by equation (1) [19]: pected considering that IOTs are heterogeneous systems with mainly
iron and silicon oxides and may present other several minerals in their
synthesis yield (%) = (M_Total - M_Catalyst) / M_Catalyst × 100 (1) composition [24].
Where,
3.1.2. Raman spectroscopy
MTotal is the final mass formed after the syntheses; The IOTs were also characterized by Raman spectroscopy. As can be
MCatalyst is the initial mass of the catalyst; seen in Fig. 1, several signs were observed in the range of 100–500 cm-1
MCatalyst for all syntheses was 500 mg.

2.4. Adsorption tests

The adsorption studies were performed in a thermostatic shaker

(Nova Técnica model 530). The samples were centrifuged in a cen-
trifuge (Quimis model Q222E). Solutions of the cationic rhodamine B
and the anionic indigo-carmine dyes were used as adsorbates as re-
ceived from Sigma-Aldrich Company. The characteristics of the dyes
can be found in Supporting Information (SI) (Table S1). As adsorbents,
the CNMs synthesized at the best condition and the IOTs were used. All
solutions were prepared using deionized water. The concentration of
the dyes was measured indirectly through spectrophotometric mea-
surements on a T-80 UV/Vis Spectrophotometer equipment, using the
λmax of each dye (indigo carmine 610 nm and rhodamine b 544 nm).

2.4.1. Adsorption kinetics experiment

The amount of dye adsorbed at each time per gram of adsorbent was
calculated from equation (2) : Fig. 1. Raman spectrum for the IOT region 125–3250 cm−1. In detail: ap-
qe,t = (Co–Ce,t)V/m (2) proximation of the region 1000 - 1500 cm−1.

29272
G.G. Guerreiro, et al. Ceramics International 46 (2020) 29271–29281

Fig. 2. SEM images for IOT.

which, as discussed extensively by Das and Hendry (2011), are char-
acteristics of iron oxides, such as hematite and goethite among other
diverse mineral phases rich in Mg and Ca. In the detail of Fig. 1, an
approximation in the region of 1000–1500 cm−1 of the Raman spec-
trum is shown. We opted to analyze this region in detail because it is
located in the same region of the first order bands D and G, which are
characteristics of carbon materials. A band is observed in the region of
1200–1300 cm-1. As proposed by Brolly, Parnell and Bowden (2016),
this band can be associated with the 2LO mode characteristic of de-
fective hematite. This signal is extremely important for the present
work, as it is located in very close regions to the D band. In this way, the
bands can overlap and therefore interfere in the analysis of carbon
materials.
3.1.3. Scanning electron microscopy
Scanning electron microscopy (SEM) was also used to characterize
the IOTs. Fig. 2 shows the SEM images of the material. It was found that
the IOTs have a very heterogeneous morphology, with particles of
different sizes and shapes. It was also observed that there are some
blended mineral phases encrusted within other. The particle diameter
ranges from 0.1 to 300 μm. Finally, through chemical analysis by EDS,
the main elements found were Si, O and Fe, which as showed by the
XRF analysis, are the main compounds present in the tailings.
3.1.4. Thermogravimetric analysis
In order to obtain information about the thermal stability of the
IOTs, a thermogravimetric analysis of this material was also carried out
in an atmosphere of synthetic air. Fig. S1 shows the results of this
characterization. Initially, a small mass gain is noted, which may be
related to the oxidation of some metallic phase that may be present in
the material. Then, a series of events are noted which may be related to
the dehydration of goethite and consequently its transformation into
hematite [27]. In general, the IOTs showed high thermal stability in the
studied temperature range as evidenced by a loss of mass of about 1%.
This result was expected since the main constituents of the IOTs are iron
and silicon oxides, which are stable in this temperature range [24].
From the results presented so far, it is observed that despite the IOTs
being highly heterogeneous both in chemical and physical aspects, they
have a large amount of iron oxide. This makes them a promising can-
didate to act as a catalyst to grow CNMs, given that several authors
have already used iron oxides as a catalyst to synthesize various types of
carbon materials [6–8,28–32].
900 °C), two synthesis times (30 and 60 min) and the carbon source
flow was employed in two different ways: 1) only at the maximum
temperature of the experiment (label A) (700, 800 and 900 °C) and 2)
throughout the whole synthesis, during both the heating and cooling
(label B). The obtained materials were named as the following example:
700_A_30 (material produced at 700 °C with ethanol flow only during
the maximum temperature for 30 min). Fig. 3 shows the synthesis yield
for all conditions tested as a function of temperature.
Firstly, it is noted that the continuity of flow of the carbon pre-
cursor, the temperature, and the reaction time significantly affect the
synthesis yield. Two clear trends are noted: 1) for the syntheses in
condition A, negative yield is observed and 2) for the samples synthe-
sized in condition B, an increase of the yield directly proportional to the
increase in temperature was observed. Therefore, it is essential for the
process to maintain the reaction system saturated with the carbon
source throughout the heating/cooling cycle (condition B). As reported
in the work by Oliveira et al. (2011), red mud (RM) tailings were used
as a catalyst to synthetize CNMs, which have similar physical-chemical
characteristics to the ones used in this work. Through chemical analyzes
of samples taken during the heating ramp at temperatures between 300
and 900 °C, under ethanol atmosphere in a CVD reactor, it was evi-
denced that the iron oxide present in the RM, is reduced during the
heating ramp in several metallic phases until reaching the maximum
concentration of Fe0 at 700 °C, which is the real catalyst of the process.
In addition, several other studies in which other reaction conditions
were used corroborate the idea that iron oxide is reduced to Fe0 par-
ticles, which is the true catalyst for the reaction [28,31,33–35].

3.2. Optimization of CNMs synthesis

The synthesis parameters were optimized using ethanol as the

carbon source. For that, three temperatures were tested (700, 800 and Fig. 3. Synthesis yield for all conditions tested.

29273
G.G. Guerreiro, et al.
Therefore, based on these works, it is possible to analyze what may
happened in our system. Starting from room temperature up to 900 °C
with a heating rate of 15 °C/min, the heating ramp lasts about 60 min.
Based on the results obtained by Oliveira et al. (2011), it is assumed
that at around 500 °C, the reduction of Fe2O3 in Fe0 starts and at 700 °C
the oxide is completely reduced. Therefore, it is assumed that the
growth of carbon structures started along with the formation of the first
iron atoms at 500 °C (after about 25 min) and lasted until the oven
cooled to 500 °C (160 min), temperature at which, ethanol starts to no
longer be decomposed, and the deposition of carbon structures is
smaller [36]. On the other hand, it can be inferred that possibly in the
syntheses carried out in condition A, which therefore, the flow of
ethanol was maintained for only 30 or 60 min, these periods of time
were not enough to reduce the iron oxides to metallic iron and enable
the growth of carbon structures, but it only made it possible to reduce
the iron oxide (among other components in lesser quantity), which
justifies the loss of mass of about 1–10% shown on the yield graph
(Fig. 3). In fact, other authors who used iron oxide for the synthesis of
CNMs, report the need of a pre-reduction step of the oxide in a nitrogen
atmosphere [15]. Moreover, regarding the effect of SiO2, Oliveira, 2019
& Sushil, 2010, studied thoroughly what happens in this type of en-
vironment (carbon precursor + heat + (SiO2 and iron oxides)) and no
additional remarks was made regarding the influence of SiO2 on carbon
nucleation. Moreover, our observations led us to believe that the SiO2
influences little or almost nothing on the carbon deposition. However,
we do not rule out the possibility that SiO2 may have a greater effect on
carbon deposition, mainly because we worked with tailings which are
very heterogenous.
Additionally, it is observed that the best yield for each temperature
was obtained in condition B_30, which were: 16.7%, 26.8% and 53.3%,
respectively, for temperatures of 700, 800 and 900 °C, making it clear
that the increase in temperature has a direct influence on the synthesis
yield, as expected by the literature [14,19,37]. It is also observed that
the increase in synthesis time from 30 to 60 min led to reduction in
yield of approximately 6.4% (average value between all temperatures),
indicating that the increase disfavored the nucleation of carbon struc-
tures, and raises the hypothesis that shorter synthesis times can lead to
a similar or higher yield. The behavior in which the temperature exerts
a directly proportional influence on the synthesis yield was also noticed
both by authors who used catalysts similar to the ones in this work (e.g.
Oliveira et al. (2011) and Mesgari Abbasi et al. (2016) that red mud
tailings were used) as well as in works that were used other types of
catalysts, (e.g. Shukrullah et al. (2019) and Chen et al. (2008). There-
fore, in terms of synthesis yield and energy efficiency, the best condi-
tion was obtained at 900 °C maintaining the flow of ethanol throughout
the whole synthesis for 30 min (900_B_30), which generated 53.3% of
yield. It should also be noted that the standard deviation of the data
obtained experimentally was between ± 1 to 10%, which can be as-
sociated with the high heterogeneity of the catalyst used (among other
factors inherent to the experiment). Table 1 shows of the synthesis yield
obtained in the present work in comparison to all the papers found in
the literature in which was used similar catalysts for synthesis of CNMs.
It is observed that the yield obtained in this work is higher than all the
other results, emphasizing that the results presented here are pro-
mising.
In addition to that, it is largely reported that the type of carbon
Table 1
Comparison of the carbon yield obtained by other works.
Catalyst Yield Reference
Tailing (RM) 50,00% [13]
Tailing (RM) 46,80% [11]
Tailing (RM) 48,00% [14]
Tailing (RM) 46,08% [34]
Tailing (IOT) 53,30% Authors of this work.
29274
Ceramics International 46 (2020) 29271–29281
source significantly affects the synthesis of CNMs by the CVD process
[34]. Thus, after optimizing the reaction parameters using ethanol as
the carbon source, synthesis with acetone was also carried out in order
to compare both precursors. The process was conducted under opti-
mized conditions (900_B_30). The synthesis using acetone yielded ap-
proximately 3.7 times more CNMs compared to the synthesis using
ethanol. This considerable difference can be explained by the fact that
acetone is significantly more volatile than ethanol and since the reac-
tion system used in this work starts from precursor in the liquid state, to
then be volatized and carried by the carrier gas, it was expected that
ethanol would lead to a lower yield [39]. The materials synthesized
with both carbon sources are now called: CNM-Et (synthesized with
ethanol) and CNM-Ac (synthesized with acetone). From this point, all.
3.3. Characterization of CNM-Et and CNM-Ac
3.3.1. Thermogravimetric analysis
Thermogravimetric analysis (TGA) is considered one of the most
practical techniques to study the purity, thermal stability and the
structural characteristics of CNMs [40–43]. Fig. 4a shows the TG curves
for CNM-Ac and CNM-Et. It is observed a small mass gain in the range of
350–450 °C, which is possibly related to the oxidation of metallic iron.
Additionally, a prominent mass loss in the temperature range of about
450–640 °C is also observed, which is characteristic of the oxidation of
carbonic structures [44]. It is noted that the TG curves have similar
characteristics, concerning the region that mass loss occurs. However,
CNM-Ac showed a higher percentage of mass loss, around 70%, against
approximately 30% for CNM-Et. This result corroborates the fact that
CNM-Ac showed a higher synthesis yield than CNM-Et.
Fig. 4b shows the DTG curves for CNM-Ac and CNM-Et. The curves
show that the samples had substantially different structural features. It
is observed that the most intense peak occurred at approximately
600 °C for both CNMs, which is characteristic of carbonaceous struc-
tures such as nanotubes and nanofibers [40]. For the CNM-Ac, a peak is
also observed at higher temperatures (639 °C), thus, indicating that the
CNMs produced by acetone generated materials whit thicker structures
than those synthesized by ethanol, mainly because bulkier carbon
materials (e.g. as MWCNTs with a greater number of layers and thicker
CNFs) have greater resistance to oxidation [45,46].
While the curve for CNM-Ac has a series of small 'shoulders', the
CNM-Et curve has a single well-defined peak and is relatively narrower
than the convolution of the CNM-Ac peaks. These results suggest that
the synthesis from acetone led to the production of CNMs with worse
structural characteristics and also led to a greater volume of dis-
organized carbon structures [47]. On the other hand, For CNM-Et, a
small peak was also observed at 439 °C, which, as previously discussed,
shows that carbon structures with less resistance to oxidation were also
formed. These results corroborate with the literature since several au-
thors have reported that ethanol generates more orderly and defect-free
carbon structures, due to the hydroxyl groups that are released during
its decomposition, thus preventing the formation of amorphous struc-
tures [48–50].
3.3.2. Scanning electron microscopy
The main factors that determine the physical and chemical prop-
erties of CNMs are structural parameters such as diameter, length of
filaments, atomic defects and the presence of other atoms along the
material [40,51]. Fig. 5 shows the SEM images for both samples. It is
possible to observe that for the material obtained from ethanol
(Fig. 5a), structures with greater similarity to carbon nanotubes were
obtained. For the sample obtained from acetone (Fig. 5b), although it is
possible to observe tube-like structures, they are less numerous, and
considerably bulkier, thicker and it is noted more amorphous struc-
tures.
From the SEM images, it is possible to suggest that CNM-Et has a
more homogeneous and organized structure than CNM-Ac. This
G.G. Guerreiro, et al. Ceramics International 46 (2020) 29271–29281

Fig. 4. a) TG curves for CNM-Ac and CNM-ET in synthetic air, b) DTG curves for CNM-Ac and CNM-ET synthetized the best condition in synthetic air.

assumption is supported by the results of the thermogravimetric ana-
lysis presented in Fig. 4, since the DTG curve obtained for CNM-Et
showed a narrower profile than the curve obtained for CNM-Ac.
3.3.3. Transmission electronic microscopy
The TEM images are shown in Fig. 6. It is confirmed the formation
of CNTs for both samples: CNM-Et (a), and CNM-Ac (b). For the CNM-
Ac sample it was also observed a considerable amount of helical carbon
nanofibers, which are formed due to defects in the hexagonal network
of the nanofibers, which led to this helical shape [52]. Moreover, it is
noted that CNTs are considerably more defective. Furthermore, it is
possible to observe that the nanotubes formed in CNM-Et are relatively
thicker than those formed in CNM-Ac and are considerably less defec-
tive. In addition, the nanotubes are similar to the bamboo like carbon
structure in the material obtained from acetone - they can be seen in
Fig. 6-c [53]. It is also important to note that the TEM images corro-
borate with the previous results of DTG and SEM, and prove that, in
fact, the material synthesized from ethanol has a more organized and
less defective carbon structures than the one synthesized from acetone.
3.3.4. Raman spectroscopy
In order to better understand the quality of the synthesized CNMs,
Raman spectroscopy was employed. Fig. S2 shows the Raman spectra
obtained for CNM-Ac and CNM-Et. The samples present the two char-
acteristic bands of carbon materials in the first order region: the D band,
located around 1350 cm-1, related to the presence of defects in systems
with sp2 hybridization, and the G band, located around 1550 cm−1,
characteristic of carbon materials with hybridized sp2 bonds, and is
related to more organized carbon structures [54]. The bands G′ and
D + G are also observed, located in the second order region in the

Fig. 5. SEM images for: a) CNM-Et and b) CNM-Ac.

29275
G.G. Guerreiro, et al.
Fig. 6. TEM images for: a) CNM-Et, b) CNM-Ac, and c) bamboo like carbon structure.
range of 2600–2900 cm−1, which are also characteristic of carbon
materials [54,55]. It is also noted the presence of significant bands in
the region of 110–600 cm−1 for CNM-Ac, which can be associated with
the oxidation of iron and its possible transformation into hematite [25].
The relationship between the intensities of bands D and G (ID/IG)
provides the degree of disorder of carbonaceous materials [40]. The ID/
IG values for the materials are very similar (CNM-Ac: 1.13 and CNM-Et:
1.17), which at first, suggest that the samples have a similar structural
quality. However, based on the results of the other characterizations
conducted in this work, it was evident that the material synthesized
from acetone has a structure that is considerably more defective and
richer in amorphous carbon. However, as discussed previously, some
authors point out that caution should be taken when analyzing Raman
spectra of carbon materials that contain hematite, because this oxide
has a vibrational mode, called 2LO, in the region of 1320 cm−1, close to
band D (1350 cm−1), opening the possibility for overlapping bands
[26]. Decoupling the D band (from carbon materials) from the 2LO
band (from hematite) is a topic that has been debated to the present
day. It is a great interest by various fields of science, mainly because it
represents a big obstacle to study soils from other planets [56]. Until
the present date, there is no consensus regarding how to solve this issue.
However, in the present work, in order to extract as much information
as possible from the obtained Raman spectra, a study of the region
between 1000 and 1800 cm−1 was carried out by means of peak de-
convolution using the Lorentz mathematical model. This method was
based on a series of other works from the literature [25,26,57,58].
According to the literature, the first order region can have five
components [59,60]. The traditional bands: D, from now on called D1
(at about 1350 cm−1), which is related to disordered structures and G
(around 1550 cm−1) which is related to the ordered carbon sp2
29276
Ceramics International 46 (2020) 29271–29281
structures. The D3 band (around 1500 cm−1) refers to defects outside
the carbon sp2 plans (e.g. amorphous carbon). The D4 band
(1050–1200 cm−1), which appears intensely only in materials with
disordered structures. Finally, the D2 band (around 1620 cm−1), which
usually appears as a shoulder of the G band and it is also associated
with imperfections. Based on the bands described above and the 2LO
mode of hematite around 1320 cm−1 (represented by the letter H), the
deconvolution of the spectra was performed. Fig. 7 shows the decon-
voluted Raman spectra for both CNMs. The adjustment to the Lorentz
mathematical model showed a 99% approximation for both Raman
spectra. It is noted that both materials had all the characteristic bands
of carbonic materials, but with slight deviations from the ideal values,
which was expected, since the position of the bands are very sensitive to
the laser wavelength and the power used during the Raman measures
[54]. It is observed that the H band was much more pronounced for
CNM-Et, which considerably mitigated the intensity of the D1 band for
this sample. From the intensities of the deconvolved bands, it was
possible to calculate a new relationship, now between D1 and G, called
ID1/IG. The values obtained were 1.13 for CNM-Ac and 0.44 for CNM-
Et. By this data treatment, it is evidenced that the CNM-Et has a more
organized structure, corroborating both with what had been observed
in other characterizations and with what is reported in the literature
which extensively emphasizes that ethanol should lead to a more or-
ganized material [48–50,61–63].
3.3.5. Nitrogen adsorption
The specific surface area of the materials was estimated by nitrogen
adsorption using the BET method. The results revealed that the sam-
ples: IOT, CNM-Et and CNM-Ac have areas equal to 0.2, 15.5, e
15.7 m2 g−1, respectively. First of all, it is noted an enormous increase
G.G. Guerreiro, et al.
Fig. 7. Raman spectra deconvoluted by the Lorentz model for a) CNM-AC, and
b) CNM-Et.
in surface area among the raw IOTs and CNMs (Ac e Et) of around 77
times. Moreover, although the CNMs have a smallest surface area when
compared to other materials in the literature [13,14,64], it is necessary
to mention that in the present work, both the CNMs and IOTs were used
without any purification or surface treatment. Therefore, the presented
results are promising because they have an enormous margin to be
improved by many functionalization and purification and routes that
already reported in the literature [65].
3.4. Adsorption tests
After the characterization, the CNM-Et and CNM-Ac were applied as
adsorbents for emerging contaminants in aqueous medium. For that,
two model molecules were used: rhodamine-B (RD+) (a cationic dye),
and indigo carmine (IC−) (an anionic dye). Fig. 8 shows the percen-
tages of removal of RD+and IC− by both CNMs and by IOT. It is ob-
served that IOT was not able to significantly adsorb either of the two
dyes. As for the CNMs, they were only able to adsorb the cationic dye.
The results suggest that this significant increase in the adsorption ca-
pacity of CNMs in comparison to raw IOT is directly related to the
presence of carbon nanostructures in CNM-Ac and CNM-Et, which
consequently increases the surface area [10]. These results are also an
indication that the synthesized CNMs have a greater affinity with ca-
tionic contaminants, or molecules with positive structure.
Regarding the adsorption of RD+ by the CNM's, the highest
29277
Ceramics International 46 (2020) 29271–29281
percentage of dye removal was 85% for both materials. It was observed
that the removal rate increases considerably in the first 50 min of the
experiment, and then continues to augment at a relatively slower speed
until reaching equilibrium after about 270 min for CNM-Ac and
300 min for CNM-Et. This phenomenon is attributed to the fact that the
dye solution is very concentrated in the first minutes of contact and
there is a large number of vacant sites in the adsorbents, over time, the
sites are occupied quickly, and as time passes the vacant sites of the
adsorbents become more and more scarce and the concentration of the
solution reduces thus, decreasing the adsorption rate [66]. Moreover, it
appears that the surface of CNM-Et, at first, favored the adsorption of
the dye RD+ more than the CNM-Ac which showed a defective struc-
ture. In order to obtain detailed information about the adsorption me-
chanisms involved in these systems, a kinetic study was carried out, and
adsorption isotherms were plotted using different models. These studies
were conducted only with RD+ and the CNM's (CNM-Et and CNM-Ac).
3.4.1. Adsorption kinetics
In practical terms aiming at future applications, the adsorption ki-
netics between the adsorbate and adsorbent is one of the main para-
meters to evaluate the adsorption properties [67]. Fig. 9 shows the
curves resulted from the nonlinear adjustments of the experimental
data for both CNM's to the kinetic models of pseudo 1st order and
pseudo 2nd order. Their kinetic parameters are shown in Table 2, re-
spectively.
The data obtained experimentally for both adsorbents were better
adjusted to the kinetic model of pseudo 2nd order (CNM-Ac:
R2 = 0.994, CNM-Et: R2 = 0.991). In addition, the values of qe cal-
culated from the kinetic model of pseudo 2nd order (17.27 mg g−1 for
CNM-Ac and 19.13 mg g−1 for CNM-Et) are consistent with the values
of qe obtained experimentally (17.04 mg g−1 for CNM-Ac and
17.01 mg g−1 for CNM-Et). Since the adsorbents showed a clear dif-
ference in the adsorption kinetics, the experimental data were analyzed
by the intraparticle diffusion model to evaluate the steps that are in-
volved in the process of adsorption of RD+ by the CNM's.
The adsorption of dyes by CNMs generally occurs through 2 me-
chanisms: 1st) diffusion of the adsorbate from the concentrated solution
to the surface of the adsorbent, followed by 2nd) the diffusion of the
adsorbate molecules to the most internal adsorption sites of the ad-
sorbent. This mechanism is called intraparticle diffusion [68]. It is as-
sumed that adsorption occurs only through intraparticle diffusion if the
curve obtained is linear and passes through the origin, namely, if all the
experimental data is better adjusted by a single line that intercedes the
origin. On the other hand, it may be presumed that the adsorption
process is not controlled only by the intraparticle diffusion mechanism,
if the experimental data show multilinearity [18]. Fig. 10 shows the
application of the intraparticle diffusion model to the experimental data
for the adsorption of the RD+ dye by both CNMs, and Table S2 presents
their respective parameters. It is observed that the data obtained ex-
perimentally were well adjusted by the model: CNM-Ac (R2: 1st
stage = 0.971, 2nd stage = 0.968) and CNM-Et (R2: 1st Stage = 0.993,
2nd stage = 0.999) indicating that this model is suitable to describe the
possible phenomena that occurs during the adsorption.
For both adsorbents, the graphs showed multilinearity throughout
the time range, suggesting that the RD+ adsorption process is not
limited by the intraparticle diffusion mechanism. Hence, there is at
least more than one adsorption mechanism involved [69]. In fact, this
has been observed through mathematical analysis. In the 1st adsorption
stage, the highest dye adsorption rate is observed for both adsorbents,
followed by the 2nd stage and finally, equilibrium is reached (CNM-Ac:
Kid-1 = 2,793, Kid-2 = 0.319, CNM-Et: Kid-1 = 1.354, Kid-
2 = 0.694). During the 1st stage, the diffusion of the RD+ molecules
occurs rapidly to the vacant sites on the surfaces of the adsorbents.
Then in the 2nd stage, the diffusion of the RD+ molecules occurs to the
innermost sites of the adsorbents considerably at slower rate than the
1st stage [18]. It is also observed that, while in the 1st stage, the Kid-1
G.G. Guerreiro, et al. Ceramics International 46 (2020) 29271–29281

Fig. 8. Removal percentages of RD + and IC- by: a) CNM-Ac, and b) CNM-Et and IOT.

Fig. 9. Kinetic curves of adsorption for the dye RD+ with the adsorbents a) CNM-Ac, and b) CNM-Et.

Table 2 3.4.2. Adsorption isotherm

Parameters of nonlinear adjustments of experimental data to kinetic models. Fig. 11 shows the curves resulting from the nonlinear adjustments of
Kinetic Models Parameters CNM_Ac CNM_Et
the experimental data of both adsorbents to the Langmuir and Freun-
dlich adsorption isotherms models, which have their respective para-
a
Pseudo 1 order −1
qe (mg g ) 16,43 16,50 meters presented in Table 3.
k1 (min−1) 0,080 0017 The data obtained experimentally for both adsorbents were better
R2 0,965 0970
adjusted to the Langmuir model (CNM-Ac: R2 = 0.932, CNM-Et:
Pseudo 2a order qe (mg g−1) 17,27 19,13
k2 (g mg−1 min−1) 0,007 0001 R2 = 0.942). These results suggest that the adsorption of RD+ occurred
R2 0,994 0991 in homogeneous and specific sites on the CNMs and indicate that the
Intraparticle diffusion 1a stage Kid-1 (mg g−1 min1/2) 2793 1354 Langmuir model can be used to represent the experimental data of
C1 (mg g−1) 0,362 −0,050
adsorption of RD+ by the CNMs [71]. The maximum adsorption ca-
R2 0,971 0993
2a stage Kid-2 (mg g−1 min1/2) 0,319 0694
pacity (qm) calculated from the Langmuir model was similar for both
C2 (mg g−1) 12,17 5177 materials (CNM-Ac: qm = 17.20 mg g−1, CNM-Et:
R2 0,968 0999 qm = 16.30 mg g−1). In addition, the adsorption process is considered
favorable when the separation factor (RL) has values between 0 and 1
[72]. In this study, the RL value was less than 1 for both adsorbents,
for CNM-Ac was about 2 times higher in relation to CNM-Et's, the op- showing that the adsorption processes were favorable (CNM-Ac:
posite behavior was observed in the 2nd stage. These results show that RL = 0.007, CNM-Et: RL = 0.005) [18]. Comparing the results obtained
the samples have different adsorption mechanisms, corroborating the in this work with the literature is complex, since no study was found
argument that materials with different morphologies have different that used tailings to synthesize carbon structures and applied it to the
adsorption behaviors [70]. adsorption of Rhodamine-B. However, even when comparing with
other works outside this scope, the literature shows that the maximum
adsorption capacity of RD+ by CNT's can vary between 28 and

29278
G.G. Guerreiro, et al. Ceramics International 46 (2020) 29271–29281

Fig. 10. Application of the intraparticle diffusion model for a) CNM-Ac, and b) CNM-Et.

Fig. 11. Adsorption isotherms for the RD+ by: a) CNM-Ac, and b) CNM-Et.

Table 3 the carbon precursor under 12 different conditions, and the best set of
Parameters of the nonlinear adjustments of the experimental data to the ad- parameters it was found at 900 °C, synthesis time of 30 min and
sorption isotherm models. maintaining the flow of carbon precursor throughout the entire synth-
Isotherms models Parameters CNM-Ac CNM-Et esis. The different carbon precursors led to materials (CNM-Et and
CNM-Ac) with substantially different structures. CNM-Et presented a
−1
Langmuir qm (mg g ) 17,20 16,30 less defective structure than CNM-Ac. Finally, the materials were tested
KL (L mg−1) 7469 10,15
as adsorbents for emerging contaminants in aqueous media, using two
RL 0,007 0005
R2 0,932 0942 model molecules, the dyes: Rhodamine-B (cationic), and Indigo
Freundlich Kf (mg g−1) 14,02 13,10 Carmine (anionic). Both CNMs proved to be efficient for adsorbing only
n (g mg−1 min−1) 11,38 7968 the cationic dye. The maximum adsorption capacity for both CNM's was
R2 0,906 0918 about 16.8 mg g−1, which is a relevant result even when compared to
other works, especially taken into account that no purification was
employed and therefore there is a huge margin to be improved.
256 mg g−1 [17,73,74]. Nevertheless, it must be taken into account
that pure CNTs were used in these studies, and most of time, functio-
nalized and in the best conditions of pH and temperature. On the other
Declaration of competing interest
hand, no method of purification and functionalization were applied to
the samples in the present work. Thus, the results presented here are
even more relevant, as they open up an enormous margin to be im- The authors declare that they have no known competing financial
proved. interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.

4. Conclusions
In the present work, we have shown for the first time, that it is
possible to synthesize various carbonaceous materials, including con-
siderable amounts of nanostructures like MWCTNs and CNFs, using
untreated iron ore tailings as the catalyst by the CVD method in a fixed-
bed reactor. The synthesis parameters were optimized using ethanol as
Acknowledgments
The authors would like to thank CNPQ and FAPEMIG for their fi-
nancial support. I would also like to thank Professor Dr. Ernesto Soares
de Freitas Neto for his collaboration with Raman Spectroscopy mea-
sures.

29279
G.G. Guerreiro, et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ceramint.2020.08.101.
References
[1] M. Armstrong, R. Petter, C. Petter, Why have so many tailings dams failed in recent
years? Resour. Pol. 63 (2019) 101412, https://doi.org/10.1016/j.resourpol.2019.
101412.
[2] U.R.V. Aires, B.S.M. Santos, C.D. Coelho, D.D. da Silva, M.L. Calijuri, Changes in
land use and land cover as a result of the failure of a mining tailings dam in
Mariana, MG, Brazil, Land Use Pol. 70 (2018) 63–70, https://doi.org/10.1016/j.
landusepol.2017.10.026.
[3] O. Kazak, Y.R. Eker, I. Akin, H. Bingol, A. Tor, A novel red mud@sucrose based
carbon composite: preparation, characterization and its adsorption performance
toward methylene blue in aqueous solution, J. Environ. Chem. Eng. 5 (2017)
2639–2647, https://doi.org/10.1016/j.jece.2017.05.018.
[4] L.A. de C. Bastos, G.C. Silva, J.C. Mendes, R.A.F. Peixoto, Using iron ore tailings
from tailing dams as road material, J. Mater. Civ. Eng. 28 (2016) 1–9, https://doi.
org/10.1061/(ASCE)MT.1943-5533.0001613.
[5] G. Young, M. Yang, Preparation and characterization of Portland cement clinker
from iron ore tailings, Construct. Build. Mater. 197 (2019) 152–156, https://doi.
org/10.1016/j.conbuildmat.2018.11.236.
[6] R. Atchudan, B.G. Cha, N. Lone, J. Kim, J. Joo, Synthesis of high-quality carbon
nanotubes by using monodisperse spherical mesoporous silica encapsulating iron
oxide nanoparticles, Kor. J. Chem. Eng. 36 (2019) 157–165, https://doi.org/10.
1007/s11814-018-0200-z.
[7] X. Jiang, W. Guo, P. Lu, D. Song, A. Guo, J. Liu, J. Liang, F. Hou, CNTs@γ-Fe 2 O 3
@C composite electrode for high capacity lithium ion storage, Int. J. Hydrogen
Energy 43 (2018) 14027–14033, https://doi.org/10.1016/j.ijhydene.2018.01.102.
[8] E. Zohourvahid-Karimi, A. Moloodi, J.V. Khaki, A study on carbon nanotubes/na-
nofibers production via SHS method in C-Al-Fe2O3 system, J. Mater. Res. Technol.
7 (2018) 212–217, https://doi.org/10.1016/j.jmrt.2017.06.005.
[9] K. Hernadi, A. Fonseca, J.B. Nagy, D. Bernaerts, A.A. Lucas, Fe-catalyzed carbon
nanotube formation, Carbon N. Y. 34 (1996) 1249–1257, https://doi.org/10.1016/
0008-6223(96)00074-7.
[10] A.A.S. Oliveira, A.R. Martins, R.V. Ferreira, I.T. Cunha, P. Serp, J.P. de Mesquita,
F.C.C. Moura, N-doped carbon nanotubes grown on red mud residue: hybrid na-
nocomposites for technological applications, Catal. Today 344 (2019) 247–258,
https://doi.org/10.1016/j.cattod.2019.04.060.
[11] O.M. Dunens, K.J. MacKenzie, A.T. Harris, Synthesis of multi-walled carbon na-
notubes on ‘red mud’ catalysts, Carbon N. Y. 48 (2010) 2375–2377, https://doi.org/
10.1016/j.carbon.2010.02.039.
[12] S. Sushil, A.M. Alabdulrahman, M. Balakrishnan, V.S. Batra, R.A. Blackley, J. Clapp,
J.S.J. Hargreaves, A. Monaghan, I.D. Pulford, J.L. Rico, Carbon deposition and
phase transformations in red mud on exposure to methane, J. Hazard Mater. 180
(2010) 409–418, https://doi.org/10.1016/j.jhazmat.2010.04.046.
[13] A.A. Oliveira, J.C. Tristão, J.D. Ardisson, A. Dias, R.M. Lago, Production of na-
nostructured magnetic composites based on Fe0 nuclei coated with carbon nano-
fibers and nanotubes from red mud waste and ethanol, Appl. Catal. B Environ. 105
(2011) 163–170, https://doi.org/10.1016/j.apcatb.2011.04.007.
[14] S. Mesgari Abbasi, A. Rashidi, A. Ghorbani, G. Khalaj, Synthesis, processing,
characterization, and applications of red mud/carbon nanotube composites, Ceram.
Int. 42 (2016) 16738–16743, https://doi.org/10.1016/j.ceramint.2016.07.146.
[15] L. Zhou, L.R. Enakonda, S. Li, D. Gary, P. Del-Gallo, C. Mennemann, J.M. Basset,
Iron ore catalysts for methane decomposition to make COx free hydrogen and
carbon nano material, J. Taiwan Inst. Chem. Eng. 87 (2018) 54–63, https://doi.org/
10.1016/j.jtice.2018.03.008.
[16] Y. Manawi, Ihsanullah, A. Samara, T. Al-Ansari, M. Atieh, A review of carbon na-
nomaterials' synthesis via the chemical vapor deposition (CVD) method, Materials
(Basel) 11 (2018) 822, https://doi.org/10.3390/ma11050822.
[17] O.A. Oyetade, V.O. Nyamori, B.S. Martincigh, S.B. Jonnalagadda, Effectiveness of
carbon nanotube–cobalt ferrite nanocomposites for the adsorption of rhodamine B
from aqueous solutions, RSC Adv. 5 (2015) 22724–22739, https://doi.org/10.
1039/C4RA15446K.
[18] M.T. Yagub, T.K. Sen, S. Afroze, H.M. Ang, Dye and its removal from aqueous so-
lution by adsorption: a review, Adv. Colloid Interface Sci. 209 (2014) 172–184,
https://doi.org/10.1016/j.cis.2014.04.002.
[19] S. Shukrullah, M.Y. Naz, N.M. Mohamed, K.A. Ibrahim, A. Ghaffar, N.M. AbdEl-
Salam, Production of bundled CNTs by floating a compound catalyst in an atmo-
spheric pressure horizontal CVD reactor, Results Phys. 12 (2019) 1163–1171,
https://doi.org/10.1016/j.rinp.2019.01.001.
[20] W.J. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution, J. Sanit.
Eng. Div. 89 (1963) 31–60 https://bit.ly/2JREAoh.
[21] Y. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (1999) 451–465, https://doi.org/10.1016/S0032-9592(98)00112-5.
[22] S. Lagergren, About the theory of so-called adsorption of solid substance,
Handlinger 24 (1898) 1–39, https://doi.org/10.4236/ss.2014.52008.
[23] I. Langmuir, The adsorption OF gases ON plane surfaces OF glass, mica and pla-
tinum, J. Am. Chem. Soc. 40 (1918) 1361–1403, https://doi.org/10.1021/
ja02242a004.
[24] P.D. Dauce, G.B. de Castro, M.M.F. Lima, R.M.F. Lima, Characterisation and mag-
netic concentration of an iron ore tailings, J. Mater. Res. Technol. 8 (2019)
29280
Ceramics International 46 (2020) 29271–29281
1052–1059, https://doi.org/10.1016/j.jmrt.2018.07.015.
[25] S. Das, M.J. Hendry, Application of Raman spectroscopy to identify iron minerals
commonly found in mine wastes, Chem. Geol. 290 (2011) 101–108, https://doi.
org/10.1016/j.chemgeo.2011.09.001.
[26] C. Brolly, J. Parnell, S. Bowden, Raman spectroscopy: caution when interpreting
organic carbon from oxidising environments, Planet. Space Sci. 121 (2016) 53–59,
https://doi.org/10.1016/j.pss.2015.12.008.
[27] H. Liu, T. Chen, X. Zou, C. Qing, R.L. Frost, Thermal treatment of natural goethite:
thermal transformation and physical properties, Thermochim. Acta 568 (2013)
115–121, https://doi.org/10.1016/j.tca.2013.06.027.
[28] Z. Yong, L. Fang, Z. Zhi-hua, Synthesis of heterostructured helical carbon nanotubes
by iron-catalyzed ethanol decomposition, Micron 42 (2011) 547–552, https://doi.
org/10.1016/j.micron.2011.01.007.
[29] B. Bahrami, A. Khodadadi, Y. Mortazavi, M. Esmaieli, Short time synthesis of high
quality carbon nanotubes with high rates by CVD of methane on continuously
emerged iron nanoparticles, Appl. Surf. Sci. 257 (2011) 9710–9716, https://doi.
org/10.1016/j.apsusc.2011.05.086.
[30] M. Felisberto, L. Sacco, I. Mondragon, G.H. Rubiolo, R.J. Candal, S. Goyanes, The
growth of carbon nanotubes on large areas of silicon substrate using commercial
iron oxide nanoparticles as a catalyst, Mater. Lett. 64 (2010) 2188–2190, https://
doi.org/10.1016/j.matlet.2010.07.016.
[31] M.C. Schnitzler, A.J.G. Zarbin, Utilization of iron oxide film obtained by CVD
process as catalyst to carbon nanotubes growth, J. Solid State Chem. 182 (2009)
2867–2872, https://doi.org/10.1016/j.jssc.2009.07.057.
[32] M.H. Khedr, K.S. Abdel Halim, N.K. Soliman, Effect of temperature on the kinetics
of acetylene decomposition over reduced iron oxide catalyst for the production of
carbon nanotubes, Appl. Surf. Sci. 255 (2008) 2375–2381, https://doi.org/10.
1016/j.apsusc.2008.07.096.
[33] H. Sato, Y. Hori, K. Hata, K. Seko, H. Nakahara, Y. Saito, Effect of catalyst oxidation
on the growth of carbon nanotubes by thermal chemical vapor deposition, J. Appl.
Phys. 100 (2006) 104321, https://doi.org/10.1063/1.2364381.
[34] 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, https://doi.org/10.1016/j.mssp.2015.08.013.
[35] A. Peigney, P. Coquay, E. Flahaut, R.E. Vandenberghe, E. De Grave, C. Laurent, A
study of the formation of single- and double-walled carbon nanotubes by a CVD
method, J. Phys. Chem. B 105 (2001) 9699–9710, https://doi.org/10.1021/
jp004586n.
[36] N.M. Mubarak, E.C. Abdullah, N.S. Jayakumar, J.N. Sahu, An overview on methods
for the production of carbon nanotubes, J. Ind. Eng. Chem. 20 (2014) 1186–1197,
https://doi.org/10.1016/j.jiec.2013.09.001.
[37] L. Chen, H. Liu, K. Yang, J. Wang, X. Wang, The effect of reaction temperature on
the diameter distribution of carbon nanotubes grown from ethylene decomposition
over a Co-La-O catalyst, Mater. Chem. Phys. 112 (2008) 407–411, https://doi.org/
10.1016/j.matchemphys.2008.05.081.
[39] Y.-L. Li, L.-H. Zhang, X.-H. Zhong, A.H. Windle, Synthesis of high purity single-
walled carbon nanotubes from ethanol by catalytic gas flow CVD reactions,
Nanotechnology 18 (2007) 225604, https://doi.org/10.1088/0957-4484/18/22/
225604.
[40] J.H. Lehman, M. Terrones, E. Mansfield, K.E. Hurst, V. Meunier, Evaluating the
characteristics of multiwall carbon nanotubes, Carbon N. Y. 49 (2011) 2581–2602,
https://doi.org/10.1016/j.carbon.2011.03.028.
[41] A.A. Balandin, Thermal properties of graphene and nanostructured carbon mate-
rials, Nat. Mater. 10 (2011) 569–581, https://doi.org/10.1038/nmat3064.
[42] L.S.K. Pang, J.D. Saxby, S.P. Chatfield, Thermogravimetric analysis of carbon na-
notubes and nanoparticles, J. Phys. Chem. 97 (1993) 6941–6942, https://doi.org/
10.1021/j100129a001.
[43] G.S.B. McKee, K.S. Vecchio, Thermogravimetric analysis of synthesis variation ef-
fects on CVD generated multiwalled carbon nanotubes, J. Phys. Chem. B 110 (2006)
1179–1186, https://doi.org/10.1021/jp054265h.
[44] F.V. Ferreira, W. Franceschi, B.R.C. Menezes, A.F. Biagioni, A.R. Coutinho,
L.S. Cividanes, Synthesis, characterization, and applications carbon nanotubes, in:
S. Yaragalla, R.K. Mishra, S. Thomas, N. Kalarikkal, H. Maria (Eds.), Carbon-Based
Nanofillers and Their Rubber Nanocomposites, first ed., Elsevier, Amsterdã, 2019,
pp. 1–45, , https://doi.org/10.1016/b978-0-12-813248-7.00008-0.
[45] D.Y. Kim, C.-M. Yang, Y.S. Park, K.K. Kim, S.Y. Jeong, J.H. Han, Y.H. Lee,
Characterization of thin multi-walled carbon nanotubes synthesized by catalytic
chemical vapor deposition, Chem. Phys. Lett. 413 (2005) 135–141, https://doi.org/
10.1016/j.cplett.2005.07.064.
[46] S. Iijima, Helical microtubules of graphitic carbon, Nature 354 (1991) 56–58,
https://doi.org/10.1038/354056a0.
[47] L.A. Montoro, P. Corio, J.M. Rosolen, A comparative study of alcohols and ketones
as carbon precursor for multi-walled carbon nanotube growth, Carbon N. Y. 45
(2007) 1234–1241, https://doi.org/10.1016/j.carbon.2007.01.025.
[48] T. Fujii, H. Kiribayashi, T. Saida, S. Naritsuka, T. Maruyama, Low temperature
growth of single-walled carbon nanotubes from Ru catalysts by alcohol catalytic
chemical vapor deposition, Diam. Relat. Mater. 77 (2017) 97–101, https://doi.org/
10.1016/j.diamond.2017.06.009.
[49] Y. Zhang, J.M. Gregoire, R.B. van Dover, A.J. Hart, Ethanol-promoted high-yield
growth of few-walled carbon nanotubes, J. Phys. Chem. C 114 (2010) 6389–6395,
https://doi.org/10.1021/jp100358j.
[50] O. Guellati, I. Janowska, D. Bégin, M. Guerioune, Z. Mekhalif, J. Delhalle,
S. Moldovan, O. Ersen, C. Pham-Huu, Influence of ethanol in the presence of H2 on
the catalytic growth of vertically aligned carbon nanotubes, Appl. Catal. A Gen.
423–424 (2012) 7–14, https://doi.org/10.1016/j.apcata.2012.02.036.
[51] J.M.H. Ramirez, R.P. Bustamante, A.A. Elguezabal, An overview of the synthesis,
G.G. Guerreiro, et al.
characterization, and applications of carbon nanotubes, in: S. Yaragalla,
R.K. Mishra, S. Thomas, N. Kalarikkal, H. Maria (Eds.), Carbon-Based Nanofillers
and Their Rubber Nanocomposites, first ed., Elsevier Inc., Amsterdã, 2019, pp.
47–75, , https://doi.org/10.1016/b978-0-12-813248-7.00002-x.
[52] F. Nitze, E. Abou-Hamad, T. Wågberg, Carbon nanotubes and helical carbon na-
nofibers grown by chemical vapour deposition on C60 fullerene supported Pd na-
noparticles, Carbon N. Y. 49 (2011) 1101–1107, https://doi.org/10.1016/j.carbon.
2010.11.015.
[53] Y. Yan, J. Miao, Z. Yang, F.-X. Xiao, H. Bin Yang, B. Liu, Y. Yang, Carbon nanotube
catalysts: recent advances in synthesis, characterization and applications, Chem.
Soc. Rev. 44 (2015) 3295–3346, https://doi.org/10.1039/C4CS00492B.
[54] M. Dresselhaus, A. Jorio, M. Hofmann, G. Dresselhaus, R. Saito, Perspectives on
carbon nanotubes and graphene Raman spectroscopy, Nano Lett. 10 (2010)
751–758, https://doi.org/10.1021/nl904286r.
[55] M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, L.G. Cançado, A. Jorio, R. Saito,
Studying disorder in graphite-based systems by Raman spectroscopy, Phys. Chem.
Chem. Phys. 9 (2007) 1276–1290, https://doi.org/10.1039/B613962K.
[56] J.P. Smith, F.C. Smith, K.S. Booksh, Spatial and spectral resolution of carbonaceous
material from hematite (α-Fe 2 O 3 ) using multivariate curve resolution-alternating
least squares (MCR-ALS) with Raman microspectroscopic mapping: implications for
the search for life on Mars, Analyst 142 (2017) 3140–3156, https://doi.org/10.
1039/C7AN00481H.
[57] C.P. Marshall, A. Olcott Marshall, Raman hyperspectral imaging of microfossils:
potential pitfalls, Astrobiology 13 (2013) 920–931, https://doi.org/10.1089/ast.
2013.1034.
[58] C.P. Marshall, A.O. Marshall, Hematite and carbonaceous materials in geological
samples: a cautionary tale, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 80
(2011) 133–137, https://doi.org/10.1016/j.saa.2011.03.006.
[59] O. Beyssac, B. Goffé, J.-P. Petitet, E. Froigneux, M. Moreau, J.-N. Rouzaud, On the
characterization of disordered and heterogeneous carbonaceous materials by
Raman spectroscopy, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 59 (2003)
2267–2276, https://doi.org/10.1016/S1386-1425(03)00070-2.
[60] A. Sadezky, H. Muckenhuber, H. Grothe, R. Niessner, U. Pöschl, Raman micro-
spectroscopy of soot and related carbonaceous materials: spectral analysis and
structural information, Carbon N. Y. 43 (2005) 1731–1742, https://doi.org/10.
1016/j.carbon.2005.02.018.
[61] I. Nurulhuda, R. Poh, M.Z. Mazatulikhma, M. Rusop, Evaporated ethanol as pre-
cursor for carbon nanotubes synthesis, Adv. Mater. Res. 832 (2013) 322–327
https://doi.org/10.4028/www.scientific.net/AMR.832.322.
[62] S.D. Shandakov, A.V. Kosobutsky, M.S. Rybakov, O.G. Sevostyanov, D.M. Russakov,
M.V. Lomakin, A.I. Vershinina, I.M. Chirkova, Effect of gaseous and condensate
products of ethanol decomposition on aerosol CVD synthesis of single-walled
carbon nanotubes, Carbon N. Y. 126 (2018) 522–531, https://doi.org/10.1016/j.
carbon.2017.10.064.
[63] J. Cheng, X.P. Zou, G.Q. Yang, X.M. Lü, C.L. Wei, Z. Sun, H.Y. Feng, Y. Yang,
29281
Ceramics International 46 (2020) 29271–29281
Temperature effects on synthesis of multi-walled carbon nanotubes by ethanol
catalyst chemical vapor deposition, Adv. Mater. Res. 123–125 (2010) 799–802
http://doi.org/10.4028/www.scientific.net/AMR.123-125.799.
[64] R.H. Gangupomu, M.L. Sattler, D. Ramirez, Comparative study of carbon nanotubes
and granular activated carbon: physicochemical properties and adsorption capa-
cities, J. Hazard Mater. 302 (2016) 362–374, https://doi.org/10.1016/j.jhazmat.
2015.09.002.
[65] J. Xu, Z. Cao, Y. Zhang, Z. Yuan, Z. Lou, X. Xu, X. Wang, A review of functionalized
carbon nanotubes and graphene for heavy metal adsorption from water: prepara-
tion, application, and mechanism, Chemosphere 195 (2018) 351–364, https://doi.
org/10.1016/j.chemosphere.2017.12.061.
[66] L. Hu, Z. Yang, Y. Wang, Y. Li, D. Fan, D. Wu, Q. Wei, B. Du, Facile preparation of
water-soluble hyperbranched polyamine functionalized multiwalled carbon nano-
tubes for high-efficiency organic dye removal from aqueous solution, Sci. Rep. 7
(2017) 3611, https://doi.org/10.1038/s41598-017-03490-6.
[67] N. Boukhalfa, M. Boutahala, N. Djebri, A. Idris, Kinetics, thermodynamics, equili-
brium isotherms, and reusability studies of cationic dye adsorption by magnetic
alginate/oxidized multiwalled carbon nanotubes composites, Int. J. Biol. Macromol.
123 (2019) 539–548, https://doi.org/10.1016/j.ijbiomac.2018.11.102.
[68] L. Ai, C. Zhang, F. Liao, Y. Wang, M. Li, L. Meng, J. Jiang, Removal of methylene
blue from aqueous solution with magnetite loaded multi-wall carbon nanotube:
kinetic, isotherm and mechanism analysis, J. Hazard Mater. 198 (2011) 282–290,
https://doi.org/10.1016/j.jhazmat.2011.10.041.
[69] Z.L. Wu, Q. Liu, X.-Q. Chen, J.-G. Yu, Preconcentration and analysis of Rhodamine B
in water and red wine samples by using magnesium hydroxide/carbon nanotube
composites as a solid-phase extractant, J. Separ. Sci. 38 (2015) 3404–3411, https://
doi.org/10.1002/jssc.201500246.
[70] Ihsanullah, Carbon nanotube membranes for water purification: developments,
challenges, and prospects for the future, Separ. Purif. Technol. 209 (2019) 307–337,
https://doi.org/10.1016/j.seppur.2018.07.043.
[71] F. Karkeh-abadi, S. Saber-Samandari, S. Saber-Samandari, The impact of functio-
nalized CNT in the network of sodium alginate-based nanocomposite beads on the
removal of Co(II) ions from aqueous solutions, J. Hazard Mater. 312 (2016)
224–233, https://doi.org/10.1016/j.jhazmat.2016.03.074.
[72] T. Ahamad, M. Naushad, G.E. Eldesoky, S.I. Al-Saeedi, A. Nafady, N.S. Al-Kadhi,
A.H. Al-Muhtaseb, A.A. Khan, A. Khan, Effective and fast adsorptive removal of
toxic cationic dye (MB) from aqueous medium using amino-functionalized magnetic
multiwall carbon nanotubes, J. Mol. Liq. 282 (2019) 154–161, https://doi.org/10.
1016/j.molliq.2019.02.128.
[73] H. Huang, J. Yu, X. Jiang, Preparation OF magnetic oxidized multi-walled carbon
nanotubes for the adsorption OF rhodamine B IN aqueous solution, Nano 9 (2014)
1450093, https://doi.org/10.1142/S1793292014500933.
[74] M.A. Shouman, N.A. Fathy, Microporous nanohybrids of carbon xerogels and multi-
walled carbon nanotubes for removal of rhodamine B dye, J. Water Process Eng. 23
(2018) 165–173, https://doi.org/10.1016/j.jwpe.2018.03.014.