RSC Advances

View Article Online

PAPER View Journal | View Issue

Carbon nanotubes synthesis using carbonization of

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Cite this: RSC Adv., 2017, 7, 28535

pretreated rice straw through chemical vapor
deposition of camphor
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

Nady A. Fathy *

There is a pressing demand to prepare low-cost carbon nanotubes (CNTs) from renewable biomass
resources as cheap carbon precursors and catalyst supports during chemical vapor deposition (CVD).
Camphor and rice straw are quite an eco-friendly, renewable and low-cost carbon sources to prepare
CNTs. Here, successful attempts for preparing CNTs through carbonization of hydrothermally treated
rice straw using either mono-catalyst of ferrocene (RS-H/Fe) or mixed catalysts of ferrocene and nickel
nitrate (RS-H/Fe–Ni) in presence of gaseous carbon source emitted from heating camphor under
flowing N2 gas were achieved. Scanning electron microscope (SEM) combined with energy-dispersive
spectroscopy (EDS), transmission electron microscope (TEM), Raman spectroscopy and thermal
gravimetric analysis (TGA) techniques were used to determine the morphology, surface, electronic
structures and thermal stability of the produced CNTs. Different structures of CNTs were grown with
outer diameters ranging from 22 nm to 66 nm. Few amounts with small outer diameters of coiled
CNTs–Fe bundles were produced over carbonized rice straw with ferrocene (RS-H/Fe) through
a bottom growth mechanism. Whereas considerable amounts of straight and large outer diameter of
CNTs-bundles (CNTs–Fe–Ni) were formed over RS-H/Fe–Ni substrate via a bottom growth mechanism
also. Raman spectra showed two main bands of CNTs; G-band at
1580 cm1 and D-band at 1356 cm1
Received 1st May 2017
Accepted 24th May 2017
or 1335 cm1 which obtained on RS-H/Fe and RS-H/Fe–Ni samples, respectively. Conclusively, the
presence of Ni with ferrocene can enhance the yield, thickness and graphitization extent of the as-
DOI: 10.1039/c7ra04882c
prepared CNTs. Therefore, conversion of available-cheap biomasses into high added-value materials
rsc.li/rsc-advances such as CNTs becomes a realistic, feasible and thus reduces the cost production of CNTs.

and cyclohexane were used extensively as CNTs precursors.3–9

1. Introduction Also, several inorganic substrates like graphite, quartz, silicon,
Carbon nanotubes (CNTs) have been one of the most popular silicon carbide, silica, alumina, zeolite, CaCO3, MgO, etc., which
one-dimensional carbon nanomaterials since their discovery by are relatively expensive materials which supported some cata-
Iijima in 1991.1 The unique structure of CNTs endows them lysts such as Fe, Ni, Co, Mo, etc., in mono-, bi- or tertiary forms
with superior electronic, optoelectronic, mechanical, and were reported in the CVD process.6–8,10–22
chemical properties, and they can be considered as semi- Based on the growing environmental concern and increasing
conducting or metallic materials.2–10 Currently, they are CNT demand, many investigations have carried out to develop
synthesized by three common processes including the arc a sustainable technology and to increase the mass production of
discharge,11 the laser ablation12 and the chemical vapor depo- CNTs. For example, renewable and eco-friendly botanical
sition (CVD) from catalytic decomposition of hydrocarbons on materials such as camphor,14,15 oiled-petroleum wastes such as
transition metals at high temperatures.13–20 Practically, CVD turpentine oil,16 deoiled asphalt17 and eucalyptus oil18 as well as
process is recognized as the most promising technique for some vegetable oils such as coconut,19 neem,20 palm oil21 or
industrial scale-up. Synthesis of CNTs is mainly controlled by waste cooking palm oil22 as starting materials in CNTs
type of carbonaceous feedstocks, catalysts, substrates and the production were studied.
necessary power consumption through CVD process.3 Different Recently, few works have focused on the optimization and
petroleum hydrocarbons in gas-form such as methane, ethylene simplication of synthesis of carbon nanotubes through utili-
and acetylene or in liquid-form like alcohols, benzene, xylene zation of agro-residues. Goodell et al.23 reported that CNTs with
outer diameters from 10 to 20 nm can be prepared from wood
ber using continuous oxidation at 240  C within several cyclic
Physical Chemistry Department, National Research Centre, 33 El Bohouth Street
(former Tahrir st.), Dokki, P.O. 12622, Giza, Egypt. E-mail: fathyna.77@hotmail.
oxidations at 400  C in presence of controlled amount of
com; [email protected]; Fax: +20 2 33370597; Tel: +20 2 33371433 oxygen, whereas no CNTs produced from pure cellulose and

This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 28535–28541 | 28535
 View Article Online

RSC Advances Paper

lignin. They proposed that the obtained molecular structure of lignin disappeared. Aer drying overnight at 100  C, a very ne
CNTs is closely related to the hexagonal arrangement of carbon powdered rice straw was obtained and labeled as RS-H.
atoms in the graphite sheets and thus the spatial and molecular
arrangement of cell wall played an important role in the 2.2. Hydrothermal treatment of RS-H supported iron
formation of CNTs. Very recently, Zhu et al.24 synthesized CNTs catalyst
from bamboo charcoal using CVD in the presence of ethanol Preparation of substrate proceeds rstly via hydrothermal
vapor and pyrolysis temperature between 1200 and 1400  C. treatment of the pretreated rice straw obtained (RS-H). This
They observed that the tips of MWCNTs produced consisted product known as a hydrochar which has surface densely
mainly of calcium silicate acting as a catalyst to accelerate the
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

functionalized polar oxygen groups such as carboxylics,

nucleation of MWCNTs. Lately; graphenated-CNTs (g-CNTs)
hydroxyls or quinones which make the surface is very active for
materials were synthesized from waste rice husk (RH) by one-
further chemical process. Typically, a certain amount of RS-H
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

step microwave plasma irradiation (MPI) process.25 Through

was added to solution containing 2 wt% ferrocene which dis-
this technique, which is very expensive and complicated, the solved in ethanol. Then, the mixture was sonicated for 90 min
obtained g-CNTs were composed of graphene standing on the and subsequently changed into a 25 mL Teon-lined autoclave
sidewalls of CNTs, in which the graphene sheets possessed tube inside a stainless steel reactor then heated in an electrical
a large amount of sharp edges, which mainly consisted of 2–6 muffle at 250  C for 120 min. A pale yellow powder of the pre-
layers, and the CNTs had several tens of micrometers in length treated rice straw was obtained and denoted as RS-H/Fe. Aer
and 50–200 in diameter.25
that, it was subjected to CVD process.
Rice straw is one of the abundant lignocellulosic waste
materials in the world where its massive production was esti-
2.3. Preparation of iron and nickel catalysts supported on
mated to be between 650 and 975 million tons per year.26,27
treated rice straw
There is no practical use for these by-products, up till now,
except as a fuel source. Up-to-date, the use of hydrothermally About 2 wt% of mixture solution containing ferrocene and nickel
treated rice straw as a potential biomass for preparation of nitrate (Ni(NO3)2$6H2O) were added to pretreated rice straw in
CNTs through a green nanotechnology method has not been a stoppered ask, heated at 100  C under stirring for 120 min then
demonstrated yet. In this study, the production of carbon followed by ltration, washing and drying. The produced solid
nanotubes (CNTs) was carried out by two sequence steps; (i) material was then hydrothermally treated in distilled water at
hydrothermal treatment and (ii) chemical vapor deposition 250  C for 120 min. Aerward, the produced sample was sepa-
method. rated from water and dried at 80  C overnight. Finally, the
The current work explores some attempts for production of resulting sample (RS-H/Fe–Ni) was subjected to CVD process.
CNTs-bundles via a chemical vapor deposition of camphor
through carbonization of hydrothermally treated rice straw, 2.4. Synthesis of carbon nanotubes (CNTs)
supported either with ferrocene or ferrocene–nickel catalysts. CVD unit comprising two separated chambers, xed on a desk
The growth morphology of CNTs during this advanced process was employed. A stainless steel tube (diameter ¼ 32 mm and
was evaluated using means of SEM and TEM while electronic
properties and thermal stability of the produced CNTs were
assessed by Raman spectroscopy and TGA techniques,
respectively.

2. Experimental
2.1. Pretreatment of rice straw by alkali-acid reagents
Prior hydrothermal treatment, the rice straw was collected from
Delta region in Egypt, washed thoroughly with hot water for
several times then dried overnight at 80  C. Rice straw was
milled, sieved in range of 0.4–0.8 mm (denoted as RS). The RS
was treated with NaOH by mass ratio 1 : 1 in 1 L distilled water
to remove the silica, lignin, hemicellulose and other pectin
substances. The mixture was stirred and heated at 100  C for
120 min then le overnight. Aer that, the alkali treated rice
straw was ltered, washed with hot water and dried overnight at
80  C. Then, acid treatment of pretreated rice straw in alkali was
employed by the reuxing as follows; 2 g of pretreated rice straw
was inserted into 250 mL a round bottle containing 100 mL of
10 v/v% H2SO4 acid and heated at 100  C for 120 min under
continuous stirring. Aer that, the suspended rice straw was Fig. 1 A flow diagram for synthesis of CNTs from camphor and pre-
ltered and washed with hot water until the brown color of treated rice straw throughout a home-made CVD unit.

28536 | RSC Adv., 2017, 7, 28535–28541 This journal is © The Royal Society of Chemistry 2017
 View Article Online

Paper RSC Advances

length ¼ 80 mm) was placed horizontally throughout two elec- obtained in the morphology of rice straw aer treating the rice
tric furnaces as shown in Fig. 1. Camphor was put inside an straw with NaOH.26 Chakraborty et al.28 affirmed that NaOH
alumina boat and transferred into the rst furnace (le hand) pretreatment can have a substantial affect on the crystallinity,
whereas the resulting substrate with catalyst (RS-H/Fe or RS-H/ pore structure, accessibility, stiffness, unit cell structure, and
Fe–Ni) was inserted in an alumina boat then taken into the orientation of brils in cellulosic bers. Such chemical struc-
other 2nd furnace (right hand). A temperature program was ture of rice straw can be thus utilized for production of CNTs.
adjusted from room temperature to 800  C with a heating rate
(10  C min1). When the temperature of 2nd furnace reached
3.1. Morphological properties of the prepared samples
800  C, it was kept for 120 min, and then the camphor was
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

heated to 250  C in order to get the carbon source in the gas Imaging with SEM was used to follow the morphological
phase which then passed throughout the second furnace by the changes in rice straw before and aer pretreatment as seen in
owing N2 gas at 800  C over additional 60 min to get CNTs
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

Fig. 2(A and B). Before any treatment, the surface of raw rice
deposited on the carbonized RS-H/Fe or RS-H/Fe–Ni. Finally, the straw showed smooth, tight and contiguous surface. Aer
two furnaces were switched off and the resulting carbon hydrothermal treatment, RS-H/Fe–Ni countered to a rough
samples were collected and denoted as CNTs–Fe and CNTs–Fe– surface with extensive anomalous porosity and vascular bundles
Ni, respectively. that seem to be severely shrunken compared with untreated rice
straw. The concave appearance of the outer surface disappeared
as a result of removal of lignin and hemicellulose from the rice
2.5. Characterization of the prepared samples
straw. Upon direct carbonization of treated rice straw (RS-H/Fe–
To draw more detailed description, the prepared samples were Ni) at 800  C, straight, porous and rolled brous of cellulose
characterized with reference to their morphologies before and microstructure was formed as depicted in Fig. 2(C). Thus, the
aer formation of CNTs. The surface structure and chemical carbonization of pretreated rice straw generated pores as an
compositions of the prepared samples were estimated by eld- anchor sites for the catalyst and to serve as growing sites for the
emission scanning electron microscope (SEM) combined with catalyst nanoparticles as well. As shown in Fig. 2(D), upon
energy-dispersive spectroscopy and electron backscatter decomposition of camphor at 250  C, meanwhile carbonization
diffraction (FE-SEM, FEI Quanta FEG-250, EDS). High resolu- of RS-H/Fe–Ni was carrying out at 800  C, numerous bundles of
tion transmission electron microscopy (HR-TEM, JEM-1230, CNTs were produced over the pyrolyzed RS-H/Fe–Ni support
Japan) was used to determine the morphologies of the result- and the resulting named as CNTs–Fe–Ni. It is observed that the
ing catalysts and carbon nanotubes (CNTs). Investigation of carbonized RS-H/Fe–Ni support was well covered by a CNTs
Raman spectra was carried out at room temperature using layer with relatively homogeneous diameter distribution. The
Sentera laser Raman spectrometer (Bruker, Germany). The as-prepared CNTs bundles seem to anchor directly on the
thermal stability of the samples was examined (Shimadzu-60 surface of the support. Also, the CNTs can grow on both the
thermal analyzer, Japan) under passing nitrogen atmosphere surface and inside the pores of this carbonized support.
at a heating rate of 10  C min1. Moreover, Brunauer–Emmett–
Teller surface area (SBET, m2 g1) was determined using
nitrogen adsorption analysis at 196  C (BEL-Sorp, Microtrac
Bel Crop, Japan).

3. Results and discussion

The chemical composition of elements in an atomic percentage
for the pretreated rice straw with NaOH and H2SO4 was found to
be: 64.7% C, 24.6% O, 2.76% Na, 0.05% Mg, 4.02% Si, 0.11% Ca,
0.37% Al, 0.80% S and 2.59% P. However, aer CVD process, the
produced CNTs–Fe–Ni has the following composition: 73.5% C,
19.8% O, 1.5% Fe, 1.90% Ni, 1.98% Na, 0.81% Si and 0.51% S.
Moreover, the total surface area of CNTs–Fe and CNTs–Fe–Ni
was found to be 20 and 35 m2 g1, respectively, which is close to
the surface area obtained in the former work.10
In general, rice straw feedstock mostly contains 32–47%
cellulose, 19–27% hemicelluloses, 5–24% lignin and 18.8%
inorganic ashes.26 The polysaccharides, cellulose and hemi-
cellulose are intimately associated with lignin in the plant cell
Fig. 2 SEM images of (A) untreated rice straw, (B) hydrothermally
wall. Alkali pretreatment is known to separate lignin and silica
treated rice straw (RS-H/Fe–Ni) at 250  C for 120 min, (C) after
from lignocellulosic biomass, whereas acid pretreatment is carbonization of RS-H/Fe–Ni sample at 800  C for 180 min and (D)
known to separate hemicellulose from inter-brillar region CNTs–Fe–Ni produced from CVD of camphor through carbonization
completely.26 In our previous study, quite differences were of RS-H/Fe–Ni sample at 800  C for 180 min.

This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 28535–28541 | 28537
 View Article Online

RSC Advances Paper

a gaseous carbon evolved from camphor at 250  C was intro-

duced and hold at this temperature for another 60 min, the
growth of few coiled CNTs-bundles could be obtained as shown
in Fig. 4. The yield of deposited carbon product was 41%.
Obviously, the as-synthesized CNTs bundles with external
diameter of
22 nm was found (Fig. 4) as a result of CVD of
camphor on RS-H/Fe catalyst. Comparing Fig. 3 and 4, it can be
suggested that the presence of graphene sheets and carbon Fe-
nanoparticles can act as an effective substrate during carbon-
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

ization of hydrothermally treated rice straw, and thus would

accelerate the nucleation of CNTs upon passing gaseous
Fig. 3 TEM images of hydrothermally treated rice straw incorporating
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

2 wt% ferrocene (RS-H/Fe).

hydrocarbons from vaporized camphor to form a bamboo-like
CNTs-bundles denoted as CNTs–Fe (Fig. 4). The tiny amount
of CNTs bundles is probably attributed to small amount of
ferrocene supported on treated rice straw, where EDX analysis
3.2. Structural properties of the prepared samples
indicated that the presence of low amount of Fe species
It has been reported that ferrocene is considered as a potential (
0.33%). Overall, the hydrothermal carbonization at 250  C
catalyst for carbon precursor such as camphor to directly could lead to formation of nanoscale spheres that are derived
prepare CNTs via CVD process.29 In this study, the preparation from the reorganization inside the amorphous structure of
of rice straw incorporated with traces of ferrocene (RS-H/Fe) lignocellulosic rice straw giving rise to ablation of cell wall-
during hydrothermal reaction at 250  C for 120 min was microbriles in the carbonized structure as described else-
carried out to act as a catalyst in preparation of CNTs. Fig. 3 where by others.23 These walls of the tubes constructed of
represents typical TEM images of the produced sample (RS-H/ a hexagonal lattice of carbon atoms and capped by fullerene-like
Fe) as a catalyst support. It can be seen that irregular gra- structures.
phene sheets incorporated with Fe-nanoparticles catalyst of In a further attempt, the rice straw treated hydrothermally
nanospheres-like were obtained under the effect of hydro- with ferrocene and nickel nitrate (RS-H/Fe–Ni) was subjected to
thermal process. The black area, appeared on the graphene CVD process in the presence of camphor and N2 gas as a carrier,
sheets, was inferred to well-dispersion of ferrocene nano- keeping the temperature and time of growth unchanged as
particles on their surface. Based on these ndings, the studied mentioned above. The product yield was calculated to be 44%.
hydrothermal conditions give rise to produce carbon nano- The morphology acquired by the prepared sample is illustrated
structures bearing various morphologies. in Fig. 5 which shows the formation of twisted individual CNTs
The strength of the binding force between the Fe or Fe–Ni bundles with large outer diameter equal to
66 nm with respect
catalyst and the support should be responsible for the different to the diameters of Fe–Ni bi-catalysts nanoparticles formed in
growth modes. As the binding force is strong, it will gain the tip of tubes (as black spots). The produced CNTs labelled as
a tremendous possibility of base/bottom-growth mode with the CNTs–Fe–Ni. Comparing the two prepared CNTs indicates that
catalyst particles entrapped in the support and otherwise it will the presence of Ni oxide nanoparticles with Fe nanoparticles
be the tip-growth mechanism. Thus, the interaction of the released from ferrocene would enhance the amount and
carbonized rice straw with the metal catalyst is strongly increase the thickness of the as-synthesized CNTs (Fig. 5). Thus
dependent on the intrinsic microstructures and surface prop- the CNTs obtained from CVD of camphor over RS-H/Fe–Ni have
erties of the porous support, which in turn affect subsequent larger outer diameters and somewhat longer length as
carbon growth.30 compared to CNTs–Fe. The results in Fig. 4 and 5 shown that
When this sample was exposed to a thermal decomposition the growth regime of CNTs over the carbonized RS-H/Fe or RS-
at 800  C under owing N2 gas as a carrier for 120 min and then

Fig. 5TEM images of CNTs–Fe–Ni synthesized (as marked by arrows)

Fig. 4 TEM images of CNTs–Fe synthesized on the carbonize RS-H/ on the carbonized RS-H/Fe–Ni sample during CVD process of
Fe sample through CVD of camphor as gaseous carbon. camphor as gaseous carbon.

28538 | RSC Adv., 2017, 7, 28535–28541 This journal is © The Royal Society of Chemistry 2017
 View Article Online

Paper RSC Advances

CNTs was applicable enough to the study in many industrial

applications, for example, the application in construction
concrete without purication due to the compatibility between
the materials.
Results of thermogravimetric (TGA) carried out under
nitrogen atmosphere from room temperature to 900  C are
illustrated in Fig. 7. For RS-H/Fe–Ni, corresponding to hydro-
thermally treated rice straw at 250  C, TGA prole shows three
thermal degradation regions; 25–250  C, 250–350  C and 350–
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

800  C. At these regions the weight losses were found to be 12.5,

Fig. 6 Raman spectra of the prepared CNTs from CVD of camphor
48.7 and 19.8%, respectively. Thus the main degradation
during carbonization of RS-H/Fe and RS-H/Fe–Ni samples at 800  C.
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

occurred at the second region due to the degradation of

cellulose-related component to form amorphous carbon, while
decomposition of lignin happened over 450  C in the third
H/Fe–Ni support follows a bottom-growth, implying a strong
region, leaving 19% residual which is possibly related to the
interaction between the carbon matrix in the carbonized rice
presence of graphitic carbon with remaining inorganic
straw with Fe and Fe–Ni.30
components.33 The high content of residual weight indicates the
The Raman technique has been proved to be a useful tool for
presence of catalyst species, considering that the prepared
determining the microstructure of crystalline ordering in
samples were puried with a mixture of acid solutions (HNO3
carbonaceous materials such as CNTs.31,32 The Raman spectra of
and H2SO4). On the other hand, TGA prole of CNTs–Fe–Ni
produced CNTs–Fe and CNTs–Fe–Ni are shown in Fig. 6. There
exhibits different interfering regions as compared to RS-H/Fe–
are two prevalent graphite bands in the Raman spectra of CNTs:
Ni. The weight loss reached to 11.2% during thermal degrada-
the band at 1580 cm1 is assigned to the in-plane vibration of
tion between room temperature and 900  C. Thus the as-
the C–C bond (G band) and considered a typical of graphite-like
prepared CNTs–Fe–Ni has a high thermal stability due to its
materials and the band at nearly 1356 cm1 for CNTs–Fe is
higher graphitic carbon content (
88.8%). During increment in
shied to 1335 cm1 for CNTs–Fe–Ni which ascribed to D-band
thermal degradation from 200 to 750  C, there is a continuous
as a result of the presence of disorder in carbon materials. On
loss of weight that may be attributed to degradation of organic
another speaking, the G-peak is attributed to the E2g mode of
matters coming from the pyrolysis of saw dust which is counted
highly oriented pyrolytic graphite structure, while the D-peak
to be
5.9% with respect to the original weight. This result is in
reects structural imperfections in the graphite sheets, such
agreement with a recent work in the literature.34
as impurities/defects in the materials.31 The graphitization of
graphene-family nanomaterials can be obtained by comparing
the relative integrated intensity of D-peak to G-peak (ID/IG). It 4. Conclusions
was found that this intensity ratio of two peaks (ID/IG) was 0.753
in CNTs–Fe–Ni and 0.942 in CNTs–Fe, i.e., the CNTs produced Here, for the rst time, the CNTs was synthesized through
over the carbonized RS-H/Fe–Ni are well-graphitized as carbonization of rice straw treated hydrothermally in presence
compared to that grown over RS-H/Fe. Thus the combination of of low doses from catalyst sources, e.g., ferrocene or ferrocene
Ni with ferrocene can enhance both the graphitization degree with nickel nitrate salt (RS-H/Fe or RS-H/Fe–Ni) via chemical
and quantity of CNTs. Also, this observation is agreed with HR- vapor deposition of camphor. Few amounts, small outer
TEM images also. In conclusion, the quality of the as-prepared diameters and coiled bundles of CNTs were produced over
carbonized rice straw with ferrocene (RS-H/Fe) through bottom

Fig. 7 TGA profiles of the prepared samples before and after synthesis CNTs.

This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 28535–28541 | 28539
 View Article Online

RSC Advances Paper

5 A. Jha, U. K. Ghorai, D. Banerjee, S. Mukherjee and

K. K. Chattopadhyay, Surface modication of amorphous
carbon nanotubes with copper phthalocyanine leading to
enhanced eld emission, RSC Adv., 2013, 3, 1227–1234.
6 H. Dai, Carbon Nanotubes: Synthesis, Integration, and
Properties, Acc. Chem. Res., 2002, 35, 1035–1044.
7 Carbon Materials for Catalysis, ed. P. Serp and J. L.
Figueiredo, John Wiley & Sons Inc, New Jersey, 2009.
8 D. Yu, E. Nagelli, F. Du and L. Dai, Metal-free carbon
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

nanomaterials become more active than metal catalysts

and last longer, J. Phys. Chem. Lett., 2010, 1, 2165–2173.
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

Fig. 8 TEM image of the prepared CNTs from hydrothermal carbon- 9 H. Chu, L. Wei, R. Cui, J. Wang and Y. Li, Carbon nanotubes
ization of RS-H/Fe–Ni. combined with inorganic nanomaterials: preparations and
applications, Coord. Chem. Rev., 2010, 254, 1117–1134.
10 A. Peigney, C. Laurent, E. Flahau, R. R. Bacsa and A. Rousset,
growth mechanism. Whereas considerable amounts of straight
Specic surface area of carbon nanotubes and bundles of
and large outer diameter of CNTs-bundles were formed over
carbon nanotubes, Carbon, 2001, 39, 507–514.
carbonized RS-H/Fe–Ni via bottom growth mechanism also as
11 C. Journet, W. K. Maser, P. Bernier, A. Loiseau, M. L. dela
detected in TEM images. Furthermore, Raman spectra
Chapelle, S. Lefrant, P. Deniard, R. Lee and J. E. Fischer,
conrmed the formation of CNTs on the carbonized rice straw
Large-scale production of single-walled carbon nanotubes
through the prescribed technique in this study. Accordingly, the
by the electric arc technique, Nature, 1997, 388(6644), 756.
structure and diameter of the produced CNTs were found to be
12 T. Guo, P. Nikolaev, A. Thess, D. T. Colbert and R. E. Smalley,
controlled by the morphological properties of the prepared
Catalytic growth of single-walled nanotubes by laser
catalysts on the carbonized rice straw. It was found that the
vaporization, Chem. Phys. Lett., 1995, 243(1–2), 49.
prepared RS-H/Fe–Ni was more efficient as compared to RS-H/
13 H. Dai, A. G. Rinzler, P. Nikolaev, A. Thess, D. T. Colbert and
Fe in the production of CNTs. Overall, the feasibility of
R. E. Smalley, Single-wall nanotubes produced by metal-
carbonized rice straw treated with Fe–Ni catalyst as an efficient
catalyzed disproportionation of carbon monoxide, Chem.
substrate for preparation of CNTs through chemical vapor
Phys. Lett., 1996, 260(3–4), 471.
deposition of camphor under owing N2 gas was successfully
14 M. Kumar and Y. Ando, Camphor–a botanical precursor
attained. However, still there are more attempts in our labora-
producing garden of carbon nanotubes, Diamond Relat.
tory to optimize the synthesis procedure and to prepare good
Mater., 2003, 12, 998–1002.
quality and high quantity of CNTs. In an ongoing study, when
15 R. J. Andrews, C. F. Smith and A. J. Alexander, Mechanism of
RS-H/Fe–Ni exposed to a thermal treatment in a closed-vertical
carbon nanotubes growth from camphor and camphor
tubular furnace at 800  C for 60 min, without ow of any inert
analogs by chemical vapor deposition, Carbon, 2006, 44,
gases, good quality of CNTs with large amount is obtained as
341–347.
shown in Fig. 8.
16 A. K. Chatterjee, M. Sharon, R. Banerjee and M. Neumann-
Spallart, CVD synthesis of carbon nanotubes using a nely
Acknowledgements dispersed cobalt catalyst and their use in double layer
electrochemical capacitors, Electrochim. Acta, 2003, 48, 3439.
The author gratefully acknowledges the nancial supports 17 X. Liu, Y. Yang, H. Liu, W. Ji, C. Zhang and B. Xu, Carbon
provided by the National Research Centre (NRC) under the nanotubes from catalytic pyrolysis of deoiled asphalt,
Project No. 11090201. Mater. Lett., 2007, 61, 3916–3919.
18 P. Ghosh, R. A. Afre, T. Soga and T. Jimbo, A simple method
References of producing single-walled carbon nanotubes from a natural
precursor: eucalyptus oil, Mater. Lett., 2007, 61, 3768–3770.
1 S. Iijima, Helical microtubules of graphitic carbon, Nature, 19 S. Paul and S. K. Samdarshi, A green precursor for carbon
1991, 354, 56–58. nanotubes synthesis, New Carbon Mater., 2011, 26, 85–88.
2 M. F. L. De Volder, S. H. Tawck, R. H. Baughman and 20 R. Kumar, R. S. Tiwari and O. N. Srivastava, Scalable synthesis
A. John Hart, Carbon Nanotubes: Present and Future of aligned carbon nanotubes bundles using green natural
Commercial Applications, Science, 2013, 339, 535–539. precursor: neem oil, Nanoscale Res. Lett., 2011, 6, 92.
3 Carbon Filaments and Nanotubes: Common Origins, Differing, 21 A. B. Suriani, A. A. Azira, S. F. Nik, R. Md Nor and M. Rusop,
Applications?, ed. L. P. Birὀ, C. A. Bernardo, G. G. Tibbetts Synthesis of vertically aligned carbon nanotubes using
and P. H. Larnbin, Kluwer Academic, Dordrecht, natural palm oil as carbon precursor, Mater. Lett., 2009, 63,
Netherlands, 2001. 2704–2706.
4 R. H. Baughman, A. A. Zakhidov and W. A. de Heer, Carbon 22 A. B. Suriani, R. Md Nor and M. Rusop, Vertically aligned
nanotubes–the route toward applications, Science, 2002, carbon nanotubes synthesized from waste cooking palm
297(787). oil, J. Ceram. Soc. Jpn., 2011, 118, 963–968.

28540 | RSC Adv., 2017, 7, 28535–28541 This journal is © The Royal Society of Chemistry 2017
 View Article Online

Paper RSC Advances

23 B. Goodell, X. Xie, Y. Qian, G. Daniel, M. Peterson and 28 S. Chakraborty, S. Chowdhury and P. Saha, Adsorption of
J. Jellison, Carbon nanotubes produced from natural crystal violet from aqueous solution onto NaOH-modied
cellulosic materials, J. Nanosci. Nanotechnol., 2008, 8(5), rice husk, Carbohydr. Polym., 2011, 86, 1533–1541.
2472–2474. 29 M. Kumar and Y. Ando, A simple method of producing
24 J. Zhu, J. Jia, F. L. Kwong, D. H. Ng and S. C. Tjong, Synthesis aligned carbon nanotubes from an unconventional
of multiwalled carbon nanotubes from bamboo charcoal precursor – Camphor, Chem. Phys. Lett., 2003, 374, 521–526.
and the roles of minerals on their growth, Biomass 30 F. Zhou, Q. Liu, W. Zhang, J. Gu, S. Zhu and D. Zhang,
Bioenergy, 2012, 36, 12–19. Fabrication of 3D carbon nanotube/porous carbon hybrid
25 Z. Wang, H. Ogata, S. Morimoto, J. Ortiz-Medina, materials, J. Mater. Sci., 2014, 49, 548–557.
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

M. Fujishige, K. Takeuchi, H. Muramatsu, T. Hayashi, 31 M. S. Dresselhaus, G. Dresselhaus, R. Saito and A. Jorio,

M. Terrones, Y. Hashimoto and M. Endo, Nanocarbons Raman spectroscopy of carbon nanotubes, Phys. Rep.,
Open Access Article. Published on 31 May 2017. Downloaded on 11/11/2018 10:47:54.

from rice husk by microwave plasma irradiation: from 2005, 409, 47–99.
graphene and carbon nanotubes to graphenated carbon 32 H. Essawy, N. Fathy, M. Tawk, S. El-Sabbagh, N. Ismail and
nanotubes hybrids, Carbon, 2015, 94, 479–484. H. Youssef, Fabrication of Single-Walled Carbon Nanotubes
26 E. B. Belal, Bioethanol production from rice straw residues, from Vulcanized Scrap Rubber via Thermal Chemical Vapor
Braz. J. Microbiol., 2013, 44, 225–234. Deposition, RCS Adv., 2017, 7, 12938–12944.
27 N. A. Fathy, O. I. El-Shafey and L. B. Khalil, Effectiveness of 33 P. Lu and Y.-L. Hsieh, Highly pure amorphous silica nano-
alkali–acid treatment in enhancement the adsorption disks from rice straw, Powder Technol., 2012, 225, 149–155.
capacity for Rice straw: the removal of methylene blue 34 M. G. S. Bernd, S. R. Braganc, N. Heck and L. C. P. da Silva
dye., ISRN Phys. Chem., 2013, 2013, 1–15. Filho, Synthesis of carbon nanostructures by the pyrolysis
of wood sawdust in a tubular reactor, J. Mater. Res.
Technol., 2017, DOI: 10.1016/j.jmrt.2016.11.003.

This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 28535–28541 | 28541