Journal of Hazardous Materials 375 (2019) 206–215

Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

An ultra-light flexible aerogel-based on methane derived CNTs as a T

reinforcing agent in silica-CMC matrix for efficient oil adsorption
⁎
Kaushal R. Parmar, D.T.K. Dora, K.K. Pant , S. Roy
Department of Chemical Engineering, Indian Institute of Technology, New Delhi, India

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Bamboo shaped multi-walled Carbon Nanotubes were synthesized by the thermo-catalytic decomposition of
Aerogels methane in a modified chemical vapour deposition reactor. The prepared carbon nanotubes were reinforced in
Carbon nanotube the mero-hydrophobic carboxymethyl cellulose and silica matrix for the preparation of low density, highly
Oil adsorption flexible aerogel. The synthesized aerogel exhibited a large specific surface area and uniform pore structure as
Porous materials
confirmed by the nitrogen adsorption-desorption analysis. The water contact angle of 148.8° for the aerogel
Flexible
demonstrated that the synthesized aerogels were superhydrophobic in nature. The performance of aerogels was
tested for the adsorption of singer oil and motor oil. Investigations revealed that aerogel can adsorb more than
28 times its weight effectively. Moreover, the adsorbed oil can be recovered by mechanical squeezing owing to
its flexible nature. In addition, the aerogel could maintain its oil adsorption capacity even after 5 regeneration
cycles, demonstrating superior recyclability. The peculiar properties – outstanding flexibility and super-
hydrophobicity exhibited by the aerogels establish them as a proficient and recyclable oil adsorbents during the
oil seepage.

1. Introduction
A rapid rise in off-shore oil industries, oil transportations, frequent
oil spillage and occasional oil seepage through developed cracks in
earth surface contribute serious menace to the marine aquatic culture,
which causes a huge economic loss [1,2]. Thus there is an urgent need
for the development of such methods and materials which can effec-
tively capture and recover the organic matters from water [1]. Several
methods have been explored by researchers, out of which adsorption is
proved to be a cost-effective method with high efficiency in many of the
cases [3]. The different sorbents have been used for oil spill cleaning
fall into three categories: mineral sorbents [4–6]; natural organic
sorbents [7,8]; and synthetic organic sorbents [9,10]. The mineral-
based sorbents have less hydrophobicity, thereby possesses less oil
adsorption capacity and also has a risk of dust formation during their
application in the open spaces. Although the natural organic based
adsorbents are biodegradable in nature, they cannot be used in case of
fire. The third type of sorbents possesses high hydrophobicity [11,12].
Carbon Nanotubes (CNTs) and their composites have been emerged
as a sorbent material due to its low density, high inherent strength, high
aspect ratio, good hydrophobicity, oleophilic characteristics and en-
vironmental chemical stability. CNT preparation method can be se-
lected based on the application and the required properties. When CNTs
are used in electronic applications, properties like electrical

⁎
Corresponding author.
E-mail address: kkpant@chemical.iitd.ac.in (K.K. Pant).

https://doi.org/10.1016/j.jhazmat.2019.04.017
Received 10 January 2019; Received in revised form 1 April 2019; Accepted 2 April 2019
Available online 30 April 2019
0304-3894/ © 2019 Elsevier B.V. All rights reserved.
K.R. Parmar, et al.
conductivity, electron mobility and current density are taken into
consideration for which the Chemical Vapour Deposition (CVD) method
is well suited. However, horizontal CVD reactors produce a low yield of
CNTs at a high cost, which is undesirable for use in bulk applications.
For such applications, a modified CVD method may be employed to
overcome these limitations [13,14]. The dispersive nature of CNTs in its
powder form hinders its usage for oil spill cleanup [15], thus a mac-
roscopic structure (aerogel) of CNT composite can be a solution to the
above problem. Investigations were carried out for synthesizing CNT
aerogels with various binders/cross-linking agents using solution
mixing method [16–26] and pure CNT aerogel using floating catalyst
chemical vapour deposition (FC-CVD) method [27–30]. The FC-CVD
method can produce ultralight CNT aerogels with high adsorption ca-
pacity in the range of 100–200 g/g, however, the low rate of produc-
tion, shape recovery issues after oil adsorption and higher production
cost hinders its commercialization [31]. Again the metal catalyst im-
purities present in the aerogel may migrate to water during its appli-
cation in oil-water systems [29]. Thus, further exploration in a cost-
effective, scalable solution based method is needed which can over-
come such issues related to FC-CVD.
Till date silica aerogel proved to be a promising commercialized
adsorbent among all aerogels due to its porous nature, low density and
high hydrophobicity. However, due to its fragile nature and lack of
strength further modification in silica aerogel is highly solicited. Thus
for the modification in silica aerogel, different investigators [25,26]
have reinforced CNTs into a silica matrix. However, CNT-silica aerogels
prepared so far have poor mechanical strength and low rate of ad-
sorption limits its usage as a macroscopic structure in oil spill cleaning.
Again owing to the non-flexible nature of such aerogels, the recovery of
the adsorbed oil becomes infeasible. To introduce flexibility and attain
structural integrity in CNT-silica aerogel a bio-degradable binder car-
boxymethyl cellulose (CMC) can be used. The CNT aerogels were al-
ready synthesized using CMC as a binder [23], but the aerogels cannot
be used for oil spill cleaning, because the aerogels do not have hydro-
phobic characteristics.
To overcome issues of bulk CNT production, multi-walled bamboo
shaped CNTs are produced from methane as the source of carbon and
alumina supported, zinc-copper promoted nickel catalyst, in a fluidized
bed reactor. Further, these multi-walled CNTs are used as a reinforcing
agent in hydrophobicized CMC and silica matrix for the synthesis of
lightweight, high surface area, flexible and highly porous CNT aerogel.
Two different types of oil were chosen to study the oil adsorption ki-
netics and regenerability of the prepared CNT aerogel.
2. Materials and methods
2.1. Materials
Carboxymethyl cellulose (CMC), N, N-dimethylformaldehyde
(DMF), Potassium carbonate, tetraethylorthosilicate (TEOS), ethanol,
trimethylchlorosilane (TMCS), hexane, Sudan Red G dye, hydrochloric
Fig. 1. Preparation procedure of CNT aerogel.
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Journal of Hazardous Materials 375 (2019) 206–215
acid, nickel nitrate hexahydrate, zinc nitrate hexahydrate and copper
nitrate hydrate were purchased from Sigma-Aldrich Pvt. Ltd. (India).
The methyl ester of repressed oil (MERO) was purchased from Krishi Oil
Limited, India. Motor oil and singer oil were collected from local sup-
pliers. Chemicals used in the present study were of > 99% purity and
were used as received.
2.2. Catalyst and CNT synthesis
CNTs were synthesized in a fluidized bed reactor by using nickel-
based copper zinc promoted and alumina supported catalyst by me-
thane cracking. The catalyst preparation technique and reactor con-
figuration were discussed elsewhere [32,33]. In brief, the catalytic
support (α-Al2O3) was impregnated by active metal using the aqueous
solution of required metal and promoter precursors. The excess water
from the slurry was removed in a rotary vacuum evaporator at 90 °C.
The residue was successively oven dried and calcined in a muffle fur-
nace at 550 °C for 5 h. The calcined catalyst was then sieved through
100–150 BSS mesh to achieve optimum particle size. After calcination
in-situ reduction of the catalyst was carried out using hydrogen/ni-
trogen gas at 550 °C and further fluidized using methane/nitrogen gas
(at twice of its minimum fluidization velocity) at 750 °C for the bulk
production of CNTs.
2.3. CNT aerogel synthesis
The CNTs obtained were treated twice with 50% diluted HNO3 for
24 h in an oil bath with a stirring speed of 120 rpm at 120 °C and then
washed until pH became 7 to remove active metal content. Further,
functionalization of CNTs was carried out by treating with a mixture of
H2SO4 and HNO3 (volume ratio of 3:1) at a temperature of 80 °C for 4 h
in an oil bath with reflux arrangement [34]. After treatment, the so-
lution was cooled down to the room temperature and then diluted with
distilled water. The obtained functionalized CNTs were continuously
washed with distilled water until the pH became 7 and then dried for
24 h at 120 °C.
MERO-hydrophobized CMC (MH-CMC) was prepared by the ester-
ification process, which is reported elsewhere [35]. Fig. 1 represents the
solution based method used for the synthesis of flexible CNT silica
aerogel. At first, a transparent MH-CMC solution was prepared by dis-
solving 1 g MH-CMC in 100 ml ethanol. The CNT solution was prepared
by adding a weighed amount of CNT to 30 ml of a solution mixture of
TEOs, ethanol and distilled water (mole ratio of 1:3:1). To carry out
silylation reaction, 0.1 mol/l of HCl was added in the solution and then
sonicated for 1 h. The obtained CNT solution was further sonicated for
30 min by adding the previously prepared MH-CMC solution to form an
alco-sol. Then prepared alco-sol was transferred to an aluminium
mould, quenched in a nitrogen bath (−182 °C) and then freeze-dried
(−50 °C and 1 Torr) for 48 h. For surface modification of CNT aerogel,
the samples were solvent exchanged with 10% of TMC/hexane solution
to achieve hydrophobic characteristics. Three different samples were
K.R. Parmar, et al. Journal of Hazardous Materials 375 (2019) 206–215

Fig. 2. (a) SEM, (b) TEM and (c) Raman spectra of CNTs.

Fig. 3. (a) Macroscopic structure of CNT aerogel, (b) CNT aerogel standing on a flower, (c) Before compression, (d) CNT aerogel supported with a weight, (e) A water
droplet on cross-sectionally cut CNT aerogel, (e) Water contact angle on CNT aerogel.

prepared by varying the mass ratio of CNT solution to the MH-CMC
solution (0.2, 0.35 and 0.5) and labelled as CNTA1, CNTA2 and CNTA3
respectively. Beyond this mass ratio, the aerogel sample loses its flex-
ibility and it becomes monolithic. Moreover, pure MH-CMC-silica
aerogels were synthesized without the addition of acid-treated CNTs,
which were used as a reference for comparison of oil adsorption ca-
pacity.
Barret-Joyner-Halenda (BJH) respectively. Renishaw Micro-Raman
spectrometer (in Via Reflex) was used to collect the Raman spectra. The
hydrophobicity of the aerogel was characterized by measuring the
water contact angle using a goniometer (DSA 400). The Fourier
Transformation Infrared spectroscopy (NICOLET iS50) was used for
confirming the presence of the functional groups in the CNT aerogel.

2.4. Characterization 2.5. Adsorption studies

The morphologies of the CNTs, CNT aerogel were characterized by
using Field Emission Scanning Electron Microscope, FESEM (FEI
Quanta 200F SEM) and Transmission Electron microscope, TEM (Tecnai
G2 20). For nitrogen adsorption-desorption analysis, Micromeritics
ASAP 2010 was used. The surface area and pore size distribution of the
CNT aerogel were characterized by Brunauer-Emmett-Teller (BET) and
To determine the oil adsorption capacity, ASTMF726-99 method
was followed [36,37]. In particular, each sample was weighed inter-
mittently at every 1 min during the exposure followed by 1 min of
dripping. Following equation was used to calculate the adsorption ca-
pacity.

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Fig. 4. (a) SEM morphology, (b) Cross-sectional Cell SEM, (c) Surface morphology, (d) after compression of CNT aerogel.

Fig. 5. Raman spectra of (a) CNTs HNO3 treated, (b) H2SO4 treated, (c) CNT Fig. 6. FTIR spectra of (a) MH-CMC, (b) CNT aerogel.
aerogel.

Pseudo-second order model,

mt − m 0
Qt =
m0 (1) t 1 1
= + t
Qt K2 Qe2 Qe (3)
where Qt is the adsorption capacity (g/g) at a time “t”, m0 is the initial
weight and mt is the weight of the aerogel (g) after adsorption of oil at a
Where Qe is the equilibrium oil adsorption capacity (g/g), Kad and K2
time “t” respectively. To investigate the adsorption kinetics, following
are the rate constants for pseudo-first-order and pseudo-second-order
kinetic models were preferred [38].
adsorption respectively.
Lagergren pseudo-first order model,
K ad
log (Qe − Qt ) = logQe − t
2.303 (2)

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K.R. Parmar, et al.
Fig. 7. Nitrogen adsorption and desorption curve for CNTA1, CNTA2, CNTA3
and acid treated CNTs.
3. Results and discussion
3.1. Morphology of CNT and CNT aerogel
Fig. 2 shows the SEM, TEM micrographs and Raman spectrum of
CNTs prepared by the thermo-catalytic decomposition of methane. SEM
micrograph (Fig. 2a) reveals that produced CNTs are of ˜23 nm OD and
˜2–3 μm in length (see Fig. S1 and Table S1). From TEM analysis
(Fig. 2b) bamboo shaped multiwall carbon fibre can be observed with
˜10 nm ID. During the CNT growth, at 750 °C, active metal-nickel pos-
sesses a semi-solid form. When methane molecule decomposes on the
surface of the nickel crystal, the produced carbon atom diffuses on its
surface by two possible mechanisms viz. bulk diffusion or surface dif-
fusion. Carbon atoms accumulated on the step edges of the nickel
particle due to lower activation energy barrier and lower coordination
number resulting in fibre formation parallel to the growth axis. As more
carbon accumulated at the step-edges, the particle became pear-shaped
(Figs. 2b and S1c, indicated by red circle) and growth of graphene
layers perpendicular to the growth axis (bamboo knot) was formed.
Continuous formation of the bamboo knot not only sealed the nanotube
internally but also shrinked the nickel particle. This shrinkage ulti-
mately elongated the nickel particle resulting into increase in effective
surface area, interface area and strain energy. Further formation of
carbon layer ejected the nickel particle forward regaining its original
shape. Continuous repetition of this process made the multiple bamboo
knots inside the tube [39]. Fig. 2c displays Raman Spectrum of treated
CNTs. Two major peaks are observed at 1342 cm−1 and 1572 cm−1
which correspond to D and G band respectively. The G band is gener-
ated due to the planer CeC bond vibration while D band is generated
due to disorder in the graphene plane [40]. The G’ band (also known as
a 2D band) is observed at ˜2690 cm−1 which is a double frequency of D
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Journal of Hazardous Materials 375 (2019) 206–215
band. The G + D overtone band is also observed at ˜2930 cm−1 [41].
Fig. 3(a) shows the macroscopic morphology of CNT aerogel with a
diameter of 2.5 cm, a height of 2 cm and a bulk density of 0.01 g/cc,
which was approximately 70% lighter than conventional CNT silica and
pure silica aerogels. The freeze drying operation facilitates the direct
sublimation of ice crystals from the frozen samples leaving behind pores
in the sample without significant shrinkage. The as-prepared CNT
aerogel can easily stand on the flower without observable bending in its
thin florets, which is clear evidence of its ultra-lightweight (Fig. 3b).
The mechanical stability of as-prepared CNT aerogel is shown in Fig. 3c
and d. Even after supporting 1500 times of its own weight, it maintains
structural integrity without collapsing and regains its original shape
without any shrinkage (Supplementary video 1). Structural cracks were
observed in pure silica and CNT-silica aerogel due to the fragile nature
of silica, which prevents flexibility and difficulty in handling during
their application. However, the introduction of MH-CMC in the aerogel
could introduce flexibility with stable structural integrity. The hydro-
phobicity of the CNT aerogel was tested by measuring its water contact
angle on a horizontally cut sample (Fig. 3e and f) and found to be
148 ± 1° ensuing the super-oleophilic characteristics of the as-pre-
pared CNT aerogel. It is observed that both the surface and the inside
cross-section of the aerogel are found hydrophobic owing to the in-
troduction of the MH-CMC. The macroscopic images of MH-CMC-silica
aerogel with the same size are represented as Fig. S2(a) and (b) (see
Supplementary file).
Fig. 4 represents the SEM micrographs of CNT aerogel. The re-
inforcement of CNTs in silica and MH-CMC matrix produces interlinked
parallel cross-sectional walls with varying thicknesses ranging from 10
to 16 μm, which in turn causes flexibility in the aerogel (Fig. 4a). Fur-
ther magnified images of a cross-section of a wall and its surface are
represented as Fig. 4b and c respectively. It is observed that the MH-
CMC is responsible for vertical binding, whereas the silica cross-linkers
are responsible for the longitudinal binding of the CNTs. After me-
chanical deformations, the aerogel shows a parabolic buckling of the
elastic cell walls and the original shape of the aerogel is recovered upon
unloading (Fig. 4d). The SEM micrographs of the MH-CMC-silica
aerogel are presented in Fig. S2(c)–(e) (see Supplementary file). It is
observed that the MH-CMC forms cross-sections clinging to the silica
particles in the formed aerogel. From the comparison of SEM images
between MHCMC-Silica-CNT aerogel (Fig. 4c) and MH-CMC-silica (Fig.
S2f), completely different morphology can be observed. As acid-treated
CNTs possess a high amount of functional groups, the complex 3D
network of Silica, CMC and CNT will be formed which ultimately led to
higher volume and lower density.
3.2. Characterization of CNT aerogel
Fig. 5 shows the Raman spectra collected for (a) CNTs washed with
HNO3 (b) CNTs HNO3 and H2SO4 treated (c) CNT aerogel. Two main
bands can be observed in the Raman spectra: G band at 1570 cm−1,
which is called graphitization band derived from in-plane lattice vi-
bration of CeC (sp2) bond and D band at 1345 cm−1, generated due to
disorder in the graphene structure. Based on the intensity of the D band,
one can predict the quality of the CNTs as its intensity is related to
disorder in the structure. Other features like D’ band (shoulder in G
band) which is the second harmonic of G band at 1601 cm−1 and G’
band which is an overtone of D band at 2688 cm−1 can also be ob-
served. In addition (G + D) band at 2915 cm−1 can be observed
[41,42]. It is further observed that the ID/IG ratio is increased from 0.84
to 0.95 due to the attachment of carboxylate and ether groups in the
side walls and ends of the CNTs. In Fig. 5(c) sharp peaks at 2902 cm−1
can be observed in silica aerogel which is assigned to C–H stretching
and also confirmed by infrared spectroscopy. The weak bands at
489 cm−1, 970 cm−1, 1420 cm−1 are assigned to SieOeSi, SieOH and
eCH3 stretching.
Fig. 6 represents the FTIR spectrum of the MH-CMC and CNT
K.R. Parmar, et al. Journal of Hazardous Materials 375 (2019) 206–215

Fig. 8. Pore size distribution and cumulative pore volume for (a) CNT acid treated, (b) CNTA1, (c) CNTA2, (d) CNTA3.

Table 1 aerogel. The eOH stretching band appears at 3284 cm−1 in both MH-
Properties of CNT aerogels. CMC and CNT aerogel. The grafting of CMC with silica and CNT cause
Sample Density (g/ Pore volume Mean pore Surface area
reduction in intensity of eOH peak at 3284 cm−1 which suggests the
name cc) (cc/g) diameter (nm) (m2/g) breakage of hydrogen bonds due to surface modification. Moreover, in
MH-CMC the band at 2896 cm-1 was assigned to asymmetric C–H
CNTA1 0.038 2.042 11.31 795.2655 stretching. The band at 1323 cm−1 was assigned to eOH bending vi-
CNTA2 0.022 2.053 10.20 788.4860
bration. Two visible transmittance bands found at 1529 and 1412 cm−1
CNTA3 0.016 2.098 10.03 780.2611
were assigned to the carboxyl group, which was also found in CNT
aerogel. In CNT aerogel the bands at 937 and 1051 cm-1 confirms the
presence of SieOH stretching and SieOH rocking, owing to the

Fig. 9. Schematic representation of formation of CNT-MH-CMC-Silica aerogel.

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K.R. Parmar, et al.
Fig. 10. Oil adsorption capacity (g/g) of CNT aerogel for (a) Singer oil, (b) Motor oil.
Fig. 11. Snapshots of CNT aerogels before and after oil adsorption.
hydrolysis and incomplete condensation of TEOS during sol-gel process.
The band at around 790 cm−1 is allocated to SieOeSi cross-linking
bonds [26].
Fig. 7 shows the N2 adsorption-desorption isotherm of the different
CNT aerogels and acid treated CNT. The location of the point of in-
flection at the relative pressure (P/P0) of the N2 adsorption and deso-
rption branching have started between 0.4 and 0.6, which confirms the
existence of mesopores in the CNT aerogel and CNT [43]. The nitrogen
adsorption capacity of the CNT aerogel is more than the acid-treated
CNTs. The flatness or no appreciable inflation is observed up to 0.85 for
CNT, which is not observed in the case of CNT aerogel, rather it
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Journal of Hazardous Materials 375 (2019) 206–215
increases exponentially with an increase in relative pressure. This may
be due to the introduction of MH-CMC, silica matrix support and the
role of CNT-COOH to bind the silica matrix and MH-CMC. It is also
observed that with an increase in the amount of CNT-silica solution in
the aerogel the adsorption capacity increases.
The pore size distribution for acid-treated CNT and CNT aerogels are
represented as Fig. 8. The majority of pore size in acid-treated CNTs and
CNT aerogels are mesoporous (5–80 nm). The average pore diameters
are found to be 11.31, 10.2 and 10.03 nm with the cumulative pore
volume of 2.022, 2.053 and 2.098 cc/g for CNTA1, CNT2 and CNTA3
respectively (Table 1). The collapse of the macropores and mesopores
occurs with the increase in weight of CNT, which in turn powered in the
increase in pore diameter and cumulative pore volume [29].
The synthesis route of CNT functionalization through acid treat-
ment, formation CNT-silica composite and the binding with MH-CMC is
presented as Fig. 9. Briefly, due to acid treatment, the CNTs were
functionalized with carboxyl and ester group, which is a key step in the
synthesis of CNT-silica composite [25]. Further, the silylation reaction
was accelerated by the addition of TEOS, in which the CNTs are cross-
linked longitudinally with the SieOH and eSieOeSie, which is also
evident from infrared spectroscopy (Fig. 6). The hydroxyl group of the
MH-CMC may react with the hydroxyl group of the CNT-silica com-
posite to increase their linkage in vertical cross-sections (Fig. 4a), which
further increase the strength and flexibility of the formed aerogel.
3.3. Oil adsorption capacity and its kinetics
The oil adsorption capacities of CNTA1, CNTA2 and CNTA3 were
investigated with two different oil systems viz. singer oil and motor oil
which are represented as Fig. 10a and b respectively. As observed, the
oil adsorption capacity of the aerogel samples increases exponentially
with time till it reaches equilibrium. The entire adsorption capacity
curve can be divided into three phases like rapid phase, sluggish phase
and then equilibrium phase. In the rapid phase, the rate of oil adsorp-
tion is fastest followed by a sluggish phase with low adsorption rate and
finally the equilibrium phase, where the maximum adsorption was
achieved. The equilibrium oil adsorption capacity for all the three
samples are found at 11 min. The oil adsorption capacities of CNTA1,
CNTA2, and CNTA3 were observed as 23, 25 and 28 g/g for singer oil
and 22, 24 and 26 g/g for motor oil at 30 °C. The oil adsorption capacity
of CNTA3 is found to be more as the higher silica content in the CNT
aerogel, which intends to lower pore diameter and higher cumulative
K.R. Parmar, et al. Journal of Hazardous Materials 375 (2019) 206–215

Fig. 12. Adsorption capacity of CNT aerogels over five adsorption cycles from a water-oil system of (a) singer oil and (b) motor oil.

Table 2 30 min. The regenerated samples were reused for oil adsorption. Fig. 12
Oil adsorption capacity of different adsorbent. shows the adsorption of both the oil for all three samples up to five
Adsorption material Oil adsorption capacity (g/g) Reference
cycles. As it is observed from Fig. 12, the CNT aerogels in this study
have good reusability characteristics. Therefore, the as-prepared CNT
CNT-vermiculite 3.8 [4] aerogel in this study exhibited its potential application in the oil spill
Expanded perlite 7.2 [5] cleaning due to their superoleophilic, superelastic and reusability
Corn Stalk 9 [8]
characteristics. A comparison of the maximum adsorption capacity of
Polyeurathane sponge 24 [9]
Polypropylene sponge 11 [10] CNT-MH-CMC-Silica aerogel with the other synthesized adsorbents re-
Chitosan-silica aerogel 19.8 [18] ported in the literature is represented as Table 2. Differences of oil
Chitosan-silica nanocomposite 0.121 [20] uptake capacity are due to the properties of each adsorbent such as
Silica aerogel 15 [25]
surface area, density and pore size distribution.
Bacterial Cellulose-silica aerogel 14 [37]
CNT-MH-CMC-silica aerogel 28 Present work
To investigate the temperature effect on oil adsorption, the oil was
heated for different temperature (40 and 50 °C) and adsorption kinetic
study was conducted. It is observed that with an increase in tempera-
pore volume. It is also observed that the more amount of singer oil ture the adsorption of oil increases slightly within the permissible error
adsorbed into the aerogels than motor oil because of the higher visc- (Table 2). This is owing to the fact that with an increase in temperature
osity and lower surface tension of motor oil than that of singer oil. The oil viscosity decreases, in turn, increases the acceleration of diffusion of
maximum oil adsorption capacity of pure silica aerogel and CNT silica oil into the aerogels [29].
aerogels from the literature are found to be 9.2 g/g [25] and 25.8 g/g The oil adsorption kinetics for CNTA3 was tested using Lagergren
[26]. Again, owing to the fragile nature and low rate of adsorption of pseudo-first-order and pseudo-second-order as presented as Eqs. (2) and
silica aerogel and CNT silica aerogel makes it impossible for the re- (3). The applicability of the two models was investigated by plotting log
covery of adsorbed oil. However, the flexible CNT aerogel in this study (Qe − Qt) vs t and (t/q) vs t, respectively for both singer oil and motor
could adsorb oil up to 28 g/g due to its flexibility and low density. oil adsorption, presented as Fig. 13. The coefficient of correlation (R2)
Again they could adsorb oil quickly without destroying its structural was calculated for both the models to quantify the applicability of the
integrity. Owing to the flexible nature of the as-prepared CNT aerogel models. The correlation coefficient, the adsorption rate constant data
the adsorbed oil can be recovered by simple mechanical squeezing. The for pseudo-first-order and pseudo second order are presented as
oil adsorption capacity of prepared MH-CMC-silica aerogel is presented Table 3. From Table 3 it is revealed that the R2 values for pseudo-
as Fig. S3 (see Supplementary file). The maximum oil adsorption ca- second order are more than pseudo-first order, thus both the oil the
pacity of MH-CMC-silica aerogel was found to be 7 g/g and 9 g/g for adsorption kinetics follows the pseudo-second-order.
motor oil and singer oil respectively. Simultaneously, the equilibrium
adsorption capacity was achieved at around 5 min. Thus, a synergistic 4. Conclusion
effect in the oil the adsorption capacity and the rate of oil adsorption
was confirmed owing to the reinforcement of bamboo shaped CNTs in In this study, a lightweight, flexible, recyclable CNT aerogel was
Silica and MH-CMC matrix. synthesized by reinforcing the prepared multi-walled bamboo shaped
The as-prepared flexible CNT aerogel exhibits excellent oil adsorp- CNTs in MH-CMC and silica matrix. The prepared aerogel exhibited a
tion properties from water as evident from Fig. 11. To obtain visual low density of 0.01 g/cc and an excellent hydrophobic characteristic
differentiation in the oil-water system, the oil was strained with the with a water contact angle of ˜149°. Additionally, the as-prepared CNT
Sudan Red G dye. A cross-sectionally cut sample was placed onto a aerogels displayed high oil adsorption capacity, in the range of 28–30
mixture of oil and water. Due to the low density and hydrophobicity of times of its own weight. Further, it could easily recyclable by two
the aerogel, the oil penetrates into the sample leaving behind the water simple steps of squeezing and acetone treatment without any appreci-
in no time. Attempts were also made by dropping pure silica aerogel able change in its adsorption capacity. Thus the use of methane-derived
and CNT silica aerogel to absorb oil from water but due to its fragile in bamboo shaped CNTs as a precursor material, its simple fabrication
nature, it was difficult to retrieve the absorbed oil. However, the rate of process, excellent performance and easy recycling process, demonstrate
adsorption of oil onto the flexible CNT aerogel is higher without de- a good potential of the synthesized flexible aerogel for its applications
stroying its structural integrity (evident from Supplementary video 2). in the oil adsorption and environmental remediation.
The reusability of the CNT aerogel samples was investigated by five
regeneration cycles. After oil adsorption reaches its equilibrium for an Acknowledgements
aerogel, the sample was treated with acetone and heated at 80 °C for
The author Kaushal R. Parmar is a recipient of Prime Minister’s

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K.R. Parmar, et al. Journal of Hazardous Materials 375 (2019) 206–215

Fig. 13. Kinetics of oil adsorption of CNTA3 according to (a) Lagergren model for singer oil (b) Pseudo-second-order model for singer oil (c) Lagergren model for
motor oil (d) Pseudo-second order model for motor oil.

Table 3 References
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