Journal of Colloid and Interface Science 570 (2020) 411–422

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Journal of Colloid and Interface Science

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

Recent advances in carbon nanotube sponge–based sorption

technologies for mitigation of marine oil spills
Deepak Kukkar a,1, Aruna Rani b,1, Vanish Kumar c,1, Sherif A. Younis d,e,1, Ming Zhang f, Sang-Soo Lee g,
Daniel C.W. Tsang h, Ki-Hyun Kim d,⇑
a
Department of Nanotechnology, Sri Guru Granth Sahib World University, Fatehgarh Sahib 140406, Punjab, India
b
Material Science Division, Intelligent Materials Pvt. Ltd. (Nanoshel Group, Co.), Punjab, India
c
National Agri-Food Biotechnology Institute (NABI), S.A.S. Nagar, Punjab 140306, India
d
Department of Civil & Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea
e
Analysis and Evaluation Department, Egyptian Petroleum Research Institute, 11727 Nasr City, Cairo, Egypt
f
Department of Environmental Engineering, China Jiliang University, Hangzhou 310018, China
g
Department of Environmental Engineering, Yonsei University, Wonju 26493, Republic of Korea
h
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Recent advances in CNT-based oil-

sorption approaches are summarized.
 Structural and oil-sorption attributes
of pristine and sponge CNTs are
compared.
 Oil-sorption capacities of CNT
sponges are reviewed along with
approaches to their synthesis.
 Performance evaluation of CNT
sponges for oil removal potential is
presented.

a r t i c l e i n f o a b s t r a c t

Article history: Hypothesis: Oil spills stemming from supertankers, drilling, and natural events represent a serious prob-
Received 23 January 2020 lem worldwide due to the potential harms to marine ecosystems and aquatic life. To date, various func-
Revised 29 February 2020 tional absorbents have been developed to treat spilled oil. Among them, carbon nanotube (CNT)-based
Accepted 2 March 2020
aerogels and sponges gained attention due to superior performance in uptake and recovery of various types
Available online 3 March 2020
of oil and organic solvents. CNT aerogel/sponge absorbents are demonstrated for a multitude of merits such
as: rapid superhydrophobic/superoleophilic absorption (water contact angle > 150°), high capacity
Keywords:
(100 mg g 1), large surface area (300–400 m2 g 1)), enhanced strength and flexibility (>95% volume
Absorption
Catalyst mediated synthesis
reduction and restoration of pristine morphology at <0.25 MPa stress), mesoporous characteristics with
CNT sponge high pore density (pore diameter = 80 nm and >99% porosity), recyclability, and easy surface modification.
Mitigation Experiments: This review compares CNT sponge–based absorbents with conventional techniques for reme-
diation/recovery of spilled oil. Typically, synthesis of CNT sponges is performed using chemical vapor

⇑ Corresponding author.
E-mail address: kkim61@hanyang.ac.kr (K.-H. Kim).
1
These authors may be considered as equal first authors as they contributed equally to the manuscript.

https://doi.org/10.1016/j.jcis.2020.03.006
0021-9797/Ó 2020 Elsevier Inc. All rights reserved.
412 D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422

Nanomaterials deposition (CVD) approach in the presence of a catalyst or using sacrificial removal of template. This work
Oil spill cleanup summarizes recent progress in strategies for oil-spill treatment based on CNT sponge techniques. The per-
Performance assessment formance of CNT sponges for oil spill removal was evaluated in terms of their adsorption capacity, com-
Template assisted synthesis
pressive stressability, and desorption methods (e.g., heat treatment, burning, or squeezing).
Findings: CNT sponges were observed to have high performance for removal of oil spills in terms of key per-
formance metrics. This review offers valuable insights into the current state of CNT-mediated oil-spill
cleanup technologies and guidance for future research at the same time. This literature survey would help
the stakeholders (researchers, scientists, entrepreneurs, and commercial houses) pursue contamination-
free water.
Ó 2020 Elsevier Inc. All rights reserved.

1. Introduction
Marine oil spills are a global environmental concern due to sub-
stantial negative effects on ecosystems, damage to the aesthetic
appeal of oceans, and loss of valuable fossil-fuel resources [1]. They
are largely the result of mishaps during loading and unloading of
supertankers, oil rig drilling, natural events, and collision accidents
[1]. Since 1970, the International Tanker Owners Pollution Federa-
tion (ITOPF, Ltd.) have managed the global database of oil spill
(persistent and non-persistent hydrocarbon oil) from floating pro-
duction storage and offloading (FPSO), oil carriers, and barges. His-
torically, oils spill data are categorized into three types based upon
the size of spill incident: (a) <7 tons, (b) 7–700 tons, and (c) >700
tons. As per the data provided by ITOPF, there has been consistent
decline in the number of marine oil spills (specifically of size >700
tons) over the past 50 years as illustrated in Fig. 1S (supplementary
information (SI)). Since 2010, an average of 1.8 per year oil spills
has been recorded by ITOPF. As of 2019, one large oil spill (>700
tons) and two medium spills (7–700 tons) were recorded by ITOPF.
In the period between 1970 and 2019, >50% of large spills were
caused by collisions and sinking of oil carriers in open waters.
Interestingly, these same reasons led to greater occurrence of spill
cases (~99%) from oil carriers in inland or restricted waters.
Despite significant reduction in number of oil spill incidents
over the past decade, the large quantity of spilled oil caused inten-
sive damage to marine ecosystems. Oil spills can persist for
extended periods, during which spilled oil undergoes various grad-
ual physicochemical processes (e.g., diffusion-driven spreading,
solubilization, formation of water-oil emulsions, evaporation, pho-
tolysis, and slow biodegradation) [2,3]. These processes can include
substantial changes in viscosity, density, and interfacial tension,
producing hazardous, water-soluble, light-hydrocarbon fractions
in the marine environment [4]. Moreover, photolysis of oil yields
active free radicals that can react with hydrocarbons and release
oxidized organic compounds to ecosystems. Such oxidized inter-
mediate compounds are toxic to the marine food web because of
their higher water solubility and reactivity compared with the
original hydrocarbons [5]. Removal of spilled oil from marine
ecosystems and other waterbodies has become a significant envi-
ronmental challenge.
1.1. Conventional approaches for mitigation of oil spills
The prinicpal approaches used for mitigation of marine oil spills
are focused toward: (a) restricting the spread of spill to offshore
areas, (b) enhancing the recovery of spilled oil, (c) increasing the
degradation of unrecovered oil, and (d) curtailing the influence
on marine ecosystem [1]. In this regard, several techniques have
been adopted to deal with marine oil spills. Traditional treatments
are generally classified into three major categories of physical,
chemical, and bioremediation methods [6]. Each of these cate-
gories comprises a number of currently used available techniques
with benefits and shortcomings. Table 1S SI) presents the most
popular traditional approaches for oil spill cleanup, along with
their merits and disadvantages. The physical methods include oil
booms and skimmers [7,8] and sorption [9]. Chemical methods
comprise chemical dispersants [10], solidifiers [11], in situ burning
[12], and photochemical oxidation [13]. Bioremediation refers to
introduction of microorganisms that can degrade spilled oil [14].
Choice and selection of one of these cleanup approaches depends
on the size and location of the oil slick, properties of spilled oils,
and weather conditions. Waves and atmospheric conditions can
affect evaporation, diffusion, and biodegradation of oils and drive
the spread of oil slicks. Booms and skimmers cannot be operated
in erratic sea conditions of high waves and high-velocity winds
[15]. The efficacy of bioremediation is time-consuming, as
petroleum-degrading bacteria require strict optimization of many
variables such as temperature, pH, oxygen content, and nutrient
availability. Moreover, because chemical methods can suppress
the activities of natural microbial scavengers feeding on oil spills,
they cannot be used in tandem with bioremediation [16]. In gen-
eral, most traditional cleanup procedures are laborious and time-
consuming, and most generate secondary pollutants [17,18].
These limitations highlight the need for fast, sustainable, and
effective solution to address the dangers posed by oil spills
[6,19]. Over the past decade, several attempts have been made to
develop efficient and innovative options to clean up oil spills with-
out imposing an impact on the environment [18,20–22]. Although
a large number of cleaning options is in the early stages of devel-
opment, sorption is emerging as a robust and efficient technology
to recover oil from both water and soil systems [23].
Numerous traditional sorbents have attracted attention as eco-
nomical oil-sorbing materials [9,23,24]. Some have been widely
utilized in oil-spill cleanups, including (1) natural inorganics such
as activated carbon (AC) [25], zeolites [26], clay [27], and diatomite
[28]; (2) natural organics or bio-based materials such as cotton
fiber and rice husks [29]), kapok fiber [30], and sugarcane bagasse
[31]; and (3) synthetic materials such as perlite [32], graphite [33],
poly (dimethylsiloxane) [34], metal organic frameworks [35], poly-
urethane (PU) foam [36,37], and electrospun polymer nanofibers
[38]. Natural inorganic materials are distinguished by low oil-
absorption capacities (<20 g g 1), poor oil/water selectivity, and
low buoyancy [39]. In contrast, natural organic materials offer
comparatively low-impact removal of spilled oil with facile recy-
cling. However, these sorbents exhibit many shortcomings, such
as poor surface hydrophobicity with oil-sorption capacities (e.g.,
Qsugarcane ~ 10.51 g g 1, Qwoodchips ~ 343 mg g 1) and low buoyancy
[39,40]. Most synthetic sorbents (e.g., PU, polypropylene, polyethy-
lene, and butyl rubber) have poor biodegradability and cumber-
some recovery [41]. These sorbents tend to submerge in
seawater during oil sorption due to their higher density relative
to that of oil (<0.9 g cm 3) [6]. As such, sorption techniques are
not amenable to onsite spillage remediation with high capacity,
unless the sorbents are enclosed [9]. Oil-treating sorbents should
have excellent oil-sorption capacity (i.e., super-hydrophobic/
oleophilic sorbents) and low fabrication cost [42].
 D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
1.2. Advances in CNT-based sorption technology for oil spill removal
With the advent of nanotechnology, development of super-
wettable surfaces with adequate toughness has been pursued to
improve the performance oil-sorbing technologies.[42] Various
carbon nanotube (CNT)-based materials have been engineered to
be super-hydrophobic oil sorbents owing to their intrinsic nan-
otextured and porous architectures with super-wetting surface
properties [41,43]. As shown in Fig. 1, CNT-based oil sorbents have
undergone a revolution in design from individual nanotubes to
recently engineered three-dimensional (3D) aerogel/sponge-
based CNT materials [44]. 3D CNT aerogel/sponge sorbents offer
numerous advantages over powdery nanotube sorbents, including
ultra-light weight (low density), inherent super-hydrophobicity/o
leophilicity, strong chemical/mechanical properties, large surface
areas, tunable porosity, and reusability [45–48]. Fabrication of
CNT-based aerogels and sponges with 3D network orientation
and controlled configuration can further enhance their ability to
take up spilled oil [49].
To effectively evaluate the efficacy of CNT sponge/aerogel sor-
bents in oil spill removal, we examined the studies on CNTs,
sponges, aerogels, oil spills, spilled oil, and oil absorption published
since 2015. The literature survey was conducted using Google
Scholar, Web of Science, Science Direct, Wiley, Springer, ACS,
RSC, and PubMed databases. More than 3500 relevant studies were
published from 2015 to 2019. A review of the last decade research
on oil-absorbing materials found a few comparisons of the perfor-
mance between various CNT-based sponges and other advanced or
conventional oil sorbents. Most published reviews focused on
functionalization strategies of CNT materials to improve hydropho-
bicity and oleophilicity for improved oil sorption. This review high-
lights the various strategies applied to synthesis and
functionalization of CNT sponge materials as effective platforms
for oil sorption and recovery. The characteristics of newly devel-
oped CNT sponge materials and their performance in oil-spill
cleanups are discussed, along with their sorption mechanisms, to
provide insights into their applicability to the practical field. The
Fig. 1. Schematic of various approaches adopted for CNT sponge fabrication and modification of their surface causing substantial improvement in structural and functional
attributes.
413
review compares various CNT sponge sorbents with other engi-
neered nanomaterials (e.g., graphene) in terms of hydrophobicity,
wettability, and sorption. This review provides a road map for
future research on scaling up applications of CNT sponge sorbents
for onsite oil-spill cleanup tasks.
2. Characteristic features of pristine and sponge CNTs
Since their discovery in 1991 [50], CNTs have been extensively
investigated for numerous applications such as microelectronics,
catalysis, sensing, and drug delivery. Their miniaturized dimen-
sions and ability to undergo chemical/physical modifications make
them a versatile tool for the aforementioned applications. Besides,
CNTs can also be modified to produce aerogels or sponge-like
structures for oil spill removal as well. In this regard, a detailed
description of the characteristic features for pristine and sponge
CNTs is presented in section S1 for the interested readers.
3. Synthesis of CNT sponges
Selection of an appropriate fabrication method for preparing
CNT sponges is key to controlling their morphology and functional
properties. 3D CNT networks are generally obtained by laser abla-
tion [51], arc discharge [52], and CVD-assisted synthesis [53]. Each
of these methods suffers from sparse contact (Van der Waals force)
between individual nanotubes. Such weak attractive forces can
cause increased sliding and scattering of electrons and phonons,
subsequently restricting the applicability and performance of
CNT arrays or CNT-based components [54]. Two approaches have
been suggested to overcome the limitations of weakly aligned
CNT networks and to enhance covalent bonding between the nan-
otubes. The first involves the use of high-energy beams of radia-
tion to enhance inter-connections between nanotubes [55].
However, high-energy radiation can degrade CNT structures [56],
and it is difficult to achieve the required scalability using this
method. The second approach utilizes a pre-defined template or
414 D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
introduction of additives into the growth medium to generate the
3D CNT network [57].
The basic characteristics of CVD-assisted approaches to fabri-
cating 3D CNT sponge materials are summarized below, along with
their merits and drawbacks. CVD is considered one of the most
widely scalable approaches available to synthesize CNT sponges
because it can grow highly aligned thin films with isotropic
macrostructure morphologies [57]. Synthesis of CNT sponges via
CVD is typically performed through one of two routes: (a) a
catalyst-mediated single-step or direct CVD approach or (b)
template-assisted growth of sponges [58]. A comparison of these
methodologies is provided in section S2 (SI).
4. Absorptive removal of oil spills with CNT sponges
The major focus in this research area is to development of eco-
nomical and recyclable super-hydrophobic sorbents with superior
efficacy for physical sorption and recovery of oil spills under ambi-
ent conditions [59]. Sorbent features can be characterized as
hydrophilic (WCA bwater < 90°), hydrophobic (bwater of 90–150°),
and super-hydrophobic/oleophilic (boil ~ 0° and bwater > 150°)
depending on flat surface wettability (contact angle) [46]. In this
regard, the super-hydrophobicity/oleophilicity (bwater > 140° and
boil ~ 0°) of CNT sponges plus their well-known advantageous
properties (e.g., a low density of 5.8–25.5 mg/cm3, chemical inert-
ness, mechanical stability in harsh pH and salinity, and rough and
incompact surface topology) make them ideal sorbents for oil spills
[60]. In fact, all these characteristics favorably support their high
oil-sorption capacity (in the range of 30–180 g g 1) and apprecia-
ble reusability (up to 1000 cycles). The resulting CNT sponges can
be regenerated by applying pressure to remove or directly burning
the used sorbent for the next round of sorption [61]. Recently
reported case studies associated with performance of various
CNT sponge sorbents for oil spill removal are highlighted and dis-
cussed below.
In a pioneering study, self-assembled 3D monolithic CNT
sponges (2 cm  1.4 cm  0.6 cm) were prepared and investigated
for chloroform sorption (e.g., saturated sorption capacity, Qt, of
180 g g 1) [48] For practical applications, the sponges were sub-
jected to instantaneous absorption of a range of oils and organic sol-
vents with various densities, including ethanol, hexane,
dimethylformamide (DMF), ethylene glycol, chloroform, gasoline,
pump oil, diesel oil, and vegetable oil (Fig. 2). The reported Qt values
of the 3D monolithic CNT sponges were substantially higher than
those of AC (two times) [48] and dense nanowire membranes (<20
times) [62]. The cleaned oil area for oil-sorbed sponges was ~800
times higher than that of a pristine CNT sponge. The high sorption
Fig. 2. Oil-spill cleanup by CNT sponges. (A) Absorption capacity (Qt) measured for various oils and organic solvents. The straight line exhibits a linear increase in Qt as a
function of oil density, (B) Qt values measured for diesel oil measured from various sorbents such as CNT sponges, cotton, loofah, polyurethane, polyester, and activated
carbon. (C) Stress recorded for 1000 cycles at e = 60% showing no strength degradation. The inset image shows snapshots of the CNT sponge before and after cyclic tests With
permission from reference [48]. Copyright 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
capacity of the 3D monolithic CNT sponge was attributed to out-
standing porosity (>99%) with tunable elasticity and a 95% com-
pressed volume reduction at set strains of 0.05–0.25 MPa.
Moreover, the physical absorption behavior of oils and organic
molecules within sponge pores led to high recovery of oil-
absorbed CNT sponges and superior reusability (e.g., up to ~1000
cycles) [61]. The authors also checked the oil-absorptive properties
of 3D CNT sponges (~7.3 mg cm 3) toward three commonly used oils
(mineral oil, vegetable oil, and diesel oil) and two organic reagents
(octane and ethyl acetate). They found that oil-sorption capacity
increased as a function of time, with an average of half of the satu-
rated sorption capacity for mineral oil (th) at ~160 s compared with
that of ethyl acetate (th ~ 2.1 s) (Fig. 7S). Overall, the reported Qt of
the sponges was higher than 120 g.g 1 irrespective of sorbate
viscosity (e.g., [Qt]mineral oil ~125.9 g.g 1, gmineral oil ~ 200 cP;
[Qt]ethyl acetate ~ 120.6 g.g 1, gethyl acetate ~ 0.426 cP) (Table 1) [61].
Moreover, the oil-sorbed sponges were easily squeezed to desorb
nearly 98% of absorbed oil, with substantial recyclability. The Qt
value for diesel oil removal rapidly decreased to 20 g g 1 from the
second cycle after squeezing up to 10 subsequent cycles. This can
be attributed to the lower pressure of mechanical stress (1 MPa)
used to extrude the sorbed diesel oil (i.e., incomplete desorption).
In contrast, regeneration of the spent 3D CNT sponges by direct
burning of the sorbed diesel oil achieved a higher Qt of 66.5 g g 1
in the second cycle and remained constant, at approximately 40 g
g 1 after 10 cycles. However, the burning process necessitates
transport of the waste to a power station, whereas the squeezing
method could be carried out on-site. These regeneration data
indicate a high recycling efficacy for CNT sponges.
Gui and co-workers further synthesized a magnetic nanocom-
posite of CNT sponges filled with magnetic iron nanowires
(Me-CNT sponge) for facile magnetic recovery of spent sorbents
during oil-spill absorption [63]. The synthesized Me-CNT sponge
demonstrated a high capability to absorb diesel oil, with a stable
Qt of 56 g g 1 for up to 1000 absorption-and-reclamation cycles.
Specifically, the sponge exhibited sufficient mechanical and tensile
strength, which was equally supported by squeeze recovery of
sorbed oil under compression (66 kPa at 60% strain) and heating
(~200–300 °C). These earlier observations were indicative of the
promising potential of CNT sponges for water purification with
respect to petroleum pollutants and oil spills in open areas.
The safe recovery of adsorbed oil from porous CNT sponges is of
great value for practical applications. In this regard, Cao and col-
leagues demonstrated electrocapillary water imbibition for des-
orption and extrusion of adsorbed oil from porous CNT sponges
[60]. For electrocapillary imbibition, a cylindrical CNT sponge
(diameter = 8 mm and length = 2 cm) was suspended over a liquid
reservoir containing an immiscible oil layer of cyclohexane on top,
Table 1
Performance comparison of various nanomaterials used for absorptive removal of oil and organic solvents.

S. No. Sorbent code Water Sorbent Sorbent Sorbate Temperature Sorption BET surface Absorption Desorption method Recycling Reference
contact mass (g) density (mg (°C) time area (m2 capacity (g times
angle (°) cm 3) (min) g 1) g 1)
CNTs
1 CNT sponge 156 – 7.3 mineral oil 25 30 – 125.9 Burning/squeezing 10 [61]
vegetable oil 104.7
diesel 112.2
octane 102.8
ethyl acetate 120.6
2 CSTN 150 5.15 0.93 vegetable oil – 5 – 26.48 burning – [58]
2.16 1.11 ethylene glycol 65.85
2.33 1.49 chloroform 74.32
3.20 0.86 gasoline 39.41
2.98 0.89 pump oil 28.16
2.98 0.79 methanol 35.02

D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
1.70 0.94 DMF 49.54
8.31 0.91 diesel 21.39
3 CNT microfiber sponge – – 45 heptane – – 28.4 43 Distillation/combustion/ 10 [99]
squeezing
pump oil 184
4 N-CNS 142 1 7 ethylene glycol – 5 – 30 – – [64]
dichlorobenzene 45
5 CNT sponge – 0.018 7.5 diesel and crude oil 20 15 – 92.3 [45]
polypropylene fiber 0.036 910 – 7.45
fabric
woolen felt 0.036 440 – 6.74
6 Me-CNT sponge 140 – 15 diesel oil – – – 66 heat treatment 1000 [63]
7 CNT sponge >150 1.5  10-3 –- Vegetable oil 30 90 –- 150 squeezing – [97]
DCB 0.01
8 MWCNTs – 0.2 – Gasoline – 120 – 10.5 heat treatment 8 [100]
Kerosene 11
Diesel no. 1 9.5
Diesel no. 2 8
9 CNT@expanded – 0.1 50–300 Vegetable oil – 8 15 3.5 – – [101]
vermiculite
mineral oil 3.7
diesel 3.8
10 CNT aerogel 10 154 – 2.5 5 W50 motor oil 25 5 191 107 burning 4 [47]
CNT aerogel 15 – 16 198 97
CNT aerogel 20 – 24 203 94
11 Carbon aerogels 132 1 18.5 Pump oil 16 ± 2 <1 – 16–26 squeezing 5 [102]
Gasoline – distillation 5
Olive oil – – –
Cooking oil – – –
Graphene
12 Spongy graphene 114 ± 2 0.32 12 ± 5 Kerosene – – 432 45 heat treatment 10 [80]
Pump oil – – 68
Dichlorobenzene – – 46
DMSO – – 63
chloroform – – 86
13 Graphene-based 125–135 1 11.3 motor oil – 1/60 – 54–165 squeezing 5 [103]
sponge

(continued on next page)

415
 416
Table 1 (continued)

S. No. Sorbent code Water Sorbent Sorbent Sorbate Temperature Sorption BET surface Absorption Desorption method Recycling Reference
contact mass (g) density (mg (°C) time area (m2 capacity (g times
angle (°) cm 3) (min) g 1) g 1)
14 Lignin-cellulose 110 0.1 19 crude oil – 12 s – 26.21 hexane washing 10 [68]
functionalized
graphene sponge
castor oil 14 s 24.21
machine oil 10 s 38.73
olive oil 8s 48.21
petrol 10 s 24.42
diesel 9s 34.10
Composites
15 CNT-PDMS/PU 154 ± 0.8 – – hexadecane 30–50 45 s – – 15 hexane washing 5 [59]
60 min
gasoline 14

D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
hexane 12
light crude oil 17
paraffin oil 17
mineral oil 19
silicone oil 24
16 CNT modified PDMS 121.8 1 – Chloroform – ~0.4 – 31 heat treatment 10 [104]
(PC10)
Petroleum 15
17 CNT/rGO aerogel 152.4 ± 2.3 – 4.1 Crude oil – 10 91 100–120 burning 10 [72]
Diesel oil 130–140
Engine oil 230–240
Gasoline 160–170
dichlorobenzene 323 ± 8
18 Graphene- CNT aerogel 147.6 ± 2 0.01 – Gasoline – 60 – 21–35 suction 8 [43]
Vegetable oil –
Paraffin –
Toluene –
THF –
19 Graphene- CNT aerogel 40–114 5.8  10-3 6.2–12.8 Lube oil – – 190 squeezing 10 [70]
Phenixin 270
20 Cu NPs@melamine 145.8 – – Organic solvents/ RT 0.5 – 60–145 squeezing 5–10 [105]
sponge Vegetable oils/
Petroleum
21 Calotropis gigantea fiber 126–140 0.01 Olive oil RT 15 – 130 – – [106]
derived carbon fiber
Kerosene 84.71 extraction 10
22 CNT reinforced PU 158 1 – Lubricating oil – – – 34.9 squeezing 150 [82]
sponge
23 Graphene/PU sponge 151.8 ± 0.5 1.2 – Hexane + oil red O 1.7–71 ~0.16 – 100 squeezing 200 [107]
Engine oil 100
Crude oil 99.1
24 SPION/b-CD CS – – N100 Lubricating oil 25 10 219 7.2 ethanol washing 5 [108]
nanostructures
25 rGO/PU sponge 127 – 8.8 Chloroform RT 5 – 80–160 squeezing 50 [109]
Diesel oil
Pump oil
Lubrication oil
Acetone
DMF
26 rGO/PU sponge 154.99 – – Chloroform – – – 110–120 – 20 [110]
Toluene 45–55
Table 1 (continued)

S. No. Sorbent code Water Sorbent Sorbent Sorbate Temperature Sorption BET surface Absorption Desorption method Recycling Reference
contact mass (g) density (mg (°C) time area (m2 capacity (g times
angle (°) cm 3) (min) g 1) g 1)
27 TiO2 nanoparticles >150 – – Chloroform water – – – – Rinsing with water and – [89]
coated cellulose sponge mixture ethanol
28 Ag nanoparticles 152 – – Atoleine – – – – – – [86]
coated stainless steel
mesh
Gasoline
Heptane
Hexane
Kerosene
Toluene
29 ZnO nanowires coated >150 – Diesel – – – – Annealing under 10 [87]
stainless steel mesh ambient oxygen

D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
Turpentine oil
Olive oil
Mustard oil
Gasoline
Hexane
Dichloroethane
Chloroform
Miscellaneous
29 PU sponge 137 – – Crude oil Ambient – – ~30 – 200 [111]
temperature
Gasoline – – 36–40 –
Lubricating oil – – 25–26 –
Silicone oil – – ~28 –
30 PU@ AEAPS @SiO2 162.5 – – toluene, 5–70 – – – Rinsing with alcohol 40 [84]
nanoparticles@ copper
mesh.
tetrachloromethane
kerosene
petroleum ether
hexane

417
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Fig. 3. Oil recovery by electrocapillary imbibition: (A) Schematic of the experimental setup for imbibition of oil and displacement of aqueous electrolyte solution into a
saturated CNT sponge. Pictures of a CNT sponge: (B) on the surface of blue-dyed cyclohexane, (C) immersed in the electrolyte, (D) saturated with oil completely immersed in
the electrolyte from which gas bubbles and oil droplets are extruded at t = 0, 1, and 20 s, respectively, upon application of 1.2 V potential (RE = reference electrode,
WE = working electrode, and CE = counter electrode). With permission from reference [60]. Copyright 2016 American Chemical Society. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

mixed with a 1 M KOH aqueous solution and 1 wt% dodecyl
trimethylammonium bromide (Fig. 3). The experimental system
comprised a three-electrode system of (a) a CNT sponge acting as
working electrode (WE) on a copper wire or (b) a contour electrode
and commercial Ag/AgCl as a reference electrode in 3 M KCl
(Fig. 3A). During measurement, the CNT sponge was held over
the oil surface (cyclohexane, density ~ 0.78 g cm 3) and then
submerged to observe oil absorption until saturation (Fig. 3B).
The oil-water interface rose upward to contact the sponge (WE)
for electrocapillary imbibition and displacement of oil (cyclohex-
ane) under application of a controlled voltage (threshold
value = 0.24 V) (Fig. 3C). The imbibition process was optimized
as a function of cyclic potential (E) in the range of 1.2 to 0.1 V
(Fig. 3D). In this case, monotonic mass increased in the range of
E = 1.2 V to 0.24 V. Further increments in voltage up to 0.1 V
led to saturation of the imbibition process. Consequently, the fully
saturated CNT sponge recovered > 95 wt% of the absorbed oil with
appreciable reusability (8 cycles). This process is more straightfor-
ward and efficient than with previously reported methods.
The practical feasibility of CNT sponges (length = 260 mm,
thickness = 8 mm, and mass = 0.018 g) was also investigated for
removal of oil from ocean waters [45]. For this purpose, mixed oil
(diesel and crude oil in a 7:1 mass ratio) was merged with seawater
in a petri dish to produce a thin (100 lm) oil film under static con-
ditions (Fig. 8S). The CNT sponge was then placed over the oil film
for absorption. Owing to their high hydrophobicity, the CNT
sponges exhibited a maximum oil sorption capacity (Qm) of
92.30 g
g 1 with excellent water-repellent properties. In compar-
ison, the Qm values for polypropylene fiber and woolen felt were
7.45 and 6.74 g g 1, respectively [45], demonstrating the superior
efficacy of CNT-based sponges for oil removal and recovery in
real-world conditions. Recently, Cortes-Lopez et al. investigated
the effects of an acetone precursor on the oil-absorption capacity
of N-CNT sponges [64]. The synthesized N-CNS was characterized
by appreciable hydrophobic characteristics (bwater > 150°; Fig. 9S
(a-c)). Remarkably, acetone-synthesized N-CNS had a lower oil
absorption capacity compared with that of N-CNS prepared using
only ethanol (e.g., Qt values of 30 g g 1 of ethylene glycol to 45 g
 D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
g 1 of dichlorobenzene; Fig. 9S(d-f)). However, the reported
absorption capacities were significantly lower than the correspond-
ing values reported earlier by Gui et al [61]. The relatively poor per-
formance of N-CNS may be attributed to its low hydrophobicity
(WCA = 142°) compared with those of the sponges reported by
Gui et al. (2011) (WCA = 156°).
The higher viscosity of heavy oils (>103 mPa s) reduces their
absorbability by conventional and nanoscale sorbents. To over-
come this problem, CNT/PDMS-modified PU sponges (CNT/PDMS-
PU) have been reported as effective photothermal sorbents to
absorb and remedy heavy oils spills from aqueous solutions [59].
In this case, CNT/PDMS-PU minimized the viscosity of heavy oils
due to its higher photothermal activity (99% light absorption under
solar simulator 1000 W m 2). This decrease in oil viscosity facil-
itated the sorption ability of CNT/PDMS-PU up to 20 times that of
its original mass. The enhanced absorbability was mainly attribu-
ted to the manifested super-hydrophobicity (WCA = 154.2 ± 0.8°)
and super-oleophilic (spreading time of hexadecane = 0.07 s) prop-
erties of CNT/PDMS-PU [59]. As such, the photothermal-assisted
sorbent approach may be a potential technology for future abate-
ment of heavy oil spills.
5. Performance comparison of CNT sponges and other
nanomaterials toward removal of oil spills
In the past decade, emergence of multifunctional nanomaterials
(NMs) has attracted considerable attention for their potential uses
in remediation of oil spills in various ecosystems. Application of
NMs for systematic and rapid oil-spill remediation relies on their
unique structural characteristics, such as light weight, surface
hydrophobicity, high surface-area-to-volume ratio, and tunable
porosity [65]. In particular, nanoporous sorbents, such as carbon
allotropes (e.g., CNTs and graphene) [47,66], magnetic nanoparti-
cles [67], biosorbents [19], and their composites [68] have been
extensively explored for sorptive removal of oil spills from aqueous
systems. Table 1 summarizes the oil-sorption performances of var-
ious CNT sponges in comparison with the most-reported NM-
based oil sorbents and natural oil sorbents such as sawdust, wool,
fiber, and zeolite.
As listed in Table 1, carbon-based materials (e.g., carbon aero-
gels, graphene foams, CNT-based sponges, carbon coatings, AC,
and ACF) have widely been used as oil sorbents owing to their high
absorption capacities (in the range of 3.8–240 g g 1), super-
oleophilicity, and reusability. Among carbon-based sorbents, the
performance of CNT sponges for oil-spill removal has been well
documented. For example, the pioneering efforts of Gui and col-
leagues produced remarkable Qm values of 125.9, 104.7, 112.2,
102.8, and 120.6 g g 1 toward removal of mineral oil, vegetable
oil, diesel, octane, and ethyl acetate, respectively [61]. In another
study, the N-CNT sponge showed absorption capacity values of
26.48, 65.85, 74.32, 39.41, 28.16, 35.02, 49.54, and 21.39 g g 1
toward mitigation of vegetable oil, ethylene glycol, chloroform,
gasoline, pump oil, methanol, DMF, and diesel oil, respectively
[58]. On a comparative note, Me-CNT sponges retained 76% of their
original Qt value over 1000 cycles, with (Qt)initial ~ 66 g g 1 and
(Qt)1000 ~ 43 g g 1, which evidently supported their excellent per-
formance as heavy oil sorbents [63].
Pristine graphene has been found to be inefficient for oil spill
removal applications. This limitation can be assigned to poor sta-
bility, poor elasticity, low porosity, and low absorption efficiency
of pristine graphene [69]. These limitations prompted the advance-
ments in the synthetic technologies for three-dimensional (3D)
graphene architectures towards enhanced oil absorption capacities
[70]. A major challenge in the synthesis of porous 3D graphene is to
impart the prepared graphene with enhanced hydrophobic charac-
teristics through the optimization of the surface roughness [71].
419
The surface roughness of porous 3D graphene nanostructures in
turn depends upon: (a) introduction of heteroatoms in the pristine
graphene framework or (b) formation of nanocomposites of gra-
phene with other nanomaterials (e.g., CNTs [72], ethylenediamine
[73], polypyrrole [74], polystyrene [75], and polyurethane [76]).
Expectedly, CVD has been the most sought out method for prepa-
ration of 3D porous networks of graphene with high hydrophobic-
ity and high elasticity [77]. In terms of cost efficacy, this synthesis
method is very much comparable to that used for CNT sponges.
Specifically, 3D graphene aerogels (GA) were demonstrated for
high elasticity (reversible strains of 50–90%), high anisotropicity,
high porosity, and high surface area [78,79]. Sponges of graphene
(a two-dimensional structure of one-atom-thick carbon) have also
attracted considerable attention for oil-spill absorption potential
(Qm in the range of 54–165 g g 1; Table 1) because of their higher
hydrophobic and oleophilic surface properties [68,80]. The high
oil-absorption capacities of graphene-based sponges can be
accounted for by their low density (0.0113 g cm 3) and high
WCA (162°). Reduced graphene (rGO)-coated PU sponges were also
prepared for rapid cleaning of oil slicks (~99% removal (Qt of 34–
41.7 g g 1) in 5 s) for up to 50 reusable cycles. The rapid absorba-
bility of oil slicks by an rGO/PU sponge can be attributed to its
higher porosity and surface hydrophobicity (bwater ~ 153°) [81].
More recently, a lignin cellulose-functionalized graphene (LCG)
sponge was developed to absorb various oils and organic solvents
[68]. The LCG sponge showed rapid absorption (8–14 s) of oils with
appreciable sorption capacity (Qt ~ 34.1–48.21 g.g 1 for diesel and
olive oil) and good recycling capabilities (10 cycles) [68].
Hybridization of CNTs with other advanced NMs is a well-
known strategy to improve oil sorption properties by CNT sponges
due to the synergistic effect of the constituents. In this regard, CNT-
reinforced PU that yielded a PU-CNT-polydopamine (PDA)-
octadecylamine (ODA) sponge was tested for separation of various
types of oils from water [82]. For fabrication of the CNT-PU sponge,
pristine CNTs were first treated with polydiacetylene (PDA)
solution to form a CNT-PDA adduct. Subsequently, a CrO3/H2SO4-
treated PU sponge was added to the adduct and formed a
PU-CNT-PDA composite, which reacted with hydrophobic ODA to
yield a PU-CNT-PDA-ODA sponge, which rapidly absorbed all lubri-
cation oil in ~5 s with a Qt of 22 to 34.9 g g 1. Efficient and rapid oil
absorption can be linked to the similar surface energies of lubrica-
tion oil (31 mN m 1) and ODA (31 mN m 1). Furthermore, the sat-
urated sponge exhibited higher mechanical strength (20  103 N
m 1) and good capability for reuse over up to 150 absorption
cycles after simple squeeze-recovery for absorbed oil due to incor-
poration of CNTs into PU (strength of PU 4  103 N m 1) [82]. Based
on the unique properties of graphene and CNTs, graphene-CNT
aerogels (GCAs) have also been developed and tested for the
removal of lube oil, polar organics (e.g., n-hexanol, ethanol, and tol-
une), and non-polar organics (e.g., Phenixin) [70]. The developed
GCA demonstrated outstanding sorption capacities of 190 and
270 g g 1 for Lube and Phenixin, respectively, indicating a high
efficacy for oil-spill cleanup applications. In addition to the afore-
mentioned materials, silicon nanoparticles and their derivatives
[83–85] and composites of metal nanoparticles with synthetic
(inorganic [86,87] and organic polymers [88]) and natural organic
materials [89] also exhibit high hydrophobicity, which makes them
an attractive candidate for oil spill remediation purpose.
Overall, the reported studies suggest a promising role for mul-
tifunctional hybrid CNT-based sponges as efficient absorbents for
large-scale oil-water separation procedures. The high hydropho-
bicity of CNTs may offer a systematic basis for enhanced oil sorp-
tion capacities of various sorbents. As discussed in this section
(as well as in Table 1), there have been numerous reports on the
synthesis and applications of CNT sponges, porous 3D graphene
macrostructures, and related sorbents for oil spill remediation.
420 D. Kukkar et al. / Journal of Colloid and Interface Science 570 (2020) 411–422
However, majority of these reports are restricted to lab-scale stud-
ies. Numerous challenges must be addressed before these sponges
can be adopted for real-world applications toward oil spill
removal. For instance, during bulk-scale oil spill remediation, the
resistant behaviour of sponges towards continuous exposure to
oil environment is still in infancy. Moreover, the tensile properties
of CNT sponges or even graphene sponges are of several order
lower in comparison to their pristine counterparts [90–92]. As
such, a better knowledge is needed to accurately describe chemical
interactions between the marine ecosystem, oils, and sponges.
Such analysis would be helpful in enhancing the feasibility of
CNT sponges as commercially effective sorbents for oil spill
removal and related environmental applications.
6. Conclusion and future prospects
CNT sponges are expected to emerge as a potential sorbent for
oil spill mitigation. In summary, this review describes the superior-
ity of CNT-based sponges [58,60] as innovative options for cleanup
of oil spills compared with conventional sorbents or traditional
techniques (e.g., containment booms [93], skimmers [94], and
use of dispersants [95]). The effectiveness of CNT sponges for oil
sorption depends mainly on their physicochemical properties.
These properties, in turn, are critically dependent on numerous
experimental parameters during fabrication (e.g., by CVD
approach) such as concentration of carbon sources (e.g., alcohol
[96]/hydrocarbon [64]/benzene derivatives [63]), flow rate of car-
rier gas, type of catalysts (e.g., Pt/Pd/Ni), and reaction temperature.
In principle, the superior CNT sponges are characterized mainly by
unique 3D structures, super-hydrophobic/oleophilic properties
(bwater > 150° and boil ~ 0°) [97], high mechanical strength (>95%
volume reduction at e > 95%) [61], excellent oil sorption capacity
(80–180 g g 1) [64], and outstanding ability for reuse up to 1000
cycles [63]. In addition to oil spill removal, CNT sponges have also
been recognized by the enhanced potential for retrieval of Au NPs
from their colloidal suspensions [98].
The efficacy of reusability cycles depends on burning or squeez-
ing desorption. Nonetheless, the cost of CNT sponges by CVD is
higher than that of conventional sorbents such as AC or biologically
derived sorbents. To overcome this limitation, a new CNT sponge
material, termed photothermal and hybrid-sorbent, has been
recently developed as a potentially effective recyclable material
for successive absorption of heavy oil spills with high viscosity
(>103 mPa s) at large scale [59]. These CNTs sponges can reduce
the cost of oil-spill cleanups substantially by increasing the number
of environmentally friendly sorption/desorption cycles. Nonethe-
less, CNT sponges suffer from several limitations such as obscure
response towards continuous exposure to oil environments, reduc-
tion in the tensile strength in comparison to the pristine CNTs [90–
92], and lack of sufficient knowledge about the chemical interac-
tions between the marine ecosystem, oils, and the sponges.
Selection of an economic carbon source and a less-expensive cat-
alyst can substantially reduce the manufacturing costs of CNT
sponges for application to oil-spill cleanups. However, remediation
of oil spills using CNT-based sponge sorbents remains limited due to
current demand for economic and scalable synthesis in higher quan-
tities. In addition, fabrication of nanocomposite CNT sponges with
other sorbents, especially graphene and metal organic frameworks,
may enhance oil-sorption characteristics. These sorbents are char-
acterized by high specific surface areas and large sorption capacities
and may synergize the oil-sorption properties of CNT sponges.
CRediT authorship contribution statement
D Kukkar and A Rani conducted conceptualization, formal anal-
ysis, developed methodology, and wrote original draft. V Kumar
and S. Younis conducted formal analysis, data curation, and wrote
original draft. M Zhang, S. Lee, and T. Dan supported data curation,
visualization, and validation. KH Kim conducted validation and
reviewed and edited the manuscript for publication.
Acknowledgements
DK acknowledges the financial support of SERB, Government of
India, under the early career research program (No.
YSS/2015/000212). KHK acknowledges support from the R&D Cen-
ter for Green Patrol Technologies through the R&D for Global Top
Environmental Technologies funded by the Ministry of the Envi-
ronment (MOE Grant No: 2018001850001) and from a grant from
the National Research Foundation of Korea (NRF) funded by the
Ministry of Science, ICT, & Future Planning (Grant No:
2016R1E1A1A01940995). VK acknowledges support from the
Department of Science and Technology, New Delhi, India, in the
form of an INSPIRE Faculty Award and from the Science and Engi-
neering Research Board (SERB), Government of India, under the
Early Career Research award (File No. ECR/2018/000748).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcis.2020.03.006.
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