p-ISSN: 0972-6268

Nature Environment and Pollution Technology (Print copies up to 2016)

2023
An International Quarterly Scientific Journal Vol. 22 No. 1 pp. 39-61
e-ISSN: 2395-3454

Review Research Paper https://doi.org/10.46488/NEPT.2023.v22i01.004

Original Research Paper Open Access Journal

Advanced Synthetic and Bio-Based Sorbents for Oil Spill Clean-up: A Review
of Novel Trends
M. G. Gote*† , H. H. Dhila* and S. R. Muley**
*School of Chemistry, Dr. Vishwanath Karad MIT World Peace University, Pune, Maharashtra, India
**Nuvation Bio Inc., 1500 Broadway, New York, NY, USA
†Corresponding author: M. G. Gote; [email protected]

ABSTRACT
Nat. Env. & Poll. Tech.
Website: www.neptjournal.com Due to immense population growth and economic development, the use of crude oil for
various energy applications has escalated in the past few decades. This has led to the large-
Received: 18-08-2022 scale exploitation of oil reserves which has further resulted in the accidental release of large
Revised: 06-10-2022
amounts of oil into our oceans. In recent years, significant emphasis has been placed on
Accepted: 19-10-2022
processes involving oil sorption by various natural and synthetic sorbents. Several sorbent
Key Words: materials based on synthetic polymers such as polypropylene, polyurethane, polystyrene,
Oil/water mixtures etc., possessing three-dimensional porous structure, large surface area, high mechanical
Sorbents strength, and exhibiting good oil recoverability and reusability, have been employed for oil-
Surface modification water separation processes. Conversely, many of these materials in their native or pristine
Polymers form are amphipathic, which prevents their large-scale use in oil spill clean-up. This has led
to researchers exploring surface modifications of commercially available sorbent polymeric
materials to enhance their oleophilicity and hydrophobicity. This review article summarizes
and discusses recent advances in the strategies for the fabrication of newer surface-modified
synthetic polymeric materials and natural bio-based sorbents, and further highlights their
effectiveness in dealing with the oil/water separation challenges.

INTRODUCTION oil discharge near oil wells, pipelines and other equipment
failures, land runoff, natural disasters, etc. Most of the
Water is an essential component of all living beings on this accidents are due to human error and some may be due to
planet. Earth’s surface has 97% saline water, and only 3% natural disasters such as earthquakes and hurricanes which
fresh water is available for us to use. Therefore, water needs cause oil tanker ships to be damaged. The various oils that
to be recycled and re-utilized in the best possible manner get mixed with water are mostly lipids, hydrocarbons, and
across the globe. In the last few decades, the rise in water fractions of petroleum products such as diesel oil, gasoline,
pollution is seriously threatening the environment and one- kerosene, etc. In oil-containing wastewater, oils may be
third of all water pollution is due to oil spillage and untreated mainly present in three forms: free oil (oil droplet size >
industrial discharge (Zhang et al. 2019). Crude oil is an 150 μm), dispersed oil (20 μm < oil droplet size < 150 μm),
important source of energy and is currently an indispensable and emulsified oil (oil droplet size < 20 μm). The amount
component of industrial development and modernization. of oil that is spilled during such accidents may range from
Several complex processes are involved in the extraction, a few hundred tons to several hundred thousand tons. A
refining, and transportation of oil to consumers (Speight recent report from ITOPF 2020 indicated that the number of
2006). However, accidental spillage of crude oil and oil incidences with spills larger than 700 tonnes has decreased
distillate products occurs quite frequently in seas and oceans significantly over the last few decades. The annual average
as a result of large offshore drilling and oil transportation number of spills reported in the 2010s was 1.8 spills, which
(Rogowska & Namieśnik 2010). There are numerous in comparison to the 1970s shows a 90% reduction in the
reasons for the occurrence of these oil spills which include number of average spills, with a loss of 164,000 tonnes of oil
from tanker spills ≥ 7 tonnes in 2010s. These oil spills have a
ORCID details of the authors: deteriorating effect on soil, water and air. The BP Deepwater
Horizon disaster which occurred in 2010, is considered to be
M. G. Gote
the worst and the largest oil spill ever (Middlebrook et al.
https://orcid.org/0000-0002-7862-9621
2012) recorded. Another recent mishap near the California
40 M. G. Gote et al.

coastline (2021) released 25,000 gallons of crude oil into the (Fig. 1) (Padaki et al. 2015). Various devices such as
waters. Although there is a trend of decreasing the number skimmers, pumps, booms, etc. are being used as mechanical
and quantity of oil spilled due to better drilling technology methods (Jamaly et al. 2015, Ramanathan et al. 2021).
and more safeguards against spills in recent years, there Additionally, chemicals such as detergents are employed
remains a significantly high risk of large oil spills causing to emulsify the spilled oils to enable their biodegradation.
environmental havoc. In-situ, localized burning of oil has also been carried out,
Oil spills are a catastrophe for marine wildlife as it but needless to say, this method can have devastating effects
suffocates fish and other aquatic fauna. Oil-coated birds and on the environment (Potter & Buist 2008). Biological
marine mammals may die from hypothermia. Photosynthesis remediation, wherein certain oil-eating bacteria are
by marine plants is also hindered due to oil spills blocking employed, causes the breakdown and further detoxification
sunlight from penetrating the water’s surface. In addition, of dangerous chemicals or contaminants present in the
textile and chemical industries release a large amount of oily polluted water (Atlas & Hazen 2011). Other technologies
wastewater that contaminates aquatic bodies causing serious which have been developed include electrochemical methods
damage to the ecosystem. The cost of oil spills is very high in specifically electrocoagulation and electroflotation, wherein
terms of both the economy and ecology. Oil spills are a serious by passing an electric current through an emulsion, oil-water
environmental crisis that needs to be dealt with relentlessly separation can be achieved. Oily waste water treatment has
to save our ecosystem. The remediation of oily wastewater is also been conducted through membrane filtration which
extremely critical and of paramount importance. Oil clean-up involves applying pressure to separate the liquids via a
and recovery of oil from the spill is however, a complicated membrane usually made of ceramic and polymeric materials
task that is influenced by numerous factors such as quantity (Fingas 2012). These oil-water separation techniques are not
and type of oil spilled, water temperature, air currents, waves, very efficient due to ineffective oil/water separation, use
type of shorelines, etc., which may take a long time to clean of energy-intensive processes, high operations costs, time-
up (Usman & Okoro 2017). consuming processes, the release of secondary pollutants,
and various other challenges (Pavlatou 2020).
CONVENTIONAL METHODS OF OIL-SPILL
Sorbents for oil-spill clean-up, owing to their structure
CLEAN UP
are materials capable of capturing a liquid primarily in their
Many conventional techniques are in use to tackle the cavities, fibers, and surfaces. The word “sorbent” comes
problem of oil-water separation. These methods include from the Latin word “sorbere” which means material that
mechanical, chemical, thermal, and biological treatments soaks with liquid. Liquid sorption occurs till the system

Fig. 1: Common methods used in oil spill clean up.

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 41

reaches the equilibrium or saturation point. In comparison their performance in oil/water separation (Khosravi & Azizian
with other conventional techniques, the application of 2015, Li et al. 2018).
sorbent materials has proven to be a more effective way of One of the research strategies has been to modify the
dealing with environmental concerns and recovering oil in surface of synthetic, polymeric sorbents by using certain
preference to water (Wu et al. 2014, Zhang & Seeger 2011). low surface energy materials to enhance their surface
The mode of action of these sorbents is either absorption or roughness to convert them into more hydrophobic and
adsorption. Absorbents work like sponges and absorb oil by oleophilic materials to achieve higher oil absorption capacity
capillary action or suction and are useful for less viscous (Lü et al. 2016). Generally, if the water contact angle
oils. On the other hand, adsorbents have a large surface (WCA) is lower than 90°, the solid surface is considered
area, high porosity, and high chemical affinity for spilled to be hydrophilic, and if the WCA is greater than 90°, it is
oil and work best for heavy, sticky oils. Some sorbents considered hydrophobic. Highly hydrophobic surfaces made
may use both modes of action to sequester oil. A wide of low surface energy materials may achieve WCA as high
array of techniques based on sorbent materials has recently as ≈ 120°. Some of the materials with highly rough surfaces
been developed as promising solutions to the oil spill may achieve a static WCA greater than 150° and a dynamic
problem (Shang et al. 2016). These absorbing or adsorbing WCA less than 10° due to the existence of air pockets under
materials are generally easily available, inexpensive, and the liquid drops and have been termed superhydrophobic
environmentally friendly (Singh et al. 2013, Yang et al. surfaces. Several reports have been published which illustrate
2015). In addition, they also have high regeneration ability the superior performance of superhydrophobic materials in
and the oil can be subsequently recovered and reused, oil-water separation applications due to their super-anti-
making the sorbents crucial in the removal of oil from water. wetting and self-cleaning properties. Extensive efforts have
Oil sorbents fall into three basic categories: organic, been dedicated in the last couple of decades to researching
inorganic synthetic materials, and biomaterials available in the preparation and synthesis of durable superhydrophobic
nature. The carbon-based biomaterials include rice husk, materials for efficient separation of oil and water during the
sugarcane bagasse, sawdust, straw, cellulose, etc. (Yue et al. clean-up of global oil-spills. One of the disadvantages of
2019). The natural inorganic sorbents include clay, perlite, the use of hydrophobic, highly porous polymeric materials
glass wool, sand, zeolites, etc. (Ruan et al. 2014, Wang & in oil-spill clean-up is the tendency of highly viscous
Geng 2015, Zhang et al. 2019). However, these sorbents oil to be trapped in the pores of the material due to their
suffer from certain drawbacks such as being amphipathic low surface tension, resulting in decreased regeneration
i.e., absorbing both oil and water, poor oil recoverability, and reusability of the material to continue adsorbing the
poor buoyancy, and poor recyclability. oil. Therefore, modification of polymeric materials to
enhance their adsorption capacity, surface self-cleaning,
SYNTHETIC SORBENTS and regeneration ability have to be evaluated in depth. In
addition, challenges related to the decreased thermal stability
Several novel synthetic sorbents have been developed in the of polymeric materials at high temperatures and low energy
form of foams, sponges, fibers, meshes, nanoparticles, etc. to conversion efficiency need to be overcome. Future research
achieve high absorption capacity, oil/water selectivity, and should also aim at making the commercial manufacture of
reusability for efficient separation and recovery of oil from functional polymeric foams more efficient, economical,
water surfaces (Gui et al. 2013, Zhang et al. 2014). Recently, widely available, and easy to deploy and use.
synthetic polymers such as polypropylene (PP), polystyrene
(PS), and polyurethane (PU), have received a lot of attention Given the plethora of research in the field of environmental
as viable sorbent materials among others since they have science in curbing the effects of aquatic pollution specifically
reasonably good oil sorption capacity (Sarbatly et al. 2016, due to oil spills, this review evaluates the latest advances
Zhang et al. 2018). They are substantiated by properties such as in the strategies for modification of polymeric materials to
lower density, high porosity, larger surface area, and excellent make them more efficient in oil-spill clean-up and assesses
mechanical strength. Polymers have several advantages in the their effectiveness and commercial applicability.
manner in which they can be easily processed, molded, and
functionalized in comparison with other materials (Guo et al. STRATEGIES EMPLOYED IN THE FABRICATION
2017, Zhou et al. 2013). However, certain drawbacks, such as OF MODIFIED SYNTHETIC SORBENTS
poor recyclability, low oil retention, and poor oil recoverability Polyurethane
still limit their performance in oil spill clean-up. Hence, it
has become imperative to modify these polymeric materials Polyurethane (PU) sorbents are some of the popular sorbents
to enhance their hydrophobicity and oleophilicity to improve due to a combination of their characteristics including low

Nature Environment and Pollution Technology • Vol. 22, No. 1, 2023

42 M. G. Gote et al.

cost, high porosity, good elasticity, large internal surface area, of various materials onto the sorbents should aim at
smaller cross-linked structure, and excellent microstructure. transforming the surface functions and not alter their bulk
PU polymers are usually synthesized by reacting a di- or properties. The following sections discuss various strategies
tri-isocyanate with a polyol and are classified as alternating for the modification of PU and other polymers to help
copolymers since PU monomers polymerize one after the improve their sorbent efficiency. A summary of modified
other in a sequence. The possibilities for the preparation and polyurethane sorbents is given in Table 1.
modification of PUs are numerous, which combined with In recent years, polymerization has been employed as
an extensive choice of additives and processing conditions a facile technique to construct superhydrophobic sponge
available, make the use of PU very widespread. However, surfaces. The polymerization reactions involve covering
due to the presence of groups like carboxyl and amino groups the surface of the sorbent with crosslinked polymer chains
in these polymers, PU is amphiphilic. Increasing the oil to produce oil-sorbing surfaces. This technique results
absorption capacity of PU sponge is therefore an essential in polymeric chains formed on the surface to facilitate
requirement for its applicability in oil spill clean-up. The the adhering of other hydrophobic materials. Graft
efficiency of PU sponges as sorbents is greatly enhanced copolymerization has been conducted with an oleophilic
when their wettability is improved upon modification of monomer as lauryl methacrylate (LMA) to modify PU
its surface with low surface energy hydrophobic materials. using divinylbenzene as the cross-linker (Li et al. 2012)
Surface-modified polyurethane has been shown to exhibit to get a highly oleophilic polyurethane. The sorption
promising results in terms of oil/water separation owing to efficiency of LMA microspheres coated onto PU cubes was
its good stability, high sorption capacity, and recyclability. also evaluated. The surface roughness of the modified PU
Specifically, methods that generally involve the coating sorbents was observed to increase upon grafting or coating

Table 1: Modified Polyurethane Sorbents.

Sorbent Treatment Material Method Sorption Capaci- Sorption Experimental Reference

ty (g/g) Conditions
PU foam Lauryl methacrylate (using DVB Graft copolymerization 50–69 Sorption conducted at 23 ± Li et al.
as a linker) 4oC by immersing sorbent 2012
into oil
PU Perfluorinated polydopa- Controlled dripping/dry- Diesel: 31.2 NDs-fPDA loading at 60%, Cao et al.
mine-coated nanodiamonds ing process Gasoline: 20.5 highest sorption capacities 2017
observed at pH 1 and 13
PU Polydopamine- hexamethyl disila- PU sponge coated with Acetone: 36 Sorption conducted at room Liu et al.
zane (HMDS) PDA nano-aggregates Chloroform: 53 temperature (RT). No specif- 2019
grafted with HMDS ic test conditions described
PU Acidified carbon nanotubes-Poly- Electrospun PU nanofib- Separation Effi- Water Permeation Flux: Huang et
dopamine ers immersed in ACNTs ciency: 99.9% 4195 – 7240 L m-2 h-1 at al. 2020
followed by self-polym- driving pressure 0.5 bar for
erization of dopamine heptane, toluene & cyclohex-
ane; SDS used as emulsifier
@ 0.001% w/w
PU Foam Lauryl methacrylate & hexade- Free radical polymeri- Diesel:132.4 Sorption with immersion for Keshawy
Waste cene, using crosslinkers like divi- zation Crude oil: 125.1 ~60 min at RT at 2% w/w et al.
nyl benzene (DVB) & 1,1,1-tri- nanoparticles loading 2020
methylolpropane trimethacrylate
(TPT)
PU Poly(dimethylsiloxane) (PDMS)- Sol-gel method followed Diesel & Pump Sponge size 1 × 1 × 2 cm3, Shuai et
TiO2 by in-situ polymerization Oil > 16.7 sorption determined at RT al. 2015
with TiO2 sol-gel loading of
13.6g/mL
PU sponge 1,3-oxazolidine, octadecyl trichlo- Solution immersion Bean Oil: 25 Oil absorption occurred Liang et
rosilane (OTS) self-assemblies Lubrication within few seconds at RT al. 2019
Oil: 23
PU sponge PU@ZnO@Fe3O4@SA Microwave and Diesel: 81 Evaluated on a round Tran &
Dip-coating Vacuum Oil: sponge, 7 cm diameter & 2 Lee 2017
110 cm thick at RT

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 43

Sorbent Treatment Material Method Sorption Capaci- Sorption Experimental Reference

ty (g/g) Conditions
PU sponge TiO2 nanoparticles Immersion Motor Oil: 105 Sponge added to oil film Wu et al.
Diesel: 90 2-6 mm thick at 20 ± 2°C & 2014
stirred at 500 rpm for 1h.
PU TiO2 nanoparticles coated PU Immersion Crude Oil: 26 Carbon content 69%; Maxi- Wei et al.
followed by GO amidated with Chloroform: 62 mum sorption occurred in <5 2018
tetradecyl amine (TDA) min at RT
PU sponge Asphaltene-capped hydrophobic Emulsion technique Crude Oil: 50 PU: HSNP-2 at 1:1 ratio Atta et al.
silica nanoparticles using sponge 2 cm thick 2019
PU sponge Carbon nanofibers Grafting Hexane: 27 Dynamic separation of oil by Baig et
Toluene: 50 Pumping oil/water mixture al. 2019
through a pipe fitted with
sponge
PU sponge Carbon nanofibers & methylene Grafting Pure System: 1 cm3 foam in contact with Visco et
diphenyl diisocyanate oligomers 5.25 50 mL water, diesel, or wa- al. 2021
Mixture: 2.56 ter/diesel mixture for 30 min
PU sponge Crosslinked reduced graphene Immersion Not Available Oil/water emulsion poured Zhu et al.
oxide over sponge strip at RT 2016
Graphene/ Graphene/N-methyl pyrrolidone In-situ polymerization Sorption Capaci- Engine oil and crude oil Kong et
PU sponge of polyols & diisocy- ty: NA, Continu- filtered through PU sponge at al. 2017
anate in the presence ous collection of 8.9 × 104 and 6.4 × 104 L*m-
2 -1
of graphene/N-methyl various oils *h respectively, at
pyrrolidone 30 kPa applied pressure
PU Octadecylamine coating using Solution immersion Crude Oil: 25 Sorbent foam in contact with Oribayo
polydopamine-reduced graphene Silicone Oil: 30 oil dispersed on the water et al.
oxide for adhesion surface at RT 2017
PU sponge Polydimethylsiloxane (PDMS) Solar-mediated grafting Castor Oil: 34 3 mm thick sponges placed Singh &
layer and carbon dots Kerosene: 52 in oil/water mixtures and Jelinek,
irradiated at 1 kW/m2 (wave- 2020
length 350-1800 nm) at 25°C
PU foam Crosslinked siloxane Immersion followed by Pump Oil: 500 – Felt piece size 3 × 1 × 0.5 Biesuz et
pyrolysis 2500% wt. gain cm3, sorption determined al. 2020
@ 25°C
PU sponge SiO2/GO nanohybrid Dip-coating 180 Cubical sorbent specimen of Lü et al.
5 × 5 × 2 mm3 dipped in 20 2016
ml oil for 5 min.
PU foam Zeolitic imidazolate (ZIF-8) In situ self-assembly Silicone Oil: 28 No specific test conditions Zhao et
framework (MOF) method Methylbenzene: described; sorption conduct- al. 2019
33 ed at RT

the PU surface with LMA. The grafting copolymerization selectivity was found to be greatest for diesel oil out of
with LMA was observed to be less efficient or incomplete the various oils evaluated. The absorbed oil was recovered
compared to the coating of PU with LMA microspheres from the sponge by a mechanical extrusion process and the
resulting in greater sorption of oil by PU-LMA microspheres recovered sponge displayed excellent reusability of more
in comparison to PU-g-LMA and blank PU cubes. A novel than 60 times.
and promising PU sponge coated with superhydrophobic There has been a surge in the exploration of multifunctional
poly(dimethylsiloxane) (PDMS)-TiO2 was reported (Shuai polydopamine (PDA) nanocoatings on a variety of substrates
et al. 2015) for the treatment of oil spills. An easy fabrication due to their versatility. In addition, they are a practical and
was carried out on the surface of the PU sponge via sol- effective approach to transforming the surface properties
gel growth of TiO2, followed by immersing the PU-TiO2 of various materials (Zhang et al. 2019). Out of the several
construct in PDMS solution for in situ polymerization. cross-linking agents, dopamine has been especially useful as
The surface was found to be superhydrophobic as proven it can self-polymerize and result in the fabrication of stable
by the WCA of 154°. The sorption capacity was observed covalent and non-covalent bonds between the materials
to increase to 16.7 g.g-1. The rate of sorption and sorption (Peng et al. 2019). Taking advantage of the adhesion

Nature Environment and Pollution Technology • Vol. 22, No. 1, 2023

44 M. G. Gote et al.

property of dopamine, a practical approach was developed to the ease with which they can be used, as well as their
by Cao et al. (2017) to fabricate stable superhydrophobic high separation effectiveness. Other advantages of using
nanodiamond particles (NDs) coated with polydopamine membrane separation processes include reproducible product
which were subsequently perfluorinated. Nanodiamonds quality, lower operating costs, and a smaller carbon footprint,
are a new class of carbonaceous material, which exhibit i.e., lower energy consumption over long durations required
high surface area, non-reactivity, and extensive surface for oil-water separation processes (Karami et al. 2020).
chemistry, and hence show great promise for a variety However, the hydrophobic properties of the membrane which
of applications. Self-polymerization of dopamine was make it an efficient oil-adsorbing agent can also shorten the
first carried out on the surface of NDs. The catechol and life of the membrane due to increased membrane fouling.
amino groups present on the polydopamine film assisted As a result, modification of membranes, specifically the
in a facile Michael addition reaction of the -SH groups of enhancement of their hydrophilicity is also essential to
1H,1H,2H,2H-perfluoro-1-decanethiol (PFDT) to prepare improve the membrane performance. Superhydrophilic/
superhydrophobic perfluorinated (NDs-fPDA) particles. underwater superoleophilic PU nanofibrous membranes
The performance of the modified sponge was improved due decorated with acidified carbon nanotubes (ACNTs), and
to its superhydrophobicity, and high oil/water separation coated with polydopamine with a core/shell structure have
properties. The sponge shows an absorption capacity 15 been fabricated by (Huang et al. 2020). Excellent stretching
to 60 times greater than its weight for a variety of solvents ability and surface stability were achieved due to extensive
and oils. It also exhibited good recyclability and good oil interfacial hydrogen bonding between the various components
recoverability. The low cost, easy fabrication method, and of the nanofibres. Better anti-fouling properties and excellent
excellent performance of this superhydrophobic sponge make oil-water separation with outstanding recyclability were
it a good candidate for oil spill clean-up. exhibited by the fabricated nanofibres. Core/shell composites
A unique flame-retardant polydopamine (PDA) coated of PDA/ACNTs and polymer nanofiber exhibited great
PU sponge was fabricated (Liu et al. 2019) via a one-step potential in oil spill clean-up.
polymerization with further surface modification carried Another pressing environmental pollution problem we
out using hexamethyl disilazane (HMDS). The PU-PDA- are facing is the daunting task of dealing with an enormous
HMDS sponge demonstrated superhydrophobicity with a quantity of plastic waste generated around the world.
contact angle of 153°. Pristine PU sponges were dipped The usage of plastic waste as a feed for the fabrication
into dopamine solution which self-polymerized. The nano of oil sorbents could therefore solve the dual problems of
aggregates of PDA rendered the surface quite rough. minimizing and management of plastic waste, as well as
However, due to the presence of hydroxyl groups on the containment of oil spills. To further investigate this approach,
PDA film, the sorbent was observed to be quite hydrophilic. Keshawy et al. (2020) evaluated the functionalization
Further grafting of HMDS on the PU-PDA surface was of the surface of polyurethane foam waste via a facile
conducted which led to the attachment of methyl groups copolymerization of hydrophobic monomers, namely lauryl
across the surface transforming the hydrophilic surface into methacrylate & hexadecene, using crosslinkers as divinyl
an oleophilic surface. The surface modification led to an benzene (DVB) and 1,1,1-trimethylolpropane trimethacrylate
enhanced oil absorption capacity in the range of 21 to 53 (TPT). Furthermore, nano magnetite was incorporated into
g.g-1 for various oils and organic solvents evaluated. Stable the coated PU foam waste which enhanced its oleophilicity.
absorption performance was demonstrated by the surface- Increasing the nanoparticle concentrations also increased the
modified PU sponge with repeated absorption-desorption sorption capacity for diesel and Egyptian crude oil to 132.4
cycles. Measurements showed that the PU-PDA-HMDS g/g and 125.1 g/g respectively. Higher oil sorption was
sponges exhibited excellent heat stability and flame- observed for DVB crosslinked coated samples compared
retardancy in comparison with the original PU or PDA- to TPT crosslinked samples. It was inferred that a denser
coated PU. The flame-retardant property was attributed to network could be achieved with TPT in comparison to DVB
the formation of a silica-hybrid char residue layer during as the crosslinker.
the combustion process. The compact nature of the char Liang et al. (2019) have prepared via a facile, mild, and
residue layer can prevent flames from reaching the interior inexpensive process, 1,3-oxazolidine-modified polyurethane
bulk of the sponge, thereby preserving the latter’s structural sponges were immersed in a solution of octadecyl trichlo-
integrity and exhibiting good flame-retardant capabilities rosilane (OTS) to generate self-assemblies. Though the
during a real fire. OTS functionalization could not alter the original structure
Membrane technology processes are rapidly emerging of the PU sponge, it still made its surface quite rough, thus
as highly viable solutions for treating oily wastewater due rendering it more hydrophobic. The sponge showed good

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 45

absorption ability for various oils and organic solvents, such modified sponge. The efficiency of the fabricated sponge in
as lubricating oil, bean oil, acetone, peanut oil, and n-hexane. oil-water separation exceeded 99%, and easy recoverability
High selectivity and absorption capacity of up to 25 times the was observed upon simple squeezing of the sponge. The
original weight were observed for the modified sorbent in superhydrophobicity and oil absorbency of the fabricated
addition to oil retention of up to 92% with good recyclability. sponge were unaltered after multiple rounds of stretching
and compression.
Surface Modification Using Nanomaterials
The fabrication of PU sponges modified with TiO2 sol has
In the pursuit of finding efficient sorbents to assuage been reported (Wu et al. 2014). TiO2 nanoparticles attached
the environmental pollution caused by the petroleum to the PU sponge were able to reduce the hydrophilicity
industry, newer technologies utilizing super oleophilic of the sponge to a great extent. An oil absorption capacity
and superhydrophobic nanomaterials have been developed of 95−110 g.g-1 was achieved by TiO2 -PU sponges with
for modification of PU and other polymeric materials to negligible uptake of water under both static and dynamic
improve the sorbents’ oil sorption capacities. Sorbents have conditions. Good reusability of up to 12 cycles with a holding
been functionalized by incorporating various nanoparticles capacity of 70% was observed for the modified sponge
along with low surface energy molecules containing long compared to the uptake capacity of the original PU sponge.
hydrophobic groups to impart them with superhydrophobic Similarly, the preparation of PU foam coated with TiO2
properties. These nanostructures have been shown to perform nanoparticles (TPU), and its further treatment with graphene
much better than conventional materials in resolving the issue oxide (GO) amidated with tetradecyl amine (TDA) to obtain
of oil spillage. Tran & Lee (2017) investigated a novel, facile, TPU-GO-TDA foam has been described (Wei et al. 2018)
and environmentally friendly method for the fabrication of as depicted in Fig. 2. Due to an extensively interconnected
a durable, magnetic, and superhydrophobic PU@ZnO@ three-dimensional pore structure in foams which are also
Fe3O4@stearic acid sponge. This work highlighted that supported by pore mesh to lend them good structural
the functionalized sponge had high surface roughness, low stability, the pores in these foams were able to store large
surface energy, and magnetic responsiveness necessary for amounts of absorbed oil. The authors hypothesized that the
high oil absorption capacity. A large static WCA of 161°, enhancement in the oil uptake capacity was probably due to
and a very low dynamic WCA of 7°, were exhibited by the the long hydrophobic chains of tetradecyl amine. The surface
fabricated sponge. Oils of varying densities and viscosities roughness was enabled by coating with TiO2 nanoparticles
were absorbed to different extents by the fabricated and and GO nanosheets. It was observed that the hydrophobicity

Fig. 2: Schematic illustration for the fabrication of TPU-GO-TDA foam sorbent. (Reprinted with permission from Wei et al. (2018).
Copyright © 2018, American Chemical Society).

Nature Environment and Pollution Technology • Vol. 22, No. 1, 2023

46 M. G. Gote et al.

was achieved only after the treatment with GO-TDA since oil ability for oil absorption and its recoverability due to the
sorption increased in comparison to unmodified TPU foam. improved flexibility and mechanical stability of the sorbent.
This was also evident from the high-WCA of around 140°. In a recent study, Visco et al. (2021) fabricated
Improved hydrophobicity of the PU sponge has also polyurethane-based nanocomposite foams by incorporating
been achieved by coating asphaltene-capped hydrophobic varying amounts of ball-milled carbon nanofibres and
silica nanoparticles onto the surface of the PU sponge. employed them for the selective recovery of oil from water.
This modified PU sponge has been used for heavy Arabian The fabrication of the grafted PU foams was carried out by
crude oil spill clean-up (Atta et al. 2019). The PU sponge mixing methylene diphenyl diisocyanate oligomers with
modification was conducted by emulsification technique, carbonaceous filler followed by the addition of polyether
and it was hypothesized that the hydrophobicity of the PU polyols (PEP) to obtain the crosslinked polymer. CNFs were
sponge was due to the interaction between the PU sponge loaded on to PU foams up to 15% by weight. A contact angle
and the reactive groups of superhydrophobic silica. Excellent greater than 90° was observed for nanocomposite sponges
and rapid collection of oil by the sponge was enabled by indicating low surface energy between liquid and solid.
the hydrophobic PU sponge, which was also reusable and Water/diesel mixtures were used to study the efficiency of the
exhibited an excellent recovery. sorbents. The absorption values for the sponges determined
Biesuz et al. (2020) developed efficient oleophilic by Visco et al. (2021) contrasted significantly with those
nanofelt by impregnating PU foams with a liquid pre- obtained by Baig et al. (2019) probably because the former
ceramic siloxane followed by controlled pyrolysis, wherein evaluated a sponge structure possessing a larger pore size
the siloxane converted into an amorphous SiOC foam at a distribution (range of 130-190 µm) with oils which varied
temperature below 800°C, and at temperature ~ 1500°C it significantly in their chemical composition and viscosity.
decomposed to give Si3N4 fibers. Oil separation from the Maximum absorption of diesel from the oil/water mixture
water was easily achieved by the nanofelt. The results showed was demonstrated for a foam with 1% w/w loading of the
a 500% to 2500% increase in weight after oil absorption. carbonaceous filler as 1: 5.25, oil-water ratio.
Simple thermal treatment was able to clean the material. The Graphene aerogels and CNTs can significantly improve
fibers developed from small pore foams were found to be the hydrophobic-oleophilic wettability of a PU surface due to
extremely stable even after repeated oil-absorption cycles. their porous interconnected structures. However, they suffer
from a few disadvantages which limit their use as good PU
Carbon Materials surface modifiers, which include their high cost which makes
Owing to their intrinsic hydrophobicity, carbon-based large-scale manufacture of CNT and graphene-grafted PU
materials such as graphene-reduced GO, carbon nanotubes more expensive, and poor stability of the grafted sorbent due
and carbon nanofibres have been explored for oil spill to weak CNT/graphene-PU interactions which decrease their
treatment. These carbon materials coated onto the sponge oil absorption capacity. Therefore, carbon derivatives that can
surface can render the original hydrophilic surface into a bond more strongly with PU are required. One such derivative
hydrophobic surface. Carbon nanofibres (CNFs) display is the reduced graphene oxide which itself can be further
exceptional hydrophobicity but have not been evaluated modified appropriately to obtain a sorbent with greater oil
in detail for their application as PU modifiers for oil spill absorption capacity. The presence of groups such as carboxyl,
clean-up. The hydrophobic characteristics of CNFs and the epoxy, and hydroxyl in the two-dimensional structure of
adsorption properties of PU can be combined to improve the graphene oxide (GO) makes it a good swelling material. Its
efficiency of the latter for oil sorption from oily wastewater. applicability as a feasible sorbent for oil spill clean-up has been
To leverage the hydrophobic nature of CNF, Baig et al. explored also because of its large specific surface area and
(2019) have investigated the grafting of CNF onto a PU excellent sorption capability (Junaidi et al. 2021). However,
surface using a dip-coating method. The formation of the hydrophilic nature of GO has to be chemically modified to
additional pores by the CNF on the surface of PU resulted render it more hydrophobic. Zhu et al. (2016) have fabricated
in a decrease in the average pore size of the PU sponge, a porous PU sponge cross-linked with reduced graphene oxide
resulting in a significant increase in the surface area and a (rGO). This was achieved by the addition of calcium carbonate
greater uptake of oil. The surface area of PU increased by nanoparticles and graphene oxide nanoparticles during PU
about 31 times from 9 m2.g-1 to 276 m2.g-1 owing to the foam synthesis, which upon etching with a mild acid resulted
grafting process, which resulted in an increase in the oil in the formation of a PU sponge with a nanosized porous
absorption capacity by approximately 50 times its weight. framework which is not present in a normal PU sponge. A
The study demonstrated the CNF-PU sponge’s repeated thin layer of rGO was then coated onto the porous PU sponge

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 47

via a crosslinking procedure. The results indicated that PU@ great potential in oil-spill containment due to their simple
rGO sponge has excellent potential use in oil-water separation. synthesis, unique optical properties, and environment-
The rGO surface coating in the porous PU@rGO structure was friendly characteristics. An innovative strategy was
found to have good electrical conductivity which prompted demonstrated involving the application of a composite
the authors to evaluate the construct to disrupt the oil in water material consisting of a PU sponge embedded with a
emulsion. polydimethylsiloxane (PDMS) layer and C-dots prepared
A microporous PU sponge coated with SiO 2 /GO from p-phenylenediamine for solar-mediated oil uptake from
nanohybrid material displayed a flexible structure with an oil spills (Singh & Jelinek 2020). The combination of the
excellent oil sorption capacity of about 180 times its own high porosity of the PU sponge structure, hydrophobicity of
weight and good recyclability (Lü et al. 2016). A high- PDMS, and the conversion of sunlight into heat by carbon
performance graphene/PU sponge was prepared by in-situ dots, facilitates greater absorption of oil from the spills.
polymerization of polyols and diisocyanate in the presence C-dots absorb sunlight in the visible region. An excess of
of graphene/N-methyl pyrrolidone (NMP) suspension (Kong electrons on the C-dot surface results in a reduction of the
et al. 2017). The strong dipole interactions between graphene HOMO-LUMO gap which further results in increased light
sheets and NMP facilitated the introduction of graphene absorption. The C-dots were immobilized in the PU-PDMS
sheets into the framework of the PU sponge, which led to matrix such that the energy absorbed by them upon exposure
better physical and chemical strength of the graphene/PU to sunlight increased the temperature of the matrix which
sponge. Continuous oil removal from the water was achieved facilitated increased oil absorption. The carbon dot-PDMS-
by using a vacuum pump. The graphene/PU sponge was polyurethane composite sponge exhibited good chemical
found to have good filtration capabilities for continuous stability and recyclability.
removal of oil due to its superior mechanical strength and Surface Modification Using Metal-Organic Frameworks
oleophilicity as evidenced by its magnificent adsorption
capacities up to 40 to 80 times its own weight. Metal-organic frameworks (MOFs) are porous materials
A PU foam derived from lignin (LPU) a plant-based composed of a metal ion or a cluster of metal ions and an
material, using green technology was subjected to surface organic molecule as a linker. They have large pores and open
modification by treating it with octadecyl amine (ODA) metal sites, thereby making them attractive for applications
using adhesive polydopamine-reduced graphene oxide such as the adsorption of pollutants from water (Fig. 3).
(rGO) (Oribayo et al. 2017). The synthetic methodology However, MOFs have certain drawbacks which include low
led to grafting long hydrophobic methylene chains and mechanical strength and poor processability, which have
alkyl groups from ODA molecules onto the surface of LPU been overcome by integrating them with more sturdy and
foam through an adhesive coating of polydopamine-rGO, inert materials to produce sorbents for efficient oil-water
resulting in a 3-D porous structure. GO contains distended separation. Zeolitic imidazolate (ZIF-8) framework, a type of
structural hydrophilic groups such as hydroxyl, epoxy, and MOF grown on flexible PU foam (MFPU) was synthesized
carboxyl groups which are responsible for its significant by Zhao et al. (2020) through an in situ self-assembly method.
swelling, intercalating and ion-exchange capabilities. An The increased surface roughness of MFPU foams resulted in
outstanding oil sorption capacity of 26–68 times its own a higher contact angle, which improved the hydrophobicity
weight could be achieved with the LPU foam which was and lipophilicity of the parent MOF. Various types of oils
prepared by covalently attaching hydrophilic GO to LPU, and organic solvents could be absorbed into these foams
followed by reducing it to hydrophobic rGO via oxidative quite efficiently with an extraordinary absorption capacity
self-polymerization of dopamine to polydopamine. This oil reaching 33 times its own weight. The ZIF-8 coating was
sorption capacity was found to be much higher than that also observed to significantly enhance the flame retardancy
of a non-woven commercial polypropylene sorbent. ODA of MFPU foams, which was determined by cone calorimeter
along with the low surface energy and hydrophobic rGO test, vertical burning test, and limited oxygen index test.
rendered the foam with varying degrees of wettability for
oil and water. rGO was responsible for introducing surface Polystyrene
roughness which affected the interaction of the foam with a Yu et al. (2016) have reported a durable and modified
wetting or non-wetting liquid. LPU-rGO-ODA foam sorbent magnetic polystyrene foam (DMMPF), synthesized via an
also showed good oil selectivity and reusability. inexpensive two-step immersion method by using oleic acid
A new class of carbon nanoparticles called the carbon coated Fe3O4 particles and PS microspheres which exhibited
dots (C-dots) have been recently identified as having excellent superhydrophobicity, superoleophilicity, and

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48 M. G. Gote et al.

fast magnetic response. The modified magnetic PS foam m2.g-1 and also good mechanical strength with Young’s
exhibited an oil absorption capacity of nearly 40 times moduli ranging from 157.7 to 2638.0 kPa. The sorbent
its original weight. Simple mechanical extrusion allowed material exhibited excellent oil absorbing capacities of up
recovery of absorbed oils and solvents from the DMMPF to 81.3, 44.4, and 41.9 g.g-1 for chloroform, olive oil, and
foam which was shown to retain its high oil absorption diesel, respectively.
capacity even after 60 use cycles. Porous PS fibers work as A superhydrophobic sorbent was fabricated from PS
effective oil sorbents by either adsorption or capillary action foam waste via a high internal phase pickering emulsion
and promising prospective in wastewater remediation. Oils (HIPPE) technique in a one-step process (Yu et al. 2019).
and solvents like diesel, lubricating oil, vegetable oil, DCM, Silica and Span 80 were used as surfactants for stabilizing the
cyclohexane, benzene, etc. were found to be absorbed by emulsion in which the PS packaging waste was introduced
the as-fabricated foam. Authors claim that the absorption as the crosslinker due to its low surface energy, thereby
capacity of DMMPF is higher than magnetic graphene making the process more facile. The as-fabricated SiO2@PS
foam and cryogels based on graphene. Damavandi & Soares sorbent had a high porosity which enabled good removal of
(2022) grafted polystyrene (PS) chains on the surface of oily contaminants from the water. The sorbent displayed a
silica-coated super magnetic iron oxide nanoparticles using high adsorption capacity of 20.4–58.1 g.g-1 and retained its
a blending technique using SI-ATRP. The use of SI-ATRP recyclability for 10 clean-up cycles. Polymeric nanofibres
conferred high hydrophobicity and oleophilicity to the PS owing to their properties such as layered structure have
graft. Oil was absorbed rapidly and to an extent of 5x in 5
great potential to collect oil from oily wastewater. Such
minutes by a nanocomposite in which 90% of the PS-SiO2-
nanofibres are fabricated through various techniques such
IONP was replaced with polystyrene. The fast oil absorption
as electrospinning, melt-blowing, bicomponent spinning,
is explained by van der Waals forces, hydrophobic effects,
and force spinning.
and stacking interactions between polystyrene molecules
grafted on PS-SiO2-IONP and the oil molecules. Nanofibrous Out of the various techniques widely used for the
syndiotactic polystyrene (sPS) monoliths were fabricated construction of nanofibres, electrospinning (Sarbatly et al.
and were demonstrated to possess superhydrophobicity by 2016) has found its niche in the manufacture of sorbents
Gui et al. (2019). These fibers were prepared by solidifying for efficient oil-water separation. The process involves
non-aqueous high internal phase emulsions (HIPEs) subjecting a jet of polymer solution to electrostatic forces
through crystallization-induced gelation. The HIPEs were to obtain the polymeric fibers with diameters in the range
formed by dispersing glycerol in 1,2,4-trichlorobenzene of 5 to 500 nm. Polystyrene-carbon nanotubes (PS-CNTs)
(TCB), stabilizing with sulfonated sPS at a relatively high prepared using the electrospinning technique were found to
temperature of 120 °C. Cooling of HIPEs resulted in their possess high oleophilicity (Wu et al. 2017). Studies indicated
solidification due to the crystallization of sPS within the that the oil absorption occurred due to intra-particle diffusion.
continuous phase to produce porous sPS monoliths. The The super-hydrophobic-oleophilic PS-CNT sorbents showed
morphological study of the prepared sPS monoliths showed reusable potential. These sorbents proved to be efficient
hierarchically porous structures (Fig. 4). They were found sorption materials for the clean-up of oil spills. Various
to exhibit a high specific surface area of approximately 420 oils such as sunflower oil, peanut oil, and motor oils were

Fig. 3: Polyurethane foam coated with a metal-organic framework to trap oil.

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 49

Fig. 4: (a) Schematic Illustration of Fabricating Emulsion-Templated sPS Monoliths through Crystallization Induced Gelation, (b) Porous sPS
Monoliths with Superhydrophobicity/Oleophilicity, Extremely Low Density, and Nanofibrous Structures, (c) Absorption of Oils on Water Surface,
Underwater Oils and Emulsified Oils Using the sPS Monolith (Reprinted with permission from Gui et al. 2019. Copyright © 2019,
American Chemical Society).

used to study the oil sorption capacity which was found pads were fabricated comprising of an outer covering
to be 116, 123, and 112 g.g-1, respectively. An increase of made of PS nanofiber membranes sandwiching sawdust
65% in oil uptake capacity was observed for the composite and used for the removal of oil spills from the surface of
in comparison to PS sorbent without CNTs. Alnaqbi et the water. An increase in temperature led to a decrease in
al. (2020) demonstrated that polymer blends have greatly the sorption capacity of the PS nanofiber membrane. The
enhanced properties and distinct advantages over original sorption capacity also decreased with an increase in pH
polymers as components of oil-sorbent materials. Their up to neutral pH while increasing slightly with a further
study highlighted the application of hydrophobic polymers increase in pH above 7. These membranes prepared by the
prepared through polymer blending, wherein blends were electrospinning technique offer better sorption capability
prepared by using PS as the matrix polymer, to which poly than the ones prepared via impregnation. This variation in
(vinyl chloride) (PVC) and polyethylene (PE) were added the performance of the membranes may be explained in terms
individually at 5–20 % w/w. Electrospinning of the blends of the process of impregnation that does not leave many
was carried out to obtain microfibers. Good removal of crude pores open for the oil to be taken up since they are covered
oil, diesel, and motor oil was achieved. In comparison to by polystyrene. A magnetic PS/Fe3O4 fibrous membrane
other commercially available polypropylene (PP) fibrous fabricated by the electrospinning technique showed high
materials for oil absorption, the blended electrospun fibers selectivity and excellent oil adsorption. The magnetic
were far more efficient for a wide range of oils. response from Fe3O4 and superiority in hydrophobicity
The removal of various oils from aqueous solutions and oleophilicity of polystyrene combined to enhance the
by PS nanofiber membranes synthesized by two methods separation efficiency as well as adsorption capacity of
namely electrospinning and impregnation filled up with magnetic fibrous sorbent in oil/water mixtures (Song et al.
different types of sawdust was demonstrated by Ghiasvand 2017). The highly porous structured PS fibrous sorbent shows
et al. (2021). The particle size of sawdust in the range of a motor oil sorption capacity of 113.87 g.g-1, approximately
40-60 mesh showed the highest sorption capacity. Separator 3-4 times that of natural sorbents and nonwoven PP fibrous

Nature Environment and Pollution Technology • Vol. 22, No. 1, 2023

50 M. G. Gote et al.

membranes. Additionally, the nanoporous fiber sorbents the branches of the sponge with hydroxyl and carboxylic
also exhibited high sorption capacity for edible oils, such groups enabling greater interaction with metal ions to
as bean oil (111.80 g.g-1) and sunflower seed oil (96.89 g.g- strongly link HPU-13 to MS. Feng et al. (2017) modified a
1
) (Lin et al. 2012). Yadav et al. (2019) demonstrated the commercially available melamine sponge with eco-friendly
recyclability of thermoplastic PS using orange peel extract. material, furfuryl alcohol. The MS was soaked in furfuryl
The method involves extracting liquid from the outer rind of alcohol solution followed by acidic polymerization to achieve
the peel (primary extract) which was further processed into surface modification. This method resulted in a reaction
three layers. PS was dissolved in the layers to get viscous of furfuryl alcohol with MS along with polymerization of
solutions. These PS solutions were then processed into fibers furfuryl alcohol onto the surface of MS, thereby making the
that exhibited high contact angle. The oil sorption capacity sponge hydrophobic. The modified MS displayed excellent
was found to be higher for fibers obtained using the top sorption capacities for various oils and organic solvents (75-
layer of extract (TLF) compared to the ones obtained from 160 g.g-1), resulting in a good hydrophobic, environment-
using the primary extract (PEF), primarily due mainly to a friendly modified melamine sponge. Xue et al. (2021)
greater surface area of TLF. Expanded polystyrene (EPS) investigated a unique superhydrophobic and superoleophilic
waste was utilized as a sorbent to clean up a crude oil spill tetradecyl amine-MXene functionalized melamine sponge
from an aquatic environment (Nasir & Hameed 2014). The for effective oil/water separation through selective oil
sorption capacity of these sorbents increases with the increase adsorption. The results showed an absorption capacity of
in surface area and sorption time. It was also observed that 60-112 times the weight of the sorbent. The functionalized
the rough surface of EPS adsorbed more oil than the smooth melamine sponge exhibited high mechanical strength,
surface. The punctured hole diameter in EPS sorbent (1.65 and chemical stability, as well as good reproducibility
mm) also enhanced the oil sorption capacity. and recyclability for oil-water separation. Arunagiri et al.
Zhu et al. (2011) investigated the viability of fibers made (2021) fabricated a chemically modified 3D porous MS with
from blended PVC-PS as a unique oil sorbent prepared by polycaprolactone and poly-D, L-Lactic acid via inexpensive
an electrospinning process. Up to a 9 times increase in the freeze-drying. The sponge displayed high hydrophobicity
oil, uptake was noted for these sorbent fibers as compared with a water contact angle of 162°. The composite material
to commercial PP sorbent due to the voids present in PS- showed an absorption capacity in the range of 3.3-8.7 g.g-1 for
PVC fibers. A one-step electrospinning process has been several oils and organic solvents such as crude oil, soyabean
demonstrated for the fabrication of nanoporous polystyrene oil, n-hexane, n-octane, etc.
fibers by Lin et al. (2012). Due to the high porosity of PS
fibers, a maximum oil sorption capacity of 113.87 g.g-1 was POLYMERIC SORBENTS AS SOLIDIFIERS
obtained for motor oil. The uptake efficiency of certain edible Conversion of spilled oil into a solid coherent mass using
oils was also found to be good with an oil absorption capacity solidifiers could be a viable option for efficient oil-water
of about 111.80 g.g-1 achieved for bean oil. separation. Though quite an attractive possibility, solidifiers
Melamine have remained an underutilized approach to alleviate the
effects of oil spills. Solidifiers can potentially help in oil-
Melamine sponges consist of formaldehyde-melamine- water separation by containing the oil spill, preventing
sodium bisulfite copolymer. Owing to the high porosity it from spreading, and promoting its removal from the
(>99%), extensive pore structure, large surface area, low environment, as well as aiding the recovery of oil. Shojaei
density, and ease of chemical modification, they are finding et al. (2021) demonstrated that oil spills can be solidified
application in the treatment of oily wastewater as sorbents using polypropylene and polyethylene fibers and granules.
(Wang et al. 2015). A highly oleophilic composite comprising The performance of these polymeric fibers and granules was
melamine, MOF (HPU-13) crystals, and carboxymethyl analyzed by gravimetric and spectrophotometric methods.
cellulose (CMC) was prepared by Xu et al. (2019). CMC The results showed a high sorption capacity of 12.5 g.g-1
sodium-treated melamine sponge (MS) sponge was able to for polypropylene fibers. The Freundlich isotherm model
facilitate the attachment of HPU-13 onto the MS leading to is consistent with the sorption characteristics of PP and
the formation of an excellent hydrophobic material proven PE granules owing to the heterogeneous surface of these
by its oil uptake capacity of up to 13000%. A hydrophilic two solidifiers. Oil adsorption tendency was attributed
cellulose polymer, carboxymethylcellulose sodium (CMC) to the heterogeneous surface of polymeric granules with
was used to impart adequate coordination of functional varying adsorption energies which resulted in enhanced oil
groups on the surface of MS. CMC was envisioned to wrap uptake. Motta et al. (2019) demonstrated an inexpensive and

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 51

simple method for the fabrication of a bio-based subclass material obtained after 24 h, was analyzed for the oil/solvent
of solidifiers constructed from sorbent amylopectin-graft- retention ability by determining the polymer weight loss
poly (methyl acrylate) (AP-g-PMA) polymer. The results avoiding the use of any external forces such as squeezing
indicated that the rapid solidification of diluted bitumen or exposing the sorbents to high temperatures. Janqamsari
in terms of contact time and solidifier-to-oil ratio could et al. (2021) developed ecofriendly sorbent aerogels
be achieved within a few minutes by AP-f-PMA. The based on recycled polyethylene terephthalate (PET) fibers
combination of the biodegradability of amylopectin and chemically modified with the polymer polyvinyl alcohol
the hydrophobicity of the synthetic polymer holds a lot of (PVA) and further with carbon nanotubes (CNTs). The
potential. Another recent study by (Lv et al. 2020) showed incorporation of CNTs in the structure of nanocomposite
the application of polymer-grafted wheat bran for oil gelling sorbent increases the oleophilicity and thereby increases
capability. Vinyl tri ethoxy silane was used to introduce the oil sorption capacity. The surface area, entanglements
vinyl functionality onto the wheat bran, which was further among the fibers and the hydrophobic interaction between
polymerized with divinyl benzene monomer, using azo bis the sorbents and oil droplets significantly affect the sorption
isobutyronitrile as the initiator. The methodology rendered capacity. The nanocomposite sorbent shows efficient oil
the wheat bran with a large BET surface area of 176 m2.g- sorption capacity and reusability even after four cycles.
1
and a maximum absorption capacity of 12.0 g.g -1 for They investigated the efficiency of the sorbent aerogels for
various oily liquids. The sorbent material was found to their density, porosity, and oil sorption capacity which were
exhibit excellent hydrophobicity and oleophilicity due to found to be 0.043-0.097 g.cm-3, 92.93-96.87%, and ~ 12
the presence of a multi-scale porous structure. g.g-1 for kerosene oil respectively. In another study, Shen
et al. (2021) demonstrated the applicability of superelastic
SORBENT GELS FOR OIL SPILL CLEAN-UP and strong polyimide (PI) nanofiber-based aerogels (NFAs)
aided by a three-dimensional (3D) structure and porosity
Unique and efficient oleophilic sorbent gels based that can also be altered. The aerogels were prepared by
on glycerol propoxylate, synthesized through a bulk freeze-drying followed by solvent-vapor treatment as
polymerization technique without the use of an activator, illustrated in Fig. 5. Silicone nanofilaments (SiNFs) were
an initiator, or a catalyst, have been reported by (Kizil & then formed on the surface of PI fibers upon treatment with
Sonmez 2017). Various organic solvents and oils were trichloromethyl silane. SiNFs-coated NFAs exhibited very
selected to study the absorption tendency of the synthesized low density, high porosity, and very high oil sorption capacity
gels. Varying concentrations of the crosslinkers were of 159x its own weight. Separation of stable water-in-oil
examined for their effect on the above-mentioned parameters emulsions was also achieved indicating that the method
wherein star-type propoxylate monomers were reacted was very energy efficient. Ali (2019) has synthesized and
with different concentrations of tris [3-(trimethoxysilyl) demonstrated the use of an oleophilic gel based on butyl
propyl] isocyanurate (ICS) crosslinker. For the PDMS acrylate polymer for the remediation of oily wastewater. The
sorbents, the capability to swell was found to depend on polymer, poly (n-butyl acrylate) was synthesized by solution
the amount of cross-linking in the polymers. Fully swollen polymerization and various parameters such as reaction time,

Fig. 5: Schematic illustration of the preparation of SiNFs/PI-NFAs. (Reprinted with permission from Shen et al. 2021. Copyright © 2021,
American Chemical Society).

Nature Environment and Pollution Technology • Vol. 22, No. 1, 2023

52 M. G. Gote et al.

the concentration of the monomer, initiator, crosslinker, and The highly hydrophobic structure of the material resulted in
the temperature were optimized for improved yield of the good oil uptake from both the surface and the bulk of water.
polymer sorbent. The sorption capacity of the sorbent under High oil sorption capacity in the range of 500-1800% and
different conditions like dry system, static system, and the fast uptake and release of oil were also observed indicating
dynamic system was found to be quite promising for various promising clean-up of oil spills. Krishnan et al. (2022)
oils such as gasoline, kerosene, diesel, xylene, octanol, and have recently demonstrated through in-situ one-step bulk
Mobil oil. copolymerization, the fabrication of a composite absorbent
with a three-dimensional cross-linked network comprised of
MISCELLANEOUS SYNTHETIC SORBENTS polystyrene-polymethyl methacrylate/divinyl benzene (PS-
PMMA/DVB) copolymer and 2D-nanosheets of BN3 (Boron
Fabrication of poly(dimethylsiloxane) based hydrophobic
Nitride)/graphene. The as-prepared composite material was
sorbents through the condensation reaction of
found to efficiently remove various organic solvents and oils
poly(dimethylsiloxane) and tris[3-(trimethoxysilyl)propyl]
from the spills and showed good flexibility. The absorption
isocyanurate cross-linker via bulk polymerization was
capability was found to be dependent on the amount of DVB
demonstrated by Askin et al. (2021). High oil absorption
used. Interestingly, the PS-PMMA/DVB composites with
capacity and a high rate of absorption-desorption were
achieved. The sorbents could be easily reused many BN3 nanosheets exhibited higher absorption capacities in
times without any major loss in the oil-uptake capacity. comparison to the ones with CG composites. The polymer
The hydrophobic polymeric sorbents have an additional composites with lower nanosheet content, i.e., 0.1 wt% were
advantage in that they selectively absorb oil from the water observed to have higher absorption capacities compared to
surface which increases their potential use in water clean-up the ones with higher nanosheet content (2.0 wt%).
applications. Additionally, Askin et al. (2021) also developed The conversion of nonwoven polyester fibers into
a unique hybrid sorbent via a bulk polymerization reaction hydrophobic oil-absorbing material by treating the fibers with
between poly (dimethylsiloxane) and fluorinated alkyl silane. poly (methylhydrodimethyl) siloxane copolymers has been
Table 2: Other Modified Polymeric Sorbents.

Sorbent Treatment Material Method Sorption Capacity Sorption Experimental Reference

(g/g) Conditions
PS foam Oleic acid-coated Fe3O4 Two-step immersion 40 Maximum absorption capacity Yu et al.
reached in 60 s 2016
PS fibers Silica-coated iron oxide Grafting Diesel: 3 20 mg of the sorbent for 5 Damavandi
nanoparticles Diluted Bitu- minutes at 23°C. & Soares
men: 5 2022
Syndiotactic Trichlorobenzene (TCB) & High internal phase 41.9-81.3 Cubic monoliths (∼1.0 × 1.0 Gui et al.
PS (sPS) mon- Glycerol emulsion crystalliza- × 1.0 cm3) with known mass 2019
oliths tion-induced gelation immersed in 20 mL of o/w
emulsion for 12 hours.
PS foam waste Silica and Span 80 High internal phase 20.4-58.1 0.1 g cylindrical-shaped foam Yu et al.
pickering emulsion sample was immersed in oil at 2019
(HIPPE) RT for 5 min.
PS Carbon nanotubes Electrospinning 111.45-122.82 Sorbent immersed in pure oil Wu et al.
for 90 min at RT. 2017
PS fibers Blended with PVC and PE Electrospinning 112- 119 0.1 g of sorbent was placed Alnaqbi et
individually onto the oil surface for 15 al. 2020
minutes.
PS -PVC Not Applicable Electrospinning 81-146 1 g of sorbent was placed on Zhu et al.
blended fibers top of 300 mL of oil at 23 ±4 2011
°C for 60 min. and drained for
2 min before weighing.
PS nanoporous Not Applicable Electrospinning Motor oil: 113.87 0.1 g of sorbent was dropped Lin et al.
fibers Bean oil: 111.80 onto the oil film and drained 2012
Sunflower seed for 10 s.
oil: 96.89
Table cont....

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 53

Sorbent Treatment Material Method Sorption Capacity Sorption Experimental Reference

(g/g) Conditions
PS nanofibres Sawdust Electrospinning Motor oil: 1.41 Reaction temperature = 25°C, Ghiasvand
Diesel oil: 1.4 pH = 4, contact time = 1 min. et al. 2021

Furnace oil: 1.5

Crude oil: 1.1
Impregnation Motor oil: 1.00
Diesel oil: 0.63
Furnace oil: 0.97
Crude oil: 0.59
PS/Fe3O4 Fe3O4 nanoparticles Electrospinning Edible oil: 87 Sorbent drained for 2 minutes Song et al.
nanofibres Saxoline: 65 before weighing. 2017
Dimethicone: 94
rPS fabric Orange peel extract Electrospinning 40.5±3.6 0.2 g sorbent in 100 mL of oil Yadav et al.
for 60 min 2019
Expanded PS Mechanical modification Mechanical Punc- Crude oil: 3.26 0.9 g of sorbent was placed Nasir &
waste with holes puncture turing Lubricating oil: on the surface of the oil/water Hameed
4.9 mixture at RT 2014
Distilled water:
0.32
PS/PVC fabric PVC Electrospinning Motor oil: 146 1 g of sorbent was placed on Zhu et al.
Peanut oil: 119 the top layer of 300 ml oil 2011
Diesel: 38 at 23±4°C for 60 min and
Ethylene Glycol: drained for 2 min before final
81 weighing.
Melamine MOF crystals Not Applicable 13000% Not Specified Xu et al.
sponge 2019
Melamine Furfuryl alcohol Immersion followed 75-160 Not Specified Feng et al.
sponge by polymerization 2017
Melamine Tetradecylamine-MXene Immersion 60-112 Sorbent immersed into oil/ Xue et al.
sponge water mixture at RT. Thermal 2021
and chemical stability tested at
pH range 2-11 for 24 hours.
Melamine Polycaprolactone and Freeze drying 3.3-8.7 Not Specified Arunagiri et
sponge poly-D, L-Lactic acid al. 2021
PP and PE fib- Not Applicable Not Applicable 12.5 Crude oil (0.5 mL, 0.49 g) Shojaei et
ers & granules in 80 mL water. Volumes of al. 2021
crude oil and saline water were
kept constant, while the solid-
ifier mass varied depending on
the SOR ratio.
Poly(methyl Amylopectin Not Applicable Not Available The sorbent was tested at RT Motta et al.
acrylate) on a 0.2 mm thick oil layer on 2019
top of fresh water by using a
contact time of 8 min for crude
oil while 32 min for diluted
bitumen.
Divinyl ben- Wheat bran Polymerization 12 Oil gelling experiment of the Lv et al.
zene-vinyltri- bran sample conducted for 10 2020
ethoxysilane min at RT
Glycerol Tris[3-(trimethoxysilyl) Bulk Polymerization Not Available Wire mesh basket sorbent Kizil &
propoxylate propyl]isocyanurate (ICS) soaked in an organic solvent Sonmez
as crosslinker for sorption studies at RT. 2017

Table cont....

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54 M. G. Gote et al.

Sorbent Treatment Material Method Sorption Capacity Sorption Experimental Reference

(g/g) Conditions
Recycled Polyvinyl alcohol followed Not Applicable 12 Performance of rPET-based oil Janqamsari
polyethylene by carbon nanotubes sorbents studied at RT et al. 2021
terephthalate
fibers
Polyimide Silicone nanofilaments Freeze drying fol- 159 Surfactant (Span 80, 10 mg) Shen et al.
aerogels (SiNFs) formed on the lowed by solvent-va- dissolved in 100 mL of organic 2021
surface of PI fibers por treatment liquid and homogenized at
10,000 rpm for 5 min.
Poly(n-butyl Not Applicable Solution Polymeri- Not Available Not Specified Ali 2019
acrylate) zation
Poly(dimethyl- Tris[3-(trimethoxysilyl) Bulk Polymerization Not Available Maximum absorbancy of 85- Askin et al.
siloxane) propyl] isocyanurate 90% achieved in 40 minutes. 2021
cross-linker
Polydimethyl- Fluorinated alkyl silane. Bulk Polymerization 500-1800% Highest sorption capacity of Askin et al.
siloxane 1800% observed for dichloro- 2021
methane due to its high polarity
PS-polymethyl 2D-nanosheets of BN3/ Bulk Polymerization Not Available Sorption efficiency depends Krishnan et
methacrylate/ graphene upon the polarity of adsorbate al. 2022
divinyl benzene and the study was conducted
in the temperature range of
30-60 °C.
Polyester fibers Poly(methylhydrodimethyl) Heterogeneous polym- Dodecane: 5.52 Square-shaped sorbent im- Cojocaru et
siloxane copolymers erization mersed in oil and reaches sat- al. 2017
Motor oil: 10.03 uration in 15 min and drained
for 30 s before weighing and
tested at 23 ± 4 °C.
Polysiloxane Viscose-maghemite/ Not Applicable Liquid HC: 15-17 Sorbent sample (0.15-0.2 g) Rotaru et al.
goethite magnetic nano- dipped in oil for 15 min till 2019
particles Motor oils: 35-37 saturation and drained for 30 s
before weighing.
PP/polyester Not Applicable Three-step process 21.9 CCl4/water mixture was passed Zhang et al.
micro/ nano- including blending, through the sorbent as a filter 2020
fibres drawing and etching set between two glass tubes.
CCl4 passed through the filter
in 60 s and water retained in
the upper glass tube.
Polyether sul- Zeolitic imidazolate (ZIF-8) One-step phase inver- Paraffin Oil: Sorption at RT for 30 min. Abbasi et al.
fone (PES) framework (MOF) sion method 37.6% (v/v) 2017
Olive Oil: 35.6%
(v/v)

demonstrated by Cojocaru et al. (2017). Novel polysiloxane goethite magnetic nanoparticles has been reported by
copolymers were synthesized which were then used to Rotaru et al. (2019). The material was found to exhibit a
treat polyester fibers to make them more hydrophobic. The sorption capacity of 15-17 g.g-1 for liquid hydrocarbons and
hydrophobic polyester fibers were evaluated for their oil- 35-37 g.g-1 for motor oils uptake. A multi-step procedure
absorbing capacities, which were found to be 5.52 g.g-1 and was employed to obtain the polymeric composite. Groove-
10.03 g.g-1 for dodecane and motor oil, respectively. Optical like rough morphology was engraved on nonwoven
microscopy identified the presence of inter-fiber voids which polypropylene/polyester microfibrous and nanofibrous
were responsible for oil absorption. Good recyclability of the material by Zhang et al. (2020), using a three-step process
sorbent was achieved as demonstrated by centrifugation tests. that involved blending, drawing and etching. The oil
The technique of engraving or etching has been used to adsorption results revealed that the nonwoven nanofibres
modify the surface morphology of micro- and nanofibres to had oil-saturated adsorption of 21.9 g.g-1 and an oil retention
improve their oil sorption capacity. Another hydrophobic rate of 10.3 g.g-1. An excellent oil/water separation efficiency
modification of polysiloxane with viscose-maghemite/ of 99% was obtained driven solely by gravity. Coating of

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 55

the zeolitic imidazolate framework (ZIF-8) on polyether excellent reusability and recyclability, with rapid recovery
sulfone (PES) was successfully carried out by Abbasi et al. of oil by mechanical squeezing. Li et al. (2018) investigated
(2017) through a simple one-step phase inversion method. the applicability of a unique chitosan-cellulose aerogel
Phase inversion refers to the process in which a homogenous which was prepared by oxidation, crosslinking, freeze-
solution of a polymer (in solvent) is reverted from a single drying, and cold plasma modification for remediation of
phase into a two-phase system. The two-phase system oily wastewater. A cellulosic aerogel was prepared by freeze
consists of a solid polymer phase which forms the membrane drying, followed by oxidation with NaIO4 and exposure to
structure and a liquid (polymer-poor) phase which forms the an acetic acid solution containing 2% w/w of chitosan. The
pores in the final film. In the composite material, the ZIF-8 amino groups from chitosan reacted with aldehydic groups of
particles were held together by the PES, and the ZIF-8 was oxidized cellulose resulting in crosslinking between the two
responsible for effectively absorbing oil. A summary of other molecules, followed by treatment with trimethyl chlorosilane
modified polymeric sorbents is given in Table 2. (TMCS) to enhance the aerogel’s hydrophobicity. Due to
the rapid absorption rate, high absorption capacity (13.77–
CHEMICALLY MODIFIED NATURAL SORBENTS 28.20 g.g-1), high oil/water selectivity, and good reusability
demonstrated by the chitosan aerogel, it can be considered a
Natural adsorbents used for oil spill cleanup have been promising sorbent for oil/water separation.
reported as the most economical, eco-friendly, and cost-
effective promising technique. Some of the bio-based Modified Celluloses
sorbents used for crude oil removal include chitosan, bagasse
from sugar cane and pith, cotton, dried straws, fibers of palm, Cellulosic sorbents are natural plant-based materials and
banana trunk and vegetables, byproducts of cork, rice hulls have been more widely used as effective sorbents due to
and fibers, onion and garlic peels, kapok, coconut fibers, their biodegradability compared to other synthetic materials.
and shells of various nuts, etc. Chemical modifications of Cellulose and lignin materials have been hydrophobically
these bio-based sorbents by acid and alkaline treatments modified by physical or chemical methods (Valdebenito et al.
have been reported to increase their sorption capacity for 2018). Physical modifications include cold plasma coating,
various pollutants (Cao et al. 2017, Gheriany et al. 2020, surface crystal growth, grafting, and sol-gel conversion
Zamparas et al. 2020). treatments (Galblaub et al. 2016, Koch & Barthlott 2009).
Chemical modifications include hydrophobic modifications
Chitosan with nanomaterials and polymers. Cotton fabric was rendered
superhydrophobic upon treating the fabric with dopamine in
Biobased aerogels/sorbents offer great advantages in terms presence of FeCl3, causing self-polymerization of dopamine
of natural abundance, low cost, environment-friendly, (polydopamine (PDA)). The PDA-cotton fabric was then
and biodegradability as compared to synthetic polymers. treated with octadecyl amine (ODA) (Yan et al. 2020) to
Chitosan is a naturally abundant polymer that has attracted form a nano construct that exhibited a 2x surface roughness
great attention worldwide due to its extraordinary properties with greater strength and robustness compared to untreated
as biodegradability and the presence of reactive functional cotton fabric. The oil separation efficiency was observed
groups (Vidal & Moraes 2019). Hu et al. (2020) successfully to increase by 96% which could be attributed to the high
fabricated aerogels of graphene oxide-modified chitosan adhesion capacity of PDA. An additional improvement in
nanosheets, followed by freeze drying of the nanosheets oil/water separation ability could be achieved by further
with silicon particles and PDMS, to impart hydrophobicity wrapping the Fe/PDA/ODA fabric around the PU sponge
to the modified aerogels for improved oil absorption. The to fabricate an adsorption bag.
composite aerogel showed promising adsorption capacity in
the range of 18-45 g.g-1 for various oils and solvents. Since A superhydrophobic magnetic cellulose sponge was
the recovery of adsorbed oil is usually achieved through the fabricated by deposition of Fe3O4 nanoparticles on the cellu-
mechanical extrusion of the oil-loaded sorbents, the aerogels lose sponge which was further modified by immersion in an
with better compressibility and stability exhibited the highest ethanolic solution of hexadecyltrimethoxysilane (Peng et al.
oil recovery. In another study, Yi et al. (2020) constructed 2016). The oil sorption capacity and oil separation efficiency
a chitosan aerogel composite in which methyl trimethoxy of natural cellulose were increased by more than 95% due
silane was bonded to the aerogel through chemical vapor to the acetylation of the modified sponge.
deposition. The rapid absorption of various oils and solvents Modified and unmodified date palm fibers (PFs) were
and oil absorption capacities in the range of 31-63 g.g-1 used as natural sorbent material for oil spill removal by Ab-
were observed. The chitosan-based aerogel also displayed delwahab et al. (2017). Various oils such as diesel oil, crude

Nature Environment and Pollution Technology • Vol. 22, No. 1, 2023

56 M. G. Gote et al.

oil, and vegetable oil were chosen to study the efficacy of Other Natural Sorbents
the sorbent fibers. Simple chemical modification was carried
out on PFs by soaking them in 2% w/v NaOH and 2% v/v Seashells and epoxy resins have been used to modify PU
H2SO4 separately at room temperature overnight, followed sponges to create eco-friendly, robust, superhydrophobic,
by drying at 80°C. The acid-base treatment made the fiber and super oleophilic adsorbents for the removal of oil from
surface rough which affected the interaction between the polluted water (Jamsaz & Goharshadi 2020). The clean PU
inner surface of the fibers and the oil such that high sorption sponge was immersed in a suspension of treated seashell
efficiency was achieved. In another study by Neelamegan powder followed by the addition of epoxy resin. The
et al. (2020), chemical modification of cellulose and lignin modified PU sponge was then freeze dried resulting in a
was carried out in the presence of carbon nanotubes (CNT) sorbent material that exhibited good recyclability and high
under basic (NaOH) conditions using CNT-COCl. The oil adsorption capacity in the range of 28.03-42.17 g.g-1.
material was further reinforced with iron oxide to enable Eze et al. (2019) have shown the use of a unique biomass
its purification. The increased hydrophobicity of the sorb- i.e., Dialium guineense (velvet tamarind) seed husk (DGSH)
ent was proven by an increased water contact angle in the chemically treated with ammonium sulfate (AS-DGHS)
range of 130‒135°. Sorption capacities for CNT-g-Cel- for the remediation of oily water collected from the Niger
lulose/Fe3O4 and CNT-g-Lignin/Fe3O4 were found to be Delta region in Nigeria. The surface morphology of both
15-25 and 10-23 g.g-1 for a variety of oils and organic modified and unmodified sorbents exhibited a certain degree
solvents. of porosity, with AS-DGSH possessing a greater porosity
than DGSH indicating that the chemical modification was
Rice Husk able to alter the surface of the biomass material. Around 50%
Wang et al. (2020) demonstrated the biological delignification of oil sequestration was achieved from polluted water at a
of cellulose derived from rice husk followed by acetylation pH of 6.1. However, a significant decrease in sorption was
to prepare a hydrophobic sorbent. Both fungi and bacteria observed for both DGSH (41.2 to 20.3%) and AS-DGSH
were employed to conduct the delignification process. The (52.6 to 27.2%) with an increase in pH from 3.0 to 9.0.
fabricated cellulosic sorbent exhibited good hydrophobicity The adsorption capacity of raw luffa fibers was evaluated
which was evident in a sorption capacity of 20 g/g. In this for various oil/water emulsions (Abdelwahab et al. 2014).
study, Langmuir and Freundlich isotherms were used to High selectivity was exhibited by luffa fibers for various oils
analyze the sorption capacity, which indicated that the oil along with excellent water repellency in its original form.
sorption capacity of rice husk fit the Langmuir model better The contact time and dose of adsorbent were observed to
than the Freundlich model. Through simple acetylation have a significant effect on the sorption capacity such that
of oil palm empty fruit bunch (OPEFB) and cocoa pod it decreased as the amount of adsorbent increased and vice
(CP) fibers under mild conditions, Onwuka et al. (2018) versa. A maximum sorption capacity was observed at 40°C
fabricated a sorbent material for the sequestration of oil for diesel oil. Other parameters that affected the efficiency of
from water. A comparison of the acetylated and unacetylated the fibrous sorbent were surface properties, temperature, the
sorbents indicated that the differences in their sorption concentration of the crude oil, and the amount of fiber used.
capacities were dependent on time and concentration. Raw luffa fibers were not very reusable since their sorption
Acetylation improved the oil sorption capacity of CP efficiency was observed to decrease after three sorption trials.
fibers. Kinetic studies demonstrated that the oil sorption The sorption capacity of raw and acetylated sugarcane
was diffusion-controlled for both physisorption and bagasse was determined for crude oil (Behnood et al. 2016). It
chemisorption. was observed that the sorption capacity of acetylated bagasse
Thermally enhanced rice husk montmorillonite was 90% greater than that of raw bagasse mainly due to the
combination (TRMC) was evaluated for handling crude oil oleophilicity of acetylated bagasse. A sorption capacity of
pollution (Akpomie et al. 2018). Studies revealed that the 11.3 g.g-1 of crude oil and 9.1 g.g-1 of oil layer in an emulsion
modified sorbent (TRMC) was more efficient in treating oil- was observed. The sugarcane bagasse, therefore, offers a
contaminated water compared to the unmodified sorbent. It significantly improved, low-cost method for the treatment
was observed that the sorption efficiency was significantly of hydrocarbon impurities in aqueous systems (Boni et al.
dependent on pH, temperature, the concentration of crude 2016). The porous nature and fibrous network structure of
oil, sorbent-oil contact time, and dosage of sorbent. TRMC natural luffa sponge were observed to assist in the removal
exhibited the maximum sorption potential as compared to the of dye and other solvents through filtration and absorption
other reported sorbents which have been used for remediation mechanisms (Wang et al. 2017). Surface modification of
of the crude oil spill.

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 REVIEW ON ADVANCED SYNTHETIC AND BIO-BASED SORBENTS FOR OIL SPILL CLEAN-UP 57

luffa with polyhedral oligomeric silsesquioxane (POSS) relatively easy to conduct on a large scale. Furthermore, the
imparted superhydrophobicity to the luffa sponge and environmental and economic impact of the techniques used
significantly enhanced its oil absorption capacity. in the fabrication of various chemically modified sorbents
should be thoroughly evaluated. The techniques discussed
CONCLUSIONS herein have so far been studied on a lab scale, and further
evaluation at an industrial scale needs to be conducted. A
This review article evaluates the advances made in oil spill combination of a variety of sorbent modification techniques
clean-up techniques based on the use of modified polymeric may be considered in identifying a cost-effective solution
and natural sorbents. The methods reported by various for mitigating an oil spill, while also considering environ-
researchers show promising prospects in dealing with such mental and economic implications. Further advancements
a hard pressing problem as the remediation of oil spills and in this field will include the generation of new functional
oily wastewater. The treatment of oily wastewater requires a oil-absorbing materials which are suitable for optimized,
great deal of research in developing cost-efficient, recyclable low-cost, large-scale manufacture of sorbents that are them-
and effective materials that can be employed in cleaning oil selves environment-friendly for widespread usage during oil
spills. The sorption characteristics of polymeric or natural spill containment and oily wastewater treatment. Extensive
oil sorbents depend on material morphology, especially research and funding will be needed to achieve these goals.
for sponge-type sorbents which have a three-dimensional
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