Environmental

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Nano
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Water purification: oil–water separation by

nanotechnology and environmental concerns
Cite this: Environ. Sci.: Nano, 2017,
4, 514 Chee Huei Lee,ab Bishnu Tiwari,a Dongyan Zhanga and Yoke Khin Yap*a

Received 19th October 2016,
Accepted 23rd December 2016
DOI: 10.1039/c6en00505e
rsc.li/es-nano
Organic pollutants from volatile organic compounds (VOCs), synthetic organic compounds (SOCs), oil
spills, and waste disposal have significantly contaminated water and our food chain. The science and engi-
neering of water purification, in particular oil–water separation, has attracted increasing attention in the past
five years. As reviewed in this article, both organic chemistry and nanotechnology have been employed for
oil–water separation. This can be achieved using materials with specific wettability. Three general
approaches have been reported: 1) the filtration technique using specific wettability that only allows oil or
water to penetrate, 2) the absorption method using porous sponges, fibers and aerogels that can selec-
tively absorb oil or water, and 3) filtration or absorption technology that is switchable and controllable in
functionality. On the other hand, the increased use of nanomaterials in water purification, sports equip-
ment, and industrial and household products has raised concern about water contamination by nano-
particles. This concern will be discussed at the end of the review. The goals of this article are 1) to provide
a comprehensive review about oil–water separation by nanotechnology and organic chemistry and 2) to
increase the awareness of environmental concerns about using nanotechnology for water purification.

Environmental significance
Because of the rapid growth of global human population, the demands for freshwater supply are increasing due to the expanding need for water in
agriculture and food production. Freshwater supply is further constrained by pollution and weaknesses in water management. Organic pollutants are
among the key sources of water contamination. The recent advancement in nanotechnology has initiated increasing efforts in using nanomaterials to
purify water by oil–water separation. It is noted that the use of nanomaterials in environmental applications will create the risk that water may be
contaminated with nanoparticles. Furthermore, there is increasing use of nanomaterials in sports equipment, as well as various industrial and household
products. All these have increased concern about the environmental and health impact of nanopollutants in water. In this review, we aim to emphasize the
relation between nanotechnology and the environment (section 2). Next, we will discuss the use of nanomaterials for oil–water separation (section 3). This
discussion presents how nanotechnology is used to help resolve contamination of water by organic pollutants. At the end of the discussion, we will present
the outlook of oil–water purification technology and bring awareness about the potential environmental concerns over using nanotechnology for water
purification. Recent effort on extracting nanomaterials away from contaminated water will be discussed.

1. Introduction clean water supply. Therefore, the science and technology of

Water is essential for life. In fact, water is important in food
security, public health, urbanization and energy generation.1
Because of the rapid growth of global human population,
pressures on freshwater supply are increasing due to the
expanding need for water in agriculture and food production.
Freshwater supply is further constrained by pollution and
weaknesses in water management. Apparently, water pollut-
ants should be avoided so as not to further constrain the
a
Department of Physics, Michigan Technological University, 1400 Townsend
Drive, Houghton, MI 49931, USA. E-mail: ykyap@mtu.edu; Tel: +1 906 487 2900
b
Engineering Product Development, Singapore University of Technology and
Design, 8 Somapah Road, Singapore 487372, Singapore
water purification has become increasingly important for life.
Organic pollutants are among the key sources of water con-
tamination. This includes the disposal of volatile organic
compounds (VOCs) and synthetic organic compounds (SOCs)
from agricultural and industrial activities,2 as well as those
from offshore mining and oil spill events. The recent advance-
ment in nanotechnology has initiated increasing efforts in
using nanomaterials to detect and decompose VOCs and
SOCs.3–8 On the other hand, nanomaterials have been used
for oil–water separation. It is noted that the use of nano-
materials in these environmental applications will create the
risk that water may be contaminated with nanoparticles. Fur-
thermore, there is increasing use of nanomaterials in sports
equipment, as well as various industrial and household

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Environmental Science: Nano
products. All these have increased concern about the environ-
mental and health impact of nanopollutants in water.
In this review, we aim to emphasize the relation between
nanotechnology and water contamination, as discussed in
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section 2. Next, we will review the use of nanomaterials for
oil–water separation in section 3. This discussion represents
how nanotechnology is used to help resolve contamination of
water by organic pollutants. At the end of the discussion, we
will present the outlook of oil–water purification technology
and bring awareness about the potential environmental con-
cerns over using nanotechnology for water purification.
2. The impacts of nanomaterials on
the environment
As shown in Fig. 1, VOCs and SOCs from agricultural and
industrial activities (1) will often be released into the air and
eventually will be (2, 3) condensed and return to the ground
in rain. The release of VOCS and SOCs (4, 5) is even more
intensive via waste water or solid disposal from manufactur-
ing sites. These and other organic pollutants, including those
from oil spills (6), will eventually contaminate rivers, lakes,
and oceans. The consequence of this is the deterioration of
our food chain as sea creatures will be poisoned (7). Large-
scale organic contaminants from oil spills or industrial dis-
posal will also contaminate groundwater and rivers (8) via
land intrusion.
As illustrated, most VOCs and SOCs would end up in
water. Therefore, water purification technology (9) in water
supply facilities becomes essential to meet the need for safe
consumption. The emerging use of nanotechnology for water
purification, for instance oil–water separation, has started to
gain tremendous attention in the past decade and will be
reviewed in section 3. Again, as an adverse effect of nanotech-
Fig. 1 Schematic diagram of water contamination from VOCs, SOCs, waste, and oil spills, etc., as well as the possible water purification cycles.
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nology, water will inevitably be contaminated with nano-
materials. Therefore, water that is treated with nanomaterials
will need to be purified again such that the nanomaterials
are extracted (10) to allow safe consumption (11). In particu-
lar, waste and drain water from industrial nano-
manufacturing sites would potentially be contaminated with
large quantities of nanoparticles (4). It is noted that conven-
tional filtration technology utilizes filters with microscale
pores which are not applicable to the clean-up of these nano-
scale contaminants. The pore size of these filters is too big to
trap the nanomaterials. Because of this shortcoming, a novel
technology must be developed to treat waste and drain water
from nano-manufacturing sites (12). In view of the impor-
tance of such a technology, the environmental concerns over
using nanotechnology for water purification will be discussed
at the end of section 3.
3. Oil–water separation by
nanotechnology and specific
wettability
One of the major environmental concerns is oil spills in the
marine ecosystem.9,10 Marine oil spills seriously endanger
sea ecosystems and coastal environments and also result in a
loss of energy resources.11 Effective oil spill cleaning technol-
ogy is therefore important for environmental protection. This
technology should also emphasize the need to reclaim the oil
by separating oil–water mixtures to meet the economic de-
mands. Because of this, the study of oil–water separation has
attracted great research interest and has started to emerge as
a rapidly growing area for the research and industrial com-
munity to resolve oil spills and resource recovery issues.
Many interesting works have been reported to achieve a
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highly effective, low cost, and simple process for oil–water
separation, using nanomaterials with superwettability. In this
section, the recent progress in this area will be summarized
to provide an overview of the current research trend and
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achievement in oil–water separation. Further details on the
technical aspects of materials with special wettability (such
as superhydrophobicity and superoleophobicity) can be
found in the literature elsewhere.12–17 Reviews on specific
applications of oil–water separation technology can also be
found, as listed in ref. 18–23.
Overall, oil–water separation can be achieved using mate-
rials with specific wettability. Three general approaches have
been exploited: 1) the filtration technique using specific wet-
tability that only allows a selected phase (either oil or water)
to penetrate, while preventing the other phase from passing
through. The structure of the filter can be in the form of
meshes or textile membranes. 2) The absorption method
using porous sponges, fibers, and aerogels that are able to se-
lectively absorb oil or water into their empty interior voids
and repel the other phase. 3) Technology based on either fil-
tration or absorption that is switchable and controllable in
functionality. The filtration-based techniques are discussed
in section 3.1, while the absorption-based approaches are
summarized in section 3.2. The controllable features of the
materials will be discussed in section 3.3.
Fig. 2 (a) A water droplet stayed on the epoxy/attapulgite-coated mesh. (b) An oil droplet glided along the surface of the water droplet and (c)
spread over the mesh surface. (d) With continuous dripping, the oil passed through the mesh. (e–h) A typical filtering experiment that separates a
mixture of oil (hexadecane in red) and water (in blue) using an epoxy/attapulgite-coated mesh. Reproduced with permission from ref. 24.
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3.1. Filtration-based oil–water separation
3.1.1. Materials with combined superhydrophobic and
superoleophilic properties. Metallic meshes, such as copper
and stainless steel (SS), are commonly used as the filtration
substrates for oil–water separation. Obviously, the mesh sur-
face needs to be modified to achieve one of the three distinct
wettability properties, as described in this section. One con-
ventional and common approach is to coat metallic meshes
with low surface energy polymers, hydrocarbon derivatives,
or nanostructures to make them superhydrophobic and
superoleophilic.24–28 The earliest work on this approach was
reported way back in 2004, wherein polytetrafluoroethylene
(PTFE) was coated on SS meshes to form micro- and nano-
structures to filter oil from water.29 There are many other
works trying to enhance the efficiency of filtration. For exam-
ple, a high separation efficiency could be achieved by coating
copper meshes with a rough silicon elastomer (Sylgard 184).30
Deposition techniques such as dip-coating and spray-
coating processes have been attempted to coat low surface
energy polymers (such as low density polyethylene (LDPE))
onto metallic meshes.24,27,31–33 Fig. 2 illustrates a typical fil-
tering experiment that demonstrates the separation of a mix-
ture of oil (hexadecane) and water.29 The mesh was coated
using epoxy/attapulgite. On the other hand, polystyrene (PS)
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nanofibers were deposited on SS meshes to achieve excellent
diesel separation from water.34 A hierarchical structure of a
superhydrophobic SS mesh was achieved by multiple fabrica-
tion processes.35 In this case, polypyrrole (PPy) micropapilla
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structures were first coated on a bare SS mesh by electro-
polymerization, followed by the coating of polyaniline (PANI)
nanofibers using chemical polymerization. Teflon was then
dip-coated on the coated samples to reduce the surface en-
ergy of these nanostructured coatings.
A simple approach was also demonstrated by direct oxida-
tion of Cu meshes to achieve the required surface roughness.
The oxidation processes can be thermal oxidation or by im-
mersing the mesh into an oxidizing solution. These oxidized
meshes can be further modified with a hydrophobic coating
to achieve superhydrophobicity and superoleophilicity.36–39
Using these modified metallic meshes, innovative ideas have
been demonstrated and employed for self-driven oil–water
separation.40,41 For example, self-driven oil–water separation
was achieved by folding such a modified Cu mesh into a
mini boat to absorb and collect oil from the water surface
by superoleophilicity.38–40 Continuous oil extraction by
means of a pumping system is also attempted, as summa-
rized in section 3.2.1.
In fact, oil–water separation by metallic meshes has
gained attention since 2011 by using coatings of one dimen-
sional (1D) nanostructures. For example, we have reported on
oil–water separation by SS meshes that were deposited with
vertically aligned carbon nanotubes (CNTs),42 as shown in
Fig. 3. These CNT meshes exhibited superhydrophobicity and
superoleophilicity that enabled the separation of the oil–
water emulsion (emulsion filtration will be specially dis-
cussed in section 3.1.4). In a recent work, a SS mesh was
modified using simple one-step immersion of hydrochloric
acid and stearic acid to form nanostructures. The subsequent
Fig. 3 Images of a stainless steel mesh coated with carbon
nanotubes, which is superhydrophobic and superoleophilic. Water of
different pH was coloured with methyl red. Reproduced with
permission from ref. 42.
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coating of ferric stearate films will convert the nanostruc-
tured SS meshes into superhydrophobic.43
3.1.2. Materials with combined superhydrophilic and
superoleophobic properties. One common issue of using
materials with combined superhydrophobic and super-
oleophilic properties is the formation of a water barrier layer
on the filter (or the so-called water fouling, to be discussed
in section 3.5.1), which prevents oil permeation during the
filtration process.18,42 This is because the denser water phase
is being repelled on the superhydrophobic surface and pre-
vents the oil from penetrating through the water barrier to
access the superoleophilic filters. It is particularly severe if
the water phase is denser than the oil phase. Therefore, it is
of great interest to develop innovative materials that have the
reversed properties, i.e., being superhydrophilic and super-
oleophobic. Materials with these combined properties will
allow water to pass through the filter mesh while repelling
oil from the filter. This will enable oil–water separation with
high separation efficiency and capacity, as well as high resis-
tance to oil fouling on the filters.
Unfortunately, achieving these combined properties is
theoretically difficult as water has a higher surface tension
compared to oils.44–46 Most surfaces that are superoleophobic
are also superhydrophobic,15 hence making oil–water separa-
tion through the superoleophobic surfaces challenging.46–48
Despite this difficulty, several articles have reported on this
unusual wettability for oil–water separation.49–52 The working
mechanism of this type of materials is based on their hydro-
responsivity. When in contact with water, the polymer chains
will rearrange themselves by the interaction between the
hydrophilic groups and the polar water molecules, such that
the hydrophilic groups are at the solid–liquid interface,
making the surface hydrophilic and oleophobic.
For example, it was demonstrated that hydrophilic
polyIJdiallyldimethylammonium chloride) (PDDA), oleophobic
sodium perfluorooctanoate (PFO) and SiO2 nanoparticles
(referred to as PDDA–PFO/SiO2) could form a composite that
exhibits this interesting property.51 At the beginning of the
filtration process, both water and oil formed spherical drop-
lets on the PDDA–PFO/SiO2 coated SS mesh, indicating the
amphiphobic (both hydro- and oleo-phobic) property of the
material. However, 9 minutes later, the water contact angle
(WCA) dropped to 0° due to the water-induced molecular
rearrangement. The PDDA–PFO/SiO2 coated SS mesh became
superhydrophilic and superoleophobic. The mesh could se-
lectively separate oil and water when the mixture was poured
onto it. Another similar work was also reported, as illustrated
in Fig. 4. Here, hydrophilic chitosan (CTS, one type of poly-
saccharides) and oleophobic PFO were used for the coat-
ings.52 This was motivated by the biodegradable, nontoxic,
and biocompatible nature of CTS as well as their ability to
react with fluorosurfactant. It is also worth mentioning that a
superoleophobic and superhydrophilic fabric filter was
patented for rapid water–oil separation53 in 2011, which can
be useful for commercial application for recovering oil spills.
Essentially, all the reported materials with combined
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Fig. 4 a) The wetting process of a water droplet on the CTS-PFO/SiO2 coating. b) The rolling process of a hexadecane droplet on the CTS-PFO/
SiO2 coating. c) Photographs of hexadecane, lubrication oil, rapeseed oil, and water placed onto the CTS-PFO/SiO2 coating. d)–f) A simple
experimental setup for oil–water separation. The oil/water separation process performed on the CTS-PFO/SiO2 coated stainless steel mesh.
Reproduced with permission from ref. 52.
hydrophobic and oleophilic properties are composed of at
least one oleophobic group (typically fluorocarbon groups)
and one hydrophilic group (typically possesses positive or
negative charges in aqueous solutions).
3.1.3. Materials with combined superhydrophilic and
underwater superoleophobic properties. Underwater super-
oleophobicity is the resistance of a surface to the wetting of
oils when the surface is immersed in water.54–56 This prop-
erty is achieved due to the superhydrophilic nature of mate-
rials that traps water into the groove of their rough hierarchi-
cal structures to reach a low-energy state. As these materials
are in contact with oil underwater, it is energetically
unfavourable for oil to replace water molecules, and thus cre-
ates oleophobicity. Theoretically, a superhydrophilic surface
in air will exhibit superoleophobicity underwater.
For example, Cu meshes were modified by direct oxidation
in a (NH4)2S2O8 solution to form a layer of CuIJOH)2 nano-
wires on the mesh.57 This CuIJOH)2 nanowire membrane was
superhydrophilic and underwater superoleophobic. The
nanowire-coated mesh was demonstrated to separate both
immiscible oil–water mixtures and oil-in-water emulsions,
solely driven by gravity. In another report, such a CuIJOH)2-
coated mesh with micro- and nanoscale hierarchical compos-
ite structures could also be obtained by immersing a Cu
mesh in 0.05 M potassium peroxydisulfate (K2S2O8) and 1.0
M sodium hydroxide (NaOH) for up to 60 minutes.58 An
electrodeposition technique could also be used to produce
such a wettability on Cu meshes.59
In addition to surface modification by chemical processes
and treatment, rough nanoscale structures can also be cre-
ated on silica glass surfaces by femtosecond laser ablation.60
The as-prepared surfaces not only exhibited underwater
superoleophobicity and ultralow oil adhesion, but they were
highly transparent in water. On the other hand, SS meshes
coated with aligned ZnO nanorods were reported to have the
superhydrophilic/underwater superoleophobic property under
UV irradiation with a 500 W Hg lamp (centred wavelength at
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365 ± 10 nm).61 These meshes showed excellent controllabil-
ity and high efficiency of oil–water separation. Furthermore,
these nanorod-coated meshes could restore their super-
hydrophobicity after storage in the dark for 7 days. This
photo-induced switchable surface property could potentially
prevent the mesh from being polluted by oil.
3.1.4. Emulsion filtration. Oil–water mixtures usually con-
sist of immiscible mixtures and emulsions with various drop-
let sizes. In many applications, for example, oil recovery from
spills remediation, water purification, industrial effluents
treatment, purification of fuel oil, etc., it is desired to sepa-
rate the oil–water emulsion effectively. It is well known that
emulsified mixtures are more difficult to separate compared
to immiscible mixtures, due to the small emulsion droplet
size and various emulsification forms (oil-in-water, water-in-
oil, surfactant-stabilized and surfactant-free emulsions, etc.).
Filtration-based oil–water separation technologies are still
attractive for their energy efficiency and cost effectiveness.
For instance, vertically aligned CNTs on SS meshes were used
to separate oil-in-water emulsions.42 However, metal mesh-
based membranes are not very effective for emulsion filtra-
tion due to the large pore size of the mesh (usually larger
than the emulsified liquid droplets). In fact, the membrane
pore size should match the emulsion droplet size for opti-
mum separation of emulsions. Thus, polymeric membranes,
with smaller and controllable pore sizes, have their unique
advantages in emulsion filtration. By modifying the poly-
meric membranes with special wettability, the filtration per-
formance (such as filtration flux, separation efficiency, and
antifouling properties) can be significantly improved.28,62 For
example, a highly flexible, superhydrophobic and super-
oleophilic polyvinylidene fluoride (PVDF) membrane had
been demonstrated to separate many types of oil–water emul-
sions with high separation efficiency.62 However, due to the
small pore size, superhydrophobic polymeric membranes suf-
fer a serious water-fouling issue. Therefore, there are motiva-
tion in using polymeric membranes with combined
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superhydrophilic and underwater superoleophobic properties
to separate oil-in-water emulsions.63–66
The filtration flux is inversely proportional to the thickness
of the membrane. In other words, thinner membranes provide
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superoleophobic, and it is excellent for oil-in-water emulsion
separation. Heat treatment can transform the membrane
back to the original (superhydrophobic) state and thus
achieve reversible and controllable bidirectional separation

a higher filtration flux. As an alternative to polymeric filtration of different types of emulsions.

membranes, membranes of randomized single-walled carbon
nanotubes (SWCNT) as thin as 30 nm were also developed for
emulsion filtration.67 These membranes are hydrophobic and
superoleophilic. Consequently, nanotube membranes allow oil
to easily permeate through, while simultaneously preventing
the permeation of water. Again, water droplets caused the foul-
ing issue and thus these membranes must be washed with
ethanol for each cycle of 15 ml emulsion filtration. To over-
come this problem, an ultrathin and flexible film based on an
SWCNT/TiO2 nanocomposite network was reported.68 With the
aid of UV light irradiation, the ultrathin network film is super-
hydrophilic and underwater superolephobic with antifouling
and self-cleaning properties. It could effectively separate both
surfactant-free and surfactant-stabilized oil-in-water emulsions
with a wide range of droplet sizes. With the adequate film
thickness and nanoscale pore size of the SWCNT/TiO2 com-
posite network film, a high flux rate and an ultrahigh separa-
tion efficiency could also be achieved.
It is worth mentioning that this type of tunable wettability
by external stimulants is a current research trend. As another
example, a copper mesh-based membrane was recently
reported to have the ability to separate both water-in-oil and
oil-in-water emulsions after treatment with a certain stimu-
lant.69 The modified copper mesh membrane was initially
superhydrophobic/superoleophilic, which is suitable for the
separation of water-in-oil emulsions. Under O2 treatment, the
membrane would become superhydrophilic/underwater
3.1.5. Tackling water-fouling issue in superhydrophobic
and superoleophilic membranes. Very recently, an inte-
grated dual-channel filtration system using the combina-
tion of a superhydrophobic membrane and an underwater
superoleophobic membrane was reported, as shown in
Fig. 5a.70 This system overcomes the fouling issue and
demonstrates continuous, high flux and high efficiency
oil–water separation. In this work, a copper mesh was
chosen as a substrate owing to its greater mechanical
strength, solvent resistance and industrial applicability. It
was first treated by solution-based oxidation to produce a
CuIJOH)2 nano-needle structure and subsequently by fluoro-
silane modification (1H,1H,2H,2H-perfluorodecyltriethoxy-
silane, PFTS) to obtain a superhydrophobic anti-water
(AW) membrane. The superhydrophilic anti-oil (AO) mem-
brane was fabricated by UV cross-linking acrylamide to a
polyacrylamide (PAM) hydrogel onto a copper mesh. As
illustrated in Fig. 5b and c, both filters were placed to
complementarily tackle oil and water at the same time
due to their opposite wettabilities. This simple design is
effective if the densities of oil and water are known prior
to the filtration. An inverted T-shaped device was designed
to separate mixtures without considering the density of
the liquids (Fig. 5d and e). A pumping system was also
demonstrated to provide evidence of continuous oil–water
separation and durability (in terms of structural and
chemical stability) of the membranes. Even though it was

Fig. 5 (a) Schematic of an integrated dual-membrane separation system. The anti-water (AW) membrane with superoleophilicity and super-
hydrophobicity and the anti-oil (AO) membrane with underwater superoleophobicity were integrated into a two-outlet tube device. By regulating
the proper membrane position, water and oil could be separated continuously. (b) The AO–AW integrated device with the AO membrane at a lower
position and AW membrane at a higher position could separate oil–water mixtures with ρoil > ρwater. (c) Swapping the places of the AO–AW mem-
branes could separate ρoil > ρwater mixtures. (d and e) If the density of oil is not known, an inverted T-shaped device that places AW–AO mem-
branes at the same horizontal position could separate mixtures without considering the density. Reproduced with permission from ref. 70.

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not performed, this technique could potentially be useful
in oil–water emulsion filtration.
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3.2. Absorption-based oil–water separation
3.2.1. 3D porous structures with combined super-
hydrophobic and superoleophilic properties. Three dimen-
sional (3D) porous materials such as cotton, aerogels,
sponges, and fibrous films can be modified to offer com-
bined superhydrophobic and superoleophilic properties for
water repelling and oil absorbing applications.40,71–82 By
taking advantage of the porous networks with a large surface
area and storage space, these superhydrophobic (and super-
oleophilic) materials can effectively absorb oil into their
porous networks, driven by the capillary force. 3D porous
structures are being considered as one of the most promising
materials to recover oil after oil spill incidents. Substantial
studies have been reported on using various types of poly-
mers and techniques to produce 3D structures with high oil
absorbing capability.
In addition to polymeric materials, various other synthetic
3D architectures can be formed in carbon-based 3D oil absor-
bents through pyrolysis. For example, raw cotton could be
converted to twisted carbon fiber (TCF) aerogels via a direct
pyrolysis process. The fibrous structure of cotton could be
maintained but it became more twisted after the pyrolysis.72
Interestingly, the surface property changed from hydrophilic
to hydrophobic after pyrolysis, attributed to the highly
twisted fiber structures and removal of all hydrophilic com-
ponents. It was demonstrated that TCF aerogels could quickly
clean up a layer of heptane on water (Fig. 6(a)) and chloro-
form at the bottom of water (Fig. 6(b)). Due to its hydropho-
bicity and low density, the TCF aerogel showed a high ab-
sorption capacity of up to 192 times its own weight.
Because of the even larger surface area from nanoscale
materials, carbon nanotube (CNT)-based aerogels/sponges
have been exploited as highly efficient absorbents for oil–
water separation.83 In addition, polymer-based graphene
foams by the self-assembly of graphene sheets on a 3D poly-
mer skeleton84 as well as reduced graphene oxide (rGO)
foams with porous and continuously cross-linked structures85
Fig. 6 Digital photos showing the absorption process of a TCF aerogel towards a) heptane floating on the surface of water, and b) chloroform at the
bottom of water, respectively. Both organic liquids are dyed with Sudan red 5B. Reproduced with permission from ref. 72.
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have been demonstrated to exhibit superhydrophobicity. By
combining the robust mechanical strength of CNTs and the
large surface area of graphene, CNT/graphene composites
could even present improved performance.86,87 For example,
Sun et al. fabricated ultra-flyweight aerogels (UFAs) through
the “sol-cryo” method using CNTs and giant graphene
sheets.86 The UFAs exhibit an extremely low density (0.16 mg
cm−3) and high porosity of around 99.9%, resulting in an
unprecedentedly high oil uptake capacity of over 900 times
its own weight. On the other hand, metallic skeletons such
as copper foams have been modified to become super-
hydrophobic for oil–water separation,88–90 having the advan-
tages of their well-developed 3D metallic network, robust
mechanical structure, and large surface area.
It is worth mentioning that it is difficult to remove oil that
has been absorbed into superhydrophobic porous materials
due to their intrinsically oleophilic nature. In a recent work,
selective absorption but continuous collection of oil spills
from the water surface has been demonstrated using an ex-
ternal pumping system together with porous hydrophobic–
oleophilic materials.76,91,92 Fig. 7(a) shows a demonstration
of the oil spill remediation pumping system. A hydrophobic
polymer sponge (HPS) was obtained by dip-coating commer-
cially available polymer sponges (PSs) with a hydrophobic
SiO2 nanoparticle/polydimethylsiloxane (PDMS) composite
solution. By partially immersing the HPS into the n-hexane–
water mixture, the n-hexane could be pumped out when a
suction force was applied to the top of the HPS. The n-hexane
around the HPS was continually absorbed into the HPS and
then collected back in the collecting vessel until all n-hexane
was separated. It should be noted that water could also be
pumped out if the pumping force is sufficient to overcome
the hydrophobic force between the interfacial layer of the
water and the sorbent (such as HPS). In principle, a refined
version of such a pumping system will improve the oil
absorption speed and the efficiency of oil spill remediation.
The idea of continuous pumping can also be extended using
metallic mesh filters33,43 or even innovatively structured cone
arrays.93 Fig. 7(b) and (c) demonstrate two different types of
continuous filtering mechanism using superhydrophobic
meshes, as described in section 3.1.1.
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Fig. 7 (a) Photographs of continuous collection of n-hexane (dyed red) in situ from a water surface with the HPS and the pumping apparatus.
Reproduced with permission from ref. 91. (b) An experimental pumping apparatus with a superhydrophobic mesh for the continuous collection of
pure oil from an oil–water mixture. At the side is the schematic diagram of the oil–water separation apparatus. Reproduced with permission from
ref. 43. (c) Left: A test tube with windows cut at its side covered with a low density polyethylene (LDPE)-coated mesh. Right: This tube was then
lowered into a beaker with floating oil. The oil passed through the mesh and was continuously pumped to an external reservoir. The photo shows
the system during operation. Oil removal occurred on the sides of the device with mesh (left and right of the test tube in the photo), but not else-
where (e.g., bottom of photo). Center: An illustration showing the integrated collection system recovering the oil; blue represents seawater, black
represents a crude oil spill. Reproduced with permission from ref. 33.

3.2.2. Simultaneous use of materials with superhydrophilicity-
underwater superoleophobicity and materials with super-
oleophilicity. As discussed in section 3.1.3, superoleophobic
materials are relatively rare.94 In fact, it is not very practical
to develop superoleophobic sorbents for oil–water separation,
due to the fact that oil is usually the contaminant that needs to
be extracted. In a recent report, superhydrophilic twines with
underwater superoleophobicity are used simultaneously with
superoleophilic twines to absorb water and oil, respectively.
The superhydrophilic twines with underwater super-
oleophobicity were prepared by plasma treatment of commer-
cial twines as the water sorbents. On the other hand, commer-
cial twines were coated with hydrophobic silica nanoparticles/
polystyrene to form superoleophilic twines for oil absorption.
Both types of twines are then applied simultaneously to absorb
water and oil from an oil–water mixture, solely driven by the
capillary force resulting from the microgaps and microgrooves
on the twines without any external driving force.95
3.3. Oil–water separation with controllability and switchability
Materials with controllable oil–water separation properties,
either by filtration or absorption, have become a new re-
search focus. For example, the absorbent can be designed to
be magnetically responsive, therefore the separation process
becomes magnetically driven and controllable.75,81,96 Besides,
specially designed nanoparticles can also be applied for oil–
water separation.97–100 As an example, Fe3O4 nanoparticles
(NPs) were coated with gold nanoparticles (Ag NPs) by using
polydopamine (PDA) as the intermediate layer.98 This type of
hybrid nanoparticles, namely Fe3O4@PDA@Ag NPs, is highly
hydrophobic/oleophilic, hence is able to capture an oil phase
compound in water. Due to the magnetic nature of Fe3O4
NPs, it can be driven by a strong external magnet, as illus-
trated in Fig. 8(a). Similar concepts using these Fe3O4 nano-
particles were also utilized to anchor onto electrospun
polyIJvinylidene fluoride) (PVDF) fibrous films.101 The as-
prepared fibrous films were superhydrophobic/superoleophilic
and exhibited excellent oil absorption capacity from water.
With Fe3O4 nanoparticles, a magnetically controlled oil re-
moval carrier could be realized.
On the other hand, a pH-controllable, on-demand oil–
water filter was demonstrated using a modified copper
mesh.102,103 The copper mesh can be superhydrophobic for
nonalkaline or acidic water and can become superhydrophilic
(and therefore superoleophobic) in alkaline water. A similar

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Fig. 8 (a) Photograph showing the oil–water separation and collection process with a magnet, using Fe3O4@PDA@Ag NPs. Reproduced with
permission from ref. 98. (b) Left: A SEM image showing photo-responsive ZnO NP-coated stainless steel mesh for on-demand oil–water separation.
The inset is a bare mesh. Right: Illustration of the on-demand oil–water separation experiment. Reproduced with permission from ref. 107. (c) Pre-
wetting induced oil–water separation using a potato residue powers coated mesh (PRCM). Schematic illustration of the selective separation of oil/
water mixtures. (d) Separation of kerosene–water mixtures for the situation of ρwater > ρoil. (e) Separation of chloroform–water mixtures for the situ-
ation of ρwater < ρoil. In (d) and (e), the water is dyed with methylene. Reproduced with permission from ref. 109.

mesh with a smart fiber membrane was fabricated by depos-
iting pH-responsive copolymer fibers on a SS mesh through
electrospinning.104 This membrane exhibited two switchable
wetting states, namely, superhydrophobicity (together with
superoleophilicity) and superhydrophilicity-underwater super-
oleophobicity. In another work, pH-driven switchable wetta-
bility of non-woven textiles and polyurethane sponges were
demonstrated.105 Using a copolymer-grafting strategy, common
materials like textiles and sponges were functionalised by a
block copolymer, comprising pH-responsive polyIJ2-
vinylpyridine) and oleophilic/hydrophobic polydimethylsiloxane
blocks (namely, P2VP-b-PDMS) to achieve the functionality.
Stimulus-responsive surface wettability, such as photo-
responsive surface wettability, has been intensively
studied.61,68,106,107 For example, ZnO is commonly used due
to its responsive property to UV illumination. As shown in
Fig. 8(b), SS meshes coated with ZnO nanoparticles were
demonstrated for their application in on-demand oil–water
separation.107 In addition, photoinduced permeation of
water through azobenzene-modified anodized alumina mem-
branes was recently reported as a photo-responsive nano-
porous membrane for water purification and desalination.106
In addition, the separation of all types of oil–water mixtures
can be triggered on-demand by applying an electric field to a
gravity driven, membrane-based filter, with high separation
efficiency.108 It is also interesting to note that the wettability
property of a material can be determined by the pre-wetting
hysteresis.109 A common superamphiphilic material, the
waste potato residue powers (PRPs) with polyurethane (PU),
was used to spray coat on a SS mesh to form a pre-wetting in-
duced (super) hydrophobic or under-water superoleophobic
mesh. The modified mesh is called a potato residue power
coated mesh (PRCM) in short. When immersed in water,
water can be infiltrated and trapped in the rough structure

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Environmental Science: Nano
because of the hydrophilic groups, hence preventing the
heavier oil droplets from coming into contact with the mesh
surface, resulting in under-water superoleophobicity with the
mesh. The result can be the opposite for under-oil super-
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hydrophobicity after immersion in oil, as illustrated in
Fig. 8(c). For selective oil–water separation, as shown in
Fig. 8(d), water can be condensed on the mesh, due to its
heavier density. After the mesh is prewetted with water, water
can be removed from the light oil–water mixture by gravity
with high separation efficiency. Likewise, heavy oil can be
removed from the oil–water mixture by gravity via the heavy
oil prewetted mesh (Fig. 8(e)).
3.4. Perspective on oil–water separation
3.4.1. Future research. The progress in oil–water separa-
tion technology is moving towards designing novel materials
with desired wettability, improving the manufacturing sim-
plicity, cost effectiveness and the possibility of reclaiming oil
after the separation process. While this field continues to
progress, it is important to make sure that the chemicals and
materials involved are environmentally friendly without intro-
ducing any secondary pollution. In addition, challenges re-
main in developing these special wettability materials with
selective oil–water separation functionality for real-world ap-
plications. Most of the reported experiments were conducted
in a controlled laboratory environment. Detailed evaluation
should be conducted under practical conditions, for instance,
with mixtures of multiple organic contaminants, with organic
contaminants that are low in viscosity, with oil–water mix-
tures with more rigorous mixing, severe vibrational condi-
tions to mimic ocean waves, etc. Scientists have made signifi-
cant progress in the science and engineering of oil–water
separation technology. Industry and government engagement
to exploit and adopt some of these new technologies to real
scenarios of oil spill recovery and water purification would
definitely stimulate further development and advancement.
3.4.2. Environmental concerns. As discussed in section 2,
attention should also be focused on preventing cross-
contamination during the oil–water separation process, par-
ticularly when nanoscale materials are involved.7,110 Recently,
we have reported a simple and universal technique to purify
water contaminated with nanomaterials.111 The results indicate
that carbon nanotubes,112,113 boron nitride nanotubes,114–117
zinc oxide nanowires,118 graphene,119 and boron nitride
nanosheets can be extracted from contaminated water at a
success rate of nearly 100%. We hope that this work would
stimulate interest in purifying water from nanoscale solid
pollutants. While this approach is beneficial to the extraction
of 1D and 2D nanomaterials, it is still unable to extract
spherical nanoparticles.
4. Conclusions
Civilization has created many man-made materials that cause
water pollution and impose negative impacts to the environ-
ment. For instance, the advancement of organic chemistry
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has created many synthetic organic compounds (SOCs) and
volatile organic compounds (VOCs). Interestingly, organic
chemistry also helps to form novel coatings with controlled
wettability of filters to purify water via oil–water separation.
The same scenario happened to nanotechnology. Nano-
materials have been used for oil–water separation, as was
reviewed here. However, the use of nanomaterials for water
purification, sports equipment, and household and industrial
products has raised concern that water will be contaminated
with nanomaterials. Obviously, there are mutual impacts
from water purification, organic chemistry and nanotechnol-
ogy. Awareness of the potential consequences of advance
science and engineering on the environment and clean water
is critically important in sustaining freshwater resources for
further civilization.
Acknowledgements
Yoke Khin Yap acknowledges the support from the National
Science Foundation (Award number DMR-1261910).
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