Review
Membranes
Specially Wettable Membranes for Oil–Water Separation
Yibin Wei,* Hong Qi, Xiao Gong, and Shuaifei Zhao
The oil–water separation has attracted heightened attention because of the
ever-increasing amounts of oily water produced from the daily activities of
humans and industrial processes. Membrane technology as an advanced
water purification approach has offered an indispensable option due to its
cost-effective, energy-efficient, and easy-to-operate characteristics. However,
traditional membrane materials suffer from severe fouling, which counteracts
the superiority of applying membranes in oil–water separation applications.
Thanks to the emerging bioinspired interface research, a series of special
wettability not only endows membrane surfaces with outstanding antifouling
properties but also breaks though the long-standing tradeoff effect between
membrane permeability and selectivity. In this review, the recent advances
of membranes used for oil–water separation with special wettability and
perspectives on the on-going research are presented. The authors first
discuss the wetting phenomenon on membrane surface, and then highlight
the gradually evolved specially wettable system and its coupling with
membrane materials. Next, relatively comprehensive preparation methods
and applications of oil–water filtration membranes utilizing special wettability
are summarized. Finally, the authors conclude the current achievements and
challenges in specially wettable membranes for oil–water separation and
outlook the future in this field.
1. Introduction
Sustainable supply of clean water is one of the most important
challenges for human societies. Since the industrial revolution,
oily water has been produced in ever-increasing amounts due to
the daily activities of humans and industrial (e.g., petrochem-
ical, oleochemical, and metallurgical) processes (Figure 1).[1–4]
Y. Wei, Dr. S. Zhao
Department of Environmental Sciences
Macquarie University
Sydney, NSW 2109, Australia
E-mail: yibin.wei@hdr.mq.edu.au
Prof. H. Qi
State Key Laboratory of Material-Oriented Chemical Engineering
Membrane Science and Technology Research Center
Nanjing Tech University
Nanjing 210009, Jiangsu, China
Prof. X. Gong
State Key Laboratory of Silicate Materials for Architectures
Wuhan University of Technology
Wuhan 430070, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/admi.201800576.
DOI: 10.1002/admi.201800576
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Additionally, accidental release of crude oil
and petrochemical products that causes
considerable environmental damage and
economic losses have occurred frequently
in the past decades. Therefore, cost-
effective separation of oil–water mixtures
is an urgent need for water, energy and
environmental securities.[4–6]
Generally, the difficulties in sepa-
rating oil–water mixtures predominantly
depends on the size of the oil droplet
and the stability of the mixture.[7] Oil–
water mixtures are commonly classi-
fied into three categories in terms of the
diameter of the oil droplet: free floating
oil (>150  µm), dispersed oil (20–150 µm)
and emulsified oil (<20 µm).[8,9] The most
challenging oily water exists in the form
of oil–water emulsions that can be further
classified into oil-in-water (o/w) and water-
in-oil (w/o) emulsions.[10,11] In an o/w
emulsion, the continuous phase is water
and the dispersed phase is oil, while in a
w/o emulsion oil is the continuous phase.
Surfactant-stabilized oil–water emulsions
have low interfacial tension between the
oil and water phases, which deters the
coalescence of droplets, contributing to the difficulty in treating
oil–water emulsions.[12,13]
Numerous physical and chemical techniques have been
applied to separate oil–water mixtures, such as gravity sepa-
ration, air floatation, adsorption, coagulation, centrifugation,
electrochemical and photocatalytic treatment.[10,14,15] However,
these conventional methods have their own limitations, e.g.,
undesirable separation efficiency, large footprint, secondary
pollution or high energy consumption.[16] Therefore, seeking
efficient approaches for oil–water separation has attracted
growing research interest.[4,17–19]
Membrane technology as an advanced separation and puri-
fication method is gaining heightened attention due to its high
efficiency, low energy cost, ease for continuous operation, and
low footprint.[20,21] Membrane separation technology has been
successfully used in desalination, wastewater treatment, food
processing, chemical and pharmaceutical industries for a few
decades, demonstrating its significant technical and economical
merits.[22] For oily water treatment, pressure-driven membrane
processes including microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF), and reverse osmosis are widely used, espe-
cially in produced water treatment.[23–26] Other membrane pro-
cesses such as thermal-driven membrane distillation (MD) and
osmotically driven forward osmosis have also been attempted
for oily wastewater purification.[27] However, the major problem
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in these membrane processes for oil–water separation is

membrane fouling, because surfactant adsorption or pore plug- Yibin Wei received his B.Eng.
ging by oil droplets can lead to diminished flux.[28] Membrane degree in chemical engi-
cleaning requires extra maintenance downtime, chemicals neering jointly offered by
and energy, which increases operation costs and may counter- Nanjing Tech University and
balance the advantages of membrane separation. Membrane University of Strathclyde in
fouling resulting from oily organic matters remains one of the 2014, and then he com-
greatest challenges in the treatment of oily wastewater.[29,30] pleted his M.Eng. degree
Ideal membrane materials should offer high selectivity, from Gachon University in
permeate flux, stability and fouling resistance.[21] In the 21st 2016. After working as a
century, nanotechnology has developed rapidly and led to a visiting scholar in Prof. Hong
material science revolution, which also offers new possibilities Qi’s group at Nanjing Tech
for oil–water separation membranes.[31] Learning from nature, University (2016–2017), he
materials with special wettability constructed by well-defined moved to Macquarie University for pursuing his Ph.D.
nanohierarchies have received increasingly extensive atten- degree. His areas of research interest include novel mem-
tions, and many novel functional interfacial nanomaterials brane materials preparation and application.
have been fabricated and applied in industry.[32] Recently,
new materials with special wettability (e.g., superlyophobic or Hong Qi is a professor in
superlyophilic) have been developed via surface engineering the State Key Laboratory of
(mainly by adjusting the surface chemical composition or Material-Oriented Chemical
topography).[33–35] Based on this new theory, a large number Engineering, Membrane
of interfacial or porous materials with special wettability have Science and Technology
been fabricated and used for oil–water separation.[8,17,36] It is Research Center, Nanjing
worth mentioning that some of these materials are even bi- Tech University. He received
functional that they could not only removal insoluble oils but his Ph.D. from Nanjing Tech
also soluble dyes, based upon different mechanism such as University in 2001 with Prof.
molecular sieving, adsorption, photodegradation, etc.[37–40] Nanping Xu. He was a vis-
Membranes, as the typical filtration materials, have been iting scholar (2007–2008) at
designed and improved with special surface wettability for oil– Inorganic Membranes Group,
water separation.[41] Up to now, material scientists have made University of Twente. His current research interest focuses
remarkable achievements in selective membranes for sepa- on porous ceramic supports and ceramic membranes with
rating oil–water mixtures to improve separation efficiency and applications in liquid and gas separation.
antifouling properties of the membranes.
Recently, many research and review articles[32,42–46] have Xiao Gong is a full professor
been published regarding applications of various wettable in the State Key Laboratory
materials for oil–water separation. However, few reviews on of Silicate Materials for
novel membrane materials with special wettability and their Architectures, Wuhan
corresponded improvements in membrane processes have University of Technology,
been summarized and published. Membrane processes are China. He received his
mature practical separation and purification technologies, Ph.D. in materials science
thus the innovation in membrane materials and their effects from Zhejiang University in
on membrane oil–water separation applications deserve to be 2009. Prior to joining Wuhan
reviewed from the view of both materials science and prac- University of Technology, he
tical engineering applications. In this review, we discuss fun- was a postdoctoral associate
damental knowledge on membrane materials with special in Prof. Lei Li’s group at the
wettability for oily water treatment. A brief introduction of University of Pittsburgh, USA. His research interests are on
the essence behind specially wettable interfacial materials for self-assembly and polymeric nanomaterials, polymer thin
oil–water separation, the wetting phenomenon, is in Section 2. films, colloid surface and interface chemistry, fabrication
We then summarize the latest advances of functionalized and characterization of nanostructured materials; interfa-
membranes with special wettability involving definitions and cial behavior of ionic liquid on solid surfaces.
general preparation procedures in Section 3. In Section 4,
membrane materials with special wettability are classified into
metallic-based, polymeric-based, ceramic-based and emerging 2. Wetting Phenomenon
nanomaterials-based membranes according to the sup-
port. The relatively comprehensive preparation methods and Wetting is a common phenomenon that can be widely found
applications of these membranes in oil–water separation are anywhere, generally defined as the ability of a liquid get-
discussed. Finally, conclusions and outlook on future develop- ting in contact with a solid surface through intermolecular
ment of membrane materials with special wettability for oily interactions between the two phases.[47] The oil–water separa-
water treatment are given. tion, in essence, is that wetting phenomenon occurs at the

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Figure 1.  Schematic illustration of oil–water mixtures produced in various industrial processes.
interface of the solid, air, water and oil phases.[17] Owing to
massive efforts on the research into a series of special wet-
tabilities inspired from nature, interfacial materials with
super-wettability or anti-wetting properties have made great
breakthrough for the application of oil–water separation. In
recent years, wetting phenomenon in membrane applications
has aroused significant interest.[48,49] Mass transfer resist-
ance and separation efficiency are influenced by wetting phe-
nomenon that is related to membrane surface energy, pore
size and porosity. Thus, a comprehensive understanding of
wetting phenomenon is of great significance in advancing
membrane materials and improving membrane separation
performance.
2.1. Contact Angles
Wettability can be studied by characterizing the contact
angle of a surface with a given liquid. Contact angle (CA), θ,
is a quantitative measure of wetting, which is geometrically
defined as the angle formed by a liquid at the three-phase
boundary where a liquid, gas and solid intersect. According
to the well-known Thomas Young equation,[50] when a sessile
drop is placed on an ideally smooth surface, it normally forms
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a spherical droplet on the surface in air (Figure 2a). The
Young’s CA, θ is a function of the interfacial tension between
the solid–liquid (SL), solid–vapor (SV), and liquid–vapor (LV)
interfaces:
γ SV − γ SL
cosθ = (1)
γ LV
where γSV, γSL, and γLV, are the surface tensions at the solid–
vapor, solid–liquid, and liquid–vapor interfaces, respectively.
The Young’s equation is based on the assumption that the
surface is chemically homogenous and topographically smooth.
This is, however, not always correct because real surfaces do
not have perfect smoothness, rigidity, or chemical homogeneity.
The relationship between surface roughness and wettability was
defined in 1936 by Wenzel,[51] who stated that increasing surface
roughness would enhance the wettability caused by the chem-
istry of the surface. When homogenous wetting occurs on a solid
rough surface (Figure 2b), the Wenzel CA (θW) is determined by
cosθ W = r cosθ (2)
where θW is the apparent contact angle which corresponds to
the stable equilibrium state, r is the roughness factor, defined
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2.2. Wetting States in Oil–Water Separation

Wetting is an intrinsic property of a surface,

governed by the chemical composition and
morphology of the surface.[49,56,57] Chemical
composition of the surface is the internal char-
acter of the material, which determines the
surface tension. Generally, oil has smaller
surface tension than water, which is the
reason why oils could be separated from
water through porous interfacial mate-
rials with special wettability. In latest a few
studies,[58–60] the concept of local texture angle
(LTA), ψ, was proposed as a supplement to
describe wetting on a hierarchical textured
Figure 2.  Wetting state of a liquid droplet on different solid surfaces in air and corresponded surface, which offers new clues for designing
contact angle (CA) models: a) Young’s, b) Wenzel’s, and c) Cassie–Baxter’s. d) Schematics of oil–water separation interfacial materials.
advancing CA, receding CA, and droplet moving along an inclined surface with a tilting angle.
Those researchers believed that formation of
the stable Cassie–Baxter state is possible only
as the ratio of the actual area of the solid surface to the if the Young’s CA is greater than the LTA. As shown in Figure 3,
apparent surface area (r  = 1 for a smooth surface and r  > 1 two types of surface texture are compared. When texture angle
for a rough one), and θ is the Young’s CA. Notably, The ψ > 90° and θ ≥ ψ, the surface texture could result in the forma-
Wenzel’s equation is based on the assumption that the liquid tion of a composite interface. If θ  < 90°, which is common for
penetrates into the roughness grooves. In cases where the oil with low surface tension on most surfaces, then the surface
liquid does not penetrate into the grooves, the Wenzel’s texture cannot maintain a stable composite interface, regardless
equation does not apply. of its surface energy or composition. However, for the same low
When dealing with a heterogeneous rough surface, a more surface tension oils with θ < 90°, it is possible to fabricate a het-
complicated model was proposed by Cassie–Baxter[52] (Figure 2c) erogeneous interface as long as θ  ≥  ψ. Such surface geometry
with ψ  < 90° is known as re-entrant texture. Re-entrant texture
allows formation of a heterogeneous interface with low surface
cosθ CB = rf f SL cosθ + f SL − 1 (3)
tension oils, which may lead to oleophobic properties. Further
concepts and design strategies for oil–water mixtures separation
where fSL represents the solid–liquid fraction under the con- membranes with special wettability are introduced in Section 3.
tact area. Distinguished from the total roughness factor r, rf
is defined as the roughness ratio of the wet part of the solid
surface and it always shows a lower value than r. Besides r, 2.3. Wetting with Membranes
the Cassie–Baxter equation suggests that the solid–liquid frac-
tion (solid–air fraction) is also an influencing parameter to the With the rapid development of research on membrane separa-
apparent CA. tion technologies, a comprehensive understanding of wetting
The difference in the three above-mentioned wetting states phenomenon with membranes plays a more and more impor-
is their CA hysteresis, which reflects the surface neterogeny.[53] tant role in improving membrane performance. For pressure-
The CA hysteresis is quite common on rough and chemical driven separation membranes, two parameters associated with
heterogeneous surfaces. CA hysteresis, i.e., the difference membrane pores (i.e., pore size and porosity) and breakthrough
between the advancing and receding CAs (Figure 2d) for the pressure should be considered in wetting study.[48]
Wenzel’s and Cassie–Baxter’s wetting states are totally different. The first critical physical characteristic is the breakthrough
On a given surface, advancing CA is the maximum value while pressure (ΔPc), defined as the maximum pressure applied on
receding CA is the minimum value, and
both of them arises due to the presence of
multiple metastable energy states on rough
and heterogeneous surfaces.[54] Typically,
CA hysteresis in the Wenzel’s state is larger
than that in the Cassie–Baxter’s state. This
is because the solid–liquid interface is
pinned on the textured surface. By contrast,
a composite solid–liquid–air interface in
the Cassie–Baxter’s state leads to lower CA
Figure 3. Composite interfaces and hierarchical texture based on Cassie–Baxter’s model.
hysteresis and higher apparent CAs when a) A concave texture with ψ > 90° and θ > 90°. b) A lower surface tension liquid (θ < 90°) on
the contact area between the solid and the convex, re-entrant texture (ψ < 90°). Reproduced with permission.[7] Copyright 2015, Cambridge
liquid is small.[55] University Press.

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Figure 4.  Summary of membrane materials with special wettability for oil–water separation.
a membrane before the membrane pores are wetted by a given
liquid (also called liquid entry pressure, LEP). It can be meas-
ured by detecting the formation of the first liquid drop on the
permeate side of the membrane. For small uniform pores with
cylindrical geometry, the breakthrough pressure (ΔPc) can be
determined by the Laplace–Young equation[61]:
2γ cosθ Y
∆Pc = L (4)
rp
where γL and rp represent the surface tension of the liquid
and the maximum membrane pore radius, respectively. As
discussed above, Young’s equation is not suitable to describe
a real rough membrane surface and the relationship between
breakthrough pressure and surface wettability could be further
corrected, but Laplace–Young equation clearly points out
that wettability of the membrane surface could significantly
influence pressure-driven membrane filtration processes.
3. Special Wettability on Membrane Surfaces
Various types of interfacial materials with special wettability
have emerged.[32] From the previous discussion, we can see
that chemical composition and architecture of the surface
are two keys to developing selective membranes for oil–water
(emulsion) separation. In this section, we will systematically
introduce advanced membrane materials with special wetta-
bility, including superhydrophobic–superoleophilic (SHB-SOL),
superhydrophilic–underwater superoleophobic (SHL-UWSOB),
superhydrophilic–superoleophobic (SHL-SOB), superam-
phiphilic (also known as superhydrophilic–superoleophilic,
SHL-SOL in-air), and superomniphobic (also known as supe-
rhydrophobic–superoleophobic, SHB-SOB) membranes from
their definitions, working principles to fabrication strategies. In
addition to these membranes with fixed wetting abilities, smart
membranes using switchable wettability and the novel Janus
membranes used for oil–water separation is also covered in this
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review. These membrane materials with special wettability for
oil–water separation are summarized in Figure 4.
3.1. Superhydrophobic–Superoleophilic Membranes
Inspired by SHB surfaces from plants and animals in nature
(e.g., lotus leaf, legs of the water strider, and the eyes of mos-
quitos), a number of surfaces with similar wettability have been
applied for selectively separating oil–water mixtures.[62–65] Porous
membranes with both SHB and SOL abilities are typical oil–
water separation materials, which can allow oil permeate while
repelling water. Such functional membranes can separate oil
from the oil–water mixture and water-in-oil emulsions. The first
artificial SHB-SOL membrane was fabricated by Feng et al.[66]
in 2004 by spraying a polytetrafluoroethylene (PTFE) coating
layer on a stainless-steel mesh (SSM). The prepared membrane
possessed micro- and nanoscale surface roughness, exhibiting a
water CA (WCA) of 156° and a diesel oil CA (OCA) of 0 ± 1.3°
(Figure 5). The membrane surface showed the self-cleaning
property, similar wettability to lotus leaves.
Thereafter, many groups have been working toward fabri-
cating this type of membranes with such a wettability for oil–
water separation. Generally, such membranes are developed by
coating a film material with selective wettability onto porous
supports. To prepare a SHB-SOL membrane, it is essential to
construct superhydrophobicity using materials with HB nature
in chemical composition. In addition to chemical composition,
the surface microstructure (roughness) is another key factor in
the construction of specially wettable surfaces. Therefore, SHB-
SOL membrane materials can be constructed by two routes: the
first is to introduce sufficient roughness onto a hydrophobic
surface and the second is to tailor the surface chemical compo-
sition with a material of low surface energy. A SHB-SOL mem-
brane usually has a water CA > 150° and a tilting angle <10°
(also known as sliding angle, SA).
Although plenty of SHB-SOL membranes have been
developed for oil–water separation, there are some intrinsic
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Figure 5.  Scanning electron microscopy (SEM) images of a) the modified SSM membrane with an average pore diameter of ≈ 115 µm; b) the coating
film ((I) ball-like and (II) block-like microstructured shapes); c,d) SEM images of the balls and blocks, and (III) the nanostructured craters with high
resolution; e) water droplet on the modified membrane surface with a WCA of 156.2° ± 2.8°, and f) spreading and permeating behaviors of a diesel oil
droplet on the membrane. Reproduced with permission.[66] Copyright 2004, Wiley.

limitations for membranes with this type of wettability. First
of all, water with higher density may cause extra transfer
resistance between the membrane and oil, particularly in
gravity-driven membrane separation processes. Another fatal
problem is membrane fouling caused by the oils adsorption
onto membrane surface or membrane pores, especially when
the mixture is viscous and sticky, resulting in severe flux
decrease. These challenges will raise operation downtime,
membrane cleaning, and membrane replacement costs when
using SHB-SOL membranes.
3.2. Superhydrophilic–Underwater Superoleophobic Membranes
It is known that fish scales can be protected from oil contamina-
tion in underwater environment. A study pointed out that fish
scales were SHL (WCA < 5°) in air and UWSOB (OCA ≈ 156°).[67]
Learning from this, a series of SHL-UWSOB interfacial mate-
rials have been rapidly developed.[67–70] Compared with SHB-
SOL membranes (oil-removal), SHL-UWSOB membrane
materials aim for water-removal, which overcomes the draw-
backs (i.e., easily fouled and even clogged by oils) in using
SHB-SOL membranes.[71] SHL-UWSOB membrane materials
can separate water from oil–water mixtures and oil-in-water
emulsions, where water with higher density tends to permeate
through the surperhydrophilic membrane while oil is repelled.
In 2011, Xue et al.[72] reported a SHL-UWSOB polyacrylamide
(PAM) hydrogel coated membrane for the first time. The PAM
hydrogel-coated SSM membrane had a rough surface with
a discrete papillae structure (80–500 nm in size) and showed
an underwater superoleophobicity with 1,2-dichloroethane CA
of 155.3 ± 1.8° (Figure 6). The as-prepared membrane also
exhibited a low oil-adhesion under water and high separation
efficiency (>99%) for separating the mixing systems of water-
crude oil, water-gasoline and water-diesel.
So far, there are two types of biomemimetic SHL-UWSOB
membranes materials reported. The first one is inspired from
rough fish scales that are covered by a thin layer, and the
layer could consist of functional hydrogels or other coating
films.[67,73] The other type is based on short clams whose shells
are always clean under water.[74] It is believed that the inorganic
CaCO3 composition and hierarchical structure of the shells are
the key to maintaining the excellent underwater oil-repellent
property. To develop SHL-UWSOB membranes, there are two
typical strategies. The first is to determine the chemical com-
positions of the material surfaces (i.e., manipulate the surface
chemistry) that are adhesive to water and repulsive against oil.
The second is to create sufficient roughness (i.e., construct the
surface architecture) on the membrane surfaces. These mate-
rials always exhibit an OCA > 150° when immersed in water.
Although membranes with SHL-UWSOB properties can be
used for separation of oil–water mixtures by gravity, and are
more resistant to fouling, they are unsuitable for the separa-
tion of surfactant free o/w or w/o emulsions. This is because
both oil and water can easily permeate through them, unless all
pores of the membrane are pre-wetted by water. Consequently,
oil permeates through the membrane if water dries out from
even a single pore of the superhydrophilic membrane, which
typically happens in a matter of minutes.
3.3. Superhydrophilic–Superoleophobic (In-Air) Membranes
Considering to overcome the limitations of SHL-UWSOB
membranes discussed above, membranes with SHL-SOB
properties in air seem more promising for removal water phase

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Figure 6.  a) SEM images of the PAM hydrogel-coated SSM membrane (average pore size ≈50 µm). b) Photos of an oil droplet (1,2-dichloroethane,
DCE, 2 µL) on the membrane surface in water with a CA of 155.3° ± 1.8° and c) an SA of 2.6° ± 0.5°. d) Optical photos of the dynamic UW oil-adhesion
measurements on the membrane. An oil droplet (DCE, 5 µL) was used to contact the surface. e) Oil–water separation tests: the coated membrane
was mounted between two glass tubes and a mixture of crude oil and water was put into the upper glass tube. Water selectively permeated through
the coated membrane, while the oil was blocked in the upper glass tube. Reproduced with permission.[72] Copyright 2011, Wiley.

from oil–water mixtures. A hydrophilic surface generally displays
oleophilicity because oil commonly has lower surface tension
(≈20–60 mN m−1) than that of water (≈72 mN m−1). Therefore, it
is very challenging to fabricate hydrophilic–oleophobic (HL-OB)
interfacial materials. Several research groups found that HL-OB
materials contain some stimuli-responsive substances, simul-
taneously exhibiting HL and OB properties based on a positive
interaction with polar liquids and a negative interaction with
nonpolar liquids.[75,76] For example, the stimuli-responsivity
could be induced by a layer of poly­electrolyte-fluorosurfactant
complexes where the polyelectrolyte are HL while the fluorosur-
factant (an oppositely charged surfactant) are OB.[77]
Although some moderate HL-OB surfaces have been
reported,[75,77] development of SHL-SOB membranes is still
a challenge. Until 2012, Yang et al.[78] first developed a poly
(diallyldimethylammonium chloride)–perfluorooctanoate/SiO2
(PDDA–PFO/SiO2) nanocomposite coating film with both
superhydrophilicity and superoleophobicity. The abundant
fluorinated groups together with carboxyl and quaternary ammo-
nium groups from the PDDA–PFO complex film generated an
HL-OB surface. In addition, the embedded SiO2 nanoparticles
(NPs) provided micro- and nanoscaled hierarchical structures,
which enhanced the superhydrophilicity–superoleophobicity of
the membrane. When the PDDA–PFO/SiO2 film was deposited
on SSMs via spray-coating, the prepared metallic membranes
exhibited a water permeation and oil repellent behavior, and
successfully achieved separation of water-oil mixture (Figure 7).
Besides, the coated-membranes are reusable after water rinsing.

Figure 7.  a,b) SEM images of the SSM membrane spray-coated with PDDA-PFO/SiO2 nanocomposite. c) Water droplet spreading on and permeating
through the membrane. d) A hexadecane droplet on the membrane surface with a CA of 157°. e,f) An oil–water separation test was conducted with
the modified membrane. Adapted with permission.[78] Copyright 2012, Royal Society of Chemistry.

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Figure 8.  Schematic illustration of the superhydrophobicity and superoleophobicity of the functionalized PET fabrics membrane. a) When pre-wetted
by oil, water droplet is blocked on the ZnO nanostructure. b) When pre-wetted by water, water can permeate the ZnO nanostructure while oil droplets
are blocked. Reproduced with permission.[82] Copyright 2015, Elsevier.
In the same year, Tuteja et al.[79] reported a hygroresponsive
membrane with superhydrophilicity and superoleophobicity
both in air and underwater. They successfully coated fluorodecyl
polyhedral oligomeric silsesquioxane (POSS) and cross-linked
polyethylene glycol diacrylate (x-PEGDA) complex onto porous
substrates, such as SSMs and polyester fabrics by dip-coating.
In air, the membrane surface was superoleophobic (rapeseed
OCA = 152°) due to the fluorodecyl POSS aggregates. When
the membrane was immersed in an aqueous environment, the
fluorodecyl POSS aggregates disappeared due to surface recon-
figuration caused by water molecules. The membrane could
separate surfactant-stabilized o/w and w/o emulsions with diam-
eters ranging from 10–20 µm by gravity with high separation
efficiency (>99%). Significantly, they utilized a coupling process
with a hygro-responsive membrane module and a conventional
HB-OL membrane module assembly in tandem for continuous
separation of oil–water emulsions, and it was found that the
fluxes of both water and oil did not reduce over a period of 100 h.
For SHL-SOB (in-air) membranes, intermolecular force
between membrane surface and water varies, while that
between membrane surface and oils stays the same. In compar-
asion with SHL-UWSOB, SHL-SOB membranes showed more
technical merits in oil–water separation applications. However,
fabrication methods of the SHL-SOB membranes are more
complicated and challenging. Although a growing number of
research groups has been working on the development of SHL-
SOB membranes and the corresponding application of these
membranes, membranes with such a special wettability are still
lack of investigation.
3.4. Superamphiphilic (In-Air) Membranes
Superamphiphilic, literally, represents superhydrophlic and
superoleophilic (in-air). Superamphiphilic membranes are
switchable in wettability, i.e., UWSOB or under oil (UO) SHB.
Compared with other types of membranes, superamphiphilic
membranes are capable for separating a wider scope of oil–
water emulsions, including both o/w and w/o emulsions. When
placed in o/w emulsions, water in the rough surface structure
can form a barrier between oil and the membrane surface to let
water permeate but repel oil, leading to UW superoleophobicity.
In contrast, superamphiphilic membranes can block water and
let oil permeate showing UOSHB wettability when used for
w/o emulsion system. To achieve this superior superwetting
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ability, the recent reported membranes are mainly based upon a
prewetting induction mechanism.[80]
One of the first reports on superamphiphilic membranes was
from Tao et al.[81] in 2014. They fabricated porous superamphi-
philic poly (vinylidene fluoride) (PVDF) membranes using a
nonwoven fabric (NWF) as a template via the phase inversion
method. Interestingly, the both UW oil and UO water droplets on
the membrane surface have CAs of 157° and 156°, respectively.
It is believed that the special (UWSOB and UOSHB) wettability
was mainly attributed to the hierarchical surface structure of the
membrane. Varying microstructures with four different sizes
and shapes, involving randomly aligned grooves, closely stacked
spherulites, petaloid microstructures, and nanofibrils, lead to a
rather raspy membrane surface (> 3500 nm in roughness) and
the corresponding superamphiphilicity.
Shortly after, Xiong et al.[82] reported an atomic-layer-
deposition-enabled nonwoven superamphiphilic membrane
with hierarchical ZnO nanostructures for switchable water-oil
separation. The membranes could separate any phase in the
oil–water mixture simply by pre-wetting the membrane surface
with the heavier component, showing excellent separation
efficiency and stability even under gravity driving force. The
superamphiphilicity was attributed to the prewetting process, in
which a thin layer of water or oil “cushion” was formed on the
interface between the ZnO hierarchical nanostructure and water
or oil, resulting in UWSOB or UOSHB properties (Figure 8).
The crucial role of prewetting was also identified in by another
group[83] and they successfully developed a switchable superam-
phiphilic membrane for oil–water separation as well.
The superamphiphilic ability endows membranes with
switchable transport characteristics, which features unique
separation efficiency, permeability and antifouling property
for various o/w and w/o emulsion separations. However,
understanding of the structure-chemistry-superamphiphilicity
mechanisms is still insufficient. Other emerging switchable
superamphiphilic mechanisms, such as CO2-induced,[84] pH-
sensitive,[85] photoresponsive[86,87] superamphiphiles, may
provide new strategies to fabricate novel oil–water separation
membranes.
3.5. Superomniphobic Membranes
In contrast to membranes with selectively superwetting
ability for water against oil or vice versa, superomniphobic
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Figure 9.  Schematic illustration of the synthetic routes of the modified membrane: a) pristine
PTFE fibrils, b) coating with ZnO film, and c) grafting monomer under plasma. Reproduced (PTFE) membrane with enhanced antifouling
with permission.[101] Copyright 2016, American Chemical Society.
membranes are super anti-wetting, repelling both oil and
water. As discussed above, the surface tension of oil is gener-
ally smaller than that of water, SHB materials in air often suf-
fers from oil-wetting.[88] In most superhydrophobic cases, the
intermolecular forces between oil molecules and solid surface
molecules/atoms are attractive forces, which allows oil to wet
the surface. However, recently materials with both SHB and
SOB properties have been fabricated.[89–94] SHB surfaces dis-
play apparent WCA > 150° and low CA hysteresis, while SOB
surfaces display CA > 150° and low CA hysteresis to low sur-
face tension substances (i.e., oils). Superomniphobic surfaces
display both superhydrophobicity and superoleophobicity.[95]
Preventing wetting of MD membranes is particularly chal-
lenging in treating shale gas wastewater with high levels of
surfactants or low surface tension oily contaminants as these
impurities may significantly reduce the liquid entry pressure
of the membrane.[96,97] To overcome this problem, novel MD
membranes with omniphobic surfaces that repel not only water
but also oil with low surface tension were reported by Elimel-
ech’s group in 2014.[98,99] They fabricated an omniphobic mem-
brane for MD by coating a hydrophilic glass fiber membrane
with silica NPs, followed by subsequent surface fluorination
and polymer coating. The omniphobic membrane had a high
WCA near 150° and could not be wetted by mineral oil, eth-
anol, and decane (CA in the range of 70°–110°). Although the
oleophobic property of the membrane was not superior because
the WCA of their membrane was lower than 150° and the CAs
of the membrane with those low surface tension liquids are still
hard to surpass 140°, it still opened a new way to develop mem-
brane materials with special wettability.
Recently, a real sense of superomniphobic membranes were
successfully fabricated and used in contacting membrane tech-
nology, which can efficiently prevent wetting of membrane pores
by the capturing media. Geyer et al. [100]
fabricated chemically and
mechanically robust superomniphobic flat-sheet membranes
based on a polyester fabric. Thick hydrophilic fabrics with inter-
woven networks of fibers were first immersed in toluene con-
taining trichloromethylsilane forming silicone nanofilaments,
and then were activated in an oxygen plasma and modified with
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1H,1H,2H,2H-perfluorodecyltrichlorosilane
to reduce the surface energy. The prepared
superomniphobic membranes could keep
their super liquid-repellency (CAs > 150°)
for water, methyl diethanolamine (MDEA),
ethylene glycol (EG) and hexadecane.
Although the membranes are designed for
membrane contactor applications and the
preparation method seemed complex, it still
offers useful insights into developing and
using superomniphobic membranes.
In addition to MD and membrane
contactor applications, omniphobic mem-
branes have also been used for oil aerosol
removal. Feng et al.[101] fabricated an omni-
phobic 1H,1H,2H,2H-perfluorodecyl acrylate
(PFDAE)-grafted ZnO@polytetrafluoroethylene
functionality and high removal efficiency.
They used atomic-layer deposition (ALD) to
coat a layer of ZnO nanoparticles onto porous PTFE matrix to
increase surface area, and then grafted PFDAE with plasma
(Figure 9). Consequently, the membrane surface showed both
superhydrophobicity and oleophobicity with a WCA and an
OCA of 150° and 125°, respectively. The membrane exhibited
exceptional organic aerosol removal efficiencies (>99.5%).
According to above cases, modifying straight- or branched-
chain molecules with fluoridated groups oriented outward on
the surfaces, the intermolecular repulsive force between oil
molecules and solid surface can be enhanced.[95] Omniphobic
membranes opens new opportunities for MD by expanding
its applications in treating oily wastewaters with low surface
tension contaminants. Other membrane contactors and direct
membrane filtration process using omniphobic membranes
are also very promising for the treating media with low surface
tension substances. It is still challenging to fabricate superom-
niphobic membranes and further studies are needed to explore
other fabrication techniques and correspondingly optimize the
performance of superomniphobic membranes.
3.6. Smart Wettability in Membranes
A surface sensitive to a certain external stimulus and then
producing a peculiar response, is defined as smart surface.[102,103]
Artificial smart interfacial materials with switchable wetting
behaviors have attracted growing interest, particularly in their
fabrications and applications for oil–water separation.[104,105]
Besides superamphiphilic (in-air) membranes that mainly
follow a special pre-wetting media-induced switchable
wettability mechanism, switchable oil–water separation based
on smart membrane surface can be realized by external stimuli,
such as light,[106–108] pH,[109–112] temperature,[113,114] electrical
field,[115,116] and magnetic field (Figure 4).[117–119] Most recently,
membrane materials with smart wettability based on these
mechanisms, have been developed for controllable oil–water
separation. These smart membranes have opened new strategies
for the treatment of oil contaminated water to meet different
demands.
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Figure 10.  Photoinduced wettability of the aligned ZnO nanoarrays-coated mesh membrane: a) Images of a water droplet on the modified membrane
when placed in dark (left) and under UV irradiation (middle) in air with a CA of ≈155° and ≈0°, respectively. The water droplet can permeate through
the membrane (right). b) Images of an oil droplet (DCE) on the mesh membrane in air (left) and UW (middle) with a CA of ≈0° and ≈156°, respectively,
and an SA of ≈2.6° (right). c) The membrane was mounted between a glass funnel and glass tube for oil–water mixture separation. A small amount
of water was added into the glass funnel to form a water environment and ensure the stability of the device before the mixture of crude oil and water
was poured in. d) Once UV light irradiated the membrane, water selectively permeated through the membrane, while the oil was repelled and kept in
the glass funnel. Reproduced with permission.[121] Copyright 2012, Royal Society of Chemistry.

Light is a very common external stimulus of smart
materials. Many transition-metal oxides (e.g., ZnO, TiO2,
WO3, and V2O5) have proved their photoresponsive wettability
under light irradiation.[120] Tian et al.[121] created a photo­
induced oil–water separation membrane with switchable
superhydrophobicity–superhydrophilicity and UW supero-
leophobicity, based on a ZnO nanorod-deposited SSM. The
as-prepared mesh membrane exhibited interesting UV light-
dominated wettability for separating oil–water mixtures
(Figure 10). Gao et al.[122] also prepared a double-layer TiO2-
based mesh membrane exhibiting switchable wetting behav-
iors under UV light irradiation. The upper layer was a TiO2
coating film with hybrid micro- and nanostructures prepared
by a facile hydrothermal process, and the lower layer was the
same TiO2 mesh film but modified by octadecyl phosphonic
acid (ODP). The prepared membrane is SHB-SOL allowing
fast oil penetration, while the surface SHB property can be
converted into SHL due to the photodecomposition of ODP by
TiO2 under UV light.
Polymers with acid or basic functional groups are always
sensitive to pH conditions showing pH-driven properties. By
grafting a block copolymer comprising of pH-responsive poly
(2-vinylpyridine) (P2VP) and HB-OL polydimethylsiloxane
(PDMS), Zhang et al.[105] developed a series of pH-responsive
smart membrane surfaces exhibiting switchable superoleophi-
licity and superoleophobicity for controllable oil–water separa-
tion. The P2VP block could alter its chemical conformation and
the corresponding wettability via protonation and deprotona-
tion under varying pH environments. Using their membranes
to separate a mixture of gasoline and water at pH 6.5, gasoline
can pass though the membrane quickly while water is blocked.
However, when the membrane is pre-wetted in an acidic water
with a pH of 2.0, the opposite separation behavior is realized
(i.e., water removal). Xiang et al.[111] developed a smart PVDF
membrane by incorporating pH-responsive N,N-dimethyl-
aminoethylmethacrylate (DMAEMA) hydrogels for oil–water
separation. The prepared membrane was UO HB and UW
OL at a pH of 7.4, but UW OB at a pH of 2.0 (Figure 11). The

Figure 11.  pH-responsive wettability of the PVDF membrane. a) A static WCA (4 µL water) at pH of 2.0 and 7.4 under n-hexane; b) an oil droplet
(chloroform, 3 µL) on the membrane surface in pure water at pH 7.4; c) an oil droplet (chloroform, 3 µL) on membrane surface in HCl-induced acidic
water with pH of 2.0. d) Schematic representation of the switchable oil permeability on the modified PVDF membrane under water at a pH of 7.4
(upper) or 2.0 (lower). Reproduced with permission.[111] Copyright 2015, Royal Society of Chemistry.

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pH-responsive wettability was caused by the protonation or
deprotonation of the tertiary amine side-groups (Figure 11d).
The pH-responsive PVDF membrane shows excellent perme-
ability, selectivity and antifouling performance in the separation
of surfactant-stabilized w/o and o/w emulsions. Guo et al.[123]
used a mixture of carboxyl- and methyl-terminated thiols to
modify a hierarchical structured copper mesh (CM) membrane.
By tuning the pH of aqueous media, protonation and deproto-
nation phenomenon are also found on membrane surface. The
membrane showed SHB-SOL to neutral and acid water yet SHL
to basic water, make it a smart membrane for bi-directional
oil–water separation.
Thermal (temperature) response has also been consid-
ered promising for controlling the wettability of an interfacial
material. Poly(N-isopropylacrylamide) (PNIPAAm) with a low
critical solution temperature (LCST) of about 32–33 °C has
been widely used to fabricate a thermal-sensitive surface with
switchable wettability.[124] Xue et al.[125] reported a polymethyl-
methacrylate (PMMA)-b-PNIPAAm block copolymer modified
mesh membrane, which are reversible in wettability between
HL-OB and HB-OL characteristics at different temperatures
(Figure 12). Interestingly, water could pass through the block
copolymer-modified membrane but oils could not when the
temperature < LCST; oil could penetrate the membrane but
water could not when the temperature > LCST. Additional,
Yu et al.[126] also developed a thermal-responsive surface which
shows great potential for oil–water separation applications. The
thermal-responsive silicon nanowire arrays (SiNWAs)-PNI-
PAAm surface can change its superhydrophilicity (WCA of 0°)
to strong hydrophobicity (WCA of 120°) from 23 °C to 37 °C.
Those thermal responsive membranes with controllable dual
water-oil on-off switch offer a promising tool for oil–water mix-
tures separation.
Electric field can also endow membrane surfaces with switch-
able wettability. For example, Liu et al.[127] reported a reversible
transition between SOB and SOL based on aligned polypyrrole
nanotube arrays, controlled by electrochemical driving poten-
tial. Their discovery opens a new strategy to develop smart
membranes for oil–water separation. In 2012, Tuteja et al.[5]
applied electric filed to switch the wettability of a nontextured
membrane and their unprecedented membrane process could
separate all types of oil–water emulsions with high separation
efficiency (>99.9%) by gravitiy and electric field (Figure 13).
Currently, magnetic field could not control the wettability of
membrane surfaces but it provides driving force to manipu-
late the transfer of magnetic fluid on interfacial materials with
special wettability for efficient oil–water separation. Recently,
Feng et al.[128] fabricated a tri-phase water-oil-solid nanoarray
interface that are UWSOB (UW OCA = 156°). The prepared
ZnO nanoarrays consisted of uniformly aligned nanorods with
diameter of 150–250 nm and length of ≈6 µm. After UV treat-
ment, the resulted ZnO nanoarrays showed superhydrophilicity
and superoleophilicity in air (WCA 6° and OCA 9°). Oil transfer
on the SOB ZnO nanoarrays could be controlled by a mag-
netic fluid via magnetic field. As shown in Figure 14, a ZnO
nanoarray-coated glass substrate were used to investigate the
top and the bottom interfaces in water. When an external mag-
netic field was put on the substrate top, the magnetic fluid
droplet became magnetized immediately and went toward the
substrate top, moving from the left to the right side by the mag-
netic field. Once the magnetic field was removed, the magnetic
fluid was demagnetized and fell down to the oil droplet due to

Figure 12.  a) Temperature dependences of WCAs and OCAs of the PMMA-b-PNIPAAm membrane: (I) WCAs increase from 42° to 107° and (II) OCAs
drop from 137° to 36° with the temperature rise from 10 to 40 °C. Inset images (1–4) are the WCAs and OCAs obtained at 10 and 40 °C, respectively.
b) Reversible water and oil CA transition on the membrane surface at different temperatures (10 °C, < LCST; 40 °C, > LCST). c) Schematic diagram
of reversible formation of intermolecular hydrogen bonding between PNIPAAm chains and water molecules below the LCST, which results in hydro-
philicity/oleophobicity, and intramolecular hydrogen bonding between CO and NH groups in PNIPAAm chains above the LCST, which leads to
hydrophobicity/oleophilicity. Reproduced with permission.[125] Copyright 2013, Wiley.

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Figure 13.  a) CAs for water and hexadecane (HD) as a function of applied voltage on the nontextured substrate. b,c) The CA of HD keeps unchanged
with increasing voltage. d,e) The CA of water decreases with increasing voltage. f) A schematic representation of the sagging at the liquid–air interface.
g) An apparatus with a liquid column of free oil (dyed red) and water (dyed blue) above the membrane before applying an electric field. h) Water permeates
through while hexadecane is repelled above the membrane when a voltage V ≈ 2.0 kV is applied. Reproduced with permission.[5] Copyright 2012, Wiley.

gravity. The mixed large magnetic oil droplet was stable at the
bottom ZnO nanoarray, which can be moved back to its initial
location driven by the external magnetic field. No losses of the
oil and magnetic fluid droplets were found during the magnetic
field-driven movement.
In general, membrane surfaces exhibiting switchable wetta-
bility are often fabricated by top-down method (assembly rough
microstructures on a stimuli-responsive material surface) or
bottom-up method (constructing rough interface with stimuli-
responsive molecular layers). These artificially intelligent
membranes with switchable wettability show great potential in
various oil–water separation applications. Nevertheless, there
are still very few reports on stimuli-responsive membranes for
practical oil–water separation so far and the relevant research is
still in its early stage. In addition, the existing types of special
stimuli-responsive materials are relatively rare which limits the
development of stimuli-responsive membranes. Further efforts
for fabricating controllable oil–water separation membranes
might be also concentrated on attempting new types of respon-
sive materials or integrated dual-/multi-responsive materials.

3.7. Janus Membranes

The Janus concept is originated from the

double-faced Roman god Janus. Janus
materials have asymmetric properties (e.g.,
wetting and charge) on each side. Such
materials widely exist in nature. For example,
the upper side of a lotus leaf is SHB in air,
and the lower surface is UWSOB, endowing
the lotus leaf self-cleaning in air and UW oil-
repellent properties.[129] Inspired by nature,
much research efforts have been made into
Figure 14.  The manipulation and movement of a UW oil droplet by a magnetic fluid droplet
Janus materials regarding their fabrication,
on the aligned ZnO arrays. a–c) The magnetic fluid droplet movement and transfer process.
d–f) The magnetic fluid droplet combines with the oil droplet with a following movement and characterization and applications.[130] A Janus
transfer process. The red triangle in each figure is the oleophilic area for fixing the droplet. membrane generally has opposing properties
Reproduced with permission.[128] Copyright 2016, Wiley. on each side (e.g., wettability, morphology

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Figure 15.  a) Schematic illustration of synthetic routes of Janus-C membrane. b) Unidirectional sions. For the o/w emulsion separation, the
penetration demonstrated by dropwise addition of water droplets (≈ 20 µL per drop) onto HB
side (top) and HL side (bottom) of the membrane. c) Directional water droplet penetration membrane was overtunred for the separation
across the membrane in UO systems. The membrane allows water droplet penetration when
the HB side is exposed to oil and prevents water penetration when reversely aligned. Repro-
duced with permission.[137] Copyright 2014, Wiley.
and surface charge[131–133]), which can be fabricated by direct
asymmetric fabrication or asymmetric post-modification.[134]
Special transport behaviors and auxiliary functions in Janus
membranes are useful for development of various advanced
oil–water separation processes.
The directional transport phenomenon inspires researchers
to prepare Janus membranes for oil–water separation.[135] For
a Janus membrane with one hydrophilic layer and one hydro-
phobic layer, water droplets could slowly penetrate through the
membrane from the hydrophobic side and rapidly spread to
the hydrophilic side. In that case, water might be pulled to the
hydrophilic layer by gravity when the hydrophobic layer is thin
enough. Hence, the thickness of the two layers with oppo-
site wettability and the driving force play vital roles in liquid
permeation. Most recently, Wang et al.[136] synthesized a Janus
membrane with both HL polyamine and SHB PDMS surfaces
to separate oil from an o/w emulsion by exposing the HL side
to the emulsion. For the separation process, water could wet
the HL surface but not pass through the entire membrane due
to the SHB barrier. Meanwhile, the polyamine layer demulsi-
fies the emulsion and assist the re-coalescence of oil droplets.
Followed by that, the oil fills into the SHB pores, which further
prevents the water permeation and pushes the oil transport.
The work achieves oil demulsification and oil–water sepa-
ration by the Janus membrane based on the unidirectional
transport of oil and water. Similarly, Tian et al.[137] fabricated
a thin 1H,1H,2H,2H-perfluorooctyltrichlorosilane (POTS)-
induced HB layer onto a HL cotton membrane (Figure 15).
By exposing the HB side to water in air (positive direction), the
water droplets permeates spontaneously from the HB to the HL
side. Whereas if the membrane is overturned (reverse direction),
water droplets are blocked and spread on the HL side. Besides,
when the membrane is placed UO in a positive direction, water
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can penetrates easily through it. In contrast,
water is blocked at the HL side UO when the
membrane is reversely configured.
The directional liquid transport behaviors
make Janus membranes with integrated
selectivity, which are intriguing and useful
for development of various separation appli-
cations, especially advanced oil–water sepa-
ration. For instance, two differently wettable
surfaces of a Janus membrane can work
individually and the membrane becomes
switchable in treating oily water by changing
the side exposed to the feed. Gu et al.[138]
reported a Janus polymer/carbon nanotube
(CNT) composite membrane by grafting HL
poly(DMAEMA) and HB poly(styrene) onto
each side, respectively. They successfully
employed the Janus membrane to separate
both surfactant-stabilized o/w and w/o emul-
HL side was exposed to the feed, while the
of the w/o emulsion.
Additionally, there are some stimuli-
responsive Janus membranes showing
switchable wettability by adjusting the
operating conditions. Because the asymmetric nanochannel can
act as a selective ion channel dominated by pH conditions,[139]
a composite CaWO4/MnO2 nanowire membrane reported
by Zhang et al. shows varying sets of wettability (i.e., HL/
HL, HB/HL and HB/SHB) when immersed in different pH
aqueous environments and the pH adjustable channels and
could be used for oil–water separation.[140] It is worth noting
that pressure-responsive wettability could be also realized by
Janus membrane due to its unique asymmetric structure. Jin’s
group[141] reported a pressure-responsive Janus membrane for
ultrafast separation of oil–water emulsions by depositing an
ultrathin layer (HL-UWOB) of polydopamine-coated single-
walled CNTs (SWCNTs) on to a porous cellulose ester substrate
and subsequently coating with another ultrathin SWCNT
layer (HB-SOL) via the vacuum suction method (Figure 16).
The applied pressure is crucial in the oil–water separa-
tion processes: when the applied pressure is higher than oil
intrusion pressure but lower than water intrusion pressure,
the membrane shows extremely high separation efficiency
(>99.95%) for w/o emulsion; similarly, when the applied pres-
sure is higher than water intrusion pressure but lower than oil
intrusion pressure, the membrane also exhibits outstanding
separation performance (i.e., separation efficiency > 99.99%)
for o/w emulsion.
Preparation and application of Janus membranes is still an
emerging research area. Practical oil–water separation applica-
tions may be beneficial from the unique (i.e., directional and
switchable) wettability offered by Janus membranes. However,
like other membranes with special wettability, constructing
heterogeneous structures and surfaces remains challenging.
Unknown influencing factors such as stimuli-responsive
effects on membrane configuration are required further
exploration.
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Figure 16.  a) SEM image of the as-prepared membrane. Inset: digital photo of the free standing bilayer membrane. b) The schematic structure of the
ultrathin bilayer membrane and a proposed pressure-responsive mechanism for on-demand oil–water separation. c) Water and oil CAs of the prepared
membrane. Reproduced with permission.[141] Copyright 2015, Royal Society of Chemistry.
4. Membranes for Oil–Water Separation
Although a wide range of membrane processes with different
wettability have been attempted in oil–water separation
field, membrane filtrations are the most predominant. In
comparison with Section 3 that focus on the recent advances
of novel special wettability in membrane materials, this sec-
tion comprehensively summarizes the synthetic methods
and applications of filtration membranes beneficial from
the special wettability for oil–water separation. Membrane
filtration processes follows complicated principles, e.g.,
adsorption, size-sieving, and electrostatic phenomenon.[3]
Conventional filtration membranes applied for separating
oily water are mainly followed by the “size-sieving” effect
driven by pressure, in which oil droplets with certain sizes
are not allowed to pass through the “pores” of the mem-
brane. With the deeper understanding of surface chemistry,
functionalization of filtration membranes with special wet-
tability could not only endow the membranes with superior
antifouling property but also lead to favourable synergetic
effects for improving the selectivity and separation efficiency
in practical applications.
It is well-known that filtration membranes can be catego-
rized by pore sizes or material types. For a conventional MF
process based on membranes with pore size ranging from
50–1000 nm, a specific operation pressure (also known as
transmembrane pressure) is required. However, there are
many oil–water separation membranes with special wettability
breaking out of their dependence on transmembrane pres-
sure. Thus, it is not appropriate to classify specially wet-
table oil–water filtration membranes according to their pore
sizes and this section is divided into four parts on the basis
of membrane materials: metal-, polymer-, ceramics-, and
nanomaterial-based. Notably, functionalized membranes are
generally fabricated with complicated fabrication procedures
and the use of harmful chemicals. Green process or using
environmentally benign materials at low-cost should be also
concerned for practical applications.[142–145]
4.1. Metal-Based Membranes
Inorganic membranes refer to membranes made of materials
such as oxides, nonoxides, carbon, metal organic frameworks,
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zeolites, metals, etc.[146–149] Inorganic membranes can be classi-
fied into two major categories based on their structures: porous
inorganic membranes and dense (nonporous) inorganic mem-
branes. Dense metallic membranes (e.g., Palladium mem-
brane) have been dominantly considered for the separation of
hot gases for ages[150] while porous thin metallic membranes
(e.g., SSM, CM, and silver membrane) with pore sizes ranging
from micro- to nanometer level have also been widely used for
water filtration. Recently, numerous bioinspired membranes
with special wettability have been fabricated on porous metallic
meshes, which can be used for separating all categories of oil–
water mixtures. It should be noted that the metallic mesh sub-
strates always have larger pore sizes than the oil droplet sizes,
but the modified substrates with rough micro- and nanostruc-
tures show exceptional separation efficiency and high flux.
The inevitable tradeoff relation (between selectivity and per-
meability) in membrane material world seems to be broken.
In addition, those metallic mesh membranes have robust sur-
faces, harsh-environment resistance and unique repeatability,
which make them suitable for practical oil–water separation
application.[151–154] Metallic mesh membranes are fabricated by
various surface modification approaches including but not lim-
ited to the layer-by-layer self-assembly (LbLSA) method,[155,156]
hydrothermal method,[157,158] and other coating methods.[159–161]
Table 1 displays some typical metallic mesh-based membranes
for oil–water separation in terms of substrates, preparation
methods, oil–water mixing systems, types of wettabilities and
separation efficiencies.[72,73,151,152,157,161–170]
Typically, Li et al.[161] prepared a series of coating layers with
hierarchical nanostructure and dual roughness onto SSMs
via LbLSA of SiO2 NPs. Followed by surface HB modification
using chemical vapor deposition (CVD), their membranes
could separate surfactant-free o/w emulsions through a non-
sieving mechanism achieving an extremely high separation
efficiency (99.4%). They found that increasing the deposition of
SiO2 NPs can rise the surface roughness of the SSM resulting
in superhydrophobicity (WCA ≈ 158°), which was attributed to
the existence of air trap in the hierarchically structured surface.
After repeating o/w emulsion filtration for 20 cycles, the sepa-
ration efficiency remained as high as 99.2%, which suggested
the coating was highly stable and durable.
Additionally, CM is another good substrate for oil–water
separation because it is easy to be processed by electrochem-
ical modification. Wang et al.[168] developed hierarchical CM
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Table 1.  Metallic mesh-based membranes for oil–water separation in terms of different substrates, modification methods, separation application,
CAs, types of wettability, and features.

Metallic membranes Modification methods WCA [°] OCA [°] Wettability Application Features Ref.
SiO2 modified SSM LbL, CVD 158 n-hexadecane, 115 SHB-OL o/w HSE [161]
MWCNTs deposited SSM CVD 150 Gasoline, 0 SHB-SOL w/o HP [164]
Glass nanofiber-coated SSM Hydrothermal 0 UW oils > 150 SHL-UWSOB o/w GD [157]
MFI zeolite-coated SSM Hydrothermal 0 UW oils > 151 SHL-UWSOB Layered o-w mixture GD [162]
PSBMA/PDA-modified SSM Dip coating 0 UW oils > 150 SHL-UWSOB w/n-hexane GD [151]
NDM/PDA-modified SSM Dip coating 144 0 HB-SOL w/diesel oil GD [163]
GO coated SSM Dip coating/O2 plasma 0 UW oils > 150 HL-UWSOB w/bean oil GD [73]
BiVO4 coated SSM Dip coating/calcination 0 UW oils > 150 SHL-UWSOB w/bean oil SC [152]
PAM hydrogel-coated SSM In situ polymerization 0 UW oils > 150 SHL-UWSOB Layered o-w mixture GD [72]
CNFs-PDMS modified SSM Vacuum suction 163 Toluene, 0 SHB-SOL w/o HP [166]
Fatty acid modified CM Electrodeposition >158 Diesel oil, ≈0 SHB-SOL w/n-hexadecane GD [168]
Cu NPs modified CM Electrodeposition 154.1 chloroform, 0 SHB-SOL w/chloroform GD [169]
Hexadecylthiol modified CM Dip coating 153 ± 1 Diesel oil, 0 SHB-SOL w/diesel oil GD [170]
AgNO3 modified CM Chemical modification 0 UW oils > 159 SHL-UWSOB w/n-hexane GD [167]
ZnO–Co3O4 overlapped CM Hydrothermal UO 157.9 UW, DCE, 159.2 SHL-SOL o/w and w/o GD [165]

Note: HSE, high separation efficiency; HP, high permeability; GD, gravity-driven; SC, self-cleaning; AF, antifouling; DCE, 1, 2-dichloroethane; DCM, dichloromethane; PW,
produced water; o/w, o/w emulsion; w/o, w/o emulsion.

membranes by electrochemically depositing copper micro-
clusters on the mesh surface. After immersing the textured
CM membranes in n-dodecanoic acid for 12 h, the mem-
brane surface had a WCA of 158 ± 2° with an SA of 2° and
a diesel OCA ≈0°. The developed SHB-SOL membrane was
found to be an effective diesel oil and water separator. Guo’s
group[169] adopted the similar electrochemical approach and
deposited a 2 µm-thick copper NPs layer on the surface of a
CM. After n-octadecyl thiol grafting, the membrane surface
exhibits a WCA of 154.1° and an OCA of chloroform of 0°.
A mixture of chloroform and water could be efficiently sep-
arated by the prepared mesh membrane solely driven by
gravity. Besides of electrochemical deposition, Wang et al.[170]
utilized a facile solution-immersion process to prepare SHB-
SHL (WAC = 153 ± 1° with SA < 5°, diesel OCA = 0°) CM
surface. The commercial CM was first etched by nitric acid
and then chemically modified with 1-hexadecanethiol (HDT).
The membrane could not only be applied for diesel ultrafast
oil–water separation through a simple filtration process, but
also showed excellent stability in corrosive acidic, basic, and
salt solutions.
Hydrothermal synthesis also provides a facile tool to modify
metallic mesh membranes for oil–water emulsion separa-
tion because it can easily grow large good-quality crystals
on membrane surface. For example, Liu et al.[165] prepared a
zinc oxide–cobalt oxide (ZnO–Co3O4) overlapped membrane
based on a hydrothermal method. The mesh pores was first
filled with pine needle-like ZnO, which aggregated together to
form a cluster structures. After hydrothermal growth of Co3O4,
the flower-like Co3O4 was uniformly distributed and coated
on the ZnO-stuffed mesh surface. Figure 17a,b schematically
shows that the overlapped membrane exhibits superoleopho-
bicity and UO superhydrophobicity at the same time. The
membrane could separate both surfactant-free and surfactant-
stabilized oil–water emulsions (including o/w and w/o) under
gravity with a high flux and separation efficiency (Figure 17c).
In conjunction with excellent antifouling property, superior
thermal stability as well as long-term use, this inorganic over-
lapped membrane showed great potential in industrial oily
wastewater treatment.
4.2. Polymer-Based Membranes
Owing to the remarkable advantages including low cost, promi-
nent flexibility, excellent processability and ease of operation,
polymeric MF and UF membranes made of polysulfone
(PSf),[171–174] polyethersulfone (PES),[175–178] PVDF,[179–181]
etc., have been widely used in oily water treatment.[182–184]
These membranes, however, are easy to trigger a cascade of
events such as accumulation, adhesion, spreading, coales-
cence and migration of suspended oil foulants as well as inevi-
tably getting clogged during treating oily wastewater, which
results in flux decline and rejection deterioration. Numerous
approaches have, thus, been developed improve hydrophi-
licity and antifouling property of the polymeric membrane by
either blending with beneficial additives or altering its surface
properties via chemical or physical modification.[24] Moreover,
polymer chemistry also provides more advanced methods such
as atom transfer radical polymerization,[185] in situ polymeri-
zation,[186] and interfacial polymerization,[187] which have also
been explored in order to prohibit membranes from fouling.
A summary of polymeric membranes for oily water treat-
ment is given in Table 2 and it is apparent that the special
wettability plays a crucial role in enhancing their separation
performance.[172–174,179,181,188–203]

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Figure 17.  a) Schematic structure of the ZnO-Co3O4 overlapped membrane and its switchable wettability when immersed in different media, and the
corresponding separation capacities of oil–water emulsions. b) Wetting behavior of the membrane toward water in air and oil in water. c) Separation
performance to various emulsions: i) Tween 20-free diesel-in-water emulsion, ii) tween 20-stabilized diesel-in-water emulsion, iii) Span 80-free water-
in-diesel emulsion, and iv) Span 80-stabilized water-in-diesel emulsion. Reproduced with permission.[165] Copyright 2015, Nature Research.

Blending a polymer matrix with beneficial additives like
hydrophilic polymers, amphiphilic copolymers and inorganic
nanoparticles during the phase inversion process is an effective
and easy-to-use method to improve the selectivity and fouling
resistance of the porous polymeric filtration membranes.[9] An
SHB-SOL PVDF membrane was fabricated by Zhang et al.[188]
by using an inert solvent-induced phase-inversion process
(Figure 18). The prepared PVDF membranes were, for the first
time, able to separate both micrometer and nanometer sized
surfactant-free and surfactant stabilized w/o emulsions solely
driven by gravity, with a high flux and separation efficiency.
Amphiphilic copolymers that are composed of both HL and
HB segments are also used as additives to blend with host
polymers.[204–206] Mayes and co-workers[207] first used a comb-
like copolymer P(MMA-r-POEM) (i.e., PMMA back bone and
poly(ethylene oxide) side chain) as an additive. The amphi-
philic polymer was blended into PVDF to form membranes
via surface segregation. Their results demonstrated that the
antifouling property of the membrane was greatly improved,
whereas the membrane structure could be maintained. Since
then, many amphiphilic copolymers, such as tri-block,[208]
comb-like,[209] and branched copolymers,[210] have been used
as additives to blend into host polymers to produce composite
membranes with enhanced antifouling properties. Among
these copolymers, ternary copolymers containing an HB
“anchoring” segment, HL fouling resistance segment or non-
polar HB segment with low surface free energy have received
much attention because of their structural merits.[211] During
the phase inversion process, dragged by the HL segments,
the nonpolar HB segment tends to migrate to the membrane
surface to form microdomains. These microdomains are
advantageous to antifouling performance because of their
low surface free energy. Thus, the flux decline of the mem-
brane could be greatly reduced during the separation of the
o/w emulsion.
In addition to polymeric additives, inorganic nanoparticles,
such as Al2O3, TiO2, ZrO2, and SiO2, have also been used to
blend with host polymers.[24] It is well known that nanopar-
ticles have large surface areas and abundant surface-active
groups. The addition of inorganic nanoparticles has been dem-
onstrated to be helpful to membrane permeability and fouling
resistance by either changing the pore structure or increasing
the hydrophilicity of the membranes. A simple and commonly
used approach is to directly blend pre-prepared nanoparticles
with polymers in solution. Li and co-workers[212] blended Al2O3
nanoparticles with PVDF UF membranes. It was observed that
the addition of a certain amount of Al2O3 nanoparticles could
slightly increase the hydrophilicity of the PVDF membrane
but had no effect on the effective pore size and porosity of the
membrane. Similarly, Yang and co-workers[213] used TiO2 NPs
to blend into a PSf UF membrane. The membrane was suc-
cessfully used for separating kerosene-emulsified wastewater
with improved antifouling property. Despite these successes
of blending HL NPs into polymer matrixes, NPs are generally
easily aggregated in polymer membranes due to their
intrinsic poor dispensability. Therefore, the approach limits

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Table 2.  Polymer-based membranes for oil–water separation in terms of different substrates, modification methods, separation application, CAs,
types of wettability, and features.

Polymer-based membranes Preparation Methods WCA [°] OCA [°] Wettability Application Feature Ref.
Inert solvent induced-PVDF Phase inversion 158 <1 SHB-SOL w/o HSE [188]
ZrO2 blended PVDF Phase inversion 52 n.a. HL o/w AF [179]
PANI/TiO2 nanofiber blended PVDF Phase inversion 61 n.a. HL o/w AF [190]
Amphiphilic block-copolymer blended PVDF Phase inversion 96.1 ± 3.2 DCM, 56.9 HL-OB o/w AF [193]
TiO2/KH550 modified PVDF Phase inversion 0 UW diesel oil, 158.6 SHL-UWSOB o/w AF [199]
PVDF-g-PTA/TiO2 hybrid Phase inversion 0 UW hexadecane, 159.3 SHL-UWSOB o/w AF [195]
PDA coated PVDF Phase inversion 53 ± 2.3 UW chloroform, 152 SHL-UWSOB w/o AF [198]
TiO2 modified PLA Phase inversion 0 UW, DCM, 154 ± 1 SHL-UWSOB w/lubricating oil AF [194]
PAA-g-PVDF Phase inversion 0 UW, DCE, 160 SHL-UWSOB w/o GD [179]
Copolymer blended PVDF hollow fiber Phase inversion 26 n.a. HL-OB Real wastewater AF [181]
Amphiphilic zwitterionic copolymer blended PES Phase inversion 29.4 hexadecane, 28.5 HL o/w AF [196]
HMO blended PES Phase inversion 16.4 n.a. HL o/w AF [192]
PEG blended PSF Phase inversion n.a. n.a. HL o/w AF [202]
Bentonite NPs blended PSF Phase inversion 62 n.a. HL Synthetic PW AF [173]
HAO blended PSF Phase inversion 10 n.a. HL w/crude oil AF [172]
PVDF–HFP nanofibrous Electrospun 0 UW, DCM, 169 ± 3 SHL-UWSOB o/w AF [201]
N-perfluorooctyl-substituted Polyurethane Electrospun >150 >150 Switchable o/w AF [197]
P34HB blended polylactide Electrospun 0 after 10s n.a. HL o/w AF [216]
PEGDA@PG nanofibrous Electrospun 0 n-hexane, 108 SHL o/w GD [212]
CA–PI nanofibrous Electrospun 48 0 SOL w/DCM GD [202]
F-SNF/Al2O3 In situ polymerization 161 Rapeseed, 0 SHB-SOL w/o GD [186]
PSF nanofibrous Interfacial polymerization 3 n.a. SHL water/soybean oil GD [174]

Note: HSE, high separation efficiency; HP, high permeability; GD, gravity-driven; SC, self-cleaning; AF, antifouling; DCE, 1, 2-dichloroethane; DCM, dichloromethane; PW,
produced water; o/w, o/w emulsion; w/o, w/o emulsion.

Figure 18.  a) Schematic illustration of the formation of a superhydrophobic–superoleophilic PVDF membrane via a modified phase-inversion process.
b) Digital photo of an as-prepared PVDF membrane with a dyed water droplet (3 µL) dropped on it. The inset is a cross-sectional SEM image of the
membrane. c) Photographs of a water droplet on the membrane showing a CA of 158° (up) and an oil droplet on the membrane showing a nearly
0 CA (down). d) Separation performance of the PVDF membrane toward w/o emulsion. Reproduced with permission.[188] Copyright 2013, Wiley.

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the improvement in the membrane permeability and anti-
fouling performance and has the risk to cause defects in the
membranes.
In comparison with porous membranes prepared by the
phase inversion method, electrospun polymeric membranes also
have outstanding characteristics, such as extremely high flux
under low operation pressure as well as relatively controllable
pore size and porosity.[214] Traditional electrospun membranes
with superhydrophobicity were used to separate oils from the
emulsions. For example, a electrospun fibrous membrane from
the polymerization product of styrene and butyl acrylate was
reported.[215] Because of its obvious affinity for oils as well as its
loose and porous structure, the oils could be completely absorbed
by membrane upon encountering the membrane surface, gen-
erating an oil film with good water repellency on the surface.
Zhang et al.[216] developed a polymer membrane composed of poly­­
lactide (PLA) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate)
(P34HB) using blend electrospinning. Taking advantages
of the structural porosity of the electrospun membrane
and the hydrophilicity of the P34HB, the electrospun mem-
brane exhibited superior water permeability, resulting in highly
efficient removal of water from a surfactant-free vacuum pump
oil–water emulsion under gravity (Figure 19). Recently Fang
et al.[197] first proposed a self-healing porous membrane concept
by electrospinning fluorine-containing polyurethane (PU). The
obtained membrane can separate surfactant-stabilized water-
in-ether emulsion solely driven by gravity with high separation
efficiency and high flux. In this case, the hierarchical micro/
nanoscale structure of the membrane incorporated with low
surface energy fluoroalkyl chains provided the membrane with
self-cleaning and self-healing properties. The fluorine-containing
PU as the healing components can migrate to the outer surface
of the fiber to heal the superhydrophobicity of the membrane.
In addition to this healing mechanism, the work give a founda-
tion of self-healing for regeneration and reuse of w/o emulsion
separation membranes, which matches well the requirements
for treating oily wastewater produced in industry and daily life.
Surface wettability modification by either chemical or phys-
ical methods is another efficient approach to enhance oil–water
separation performance of polymeric membranes. Surface
modification through chemical reactions could firmly introduce
Figure 19.  a) SEM images of the electrospun membrane and the inset is the optical images of
the time-dependent water droplets on the membrane surface. b) Optical images of the separa-
tion performance of the as-prepared electrospun membrane under gravity. Reproduced with
permission.[216] Copyright 2015, Elsevier.
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HL polymers such as poly(ethylene glycol) methyl ether meth-
acrylate (PEGMA),[217] poly(2-hydroxy-ethyl methacrylate),[218]
zwitterionic polyelectrolyte,[219] or small molecules[220] onto
membrane surfaces via the formation of covalent bonds. The
introduced HL materials form compact hydrated layers to
prevent the fouling of oil droplets on membrane surfaces and
allow the fouled oils to be easily removed during the following
cleaning process. Jiang and co-workers[220] conducted an inten-
sive study regarding surface grafting on filtration membranes
and they recently grafted a low surface free energy molecule
(pentadecafluorooctanoic acid) onto the surface of an aminated
polyacrylonitrile UF membrane via an acrylated reaction. The
modified membrane exhibited excellent antifouling property.
In addition to chemical reactions, directly coating HL poly-
mers and zwitterionic polymer onto membrane surfaces via
physical absorption is also feasible. For example, Chu and
co-workers[221] reported the surface modification of the HL layer
on nanofibrous UF membranes to achieve high flux for o/w
emulsion separation. A nanofibrous polyacrylonitrile weave
as a scaffold was first placed onto a nonwoven poly (ethylene
terephathalate) microfilter substrate, and then, chitosan, as
the hydrophilic layer, was spin-coated onto the polyacrylonitrile
weave to form a three-tier nanofibrous membrane. Because of
the high porosity and thin and smooth barrier layer of the
membrane, the membrane exhibited outstanding performance
including high flux and antifouling property. During the long
cross-flow filtration experiment using an o/w emulsion as the
feed, the water flux maintained a much higher value than the
commercial prisitine membrane, and no obvious decline of oil
rejection was found. Kim et al.[222] reported a PSf UF membrane
coated with a star-shaped block copolymer containing PEGMA
and methyl methacrylate (MMA) moieties using a spinning
method. The as-prepared membrane can separate surfactant-
stabilized o/w emulsion. The amphiphilic membrane surfaces,
consisting of both HL poly (ethylene glycol) (PEG) and HB moi-
eties exhibited higher oil-fouling resistance than that of the sur-
face with only HL PEG moieties. Interestingly, in this work, it
is found that by controlling the surface morphology of polymer
coatings with no oil-repellent moieties, the oil-fouling resist-
ance can also be increased. The favorable interactions between
the PMMA core blocks and the PSf membrane surface, caused
the larger content of denser PEG moieties
on the surfaces, which could weaken the
interactions between the oil foulants and the
membrane surface.
In situ polymerization, is a process in
which reactive monomers are filled in the
layers located in the lamellar and the relevant
polymerization is accordingly conducted. For
example, a novel flexible and hierarchically
porous silica nanofibrous (SNF) membrane
with superhydrophilicity and underwater
superoleophobicity was prepared by a facile
in situ polymerization method coupling with
electrospun,[186] which can effectively separate
microsize surfactant-stabilized o/w emul-
sions solely by gravity, with an extremely
high flux of 2237 L m−2 h−1 (Figure 20). The
enhanced fouling resistance of the SNF
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Figure 20.  SEM images of a) SNF, b) fluorinated SNF (F-SNF), and c) F-SNF/Al2O3 membranes, respectively; the insets show the optical profiles of
water droplets on the relevant membrane surfaces. Droplets of rapeseed oil (dyed red) and water (dyed blue) on the a’) SNF, b’) F-SNF, and c’) F-SNF/
Al2O3 membranes, respectively. d) Schematic illustration of the CA hysteresis and SA of a liquid droplet. e) A water droplet (10 µL) sliding at a low
angle of 3.8° on the as-prepared F-SNF/Al2O3 membrane. f) The gravity-driven separation for oil–water emulsions using the F-SNF/Al2O3 membrane.
Photos and optical microscopic photos of the oil–water emulsion before and after separation. Reproduced with permission.[186] Copyright 2013, Royal
Society of Chemistry.

membrane arose from its outstanding surface wettability, which
resulted in water layer formation on the membrane surface and
restrained from direct contact between the oil and membrane
surface during separation. What is more, the SNF membrane
also exhibits robust mechanical strength, high thermal stability,
and easy cycling for long-term use. Therefore, as an efficient
and diverse method, in situ polymerization could sturdily bind
some functional NPs (such as SiO2 NPs) on the polymeric sub-
strates and create a nanoscale roughness with special wettability
and enhanced mechanical strength, which make those mem-
branes promising candidates for oil–water emulsion separation.
4.3. Ceramic-Based Membranes
In the family of membranes, porous ceramic membranes are
an important category because of their high chemical, thermal
and mechanical stability, which make them suitable for use in
harsh conditions such as corrosive and high temperature envi-
ronments. These membranes are made from alumina, titania,
zirconia or silica oxides, silicon carbide, etc.[223] Typical ceramic
membranes are made in layers with different porous structure:
a support (also known as substrate) layer and a thin separa-
tion (also known as top) layer. It is worth noted that sometimes
an intermediate layer might exist in a ceramic membrane.
Ceramic supports usually consist of by above-mentioned
metal oxide or inorganic powders, to which binders and plas-
ticizers may be added. The resulting mixture is then pressed,
extruded or slip cast prior to a sintering process. To obtain a
ceramic membrane, the ceramic support surface has to be
smoothed first. Then the flat ceramic support is usually dip-
coated with a casting solution via capillary force and then dried
for a certain time.[224–226] In order to get a desired membrane
structure with certain thickness, the coating procedure must
be well-controlled. Followed by coating and drying, separation
layer made of ceramic microcrystals is obtained by further
calcination. These processes finally leave a fixed roughness on
ceramic membrane surfaces. As discussed previously, surface
roughness is a key factor associated with membrane wettability
that affects membrane performance in oil–water separation.
Over the past few years many works (Table 3) have been sig-
nificantly focusing on the development of high performance
ceramic MF and UF membranes for oily wastewater treat-
ment.[223,227–235] Although very few reports[232,236] stated that
their enhancement in ceramic membranes for in oil–water
separation application is attributed to membrane surface wet-
tability, these work coincidently concentrated on the control of
roughness and HL modification of membrane surface. This is
consistent with our viewpoint that wettability plays a critical
role for ceramic membranes in the applications of oily water
treatment.
It is well-known that ceramic membranes mainly consisting
of metal oxides always show hydrophilicity, thus nearly all
membrane scientists have paid their attention on the design of
HL-UW OB ceramic membranes for oily water treatment. For
example, without introduction of any chemical modification,
Xing and co-workers[227] first investigated the effect of surface
roughness on HL ceramic membranes for oily water treatment.
They prepared a series of ceramic membranes with controllable
surface roughness using PMMA particles as the template with
different diameters. It was found that surface roughness had
little effect on the pure water flux of membrane and oil rejec-
tion, but it played an important role in the filtration flux of oily
wastewater. In addition, Chang and co-workers systematically
studied the application of Al2O3 MF membranes for oily water
treatment by modifying the hydrophilic HL nanosized ZrO2,[235]

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Table 3.  Ceramic-based membranes for oil–water separation in terms of different substrates, modification methods, separation application, CAs,
improvements of wettability, and features.

Ceramic membranes Modification WCA(°) OCA(°) Improvements Application Features Ref.

Al2O3 MF Template n.a. n.a. Surface roughness o/w HP [223]
Mullite-titania Sol–gel 11 n.a. HL modification o/w HSE [227]
TiO2 modified MF Hydrothermal 14.57 ± 0.5 n.a. HL modification o/w AF [231]
γ-Al2O3 modified MF Hydrothermal 19.4 ± 1.1 n.a. HL modification o/w AF [231]
NaA zeolite on ceramic Hydrothermal n.a. n.a. HL modification o/w AF [230]
Zeolite MCM-22/α-Al2O3 Hydrothermal n.a. n.a. HB modification o/w AF [232]
Nano-TiO2 on MF Sol–gel 8 n.a. HL modification o/w AF [228]
Nanosized ZrO2 on MF Sol–gel 20 n.a. HL modification o/w AF [235]
GO modified Al2O3 MF Vacuum suction n.a. n.a. HL modification o/w HP [233]
Silica NPs modified Sol–gel 3 UW, >150 SHL-UWSOB o/w AF [234]
PU-PDMS coated MF Sol–gel 161.2 kerosene, 0 SHB-SOL w/kerosene AF [229]

Note: HSE, high separation efficiency; HP, high permeability; GD, gravity-driven; SC, self-cleaning; AF, antifouling; DCE, 1,2-dichloroethane; DCM, dichloromethane; PW,
produced water; o/w, o/w emulsion; w/o, w/o emulsion.

nano-TiO2,[228] and graphene oxide nanosheets,[233] respectively.
Notably, all modified membranes have a better performance on
antifouling than that of the unmodified membrane because the
HL coatings prevents the oil droplets from adhering or pene-
trating. These modified membranes also exhibited an enhanced
and stable flux for oil–water emulsion separation compared
with the pristine Al2O3 MF membrane.
Very recently, Chen et al.[234] fabricated a SHL-UWSOB
hierarchically structured ceramic membrane for separating
oily wastewater (Figure 21). A SHL-UWSOB silica sol was pre-
pared via the well-known Stöber process and the hierarchically
structured ceramic membrane surface is constructed through
a dip-coating process. Their membrane can separate the
oily wastewater with a mean oil droplet diameter of 1.54 µm
and the oil separation efficiency is extremely high (99.95%).
Completely different from conventional pore size sieving
mechanism (the average pore size is determined as 3.62 µm),
they claimed that their membrane mainly depend on the
special wettability of the separation layer, where water spread
on the membrane surface initiatively and form a layer of water
film to repel oil droplets due to the natural incompatibility
between water and oil.
In contrast to SHL-UWSOB ceramic membranes, Su et al.[229]
reported a porous ceramic membrane with a SHB-SOL surface
which could be used for reclaiming oil from oily water (Figure 22).
A commercial porous ceramic tube was first coated with a tetra-
ethoxysilane-derived silica sol and then the membrane surface
was modified with a PU-PDMS film. The resulting ceramic
membrane shows a WCA of 161.2° while a kerosene OCA of 0°,
which could be used to separate a mixture of water–kerosene–clay.

Figure 21.  SEM images of the silica NPs-modified membrane prepared at 60 °C. The inset is the shape of adding a water droplet on the membrane
surface. b) Spreading and adhesion behaviors of water and oil droplets. c) Separation performance of the membrane to oil field o-wo wastewater.
Photograph and optical microscopic images of the wastewater before and after filtration. Reproduced with permission.[234] Copyright 2016, Elsevier.

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Figure 22.  a) SEM images of the pore wall of the porous ceramic tube with SHB- SOL surface. The inset is the SEM image with magnification of
20 000 times. b) Optical images of water and kerosene droplets on the inner membrane surface (WCA is 161.2° and kerosene CA is 0°). c) Optical
images of the oily water containing clay particles and the filtrate collected from the separator. Reproduced with permission.[229] Copyright 2012, Elsevier.

It is found that the oil recovery efficiency, to a great extent,
depends on the component of target mixtures and separa-
tion velocity. Clay particles can clog the pore and adhere on the
surface to decrease the effective surface for separation, and there
are new common channels for kerosene and water between clay
particles Although the best oil recovery efficiency of their mem-
brane is only 67.6% when the feed consists of 3840 g water and
160 g kerosene, their work opens up the new world of making
ceramic filtration membrane SHB-SOL for oil recovery from oil–
water mixtures.
4.4. Nanomaterial-Based Free-Standing Membranes
With tremendous interest in nanotechnology, various types of
metallic and several carbonaceous nanomaterials have drawn
significant attention in recent years for water treatment.[31] In
the field of oily water treatment membrane, nanomaterials
have been used not only for modifying membrane surfaces
but also for constructing nanomaterial-based free-standing
thin membranes. An ideal membrane is expected to have an
active separation layer, which should be as thin as possible
for pursuing low transport resistance and high flux. There-
fore, taking advantages of their high surface area and special
surface properties, 1D or 2D nanomaterials have made impres-
sive progress in fabricating ultrathin filtration membranes with
innovative structures which could exhibit low weight, high
permeability and high rejection rate compared with traditional
filtration membrane materials in oil–water separation applica-
tions (Table 4).[141,237–245]
In the recent years, 1D nanomaterials, especially nanotube,
nanowires and nanofibers have attracted intensive attention
for constructing free-standing membranes with special wetta-
bility for oily water treatment. It is of great interest to assemble
1D nanomaterials into fibrous macroscopic architectures
with separation performance. Among the existing 1D nano-
materials, carbonaceous nanomaterials including single- or
multiwalled carbon nanotube (SWCNT or MWCNT) are the
most attractive candidates for constructing free-standing mem-
branes for oil–water separation. Jin and her co-workers did a
lot of pioneering work with CNTs,[238,246–249] for example, they
prepared an ultrathin free-standing SWCNT membrane with
tunable thickness for the ultrafast separation of emulsified
oil–water mixtures by using a vacuum suction method. The
SWCNT membrane are HB-SOL that could effectively separate
both micrometer- and nanometer-sized surfactant-free and sur-
factant-stabilized w/o emulsions with both efficiencies higher
than 99%. Furthermore, after 20 recycling cycles, the separation

Table 4.  Nanomaterial-based free-standing membranes for oil–water separation in terms of different substrates, modification methods, separation
application, CAs, types of wettability, and features.

Free-standing membranes Fabrication WCA [°] OCA [°] Wettability Application Feature Ref.
SWCNT Vacuum suction 94 DCM, 0 OB-SOL o/w GD [237]
PDA-coated SWCNT Vacuum suction 104 0 HB-SOL o/w and w/o HSE [238]
PEI@CNT-TMC Vacuum suction 51 ± 0.7 UW oils > 152 HL-UWSOB o/w AF [241]
Cryptomelane nanowire Hydrothermal, CVD 172;0 at 390 °C n.a. SHL-SHB w/toluene Switchable [242]
SiO2/carbon composite Electrospun 144.2 ± 1.2 DCM, 0 HB-SOL w/hexane GD [243]
MnO2 nanowire Vacuum suction 32–143 n.a. HL-HB n.a Switchable [244]
PDA coated rGO Vacuum suction 0 UW oils > 150 SHL-UWSOB o/w AF [239]
Graphene–TiO2 composite Vacuum suction 0 UW oils > 151 SHL-UWSOB o/w SC [240]
GO-Palygorskite Vacuum suction 44 >150 HL-UWSOB o/w HP [250]

Note: HSE, high separation efficiency; HP, high permeability; GD, gravity-driven; SC, self-cleaning; AF, antifouling; DCE, 1,2-dichloroethane; DCM, dichloromethane; PW,
produced water; o/w, o/w emulsion; w/o, w/o emulsion.

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www.advancedsciencenews.com
efficiency and flux remained same indicating that the mem-
brane have excellent stability and antifouling properties for
long-term w/o separations.[246]
Instead of carbon-dominated nanomaterials, Yuan et al.[242]
used a self-assembly method to construct thermally stable,
free-standing cryptomelane nanowire membranes that exhibit
switchable superwetting behavior ranging from SHL to SHB.
The prepared membranes can selectively absorb oils including
cyclohexane, 1,2-dichlorobenzene, gasoline, motor oil, petro-
leum ether and toluene up to 20 times the membrane’s weight
in water through a combination of superhydrophobicity and
capillary action. This result suggests the free-standing mem-
brane can removal oils from water and could be used for oil/
water filtration separation and particularly for oil spill cleanup.
Similarly, Lan et al.[244] reported a multifunctional free-standing
membrane from the self-assembly of ultralong MnO2 nano­
wires via the vacuum suction method. MnO2 nanowires with
50 nm in width and up to 100 µm in length were assembled
as a free-standing membrane with strong mechanical stability
and flexibility. Interestingly, a reversible wettability between
hydrophilicity and hydrophobicity of the membrane could be
achieved by incorporating triethoxy(octyl)silane into the MnO2
scaffold. As shown in Figure 23, it is found that when treated
by ethanol and heat-treatment at 60 °C for 5 min, the wetta-
bility of membrane could be switched between hydrophilicity
(WCA of ≈32°) and hydrophobicity (WCA of 143°). The free-
standing membranes also show a great potential for oil–water
separation.
In addition to 1D nanomaterials, 2D nanomaterials especially
graphene-based nanomaterials have been extensively attempted
to fabricate free-standing membranes with special wettability
for oil–water separation. Graphene oxide (GO) nanosheet is
an oxidized derivative of graphene which can be regarded as a
graphene scaffold with different oxygenous functional groups
including epoxy, carboxyl, hydroxyl, and carbonyl. Due to the
hydrophilic nature, high surface area and abundant reaction
sites, GO nanosheet allows a vast of chemical decorations that
Figure 23.  a) SEM image of the the membrane and the inset is the photographs of the free-standing membrane. b) Photographs of the water droplet
shape on the membrane before and after treatment with ethanol. c) Reversible HB-to-HL transformation of the as-prepared membrane under cycled
ethanol treatment and 60 °C heating. Reproduced with permission.[244] Copyright 2013, American Chemical Society.
Adv. Mater. Interfaces 2018, 1800576 1800576  (22 of 27)
www.advmatinterfaces.de
is promising building block for building laminate membrane
structure with tunable passageway for water molecules.[237] With
vacuum-assisted filtration self-assembly, Zhao et al.[250] utilized
palygorskite (PGS) nanorods to intercalate into adjacent GO
nanosheets to form a laminate free-standing membrane (GOP)
through π−π stacking and cation cross-linking (Figure 24).
The palygorskite nanorods in the membranes could enlarge
mass transfer channels, elevate hydration capacity, and create
hierarchical nanostructures of membrane surfaces. The hydra-
tion capacity and hierarchical nanostructures synergistically
endow the membranes with underwater superoleophobic and
low oil-adhesive water/membrane interfaces and the mem-
branes exhibit outstanding separation performance and anti-
fouling properties for various oil-in-water emulsion systems
(with different concentration, pH, or oil species). In contrast to
GO nanosheet, chemically reduced GO (rGO) has also widely
proposed for constructing free-standing filtration membranes.
Typically, Feng’s group[239] reported a facile route to fabricate
ultralight free-standing rGO membranes with superhydrophi-
licity-UW superoleophobicity. The membrane was obtained by
vacuum filtration a suspension of polydopamine-coated rGO
nanosheets onto a commercial mixed cellulose ester filter. The
membrane is capable of separating multiple types of surfactant
stabilized o/w emulsions with oil droplets of nano/sub-
micrometer size, as well as display high separation efficiency
and excellent anti-fouling properties, endowing them high-
lighted alternatives for oily water treatment.
5. Conclusions and Outlook
Membrane technology, as a widely utilized unit operation for
tackling the world-class challenge of treating oily water pro-
duced from various industrial processes and daily life, has
been considered as the most promising method due to its
high separation efficiency and relatively simple process. How-
ever, traditional membrane materials suffer from variety of
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
www.advmatinterfaces.de

Figure 24.  a) Schematic illustration of fabricating of GOP membranes via vacuum-assisted filtration self-assembly. b) Apparent WCAs in air and
c) apparent OCAs UW of GOP membranes with different PGS/GO mass ratios. d) Schematic of the oil–water-membrane interfaces of GO and GOP
membranes. Reproduced with permission.[250] Copyright 2016, American Chemical Society.

problems, such as severe fouling, low separation efficiency and
huge energy consumption. Significant advances in the field of
special wettability have opened new possibilities to improve
membrane materials and their performances in separation pro-
cesses. This review offers a state-of-the-art assessment of the
latest research work on selective membrane materials under the
concept of special wettability for highly efficient oil–water sepa-
ration. Wetting on membrane surfaces has received increasing
attention among membranologists. Moreover, a comprehensive
understanding of the emerging advanced membrane mate-
rials with specific wettability is systematically presented in
terms of membrane classifications, definitions, general design
principles, characteristics and applications. The detailed dem-
onstration of metallic-, polymeric-, ceramic- and nanomaterial-
based filtration membranes in separating oil–water mixtures
may offer practical insights into developing oil–water separa-
tion membranes. This article also provides new insights into
the construction of oil–water separation membrane materials
with remarkably enhanced or newly derived functionalities/
characteristics.
Despite enormous progress having been made of mem-
branes with special wettability for oily water treatment, there
are still some challenges and opportunities for both the scien-
tific and industrial communities. For creating special wettability
with membrane materials, some challenges are highlighted as
follows. 1) SHB-SOL membrane materials have been extensively
developed, however gravity separation is not applicable for this
type of membrane if water contacts the membrane before oil,
and fouling can still form when oils adsorb to the membrane
surface. 2) SHL-UWSOB membrane materials can be utilized
for gravity-driven separation of layered oil–water mixtures with
excellent fouling resistance but they are unsuitable for the
separation of emulsified oil–water mixtures. 3) SHL-SOB (in-
air) membranes are promising in various industrial processes
requiring oily water treatment and can be used for clean-up of
oil spills, but the fabrication methods of the SHL-SOB mem-
brane materials are complicated and still very challenging.
4) Superamphiphilic membranes exhibit excellent separation
performance for emulsified oil/water mixtures and are suitable
for large-scale production process. However, the understanding

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www.advancedsciencenews.com
of superamphiphilic mechanisms is still insufficient so far.
5) (Super) omniphobic ability provides enormous opportunities
for MD to extend its application for treating oily wastewaters
with low surface tension contaminants. Other membrane
contactors and direct membrane filtration processes may take
advantages of omniphobicity as well. The fabrication techniques
for superomniphobic membranes remain challenges that
are still lack of investigation. 6) The research on membranes
with switchable wettability based on different mechanisms,
such as smart stimuli-responsibilities and Janus effects are still
in their early stages and further efforts are highly required. New
types of responsive or multi-responsive materials are prom-
ising to construct membranes with tunable wettability. Janus
membranes with opposing wettability may give a rise for the
unidirectional or switchable separation of oil–water mixtures.
Although many membrane processes are feasible, the
membrane filtration processes have played and will still
play a predominant role in oil–water separation due to the
simplicity of the operation, benign experimental conditions
and high separation efficiency. As to the possible futures
for the filtration membranes with special wettability for
oil–water filtration, perspectives on technical advances and
market potential are highlighted as follows. 1) Chemically and
mechanically robust composite membrane materials with high
oil fouling resistance should and will be developed with even
more facile methods at low costs. 2) Low pressure or gravity-
driven filtration processes integrated with smart membrane
surfaces and modules will lead to more advanced membrane
engineering, which may bring more solutions to treating oily
water. 3) The on-going research of artificial intelligent respon-
sive membrane, in essence, is about the membrane resistance
to convection and diffusion of solvent and solute when an
external stimuli changes physicochemical characteristics on
membrane surface. Such membranes will be finally in wide
use based on full understanding of their mechanisms. 4) As
there is a growing tendency applying ceramic MF/UF mem-
branes for oily water treatment, constructing a specially and
selectively wettable layer onto the membrane surface makes
ceramic membranes more attractive on a lifecycle cost basis.
5) Nanotechnology plays a growing role in material science
and membrane fabrication techniques, and nanomate-
rial-based membranes enrich filtration membrane family.
Free-standing membranes constructed by low-dimensional
nanomaterials that break through the traditional membrane’s
tradeoff between permeability and selectivity may bring
continuous miracles in water treatment industry.
Acknowledgements
Y.W. thanks the Australian Government for providing the International
Research Training Program (iRTP) scholarship. X.G. acknowledges the
National Natural Science Foundation of China (No. 21774098) for the
financial support.
Conflict of Interest
The authors declare no conflict of interest.
Adv. Mater. Interfaces 2018, 1800576 1800576  (24 of 27)
www.advmatinterfaces.de
Keywords
membrane, oil–water separation, surface modification, wettability
Received: April 16, 2018
Revised: July 5, 2018
Published online:
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