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Special oleophobic and hydrophilic surfaces:

approaches, mechanisms, and applications
Cite this: J. Mater. Chem. A, 2017, 5,
3759
Yongjin Wangab and Xiao Gong*a

Received 6th December 2016
Accepted 16th January 2017
DOI: 10.1039/c6ta10474f
rsc.li/materials-a
An oleophobic and hydrophilic surface is a surface that is more wettable to water than to oil. In recent years,
this novel surface has attracted significant attention since it is highly desirable in many important
applications such as long-term anti-fogging, detergent-free cleaning, and oil and water separation. In
this study, we focused on recent advances in oleophobic and hydrophilic surfaces. We briefly
summarized three approaches, including simultaneously oleophobic/hydrophilic behavior, oleophobic/
hydrophobic to hydrophilic switching behavior, and hydrophilic/underwater superoleophobic behavior,
to achieve this surface. Moreover, we discussed the underlying mechanisms and the potential
applications of this surface have also been introduced.

detergent-related pollution, which are current environmental

1. Introduction
When a liquid is placed on a solid surface, the equilibrium
contact angle (q) is related to the liquid surface tension (gl), solid
surface tension (gs), and solid–liquid interfacial tension (gsl),
which can be described by the Young's equation1 as follows:
gl cos q + gsl ¼ gs
According to both classic theory models2,3 and experimental
challenges.12 It can also be used as an anti-fogging surface, which
is crucial for eyeglasses, camera lenses, automobiles, and
medical instruments such as infrared microscopes.13–16 More-
over, the oleophobic/hydrophilic wetting behavior can be used to
enhance the oil–water separation efficiency since the increase in
the water permeability is relative to the oil permeability.17,18
Although several previously reported reviews19–26 have intro-
duced different surfaces with different wetting behaviors, such
as superoleophobicity,19,24 superhydrophilicity,20 super-
hydrophobicity, and superoleophilicity,22 and have highlighted
25

results,4,5 it has generally been accepted that the higher the
liquid surface tension, the larger the liquid contact angle on the
same solid surface. For example, hexadecane (gl ¼ 27.47 mN
m1, 20  C) has a much lower surface tension than water (gl ¼
72.80 mN m1, 20  C) on the same solid surface; thus, the water
contact angle (WCA) has been reported to be larger than the
hexadecane contact angle (HCA).4–7 In other words, a given solid
surface is expected to be more wettable to oil than to water.
However, a few studies indicate that it is possible to achieve
a surface that is more wettable to water than to oil, which is
called an oleophobic/hydrophilic surface.
Recently, oleophobic/hydrophilic surfaces have attracted
signicant attention since it is highly desirable in many impor-
tant applications; for example, since the surface is more wettable
to water than to oil, it can be used as a detergent-free cleaning
surface where water can easily replace the oil contaminants and
ush the oils away.8–11 This self-cleaning surface can reduce the
consumption of detergents that are made from petroleum.
Therefore, it can save energy and protect the environment from
their applications, a more detailed review that only focuses on
the special oleophobic/hydrophilic surface is rare. Therefore, it
is required to gather attention on this converse-theory novel
surface because of its highly potential applications. Hence, this
review aimed to introduce a special surface with oleophobic/
hydrophilic wetting behavior. Herein, we summarized three
approaches via which this wetting behavior can be achieved and
the underlying mechanisms have been discussed. The applica-
tions have also been introduced in this review.
2. Approaches
In this review, three approaches, including simultaneously
oleophobic/hydrophilic behavior, oleophobic/hydrophobic to
hydrophilic switching behavior, and hydrophilic/underwater
superoleophobic behavior, have been reported to achieve an
oleophobic/hydrophilic surface. The advanced features and
fabrication techniques of each surface have also been
mentioned herein.

a
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of 2.1. Simultaneously oleophobic/hydrophilic behavior
Technology, Wuhan 430070, China. E-mail: xgong@whut.edu.cn
b
Department of Chemical & Petroleum Engineering, Swanson School of Engineering, In 2000, Badyal et al.8,9 reported that cationic uorosurfactants
University of Pittsburgh, Pittsburgh, PA 15261, USA complexed to the plasma polymer of maleic anhydride9 and

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arylic acid8-functionalized solid surfaces exhibited a smart
behavior and could repel oil and wet water at the same time. In
the same year, Nakajima et al.27 reported that aer 48 hour UV
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illumination, the polycrystalline TiO2 thin lm surface could
have a larger HCA (25 ) than WCA (0 ). Moreover, the simulta-
neously oleophobic/hydrophilic surface has attracted signi-
cant interest and has been investigated and developed. Usually,
the simultaneously oleophobic/hydrophilic surface is fabricated
by applying polymers on solid substrates via the fabrication
techniques such as layer-by-layer deposition,28,29 covalently
gra,10,11,17 dip-coated,30,31 UV irradiation,27,32 and
copolymerization.33
Brown et al.28,29 fabricated a surface that could repel oil while
being hydrophilic using a poly(diallyldimethylammonium
chloride) (PDDA) and uorosurfactant layer (FL) via a layer-by-
layer spray deposition technique. The wetting behavior of this
surface could be further improved by adding a SiO2 nano-
particle layer, resulting in a HCA as large as 157 , whereas
a WCA smaller than 5 . The schematic of the layer-by-layer
composite coating is shown in Fig. 1. This surface was also
found to have a good wear resistance, and the wetting perfor-
mance of the coating almost did not change before and aer the
wear experiments via tribometer. Similarly, Yoon et al.34
synthesized a membrane using a PDDA polymer, per-
uorooctanoate (PFO) polymer, and SiO2 nanoparticles via
Fig. 1 Schematic of the layer-by-layer composite coating. Each layer
is separately spray-coated. Also, the chemical composition and charge
of each layer are shown. (Reprinted with permission from ref. 28.)
3760 | J. Mater. Chem. A, 2017, 5, 3759–3773
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a one-step dip-coating fabrication technique. This composite
membrane presented an excellent oleophobic and super-
hydrophilic property.
Howarter and Youngblood10,11,17 fabricated a stimuli-
responsive surface by covalently graing polyethylene glycol
with short peruorinated end caps (f-PEGs) to silica with
isocyanate-functionalized silane and the schematic of the
reaction mechanism is shown in Fig. 2. At the optimized
graing reaction time (24 h), the receding HCA on the surface
could reach 67 , which is higher than the advancing WCA (30 ).
This surface presented a truly oleophobic and hydrophilic
behavior as the receding oil contact angle was higher than the
advancing water contact angle. Furthermore, they synthesized f-
PEGs copolymers using acrylic acid and hydroxyethyl methac-
rylate to simplify materials processing and ease the applications
compared to the graing method. The oleophobic/hydrophilic
behavior could also be observed with the optimized combina-
tion ratio of the copolymers.33
Wang et al.30,31 studied the wetting behavior of nanometer
thick peruoropolyether (PFPEs) polymers, including Zdol, Z-
tetraol, and Z-03, which have similar backbones but different
end-groups. They reported that the simultaneously oleophobic/
hydrophilic behavior was observed only for Zdol-coated high-
surface-tension substrates. The appropriate number of hydroxyl
end-groups and the uorinated backbone of Zdol polymer could
interact with the substrate to form a right structure, resulting in
a larger HCA and smaller WCA. Moreover, this right structure can
be fabricated using a polymer without polar end-groups (Z-03) via
a photochemical approach32 to construct the oleophobic/
hydrophilic surface at a low-cost. Moreover, Zhu et al.35 devel-
oped a novel membrane that was synthesized by adding the
polymer AP1 (ref. 36) to the base matrix polymer of polyvinylidene
uoride (PVDF).37 When the prepared concentration of the
casting solution was 20 wt% and the ratio between PVDF and AP1
in the solution was 8 : 2 or 7 : 3, the membrane presented
a simultaneously oleophobic/hydrophilic behavior. This
membrane can be fabricated into a novel hollow ber membrane
that can be used for oil and water separation.38 Note that this
study has been rstly reported to achieve a simultaneously
oleophobicity/hydrophilicity with a porous membrane structure.
In addition, the hygro-responsive membranes39 and polystyrene
(PS)/peruoropolyether cationic ammonium salt (FOMMT) coat-
ings40 have also been reported to have a simultaneously
oleophobic/hydrophilic property.41,42 Moreover, this property can
be achieved by changing the electric eld around the coatings.43
The abovementioned oleophobic behavior is created by the
uorinated groups, which are usually harmful chemicals. To
improve this, Rohrbach et al.44 fabricated an environmentally
friendly simultaneously oleophobic/hydrophilic paper lter
with a nanobrillated cellulose (NFC) hydrogel, as shown in
Fig. 3. Similarly, Tang et al.45 developed an oleophobic/
hydrophilic paper substrate with a non-uorinated coating
material, which was a mixture of methyltrimethoxysilane
(MTMS) and hydrochloric acid.
Table 1 summarizes the WCA and HCA on various simulta-
neously oleophobic/hydrophilic surfaces. The type of polymers
that can achieve this property, the fabrication techniques for
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Fig. 2 Two-step grafting procedure. Isocyanate-functionalized silane monolayer is formed on silica. The isocyanate is reactive towards the
terminating alcohol of the f-PEG oligomer (y ¼ 5 and x ¼ 9). (Reprinted with permission from ref. 10.)
Fig. 3 Schematic of water/oil separation using a hydrated filter. Water
passes through, whereas oil is retained above. (Reprinted with
permission from ref. 44.)
applying the polymers on the substrates, and the special
features that are different from other surfaces have been listed
for each surface.
2.2. Oleophobic/hydrophobic to hydrophilic switching
behavior
On simultaneously oleophobic/hydrophilic surfaces, water
droplets can immediately wet the surface and present a smaller
contact angle than that of hexadecane. Several studies have re-
ported other oleophobic/hydrophilic surfaces that rst present
an oleophobic/hydrophobic behavior, and then are gradually
wetted by water up to several minutes, which leads to switching
of an oleophobic/hydrophobic behavior to hydrophilic behavior.
The oleophobic/hydrophobic–hydrophilic switching
behavior was rst reported by Sawada et al.46 in 1996. The
samples were prepared with uoroalkanoy (RF), aryloylmor-
pholine (ACMO), and trimethoxyvinylsilane (VMOSi) to fabri-
cate different uoroalkylated silane coupling agents. They
indicated that dodecane contact angle did not change with
time, whereas the WCA decreased on all surfaces, as shown in
Table 2. Furthermore, Sawada et al. developed and synthesized
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more oleophobic/hydrophobic–hydrophilic switching surfaces
with uoroalkylated oligomers/silica gel polymer hybrids,47,48
uoroalkyl end-capped acrylic acid oligomer/silica nano-
composites,49 and uoroalkyl end-capped vinyltrimethoxysilane
oligomer/calcium silicide nanocomposites.50
Yang et al.18 found that the WCA could decrease from 97 to

52 in 10 min on the smooth lm of PDDA and sodium PFO.
Based on this PDDA–PFO coating, they fabricated a novel
superhydrophilic and superoleophobic nanocomposite coating,
which was named as PDDA–PFO/SiO2, by providing the required
texture and chemical structure.51,52 As shown in Fig. 4, the WCA
on this coating gradually decreased from 165 to 0 within
9 min, whereas the HCA maintained a value of 155 within the
same time period.18 Additionally, chitosan (CTS)–PFO/SiO2 (ref.
53) and polyelectrolyte–uorosurfactant (PFC)/SiO2 (ref. 54)
were shown to have the similar property.
Moreover, Darmanin and Guittard55,56 obtained super-
oleophobic behavior57 by complexing the monomer EDOP-C11-
NH-F4 (ref. 58) that contains a short peruorobutyl chain
(C4F9)59 with different bis(triuoromethane) sulfonimide salts
as an electrolyte. They found that the hydrophobic–hydrophilic
switching behavior could be observed when the complexant
ions (Na+, Mg2+, Ca2+, Ba2+) were used as the electrolyte cation.
The switching hydrophobic–hydrophilic/oleophobic coatings
can also be applied to cellulosic materials such as lter paper60
and cotton fabric surfaces.61
The applications of oleophobic/hydrophobic–hydrophilic
switching surfaces are limited by the switching time, which
usually takes several minutes. Brown et al. improved this
surface by fabricating a smooth poly(Et-alt-MA)–uo-
rosurfactant complex lm with an ultrafast switching time (10
s).62–64 They further enhanced the oleophobicity by increasing
the roughness of the surface.62–64 Table 3 summarizes the
oleophobic/hydrophobic–hydrophilic switching surfaces,
including the type of the surface, the static HCA, the WCA
before and aer switching, and the switching time.
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Table 1 WCA and HCA of various simultaneously oleophobic/hydrophilic surfaces fabricated via different fabrication techniques. The special
features of the surfaces are also highlighted
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Type of polymer Fabrication technique Feature WCA ( ) HCA ( ) Ref.

Complexation of cationic Solution-phase synthesis <20 82  4 8

uorosurfactants to plasma polymer of
acrylic acid
Complexation of cationic 22  2 79  1 9
uorosurfactants to plasma polymer of
maleic anhydride
Polycrystalline TiO2 thin lm UV illumination 0 25 27
Complex PDDA and FL Layer-by-layer spray Wear resistance 10  2 79  1 28 and 29
Complex PDDA, FL, and SiO2 deposition <5 157  1
nanoparticles
Complex PDDA, PFO, and SiO2 Dip-coating Easy fabrication 0 95  2 34
nanoparticles
Polyethylene glycol with short Covalently graing Truly oleophobic and 30 (adv.) 79 (adv.) 10 and 11
peruorinated end caps (f-PEGs) hydrophilic 0 (rev.) 67 (rev.)
Acrylic acid and f-PEG copolymers Copolymerization No need of covalent 40 (adv.) 73 (adv.) 33
Hydroxyethyl methacrylate and f-PEG graing 41 (adv.) 70 (adv.)
copolymers
Diolic peruoro-poly(oxyethylene-ran- Dip-coating Easy fabrication 46.5  0.9 70.1  0.9 30 and 31
oxymethylene) (Zdol)
Peruoro-poly-(oxyethylene-ran- Dip-coating and Low-cost compared to 0 60.6  0.6 32
oxymethylene) (Z-03) UV irradiation that of Zdol
Combine AP1 with PVDF (ratio 2 : 8) Solution casting Membranes 31  2.8 63  3.2 35
Combine AP1 with PVDF (ratio 3 : 7) 26  2.6 74  5.9
PEGDA, Darocur1173 and uorodecyl Dip/spin coating 0 152 39
POSS
PS/FOMMT Spin coating 32  4 58  5 40
Fluorodecyl POSS + PDMS Add electric eld Physical method 56 72 43
Nanobrillated cellulose (NFC) hydrogel Dipping and drying process Environmentally friendly 44
MTMS and hydrochloric acid One-step solution coating 0 64.7  1.4 45
(motor oil)

Table 2 Contact angles of dodecane and water treated with RF–(ACMO)x–(VMOSi)y–RF (reprinted with permission from ref. 46)

Contact angle (degree)

Water

RF [Mn] Dodecane 0 min 5 min 10 min 15 min 20 min 25 min 30 min

C3F7
[2720] 39 70 68 48 30 18 0

CF(CF3)OC3F7
[3520] 49 78 68 48 30 18 0

CF(CF3)OCF2CF(CF3)OC3F7
[5060] 57 79 67 49 32 13 0

CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OC3F7
[6420] 60 72 60 50 42 23 8 0

2.3. Hydrophilic/underwater superoleophobic behavior
Another approach to achieve the oleophobic/hydrophilic prop-
erty is by changing the surrounding environment of the surface.
Several studies have reported surfaces that can present hydro-
philicity in air and superoleophobicity in water.
Instead of focusing on designing and preparing materials
with different chemical compositions, Jiang's group66 focused
on the surface geometry and created a micro/nano-hierarchical
structure that presented a low-adhesive underwater super-
oleophobic behavior, which was inspired by the phenomenon of
sh keeping their skin clean in oil-polluted water. As shown in

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Fig. 4 (a) Images of water and hexadecane (colored with oil red O) droplets on the as-prepared PDDA–PFO/SiO2 coating before and after being
placed for 9 min. (b) Time-dependence of the contact angles for water and hexadecane on the PDDA–PFO/SiO2 coating. (Reprinted with
permission from ref. 18.)

Table 3 Type of oleophobic/hydrophobic–hydrophilic switching surfaces and their wetting behavior

WCA ( ) WCA ( ) Switching

Type of surface HCA ( ) (t ¼ 0 s) (aer switching) time Ref.

Fluoroalkylated silane coupling agents 39–60 (dodecane) 70–79 0 25–30 min 46

containing morpholino groups
Fluoroalkylated oligomers/silica gel polymer hybrids 27–43 (dodecane) 29–44 0 30 min 47 and 48
Fluoroalkylated oligomers/calcium silicide nanocomposites 63–76 (dodecane) 114–121 0 30 min 50
Polyurethanes containing PFPE, PDMS, and PEG 67 115 54 20 min 65
PDDA–PFO 72 97  1 52  2 10 min 18
PDDA–PFO/SiO2 155  1 165  2 0 9 min 18
CTS–PFO 134  1 67  2 10 min 53
CTS–PFO/SiO2 157  1 0 20 s 53
PFC 83  2 123  2 42  2 7 min 54
PFC/50 wt% SiO2 158  1 167  1 0 7 min 54
Poly(Et-alt-MA)–uorosurfactant 74  1 88  2 <10 10 s 63

Fig. 5d, the 1,2-dichloroethane (C2H4Cl2) contact angle on the
micro/nano-hierarchical silicon surface could reach 174.8 in
a water environment. On the basis of this micro/nano-
hierarchical structure, many different surfaces, including PAM
hydrogel-coated mesh,68 poly(3,4-ethylenedioxythiophene)–pol-
y(styrenesulfonate) (PEDOT–PSS) hydrogel meshes,69 hierar-
chical PNIPAAm–nanoclay hydrogels,70 PMMA-b-PNIPAAm
lm,71 polyaniline (PANI) nanowire lms,72 and poly(acrylic
acid)-graed PVDF (PAA-g-PVDF) ltration membranes,75 have
been developed.67–77
Moreover, the same group was inspired by the internal shell
surfaces of the short clam and extended the organic-based micro/
nano-hierarchical structures to inorganic membranes, such as
CuO coatings78,79 and Cu(OH)2 nanowire-haired membranes,80,81
via surface oxygen-adsorption corrosion and surface oxidation
techniques, respectively. Liu et al.82 reported the contact angle on
the Cu(OH)2-covered mesh with micro/nano-hierarchical struc-
tures in air and water. As shown in Fig. 6, the original smooth
copper presented a normal wetting behavior with hydrophobicity
and underwater superoleophobicity. However, the Cu(OH)2-
covered mesh with micro/nano-hierarchical structures presented
a superhydrophilic behavior in air, whereas a superoleophobic
behavior underwater.
Zhang et al.83 reported a nylon membrane that was coated
with polydopamine (PDA), polyethylenepolyamine (PEPA), and
a disulde bond. This surface not only exhibited the wetting
behavior of superhydrophilic in air/superoleophobic in water, as
shown in Fig. 7, but also had the capability of adsorbing protein,
which was highly useful and important for the application of oil
and water separation. Hou et al. fabricated a bioinspired under-
water superoleophobic surface by femtosecond laser treatment
on silica glass with hierarchical micro/nanostructure.84–88 Addi-
tionally, Sun's group was also inspired by the structure of sh
scale and facilely fabricated an underwater superoleophobic
membrane by coating graphene oxide on wire meshes.89,90 The
anti-oil performance of this membrane was related to the pore
size of the wire mesh, and the 300-mesh with a pore size of 45 mm
was reported to exhibit the best performance.90
Additionally, zeolite-coated mesh lms, which are highly
stable in harsh environments,91 pH-responsive polymer-coated
textiles,92 and copper mesh,93 layer-by-layer assembly of
sodium silicate and TiO2 nanoparticles on the stainless steel
mesh,94–96 PDA/SiNPs–PVDF composite membranes with
a hydrophilic and negatively/positively charged surfaces,97 and
so on98–100 were reported to have the wetting behavior of
superhydrophilic in air/superoleophobic in water. Table 4

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Table 4 The wetting behavior of selected hydrophilic/underwater superoleophobic surfaces and their features

Type of surface WCA ( ) C2H4Cl2 CA ( ) in water Feature Ref.

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Polyacrylamide hydrogel lms <5 174.8  2.3 Bio-inspired (rst) 66

PAM hydrogel-coated mesh Super hydrophilic 155.3  1.8 High separation efficiency 68
and anti-fouling
PEDOT–PSS hydrogel mesh 0 156 Good environmental stability 69
Hierarchical PNIPAAm– Super hydrophilic 159.1  1.6 Robust and low-adhesion property 70
nanoclay hydrogels
PMMA-b-PNIPAAm lm 42 (10  C), 107 (40  C) 137 (10  C), Temperature dependences 71
36 (40  C) (hexane)
Aligned PANI nanowire lm 19.7  1.3 161 Electrode potential modulated 72
Modied PDMS bio-surface 5  0.6 175  3 Microuidic channel 74
Copper oxide coating 1.6  0.8 163.0  4.5 Inorganic coating 78
Cu(OH)2 nanowire-haired membrane 0 155 Inorganic coating 80
PDA/PEPA/disulde bond-coated Spread 154.1  0.5 Capable of adsorbing protein 83
dual function membrane
Femtosecond laser-treated silica Near 0 160.2  1 High transparency 84
glass surface
Solution-assisted femtosecond 4.01 166.16 Easy method for 86
laser-irradiated nickel surface large-area fabrication
TiO2 surface with different modications 154.5  2.5 4, 160.5  2 Photoinduced switchable 88 and 96
(UV irradiation) (UV irradiation) wetting behavior
Graphene oxide-coated mesh 10 >150 Achieved by novel materials 89 and 90
Zeolite-coated mesh lms <10 >150 Nanoporous structure and 91
corrosion-resistant

3.1. Liquids penetration

To summarize all the oleophobic/hydrophilic polymer coatings,
it was found that most of them contained both hydrophobic
and hydrophilic segments and were coated on the substrate
with high surface tension. Usually, the polymer makes
a conformation on the surface aer coating wherein the
hydrophobic parts, such as the uorinated tails, stay on the top
of the coatings at the air interface, whereas the hydrophilic
parts, such as hydroxyl groups, are attracted to the substrates at
the solid interface. Aer placing oil and water on the surface,
large oil molecules are trapped at the hydrophobic parts on the
top, whereas small water molecules can penetrate the hydro-
phobic layer down to the more hydrophilic sub-layer.28 There-
fore, a larger HCA, due to the hydrophobic parts on the top, and
a smaller WCA, due to the hydrophilic attraction with the sub-

Fig. 5 Images of the oil droplets on different surfaces in water and

SEM images of substrates at low and high magnifications. (a) PAM film
with fish-scale structures. (b) Smooth silicon surface. (c) Micro-
structured silicon surfaces. (d) Micro/nanostructured silicon surface.
(Reprinted with permission from ref. 66.)

summarizes the wetting behavior of selected hydrophilic/

underwater superoleophobic surfaces and their features.

3. Mechanisms
To date, the underlying mechanism of oleophobic/hydrophilic
behavior is still unclear and being investigated and discussed.
Herein, we briey discussed three main plausible proposals
that may reveal the mechanism.
Fig. 6 CA measurements of the original smooth copper mesh (a–c)
and the as-prepared Cu(OH)2-covered mesh (d–f). (Reprinted with
permission from ref. 82.)

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Fig. 7 Oil (methylbenzene, hexane, gasoline, and dichloroethane)
contact angle in water and water contact angle in air. (Reprinted with
permission from ref. 83.)
substrate, can be observed. Wang et al.30,31 supported this
mechanism by indicating that hexadecane could also penetrate
the simultaneously oleophobic/hydrophilic coating but with
a much slower rate compared to water due to its larger molec-
ular size. As shown in Fig. 8, HCA could gradually decrease from
70 to 20 in 24 hours on the Zdol/Si surface, which is simul-
taneously oleophobicity/hydrophilicity surface.
Fig. 9 shows the mechanism of liquid penetration and
proposes that both water and hexadecane exhibit the trend to
penetrate the polymer coating aer they are placed on the
surface. Since the molecular size of water is smaller than the
Fig. 8 Change in the hexadecane contact angles on Zdol (0.9 nm)/Si with time ((a): 0 min; (b): 5 min; (c): 300 min; and (d): 1440 min) (reprinted
with permission from ref. 30).
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molecular size of hexadecane, the penetration rate of water
would be faster than that of hexadecane. Therefore, immediately
aer the contact angle test, an HCA higher than WCA is observed
on the simultaneously oleophobic/hydrophilic surface. For
a long time period, hexadecane may also slowly penetrate the
polymer coating, presenting a decrease of HCA with time.31
3.2. Coating ip-op
The mechanism of liquids penetration is that the coatings
remain static and the liquid can or cannot immediately pene-
trate the coatings, resulting in a different wetting behavior. In
contrast, a ip-op mechanism that the coatings will reorganize
when exposed to water has been proposed.101 During the
reconstruction of the surface,8,9 water will be attracted to the
more hydrophilic segments, resulting in a gradually decreasing
WCA and nally presenting hydrophilicity.
Sawada et al.46 rst indicated the mechanism of ip-op in
1996. They proposed that the hydrophobic segments were
gradually replaced by the hydrophilic segments at the water-
coating interface and the coating was likely to be rearranged
at the water interface. To investigate the mechanism of this
switching behavior, Ashish et al.65 synthesized a class of poly-
urethanes containing PEG, PDMS, and PFPE. The PFPE
segments are usually segregated at the air–polymer interface
due to their lowest surface energy within the polymer coating.
When the polymer coating will contact water, the PFPE
segments will be repelled by water and will drag the PEG-
segment segregate to the water–polymer interface, resulting in
hydrophilicity due to the hydrophilic property of PEG. The
abovementioned proposal has been described by the schematic
shown in Fig. 10.
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Fig. 9 Schematic of the penetration mechanism of water and hexadecane on Zdol/Si (not shown to scale). (Reprinted with permission from
ref. 31.)
Another example where the metal ions can migrate to the top
of the coating when a water droplet is placed on the surface, due
to the high polarity of water, changing the wettability from
hydrophobic to hydrophilic, is shown in Fig. 11.56 However, this
migration cannot occur for an oily liquid due to the non-polarity
of oil and the apparent oil contact angle was very stable.
Therefore, the migration of the ions induced a decrease in the
hydrophobicity of the surface.56
Fig. 10 Drops of water (left) and hexadecane (right) separated by
a distance of 2 mm on a SPU-004 surface at t ¼ 0 (a) and after 20
minutes (b). (Reprinted with permission from ref. 65.)
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3.3. Wenzel model and Cassie–Baxter model
As abovementioned, the oleophobic/hydrophilic behavior
cannot be understood by the traditional wetting models.
However, if the phenomenon is categorized as hydrophilic in
air/oleophobic in water, traditional wetting models, such as
Wenzel models102 and Cassie–Baxter models,103 can be used to
explain this behavior.
For example, Jiang et al.66 discussed the mechanism of
hydrophilicity/underwater oleophobicity in three-phase system.
As shown in Fig. 12a, the contact angle of q3 can be calculated by
the Young's equation1 as follows:
gl1 s  gl2 s
cos q3 ¼
gl1 l2
where gl1–s is the liquid 1/solid interface tension, gl2–s is the
liquid 2/solid interface tension, gl1–l2 is the liquid 1/liquid 2
interface tension, and q3 is the contact angle of liquid 1 in liquid
2. For a rough surface, the apparent contact angle for the
homogeneous and heterogeneous surfaces can be calculated by
Wenzel model and Cassie–Baxter model, respectively. In Jiang's
study, the roughness of the surface was due to the micro/nano-
hierarchical structures that were fabricated from hydrogel.
Therefore, water would trap below the oil droplet in an oil/
water/solid system, as shown in Fig. 12c. The apparent oil
contact angle (q0 3) in water environment could be calculated by
Cassie–Baxter model103 as follows:
cos q0 3 ¼ f cos q3 + f  1
where f is the area fraction of solid. According to the modeling
calculation, Jiang et al. proved that the modied micro/nano-
hierarchical silicon surface had the superhydrophilic property
in air, whereas superhydrophobic property in water, which was
consistent with their experimental results.66
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Fig. 11 Schematic of the migration of metal ions (Mn+) when the surface is in contact with water (b) compared to oil (a). (Reprinted with
permission from ref. 56.)
4. Applications
The unique oleophobic–hydrophilic surfaces are highly desir-
able in many important applications due to their special wetting
behavior. This review mainly focuses on the selected
Fig. 12 Effect of surface structure on the wetting behaviors of solid
substrates in solid/oil/water three-phase systems. (a) Schematic of the
Young's equation at the condition of a liquid 1 droplet on a smooth
surface with a contact angle q3 in a liquid 2 phase. (b) An oil droplet on
a microstructured substrate in water, in which l1 represents oil and l2
represents water. (c) Same system on a micro/nanostructured
substrate. (Reprinted with permission from ref. 66.)
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Journal of Materials Chemistry A
applications of anti-fogging, detergent-free self-cleaning, water
and oil separation, and anti-fouling.
4.1. Anti-fogging
Fogging occurs due to the condensation of water vapors on the
solid surfaces.104 When the surface is hydrophilic, a uniform
water lm is formed and fogging does not occur, whereas when
the surface is hydrophobic, a water droplet is formed on the
surface and fogging occurs.105 Usually, anti-fogging surfaces are
achieved by applying superhydrophilic surface.106–109 However,
the disadvantage of this surface is that it can be easily damaged
by hydrocarbon contamination in the ambient air, which can
lower the surface energy, therefore, changes the surface from
hydrophilic to hydrophobic.11 Or it can be ruined by oil fouling
such as ngerprints.10 If a surface is oleophobic/hydrophilic, it
can reduce the hydrocarbon contamination and can retain the
hydrophilic property. Thus, a long time anti-fogging capability
can be anticipated.10,11,31,32
For example, Howarter and Youngblood proved that the f-
PEG-coated glass slide, which was simultaneously oleophobic/
Fig. 13 Fogging of various surfaces in response to being held over
boiling water. From left to right: hydrophobic glass, f-PEG-modified
surface, and clean glass. (Reprinted with permission from ref. 11.)
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hydrophilic, could perform a good anti-fogging capability, as
shown in Fig. 13.11 Three-glass slides with different wetting
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behaviors were held over boiling water. The hydrophobic glass
slide exhibited heavy fogging due to its hydrophobicity. The clean
glass exhibited mild fogging since it was contaminated with oil in
the lab environment, which reduced the hydrophilic property.
The f-PEG-modied surface had the capability to repel oil and
could retain a good hydrophilic property; thus, water condensed
on the surface to form a water lm and no fogging occurred.11
Wang et al.31 experimentally proved that the simultaneously
oleophobic/hydrophilic surface could reduce the hydrocarbon
contamination, resulting in a long term anti-fogging perfor-
mance. As shown in Fig. 14 (le), Z-tetraol presented a bad anti-
fogging performance on both day 1 and day 14 due to its hydro-
phobicity. Zdol and Z-03 both had a good anti-fogging perfor-
mance on day 1 because the fresh samples had a good
hydrophilicity. However, on day 14, Zdol could still retain a good
anti-fogging property, whereas Z-03 could not. This was attributed
to the hydrocarbon contamination, which was self-repelled by
oleophobic Zdol surface, whereas ruined the oleophilic Z-03
surface. The percentage of hydrocarbon contamination was
measured by XPS, as shown in Fig. 14 (right), which indeed
proved that Zdol could reduce the hydrocarbon contamination
compared to Z-03. Therefore, the simultaneously oleophobic/
hydrophilic Zdol could exhibit a long term anti-fogging capability.
4.2. Detergent-free self-cleaning
Inspired by the “lotus effect”, superhydrophobic wetting
behavior is usually used to achieve self-cleaning surface, which
can remain free from dirt and grime.110–112 However, most of
these surfaces will lose the self-cleaning capability if the surface
is ruined with oil contaminants due to its oleophilicity.11,113 To
solve this problem, a surface that is more wettable to water than
to oil can be used as the next generation self-cleaning surface.11
On this oleophobic/hydrophilic surface, water itself can wash
the oil away and no detergent is required; therefore, this surface
can also be called detergent-free self-cleaning surface.
Howarter and Youngblood10 investigated the self-cleaning
capability of simultaneously oleophobic/hydrophilic f-PEG-
coated glass slides and the results are shown in Fig. 15(1). Oil
Fig. 14 The anti-fogging performance (left) and the amounts of hydrocarbon contaminants (right) of PFPE-coated glass on day 1 and day 14.
(Reprinted with permission from ref. 31.)
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and water dyed with red color were sequentially placed on the
surface. Aer little bit tilting the substrate, all the oil droplets
were displaced by water and were washed away from the glass
slides. They also performed comparable experiments with
hydrophobic-modied and clean glass slides. The oil droplets
stayed on these two substrates and could not get washed away by
water only. Brown et al.63 carried out the similar experiment to
demonstrate the self-cleaning capability of glass slide modied
with oleophobic/hydrophilic coating. Hexadecane on the coated
glass slide could be rinsed away with water, leaving a clean
surface as shown in Fig. 15(2). Moreover, Pan et al.61 extended
the substrate from glass slide to cotton fabrics that are highly
desired for the self-cleaning property in our daily life and the
good self-cleaning property was observed, as shown in Fig. 15(3).
4.3. Anti-fouling
Fouling occurs because the adhesion of some unwanted mate-
rials on the surface damages the function of this surface.
Generally, a hydrophilic surface is found to have a good anti-
fouling performance and it can especially be used against
organic and biological fouling.114–116 This is because the hydro-
philic surface can form a defense layer of steric hydration,
which can repel the adsorption of the foulants, resulting in an
anti-fouling performance.37,117 However, the hydrophilic surface
can be easily ruined by oil-style components and an additional
process to remove these oil foulants is required for anti-fouling
functional surfaces. Therefore, a both oleophobic and hydro-
philic surface, which not only can reduce the adsorption of
organic and biological foulants but can also repel the contam-
ination of the oils, is anticipated to solve this problem.
Zhu et al.35,38 synthesized a novel polymeric membrane with
both hydrophilic and oleophobic properties. This membrane was
demonstrated to not only have a good resistance for organic and
biological fouling but also provide a high ux of water. For example,
PVDF with 30 wt% AP1 membrane could present an almost 100%
anti-fouling capability with the ltration tests up to two hours.35
4.4. Oil and water separation
Oil and water separation is a very important technology for
environmental protection not only because of the various oil-
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Fig. 15 Self-cleaning response of f-PEG: (1a–1d). Demonstration of self-cleaning: (2a) an uncoated glass slide and a poly(Et-alt-MA)–fluo-
rosurfactant complex coating solvent cast from DMF fouled with hexadecane; (2b) after a quick rinse with water. Process of oil replacement and
surface self-cleaning: (3A) flat smart coating and (3B) smart SOP cotton fabrics: oil stains can be easily replaced and rinsed off by water without
any detergent. (Reprinted with permission from ref. 10, 61 and 63.)

related pollutions generated from the industries,118,119 but also membrane is crucial for the separation efficiency.122,123 The
due to the frequently occurred oil spilling accidents selection of membranes with different wetting behaviors for oil
recently.120,121 Membrane ltration method is widely used for oil and water gravity-driven separation is dependent on the density
and water separation, and the surface property of the difference of water and oil.22,124–127 When oil is heavier than

Fig. 16 Oil/water separation studies of the PAM hydrogel-coated mesh. The pore size of the mesh is about 50 mm. (a) The coated mesh was fixed
between two glass tubes, the mixture of crude oil and water was put into the upper glass tube. (b) Water selectively permeated through the
coated mesh, while the oil was repelled and kept in the upper glass tube. (c) The separation efficiency of the PAM hydrogel-coated mesh for
a selection of oils in terms of their oil rejection coefficient. (d) The theoretical and experimental values of intrusion pressures for a series of oils.
(Reprinted with permission from ref. 68.)

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water, superhydrophobic/oleophilic membrane can be used to
separate oil and water emulsion.128 However, this membrane
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can be fouled with oil, resulting in a decrease of separation
selectivity and efficiency in a long time.38 Moreover, in nature,
the density of water is usually larger than that of the most of the
oils and organic solvents. Superhydrophobic/oleophilic
membrane cannot be used for the gravity-driven separation
when oil is lighter than water, whereas hydrophilic and oleo-
phobic membrane is able to solve these problem. It can not only
reduce the oil fouling, but also can separate water and lighter oil
emulsions.22
Jiang's group fabricated and developed a series of
hydrophilic/underwater oleophobic surfaces, which presented
a very good oil and water separation property.68,69,71 For
example, they used a PAM hydrogel-coated stainless steel as
the separation membrane to testify the separation efficiencies
of selected oils and water. As shown in Fig. 16(a and b), aer
pouring water and oil mixture solution on the separation
mesh, almost all the water could penetrate the mesh, whereas
all the oil could remain on the top of the mesh. The experi-
mental results showed that the separation efficiencies of
different oils and water could all reach as high as 99%, as
shown in Fig. 16c.68
Moreover, the hydrophilic/underwater superoleophobic
membranes not only presented a high efficiency of oil/water
separation, but also had the abilities of excellent durability
and stability,69,75,99 protein adsorption,83 anti-fouling and
corrosion resistant,68,91 and robustness.70
Fig. 17 (a) The solely gravity-driven separation for oil–water mixtures
using the x-PEGDA@PG-8 NF membrane. For convenience oil was
dyed red. (b) Images of the oil–water mixture (soybean oil) and water
and oil collected after separation. (c) Images and optical micrographs
of the oil–water emulsion before and after separation. (Reprinted with
permission from ref. 99.)
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For example, Aikifa et al.99 indicated that the super-
hydrophilic and oleophobic x-PEGDA@PG-8 NF membrane had
an ultrafast oil and water separation rate and high separation
efficiency (as shown in Fig. 17). Moreover, they proved that this
membrane could achieve a long time separation performance
due to its special wetting behavior: it continuously separated
10 L of water and oil mixture solution without reducing the ux
of the liquid. These anti-fouling water and oil separation
membranes have high potential applications in the industry
and daily life in the future.
Additionally, Zhang et al. testied the oil and water separation
performance of PDA/PEPA/disulde bond-coated membrane and
found that the separation efficiency of this underwater super-
oleophobic membrane could be larger than 99.9% for various
oils such as hexane, gasoline, and methylbenzene. Moreover, it
could adsorb all the protein (bovine serum) that dissolved in
water during the separation process.83 Lin et al. investigated
the compressive properties of hydrogels. It was found that
C-hydrogels that are used to fabricate underwater super-
hydrophobic surfaces could resist high stress and presented very
good mechanical property. This robust property is able to adapt
different underwater environment for real life applications.70
5. Conclusions and outlook
In this review, surfaces with special oleophobic/hydrophilic
wetting behavior have been discussed. We summarized three
approaches, including simultaneously oleophobic/
hydrophilic behavior, oleophobic/hydrophobic to hydro-
philic switching behavior, and hydrophilic/underwater oleo-
phobic behavior, to achieve this special behavior. These
surfaces are usually fabricated using selected polymers
comprising both hydrophilic and hydrophobic segments via
different techniques such as dip-coating, UV illumination,
and solution casting. Besides preparing functional materials,
oleophobic/hydrophilic behavior can also be realized by
designing the surface geometry such as micro/nano-
hierarchical structure-based surfaces. Furthermore, three
plausible proposals of the underlying mechanisms were
reviewed. The penetration mechanism proposed that the
novel wetting behavior may be due to the fact that small water
molecules can immediately penetrate the polymer coating,
whereas the large oil molecules cannot penetrate or much
more slowly penetrate. In contrast, the ip-op mechanism
proposed that the polymer coatings may take different
conformations on top of the surface when facing with water
and oil: more hydrophilic segments will be attracted with
water, resulting in a hydrophilic property. Moreover, tradi-
tional wetting theory, such as Cassie–Baxter model, can be
applied to explain the special hydrophilic/underwater oleo-
phobic behavior. Last but not the least, we selectively intro-
duced the possible applications of oleophobic/hydrophilic
surface. Since this surface can wet water and repel the oil in
a long term, it can be used to solve many traditional applica-
tion problems such as fouling for oil and water separation
membrane, oil contaminated on the anti-fogging surfaces,
and detergent-involved self-cleaning surfaces.
This journal is © The Royal Society of Chemistry 2017

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To date, the oleophobic/hydrophilic wetting behavior
surfaces have still rarely been reported and more development
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and exploitation are required on this topic since this surface has
high potential benets in many important applications. More-
over, the underlying mechanism of the oleophobic/hydrophilic
surface is still under debate and an acceptable and well-proved
mechanism is required to be indicated. The surface stability
and surface economic effectiveness are also required to be
considered for the real life applications.
Acknowledgements
This study was nancially supported by the National Natural
Science Foundation of China (No. 21104069). This study was
also supported by “the Fundamental Research Funds for the
Central Universities (WUT: 2017IVA089)”.
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