Accepted Manuscript

Switchable oil/water separation with efficient and robust Janus nanofiber membranes

Yunshan Jiang, Jingwei Hou, Jia Xu, Baotian Shan

PII: S0008-6223(17)30063-5
DOI: 10.1016/j.carbon.2017.01.053
Reference: CARBON 11662

To appear in: Carbon

Received Date: 9 November 2016

Revised Date: 15 January 2017
Accepted Date: 16 January 2017

Please cite this article as: Y. Jiang, J. Hou, J. Xu, B. Shan, Switchable oil/water separation with efficient
and robust Janus nanofiber membranes, Carbon (2017), doi: 10.1016/j.carbon.2017.01.053.

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Switchable Oil/Water Separation with Efficient and Robust Janus Nanofiber Membranes
Yunshan Jianga, Jingwei Houb, Jia Xua*, Baotian Shana*
a.
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education; School of Medicine and Pharmacy, Ocean University of
China, Qingdao, 266100, P. R. China. jiapipi2@163.com; btshan@ouc.edu.cn
b.
UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, The University of New South Wales, Sydney, NSW
2052, Australia.

Abstract

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In this study, we proposed a facile approach to fabricate Janus membranes showing switchable
separations of oil-in-water and water-in-oil emulsions. The Janus membrane was constructed via
a hydrophilic polyacrylonitrile electrospun nanofiber (PANEN) membrane with a single-side

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hydrophobic carbon nanotube (CNTs) network coating. The growth mechanism of the CNTs
network on a nanofiber membrane was proposed and experimentally verified via modulating
CNTs loading and depositing time. By introducting an ultralow amount of CNTs (loading of
1.6-31.8 mg m-2) , the membrane exhibited both satisfactory mechanical and chemistry stability.

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Moreover, the CNTs@PANEN membrane exhibited asymmetric wettability on each side: the
hydrophilic PANEN side had underwater oleophobicity, and the hydrophobic CNTs side had
underwater oleophilicity. As a result, the CNTs@PANEN membranes had a switchable oil/water

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separation performance in different operating modes: highly efficient oil-in-water emulsion
separation with the PANEN side and water-in-oil emulsion separation with the CNTs side. Due to
their highly porous and surface anisotropic nature, the Janus nanofiber membranes had an
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ultrahigh operational flux and separation efficiency, and the incorporation of CNTs could
promote the water flux via the facilitated water detachment on the permeate side, promising for
water remediation in practice.
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Keywords

Janus nanofiber membrane; Electrospun nanofiber; Carbon nanotube; Switchable oil/water

separation; Mechanical stability
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1. Introduction
With the rapid development of global industry and frequent occurrence of oil spill accidents,
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the oil-containing wastewater has become a serious problem.[1, 2] It is urgent to develop a

method to effectively separate oil/water mixtures, and this aspect has received broad attention
in recent years. Many techniques such as oil-absorbing materials,[3] oil skimmers[4] and
floatation[5] have been developed for the oil/water separation. Even though the separation of
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immiscible oil/water can be achieved, an effective separation of oil/water emulsions is still

challenging. Current research focused on the development of new material with special surface
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wettability for selective absorption and filtration.[6-8] Among them, membranes have attracted
widespread interest for their capability for highly efficient oil/water separation and continuous
operation. For example, Xu’s group has developed a series of superhydrophilic membrane via the
bio-inspired mineralization on polymer membrane surface, and then the hydrophilic membranes
were applied for oil-in-water emulsion separation.[9, 10] On the other hand, the water-in-oil
emulsion separation can be realized with the hydrophobic membranes.[11]
Among different membrane fabrication process, the electrospinning is a relatively facile
approach to prepare nonwoven membranes.[12-14] It can generate micron-sized or even
nano-sized fibers consisting highly porous membrane structure.[15-17] So far, the electrospun
nanofiber membranes (ENMs) have been applied in various applications in water treatment, such
as ultrafiltration, nanofiltration and forward osmosis.[18-22] In addition, the ENM exhibits
enormous potential in oil/water emulsion separation due to their high porosity, interconnected
porous structure, controllable pore size, and large surface area to volume ratio.[23, 24] However,
the high porosity as well as the weak bonding due to the separation and overlap of individual
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fibers also lead to poor mechanical strength for these membranes.[23, 25, 26]
In order to improve the ENMs durability, various techniques have been employed such as
fabricating self-bundled fiber yarns,[27] blending carbon nanotubes,[28] silicates and graphite
nanoplatelets[29] into electrospinning precursor solution, which all focused on the enhancement
in mechanical strength of single or bundled fiber. In order to strengthen the bonding between
separated fibers, ENM surface coating might be a viable and facile approach, which also would
provide extra properties to the ENMs such as a “Janus” membrane with asymmetric chemistry on
each side.
Because of their interestingly anisotropic surface activities, Janus membranes have attracted
tremendous attention nowadays in various potential applications including liquid directional
transport, gas liquid contactor and aerator.[30-32] Besides, the feasibility of Janus membrane was

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also examined for oil/water separation recently. Due to their asymmetric wettability on each side,
the bilayer membranes could show the “switchable” behavior to separate oil-in-water or
water-in-oil emulsions under different operation conditions.[33, 34] For example, Hu et al. coated a

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thin layer of hydrophobic carbon nanotubes (CNTs) on a polydopamine-modified hydrophilic CNTs
support to fabricate a Janus CNTs membrane, exhibiting both water-in-oil and oil-in-water
separation behavior in respond to the applied feed pressure.[34] Gu et al. fabricated a Janus
membrane by grafting hydrophobic polymer and hydrophilic polymer from different sides of CNT

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membranes respectively via photografting and photopolymerization.[33] Although this membrane
had great potential for oil/water separation, the complicated fabricating operation makes it a
challenge in practical manufacture. As a result, the ENM based Janus membrane would
potentially provide highly efficient and switchable transport performance for both water-in-oil

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and oil-in-water emulsions. However, to the best knowledge of the authors, no such Janus
membrane has been reported to date.
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By taking advantage of Janus membranes and ENM, herein, we first report a remarkably facile
approach toward designing a Janus-type electrospun nanofiber membrane with opposing
wettability and strong mechanical property for highly effective separation of both water-in-oil
and oil-in-water emulsions. In this study, the hydrophilic polyacrylonitrile (PAN) nanofiber
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membrane was firstly prepared via electrospinning technique and subsequently coating with an
ultrathin layer of hydrophobic CNTs on a single side to achieve the strong bonding between
separated fibers and anisotropic surface activities. Comprehensive characterization of the
obtained Janus CNTs@PANEN membrane was carried out to study the effects of CNTs coating on
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the membrane mechanical properties and wettability. Separation performance of the Janus
membrane for both oil-in-water and water-in-oil emulsions was investigated and compared with
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that of pure ENM membrane. In addition, CNTs deposition technologies such as dropping or spin
coating could make CNTs deposited on the nanofiber membrane a uniform coating in a large area
and thus the Janus CNTs@PANEN membrane is designed to match the size and shape of a practical
filter. Based on its unique features, the Janus CNTs@PANEN membrane exhibited ultrahigh
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permeation flux and separation efficiency in oil/water separation, promising for water
remediation in practice.
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2. Experimental
2.1 Materials
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Polyacrylonitrile (PAN, Mw ~ 50000) was purchased from the Shanghai Jingshan Petrochemical
Company. N,N-dimethylformamide (DMF, analytical grade) was purchased from the Tianjin Fuyu
Fine Chemicals Co. Ltd, China. Commercial Single-walled CNTs (SWCNTs) (OD: <2 nm, length: 5-30
μm, purity: >95%) used in this work were supplied by Nanjing XFNANO Materials Tech Co. Ltd,
China. Deionized (DI) water used in all experiments was further purified using a Millipore water
purification system to a minimum resistivity of 18.0 MΩ cm-1. Petroleum ether and chloroform
used as the oily component in oil/water emulsions were purchased from the Tianjin Fuyu Fine
Chemicals Co. Ltd, China.

2.2 Fabrication of Janus CNTs@PANEN Membranes

Electrospinning precursor solution composed of 14 wt% PAN and 86 wt% DMF was stirred at
80°C for 24 h to form a homogeneous solution. Then the precursor solution was filled into a
plastic syringe with a 25-gauge (inner diameter 0.25 mm) flat needle which was then connected
to a high voltage. An aluminum foil collector was centered vertically at a distance of 18 cm from
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the flat needle. Electrospinning operation was conducted at a voltage of 18 kV for 1 h with a flow
rate of precursor solution at 2 mL h-1 and the PANEN membrane was subsequently obtained. After
the completion of electrospinning, the obtained PANEN membrane was placed in a filter with a
filtration cell of 44 mm in effective diameter. CNTs suspension (concentration = 0.04 mg ml-1) was
prepared according to the previous study [12] for the CNTs coating. The Janus membrane was
fabricated by depositing an ultrathin CNTs layer onto the PANEN membrane via a vacuum filtration
technique at 0.07 MPa. Finally, the obtained Janus CNTs@PANEN membrane was incubated in an
oven at 60 °C for 8 min, ensuring that the CNTs are packed closely. In addition, the loading of
CNTs on the PANEN membrane was modulated by the CNTs suspension volume ranging from
0.05-1.0 mL. The resultant membrane was referred as CNTsx@PANEN membrane (hereafter CNTsx,

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where subscript x denotes the volume (mL) of CNTs suspension deposited).

2.3 Characterizations
Surface and cross-sectional morphology of the membrane was observed using a field emission

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scanning electron microscopy (SEM, HITACHI, S-4800, Japan). PAN fiber diameter was processed
by the image-pro-plus software using 100 fiber images. Mechanical strength of the membrane
was determined by a tensile testing equipment (SHIMAZDU, AGS-J) at an elongation speed of 1
mm/min. Static contact angle (CA) in air and underwater for both sides of the Janus membrane

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was measured using an optical contact angle meter (DSA100, KRUSS, Germany). Hydrodynamic
diameters of emulsions were measured using dynamic light scattering (DLS, Zetasizer Nano S90,
England) and an optical microscopy (Olympus BX51). Concentrations of oil and water in the feed
and filtrate were measured using a total organic carbon analyzer (TOC, liquid TOC II, America) and

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a trace moisture titrator (870 KF Titrino plus, Switzerland), respectively.
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2.4 Preparation and Separation of Oil-in-Water and Water-in-Oil Emulsions
For the petroleum ether-in-water emulsion, a mixture containing DI water and petroleum
ether with a volume ratio of 9:1 was sonicated under 300 W for 3 h and stirred overnight. For the
water-in-chloroform emulsion, the mixture of 99 ml chloroform and 1 ml water was sonicated
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under 300 W for 3 h and stirred overnight with the aid of 0.05 g SPAN 80. All the prepared
emulsions were stable for 12 h, and no demulsification was observed. The emulsions were
performed for oil/water separation once prepared. Oil/water separation experiments (Figure S1,
Supporting Information) were carried out with a vacuum driven filtration system with the vacuum
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degree at -0.07 MPa. The diameter of filtration cell is 44 mm. All the membranes were
pre-compacted for 30-60 min with DI water until their permeation flux was stable. Each side of
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the Janus CNTs@PANEN membrane was tested for both water-in-oil and oil-in-water separation,
respectively. Water flux for DI water and permeation flux for emulsions of the membrane can be
determined by calculating the volume of permeate in unit time using equation (1). Separation
efficiency characterized by rejection for emulsions was calculated using equation (2).
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V
Flux = (1)
A × ∆t × P
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Cfiltrate
R = (1 − ) × 100% (2)
Cfeed
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where V is the volume of permeate, A is the effective area of the membrane, P is the vacuum
pressure and Δt is the testing time. Cfiltrate and Cfeed are concentrations of filtrate and the original
oil/water feed after one time separation, respectively.

3. Results and discussion

3.1 Membrane Morphology
The overall fabrication process of the Janus CNTs@PANEN membrane is illustrated in Figure 1,
including only two simple steps: firstly electrospinning followed by CNTs coating. PANEN layer was
prepared on aluminum foil substrate via electrospinning technology and then we carefully
stripped away the free-standing PANEN membrane from the substrate while keeping the PANEN
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membrane intact (Figure S1, Supporting Information). Representative SEM images of PANEN
membrane are shown in Figure S1 (Supporting Information), exhibiting a highly porous surface
and cross-sectional morphologies and symmetrical structure for both top and bottom surfaces.
An even thickness of approximately 13 μm and remarkably uniform fibers with an average
diameter of approximately 211 nm (Figure 2a) were also observed. Actually, the CNTs loading on
the PANEN membrane surface can be finely modulated by tuning the volume of CNTs suspension
deposited, because CNTs can be entirely retained by the frameworks constructed by nano-sized
fibers of the PANEN membrane, which was confirmed by UV measurements for the filtrate from
CNTs suspension (Figure S2, supporting information). Under our coating conditions, the
corresponding CNTs loadings were in the range of 1.6-31.8 mg m-2 (Figure 2b).

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Figure 1. Schematic illustration of the fabrication process for Janus CNTs@PANEN membranes.

SEM was used to investigate the morphology information, as shown in Figure 2c and Figure S3
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(Supporting Information), demonstrating a significant impact of CNTs loading on the CNTs

interpenetrating distribution and the formation mechanism of CNTs coating on the nanofiber
membrane surface. With an ultralow CNTs loading of 1.6 mg m-2, the CNTs was just deposited at
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the inter-nanofiber junctions of PANEN membrane surface and entangled the junctions of
individual fibers, which had little impact on the porosity and pore structure of PANEN membrane.
With an increase in the CNTs loading of more than 3.2 mg m-2, apart from the entanglement of
inter-nanofiber junctions of PANEN fibers, overlapping interactions between CNTs appeared to
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gradually construct an interpenetrating network nanostructure. The pore size on the

CNTs@PANEN membrane surface became narrower with the CNTs loading. When the CNTs loading
increased to 31.8 mg m-2, the PANEN membrane was visible no longer and completely covered by
a randomly oriented interpenetrating CNTs networks. Such a network showed a similar
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morphology and porosity to those SWCNT films formed on the conventional microfiltration
substrates such as mixed cellulose ester.[12,37] From the cross-sectional SEM images, it can be seen
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that the all the CNTs were deposited on the top surface of PANEN membrane, while there was no
CNTs observed inside the PANEN membrane or on the bottom surface.
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Figure 2. (a) Fiber size distribution of the CNTs@PANEN membranes. (b) CNTs loading of the
CNTs@PANEN membranes with different CNTs suspension volumes. (c) Photos and SEM images of
the CNTs side, PANEN side and cross-section with scale bars for the CNTs@PANEN membranes with
different CNTs loadings.

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In addition, we found that the growth evolution of CNTs network on the nanofiber surface with
depositing time was perfectly consistent with its gradual formation with CNTs loading (Figure S4,
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Supporting Information), mainly experiencing three stages: solidification of inter-nanofibers
junctions, self-entanglement of CNTs and final interpenetrating network. The growth mechanism
would also facilitate a good interfacial compatibility between PANEN membrane and CNTs coating,
which could potentially enhance the mechanical strength of the Janus CNTs@PANEN membrane.
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3.2 Mechanical and Chemical Stability

Ideally, the composite Janus fibrous membrane should be able to conduct filtration
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independent of extra substrate. Any extra substrate would not only increase the membrane mass
transfer resistance, but also change the surface wettability and thus deteriorate the oil/water
separation efficiency.[34] In this work, the introduction of CNTs layer and the good interfacial
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compatibility between CNTs and PANEN fiber would promote the whole composite membrane
mechanical property.[35] In order to verify this, the tensile strength, initial modulus and elongation
at break of PANEN and CNTs@PANEN membranes were measured (Figure 3). The results clearly
suggested an improvement in the mechanical properties after even the CNTs coating with
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ultralow loading (1.6 mg m-2). It can be explained considering by the effectiveness of the positive
solidification of inter-nanofibers junctions via CNTs entanglement to improve the interconnection
between the PANEN fibers. It also facilitated the interface stability between PANEN membrane and
CNTs coating, which was confirmed by the integrity of the CNTs@PANEN membrane without
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peeling off of CNTs coating after the separation of oil-in-water emulsion with PANEN side facing
the emulsion.
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In addition, generally with the increase of CNTs loading, higher elongation at break, tensile
strength and initial modulus values were observed, indicating a further enhancement in the
mechanical properties of the CNTs@PANEN membranes. In this work, CNTs were firstly dispersed
in water and then deposited onto the PANEN membrane. During the drying process for the
membrane with CNTs self-entanglement, strong CNT-CNT internanotube van der Waal attractions
(π-π stacking) are generated due to the capillary effect and hydrophobic interaction,[36] leading to
a robust interaction between CNTs and better compatibility between CNTs network and PANEN
membrane. However, the only exception was the CNTs1.0@PANEN membrane, where an obvious
loss of initial modulus was observed. It could be attributed to the difficulty in achieving a
homogeneous CNTs coating when the CNTs loading was relatively high because CNTs tend to form
aggregates to minimize their surface energy due to their hydrophobic nature in the aqueous
environment.
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Figure 3. Mechanical properties of the PANEN and CNTs@PANEN membranes with different CNTs
loadings. (a) Stress-strain curves. (b) elongation at break, tensile strength and initial modulus.

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For a practical oil/water separation, another important aspect of the composite membrane is
the chemical stability. We soaked the Janus CNTs@PANEN membranes into solution with different

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pH (1, 5, 7, 9 and 14) for 48 hours. Based on the visual observation (Figure S5, Supporting
Information), SEM (Figure S6, Supporting Information) and UV-Vis measurements (Figure S7,
Supporting Information), the Janus CNTs@PANEN membranes exhibited a satisfactory stability
and no detachment of CNTs was observed. It can be attributed to the significant chemical

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resistance for both PAN and CNTs as well as the strong compatible entanglement between two
separated layers.
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3.3 Wettability
In order to explore the Janus property of the CNTs@PANEN membrane, comprehensive
spreading and wetting tests were carried out to understand the water/oil wettability as well as
underwater oil/underoil water wettability for both sides of the membranes. As shown in Figure
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4a, Table S1 (Supporting Information) and Figure S8 (Supporting Information), for the pure PANEN
membrane, the water droplet spread rapidly on the membrane surface, attributing to the
significantly hydrophilic and highly porous natures on both sides of the PANEN membrane. In
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terms of the Janus membrane (Figure 4), the CNTs1.0@PANEN membrane clearly had opposing
wettability by water on each side. For the hydrophobic CNTs side, the initial water contact angle
was around 100°, then the water droplet gradually permeated into the membrane with a
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decrease of conjugated diameter. This observation aligned the directional transport behavior of a
Janus membrane.[31, 37] In this study, the CNTs1.0@PANEN membrane consisted by a thin
hydrophobic CNTs layer on a porous hydrophilic PANEN support. When a water droplet was placed
onto the CNTs layer, it tends to reduce its surface energy by spreading into the PANEN support. In
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addition, we also investigated the effect of the CNTs loading on the surface water and oil
wettability (Figure S8, Supporting Information). It is clear that with the increase of CNTs loading,
the CNTs side became increasingly hydrophobic and oleophilic, while the PANEN side was
relatively unchanged. This observation was in good agreement with previous SEM images (Figure
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2c), where more and more CNTs were deposited on the top surface rather than the bottom
surface of PANEN membrane with the CNTs loading. The increased hydrophobicity on the CNTs
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side could be attributed to the hydrophobic nature of CNTs and the nano-scale roughness on the
CNTs coating layer.[30]
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Figure 4. Spreading and wetting behaviors of water and oil droplet on the PANEN and
CNTs1@PANEN membrane surface (oil: petroleum ether).

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Good hydrophilicity generally leads to high oleophobicity in a water environment.[9, 10] As
presented in Figure 5, the hydrophilic PANEN side of the CNTs@PANEN membrane exhibited a good
underwater oleophobicity. Here, chloroform was selected to investigate the underwater oil

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wettability due to its higher density than water. Based on the SEM images in Figure 2c, the PAN
fiber surface had nano-scale roughness. As a result, the water entrapped within the PAN fibrous
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matrix and the surface nanostructures resulted in the “Cassie-Baxter” synergic effect at the
solid/water/oil interface, and the underwater oil contact angle can be expressed the following
equation.[38] It contributed to an improved the surface underwater oleophobicity of the PANEN
side, suggesting a good potential of the CNTs@PANEN membrane to separate the oil-in-water
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emulsions, which will be discussed later.

cos θ * = f ( R f cos θ + 1) − 1 (3)

where θ* is the static underwater oil contact angle, f is the effective surface area of solid-oil
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interface, Rf is a factor of surface roughness and θ is the underwater oil contact angle of a flat
surface.
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Figure 5. Underwater oil wettability of the CNTs@PANEN membrane with different CNTs loadings.
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In terms of the CNTs side of the CNTs@PANEN membrane, higher CNTs loading led to an
increasing underwater oleophilicity, as the oil tended to spread on the hydrophobic CNTs layer to
minimize the surface energy. The observed distinct underwater oleophobicity and oleophilicity
for the PANEN and CNTs sides, respectively, provide an excellent basis for its application in
separating both water-in-oil and oil-in-water emulsions. Besides, in this work, we also
investigated the underoil water wettability of the CNTs@PANEN membranes and the results are
shown in Figure S9 (Supporting Information). Under oil environment, the membrane presented
hydrophobicity on both sides, including the hydrophilic PANEN side. Although higher affinity

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between PANEN and water can be expected, the presence of oil in the micro/nanostructures
prevents the wetting of the PANEN side by water. Such hysteresis was also observed by other
researchers.[39]

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3.4 Separation Performance for Oil-in-Water and Water-in-Oil Emulsions
The most remarkable property of the Janus membranes is their opposing wettability on each
side.[40] However, how this property affects the oil/water separation behavior has not been fully
understood. In this work, we applied the CNTs@PANEN membrane to separate oil-in-water and

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water-in-oil emulsions using both sides and investigated the utility of anisotropic wettability of
each side on the separation performance.

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Figure 6. Separation performance of oil-in-water emulsion using the PANEN side of CNTs@PANEN
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membranes. (a) Pure water flux, water flux and oil rejection by the pure PANEN and CNTs@PANEN
membrane, and (b-c) separation results by the PANEN side of the CNTs0.5@PANEN membrane.

We firstly tested the filtration of pure water and separation of an oil-in-water emulsion with
the PANEN side. As presented in Figure 6a, the original PANEN membrane was highly permeable,
with a pure water flux of ~130,000 L m-2h-1bar-1. This can be attributed to the highly porous
structure and surface hydrophilicity of the PANEN membrane. While for separating the
oil-in-water emulsion, the water flux of the PANEN membrane reduced to ~55,000 L m-2h-1bar-1
with an oil rejection of more than 95%. The relative high rejection is obtained due to its
underwater oil-repellency of the hydrophilic PANEN surface (Figure 5). The rejected oil would
accumulate and form an oil layer on the membrane surface with filtrating time, which would
increase the mass transfer resistance and lead to a lower permeation capacity.[9, 10] Based on the
DLS data for the oil-in-water emulsion (Figure 6b), the oil droplet had an average diameter of ~1
µm. Due to the presence of micron-scale pores on the PAN fibrous membrane, some small oil
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droplets could still permeate through the pure PANEN membrane, resulting in its lower oil
rejection.
In terms of the CNTs@PANEN membranes using PANEN side facing the pure water (Figure 6a),
with the increase of CNTs loading on the membrane, the pure water flux firstly increased and
then reduced significantly. Here, we believe that the CNTs coating has three opposing effects on
the pure water permeability of the CNTs@PANEN membrane. Firstly, it can improve the
mechanical rigidity of the nanofiber membrane, which provides extra resistance to the pressure
induced compaction during the filtration process and better preserved the original porous
structure. Secondly, during the filtration test, the CNTs layer was contact with the permeate side.
Its hydrophobic nature would facilitate the rapid detachment of water droplets under gravity,

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leading to a higher water flux. And thirdly, the incorporation of CNTs layer would also increase
the mass transfer resistance and thus reduce the water flux. The change in pure water flux with
different CNTs loading was a result of the above-mentioned synergistic effects, especially effect 2
and 3. In terms of the separation of oil-in-water emulsion using the same side of CNTs@PANEN

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membranes, the water flux followed a similar profile as the pure water flux that the increase of
CNTs loading firstly enhanced the flux followed by an obvious reduction. In addition, the
incorporation of CNTs also increased the oil rejection dramatically, with over 99.5 % removal of
oil when the CNTs loading was higher than 3.2 mg m-2 (the corresponding volume of CNTs

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suspension of 0.1 mg mL-1) (Figure 6a). This can be explained by two aspects: the CNTs layer with
smaller pores can effectively seize the oil droplets; and the reduced water flux increased the
retention time of emulsion within the membrane matrix, allowing the small droplets to merge.

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We further investigated oil-in-water emulsion separation with the CNTs side of the
CNTs@PANEN membrane, and the results are presented in Figure S10 (Supporting Information). It
is clear that both the water flux and oil rejection were lowered significantly. As presented in
Figure 5, the underwater oleophilic CNTs coating layer can absorb oil droplets from the emulsion.
The resultant oil layer not only blocked the water transport pathway, the highly locally
concentrated oil layer may potentially lead to the re-emulsification effect under the
filtration-induced hydraulic shear force conditions. Therefore, based on above results, the PANEN
side of the CNTs@PANEN membrane is suitable for the oil-in-water emulsion separation. It should
be noted that the pure water flux for the CNTs side of CNTs@PANEN membranes exhibited
different tendency from that for the PANEN side. When the CNTs side was in contact with the DI

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water, the pure water flux constantly reduced with an increase in CNTs loading in the whole
testing range of CNTs loadings, while for the PANEN side an increase of the flux was observed
when a relatively low amount of CNTs was coated (Figure 6a). Considering both their membrane
material and structure are identical, the flux difference should be originated from the rapid water

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detachment effect when the hydrophobic CNTs layer was facing the permeate side as discussed
above.
In order to study the feasibility of the CNTs@PANEN membrane for the water-in-oil emulsion
separation, the membrane was firstly placed into the filtration cell with CNTs side facing the

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water-in-oil emulsion feed. As shown in Figure 7a, high water rejection was obtained with all
membranes and the incorporation of hydrophobic CNTs slightly increased the rejection, which
was related to their underoil hydrophobic property. As shown in Figure S9 (Supporting
Information), both PANEN and CNTs exhibited underoil hydrophobicity, and a slightly higher

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underoil water contact angle was observed with CNTs. On the other hand, during the filtration
process, the water droplet on the thin CNTs layer could gradually migrate through the thin
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hydrophobic CNTs layer into the hydrophilic PANEN layer, as per the directional water transport
discussed earlier. This would eventually lead to re-emulsification and be detrimental to the
effective water separation. However, this unwanted phenomenon could be eased by the increase
of CNTs loading, as the increasing integrity of CNTs layer would mitigate the spontaneous water
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migration. Similarly, we also observed the increase of oil flux with the initial incorporation of
CNTs, and this can be attributed to the oleophilic nature of CNTs. Further increase of the CNTs
loading led to the loss of the emulsion flux, mainly due to the increased mass transfer resistance.
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Figure 7. Separation performance of water-in-oil emulsion using the CNTs@PANEN membranes. (a)
Oil flux and water rejection by the pure PANEN and CNTs side of CNTs@PANEN membranes, (b-c)
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separation results by the CNTs side of the CNTs0.5@PANEN membrane.

We finally conducted the water-in-oil emulsion separation with the PANEN side of CNTs@PANEN
membrane (Figure S11, Supporting Information), and slightly lower water rejection and oil flux
were observed, which is attributed to its lower underoil hydrophobicity compared with the CNTs
side (Figure S9, Supporting Information). These results prove that the CNTs side of CNTs@PANEN
membrane is more suitable for the water-in-oil emulsion separation.

3.5 Comparison with other membrane for oil/water separation

The development of highly efficient membrane for oil/water separation has attracted great

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attention lately. Hereby we summarized some representative examples of the membranes for
effective separations of water-in-oil and oil-in-water emulsions (Table 1). However, it should be
noted that the direct quantitative comparisons of the separation efficiency is very difficult as
most researchers only reported the change in oil purity or water content in filtrate regardless of

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their contents in feed. It is clearly seen from Table 1 that the membrane we developed exhibited
both ultrahigh flux for both water-in-oil and oil-in-water emulsions without compromising the
rejection. On the other hand, by introducing an ultralow amount of CNTs (loading of 1.6-31.8 mg
m-2) onto the electrospun nanofiber membrane, the resultant membrane exhibited both

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satisfactory mechanical and chemistry stability due to the strong bonding between separated
fibers. In addition, the facile, economical fabrication technique via electrostatic spinning and
subsequent single-side filtration coating significantly simplified the Janus membrane fabrication
process, promising for water remediation in practice.

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Table 1 Separation performance of the membranes for water-in-oil and oil-in-water emulsions
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Water-in-oil emulsion Oil2flux Rejection Oil Reference
Membrane Fabrication step (L/m hbar) (%) purity
M

Janus 99 mL chloroform, 1
CNTs@PANE 1. Electrospinning; mL water, 0.05 g
~12000 ~99.2% ~99.96 This work
N 2. CNTs filtration. SPAN 80. Sonication
membrane under 300 W for 3 h.
D

1. CNTs membrane;
Janus 2. Photo-grafting of
114 mL chloroform, 1
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polymer/ hydrophobic polymer; 33

mL water, 1.2 g SPAN ~7300 / ~99.95
CNTs 3. Photo-polymerization
80. Stirring for 3 h.
membranes of hydrophilic polymer on
another side.
1. CNTs membrane;
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Janus 100 mL chloroform, 1

2. PDA modification of
CNTs/PDA-C mL water, 0.08 g 17000- 34
CNTs filtration. / ~99.95
NTs SPAN 80. Stirring 40000
3. PDA-coated CNTs
membrane overnight.
filtration.
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1140 mL toluene
1. CNTs membrane;
CNTs ether, 10 mL water, 1 7
2. Dissolution of ~16000 / ~99.96
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membrane g SPAN 80. Stirring

substrate.
for 3h.
90 mL petroleum
PVDF-ammo 1. Casting solution
ether, 10 mL water. 41
nia preparation; ~3450 / ~99.94
Sonication under
membrane 2. Phase inversion.
1500 W for 1.5 h.
Janus PVDF 1. Casting solution
114 mL chloroform, 1
without preparation; 11
mL water, 0.5 g SPAN ~9554 / ~99.96
substrate 2. Phase inversion;
80. Stirring for 3 h.
membrane 3. Peeling off substrates.
Water flux Rejection Oil
Membrane Fabrication step Oil-in-water emulsion 2
(L/m hbar) (%) content Reference
(mg/L)
Janus 90 mL water, 10 mL
1. Electrospinning;
CNTs@PANE petroleum ether. ~80000 ~99.7 8-10 This work
2. CNTs filtration.
N Sonication under 300
 ACCEPTED MANUSCRIPT
membrane W for 3 h.

1. CNTs membrane;
Janus 2. Photo-grafting of
120 mL water, 4 mL
polymer/ hydrophobic polymer; 33
toluene, 1.2 g Tween ~5800 / /
CNTs 3. Photo-polymerization
80. Stirring for 3 h.
membranes of hydrophilic polymer on
another side.
1. CNTs membrane; 99 mL water, 1 mL
Janus
2. PDA modification of n-hexane, 0.01 g
CNTs/PDA-C 8000- 34
CNTs filtration. sodium dodecyl ~99.98 /

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NTs 40000
3. PDA-coated CNTs sulfate. Stirring for 1
membrane
filtration. day.
Cu(OH)2 1. Pre-clean of copper
90 mL water, 10 mL
nanowire-h mesh;

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n-hexane. Sonication 42
aired 2. Immersion of mesh 160000 / 20-30
under 2000 W for 0.5
copper into NaOH/(NH4)2S2O8
h.
mesh solution.

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Janus PVDF 1. Casting solution
120 mL water, 4 mL
without preparation; ~80 11
n-hexane. Sonication ~9380 /
substrate 2. Phase inversion; (UV-VIS)
under 450 W for 2 h.
membrane 3. Peeling off substrates.
90 mL water, 10 mL

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TiO2-modifi
1. CNTs membrane; petroleum ether. 43
ed CNTs ~32000 / 9
2. TiO2 sol-gel process. Sonication under
membrane
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2000 W for 0.5 h.

4. Conclusions
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To conclude, we have demonstrated for the first time the fabrication of a Janus nanofiber
membrane with an improved mechanical property and its feasibility in both oil-in-water and
water-in-oil emulsion separations. The fabricating technique of the Janus CNTs@PANEN
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membrane via electrospinning and subsequent CNTs network coating is remarkably facile, cost
effective and resource saving because an ultralow amount (1.6-31.8 mg) of CNTs is sufficient for
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making a square meter of the Janus nanofiber membrane. The introduction of such a small
amount of CNTs not only improved the mechanical and chemistry stability of the CNTs@PANEN
membrane, but only endowed the membrane with asymmetrically wetting property on each side.
Results showed that the hydrophilic PANEN side had underwater oleophobicity, while the
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hydrophobic CNTs side had underwater oleophilicity. As a result, the CNTs@PANEN membranes
had a switchable oil/water separation performance in different operating mode: highly efficient
oil-in-water emulsion separation with the PANEN side and water-in-oil emulsion separation with
the CNTs side. Due to their highly porous and Janus nature, the Janus CNTs@PANEN membrane
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had an ultrahigh operational flux and separation efficiency, and the incorporation of CNTs could
promote the water flux via the facilitated water detachment on the permeate side. Moreover, the
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growth mechanism of the CNTs network on a nanofiber membrane was proposed and
experimentally verified, mainly experiencing three stages: solidification of inter-nanofibers
junctions, self-entanglement of CNTs and final interpenetrating network. The integration of high
performance, low cost, and simple solution-based fabrication promises the Janus nanofilber
membranes a significant opportunity in a great potential application such as oil/water emulsion
separation.

Acknowledgements
This work was supported by NSFC (21306178), Shandong Province Key Project (2014GHY115033)
and Qingdao applied basic research project (15-9-1-21-jch).

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