Journal of Hazardous Materials 432 (2022) 128649

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Research Paper

Collagen fiber membrane as multi-functional support enabled rational

design of ultrahigh-flux separation membrane for the remediation of oil
contamination in water
Ni Xue a, Yiwen Cui a, Hanzhong Xiao a, Yujia Wang a, Yawen Huang a, Xin Huang a, b, *, Bi Shi a, b
a
National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065, PR China
b
Department of Biomass Chemistry and Engineering, Sichuan University, Chengdu 610065, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Collagen fiber membrane (CFM) played

the role as multi-functional support.
• CFM was able to provide separation
effectiveness and boost separation flux.
• A polyacrylonitrile layer in-situ grown
on CFM was hydrophilic and underwa­
ter superoleophobic.
• The composite membrane enabled effi­
cient separation of oil contamination in
water.
• Ultrahigh separation flux and separation
effectiveness were achieved.

A R T I C L E I N F O A B S T R A C T

Editor: Baiyang Chen Membrane separation is a promising approach for the remediation of oil contamination in water. High-flux
separation of membrane relies on the rational design of ultrathin active layer to significantly reduce mass
Keywords: transfer distance for achieving high separation flux, while the ultrathin active layer is usually fragile with poor
Oil contamination mechanical strength, which has to be supported on a support. Herein, we employed collagen fiber membrane
Collagen fiber membrane
(CFM) as multi-functional support for the in-situ growth of polyacrylonitrile (PAN) layer by electrospinning to
Multi-functional support
prepare the high-performance PAN/CFM composite membrane. Due to the amphiphilic nature and strong
Ultrahigh-flux separation membrane
Emulsion separation capillary effect, CFM played the role as multi-functional support to provide separation effectiveness and boosted
separation flux. The PAN/CFM composite membrane enabled ultrahigh separation flux (e.g., 51751.59 L m− 2 h− 1
bar− 1) to a variety of oil-in-water emulsion, which was one order of magnitude higher than that of commercial
polyethersulfone membrane and 1.86-fold to that of cellulose acetate membrane. Furthermore, the PAN/CFM
composite membrane retained high separation flux (e.g., 11046.97 L m− 2 h− 1 bar− 1) during the 5th separation
cycle, providing appreciable anti-fouling capability. Therefore, our findings provided a promising way to
effectively resolve the problem of oil contamination in water.

* Corresponding author at: National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065, PR China.
E-mail address: xhuangscu@163.com (X. Huang).

https://doi.org/10.1016/j.jhazmat.2022.128649
Received 24 December 2021; Received in revised form 14 February 2022; Accepted 6 March 2022
Available online 8 March 2022
0304-3894/© 2022 Elsevier B.V. All rights reserved.
N. Xue et al.
1. Introduction
Petrochemical industry, mechanical manufacturing, food processing,
textile dyeing and finishing industries produce a large amount of oily
wastewater, which seriously imperils the ecological environment (Gupta
et al., 2017; Zhang et al., 2020; Jjagwe et al., 2021; Yang et al., 2022).
Conventional treatment approaches, such as flocculation, gravity
centrifugation and oil skimming, are capable of treating immiscible oily
wastewater (Shalaby et al., 2021; Gao et al., 2014), but they suffer from
low separation effectiveness to emulsified oily wastewater (i.e., emul­
sion) with small droplet size, low surface energy, high dispersity and
high stability (Kang et al., 2012; Suzuki and Maruyama, 2005). Mem­
brane separation has attracted tremendous attentions as a promising
alternative for remedying the contamination caused by emulsified oily
wastewater due to the distinctive advantages of high separation effec­
tiveness, low energy consumption and simple operation (Ying et al.,
2020; Yue et al., 2018; Geng et al., 2022; Lu et al., 2021).
In general, separation membranes consist of active layer and the
support. The active layer, providing separation selectivity, lies in the top
layer of the membrane and is directly contacted with the emulsions
during the separation process. However, the active layer is usually
fragile with poor mechanical strength because of the thin thickness,
which has to be supported on the support that provides the membrane
with sufficient mechanical strength. Normally, the support is macro­
porous, which merely provides the membrane with needed mechanical
strength while has no contribution to separation selectivity or separation
flux (Samaei et al., 2018). For realizing high-flux separation, the most
widely utilized strategy is to design ultrathin active layer that relies on
significantly reduced mass transfer distance to enhance separation flux
(Zhang et al., 2019; Gao et al., 2018). However, the ultrathin active
layer is very fragile and is readily to wrinkle and even be damaged
during the transfer onto the support. In-situ growth strategy has been
developed to address the transfer problem of active layer (Wang et al.,
2016; Cheng et al., 2020), which eliminated the necessity of active layer
transfer completely. Besides the in-situ growth strategy, nanoparticle
reinforcement is another frequently utilized strategies to improve the
mechanical properties of membrane (Ma et al., 2022; Bay et al., 2020).
Although progressive achievements have been made in developing
high-flux separation membrane, it is still essential to find new way for
further improving the separation performance of membrane so as to
realize high-performance emulsion separation. In principle, if the sup­
port is capable of providing separation effectiveness and enhanced mass
transfer kinetics to the filtrate, high separation effectiveness combined
with ultrahigh flux is possible to accomplish without the necessary to
drastically reduce the thinness of active layer in the membrane. As a
consequence, we focused on exploring multi-functional support to
develop high-performance separation membranes that are capable of
separating oil contamination in water efficiently.
Collagen fibers are amphiphilic structural proteins widely existing in
animal skins, which feature supramolecular self-assembly of type I
collagen molecules, showing fiber structure at both nanoscale and
microscale (Li et al., 2021a). Due to the structural hierarchy as fibers,
collagen fiber exhibits distinctive mechanical properties, including
viscoelasticity, tensile strength and tear strength (Andriotis et al., 2015;
Woessner et al., 2021). Animal skin treated by tanning process, well
known as leather, is formed by the interwoven collagen fibers, which
therefore can be considered as amphiphilic collagen fiber membrane
(CFM) that has high mechanical strength (Huang et al., 2018), with the
tensile strength up to 27 MPa and the tear strength reaching 84 N mm− 1.
More importantly, when leather is utilized as CFM, the amphiphilic
collagen fibers comprised in leather are possible to provide separation
effectiveness due to their varied affinity to water and oil, and the hier­
archically fibrous structure of collagen fibers is able to provide efficient
capillary effect for realizing ultrafast liquid transport along the fiber so
as to boost the separation flux (Xiao et al., 2021). Polyacrylonitrile
(PAN) is widely used in fabricating separation membranes (Cai et al.,
2
Journal of Hazardous Materials 432 (2022) 128649
2017; Li et al., 2021b; Wu et al., 2020) because of its good chemical
resistance and hydrophilicity. Moreover, PAN contains strong polar
group of -CN on the molecular chain. The polar-polar interactions be­
tween the polar groups of PAN and the polar amino acid residuals of
CFM are expected to provide affinity and compatibility with each other
(Rana et al., 1996, 2000; Yong and Zhang, 2021; White et al., 2020).
Therefore, it is possible to develop a new type of high-flux separation
membrane based on the combination of PAN with CFM. In the present
investigation, we employed chrome-tanned cattle hide as CFM to serve
as multi-functional support for the in-situ growth of underwater super­
oleophobic layer of PAN by electrospinning to prepare the
high-performance PAN/CFM composite membrane. Due to the utiliza­
tion of CFM as multi-functional support with capillary effect, there is no
need for the PAN active layer to keep ultrathin thickness at nanoscaled
for improving the flux, which is as thick as 80 µm to ensure high me­
chanical stability for long-term separation while still successfully
obtaining ultrahigh separation flux (e.g., 51751.59 L m− 2 h− 1 bar− 1).
Furthermore, the varied affinity of amphiphilic CFM to water and oil
made contribution to separation effectiveness for the emulsions to be
separated. Therefore, the as-prepared PAN/CFM composite membrane
successfully realized ultrahigh-flux separations to a variety of
oil-in-water (O/W) emulsions (including SDS stabilized
dodecane-in-water emulsion, SDBS stabilized octane-in-water emulsion,
CTAB stabilized heptane-in-water emulsion and surfactant-free stabi­
lized dodecane-in-water emulsion), with separation effectiveness higher
than 99.99%. The separation flux of PAN/CFM composite membrane to
O/W emulsions was high up to 51751.59 L m− 2 h− 1 bar− 1. As far as we
know, this the highest separation flux so far obtained in O/W emulsion
separation. We also unfolded a 2-step separation mechanism of
PAN/CFM composite membrane to O/W emulsions. For the 1st separa­
tion step, the PAN layer provided separation effectiveness to the O/W
emulsion through binding with water molecules to form a hydration
layer that selectively permitted water permeation while prevented oil
penetration. In the 2nd separation step, the emulsion droplets remaining
unseparated by the PAN layer further penetrated through the PAN layer,
and then, were separated by the support of amphiphilic CFM that
destabilized the emulsion droplets via selective water permeation and oil
rejection. Besides the high separation flux, the PAN/CFM composite
membrane also exhibited appreciable antifouling property by showing
ultrahigh separation flux of 11046.97 L m− 2 h− 1 bar− 1 during the 5th
cycle of separation for dodecane-in-water emulsion. Therefore, we
provided a new strategy for developing high-performance separation
membranes that were promising candidate for the remediation of oil
contamination in water.
2. Experimental section
2.1. Materials
Chrome-tanned cattle hide was supplied by Ruixing Leather Co., Ltd
(Haining, China), which was shaved to remove the grain surface, and the
resultant material with the thickness controlled at 1.2 mm was used as
collagen fiber membrane (CFM). Dodecane was purchased from Beijing
Jintong Hetai Chemical Products Co., Ltd (Beijing, China). Poly­
acrylonitrile (PAN) (average Mw = 150,000) was purchased from
Sigma-Aldrich (Shanghai, China). The commercial double-sided poly­
tetrafluoroethylene (PTFE) membrane (with the average pore size of
0.45 µm) and double-sided polyvinylidene fluoride (PVDF) membrane
(with the average pore size of 0.45 µm), were purchased from Haining
Yanguan Town Laisheng Filter Equipment Manufactory (Haining,
China). The commercial cellulose acetate (CA) membrane and poly­
ethersulfone (PES) membrane with the average pore size of 0.45 µm
were obtained from Aladdin Biochemical Technology Co., Ltd
(Shanghai, China). Nile red was purchased from Hefei BOSF Biotech­
nology Co., Ltd (Hefei, China). 1,2-dichloroethane was obtained from
Chengdu Jinshan Chemical Reagent Co., Ltd (Chengdu, China).
N. Xue et al.
Heptane, octane, sodium dodecyl benzene sulfonate (SDBS), sodium
dodecyl sulfate (SDS), hexadecyl trimethyl ammonium bromide (CTAB),
N,N-dimethylformamide (DMF), ethanol and other chemicals were
analytical grade reagents.
2.2. Fabrication of the PAN(x)/CFM composite membranes
CFM with the diameter of 16 mm was rinsed with deionized water
and ethanol successively, followed by drying. 10 g of PAN was dissolved
in 90 g of DMF solvent and stirred continuously at speed of 500 rpm for
24 h to form the PAN solution. The above prepared PAN solution was
added into a syringe (10 mL) with a needle (21 G, ID 0.5 mm). Subse­
quently, PAN solutions were electrospun and deposited on the surface of
CFM covered on aluminum foil that was replaced on the surface of a
metal collector. The flow rate was controlled at 0.60 mL h− 1 and the
collection distance between needle and metal collector was 15 cm with
an applied voltage of 14 kV. The temperature and humidity were kept at
35 ◦ C and 45%, respectively. When the electrospinning was completed,
the PAN/CFM composite membrane was obtained by removing from the
metal collector and subsequently used for emulsion separation. A series
of PAN(x)/CFM composite membranes were prepared, where x was the
electrospinning time (h), equaling to 1.0, 3.0 and 5.0, respectively.
2.3. Preparation of oil-in-water (O/W) emulsions
A variety of O/W emulsions (E1, E2, E3 and E4) were prepared,
including SDS stabilized dodecane-in-water emulsion (E1), SDBS stabi­
lized octane-in-water emulsion (E2), CTAB stabilized heptane-in-water
emulsion (E3), and surfactant-free stabilized dodecane-in-water emul­
sion (E4). The detailed ingredients of O/W emulsions are summarized in
Table S1.
For the preparation of E1, 0.01 g of SDS was added into 1000 mL of
deionized water and stirred at 1000 rpm. Then, 10 mL of dodecane was
drop-wise added into above solution, followed by stirring at 2000 rpm
for 1.0 h. E2, E3 and E4 were prepared according to the similar prepa­
ration method of E1 except the utilized surfactant type, surfactant
content and/or oil, as shown in Table S1.
The separation behavior of CFM and PAN(x)/CFM composite mem­
branes were observed by separating O/W emulsion (E5) with the oil
phase (1,2-dichloroethane) dyed with Nile red (Yang et al., 2019; Li
et al., 2020). For the preparation of Nile red-dyed E5, 1.0 mg of SDS was
added into 200 mL of deionized water and stirred at 1000 rpm. Then, 20
mL of 1,2-dichloroethane containing 1.0 mg of Nile red was drop-wise
added into above solution, followed by stirring at 2000 rpm for 1.0 h.
2.4. Emulsion separation
Emulsion separation was carried out by an H-shaped separation de­
vice equipped with vacuum pump (Fig. S1), where the separation
membrane was sandwiched between the two half-cells. For the emulsion
separation, the emulsion was fed into the feed cell and the filtrate was
collected in the collection cell under the vacuum pressure of 0.1 bar. The
oil contents in the filtrates of O/W emulsions (E1, E2, E3 and E4) were
determined by an infrared photometer oil content analyzer (Oil 460,
Beijing Chinainvent Instrument Co., Ltd) after extracted by tetra­
chloroethylene (C2Cl4).
The flux was calculated by the following equation:
J = V/(StP) (1)
where J (L m− 2 h− 1 bar− 1) is the flux, V (L) is the volume of collected
filtrate, S (m2) is the area of utilized PAN(x)/CFM composite membrane,
P (bar) is the applied pressure, and t (h) is the separation time.
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Journal of Hazardous Materials 432 (2022) 128649
2.5. Measurement of porosity and water uptake of PAN layer
The porosity and water uptake capability of PAN layer was measured
by a dry-wet weight method (Cheng et al., 2020; Wu et al., 2020; Park
et al., 2018; Augustine et al., 2019). Specifically, the PAN layer prepared
by different electrospinning time (1.0 h, 3.0 h and 5.0 h) was weighed
and soaked in water for 24 h, which was then collected and weighed.
The porosity (ε) of PAN layer was determined by the following equation:
ε = [(Mwet - Mdry)/ρw]/[(Mwet - Mdry)/ρw + Mdry/ρPAN] (2)
where ε (%) is the porosity, Mwet (g) and Mdry (g) are the weight of PAN
layer in wet and dry state, respectively, ρw (g cm− 3) and ρPAN (g cm− 3)
are the densities of water and PAN, respectively.
The water uptake (Wup) of PAN layer was calculated by the following
equation:
Wup = (Mwet - Mdry)/Mdry × 100% (3)
Where Wup (%) is the water uptake, Mwet (g) and Mdry (g) are the weight
of PAN layer in wet and dry state, respectively.
2.6. Characterization
The surface morphology of the samples were observed by Field-
emission scanning electron microscopy (FESEM) operated at 5.0 kV
(Nova NanoSEM 450, USA). All the contact angles were measured on a
contact angle goniometer (Krüss, DSA30, Germany). Dynamic light
scattering (DLS) analyses were carried out using a particle size analyzer
(Brookhaven, NanoBrook, America). The effective average pore size and
pore size distribution were analyzed using a capillary flow porometer
(CFP) (Porous Materials Inc., CFP-1500AE, America). The tensile prop­
erties and tear properties were measured by using a tensile machine
(Gotech, Al-7000 SN, China). The values of average tensile strength and
tear strength were obtained from the measurement of four parallel
samples. The thickness of PAN layer and CFM were measured by using
thickness gauge (Gotech, GT-313-A, China). CFM was sliced by a
freezing microtome (Leica, CM1950, Germany), and the obtained slice
of CFM was observed using inverted fluorescence microscope (Leica,
DMi8, Germany). The chemical oxygen demand (COD) was measured by
a COD tester (HACH, DRB200, China).
3. Results and discussion
Fig. 1a is the schematic illustration showing the architecture of PAN/
CFM composite membrane. We employed CFM as multi-functional
support for the in-situ growth of underwater superoleophobic layer of
PAN by electrospinning. We prepared a series of PAN(x)/CFM composite
membranes, where x is the electrospinning time (h) of PAN, equaling to
1.0, 3.0, and 5.0, respectively. As shown in Fig. 1b–c, S2, FESEM image
shows the PAN layer of PAN(5)/CFM composite membrane at different
magnifications and it is evident that the nanofibers with the average
diameter of 830 nm show smooth surfaces and these nanofibers are
entangled with each other by forming interfiber overlaps. Based on the
CFP measurement, the PAN layer of PAN(5)/CFM composite membrane
has the average pore size of 0.66 µm (Fig. 1d), while the corresponding
porosity of PAN layer was determined to be 89.59%. As for the PAN(1)/
CFM and PAN(3)/CFM composite membranes, their porosities were
measured to be 92.36% and 89.81%. Compared with the PAN(1)/CFM
and PAN(3)/CFM composite membranes, the declined porosity of PAN
(5)/CFM composite membrane is attributed to the increased density of
PAN nanofibers in the PAN layer. Below the PAN layer, CFM served as
multi-functional support, which features hierarchically fibrous struc­
ture, including nanofibers, microfibers and fiber bundles. As shown in
the insert in Fig. 1f, the primary nanofibers of CFM show typical D-
periodicity of 67 nm, which are formed by an adjacent molecule quarter-
staggered end-overlap fashion. The average diameter of nanofibers was
N. Xue et al. Journal of Hazardous Materials 432 (2022) 128649

Fig. 1. Schematic illustration showing the architecture of PAN/CFM composite membrane (a), FESEM images of the PAN layer at different magnifications (b, c), pore
size distribution of the PAN layer measured by CFP (d), FESEM images of microfiber (e) and fiber bundle (f) (insert in f shows FESEM image of nanofiber), the
permeation fluxes of different liquids on CFM, CA, PES, PTFE and PVDF membranes, respectively (g).

measured to be 50–200 nm. The microfiber structures of CFM are
formed by the self-assembled nanofibers, which show the average
diameter of 2–10 µm (Fig. 1e). The microfibers further form microscaled
fiber bundles (Fig. 1f). The structural hierarchy of fibers endowed CFM
with outstanding mechanical properties, with the tensile strength up to
27 MPa and the tear strength reaching 84 N mm− 1, which afford suffi­
cient mechanical supporting to the PAN layer. The well developed
fibrous structure also provides CFM with excellent capillary effect for
efficient liquid transport to gain ultrahigh permeability. As shown in
Fig. 1g, the permeation flux of CFM for dodecane (437898.09 L m− 2 h− 1
bar− 1) is one order of magnitude higher than that of PTFE membrane
(47770.70 L m− 2 h− 1 bar− 1) and PVDF membrane (37320.86 L m− 2 h− 1
bar− 1), and the permeation flux of CFM for water (366242.04 L m− 2 h− 1
bar− 1) is over 5-fold to that of CA membrane (66182.32 L m− 2 h− 1
bar− 1) and PES membrane (72651.27 L m− 2 h− 1 bar− 1). These results
manifest that the outstanding permeability of CFM is superior to those of
commercial CA, PES, PTFE and PVDF membranes, which provides the
possibility for realizing ultrahigh-flux separation of emulsions by

Fig. 2. DLS curves of E1 before and after the separation by CFM and the PAN(x)/CFM composite membranes (a), respectively, the permeation fluxes of E1 separated
by CFM and the PAN(x)/CFM composite membranes (b), DLS curves and the corresponding digital photographs of E2, E3 and E4 before (c-e) and after (g-i) the
separation of PAN(5)/CFM composite membrane, fluxes and separation efficiencies of E1, E2, E3 and E4 separated by the PAN(5)/CFM composite membrane (f), oil
contents in the filtrates of E1, E2, E3 and E4 separated by the PAN(5)/CFM composite membrane (j).

4
N. Xue et al.
enhancing the permeation of filtrate to ensure an efficient and contin­
uous separation of emulsion.
The PAN(x)/CFM composite membranes were further applied in the
separation of emulsions. Dynamic light scattering (DLS) curves of E1
before and after the separation were analyzed. Fig. 2a shows the DLS
curves of E1 before and after the separation by CFM and the PAN(x)/
CFM composite membranes. After the separation by CFM, the particle
size distribution shifts from 407.46–541.55 nm to 268.19–310.10 nm,
and shows an obviously narrowed distribution, which suggests that the
support of CFM in the PAN(x)/CFM composite membranes not only
provides the composite membrane with needed mechanical strengthen
but also has considerable contribution to the separation effectiveness of
E1. Compared with CFM, the PAN(1)/CFM composite membrane pro­
vides the filtrate with smaller particle size distribution
(185.69–211.37 nm) with further narrowed distribution region. As for
the PAN(3)/CFM composite membrane, the particle size distribution of
collected filtrate further shifts to 49.48–69.69 nm. When the PAN(5)/
CFM composite membrane was used for the separation of E1, only a
narrow particle size distribution was observed near the y axis, which
suggests the successful separation of E1. The oil content in the filtrate
collected by the PAN(5)/CFM composite membrane was measured to be
21.894 ppm (Fig. 2j), and therefore, the corresponding separation effi­
ciency was calculated as high as 99.998% (Fig. 2f). We measured the
COD in the filtrates collected by CFM and the PAN(x)/CFM composite
membranes. Before the separation, the COD of E1 was as high as
728 mg L− 1, which was reduced to 167 mg L− 1 after the separation of
CFM, demonstrating the contribution of CFM to the separation of E1. As
for the filtrates collected by the PAN(1)/CFM and PAN(3)/CFM com­
posite membranes, the corresponding COD were measured to be 161 and
94 mg L− 1, respectively. When the PAN(5)/CFM composite membrane
was used for the separation of E1, the COD in the collected filtrate was as
low as 69 mg L− 1. These results confirm the successful separation of E1
by the PAN(5)/CFM composite membrane. As for the used PAN(5)/CFM
composite membrane, the CFM still preserved the hierarchically fibrous
structure (Fig. S3a, b) and the nanofibers of PAN layer also showed no
obvious change (Fig. S3c).
As for the separation of E1, the permeation of filtrates collected by
the PAN(x)/CFM composite membranes shows a proportional decline
from 66679.94 L m− 2 h− 1 bar− 1 to 40804.14 L m− 2 h− 1 bar− 1 along
with the increasing electrospinning time from 1.0 to 5.0 h (Fig. 2b).
Without the coverage of PAN layer, CFM provides the highest filtrate
permeation compared with the PAN(x)/CFM composite membranes,
which reaches an ultrahigh flux of 69167.99 L m− 2 h− 1 bar− 1. These
results suggest that the support of CFM plays critical role in providing
high separation flux for the PAN(x)/CFM composite membranes.
Although the coverage of PAN layer with nanoscaled overlaps on CFM
increases mass transfer resistance, the PAN(5)/CFM composite mem­
brane still presented ultrahigh separation flux of 40804.14 L m− 2 h− 1
bar− 1. As demonstrated in Fig. 1g, CFM is capable of providing large
permeation to both water and oil for its structural hierarchy-enabled
strong capillary effect. Therefore, the filtrate of separated E1 was able
to transport across CFM in an ultra-efficient way (especially under
negative pressure conditions in the present investigation), with the
obtaining of ultrahigh flux. Notably, the proportionally declined filtrate
permeation from CFM to the PAN(5)/CFM composite membrane indi­
cate that for the as-prepared PAN(x)/CFM composite membrane, the
separation flux should be mainly determined by the permeation of
filtrate through the support of CFM otherwise the separation flux of PAN
(x)/CFM composite membrane for E1 would be considerably lower than
the filtrate permeation of CFM for E1. Due to the dominant role of CFM
played in determining the separation flux of PAN(x)/CFM composite
membrane, the strong capillary effect enabled by the structural hierar­
chy of CFM therefore guarantees the ultrahigh separation performance
to emulsions.
Other three types of O/W emulsions were also employed to evaluate
the separation capabilities of PAN(5)/CFM composite membrane,
5
Journal of Hazardous Materials 432 (2022) 128649
including SDBS stabilized octane-in-water emulsion (E2), CTAB stabi­
lized heptane-in-water emulsion (E3), and surfactant-free stabilized
dodecane-in-water emulsion (E4). Before the separation, the DLS curves
of E2, E3 and E4 show wide particle size distributions (Fig. 2c–e), while
no particle size distribution was observed in the DLS curves of the fil­
trates collected by PAN(5)/CFM composite membrane (Fig. 2g–i). It was
also observed that the milky white E2, E3 and E4 became clear and
transparent after the separation of PAN(5)/CFM composite membrane
(Fig. 2c–e and g–i). The oil contents in the filtrates of E2, E3 and E4 were
measured to be 12.577, 15.866 and 11.789 ppm (Fig. 2j), respectively,
and the corresponding separation efficiencies were determined to be
99.999% and 99.998% and 99.999%, respectively (Fig. 2f). After the
separation of PAN(5)/CFM composite membrane, the COD in the fil­
trates of E2, E3 and E4 were measured to be 106, 68 and 50 mg L− 1,
respectively, and the corresponding removal percentage of COD were
determined to be 85.78% and 96.53% and 90.68%, respectively
(Fig. S4). Notably, ultrahigh separation flux of E2, E3 and E4 are still
achieved by the separation of PAN(5)/CFM composite membrane, with
the separation flux as high as 32344.75, 46775.48 and 51751.59 L m− 2
h− 1 bar− 1, respectively (Fig. 2f).
We compared the separation performance of PAN(5)/CFM composite
membrane with the commercial CA membrane and PES membrane. As
for the separation of E1, the separation flux of PAN(5)/CFM composite
membrane is 40804.14 L m− 2 h− 1 bar− 1, which is one order of magni­
tude higher than that of PES membrane (4130.18 L m− 2 h− 1 bar− 1) and
1.86-fold to that of CA membrane (21894.90 L m− 2 h− 1 bar− 1), as
shown in Fig. 3a. The oil contents in the filtrates of E1 separated by PES
membrane (262.588 ppm) and CA membrane (123.663 ppm) are one
order of magnitude higher than that of PAN(5)/CFM composite mem­
brane (21.894 ppm), as shown in Fig. 3b. When CA and PES membranes
were applied to the separation of E2, the separation flux of PAN(5)/CFM
composite membrane (32344.75 L m− 2 h− 1 bar− 1) is 2.21-fold of CA
membrane (14629.78 L m− 2 h− 1 bar− 1) and 1.95-fold of PES membrane
(16620.22 L m− 2 h− 1 bar− 1), respectively (Fig. 3a). The oil content in
the filtrate of E2 separated by CA membrane (141.738 ppm) is one order
of magnitude higher than that of PAN(5)/CFM composite membrane
(12.577 ppm), while the oil content in the filtrate of E2 separated by PES
membrane is 68.285 ppm, which is 4.43-fold higher than that of PAN
(5)/CFM composite membrane (Fig. 3b). These results manifest the su­
periority of PAN(5)/CFM composite membrane in obtaining ultrahigh-
flux emulsion separation. As shown in Table 1, the PAN(5)/CFM com­
posite membrane still exhibits superiority in accomplishing ultrahigh
separation flux as compared with the previously reported high-
performance separation membranes that are prepared based on the
use of diverse supports, such as cellulose membrane, mixed cellulose
ester filter membrane and polyvinylidene fluoride membrane.
The anti-fouling property of PAN(5)/CFM composite membrane was
further evaluated. After the continuous separation of E4 for 1.0 h, the
PAN(5)/CFM composite membrane was regenerated by immersing into
50 mL of ethanol for 30 min, which was then dried at 50 ◦ C, followed by
reuse in the next cycle. As shown in Fig. 3c, the separation flux is
maintained at high level in the 5th cycle at 60 min (11046.97 L m− 2 h− 1
bar− 1), which is still considerably higher than those of previously re­
ported separation membranes (Table 1). In addition, the separation ef­
ficiencies show no obvious decline during the cycling tests, and in the
5th cycle the separation efficiency is high up to 99.999% (Fig. 3d).
Therefore, the PAN(5)/CFM composite membrane exhibits appreciable
anti-fouling property in O/W emulsion separation.
To reveal the separation mechanism of PAN(5)/CFM composite
membrane to O/W emulsions, the wetting properties of PAN(5)/CFM
composite membrane were investigated by observing the wetting be­
haviors of water and oil droplets on the surface of PAN layer and CFM,
respectively. As shown in Fig. 4a, the PAN layer is hydrophilic with the
complete infiltration of water droplet in 6.6 s. The water uptake of PAN
layer was calculated to be as high as 727.37%. At the same time, the PAN
layer exhibits underwater superoleophobicity. The oil
N. Xue et al. Journal of Hazardous Materials 432 (2022) 128649

Fig. 3. Fluxes (a) and oil contents in the filtrates (b) of E1 and E2 separated by the PAN(5)/CFM composite membrane, CA membrane and PES membrane,
respectively, fluxes (c) and separation efficiencies (d) of E4 obtained during the five separation cycles by using the PAN(5)/CFM composite membrane.

Table 1
Comparisons of the PAN(5)/CFM composite membrane in this work with other membrane reported previously for the separation of O/W emulsion.
2 1
Membrane type Emulsion type Flux (L m− h− bar− 1) Pressure (bar) Substrate Reference

ZnO-NRCM/UL-MnO2-NWs membrane Hexadecane-in-water 1374 0.3 Cellulose membrane Yue et al. (2018)
SWCNT/PD/PEI film Industrial oil-in-water 6060 0.5 Mixed cellulose ester membrane Gao et al. (2015)
CNTs membrane Hexane-in-water 6800 0.9 – Gu et al. (2014)
PVDF/TA/β-FeOOH membrane Petroleum ether-in-water 2106 0.1 Polyvinylidene fluoride membrane Xie et al. (2019)
PVDF/NM88B membrane Petroleum ether-in-water 1970 0.1 Polyvinylidene fluoride membrane Xie et al. (2020)
CNTs/PS@AuNPs membrane Soyben oil-in-water 3500 1.0 Mixed cellulose ester membrane Zhang et al. (2016)
PAN(5)/CFM composite membrane Dodecane-in-water 51751.59 0.1 Collagen fiber membrane This work

(dichloromethane) droplet remains spherical shape on the surface of
PAN layer under water, and the corresponding oil contact angle of PAN
layer under water was measured to be 153.7◦ , as shown in Fig. 4b. As
shown in Fig. 4c, d, CFM exhibits hydrophilicity and underwater
superoleophobicity, with the complete infiltration of water droplet in
20.4 s and the underwater oil contact angle of 152.1◦ .
The hydrophilicity and underwater superoleophobicity of PAN layer
allow the continuous water phase of O/W emulsion to penetrate through
the PAN layer while strictly rejecting the dispersed oil phase. Because of
the hydrophilicity and underwater superoleophobicity, CFM is feasible
to make contribution to separation effectiveness by selectively perme­
ating the continuous water phase of O/W emulsion when plays the role
as support. Therefore, we proposed a 2-step separation mechanism for
separating O/W emulsions by the PAN(5)/CFM composite membrane.
As shown in Fig. 5, when the emulsion droplets contact with the hy­
drophilic and underwater superoleophobic PAN layer, the PAN layer
enables the demulsification of O/W emulsion droplets by binding with
water molecules to form a hydration layer that selectively permits water
permeation and prevents oil penetration strictly, which results in the
separation of oil from water. Since the separation process is applied
under vacuum pressure of 0.1 bar, the emulsion droplets remaining
unseparated by the PAN layer are flowed with the filtrate into CFM. The
unseparated emulsion droplets are further separated by CFM that rejects
oil while permits free permeation of water. Due to the capillary effect of
CFM, the permeated water is rapidly transported along the fiber direc­
tion of CFM, thus providing ultrahigh separation flux as well as high
separation effectiveness.
To further prove the 2-step separation mechanism for separating O/
W emulsions, we prepared the O/W emulsion (E5) with the oil phase
(1,2-dichloroethane) dyed with Nile red and investigated the separation
behaviors of CFM and PAN(x)/CFM composite membrane to Nile red-
dyed E5 by using inverted fluorescence microscope and particle size
analyzer. Fig. 6a shows the DLS curves of Nile red-dyed E5 before and
after the separation by CFM and PAN(x)/CFM composite membranes.
After the separation of CFM, the particle size distribution in the DLS
curve of collected filtrate shifts from 403.97–414.93 nm to
739.20–901.23 nm, and the digital photographs show that the cloudy
Nile red-dyed emulsion obviously becomes cleaner while the

6
N. Xue et al.
Fig. 4. Water droplet (2.0 μL) adsorption process in air on the surface of PAN layer (a) and CFM (c), digital photographs showing droplets of dichloromethane on the
surface of PAN layer (b) and CFM (d) under water and corresponding contact angles.
Fig. 5. Schematic illustration showing the proposed 2-step separation mechanism of O/W emulsions separated by the PAN/CFM composite membrane.
aggregations of Nile red-dyed emulsion droplets remains exist. The
observation of inverted fluorescence microscope confirms that the
fluorescence of Nile red-dyed emulsion droplets are significantly
reduced in the filtrate collected by the separation of CFM (Fig. 6b, c).
These results indicate that the support of CFM has contribution to the
separation effectiveness of Nile red-dyed E5. When the PAN(1)/CFM
composite membrane was utilized to the separation of Nile red-dyed E5,
the particle size distribution in the DLS curve of collected filtrate is
observed near the y axis, and a trace amount of Nile red and Nile red-
dyed emulsion droplets in the filtrate emit fluorescence (Fig. 6a, d). As
for the separation of Nile red-dyed E5 by the PAN(3)/CFM composite
membrane and PAN(5)/CFM composite membrane, the collected fil­
trates are clear and transparent without fluorescence emission observed
(Fig. 6a, e–f). These results indicate that the PAN layer in the PAN(x)/
CFM composite membranes is essential for the separation of O/W
emulsion, and the support of CFM provides not only the needed me­
chanical strengthen but also separation capabilities to O/W emulsion.
We applied the PAN(5)/CFM composite membrane in separation of Nile
red-dyed E5 for 10 min and 30 min, and then the support of CFM was
sliced by a freezing microtome, followed by observation using inverted
fluorescence microscope. Compared with the fresh CFM without fluo­
rescence emission (Fig. 6g), the slice of CFM collected form the PAN(5)/
CFM composite membrane used for 10 min separation of Nile red-dyed
7
Journal of Hazardous Materials 432 (2022) 128649
E5 shows evident red fluorescence emission (Fig. 6h), and significantly
enhanced fluorescence emission is observed from the slice of CFM
collected form the PAN(5)/CFM composite membrane used for 30 min
separation of Nile red-dyed E5 (Fig. 6i). These results suggest that along
with the separation to proceed, the Nile red gradually accumulated in
CFM because the emulsion droplets unseparated by the PAN layer are
constant separated by CFM. Consequently, it is rational to reasoned that
the PAN(5)/CFM composite membrane is based on a 2-step separation
process to accomplish ultrahigh flux separation of O/W emulsions,
which involves the separation of PAN layer as well as the separation by
the support of CFM.
4. Conclusion
In conclusion, we have successfully fabricated the high-performance
PAN/CFM composite membrane, which employed the multi-functional
support of CFM for the in-situ growth of PAN layer by electrospinning.
The PAN active layer exhibited hydrophilicity and underwater super­
oleophobicity, which selectively permitted the continuous water phase
permeation while rejected the dispersed oil phase strictly during the O/
W emulsion separation. The CFM as multi-functional support made
contribution to separation effectiveness for O/W emulsion and enhanced
the separation flux. We demonstrated a 2-step separation mechanism of
N. Xue et al.
Fig. 6. DLS curves and the corresponding digital photographs of Nile red-dyed E5 before and after the separation of CFM and PAN(x)/CFM composite membranes
(a), respectively, fluorescence micrographs of Nile red-dyed E5 (b), the filtrates collected by the separation of CFM (c) and PAN(x)/CFM composite membranes (d-f),
respectively, fluorescence micrographs of the fresh CFM (g), fuorescence micrographs of the slice of CFM collected from the PAN(5)/CFM composite membrane used
for 10 min (h) and 30 min (i) separation of Nile red-dyed E5.
PAN/CFM composite membrane to O/W emulsion. The PAN/CFM
composite membrane achieved ultrahigh separation flux towards O/W
emulsion (e.g., 51751.59 L m− 2 h− 1 bar− 1), showing evident advantage
of separation flux as compared with the commercial cellulose acetate
(CA) membrane and polyethersulfone (PES) membrane. Furthermore,
the PAN/CFM composite membrane exhibited outstanding antifouling
property. Therefore, we provided a new conceptual way for developing
high-performance separation membrane that was capable of realizing
ultrahigh-flux separation of O/W emulsions, showing the possibility to
efficiently resolve the problem of oil contamination in water.
CRediT authorship contribution statement
Xin Huang conceived the idea. Ni Xue and Yiwen Cui carried out
materials preparation. Ni Xue and Hanzhong Xiao carried out materials
characterization. Ni Xue, Yujia Wang and Yawen Huang carried out
separation experiments. Ni Xue, Xin Huang and Bi Shi drafted the
manuscript. All authors analyzed the experimental results.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
8
Journal of Hazardous Materials 432 (2022) 128649
Acknowledgements
This work was financially supported by the National Natural Science
Funds for Excellent Youth Scholars (No. 21922808), the National Nat­
ural Science Foundation of China (No. 22178232, No. 21978176), the
National Key Research and Development Program (No.
2018YFC1901101), the Fok Ying Tong Education Foundation for Young
Teachers in the Higher Education Institutions of China (No. 161099), the
Key Research and Development Program of Science and Technology
Department of Sichuan Province (2021ZYCD009) and the Program of
Sichuan University Featured Research Groups in Engineering
Disciplines.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jhazmat.2022.128649.
References
Andriotis, O.G., Chang, S.W., Vanleene, M., Howarth, P.H., Davies, D.E., Shefelbine, S.J.,
Buehler, M.J., Thurner, P.J., 2015. Structure-mechanics relationships of collagen
fibrils in the osteogenesis imperfecta mouse model. J. R. Soc. Interface 12,
20150701. https://doi.org/10.1098/rsif.2015.0701.
Augustine, R., Dan, P., Schlachet, I., Rouxel, D., Menu, P., Sosnik, A., 2019. Chitosan
ascorbate hydrogel improves water uptake capacity and cell adhesion of electrospun
N. Xue et al.
poly(epsilon-caprolactone) membranes. Int. J. Pharm. 559, 420–426. https://doi.
org/10.1016/j.ijpharm.2019.01.063.
Bay, R.K., Zarybnicka, K., Jancar, J., Crosby, A.J., 2020. Mechanical properties of
ultrathin polymer nanocomposites. ACS Appl. Polym. Mater. 2, 2220–2227. https://
doi.org/10.1021/acsapm.0c00201.
Cai, Y.H., Chen, D.Y., Li, N.J., Xu, Q.F., Li, H., He, J.H., Lu, J.M., 2017. Nanofibrous
metal-organic framework composite membrane for selective efficient oil/water
emulsion separation. J. Membr. Sci. 543, 10–17. https://doi.org/10.1016/j.
memsci.2017.08.047.
Cheng, X.Q., Sun, Z.K., Yang, X.B., Li, Z.X., Zhang, Y.J., Wang, P., Liang, H., Ma, J.,
Shao, L., 2020. Construction of superhydrophilic hierarchical polyacrylonitrile
nanofiber membranes by in situ asymmetry engineering for unprecedently ultrafast
oil-water emulsion separation. J. Mater. Chem. A 8, 16933–16942. https://doi.org/
10.1039/D0TA03011B.
Gao, S.J., Shi, Z., Zhang, W.B., Zhang, F., Jin, J., 2014. Photoinduced superwetting
single-walled carbon nanotube/TiO2 ultrathin network films for ultrafast separation
of oil-in-water emulsions. ACS nano 8, 6344–6352. https://doi.org/10.1021/
nn501851a.
Gao, S.J., Zhu, Y.Z., Zhang, F., Jin, J., 2015. Superwetting polymer-decorated SWCNT
composite ultrathin films for ultrafast separation of oil-in-water nanoemulsions.
J. Mater. Chem. A 3, 2895–2902. https://doi.org/10.1039/C4TA05624H.
Gao, S.J., Zhu, Y.Z., Wang, J.L., Zhang, F., Li, J.Y., Jin, J., 2018. Layer-by-layer
construction of Cu2+/alginate multilayer modified ultrafiltration membrane with
bioinspired superwetting property for high-efficient crude-oil-in-water emulsion
separation. Adv. Funct. Mater. 28, 1801944. https://doi.org/10.1002/
adfm.201801944.
Geng, Q., Pu, Y., Li, Y.J., Yang, X., Wu, H.Z., Dong, S.J., Yuan, D., Ning, X., 2022. Multi-
component nanofiber composite membrane enabled high PM0.3 removal efficiency
and in complex environment. J. Hazard. Mater. 422, 126835 https://doi.org/
10.1016/j.jhazmat.2021.126835.
Gu, J.C., Xiao, P., Chen, J., Zhang, J.W., Huang, Y.J., Chen, T., 2014. Janus polymer/
carbon nanotube hybrid membranes for oil/water separation. ACS Appl. Mater.
Interfaces 6, 16204–16209. https://doi.org/10.1021/am504326m.
Gupta, R.K., Dunderdale, G.J., England, M.W., Hozumi, A., 2017. Oil/water separation
techniques: a review of recent progresses and future directions. J. Mater. Chem. A 5,
16025–16058. https://doi.org/10.1039/C7TA02070H.
Huang, X., Kong, X., Cui, Y.W., Ye, X.X., Wang, X.L., Shi, B., 2018. Durable
superhydrophobic materials enabled by abrasion-triggered roughness regeneration.
Chem. Eng. J. 336, 633–639. https://doi.org/10.1016/j.cej.2017.12.036.
Jjagwe, J., Olupot, P.W., Menya, E., Kalibbalac, H.M., 2021. Synthesis and application of
granular activated carbon from biomass waste materials for water treatment: a
review. J. Bioresour. Bioprod. 6, 292–322. https://doi.org/10.1016/j.
jobab.2021.03.003.
Kang, W.L., Guo, L.M., Fan, H.M., Meng, L.W., Li, Y.H., 2012. Flocculation, coalescence
and migration of dispersed phase droplets and oil-water separation in heavy oil
emulsion. J. Pet. Sci. Eng. 81, 177–181. https://doi.org/10.1016/j.
petrol.2011.12.011.
Li, H.F., Zheng, W., Xiao, H.Z., Hao, B.C., Wang, Y.N., Huang, X., Shi, B., 2021a. Collagen
fiber membrane-derived chemically and mechanically durable superhydrophobic
membrane for high-performance emulsion separation. J. Leather Sci. Eng. 3, 1–10.
https://doi.org/10.1186/s42825-021-00060-5.
Li, H.N., Yang, J., Xu, Z.K., 2020. Hollow fiber membranes with Janus surfaces for
continuous deemulsification and separation of oil-in-water emulsions. J. Membr. Sci.
602, 117964 https://doi.org/10.1016/j.memsci.2020.117964.
Li, H.Y., Mu, P., Li, J., Wang, Q.T., 2021b. Inverse desert beetle-like ZIF-8/PAN
composite nanofibrous membrane for highly efficient separation of oil-in-water
emulsions. J. Mater. Chem. A 9, 4167–4175. https://doi.org/10.1039/D0TA08469G.
Lu, T., Deng, Y.K., Cui, J.X., Cao, W.X., Qu, Q.L., Wang, Y.L., Xiong, R.H., Ma, W.J.,
Lei, J.D., Huang, C.B., 2021. Multifunctional applications of blow-spinning setaria
viridis structured fibrous membranes in water purification. ACS Appl. Mater.
Interfaces 13, 22874–22883. https://doi.org/10.1021/acsami.1c05667.
Ma, W.J., Jiang, Z.C., Lu, T., Xiong, R.H., Huang, C.B., 2022. Lightweight, elastic and
superhydrophobic multifunctional nanofibrous aerogel for self-cleaning, oil/water
separation and pressure sensing. Chem. Eng. J. 430, 132989 https://doi.org/
10.1016/j.cej.2021.132989.
Park, M.J., Gonzales, R.R., Abdel-Wahab, A., Phuntsho, S., Shon, H.K., 2018. Hydrophilic
polyvinyl alcohol coating on hydrophobic electrospun nanofiber membrane for high
performance thin film composite forward osmosis membrane. Desalination 426,
50–59. https://doi.org/10.1016/j.desal.2017.10.042.
Rana, D., Mandal, B.M., Bhattacharyya, S.N., 1996. Analogue calorimetry of polymer
blends: poly (styrene-co-acrylonitrile) and poly (phenyl acrylate) or poly (vinyl
Journal of Hazardous Materials 432 (2022) 128649
benzoate). Polymer 37, 2439–2443. https://doi.org/10.1016/0032-3861(96)85356-
0.
Rana, D., Bag, K., Bhattacharyya, S.N., Mandal, B.M., 2000. Miscibility of poly (styrene-
co-butyl acrylate) with poly (ethyl methacrylate): existence of both UCST and LCST.
Polym. Chem. 38, 369–375. https://doi.org/10.1039/D2PY00032F.
Samaei, S.M., Gato-Trinidad, S., Altaee, A., 2018. The application of pressure-driven
ceramic membrane technology for the treatment of industrial wastewaters-a review.
Sep. Purif. Technol. 200, 198–220. https://doi.org/10.1016/j.seppur.2018.02.041.
Shalaby, M.S., Sołowski, G., Abbas, W., 2021. Recent aspects in membrane separation for
oil/water emulsion. Adv. Mater. Interfaces 8, 2100448. https://doi.org/10.1002/
admi.202100448.
Suzuki, Y., Maruyama, T., 2005. Removal of emulsified oil from water by coagulation
and foam separation. Sep. Sci. Technol. 40, 3407–3418. https://doi.org/10.1080/
01496390500423755.
Wang, Z.J., Liu, G.J., Huang, S.S., 2016. In situ generated Janus fabrics for the rapid and
efficient separation of oil from oil-in-water emulsions. Angew. Chem. Int. Ed. 55,
14610–14613. https://doi.org/10.1002/anie.201607581.
White, R.P., Aoki, Y., Higgins, J.S., Keddie, J.L., Lipson, J.E.G., Cabral, J.T., 2020.
Thermodynamics of model P alpha MSAN/dPMMA blend: a combined study by
SANS, ellipsometry, and locally correlated lattice (LCL) theory. Macromolecules 53,
7084–7095. https://doi.org/10.1021/acs.macromol.0c00706.
Woessner, A.E., Jones, J.D., Witt, N.J., Sander, E.A., Quinn, K.P., 2021. Three-
dimensional quantification of collagen microstructure during tensile mechanical
loading of skin. Front. Bioeng. Biotech. 9, 642866 https://doi.org/10.3389/
fbioe.2021.642866.
Wu, M.M., Liu, W.M., Mu, P., Wang, Q.T., Li, J., 2020. Sacrifice template strategy to the
fabrication of a self-cleaning nanofibrous membrane for efficient crude oil-in-water
emulsion separation with high flux. ACS Appl. Mater. Interfaces 12, 53484–53493.
https://doi.org/10.1021/acsami.0c15387.
Xiao, H.Z., Wang, Y.J., Hao, B.C., Cao, Y.R., Cui, Y.W., Huang, X., Shi, B., 2021. Collagen
fiber-based advanced separation materials: recent developments and future
perspectives. Adv. Mater. 2107891. https://doi.org/10.1002/adma.202107891.
Xie, A.T., Cui, J.Y., Yang, J., Chen, Y.Y., Dai, J.D., Lang, J.H., Li, C.X., Yan, Y.S., 2019.
Photo-Fenton self-cleaning membranes with robust flux recovery for an efficient oil/
water emulsion separation. J. Mater. Chem. A 7, 8491–8502. https://doi.org/
10.1039/C9TA00521H.
Xie, A.T., Cui, J.Y., Yang, J., Chen, Y.Y., Lang, J.H., Li, C.X., Yan, Y.X., Dai, J.D., 2020.
Photo-Fenton self-cleaning PVDF/NH2-MIL-88B(Fe) membranes towards highly-
efficient oil/water emulsion separation. J. Membr. Sci. 595, 117499 https://doi.org/
10.1016/j.memsci.2019.117499.
Yang, J., Li, H.N., Chen, Z.X., He, A., Zhong, Q.Z., Xu, Z.K., 2019. Janus membranes with
controllable asymmetric configurations for highly efficient separation of oil-in-water
emulsions. J. Mater. Chem. A 7, 7907–7917. https://doi.org/10.1039/C9TA00575G.
Yang, J., Zhang, Y.C., Zhou, L., Zhang, F.S., Jing, Y., Huang, M.Z., Liu, H.B., 2022.
Quality-related monitoring of papermaking wastewater treatment processes using
dynamic multiblock partial least squares. J. Bioresour. Bioprod. 7, 73–82. https://
doi.org/10.1016/j.jobab.2021.04.003.
Ying, T., Su, J., Jiang, Y., Ke, Q.F., Xu, H., 2020. A pre-wetting induced
superhydrophilic/superlipophilic micro-patterned electrospun membrane with self-
cleaning property for on-demand emulsified oily wastewater separation. J. Hazard.
Mater. 384, 121475 https://doi.org/10.1016/j.jhazmat.2019.121475.
Yong, W.F., Zhang, H., 2021. Recent advances in polymer blend membranes for gas
separation and pervaporation. Prog. Mater. Sci. 116, 100713 https://doi.org/
10.1016/j.pmatsci.2020.100713.
Yue, X.J., Zhang, T., Yang, D.Y., Qiu, F.X., Li, Z.D., 2018. Janus ZnO-cellulose/MnO2
hybrid membranes with asymmetric wettability for highly-efficient emulsion
separations. Cellulose 25, 5951–5965. https://doi.org/10.1007/s10570-018-1996-8.
Zhang, L., Gu, J.C., Song, L.P., Chen, L., Huang, Y.J., Zhang, J.W., Chen, T., 2016.
Underwater superoleophobic carbon nanotubes/core-shell polystyrene@Au
nanoparticles composite membrane for flow-through catalytic decomposition and
oil/water separation. J. Mater. Chem. A 4, 10810–10815. https://doi.org/10.1039/
C6TA04362C.
Zhang, L., Lin, Y.Q., Wu, H.C., Cheng, L., Sun, Y.C., Yasui, T., Yang, Z., Wang, S.Y.,
Yoshioka, T., Matsuyama, H., 2019. An ultrathin in situ silicification layer developed
by an electrostatic attraction force strategy for ultrahigh-performance oil-water
emulsion separation. J. Mater. Chem. A 7, 24569–24582. https://doi.org/10.1039/
C9TA07988B.
Zhang, M.J., Ma, W.J., Cui, J.X., Wu, S.T., Han, J.Q., Zou, Y., Huang, C.B., 2020.
Hydrothermal synthesized UV-resistance and transparent coating composited
superoloephilic electrospun membrane for high efficiency oily wastewater
treatment. J. Hazard. Mater. 383, 121152 https://doi.org/10.1016/j.
jhazmat.2019.121152.