Green Chemistry

View Article Online

PAPER View Journal | View Issue

Facile preparation of loess-coated membranes for

multifunctional surfactant-stabilized oil-in-water
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.

Cite this: Green Chem., 2019, 21,

3190 emulsion separation†
Xiaoyang Wang,a Mouji Li,a Yongqian Shen,*b Yaoxia Yang,a Hua Fenga and
Jian Li *a

Received 2nd March 2019,
Accepted 7th May 2019
DOI: 10.1039/c9gc00747d
rsc.li/greenchem
Frequent oil spill accidents and industrial wastewater discharge result in severe health and ecological pro-
blems to human beings. Generally, industrial wastewater contains not only various kinds of oils, but also
water-soluble dyes and heavy metal ions. Elimination of these contaminants in the process of oil/water
separation is very important in industrial applications and still remains unsolved. Even though some mem-
branes with underwater superoleophobicity have been extensively used toward oil-in-water emulsion
separation, the bulk of them lack the capacity of removing the water-soluble pollutants from water during
oil/water separation. Herein, a novel loess-coated polyvinylidene fluoride (PVDF) membrane was success-
fully fabricated through depositing the loess and sodium alginate suspension onto a PVDF membrane
with a vacuum pump. The loess-coated PVDF membrane displayed extraordinary underwater superoleo-
phobicity with oil contact angles larger than 150° and sliding angles smaller than 10° toward different oils,
including crude oil with high viscosity. Besides, the loess-coated PVDF membrane can separate various
oil-in-water emulsions with separation efficiencies up to 99.6% and flux as high as 910.4 L m−2 h−1 bar−1.
Moreover, the coated membrane retained excellent separation performances even after 10 cycles. In
addition, the coated membrane showed outstanding resistance to corrosive liquids, and could separate
oil-in-water emulsions in corrosive solutions effectively. Furthermore, the as-prepared membrane dis-
played outstanding mechanical performance and flexibility. More importantly, the loess-coated PVDF
membrane exhibited effective adsorption toward dyes and heavy metal ions. This cost-efficient, environ-
mentally friendly and multifunctional loess-coated PVDF membrane not only allows natural loess
resources to be used rationally, but also effectively solves the problems of water pollution.

1. Introduction materials with special wettability is a facile method.9–11

Water pollution due to frequent oil spills and rapid expansion
of industrial oily wastewater has attracted widespread
concern.1–4 Oil spills and oily wastewater not only result in
serious problems to the aquatic environment and lives, but
also lead to a waste of precious resources.5–8 Thus, effective
oil/water separation is highly desired. Since oil/water separ-
ation is governed by interfacial phenomena, designing
a
Research Center of Gansu Military and Civilian Integration Advanced Structural
Materials, College of Chemistry and Chemical Engineering, Northwest Normal
University, Lanzhou 730070, P. R. China. E-mail: jianli83@126.com;
Tel: +86 931 7971533
b
State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals,
Key Laboratory of Nonferrous Metal alloys and Processing, Ministry of Education,
School of Materials Science & Engineering, Lanzhou University of Technology,
Lanzhou 730050, P. R. China. E-mail: syqch@163.com
† Electronic supplementary information (ESI) available: Additional figures and
movies. See DOI: 10.1039/c9gc00747d
Generally, plenty of superwettable materials have been fabri-
cated via constructing micro/nanoscale rough structure as well
as modifying with suitable surface energy, which are mainly
divided into two categories: “oil-removing” and “water-remov-
ing” materials.12–18 The “oil-removing” materials always
exhibit superhydrophobicity and superoleophilicity, which can
prevent the passage of water droplets while allowing oil to pass
through the materials easily.19–22 However, this type of
material is not suitable for separating the light oil/water mix-
tures or oil-in-water emulsions. Due to the fact that water gen-
erally possesses a larger density than oils, “water-removing”
materials with underwater superoleophobic property would be
an optimal choice to separate the water-rich oil/water mixtures
and oil-in-water emulsions.23–25 In recent years, a hydrogel-
coated mesh had been reported for oil/water separation by the
group of Jiang, which possessed superhydrophilic/underwater
superoleophobic properties.26 Inspired by the pioneering
work, many underwater superoleophobic materials were suc-

3190 | Green Chem., 2019, 21, 3190–3199 This journal is © The Royal Society of Chemistry 2019

Green Chemistry
cessfully fabricated for separating oil/water mixtures
efficiently.27–30 However, most of these “water-removing”
materials could not achieve the oil-in-water emulsion separ-
ation owing to their large pore size.31 Oil/water emulsions that
are composed of emulsified droplets with the size less than
20 µm are more difficult to separate than the immiscible oil/
water mixtures.32–37 Recently, various materials with super-
hydrophilic/underwater superoleophobic properties, such as
polymer membranes,38 silica,39 TiO2 40,41 and graphene
oxide,42 have been fabricated to separate oil-in-water emul-
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
sions successfully. However, it is inevitable to encounter cor-
rosive environment in real life, such as household and indus-
trial wastewater. Therefore, the chemical stability of the
material was of vital importance for practical application.
Besides, the separation of crude oil emulsion is also a great
challenge. Moreover, most solvents used for making mem-
branes are often toxic, which poses a threat to human and
environmental safety.43 There is a need to fabricate mem-
branes using green solvents. In order to follow the green and
environmental concept, some works have been reported in
recent years. Zhao et al. reported a high-performance nano-
filtration membrane, which was based on interpenetrating
polymer networks incorporating PDA and polybenzimid-
azole.44 Szekely et al. explored the effect of solvent treatment
in membrane separations.45 Miele et al. produced a porous
membrane using polyvinyl alcohol as the material.46 However,
much more effort should be put into the preparation of the
membrane using green and sustainable resources for actual
applications.
Apart from oil pollutions, the discharge of water-soluble
dyes and heavy metal ions also lead to serious health threats
and ecological problems.47,48 Since most oily wastewater con-
tains water-soluble dyes and heavy metal ions, removing these
contaminants is of significant importance during oil/water
separation.49,50 However, most materials are limited in practi-
cal applications due to the single function of just separating
oil/water mixtures. That is to say, they are only applicable to
separate immiscible oil/water mixtures or emulsions, lacking
the ability to remove water-soluble pollutants from water.
Hence, designing low-cost, environmentally friendly and multi-
functional materials that can remove water-soluble dyes and
heavy metal ions during the purification of emulsified oily
wastewater would be highly desirable.
Loess is inexpensive and environmentally friendly. It is
widely distributed in nature, especially in western China, and
is in line with the concept of “green” and “sustainable”
materials. However, to the best of our knowledge, we are
unaware of any previously reported studies on the application
of loess in oil/water separation. Herein, a loess-coated PVDF
membrane was successfully fabricated through a facile leach-
ing with a vacuum pump for the separation of various oil-in-
water emulsions. It is worth mentioning that water was
selected as the solvent with no harm to the environment. The
coated PVDF membrane not only displayed extraordinary
underwater superoleophobicity, but also possessed excellent
chemical resistance to corrosive conditions. Based on these
This journal is © The Royal Society of Chemistry 2019
View Article Online
Paper
features, it showed prominent performance in the separation
of oil-in-water emulsions even under harsh conditions. The
separation efficiency of various surfactant-stabilized oil-in-
water emulsions including crude oil-in-water emulsion was
above 99.6% with the flux as high as 910.4 L m−2 h−1 bar−1. In
addition, the coated membrane displayed excellent mechani-
cal performance and flexibility, which can be used in real
applications. Furthermore, the as-prepared membrane exhibi-
ted efficient adsorption of dyes and heavy metal ions owing to
its rich pore structure and large specific surface area. It is
meaningful to use loess-coated membrane to achieve the oil-
in-water emulsion separation as well as the adsorption of dyes
and heavy metal ions. The loess-coated membrane can be a
successful example of introducing eco-friendly, easy to operate
and multifunctional material into the field of oil/water separ-
ation, which has great application potential in the future.
2. Experimental section
2.1. Materials
Loess was obtained for free from a mountain in Jingyuan
County, Gansu province, China. Polyvinylidene fluoride mem-
brane (PVDF) was acquired from Shanghai Xingya Co., Ltd.
The thickness of the PVDF membrane is about 150 μm
(Fig. S1†). Oils (kerosene, diesel) and organic solvents
(heptane, hexane and petroleum ether) were supplied from
Guangdong Guanghua Sci-Tech Co., Ltd. Crude oil (density:
0.85 g cm−3, viscosity: 136.64 mPa S; purity: 99.6%) was sup-
plied by China petroleum Lanzhou chemical research center.
Methylene blue, crystal violet, CuSO4·5H2O, Zn(NO3)2·6H2O,
and PbCl2 were provided by Sinopharm Chemical Reagent Co.,
Ltd. NaCl, NaOH, and HCl were purchased from Shanghai
Zhongqin Chemical Reagent Co., Ltd. These above-mentioned
agents were all of analytical grade and all solutions were pre-
pared with deionized water.
2.2. Preparation of loess-coated PVDF membrane
The loess-coated PVDF membrane was obtained as follows. First,
the loess was activated by 4 M HCl solution before use. 0.4 g
sodium alginate was dispersed in 40 mL water under continuous
shaking. Second, 0.25 g pre-treated loess and 2 mL sodium algi-
nate solution were incorporated into 35 mL water and stirred the
resultant suspension magnetically for at least 1 h at room temp-
erature to get a uniform turbid liquid. Subsequently, 3 mL of the
solution was leached onto a polyvinylidene fluoride (PVDF)
membrane under the pressure of 0.085 MPa by a vacuum pump;
the radius of the loess-coated area was about 2 cm. Finally, the
membrane was dried at 50 °C for 30 min.
2.3. Preparation of multifarious surfactant-stabilized oil-in-
water emulsions
Kerosene, diesel, heptane, hexane, petroleum ether and crude
oil were chosen as the oil phases. Deionized water, HCl
aqueous solution, NaOH aqueous solution, and 3.5 wt% NaCl
solution were selected as the water phases. First, 0.1 g Tween
Green Chem., 2019, 21, 3190–3199 | 3191

Paper
80 was added into the water phase, and then each kind of oil
was mixed into the mixture. It was worth noting that the
volume ratio of oil and water phases was 1 : 50. Finally, the sur-
factant-stabilized emulsion was obtained under vigorous stir-
ring after 8 h.
2.4. Characterization
The morphologies of the original PVDF membrane and the
loess-coated PVDF membrane were characterized using a field
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
emission scanning electron microscope (FE-SEM, Zeiss). The
chemical composition was acquired by energy-dispersive spec-
trometry (EDS). The SL200KB apparatus was used to measure
the contact angles and sliding angles. FT-IR analysis (Bio-Rad
FTS-165) of the loess particles was also carried out to monitor
its functional moieties. Atomic force microscopy (AFM)
measurements were performed on an Agilent Technologies
5500 AFM under ambient conditions. Optical images of the
emulsion droplets were taken on the Olympus U-RFL-T. In
addition, the droplet size distribution of the emulsion was
obtained by the Malvern Zetasizer Nano Zs. The infrared oil
instrument (SN-OIL480) was used for measuring the oil
content in the collected filtrate. The concentration of dyes was
determined by using a UV-vis spectrophotometer (Agilent-
8453). An atomic absorption spectrophotometer (Z-2000
Atomic Absorption Spectrophotometer (AAS) (Hitachi, Japan))
was used to assess the concentration of heavy metal ions.
3. Results and discussion
The fabrication process of the loess-coated PVDF membrane
and its applications are illustrated in Fig. 1. Driven by a
vacuum filtration system, the loess and sodium alginate sus-
pension were successfully coated onto a PVDF membrane. The
loess-coated membrane can not only be applied to a series of
oil-in-water emulsion separation, even in strong acid, alkaline,
and high salt environments, but also be utilized for adsorbing
water-soluble dyes and heavy metal ions.
Fig. 1 Illustration of the preparation processes of the loess-coated PVDF membrane and its application in oil-in-water emulsion separation and the
adsorption of dyes and heavy metal ions.
3192 | Green Chem., 2019, 21, 3190–3199
View Article Online
Green Chemistry
The FE-SEM images of the pristine PVDF membrane exhibi-
ted that it possessed a smooth surface with an average pore
diameter of 450 nm (Fig. 2a). After leaching of the activated
loess and sodium alginate suspension, the loess-coated PVDF
membrane was fabricated successfully. The particle size distri-
bution of the activated loess was shown in Fig. S2.† Compared
with the original PVDF membrane, numerous loess particles
with different sizes and irregular shapes were distributed on
the surface of the loess-coated PVDF membrane, resulting in a
rough structure (Fig. 2b). In addition, plenty of nanoscale
debris can be found on the loess-coated surfaces, as exhibited
in the inset of magnified Fig. 2b. Moreover, the average pore
size of the loess-coated membrane is determined to be
approximately 81 nm, which is much smaller than that of the
substrate (Fig. S3†). The cross-sectional image of the as-pre-
pared membrane was also characterized; it could be seen that
the thickness of the loess layer is approximated to 6.30 µm, as
displayed in Fig. 2c. Moreover, AFM images of the loess-coated
PVDF and original PVDF membranes are shown in Fig. 2d and
Fig. S4,† respectively. The root mean square roughness (Rq) of
the loess-coated PVDF membrane was about 68.9 nm, while
the corresponding value of the original PVDF membrane was
about 58.9 nm. The hierarchical and rough structures are ben-
eficial for preparing superwetting materials. Besides, the
chemical composition of the resultant membrane was also
analyzed, as shown in Fig. 2e and Fig. S5.† It is clear that the
loess-coated PVDF membrane contains carbon, oxygen, silicon
and aluminum elements. The XRD patterns of acidified loess
powders were also investigated (Fig. S6†). There are two strong
diffraction peaks at 2θ = 20.8° and 26.6°, which are attributed
to silicon oxide (JCPDS No: 77-1060). The peaks at 2θ = 22.0°,
23.5° and 27.9° can be assigned to the structure of aluminosili-
cate (JCPDS No: 84-0752). Furthermore, the FT-IR spectra of
the loess particles were also investigated, as exhibited in
Fig. 2f. The strong and broad peak at 3423 cm−1 can be attribu-
ted to the hydroxyl groups. The peak appearing at 2926 cm−1
confirms the presence of C–H groups, while the absorption
band at 1618 cm−1 corresponds to CvO groups. The absorp-
This journal is © The Royal Society of Chemistry 2019
 View Article Online

Green Chemistry Paper

Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.

Fig. 2 FE-SEM images of (a) the original PVDF and (b) the loess-coated PVDF membrane at low and high magnifications. (c) Cross-sectional image
of the loess-coated PVDF membrane. (d) AFM image of the loess-coated PVDF membrane surface. (e) EDS mapping of the loess-coated PVDF mem-
brane. (f ) FT-IR spectra of the loess particles.

tion bands at 1036 cm−1 and 466 cm−1 are ascribed to the
Si–O–Si stretching and bending vibrations, respectively, and
the peaks at 797 cm−1 are attributed to the SiO2 groups of
loess. The FT-IR spectra of the added binder, sodium alginate,
were also characterized (Fig. S7†). Fortunately, sodium alginate
also contains massive amphiphilic functional groups. The
synergistic effect of the hydrophilic compositions and func-
tional groups present in sodium alginate and loess endows the
as-prepared membrane with excellent water attraction and
retention capacities.
As we all know, the wettability of the material depends on
its surface hierarchical roughness and chemical compositions.
The droplets of water and oil were rapidly spread out while
they were dropped onto the surface, and the contact angles
were nearly 0°, which are displayed in Fig. 3a and b. This
phenomenon implied that the as-prepared membrane pos-
sessed superamphiphilicity towards water and oil in the air.
This is ascribed to the cooperative effect of the existence of
massive hydroxyl groups (the loess powders and sodium algi-
nate are both terminated with hydroxyl groups) and the hier-

Fig. 3 Wetting behaviors of the loess-coated PVDF membrane toward (a) water and (b) oil in air and (c) oil in water. (d) Oil contact angles and
sliding angles for different oils on the loess-coated membrane under water. (e) Underwater oil adhesion measurements on the loess-coated PVDF
membrane using dichloromethane droplets as an example.

This journal is © The Royal Society of Chemistry 2019 Green Chem., 2019, 21, 3190–3199 | 3193

Paper
archical roughness. When the droplet of hexane was placed
underwater, the oil contact angle was 157° ± 1° (Fig. 3c). In
addition, a series of oils were used to probe the underwater
superoleophobicity of the loess-coated membrane. Obviously,
the oil contact angles were all larger than 150° while the oil
sliding angles were less than 10° including those of crude oil
with high viscosity (Fig. 3d). The underwater superoleophobi-
city was achieved in an oil/water/solid three-phase system by
introducing the repulsive water phase into the rough struc-
tured surface. Therefore, when the loess-coated membranes
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
come in contact with the oil droplets, water trapped in the
rough nanostructures provides a strong repulsive force, result-
ing in greater oil contact angles and lower oil sliding angles.
The experiment of underwater oil adhesion was also con-
ducted; the oil droplet (dichloromethane) showed no sticki-
ness to the loess-coated PVDF surface as displayed in Fig. 3e.
This characteristic of underwater superoleophobicity and ultra-
low oil adhesion can prevent the as-prepared membrane from
being contaminated by the oil droplets in the process of separ-
ating oil-in-water emulsions.
As is well known, two basic conditions, namely, suitable
pore size and special wettability should be met for a mem-
brane of effective emulsion separation. In order to ensure the
effective screening effect of the membrane, the pore size of the
membrane should be less than the diameter of emulsion dro-
plets. In addition, the membrane should have opposite
wetting ability for the two components in the emulsion. In
other words, the membrane should be wetted by the continu-
ous phase and unwetted by the dispersed phase. As for oil-in-
water emulsion separation, the membrane should allow water
to immediately permeate through it and retain the oil on it.
Fig. 4 Images and particle size analysis of (a) kerosene-in-water (b) crude oil-in-water emulsions before and after separation. (c) Separation
efficiency and oil content in the filtrate of various oil-in-water emulsions. (d) Filtrate flux of various oil-in-water emulsions. (e) Separation efficiency
and flux of the emulsion after 10 separation cycles (taking 100 mL hexane-in-water emulsion as an example per cycle).
3194 | Green Chem., 2019, 21, 3190–3199
View Article Online
Green Chemistry
Due to the unique characteristic of underwater superoleopho-
bicity as well as smaller pore size than that of emulsions, the
loess-coated PVDF membrane can realize various oil-in-water
emulsion separations. The separation process was conducted
with a vacuum system, as shown in Fig. S8.† Herein, the kero-
sene-in-water and crude oil-in-water emulsions as typical
samples were poured onto the loess-coated PVDF membrane.
As shown in Fig. 4a and b, the original cloudy feed emulsion
became clear after permeating through the loess-coated PVDF
membrane. Besides, as for the phase composition, there was
an obvious difference between the emulsion and the collected
filter. For the emulsions before separation, numerous oil dro-
plets bestrewed the entire view, while no oil droplets were seen
in the filtrate. This demonstrated that the loess-coated PVDF
membrane can effectively remove the tiny oil droplets existing
in the emulsions. Moreover, the droplet size distributions had
been characterized before and after emulsion separation. The
droplet size of the kerosene-in-water emulsion before separ-
ation ranged from 100 nm to 460 nm while that of the crude
oil-in-water emulsion was between 100 nm and 1000 nm,
which were larger than the pore size of the coated membrane.
However, the droplet sizes of the filtrates were smaller than
the threshold of the instrument, as exhibited in the inset of
Fig. 4a4 and b4, demonstrating excellent separation efficiency.
Furthermore, other types of oil-in-water emulsions such as pet-
roleum ether, hexane, heptane and diesel in water were also
successfully separated. The optical microscopy images and
droplet sizes of these emulsions are displayed in Fig. S9.† It is
worth mentioning that the droplet size distributions of the fil-
trates are same as that of the filtrate of kerosene-in-water emul-
sion. This phenomenon indicated that the as-prepared mem-
This journal is © The Royal Society of Chemistry 2019
 View Article Online

Green Chemistry Paper

brane possessed superior tiny oil droplet removal ability from
various oil-in-water emulsions. The following eqn (1) was used
to calculate the separation efficiency (R1):
Ci
R1 ¼ 1   100%
C0
where Ci (mg L−1) is the oil content of the collected filtrate and
C0 (mg L−1) is the oil content of the original oil-in-water emul-
sion. The flux (F) was also measured by using eqn (2):28
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
cycles, as shown in Fig. 4e. In addition, the oil content in
water was also detected after separation (Fig. S11†). In order to
minimize the loss of flux after each cycle, the membrane can
be washed with ethanol and water sequentially and reused.
ð1Þ The permeation flux of the loess-coated membrane for cyclic
separation experiments containing deionized water and surfac-
tant-stabilized hexane-in-water emulsion is shown in Fig. S12.†
It can be concluded that the flux recovery ratio (FRR) for the
membrane was about 93.6% after five cycles of separation
experiments. In addition, the separation experiment on the

V
F¼
St
where V (L) is the volume of the filtrate that passes through the
membrane in one minute and S (m2) is the area of the loess-
coated area. As shown in Fig. 4c, the content of oil droplets in
all the filtrates was lower than 135 ppm, and the corres-
ponding separation efficiency was larger than 99.2%. It is
worth mentioning that the separation efficiency of crude oil-
in-water emulsion was above 99.4% with the crude oil content
of less than 90 ppm. In addition, filtrate flux of various oil-in-
water emulsions was also calculated (Fig. 4d). Taking pet-
roleum ether-in-water emulsion as an example, the flux even
reaches as high as 910.4 L m−2 h−1 bar−1 (Fig. 4d). The water
flux of the pure PVDF and loess-coated PVDF membranes were
also investigated, as exhibited in Fig. S10.† The separation per-
formances are comparable to those of the previously reported
superwettable separation membranes, as shown in Table 1.
The loess-coated membrane could be used for separating the
surfactant-stabilized nanoscale emulsions including the crude
oil-in-water emulsion with high separation efficiency and flux,
which differed from the previously reported materials applied
to separate microscale emulsions.51–54 Moreover, the separ-
ation efficiency and flux versus the recycle numbers was also
investigated by taking the hexane-in-water emulsion as an
example. The loess-coated membrane retained excellent separ-
ation performances with the separation efficiency larger than
99.5% and flux as high as 583.2 L m−2 h−1 bar−1 after 10
ð2Þ pure PVDF membrane was conducted to examine the separ-
ation performance of the original membrane (Fig. S13†). The
videos of the separation process on the PVDF and loess-coated
membranes are also shown in the ESI.† The results indicated
that the filtrate of the original PVDF membrane still looked
turbid, whereas the filtrate of the loess-coated PVDF mem-
brane was transparent after one-time separation. These
phenomena suggested that the loess-coated PVDF membrane
had a clear advantage in separating oil-in-water emulsions.
Furthermore, the mass of the emulsion is equal to the sum of
the mass of pure water and retentate, following the law of
mass balance.
The stability is a key factor to affect the practical appli-
cations of the membrane during oil-in-water emulsion separ-
ation. The loess-coated membrane was robust and flexible due
to the addition of sodium alginate, which increases the
binding force between the PVDF substrate and loess par-
ticles.55 There were no cracks after bending it for 200 cycles, as
shown in Fig. 5a. The sodium alginate bonding mechanism
with the loess is shown in Fig. S14.† To evaluate harsh chemi-
cal resistance of the loess-coated PVDF membrane, 3.5 wt%
NaCl solution, 3 M HCl solution, and 1 M NaOH solution were
used in the tests. Obviously, the contact angles of various oils
were larger than 150° under harsh aqueous conditions (Fig. 5).
Moreover, chemical stability of the as-prepared membranes
was also investigated by immersing the coated membranes
into 3.5 wt% NaCl, 3 M HCl and 1 M NaOH solutions for 10 h,

Table 1 Comparison of various membranes used to separate oil-in-water emulsions

Separation substances and Flux

Materials Separation Droplets size efficiency (%) (L m−2 h−1 bar−1) Ref.

PAA-g-PVDF membranes Surfactant-stabilized oil-in- ∼5 μm Hexadecane, toluene, diesel >99.9 80–130 38

water emulsions
Silica-decorated PPMM Surfactant-stabilized oil-in- >1 μm Diesel, gasoline, petroleum ether, 3000–3577 39
membranes water emulsions n-hexane >99.1
TiO2/PVDF membranes Oil-in-water emulsions 1–20 μm n-Hexadecane, trimethylbenzene, 424–672 40
diesel, petroleum ether >98.8
Cellulose/electrospun Surfactant-free oil-in-water >20 μm Corn oil, gasoline, motor oil, crude 124–1781 51
PVDF–HFP membranes emulsions oil >90.1
Hygro-responsive Microscale oil-in-water 10–100 μm Hexadecane >99 90 52
membranes emulsions
HBPU/F-SiO2 composite Microscale oil-in-water 0.5–1.4 μm Hexane, toluene, gasoline, diesel 549–687 53
membranes emulsions dichloromethane >99
GO membrane Oil-in-water emulsions ∼2 μm Toluene, octane, isopar G >99 592–688 54
SiO2 nanofibrous Surfactant-stabilized oil-in- 100 nm Petroleum ether, n-hexane, diesel 267–647 31
membranes water emulsions >96.5
Loess coated PVDF Surfactant-stabilized 100–1000 nm Crude oil, kerosene, diesel, heptane, 423–910 This work
membrane nanoscale emulsions hexane, petroleum ether >99.2

This journal is © The Royal Society of Chemistry 2019 Green Chem., 2019, 21, 3190–3199 | 3195
 View Article Online

Paper Green Chemistry

Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.

Fig. 5 (a) Digital photographs of the loess-coated PVDF membrane before and after bending for over 200 cycles. Oil contact angles on the loess-
coated PVDF membrane in (b) 3.5 wt% NaCl solution, (c) 3 M HCl solution, (d) 1 M NaOH solution and after immersion into these solutions for 10 h,
respectively.

respectively. It was clear that the oil contact angles after
soaking in harsh environments were reduced slightly com-
pared with the original contact angles. It is proved that the
loess-coated PVDF membrane has excellent chemical resis-
tance, mechanical performance and flexibility. In general,
3.5 wt% NaCl solution is usually used as simulated seawater.
After a series of concentration gradient experiments, it was
found that the as-prepared membrane exhibited the best per-
formance under 3 M HCl and 1 M NaOH solutions and was
not damaged. This provides references for practical appli-
cations and possibilities for separating oil-in-water emulsions
under corrosive media. The separation result of the tween
80-stabilized kerosene-in-HCl and crude oil-in-HCl emulsions
are exhibited in Fig. 6. Similar to the above oil-in-water emul-

Fig. 6 (a and c) The optical microscopy images and (b) the digital images and (d) particle size analysis of the kerosene-in-HCl and crude oil-in-HCl
emulsions before and after separation. (e) Separation efficiency and (f ) flux of kerosene-in-water, and crude oil-in-water emulsions under corrosive
environments on the loess-coated PVDF membrane.

3196 | Green Chem., 2019, 21, 3190–3199 This journal is © The Royal Society of Chemistry 2019

Green Chemistry
sion separation, the original cloudy feed became clear after the
separation (Fig. 6b). There were no evident oil droplets visible in
the filtrate from the optical images (Fig. 6a and c). In addition,
the droplet size distribution of the emulsions before separation
is wide, while no distribution can be detected after separation
(Fig. 6d). Besides, the loess-coated PVDF membrane can also
achieve the separation of kerosene and crude oil in NaCl and
NaOH emulsions, which further proved the excellent separation
capacity for separating oil-in-corrosive aqueous emulsions
(Fig. S15†). The FE-SEM images of the loess-coated PVDF mem-
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
brane after separation are provided in Fig. S16.† Fig. 6e and f
show the separation efficiency and flux of oil-in-water emulsions
under harsh conditions, respectively. It showed that the separ-
ation efficiency of kerosene-in-water and crude oil-in-water
emulsions under corrosive environments is more than 99.0%
and the flux is larger than 435.0 L m−2 h−1 bar−1.
For the application of loess-coated PVDF membrane in mul-
tifunctional wastewater treatment, it could not only achieve the
separation of oil-in-water emulsions but also realize the
removal of organic dyes. Adsorption studies towards crystal
violet and methylene blue on the loess-coated PVDF mem-
brane were carried out by changing the concentration of dyes.
10 mL of each sample was used in the process of dye adsorp-
tion experiments. The UV-vis absorption spectra of methylene
blue and crystal violet solutions are plotted in Fig. 7a and b,
respectively. Evidently, the filter spectra of loess-coated PVDF
membrane after absorption were almost a straight line while
the spectra of original PVDF membrane had high peaks at the
concentration of 80 mg L−1. The photographs before and after
dye adsorption are exhibited in Fig. S17;† it was clear that the
two dyes with various concentrations became colorless after
adsorption by the loess-coated membrane while the loess-
coated membrane turned blue or violet, indicating that the as-
Fig. 7 UV-vis absorption spectra of the original and collected (a)
methylene blue and (b) crystal violet solutions. (c) Adsorption efficiency
of dyes as a function of initial solution concentrations. (d) Adsorption
efficiency of dyes at a concentration of 80 mg L−1 on the loess-coated
PVDF and original PVDF membranes.
This journal is © The Royal Society of Chemistry 2019
View Article Online
Paper
prepared membrane possessed excellent adsorption perform-
ance. Moreover, Fig. 7c shows the effect of the initial concen-
tration on the adsorption efficiency. In addition, the adsorp-
tion efficiency is calculated according to the following
equation:56
Cj
R2 ¼ 1   100% ð3Þ
C0
where Cj (mg L−1) is the final concentration and C0 (mg L−1) is
the initial concentration of dyes. Obviously, the adsorption
efficiency of the two dyes increased with the increase in the
initial dye concentration, but the adsorption rate slowed down.
The reason is that there are sufficient active sites on the
surface for methylene blue or crystal violet adsorption when at
its low concentration. With the increase in concentration,
active sites are almost completely covered, resulting in a
reduction of the removal rate. Additionally, adsorption
efficiency was obtained at the initial concentration of 80 mg
L−1 of two dyes on the loess-coated PVDF and original PVDF
membranes (Fig. 7d). It is evident that the loess-coated mem-
brane has higher adsorption efficiency than the original PVDF
membrane, which proves that the loess-coated PVDF mem-
brane possesses excellent adsorption activity for dyes. In
addition, the idea of using loess for dye adsorption agrees
with the concept of “green” and “sustainable” materials.
The loess-coated PVDF membrane can also remove heavy
metal ions in aqueous solution. Herein, Cu2+, Pb2+ and Zn2+
aqueous solutions were prepared at a series of concentrations.
Then, 10 mL aqueous solution was added on the loess-coated
PVDF membrane; the corresponding filtrate was collected
through vacuum filtration. Adsorption efficiency can be
measured by eqn (3), where C0 (mg L−1) and Cj (mg L−1) are the
original and final concentrations of heavy metal ions in
aqueous solution, respectively. It was evident that the adsorp-
tion efficiency towards Pb2+ increased from 81.4% to 94.8%,
when the concentration increased from 5 to 30 mg L−1
(Fig. 8a). In addition, after this, a slight decrease of adsorption
for Pb2+ could be observed. Such adsorption process is attribu-
ted to the fact that many available adsorption sites exist on the
surface at the low concentration of Pb2+, which means a high
efficiency. With the increase in the concentration of Pb2+, the
active site on the loess-coated surface would be exhausted,
Fig. 8 (a) Adsorption efficiency for Cu2+, Pb2+ and Zn2+ on the loess-
coated PVDF membrane at different concentrations. (b) Adsorption
efficiency for Cu2+, Pb2+ and Zn2+ at 30 mg L−1 metallic salt solution on
the original PVDF and the loess-coated PVDF membrane.
Green Chem., 2019, 21, 3190–3199 | 3197

Paper
which caused a decrease in the efficiency. The adsorption prin-
ciple of Cu2+ and Zn2+ was similar to that of Pb2+. However, the
chart showed that the adsorption efficiency towards Zn2+
decreased sharply with the increase in the initial concentration.
Nevertheless, the adsorption efficiency for Zn2+ still reached up
to 92.0%, while the corresponding concentration was 5 mg L−1.
In addition, the EDS spectra of the loess-coated PVDF mem-
branes after the adsorption of Cu2+, Pb2+ and Zn2+ were ana-
lysed (Fig. S18†). The results demonstrate that the Cu2+, Pb2+
and Zn2+ are successfully adsorbed on the loess-coated mem-
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
branes. Fig. 8b exhibited the adsorption efficiency of the metal
ions at 30 mg L−1 on the original PVDF membrane and the
loess-coated PVDF membrane. It was clear that the adsorption
efficiency of the loess-coated PVDF membrane increased
remarkably in contrast to that of the original PVDF membrane,
which implies that the loess-coated PVDF membrane possesses
outstanding adsorption ability towards heavy metal ions.
4. Conclusion
In summary, the loess-coated PVDF membrane with under-
water superoleophobicity has been fabricated successfully
using a facile and green method. The as-prepared membrane
can achieve various oil-in-water emulsion separations as well
as the adsorption of dyes and heavy metal ions. The loess-
coated PVDF membrane displayed extraordinary underwater
superoleophobicity with oil contact angles larger than 150°
and sliding angles smaller than 10° toward different oils,
including crude oil with high viscosity. Furthermore, the sep-
aration efficiency of various oil-in-water emulsions is larger
than 99.2% and the flux can reach up to 910.4 L m−2 h−1
bar−1. In addition, the coated membrane retained excellent
separation performances even after 10 separation cycles.
Moreover, the resultant membrane can be utilized for separ-
ating oil-in-water emulsions in corrosive aqueous environ-
ments. Besides, the loess-coated PVDF membrane showed
excellent mechanical performance and flexibility. Based on the
above-mentioned results, the loess-coated PVDF membrane
can be a promising candidate for removing oils, water-soluble
dyes and heavy metal ions in water remediation. Taking the
resourceful loess as the water treatment material can not only
greatly reduce the cost of wastewater treatment and maximize
resource utilization, but also contribute to sustainable develop-
ment. This research would open a new window for designing
versatile materials in multifunctional wastewater treatment.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This project was funded by the National Natural Science
Foundation of China (no. 51872245), the Fok Ying-Tong
3198 | Green Chem., 2019, 21, 3190–3199
View Article Online
Green Chemistry
Education Foundation of China (161044), the Natural Science
Foundation for Distinguished Young Scholars of Gansu
Province, China (18JR3RA083), China Postdoctoral Science
Foundation (2018T110025, 2017M610031), and the Young
Teacher Research Group Foundation of Northwest Normal
University (NWNU-LKQN-16-6). We also thank the Gansu
International Scientific and Technological Cooperation Base of
Water-Retention Chemical Functional Materials for financial
support.
References
1 J. Ge, J. Zhang, F. Wang, Z. Li, J. Yu and B. Ding, J. Mater.
Chem. A, 2017, 5, 497–502.
2 J. Huang, Y. Liu, Q. Jin, X. Wang and J. Yang, J. Hazard.
Mater., 2007, 143, 541–548.
3 U. Habiba, A. M. Afifi, A. Salleh and B. C. Ang, J. Hazard.
Mater., 2017, 322, 182–194.
4 L. Zhang, H. Li, X. Lai, X. Su, T. Liang and X. Zeng, Chem.
Eng. J., 2017, 316, 736–743.
5 C. H. Peterson, S. D. Rice, J. W. Short, D. Esler,
J. L. Bodkin, B. E. Ballachey and D. B. Irons, Science, 2003,
302, 2082–2086.
6 Y. Liu, Y. Su, J. Guan, J. Cao, R. Zhang, M. He, K. Gao,
L. Zhou and Z. Jiang, Adv. Funct. Mater., 2018, 28, 1706545.
7 B. Chen, W. Wang and Y. Huang, Talanta, 2012, 88, 237–
243.
8 W. Liu, M. Cui, Y. Shen, G. Zhu, L. Luo, M. Li and J. Li,
J. Colloid Interface Sci., 2019, 549, 114–122.
9 B. Wang, W. Liang, Z. Guo and W. Liu, Chem. Soc. Rev.,
2015, 44, 336–361.
10 Z. Xue, Y. Cao, N. Liu, L. Feng and L. Jiang, J. Mater. Chem.
A, 2014, 2, 2445–2460.
11 Z. Chu, Y. Feng and S. Seeger, Angew. Chem., Int. Ed., 2015,
54, 2328–2338.
12 W. Zhang, N. Liu, Y. Cao, X. Lin, Y. Liu and L. Feng, Adv.
Mater. Interfaces, 2017, 1600029.
13 H. Cao, H. Zheng, K. Liu and J. H. Warner, ChemPhysChem,
2010, 11, 489–494.
14 X. Wang, B. Ding, J. Yu and M. Wang, Nano Today, 2011, 6,
510–530.
15 X. Wang, H. Hu, Q. Ye, T. Gao, F. Zhou and Q. Xue,
J. Mater. Chem., 2012, 22, 9624.
16 X. Qiu, Z. Yang, H. Wu, J. Guo, Z. Zhang, J. Feng, G. Chai
and A. Liu, Appl. Surf. Sci., 2018, 456, 602–608.
17 B. Cheng, Z. Li, Q. Li, J. Ju, W. Kang and M. Naebe,
J. Membr. Sci., 2017, 534, 1–8.
18 L. Zhang, Z. Zhang and P. Wang, NPG Asia Mater., 2012, 4, e8.
19 L. Feng, Z. Zhang, Z. Mai, Y. Ma, B. Liu, L. Jiang and
D. Zhu, Angew. Chem., 2004, 116, 2046–2048.
20 Y. Yu, H. Chen, Y. Liu, V. Craig, L. H. Li and Y. Chen, Adv.
Mater. Interfaces, 2014, 1, 1300002.
21 S. Li, J. Huang, M. Ge, C. Cao, S. Deng, S. Zhang, G. Chen,
K. Zhang, S. S. Al-Deyab and Y. Lai, Adv. Mater. Interfaces,
2015, 2, 1500220.
This journal is © The Royal Society of Chemistry 2019

Green Chemistry
22 Q. An, Y. Zhang, K. Lv, X. Luan, Q. Zhang and F. Shi,
Nanoscale, 2015, 7, 4553–4558.
23 Y. Dong, J. Li, L. Shi, X. Wang, Z. Guo and W. Liu, Chem.
Commun., 2014, 50, 5586–5589.
24 S. Song, H. Yang, C. Zhou, J. Cheng, Z. Jiang, Z. Lu and
J. Miao, Chem. Eng. J., 2017, 320, 342–351.
25 Z.-Y. Luo, K.-X. Chen, J.-H. Wang, D.-C. Mo and S.-S. Lyu,
J. Mater. Chem. A, 2016, 4, 10566–10574.
26 Z. Xue, S. Wang, L. Lin, L. Chen, M. Liu, L. Feng and
L. Jiang, Adv. Mater., 2011, 23, 4270–4273.
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/17/2019 11:20:41 AM.
27 J. Li, L. Yan, H. Li, W. Li, F. Zha and Z. Lei, J. Mater. Chem.
A, 2015, 3, 14696–14702.
28 J. Li, D. Li, Y. Yang, J. Li, F. Zha and Z. Lei, Green Chem.,
2016, 18, 541–549.
29 X. Gao, L. P. Xu, Z. Xue, L. Feng, J. Peng, Y. Wen, S. Wang
and X. Zhang, Adv. Mater., 2014, 26, 1771–1775.
30 Q. Wen, J. Di, L. Jiang, J. Yu and R. Xu, Chem. Sci., 2013, 4,
591–595.
31 J. Ge, Q. Jin, D. Zong, J. Yu and B. Ding, ACS Appl. Mater.
Interfaces, 2018, 10, 16183–16192.
32 M. Huang, Y. Si, X. Tang, Z. Zhu, B. Ding, L. Liu, G. Zheng,
W. Luo and J. Yu, J. Mater. Chem. A, 2013, 1, 14071.
33 J. Wang, A. Raza, Y. Si, L. Cui, J. Ge, B. Ding and J. Yu,
Nanoscale, 2012, 4, 7549–7556.
34 J. Lin, F. Tian, Y. Shang, F. Wang, B. Ding and J. Yu,
Nanoscale, 2012, 4, 5316–5320.
35 W. Zhang, Z. Shi, F. Zhang, X. Liu, J. Jin and L. Jiang, Adv.
Mater., 2013, 25, 2071–2076.
36 G. Wang, Y. He, H. Wang, L. Zhang, Q. Yu, S. Peng, X. Wu,
T. Ren, Z. Zeng and Q. Xue, Green Chem., 2015, 17, 3093–3099.
37 J. Li, C. Xu, C. Guo, H. Tian, F. Zha and L. Guo, J. Mater.
Chem. A, 2018, 6, 223–230.
38 W. Zhang, Y. Zhu, X. Liu, D. Wang, J. Li, L. Jiang and J. Jin,
Angew. Chem., Int. Ed., 2014, 53, 856–860.
39 H. C. Yang, J. K. Pi, K. J. Liao, H. Huang, Q. Y. Wu,
X. J. Huang and Z. K. Xu, ACS Appl. Mater. Interfaces, 2014,
6, 12566–12572.
This journal is © The Royal Society of Chemistry 2019
View Article Online
Paper
40 H. Shi, Y. He, Y. Pan, H. Di, G. Zeng, L. Zhang and
C. Zhang, J. Membr. Sci., 2016, 506, 60–70.
41 K. Suresh, T. Srinu, A. K. Ghoshal and G. Pugazhenthi, RSC
Adv., 2016, 6, 4877–4888.
42 C. Cui, A. T. O. Lim and J. Huang, Nat. Nanotechnol., 2017,
12, 834–835.
43 M. A. Rasool and I. F. J. Vankelecom, Green Chem., 2019,
21, 1054–1064.
44 D. Zhao, J. F. Kim, G. Ignacz, P. Pogany, Y. M. Lee and
G. Szekely, ACS Nano, 2019, 13, 125–133.
45 M. Razali, C. Didaskalou, J. F. Kim, M. Babaei, E. Drioli,
Y. M. Lee and G. Szekely, ACS Appl. Mater. Interfaces, 2017,
9, 11279–11289.
46 D. Gonzalez-Ortiz, C. Pochat-Bohatier, S. Gassara,
J. Cambedouzou, M. Bechelany and P. Miele, Green Chem.,
2018, 20, 4319–4329.
47 M. P. Wei, H. Chai, Y. L. Cao and D. Z. Jia, J. Colloid
Interface Sci., 2018, 524, 297–305.
48 Y. Duan, A. Freyburger, W. Kunz and C. Zollfrank,
ACS Sustainable Chem. Eng., 2018, 6, 6965–
6973.
49 J. Xu, S. Zhu, P. Liu, W. Gao, J. Li and L. Mo, RSC Adv.,
2017, 7, 44751–44758.
50 S. Gopi, P. Balakrishnan, A. Pius and S. Thomas,
Carbohydr. Polym., 2017, 165, 115–122.
51 F. Ejaz Ahmed, B. S. Lalia, N. Hilal and R. Hashaikeh,
Desalination, 2014, 344, 48–54.
52 A. K. Kota, G. Kwon, W. Choi, J. M. Mabry and A. Tuteja,
Nat. Commun., 2012, 3, 1025.
53 W. Fang, L. Liu and G. Guo, Chemistry, 2017, 23, 11253–
11260.
54 T. Huang, L. Zhang, H. Chen and C. Gao, J. Mater. Chem. A,
2015, 3, 19517–19524.
55 Y. Long, Y. Shen, H. Tian, Y. Yang, H. Feng and J. Li,
J. Membr. Sci., 2018, 565, 85–94.
56 Y. Zhao, E. Abdullayev, A. Vasiliev and Y. Lvov, J. Colloid
Interface Sci., 2013, 406, 121–129.
Green Chem., 2019, 21, 3190–3199 | 3199