Journal of Membrane Science 640 (2021) 119824

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Journal of Membrane Science

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

Omniphobic membrane with nest-like re-entrant structure via

electrospraying strategy for robust membrane distillation
Wei Zhang a, b, c, d, Zhi Wang a, b, c, d, Baoan Li e, *
a
Chemical Engineering Research Center, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, PR China
b
State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin, 300072, PR China
c
Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin, 300072, PR China
d
Tianjin Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, PR China
e
College of Environmental Science and Engineering, Nankai University, Tianjin, 300350, PR China

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

Keywords: Omniphobic membranes have acquired some recognitions for alleviating the membrane wetting in the robust
Omniphobic membrane membrane distillation because of the super-repulsion towards different surface tension liquids. In this study, the
Electrospraying Ti-CNFs/PVDF composite membrane with omniphobicity and high permeate flux was fabricated via electro­
Carbon nanofibers
spraying multilevel heat-conducting nanofibers on the PVDF membrane and fluorosilane treatment simulta­
Re-entrant
neously with one-step strategy. In detail, carbon nanofibers decorated by TiO2 with hydrothermal treatment were
DCMD
Anti-fouling immobilized on the surface by the adhesive attraction of PDMS to establish the re-entrant structure. Meanwhile,
Anti-wetting 1H,1H,2H,2H-perfluorodecyltriethoxysilane was presented in the spraying liquid to gain the low surface energy
for the surface. Additionally, the composite nanofibers played a role in mitigating the temperature polarization.
A series of characterizations on membrane morphologies, wetting behaviors, structural peculiarities and stable
properties were investigated systematically. The results showed that the re-entrant morphology consisted of the
intersecting nanofibers was constructed skillfully, looking like the nest’s hierarchical structure. The composite
membrane displayed outstanding contact angles of 172.0 ± 1.8◦ , 170.5 ± 3.5◦ , 160.1 ± 2.6◦ , 165.0 ± 3.0◦ ,
162.5 ± 4.5◦ , 151.0 ± 1.5◦ , 153.5 ± 3.5◦ and 118.0 ± 3.0◦ towards DI water, 3.5 wt% NaCl, 0.4 mM SDS, 0.4 mM
CTAB, 0.4 mM Tween-20, ethanol, soybean milk and dodecane, respectively. The modified membrane presented
a 167% LEP measurement of the pristine membrane and satisfactory chemical and thermal stabilities along with
silver mirror phenomena. Furthermore, the omniphobic membrane exhibited anti-fouling and anti-wetting
performances with high and stable permeate fluxes (36.3 kg/m2⋅h) as well as a nearly 100% salt rejection
rate in the consecutive DCMD tests, where HA and diverse surfactants were added to the brine feed. This suggests
the omniphobic membrane as a promising alternative for wastewater treatment in membrane distillation.

1. Introduction are reverse osmosis (RO), nanofiltration (NF), forward osmosis (FO),
membrane distillation (MD), etc. Among them, RO is considered as the
With the environment deterioration, water systems around the world most popularly implemented membrane-based desalination process in
are polluted to different extent and freshwater scarcity has been an ur­ large capacities of desalination plants across the globe [12,13]. Never­
gent issue to be addressed [1–3]. At present, seawater and brackish theless, the produced RO brine is discharged to sea directly in practice
water desalination as well as wastewater reclamation are common sus­ with an extremely adverse impact on the marine ecosystem [14]. From
tainable strategies to relieve the crisis of freshwater shortage [4–7]. the perspective of protecting the environment, the MD desalination
Compared to traditional thermal treatment technologies (i.e., process towards the goal of zero liquid discharge (ZLD) is of great
multi-effect distillation (MED) and multi-stage flash (MSF)), membrane concern.
separation techniques have drawn more attention to desalination due to MD, as an emerging separation technique, is driven by the vapor
less occupied footprint, lower energy consumption and simpler opera­ pressure difference ascribed to the temperature difference across the
tion process [8–11]. The conventional membrane separation techniques membrane with hydrophobic and porous features [15–17]. MD is a

* Corresponding author.
E-mail address: [email protected] (B. Li).

https://doi.org/10.1016/j.memsci.2021.119824
Received 1 August 2021; Received in revised form 29 August 2021; Accepted 30 August 2021
Available online 5 September 2021
0376-7388/© 2021 Elsevier B.V. All rights reserved.
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

non-isothermal membrane process and there is the temperature gradient assistance of electrostatic interaction and chemical bonding. The resul­
in the vertical direction of membrane pores. Specifically, volatile com­ tant membranes showed high contact angles towards
ponents including liquid water are transformed to the gas phase at the low-surface-tension liquids and prevented the wetting and fouling
interface of the hot feed and the hydrophobic membrane, and they effectively to occur in MD tests with the saline solution containing
would diffuse through membrane pores to the permeate in a gaseous surfactants as the feed. Other methods such as layer-by-layer (LBL) as­
form. Then vapors are condensed into liquids at the cold permeate side, sembly [46] and CF4 plasma etching treatment [47] were also adopted
thus obtaining the target product with high quality. In the MD process, to construct rough surfaces. The formation of re-entrant structures and
the heat demand of the feed could be supplied by alternative sources and the fluorinated treatment are carried out individually in the fabrication
renewable energy containing low-grade industrial waste heat, solar process of preceding omniphobic membranes. However, the separate
power and geothermal energy [18,19]. MD is performed under mild operations increase the time consuming and the process complexity.
conditions such as the low operating pressure and no external hydraulic Additionally, most of the omniphobic membranes obtained a relatively
pressure requirement [20]. This presents lower equipment costs and lower flux after modification, compared to the unmodified membranes.
higher energy efficiency, in comparison with pressure-driven membrane It has been demonstrated that the membrane water flux increases when
processes (RO and NF) [21,22]. Besides, hydrophobic membrane pores the membrane surface is modified by carbon nanomaterials [21,48].
only allow volatile components to pass from the feed to the permeate, Herein, we propose to apply multi-level carbon nanomaterials for the
thereby demonstrating the 100% rejection rate of dissolved and design of the omniphobic membrane with the one-step strategy.
nonvolatile compounds (i.e., salts) in theory [23,24]. The treatment of In this work, the Ti-CNFs/PVDF composite membrane with omni­
challenging wastewater (i.e., RO concentrated brine and hypersaline phobic characteristics was developed with a versatile method, namely
wastewater) is feasible with MD in severe conditions [25,26]. The MD electrospraying multi-scale Ti-CNFs on the conventional PVDF mem­
process also can work in conjunction with other membrane processes brane and fluorosilane treatment simultaneously. The Ti-CNFs was ob­
(such as RO, FO) [23,25] for different applications and industries, being tained by in-situ forming TiO2 on the carbon nanofibers under the
less sensitive to the feed concentration. hydrothermal treatment, and then used to construct the re-entrant
Despite numerous advantages over other desalination technologies, structure for the membrane surface. The morphology features and
MD has not yet been widely industrialized in a large-scale level. One chemical compositions of the membranes were characterized in detail.
reason is that the lack of suitable membranes restricts the application of The chemical and thermal stabilities and the wetting behaviors of the
MD, and membrane fouling and wetting are still major issues in MD membranes were evaluated in harsh conditions. What’s more, the
[27–29]. As a physical barrier, the MD membrane plays a crucial role in permeate fluxes and the anti-fouling and anti-wetting performances of
the separation process, determining the separation performance and the the membranes with the complex saline wastewater containing organic
permeate quality. Currently, commercial MD membranes with hydro­ matters and surfactants were explored and compared systematically by
phobic surfaces are made of polymer materials including polyethylene consecutive direct contact membrane distillation (DCMD) tests.
(PE), polypropylene (PP), polytetrafluoroethylene (PTFE) and poly­
vinylidene fluoride (PVDF) [30]. Although hydrophobic membranes 2. Experimental
exhibit the repellency to water, they are extremely vulnerable to low
surface tension contaminants in the feed [31]. These conventional hy­ 2.1. Materials and chemicals
drophobic membranes present poor stabilities in the long-term MD
practical operation, owing to the limitation of the hydrophobicity. In Carbon nano fibers (CNFs, outer diameter: 50–200 nm, length: 1–15
particular, dissolved organic matters and surfactants emerging in the μm, purity: >95%) were purchased from Nanjing XFNANO Materials
treatment liquid accelerate the membrane fouling and wetting, resulting Technology Co., Ltd, China. Sulfuric acid (H2SO4, 95%–98%), nitric acid
in the loss of membrane hydrophobicity and the deterioration of mem­ (HNO3, 65%–68%), hydrochloric acid (HCl, 36.5%–38%), anhydrous
brane performances. Consequently, it is indispensable to exploit new ethanol (AR), n-hexane (AR), calcium carbonate (CaCO3, AR), dodecane
membranes with robust antifouling and antiwetting properties as well as (AR) and sodium chloride (NaCl, AR) were provided by Tianjin Kermel
satisfactory stabilities for MD desalination. Inspired by the lotus effect in Chemical Technology Co., Ltd., China. Hydroxy-terminated poly­
nature, researchers are interested in superhydrophobic surfaces with the dimethylsiloxane (PDMS) and 1H,1H,2H,2H-perfluorodecyltriethoxysi­
water contact angle above 150◦ and the water sliding angle below 10◦ lane (CF3(CF2)7(CH2)2Si(OC2H5)3, PFDTS, 98%) was gained from
[32,33]. Superhydrophobic membranes prepared via various modifica­ Tianjin HEOWNS Science and Technology Co., Ltd., China. Tetrabutyl
tion methods demonstrate superior self-cleaning capability and anti­ titanate (TBOT, 98%), 3-Aminopropyltriethoxysilane (APTES, 99%),
fouling performance for inorganic salts and dissolved organic humic acid (HA, AR), sodium dodecyl sulfate (SDS, AR), cetyltrimethyl
compounds, but they are liable to being wetted by low-surface-tension ammonium bromide (CTAB, AR), Tween-20 (AR), sodium hydroxide
liquids in MD [34,35]. (NaOH, AR) and ethanol (75%, AR) were purchased from Shanghai
Recently, omniphobic membranes have been considered as potential Aladdin Biochemical Technology Co., Ltd., China. Soybean milk was
solutions to deal with the challenging feed for MD, which display strong supplied from YON HO food (China) Co., Ltd. All chemicals and reagents
repulsion forces towards water and liquids with a wide range of surface were used directly without further purification. Deionized (DI) water
tensions [36–38]. The omniphobic surface is usually created by the was produced from an ultrapure water purification system (resistivity
re-entrant hierarchical structure and the ultra-low surface energy [15, >18.0 MΩ cm, Millipore). A flat sheet PVDF membrane (Immobilon-PSQ
39,40]. The construction of re-entrant structures is in favor of air pockets ISEQ00010, 0.22 μm) was supplied by Merck Millipore Co., Ltd.,
in voids and surface roughness. The low-surface-energy fluorination Germany.
agent with long fluorocarbon chains is introduced to decrease the sur­
face energy. The combination of air pockets and the low-surface-energy 2.2. Synthesis of titanium dioxide coated carbon nanofibers (Ti-CNFs)
makes contaminants difficult to adsorb and stay on the surface. Based on
these principles, omniphobic membranes designed successfully with Raw CNFs (500 mg) were added into the mixture of H2SO4 (60 ml)
diverse thoughts have been reported and applied in robust MD tests. and HNO3 (20 ml) under constant magnetic stirring. The suspension was
Some groups developed omniphobic membranes via depositing or disposed of refluxing for 6 h at 60 ◦ C to activate CNFs. The homogeneous
spraying coating micro-/nano-sized particles or nanorods (i.e., SiO2 [41, black liquid was diluted with DI water, and then filtrated and rinsed
42], TiO2 [22,43], ZnO [14,44] and polystyrene (PS) [45]) on the repeatedly under vacuum until the filtrate was close to neutral (pH = 6).
membrane surface, followed by surface fluorination. These additional The filter cake was dried overnight in a vacuum oven at 80 ◦ C to obtain
nanoparticles were utilized to create the hierarchical texture with the the activated CNFs (named as a-CNFs).

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W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

The a-CNFs (100 mg) were dispersed in a uniform precursor solution membranes were imaged via scanning electron microscopy (SEM,
under the ultrasonic treatment for 2 h at room temperature. The pre­ HITACHI S-4800, Japan) under a 5.0 kV operating voltage, and a cor­
cursor was prepared via adding TBOT (1.5 ml) to diluted HCl solution responding energy dispersive spectrometer (EDS, Kevex, USA) was
(The volumes of hydrochloric acid and DI water are all 30 ml). The attached to it with a 15.0 kV accelerating voltage. The two-dimensional
above mixture was transferred to a 100 ml Teflon-lined stainless steel (2D), three-dimensional (3D) and surface roughness structures of
autoclave to conduct a hydrothermal synthesis reaction at 150 ◦ C for 24 membrane samples were observed using atomic force microscopy (AFM,
h. After the autoclave was cooled to room temperature, the homoge­ Bruker, Germany) with a 5.0 μm × 5.0 μm scanning area.
neous liquid was centrifuged at 10,000 rpm and washed with DI water The chemical functional groups of samples were analyzed by the
repetitiously until neutral. The obtained product labeled as Ti-CNFs was attenuated total reflectance-Fourier transform infrared spectroscopy
dried under vacuum at 80 ◦ C for 12 h. (ATR-FTIR, Bruker Tensor II, Germany) in the scanning region from
4000 cm− 1 to 400 cm− 1 wavenumbers with a 4 cm− 1 resolution.
2.3. Fabrication of Ti-CNFs/PVDF composite membrane Furthermore, the surface chemical compositions and element pro­
portions of samples were characterized by X-ray photoelectron spec­
The Ti-CNFs were ultrasonically dispersed in anhydrous ethanol (25 troscopy (XPS, Thermo Fisher Scientific K-Alpha+, UK) with Al-Kα as a
ml) at ambient temperature for 60 min. Then APTES (500 μL) was added radiation source at 1486.6 eV. The spectra were recorded under an
into the dispersion and they were mechanically stirred on full speed at analytical mode of the 50.0 eV pass energy with a 400 μm spot size. X-
30 ◦ C for 2 h. After that, PFDTS (1000 μL) was dropped into the sus­ ray diffraction (XRD, Bruker AXS D8-Focus, Germany) patterns with a
pension slowly and stirred unceasingly for a further 3 h. The above Cu-Kα radiation source were used to investigate the crystal structure of
mixed solution was denoted as solution A. Additionally, PDMS (1.0 g) specimens, performed in a range of 10◦ –80◦ under 40 mA and 40 mV.
was dissolved in n-hexane (25 ml) by magnetic stirring and ultrasonic The thermal stabilities of samples were explored by the thermogra­
treatment at 25 ◦ C for 60 min, respectively. The uniform solution was vimetric analyzer (TGA, Netzsch TG 209F3, Germany), and the corre­
marked as solution B. Subsequently, the solution B was mingled with the sponding thermograms were documented at a linear heating rate of
solution A under mechanical stirring for another 3 h. The resultant 10 ◦ C/min from the room temperature to 800 ◦ C in air atmosphere.
mixture was sprayed onto the pretreated PVDF membrane for 15 s with a The pore sizes of membranes were evaluated via the capillary flow
distance of 20 cm (between the spray gun and the membrane) under a porometer (3H–2000 PB, Beijing Beishide Instrument, China). Before
pressure of 0.20 MPa. Beforehand, the pristine PVDF membrane was measurement, the right size membrane was immersed into Porefil (a
washed by anhydrous ethanol and DI water repeatedly, and air-dried at wetting agent) with a low surface tension (16 dyn/cm) at atmospheric
60 ◦ C for 2 h. After the spraying process, the modified membrane was temperature and pressure for 24 h to achieve the membrane pores filled
shifted to the vacuum oven and heated at 120 ◦ C for 2 h to cure the with liquids completely. Based on the bubble pressure method and the
coating layer. According to the mass fraction of Ti-CNFs (0.05%, 0.1%, Young-Laplace equation, the pore sizes of membranes could be gained
0.2%, 0.4% and 0.6%), the modified PVDF membrane was recorded as and calculated using Eq. (1) [16,49,50]:
Ti-CNFs-X/PVDF composite membrane (Ti-CNFs-1/PVDF, Ti-CNFs-2/ 4γcosθ
PVDF, Ti-CNFs-3/PVDF, Ti-CNFs-4/PVDF and Ti-CNFs-5/PVDF, di = (1)
ΔPi
respectively). Furthermore, the entire fabrication process of the Ti-
CNFs/PVDF composite membrane is presented in Fig. 1. in which di is the pore size of the sample (μm), γ is the surface tension
of the wetting fluid (dyn/cm), θ is the contact angle of the wetting fluid
2.4. Characterization methods (◦ ), and ΔPi is the pressure difference across the membrane (bar).
The porosities of membranes were measured by the gravimetric
The morphologies of powder samples were detected by transmission method. The dry membrane sample was submerged in Porefil and
electron microscopy (TEM, JEOL JEM-F200, Japan) equipped with an anhydrous ethanol for 2 h in sequence. Then the wetted membrane
energy dispersive spectrometer (EDS, Kevex, USA) at an accelerating sample was soaked renewedly into anhydrous ethanol for another 12 h
voltage of 200 kV. The surface and cross-section morphologies of to ensure the wetting absolutely. The weights of dry and wet membranes

Fig. 1. The dehydration reactions among molecules and the fabrication process of the Ti-CNFs/PVDF composite membrane.

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W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

were weighed and recorded separately. The porosity of the membrane (m2), and Δt is the interval time in the test (h).
could be calculated using Eq. (2) [16,49]: The anti-wetting and anti-fouling properties of composite mem­
branes were compared with those of the pristine membrane. The saline
(m2 − m1 )ρ1
ε= × 100% (2) solutions of different concentrations (35 g/L NaCl and 100 g/L NaCl) as
ρ1 m2 + (ρ2 − ρ1 )m1
well as various foulants (HA and surfactants) were added to the feed to
in which ε is the membrane porosity; m1 and m2 are the weight of the explore the membrane performances. The quality of the permeate was
dry membrane and wet membrane, respectively (g); ρ1 and ρ2 are the evaluated with the electric conductivity, monitored periodically by an
density of anhydrous ethanol (0.79 g/cm3) and polymer PVDF (1.78 g/ electric conductivity gauge (DDSJ-308A, INESA Scientific Instrument
cm3). In addition, the thicknesses of membranes could be obtained by a Co., Ltd, China). The conductivity measurement was applied to judge
micrometer caliper (Suce, China) or the cross-sectional images with the the salt rejection of membranes. The salt rejection coefficient was
scale. At least three individual samples were gauged and the average calculated by Eq. (5), as follows [16,51]:
with standard errors was served as the reference data. ( )
Cf − Cp Cp
The wetting property of membrane samples was characterized using R= × 100% = 1 − × 100% (5)
Cf Cf
the contact angle (CA) with the assistance of the contact angle
measuring instrument (OCA 15 EC, Data Physics, Germany). The images in which R is the salt rejection coefficient, Cf is the total dissolved salt
of liquid droplets contacted with the sample surface were captured by concentration of the feed (mg/L), and Cp is the salt concentration of the
the matched high-definition video camera, and contact angle values of permeate (mg/L).
the droplets were calculated via the sessile drop method. Besides, the
critical angle between a bevel and the horizontal plane was denoted as 3. Results and discussion
sliding angle, when liquid droplets moved on the inclined surface. The
sliding angle (SA) was also used to represent the wettability of mem­ 3.1. Characterizations of Ti-CNFs powder
brane samples. At least three different locations for each sample were
measured to obtain the average with standard deviations as the result. The morphologies and chemical compositions of CNFs, a-CNFs and
The liquid entry pressure (LEP) of membranes was tested by means of Ti-CNFs were characterized by TEM as well as EDS mapping, ATR-FTIR
the home-made set-up connected with a nitrogen cylinder, shown in and XRD to confirm the development of titanium dioxide (TiO2) on the
Fig. S1 (Supplementary Information). The dry membrane sample with a CNFs. As presented in Fig. 2a, the surface of raw CNFs is smooth rela­
3.00 cm diameter was placed in the membrane cell, and then DI water tively and the diameter is around 100 nm. After strong acid treatment,
was filled into it. During the test, the nitrogen pressure was augmented the surface of a-CNFs is rougher than that of raw CNFs and there is a
step-wise at a rate of 10 kPa/min and each pressure was stayed for at slightly decrease in diameter for a-CNFs (Fig. 2b). On the basis of hy­
least 5 min. When the first water droplet was appeared from the filtrate drothermal reaction, numerous particulate matters are developed on the
side, the pressure at this point was defined as the LEPw (liquid entry surface of Ti-CNFs and the fiber diameter is twice or triple as large as
pressure of water) value. Moreover, the LEP also could be analyzed and what it is (Fig. 2c). Besides, Ti and O elements are detected distinctly in
compared via Eq. (3) (the Laplace equation), as follows [16,51]: the Ti-CNFs by EDS mapping images (Fig. 2d). Due to the strong effect of
concentrated H2SO4 and concentrated HNO3, the surface of CNFs is
− 2Bγcosθ
LEP = Pliquid − Pvapor = (3) oxidized and the oxygen-containing functional groups are grafted on the
rmax
nanofibers [52]. TBOT is hydrolyzed to TiO2 in diluted hydrochloric
in which γ is the surface tension of liquid (dyn/cm), B is the geo­ acid with the hydrothermal treatment. The rough surfaces and the
metric factor relying on the pore structure of membranes, θ is the oxygeous groups of nanofibers are beneficial to the TiO2 loading.
intrinsic liquid-solid contact angle with the membrane material (◦ ), and In Fig. 2e, it is clear that some new characteristic absorbance peaks
rmax is the maximum pore size of the membrane (μm). are displayed in the ATR-FTIR spectra of a-CNFs and Ti-CNFs. In detail,
the broad band around 3442 cm− 1 and the absorption band at 1413
2.5. Membrane performance tests in DCMD cm− 1 are attributed to –OH functional groups [52], and the character­
istic bands between 1550 cm− 1 and 1750 cm− 1 are assigned to –C– –O
The performances of membranes including permeate fluxes and stretching vibration of –COOH groups [53]. Additionally, a new broad
separation behaviors as well as anti-wetting and anti-fouling capacities peak around 700 cm− 1 ascribed to Ti–O stretching vibration is shown in
were estimated by a lab-scale DCMD system, exhibited in Fig. S2 (Sup­ the spectrum of Ti-CNFs, indicating the decoration of TiO2 successfully
plementary Information). In the membrane module, the effective area of [54,55]. To further demonstrate the existence of TiO2 on the Ti-CNFs,
a flat-sheet membrane was approximately 28.26 cm2. During the DCMD the crystalline structure of all the nanofibers was characterized by
test, the feed temperature entering into the membrane module was XRD patterns (Fig. 2f). In terms of Ti-CNFs, new representative peaks
maintained at 65 ± 1 ◦ C, and the cold side temperature was kept at 15 ± (2θ) at 27.4◦ , 36.1◦ , 41.2◦ , 54.3◦ , 56.6◦ , 63.0◦ , 64.0◦ , 69.0◦ and 69.8◦ are
1 ◦ C. The details were shown in Supplementary Information. The liquids corresponded to the (110), (101), (111), (211), (200), (204), (310),
on both sides of the membrane were circulated with magnetic driving (116) and (112) diffraction planes of TiO2 crystals, respectively. All
pumps to form circuits severally, and the crossflow velocities of hot and diffraction peaks are consistent with the standard crystalline phase of
cold fluids were controlled at 0.20 ± 0.01 m/s. TiO2 (JCPDS NO. 21–1272 and JCPDS NO. 21–1276) [22,54,55]. Due to
The permeate fluxes of pristine and composite membranes using DI these oxygen-containing functional groups (–OH and –COOH) on the
water as the feed were investigated under different temperature differ­ a-CNFs, the bonding force between TiO2 and nanofibers increases and
ences. The temperature difference on both sides of the membrane was TiO2 crystalloids grow gradually with the reaction time extending. The
50 ◦ C, 40 ◦ C, 30 ◦ C and 20 ◦ C, respectively. The weight variation of the above results manifest that particulate matters on the nanofibers are
permeate was monitored via an electronic analytical balance TiO2 and Ti-CNFs is synthesized triumphantly.
(BSA4202S, Sartorius, Germany), and the membrane flux was calculated Furthermore, XPS spectra of CNFs, a-CNFs and Ti-CNFs are exhibited
by Eq. (4), as follows [16,51]: in Fig. S3a (Supplementary Information). Through contrastive analysis,
O 1s peak is presented in the a-CNFs and Ti-CNFs, and Ti 2p3 and Ti 3p
ΔW
J= (4) peaks are only emerged in the Ti-CNFs. Meanwhile, the surface element
AΔt
compositions on the nanofibers indicate the presence of Ti element and
in which J is the membrane flux (kg/m2⋅h), ΔW is the incremental the content fraction of Ti element is 7.47% after the hydrothermal
weight of the permeate (kg), A is the effective area of the membrane

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W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

Fig. 2. TEM micrographs of CNFs (a), a-CNFs (b) and Ti-CNFs (c); EDS mapping images of C, O and Ti element distributions in the Ti-CNFs powder (d); ATR-FTIR
spectra (e) and XRD patterns (f) of CNFs, a-CNFs and Ti-CNFs.

Fig. 3. SEM surface micrographs of the unmodified PVDF membrane (a) and composite membranes: Ti-CNFs-1/PVDF (b), Ti-CNFs-2/PVDF (c), Ti-CNFs-3/PVDF (d),
Ti-CNFs-4/PVDF (e) and Ti-CNFs-5/PVDF (f); the corresponding images at a higher magnification are shown in the upper right. SEM cross-sectional micrographs of
the unmodified PVDF membrane (A), Ti-CNFs-3/PVDF composite membrane (B) and Ti-CNFs-3/PVDF composite membrane at a higher magnification (b1); the
corresponding EDS mapping image of Ti element distribution on the cross-section of Ti-CNFs-3/PVDF composite membrane (b2).

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W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

treatment (Fig. S3b, Supplementary Information). As shown in Fig. S3c without any influence on the internal pore structure.
(Supplementary Information), TGA curves record the weight variation To further characterize the surface morphology and the rough
of CNFs, a-CNFs and Ti-CNFs. As the temperature increases, CNFs, a- structure of membranes, AFM images including 3D and 2D photographs
CNFs and Ti-CNFs show different weight losses. The weights of CNFs, a- and the correlative linearity pictures of hierarchical structure are pre­
CNFs and Ti-CNFs are just 60.60 wt%, 26.83 wt% and 85.41 wt% of the sented in Fig. 4. In the 3D and 2D images, bright sections and dark re­
initial values under 800 ◦ C, respectively. The weight of a-CNFs decreases gions denote the ridges and the valleys of membrane surfaces,
by 33.77 wt% and the weight of Ti-CNFs increases by 24.81 wt%, respectively [51]. The maximum numerical value of z-axis represents
compared to raw CNFs (Fig. S3d, Supplementary Information). The re­ the ridge height in the 3D image. By comparison, the ridge height of the
sults are attributed to the introduction of hydroxyl and carboxyl func­ composite membrane is larger than that of the pristine membrane, and
tional groups as well as the loading of TiO2 on the nanofibers. It proves the ridge height increases with the addition of Ti-CNFs content. Like­
that the thermal stability of the nanofibers enhances significantly under wise, there is the biggest difference between the ridge and the valley for
the TiO2 formation. Ti-CNFs-5/PVDF membrane, as shown in the AFM linearity images. In
general, the average roughness (Ra) and the root-mean-square rough­
3.2. Characterizations of Ti-CNFs/PVDF composite membrane ness (RMS) are used to signify the rough degree of membrane surfaces.
Ra and RMS values of pristine and composite membranes are listed in
The silane coupling agent APTES was hydrolyzed in anhydrous Table 1. It is noted that Ra and RMS of the pristine PVDF membrane are
ethanol, and then the hydrolysis product was easily combined with Ti- lower than those of Ti-CNFs/PVDF composite membranes, due to the
CNFs because of the interactions among hydroxyl groups. The Ti-CNFs relatively flat surface. Besides, Ra and RMS of composite membranes
modified by APTES were abbreviated to N–Ti-CNFs. Subsequently, the increase with the concentration of Ti-CNFs from Ti-CNFs-1/PVDF to
hydrolyzed PFDTS was grafted on the N–Ti-CNFs via fluorosilanization Ti-CNFs-4/PVDF. However, Ti-CNFs-5/PVDF demonstrates the smaller
and electrostatic interaction. In addition, PDMS with hydroxyl terminal value of Ra and RMS in comparison with Ti-CNFs-4/PVDF, which is
groups not only acted as a binder to immobilize the nanofibers, but it ascribed to the abundant agglomerations of Ti-CNFs nanofibers. Ac­
was also modified by the hydrolytic PFDTS. Thus, the surface energy of cording to the definition of Ra and RMS, an enormous difference be­
nanofibers and PDMS decreased dramatically. After the spraying pro­ tween the ridge and the valley is disadvantageous to the improvement of
cess, the nanofibers coating was attached to the membrane surface roughness. Furthermore, the emergence of aggregations is not friendly
firmly with the assistance of PDMS. As a result, Ti-CNFs/PVDF com­ to the construction of the homogeneous surface, and thus it influences
posite membranes were achieved successfully. The properties of Ti- the re-entrant structure.
CNFs/PVDF composite membranes are investigated specifically in the The chemical compositions of membranes are characterized by XPS
following aspects: morphology feature, chemical composition and spectra to analyze the chemical bonding state on the membrane surface.
structural characteristic. To be specific, the full spectra and the element percent ratio of mem­
The SEM surface morphologies of the unmodified PVDF membrane branes as well as the narrow spectrum of each element for the composite
and Ti-CNFs/PVDF composite membranes with different concentrations membrane are demonstrated in Fig. 5. From the full spectra of the un­
of nanofibers are exhibited in Fig. 3(a-f). It can be observed that the modified PVDF membrane and the Ti-CNFs-3/PVDF composite mem­
surfaces of Ti-CNFs/PVDF composite membranes are different appar­ brane, it is observed that O 1s, Ti 2p, N 1s, Si 2s and Si 2p peaks are
ently from that of the pristine PVDF membrane. As shown in Fig. 3a, the brought in the composite membrane (Fig. 5a). The proportion of Ti
pristine membrane surface is porous, resulting from inter-connected element increases from 0 to 1.24% and the percentage of Si element
chains and “flower buds” crystalloids of the semi-crystalline PVDF enhances from 0 to 3.16%, respectively. Additionally, the percent ratio
polymer. The Ti-CNFs/PVDF composite membranes demonstrate of O element rises exceptionally, as shown in Fig. 5b. The results are
diverse surface morphologies, and the synthesized Ti-CNFs nanofibers attributed to the modification of Ti-CNFs nanofibers and the introduc­
are occurred on the membrane surface. When the Ti-CNFs concentration tion of fluoroalkylsilane PFDTS on the membrane surface. New repre­
is low, only a thin layer of nanofibers is covered on the surface and it sentative peaks at 285.48 eV, 286.38 eV, 287.8 eV, 288.9 eV and 293.85
looks relatively smooth (Fig. 3b). With the increasing of the Ti-CNFs eV are rendered in the C 1s spectrum of the Ti-CNFs-3/PVDF composite
concentration in the spraying liquid, coarse surfaces consisted of the membrane (Fig. 5c), compared to that of the pristine PVDF membrane
jointed nanofibers are formed, as displayed in Fig. 3(c and d). The sur­ (Fig. S4, Supplementary information), and they are assigned to C–O/
face morphology of Ti-CNFs-3/PVDF looks like a bird’s nest, compared C–N, C–Si, C– – O, O–– C–O and CF2-CF3 bonds, respectively [51,56]. In
to that of Ti-CNFs-2/PVDF. The nest structure is favorable for the terms of the composite membrane, the O 1s spectrum is divided into four
improvement of omniphobic membrane performances. However, as the characteristic peaks at 530.27 eV, 531.94 eV, 532.46 eV and 533.29 eV,
concentration of Ti-CNFs increases continuously, nanofibers accumulate corresponding to O–C, O– – C, Si–O and Ti–O–C bonds, respectively
gradually and large aggregations are generated, as revealed in Fig. 3(e (Fig. 5d) [41]. The Ti 2p spectrum is resolved into two typical peaks for
and f). These aggregations would lead to the irregular surface and the Ti 2p3/2 (458.6 eV) and Ti 2p1/2 (464.4 eV) [54], as displayed in Fig. 5e.
bigger surface height difference. This surface morphology enhances the Moreover, the F 1s spectrum is fitted with two characteristic peaks about
mass transfer resistance and it is not conducive to the creation of the re- C–F bonds deriving from CF2 and CF3 groups (Fig. 5f) [45]. These nar­
entrant structure. row spectra confirm the chemical states of the main elements on the
The cross-sectional morphologies of membranes before and after composite membrane. The C–O, C– – O and Ti–O–C bonds as well as the
modification are displayed in Fig. 3(A and B). The cross-section micro­ Ti 2p peaks demonstrate the existence of Ti-CNFs. The C–Si, Si–O and
graph of the Ti-CNFs-3/PVDF membrane at a higher magnification and CF2-CF3 bonds are detected obviously, coming from fluorosilanes. In
the corresponding EDS mapping image of Ti element distribution are detail, dehydration condensation reactions among hydrolyzed PFDTS,
depicted in Fig. 3(b1 and b2). It is shown that there is no obvious change Ti-CNFs and PDMS appeared after the heating treatment. Thus, the
about the internal pore structure for pristine and Ti-CNFs-3/PVDF fluoroalkylsilane PFDTS was grafted strongly on the membrane surface.
membranes, still remaining sponge-like pores. The modification pro­ The structural characteristics of the pristine PVDF membrane and Ti-
cess is just occurred on the membrane surface. The Ti-CNFs-3/PVDF CNFs/PVDF composite membranes are summarized in Fig. 6. As for pore
composite membrane presents a larger thickness because of the modi­ size parameters, the bubble pore size, the minimum pore size and the
fied layer. The thickness of the coating is 4.5 ± 0.3 μm, as shown in average pore size of Ti-CNFs/PVDF composite membranes are smaller
Fig. 3b1. In Fig. 3b2, Ti element is merely distributed on the coating of than those of the pristine membrane. It is caused by the coating on the
the composite membrane, deriving from the synthesized Ti-CNFs. These composite membrane surface, and the modified layer would compro­
demonstrate that the rough Ti-CNFs are loaded on the membrane surface mise membrane pores. Besides, pore sizes of Ti-CNFs-4/PVDF and Ti-

6
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

Fig. 4. AFM images of the pristine PVDF membrane (a) and composite membranes with different contents of Ti-CNFs: Ti-CNFs-1/PVDF (b), Ti-CNFs-2/PVDF (c), Ti-
CNFs-3/PVDF (d), Ti-CNFs-4/PVDF (e) and Ti-CNFs-5/PVDF (f).

unmodified membrane with 0.353 ± 0.015 μm, the porosity of the Ti-
Table 1
CNFs-3/PVDF membrane (76.59 ± 0.75%) is greater than that of the
The roughness values of the pristine PVDF membrane and Ti-CNFs/PVDF
pristine membrane (74.54 ± 0.52%). On the Ti-CNFs-3/PVDF mem­
composite membranes.
brane surface, the nest structure facilitates the formation of voids, which
The Pristine Ti- Ti- Ti- Ti- Ti- are advantageous for the enhancement of the porosity. The thickness of
roughness PVDF CNFs- CNFs- CNFs- CNFs- CNFs-
value (nm) 1/ 2/ 3/ 4/ 5/
the composite membrane is larger than that of the pristine membrane,
PVDF PVDF PVDF PVDF PVDF since the coating is formed on the surface. Moreover, the thickness of the
composite membrane increases with the concentration of Ti-CNFs on the
Ra 101.0 ± 155.0 207.0 346.0 389.0 362.0
3.0 ± 2.5 ± 3.5 ± 3.0 ± 2.5 ± 8.0 modified layer.
RMS 132.0 ± 196.0 280.0 451.0 469.0 448.0
2.0 ± 3.0 ± 2.0 ± 3.0 ± 5.0 ± 6.0
3.3. Properties of Ti-CNFs/PVDF composite membrane

CNFs-5/PVDF membranes decrease dramatically, due to the emergence The wetting behaviors of membranes have a crucial effect on the
of Ti-CNFs agglomerations. These aggregations give rise to the partial membrane performance in the membrane distillation. To investigate the
blockage of membrane pores, thus leading to the decline of the pore wettability of pristine and modified membranes, contact angles (CAs)
sizes. Similarly, the nanofibers’ aggregations have an adverse effect on and sliding angles (SAs) were measured with different liquids including
the porosity of membranes. Despite the average pore size of the Ti-CNFs- 3.5 wt% NaCl, 0.4 mM SDS, 0.4 mM CTAB, 0.4 mM Tween-20, DI water,
3/PVDF membrane with 0.331 ± 0.005 μm is less than that of the ethanol, soybean milk and dodecane, respectively. The measurements of

7
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

Fig. 5. XPS spectra of the pristine PVDF membrane and the Ti-CNFs/PVDF composite membrane: 3D full spectra of membranes (a), surface element compositions of
membranes (b), C 1s narrow spectrum of the Ti-CNFs-3/PVDF composite membrane (c), O 1s narrow spectrum of the Ti-CNFs-3/PVDF composite membrane (d), Ti
2p partial magnification of the Ti-CNFs-3/PVDF composite membrane (e) and F 1s narrow spectrum of the Ti-CNFs-3/PVDF composite membrane (f).

easily by the feed in the membrane distillation. Compared to the pristine

membrane, the modified membrane (Ti-CNFs-3/PVDF) displayed higher
CAs towards DI water (~172.0◦ ), 3.5 wt% NaCl (~170.5◦ ), 0.4 mM SDS
(~160.1◦ ), 0.4 mM CTAB (~165.0◦ ), 0.4 mM Tween-20 (~162.5◦ ),
ethanol (~151.0◦ ), soybean milk (~153.5◦ ) and dodecane (~118.0◦ ),
respectively. After 300 s, these droplets still remained initial shapes and
there was no obvious wicking phenomenon on the membrane surface, as
demonstrated in Fig. 7c. The Ti-CNFs-3/PVDF composite membrane
possessed super-repellent to various liquids, derived from the excellent
omniphobic characteristic, owing to the re-entrant structure and the
ultra-low surface energy. In Fig. 7b, the SAs of liquid droplets (except for
dodecane) on the composite membrane were below 10.0◦ , however,
those of the pristine membrane were beyond 90.0◦ . It implies that the
droplets could roll off the surface easily and the omniphobic membrane
possesses wetting and fouling resistance.
Besides, it is observed that the rolling water droplets could take away
Fig. 6. The structural parameters of the pristine PVDF membrane and Ti-CNFs/ the solid powder (i.e., calcium carbonate) sprinkled on the membrane
PVDF composite membranes, containing bubble pore size, minimum pore size, surface without leaving any track in Video. S1 (Supplementary Infor­
average pore size, porosity and thickness. Standard deviations were obtained mation). The Ti-CNFs-3/PVDF composite membrane reflects the satis­
from at least three different measurements. factory self-cleaning capacity. When all kinds of liquids (i.e., saline
solution and different surfactants’ emulsions such as SDS, CTAB and
CA and SA as well as the corresponding photographs of liquid droplets Tween-20) were injected onto the Ti-CNFs-3/PVDF composite mem­
on the membrane are presented in Fig. 7. The pristine PVDF membrane brane with a micro-syringe, the droplets could bounce off from the
exhibited high CAs towards DI water (~125.0◦ ) and 3.5 wt% NaCl surface in a V-shaped route. Meanwhile, there was no residual droplet
(~119.0◦ ), when the droplets were contacted with the membrane sur­ clinging to the membrane surface, as presented in Video. S2 (Supple­
face, due to the hydrophobic nature of PVDF (Fig. 7a and c). However, mentary Information). It is also illustrated that the composite membrane
the low CAs of the original membrane towards 0.4 mM SDS, 0.4 mM demonstrates the strong repulsive force for low-surface-tension liquids.
CTAB, 0.4 mM Tween-20 and soybean milk were 80.0 ± 1.0◦ , 100.5 ± To further investigate the affinity between liquids and membrane
2.5◦ , 86.5 ± 1.5◦ and 108.5 ± 2.0◦ , respectively. Additionally, with the surfaces, a 10–15 μL high-salinity droplet (10.0 wt% NaCl) was dropped
time going (after 300 s), the surfactant droplets are adsorbed onto the onto the membrane surface and the dynamic behavior of liquid droplets
membrane surface gradually, since the wetting process of surfactant on the surface was presented in Fig. 7e. The high-salinity droplet was
emulsions (SDS, CTAB and Tween-20) with a certain surface-tension adsorbed on the pristine membrane surface, yet the droplet could roll on
takes time [57], as shown in Fig. 7c. For ethanol and dodecane, once the omniphobic membrane surface freely and not stay at the initial
the droplets contacted with the pristine membrane, they would propa­ position. The result is ascribed to the modification of the jointed Ti-CNFs
gate along the membrane surface and penetrate into the membrane with the nest structure and the fluorosilane grafting, which are condu­
pore. Thus, the instant wicking phenomenon was occurred and no CA cive to the reduction of the affinity between the high-salinity emulsions
could be measured. These results are ascribed to the poor omniphobicity and membrane surfaces.
of the PVDF membrane, and the pristine membrane is wetted and fouled LEP, as another vital factor, is used for characterizing the wetting

8
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

Fig. 7. The wettability characterizations

and LEP results: contact angles (a) and
sliding angles (b) of various tested liquids for
the pristine PVDF and Ti-CNFs-3/PVDF
composite membranes at ambient tempera­
ture, the photographs’ comparison of
different liquid droplets on the pristine
PVDF and Ti-CNFs-3/PVDF composite
membranes after 300 s (c), LEP measure­
ments with DI water for pristine PVDF and
Ti-CNFs/PVDF composite membranes (d)
and the dynamic behavior of high-salinity
liquid droplets on the surface of the pris­
tine PVDF and Ti-CNFs-3/PVDF composite
membranes (e). In part c, dark areas for the
pristine PVDF membrane indicate that low
surface tension liquid droplets (ethanol and
dodecane) have been wicked into the mem­
brane. Standard deviations of contact angles,
sliding angles and LEP results were gained
from at least three different measurements.

resistance of membranes and the measurements with DI water are depends on the surface features, such as geometrical morphology and
summarized in Fig. 7d. According to the definition of the LEP, once the surface free energy. The water wetting behavior of the pristine PVDF
hydraulic pressure of the feed is beyond LEP, the feed would conquer membrane is in a transition regime between the Wenzel state and the
surface resistance and enter membrane pores to the other side, thus Cassie-Baxter state [58], due to the relatively low roughness surface
deteriorating the separation performance in the membrane distillation. structure and high surface free energy. Despite the water penetrates into
The LEP measurements of Ti-CNFs/PVDF composite membranes are the top part of the voids and the grooves are not filled with water on the
larger than that of the pristine PVDF membrane (240 ± 5 KPa). Based on surface completely, the actual solid-liquid contact area is larger than the
the Laplace equation, LEP is determined by a combination of many apparent contact area, as shown in Fig. 8a. Therefore, the pristine
factors, such as the liquid surface tension, pore structure, membrane membrane demonstrates the poor wettability. As for the
material and so on [57]. As for the pristine membrane and composite Ti-CNFs-3/PVDF composite membrane, TiO2 developed on the nano­
membranes, the tested liquid is united. On account of the hierarchical fibers promotes the formation of the hierarchical structure and the
surface structure and the low surface energy for composite membranes, interlinked nanofibers construct the re-entrant surface structure. The
abundant air pockets with strong omniphobicity are captured beneath creation of the secondary architecture not only increases the surface
the interfaces of rough surfaces, and the energy barrier of liquid wetting roughness but also boosts the membrane porosity. Thus, more air is
the membrane pore increases. Moreover, the pore size of the composite filled in the rough multilevel structure. When the water droplet falls on
membrane is less than that of the pristine membrane. Hence, it is more the membrane surface, the liquid-air contact area aggrandizes and the
difficult for the composite membrane pores to be wetted by DI water, solid-liquid contact area decreases at the three-phase interface. Addi­
and the larger external pressure should be provided to obtain the LEP tionally, the air pockets underneath the droplet enhance the energy
measurement. barrier and the resistance to enter membrane pores. On the composite
The stable properties of membranes are also of the essence in the membrane surface, the droplets are in the metastable thermodynamic
membrane distillation test. To explore the chemical stability and the Cassie-Baxter state and they possess the flexible mobility [58], as illus­
thermal stability, the Ti-CNFs-3/PVDF composite membrane was trated in Fig. 8b. As a consequence, the Ti-CNFs-3/PVDF composite
immersed in different pH aqueous solutions (pH = 2, pH = 7 and pH = membrane presents the outstanding anti-wetting ability and the favor­
12) and boiling water, respectively. From the view of the appearance, able omniphobicity.
there is no obvious change and the silver mirror phenomenon still exists
on the membrane surface before and after 24 h, as demonstrated in
3.4. Membrane performances in DCMD
Fig. S5 (Supplementary Information). After immersion, water contact
angle (WCA) and SA of the Ti-CNFs-3/PVDF membrane surface were
In terms of the omniphobic membrane, the high permeate flux, the
measured and the results were exhibited in Fig. S5 (Supplementary In­
preeminent anti-wettability and the favorable anti-fouling capacity are
formation). It is observed that WCA and SA remain nearly constant in the
all quite significant during the direct contact membrane distillation
liquids with different characteristics, so the omniphobic membrane
process. In the first place, for the pristine PVDF membrane and Ti-CNFs/
presents satisfactory chemical and thermal stabilities.
PVDF composite membranes, the permeate fluxes of pure water are
There are different states for the same liquid droplet on the surface of
measured under different temperature differences and the measure­
the pristine PVDF membrane and the Ti-CNFs-3/PVDF composite
ments are exhibited in Fig. 9a and Fig. S6 (Supplementary Information).
membrane. The phenomenon indicates that the membrane wettability
Compared to the original membrane, Ti-CNFs/PVDF composite

9
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

Fig. 8. The anti-wetting mechanisms of commercial PVDF membrane surface (a) and omniphobic membrane coated with composite nanofibers on the surface (b).

Fig. 9. The comparations of the perme­

ability under different temperature differ­
ences and the variations of DCMD
performances with the operating time for
pristine PVDF and Ti-CNFs-3/PVDF mem­
branes: the permeate fluxes of pure water
under the temperature difference of 20 ◦ C,
30 ◦ C, 40 ◦ C and 50 ◦ C, respectively (a); the
permeate fluxes and the conductivities vary
with the operating time in different feed
solutions: 35 g/L NaCl + 100 g/L NaCl (b),
35 g/L NaCl and 50 mg/L HA (c), 35 g/L
NaCl, 50 mg/L HA and different concentra­
tions of SDS (d), 35 g/L NaCl, 50 mg/L HA
and different concentrations of CTAB (e) and
35 g/L NaCl, 50 mg/L HA and different
concentrations of Tween-20 (f).

membranes possess higher permeate fluxes at the identical temperature Then, based on the high permeate flux and the excellent anti-wetting
difference. It benefits from the high thermal conductivity of the Ti-CNFs property, the Ti-CNFs-3/PVDF composite membrane with a particular
coating. As is known to all, the thermal conductivity of CNFs (400–700 focus was utilized to further investigate the resistance to contaminants.
W/m⋅K) is far greater than that of the macromolecule polymer PVDF Different concentrations of saline solutions and various organics
(0.22 W/m⋅K) [53,55]. In terms of the MD mechanism, the existence of including HA and surfactants (such as anionic-type, cationic-type and
temperature polarization in the feed-membrane interface causes the nonionic-type) were added into the feed to implement the consecutive
reduction of the vapor flux. After the Ti-CNFs nanofibers are sprayed on DCMD tests. The correlative variation results of the permeate fluxes and
the surface, the high temperature of the feed is transferred to the com­ the conductivities are shown in Fig. 9(b-f).
posite membrane more quickly, thereby weakening the temperature Firstly, the effect of inorganic salts on the membrane performance is
polarization phenomenon between the hot feed and the membrane explored and the detailed process is demonstrated in Fig. 9b. Initially, DI
surface. The driving force caused by the temperature difference between water was poured into the feed tank to stabilize the DCMD system at
both sides of the membrane increases, consequently enhancing the 65 ◦ C for 2 h. The permeate flux of pure water for the Ti-CNFs-3/PVDF
permeate flux of the composite membrane. In addition, the composite membrane (~36.3 kg/m2⋅h) is higher than that for the pris­
Ti-CNFs-3/PVDF membrane presents the largest permeate flux among tine PVDF membrane (~29.9 kg/m2⋅h). It is consistent with the result of
the composite membranes, due to the especial surface structure and the Fig. 9a. Subsequently, 35 g/L NaCl solution was selected as the feed and
bigger specific surface area. The nest morphology expands the contact the test was performed for 72 h. It is displayed that the permeate flux of
surface and improves the water vaporization at the membrane interface, the Ti-CNFs-3/PVDF composite membrane maintains constant and the
and thus more liquid water would be acquired in the cold side. electrical conductivity (~1.73 μs/cm) is approximately equal to that of

10
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

DI water (~1.56 μs/cm). With regard to the pristine membrane, the degrees and covered with NaCl crystals, organics and surfactant adsor­
permeate flux only has a mild decrease and the electrical conductivity bates, as displayed in Fig. S7(a-c) (Supplementary Information).
has a bit increase, nearly 5 μs/cm. Overall, the low concentration of Whereas, the re-entrant multilevel surface structure and the ultra-low
NaCl solution has almost no adverse effect for the performances of Ti- surface free energy deriving from the Ti-CNFs nanofibers grafted by
CNFs/PVDF and pristine membranes. In the next 72 h, 100 g/L NaCl fluorosilane provide the protection for the Ti-CNFs-3/PVDF composite
solution was substituted for the previous feed and it was condensed into membrane. This makes them difficult for surfactants to get close to the
twice of the initial. After the concentration of the inorganic salt in the membrane surface in a short period, thus weakening the wetting
feed increases, the permeate flux of the pristine membrane descends to behavior. The composite membrane still maintains the undefiled surface
24.5 kg/m2⋅h and the conductivity rises to 37.25 μs/cm gradually, while appearance after the membrane distillation test, as demonstrated in
those of the Ti-CNFs-3/PVDF composite membrane still remain almost Fig. S7(d-f) (Supplementary Information).
unchanged. For the hypersaline feed, the concentration polarization In detail, it could be observed that the permeate flux of the pristine
phenomenon at the membrane interface accelerates the precipitation of PVDF membrane declined to 6.8 kg/m2⋅h and it decreased by 77.26%,
NaCl crystals on the pristine membrane, leading to the membrane pores with the increase of SDS concentration in the feed. Meanwhile, the
blocked and wetted in some degree. Thus, the permeate flux decreases corresponding permeate conductivity increased from 1.56 μs/cm to
and the conductivity increases for the pristine membrane. Instead, it is 4280 μs/cm sharply (Fig. 9d). Besides, the pristine membrane also
difficult for NaCl crystals to stay on the Ti-CNFs-3/PVDF membrane due presented the fast reduction of the permeate flux and the distinct
to the superhydrophobic characteristic, hence having almost no impact augment of the permeate conductivity, when CTAB and Tween-20 were
on the structure and the permeate flux of the composite membrane as added to the feed, respectively (Fig. 9(e and f)). In comparison, the
well as the conductivity of the permeate fluid. introduction of surfactants had a negligible effect on the composite
Secondly, as a representative natural organic matter, HA was added membrane performances. Moreover, Table 2 summarized the omni­
into the feed to investigate and compare the performances of mem­ phobic properties and membrane performances of previously reported
branes. During the DCMD test, DI water was regarded as the feed in the and current membranes in membrane distillation application. Compared
first 2 h, and then it was replaced by the saline solution containing the to the literature values, the omniphobic Ti-CNFs-3/PVDF membrane in
organic contaminant (35 g/L NaCl and 50 mg/L HA). Meanwhile, the this work displayed higher permeate flux than the membrane substrate
feed was concentrated gradually and the corresponding conductivity and superior surfactants tolerances, suggesting the potential to be
aggrandized from 51.1 ms/cm to 98.6 ms/cm. As displayed in Fig. 9c, applied in robust membrane distillation.
the permeate flux of the pristine membrane decreases from 29.9 kg/ The occurrence of all three surfactants in the saline feed enhances the
m2⋅h to 21.0 kg/m2⋅h, while that of the Ti-CNFs-3/PVDF composite PVDF-water affinity, thus promoting the wetting behavior and wors­
membrane is almost the same. Moreover, the permeate electrical con­ ening the membrane performance [59]. The feed possesses a lower
ductivity of the pristine membrane increases from 1.56 μs/cm to 125.12 surface tension with the occurrence of surfactants, leading to the
μs/cm, yet the Ti-CNFs-3/PVDF composite membrane keeps a low decrease of the LEP and the smaller resistance to be overcome. The in­
conductivity for the permeate during the condensed process. The salt teractions between the hydrophobic tails of surfactants and the hydro­
rejection rate of the Ti-CNFs-3/PVDF composite membrane is basically phobic PVDF surface accelerate the adsorption of surfactants onto the
equivalent to the theoretical value 100% by calculation. Based on the membrane surface, facilitating their migration into pores and reducing
hydrophobic–hydrophobic interaction, the organic substance HA was the surface tension of pores [60]. Moreover, advective transport and
liable to adsorb on the surface of the pristine PVDF membrane with diffusive transport from the main feed to the wetting frontier would
regular hydrophobicity. Therefore, membrane pores were blocked and accelerate the forward propagation of the wetting towards the permeate.
wetted partially, giving rise to the decline of membrane performance to When the adsorption of surfactants reaches the saturated state at one
some extent. By contrast, the Ti-CNFs-3/PVDF composite membrane pore region, the wetting frontier will advance and exploit a new area to
presents stable properties because of the hierarchical re-entrant surface repeat the previous process with the concentration driving force [61,
morphology and the ultra-low surface energy. Air pockets embedded in 62]. Under the combination of adsorption-driven and transport-driven
the multilevel structure are beneficial to the diminution of the actual functions, the pores of the PVDF membrane are wetted easily by the
liquid-solid contact area at the three-phase interface, thus improving the surfactant-containing feed. Nevertheless, there are different impacts on
hindrance to the adhesion of HA on the membrane surface. the membrane wetting behavior for SDS, CTAB and Tween-20.
Thirdly, different charge types of surfactants, such as anionic SDS, Compared to cationic CTAB and non-ionic Tween-20 surfactants, the
cationic CTAB and non-ionic Tween-20, were gained into the brine to anionic SDS surfactant deteriorates the membrane performance so
further research the anti-wettability for pristine and Ti-CNFs-3/PVDF much, resulting from the greatest surfactant-water affinity, the greatest
membranes. DI water as the feed was applied to conduct the DCMD PVDF-water affinity and the attractive surfactant-surfactant interaction
for 120 min, and then conventional saline solution (35 g/L NaCl) was energy [63]. The worsening membrane performance is tied to the
considered as the feed to continue the test for another 120 min. Next, increased PVDF-water affinity. Hydration effects would act a crucial role
each surfactant was added to the fore-mentioned brine at a concentra­ in the membrane wetting when surfactants’ charge varies in the feed
tion of 0.1 mM every 240 min. With the increase of the surfactant’s [63]. The attractive interactions of water and membrane motivate the
content in the feed, permeate fluxes and conductivities of pristine and formation of the water network near the membrane, further improving
Ti-CNFs-3/PVDF membranes presented some changes, shown in Fig. 9 the wetting potential. The SDS increases the attractive interactions of
(d-f). In general, whatever surfactant it was, the permeate flux had a water and membrane, more than CTAB and Tween-20. Additionally, the
sharp decline and the conductivity demonstrated a rapid ascent for the coupling of SDS and NaCl could generate quickly membrane
pristine membrane. However, the Ti-CNFs-3/PVDF composite mem­ pore-wetting and the worst membrane wetting, which is relevant to the
brane revealed the low electrical conductivity fairly and exhibited PVDF membrane-SDS affinity and SDS mobility. The anionic SDS has
merely a bit reduction for the permeate flux. It could be interpreted as attractive surfactant-surfactant interactions, which may be linked to the
follows: surfactants are easily attached to the pristine membrane, due to worsening of membrane performance and this needs to be further
its flat surface morphology and high surface energy comparatively. With verified [63].
the accumulation of surfactants on the surface, blocking and wetting
phenomena of membrane pores happened increasingly, thus leading to 4. Conclusions
the degeneration of membrane performances. Meanwhile, the possibil­
ity of NaCl crystalloids and organics HA cling to the membrane surface is The Ti-CNFs/PVDF composite membrane with omniphobic charac­
enhanced by the way. The original membrane is fouled in different teristics was prepared via convenient and versatile electrospraying

11
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

Table 2
Comparison of omnipobic membranes for membrane distillation application.
Membrane Modification method Treated Omniphobicity Mean MD Feed composition Temperature Initial Test Ref.
substance membrane pore style difference flux (L/ duration
size (◦ C) m2⋅h or (h)
(μm) LMH)

PVDF Solvent-thermal PFTS/ WCA: ~170◦ , CA: 0.358 DCMD 3.5 wt% NaCl with 40 17–20 6–8 [36]
nanofibrous induced roughening PDA/STIR- >150◦ for 3.5 wt% ± different
membrane followed by PFTS PVDF NaCl with 0.25 mM 0.035 concentrations of
(0.909 ± coating SDS SDS (or mineral
0.005 μm, oil)
25–26 LMH)
PVDF-HFP Organosilane- ePFP-25Z WCA: > 161◦ , CA: 0.49 ± DCMD 1 M NaCl, 20 mM 40 22.7 14 [14]
nanofibrous functionalized ~131◦ for oil and 0.07 CaCl2 and 0.1 mM
membrane substrate followed ethanol SDS
(0.56 ± 0.06 by electrospraying
μm, 24.3 FAS + ZnO NPs
LMH)
Commercial The top layer Janus WCA: ~163.9◦ , CA: 0.22 DCMD 3.5 wt% NaCl with 40 16.21 10 [15]
PTFE/PET modified by spraying ~154.8◦ for 4 mM different
flat-sheet fluorinated PAL and SDS, CA>124◦ for n- concentrations of
membrane the bottom layer hexadecane (top SDS
(0.22 μm, modified by PDA layer)
15.04 LMH)
PVDF-HFP Growing TiO2 PVDF- WCA: 168◦ , CA: 153◦ 0.52 ± DCMD 35 g/L NaCl with 40 21.3 ~6 [43]
nanofibrous nanorods using a HFP/TiO2- for mineral oil 0.03 different
membrane hydrothermal NRs-FOTS concentrations of
(0.85 ± 0.05 method followed by SDS (or mineral
μm, 22.6 fluorination oil)
LMH) treatment
Commercial Electrospraying cPFP-30Z WCA: 159.0 ± 3.1◦ , 0.39 ± DCMD 3.5 wt% NaCl with 40 24.29 8 [44]
PVDF flat- fluorinated ZnO NPs CA: 129.6 ± 2.2◦ , 0.02 different
sheet mixed with PVDF- 130.4 ± 4.1◦ and concentrations of
membrane HFP on the 126.1 ± 1.2◦ for 0.3 SDS (or oil)
(0.46 ± 0.05 organosilane mM SDS in 3.5%
μm, 26.13 functionalized PVDF NaCl, ethanol and
LMH) vegetable oil,
respectively
Commercial Spray coating SiNPs MSF-PVDF WCA: 176◦ , CA: 0.258 DCMD 0.24 g/L SDS, 2.4 40 ~9.0 ~16.6 [45]
PVDF flat- + PS followed by PA 138.4◦ for ± g/L hexadecane
sheet 174 and 17-FAS hexadecane 0.045 and 10 g/L NaCl
membrane coating
(0.313 ±
0.010 μm,
~10.8 LMH)
PVDF flat-sheet Layer-by-layer PDDA-SiA- WCA: ~170◦ , CA: 0.09 ± AGMD RO brine including 40 11.22 12 [46]
membrane assembly SiA and FTCS >160◦ for ethylene 0.01 SDS with
(0.20 ± 0.03 FTCS and glycol, mineral oil conductivity of
μm, 13.17 interconnecting around 22.6 ms/
LMH) them with PDDA cm
Commercial Electrospraying Ti-CNFs/ WCA: 172.0 ± 1.8◦ , 0.331 DCMD 35 g/L NaCl, 50 50 ~36.3 20 This
PVDF flat- heat-conducting PVDF CA: >160◦ and ± mg/L HA and work
sheet carbon nanofibers >151◦ for 0.4 mM 0.010 different
membrane coated by TiO2 and SDS and ethanol, concentrations of
(0.353 ± PFDTS via one-step respectively SDS (CTAB or
0.010 μm, strategy Tween-20)
~29.9 LMH)

method with one-step strategy, namely synthesized heat-conducting membrane was endowed with omniphobicity, benefiting from the syn­
nanofibers immobilized on the PVDF pristine membrane and fluo­ ergistic effect of the re-entrant structure and the ultra-low surface en­
rosilane treatment for the surface simultaneously. A series of charac­ ergy. The omniphobic membrane possessed strong repulsions to various
terizations on nanofibers’ morphologies and surface analysis, as well as liquid droplets, including brine, surfactant emulsions, low surface ten­
morphology features, chemical compositions and structural peculiarities sion and high-salinity liquids. Besides, it also demonstrated a greater
of membranes were performed one at a time. Subsequently, wetting LEP measurement and satisfactory chemical and thermal stabilities
behaviors, LEP measurements and stable properties of modified mem­ along with silver mirror phenomena. In the DCMD experiments,
branes were investigated intuitively. Consecutive DCMD tests were compared to the original PVDF membrane, the Ti-CNFs/PVDF mem­
conducted to explore and compare anti-fouling and anti-wetting per­ brane acquired a higher permeate flux, attributed to the outstanding
formances of pristine and composite membranes with NaCl, HA and thermal conductivity of the composite Ti-CNFs coating. Simultaneously,
diverse surfactants as the feed. the composite membrane presented favorable anti-fouling and anti-
The results showed that carbon nanofibers decorated by TiO2 were wetting performances, that is, steady permeate fluxes and conductiv­
fixed on the membrane surface by the adhesive attraction of PDMS, and ities. In conclusion, the Ti-CNFs/PVDF omniphobic membrane was
the re-entrant morphology with the nest hierarchical structure was fabricated successfully with the high permeate flux, and the omnipho­
constructed skillfully. In addition, fluoroalkyl silane was also modified bicity could make it have the potential to be applied in wastewater
on the membrane to achieve the ultra-low surface energy. The composite treatment for membrane distillation.

12
W. Zhang et al. Journal of Membrane Science 640 (2021) 119824

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