International Journal of Biological Macromolecules 283 (2024) 137718

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

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

Fluorine-free, superhydrophobic self-healing and UV-blocking cotton fabric

for oil/water separation
Xiang Feng a , Xiaoyuan Zhang a , Weixia Yan a , Kailong Chen a , Xin Guo b , Yuanfen Huang a ,
Jinfeng Zhang b, Dongzhi Chen a,b,*
a
School of Materials Science and Engineering, Wuhan Textile University, Wuhan 430200, PR China
b
State Key Laboratory of New Textile Materials & Advanced Processing Technology, Wuhan Textile University, Wuhan 430073, PR China

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

Keywords: The discharge of oily wastewater not only pollutes waters but also deteriorates our living environment. Super­
UV-blocking cotton fabric hydrophobic cotton fabric is considered as an important remedy material for oily wastewater cleanup due to
Superhydrophobicity outstanding advantages including low cost, high porosity and switchable wettability. However, the existing
Self-healing
superhydrophobic fabrics cannot exhibit durable superhydrophobicity during real-life applications due to poor
interaction between the coatings and fabric substrates. To address this issue, one-step strategy is proposed to
fabricate superhydrophobic cotton fabric by immersion in a octa-[2-(carboxyl methyl thio) ethyl]-polyhedral
oligomeric silsesquioxane/cerium dioxide/polydimethylsiloxane (POSS/CeO2/PDMS) coating. As expected, the
finished cotton fabric exhibits robust superhydrophobic resistance to mechanical abrasion and chemical corro­
sions. Notably, the finished cotton fabric shows thermal self-healing superhydrophobicity even if undergone
repetitive abrasion cycles and air plasma etching. It is proposed that the rising temperature accelerates the ro­
tations of PDMS chains and the migrations of MAPOSS and CeO2, contributing superhydrophobic self-healing of
the damaged cotton fabric. Meanwhile, the superhydrophobic fabric displays high oil/water separation efficiency
even in strong acid and alkali environments. Additionally, the POSS/CeO2/PDMS coating improves mechanical,
thermal and UV-blocking properties of the finished cotton fabric. This work will pave a way to exploitation and
applications of novel multifunctional textiles.

1. Introduction separation, biological methods, adsorption, gravity separation, in-situ

burning and air flotation [4]. Nevertheless, these methods have some
As increasing growth of industries related to petroleum, chemical drawbacks such as high cost, complex operation and maintenance, high
and medicine, freshwater resources are becoming scarce due to pollu­ energy consumption, and the potential secondary pollution to the
tions from discharge of oily waste-water [1,2]. The reclamation of environment.
precious water from oily wastewater is essential for human survival, and In the past decade, superhydrophobic cotton fabrics have attracted
the oil recovery is equally important to improve living environment. increasing attention in the field of oil/water separation due to their
Generally, oil/water mixtures can be classified into two types: immis­ advantages including low cost, high porosity and switchable wettability
cible oil/water mixtures and oil/water emulsions. Separation of [5]. Inspired by lotus leaves, water droplets on leaves carry the accu­
immiscible oil/water mixtures can be achieved through oleophilic and mulative dust, and quickly roll away under disturbance of light wind,
hydrophobic devices [3]. But the oil/water emulsions are difficult to indicating self-cleaning phenomenon [6]. Based on the Cassie-Baxter
separate due to small size. Moreover, oily wastewater with a complex equation, the artificial superhydrophobic surface, defined with a water
composition is difficult to degrade in nature. During oil/water separa­ contact angle (WCA) >150◦ and a sliding angle (SA) <10◦ , can be
tion, fouling leads to a significant decline in separation performance, constructed by rational combination of increasing surface micro/nano
and even deteriorates surface wettability. Therefore, it is still confronted structures and lowering surface energy of substrates [7]. To construct
with a formidable challenge to separating oil/water mixtures. Conven­ micro/nano structures on cotton fibers, many inorganic nanoparticles
tional methods for treating oily waste-water include membrane have been extensively employed, such as silicon dioxide [8,9], titanium

* Corresponding author at: School of Materials Science and Engineering, Wuhan Textile University, Wuhan 430200, PR China.
E-mail address: [email protected] (D. Chen).

https://doi.org/10.1016/j.ijbiomac.2024.137718
Received 12 August 2024; Received in revised form 1 November 2024; Accepted 14 November 2024
Available online 15 November 2024
0141-8130/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

Scheme 1. The fabrication process of the functionalized cotton fabric

dioxide [10,11], zinc oxide [12] and so forth [13]. But little attention energy [35]. The organic substituent groups provide tailorable re­
has been paid to cerium dioxide nanoparticles (CeO2) and their potential activities that enable POSS molecules to form strong covalent bonds
applications. Very recently, CeO2 nanoparticles have attracted with the substrate interfaces [36]. For instance, Chen et al. reported that
increasing attention due to unique chemical and electronic properties, the introduction of POSS cross-linkers increases the dimensionality of
catalysis, UV absorption, chemical-mechanical polishing [14–16]. On cross-linked networks in novel RTV silicone rubbers, which exhibited
the other hand, some low-surface-energy materials, such as poly­ significantly enhanced effects on thermal stabilities, mechanical prop­
thiophene, polydopamine, polydimethylsiloxane (PDMS) [17], stearic erties and hardness as compared to the PDMS polymers prepared with
acid, fluorinated chemicals and so on [18–25], have been further the traditional tetra-functional TMOS and TEOS cross-linkers [37]. Gao
employed to immobilize the mimic micro/nano structures on cotton fi­ et al. prepared PDMS slippage coatings by combining a soft architecture-
bers to achieve surface hydrophobicity. Although great progress has driven branched PDMS with partial short PDMS-functionalized POSS as
been made in fabricating superhydrophobic fabrics, their service a co-cross-linker, finding that the introduction of the functionalized
longevity is too short because surface coatings are easily peeled off POSS brought about a significant enhancement on mechanical resistance
during real-life applications due to poor bridge with cotton fabrics and in abrasion [38]. Therefore, POSS can be used as reinforcing reagents to
these coatings [26,27]. Moreover, changes of surface chemical compo­ improve overall properties of the PDMS composites.
sitions and temperature greatly affect hydrophobicity when they are To address the issues mentioned above, both POSS and CeO2 are
exposed to outdoor environment. Therefore, it is still a non­ introduced to PDMS matrix, which is expected to enhance mechanical
circumventable challenge to constructing durable superhydrophobic properties of the PDMS coating, and to create more micro-nano struc­
surfaces. tures on fiber surfaces, respectively. Based on the hypothesis, a durable
To date, some strategies have been utilized to enhance super­ superhydrophobic composite coating composed of POSS, PDMS and
hydrophobic durability, such as creating multi-scale roughness on the CeO2 was exploited for cotton fabric. Then the functionalized cotton
substrate [28], bridging chemical bonding between the coating and the fabric was fabricated by a one-pot dipping method. Subsequently, its
substrate [29], Coating mechanical robust binders [30], and introducing surface morphology, wettability, self-cleaning, delaying icing proper­
self-healing components [31,32]. In particular, self-healing coating has ties, superhydrophobic stability, self-healing capability and oil/water
received increasing attention in improving superhydrophobic durability separation performance were discussed, respectively. Meanwhile, its
due to easy recovery of intrinsic properties. The superhydrophobic self- mechanical properties, thermal stability, breathability and UV shielding
healing behavior happens upon heat treatment because heating accel­ property were examined, respectively.
erates the mobilities and migrations of healing components towards the
surfaces to restore the damaged surface [33,34]. Nevertheless, a ma­ 2. Experimental section
jority of the self-healing superhydrophobic coatings have fluorine-
containing chemicals, such as perfluorinated polymer, long-chain fluo­ 2.1. Materials and chemicals
rosilane and fluoroalkanes, which are non-degradable and accumulative
in organisms, causing potential health risks. In comparison with costly Cotton fabric (200 g/m2) was obtained from Jinqiu Textile Company,
and hazardous fluorinated materials, PDMS offers outstanding merits Shaoxing, China. Cerium dioxide (20–50 nm, 99.5%), sodium bicar­
such as abundant availability, high transparency, high flexibility, low bonate (AR), sodium chloride (AR), hydrochloric acid (36%–38%), so­
toxicity, excellent biocompatibility and low surface energy, which is dium hydroxide (AR), tween 40 (CP), span 80 (CP), methylene blue
becoming the optimum candidate for constructing superhydrophobic (AR), Sudan III (AR), tetrahydrofuran (AR), toluene (AR), dichloro­
coatings. However, the pure PDMS materials show poor mechanical methane (AR), trichlormethane (AR), petroleum ether (AR), acetone
properties due to weak molecular chain interaction, limiting PDMS (AR), and ethyl acetate (AR) were obtained from Sinopharm Chemical
application ranges. Reagent Co., Ltd. Vinyl terminated polydimethylsiloxane (VPDMS, vis­
Recently, polyhedral oligomeric silsesquioxanes (POSS), as an cosity: 10,000 cSt, vinyl content: 0.25 wt%) and poly­
emerging class of organic/inorganic nanomaterials with empirical for­ methylhydrogenosiloxane (PMHS, viscosity, 50 cSt, hydrogen content:
mula of (RSiO1.5)n, have been extensively used in fabricating super- 0.5 wt%) were kindly provided by Shandong Dayi chemical co., Ltd.
wetting materials. POSS are main composed of inorganic cage and Karstedt catalyst (Platinum divinyltetramethyldisiloxane complex) was
organic substituent groups. The inorganic cage, made of Si-O-Si, con­ prepared in our laboratory. The deionized water (18.2 MΩ cm) was
tributes excellent thermal stability, good UV resistance and low surface produced by the water purification device (UPC-II-10 T, ULUPURE,

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X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

Shanghai, China). The octavinyl POSS (OVPOSS) were prepared by

literature method. [37]

2.2. Fabrication of the functionalized cotton fabric

Octa-[2-(carboxyl methyl thio) ethyl]-polyhedral oligomeric silses­

quioxane (MAPOSS) was synthesized through thiol-ene click reaction
using OVPOSS and 2-mercaptoacetic acid as the starting materials ac­
cording to previous literature [10]. Scheme 1 concisely illustrates a di­
agram for fabricating functionalized cotton fabrics. Before
functionalization, the cotton fabric was washed to remove the surface
lipid and impurities in the NaHCO3 solution (1.0 wt%), and deionized
water for 1 h, respectively. Afterwards, the MAPOSS/CeO2/PDMS
coating was fabricated according to the following procedure. Firstly, the
clear MAPOSS/PDMS solution was obtained by dissolving 2.0 g VPDMS,
20 μL Karstedt catalyst, 0.06 g PMHS and 1.37 g MAPOSS in 100 mL THF
in a beaker. Then, 0.10 g CeO2 were dispersed in MAPOSS/PDMS so­
Fig. 1. a) SEM image of pristine cotton fabric, and b) the magnified SEM image
lution by stirring, and the dispersion was further subjected to ultrasonic
of the select domain (the dashed box) in a. c) SEM image of the functionalized
treatment for 5 min to afford a homogeneous MAPOSS/CeO2/PDMS
fabric, and d) the magnified SEM image of the select domain (the dashed box)
coating. Subsequently, the cleaned cotton fabric was immersed in the in c. e) SEM image of the modified fabric for element mappings: f) carbon, g)
MAPOSS/CeO2/PDMS dispersion with magnetic stirring for 1 h. After oxygen, h) silicon, i) cerium, and j) sulfur element distributions. k) EDS spec­
treatment, the cotton fabric was taken out from the beaker, and dried in trum of the treated fabric. L) AFM image of the finished fabric.
an air oven at 120 ◦ C for 1 h. The weight add-on value of the finished
cotton fabric was 10.7%, and was denoted as PACe/Fabric. For conve­ which is defined as one abrasion cycle. The washing durability was
nient comparison, the CeO2/Fabric, POSS/Fabric and PDMS/Fabric assessed following the modified AATCC Test Method 61–2006 (No 2 A)
were also prepared by replacing the MAPOSS/CeO2/PDMS coating with [10]. In a single washing cycle, the functionalized fabric was immersed
the only CeO2 dispersion, POSS and PDMS solutions under the same in a 150 mL water solution containing 0.15 wt% of soap powder, and
conditions, respectively. washed at the stirring speed of 40 r/min and the temperature of 40 ◦ C for
45 min by magnetic stirring. Afterwards, the functionalized fabric was
2.3. Characterization rinsed with deionized water and dried at 100 ◦ C. The functionalized
fabric was subjected to immersion in 1 M HCl solution, 1 M NaOH so­
The surface morphology was observed by scanning electron micro­ lution and 1 M NaCl solution for 3 days and different organic solvents for
scopy (SEM) (JSM-IT500HR, JEOL Ltd., Tokyo, Japan) operated at a 10 7 days to evaluate chemical resistance. To assess environmental stabil­
kV accelerating voltage. Static water contact angles (WCAs) and sliding ity, the functionalized fabrics were irradiated with UV light (365 nm,
angles (SAs) were measured using deionized water droplets (i.e., 5 μL for 500 W) for 12 h at a constant distance of 15 cm, and treated at various
static contact angle and 10 μL for sliding angle) with a KRUSS contact high temperatures for 5 h, respectively. The functionalized fabric was
angle instrument (DSA 100, Germany). The average values of WCAs and etched by air plasma for 120 s and then heated at 120 ◦ C for 20 min to
SAs were obtained by measuring at least five different positions on the investigate the etching/healing capability. The abrased fabric was
same cotton fabric. The UV-blocking property of the functionalized heated at 120 ◦ C for 20 min to study the abrasion/healing capability.
cotton fabric was examined by a UV protection factor (UPF) tester (YG
(B)912E, China) according to the GB/T 18830–2009. The chemical 2.3.2. Oil/water separation experiment
compositions of specimen were measured by energy dispersive X-ray To separate the mixtures of heavy/light oil and water, two sets of
spectrometry apparatus (ZEISS Gemini SEM 300, Germany). The etching devices have been designed using the functionalized cotton fabric as the
damage of the functionalized fabric was performed in an air plasma filter. A piece of cotton fabric was placed between a glass funnel and a
cleaner HPT-200. Optical microscopy images of oil/water emulsions filter without the sand core to serve as a filter during heavy oil/water
before and after separation were measured on Olympus Biological Mi­ separation test. For light oil/water separation, the functionalized cotton
croscope BX43 (Olympus, Japan). The air permeability of the func­ fabric was placed between two glass funnels. Meanwhile, it is necessary
tionalized cotton fabric was assessed using a YG(B)461G automatic air to tilt the equipment at a specific angle to facilitate oil to pass through
permeability tester in accordance with the GB/T5453–1997 standard. the cotton fabric. The cotton fabric with an effective contact area of
During the test, controlled airflow was directed through the cotton 12.56 cm2 was used to separate mixtures of 50 mL oil (dyed by Sudan III)
fabric and the air valve was adjusted to maintain a pressure drop of 100 and 50 mL water. The separation efficiency (η) for oil/water mixtures is
Pa across the cotton fabric. The mechanical property of specimen was calculated by Eq. (1):
evaluated in accordance with the GB/T 3923–2013 standard test
method, wherein three measurements were recorded for each sample. η = W2 /W1 × 100% (1)
The thermal degradation behavior of specimen was studied by using
thermogravimetric analysis (TGA) on the Discovery TGA 55 instrument where W1 and W2 are the weight of oil before and after separation,
(America Instruments), with a gas flow rate of 40 mL/min. The sample respectively.
(approximately 10 mg) was subjected to heating in a crucible at a rate of The gravity-driven pure oil flux (Q) is calculated by Eq. (2):
10 ◦ C/min under a nitrogen atmosphere, ranging from ambient tem­ Q = V/(S × Δt) (2)
perature to 800 ◦ C.
where V, S and Δt are the volume of oil (L), effective area (m2), and
2.3.1. Stability and durability evaluation for the functionalized cotton penetration time (h), respectively.
fabric
In the abrasion test, the functionalized fabric was placed faced-down
on 1200 mesh sandpaper with a load of 200 g, and dragged back and
forth in one direction at a rate of 4 cm⋅s− 1 with a cycle distance of 20 cm,

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X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

Fig. 2. Experimental photographs: a) water and oil wettability of the pristine cotton fabrics. Water-repellent properties of the functionalized fabrics: b) the static
water droplets and water-soluble liquid drops on surface of the functionalized fabric including milk, tea and ink, c) the dynamic water adhesion behavior on the
functionalized fabric, d) water flow on surface of the functionalized fabric, e) the rolling angle of the functionalized fabric. f) Self-cleaning behavior of the func­
tionalized cotton fabric against methylene blue and methyl orange powders. g) The anti-fouling behavior of the functionalized cotton fabric against coffee solution. h)
Water droplets keep standing on the functionalized cotton fabric for 30 min, and i) the delaying icing property of the functionalized cotton fabric.

3. Results and discussion (21.4 %), Si (13.0 %), Ce (3.3 %), and S (3.2 %) elements are found and
uniformly distributed on the surfaces of the functionalized fabrics,
3.1. Morphology and surface composition analysis of the functionalized further demonstrating that the cotton fabrics are successfully function­
cotton fabric alized by MAPOSS/CeO2/PDMS composite coatings, as exhibited in
Fig. 1e-k. In addition, the surface roughness was characterized by the
Generally, CeO2 nanoparticles are easily detached from fiber surfaces AFM. As revealed in Fig. 1L, the root-mean-square roughness (Rq) value
due to weak hydrogen bonding. To protect CeO2 nanoparticles from of functionalized fabric is 226.80 nm, which is far higher than 18.35 nm
falling off during practical applications, the MAPOSS/PDMS composite for the pristine cotton fabric [39], further confirming successful con­
coating was further employed, which hypothetically incorporate the struction of micro-nano structures on surfaces of cotton fibers. There­
CeO2 nanoparticles into the PDMS matrix, enabling them to firmly bond fore, micro-nano structures are successfully constructed on cotton fibers
with the surface of cotton fibers. Fig. 1a-b clearly exhibits that the and the cotton fabric is successfully modified by the MAPOSS/CeO2/
pristine cotton fibers have some flat and clean appearance with some PDMS composite coating.
wrinkles. After the MAPOSS/CeO2/PDMS composite coating was
deposited on the surfaces of the cotton fibers, the intrinsic texture
feature of cotton fibers disappears, and many micro structures are 3.2. Wettability, self-cleaning and delaying icing properties of the
formed, as shown in Fig. 1c. Meanwhile, it is clearly observable that a functionalized cotton fabric
dense and uniform coating with microparticles embedded covers on.
surfaces of cotton fibers from the functionalized fabric, demon­ Fig. 2a reveals that the amphiphilicity of the pristine cotton fabric
strating that the micro structures are immobilized on surfaces of cotton enable it to absorb both water (dyed with methylene blue) and oil
fibers, as shown in Fig. 1d. According to EDS analysis, C (59.1 %), O (dichloromethane dyed with Sudan III). After modification, the cotton
fabric shows an obvious transformation from hydrophilicity to

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X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

Fig. 3. Static WCA of the finished cotton fabric under different conditions: a) abrasion test, b) laundering test, immersion in c) acid, salt and base solutions (1 M HCl
solution, 1 M NaCl solution and 1 M NaOH solution) for 3 days, and d) various organic solvents for 7 days, e) UV irradiation for different time, f) high-temperature
treatment, g) air plasma etching/heating cycle, h) abrasion/heating cycle, i) the healing time of the abrased fabric at varying temperature.

hydrophobicity with a WCA of 168.3◦ . At the same time, the finished fabric is >20 min, which is much longer than that of water droplets on
fabric has a repellent effect on common aqueous solutions including the pristine cotton fabric (within 5 min). The long icing time indicates
milk, tea and ink, as exhibited in Fig. 2b. Due to the excellent hydro­ that the functionalized fabrics can effectively delay nucleation of ice
phobicity, water droplets hardly adhere to the surface of the function­ because the limited contact area restricts heat transfer.
alized fabric, as shown in Fig. 2c. Similarly, the flushed water is
remained on surface of the functionalized fabric without any penetra­
tion, indicating excellent waterproof capability for the treated cotton 3.3. Superhydrophobic stability and self-healing mechanism of the
fabric. Meanwhile, the mirror-like phenomenon is clearly observable in functionalized cotton fabric
Fig. 2d, which originates from light reflection at the air layer between
water and the finished fabric. Fig. 2e shows that the rolling angle of the Superhydrophobic stability depends on service life of the function­
functionalized cotton fabric is 6.7◦ . The low rolling angle could allow alized fabric. Therefore, the superhydrophobic stability of the func­
the rolling water droplets to remove some stains on the fabric surface, tionalized fabric were evaluated under harsh conditions. It is well-
thereby endowing the finished cotton fabric with a self-cleaning capa­ known that the continuous mechanical rubbing will inevitably destroy
bility. Fig. 2f exhibits that both methylene blue and methyl orange surface morphology and internal structure of superhydrophobic cotton
powders on the surfaces of the functionalized cotton fabrics can be fabric, and eventually leading to the loss of superhydrophobicity. It is
carried away by rolling water droplets, no residual stains are observed, noteworthy that the WCA value of the functionalized fabrics keeps up to
indicating the excellent self-cleaning ability. To further examine anti- 152.9◦ after suffering from 240 abrasion cycles, indicating excellent
smudgy performance, the functionalized cotton fabric is immersed in superhydrophobic stability, as shown in Fig. 3a. Meanwhile, the WCA
the coffee solution and then taken out from. Notably, the functionalized value of the functionalized fabric just reduces by about 5◦ even if un­
cotton fabric keeps surface clean and tidy, implicating that the func­ dergoing 100 laundering tests, as demonstrated in Fig. 3b. These find­
tionalized cotton fabric possesses an outstanding anti-fouling ability ings prove that the functionalized fabric has exceptional resistance to
against the coffee solution, as demonstrated in Fig. 2g. At the same time, mechanical damage. Apart from the mechanical stability, the acid-alkali
the water droplets also keep spherical appearance on the functionalized resistance stability was also evaluated by immersing the functionalized
fabrics even if placed for 30 min, proving that the functionalized cotton fabrics into highly concentrated acidic solution, salt solution and alka­
fabric probably has a durable superhydrophobicity, as revealed in line solution for 3 days. As shown in Fig. 3c and Fig. S1, WCA values of
Fig. 2h. Subsequently, the delaying icing properties of the finished fabric the immersed fabrics are >160◦ , and their SA values are <7.2◦ , indi­
were evaluated. It is clearly observed that the yellow water droplet on cating that the functionalized fabrics have excellent acid-alkali resis­
the surface of the functionalized cotton fabric is finally frozen into an tance. Meanwhile, the effect of organic solvents on superhydrophobic
opaque ice bead at low temperature. After melting, the ice bead can roll stability of the functionalized fabrics was also studied. Interestingly, the
off the surface of the functionalized cotton fabric without any contam­ WCA values of the functionalized fabrics are >164.5◦ , and their SA
ination, as displayed in Fig. 2i. Interestingly, in the − 26.5 ◦ C environ­ values are <9.2◦ even if immersed in various organic solvents for 7 days,
ment, the complete freezing time of water droplets on the functionalized implying that the functionalized fabrics possess exceptional super­
hydrophobic stability, as shown in Fig. 3d and Fig. S2. The chemical

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Table 1
Performance comparison of various superhydrophobic cotton fabrics in
literature.
Materials Durability Self-healing Oil/water Ref.
capability separation

WCA = 154.2◦
CeO2/PDMS after 30 cycles of – – [14]
abrasion
WCA = 111.1◦
OV-POSS/
after 175 cycles of – – [38]
PDMS
abrasion.
WCA = 132◦ after
the 6th wash; η > 95% after
AgBr–TiO2/
WCA = 136.9◦ – 30 separation [41]
OV-P-OSS
after 20 cycles of cycles
abrasion.
WCA = 154.6◦
after 110 abrasion η > 96.3 %
Rosin acid cycles; WCA after 10
– [42]
and SiO2 =154.2◦ after separation
laundering for 50 cycles
cycles.
30 cycles of
WCA = 141.1◦
abrasion/
SiO2/PDMS after 30 abrasion – [43]
heating. (120 ◦ C
cycles; Fig. 4. Surface composition analyses of the abrased fabric before and after heat
for 30 min)
WCA = 150◦ after treatments: a) SEM image of the abrased fabric after 200 abrasion cycles by
OVPOSS/ 10 cycles of sandpaper, and C, O, Si, Ce and S element mappings of the abrased surface; b)
2000 abrasion
FAS/ etching/healing.
cycles; WCA = – [44] SEM image of the abrased fabric after thermal treatment for 20 min at tem­
MPTES/ (135 ◦ C for 30
150.2◦ after 150 perature of 120 ◦ C, and C, O, Si, Ce and S element mappings of the heated
PFDT min)
cleaning cycles surface; EDS analysis of the abrased fabric: c) element percentage after 200
WCA =151◦ after abrasion cycles by sandpaper without heat treatment, and d) element per­
300 times of centage after thermal treatment for 20 min at temperature of 120 ◦ C; e) the
S-PDMS/OV- 28 cycles of η > 98% after
abrasion;
POSS/ washing (140 ◦ C, 10 separation [34] proposed superhydrophobic thermal self-healing mechanism of the MAPOSS/
WCA = 149◦ after
MPTES
laundering for 16
30 min) cycles CeO2/PDMS coating on the functionalized fabric.
cycles

WCA = 164.2◦
240 cycles of to >163.0◦ after withstanding mechanical damage, confirming striking
abrasion/
after 30 abrasion superhydrophobic self-healing capability, as shown in Fig. 3h. But, the
CeO2/ heating; 30 η > 99% after
MAPOSS/
cycles; WCA =
cycles of 15 separation
This SA values of the functionalized fabric after heating increase from 6.7◦ to
162.4◦ after 100 work 17.2◦ with abrasion times, which should be ascribed to hindrance of the
PDMS etching/heating. cycles
cycles of
laundering.
(120 ◦ C for 20 worn fibers, as shown in Fig. S4. The damaged fibers could easily retard
min) rolling of the water droplets, remarkably leading to the increasing SA
value for the abrased fabrics with friction times. To further study effect
of temperature on the self-healing capability, the self-healing time of the
abrased fabric at varying temperatures was explored. As shown in
stability of the functionalized cotton fabrics is relative to chemical Fig. 3i, the self-healing time of the abrased fabric is shortened with the
inertness of three dimensional cross-linked PDMS coatings on fibers, increment of the treatment temperature. For example, the abrased fabric
which effectively protect nanoparticles and fibers from chemical can restore superhydrophobicity through heat treatment at 150 ◦ C for
corrosion. Furthermore, the WCAs of the functionalized fabrics maintain 10 min. In addition, the functionalized fabrics with MAPOSS/CeO2/
above 162◦ even if they were exposed to UV light for 12 h or treated at PDMS coating exhibit superior durability, self-healing capability and
the temperature of 240 ◦ C for 5 h, as depicted in Fig. 3e-f. Therefore, the oil/water separation performance, compared to other superhydrophobic
MAPOSS/CeO2/PDMS composite coating could impart the cotton fab­ textiles, as listed in Table 1.
rics with superior superhydrophobic stability under varying harsh To gain insight into the superhydrophobic self-healing mechanism of
conditions. the cotton fabric finished with MAPOSS/CeO2/PDMS composite
To further assess superhydrophobic durability, the functionalized coating, morphologies and surface chemical compositions of the abrased
cotton fabric was etched by plasma treatment using air as gas source. fabric before and after heat treatments were characterized by SEM and
After air-plasma etching, the functionalized fabric becomes super­ EDS, respectively. It is clearly found that some fibers on surface of the
hydrophilic due to the surface oxidation, with a WCA of 0◦ [40]. finished fabric were damaged after 200 abrasion cycles by sandpaper.
Interestingly, the plasma-treated fabric can restore to the super­ But C, O, Si, Ce and S elements are still well-distributed on its surface, as
hydrophobic state through thermal treatment at 120 ◦ C for 20 min. As displayed in Fig. 4a. After heat treatment, the damaged fibers on the
depicted in Fig. 3g and Fig. S4, the WCA value of the functionalized surface of the abrased fabric are still observed clearly, cannot restored to
fabric still recovers to 163.0◦ , and its SA value is <7◦ even if suffered its original morphology, as shown in Fig. 1e and Fig. 4b. However,
from 30 etching/heating cycles. The reversible switch from super­ surface chemical compositions of the abrased fabric are changed clearly
hydrophilicity to superhydrophobicity verifies that the MAPOSS/CeO2/ before and after heat treatments. After abrasion, the surface C, Si, and S
PDMS coating endows excellent self-healing ability to the functionalized weight percent of the abrased fabric decreases, while its O weight per­
fabric. Afterwards, the superhydrophobic self-healing of the function­ centage increases as compared to those of the finished fabric (Fig. 1k),
alized fabric was further examined by abrasion/heating tests. As afore­ suggesting that PDMS coating with particles embedded on the outer
mentioned, the static WCA of the functionalized fabric decreases surface of the modified fibers is damaged partly, as demonstrated in
gradually with an increase in the abrasion times. After heat treatment at Fig. 4c. Therefore, some oxygen-containing groups (-OH groups) origi­
120 ◦ C, the static WCA of the abrased cotton fabric is similarly restored nating from fibers and CeO2 are exposed on the surface of the finished

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Fig. 5. a) The functionalized fabric selectively absorbing petroleum ether and dichloromethane (dyed by Sudan III) from water. b) A schematic diagram for the oil/
water separation process. Oil/water separations of the functionalized fabric for different oil/water mixtures including dichloromethane/water, trichloromethane/
water, petroleum ether/water, ethyl acetate/water and toluene/water: c) separation efficiencies and d) oil fluxes. e) The adsorption capacity of the functionalized
cotton fabric to various pure oils. Changes in separation efficiencies of the functionalized fabric for separating the same oil in varying electrolytes after different
separation cycles: (f) CH2Cl2/NaCl (aq), (g) CH2Cl2/HCl (aq), and (h) CH2Cl2/NaOH (aq).

fabric, resulting in weakening water-repellence. After heating for 20 min 3.4. Oil/water separation performance of the functionalized cotton fabric
at 120 ◦ C, the surface Si and S content of the finished fabric increases to
11.3 % and 3.3 %, respectively, while its surface O percentage decreases Due to the advantages of high efficiency, low cost, reusable and
to 28.2 %, as shown in Fig. 4d. The changes in percentage of Si, S and O environment-friendly, superhydrophobic cotton fabrics have been
elements can be ascribed to the rotations of PDMS chains and the mi­ widely used in the field of oil/water separation. For this purpose, the oil/
grations of MAPOSS and CeO2. Upon heating, both MAPOSS and CeO2 water separation performance of the functionalized fabric are examined.
migrate and accumulate on the outer surface, and the rotated PDMS Fig. S5 clearly demonstrates that the pristine cotton fabric cannot absorb
chains arrange new orientations of nonpolar (methyl groups) and polar the red oily droplet underwater. On the contrary, the finished fabric can
groups including hydroxyl groups and carbonyl groups, which acceler­ repel the water layer and selectively absorb the oil droplets (petroleum
ates the reconstruction of surface morphology and minimizes surface ether and dichloromethane) after modifying with MAPOSS/CeO2/PDMS
free energy. The reconstructed morphology contributes super­ coating, demonstrating a great application potential in the field of oil/
hydrophobic recovery of the abrased fabric under heat stimulus, as water separation [45], as exhibited in Fig. 5a. During oil/water sepa­
proposed in Fig. 4e. Collectively, it is concluded that the MAPOSS/ ration, the water droplets accumulate on the surface of the functional­
CeO2/PDMS composite coating endows the cotton fabric with excellent ized fabric, while the oil phase can rapidly penetrate through the surface
superhydrophobic self-healing ability, which will prolong service life­ to achieve oil and water separation, as depicted in Fig. 5b. It is worth­
span of the cotton fabric and enable it suitable for a widespread appli­ while that the separation efficiencies of the functionalized fabric for
cation in the future. various oil/water mixtures are >99.2%, and all the oil fluxes exceed
14,500 L⋅m− 2⋅h− 1, indicating extraordinary oil/water separation per­
formance, as shown in Fig. 5c-d. Additionally, the add-on weight of the
functionalized fabric for various oils are above 160 %, showing

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X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

Fig. 6. a) The optical microscope image of water-in-oil emulsion, b) the size distribution of water-in-oil emulsion, and c) the optical microscope image of water-in-oil
emulsion after separation. d) The optical microscope image of oil-in-water emulsion, e) the size distribution of oil-in-water emulsion, and f) the optical microscope
image of oil-in-water emulsion after separation.

emulsion (1 mL dichloromethane, 49 mL water, and 10 mg Tween 40)

were also prepared. The functionalized fabric can separate the
surfactant-stabilized water-in-oil emulsion using the same oil-water
separation device. As shown in Fig. 6a, the optical microscope image
of the prepared water-in-oil emulsion exhibits numerous, dense, and
spherical droplets. Fig. 6b presents the size of the resultant water-in-oil
emulsion ranges from 0 to 30 μm, with an average diameter of 15.4 μm.
Notably, no water droplets are observed in the oil phase after separation,
as displayed in Fig. 6c. However, the oil-in-water emulsion with an
average size of 20.4 μm (Fig. 6d-e) cannot be separated in the same way.
During the separation process, the functionalized fabric is needed to
soak into the oil-in-water emulsion with stirring for 2 min. After im­
mersion, the oil droplets are completely absorbed and removed,
corroborating excellent emulsion separation performance, as shown in
Fig. 6d and Fig. 6f.

3.5. Mechanical and thermal properties of the functionalized cotton fabric

After the pristine cotton fabrics were finished with CeO2 dispersion
Fig. 7. Mechanical properties of the pristine fabric and the finished fabrics: a) and POSS solution, their loads at rupture are 196.8±12.9 N and 207.6
Load at rupture and b) elongation at rupture; thermal degradation behavior of ±5.3 N, respectively, which are much higher than 150.3±11.1 N for the
the pristine fabric and the finished fabrics under nitrogen atmosphere: c) TGA pristine cotton fabric, as shown in Fig. 7a. The reinforced tensile prop­
curves and d) DTG curves. erties of both CeO2/Fabric and POSS/Fabric should be mainly ascribed
to physical hydrogen bonding between particles and fibers. As the
outstanding lipophilicity capacity. Considering complexity and vari­ pristine cotton fabric was finished with PDMS solution, the load at
ability of the outdoor environments, the deionized water was replaced rupture is improved to 246.4±8.9 N. The improved load at rupture for
with strong acidic (1 M HCl solution), salt (1 M NaCl solution), and the PDMS/fabric should be attributable to 3D network formations of
strong alkaline (1 M NaOH solution) to examine the stability of oil/ PDMS. After further modification by MAPOSS/CeO2/PDMS coating,
water separation performance of the functionalized fabrics, respectively. PACe/Fabric exhibits the maximum load (306.9±20.2 N) at rupture
Surprisingly, the oil separation efficiencies remain above 98.4% even among the finished fabrics, implying the existence of synergistic effect
after 15 separation cycles, substantiating the excellent stability of the among CeO2, POSS and PDMS. But no marked change is found in the
functionalized fabric in oil/water separation, as shown in Fig. 5f-h. elongation at rupture (around 10.5 %), as shown in Fig. 7b. The
To further examine oil-water separation performance of the func­ improvement on mechanical properties is mainly due to the synergistic
tionalized fabric, the surfactant-stabilized water-in-oil emulsion (1 mL effect of the cured MAPOSS/CeO2/PDMS coating, which can effectively
water, 49 mL dichloromethane, and 10 mg Span 80) and oil-in-water transfer stress throughout the cotton fabric and weaken the stress

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X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

Table 2 increases to 239.0. In this case, two factors should be taken into account
The TGA results of the pristine cotton and the functionalized fabrics. for the enhancement on the UV-blocking property. On one hand, the
Sample T5% (◦ C) T75% (◦ C) Tmax (◦ C) Char yield at 800 ◦ C (%) MAPOSS/PDMS coating increases the UV-shielding property. On the
other hand, the CeO2 particles embedded into MAPOSS/PDMS coating
Pristine fabric 310.0 376.6 368.7 9.7
CeO2/Fabric 319.4 381.3 370.8 12.0 also provides UV absorbing and scattering effects. Subsequently, the
PACe/Fabric 317.9 452.2 367.9 16.2 stability of UV-blocking property of the functionalized fabric is also
evaluated. As listed in Table 3, the functionalized fabric still exhibits
UPF value of 100.48 even if suffered from 240 abrasion cycles, which is
concentration [46]. In addition, the thermal degradation behavior of far higher than the required standard value for UV screening garments,
cotton fabrics was investigated by TGA characterization. As shown in implying excellent UV-blocking capability. In addition, the UPF values
Fig. 7c-d, the pristine cotton fabric undergoes two distinct degradation of the functionalized fabrics remain 213.53, 217.36, and 165.91 under
steps under nitrogen atmosphere. In the first stage, evaporation of harsh conditions such as abrasion, ultrasonic treatment, acid and alkali
moisture absorbed by the cotton fabric takes place within temperature corrosions, respectively, exhibiting superior UV-blocking performance.
range from 30 to 150 ◦ C. In the second step, the main depolymerization Therefore, POSS/CeO2/PDMS composite coating endows the function­
of glycosyl units from the cellulose fabric occurs in the temperature alized fabric with durable and exceptional UV-blocking performance,
range of 280 to 400 ◦ C, resulting in the formation of levoglucosan and which can provide skin with sufficient protection against the detri­
evaporation of degradative small molecules. Due to the excellent ther­ mental effects of UV radiation from sun.
mal stability of CeO2, no new degradation step is observed during the
thermal degradation of CeO2/Fabric. But PACe/Fabric displays three
4. Conclusion
distinct degradation stages, a new degradation stage clearly belongs to
the thermal degradation of the MAPOSS, where the scission of Si-O-Si
In this work, a multifunctional cotton fabric is successfully fabricated
bonds and the formation of Si-O-Si ceramics occur at high tempera­
by synergistically combing the advantages of CeO2, MAPOSS and PDMS.
tures [35]. Owing to the thermal insulation effect of the coating, the
The functionalized fabric has a WCA of 168.3◦ and a SA of 6.7◦ , and
onset degradation temperature (T5%) improves from 310.0 ◦ C for the
exhibits excellent superhydrophobicity even if suffered from some
pristine fabric to 319.4 ◦ C for CeO2/Fabric and 317.9 ◦ C for PACe/
extreme testing conditions including mechanical damage, chemical
Fabric, respectively, as listed in Table 2. Moreover, the ceramic barriers
corrosion, UV-irradiation and high temperature. What’s more, the
generated by the degradation process of the MAPOSS/PDMS composite
damaged cotton fabric can recover to superhydrophobic state by simple
coating further hinder the heat and mass exchange between external
heating even if suffered from drastic abrasion cycles or air plasma
vapor and underlying matrix, leading to the improvement on thermal
etching, demonstrating excellent superhydrophobic self-healing capa­
stability of the functionalized fabric [47]. Accordingly, the T75% of
bility. Meanwhile, the functionalized fabric also showcases superior
PACe/Fabric increases from 376.6 ◦ C for the pristine cotton fabric to
performance in self-cleaning, anti-fouling, oil/water separation (>99%)
452.2 ◦ C, exhibiting excellent thermal stability. As a result, the char
and emulsion separation. Due to UV scattering and absorbing effects of
yield at 800 ◦ C is enhanced from 9.7% for the pristine fabric to 16.2% for
CeO2 nanoparticles and protection of MAPOSS/PDMS coating for CeO2
PACe/Fabric, respectively, indicating that CeO2, MAPOSS and PDMS
nanoparticles, the UPF value of the functionalized fabric increase to
synergistically improve thermal stability of the functionalized fabric.
239.0, showing excellent and stable UV-blocking capability. In addition,
the mechanical and thermal properties of the functionalized fabric are
greatly improved without compromising its air permeability. These
3.6. Breathability and UV-blocking properties of the functionalized cotton
fabric
Table 3
In Fig. 8a, the air permeability rate of the functionalized fabric de­ UPF values of the functionalized fabric after experiencing the different
treatments.
creases to 64.6 mm/s for the functionalized cotton fabric with a
reduction of 13.2%, which cannot cause significant discomfort to skin. After 240 After ultrasonic After immersion After immersion
abrasion treatment for in 1 M HCl in 1 M NaOH
Additionally, the ultraviolet (UV) blocking property of the functional­
cycles 24 h solution for 24 h solution for 24 h
ized cotton fabric is also evaluated. Fig. 8b presents that the UPF value of
the pristine fabric is 28.8, indicating a relatively weak UV-blocking UVA
4.45 ± 0.07 3.71 ± 0.26 3.46 ± 0.26 4.32 ± 0.22
(%)
capability. Interestingly, the UPF value of CeO2/Fabric is dramatically UVB
improved to 186.7, which is ascribed to UV absorbing and scattering 0.50 ± 0.02 0.24 ± 0.02 0.24 ± 0.03 0.31 ± 0.03
(%)
effects of the CeO2 nanoparticles. Besides, the UPF value of the cotton UPF 100.48 ± 1.67 213.53 ± 14.41 217.36 ± 17.69 165.91 ± 13.95
fabric treated by the MAPOSS/CeO2/PDMS composite coating further

Fig. 8. a) The air permeability rate, and b) UPF value of the finished fabrics.

9
X. Feng et al. International Journal of Biological Macromolecules 283 (2024) 137718

findings will pave the way to exploitation and applications of novel [11] X. Zang, J. Bian, Y. Ni, W. Zheng, T. Zhu, Z. Chen, X. Cao, J. Huang, Y. Lai, Z. Lin,
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robust superhydrophobic coatings with damage sensitive photoluminescence,
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Xiang Feng: Writing – original draft, Methodology, Conceptualiza­ [13] H. Yue, J. Wang, H. Wang, Z. Du, X. Cheng, X. Du, Flame-retardant and form-stable
tion. Xiaoyuan Zhang: Investigation, Data curation. Weixia Yan: Re­ phase-change composites based on phytic acid/ZnO-decorated surface-carbonized
delignified wood with superior solar-thermal conversion efficiency and improved
sources, Formal analysis. Kailong Chen: Software. Xin Guo: thermal conductivity, ACS Appl. Mater. Interfaces 15 (6) (2023) 8093–8104.
Visualization. Yuanfen Huang: Project administration. Jinfeng Zhang: [14] K. An, C. Long, Y. Sui, Y. Qing, G. Zhao, Z. An, L. Wang, C. Liu, Large-scale
Validation. Dongzhi Chen: Writing – review & editing, Supervision, preparation of superhydrophobic cerium dioxide nanocomposite coating with UV
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Technol. 384 (2020) 125312.
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